Mechanistic Insight into Nanoparticle Surface Adsorption by Solution NMR Spectroscopy in an Aqueous Gel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Egner, Timothy K.; Naik, Pranjali; Nelson, Nicholas C.

Engineering nanoparticle (NP) functions at the molecular level requires a detailed understanding of the dynamic processes occurring at the NP surface. Herein we show that a combination of dark-state exchange saturation transfer (DEST) and relaxation dispersion (RD) NMR experiments on gel-stabilized NP samples enables the accurate determination of the kinetics and thermodynamics of adsorption. We used the former approach to describe the interaction of cholic acid (CA) and phenol (PhOH) with ceria NPs with a diameter of approximately 200 nm. Whereas CA formed weak interactions with the NPs, PhOH was tightly bound to the NP surface. Interestingly, we found thatmore » the adsorption of PhOH proceeds via an intermediate, weakly bound state in which the small molecule has residual degrees of rotational diffusion. Here we believe the use of aqueous gels for stabilizing NP samples will increase the applicability of solution NMR methods to the characterization of nanomaterials.« less

Mechanistic Insight into Nanoparticle Surface Adsorption by Solution NMR Spectroscopy in an Aqueous Gel

DOE PAGES

Egner, Timothy K.; Naik, Pranjali; Nelson, Nicholas C.; ...

2017-06-22

Engineering nanoparticle (NP) functions at the molecular level requires a detailed understanding of the dynamic processes occurring at the NP surface. Herein we show that a combination of dark-state exchange saturation transfer (DEST) and relaxation dispersion (RD) NMR experiments on gel-stabilized NP samples enables the accurate determination of the kinetics and thermodynamics of adsorption. We used the former approach to describe the interaction of cholic acid (CA) and phenol (PhOH) with ceria NPs with a diameter of approximately 200 nm. Whereas CA formed weak interactions with the NPs, PhOH was tightly bound to the NP surface. Interestingly, we found thatmore » the adsorption of PhOH proceeds via an intermediate, weakly bound state in which the small molecule has residual degrees of rotational diffusion. Here we believe the use of aqueous gels for stabilizing NP samples will increase the applicability of solution NMR methods to the characterization of nanomaterials.« less

Crystal-face-selective adsorption of Au nanoparticles onto polycrystalline diamond surfaces.

PubMed

Kondo, Takeshi; Aoshima, Shinsuke; Hirata, Kousuke; Honda, Kensuke; Einaga, Yasuaki; Fujishima, Akira; Kawai, Takeshi

2008-07-15

Crystal-face-selective adsorption of Au nanoparticles (AuNPs) was achieved on polycrystalline boron-doped diamond (BDD) surface via the self-assembly method combined with a UV/ozone treatment. To the best of our knowledge, this is the first report of crystal-face-selective adsorption on an inorganic solid surface. Hydrogen-plasma-treated BDD samples and those followed by UV/ozone treatment for 2 min or longer showed almost no adsorption of AuNP after immersion in the AuNP solution prepared by the citrate reduction method. However, the samples treated by UV/ozone for 10 s showed AuNP adsorption on their (111) facets selectively after the immersion. Moreover, the sample treated with UV/ozone for 40-60 s showed AuNP adsorption on the whole surface. These results indicate that the AuNP adsorption behavior can be controlled by UV/ozone treatment time. This phenomenon was highly reproducible and was applied to a two-step adsorption method, where AuNPs from different batches were adsorbed on the (111) and (100) surface in this order. Our findings may be of great value for the fabrication of advanced nanoparticle-based functional materials via bottom-up approaches with simple macroscale procedures.

Effect of gold nanoparticle size and coating on labeling monocytes for CT tracking

PubMed Central

Chhour, Peter; Kim, Johoon; Benardo, Barbara; Tovar, Alfredo; Mian, Shaameen; Litt, Harold I.; Ferrari, Victor A.; Cormode, David P.

2017-01-01

With advances in cell therapies, interest in cell tracking techniques to monitor the migration, localization and viability of these cells continues to grow. X-ray computed tomography (CT) is a cornerstone of medical imaging but has been limited in cell tracking applications due to its low sensitivity towards contrast media. In this study, we investigate the role of size and surface functionality of gold nanoparticles for monocyte uptake to optimize the labeling of these cells for tracking in CT. We synthesized gold nanoparticles (AuNP) that range from 15 to 150 nm in diameter and examined several capping ligands, generating 44 distinct AuNP formulations. In vitro cytotoxicity and uptake experiments were performed with the RAW 264.7 monocyte cell line. The majority of formulations at each size were found to be biocompatible, with only certain 150 nm PEG functionalized particles reducing viability at high concentrations. High uptake of AuNP was found using small capping ligands with distal carboxylic acids (11-MUA and 16-MHA). Similar uptake values were found with intermediate sizes (50 and 75 nm) of AuNP when coated with 2000 MW poly(ethylene-glycol) carboxylic acid ligands (PCOOH). Low uptake values were observed with 15, 25, 100, and 150 nm PCOOH AuNP, revealing interplay between size and surface functionality. TEM and CT performed on cells revealed similar patterns of high gold uptake for 50 nm PCOOH and 75 nm PCOOH AuNP. These results demonstrate that highly negatively charged carboxylic acid coatings for AuNP provide the greatest internalization of AuNP in monocytes, with a complex dependency on size. PMID:28095688

Cationic albumin-conjugated pegylated nanoparticles as novel drug carrier for brain delivery.

PubMed

Lu, Wei; Zhang, Yan; Tan, Yu-Zhen; Hu, Kai-Li; Jiang, Xin-Guo; Fu, Shou-Kuan

2005-10-20

In this paper, a novel drug carrier for brain delivery, cationic bovine serum albumin (CBSA) conjugated with poly(ethyleneglycol)-poly(lactide) (PEG-PLA) nanoparticle (CBSA-NP), was developed and its effects were evaluated. The copolymers of methoxy-PEG-PLA and maleimide-PEG-PLA were synthesized by ring opening polymerization of D,L-lactide initiated by methoxy-PEG and maleimide-PEG, respectively, which were applied to prepare pegylated nanoparticles by means of double emulsion and solvent evaporation procedure. Native bovine serum albumin (BSA) was cationized and thiolated, followed by conjugation through the maleimide function located at the distal end of PEG surrounding the nanoparticle's surface. Transmission electron micrograph (TEM) and dynamic light scattering results showed that CBSA-NP had a round and regular shape with a mean diameter around 100 nm. Surface nitrogen was detected by X-ray photoelectron spectroscopy (XPS), and colloidal gold stained around the nanoparticle's surface was visualized in TEM, which proved that CBSA was covalently conjugated onto its surface. To evaluate the effects of brain delivery, BSA conjugated with pegylated nanoparticles (BSA-NP) was used as the control group and 6-coumarin was incorporated into the nanoparticles as the fluorescent probe. The qualitative and quantitative results of CBSA-NP uptake experiment compared with those of BSA-NP showed that rat brain capillary endothelial cells (BCECs) took in much more CBSA-NP than BSA-NP at 37 degrees C, at different concentrations and time incubations. After a dose of 60 mg/kg CBSA-NP or BSA-NP injection in mice caudal vein, fluorescent microscopy of brain coronal sections showed a higher accumulation of CBSA-NP in the lateral ventricle, third ventricle and periventricular region than that of BSA-NP. There was no difference on BCECs' viability between CBSA-conjugated and -unconjugated pegylated nanoparticles. The significant results in vitro and in vivo showed that CBSA-NP was a promising brain drug delivery carrier with low toxicity.

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

PubMed Central

Wu, Di; Navrotsky, Alexandra

2015-01-01

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. Herein, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. These thermochemical observations directly support a structure where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. These differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces. PMID:25870281

Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions.

PubMed

Bedford, Nicholas M; Hughes, Zak E; Tang, Zhenghua; Li, Yue; Briggs, Beverly D; Ren, Yang; Swihart, Mark T; Petkov, Valeri G; Naik, Rajesh R; Knecht, Marc R; Walsh, Tiffany R

2016-01-20

Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction data and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.

Preparation and characterization of lysine-immobilized poly(glycidyl methacrylate) nanoparticle-coated capillary for the separation of amino acids by open tubular capillary electrochromatography.

PubMed

Xu, Liang; Cui, Pengfei; Wang, Dongmei; Tang, Cheng; Dong, Linyi; Zhang, Can; Duan, Hongquan; Yang, Victor C

2014-01-03

In this study, poly(glycidyl methacrylate) (PGMA) nanoparticles (NPs) were prepared and chemically immobilized for the first time onto a capillary inner wall for open tubular capillary electrochromatography (OTCEC). The immobilization of PGMA NPs onto the capillary was attained by a ring-opening reaction between the NPs and an amino-silylated fused capillary inner surface. Scanning electron micrographs clearly demonstrated that the NPs were bound to the capillary inner surface in a dense monolayer. The PGMA NP-coated column was then functionalized by lysine (Lys). After fuctionalization, the capillary can afford strong anodic electroosmotic flow, especially in acidic running buffers. Separations of three amino acids (including tryptophan, tyrosine and phenylalanine) were performed in NP-modified, monolayer Lys-functionalized and bare uncoated capillaries. Results indicated that the NP-coated column can provide more retention and higher resolution for analytes due to the hydrophobic interaction between analytes and the NP-coating. Run-to-run and column-to-column reproducibilities in the separation of the amino acids using the NP-modified column were also demonstrated. Copyright © 2013 Elsevier B.V. All rights reserved.

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

DOE PAGES

Wu, Di; Navrotsky, Alexandra

2015-04-13

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. In this paper, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. Furthermore, these thermochemical observations directly support a structuremore » where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. Finally, these differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces.« less

A rational design approach to nanostructured catalysts for the oxidation of carbon monoxide

NASA Astrophysics Data System (ADS)

Karwacki, Christopher

The extraordinary energetic properties of subnanometer (<10 nm) structures consisting of reduced metals, metal oxides, and graphitic carbons are emerging as the principal technologies involving catalytic reactions at ambient temperatures, for such applications as respiratory protection, pollution abatement, chemical synthesis, sensors, and energy conversion. Gold nanoparticles (Au NP) possess unique reactive properties not present in the bulk state and have served in the past decade as a model for the nanosciences, where molecular species are synthesized, scaled, and engineered into functional materials. Gold nanoparticles as isolated structures are not useful as real catalysts and must co-exist with supports that provide enhanced stability and activity. Support oxides such as TiO2, Fe2O 3, CeO2, SiO2, Al2O3, ZrO 2, and graphitic (active) carbons have been shown to increase the active nature of AuNP and have been the subject of several thousand publications in the past decade. Zirconia compared to titania as a support for Au NP catalysis has been studied with limited success. In fact, the majority of observations show that zirconia is one of the lowest performing metal oxide supports involving Au NP oxidation catalysis. The likely reason for these observations is a lack of understanding of the relationship between structure and surface functionality as it pertains to ambient temperature oxidation catalysis (ATOC). Furthermore, virtually all substrate and catalyst preparations in earlier work were performed at high temperatures, typically 400--900°C, thus forming progressively monomorphic structures containing larger crystals with reduced surface functionality and porosity. In this research, I established the hypothesis based on a structural model that surface functional hydroxides are important to sustained hydrolytic reactions, such as those involving Au NP for the oxidation of CO to CO 2. Theoretical calculations by Ignatchenko, Vittadini, et al. show that zirconia readily dissociates adsorbed water on the most active and stable crystal structures (111) compared to other metal oxides, such as the common anatase (101) form of titania. Also, the support must provide a source of activated oxygen as a means to oxidize intermediate carbonates with CO 2 formation. The role of the support is to provide lattice oxygen in an activated state (O2-) for oxidation of adsorbed CO the Au NP:support interface. Furthermore, the primary interest is the energy associated Au NP in proximity to the support surface. Advancing the understanding of this region is believed to be crucial to the future design of active nanostructured materials that function under ambient conditions. The proposed model involves a structure consisting of properly sized and highly dispersed Au NP supported on a hydroxylated form of nanocrystalline zirconia. This type of zirconia is in a highly polymorphic form consisting of aggregates of small crystals less than 10 nm. The structure is highly porous, containing undercoordinated zirconium atoms, and provides an environment for rapid dissociation of molecular water. In this research and in collaboration with Mogilevsky et al., 37 I introduce a novel method for quantifying the surface concentration of two major forms of hydroxide that form on zirconia. Furthermore, in this research I show how both the porosity of the zirconia support and the size of the crystalline aggregates affect the type and surface concentration of hydroxyl groups. This relationship is thus directly related to the oxidation activity of the catalyst consisting of Au NP supported on hydroxylated ZrO 2. These phenomena are exemplified by a reduction in structural porosity and surface hydroxyl groups with increasing temperature treatments of the zirconia support. Gold NP and ZrO2 supports were extended to studies that included interactions with activated carbons. This work was done on the premise that graphitic carbons, based on their tunable porosities and surface chemistries, can enhance or stabilize the catalytic activity of neighboring Au NP. Gold dispersed on active carbon and hybrid structures consisting of Au/ZrO 2/C shows interesting properties, which lend themselves to catalytic particle stabilization and to the advancement of multifunctional material design.

Gold nanoparticles: role of size and surface chemistry on blood protein adsorption

NASA Astrophysics Data System (ADS)

Benetti, F.; Fedel, M.; Minati, L.; Speranza, G.; Migliaresi, C.

2013-06-01

Material interaction with blood proteins is a critical issue, since it could influence the biological processes taking place in the body following implantation/injection. This is particularly important in the case of nanoparticles, where innovative properties, such as size and high surface to volume ratio can lead to a behavioral change with respect to bulk macroscopic materials and could be responsible for a potential risk for human health. The aim of this work was to compare gold nanoparticles (AuNP) and planar surfaces to study the role of surface curvature moving from the macro- to the nano-size in the process of blood protein adsorption. In the course of the study, different protocols were tested to optimize the analysis of protein adsorption on gold nanoparticles. AuNP with different size (10, 60 and 200 nm diameter) and surface coatings (citrate and polyethylene glycol) were carefully characterized. The stabilizing action of blood proteins adsorbed on AuNP was studied measuring the variation of size and solubility of the nanoparticles following incubation with single protein solutions (human serum albumin and fibrinogen) and whole blood plasma. In addition, we developed a method to elute proteins from AuNP to study the propensity of gold materials to adsorb plasma proteins in function of dimensional characteristics and surface chemistry. We showed a different efficacy of the various eluting media tested, proving that even the most aggressive agent cannot provide a complete detachment of the protein corona. Enhanced protein adsorption was evidenced on AuNP if compared to gold laminae (bare and PEGylated) used as macroscopic control, probably due to the superior AuNP surface reactivity.

Functionalized magnetic nanoparticles for the decontamination of water polluted with cesium

NASA Astrophysics Data System (ADS)

Helal, Ahmed S.; Decorse, Philippe; Perruchot, Christian; Novak, Sophie; Lion, Claude; Ammar, Souad; El Hage Chahine, Jean-Michel; Hémadi, Miryana

2016-05-01

Magnetic nanoparticles are attracting considerable interest because of their potential applications in practically all fields of science and technology, including the removal of heavy metals from contaminated waters. It is, therefore, of great importance to adapt the surfaces of these nanoparticles according to the application. In this work advanced nanoparticles (NPs) with well-tailored surface functionalities were synthesized using the polyol method. The efficiency of a chelating agent, succinyl-β-cyclodextrin (SBCD), was first investigated spectrophotometrically and by Isothermal Titration Calorimetry (ITC). SBCD was then grafted onto nanoparticles previously functionalized with 3-aminopropyl triethoxsilane (NP-APTES). The resulting NP-SBCD system was then incubated with a solution of cesium. After magnetic separation, the solid residue was removed from the supernatant and characterized by X-Ray Photoelectron spectrometry (XPS), X-Ray Fluorescence spectrometry (XRF) and Superconducting QUantum Interference Device (SQUID) magnetometry. These characterizations show the presence of cesium in the solid residue, which indicates Cs uptake by the NP-SBCD system. This nanohybrid system constitutes a promising model for heavy metal decontamination.

Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bedford, Nicholas M.; Hughes, Zak E.; Tang, Zhenghua

Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction datamore » and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.« less

Global transcriptomic analysis of model human cell lines exposed to surface-modified gold nanoparticles: the effect of surface chemistry

NASA Astrophysics Data System (ADS)

Grzincic, E. M.; Yang, J. A.; Drnevich, J.; Falagan-Lotsch, P.; Murphy, C. J.

2015-01-01

Gold nanoparticles (Au NPs) are attractive for biomedical applications not only for their remarkable physical properties, but also for the ease of which their surface chemistry can be manipulated. Many applications involve functionalization of the Au NP surface in order to improve biocompatibility, attach targeting ligands or carry drugs. However, changes in cells exposed to Au NPs of different surface chemistries have been observed, and little is known about how Au NPs and their surface coatings may impact cellular gene expression. The gene expression of two model human cell lines, human dermal fibroblasts (HDF) and prostate cancer cells (PC3) was interrogated by microarray analysis of over 14 000 human genes. The cell lines were exposed to four differently functionalized Au NPs: citrate, poly(allylamine hydrochloride) (PAH), and lipid coatings combined with alkanethiols or PAH. Gene functional annotation categories and weighted gene correlation network analysis were used in order to connect gene expression changes to common cellular functions and to elucidate expression patterns between Au NP samples. Coated Au NPs affect genes implicated in proliferation, angiogenesis, and metabolism in HDF cells, and inflammation, angiogenesis, proliferation apoptosis regulation, survival and invasion in PC3 cells. Subtle changes in surface chemistry, such as the initial net charge, lability of the ligand, and underlying layers greatly influence the degree of expression change and the type of cellular pathway affected.Gold nanoparticles (Au NPs) are attractive for biomedical applications not only for their remarkable physical properties, but also for the ease of which their surface chemistry can be manipulated. Many applications involve functionalization of the Au NP surface in order to improve biocompatibility, attach targeting ligands or carry drugs. However, changes in cells exposed to Au NPs of different surface chemistries have been observed, and little is known about how Au NPs and their surface coatings may impact cellular gene expression. The gene expression of two model human cell lines, human dermal fibroblasts (HDF) and prostate cancer cells (PC3) was interrogated by microarray analysis of over 14 000 human genes. The cell lines were exposed to four differently functionalized Au NPs: citrate, poly(allylamine hydrochloride) (PAH), and lipid coatings combined with alkanethiols or PAH. Gene functional annotation categories and weighted gene correlation network analysis were used in order to connect gene expression changes to common cellular functions and to elucidate expression patterns between Au NP samples. Coated Au NPs affect genes implicated in proliferation, angiogenesis, and metabolism in HDF cells, and inflammation, angiogenesis, proliferation apoptosis regulation, survival and invasion in PC3 cells. Subtle changes in surface chemistry, such as the initial net charge, lability of the ligand, and underlying layers greatly influence the degree of expression change and the type of cellular pathway affected. Electronic supplementary information (ESI) available: UV-Vis spectra of Au NPs, the most significantly changed genes of HDF cells after Au NP incubation under GO accession number GO:0007049 ``cell cycle'', detailed information about the primer/probe sets used for RT-PCR validation of results. See DOI: 10.1039/c4nr05166a

Lights, Camera, Reaction! The Influence of Interfacial Chemistry on Nanoparticle Photoreactivity

NASA Astrophysics Data System (ADS)

Farner Budarz, Jeffrey Michael

The ability of photocatalytic nanoparticles (NPs) to produce reactive oxygen species (ROS) has inspired research into several new applications and technologies, including water purification, contaminant remediation, and self-cleaning surface coatings. As a result, NPs continue to be incorporated into a wide variety of increasingly complex products. With the increased use of NPs and nano-enabled products and their subsequent disposal, NPs will make their way into the environment. Currently, many unanswered questions remain concerning how changes to the NP surface chemistry that occur in natural waters will impact reactivity. This work seeks to investigate potential influences on photoreactivity - specifically the impact of functionalization, the influence of anions, and interactions with biological objects - so that ROS generation in natural aquatic environments may be better understood. To this aim, titanium dioxide nanoparticles (TiO2) and fullerene nanoparticles (FNPs) were studied in terms of their reactive endpoints: ROS generation measured through the use of fluorescent or spectroscopic probe compounds, virus and bacterial inactivation, and contaminant degradation. Physical characterization of NPs included light scattering, electron microscopy and electrophoretic mobility. These systematic investigations into the effect of functionalization, sorption, and aggregation on NP aggregate structure, size, and reactivity improve our understanding of trends that impact nanoparticle reactivity. Engineered functionalization of FNPs was shown to impact NP aggregation, ROS generation, and viral affinity. Fullerene cage derivatization can lead to a greater affinity for the aqueous phase, smaller mean aggregate size, and a more open aggregate structure, favoring greater rates of ROS production. At the same time however, fullerene derivatization also decreases the 1O2 quantum yield and may either increase or decrease the affinity for a biological surface. These results suggest that the biological impact of fullerenes will be influenced by changes in the type of surface functionalization and extent of cage derivatization, potentially increasing the ROS generation rate and facilitating closer association with biological targets. Investigations into anion sorption onto the surface of TiO2 indicate that reactivity will be strongly influenced by the waters they are introduced into. The type and concentration of anion impacted both aggregate state and reactivity to varying degrees. Specific interactions due to inner sphere ligand exchange with phosphate and carbonate have been shown to stabilize NPs. As a result, waters containing chloride or nitrate may have little impact on inherent reactivity but will reduce NP transport via aggregation, while waters containing even low levels of phosphate and carbonate may decrease "acute" reactivity but stabilize NPs such that their lifetime in the water column is increased. Finally, ROS delivery in a multicomponent system was studied under the paradigm of pesticide degradation. The presence of bacteria or chlorpyrifos in solution significantly decreased bulk ROS measurements, with almost no •OH detected when both were present. However, the presence of bacteria had no observable impact on the rate of chlorpyrifos degradation, nor chlorpyrifos on bacterial inactivation. These results imply that investigating reactivity in simplified systems may significantly over or underestimate photocatalytic efficiency in realistic environments, depending on the surface affinity of a given target. This dissertation demonstrates that the reactivity of a system is largely determined by NP surface chemistry. Altering the NP surface, either intentionally or incidentally, produces significant changes in reactivity and aggregate characteristics. Additionally, the photocatalytic impact of the ROS generated by a NP depends on the characteristics of potential targets as well as on the characteristics of the NP itself. These are complicating factors, and the myriad potential exposure conditions, endpoints, and environmental systems to be considered for even a single NP highlight the need for functional assays that employ environmentally relevant conditions if risk assessments for engineered NPs are to be made in a timely fashion so as not to be outpaced by, or impede, technological advances.

Canopy Dynamics in Nanoscale Ionic Materials Probed by NMR

NASA Astrophysics Data System (ADS)

Mirau, Peter

2013-03-01

Nanoscale ionic materials (NIMs) are hybrids prepared from ionically functionalized nanoparticles (NP) neutralized by oligomeric polymer counter-ions. NIMs are designed to behave as liquids under ambient conditions in the absence of solvent and have no volatile organic content, making them useful for a number of applications. We have used NMR relaxation and pulse-field gradient NMR to probe local and collective canopy dynamics in NIMs based on silica nanoparticles (NP), fullerols and proteins in order to understand the relationship between the core and canopy structure and the bulk properties. The NMR studies show that the canopy dynamics depend on the degree of neutralization, the canopy radius of gyration and molecular crowding at the ionically modified NP surface. The viscosity in NIMs can be directly controlled with the addition of ions that enhance the exchange rate for polymers at the NP surface. These results show that NIMs for many applications can be prepared by controlling the dynamics of the NP interface.

Probing the influence of cell surface polysaccharides on nanodendrimer binding to Gram-negative and Gram-positive bacteria using single-nanoparticle force spectroscopy.

PubMed

Beaussart, Audrey; Beloin, Christophe; Ghigo, Jean-Marc; Chapot-Chartier, Marie-Pierre; Kulakauskas, Saulius; Duval, Jérôme F L

2018-06-27

The safe use and design of nanoparticles (NPs) ask for a comprehensive interpretation of their potentially adverse effects on (micro)organisms. In this respect, the prior assessment of the interactions experienced by NPs in the vicinity of - and in contact with - complex biological surfaces is mandatory. It requires the development of suitable techniques for deciphering the processes that govern nano-bio interactions when a single organism is exposed to an extremely low dose of NPs. Here, we used atomic force spectroscopy (AFM)-based force measurements to investigate at the nanoscale the interactions between carboxylate-terminated polyamidoamine (PAMAM) nanodendrimers (radius ca. 4.5 nm) and two bacteria with very distinct surface properties, Escherichia coli and Lactococcus lactis. The zwitterionic nanodendrimers exhibit a negative peripheral surface charge and/or a positive intraparticulate core depending on the solution pH and salt concentration. Following an original strategy according to which a single dendrimer NP is grafted at the very apex of the AFM tip, the density and localization of NP binding sites are probed at the surface of E. coli and L. lactis mutants expressing different cell surface structures (presence/absence of the O-antigen of the lipopolysaccharides (LPS) or of a polysaccharide pellicle). In line with electrokinetic analysis, AFM force measurements evidence that adhesion of NPs onto pellicle-decorated L. lactis is governed by their underlying electrostatic interactions as controlled by the pH-dependent charge of the peripheral and internal NP components, and the negatively-charged cell surface. In contrast, the presence of the O-antigen on E. coli systematically suppresses the adhesion of nanodendrimers onto cells, may the apparent NP surface charge be determined by the peripheral carboxylate groups or by the internal amine functions. Altogether, this work highlights the differentiated roles played by surface polysaccharides in mediating NP attachment to Gram-positive and Gram-negative bacteria. It further demonstrates that the assessment of NP bioadhesion features requires a critical analysis of the electrostatic contributions stemming from the various structures composing the stratified cell envelope, and those originating from the bulk and surface NP components. The joint use of electrokinetics and AFM provides a valuable option for rapidly addressing the binding propensity of NPs to microorganisms, as urgently needed in NP risk assessments.

Approach to Rapid Synthesis and Functionalization of Iron Oxide Nanoparticles for High Gene Transfection.

PubMed

Stephen, Zachary R; Dayringer, Christopher J; Lim, Josh J; Revia, Richard A; Halbert, Mackenzie V; Jeon, Mike; Bakthavatsalam, Arvind; Ellenbogen, Richard G; Zhang, Miqin

2016-03-01

Surface functionalization of theranostic nanoparticles (NPs) typically relies on lengthy, aqueous postsynthesis labeling chemistries that have limited ability to fine-tune surface properties and can lead to NP heterogeneity. The need for a rapid, simple synthesis approach that can provide great control over the display of functional moieties on NP surfaces has led to increased use of highly selective bioorthoganol chemistries including metal-affinity coordination. Here we report a simple approach for rapid production of a superparamagnetic iron oxide NPs (SPIONs) with tunable functionality and high reproducibility under aqueous conditions. We utilize the high affinity complex formed between catechol and Fe((III)) as a means to dock well-defined catechol modified polymer modules on the surface of SPIONs during sonochemical coprecipitation synthesis. Polymer modules consisted of chitosan and poly(ethylene glycol) (PEG) copolymer (CP) modified with catechol (CCP), and CCP functionalized with cationic polyethylenimine (CCP-PEI) to facilitate binding and delivery of DNA for gene therapy. This rapid synthesis/functionalization approach provided excellent control over the extent of PEI labeling, improved SPION magnetic resonance imaging (MRI) contrast enhancement and produced an efficient transfection agent.

Role of plasma membrane surface charges in dictating the feasibility of membrane-nanoparticle interactions

NASA Astrophysics Data System (ADS)

Sinha, Shayandev; Jing, Haoyuan; Sachar, Harnoor Singh; Das, Siddhartha

2017-12-01

Receptor-ligand (R-L) binding mediated interactions between the plasma membrane (PM) and a nanoparticle (NP) require the ligand-functionalized NPs to come to a distance of separation (DOS) of at least dRL (length of the R-L complex) from the receptor-bearing membranes. In this letter, we establish that the membrane surface charges and the surrounding ionic environment dictate whether or not the attainment of such a critical DOS is possible. The negatively charged membrane invariably induces a negative electrostatic potential at the NP surface, repelling the NP from the membrane. This is countered by the attractive influences of the thermal fluctuations and van der Waals (vdw) interactions that drive the NP close to the membrane. For a NP approaching the membrane from a distance, the ratio of the repulsive (electrostatic) and attractive (thermal and vdW) effects balances at a critical NP-membrane DOS of dg,c. For a given set of parameters, there can be two possible values of dg,c, namely, dg,c,1 and dg,c,2 with dg,c,1 ≫ dg,c,2. We establish that any R-L mediated NP-membrane interaction is possible only if dRL > dg,c,1. Therefore, our study proposes a design criterion for engineering ligands for a NP that will ensure the appropriate length of the R-L complex in order to ensure the successful membrane-NP interaction in the presence of a given electrostatic environment. Finally, we discuss the manner in which our theory can help designing ligand-grafted NPs for targeted drug delivery, design biomimetics NPs, and also explain various experimental results.

Synthesis of liquid crystal silane-functionalized gold nanoparticles and their effects on the optical and electro-optic properties of a structurally related nematic liquid crystal.

PubMed

Mirzaei, Javad; Urbanski, Martin; Kitzerow, Heinz-S; Hegmann, Torsten

2014-05-19

Chemically and thermally robust liquid crystal silane-functionalized gold nanoparticles (i.e. AuNP1-AuNP3) were synthesized through silane conjugation. Colloidal dispersions of these particles with mesogenic ligands that are structurally identical (as in AuNP1, AuNP2) or compatible (as in AuNP3) with molecules of the nematic liquid crystal (N-LC) host showed superior colloidal stability and dispersibility. The thermal, optical, and electro-optic behaviors of the N-LC composites at different concentrations of each gold nanoparticle were investigated. All dispersions showed lower values for the rotational viscosity and elastic constant, but only AuNP3 with a dissimilar structure between the nanoparticle ligand and the host displayed the most drastic thermal effects and overall strongest impact on the electro-optic properties of the host. The observed results were explained considering both the structure and the density of the surface ligands of each gold nanoparticle. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hyaluronic acid-functionalized polymeric nanoparticles for colon cancer-targeted combination chemotherapy

NASA Astrophysics Data System (ADS)

Xiao, Bo; Han, Moon Kwon; Viennois, Emilie; Wang, Lixin; Zhang, Mingzhen; Si, Xiaoying; Merlin, Didier

2015-10-01

Nanoparticle (NP)-based combination chemotherapy has been proposed as an effective strategy for achieving synergistic effects and targeted drug delivery for colon cancer therapy. Here, we fabricated a series of hyaluronic acid (HA)-functionalized camptothecin (CPT)/curcumin (CUR)-loaded polymeric NPs (HA-CPT/CUR-NPs) with various weight ratios of CPT to CUR (1 : 1, 2 : 1 and 4 : 1). The resultant spherical HA-CPT/CUR-NPs had a desirable particle size (around 289 nm), relative narrow size distribution, and slightly negative zeta potential. These NPs exhibited a simultaneous sustained release profile for both drugs throughout the time frame examined. Subsequent cellular uptake experiments demonstrated that the introduction of HA to the NP surface endowed NPs with colon cancer-targeting capability and markedly increased cellular uptake efficiency compared with chitosan-coated NPs. Importantly, the combined delivery of CPT and CUR in one HA-functionalized NP exerted strong synergistic effects. HA-CPT/CUR-NP (1 : 1) showed the highest antitumor activity among the three HA-CPT/CUR-NPs, resulting in an extremely low combination index. Collectively, our findings indicate that this HA-CPT/CUR-NP can be exploited as an efficient formulation for colon cancer-targeted combination chemotherapy.Nanoparticle (NP)-based combination chemotherapy has been proposed as an effective strategy for achieving synergistic effects and targeted drug delivery for colon cancer therapy. Here, we fabricated a series of hyaluronic acid (HA)-functionalized camptothecin (CPT)/curcumin (CUR)-loaded polymeric NPs (HA-CPT/CUR-NPs) with various weight ratios of CPT to CUR (1 : 1, 2 : 1 and 4 : 1). The resultant spherical HA-CPT/CUR-NPs had a desirable particle size (around 289 nm), relative narrow size distribution, and slightly negative zeta potential. These NPs exhibited a simultaneous sustained release profile for both drugs throughout the time frame examined. Subsequent cellular uptake experiments demonstrated that the introduction of HA to the NP surface endowed NPs with colon cancer-targeting capability and markedly increased cellular uptake efficiency compared with chitosan-coated NPs. Importantly, the combined delivery of CPT and CUR in one HA-functionalized NP exerted strong synergistic effects. HA-CPT/CUR-NP (1 : 1) showed the highest antitumor activity among the three HA-CPT/CUR-NPs, resulting in an extremely low combination index. Collectively, our findings indicate that this HA-CPT/CUR-NP can be exploited as an efficient formulation for colon cancer-targeted combination chemotherapy. Electronic supplementary information (ESI) available: Representative flow cytometry plots of cells incubated with or without cationic CPT/CUR-NPs (1 : 1) for 3 h; Cytotoxicity of blank chitosan-coated NPs and blank HA-functionalized NPs at different concentrations against Colon-26 cells after 48 h of co-incubation. See DOI: 10.1039/c5nr04831a

Silver nanoparticle-human hemoglobin interface: time evolution of the corona formation and interaction phenomenon

NASA Astrophysics Data System (ADS)

Bhunia, A. K.; Kamilya, T.; Saha, S.

2017-10-01

In this paper, we have used spectroscopic and electron microscopic analysis to monitor the time evolution of the silver nanoparticles (Ag NP)-human hemoglobin (Hb) corona formation and to characterize the interaction of the Ag NPs with Hb. The time constants for surface plasmon resonance binding and reorganization are found to be 9.51 and 118.48 min, respectively. The drop of surface charge and the increase of the hydrodynamic diameter indicated the corona of Hb on the Ag NP surface. The auto correlation function is found to broaden with the increasing time of the corona formation. Surface zeta potential revealed that positively charged Hb interact electrostatically with negatively charged Ag NP surfaces. The change in α helix and β sheet depends on the corona formation time. The visualization of the Hb corona from HRTEM showed large number of Hb domains aggregate containing essentially Ag NPs and without Ag NPs. Emission study showed the tertiary deformation, energy transfer, nature of interaction and quenching under three different temperatures.

Silver nanoparticle-human hemoglobin interface: time evolution of the corona formation and interaction phenomenon.

PubMed

Bhunia, A K; Kamilya, T; Saha, S

2017-01-01

In this paper, we have used spectroscopic and electron microscopic analysis to monitor the time evolution of the silver nanoparticles (Ag NP)-human hemoglobin (Hb) corona formation and to characterize the interaction of the Ag NPs with Hb. The time constants for surface plasmon resonance binding and reorganization are found to be 9.51 and 118.48 min, respectively. The drop of surface charge and the increase of the hydrodynamic diameter indicated the corona of Hb on the Ag NP surface. The auto correlation function is found to broaden with the increasing time of the corona formation. Surface zeta potential revealed that positively charged Hb interact electrostatically with negatively charged Ag NP surfaces. The change in α helix and β sheet depends on the corona formation time. The visualization of the Hb corona from HRTEM showed large number of Hb domains aggregate containing essentially Ag NPs and without Ag NPs. Emission study showed the tertiary deformation, energy transfer, nature of interaction and quenching under three different temperatures.

Nitrogen to phosphorus ratio of plant biomass versus soil solution in a tropical pioneer tree, Ficus insipida.

PubMed

Garrish, Valerie; Cernusak, Lucas A; Winter, Klaus; Turner, Benjamin L

2010-08-01

It is commonly assumed that the nitrogen to phosphorus (N:P) ratio of a terrestrial plant reflects the relative availability of N and P in the soil in which the plant grows. Here, this was assessed for a tropical pioneer tree, Ficus insipida. Seedlings were grown in sand and irrigated with nutrient solutions containing N:P ratios ranging from <1 to >100. The experimental design further allowed investigation of physiological responses to N and P availability. Homeostatic control over N:P ratios was stronger in leaves than in stems or roots, suggesting that N:P ratios of stems and roots are more sensitive indicators of the relative availability of N and P at a site than N:P ratios of leaves. The leaf N:P ratio at which the largest plant dry mass and highest photosynthetic rates were achieved was approximately 11, whereas the corresponding whole-plant N:P ratio was approximately 6. Plant P concentration varied as a function of transpiration rate at constant nutrient solution P concentration, possibly due to transpiration-induced variation in the mass flow of P to root surfaces. The transpiration rate varied in response to nutrient solution N concentration, but not to nutrient solution P concentration, demonstrating nutritional control over transpiration by N but not P. Water-use efficiency varied as a function of N availability, but not as a function of P availability.

Novel hybrid structure silica/CdTe/molecularly imprinted polymer: synthesis, specific recognition, and quantitative fluorescence detection of bovine hemoglobin.

PubMed

Li, Dong-Yan; He, Xi-Wen; Chen, Yang; Li, Wen-You; Zhang, Yu-Kui

2013-12-11

This work presented a novel strategy for the synthesis of the hybrid structure silica/CdTe/molecularly imprinted polymer (Si-NP/CdTe/MIP) to recognize and detect the template bovine hemoglobin (BHb). First, amino-functionalized silica nanoparticles (Si-NP) and carboxyl-terminated CdTe quantum dots (QDs) were assembled into composite nanoparticles (Si-NP/CdTe) using the EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride) chemistry. Next, Si-NP/CdTe/MIP was synthesized by anchoring molecularly imprinted polymer (MIP) layer on the surface of Si-NP/CdTe through the sol-gel technique and surface imprinting technique. The hybrid structure possessed the selectivity of molecular imprinting technique and the sensitivity of CdTe QDs as well as well-defined morphology. The binding experiment and fluorescence method demonstrated its special recognition performance toward the template BHb. Under the optimized conditions, the fluorescence intensity of the Si-NP/CdTe/MIP decreased linearly with the increase of BHb in the concentration range 0.02-2.1 μM, and the detection limit was 9.4 nM. Moreover, the reusability and reproducibility and the successful applications in practical samples indicated the synthesis of Si-NP/CdTe/MIP provided an alternative solution for special recognition and determination of protein from real samples.

Chemically engineered graphene-based 2D organic molecular magnet.

PubMed

Hong, Jeongmin; Bekyarova, Elena; de Heer, Walt A; Haddon, Robert C; Khizroev, Sakhrat

2013-11-26

Carbon-based magnetic materials and structures of mesoscopic dimensions may offer unique opportunities for future nanomagnetoelectronic/spintronic devices. To achieve their potential, carbon nanosystems must have controllable magnetic properties. We demonstrate that nitrophenyl functionalized graphene can act as a room-temperature 2D magnet. We report a comprehensive study of low-temperature magnetotransport, vibrating sample magnetometry (VSM), and superconducting quantum interference (SQUID) measurements before and after radical functionalization. Following nitrophenyl (NP) functionalization, epitaxially grown graphene systems can become organic molecular magnets with ferromagnetic and antiferromagnetic ordering that persists at temperatures above 400 K. The field-dependent, surface magnetoelectric properties were studied using scanning probe microscopy (SPM) techniques. The results indicate that the NP-functionalization orientation and degree of coverage directly affect the magnetic properties of the graphene surface. In addition, graphene-based organic magnetic nanostructures were found to demonstrate a pronounced magneto-optical Kerr effect (MOKE). The results were consistent across different characterization techniques and indicate room-temperature magnetic ordering along preferred graphene orientations in the NP-functionalized samples. Chemically isolated graphene nanoribbons (CINs) were observed along the preferred functionality directions. These results pave the way for future magnetoelectronic/spintronic applications based on promising concepts such as current-induced magnetization switching, magnetoelectricity, half-metallicity, and quantum tunneling of magnetization.

Incorporation of silver nanoparticles on the surface of orthodontic microimplants to achieve antimicrobial properties

PubMed Central

Venugopal, Adith; Muthuchamy, Nallal; Tejani, Harsh; Gopalan, Anantha-Iyengar; Lee, Kwang-Pill; Lee, Heon-Jin

2017-01-01

Objective Microbial aggregation around dental implants can lead to loss/loosening of the implants. This study was aimed at surface treating titanium microimplants with silver nanoparticles (AgNPs) to achieve antibacterial properties. Methods AgNP-modified titanium microimplants (Ti-nAg) were prepared using two methods. The first method involved coating the microimplants with regular AgNPs (Ti-AgNP) and the second involved coating them with a AgNP-coated biopolymer (Ti-BP-AgNP). The topologies, microstructures, and chemical compositions of the surfaces of the Ti-nAg were characterized by scanning electron microscopy (SEM) equipped with energy-dispersive spectrometer (EDS) and X-ray photoelectron spectroscopy (XPS). Disk diffusion tests using Streptococcus mutans, Streptococcus sanguinis, and Aggregatibacter actinomycetemcomitans were performed to test the antibacterial activity of the Ti-nAg microimplants. Results SEM revealed that only a meager amount of AgNPs was sparsely deposited on the Ti-AgNP surface with the first method, while a layer of AgNP-coated biopolymer extended along the Ti-BP-AgNP surface in the second method. The diameters of the coated nanoparticles were in the range of 10 to 30 nm. EDS revealed 1.05 atomic % of Ag on the surface of the Ti-AgNP and an astounding 21.2 atomic % on the surface of the Ti-BP-AgNP. XPS confirmed the metallic state of silver on the Ti-BP-AgNP surface. After 24 hours of incubation, clear zones of inhibition were seen around the Ti-BP-AgNP microimplants in all three test bacterial culture plates, whereas no antibacterial effect was observed with the Ti-AgNP microimplants. Conclusions Titanium microimplants modified with Ti-BP-AgNP exhibit excellent antibacterial properties, making them a promising implantable biomaterial. PMID:28127534

Impact of protein pre-coating on the protein corona composition and nanoparticle cellular uptake.

PubMed

Mirshafiee, Vahid; Kim, Raehyun; Park, Soyun; Mahmoudi, Morteza; Kraft, Mary L

2016-01-01

Nanoparticles (NPs) are functionalized with targeting ligands to enable selectively delivering drugs to desired locations in the body. When these functionalized NPs enter the blood stream, plasma proteins bind to their surfaces, forming a protein corona that affects NP uptake and targeting efficiency. To address this problem, new strategies for directing the formation of a protein corona that has targeting capabilities are emerging. Here, we have investigated the feasibility of directing corona composition to promote targeted NP uptake by specific types of cells. We used the well-characterized process of opsonin-induced phagocytosis by macrophages as a simplified model of corona-mediated NP uptake by a desired cell type. We demonstrate that pre-coating silica NPs with gamma-globulins (γ-globulins) produced a protein corona that was enriched with opsonins, such as immunoglobulins. Although immunoglobulins are ligands that bind to receptors on macrophages and elicit phagocytois, the opsonin-rich protein corona did not increase NP uptake by macrophage RAW 264.7 cells. Immunolabeling experiments indicated that the binding of opsonins to their target cell surface receptors was impeded by other proteins in the corona. Thus, corona-mediated NP targeting strategies must optimize both the recruitment of the desired plasma proteins as well as their accessibility and orientation in the corona layer. Copyright © 2015 Elsevier Ltd. All rights reserved.

Modulation of Human Macrophage Responses to Mycobacterium tuberculosis by Silver Nanoparticles of Different Size and Surface Modification

PubMed Central

Sarkar, Srijata; Leo, Bey Fen; Carranza, Claudia; Chen, Shu; Rivas-Santiago, Cesar; Porter, Alexandra E.; Ryan, Mary P.; Gow, Andrew; Chung, Kian Fan; Tetley, Teresa D.; Zhang, Junfeng (Jim); Georgopoulos, Panos G.; Ohman-Strickland, Pamela A.; Schwander, Stephan

2015-01-01

Exposure to silver nanoparticles (AgNP) used in consumer products carries potential health risks including increased susceptibility to infectious pathogens. Systematic assessments of antimicrobial macrophage immune responses in the context of AgNP exposure are important because uptake of AgNP by macrophages may lead to alterations of innate immune cell functions. In this study we examined the effects of exposure to AgNP with different particle sizes (20 and 110 nm diameters) and surface chemistry (citrate or polyvinlypyrrolidone capping) on cellular toxicity and innate immune responses against Mycobacterium tuberculosis (M.tb) by human monocyte-derived macrophages (MDM). Exposures of MDM to AgNP significantly reduced cellular viability, increased IL8 and decreased IL10 mRNA expression. Exposure of M.tb-infected MDM to AgNP suppressed M.tb-induced expression of IL1B, IL10, and TNFA mRNA. Furthermore, M.tb-induced IL-1β, a cytokine critical for host resistance to M.tb, was inhibited by AgNP but not by carbon black particles indicating that the observed immunosuppressive effects of AgNP are particle specific. Suppressive effects of AgNP on the M.tb-induced host immune responses were in part due to AgNP-mediated interferences with the TLR signaling pathways that culminate in the activation of the transcription factor NF-κB. AgNP exposure suppressed M.tb-induced expression of a subset of NF-κB mediated genes (CSF2, CSF3, IFNG, IL1A, IL1B, IL6, IL10, TNFA, NFKB1A). In addition, AgNP exposure increased the expression of HSPA1A mRNA and the corresponding stress-induced Hsp72 protein. Up-regulation of Hsp72 by AgNP can suppress M.tb-induced NF-κB activation and host immune responses. The observed ability of AgNP to modulate infectious pathogen-induced immune responses has important public health implications. PMID:26580078

Modulation of Human Macrophage Responses to Mycobacterium tuberculosis by Silver Nanoparticles of Different Size and Surface Modification.

PubMed

Sarkar, Srijata; Leo, Bey Fen; Carranza, Claudia; Chen, Shu; Rivas-Santiago, Cesar; Porter, Alexandra E; Ryan, Mary P; Gow, Andrew; Chung, Kian Fan; Tetley, Teresa D; Zhang, Junfeng Jim; Georgopoulos, Panos G; Ohman-Strickland, Pamela A; Schwander, Stephan

2015-01-01

Exposure to silver nanoparticles (AgNP) used in consumer products carries potential health risks including increased susceptibility to infectious pathogens. Systematic assessments of antimicrobial macrophage immune responses in the context of AgNP exposure are important because uptake of AgNP by macrophages may lead to alterations of innate immune cell functions. In this study we examined the effects of exposure to AgNP with different particle sizes (20 and 110 nm diameters) and surface chemistry (citrate or polyvinlypyrrolidone capping) on cellular toxicity and innate immune responses against Mycobacterium tuberculosis (M.tb) by human monocyte-derived macrophages (MDM). Exposures of MDM to AgNP significantly reduced cellular viability, increased IL8 and decreased IL10 mRNA expression. Exposure of M.tb-infected MDM to AgNP suppressed M.tb-induced expression of IL1B, IL10, and TNFA mRNA. Furthermore, M.tb-induced IL-1β, a cytokine critical for host resistance to M.tb, was inhibited by AgNP but not by carbon black particles indicating that the observed immunosuppressive effects of AgNP are particle specific. Suppressive effects of AgNP on the M.tb-induced host immune responses were in part due to AgNP-mediated interferences with the TLR signaling pathways that culminate in the activation of the transcription factor NF-κB. AgNP exposure suppressed M.tb-induced expression of a subset of NF-κB mediated genes (CSF2, CSF3, IFNG, IL1A, IL1B, IL6, IL10, TNFA, NFKB1A). In addition, AgNP exposure increased the expression of HSPA1A mRNA and the corresponding stress-induced Hsp72 protein. Up-regulation of Hsp72 by AgNP can suppress M.tb-induced NF-κB activation and host immune responses. The observed ability of AgNP to modulate infectious pathogen-induced immune responses has important public health implications.

Controlled preparation of carbon nanotube-iron oxide nanoparticle hybrid materials by a modified wet impregnation method

NASA Astrophysics Data System (ADS)

Tsoufis, Τheodoros; Douvalis, Alexios P.; Lekka, Christina E.; Trikalitis, Pantelis N.; Bakas, Thomas; Gournis, Dimitrios

2013-09-01

We report a novel, simple, versatile, and reproducible approach for the in situ synthesis of iron oxide nanoparticles (NP) on the surface of carbon nanotubes (CNT). Chemically functionalized single- or multi-wall CNT were used as nanotemplates for the synthesis of a range of very small (<10 nm) ferrimagnetic and/or anti-ferromagnetic iron oxide NP on their surface. For the synthesis of the hybrid materials, we employed for the first time a modified wet impregnation method involving the adsorption of ferric cations (as nanoparticle's precursor) on the functionalized nanotube surface and the subsequent interaction with acetic acid vapors followed by calcination at 400 °C under different atmospheres (air, argon, and oxygen). X-ray diffraction, transmission electron microscopy, Mössbauer spectroscopy, and magnetization measurements were used to study in-detail the morphology, size, and type of crystalline phases in the resulting hybrid materials. In addition, Raman measurements were used to monitor possible structural changes of the nanotubes during the synthetic approach. The experimental results were further supported by density functional theory calculations. These calculations were also used to disclose, how the type of the carbon nanotube template affects the nature and the size of the resulting NP in the final hybrids.

Improved molecular fingerprint analysis employing multi-branched gold nanoparticles in conjunction with surface-enhanced Raman scattering.

PubMed

Johnston, Jencilin; Taylor, Erik N; Gilbert, Richard J; Webster, Thomas J

2016-01-01

Vibrational spectroscopy is a powerful analytical tool that assesses molecular properties based on spectroscopic signatures. In this study, the effect of gold nanoparticle morphology (spherical vs multi-branched) was assessed for the characterization of a Raman signal (ie, molecular fingerprint) that may be helpful for numerous medical applications. Multi-branched gold nanoparticles (MBAuNPs) were fabricated using a green chemistry method which employed the reduction of gold ion solute by 2-[4-(2-hydroxyethyl)-1-piperazyl] ethane sulfonic acid. Two types of reporter dyes, indocyanine (IR820 and IR792) and carbocyanine (DTTC [3,3'-diethylthiatricarbocyanine iodide] and DTDC [3,3'-diethylthiadicarbocyanine iodide]), were functionalized to the surface of the MBAuNPs and stabilized with denatured bovine serum albumin, thus forming the surface-enhanced Raman spectroscopy tag. Fluorescein isothiocyanate-conjugated anti-epidermal growth factor receptor to the surface-enhanced Raman spectroscopy tags and the properties of the resulting conjugates were assessed through determination of the Raman signal. Using the MBAuNP Raman probes synthesized in this manner, we demonstrated that MBAuNP provided significantly more surface-enhanced Raman scattering signal when compared with the associated spherical gold nanoparticle of similar size and concentration. MBAuNP enhancements were retained in the surface-enhanced Raman spectroscopy tags complexed to anti-epidermal growth factor receptor, providing evidence that this could be a useful biological probe for enhanced Raman molecular fingerprinting. Furthermore, while utilizing IR820 as a novel reporter dye linked with MBAuNP, superior Raman signal fingerprint results were obtained. Such results provide significant promise for the use of MBAuNP in the detection of numerous diseases for which biologically specific surface markers exist.

Improved molecular fingerprint analysis employing multi-branched gold nanoparticles in conjunction with surface-enhanced Raman scattering

PubMed Central

Johnston, Jencilin; Taylor, Erik N; Gilbert, Richard J; Webster, Thomas J

2016-01-01

Vibrational spectroscopy is a powerful analytical tool that assesses molecular properties based on spectroscopic signatures. In this study, the effect of gold nanoparticle morphology (spherical vs multi-branched) was assessed for the characterization of a Raman signal (ie, molecular fingerprint) that may be helpful for numerous medical applications. Multi-branched gold nanoparticles (MBAuNPs) were fabricated using a green chemistry method which employed the reduction of gold ion solute by 2-[4-(2-hydroxyethyl)-1-piperazyl] ethane sulfonic acid. Two types of reporter dyes, indocyanine (IR820 and IR792) and carbocyanine (DTTC [3,3′-diethylthiatricarbocyanine iodide] and DTDC [3,3′-diethylthiadicarbocyanine iodide]), were functionalized to the surface of the MBAuNPs and stabilized with denatured bovine serum albumin, thus forming the surface-enhanced Raman spectroscopy tag. Fluorescein isothiocyanate-conjugated anti-epidermal growth factor receptor to the surface-enhanced Raman spectroscopy tags and the properties of the resulting conjugates were assessed through determination of the Raman signal. Using the MBAuNP Raman probes synthesized in this manner, we demonstrated that MBAuNP provided significantly more surface-enhanced Raman scattering signal when compared with the associated spherical gold nanoparticle of similar size and concentration. MBAuNP enhancements were retained in the surface-enhanced Raman spectroscopy tags complexed to anti-epidermal growth factor receptor, providing evidence that this could be a useful biological probe for enhanced Raman molecular fingerprinting. Furthermore, while utilizing IR820 as a novel reporter dye linked with MBAuNP, superior Raman signal fingerprint results were obtained. Such results provide significant promise for the use of MBAuNP in the detection of numerous diseases for which biologically specific surface markers exist. PMID:26730189

Achieving 3-D Nanoparticle Assembly in Nanocomposite Thin Films via Kinetic Control

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Jingyu; Xiao, Yihan; Xu, Ting

Nanocomposite thin films containing well-ordered nanoparticle (NP) assemblies are ideal candidates for the fabrication of metamaterials. Achieving 3-D assembly of NPs in nanocomposite thin films is thermodynamically challenging as the particle size gets similar to that of a single polymer chain. The entropic penalties of polymeric matrix upon NP incorporation leads to NP aggregation on the film surface or within the defects in the film. Controlling the kinetic pathways of assembly process provides an alternative path forward by arresting the system in nonequilibrium states. Here, we report the thin film 3-D hierarchical assembly of 20 nm NPs in supramolecules withmore » a 30 nm periodicity. By mediating the NP diffusion kinetics in the supramolecular matrix, surface aggregation of NPs was suppressed and NPs coassemble with supramolecules to form new 3-D morphologies in thin films. Lastly, the present studies opened a viable route to achieve designer functional composite thin films via kinetic control.« less

Achieving 3-D Nanoparticle Assembly in Nanocomposite Thin Films via Kinetic Control

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Jingyu; Xiao, Yihan; Xu, Ting

Nanocomposite thin films containing well-ordered nanoparticle (NP) assemblies are ideal candidates for the fabrication of metamaterials. Achieving 3-D assembly of NPs in nanocomposite thin films is thermodynamically challenging as the particle size gets similar to that of a single polymer chain. The entropic penalties of polymeric matrix upon NP incorporation leads to NP aggregation on the film surface or within the defects in the film. Controlling the kinetic pathways of assembly process provides an alternative path forward by arresting the system in nonequilibrium states. Here, we report the thin film 3-D hierarchical assembly of 20 nm NPs in supramolecules withmore » a 30 nm periodicity. By mediating the NP diffusion kinetics in the supramolecular matrix, surface aggregation of NPs was suppressed and NPs coassemble with supramolecules to form new 3-D morphologies in thin films. The present studies opened a viable route to achieve designer functional composite thin films via kinetic control.« less

Achieving 3-D Nanoparticle Assembly in Nanocomposite Thin Films via Kinetic Control

DOE PAGES

Huang, Jingyu; Xiao, Yihan; Xu, Ting

2017-02-20

Nanocomposite thin films containing well-ordered nanoparticle (NP) assemblies are ideal candidates for the fabrication of metamaterials. Achieving 3-D assembly of NPs in nanocomposite thin films is thermodynamically challenging as the particle size gets similar to that of a single polymer chain. The entropic penalties of polymeric matrix upon NP incorporation leads to NP aggregation on the film surface or within the defects in the film. Controlling the kinetic pathways of assembly process provides an alternative path forward by arresting the system in nonequilibrium states. Here, we report the thin film 3-D hierarchical assembly of 20 nm NPs in supramolecules withmore » a 30 nm periodicity. By mediating the NP diffusion kinetics in the supramolecular matrix, surface aggregation of NPs was suppressed and NPs coassemble with supramolecules to form new 3-D morphologies in thin films. Lastly, the present studies opened a viable route to achieve designer functional composite thin films via kinetic control.« less

Recognition-mediated activation of therapeutic gold nanoparticles inside living cells

NASA Astrophysics Data System (ADS)

Kim, Chaekyu; Agasti, Sarit S.; Zhu, Zhengjiang; Isaacs, Lyle; Rotello, Vincent M.

2010-11-01

Supramolecular chemistry provides a versatile tool for the organization of molecular systems into functional structures and the actuation of these assemblies for applications through the reversible association between complementary components. Use of this methodology in living systems, however, represents a significant challenge owing to the chemical complexity of cellular environments and lack of selectivity of conventional supramolecular interactions. Herein, we present a host-guest system featuring diaminohexane-terminated gold nanoparticles (AuNP-NH2) and complementary cucurbit[7]uril (CB[7]). In this system, threading of CB[7] on the particle surface reduces the cytotoxicity of AuNP-NH2 through sequestration of the particle in endosomes. Intracellular triggering of the therapeutic effect of AuNP-NH2 was then achieved through the administration of 1-adamantylamine (ADA), removing CB[7] from the nanoparticle surface, causing the endosomal release and concomitant in situ cytotoxicity of AuNP-NH2. This supramolecular strategy for intracellular activation provides a new tool for potential therapeutic applications.

Functionalization of magnetic nanocrystals by oligo (ethylene oxide) chains carrying diazonium and iniferter end groups.

PubMed

Ahmad, Randa; Griffete, Nébéwia; Lamouri, Aazdine; Mangeney, Claire

2013-10-01

The water stability of iron oxide nanoparticles (NPs) is a major issue for biomedical and biological applications. This paper presents a versatile approach for preparing water-soluble iron oxide nanoparticles coated by bifunctional oligo(ethylene oxide) (OEO) chains, carrying on the one side a diazonium end group for covalent grafting at the NP surface and on the other side an iniferter group (diethyl dithiocarbamate) for initiating the growing of poly(methacrylic acid). The nanoparticles were synthesized by coprecipitation in basic media and functionalized in situ by adding the diazonium salt directly in the synthesis medium. Oligo(ethylene oxide) with various chain lengths (from one to three monomer units) was grafted at the NP surface using this approach. The length of the OEO spacer between the NP surface and the iniferter end group was found to be a critical parameter for controlling the colloidal stability of the hybrid NPs. The polymerization time was also shown to strongly influence their colloidal stability, emphasizing the interest to control the interfacial properties of the hybrids for obtaining stable dispersions in water. Copyright © 2013 Elsevier Inc. All rights reserved.

Toxicity Effects of Functionalized Quantum Dots, Gold and Polystyrene Nanoparticles on Target Aquatic Biological Models: A Review.

PubMed

Libralato, Giovanni; Galdiero, Emilia; Falanga, Annarita; Carotenuto, Rosa; de Alteriis, Elisabetta; Guida, Marco

2017-08-31

Nano-based products are widespread in several sectors, including textiles, medical-products, cosmetics, paints and plastics. Nanosafety and safe-by-design are driving nanoparticle (NP) production and applications through NP functionalization (@NPs). Indeed, @NPs frequently present biological effects that differ from the parent material. This paper reviews the impact of quantum dots (QDs), gold nanoparticles (AuNPs), and polystyrene-cored NPs (PSNPs), evidencing the role of NP functionalization in toxicity definition. Key biological models were taken into consideration for NP evaluation: Saccharomyces cerevisiae , fresh- (F) and saltwater (S) microalgae ( Raphidocelis subcapitata (F), Scenedesmus obliquus (F) and Chlorella spp. (F), and Phaeodactylum tricornutum (S)), Daphnia magna , and Xenopus laevis . QDs are quite widespread in technological devices, and they are known to induce genotoxicity and oxidative stress that can drastically change according to the coating employed. For example, AuNPs are frequently functionalized with antimicrobial peptides, which is shown to both increase their activity and decrease the relative environmental toxicity. P-NPs are frequently coated with NH₂ - for cationic and COOH - for anionic surfaces, but when positively charged toxicity effects can be observed. Careful assessment of functionalized and non-functionalized NPs is compulsory to also understand their potential direct and indirect effects when the coating is removed or degraded.

Titanium Surface Priming with Phase-Transited Lysozyme to Establish a Silver Nanoparticle-Loaded Chitosan/Hyaluronic Acid Antibacterial Multilayer via Layer-by-Layer Self-Assembly.

PubMed

Zhong, Xue; Song, Yunjia; Yang, Peng; Wang, Yao; Jiang, Shaoyun; Zhang, Xu; Li, Changyi

2016-01-01

The formation of biofilm around implants, which is induced by immediate bacterial colonization after installation, is the primary cause of post-operation infection. Initial surface modification is usually required to incorporate antibacterial agents on titanium (Ti) surfaces to inhibit biofilm formation. However, simple and effective priming methods are still lacking for the development of an initial functional layer as a base for subsequent coatings on titanium surfaces. The purpose of our work was to establish a novel initial layer on Ti surfaces using phase-transited lysozyme (PTL), on which multilayer coatings can incorporate silver nanoparticles (AgNP) using chitosan (CS) and hyaluronic acid (HA) via a layer-by-layer (LbL) self-assembly technique. In this study, the surfaces of Ti substrates were primed by dipping into a mixture of lysozyme and tris(2-carboxyethyl)phosphine (TCEP) to obtain PTL-functionalized Ti substrates. The subsequent alternating coatings of HA and chitosan loaded with AgNP onto the precursor layer of PTL were carried out via LbL self-assembly to construct multilayer coatings on Ti substrates. The results of SEM and XPS indicated that the necklace-like PTL and self-assembled multilayer were successfully immobilized on the Ti substrates. The multilayer coatings loaded with AgNP can kill planktonic and adherent bacteria to 100% during the first 4 days. The antibacterial efficacy of the samples against planktonic and adherent bacteria achieved 65%-90% after 14 days. The sustained release of Ag over 14 days can prevent bacterial invasion until mucosa healing. Although the AgNP-containing structure showed some cytotoxicity, the toxicity can be reduced by controlling the Ag release rate and concentration. The PTL priming method provides a promising strategy for fabricating long-term antibacterial multilayer coatings on titanium surfaces via the LbL self-assembly technique, which is effective in preventing implant-associated infections in the early stage.

Charged nanoparticle attraction in multivalent salt solution: A classical-fluids density functional theory and molecular dynamics study

DOE PAGES

Salerno, K. Michael; Frischknecht, Amalie L.; Stevens, Mark J.

2016-04-08

Here, negatively charged nanoparticles (NPs) in 1:1, 1:2, and 1:3 electrolyte solutions are studied in a primitive ion model using molecular dynamics (MD) simulations and classical density functional theory (DFT). We determine the conditions for attractive interactions between the like-charged NPs. Ion density profiles and NP–NP interaction free energies are compared between the two methods and are found to be in qualitative agreement. The NP interaction free energy is purely repulsive for monovalent counterions, but can be attractive for divalent and trivalent counterions. Using DFT, the NP interaction free energy for different NP diameters and charges is calculated. The depthmore » and location of the minimum in the interaction depend strongly on the NPs’ charge. For certain parameters, the depth of the attractive well can reach 8–10 k BT, indicating that kinetic arrest and aggregation of the NPs due to electrostatic interactions is possible. Rich behavior arises from the geometric constraints of counterion packing at the NP surface. Layering of counterions around the NPs is observed and, as secondary counterion layers form the minimum of the NP–NP interaction free energy shifts to larger separation, and the depth of the free energy minimum varies dramatically. We find that attractive interactions occur with and without NP overcharging.« less

Albumin-based nanoparticle trehalose lyophilisation stress-down to preserve structure/function and enhanced binding.

PubMed

Siri, Macarena; Grasselli, Mariano; Alonso, Silvia Del V

2016-07-15

The aim of this study was to preserve albumin nanoparticle structure/function during the lyophilisation process. Bovine serum albumin nanoparticles were obtained by γ-irradiation. Nanoparticles were lyophilised in buffer, miliQ water or in trehalose/miliQ solution. The size and charge of the nanoparticles were tested after lyophilisation by light scattering and Z potential. The most relevant results in size of BSA nanoparticle were those lyophilised in PBS between 20 and 350nm, assembled in different aggregates, and negative Z potential obtained was 37±8mV in all, and those nanoparticles lyophilised with trehalose had a size range of 70±2nm and a negative Z potential of 20±5mV. Structure determination of surface aminoacids SH groups in the BSA NP lyophilised in PBS showed an increase in the free SH groups. Different aggregates had different amount of SH groups exposure from 55 to 938 (from smaller to bigger aggregates), whereas BSA NP lyophilised with trehalose showed no significant difference if compared with BSA NP. The binding properties of the BSA nanoparticle with a theragnostic probe (merocyanine 540) were studied after lyophilisation. Results showed more affinity between the BSA NP lyophilised with trehalose than that observed with non lyophilised BSA NP. As a result, the lyophilisation condition in trehalose 100μM solution is the best one to preserve the BSA NP structure/function and the one with the enhance binding affinity of the BSA NP. Copyright © 2016 Elsevier B.V. All rights reserved.

Hierarchical Nanoparticle Topography in Amphiphilic Copolymer Films Controlled by Thermodynamics and Dynamics

PubMed Central

Caporizzo, M. A.; Ezzibdeh, R. M.

2016-01-01

This study systematically investigates how polymer composition changes nanoparticle (NP) grafting and diffusion in solvated random copolymer thin films. By thermal annealing from 135 to 200 °C, thin films with a range of hydrophobicity are generated by varying acrylic acid content from 2% (SAA2) to 29% (SAA29). Poly(styrene-random-tert butyl acrylate) films, 100 nm thick, that are partially converted to poly(styrene-random-acrylic acid), SAA, reversibly swell in ethanol solutions containing amine-functionalized SiO2 nanoparticles with a diameter of 45 nm. The thermodynamics and kinetics of NP grafting are directly controlled by the AA content in the SAA films. At low AA content, namely SAA4, NP attachment saturates at a monolayer, consistent with a low solubility of NPs in SAA4 due to a weakly negative χ parameter. When the AA content exceeds 4%, NPs sink into the film to form multilayers. These films exhibit hierarchical surface roughness with a RMS roughness greater than the NP size. Using a quartz crystal microbalance, NP incorporation in the film is found to saturate after a mass equivalence of about 3 close-packed layers of NPs have been incorporated within the SAA. The kinetics of NP grafting is observed to scale with AA content. The surface roughness is greatest at intermediate times (5–20 min) for SAA13 films, which also exhibit superhydrophobic wetting. Because clustering and aggregation of the NPs within SAA29 films reduce film transparency, SAA13 films provide both maximum hydrophobicity and transparency. The method in this study is widely applicable because it can be applied to many substrate types, can cover large areas, and retains the amine functionality of the particles which allows for subsequent chemical modification. PMID:25689222

"Turn-on" fluorescence detection of lead ions based on accelerated leaching of gold nanoparticles on the surface of graphene.

PubMed

Fu, Xiuli; Lou, Tingting; Chen, Zhaopeng; Lin, Meng; Feng, Weiwei; Chen, Lingxin

2012-02-01

A novel platform for effective "turn-on" fluorescence sensing of lead ions (Pb(2+)) in aqueous solution was developed based on gold nanoparticle (AuNP)-functionalized graphene. The AuNP-functionalized graphene exhibited minimal background fluorescence because of the extraordinarily high quenching ability of AuNPs. Interestingly, the AuNP-functionalized graphene underwent fluorescence restoration as well as significant enhancement upon adding Pb(2+), which was attributed to the fact that Pb(2+) could accelerate the leaching rate of the AuNPs on graphene surfaces in the presence of both thiosulfate (S(2)O(3)(2-)) and 2-mercaptoethanol (2-ME). Consequently, this could be utilized as the basis for selective detection of Pb(2+). With the optimum conditions chosen, the relative fluorescence intensity showed good linearity versus logarithm concentration of Pb(2+) in the range of 50-1000 nM (R = 0.9982), and a detection limit of 10 nM. High selectivity over common coexistent metal ions was also demonstrated. The practical application had been carried out for determination of Pb(2+) in tap water and mineral water samples. The Pb(2+)-specific "turn-on" fluorescence sensor, based on Pb(2+) accelerated leaching of AuNPs on the surface of graphene, provided new opportunities for highly sensitive and selective Pb(2+) detection in aqueous media.

Role of surface charge and oxidative stress in cytotoxicity of organic monolayer-coated silicon nanoparticles towards macrophage NR8383 cells

PubMed Central

2010-01-01

Background Surface charge and oxidative stress are often hypothesized to be important factors in cytotoxicity of nanoparticles. However, the role of these factors is not well understood. Hence, the aim of this study was to systematically investigate the role of surface charge, oxidative stress and possible involvement of mitochondria in the production of intracellular reactive oxygen species (ROS) upon exposure of rat macrophage NR8383 cells to silicon nanoparticles. For this aim highly monodisperse (size 1.6 ± 0.2 nm) and well-characterized Si core nanoparticles (Si NP) were used with a surface charge that depends on the specific covalently bound organic monolayers: positively charged Si NP-NH2, neutral Si NP-N3 and negatively charged Si NP-COOH. Results Positively charged Si NP-NH2 proved to be more cytotoxic in terms of reducing mitochondrial metabolic activity and effects on phagocytosis than neutral Si NP-N3, while negatively charged Si NP-COOH showed very little or no cytotoxicity. Si NP-NH2 produced the highest level of intracellular ROS, followed by Si NP-N3 and Si NP-COOH; the latter did not induce any intracellular ROS production. A similar trend in ROS production was observed in incubations with an isolated mitochondrial fraction from rat liver tissue in the presence of Si NP. Finally, vitamin E and vitamin C induced protection against the cytotoxicity of the Si NP-NH2 and Si NP-N3, corroborating the role of oxidative stress in the mechanism underlying the cytotoxicity of these Si NP. Conclusion Surface charge of Si-core nanoparticles plays an important role in determining their cytotoxicity. Production of intracellular ROS, with probable involvement of mitochondria, is an important mechanism for this cytotoxicity. PMID:20831820

Structural evolution and mechanical behaviour of Pt nanoparticle superlattices at high pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jinlong; Quan, Zewei; Wang, Chenyu

High pressure is an effective means for tuning the interparticle distances of nanoparticle (NP) superlattice and thus for modifying their physical properties and functionalities. In this work, we determined the evolutio of inter-NP distances of a Pt NP superlattice with increasing pressure using an in situ synchrotro small-angle X-ray scattering (SAXS) technique in a diamond-anvil cell (DAC). Transmission electro microscopy (TEM) was used to characterize the microstructures of pre- and post-compression samples Our results demonstrate that the evolution of Pt NP assemblies with increasing pressure consists of fou stages: (1) ligand elastic response, (2) uniform compression, (3) ligand detachment frommore » NP surfaces, an (4) deviatoric compression of ligands between neighboring NPs. Lastly, by controlling the magnitudes of applie pressure and deviatoric stress, one can sinter NPs into novel architectures such as nanowires an nanoceramics.« less

Structural evolution and mechanical behaviour of Pt nanoparticle superlattices at high pressure

DOE PAGES

Zhu, Jinlong; Quan, Zewei; Wang, Chenyu; ...

2016-02-05

High pressure is an effective means for tuning the interparticle distances of nanoparticle (NP) superlattice and thus for modifying their physical properties and functionalities. In this work, we determined the evolutio of inter-NP distances of a Pt NP superlattice with increasing pressure using an in situ synchrotro small-angle X-ray scattering (SAXS) technique in a diamond-anvil cell (DAC). Transmission electro microscopy (TEM) was used to characterize the microstructures of pre- and post-compression samples Our results demonstrate that the evolution of Pt NP assemblies with increasing pressure consists of fou stages: (1) ligand elastic response, (2) uniform compression, (3) ligand detachment frommore » NP surfaces, an (4) deviatoric compression of ligands between neighboring NPs. Lastly, by controlling the magnitudes of applie pressure and deviatoric stress, one can sinter NPs into novel architectures such as nanowires an nanoceramics.« less

Predicting signatures of anisotropic resonance energy transfer in dye-functionalized nanoparticles† †Electronic supplementary information (ESI) available: Molecular structure and TDM of Cy3B. Table of dielectric constants. Dielectric mismatch at the surface of the NP: excitonic states and TEF of the NP. Additional data in RET rates calculation. Experimental absorption and PL spectra of the dye and the NP. Master equations and time-dependent populations. Steady-state rates and spectra. Blocking and back-transfer effects. Octahedral tessellation. Average RET rates. Details on Fig. 5 inset of the main text. Poisson distribution of the number of dyes per NP. See DOI: 10.1039/c6ra22433d Click here for additional data file.

PubMed Central

Corni, Stefano; Delgado, Alain; Bertoni, Andrea; Goldoni, Guido

2016-01-01

Resonance energy transfer (RET) is an inherently anisotropic process. Even the simplest, well-known Förster theory, based on the transition dipole–dipole coupling, implicitly incorporates the anisotropic character of RET. In this theoretical work, we study possible signatures of the fundamental anisotropic character of RET in hybrid nanomaterials composed of a semiconductor nanoparticle (NP) decorated with molecular dyes. In particular, by means of a realistic kinetic model, we show that the analysis of the dye photoluminescence difference for orthogonal input polarizations reveals the anisotropic character of the dye–NP RET which arises from the intrinsic anisotropy of the NP lattice. In a prototypical core/shell wurtzite CdSe/ZnS NP functionalized with cyanine dyes (Cy3B), this difference is predicted to be as large as 75% and it is strongly dependent in amplitude and sign on the dye–NP distance. We account for all the possible RET processes within the system, together with competing decay pathways in the separate segments. In addition, we show that the anisotropic signature of RET is persistent up to a large number of dyes per NP. PMID:28066545

Effects of charge and surface ligand properties of nanoparticles on oxidative stress and gene expression within the gut of Daphnia magna

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dominguez, Gustavo A.; Lohse, Samuel E.; Torelli, Marco

2015-05-01

Concern has been raised regarding the current and future release of engineered nanomaterials into aquatic environments from industry and other sources. However, not all nanomaterials may cause an environ-mental impact and identifying which nanomaterials may be of greatest concern has been difficult. It is thought that the surface groups of a functionalized nanoparticles (NPs) may play a significant role in determining their interactions with aquatic organisms, but the way in which surface properties of NPs impact their toxicity in whole organisms has been minimally explored. A major point of interaction of NPs with aquatic organisms is in the gastrointestinal tractmore » as they ingest particulates from the water column or from the sediment. The main goal of this study was to use model gold NP (AuNPs) to evaluate the potential effects of the different surfaces groups on NPs on the gut of an aquatic model organism, Daphnia magna. In this study, we exposed daphnids to a range of AuNPs concentrations and assessed the impact of AuNP exposure in the daphnid gut by measuring reactive oxygen species (ROS) production and expression of genes associated with oxidative stress and general cellular stress: glutathione S-transferase(gst), catalase (cat), heat shock protein 70 (hsp70), and metallothionein1 (mt1). We found ROS formation and gene expression were impacted by both charge and the specific surface ligand used. We detected some degree of ROS production in all NP exposures, but positively charged AuNPs induced a greater ROS response. Similarly, we observed that, compared to controls, both positively charged AuNPs and only one negatively AuNP impacted expression of genes associated with cellular stress. Finally, ligand-AuNP exposures showed a different toxicity and gene expression profile than the ligand alone, indicating a NP specific effect.« less

Stabilization and functionalization of iron oxide nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

Amstad, Esther; Textor, Marcus; Reimhult, Erik

2011-07-01

Superparamagnetic iron oxide nanoparticles (NPs) are used in a rapidly expanding number of research and practical applications in the biomedical field, including magnetic cell labeling separation and tracking, for therapeutic purposes in hyperthermia and drug delivery, and for diagnostic purposes, e.g., as contrast agents for magnetic resonance imaging. These applications require good NP stability at physiological conditions, close control over NP size and controlled surface presentation of functionalities. This review is focused on different aspects of the stability of superparamagnetic iron oxide NPs, from its practical definition to its implementation by molecular design of the dispersant shell around the iron oxide core and further on to its influence on the magnetic properties of the superparamagnetic iron oxide NPs. Special attention is given to the selection of molecular anchors for the dispersant shell, because of their importance to ensure colloidal and functional stability of sterically stabilized superparamagnetic iron oxide NPs. We further detail how dispersants have been optimized to gain close control over iron oxide NP stability, size and functionalities by independently considering the influences of anchors and the attached sterically repulsive polymer brushes. A critical evaluation of different strategies to stabilize and functionalize core-shell superparamagnetic iron oxide NPs as well as a brief introduction to characterization methods to compare those strategies is given.Superparamagnetic iron oxide nanoparticles (NPs) are used in a rapidly expanding number of research and practical applications in the biomedical field, including magnetic cell labeling separation and tracking, for therapeutic purposes in hyperthermia and drug delivery, and for diagnostic purposes, e.g., as contrast agents for magnetic resonance imaging. These applications require good NP stability at physiological conditions, close control over NP size and controlled surface presentation of functionalities. This review is focused on different aspects of the stability of superparamagnetic iron oxide NPs, from its practical definition to its implementation by molecular design of the dispersant shell around the iron oxide core and further on to its influence on the magnetic properties of the superparamagnetic iron oxide NPs. Special attention is given to the selection of molecular anchors for the dispersant shell, because of their importance to ensure colloidal and functional stability of sterically stabilized superparamagnetic iron oxide NPs. We further detail how dispersants have been optimized to gain close control over iron oxide NP stability, size and functionalities by independently considering the influences of anchors and the attached sterically repulsive polymer brushes. A critical evaluation of different strategies to stabilize and functionalize core-shell superparamagnetic iron oxide NPs as well as a brief introduction to characterization methods to compare those strategies is given. This article was submitted as part of a collection of articles on surface nanotechnology for biological applications. Other papers on this topic can be found in issue 2 of vol. 3 (2011). This issue can be found from the Nanoscale homepage [http://www.rsc.org/nanoscale].

Surface chemistry of gold nanoparticles determines the biocorona composition impacting cellular uptake, toxicity and gene expression profiles in human endothelial cells.

PubMed

Chandran, Parwathy; Riviere, Jim E; Monteiro-Riviere, Nancy A

2017-05-01

This study investigated the role of nanoparticle size and surface chemistry on biocorona composition and its effect on uptake, toxicity and cellular responses in human umbilical vein endothelial cells (HUVEC), employing 40 and 80 nm gold nanoparticles (AuNP) with branched polyethyleneimine (BPEI), lipoic acid (LA) and polyethylene glycol (PEG) coatings. Proteomic analysis identified 59 hard corona proteins among the various AuNP, revealing largely surface chemistry-dependent signature adsorbomes exhibiting human serum albumin (HSA) abundance. Size distribution analysis revealed the relative instability and aggregation inducing potential of bare and corona-bound BPEI-AuNP, over LA- and PEG-AuNP. Circular dichroism analysis showed surface chemistry-dependent conformational changes of proteins binding to AuNP. Time-dependent uptake of bare, plasma corona (PC) and HSA corona-bound AuNP (HSA-AuNP) showed significant reduction in uptake with PC formation. Cell viability studies demonstrated dose-dependent toxicity of BPEI-AuNP. Transcriptional profiling studies revealed 126 genes, from 13 biological pathways, to be differentially regulated by 40 nm bare and PC-bound BPEI-AuNP (PC-BPEI-AuNP). Furthermore, PC formation relieved the toxicity of cationic BPEI-AuNP by modulating expression of genes involved in DNA damage and repair, heat shock response, mitochondrial energy metabolism, oxidative stress and antioxidant response, and ER stress and unfolded protein response cascades, which were aberrantly expressed in bare BPEI-AuNP-treated cells. NP surface chemistry is shown to play the dominant role over size in determining the biocorona composition, which in turn modulates cell uptake, and biological responses, consequently defining the potential safety and efficacy of nanoformulations.

Development of preservative-free nanoparticles-based emulsions: Effects of NP surface properties and sterilization process.

PubMed

Rowenczyk, Laura; Picard, Céline; Duclairoir-Poc, Cécile; Hucher, Nicolas; Orange, Nicole; Feuilloley, Marc; Grisel, Michel

2016-08-20

Model emulsions were developed with or without commercial titanium dioxide nanoparticles (NP) carrying various surface treatments in order to get close physicochemical properties whatever the NP surface polarity (hydrophilic and hydrophobic). Rheology and texturometry highlighted that the macroscopic properties of the three formulated emulsions were similar. However, characterizations by optical microscopy, static light scattering and zetametry showed that their microstructures reflected the diversity of the incorporated NP surface properties. In order to use these model emulsions as tools for biological evaluations of the NP in use, they had to show the lowest initial microbiological charge and, specifically for the NP-free emulsion, the lowest bactericidal effect. Hence, formulae were developed preservative-free and a thermal sterilization step was conducted. Efficiency of the sterilization and its impact on the emulsion integrity were monitored. Results highlighted the effect of the NP surface properties: only the control emulsion and the emulsion containing hydrophilic NP fulfilled both requirements. To ensure the usability of these model emulsions as tools to evaluate the 'NP effect' on representative bacteria of the skin microflora (S. aureus and P. fluorescens), impact on the bacterial growth was measured on voluntary inoculated formulae. Copyright © 2016 Elsevier B.V. All rights reserved.

Recent advances in magnetic nanoparticles with bulk-like properties

NASA Astrophysics Data System (ADS)

Batlle, Xavier

2013-03-01

Magnetic nanoparticles (NP) are an excellent example of nanostructured materials and exhibit fascinating properties with applications in high-density recording and biomedicine. Controlling the effects of the nanostructure and surface chemistry and magnetism at the monolayer level have become relevant issues. As the size is reduced below 100 nm, deviations from bulk behavior have been attributed to finite-size effects and changes in the magnetic ordering at the surface, thus giving rise to a significant decrease in the magnetization and increase in the magnetic anisotropy. The existence of a surface spin glass-like state due to magnetic frustration has been widely suggested in ferrimagnetic NP. However, in this talk, we will show that high crystal quality magnetite Fe3-xO4 NP of about a few nanometers in diameter and coated with different organic surfactants display bulk-like structural, magnetic and electronic properties. Magnetic measurements, transmission electron microscopy, X-ray absorption and magnetic circular dichroism and Monte Carlo simulations, evidenced that none of the usual particle-like behavior is observed in high quality NP of a few nm. Consequently, the magnetic and electronic disorder phenomena typically observed in those single-phase ferrimagnetic NP should not be considered as an intrinsic effect. We also performed a real-space characterization at the sub-nanometer scale, combining scanning transmission electron microscopy, electron energy loss spectroscopy and electron magnetic chiral dichroism. For the first time, we found that the surface magnetization is as high as about 70% of that of the core. The comparison to density functional theory suggested the relevance of the strong surface bond between the Fe ions and the organic surfactant. All the foregoing demonstrates the key role of both the crystal quality and surface bond on the physical properties of ferrimagnetic NP and paves the way to the fabrication of the next generation of NP with optimal magnetic properties. Some bio-applications will also be discussed. In collaboration with A Labarta, N Perez, O Iglesias, A Fraile, C Moya(U Barcelona); A Roca, MP Morales, CJ Serna (ICMM-CSIC); F Bartolome, LM Garcia, J. Bartolome (CSIC-U Zaragoza); R Mejias, DF Barber (CNB-CSIC); M Varela, J Gazquez, J Salafranca, SJ Pennycook (ORNL), ST Pantelides (Vanderbilt U).

Off to the Organelles - Killing Cancer Cells with Targeted Gold Nanoparticles

PubMed Central

Kodiha, Mohamed; Wang, Yi Meng; Hutter, Eliza; Maysinger, Dusica; Stochaj, Ursula

2015-01-01

Gold nanoparticles (AuNPs) are excellent tools for cancer cell imaging and basic research. However, they have yet to reach their full potential in the clinic. At present, we are only beginning to understand the molecular mechanisms that underlie the biological effects of AuNPs, including the structural and functional changes of cancer cells. This knowledge is critical for two aspects of nanomedicine. First, it will define the AuNP-induced events at the subcellular and molecular level, thereby possibly identifying new targets for cancer treatment. Second, it could provide new strategies to improve AuNP-dependent cancer diagnosis and treatment. Our review summarizes the impact of AuNPs on selected subcellular organelles that are relevant to cancer therapy. We focus on the nucleus, its subcompartments, and mitochondria, because they are intimately linked to cancer cell survival, growth, proliferation and death. While non-targeted AuNPs can damage tumor cells, concentrating AuNPs in particular subcellular locations will likely improve tumor cell killing. Thus, it will increase cancer cell damage by photothermal ablation, mechanical injury or localized drug delivery. This concept is promising, but AuNPs have to overcome multiple hurdles to perform these tasks. AuNP size, morphology and surface modification are critical parameters for their delivery to organelles. Recent strategies explored all of these variables, and surface functionalization has become crucial to concentrate AuNPs in subcellular compartments. Here, we highlight the use of AuNPs to damage cancer cells and their organelles. We discuss current limitations of AuNP-based cancer research and conclude with future directions for AuNP-dependent cancer treatment. PMID:25699096

The generation and functional characterization of induced pluripotent stem cells from human intervertebral disc nucleus pulposus cells.

PubMed

Zhu, Yanxia; Liang, Yuhong; Zhu, Hongxia; Lian, Cuihong; Wang, Liang; Wang, Yiwei; Gu, Hongsheng; Zhou, Guangqian; Yu, Xiaoping

2017-06-27

Disc degenerative disease (DDD) is believed to originate in the nucleus pulposus (NP) region therefore, it is important to obtain a greater number of active NP cells for the study and therapy of DDD. Human induced pluripotent stem cells (iPSCs) are a powerful tool for modeling the development of DDD in humans, and have the potential to be applied in regenerative medicine. NP cells were isolated from DDD patients following our improved method, and then the primary NP cells were reprogramed into iPSCs with Sendai virus vectors encoding 4 factors. Successful reprogramming of iPSCs was verified by the expression of surface markers and presence of teratoma. Differentiation of iPSCs into NP-like cells was performed in a culture plate or in hydrogel, whereby skin fibroblast derived-iPSCs were used as a control. Results demonstrated that iPSCs derived from NP cells displayed a normal karyotype, expressed pluripotency markers, and formed teratoma in nude mice. NP induction of iPSCs resulted in the expression of NP cell specific matrix proteins and related genes. Non-induced NP derived-iPSCs also showed some NP-like phenotype. Furthermore, NP-derived iPSCs differentiate much better in hydrogel than that in a culture plate. This is a novel method for the generation of iPSCs from NP cells of DDD patients, and we have successfully differentiated these iPSCs into NP-like cells in hydrogel. This method provides a novel treatment of DDD by using patient-specific NP cells in a relatively simple and straightforward manner.

Delivery of antagomiR204-conjugated gold nanoparticles from PLGA sheets and its implication in promoting osseointegration of titanium implant in type 2 diabetes mellitus.

PubMed

Liu, Xiangwei; Tan, Naiwen; Zhou, Yuchao; Wei, Hongbo; Ren, Shuai; Yu, Fan; Chen, Hui; Jia, Chengming; Yang, Guodong; Song, Yingliang

2017-01-01

Impaired osseointegration of the implant remains the big hurdle for dental implant therapy in diabetic patients. In this study, the authors first identified that miR204 was strikingly highly expressed in the bone mesenchymal stem cells (BMSCs) of diabetic rats. Forced expression of miR204 repressed the osteogenic potential of BMSCs, while inhibition of miR204 significantly increased the osteogenic capacity. Moreover, the miR204 inhibitor was conjugated with gold nanoparticles (AuNP-antagomiR204) and dispersed them in the poly(lactic-co-glycolic acid) (PLGA) solution. The AuNP-antagomiR204 containing PLGA solution was applied for coating the surface of titanium implant. Electron microscope revealed that an ultrathin sheet was formed on the surface of the implant, and the AuNPs were evenly dispersed in the coated PLGA sheet. Cellular experiments revealed that these encapsulated AuNP-antagomiR204 were able to be released from the PLGA sheet and uptaken by adherent BMSCs. In vivo animal study further confirmed that the AuNP-antagomiR204 released from PLGA sheet promoted osseointegration, as revealed by microcomputerized tomography (microCT) reconstruction and histological assay. Taken together, this study established that miR204 misexpression accounted for the deficient osseointegation in diabetes mellitus, while PLGA sheets aided the release of AuNP-antagomiR204, which would be a promising strategy for titanium implant surface functionalization toward better osseointegration.

Optical properties of metal nanoparticles embedded in amorphous silicon analysed using discrete dipole approximation

NASA Astrophysics Data System (ADS)

Fantoni, Alessandro; Fernandes, Miguel; Vygranenko, Yuri; Vieira, Manuela; Oliveira-Silva, Rui P.; Prazeres, D. M. F.; Ribeiro, Ana P. C.; Alegria, Elisabete C. B. A.

2018-02-01

Localized surface plasmons (LSP) can be excited in metal nanoparticles (NP) by UV, visible or NIR light and are described as coherent oscillation of conduction electrons. Taking advantage of the tunable optical properties of NPs, we propose the realization of a plasmonic structure, based on the LSP interaction of NP with an embedding matrix of amorphous silicon. This study is directed to define the characteristics of NP and substrate necessary to the development of a LSP proteomics sensor that, once provided immobilized antibodies on its surface, will screen the concentration of selected antigens through the determination of LSPR spectra and peaks of light absorption. Metals of interest for NP composition are: Aluminium and Gold. Recent advances in nanoparticle production techniques allow almost full control over shapes and size, permitting full control over their optical and plasmonic properties and, above all, over their responsive spectra. Analytical solution is only possible for simple NP geometries, therefore our analysis, is realized recurring to computer simulation using the Discrete Dipole Approximation method (DDA). In this work we use the free software DDSCAT to study the optical properties of metal nanoparticles embedded in an amorphous silicon matrix, as a function of size, shape, aspect-ratio and metal type. Experimental measurements realized with arrays of metal nanoparticles are compared with the simulations.

Novel immortal human cell lines reveal subpopulations in the nucleus pulposus

PubMed Central

2014-01-01

Introduction Relatively little is known about cellular subpopulations in the mature nucleus pulposus (NP). Detailed understanding of the ontogenetic, cellular and molecular characteristics of functional intervertebral disc (IVD) cell populations is pivotal to the successful development of cell replacement therapies and IVD regeneration. In this study, we aimed to investigate whether phenotypically distinct clonal cell lines representing different subpopulations in the human NP could be generated using immortalization strategies. Methods Nondegenerate healthy disc material (age range, 8 to 15 years) was obtained as surplus surgical material. Early passage NP monolayer cell cultures were initially characterized using a recently established NP marker set. NP cells were immortalized by simian virus 40 large T antigen (SV40LTag) and human telomerase reverse transcriptase expression. Immortalized cells were clonally expanded and characterized based on collagen type I, collagen type II, α1 (COL2A1), and SRY-box 9 (SOX9) protein expression profiles, as well as on expression of a subset of established in vivo NP cell lineage markers. Results A total of 54 immortal clones were generated. Profiling of a set of novel NP markers (CD24, CA12, PAX1, PTN, FOXF1 and KRT19 mRNA) in a representative set of subclones substantiated successful immortalization of multiple cellular subpopulations from primary isolates and confirmed their NP origin and/or phenotype. We were able to identify two predominant clonal NP subtypes based on their morphological characteristics and their ability to induce SOX9 and COL2A1 under conventional differentiation conditions. In addition, cluster of differentiation 24 (CD24)–negative NP responder clones formed spheroid structures in various culture systems, suggesting the preservation of a more immature phenotype compared to CD24-positive nonresponder clones. Conclusions Here we report the generation of clonal NP cell lines from nondegenerate human IVD tissue and present a detailed characterization of NP cellular subpopulations. Differential cell surface marker expression and divergent responses to differentiation conditions suggest that the NP subtypes may correspond to distinct maturation stages and represent distinct NP cell subpopulations. Hence, we provide evidence that the immortalization strategy that we applied is capable of detecting cell heterogeneity in the NP. Our cell lines yield novel insights into NP biology and provide promising new tools for studies of IVD development, cell function and disease. PMID:24972717

Novel immortal human cell lines reveal subpopulations in the nucleus pulposus.

PubMed

van den Akker, Guus G H; Surtel, Don A M; Cremers, Andy; Rodrigues-Pinto, Ricardo; Richardson, Stephen M; Hoyland, Judith A; van Rhijn, Lodewijk W; Welting, Tim J M; Voncken, Jan Willem

2014-06-27

Relatively little is known about cellular subpopulations in the mature nucleus pulposus (NP). Detailed understanding of the ontogenetic, cellular and molecular characteristics of functional intervertebral disc (IVD) cell populations is pivotal to the successful development of cell replacement therapies and IVD regeneration. In this study, we aimed to investigate whether phenotypically distinct clonal cell lines representing different subpopulations in the human NP could be generated using immortalization strategies. Nondegenerate healthy disc material (age range, 8 to 15 years) was obtained as surplus surgical material. Early passage NP monolayer cell cultures were initially characterized using a recently established NP marker set. NP cells were immortalized by simian virus 40 large T antigen (SV40LTag) and human telomerase reverse transcriptase expression. Immortalized cells were clonally expanded and characterized based on collagen type I, collagen type II, α1 (COL2A1), and SRY-box 9 (SOX9) protein expression profiles, as well as on expression of a subset of established in vivo NP cell lineage markers. A total of 54 immortal clones were generated. Profiling of a set of novel NP markers (CD24, CA12, PAX1, PTN, FOXF1 and KRT19 mRNA) in a representative set of subclones substantiated successful immortalization of multiple cellular subpopulations from primary isolates and confirmed their NP origin and/or phenotype. We were able to identify two predominant clonal NP subtypes based on their morphological characteristics and their ability to induce SOX9 and COL2A1 under conventional differentiation conditions. In addition, cluster of differentiation 24 (CD24)-negative NP responder clones formed spheroid structures in various culture systems, suggesting the preservation of a more immature phenotype compared to CD24-positive nonresponder clones. Here we report the generation of clonal NP cell lines from nondegenerate human IVD tissue and present a detailed characterization of NP cellular subpopulations. Differential cell surface marker expression and divergent responses to differentiation conditions suggest that the NP subtypes may correspond to distinct maturation stages and represent distinct NP cell subpopulations. Hence, we provide evidence that the immortalization strategy that we applied is capable of detecting cell heterogeneity in the NP. Our cell lines yield novel insights into NP biology and provide promising new tools for studies of IVD development, cell function and disease.

Biologically Assembled Quantum Electronic Arrays

DTIC Science & Technology

2013-06-07

characterizing the NP arrays. Theory of gate-tunable exchange coupling in the case of cobalt NP on graphene . Used Spin-density-functional theory and...polarization. We can estimate this field using the material parameters for Cobalt , which gives B neEo:N~ M;r; "󈧶 T zrv M M "’ m s s Here N1 is the...minority spin density of states at the Fermi surface for Cobalt , M5 is its saturation magnetization, while M:x is the x-component of the magnetization

Shape-Specific Patterning of Polymer-Functionalized Nanoparticles

DOE PAGES

Galati, Elizabeth; Tebbe, Moritz; Querejeta-Fernández, Ana; ...

2017-05-01

Chemically and topographically patterned nanoparticles (NPs) with dimensions on the order of tens of nanometers have a diverse range of applications and are a valuable system for fundamental research. Recently, thermodynamically controlled segregation of a smooth layer of polymer ligands into pinned micelles (patches) offered an approach to nanopatterning of polymer-functionalized NPs. Control of the patch number, size, and spatial distribution on the surface of spherical NPs has been achieved, however, the role of NP shape remained elusive. Here, we report the role of NP shape, namely, the effect of the local surface curvature, on polymer segregation into surface patches.more » For polymer-functionalized metal nanocubes, we show experimentally and theoretically that the patches form preferentially on the high-curvature regions such as vertices and edges. An in situ transformation of the nanocubes into nanospheres leads to the change in the number and distribution of patches; a process that is dominated by the balance between the surface energy and the stretching energy of the polymer ligands. The experimental and theoretical results presented in this work are applicable to surface patterning of polymer-capped NPs with different shapes, which then enables the exploration of patch-directed self-assembly, as colloidal surfactants, and as templates for the synthesis of hybrid nanomaterials.« less

Functionalization and Characterization of Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Techane, Sirnegeda D.

2011-12-01

Surface characterization of gold nanoparticles (AuNPs) is necessary to obtain a thorough understanding of the AuNP properties and ultimately realize their full potential in applications. The work described in this dissertation strives to the structure and composition of AuNPs using highly surface sensitive techniques such as X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) in addition to the more widely used characterization techniques such as transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR) and UV-VIS spectroscopy. Self-assembled monolayers (SAMs) of alkanethiols were used to modify AuNPs surfaces to create positively and negatively charged surfaces. Functionalization with carboxylic acid terminated alkanethiol SAMs (COON-SAMs) was first optimized to produce clean and stable negatively charged AuNPs. Using 14nm and 40nm diameter AuNPs in combination with C11 and C16 chain length COOH-SAMs, it was found that addition of NH4OH during functionalization coupled with dialysis purification produced AuNPs that did not aggregate and did not have unbound thiols. Effects of AuNP size and COOH-SAM chain lengths were studied using 14, 25 and 40nm average diameter AuNPs functionalized with C6, C8, C11 and C16 COOH-SAMs. Flat Au surfaces were also functionalized with the COOH-SAMs for comparison. It was shown that the 14nm AuNPs with C16 COOH-SAMs were the most stable and had crystalline-like, well-ordered SAM structures. The SAMs on the 40nm AuNPs had similar surface chemistry as the SAMs on the flat Au surfaces. The effective photoelectron take-off angle of the C16 COOH-SAM decreased when the size of the AuNP increased. It was also shown that when using Kratos AxisUltra DLD XPS instrument in the hybrid mode, it was important to consider effects of both the hybrid mode and the AuNPs curvature when calculating overlayer thickness of the SAMs on AuNPs. Using the Kratos in the electrostatic mode, the overlayer thickness of C16 COON-SAM was 21A on a flat Au surface, which was comparable with previously reported values. However, the apparent thickness of the same SAM on the 14nm AuNPs was 31A, indicating the curvature of the AuNPs had an effect on the XPS measurements. To produce the positively charged AuNP surfaces, amine terminated alkanethiols (NH2 -thiols) with a C2 chain length were used in one-step AuNP synthesis and functionalization process followed by a ligand-exchange reaction with C11 chain length NH2-thiols. It was found that 14 days were needed for the ligand-exchange to be complete. After the ligand-exchange, it was found that the AuNPs with C11 NH2-SAMs were stable and could be purified, unlike AuNPs with C2 NH2-SAMs which aggregated upon purification. The C11 NH2-SAMs had both unbound and oxidized sulfur, which could be removed/converted after hydrochloric acid treatment. SESSA (simulation of electron spectra for surface analysis) allowed better interpretation of the XPS data of SAMs on AuNPs and flat Au. Comparing SESSA and experimental XPS data, it was found that C16 COON-SAM on a flat Au surface was 20A thick with a 1.5A hydrocarbon contamination overlayer and 1.05 relative surface roughness. After geometric weighing of angle-resolved XPS and SESSA data, it was found that C16 COOH-SAMs on 14nm AuNPs were 17A thick with a 1.5A hydrocarbon contamination. The decreased SAM thickness on the AuNPs is likely due to an increased tilt angle of the alkane chains or increased disorder in the SAM.

Protein corona - from molecular adsorption to physiological complexity.

PubMed

Treuel, Lennart; Docter, Dominic; Maskos, Michael; Stauber, Roland H

2015-01-01

In biological environments, nanoparticles are enshrouded by a layer of biomolecules, predominantly proteins, mediating its subsequent interactions with cells. Detecting this protein corona, understanding its formation with regards to nanoparticle (NP) and protein properties, and elucidating its biological implications were central aims of bio-related nano-research throughout the past years. Here, we discuss the mechanistic parameters that are involved in the protein corona formation and the consequences of this corona formation for both, the particle, and the protein. We review consequences of corona formation for colloidal stability and discuss the role of functional groups and NP surface functionalities in shaping NP-protein interactions. We also elaborate the recent advances demonstrating the strong involvement of Coulomb-type interactions between NPs and charged patches on the protein surface. Moreover, we discuss novel aspects related to the complexity of the protein corona forming under physiological conditions in full serum. Specifically, we address the relation between particle size and corona composition and the latest findings that help to shed light on temporal evolution of the full serum corona for the first time. Finally, we discuss the most recent advances regarding the molecular-scale mechanistic role of the protein corona in cellular uptake of NPs.

Statistical prediction of nanoparticle delivery: from culture media to cell

NASA Astrophysics Data System (ADS)

Rowan Brown, M.; Hondow, Nicole; Brydson, Rik; Rees, Paul; Brown, Andrew P.; Summers, Huw D.

2015-04-01

The application of nanoparticles (NPs) within medicine is of great interest; their innate physicochemical characteristics provide the potential to enhance current technology, diagnostics and therapeutics. Recently a number of NP-based diagnostic and therapeutic agents have been developed for treatment of various diseases, where judicious surface functionalization is exploited to increase efficacy of administered therapeutic dose. However, quantification of heterogeneity associated with absolute dose of a nanotherapeutic (NP number), how this is trafficked across biological barriers has proven difficult to achieve. The main issue being the quantitative assessment of NP number at the spatial scale of the individual NP, data which is essential for the continued growth and development of the next generation of nanotherapeutics. Recent advances in sample preparation and the imaging fidelity of transmission electron microscopy (TEM) platforms provide information at the required spatial scale, where individual NPs can be individually identified. High spatial resolution however reduces the sample frequency and as a result dynamic biological features or processes become opaque. However, the combination of TEM data with appropriate probabilistic models provide a means to extract biophysical information that imaging alone cannot. Previously, we demonstrated that limited cell sampling via TEM can be statistically coupled to large population flow cytometry measurements to quantify exact NP dose. Here we extended this concept to link TEM measurements of NP agglomerates in cell culture media to that encapsulated within vesicles in human osteosarcoma cells. By construction and validation of a data-driven transfer function, we are able to investigate the dynamic properties of NP agglomeration through endocytosis. In particular, we statistically predict how NP agglomerates may traverse a biological barrier, detailing inter-agglomerate merging events providing the basis for predictive modelling of nanopharmacology.

One-step synthesis of large-scale graphene film doped with gold nanoparticles at liquid-air interface for electrochemistry and Raman detection applications.

PubMed

Zhang, Panpan; Huang, Ying; Lu, Xin; Zhang, Siyu; Li, Jingfeng; Wei, Gang; Su, Zhiqiang

2014-07-29

We demonstrated a facile one-step synthesis strategy for the preparation of a large-scale reduced graphene oxide multilayered film doped with gold nanoparticles (RGO/AuNP film) and applied this film as functional nanomaterials for electrochemistry and Raman detection applications. The related applications of the fabricated RGO/AuNP film in electrochemical nonenzymatic H2O2 biosensor, electrochemical oxygen reduction reaction (ORR), and surface-enhanced Raman scattering (SERS) detection were investigated. Electrochemical data indicate that the H2O2 biosensor fabricated by RGO/AuNP film shows a wide linear range, low limitation of detection, high selectivity, and long-term stability. In addition, it was proved that the created RGO/AuNP film also exhibits excellent ORR electrochemical catalysis performance. The created RGO/AuNP film, when serving as SERS biodetection platform, presents outstanding performances in detecting 4-aminothiophenol with an enhancement factor of approximately 5.6 × 10(5) as well as 2-thiouracil sensing with a low concentration to 1 μM. It is expected that this facile strategy for fabricating large-scale graphene film doped with metallic nanoparticles will spark inspirations in preparing functional nanomaterials and further extend their applications in drug delivery, wastewater purification, and bioenergy.

Investigations on pharmacokinetics and biodistribution of polymeric and solid lipid nanoparticulate systems of atypical antipsychotic drug: effect of material used and surface modification.

PubMed

Joseph, Emil; Saha, Ranendra N

2017-04-01

The present study focuses on the effect of material used for the preparation of nanoparticulate (NP) systems and surface modification on the pharmacokinetics and biodistribution of atypical antipsychotic, olanzapine (OLN). NP carriers of OLN were prepared from two different materials such as polymer (polycaprolactone) and solid lipid (Glyceryl monostearate). These systems were further surface modified with surfactant, Polysorbate 80 and studied for pharmacokinetics-biodistribution in Wistar rats using in-house developed bioanalytical methods. The pharmacokinetics and biodistribution studies resulted in a modified and varied distribution of NP systems with higher area under curve (AUC) values along with prolonged residence time of OLN in the rat blood circulation. The distribution of OLN to the brain was significantly enhanced with surfactant surface-modified NP systems, followed by nonsurface-modified NP formulations as compared with pure OLN solution. Biodistribution study demonstrated a low uptake of obtained NP systems by kidney and heart, thereby decreasing the nephrotoxicity and adverse cardiovascular effects. By coating the NP with surfactant, uptake of macrophage was found to be reduced. Thus, our studies confirmed that the biodistribution OLN could be modified effectively by incorporating in NP drug delivery systems prepared from different materials and surface modifications. A judicious selection of materials used for the preparation of delivery carriers and surface modifications would help to design a most efficient drug delivery system with better therapeutic efficacy.

Preparation and measurement methods for studying nanoparticle aggregate surface chemistry.

PubMed

Szakal, Christopher; McCarthy, James A; Ugelow, Melissa S; Konicek, Andrew R; Louis, Kacie; Yezer, Benjamin; Herzing, Andrew A; Hamers, Robert J; Holbrook, R David

2012-07-01

Despite best efforts at controlling nanoparticle (NP) surface chemistries, the environment surrounding nanomaterials is always changing and can impart a permanent chemical memory. We present a set of preparation and measurement methods to be used as the foundation for studying the surface chemical memory of engineered NP aggregates. We attempt to bridge the gap between controlled lab studies and real-world NP samples, specifically TiO(2), by using well-characterized and consistently synthesized NPs, controllably producing NP aggregates with precision drop-on-demand inkjet printing for subsequent chemical measurements, monitoring the physical morphology of the NP aggregate depositions with scanning electron microscopy (SEM), acquiring "surface-to-bulk" mass spectra of the NP aggregate surfaces with time-of-flight secondary ion mass spectrometry (ToF-SIMS), and developing a data analysis scheme to interpret chemical signatures more accurately from thousands of data files. We present differences in mass spectral peak ratios for bare TiO(2) NPs compared to NPs mixed separately with natural organic matter (NOM) or pond water. The results suggest that subtle changes in the local environment can alter the surface chemistry of TiO(2) NPs, as monitored by Ti(+)/TiO(+) and Ti(+)/C(3)H(5)(+) peak ratios. The subtle changes in the absolute surface chemistry of NP aggregates vs. that of the subsurface are explored. It is envisioned that the methods developed herein can be adapted for monitoring the surface chemistries of a variety of engineered NPs obtained from diverse natural environments.

Multifunctional iron oxide nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

Bloemen, M.; Denis, C.; Van Stappen, T.; De Meester, L.; Geukens, N.; Gils, A.; Verbiest, T.

2015-03-01

Multifunctional nanoparticles have attracted a lot of attention since they can combine interesting properties like magnetism, fluorescence or plasmonic effects. As a core material, iron oxide nanoparticles have been the subject of intensive research. These cost-effective and non-toxic particles are used nowadays in many applications. We developed a heterobifunctional PEG ligand that can be used to introduce functional groups (carboxylic acids) onto the surface of the NP. Via click chemistry, a siloxane functionality was added to this ligand, for a subsequent covalent ligand exchange reaction. The functionalized nanoparticles have an excellent colloidal stability in complex environments like buffers and serum or plasma. Antibodies were coupled to the introduced carboxylic acids and these NP-antibody bioconjugates were brought into contact with Legionella bacteria for magnetic separation experiments.

Hyperbranched polyglycerol-grafted titanium oxide nanoparticles: synthesis, derivatization, characterization, size separation, and toxicology

NASA Astrophysics Data System (ADS)

Qin, Hongmei; Maruyama, Kyouhei; Amano, Tsukuru; Murakami, Takashi; Komatsu, Naoki

2016-10-01

We have been developing surface functionalization of various nanoparticles including nanodiamond and iron oxide nanoparticles in view of biomedical applications. In this context, TiO2 nanoparticles (TiO2 NP) are functionalized with polyglycerol (PG) to provide water-dispersible TiO2-PG, which is further derivatized through multi-step organic transformations. The resulting TiO2-PG and its derivatives are fully characterized by various analyses including solution-phase 1H and 13C NMR. TiO2-PG was size-tuned with centrifugation by changing the acceleration and duration. At last, no cytotoxicity of TiO2 NP, TiO2-PG, and TiO2-PG functionalized with RGD peptide was observed under dark conditions.

Plasmonic photocatalysts based on silver nanoparticles - layered double hydroxides for efficient removal of toxic compounds using solar light

NASA Astrophysics Data System (ADS)

Gilea, Diana; Radu, Teodora; Muresanu, Mihaela; Carja, Gabriela

2018-06-01

Plasmon-enhanced photocatalysis holds important promise for chemical processes and outcomes. We present here the self-assemblies of silver nanoparticles (AgNP)/layered double hydroxides (LDHs: MeAlLDHs with Me2+ = Zn2+;Mg2+) and their derived AgNP/MMOs (type AgNP/MgAl2O4; AgNP/ZnO/ZnAl2O4) as novel plasmonic photocatalysts exhibiting activity for phenol photodegradation from aqueous solution by solar-light. The fabrication procedure of AgNP/LDHs assemblies is simple and cost effective and is based on the in-situ synthesis of AgNP on the LDHs matrices during the reconstruction of MgAlLDH and ZnAlLDH in the aqueous solution of Ag2SO4. The tested catalysts were thoroughly investigated - techniques to obtain information on their crystalline structure (XRD), surface properties (XPS), morphological features (TEM) and optical properties (UV-vis). The results show that the solar photocatalytic response of the catalysts is ascribed to the plasmonic response of AgNP though the catalytic efficiency is strongly influenced by the composition of the MeAlLDHs. The best photocatalytic performance was obtained on AgNP/ZnAlLDH750 catalyst that degraded 100% of phenol after 80 min of irradiation with solar light. The results reveal the high potential to tailor AgNP/LDHs and AgNP/MMOs as efficient photo-functional plasmonic hybrids for waste-water cleaning.

Surfactants, not size or zeta-potential influence blood-brain barrier passage of polymeric nanoparticles.

PubMed

Voigt, Nadine; Henrich-Noack, Petra; Kockentiedt, Sarah; Hintz, Werner; Tomas, Jürgen; Sabel, Bernhard A

2014-05-01

Nanoparticles (NP) can deliver drugs across the blood-brain barrier (BBB), but little is known which of the factors surfactant, size and zeta-potential are essential for allowing BBB passage. To this end we designed purpose-built fluorescent polybutylcyanoacrylate (PBCA) NP and imaged the NP's passage over the blood-retina barrier - which is a model of the BBB - in live animals. Rats received intravenous injections of fluorescent PBCA-NP fabricated by mini-emulsion polymerisation to obtain various NP's compositions that varied in surfactants (non-ionic, anionic, cationic), size (67-464nm) and zeta-potential. Real-time imaging of retinal blood vessels and retinal tissue was carried out with in vivo confocal neuroimaging (ICON) before, during and after NP's injection. Successful BBB passage with subsequent cellular labelling was achieved if NP were fabricated with non-ionic surfactants or cationic stabilizers but not when anionic compounds were added. NP's size and charge had no influence on BBB passage and cell labelling. This transport was not caused by an unspecific opening of the BBB because control experiments with injections of unlabelled NP and fluorescent dye (to test a "door-opener" effect) did not lead to parenchymal labelling. Thus, neither NP's size nor chemo-electric charge, but particle surface is the key factor determining BBB passage. This result has important implications for NP engineering in medicine: depending on the surfactant, NP can serve one of two opposite functions: while non-ionic tensides enhance brain up-take, addition of anionic tensides prevents it. NP can now be designed to specifically enhance drug delivery to the brain or, alternatively, to prevent brain penetration so to reduce unwanted psychoactive effects of drugs or prevent environmental nanoparticles from entering tissue of the central nervous system. Copyright © 2014 Elsevier B.V. All rights reserved.

Nanoparticle-macrophage interactions: A balance between clearance and cell-specific targeting

PubMed Central

Rattan, Rahul; Bhattacharjee, Somnath; Zong, Hong; Swain, Corban; Siddiqui, Muneeb A.; Visovatti, Scott H.; Kanthi, Yogendra; Desai, Sajani; Pinsky, David J.; Goonewardena, Sascha N.

2017-01-01

The surface properties of nanoparticles (NPs) are a major factor that influences how these nanomaterials interact with biological systems. Interactions between NPs and macrophages of the reticuloendothelial system (RES) can reduce the efficacy of NP diagnostics and therapeutics. Traditionally, to limit NP clearance by the RES system, the NP surface is neutralized with molecules like poly(ethylene glycol) (PEG) which are known to resist protein adsorption and RES clearance. Unfortunately, PEG modification is not without drawbacks including difficulties with the synthesis and associations with immune reactions. To overcome some of these obstacles, we neutralized the NP surface by acetylation and compared this modification to PEGylation for RES clearance and tumor-specific targeting. We found that acetylation was comparable to PEGylation in reducing RES clearance. Additionally, we found that dendrimer acetylation did not impact folic acid (FA)-mediated targeting of tumor cells whereas PEG surface modification reduced the targeting ability of the NP. These results clarify the impact of different NP surface modifications on RES clearance and cell-specific targeting and provide insights into the design of more effective NPs. PMID:28705434

Direct Visualization of Planar Assembly of Plasmonic Nanoparticles Adjacent to Electrodes in Oscillatory Electric Fields.

PubMed

Ferrick, Adam; Wang, Mei; Woehl, Taylor J

2018-05-29

Electric field-directed assembly of colloidal nanoparticles (NPs) has been widely adopted for fabricating functional thin films and nanostructured surfaces. While first-order electrokinetic effects on NPs are well-understood in terms of classical models, effects of second-order electrokinetics that involve induced surface charge are still poorly understood. Induced charge electroosmotic phenomena, such as electrohydrodynamic (EHD) flow, have long been implicated in electric field-directed NP assembly with little experimental basis. Here, we use in situ dark-field optical microscopy and plasmonic NPs to directly observe the dynamics of planar assembly of colloidal NPs adjacent to a planar electrode in low-frequency (<1 kHz) oscillatory electric fields. We exploit the change in plasmonic NP color resulting from interparticle plasmonic coupling to visualize the assembly dynamics and assembly structure of silver NPs. Planar assembly of NPs is unexpected because of strong electrostatic repulsion between NPs and indicates that there are strong attractive interparticle forces oriented perpendicular to the electric field direction. A parametric investigation of the voltage- and frequency-dependent phase behavior reveals that planar NP assembly occurs over a narrow frequency range below which irreversible ballistic deposition occurs. Two key experimental observations are consistent with EHD flow-induced NP assembly: (1) NPs remain mobile during assembly and (2) electron microscopy observations reveal randomly close-packed planar assemblies, consistent with strong interparticle attraction. We interpret planar assembly in terms of EHD fluid flow and develop a scaling model that qualitatively agrees with the measured phase regions. Our results are the first direct in situ observations of EHD flow-induced NP assembly and shed light on long-standing unresolved questions concerning the formation of NP superlattices during electric field-induced NP deposition.

Gold Nanoparticle Monolayers from Sequential Interfacial Ligand Exchange and Migration in a Three-Phase System

PubMed Central

Yang, Guang; Hallinan, Daniel T.

2016-01-01

Using a three-phase system, centimeter-scale monolayer gold nanoparticle (Au NP) films have been prepared that have long-range order and hydrophobic ligands. The system contains an interface between an aqueous phase containing Au NPs and an oil phase containing one of various types of amine ligands, and a water/air interface. As the Au NPs diffuse to the water/oil interface, ligand exchange takes place which temporarily traps them at the water/oil interface. The ligand-exchanged particles then spontaneously migrate to the air/water interface, where they self-assemble, forming a monolayer under certain conditions. The spontaneous formation of the NP film at the air/water interface was due to the minimization of the system Helmholtz free energy. However, the extent of surface functionalization was dictated by kinetics. This decouples interfacial ligand exchange from interfacial self-assembly, while maintaining the simplicity of a single system. The interparticle center-to-center distance was dictated by the amine ligand length. The Au NP monolayers exhibit tunable surface plasma resonance and excellent spatial homogeneity, which is useful for surface-enhanced Raman scattering. The “air/water/oil” self-assembly method developed here not only benefits the fundamental understanding of NP ligand conformations, but is also applicable to the manufacture of plasmonic nanoparticle devices with precisely designed optical properties. PMID:27762394

Probing the nanoscale interaction forces and elastic properties of organic and inorganic materials using force-distance (F-D) spectroscopy

NASA Astrophysics Data System (ADS)

Vincent, Abhilash

Due to their therapeutic applications such as radical scavenging, MRI contrast imaging, Photoluminescence imaging, drug delivery, etc., nanoparticles (NPs) have a significant importance in bio-nanotechnology. The reason that prevents the utilizing NPs for drug delivery in medical field is mostly due to their biocompatibility issues (incompatibility can lead to toxicity and cell death). Changes in the surface conditions of NPs often lead to NP cytotoxicity. Investigating the role of NP surface properties (surface charges and surface chemistry) on their interactions with biomolecules (Cells, protein and DNA) could enhance the current understanding of NP cytotoxicity. Hence, it is highly beneficial to the nanotechnology community to bring more attention towards the enhancement of surface properties of NPs to make them more biocompatible and less toxic to biological systems. Surface functionalization of NPs using specific ligand biomolecules have shown to enhance the protein adsorption and cellular uptake through more favorable interaction pathways. Cerium oxide NPs (CNPs also known as nanoceria) are potential antioxidants in cell culture models and understanding the nature of interaction between cerium oxide NPs and biological proteins and cells are important due to their therapeutic application (especially in site specific drug delivery systems). The surface charges and surface chemistry of CNPs play a major role in protein adsorption and cellular uptake. Hence, by tuning the surface charges and by selecting proper functional molecules on the surface, CNPs exhibiting strong adhesion to biological materials can be prepared. By probing the nanoscale interaction forces acting between CNPs and protein molecules using Atomic Force Microscopy (AFM) based force-distance (F-D) spectroscopy, the mechanism of CNP-protein adsorption and CNP cellular uptake can be understood more quantitatively. The work presented in this dissertation is based on the application of AFM in studying the interaction forces as well as the mechanical properties of nanobiomaterials. The research protocol employed in the earlier part of the dissertation is specifically aimed to understand the operation of F-D spectroscopy technique. The elastic properties of thin films of silicon dioxide NPs were investigated using F-D spectroscopy in the high force regime of few 100 nN to 1 microN. Here, sol-gel derived porous nanosilica thin films of varying surface morphology, particle size and porosity were prepared through acid and base catalyzed process. AFM nanoindentation experiments were conducted on these films using the F-D spectroscopy mode and the nanoscale elastic properties of these films were evaluated. The major contribution of this dissertation is a study exploring the interaction forces acting between CNPs and transferrin proteins in picoNewton scale regime using the force-distance spectroscopy technique. This study projects the importance of obtaining appropriate surface charges and surface chemistry so that the NP can exhibit enhanced protein adsorption and NP cellular uptake.

Functional Silver-Silicone-Nanofilament-Composite Material for Water Disinfection.

PubMed

Meier, Margrith; Suppiger, Angela; Eberl, Leo; Seeger, Stefan

2017-01-01

The roughness of superhydrophobic silicone nanofilaments (SNFs) is exploited to enlarge the contact area of conventional filter material. As an efficient wetting of the filter material is crucial for water treatment, the wettability of SNFs is readily modified from superhydrophobic to hydrophilic during the functionalization process. SNFs are coated on glass beads and subsequently modified with biocidal silver nanoparticles (AgNPs). The enlarged surface area of SNFs allows a 30 times higher loading of AgNPs in comparison to glass beads without SNF coating. Thus, in column experiments, the AgNP-SNF-nanocomposite-modified glass beads exert superior antibacterial activity towards suspensions of E. coli K12 compared to AgNP functionalized glass beads without SNFs. Additionally, reusing the AgNP-SNF-nanocomposite-coated glass beads with fresh bacteria contaminated medium increases their efficacy and reduces the colony forming units by ≈6 log units. Thereby, the silver loss during percolation is below 0.1 μg mL -1 . These results highlight, first, the potential of AgNP-SNF-nanocomposite-modified glass beads as an effective filter substrate for water disinfection, and second, the efficiency of SNF coating in increasing the contact area of conventional filter material. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galati, Elizabeth; Tebbe, Moritz; Querejeta-Fernández, Ana

Chemically and topographically patterned nanoparticles (NPs) with dimensions on the order of tens of nanometers have a diverse range of applications and are a valuable system for fundamental research. Recently, thermodynamically controlled segregation of a smooth layer of polymer ligands into pinned micelles (patches) offered an approach to nanopatterning of polymer-functionalized NPs. Control of the patch number, size, and spatial distribution on the surface of spherical NPs has been achieved, however, the role of NP shape remained elusive. Here, we report the role of NP shape, namely, the effect of the local surface curvature, on polymer segregation into surface patches.more » For polymer-functionalized metal nanocubes, we show experimentally and theoretically that the patches form preferentially on the high-curvature regions such as vertices and edges. An in situ transformation of the nanocubes into nanospheres leads to the change in the number and distribution of patches; a process that is dominated by the balance between the surface energy and the stretching energy of the polymer ligands. The experimental and theoretical results presented in this work are applicable to surface patterning of polymer-capped NPs with different shapes, which then enables the exploration of patch-directed self-assembly, as colloidal surfactants, and as templates for the synthesis of hybrid nanomaterials.« less

Quantitative characterization of colloidal assembly of graphene oxide-silver nanoparticle hybrids using aerosol differential mobility-coupled mass analyses.

PubMed

Nguyen, Thai Phuong; Chang, Wei-Chang; Lai, Yen-Chih; Hsiao, Ta-Chih; Tsai, De-Hao

2017-10-01

In this work, we develop an aerosol-based, time-resolved ion mobility-coupled mass characterization method to investigate colloidal assembly of graphene oxide (GO)-silver nanoparticle (AgNP) hybrid nanostructure on a quantitative basis. Transmission electron microscopy (TEM) and zeta potential (ZP) analysis were used to provide visual information and elemental-based particle size distributions, respectively. Results clearly show a successful controlled assembly of GO-AgNP by electrostatic-directed heterogeneous aggregation between GO and bovine serum albumin (BSA)-functionalized AgNP under an acidic environment. Additionally, physical size, mass, and conformation (i.e., number of AgNP per nanohybrid) of GO-AgNP were shown to be proportional to the number concentration ratio of AgNP to GO (R) and the selected electrical mobility diameter. An analysis of colloidal stability of GO-AgNP indicates that the stability increased with its absolute ZP, which was dependent on R and environmental pH. The work presented here provides a proof of concept for systematically synthesizing hybrid colloidal nanomaterials through the tuning of surface chemistry in aqueous phase with the ability in quantitative characterization. Graphical Abstract Colloidal assembly of graphene oxide-silver nanoparticle hybrids characterized by aerosol differential mobility-coupled mass analyses.

Comparison of nickel oxide and palladium nanoparticle loaded on activated carbon for efficient removal of methylene blue: kinetic and isotherm studies of removal process.

PubMed

Arabzadeh, S; Ghaedi, M; Ansari, A; Taghizadeh, F; Rajabi, M

2015-02-01

Palladium nanoparticles (Pd-NPs) and nickel oxide nanoparticles (NiO-NPs) were synthesized and loaded on activated carbon (AC). This novel material successfully used for the removal of methylene blue (MB) dye from aqueous medium. Full characterization of both material using X-ray diffraction, transmission electron microscopy, scanning electron microscopy and Brunauer-Emmet-Teller analyses for Pd-NP show their high surface area (>1340 m(2)/g) and low pore size (<20 Å) and average particle size lower than 45 Å and for NiO-NP show their high surface area (>1316.1554 m(2)/g) and low pore size (<20 Å) and average particle size lower than 46 Å in addition to high reactive atom and presence of various functional groups. These unique properties make them possible for efficient removal of MB. In batch experimental set-up, optimum conditions for maximum removal of MB by both adsorbents were attained following searching effect of variables such as central composite design. The Langmuir isotherm was found to be highly recommended for fitting the experimental equilibrium data. The kinetic of adsorption of MB on both adsorbents strongly can be fitted by a combination of pseudo-second order and intraparticle diffusion pathway. The experimental result achieved in this article shows the superiority of Pd-NP-AC for MB removal than NiO-NP-AC, so the maximum adsorption capacities of Pd-NP-AC and NiO-NP-AC were 555.5 mg/g and 588.2 mg/g, respectively. © The Author(s) 2015.

Electrochemical characterization of p(+)n and n(+)p diffused InP structures

NASA Technical Reports Server (NTRS)

Wilt, David M.; Faur, Maria; Faur, Mircea; Goradia, M.; Vargas-Aburto, Carlos

1993-01-01

The relatively well documented and widely used electrolytes for characterization and processing of Si and GaAs-related materials and structures by electrochemical methods are of little or no use with InP because the electrolytes presently used either dissolve the surface preferentially at the defect areas or form residual oxides and introduce a large density of surface states. Using an electrolyte which was newly developed for anodic dissolution of InP, and was named the 'FAP' electrolyte, accurate characterization of InP related structures including nature and density of surface states, defect density, and net majority carrier concentration, all as functions of depth was performed. A step-by-step optimization of n(+)p and p(+)n InP structures made by thermal diffusion was done using the electrochemical techniques, and resulted in high performance homojunction InP structures.

Extraction of Dysprosium Ions with DTPA Functionalized Superparamagnetic Nanoparticles Probed by Energy Dispersive X-ray Fluorescence and TEM/High-Angle Annular Dark Field Imaging.

PubMed

Melo, Fernando Menegatti de; Almeida, Sabrina da Nobrega; Uezu, Noemi Saori; Ramirez, Carlos Alberto Ospina; Santos, Antonio Domingues Dos; Toma, Henrique Eisi

2018-06-01

The extraction of dysprosium (Dy3+) ions from aqueous solution was carried out successfully, using magnetite (Fe3O4) nanoparticles functionalized with diethylenetriaminepentaacetic acid (MagNP@DTPA). The process was monitored by energy dispersive X-ray fluorescence spectroscopy, as a function of concentration, proceeding according to a Langmuir isotherm with an equilibrium constant of 2.57 × 10-3 g(MagNP) L-1 and a saturation limit of 63.2 mgDy/gMagNP. The presence of paramagnetic Dy3+ ions attached to the superparamagnetic nanoparticles led to an overall decrease of magnetization. By imaging the nanoparticles surface using scanning transmission electron microscopy equipped with high resolution elemental analysis, it was possible to probe the binding of the Dy3+ ions to DTPA, and to show their distribution in a region of negative magnetic field gradients. This finding is coherent with the observed decrease of magnetization, associated with the antiferromagnetic coupling between the lanthanide ions and the Fe3O4 core.

Visual discrimination of dihydroxybenzene isomers based on a nitrogen-doped graphene quantum dot-silver nanoparticle hybrid

NASA Astrophysics Data System (ADS)

Shi, Bingfang; Su, Yubin; Zhao, Jingjin; Liu, Rongjun; Zhao, Yan; Zhao, Shulin

2015-10-01

A room temperature reducing agent-free strategy for the synthesis of a nitrogen-doped graphene quantum dot-silver nanoparticle (N-GQD/AgNP) hybrid was presented. In this strategy, N-GQDs were used as a reducing agent and stabilizer for the formation of the N-GQD/AgNP hybrid, and the formation of the N-GQD/AgNP hybrid may result from the extraordinary reduction properties of N-GQDs, which are attributed to the nature of the surface oxygen-containing functional groups. The N-GQD/AgNP hybrid exhibits good dispersity and outstanding catalytic ability toward the oxidation of catechol (CC) and hydroquinone (HQ) by Ag+. In the presence of the N-GQD/AgNP hybrid, the reduction of Ag+ by CC and HQ was improved. CC enhanced the absorbance of the N-GQD/AgNP-Ag+ system the most, and HQ followed, while resorcinol (RC) had only a little effect on the absorption intensity of the system. Thus, a sensitive and selective colorimetric sensing method based on the N-GQD/AgNP-Ag+ system was developed for the discrimination of CC, HQ and RC. A good linear relationship was obtained from 0.1 to 15.0 μM for CC and from 0.3 to 20.0 μM for HQ. The detection limits of CC and HQ were 0.03 and 0.1 μM, respectively. In addition, the proposed method also shows a high selectivity for the detection of CC and HQ, and appreciable changes in color of the N-GQD/AgNP-Ag+ system toward CC, RC and HQ were observed.A room temperature reducing agent-free strategy for the synthesis of a nitrogen-doped graphene quantum dot-silver nanoparticle (N-GQD/AgNP) hybrid was presented. In this strategy, N-GQDs were used as a reducing agent and stabilizer for the formation of the N-GQD/AgNP hybrid, and the formation of the N-GQD/AgNP hybrid may result from the extraordinary reduction properties of N-GQDs, which are attributed to the nature of the surface oxygen-containing functional groups. The N-GQD/AgNP hybrid exhibits good dispersity and outstanding catalytic ability toward the oxidation of catechol (CC) and hydroquinone (HQ) by Ag+. In the presence of the N-GQD/AgNP hybrid, the reduction of Ag+ by CC and HQ was improved. CC enhanced the absorbance of the N-GQD/AgNP-Ag+ system the most, and HQ followed, while resorcinol (RC) had only a little effect on the absorption intensity of the system. Thus, a sensitive and selective colorimetric sensing method based on the N-GQD/AgNP-Ag+ system was developed for the discrimination of CC, HQ and RC. A good linear relationship was obtained from 0.1 to 15.0 μM for CC and from 0.3 to 20.0 μM for HQ. The detection limits of CC and HQ were 0.03 and 0.1 μM, respectively. In addition, the proposed method also shows a high selectivity for the detection of CC and HQ, and appreciable changes in color of the N-GQD/AgNP-Ag+ system toward CC, RC and HQ were observed. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04659a

Impacts of select organic ligands on the colloidal stability, dissolution dynamics, and toxicity of silver nanoparticles.

PubMed

Pokhrel, Lok R; Dubey, Brajesh; Scheuerman, Phillip R

2013-11-19

Key understanding of potential transformations that may occur on silver nanoparticle (AgNP) surface upon interaction with naturally ubiquitous organic ligands (e.g., -SH (thoil), humic acid, or -COO (carboxylate)) is limited. Herein we investigated how dissolved organic carbon (DOC), -SH (in cysteine, a well-known Ag(+) chelating agent), and -COO (in trolox, a well-known antioxidant) could alter the colloidal stability, dissolution rate, and toxicity of citrate-functionalized AgNPs (citrate-AgNPs) against a keystone crustacean Daphnia magna. Cysteine, DOC, or trolox amendment of citrate-AgNPs differentially modified particle size, surface properties (charge, plasmonic spectra), and ion release dynamics, thereby attenuating (with cysteine or trolox) or promoting (with DOC) AgNP toxicity. Except with DOC amendment, the combined toxicity of AgNPs and released Ag under cysteine or trolox amendment was lower than of AgNO3 alone. The results of this study show that citrate-AgNP toxicity can be associated with oxidative stress, ion release, and the organism biology. Our evidence suggests that specific organic ligands available in the receiving waters can differentially surface modify AgNPs and alter their environmental persistence (changing dissolution dynamics) and subsequently the toxicity; hence, we caveat to generalize that surface modified nanoparticles upon environmental release may not be toxic to receptor organisms.

Cytotoxicity of ZnO Nanoparticles Can Be Tailored by Modifying Their Surface Structure: A Green Chemistry Approach for Safer Nanomaterials.

PubMed

Punnoose, Alex; Dodge, Kelsey; Rasmussen, John W; Chess, Jordan; Wingett, Denise; Anders, Catherine

2014-07-07

ZnO nanoparticles (NP) are extensively used in numerous nanotechnology applications; however, they also happen to be one of the most toxic nanomaterials. This raises significant environmental and health concerns and calls for the need to develop new synthetic approaches to produce safer ZnO NP, while preserving their attractive optical, electronic, and structural properties. In this work, we demonstrate that the cytotoxicity of ZnO NP can be tailored by modifying their surface-bound chemical groups, while maintaining the core ZnO structure and related properties. Two equally sized (9.26 ± 0.11 nm) ZnO NP samples were synthesized from the same zinc acetate precursor using a forced hydrolysis process, and their surface chemical structures were modified by using different reaction solvents. X-ray diffraction and optical studies showed that the lattice parameters, optical properties, and band gap (3.44 eV) of the two ZnO NP samples were similar. However, FTIR spectroscopy showed significant differences in the surface structures and surface-bound chemical groups. This led to major differences in the zeta potential, hydrodynamic size, photocatalytic rate constant, and more importantly, their cytotoxic effects on Hut-78 cancer cells. The ZnO NP sample with the higher zeta potential and catalytic activity displayed a 1.5-fold stronger cytotoxic effect on cancer cells. These results suggest that by modifying the synthesis parameters/conditions and the surface chemical structures of the nanocrystals, their surface charge density, catalytic activity, and cytotoxicity can be tailored. This provides a green chemistry approach to produce safer ZnO NP.

Serum Proteins Enhance Dispersion Stability and Influence the Cytotoxicity and Dosimetry of ZnO Nanoparticles in Suspension and Adherent Cancer Cell Models.

PubMed

Anders, Catherine B; Chess, Jordan J; Wingett, Denise G; Punnoose, Alex

2015-12-01

Agglomeration and sedimentation of nanoparticles (NPs) within biological solutions is a major limitation in their use in many downstream applications. It has been proposed that serum proteins associate with the NP surface to form a protein corona that limits agglomeration and sedimentation. Here, we investigate the effect of fetal bovine serum (FBS) proteins on the dispersion stability, dosimetry, and NP-induced cytotoxicity of cationic zinc oxide nanoparticles (nZnO) synthesized via forced hydrolysis with a core size of 10 nm. Two different in vitro cell culture models, suspension and adherent, were evaluated by comparing a phosphate buffered saline (PBS) nZnO dispersion (nZnO/PBS) and an FBS-stabilized PBS nZnO dispersion (nZnO - FBS/PBS). Surface interactions of FBS on nZnO were analyzed via spectroscopic and optical techniques. Fourier transformed infrared spectroscopy (FTIR) confirmed the adsorption of negatively charged protein components on the cationic nZnO surface through the disappearance of surfaced-adsorbed carboxyl functional groups and the subsequent detection of vibrational modes associated with the protein backbone of FBS-associated proteins. Further confirmation of these interactions was noted in the isoelectric point shift of the nZnO from the characteristic pH of 9.5 to a pH of 6.1. In nZnO - FBS/PBS dispersions, the FBS reduced agglomeration and sedimentation behaviors to impart long-term improvements (>24 h) to the nZnO dispersion stability. Furthermore, mathematical dosimetry models indicate that nZnO - FBS/PBS dispersions had consistent NP deposition patterns over time unlike unstable nZnO/PBS dispersions. In suspension cell models, the stable nZnO - FBS/PBS dispersion resulted in a ~33 % increase in the NP-induced cytotoxicity for both Jurkat leukemic and Hut-78 lymphoma cancer cells. In contrast, the nZnO - FBS/PBS dispersion resulted in 49 and 71 % reductions in the cytotoxicity observed towards the adherent breast (T-47D) and prostate (LNCaP) cancer cell lines, respectively. Presence of FBS in the NP dispersions also increased the reactive oxygen species generation. These observations indicate that the improved dispersion stability leads to increased NP bioavailability for suspension cell models and reduced NP sedimentation onto adherent cell layers resulting in more accurate in vitro toxicity assessments.

Serum Proteins Enhance Dispersion Stability and Influence the Cytotoxicity and Dosimetry of ZnO Nanoparticles in Suspension and Adherent Cancer Cell Models

NASA Astrophysics Data System (ADS)

Anders, Catherine B.; Chess, Jordan J.; Wingett, Denise G.; Punnoose, Alex

2015-11-01

Agglomeration and sedimentation of nanoparticles (NPs) within biological solutions is a major limitation in their use in many downstream applications. It has been proposed that serum proteins associate with the NP surface to form a protein corona that limits agglomeration and sedimentation. Here, we investigate the effect of fetal bovine serum (FBS) proteins on the dispersion stability, dosimetry, and NP-induced cytotoxicity of cationic zinc oxide nanoparticles (nZnO) synthesized via forced hydrolysis with a core size of 10 nm. Two different in vitro cell culture models, suspension and adherent, were evaluated by comparing a phosphate buffered saline (PBS) nZnO dispersion (nZnO/PBS) and an FBS-stabilized PBS nZnO dispersion (nZnO - FBS/PBS). Surface interactions of FBS on nZnO were analyzed via spectroscopic and optical techniques. Fourier transformed infrared spectroscopy (FTIR) confirmed the adsorption of negatively charged protein components on the cationic nZnO surface through the disappearance of surfaced-adsorbed carboxyl functional groups and the subsequent detection of vibrational modes associated with the protein backbone of FBS-associated proteins. Further confirmation of these interactions was noted in the isoelectric point shift of the nZnO from the characteristic pH of 9.5 to a pH of 6.1. In nZnO - FBS/PBS dispersions, the FBS reduced agglomeration and sedimentation behaviors to impart long-term improvements (>24 h) to the nZnO dispersion stability. Furthermore, mathematical dosimetry models indicate that nZnO - FBS/PBS dispersions had consistent NP deposition patterns over time unlike unstable nZnO/PBS dispersions. In suspension cell models, the stable nZnO - FBS/PBS dispersion resulted in a ~33 % increase in the NP-induced cytotoxicity for both Jurkat leukemic and Hut-78 lymphoma cancer cells. In contrast, the nZnO - FBS/PBS dispersion resulted in 49 and 71 % reductions in the cytotoxicity observed towards the adherent breast (T-47D) and prostate (LNCaP) cancer cell lines, respectively. Presence of FBS in the NP dispersions also increased the reactive oxygen species generation. These observations indicate that the improved dispersion stability leads to increased NP bioavailability for suspension cell models and reduced NP sedimentation onto adherent cell layers resulting in more accurate in vitro toxicity assessments.

Partner-facilitating transmembrane penetration of nanoparticles: a biological test in silico.

PubMed

Wang, W; Yang, R; Zhang, F; Yuan, B; Yang, K; Ma, Y

2018-06-21

Transmembrane penetration of nanoparticles (NPs) promises an effective pathway for cargo delivery into cells, and offers the possibility of organelle-specific targeting for biomedical applications. However, a full understanding of the underlying NP-membrane interaction mechanism is still lacking. In this work, the membrane penetration behavior of NPs is statistically analyzed based on the simulations of over 2.2 ms, which are performed with dissipative particle dynamics (DPD). Influences from multiple factors including the NP concentration, shape and surface chemistry are taken into account. It is interesting to find that, the introduction of a partner NP would greatly facilitate the transmembrane penetration of a host spherical NP. This is probably due to the membrane-mediated cooperation between the NPs. Moreover, the proper selection of a partner NP with specific surface chemistry is of great significance. For example, the best partner for a hydrophilic NP to achieve transmembrane penetration is a Janus-like one, in comparison with the hydrophilic, hydrophobic or randomly surface-decorated NPs. Furthermore, such a partner-facilitating effect in NP translocation also works for a shaped NP although less pronounced. Our results are helpful for a better understanding of the complicated nano-bio interactions, and offer a practical guide to the NP-based drug delivery strategy with high efficiency.

Nanobarcoding for improved nanoparticle detection in nanomedical biodistribution studies

NASA Astrophysics Data System (ADS)

Eustaquio, Trisha

Determination of the fate of nanoparticles (NPs) in a biological system, or NP biodistribution, is critical in evaluating a NP formulation for nanomedicine. Unlike small-molecule drugs, NPs impose unique challenges in the design of appropriate biodistribution studies due to their small size and subsequent detection signal. Current methods to determine NP biodistribution are greatly inadequate due to their limited detection thresholds. There is an overwhelming need for a sensitive and efficient imaging-based method that can (1) detect and measure small numbers of NPs of various types, ideally single NPs, (2) associate preferential NP uptake with histological cell type by preserving spatial information in samples, and (3) allow for relatively quick and accurate NP detection in in vitro (and possibly ex vivo) samples for comprehensive NP biodistribution studies. Herein, a novel method for improved NP detection is proposed, coined "nanobarcoding." Nanobarcoding utilizes a non-endogenous oligonucleotide, or "nanobarcode" (NB), conjugated to the NP surface to amplify the detection signal from a single NP via in situ polymerase chain reaction (ISPCR), and this signal amplification will facilitate rapid and precise detection of single NPs inside cells over large areas of sample such that more sophisticated studies can be performed on the NP-positive subpopulation. Moreover, nanobarcoding has the potential to be applied to the detection of more than one NP type to study the effects of physicochemical properties, targeting mechanisms, and route of entry on NP biodistribution. The nanobarcoding method was validated in vitro using NB-functionalized superparamagnetic iron oxide NPs (NB-SPIONs) as the model NP type for improved NP detection inside HeLa human cervical cancer cells, a cell line commonly used for ISPCR-mediated detection of human papilloma virus (HPV). Nanotoxicity effects of NB-SPIONs were also evaluated at the single-cell level using LEAP (Laser-Enabled Analysis and Processing, Intrexon, San Diego, CA), and NB-SPIONs were found to be less toxic than its precursor, carboxylated SPIONs (COOH-SPIONs).

Nanoparticle Clusters: Assembly and Control Over Internal Order, Current Capabilities, and Future Potential.

PubMed

Stolarczyk, Jacek K; Deak, Andras; Brougham, Dermot F

2016-07-01

The current state of the art in the use of colloidal methods to form nanoparticle assemblies, or clusters (NPCs) is reviewed. The focus is on the two-step approach, which exploits the advantages of bottom-up wet chemical NP synthesis procedures, with subsequent colloidal destabilization to trigger assembly in a controlled manner. Recent successes in the application of functional NPCs with enhanced emergent collective properties for a wide range of applications, including in biomedical detection, surface enhanced Raman scattering (SERS) enhancement, photocatalysis, and light harvesting, are highlighted. The role of the NP-NP interactions in the formation of monodisperse ordered clusters is described and the different assembly processes from a wide range of literature sources are classified according to the nature of the perturbation from the initial equilibrium state (dispersed NPs). Finally, the future for the field and the anticipated role of computational approaches in developing next-generation functional NPCs are briefly discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoporous Gold as a Neural Interface Coating: Effects of Topography, Surface Chemistry, and Feature Size

DOE PAGES

Chapman, Christopher A. R.; Chen, Hao; Stamou, Marianna; ...

2015-02-23

We report that designing neural interfaces that maintain close physical coupling of neurons to an electrode surface remains a major challenge for both implantable and in vitro neural recording electrode arrays. Typically, low-impedance nanostructured electrode coatings rely on chemical cues from pharmaceuticals or surface-immobilized peptides to suppress glial scar tissue formation over the electrode surface (astrogliosis), which is an obstacle to reliable neuron–electrode coupling. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a promising candidate to reduce astrogliosis solely through topography by taking advantage of its tunable length scale. In the present in vitro study on np-Au’s interactionmore » with cortical neuron–glia co-cultures, we demonstrate that the nanostructure of np-Au achieves close physical coupling of neurons by maintaining a high neuron-to-astrocyte surface coverage ratio. Atomic layer deposition-based surface modification was employed to decouple the effect of morphology from surface chemistry. Additionally, length scale effects were systematically studied by controlling the characteristic feature size of np-Au through variations in the dealloying conditions. In conclusion, our results show that np-Au nanotopography, not surface chemistry, reduces astrocyte surface coverage while maintaining high neuronal coverage and may enhance neuron–electrode coupling through nanostructure-mediated suppression of scar tissue formation.« less

Formation and coarsening of near-surface Ga nanoparticles on SiN{sub x}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Canniff, J. C.; Jeon, S.; Huang, S.

2015-06-15

We have investigated the formation and coarsening of near-surface Ga nanoparticles (NPs) in SiN{sub x} using Ga{sup +} focused-ion-beam-irradiation of SiN{sub x}, followed by rapid thermal annealing. For surfaces with minimal curvature, diffusive growth is apparent, leading to nearly close packed arrays with NP diameters as small as 3 nm and densities as high as ∼4 × 10{sup 12} cm{sup −2}. The diffusive flux increases with annealing temperature, leading to NP coarsening by Ostwald ripening. For surfaces with increased curvature, diffusion towards the valleys also increases during annealing, leading to Ga NP coalescence and a bi-modal distribution of NP sizes.

Parallel nano-assembling of a multifunctional GO/HapNP coating on ultrahigh-purity magnesium for biodegradable implants

NASA Astrophysics Data System (ADS)

Santos, C.; Piedade, C.; Uggowitzer, P. J.; Montemor, M. F.; Carmezim, M. J.

2015-08-01

This work reports the one-step fabrication of a novel coating on ultra high purity magnesium using a parallel nano assembling process. The multifunctional biodegradable surface was obtained by adding hydroxyapatite nanoparticles (HapNP) plus graphene oxide (GO). The coating was characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffractometer (XRD), micro-Raman spectroscopy. The thin phosphate coating (thickness of 1 μm) reveals a uniform coverage with cypress like structures. The incorporation of HapNP and GO promotes the hydrophilic behavior of the coating surface. The results revealed that the proposed coating can be used to tailor the surface properties such as wettability by adjusting the contents of HapNP and GO. The in vitro degradation rate of the coated magnesium suggests that the presence of HapNP and GO/HapNP in the phosphate coating decreased the current density compared to the single phosphate coating and uncoated magnesium. This study also reveals the HapNP/GO/phosphate coating induces apatite formation, showing suitable degradability that makes it a promising coating candidate for enhanced bone regeneration.

Investigation of the mechanical and chemical characteristics of nanotubular and nano-pitted anodic films on grade 2 titanium dental implant materials.

PubMed

Weszl, Miklós; Tóth, Krisztián László; Kientzl, Imre; Nagy, Péter; Pammer, Dávid; Pelyhe, Liza; Vrana, Nihal E; Scharnweber, Dieter; Wolf-Brandstetter, Cornelia; Joób F, Árpád; Bognár, Eszter

2017-09-01

The objective of this study was to investigate the reproducibility, mechanical integrity, surface characteristics and corrosion behavior of nanotubular (NT) titanium oxide arrays in comparison with a novel nano-pitted (NP) anodic film. Surface treatment processes were developed to grow homogenous NT and NP anodic films on the surface of grade 2 titanium discs and dental implants. The effect of process parameters on the surface characteristics and reproducibility of the anodic films was investigated and optimized. The mechanical integrity of the NT and NP anodic films were investigated by scanning electron microscopy, surface roughness measurement, scratch resistance and screwing tests, while the chemical and physicochemical properties were investigated in corrosion tests, contact angle measurement and X-ray photoelectron spectroscopy (XPS). The growth of NT anodic films was highly affected by process parameters, especially by temperature, and they were apt to corrosion and exfoliation. In contrast, the anodic growth of NP film showed high reproducibility even on the surface of 3-dimensional screw dental implants and they did not show signs of corrosion and exfoliation. The underlying reason of the difference in the tendency for exfoliation of the NT and NP anodic films is unclear; however the XPS analysis revealed fluorine dopants in a magnitude larger concentration on NT anodic film than on NP surface, which was identified as a possible causative. Concerning other surface characteristics that are supposed to affect the biological behavior of titanium implants, surface roughness values were found to be similar, whereas considerable differences were revealed in the wettability of the NT and NP anodic films. Our findings suggest that the applicability of NT anodic films on the surface of titanium bone implants may be limited because of mechanical considerations. In contrast, it is worth to consider the applicability of nano-pitted anodic films over nanotubular arrays for the enhancement of the biological properties of titanium implants. Copyright © 2017 Elsevier B.V. All rights reserved.

Short communication: Unexpected findings on the physicochemical characterization of the silver nanoparticle surface

NASA Astrophysics Data System (ADS)

Loran, S.; Yelon, A.; Sacher, E.

2018-01-01

The bactericidal properties of silver nanoparticles (Ag NPs) have been variously attributed to the action of the NP surface and/or the Ag ions released therefrom. However, the published literature does not appear to contain any information on the physicochemical characterization of the NP surface. Herein, we report on the surprisingly reactive surface of the Ag NP, which has an almost total lack of free Ag on atmospheric exposure. Rather, an abundance of surface hydrocarbons, hydrides and oxides, as well as amines and oxidized N, argues for a reinterpretation of their bactericidal action.

Interfacing Nanoparticles and Biology: New Strategies for Biomedicine

PubMed Central

Tonga, Gulen Yesilbag; Saha, Krishnendu; Rotello, Vincent M.

2014-01-01

The exterior surface of nanoparticles (NPs) dictates the behavior of these systems with the outside world. Understanding the interactions of NP surface functionality with biosystems enables the design and fabrication of effective platforms for therapeutics, diagnostics, and imaging agents. In this review, we highlight the role of chemistry in the engineering of nanomaterials, focusing on the fundamental role played by surface chemistry in controlling the interaction of NPs with proteins and cells. PMID:24105763

Cytotoxicity of ZnO Nanoparticles Can Be Tailored by Modifying Their Surface Structure: A Green Chemistry Approach for Safer Nanomaterials

PubMed Central

2015-01-01

ZnO nanoparticles (NP) are extensively used in numerous nanotechnology applications; however, they also happen to be one of the most toxic nanomaterials. This raises significant environmental and health concerns and calls for the need to develop new synthetic approaches to produce safer ZnO NP, while preserving their attractive optical, electronic, and structural properties. In this work, we demonstrate that the cytotoxicity of ZnO NP can be tailored by modifying their surface-bound chemical groups, while maintaining the core ZnO structure and related properties. Two equally sized (9.26 ± 0.11 nm) ZnO NP samples were synthesized from the same zinc acetate precursor using a forced hydrolysis process, and their surface chemical structures were modified by using different reaction solvents. X-ray diffraction and optical studies showed that the lattice parameters, optical properties, and band gap (3.44 eV) of the two ZnO NP samples were similar. However, FTIR spectroscopy showed significant differences in the surface structures and surface-bound chemical groups. This led to major differences in the zeta potential, hydrodynamic size, photocatalytic rate constant, and more importantly, their cytotoxic effects on Hut-78 cancer cells. The ZnO NP sample with the higher zeta potential and catalytic activity displayed a 1.5-fold stronger cytotoxic effect on cancer cells. These results suggest that by modifying the synthesis parameters/conditions and the surface chemical structures of the nanocrystals, their surface charge density, catalytic activity, and cytotoxicity can be tailored. This provides a green chemistry approach to produce safer ZnO NP. PMID:25068096

SERS-barcoded colloidal gold NP assemblies as imaging agents for use in biodiagnostics

NASA Astrophysics Data System (ADS)

Dey, Priyanka; Olds, William; Blakey, Idriss; Thurecht, Kristofer J.; Izake, Emad L.; Fredericks, Peter M.

2014-03-01

There is a growing need for new biodiagnostics that combine high throughput with enhanced spatial resolution and sensitivity. Gold nanoparticle (NP) assemblies with sub-10 nm particle spacing have the benefits of improving detection sensitivity via Surface enhanced Raman scattering (SERS) and being of potential use in biomedicine due to their colloidal stability. A promising and versatile approach to form solution-stable NP assemblies involves the use of multi-branched molecular linkers which allows tailoring of the assembly size, hot-spot density and interparticle distance. We have shown that linkers with multiple anchoring end-groups can be successfully employed as a linker to assemble gold NPs into dimers, linear NP chains and clustered NP assemblies. These NP assemblies with diameters of 30-120 nm are stable in solution and perform better as SERS substrates compared with single gold NPs, due to an increased hot-spot density. Thus, tailored gold NP assemblies are potential candidates for use as biomedical imaging agents. We observed that the hot-spot density and in-turn the SERS enhancement is a function of the linker polymer concentration and polymer architecture. New deep Raman techniques like Spatially Offset Raman Spectroscopy (SORS) have emerged that allow detection from beneath diffusely scattering opaque materials, including biological media such as animal tissue. We have been able to demonstrate that the gold NP assemblies could be detected from within both proteinaceous and high lipid containing animal tissue by employing a SORS technique with a backscattered geometry.

Structure-based design of novel naproxen derivatives targeting monomeric nucleoprotein of Influenza A virus

PubMed Central

Tarus, Bogdan; Bertrand, Hélène; Zedda, Gloria; Di Primo, Carmelo; Quideau, Stéphane; Slama-Schwok, Anny

2015-01-01

The nucleoprotein (NP) binds the viral RNA genome as oligomers assembled with the polymerase in a ribonucleoprotein complex required for transcription and replication of influenza A virus. Novel antiviral candidates targeting the nucleoprotein either induced higher order oligomers or reduced NP oligomerization by targeting the oligomerization loop and blocking its insertion into adjacent nucleoprotein subunit. In this study, we used a different structure-based approach to stabilize monomers of the nucleoprotein by drugs binding in its RNA-binding groove. We recently identified naproxen as a drug competing with RNA binding to NP with antiinflammatory and antiviral effects against influenza A virus. Here, we designed novel derivatives of naproxen by fragment extension for improved binding to NP. Molecular dynamics simulations suggested that among these derivatives, naproxen A and C0 were most promising. Their chemical synthesis is described. Both derivatives markedly stabilized NP monomer against thermal denaturation. Naproxen C0 bound tighter to NP than naproxen at a binding site predicted by MD simulations and shown by competition experiments using wt NP or single-point mutants as determined by surface plasmon resonance. MD simulations suggested that impeded oligomerization and stabilization of monomeric NP is likely to be achieved by drugs binding in the RNA grove and inducing close to their binding site conformational changes of key residues hosting the oligomerization loop as observed for the naproxen derivatives. Naproxen C0 is a potential antiviral candidate blocking influenza nucleoprotein function. PMID:25333630

Structure-based design of novel naproxen derivatives targeting monomeric nucleoprotein of Influenza A virus.

PubMed

Tarus, Bogdan; Bertrand, Hélène; Zedda, Gloria; Di Primo, Carmelo; Quideau, Stéphane; Slama-Schwok, Anny

2015-09-01

The nucleoprotein (NP) binds the viral RNA genome as oligomers assembled with the polymerase in a ribonucleoprotein complex required for transcription and replication of influenza A virus. Novel antiviral candidates targeting the nucleoprotein either induced higher order oligomers or reduced NP oligomerization by targeting the oligomerization loop and blocking its insertion into adjacent nucleoprotein subunit. In this study, we used a different structure-based approach to stabilize monomers of the nucleoprotein by drugs binding in its RNA-binding groove. We recently identified naproxen as a drug competing with RNA binding to NP with antiinflammatory and antiviral effects against influenza A virus. Here, we designed novel derivatives of naproxen by fragment extension for improved binding to NP. Molecular dynamics simulations suggested that among these derivatives, naproxen A and C0 were most promising. Their chemical synthesis is described. Both derivatives markedly stabilized NP monomer against thermal denaturation. Naproxen C0 bound tighter to NP than naproxen at a binding site predicted by MD simulations and shown by competition experiments using wt NP or single-point mutants as determined by surface plasmon resonance. MD simulations suggested that impeded oligomerization and stabilization of monomeric NP is likely to be achieved by drugs binding in the RNA grove and inducing close to their binding site conformational changes of key residues hosting the oligomerization loop as observed for the naproxen derivatives. Naproxen C0 is a potential antiviral candidate blocking influenza nucleoprotein function.

Using ruthenium polypyridyl functionalized ZnO mesocrystals and gold nanoparticle dotted graphene composite for biological recognition and electrochemiluminescence biosensing

NASA Astrophysics Data System (ADS)

Liu, Suli; Zhang, Jinxing; Tu, Wenwen; Bao, Jianchun; Dai, Zhihui

2014-01-01

Using ruthenium polypyridyl functionalized ZnO mesocrystals as bionanolabels, a universal biological recognition and biosensing platform based on gold nanoparticle (AuNP) dotted reduced graphene oxide (rGO) composite was developed. AuNP-rGO accelerated electron transfer between the detection probe and the electrode, and increased the surface area of the working electrode to load greater amounts of the capture antibodies. The large surface area of ZnO mesocrystals was beneficial for loading a high content ruthenium polypyridyl complex, leading to an enhanced electrochemiluminescence signal. Using α-fetoprotein (AFP) as a model, a simple and sensitive sandwich-type electrochemiluminescence biosensor with tripropylamine (TPrA) as a coreactant for detection of AFP was constructed. The designed biosensor provided a good linear range from 0.04 to 500 ng mL-1 with a low detection limit of 0.031 ng mL-1 at a S/N of 3 for AFP determination. The proposed biological recognition and biosensing platform extended the application of ruthenium polypyridyl functionalized ZnO mesocrystals, which provided a new promising prospect.

Hemoglobin–Albumin Cluster Incorporating a Pt Nanoparticle: Artificial O2 Carrier with Antioxidant Activities

PubMed Central

Hosaka, Hitomi; Haruki, Risa; Yamada, Kana; Böttcher, Christoph; Komatsu, Teruyuki

2014-01-01

A covalent core–shell structured protein cluster composed of hemoglobin (Hb) at the center and human serum albumins (HSA) at the periphery, Hb-HSAm, is an artificial O2 carrier that can function as a red blood cell substitute. Here we described the preparation of a novel Hb-HSA3 cluster with antioxidant activities and its O2 complex stable in aqueous H2O2 solution. We used an approach of incorporating a Pt nanoparticle (PtNP) into the exterior HSA unit of the cluster. A citrate reduced PtNP (1.8 nm diameter) was bound tightly within the cleft of free HSA with a binding constant (K) of 1.1×107 M−1, generating a stable HSA-PtNP complex. This platinated protein showed high catalytic activities for dismutations of superoxide radical anions (O2 •–) and hydrogen peroxide (H2O2), i.e., superoxide dismutase and catalase activities. Also, Hb-HSA3 captured PtNP into the external albumin unit (K = 1.1×107 M−1), yielding an Hb-HSA3(PtNP) cluster. The association of PtNP caused no alteration of the protein surface net charge and O2 binding affinity. The peripheral HSA-PtNP shell prevents oxidation of the core Hb, which enables the formation of an extremely stable O2 complex, even in H2O2 solution. PMID:25310133

In Vitro Characterization of a Stem-Cell-Seeded Triple-Interpenetrating-Network Hydrogel for Functional Regeneration of the Nucleus Pulposus

PubMed Central

Smith, Lachlan J.; Gorth, Deborah J.; Showalter, Brent L.; Chiaro, Joseph A.; Beattie, Elizabeth E.; Elliott, Dawn M.; Mauck, Robert L.; Chen, Weiliam

2014-01-01

Intervertebral disc degeneration is implicated as a major cause of low-back pain. There is a pressing need for new regenerative therapies for disc degeneration that restore native tissue structure and mechanical function. To that end we investigated the therapeutic potential of an injectable, triple-interpenetrating-network hydrogel comprised of dextran, chitosan, and teleostean, for functional regeneration of the nucleus pulposus (NP) of the intervertebral disc in a series of biomechanical, cytotoxicity, and tissue engineering studies. Biomechanical properties were evaluated as a function of gelation time, with the hydrogel reaching ∼90% of steady-state aggregate modulus within 10 h. Hydrogel mechanical properties evaluated in confined and unconfined compression were comparable to native human NP properties. To confirm containment within the disc under physiological loading, toluidine-blue-labeled hydrogel was injected into human cadaveric spine segments after creation of a nucleotomy defect, and the segments were subjected to 10,000 cycles of loading. Gross analysis demonstrated no implant extrusion, and further, that the hydrogel interdigitated well with native NP. Constructs were next surface-seeded with NP cells and cultured for 14 days, confirming lack of hydrogel cytotoxicity, with the hydrogel maintaining NP cell viability and promoting proliferation. Next, to evaluate the potential of the hydrogel to support cell-mediated matrix production, constructs were seeded with mesenchymal stem cells (MSCs) and cultured under prochondrogenic conditions for up to 42 days. Importantly, the hydrogel maintained MSC viability and promoted proliferation, as evidenced by increasing DNA content with culture duration. MSCs differentiated along a chondrogenic lineage, evidenced by upregulation of aggrecan and collagen II mRNA, and increased GAG and collagen content, and mechanical properties with increasing culture duration. Collectively, these results establish the therapeutic potential of this novel hydrogel for functional regeneration of the NP. Future work will confirm the ability of this hydrogel to normalize the mechanical stability of cadaveric human motion segments, and advance the material toward human translation using preclinical large-animal models. PMID:24410394

In situ synthesis of silver-nanoparticles/bacterial cellulose composites for slow-released antimicrobial wound dressing.

PubMed

Wu, Jian; Zheng, Yudong; Song, Wenhui; Luan, Jiabin; Wen, Xiaoxiao; Wu, Zhigu; Chen, Xiaohua; Wang, Qi; Guo, Shaolin

2014-02-15

Bacterial cellulose has attracted increasing attention as a novel wound dressing material, but it has no antimicrobial activity, which is one of critical skin-barrier functions in wound healing. To overcome such deficiency, we developed a novel method to synthesize and impregnate silver nanoparticles on to bacterial cellulose nanofibres (AgNP-BC). Uniform spherical silver nano-particles (10-30 nm) were generated and self-assembled on the surface of BC nano-fibers, forming a stable and evenly distributed Ag nanoparticles coated BC nanofiber. Such hybrid nanostructure prevented Ag nanoparticles from dropping off BC network and thus minimized the toxicity of nanoparticles. Regardless the slow Ag(+) release, AgNP-BC still exhibited significant antibacterial activities with more than 99% reductions in Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa. Moreover, AgNP-BC allowed attachment and growth of epidermal cells with no cytotoxicity emerged. The results demonstrated that AgNP-BC could reduce inflammation and promote wound healing. Copyright © 2013 Elsevier Ltd. All rights reserved.

Highly Sensitive Detection of Target Biomolecules on Cell Surface Using Gold Nanoparticle Conjugated with Aptamer Probe

NASA Astrophysics Data System (ADS)

Kim, Hyonchol; Terazono, Hideyuki; Hayashi, Masahito; Takei, Hiroyuki; Yasuda, Kenji

2012-06-01

A method of gold nanoparticle (Au NP) labeling with backscattered electron (BE) imaging of field emission scanning electron microscopy (FE-SEM) was applied for specific detection of target biomolecules on a cell surface. A single-stranded DNA aptamer, which specifically binds to the target molecule on a human acute lymphoblastic leukemia cell, was conjugated with a 20 nm Au NP and used as a probe to label its target molecule on the cell. The Au NP probe was incubated with the cell, and the interaction was confirmed using BE imaging of FE-SEM through direct counting of the number of Au NPs attached on the target cell surface. Specific Au NP-aptamer probes were observed on a single cell surface and their spatial distributions including submicron-order localizations were also clearly visualized, whereas the nonspecific aptamer probes were not observed on it. The aptamer probe can be potentially dislodged from the cell surface with treatment of nucleases, indicating that Au NP-conjugated aptamer probes can be used as sensitive and reversible probes to label target biomolecules on cells.

Partitioning of Nanoparticles into Organic Phases and Model Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Posner, J.D.; Westerhoff, P.; Hou, W-C.

2011-08-25

There is a recognized need to understand and predict the fate, transport and bioavailability of engineered nanoparticles (ENPs) in aquatic and soil ecosystems. Recent research focuses on either collection of empirical data (e.g., removal of a specific NP through water or soil matrices under variable experimental conditions) or precise NP characterization (e.g. size, degree of aggregation, morphology, zeta potential, purity, surface chemistry, and stability). However, it is almost impossible to transition from these precise measurements to models suitable to assess the NP behavior in the environment with complex and heterogeneous matrices. For decades, the USEPA has developed and applies basicmore » partitioning parameters (e.g., octanol-water partition coefficients) and models (e.g., EPI Suite, ECOSAR) to predict the environmental fate, bioavailability, and toxicity of organic pollutants (e.g., pesticides, hydrocarbons, etc.). In this project we have investigated the hypothesis that NP partition coefficients between water and organic phases (octanol or lipid bilayer) is highly dependent on their physiochemical properties, aggregation, and presence of natural constituents in aquatic environments (salts, natural organic matter), which may impact their partitioning into biological matrices (bioaccumulation) and human exposure (bioavailability) as well as the eventual usage in modeling the fate and bioavailability of ENPs. In this report, we use the terminology "partitioning" to operationally define the fraction of ENPs distributed among different phases. The mechanisms leading to this partitioning probably involve both chemical force interactions (hydrophobic association, hydrogen bonding, ligand exchange, etc.) and physical forces that bring the ENPs in close contact with the phase interfaces (diffusion, electrostatic interactions, mixing turbulence, etc.). Our work focuses on partitioning, but also provides insight into the relative behavior of ENPs as either "more like dissolved substances" or "more like colloids" as the division between behaviors of macromolecules versus colloids remains ill-defined. Below we detail our work on two broadly defined objectives: (i) Partitioning of ENP into octanol, lipid bilayer, and water, and (ii) disruption of lipid bilayers by ENPs. We have found that the partitioning of NP reaches pseudo-equilibrium distributions between water and organic phases. The equilibrium partitioning most strongly depends on the particle surface charge, which leads us to the conclusion that electrostatic interactions are critical to understanding the fate of NP in the environment. We also show that the kinetic rate at which particle partition is a function of their size (small particles partition faster by number) as can be predicted from simple DLVO models. We have found that particle number density is the most effective dosimetry to present our results and provide quantitative comparison across experiments and experimental platforms. Cumulatively, our work shows that lipid bilayers are a more effective organic phase than octanol because of the definable surface area and ease of interpretation of the results. Our early comparison of NP partitioning between water and lipids suggest that this measurement can be predictive of bioaccumulation in aquatic organisms. We have shown that nanoparticle disrupt lipid bilayer membranes and detail how NP-bilayer interaction leads to the malfunction of lipid bilayers in regulating the fluxes of ionic charges and molecules. Our results show that the disruption of the lipid membranes is similar to that of toxin melittin, except single particles can disrupt a bilayer. We show that only a single particle is required to disrupt a 150 nm DOPC liposome. The equilibrium leakage of membranes is a function of the particle number density and particle surface charge, consistent with results from our partitioning experiments. Our disruption experiments with varying surface functionality show that positively charged particles (poly amine) are most disruptive, consistent with in in vitro toxicity panels using cell cultures. Overall, this project has resulted in 8 published or submitted archival papers and has been presented 12 times. We have trained five students and provided growth opportunities for a postdoc.« less

Effect of surface density silver nanoplate films toward surface-enhanced Raman scattering enhancement for bisphenol A detection

NASA Astrophysics Data System (ADS)

Bakar, N. A.; Salleh, M. M.; Umar, A. A.; Shapter, J. G.

2018-03-01

This paper reports a study on surface-enhanced Raman scattering (SERS) phenomenon of triangular silver nanoplate (NP) films towards bisphenol A (BPA) detection. The NP films were prepared using self-assembly technique with four different immersion times; 1 hour, 2 hours, 5 hours, and 8 hours. The SERS measurement was studied by observing the changes in Raman spectra of BPA after BPA absorbed on the NP films. It was found that the Raman intensity of BPA peaks was enhanced by using the prepared SERS substrates. This is clearly indicated that these SERS silver substrates are suitable to sense industrial chemical and potentially used as SERS detector. However, the rate of SERS enhancement is depended on the distribution of NP on the substrate surface.

Transport of silver nanoparticles in single fractured sandstone

NASA Astrophysics Data System (ADS)

Neukum, Christoph

2018-02-01

Silver nanoparticles (Ag-NP) are used in various consumer products and are one of the most prevalent metallic nanoparticle in commodities and are released into the environment. Transport behavior of Ag-NP in groundwater is one important aspect for the assessment of environmental impact and protection of drinking water resources in particular. Ag-NP transport processes in saturated single-fractured sandstones using triaxial flow cell experiments with different kind of sandstones is investigated. Ag-NP concentration and size are analyzed using flow field-flow fractionation and coupled SEM-EDX analysis. Results indicate that Ag-NP are more mobile and show generally lower attachment on rock surface compared to experiments in undisturbed sandstone matrix and partially fractured sandstones. Ag-NP transport is controlled by the characteristics of matrix porosity, time depending blocking of attachment sites and solute chemistry. Where Ag-NP attachment occur, it is heterogeneously distributed on the fracture surface.

Rapid ultrasensitive single particle surface-enhanced Raman spectroscopy using metallic nanopores.

PubMed

Cecchini, Michael P; Wiener, Aeneas; Turek, Vladimir A; Chon, Hyangh; Lee, Sangyeop; Ivanov, Aleksandar P; McComb, David W; Choo, Jaebum; Albrecht, Tim; Maier, Stefan A; Edel, Joshua B

2013-10-09

Nanopore sensors embedded within thin dielectric membranes have been gaining significant interest due to their single molecule sensitivity and compatibility of detecting a large range of analytes, from DNA and proteins, to small molecules and particles. Building on this concept we utilize a metallic Au solid-state membrane to translocate and rapidly detect single Au nanoparticles (NPs) functionalized with 589 dye molecules using surface-enhanced resonance Raman spectroscopy (SERRS). We show that, due to the plasmonic coupling between the Au metallic nanopore surface and the NP, signal intensities are enhanced when probing analyte molecules bound to the NP surface. Although not single molecule, this nanopore sensing scheme benefits from the ability of SERRS to provide rich vibrational information on the analyte, improving on current nanopore-based electrical and optical detection techniques. We show that the full vibrational spectrum of the analyte can be detected with ultrahigh spectral sensitivity and a rapid temporal resolution of 880 μs.

Occurrence of nonylphenol and nonylphenol monoethoxylate in soil and vegetables from vegetable farms in the Pearl River Delta, South China.

PubMed

Cai, Quan-Ying; Huang, Hui-Juan; Lü, Huixiong; Mo, Ce-Hui; Zhang, Jun; Zeng, Qiao-Yun; Tian, Jun-Jian; Li, Yan-Wen; Wu, Xiao-Lian

2012-07-01

Low molecular-mass nonylphenol ethoxylates (NPEOs) and 4-nonylphenol (NP) are biodegradation products of higher molecular mass NPEOs used as surface active agents, and they are endocrine-disrupting contaminants. In this study, surface soil (0-20 cm) samples and different vegetable samples were collected from 27 representative vegetable farms located in Shenzhen, Dongguan, and Huizhou within the Pearl River Delta region, South China, and NP and nonylphenol monoethoxylate (NP(1)EO) were analyzed using high-performance liquid chromatography with ultraviolet detection. The results show that NP and NP(1)EO were detected in soil and vegetable samples. The concentrations of NP and NP(1)EO in soil samples ranged from nondetectable (ND) to 7.22 μg kg(-1) dry weight (dw) and from ND to 8.24 μg kg(-1) dw, respectively. The average concentrations of both NP and NP(1)EO in soil samples decreased in the following order: Dongguan > Huizhou > Shenzhen. The levels of NP and NP(1)EO in vegetable samples varied from 1.11 to 4.73 μg kg(-1) dw and from 1.32 to 5.33 μg kg(-1) dw, respectively. The greatest levels of both NP and NP(1)EO were observed in water spinach, and the lowest levels of NP and NP(1)EO were recorded in cowpea. The bioconcentration factors (the ratio of contaminant concentration in plant tissue to soil concentration) of NP and NP(1)EO were <1.0 (mean 0.535 and 0.550, respectively). The occurrences of NP and NP(1)EO in this study are compared with other studies, and their potential sources are discussed.

Electrochemistry at One Nanoparticle.

PubMed

Mirkin, Michael V; Sun, Tong; Yu, Yun; Zhou, Min

2016-10-18

Electrochemistry at metal nanoparticles (NPs) is of significant current interest because of its applications in catalysis, energy conversion and storage, and sensors. The electrocatalytic activity of NPs depends strongly on their size, shape, and surface attachment. The use of a large number of particles in most reported kinetic experiments obscured the effects of these factors because of polydispersity and different NP orientations. Recent efforts to probe electrochemistry at single NPs included recording of the catalytically amplified current produced by random collisions of particles with the electrode surface, immobilizing an NP on the surface of a small electrode, and delivering individual NPs to electrode surfaces. Although the signals recorded in such experiments were produced by single NPs, the characterization issues and problems with separating an individual particle from other NPs present in the system made it difficult to obtain spatially and/or temporally resolved information about heterogeneous processes occurring at a specific NP. To carry out electrochemical experiments involving only one NP and characterize such an NP in situ, one needs nanoelectrochemical tools with the characteristic dimension smaller than or comparable to those of the particle of interest. This Account presents fundamentals of two complementary approaches to studying NP electrochemistry, i.e., probing single immobilized NPs with the tip of a scanning electrochemical microscope (SECM) and monitoring the collisions between one catalytic NP and a carbon nanopipette. The former technique can provide spatially resolved information about NP geometry and measure its electron transfer properties and catalytic activity under steady-state conditions. The emphasis here is on the extraction of quantitative physicochemical information from nanoelectrochemical data. By employing a polished disk-type nanoelectrode as an SECM tip, one can characterize a specific nanoparticle in situ and then use the same NP for kinetic experiments. A new mode of SECM operation based on tunneling between the tip and nanoparticle can be used to image the NP topography with a lateral resolution of ∼1 nm. An alternative approach employs carbon nanoprobes produced by chemical vapor deposition of carbon into quartz nanopipettes. One metal NP is captured inside the carbon nanocavity to probe the dynamics of its interactions with the electrode surface on the microsecond time scale. The use of high-resolution transmission electron microscopy is essential for interpreting the results of single-NP collision experiments. A brief discussion of the nanoelectrochemical methodology, recent advances, and future directions is included.

Dynamic development of the protein corona on silica nanoparticles: composition and role in toxicity

NASA Astrophysics Data System (ADS)

Mortensen, Ninell P.; Hurst, Gregory B.; Wang, Wei; Foster, Carmen M.; Nallathamby, Prakash D.; Retterer, Scott T.

2013-06-01

The formation and composition of the protein corona on silica (SiO2) nanoparticles (NP) with different surface chemistries was evaluated over time. Native SiO2, amine (-NH2) and carboxy (-COO-) modified NP were examined following incubation in mammalian growth media containing fetal bovine serum (FBS) for 1, 4, 24 and 48 hours. The protein corona transition from its early dynamic state to the later more stable corona was evaluated using mass spectrometry. The NP diameter was 22.4 +/- 2.2 nm measured by scanning transmission electron microscopy (STEM). Changes in hydrodynamic diameter and agglomeration kinetics were studied using dynamic light scattering (DLS). The initial surface chemistry of the NP played an important role in the development and final composition of the protein corona, impacting agglomeration kinetics and NP toxicity. Particle toxicity, indicated by changes in membrane integrity and mitochondrial activity, was measured by lactate dehydrogenase (LDH) release and tetrazolium reduction (MTT), respectively, in mouse alveolar macrophages (RAW264.7) and mouse lung epithelial cells (C10). SiO2-COO- NP had a slower agglomeration rate, formed smaller aggregates, and exhibited lower cytotoxicity compared to SiO2 and SiO2-NH2. Composition of the protein corona for each of the three NP was unique, indicating a strong dependence of corona development on NP surface chemistry. This work underscores the need to understand all aspects of NP toxicity, particularly the influence of agglomeration on effective dose and particle size. Furthermore, the interplay between materials and local biological environment is emphasized and highlights the need to conduct toxicity profiling under physiologically relevant conditions that provide an appropriate estimation of material modifications that occur during exposure in natural environments.The formation and composition of the protein corona on silica (SiO2) nanoparticles (NP) with different surface chemistries was evaluated over time. Native SiO2, amine (-NH2) and carboxy (-COO-) modified NP were examined following incubation in mammalian growth media containing fetal bovine serum (FBS) for 1, 4, 24 and 48 hours. The protein corona transition from its early dynamic state to the later more stable corona was evaluated using mass spectrometry. The NP diameter was 22.4 +/- 2.2 nm measured by scanning transmission electron microscopy (STEM). Changes in hydrodynamic diameter and agglomeration kinetics were studied using dynamic light scattering (DLS). The initial surface chemistry of the NP played an important role in the development and final composition of the protein corona, impacting agglomeration kinetics and NP toxicity. Particle toxicity, indicated by changes in membrane integrity and mitochondrial activity, was measured by lactate dehydrogenase (LDH) release and tetrazolium reduction (MTT), respectively, in mouse alveolar macrophages (RAW264.7) and mouse lung epithelial cells (C10). SiO2-COO- NP had a slower agglomeration rate, formed smaller aggregates, and exhibited lower cytotoxicity compared to SiO2 and SiO2-NH2. Composition of the protein corona for each of the three NP was unique, indicating a strong dependence of corona development on NP surface chemistry. This work underscores the need to understand all aspects of NP toxicity, particularly the influence of agglomeration on effective dose and particle size. Furthermore, the interplay between materials and local biological environment is emphasized and highlights the need to conduct toxicity profiling under physiologically relevant conditions that provide an appropriate estimation of material modifications that occur during exposure in natural environments. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr33280b

Gold Nanoparticle-Quantum Dot Fluorescent Nanohybrid: Application for Localized Surface Plasmon Resonance-induced Molecular Beacon Ultrasensitive DNA Detection

NASA Astrophysics Data System (ADS)

Adegoke, Oluwasesan; Park, Enoch Y.

2016-11-01

In biosensor design, localized surface plasmon resonance (LSPR)-induced signal from gold nanoparticle (AuNP)-conjugated reporter can produce highly sensitive nanohybrid systems. In order to retain the physicochemical properties of AuNPs upon conjugation, high colloidal stability in aqueous solution is needed. In this work, the colloidal stability with respect to the zeta potential (ZP) of four negatively charged thiol-functionalized AuNPs, thioglycolic (TGA)-AuNPs, 3-mercaptopropionic acid (MPA)-AuNPs, l-cysteine-AuNPs and l-glutathione (GSH)-AuNPs, and a cationic cyteamine-capped AuNPs was studied at various pHs, ionic strength, and NP concentration. A strong dependence of the ZP charge on the nanoparticle (NP) concentration was observed. High colloidal stability was exhibited between pH 3 and 9 for the negatively charged AuNPs and between pH 3 and 7 for the cationic AuNPs. With respect to the ionic strength, high colloidal stability was exhibited at ≤104 μM for TGA-AuNPs, l-cysteine-AuNPs, and GSH-AuNPs, whereas ≤103 μM is recommended for MPA-AuNPs. For the cationic AuNPs, very low ionic strength of ≤10 μM is recommended due to deprotonation at higher concentration. GSH-AuNPs were thereafter bonded to SiO2-functionalized alloyed CdZnSeS/ZnSe1.0S1.3 quantum dots (SiO2-Qdots) to form a plasmon-enhanced AuNP-SiO2-Qdots fluorescent nanohybrid. The AuNP-SiO2-Qdots conjugate was afterward conjugated to a molecular beacon (MB), thus forming an ultrasensitive LSPR-induced SiO2-Qdots-MB biosensor probe that detected a perfect nucleotide DNA sequence at a concentration as low as 10 fg/mL. The limit of detection was 11 fg/mL (1.4 fM) while the biosensor probe efficiently distinguished between single-base mismatch and noncomplementary sequence target.

Thrombin-inhibiting nanoparticles rapidly constitute versatile and detectable anticlotting surfaces

NASA Astrophysics Data System (ADS)

Wheatley Myerson, Jacob; He, Li; Allen, John Stacy; Williams, Todd; Lanza, Gregory; Tollefsen, Douglas; Caruthers, Shelton; Wickline, Samuel

2014-09-01

Restoring an antithrombotic surface to suppress ongoing thrombosis is an appealing strategy for treatment of acute cardiovascular disorders such as erosion of atherosclerotic plaque. An antithrombotic surface would present an alternative to systemic anticoagulation with attendant risks of bleeding. We have designed thrombin-targeted nanoparticles (NPs) that bind to sites of active clotting to extinguish local thrombin activity and inhibit platelet deposition while exhibiting only transient systemic anticoagulant effects. Perfluorocarbon nanoparticles (PFC NP) were functionalized with thrombin inhibitors (either D-phenylalanyl-L-prolyl-L-arginyl-chloromethyl ketone or bivalirudin) by covalent attachment of more than 15 000 inhibitors to each PFC NP. Fibrinopeptide A (FPA) ELISA demonstrated that thrombin-inhibiting NPs prevented cleavage of fibrinogen by both free and clot-bound thrombin. Magnetic resonance imaging (MRI) confirmed that a layer of thrombin-inhibiting NPs prevented growth of clots in vitro. Thrombin-inhibiting NPs were administered in vivo to C57BL6 mice subjected to laser injury of the carotid artery. NPs significantly delayed thrombotic occlusion of the artery, whereas an equivalent bolus of free inhibitor was ineffective. For thrombin-inhibiting NPs, only a short-lived (˜10 min) systemic effect on bleeding time was observed, despite prolonged clot inhibition. Imaging and quantification of in vivo antithrombotic NP layers was demonstrated by MRI of the PFC NP. 19F MRI confirmed colocalization of particles with arterial thrombi, and quantitative 19F spectroscopy demonstrated specific binding and retention of thrombin-inhibiting NPs in injured arteries. The ability to rapidly form and image a new antithrombotic surface in acute vascular syndromes while minimizing risks of bleeding would permit a safer method of passivating active lesions than current systemic anticoagulant regimes.

Surface colonized silver nano particles over chitosan poly-electrolyte micro-spheres and their multi-functional behavior

NASA Astrophysics Data System (ADS)

Prakash, B.; Asha, S.; Nimrodh Ananth, A.; Vanithakumari, G.; Okram, G. S.; Jose, Sujin P.; Jothi Rajan, M. A.

2018-02-01

Chitosan/tripolyphosphate polyelectrolyte (TPP) microspheres, decorated and surface functionalized with silver nanoparticles (NPs) of average diameter of 15 nm, were synthesized following a simple two-step procedure. These Ag NP-functionalized polyelectrolyte microspheres (Ag-CSPMs) are found to be biocompatible and enhancing the reactive oxygen species in curcumin with excellent anti-bacterial activity for selected Gram-positive and negative bacterial strains, making them much attractive relative to bare surface counterparts; the well-stabilized silver NPs do not form any agglomerations on the surface of the chitosan microspheres. They also show excellent cytotoxic behavior towards MCF7 cell lines, showing a half-maximal inhibitory concentration (IC50) of 32 μg ml-1. Therefore, Ag-CSPMs exhibit multi-functional ability having potential towards theranostics applications.

Self-assembling Gold Nanoparticle Monolayers in a Three-phase System - Overcoming Ligand Size Limitations

NASA Astrophysics Data System (ADS)

Yang, Guang; Nanda, Jagjit; Wang, Boya; Chen, Gang; Hallinan, Daniel T., Jr.

An effective self-assembly technique was developed to prepare centimeter-scale monolayer gold nanoparticle (Au NP) films of long-range order with hydrophobic ligands. Aqueous Au NPs were entrapped in the organic/aqueous interface where the Au NP surface was in situ modified with different types of amine ligands, including amine-terminated polystyrene. The Au NPs then spontaneously relocated to the air/water interface to form an NP monolayer. The spontaneous formation of an Au NP film at the organic/water interface was due to the minimization of the system Helmholtz free energy. Self-assembled Au NP films has a hexagonal close packed structure. The interparticle spacing was dictated by the amine ligand length. Thus-assembled Au NP monolayers exhibit tunable surface plasma resonance and excellent spacial homogeneity of surface-enhanced Raman-scattering. The ``air/water/oil'' self-assembly method developed in this study not only benefits the fundamental understanding of NP ligand conformations, but is also promising to scale up the manufacture of plasmonic nanoparticle devices with precisely designed optical properties. This study was financially supported by start-up funding supplied by the Florida State University and the FAMU-FSU College of Engineering.

Monolayer-protected clusters of gold nanoparticles: impacts of stabilizing ligands on the heterogeneous electron transfer dynamics and voltammetric detection.

PubMed

Pillay, Jeseelan; Ozoemena, Kenneth I; Tshikhudo, Robert T; Moutloali, Richard M

2010-06-01

Surface electrochemistry of novel monolayer-protected gold nanoparticles (MPCAuNPs) is described. Protecting ligands, (1-sulfanylundec-11-yl)tetraethylene glycol (PEG-OH) and (1-sulfanylundec-11-yl)poly(ethylene glycol)ic acid (PEG-COOH), of three different percent ratios (PEG-COOH:PEG-OH), 1:99 (MPCAuNP-COOH(1%)), 50:50 (MPCAuNP-COOH(50%)), and 99:1 (MPCAuNP-COOH(99%)), were studied. The electron transfer rate constants (k(et)/s(-1)) in organic medium decreased as the concentration of the surface-exposed -COOH group in the protecting monolayer ligand is increased: MPCAuNP-COOH(1%) (approximately 5 s(-1)) > MPCAuNP-COOH(50%) (approximately 4 s(-1)) > MPCAuNP-COOH(99%) (approximately 0.5 s(-1)). In aqueous medium, the trend is reversed. The surface pK(a) was estimated as approximately 8.2 for the MPCAuNP-COOH(1%), while both MPCAuNP-COOH(50%) and MPCAuNP-COOH(99%) showed two pK(a) values of about 5.0 and approximately 8.0. These results have been interpreted in terms of the quasi-solidity and quasi-liquidity of the terminal -OH and -COOH head groups, respectively. MPCAuNP-COOH(99%) excellently suppressed the voltammetric response of the ascorbic acid but enhanced the electrocatalytic detection of epinephrine compared to the other MPCAuNPs studied. This study reveals important factors that should be considered when designing electrode devices that employ monolayer-protected gold nanoparticles and possibly for some other redox-active metal nanoparticles.

X-ray photoelectron spectroscopic and morphologic studies of Ru nanoparticles deposited onto highly oriented pyrolytic graphite

NASA Astrophysics Data System (ADS)

Bavand, R.; Yelon, A.; Sacher, E.

2015-11-01

Ruthenium nanoparticles (Ru NPs) function as effective catalysts in specific reactions, such as methanation and Fischer-Tropsch syntheses. It is our purpose to physicochemically characterize their surfaces, at which catalysis occurs, by surface-sensitive X-ray photoelectron spectroscopy (XPS), using the symmetric peak component anaylsis technique developed in our laboratory to reveal previously hidden components. Ru NPs were deposited by evaporation (0.25-1.5 nm nominal deposition range) onto highly oriented pyrolytic graphite (HOPG). In addition to their surfaces being characterized by XPS, an indication of morphology was obtained from transmission electron microscopy (TEM). Our use of symmetric peak component XPS analysis has revealed detailed information on a previously unidentified surface oxide initially formed, as well as on the valence electronic structure and its variation with NP size, information that is of potential importance in the use of these NPs in catalysis. Each of the several Ru core XPS spectra characterized (3d, 3p and 3s) was found to be composed of three symmetric components. Together with two metal oxide O1s components, these give evidence of a rather complex, previously unidentified oxide that is initially formed. The Ru valence band (4d and 5s) spectra clearly demonstrate a loss of metallicity, a simultaneous increase of the Kubo gap, and an abrupt transfer in valence electron density from the 4d to the 5s orbitals (known as electron spill-over), as the NP size decreases below 0.5 nm. TEM photomicrographs, as a function of deposition rate, show that, at a rate that gives insufficient time for the NP condensation energy to dissipate, the initially well-separated NPs are capable of diffusing laterally and aggregating. This indicates weak NP bonding to the HOPG substrate. Carbide is formed, at both high and low deposition rates, at Ru deposition thicknesses greater than 0.25 nm, its formation explained by Ru NPs reacting with residual hydrocarbon vapor, under the influence of the heat of condensation released on Ru deposition, and not by Ru reacting with the HOPG substrate.

Paradoxical Roles of Nanoparticles in Cancer Therapeutics and Carcinogenesis

NASA Astrophysics Data System (ADS)

Despeaux, Emily

Nanoparticles (NPs) are becoming increasingly common in consumer goods and are under investigation for a variety of industrial and biomedical applications. However, challenges in determining NP toxicity may prevent them from reaching their full potential. NPs cannot be treated as single class for toxicity evaluations. Even among particles made from the same material, particle-specific physical properties, including size, shape, surface charge, agglomeration state, and surface modifications have a strong effect on the toxicity. Even so, the obstacles to conclusively and reproducibly evaluating toxicity span all NP classes. NP literature is riddled with confusing and often contradictory reports regarding the biocompatibility of both engineered NPs, designed with biocompatibility as a priority, and NPs from occupational or environmental exposures. Incomplete NP characterization and sample inhomogeneity represent major confounding factors in disparate results from seemingly comparable study setups. Additionally, NPs can interfere with many conventional toxicity screening methods. Inappropriate doses, exposure routes, and toxicity endpoints further diminish the utility of many published studies. Given the burgeoning interest in NP-based therapeutic agents, consistent, reliable standards are needed to ensure the biocompatibility of new formulations. To those ends, the synthesis, characterization, and in vitro toxicity of a multi-functional NP therapeutic were investigated (Chapter 2). Specifically, superparamagnetic iron oxide nanoparticles (SPIONs) were coated with amphiphilic polymer and functionalized with antisense oligonucleotides targeting survivin, an anti-apoptotic protein that is highly overexpressed in cancer. SPION physical properties, including particle size and composition, were characterized at each step of synthesis. Our results showed that the SPION platform is biocompatible and capable of delivering functional antisense oligonucleotides to regulate survivin expression; however, significant refinement of the DNA-to-SPION coupling step is needed. Applied clinically, antisense survivin coupled SPIONs can reduce the required dose of, adverse effects from, and resistance to, current cancer chemotherapy regimens. In contrast to engineered NPs for biomedical applications, where real-world exposures would involve careful control of both exposure time- and dose, occupational NP exposures are variable, chronic, and difficult to model in laboratory settings. Chapter 3 focuses on identifying the mechanisms behind carbon nanotube (CNT)-induced malignant transformation of bronchial epithelial cells using a chronic in vitro exposure model. We specifically investigated the role of mesothelin (MSLN), a cell-surface protein that is highly overexpressed in many cancers, in the aggressive phenotype noted following chronic, low-dose CNT exposure. MSLN knockdown resulted in significantly decreased invasion, migration, colonies on soft agar, and tumor sphere formation. In vivo, MSLN knockdown cells formed smaller primary tumors and less metastases. The mechanism by which MSLN contributes to these more aggressive behaviors was investigated using Ingenuity Pathway Analysis, which predicted that increased MSLN could induce cyclin E, a cell cycle regulator known to be associated with human cancer. We found that MSLN knockdown cells had decreased cyclin E, and their proliferation rate was reverted to nearly that of untransformed cells. Cell cycle analysis results were consistent with the decreased rate of proliferation. Together, our results indicate a novel role of MSLN in the malignant transformation of bronchial epithelial cells following CNT exposure, suggesting its utility as a potential biomarker and drug target for CNT-induced malignancies. As demonstrated by the two studies presented here, NPs have the potential to function as both cancer therapeutics and carcinogens. Careful evaluation of toxicity, ensuring that appropriate doses, assays, exposure routes, and endpoints are used, is imperative. Elucidating the physical properties and functionalization that contribute to toxicity, and the mechanisms of that toxicity, will allow NP benefits to be fully exploited while minimizing the risk of widespread, detrimental public health effects.

Stabilization of AuNPs by monofunctional triazole linked to ferrocene, ferricenium, or coumarin and applications to synthesis, sensing, and catalysis.

PubMed

Li, Na; Zhao, Pengxiang; Igartua, María E; Rapakousiou, Amalia; Salmon, Lionel; Moya, Sergio; Ruiz, Jaime; Astruc, Didier

2014-11-03

Monofunctional triazoles linked to ferrocene, ferricenium, or coumarin (Cou), easily synthesized by copper-catalyzed azide alkyne (CuAAC) "click" reactions between the corresponding functional azides and (trimethylsilyl)acetylene followed by silyl group deprotection, provide a variety of convenient neutral ligands for the stabilization of functional gold nanoparticles (AuNPs) in polar organic solvents. These triazole (trz)-AuNPs are very useful toward a variety of applications to synthesis, sensing, and catalysis. Both ferrocenyl (Fc) and isostructural ferricenium linked triazoles give rise to AuNP stabilization, although by different synthetic routes. Indeed, the first direct synthesis and stabilization of AuNPs by ferricenium are obtained by the reduction of HAuCl4 upon reaction with a ferrocene derivative, AuNP stabilization resulting from a synergy between electrostatic and coordination effects. The ferricenium/ferrocene trz-AuNP redox couple is fully reversible, as shown by cyclic voltammograms that were recorded with both redox forms. These trz-AuNPs are stable for weeks in various polar solvents, but at the same time, the advantage of trz-AuNPs is the easy substitution of neutral trz ligands by thiols and other ligands, giving rise to applications. Indeed, this ligand substitution of trz at the AuNP surface yields a stable Fc-terminated nanogold-cored dendrimer upon reaction with a Fc-terminated thiol dendron, substitution of Cou-linked trz with cysteine, homocysteine, and glutathione provides remarkably efficient biothiol sensing, and a ferricenium-linked trz-AuNP catalyst is effective for NaBH4 reduction of 4-nitrophenol to 4-aminophenol. In this catalytic example, the additional electrostatic AuNP stabilization modulates the reaction rate and induction time.

Nonylphenol and estrogenic activity in aquatic environmental samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tanghe, T.; Devriese, G.; Verstraete, W.

1999-03-01

The authors surveyed a series of surface waters and sewage treatment plants in Flanders (north of Belgium) for the presence of estrogenic activity and a xeno-estrogenic compound para-nonylphenol (NP), respectively. The surface waters of rural origin, used for drinking water production were free of significant levels of estrogenic activity and NP. Domestic sewage, after proper treatment, appeared to be no major source of this chemical. Yet, in some industrial effluents and surface waters of highly industrialized regions, NP and/or estrogenic activity was prominent, that is, <1 to 122 {micro}g NP/L and 11 to 42 {micro}g NP/L, respectively. This is becausemore » of the ongoing use of NP polyethoxylates in industry. The response of the recombinant yeast estrogen assay to the environmental samples tested was not consistent with the detected concentrations of NP. Standard addition of a natural estrogen, 17{beta}-estradiol, generated no or a reduced response compared to the standard curve concentration. Application of humic acids to standard series of NP and 17{beta}-estradiol resulted in a dose-dependent decrease of the estrogenic response. It appears that this bioassay is subject to considerable interferences due to the complexity of environmental samples. Parallel implementation of extensive chemical screening for xenobiotics and use of the bioassay are needed for adequate assessment of the potential estrogenic hazard to avoid false negative evaluations.« less

Nanoparticle-induced oxidation of corona proteins initiates an oxidative stress response in cells†

PubMed Central

Jayaram, Dhanya T.; Runa, Sabiha; Kemp, Melissa L.

2017-01-01

Titanium dioxide nanoparticles (TiO2 NPs), used as pigments and photocatalysts, are ubiquitous in our daily lives. Previous work has observed cellular oxidative stress in response to the UV-excitation of photocatalytic TiO2 NPs. In comparison, most human exposure to TiO2 NPs takes place in the dark, in the lung following inhalation or in the gut following consumption of TiO2 NP food pigment. Our spectroscopic characterization shows that both photocatalytic and food grade TiO2 NPs, in the dark, generate low levels of reactive oxygen species (ROS), specifically hydroxyl radicals and superoxides. These ROS oxidize serum proteins that form a corona of proteins on the NP surface. This protein layer is the interface between the NP and the cell. An oxidized protein corona triggers an oxidative stress response, detected with PCR and western blotting. Surface modification of TiO2 NPs to increase or decrease surface defects correlates with ROS generation and oxidative stress, suggesting that NP surface defects, likely oxygen vacancies, are the underlying cause of TiO2 NP-induced oxidative stress. PMID:28537609

Continuous and Delayed Photohemolysis Sensitized With Methylene Blue and Iron Oxide Nanoparticles (Fe3O4)

NASA Astrophysics Data System (ADS)

AL-Akhras, M.-Ali; Aljarrah, Khaled; Albiss, Borhan; Alhaji Bala, Abba

2015-10-01

This research present the sensitization of methylene blue (MB), as a potential photodynamic therapy photo sensitizer which showed phototoxicity for many tumor cells in vitro incorporated with iron oxide nanoparticles (Fe3O4, IO-NP), which offer magnificent interaction both inside and outside the surface of biomolecules together with red blood cells (RBC's) with significant change in hemolysis process. The study investigated the sensitization of continuous photohemolysis (CPH) for MB and MB with IO-NP, delayed photohemolysis (DPH) at different irradiation temperature (Tirr). The photohemolysis rate for CPH at room temperature has a power dependence of 0.39 ± 0.05 with relative of steepness of 1.25 ± 0.02 and for different concentration of MB and power dependent of 0.15 ± 0.03 with relative steepness of 1.34 ± 0.01 for different MB and IO-NP. Logistic and Gompertz functions were applied as appropriate mathematical models to fit the collected experimental data for CPH and DPH respectively, and to calculate fractional photohemolysis rate with minimum errors. The Logistic function parameter; α, the hemolysis rate, increases with increasing concentrations of MB and decreases with increasing IO-NP concentrations in the presence of 6 μg/ml of MB. The parameter β the time required to reduce the maximum number of RBCs to one half of its value, decreases with increasing MB concentration and increases with increasing IO-NP concentrations in the presence of 6 pg/ml of MB. In DPH at different Tirr, the Gompertz parameter; a, fractional hemolysis ratio, is independent of temperature in both case MB and MB plus IO-NP, while the parameter; b, rate of fractional hemolysis change, increases with increasing Tirr, in both case MB and MB plus IO-NP. The apparent activation energy of colloid-osmotic hemolysis is 9.47±0.01 Kcal/mol with relative steepness of 1.31 ± 0.05 for different MB and 6.06±0.03 Kcal/mol with relative steepness of 1.41 ± 0.09 for MB with iron oxide. Our results suggest that Logistic equation is the best fit for the CPH and Gompertz function for the DPH. Both models predict also that the relative steepness is independent of the light dose, sensitizer and IO-NP concentrations.

Bio-inspired Self-healing Composite Hydrogel with Iron Oxide Nanoparticle as Coordination Crosslinker

NASA Astrophysics Data System (ADS)

Li, Qiaochu; Barret, Devin G.; Messersmith, Phillip B.; Holten-Andersen, Niels

2014-03-01

Polymer-nanoparticle (NP) composites have attracted renewed attention due to enhanced mechanical strength combined with various functionalities, but controlling the interfacial chemistry between NPs and polymer matrix, which is crucial for the composite's mechanical behavior, remains a major challenge. Inspired by the adhesion chemistry of mussel fibers, we investigated a novel approach to incorporate Fe3O4 NPs into hydrogel matrix. A polyethylene glycol polymer is designed with both ends conjugated by catechol groups, which have strong coordination affinity to Fe. The polymer network is crosslinked via coordination bonding at the surface of Fe3O4 NPs, yielding a stiff nanocomposite hydrogel. Due to the reversible nature of coordination bonding, the hydrogel presents self-healing behavior. Oscillatory rheology allows comparative kinetic studies of self-healing driven by catechol bonding at Fe3O4 NP interfaces and by catechol-Fe3+ coordination complexes. Furthermore, the superparamagnetic property of Fe3O4 NP is preserved after gelation, allowing for response to external stimuli. This gelation motif can serve as a versatile platform for tuning functional and mechanical properties for future polymer nanocomposite materials.

Nanoparticles for Biomedical Imaging: Fundamentals of Clinical Translation

PubMed Central

Choi, Hak Soo; Frangioni, John V.

2010-01-01

Because of their large size compared to small molecules, and their multi-functionality, nanoparticles (NPs) hold promise as biomedical imaging, diagnostic, and theragnostic agents. However, the key to their success hinges on a detailed understanding of their behavior after administration into the body. NP biodistribution, target binding, and clearance are a complex function of their physicochemical properties in serum, which include hydrodynamic diameter, solubility, stability, shape and flexibility, surface charge, composition, and formulation. Moreover, many materials used to construct NPs have real or potential toxicity, or may interfere with other medical tests. In this review, we discuss the design considerations that mediate NP behavior in the body and the fundamental principles that govern clinical translation. By analyzing those nanomaterials that have already received regulatory approval, most of which are actually therapeutic agents, we attempt to predict which types of NPs hold potential as diagnostic agents for biomedical imaging. Finally, using quantum dots as an example, we provide a framework for deciding whether an NP-based agent is the best choice for a particular clinical application. PMID:21084027

Surface premelting/recrystallization governing the collapse of open-cell nanoporous Cu via thermal annealing.

PubMed

Wang, L; Zhang, X M; Deng, L; Tang, J F; Xiao, S F; Deng, H Q; Hu, W Y

2018-06-04

We systematically investigate the collapse of a set of open-cell nanoporous Cu (np-Cu) materials with the same porosity and shape but different specific surface areas, during thermal annealing, by performing large-scale molecular dynamics simulations. Two mechanisms govern the collapse of np-Cu. One is direct surface premelting, facilitating the collapse of np-Cu, when the specific surface area is less than a critical value (∼2.38 nm-1). The other is recrystallization followed by surface premelting, accelerating the sloughing of ligaments and the annihilation of voids, when the critical specific surface area is exceeded. Surface premelting results from surface reconstruction by prompting localized "disordering" and "chaos" on the surface, and the melting temperature reduces linearly with the increase of the specific surface area. Recrystallization is followed by surface premelting as the melting temperature is below the supercooling point, where a liquid is unstable and instantaneously recrystallizes.

Monolayer nanoparticle-covered liquid marbles derived from a sol-gel coating

NASA Astrophysics Data System (ADS)

Li, Xiaoguang; Wang, Yiqi; Huang, Junchao; Yang, Yao; Wang, Renxian; Geng, Xingguo; Zang, Duyang

2017-12-01

A sol-gel coating consisting of hydrophobic SiO2 nanoparticles (NPs) was used to produce monolayer NP-covered (mNPc) liquid marbles. The simplest approach was rolling a droplet on this coating, and an identifiable signet allowed determination of the coverage ratio of the resulting liquid marble. Alternatively, the particles were squeezed onto a droplet surface with two such coatings, generating surface buckling from interfacial NP jamming, and then a liquid marble was produced via a jamming-relief process in which water was added into the buckled droplet. This process revealed an ˜7% reduction in particle distance after interfacial jamming. The mNPc liquid marbles obtained by the two methods were transparent with smooth profiles, as naked droplets, and could be advantageously used in fundamental and applied researches for their unique functions.

New measurements of the sticking coefficient and binding energy of molecules on non-porous amorphous solid water in the submonolayer regime

NASA Astrophysics Data System (ADS)

He, Jiao; Acharyya, Kinsuk; Emtiaz, S. M.; Vidali, Gianfranco

2016-06-01

Sticking and adsorption of molecules on dust grains are two important processes in gas-grain interactions. We accurately measured both the sticking coefficient and the binding energy of several key molecules on the surface of amorphous solid water as a function of coverage.A time-resolved scattering technique was used to measure sticking coefficient of H2, D2, N2, O2, CO, CH4, and CO2 on non-porous amorphous solid water (np-ASW) in the low coverage limit over a wide range of surface temperatures. We found that the time-resolved scattering technique is advantageous over the conventional King-Wells method that underestimates the sticking coefficient. Based on the measured values we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy.We measured the binding energy of N2, CO, O2, CH4, and CO2 on np-ASW, and of N2 and CO on porous amorphous solid water (p-ASW). We were able to measure binding energies down to a fraction of 1% of a layer, thus making these measurements more appropriate for astrochemistry than the existing values. We found that CO2 forms clusters on np-ASW surface even at very low coverage; this may help in explaining the segregation of CO2 in ices. The binding energies of N2, CO, O2, and CH4 on np-ASW decrease with coverage in the submonolayer regime. Their values in the low coverage limit are much higher than what is commonly used in gas-grain models. An empirical formula was used to describe the coverage dependence of the binding energies. We used the newly determined binding energy distributions in a simulation of gas-grain chemistry for cold dense clouds and hot core models. We found that owing to the higher value of desorption energy in the sub-monlayer regime a fraction of all these ices stays much longer and to higher temperature on the grain surface compared to the case using single value energies as currently done in astrochemical models.This work was supported in part by a grant to GV from NSF --- Astronomy & Astrophysics Division (#1311958)

Surfactant titration of nanoparticle-protein corona.

PubMed

Maiolo, Daniele; Bergese, Paolo; Mahon, Eugene; Dawson, Kenneth A; Monopoli, Marco P

2014-12-16

Nanoparticles (NP), when exposed to biological fluids, are coated by specific proteins that form the so-called protein corona. While some adsorbing proteins exchange with the surroundings on a short time scale, described as a "dynamic" corona, others with higher affinity and long-lived interaction with the NP surface form a "hard" corona (HC), which is believed to mediate NP interaction with cellular machineries. In-depth NP protein corona characterization is therefore a necessary step in understanding the relationship between surface layer structure and biological outcomes. In the present work, we evaluate the protein composition and stability over time and we systematically challenge the formed complexes with surfactants. Each challenge is characterized through different physicochemical measurements (dynamic light scattering, ζ-potential, and differential centrifugal sedimentation) alongside proteomic evaluation in titration type experiments (surfactant titration). 100 nm silicon oxide (Si) and 100 nm carboxylated polystyrene (PS-COOH) NPs cloaked by human plasma HC were titrated with 3-[(3-Cholamidopropyl) dimethylammonio]-1-propanesulfonate (CHAPS, zwitterionic), Triton X-100 (nonionic), sodium dodecyl sulfate (SDS, anionic), and dodecyltrimethylammonium bromide (DTAB, cationic) surfactants. Composition and density of HC together with size and ζ-potential of NP-HC complexes were tracked at each step after surfactant titration. Results on Si NP-HC complexes showed that SDS removes most of the HC, while DTAB induces NP agglomeration. Analogous results were obtained for PS NP-HC complexes. Interestingly, CHAPS and Triton X-100, thanks to similar surface binding preferences, enable selective extraction of apolipoprotein AI (ApoAI) from Si NP hard coronas, leaving unaltered the dispersion physicochemical properties. These findings indicate that surfactant titration can enable the study of NP-HC stability through surfactant variation and also selective separation of certain proteins from the HC. This approach thus has an immediate analytical value as well as potential applications in HC engineering.

Quantification of bisphenol A, 353-nonylphenol and their chlorinated derivatives in drinking water treatment plants.

PubMed

Dupuis, Antoine; Migeot, Virginie; Cariot, Axelle; Albouy-Llaty, Marion; Legube, Bernard; Rabouan, Sylvie

2012-11-01

Bisphenol A (BPA) and nonylphenols (NP) are of major concern to public health due to their high potential for human exposure and to their demonstrated toxicity (endocrine disruptor effect). A limited number of studies have shown that BPA and NP are present in drinking water. The chlorinated derivatives that may be formed during the chlorination step in drinking water treatment plants (DWTP) exhibit a higher level of estrogenic activity than their parent compounds. The aim of this study was to investigate BPA, 353NP, and their chlorinated derivative concentrations using an accurate and reproducible method of quantification. This method was applied to both surface and treated water samples from eight French DWTPs producing from surface water. Solid-phase extraction followed by liquid chromatography-tandem mass spectrometry was developed in order to quantify target compounds from water samples. The limits of detection ranged from 0.3 to 2.3 ng/L for BPA and chlorinated BPA and from 1.4 to 63.0 ng/L for 353NP and chlorinated 353NP. BPA and 353NP were found in most analyzed water samples, at a level ranging from 2.0 to 29.7 ng/L and from 0 to 124.9 ng/L, respectively. In most of DWTPs a decrease of BPA and 353NP was observed between surface water and treated water (36.6 to 78.9 % and 2.2 to 100.0 % for BPA and 353NP, respectively). Neither chlorinated BPA nor chlorinated 353NP was detected. Even though BPA and 353NP have been largely removed in the DWTPs studied, they have not been completely eliminated, and drinking water may consequently remain a source of human exposure.

Sunlight-Triggered Nanoparticle Synergy: Teamwork of Reactive Oxygen Species and Nitric Oxide Released from Mesoporous Organosilica with Advanced Antibacterial Activity.

PubMed

Gehring, Julia; Trepka, Bastian; Klinkenberg, Nele; Bronner, Hannah; Schleheck, David; Polarz, Sebastian

2016-03-09

Colonization of surfaces by microorganisms is an urging problem. In combination with the increasing antibiotic resistance of pathogenic bacteria, severe infections are reported more frequently in medical settings. Therefore, there is a large demand to explore innovative surface coatings that provide intrinsic and highly effective antibacterial activity. Materials containing silver nanoparticles have been developed in the past for this purpose, but this solution has come into criticism due to various disadvantages like notable toxicity against higher organisms, the high price, and low abundance of silver. Here, we introduce a new, sunlight-mediated organosilica nanoparticle (NP) system based on silver-free antibacterial activity. The simultaneous release of nitric oxide (NO) in combination with singlet oxygen and superoxide radicals (O2(•-)) as reactive oxygen species (ROS) leads to the emergence of highly reactive peroxynitrite molecules with significantly enhanced biocidal activity. This special cooperative effect can only be realized, if the ROS-producing moieties and the functional entities releasing NO are spatially separated from each other. In one type of particle, Rose Bengal as an efficient singlet oxygen ((1)O2) producer was covalently bound to SH functionalities applying thiol-ene click chemistry. "Charging" the second type of particles with NO was realized by quantitatively transferring the thiol groups into S-nitrosothiol functionalities. We probed the oxidation power of ROS-NP alone and in combination with NO-NP using sunlight as a trigger. The high antibacterial efficiency of dual-action nanoparticles was demonstrated using disinfection assays with the pathogenic bacterium Pseudomonas aeruginosa.

Bis-demethoxy curcumin analog nanoparticles: synthesis, characterization, and anticancer activity in vitro.

PubMed

Francis, Arul Prakash; Murthy, Prakhya Balakishna; Devas, Thiyagarajan

2014-07-01

We have optimized a protocol for the preparation of bisdemethoxy curcumin analog nanoparticles (BDMCA-NP) by the solvent assisted process. The structural similarities between bulk and nano BDMCA were determined by Co-TLC, NMR and F-TIR. This shows that our synthesis protocol enhanced the dispersibility and reduce the size of BDMCA without altering the integrity of functional moieties and structure, which is crucial for anticancer and antioxidant activities. The morphology and size of BDMCA-NP as determined by SEM, HRTEM and DLS was found to be around 80 nm. BDMCA-NP treated breast cancer cell lines (MCF 7) showed cell death as characterized by MTT assay. Flow cytometric analysis of BDMCA-NP treated MCF 7 cell lines showed an increase of cell count in G2/M phase indicates the cell cycle arrest. Western blot analysis revealed the presence of caspase 3, caspase 9, cleaved fragments of PARP and Bax proteins in the BDMCA-NP treated MCF 7 cell lines, but not in untreated cell lines. To recap, we have prepared BDMCA-NP by solvent assisted process, which exerted anticancer activity against breast cancer cells, which may be due to (i) enhanced dispersibility and surface: volume ratio, (ii) apoptosis (iii) mitochondrial pathway induced cell death, (iv) G2/M phase cell cycle arrest and (v) disassembly of mitotic spindle of the cancer cells. Thus, nano BDMCA can be used as a potent anticancer agent.

Role of block copolymer adsorption versus bimodal grafting on nanoparticle self-assembly in polymer nanocomposites.

PubMed

Zhao, Dan; Di Nicola, Matteo; Khani, Mohammad M; Jestin, Jacques; Benicewicz, Brian C; Kumar, Sanat K

2016-09-14

We compare the self-assembly of silica nanoparticles (NPs) with physically adsorbed polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) copolymers (BCP) against NPs with grafted bimodal (BM) brushes comprised of long, sparsely grafted PS chains and a short dense carpet of P2VP chains. As with grafted NPs, the dispersion state of the BCP NPs can be facilely tuned in PS matrices by varying the PS coverage on the NP surface or by changes in the ratio of the PS graft to matrix chain lengths. Surprisingly, the BCP NPs are remarkably better dispersed than the NPs tethered with bimodal brushes at comparable PS grafting densities. We postulate that this difference arises because of two factors inherent in the synthesis of the NPs: In the case of the BCP NPs the adsorption process is analogous to the chains being "grafted to" the NP surface, while the BM case corresponds to "grafting from" the surface. We have shown that the "grafted from" protocol yields patchy NPs even if the graft points are uniformly placed on each particle. This phenomenon, which is caused by chain conformation fluctuations, is exacerbated by the distribution function associated with the (small) number of grafts per particle. In contrast, in the case of BCP adsorption, each NP is more uniformly coated by a P2VP monolayer driven by the strongly favorable P2VP-silica interactions. Since each P2VP block is connected to a PS chain we conjecture that these adsorbed systems are closer to the limit of spatially uniform sparse brush coverage than the chemically grafted case. We finally show that the better NP dispersion resulting from BCP adsorption leads to larger mechanical reinforcement than those achieved with BM particles. These results emphasize that physical adsorption of BCPs is a simple, effective and practically promising strategy to direct NP dispersion in a chemically unfavorable polymer matrix.

Transport and abatement of fluorescent silica nanoparticle (SiO2 NP) in granular filtration: effect of porous media and ionic strength

NASA Astrophysics Data System (ADS)

Zeng, Chao; Shadman, Farhang; Sierra-Alvarez, Reyes

2017-03-01

The extensive production and application of engineered silica nanoparticles (SiO2 NPs) will inevitably lead to their release into the environment. Granular media filtration, a widely used process in water and wastewater treatment plants, has the potential for NP abatement. In this work, laboratory-scale column experiments were performed to study the transport and retention of SiO2 NPs on three widely used porous materials, i.e., sand, anthracite, and granular activated carbon (GAC). Synthetic fluorescent core-shell SiO2 NPs (83 nm) were used to facilitate NP detection. Sand showed very low capacity for SiO2 filtration as this material had a surface with limited surface area and a high concentration of negative charge. Also, we found that the stability and transport of SiO2 NP were strongly dependent on the ionic strength of the solution. Increasing ionic strength led to NP agglomeration and facilitated SiO2 NP retention, while low ionic strength resulted in release of captured NPs from the sand bed. Compared to sand, anthracite and GAC showed higher affinity for SiO2 NP capture. The superior capacity of GAC was primarily due to its porous structure and high surface area. A process model was developed to simulate NP capture in the packed bed columns and determine fundamental filtration parameters. This model provided an excellent fit to the experimental data. Taken together, the results obtained indicate that GAC is an interesting material for SiO2 NP filtration.

Ru(II)-polypyridyl surface functionalised gold nanoparticles as DNA targeting supramolecular structures and luminescent cellular imaging agents.

PubMed

Martínez-Calvo, Miguel; Orange, Kim N; Elmes, Robert B P; la Cour Poulsen, Bjørn; Williams, D Clive; Gunnlaugsson, Thorfinnur

2016-01-07

The development of Ru(II) functionalized gold nanoparticles 1–3·AuNP is described. These systems were found to be mono-disperse with a hydrodynamic radius of ca. 15 nm in water but gave rise to the formation of higher order structures in buffered solution. The interaction of 1–3·AuNP with DNA was also studied by spectroscopic and microscopic methods and suggested the formation of large self-assembly structures in solution. The uptake of 1–3·AuNP by cancer cells was studied using both confocal fluorescence as well as transmission electron microscopy (TEM), with the aim of investigating their potential as tools for cellular biology. These systems displaying a non-toxic profile with favourable photophysical properties may have application across various biological fields including diagnostics and therapeutics.

Pt based PEMFC catalysts prepared from colloidal particle suspensions--a toolbox for model studies.

PubMed

Speder, Jozsef; Altmann, Lena; Roefzaad, Melanie; Bäumer, Marcus; Kirkensgaard, Jacob J K; Mortensen, Kell; Arenz, Matthias

2013-03-14

A colloidal synthesis approach is presented that allows systematic studies of the properties of supported proton exchange membrane fuel cell (PEMFC) catalysts. The applied synthesis route is based on the preparation of monodisperse nanoparticles in the absence of strong binding organic stabilizing agents. No temperature post-treatment of the catalyst is required rendering the synthesis route ideally suitable for comparative studies. We report work concerning a series of catalysts based on the same colloidal Pt nanoparticle (NP) suspension, but with different high surface area (HSA) carbon supports. It is shown that for the prepared catalysts the carbon support has no catalytic co-function, but carbon pre-treatment leads to enhanced sticking of the Pt NPs on the support. An unwanted side effect, however, is NP agglomeration during synthesis. By contrast, enhanced NP sticking without agglomeration can be accomplished by the addition of an ionomer to the NP suspension. The catalytic activity of the prepared catalysts for the oxygen reduction reaction is comparable to industrial catalysts and no influence of the particle size is found in the range of 2-5 nm.

Surface modification of nanoporous alumina layers by deposition of Ag nanoparticles. Effect of alumina pore diameter on the morphology of silver deposit and its influence on SERS activity

NASA Astrophysics Data System (ADS)

Pisarek, Marcin; Nowakowski, Robert; Kudelski, Andrzej; Holdynski, Marcin; Roguska, Agata; Janik-Czachor, Maria; Kurowska-Tabor, Elżbieta; Sulka, Grzegorz D.

2015-12-01

Self-organized Al2O3 nanoporous/nanotubular (Al2O3-NP) oxide layers decorated with silver nanoparticles (Ag-NPs) exhibiting specific properties may serve as attractive SERS substrates for investigating the interactions between an adsorbate and adsorbent, or as stable platforms for detecting various organic compounds. This article presents the influence of the size of the alumina nanopores with a deposit of silver nanoparticles obtained by the magnetron sputtering technique on the morphology of silver film. Moreover, the effect of pore diameter on the intensity of SERS spectra in Ag-NPs/Al2O3-NP/Al composites has also been estimated. For such investigations we used pyridine as a probe molecule, since it has a large cross-section for Raman scattering. To characterize the morphology of the composite oxide layer Ag-NPs/Al2O3-NP/Al, before and after deposition of Ag-NPs by PVD methods (Physical Vapor Deposition), we used scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface analytical technique of surface-enhanced Raman spectroscopy (SERS) was used to investigate the surface activity of the composite. The results obtained show that, for a carefully controlled amount of Ag (0.020 mg/cm2 - deposited on the top of alumina nanopores whose average size varies from ∼86 nm up to ∼320 nm) in the composites investigated, pore size significantly affects SERS enhancement. We obtained distinctly higher intensities of SERS spectra for substrates with an Ag-NPs deposit having a larger diameter of the alumina nanopores. AFM results suggest that both the lateral and perpendicular distribution of Ag-NPs within and on the top of the largest pores is responsible for the highest SERS activity of the resulting Ag-NPs/Al2O3-NP/Al composite layer, since it produces a variety of cavities and slits which function as resonators for the adsorbed molecules. The Ag-NPs/MeOx-NP/Me composite layers obtained ensure a good reproducibility of the SERS measurements.

Estimation of Nanodiamond Surface Charge Density from Zeta Potential and Molecular Dynamics Simulations.

PubMed

Ge, Zhenpeng; Wang, Yi

2017-04-20

Molecular dynamics simulations of nanoparticles (NPs) are increasingly used to study their interactions with various biological macromolecules. Such simulations generally require detailed knowledge of the surface composition of the NP under investigation. Even for some well-characterized nanoparticles, however, this knowledge is not always available. An example is nanodiamond, a nanoscale diamond particle with surface dominated by oxygen-containing functional groups. In this work, we explore using the harmonic restraint method developed by Venable et al., to estimate the surface charge density (σ) of nanodiamonds. Based on the Gouy-Chapman theory, we convert the experimentally determined zeta potential of a nanodiamond to an effective charge density (σ eff ), and then use the latter to estimate σ via molecular dynamics simulations. Through scanning a series of nanodiamond models, we show that the above method provides a straightforward protocol to determine the surface charge density of relatively large (> ∼100 nm) NPs. Overall, our results suggest that despite certain limitation, the above protocol can be readily employed to guide the model construction for MD simulations, which is particularly useful when only limited experimental information on the NP surface composition is available to a modeler.

In situ spectroscopic evidence for neptunium(V)-carbonate inner-sphere and outer-sphere ternary surface complexes on hematite surfaces.

PubMed

Arai, Yuji; Moran, P B; Honeyman, B D; Davis, J A

2007-06-01

Np(V) surface speciation on hematite surfaces at pH 7-9 under pC2 = 10(-3.45) atm was investigated using X-ray absorption spectroscopy (XAS). In situ XAS analyses suggest that bis-carbonato inner-sphere and tris-carbonato outer-sphere ternary surface species coexist at the hematite-water interface at pH 7-8.8, and the fraction of outer-sphere species gradually increases from 27 to 54% with increasing pH from 7 to 8.8. The results suggest that the heretofore unknown Np(V)-carbonato ternary surface species may be important in predicting the fate and transport of Np(V) in the subsurface environment down gradient of high-level nuclear waste respositories.

Nanoparticles as conjugated delivery agents for therapeutic applications

NASA Astrophysics Data System (ADS)

Muroski, Megan Elizabeth

This dissertation explores the use of nanoparticles as conjugated delivery agents. Chapter 1 is a general introduction. Chapter 2 discusses the delivery by a nanoparticle platform provides a method to manipulate gene activation, by taking advantage of the high surface area of a nanoparticle and the ability to selectively couple a desired biological moiety to the NP surface. The nanoparticle based transfection approach functions by controlled release of gene regulatory elements from a 6 nm AuNP (gold nanoparticle) surface. The endosomal release of the regulatory elements from the nanoparticle surface results in endogenous protein knockdown simultaneously with exogenous protein expression for the first 48 h. The use of fluorescent proteins as the endogenous and exogenous signals for protein expression enables the efficiency of co-delivery of siRNA (small interfering RNA) for GFP (green fluorescent protein) knockdown and a dsRed-express linearized plasmid for induction to be optically analyzed in CRL-2794, a human kidney cell line expressing an unstable green fluorescent protein. Delivery of the bimodal nanoparticle in cationic liposomes results in 20% GFP knockdown within 24 h of delivery and continues exhibiting knockdown for up to 48 h for the bimodal agent. Simultaneous dsRed expression is observed to initiate within the same time frame with expression levels reaching 34% after 25 days although cells have divided approximately 20 times, implying daughter cell transfection has occurred. Fluorescence cell sorting results in a stable colony, as demonstrated by Western blot analysis. The simultaneous delivery of siRNA and linearized plasmid DNA on the surface of a single nanocrystal provides a unique method for definitive genetic control within a single cell and leads to a very efficient cell transfection protocol. In Chapter 3, we wanted to understand the NP complex within the cell, and to look at the dynamics of release utilizing nanometal surface energy transfer as a molecular beacon. The development of non-viral transfection approaches using gold nanoparticles (AuNP) as a gene carrier allows the implementation of advanced biophysical tools to follow the transfection cycle by utilizing nanometal surface energy transfer (NSET) molecular beacon methods coupled to delivery of a gene that induces a fluorescent protein. The change in photoluminescence of an appended dye following gene release from the AuNP surface within endosomes can be tempo-rally and spatially followed. The ability to correlate the release events with the protein expression event by simultaneously monitoring fluorescent protein production provides insight into package uptake, nanoparticle disassembly, and final gene expression. Employing AuNP transfection constructs and then monitoring the stages of the transfection cycle via NSET, indicates delivery of the constructs leads to gene release from the AuNP surface within the endosome followed by slow cytosolic diffusion. The slow diffusion is the limiting step for transfection and impacts the protein yield due to competing degradation processes. Chapter 4 aims to improve the NP conjugate through the use of cell penetrating peptides (CPP) to Transfect Primary Cells. All future clinical applications of mesenchymal stem cell (MSC) therapies must allow the MSC to be harvested, transfected, and induced to express a desired protein or selection of proteins to have medical benefit. For the full potential of MSC cell therapy to be realized, it is desirable to be able to systematically alter the protein expression in harvested MSC cells with high fidelity in a single transfection event. We have developed a bimodal delivery platform based on the use of a solid gold core nanoparticle that has been surface modified to produce a chimera containing a protein transduction domain (PTD) sequence to enhance cellular uptake and a linearized expression vector to induce protein production. The transfection chimera is observed to be an efficient inducer of protein expression following a single treatment of femur bone marrow isolated rat MSCs. Use of the neutral penta-peptide, Ku70, designed from Bax-inhibiting peptides in a 500:1 ratio to the linearized gene yields >80% transfection efficiencies. Chapter 5 further develops this idea by using cell penetrating peptides. Research over the past decade has identified several of the key limiting features in multidrug resistance therapy applications, such as, cellular targeting, protection from multidrug resistant mediators and retention of intact and functional drugs. Cell penetrating peptides are able to overcome the difficulties of drug transport resulting in improved efficacy of delivery. Functionalizing the cell penetrating peptide onto the surface of a quantum dot, allows the capability of creating an individualized package for further downstream studies. Four distinct cell penetrating peptides, TAT, VP-22, Ku-70, and hCT (9-32), were utilized to study the different profiles in gliosarcoma lines (rat 9L) with varying resistances to one of the most prescribed drugs in treating glioblastoma in the clinic; BCNU. (Abstract shortened by UMI.)

Anti-inflammatory and antioxidant effect of cerium dioxide nanoparticles immobilized on the surface of silica nanoparticles in rat experimental pneumonia.

PubMed

Serebrovska, Z; Swanson, R J; Portnichenko, V; Shysh, A; Pavlovich, S; Tumanovska, L; Dorovskych, A; Lysenko, V; Tertykh, V; Bolbukh, Y; Dosenko, V

2017-08-01

A massage with the potent counter-inflammatory material, cerium dioxide nanoparticles, is promising and the antioxidant properties of CeO 2 are considered the main, if not the only, mechanism of this action. Nevertheless, the elimination of ceria nano-particles from the organism is very slow and there is a strong concern for toxic effect of ceria due to its accumulation. To overcome this problem, we engineered a combined material in which cerium nanoparticles were immobilized on the surface of silica nanoparticles (CeO 2 NP), which is shown to be easily removed from an organism and could be used as carriers for nano-ceria. In our study particle size was 220±5nm, Zeta-potential -4.5mV (in water), surface charge density -17.22μC/cm 2 (at pH 7). Thirty-six male Wistar rats, 5 months old and 250-290g were divided into four groups: 1) control; 2) CeO 2 NP treatment; 3) experimental pneumonia (i/p LPS injection, 1mg/kg); and 4) experimental pneumonia treated with CeO 2 NP (4 times during the study in dosage of 0.6mg/kg with an orogastric catheter). Gas exchange and pulmonary ventilation were measured four times: 0, 1, 3 and 24h after LPS injection in both untreated and CeO 2 NP-treated animals. The mRNA of TNF-α, Il-6, and CxCL2 were determined by RT-PCR. ROS-generation in blood plasma and lung tissue homogenates were measured by means of lucigenin- and luminol-enhanced chemiluminescence. Endotoxemia in the acute phase was associated with: (1) pathological changes in lung morphology; (2) increase of ROS generation; (3) enhanced expression of CxCL2; and (4) a gradual decrease of VO 2 and V E . CeO2 NP treatment of intact animals did not make any changes in all studied parameters except for a significant augmentation of VO 2 and V E. CeO 2 NP treatment of rats with pneumonia created positive changes in diminishing lung tissue injury, decreasing ROS generation in blood and lung tissue and decreasing pro-inflammatory cytokine expression (TNF-α, Il-6 and CxCL2). Oxygen consumption in this group was increased compared to the LPS pneumonia group. In our study we have shown anti-inflammatory and antioxidant effects of CeO 2 NP. In addition, this paper is the first to report that CeO 2 NP stimulates oxygen consumption in both healthy rats, and rats with pneumonia. We propose the key in understanding the mechanisms behind the phenomena lies in the property of CeO 2 NP to scavenge ROS and the influence of this potent antioxidant on mitochondrial function. The study of biodistribution and elimination of СеО 2 NP is the purpose of our ongoing study. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Synergistic Enhancement of Electrocatalytic CO 2 Reduction with Gold Nanoparticles Embedded in Functional Graphene Nanoribbon Composite Electrodes

DOE PAGES

Rogers, Cameron; Perkins, Wade S.; Veber, Gregory; ...

2017-02-24

Regulating the complex environment accounting for the stability, selectivity, and activity of catalytic metal nanoparticle interfaces represents a challenge to heterogeneous catalyst design. Here in this paper, we demonstrate the intrinsic performance enhancement of a composite material composed of gold nanoparticles (AuNPs) embedded in a bottom-up synthesized graphene nanoribbon (GNR) matrix for the electrocatalytic reduction of CO 2. Electrochemical studies reveal that the structural and electronic properties of the GNR composite matrix increase the AuNP electrochemically active surface area (ECSA), lower the requisite CO 2 reduction overpotential by hundreds of millivolts (catalytic onset > -0.2 V versus reversible hydrogen electrodemore » (RHE)), increase the Faraday efficiency (>90%), markedly improve stability (catalytic performance sustained over >24 h), and increase the total catalytic output (>100-fold improvement over traditional amorphous carbon AuNP supports). The inherent structural and electronic tunability of bottom-up synthesized GNR-AuNP composites affords an unrivaled degree of control over the catalytic environment, providing a means for such profound effects as shifting the rate-determining step in the electrocatalytic reduction of CO 2 to CO, and thereby altering the electrocatalytic mechanism at the nanoparticle surface.« less

C-terminal cleavage of DeltaNp63alpha is associated with TSA-induced apoptosis in immortalized corneal epithelial cells.

PubMed

Robertson, Danielle M; Ho, Su-Inn; Cavanagh, H Dwight

2010-08-01

In the central human corneal epithelium, loss of DeltaNp63 occurs in all surface epithelial cells preparing to undergo desquamation, suggesting a potential role for DeltaNp63 isoforms in mediating surface cell apoptotic shedding. In this study, the authors investigated a role for DeltaNp63 isoforms in caspase-mediated apoptosis in a telomerase-immortalized corneal epithelial cell line. For in vitro studies, hTCEpi cells were cultured in KGM-2 serum-free culture media containing 0.15 mM calcium. To assess dynamic protein interactions among individual DeltaNp63 isoforms, DeltaNp63-EGFP expression plasmids were transiently expressed in hTCEpi cells and evaluated by FRAP. Trichostatin-A (TSA; 3.31 muM) was used to induce cell death as measured by caspase activity. Cleavage and loss of endogenous DeltaNp63alpha, DeltaNp63-EGFP expression plasmids, and p53 were assessed after treatment with TSA and siRNA. Transient expression of DeltaNp63-EGFP alpha and beta isoforms resulted in the formation of a smaller isoform similar in size to DeltaNp63gamma-EGFP. FRAP demonstrated that DeltaNp63alpha-EGFP has greater immobile fraction than beta or gamma. TSA induced caspase-mediated apoptotic pathways; caspase induction was accompanied by a decrease in endogenous DeltaNp63alpha and p53. TSA upregulated DeltaNp63-EGFP plasmid expression; this was accompanied by a selective increase in cleavage of DeltaNp63alpha-EGFP. siRNA knockdown of DeltaNp63alpha correlated with a reduction in p53 independently of TSA. DeltaNp63alpha is the dominant active isoform in corneal epithelial cell nuclei. Loss of DeltaNp63alpha occurs during apoptotic signaling by cleavage at the C terminus. The corresponding loss of p53 suggests that a significant relationship appears to exist between these two regulatory proteins.

Aptamer-functionalized PEG-PLGA nanoparticles for enhanced anti-glioma drug delivery.

PubMed

Guo, Jianwei; Gao, Xiaoling; Su, Lina; Xia, Huimin; Gu, Guangzhi; Pang, Zhiqing; Jiang, Xinguo; Yao, Lei; Chen, Jun; Chen, Hongzhuan

2011-11-01

Targeted delivery of therapeutic nanoparticles in a disease-specific manner represents a potentially powerful technology especially when treating infiltrative brain tumors such as gliomas. We developed a nanoparticulate drug delivery system decorated with AS1411 (Ap), a DNA aptamer specifically binding to nucleolin which was highly expressed in the plasma membrane of both cancer cells and endothelial cells in angiogenic blood vessels, as the targeting ligand to facilitate anti-glioma delivery of paclitaxel (PTX). Ap was conjugated to the surface of PEG-PLGA nanoparticles (NP) via an EDC/NHS technique. With the conjugation confirmed by Urea PAGE and XPS, the resulting Ap-PTX-NP was uniformly round with particle size at 156.0 ± 54.8 nm and zeta potential at -32.93 ± 3.1 mV. Ap-nucleolin interaction significantly enhanced cellular association of nanoparticles in C6 glioma cells, and increased the cytotoxicity of its payload. Prolonged circulation and enhanced PTX accumulation at the tumor site was achieved for Ap-PTX-NP, which eventually obtained significantly higher tumor inhibition on mice bearing C6 glioma xenografts and prolonged animal survival on rats bearing intracranial C6 gliomas when compared with PTX-NP and Taxol(®). The results of this contribution demonstrated the potential utility of AS1411-functionalized nanoparticles for a therapeutic application in the treatment of gliomas. Copyright © 2011 Elsevier Ltd. All rights reserved.

G-CSF loaded nanofiber/nanoparticle composite coated with collagen promotes wound healing in vivo.

PubMed

Tanha, Shima; Rafiee-Tehrani, Morteza; Abdollahi, Mohamad; Vakilian, Saeid; Esmaili, Zahra; Naraghi, Zahra Safaei; Seyedjafari, Ehsan; Javar, Hamid Akbari

2017-10-01

Sustained release of functional growth factors can be considered as a beneficial methodology for wound healing. In this study, recombinant human granulocyte colony-stimulating factor (G-CSF)-loaded chitosan nanoparticles were incorporated in Poly(ε-caprolactone) (PCL) nanofibers, followed by surface coating with collagen type I. Physical and mechanical properties of the PCL nanofibers containing G-CSF loaded chitosan nanoparticles PCL/NP(G-CSF) and in vivo performance for wound healing were investigated. G-CSF structural stability was evaluated through SDS_PAGE, reversed phase (RP) HPLC and size-exclusion chromatography, as well as circular dichroism. Nanofiber/nanoparticle composite scaffold was demonstrated to have appropriate mechanical properties as a wound dresser and a sustained release of functional G-CSF. The PCL/NP(G-CSF) scaffold showed a suitable proliferation and well-adherent morphology of stem cells. In vivo study and histopathological evaluation outcome revealed that skin regeneration was dramatically accelerated under PCL/NP(G-CSF) as compared with control groups. Superior fibroblast maturation, enhanced collagen deposition and minimum inflammatory cells were also the beneficial properties of PCL/NP(G-CSF) over the commercial dressing. The synergistic effect of extracellular matrix-mimicking nanofibrous membrane and G-CSF could develop a suitable supportive substrate in order to extensive utilization for the healing of skin wounds. © 2017 Wiley Periodicals Inc. J Biomed Mater Res Part A: 105A: 2830-2842, 2017. © 2017 Wiley Periodicals, Inc.

Interaction of Pb(II) and biofilm associated extracellular polymeric substances of a marine bacterium Pseudomonas pseudoalcaligenes NP103

NASA Astrophysics Data System (ADS)

Kumari, Supriya; Mangwani, Neelam; Das, Surajit

2017-02-01

Three-dimensional excitation-emission matrix (3D EEM) fluorescence spectroscopy and attenuated total reflectance fourier-transformed infrared spectroscopy (ATR-FTIR) was used to evaluate the interaction of biofilm associated extracellular polymeric substances (EPS) of a marine bacterium Pseudomonas pseudoalcaligenes NP103 with lead [Pb(II)]. EEM fluorescence spectroscopic analysis revealed the presence of one protein-like fluorophore in the EPS of P. pseudoalcaligenes NP103. Stern-Volmer equation indicated the existence of only one binding site (n = 0.789) in the EPS of P. pseudoalcaligenes NP103. The interaction of Pb(II) with EPS was spontaneous at room temperature (Δ G = - 2.78 kJ/K/mol) having binding constant (Kb) of 2.59 M- 1. ATR-FTIR analysis asserted the involvement of various functional groups such as sulphydryl, phosphate and hydroxyl and amide groups of protein in Pb(II) binding. Scanning electron microscopy (SEM) and fluorescence microscopy analysis displayed reduced growth of biofilm with altered surface topology in Pb(II) supplemented medium. Energy dispersive X-ray spectroscopy (EDX) analysis revealed the entrapment of Pb in the EPS. Uronic acid, a characteristic functional group of biofilm, was observed in 1H NMR spectroscopy. The findings suggest that biofilm associated EPS are perfect organic ligands for Pb(II) complexation and may significantly augment the bioavailability of Pb(II) in the metal contaminated environment for subsequent sequestration.

Reductive precipitation of neptunium on iron surfaces under anaerobic conditions

NASA Astrophysics Data System (ADS)

Yang, H.; Cui, D.; Grolimund, D.; Rondinella, V. V.; Brütsch, R.; Amme, M.; Kutahyali, C.; Wiss, A. T.; Puranen, A.; Spahiu, K.

2017-12-01

Reductive precipitation of the radiotoxic nuclide 237Np from nuclear waste on the surface of iron canister material at simulated deep repository conditions was investigated. Pristine polished as well as pre-corroded iron specimens were interacted in a deoxygenated solution containing 10-100 μM Np(V), with 10 mM NaCl and 2 mM NaHCO3 as background electrolytes. The reactivity of each of the two different systems was investigated by analyzing the temporal evolution of the Np concentration in the reservoir. It was observed that pre-oxidized iron specimen with a 40 μm Fe3O4 corrosion layer are considerably more reactive regarding the reduction and immobilization of aqueous Np(V) as compared to pristine polished Fe(0) surfaces. 237Np immobilized by the reactive iron surfaces was characterized by scanning electron microscopy as well as synchrotron-based micro-X-ray fluorescence and X-ray absorption spectroscopy. At the end of experiments, a 5-8 μm thick Np-rich layer was observed to be formed ontop of the Fe3O4 corrosion layer on the iron specimen. The findings from this work are significant in the context of performance assessments of deep geologic repositories using iron as high level radioactive waste (HLW) canister material and are of relevance regarding removing pollutants from contaminated soil or groundwater aquifer systems.

Low-Volatility Model Demonstrates Humidity Affects Environmental Toxin Deposition on Plastics at a Molecular Level.

PubMed

Hankett, Jeanne M; Collin, William R; Yang, Pei; Chen, Zhan; Duhaime, Melissa

2016-02-02

Despite the ever-increasing prevalence of plastic debris and endocrine disrupting toxins in aquatic ecosystems, few studies describe their interactions in freshwater environments. We present a model system to investigate the deposition/desorption behaviors of low-volatility lake ecosystem toxins on microplastics in situ and in real time. Molecular interactions of gas-phase nonylphenols (NPs) with the surfaces of two common plastics, poly(styrene) and poly(ethylene terephthalate), were studied using quartz crystal microbalance and sum frequency generation vibrational spectroscopy. NP point sources were generated under two model environments: plastic on land and plastic on a freshwater surface. We found the headspace above calm water provides an excellent environment for NP deposition and demonstrate significant NP deposition on plastic within minutes at relevant concentrations. Further, NP deposits and orders differently on both plastics under humid versus dry environments. We attributed the unique deposition behaviors to surface energy changes from increased water content during the humid deposition. Lastly, nanograms of NP remained on microplastic surfaces hours after initial NP introduction and agitating conditions, illustrating feasibility for plastic-bound NPs to interact with biota and surrounding matter. Our model studies reveal important interactions between low-volatility environmental toxins and microplastics and hold potential to correlate the environmental fate of endocrine disrupting toxins in the Great Lakes with molecular behaviors.

Using mutagenesis to explore conserved residues in the RNA-binding groove of influenza A virus nucleoprotein for antiviral drug development

NASA Astrophysics Data System (ADS)

Liu, Chia-Lin; Hung, Hui-Chen; Lo, Shou-Chen; Chiang, Ching-Hui; Chen, I.-Jung; Hsu, John T.-A.; Hou, Ming-Hon

2016-02-01

Nucleoprotein (NP) is the most abundant type of RNA-binding viral protein in influenza A virus-infected cells and is necessary for viral RNA transcription and replication. Recent studies demonstrated that influenza NP is a valid target for antiviral drug development. The surface of the groove, covered with numerous conserved residues between the head and body domains of influenza A NP, plays a crucial role in RNA binding. To explore the mechanism by which NP binds RNA, we performed a series of site-directed mutagenesis in the RNA-binding groove, followed by surface plasmon resonance (SPR), to characterize the interactions between RNA and NP. Furthermore, a role of Y148 in NP stability and NP-RNA binding was evaluated. The aromatic residue of Y148 was found to stack with a nucleotide base. By interrupting the stacking interaction between Y148 and an RNA base, we identified an influenza virus NP inhibitor, (E, E)-1,7-bis(4-hydroxy-3-methoxyphenyl) -1,6-heptadiene-3,5-dione; this inhibitor reduced the NP’s RNA-binding affinity and hindered viral replication. Our findings will be useful for the development of new drugs that disrupt the interaction between RNA and viral NP in the influenza virus.

Structure-Based Discovery of the Novel Antiviral Properties of Naproxen against the Nucleoprotein of Influenza A Virus

PubMed Central

Lejal, Nathalie; Tarus, Bogdan; Bouguyon, Edwige; Chenavas, Sylvie; Bertho, Nicolas; Delmas, Bernard; Ruigrok, Rob W. H.; Di Primo, Carmelo

2013-01-01

The nucleoprotein (NP) binds the viral RNA genome and associates with the polymerase in a ribonucleoprotein complex (RNP) required for transcription and replication of influenza A virus. NP has no cellular counterpart, and the NP sequence is highly conserved, which led to considering NP a hot target in the search for antivirals. We report here that monomeric nucleoprotein can be inhibited by a small molecule binding in its RNA binding groove, resulting in a novel antiviral against influenza A virus. We identified naproxen, an anti-inflammatory drug that targeted the nucleoprotein to inhibit NP-RNA association required for NP function, by virtual screening. Further docking and molecular dynamics (MD) simulations identified in the RNA groove two NP-naproxen complexes of similar levels of interaction energy. The predicted naproxen binding sites were tested using the Y148A, R152A, R355A, and R361A proteins carrying single-point mutations. Surface plasmon resonance, fluorescence, and other in vitro experiments supported the notion that naproxen binds at a site identified by MD simulations and showed that naproxen competed with RNA binding to wild-type (WT) NP and protected active monomers of the nucleoprotein against proteolytic cleavage. Naproxen protected Madin-Darby canine kidney (MDCK) cells against viral challenges with the H1N1 and H3N2 viral strains and was much more effective than other cyclooxygenase inhibitors in decreasing viral titers of MDCK cells. In a mouse model of intranasal infection, naproxen treatment decreased the viral titers in mice lungs. In conclusion, naproxen is a promising lead compound for novel antivirals against influenza A virus that targets the nucleoprotein in its RNA binding groove. PMID:23459490

The discovery of silicon oxide nanoparticles in space-weathered of Apollo 15 lunar soil grains

NASA Astrophysics Data System (ADS)

Gu, Lixin; Zhang, Bin; Hu, Sen; Noguchi, Takaaki; Hidaka, Hiroshi; Lin, Yangting

2018-03-01

Space weathering is an important process on the Moon and other airless celestial bodies. The most common space weathering effects are amorphization of the top surface of soil grains and formation of nanophase iron particles (npFe) within the partially amorphous rims. Hence, space weathering significantly affects optical properties of the surface of the Moon and other airless celestial bodies. Transmission electron microscope (TEM) analysis of Apollo 15 soil grains displays npFe (≤5 nm in size) embedded in the space-weathered rim (∼60 nm in thickness) of a pyroxene grain, consistent with previous studies. In contrast, submicron-sized fragments that adhere to the pyroxene grain show distinct space weathering features. Silicon oxide nanoparticles (npSiOx) were observed with npFe in a submicron-sized Mg-Fe silicate fragment. This is the first discovery of npSiOx as a product of space weathering. The npSiOx and the coexisting npFe are ∼10-25 nm in size, significantly larger than the typical npFe in the space weathered rim of the pyroxene grain. The coexisting npSiOx and npFe were probably formed directly in micrometeorite shock-induced melt, instead of in a solar-wind generated vapor deposit or irradiated rim. This new observation will shed light on space weathering processes on the Moon and airless celestial bodies.

Counterintuitive cooperative endocytosis of like-charged nanoparticles in cellular internalization: computer simulation and experiment

NASA Astrophysics Data System (ADS)

Li, Ye; Yuan, Bing; Yang, Kai; Zhang, Xianren; Yan, Bing; Cao, Dapeng

2017-02-01

The nanoparticles (NPs) functionalized with charged ligands are of particular significance due to their potential drug/gene delivery and biomedical applications. However, the molecular mechanism of endocytosis of the charged NPs by cells, especially the effect of the NP-NP and NP-biomembrane interactions on the internalization pathways is still poorly understood. In this work, we systematically investigate the internalization behaviors of the positively charged NPs by combining experiment technology and dissipative particle dynamics (DPD) simulation. We experimentally find an interesting but highly counterintuitive phenomenon, i.e. the multiple positively charged NPs prefer to enter cells cooperatively although the like-charged NPs have obvious electrostatic repulsion. Furthermore, we adopt the DPD simulation to confirm the experimental findings, and reveal that the mechanism of the cooperative endocytosis between like-charged NPs is definitely caused by the interplay of particle size, the charged ligand density on particle surface and local concentration of NPs. Importantly, we not only observe the normal cooperative endocytosis of like-charged NPs in cell biomembrane like neutral NP case, but also predict the ‘bud’ cooperative endocytosis of like-charged NPs which is absence in the neutral NP case. The results indicate that electrostatic repulsion between the positively charged nanoparticles plays an important role in the ‘bud’ cooperative endocytosis of like-charged NPs.

The C-terminal region of lymphocytic choriomeningitis virus nucleoprotein contains distinct and segregable functional domains involved in NP-Z interaction and counteraction of the type I interferon response.

PubMed

Ortiz-Riaño, Emilio; Cheng, Benson Yee Hin; de la Torre, Juan Carlos; Martínez-Sobrido, Luis

2011-12-01

Several arenaviruses cause hemorrhagic fever (HF) disease in humans that is associated with high morbidity and significant mortality. Arenavirus nucleoprotein (NP), the most abundant viral protein in infected cells and virions, encapsidates the viral genome RNA, and this NP-RNA complex, together with the viral L polymerase, forms the viral ribonucleoprotein (vRNP) that directs viral RNA replication and gene transcription. Formation of infectious arenavirus progeny requires packaging of vRNPs into budding particles, a process in which arenavirus matrix-like protein (Z) plays a central role. In the present study, we have characterized the NP-Z interaction for the prototypic arenavirus lymphocytic choriomeningitis virus (LCMV). The LCMV NP domain that interacted with Z overlapped with a previously documented C-terminal domain that counteracts the host type I interferon (IFN) response. However, we found that single amino acid mutations that affect the anti-IFN function of LCMV NP did not disrupt the NP-Z interaction, suggesting that within the C-terminal region of NP different amino acid residues critically contribute to these two distinct and segregable NP functions. A similar NP-Z interaction was confirmed for the HF arenavirus Lassa virus (LASV). Notably, LCMV NP interacted similarly with both LCMV Z and LASV Z, while LASV NP interacted only with LASV Z. Our results also suggest the presence of a conserved protein domain within NP but with specific amino acid residues playing key roles in determining the specificity of NP-Z interaction that may influence the viability of reassortant arenaviruses. In addition, this NP-Z interaction represents a potential target for the development of antiviral drugs to combat human-pathogenic arenaviruses.

Refractive index sensing in the visible/NIR spectrum using silicon nanopillar arrays.

PubMed

Visser, D; Choudhury, B Dev; Krasovska, I; Anand, S

2017-05-29

Si nanopillar (NP) arrays are investigated as refractive index sensors in the visible/NIR wavelength range, suitable for Si photodetector responsivity. The NP arrays are fabricated by nanoimprint lithography and dry etching, and coated with thin dielectric layers. The reflectivity peaks obtained by finite-difference time-domain (FDTD) simulations show a linear shift with coating layer thickness. At 730 nm wavelength, sensitivities of ~0.3 and ~0.9 nm/nm of SiO 2 and Si 3 N 4 , respectively, are obtained; and the optical thicknesses of the deposited surface coatings are determined by comparing the experimental and simulated data. The results show that NP arrays can be used for sensing surface bio-layers. The proposed method could be useful to determine the optical thickness of surface coatings, conformal and non-conformal, in NP-based optical devices.

Flexible hybrid circuit fully inkjet-printed: Surface mount devices assembled by silver nanoparticles-based inkjet ink

NASA Astrophysics Data System (ADS)

Arrese, J.; Vescio, G.; Xuriguera, E.; Medina-Rodriguez, B.; Cornet, A.; Cirera, A.

2017-03-01

Nowadays, inkjet-printed devices such as transistors are still unstable in air and have poor performances. Moreover, the present electronics applications require a high degree of reliability and quality of their properties. In order to accomplish these application requirements, hybrid electronics is fulfilled by combining the advantages of the printing technologies with the surface-mount technology. In this work, silver nanoparticle-based inkjet ink (AgNP ink) is used as a novel approach to connect surface-mount devices (SMDs) onto inkjet-printed pads, conducted by inkjet printing technology. Excellent quality AgNP ink-junctions are ensured with high resolution picoliter drop jetting at low temperature (˜150 °C). Electrical, mechanical, and morphological characterizations are carried out to assess the performance of the AgNP ink junction. Moreover, AgNP ink is compared with common benchmark materials (i.e., silver epoxy and solder). Electrical contact resistance characterization shows a similar performance between the AgNP ink and the usual ones. Mechanical characterization shows comparable shear strength for AgNP ink and silver epoxy, and both present higher adhesion than solder. Morphological inspections by field-emission scanning electron microscopy confirm a high quality interface of the silver nanoparticle interconnection. Finally, a flexible hybrid circuit on paper controlled by an Arduino board is manufactured, demonstrating the viability and scalability of the AgNP ink assembling technique.

Direct patterning of gold nanoparticles using flexographic printing for biosensing applications

NASA Astrophysics Data System (ADS)

Benson, Jamie; Fung, Chung Man; Lloyd, Jonathan Stephen; Deganello, Davide; Smith, Nathan Andrew; Teng, Kar Seng

2015-03-01

In this paper, we have presented the use of flexographic printing techniques in the selective patterning of gold nanoparticles (AuNPs) onto a substrate. Highly uniform coverage of AuNPs was selectively patterned on the substrate surface, which was subsequently used in the development of a glucose sensor. These AuNPs provide a biocompatible site for the attachment of enzymes and offer high sensitivity in the detection of glucose due to their large surface to volume ratio. The average size of the printed AuNPs is less than 60 nm. Glucose sensing tests were performed using printed carbon-AuNP electrodes functionalized with glucose oxidase (GOx). The results showed a high sensitivity of 5.52 μA mM-1 cm-2 with a detection limit of 26 μM. We have demonstrated the fabrication of AuNP-based biosensors using flexographic printing, which is ideal for low-cost, high-volume production of the devices.

Anisotropic growth of NiO nanorods from Ni nanoparticles by rapid thermal oxidation.

PubMed

Koga, Kenji; Hirasawa, Makoto

2013-09-20

NiO nanorods with extremely high crystallinity were grown by rapid thermal oxidation through exposure of Ni nanoparticles (NPs) heated above 400° C to oxygen. Oxidation proceeds by nucleation of a NiO island on a Ni NP that grows anisotropically to produce a NiO nanorod. This process differs completely from that under mild oxidation conditions, where the surface of the NPs is completely covered with an oxide film during the early stage of oxidation. The observed novel behaviour strongly suggests an interfacial oxidation mechanism driven by the dissolution of adsorbed oxygen into the Ni NP sub-surface region, subsequent diffusion and reaction at the NiO/Ni interface. The early oxidation conditions of metal NPs impose a significant influence on the entire oxidation process at the nanoscale and are therefore inherently important for the precise morphological control of oxidized NPs to design functional nanomaterials.

Carboxyl-functionalized polyurethane nanoparticles with immunosuppressive properties as a new type of anti-inflammatory platform

NASA Astrophysics Data System (ADS)

Huang, Yen-Jang; Hung, Kun-Che; Hsieh, Fu-Yu; Hsu, Shan-Hui

2015-12-01

The interaction of nanoparticles (NPs) with the body immune system is critically important for their biomedical applications. Most NPs stimulate the immune response of macrophages. Here we show that synthetic polyurethane nanoparticles (PU NPs, diameter 34-64 nm) with rich surface COO- functional groups (zeta potential -70 to -50 mV) can suppress the immune response of macrophages. The specially-designed PU NPs reduce the gene expression levels of proinflammatory cytokines (IL-1β, IL-6, and TNF-α) for endotoxin-treated macrophages. The PU NPs increase the intracellular calcium of macrophages (4.5-6.5 fold) and activate autophagy. This is in contrast to the autophagy dysfunction generally observed upon NP exposure. These PU NPs may further decrease the nuclear factor-κB-related inflammation via autophagy pathways. The immunosuppressive activities of PU NPs can prevent animal death by inhibiting the macrophage recruitment and proinflammatory responses, confirmed by an in vivo zebrafish model. Therefore, the novel biodegradable PU NPs demonstrate COO- dependent immunosuppressive properties without carrying any anti-inflammatory agents. This study suggests that NP surface chemistry may regulate the immune response, which provides a new paradigm for potential applications of NPs in anti-inflammation and immunomodulation.The interaction of nanoparticles (NPs) with the body immune system is critically important for their biomedical applications. Most NPs stimulate the immune response of macrophages. Here we show that synthetic polyurethane nanoparticles (PU NPs, diameter 34-64 nm) with rich surface COO- functional groups (zeta potential -70 to -50 mV) can suppress the immune response of macrophages. The specially-designed PU NPs reduce the gene expression levels of proinflammatory cytokines (IL-1β, IL-6, and TNF-α) for endotoxin-treated macrophages. The PU NPs increase the intracellular calcium of macrophages (4.5-6.5 fold) and activate autophagy. This is in contrast to the autophagy dysfunction generally observed upon NP exposure. These PU NPs may further decrease the nuclear factor-κB-related inflammation via autophagy pathways. The immunosuppressive activities of PU NPs can prevent animal death by inhibiting the macrophage recruitment and proinflammatory responses, confirmed by an in vivo zebrafish model. Therefore, the novel biodegradable PU NPs demonstrate COO- dependent immunosuppressive properties without carrying any anti-inflammatory agents. This study suggests that NP surface chemistry may regulate the immune response, which provides a new paradigm for potential applications of NPs in anti-inflammation and immunomodulation. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06379e

Minimizing distortion and internal forces in truss structures by simulated annealing

NASA Technical Reports Server (NTRS)

Kincaid, Rex K.

1989-01-01

Inaccuracies in the length of members and the diameters of joints of large truss reflector backup structures may produce unacceptable levels of surface distortion and member forces. However, if the member lengths and joint diameters can be measured accurately it is possible to configure the members and joints so that root-mean-square (rms) surface error and/or rms member forces is minimized. Following Greene and Haftka (1989) it is assumed that the force vector f is linearly proportional to the member length errors e(sub M) of dimension NMEMB (the number of members) and joint errors e(sub J) of dimension NJOINT (the number of joints), and that the best-fit displacement vector d is a linear function of f. Let NNODES denote the number of positions on the surface of the truss where error influences are measured. The solution of the problem is discussed. To classify, this problem was compared to a similar combinatorial optimization problem. In particular, when only the member length errors are considered, minimizing d(sup 2)(sub rms) is equivalent to the quadratic assignment problem. The quadratic assignment problem is a well known NP-complete problem in operations research literature. Hence minimizing d(sup 2)(sub rms) is is also an NP-complete problem. The focus of the research is the development of a simulated annealing algorithm to reduce d(sup 2)(sub rms). The plausibility of this technique is its recent success on a variety of NP-complete combinatorial optimization problems including the quadratic assignment problem. A physical analogy for simulated annealing is the way liquids freeze and crystallize. All computational experiments were done on a MicroVAX. The two interchange heuristic is very fast but produces widely varying results. The two and three interchange heuristic provides less variability in the final objective function values but runs much more slowly. Simulated annealing produced the best objective function values for every starting configuration and was faster than the two and three interchange heuristic.

Nanoparticles-cell association predicted by protein corona fingerprints

NASA Astrophysics Data System (ADS)

Palchetti, S.; Digiacomo, L.; Pozzi, D.; Peruzzi, G.; Micarelli, E.; Mahmoudi, M.; Caracciolo, G.

2016-06-01

In a physiological environment (e.g., blood and interstitial fluids) nanoparticles (NPs) will bind proteins shaping a ``protein corona'' layer. The long-lived protein layer tightly bound to the NP surface is referred to as the hard corona (HC) and encodes information that controls NP bioactivity (e.g. cellular association, cellular signaling pathways, biodistribution, and toxicity). Decrypting this complex code has become a priority to predict the NP biological outcomes. Here, we use a library of 16 lipid NPs of varying size (Ø ~ 100-250 nm) and surface chemistry (unmodified and PEGylated) to investigate the relationships between NP physicochemical properties (nanoparticle size, aggregation state and surface charge), protein corona fingerprints (PCFs), and NP-cell association. We found out that none of the NPs' physicochemical properties alone was exclusively able to account for association with human cervical cancer cell line (HeLa). For the entire library of NPs, a total of 436 distinct serum proteins were detected. We developed a predictive-validation modeling that provides a means of assessing the relative significance of the identified corona proteins. Interestingly, a minor fraction of the HC, which consists of only 8 PCFs were identified as main promoters of NP association with HeLa cells. Remarkably, identified PCFs have several receptors with high level of expression on the plasma membrane of HeLa cells.In a physiological environment (e.g., blood and interstitial fluids) nanoparticles (NPs) will bind proteins shaping a ``protein corona'' layer. The long-lived protein layer tightly bound to the NP surface is referred to as the hard corona (HC) and encodes information that controls NP bioactivity (e.g. cellular association, cellular signaling pathways, biodistribution, and toxicity). Decrypting this complex code has become a priority to predict the NP biological outcomes. Here, we use a library of 16 lipid NPs of varying size (Ø ~ 100-250 nm) and surface chemistry (unmodified and PEGylated) to investigate the relationships between NP physicochemical properties (nanoparticle size, aggregation state and surface charge), protein corona fingerprints (PCFs), and NP-cell association. We found out that none of the NPs' physicochemical properties alone was exclusively able to account for association with human cervical cancer cell line (HeLa). For the entire library of NPs, a total of 436 distinct serum proteins were detected. We developed a predictive-validation modeling that provides a means of assessing the relative significance of the identified corona proteins. Interestingly, a minor fraction of the HC, which consists of only 8 PCFs were identified as main promoters of NP association with HeLa cells. Remarkably, identified PCFs have several receptors with high level of expression on the plasma membrane of HeLa cells. Electronic supplementary information (ESI) available: Table S1. Cell viability (%) and cell association of the different nanoparticles used. Table S2. Total number of identified proteins on the different nanoparticles used. Tables S3-S18. Top 25 most abundant corona proteins identified in the protein corona of nanoparticles NP2-NP16 following 1 hour incubation with HP. Table S19. List of descriptors used. Table S20. Potential targets of protein corona fingerprints with its own interaction score (mentha) and the expression median value in Hela cells. Fig. S1 and S2. Effect of exposure to human plasma on size and zeta potential of NPs. Fig. S3. Predictive modeling of nanoparticle-cell association. See DOI: 10.1039/c6nr03898k

Preparation, Modification, Characterization, and Biosensing Application of Nanoporous Gold Using Electrochemical Techniques

PubMed Central

Neupane, Dharmendra; Nepal, Bishal; Mikhaylov, Vasilii; Stine, Keith J.

2018-01-01

Nanoporous gold (np-Au), because of its high surface area-to-volume ratio, excellent conductivity, chemical inertness, physical stability, biocompatibility, easily tunable pores, and plasmonic properties, has attracted much interested in the field of nanotechnology. It has promising applications in the fields of catalysis, bio/chemical sensing, drug delivery, biomolecules separation and purification, fuel cell development, surface-chemistry-driven actuation, and supercapacitor design. Many chemical and electrochemical procedures are known for the preparation of np-Au. Recently, researchers are focusing on easier and controlled ways to tune the pores and ligaments size of np-Au for its use in different applications. Electrochemical methods have good control over fine-tuning pore and ligament sizes. The np-Au electrodes that are prepared using electrochemical techniques are robust and are easier to handle for their use in electrochemical biosensing. Here, we review different electrochemical strategies for the preparation, post-modification, and characterization of np-Au along with the synergistic use of both electrochemistry and np-Au for applications in biosensing. PMID:29547580

Preparation, Modification, Characterization, and Biosensing Application of Nanoporous Gold Using Electrochemical Techniques.

PubMed

Bhattarai, Jay K; Neupane, Dharmendra; Nepal, Bishal; Mikhaylov, Vasilii; Demchenko, Alexei V; Stine, Keith J

2018-03-16

Nanoporous gold (np-Au), because of its high surface area-to-volume ratio, excellent conductivity, chemical inertness, physical stability, biocompatibility, easily tunable pores, and plasmonic properties, has attracted much interested in the field of nanotechnology. It has promising applications in the fields of catalysis, bio/chemical sensing, drug delivery, biomolecules separation and purification, fuel cell development, surface-chemistry-driven actuation, and supercapacitor design. Many chemical and electrochemical procedures are known for the preparation of np-Au. Recently, researchers are focusing on easier and controlled ways to tune the pores and ligaments size of np-Au for its use in different applications. Electrochemical methods have good control over fine-tuning pore and ligament sizes. The np-Au electrodes that are prepared using electrochemical techniques are robust and are easier to handle for their use in electrochemical biosensing. Here, we review different electrochemical strategies for the preparation, post-modification, and characterization of np-Au along with the synergistic use of both electrochemistry and np-Au for applications in biosensing.

Bioengineered-inorganic nanosystems for nanophotonics and bio-nanotechnology

NASA Astrophysics Data System (ADS)

Leong, Kirsty; Zin, Melvin T.; Ma, Hong; Huang, Fei; Sarikaya, Mehmet; Jen, Alex K.

2008-08-01

Here we nanoengineered tunable quantum dot and cationic conjugated polymer nanoarrays based on surface plasmon enhanced fluorescence where we achieved a 15-fold and 25-fold increase in their emission intensities, respectively. These peptide mediated hybrid systems were fabricated by horizontally tuning the localized surface plasmon resonance of gold nanoarrays and laterally tuning the distance of the fluorophore from the metal surface. This approach permits a comprehensive control both laterally (i.e., lithographically defined gold nanoarrays) and vertically (i.e., QD/CCP-metal distance) of the collectively behaving QD-NP and CP-NP assemblies by way of biomolecular recognition. The highest photoluminescence was achieved when the quantum dots and cationic conjugated polymers were self-assembled at a distance of 16.00 nm and 18.50 nm from the metal surface, respectively. Specifically, we demonstrated the spectral tuning of plasmon resonant metal nanoarrays and the self-assembly of protein-functionalized QDs/CCPs in a step-wise fashion with a concomitant incremental increase in separation from the metal surface through biotin-streptavidin spacer units. These well-controlled self-assembled patterned arrays provide highly organized architectures for improving optoelectronic devices and/or increasing the sensitivity of bio-chemical sensors.

Long-term effects of nickel oxide nanoparticles on performance, microbial enzymatic activity, and microbial community of a sequencing batch reactor.

PubMed

Wang, Sen; Li, Zhiwei; Gao, Mengchun; She, Zonglian; Guo, Liang; Zheng, Dong; Zhao, Yangguo; Ma, Bingrui; Gao, Feng; Wang, Xuejiao

2017-02-01

The nitrogen and phosphorus removal, microbial enzymatic activity, and microbial community of a sequencing batch reactor (SBR) were evaluated under long-term exposure to nickel oxide nanoparticles (NiO NPs). High NiO NP concentration (over 5 mg L -1 ) affected the removal of chemical oxygen demand, nitrogen, and phosphorus. The presence of NiO NP inhibited the microbial enzymatic activities and reduced the nitrogen and phosphorus removal rates of activated sludge. The microbial enzymatic activities of the activated sludge showed a similar variation trend to the nitrogen and phosphorus removal rates with the increase in NiO NP concentration from 0 to 60 mg L -1 . The Ni content in the effluent and activated sludge showed an increasing trend with the increase in NiO NP concentration. Some NiO NPs were absorbed on the sludge surface or penetrate the cell membrane into the interior of microbial cells in the activated sludge. NiO NP facilitated the increase in reactive oxygen species by disturbing the balance between the oxidation and anti-oxidation processes, and the variation in lactate dehydrogenase demonstrated that NiO NP could destroy the cytomembrane and cause variations in the microbial morphology and physiological function. High-throughput sequencing demonstrated that the microbial community of SBR had some obvious changes at 0-60 mg L -1 NiO NPs at the phyla, class and genus levels. Copyright © 2016 Elsevier Ltd. All rights reserved.

pH-Triggered Molecular Alignment for Reproducible SERS Detection via an AuNP/Nanocellulose Platform

PubMed Central

Wei, Haoran; Vikesland, Peter J.

2015-01-01

The low affinity of neutral and hydrophobic molecules towards noble metal surfaces hinders their detection by surface-enhanced Raman spectroscopy (SERS). Herein, we present a method to enhance gold nanoparticle (AuNP) surface affinity by lowering the suspension pH below the analyte pKa. We developed an AuNP/bacterial cellulose (BC) nanocomposite platform and applied it to two common pollutants, carbamazepine (CBZ) and atrazine (ATZ) with pKa values of 2.3 and 1.7, respectively. Simple mixing of the analytes with AuNP/BC at pH < pKa resulted in consistent electrostatic alignment of the CBZ and ATZ molecules across the nanocomposite and highly reproducible SERS spectra. Limits of detection of 3 nM and 11 nM for CBZ and ATZ, respectively, were attained. Tests with additional analytes (melamine, 2,4-dichloroaniline, 4-chloroaniline, 3-bromoaniline, and 3-nitroaniline) further illustrate that the AuNP/BC platform provides reproducible analyte detection and quantification while avoiding the uncontrolled aggregation and flocculation of AuNPs that often hinder low pH detection. PMID:26658696

pH-Triggered Molecular Alignment for Reproducible SERS Detection via an AuNP/Nanocellulose Platform

NASA Astrophysics Data System (ADS)

Wei, Haoran; Vikesland, Peter J.

2015-12-01

The low affinity of neutral and hydrophobic molecules towards noble metal surfaces hinders their detection by surface-enhanced Raman spectroscopy (SERS). Herein, we present a method to enhance gold nanoparticle (AuNP) surface affinity by lowering the suspension pH below the analyte pKa. We developed an AuNP/bacterial cellulose (BC) nanocomposite platform and applied it to two common pollutants, carbamazepine (CBZ) and atrazine (ATZ) with pKa values of 2.3 and 1.7, respectively. Simple mixing of the analytes with AuNP/BC at pH < pKa resulted in consistent electrostatic alignment of the CBZ and ATZ molecules across the nanocomposite and highly reproducible SERS spectra. Limits of detection of 3 nM and 11 nM for CBZ and ATZ, respectively, were attained. Tests with additional analytes (melamine, 2,4-dichloroaniline, 4-chloroaniline, 3-bromoaniline, and 3-nitroaniline) further illustrate that the AuNP/BC platform provides reproducible analyte detection and quantification while avoiding the uncontrolled aggregation and flocculation of AuNPs that often hinder low pH detection.

Surface charges promote nonspecific nanoparticle adhesion to stiffer membranes

NASA Astrophysics Data System (ADS)

Sinha, Shayandev; Jing, Haoyuan; Sachar, Harnoor Singh; Das, Siddhartha

2018-04-01

This letter establishes the manner in which the electric double layer induced by the surface charges of the plasma membrane (PM) enhances the nonspecific adhesion (NSA) of a metal nanoparticle (NP) to stiffer PMs (i.e., PMs with larger bending moduli). The NSA is characterized by the physical attachment of the NP to the membrane and occurs when the decrease in the surface energy (or any other mechanism) associated with the attachment process provides the energy for bending the membrane. Such an attachment does not involve receptor-ligand interactions that characterize the specific membrane-NP adhesion. Here, we demonstrate that a significant decrease in the electrostatic energy caused by the NP-attachment-induced destruction of the charged-membrane-electrolyte interface is responsible for providing the additional energy needed for bending the membrane during the NP adhesion to stiffer membranes. A smaller salt concentration and a larger membrane charge density augment this effect, which can help to design drug delivery to cells with stiffer membranes due to pathological conditions, fabricate NPs with biomimetic cholesterol-rich lipid bilayer encapsulation, etc.

QED induced redshift and anomalous microwave emission from dust

NASA Astrophysics Data System (ADS)

Prevenslik, Thomas V.

2015-08-01

The Planck satellite imaging of CMB polarizations at 353 GHz extrapolated to 160 GHz suggested the AME was caused by dust and not as a relic of gravity waves from Universe expansion. AME stands for anomalous microwave emisssion. Similarly, dust has also been implicated in questioning Universe expansion by exaggerating Hubble redshift measurements. In this regard, QED induced EM radiation in dust NPs may be the commonality by which an expanding Universe may be assessed. QED stands for quantum electrodynamics, EM for electromagnetic, and NPs for nanoparticles. QED radiation is a consequence of QM that denies the atoms in NPs under TIR confinement the heat capacity to allow increases in NP temperature upon absorbing galaxy light. QM stands for quantum mechanics and TIR for total internal reflection.In this paper, the only galaxy light considered are single Lyα photons absorbed in spherical dust NPs. Since NPs have high surface to volume ratios, an absorbed Lyα photon is induced by QED to be totally confined by TIR to the NP surface. Hence, the TIR wavelength λ of the QED photon moving at velocity c/n in the NP surface is λ = 2πa, where c is the speed of light, and n and a are the refractive index and radius of the NP. The boundary between QED induced spinning and redshift depends on the NP material. For amorphous silicate, small NPs with a < 0.040 microns conserve the Lyα photon energy by NP spinning; whereas, the larger NPs having a > 0.040 microns redshift the Lyα photon to produce VIS and near IR galaxy light.Since the TIR mode is tangential to the surface of the NP, the Lyα photon produces circularly polarized light during absorption thereby exerting a momentary torque on the NP. Conserving the Lyα photon energy hc/λ* with the rotational energy ½ Jω2 of the NP gives the spin ω = √ (2 hc/Jλ*). Here, h is Planck’s constant, λ* the Lyα wavelength, J the NP rotational moment of inertia, J = 2 ma2/5, m the NP mass, m = 4πρa3/3, and ρ the NP density. Hence, the spin rate ω for amorphous silicate NPs having radii 0.001 < a < 0.04 microns suggests AME from 0.1 to 860 GHz as well as redshift produced in dust may be used to assess Universe expansion.

Multi-functionality Redefined with Colloidal Carotene Carbon Nanoparticles for Synchronized Chemical Imaging, Enriched Cellular Uptake and Therapy.

PubMed

Misra, Santosh K; Mukherjee, Prabuddha; Chang, Huei-Huei; Tiwari, Saumya; Gryka, Mark; Bhargava, Rohit; Pan, Dipanjan

2016-07-11

Typically, multiplexing high nanoparticle uptake, imaging, and therapy requires careful integration of three different functions of a multiscale molecular-particle assembly. Here, we present a simpler approach to multiplexing by utilizing one component of the system for multiple functions. Specifically, we successfully synthesized and characterized colloidal carotene carbon nanoparticle (C(3)-NP), in which a single functional molecule served a threefold purpose. First, the presence of carotene moieties promoted the passage of the particle through the cell membrane and into the cells. Second, the ligand acted as a potent detrimental moiety for cancer cells and, finally, the ligands produced optical contrast for robust microscopic detection in complex cellular environments. In comparative tests, C(3)-NP were found to provide effective intracellular delivery that enables both robust detection at cellular and tissue level and presents significant therapeutic potential without altering the mechanism of intracellular action of β-carotene. Surface coating of C(3) with phospholipid was used to generate C(3)-Lipocoat nanoparticles with further improved function and biocompatibility, paving the path to eventual in vivo studies.

Multi-functionality Redefined with Colloidal Carotene Carbon Nanoparticles for Synchronized Chemical Imaging, Enriched Cellular Uptake and Therapy

PubMed Central

Misra, Santosh K.; Mukherjee, Prabuddha; Chang, Huei-Huei; Tiwari, Saumya; Gryka, Mark; Bhargava, Rohit; Pan, Dipanjan

2016-01-01

Typically, multiplexing high nanoparticle uptake, imaging, and therapy requires careful integration of three different functions of a multiscale molecular-particle assembly. Here, we present a simpler approach to multiplexing by utilizing one component of the system for multiple functions. Specifically, we successfully synthesized and characterized colloidal carotene carbon nanoparticle (C3-NP), in which a single functional molecule served a threefold purpose. First, the presence of carotene moieties promoted the passage of the particle through the cell membrane and into the cells. Second, the ligand acted as a potent detrimental moiety for cancer cells and, finally, the ligands produced optical contrast for robust microscopic detection in complex cellular environments. In comparative tests, C3-NP were found to provide effective intracellular delivery that enables both robust detection at cellular and tissue level and presents significant therapeutic potential without altering the mechanism of intracellular action of β-carotene. Surface coating of C3 with phospholipid was used to generate C3-Lipocoat nanoparticles with further improved function and biocompatibility, paving the path to eventual in vivo studies. PMID:27405011

Multi-functionality Redefined with Colloidal Carotene Carbon Nanoparticles for Synchronized Chemical Imaging, Enriched Cellular Uptake and Therapy

NASA Astrophysics Data System (ADS)

Misra, Santosh K.; Mukherjee, Prabuddha; Chang, Huei-Huei; Tiwari, Saumya; Gryka, Mark; Bhargava, Rohit; Pan, Dipanjan

2016-07-01

Typically, multiplexing high nanoparticle uptake, imaging, and therapy requires careful integration of three different functions of a multiscale molecular-particle assembly. Here, we present a simpler approach to multiplexing by utilizing one component of the system for multiple functions. Specifically, we successfully synthesized and characterized colloidal carotene carbon nanoparticle (C3-NP), in which a single functional molecule served a threefold purpose. First, the presence of carotene moieties promoted the passage of the particle through the cell membrane and into the cells. Second, the ligand acted as a potent detrimental moiety for cancer cells and, finally, the ligands produced optical contrast for robust microscopic detection in complex cellular environments. In comparative tests, C3-NP were found to provide effective intracellular delivery that enables both robust detection at cellular and tissue level and presents significant therapeutic potential without altering the mechanism of intracellular action of β-carotene. Surface coating of C3 with phospholipid was used to generate C3-Lipocoat nanoparticles with further improved function and biocompatibility, paving the path to eventual in vivo studies.

Biodistribution of indocyanine green-loaded nanoparticles with surface modifications of PEG and folic acid.

PubMed

Ma, Ying; Sadoqi, Mostafa; Shao, Jun

2012-10-15

To establish the biodistribution profile of the PLGA nanoparticles with dual surface modifications of PEG and folic acid (FA) in mice xenografted with MDA-MB-231 human breast cancer cells with high expression of folate receptor (FR); and to illustrate that the modified nanoparticles can target the loaded indocyanine green (ICG) to the tumor with high FR expression. ICG-loaded nanoparticles were prepared with PLGA (non-modified nanoparticles, NM-NP) or mPEG-PLGA and FA-PLGA (dual modified nanoparticles, DM-NP). Biodistribution of the ICG-loaded nanoparticles (1.25 mg/kg) after i.v. injection was investigated on athymic mice transplanted with MDA-MB-231 tumor. ICG concentration in plasma from the DM-NP group was significantly (p<0.05) higher than the NM-NP group from 90 min to the end of the study (12 h). After 4 h, the drug concentration in the tumor tissue from the DM-NP started to be significantly (p<0.05) higher than the NM-NP until 12 h. Compared to the NM-NP, the DM-NP increased the AUC(0-12 h) in plasma by 245% and the AUC(0-12 h) in tumor by 194%, while decreased the AUC(0-12 h) in liver by 13%. The accumulation of DM-NP into the tumor was significantly higher than NM-NP due to the long circulation and FR-mediated uptake. Copyright © 2012 Elsevier B.V. All rights reserved.

Vesicular gold assemblies based on host-guest inclusion and its controllable release of doxorubicin

NASA Astrophysics Data System (ADS)

Ha, Wei; Kang, Yang; Peng, Shu-Lin; Ding, Li-Sheng; Zhang, Sheng; Li, Bang-Jing

2013-12-01

We have developed a kind of gold nanoparticle (AuNP) in which polyethylene glycol (PEG) and poly(N-isopropylacrylamide) (PNIPAM) are attached on the surface of a gold nanocrystal through the host-guest inclusion between adamantane groups (ADA) and β-cyclodextrin (β-CD). The resulting AuNPs become amphiphilic in water above body temperature and self-assemble into vesicles. It is found that these vesicles can load doxorubicin (Dox) effectively. With a decrease in temperature, the PNIPAM shifted from hydrophobic to hydrophilic, causing Au vesicles to disassemble into stable small AuNPs, triggering the release of Dox. These hybrid vesicles, combining polymer functionality with the intriguing properties of AuNPs, can first release free Dox and AuNP/Dox at a site of a tumor through the application of either simple ice packs or deeply penetrating cryoprobes, then the AuNP/Dox can be taken in by tumor cells and destroy them like miniature munitions. Furthermore, these vesicles showed other therapeutic possibilities due to the presence of gold. We believe that the development of such multi-functional vesicles will provide new and therapeutically useful means for medical applications.

Inherited biallelic CSF3R mutations in severe congenital neutropenia.

PubMed

Triot, Alexa; Järvinen, Päivi M; Arostegui, Juan I; Murugan, Dhaarini; Kohistani, Naschla; Dapena Díaz, José Luis; Racek, Tomas; Puchałka, Jacek; Gertz, E Michael; Schäffer, Alejandro A; Kotlarz, Daniel; Pfeifer, Dietmar; Díaz de Heredia Rubio, Cristina; Ozdemir, Mehmet Akif; Patiroglu, Turkan; Karakukcu, Musa; Sánchez de Toledo Codina, José; Yagüe, Jordi; Touw, Ivo P; Unal, Ekrem; Klein, Christoph

2014-06-12

Severe congenital neutropenia (SCN) is characterized by low numbers of peripheral neutrophil granulocytes and a predisposition to life-threatening bacterial infections. We describe a novel genetic SCN type in 2 unrelated families associated with recessively inherited loss-of-function mutations in CSF3R, encoding the granulocyte colony-stimulating factor (G-CSF) receptor. Family A, with 3 affected children, carried a homozygous missense mutation (NM_000760.3:c.922C>T, NP_000751.1:p.Arg308Cys), which resulted in perturbed N-glycosylation and aberrant localization to the cell surface. Family B, with 1 affected infant, carried compound heterozygous deletions provoking frameshifts and premature stop codons (NM_000760.3:c.948_963del, NP_000751.1:p.Gly316fsTer322 and NM_000760.3:c.1245del, NP_000751.1:p.Gly415fsTer432). Despite peripheral SCN, all patients had morphologic evidence of full myeloid cell maturation in bone marrow. None of the patients responded to treatment with recombinant human G-CSF. Our study highlights the genetic and morphologic SCN variability and provides evidence both for functional importance and redundancy of G-CSF receptor-mediated signaling in human granulopoiesis. © 2014 by The American Society of Hematology.

Inherited biallelic CSF3R mutations in severe congenital neutropenia

PubMed Central

Triot, Alexa; Järvinen, Päivi M.; Arostegui, Juan I.; Murugan, Dhaarini; Kohistani, Naschla; Dapena Díaz, José Luis; Racek, Tomas; Puchałka, Jacek; Gertz, E. Michael; Schäffer, Alejandro A.; Kotlarz, Daniel; Pfeifer, Dietmar; Díaz de Heredia Rubio, Cristina; Ozdemir, Mehmet Akif; Patiroglu, Turkan; Karakukcu, Musa; Sánchez de Toledo Codina, José; Yagüe, Jordi; Touw, Ivo P.; Unal, Ekrem

2014-01-01

Severe congenital neutropenia (SCN) is characterized by low numbers of peripheral neutrophil granulocytes and a predisposition to life-threatening bacterial infections. We describe a novel genetic SCN type in 2 unrelated families associated with recessively inherited loss-of-function mutations in CSF3R, encoding the granulocyte colony-stimulating factor (G-CSF) receptor. Family A, with 3 affected children, carried a homozygous missense mutation (NM_000760.3:c.922C>T, NP_000751.1:p.Arg308Cys), which resulted in perturbed N-glycosylation and aberrant localization to the cell surface. Family B, with 1 affected infant, carried compound heterozygous deletions provoking frameshifts and premature stop codons (NM_000760.3:c.948_963del, NP_000751.1:p.Gly316fsTer322 and NM_000760.3:c.1245del, NP_000751.1:p.Gly415fsTer432). Despite peripheral SCN, all patients had morphologic evidence of full myeloid cell maturation in bone marrow. None of the patients responded to treatment with recombinant human G-CSF. Our study highlights the genetic and morphologic SCN variability and provides evidence both for functional importance and redundancy of G-CSF receptor-mediated signaling in human granulopoiesis. PMID:24753537

Ultrasensitive electroanalytical tool for detecting, sizing, and evaluating the catalytic activity of platinum nanoparticles.

PubMed

Dasari, Radhika; Robinson, Donald A; Stevenson, Keith J

2013-01-16

Here we describe a very simple, reliable, low-cost electrochemical approach to detect single nanoparticles (NPs) and evaluate NP size distributions and catalytic activity in a fast and reproducible manner. Single NPs are detected through an increase in current caused by electrocatalytic oxidation of N(2)H(4) at the surface of the NP when it contacts a Hg-modified Pt ultramicroelectrode (Hg/Pt UME). Once the NP contacts the Hg/Pt UME, Hg poisons the Pt NP, deactivating the N(2)H(4) oxidation reaction. Hence, the current response is a "spike" that decays to the background current level rather than a stepwise "staircase" response as previously described for a Au UME. The use of Hg as an electrode material has several quantitative advantages including suppression of the background current by 2 orders of magnitude over a Au UME, increased signal-to-noise ratio for detection of individual collisions, precise integration of current transients to determine charge passed and NP size, reduction of surface-induced NP aggregation and electrode fouling processes, and reproducible and renewable electrodes for routine detection of catalytic NPs. The NP collision frequency was found to scale linearly with the NP concentration (0.016 to 0.024 pM(-1)s(-1)). NP size distributions of 4-24 nm as determined from the current-time transients correlated well with theory and TEM-derived size distributions.

Surface functionalized amorphous nanosilica and microsilica with nanopores as promising tools in biomedicine

NASA Astrophysics Data System (ADS)

Rahman, Ayesha; Seth, Dipankar; Mukhopadhyaya, Sunit K.; Brahmachary, Ratan L.; Ulrichs, Christian; Goswami, Arunava

2009-01-01

Cellular interactions with engineered nanoparticles (NPs) are dependent on many properties, inherent to the nanoparticle (viz. size, shape, surface characteristics, degradation, agglomeration/dispersal, and charge, etc.). Modification of the surface reactivity via surface functionalization of the nanoparticles to be targeted seems to be important. Utilization of different surface functionalization methods of nanoparticles is an emerging field of basic and applied nanotechnology. It is well known that many disease-causing organisms induce host lipids and if deprived, their growth is inhibited in vivo. Amorphous nanosilica (ANS) and amorphous microsilica with nanopores (AMS) were prepared by a combination of wet chemistry and high-energy ball milling. Lipophilic moieties were attached to both ANS and AMS via chemical surface functionalization method. Lipophilic ANS and AMS were found to inhibit the growth of Bombyx mori nuclear polyhedrosis virus (BmNPV) and chicken malarial parasites via absorption of silkworm hemolymph and chicken serum lipids/lipoproteins, respectively, in vivo. Therefore, intelligent surface functionalization of NP is an important concept, and its application in curing chicken malaria and BmNPV is presented here. Surface functionalization method reported in this paper might serve as a valuable technology for treating many diseases where pathogens induce host lipid.

Gold nanoparticle aerosols for rodent inhalation and translocation studies

NASA Astrophysics Data System (ADS)

Möller, Winfried; Gibson, Neil; Geiser, Marianne; Pokhrel, Suman; Wenk, Alexander; Takenaka, Shinji; Schmid, Otmar; Bulgheroni, Antonio; Simonelli, Federica; Kozempel, Jan; Holzwarth, Uwe; Wigge, Christoph; Eigeldinger-Berthou, Sylvie; Mädler, Lutz; Kreyling, Wolfgang G.

2013-04-01

The intensive use of nano-sized particles in many different applications necessitates studies on their risk assessment as there are still open questions on their safe handling and utilization. For reliable risk assessment, the interaction of nanoparticles (NP) with biological systems after various routes of exposure needs to be investigated using well-characterized NP. We report here on the generation of gold-NP (Au-NP) aerosols for inhalation studies with the spark ignition technique, and their characterization in terms of chemical composition, physical structure, morphology, and specific surface area, and on interaction with lung tissues and lung cells after 1 h inhalation by mice. The originally generated agglomerated Au-NP were converted into compact spherical Au-NP by thermal annealing at 600 °C, providing particles of similar mass, but different size and specific surface area. Since there are currently no translocation data available on inhaled Au-NP in the 10-50 nm diameter range, the emphasis was to generate NP as small as 20 nm for inhalation in rodents. For anticipated in vivo systemic translocation and dosimetry analyses, radiolabeled Au-NP were created by proton irradiating the gold electrodes of the spark generator, thus forming gamma ray emitting 195Au with 186 days half-life, allowing long-term biokinetic studies. The dissolution rate of 195Au from the NP was below detection limits. The highly concentrated, polydisperse Au-NP aerosol (1-2 × 107 NP/cm3) proved to be constant over several hours in terms of its count median mobility diameter, its geometric standard deviation and number concentration. After collection on filters particles can be re-suspended and used for instillation or ingestion studies.

Study on surface-enhanced Raman scattering efficiency of Ag core-Au shell bimetallic nanoparticles

NASA Astrophysics Data System (ADS)

Dong, Xiao; Gu, Huaimin; Kang, Jian; Yuan, Xiaojuan

2009-08-01

In this article, the relationship between the states of Ag core-Au shell (core-shell) nanoparticles (NP) and the intensity of Raman scattering of analytes dissolved in the water and adsorbed on the NP was studied. The core-shell NP were synthesised by coating Au layers over Ag seeds by the method of "seed-growth". To highlight the advantage of the core-shell NP, Ag colloid and Au colloid were chosen for contrasting. The analyte that were chosen for this testing were methylene blue (MB) for the reason that MB has very strong signal in surface-enhanced Raman scattering (SERS). The SERS activity of optimalizing states of Ag and Au colloids were compared with that of core-shell NP when MB was used as analyte. In this study, sodium chloride, sodium sulfate and sodium nitrate were used as aggregating agents for Ag, Au colloids and core-shell NP, because anions have a strong influence on the SERS efficiency and the stability of colloids. The results indicate that core-shell NP can obviously enhance the SERS of MB. The aim of this study is to prove that compared with the metal colloid, the core-shell NP is a high efficiency SERS active substrate.

Amino acid substitutions affecting aspartic acid 605 and valine 606 decrease the interaction strength between the influenza virus RNA polymerase PB2 '627' domain and the viral nucleoprotein.

PubMed

Hsia, Ho-Pan; Yang, Yin-Hua; Szeto, Wun-Chung; Nilsson, Benjamin E; Lo, Chun-Yeung; Ng, Andy Ka-Leung; Fodor, Ervin; Shaw, Pang-Chui

2018-01-01

The influenza virus RNA genome is transcribed and replicated in the context of the viral ribonucleoprotein (vRNP) complex by the viral RNA polymerase. The nucleoprotein (NP) is the structural component of the vRNP providing a scaffold for the viral RNA. In the vRNP as well as during transcription and replication the viral polymerase interacts with NP but it is unclear which parts of the polymerase and NP mediate these interactions. Previously the C-terminal '627' domain (amino acids 538-693) of PB2 was shown to interact with NP. Here we report that a fragment encompassing amino acids 146-185 of NP is sufficient to mediate this interaction. Using NMR chemical shift perturbation assays we show that amino acid region 601 to 607 of the PB2 '627' domain interacts with this fragment of NP. Substitutions of these PB2 amino acids resulted in diminished RNP activity and surface plasmon resonance assays showed that amino acids D605 was essential for the interaction with NP and V606 may also play a partial role in the interaction. Collectively these results reveal a possible interaction surface between NP and the PB2 subunit of the RNA polymerase complex.

Plasmon Ruler with Ångstrom Length Resolution

PubMed Central

Hill, Ryan T.; Mock, Jack J.; Hucknall, Angus; Wolter, Scott D.; Jokerst, Nan M.; Smith, David R.; Chilkoti, Ashutosh

2012-01-01

We demonstrate a plasmon nanoruler using a coupled film-nanoparticle (film-NP) format that is well suited for investigating the sensitivity extremes of plasmonic coupling. Because it is relatively straightforward to functionalize bulk, surface plasmon supporting films such as gold, we are able to precisely control plasmonic gap dimensions by creating ultra-thin molecular spacer layers on the gold films, on top of which we immobilize plasmon resonant nanoparticles (NPs). Each immobilized NP becomes coupled to the underlying film and functions as a plasmon nanoruler, exhibiting a distance-dependent resonance red-shift in its peak plasmon wavelength as it approaches the film. Due to the uniformity of response from the film-NPs to separation distance, we are able to use extinction and scattering measurements from ensembles of film-NPs to characterize the coupling effect over a series of very short separation distances – ranging from 5 – 20 Å – and combine these measurements with similar data from larger separation distances extending out to 27 nm. We find that the film-NP plasmon nanoruler is extremely sensitive at very short film-NP separation distances, yielding spectral shifts as large as 5 nm for every 1 Å change in separation distance. The film-NP coupling at extremely small spacings is so uniform and reliable that we are able to usefully probe gap dimensions where the classical Drude model of the conducting electrons in the metals is no longer descriptive; for gap sizes smaller than a few nanometers, either quantum or semi-classical models of the carrier response must be employed to predict the observed wavelength shifts. We find that, despite the limitations, large field enhancements and extreme sensitivity persist down to even the smallest gap sizes. PMID:22966857

Plasmon ruler with angstrom length resolution.

PubMed

Hill, Ryan T; Mock, Jack J; Hucknall, Angus; Wolter, Scott D; Jokerst, Nan M; Smith, David R; Chilkoti, Ashutosh

2012-10-23

We demonstrate a plasmon nanoruler using a coupled film nanoparticle (film-NP) format that is well-suited for investigating the sensitivity extremes of plasmonic coupling. Because it is relatively straightforward to functionalize bulk surface plasmon supporting films, such as gold, we are able to precisely control plasmonic gap dimensions by creating ultrathin molecular spacer layers on the gold films, on top of which we immobilize plasmon resonant nanoparticles (NPs). Each immobilized NP becomes coupled to the underlying film and functions as a plasmon nanoruler, exhibiting a distance-dependent resonance red shift in its peak plasmon wavelength as it approaches the film. Due to the uniformity of response from the film-NPs to separation distance, we are able to use extinction and scattering measurements from ensembles of film-NPs to characterize the coupling effect over a series of very short separation distances-ranging from 5 to 20 Å-and combine these measurements with similar data from larger separation distances extending out to 27 nm. We find that the film-NP plasmon nanoruler is extremely sensitive at very short film-NP separation distances, yielding spectral shifts as large as 5 nm for every 1 Å change in separation distance. The film-NP coupling at extremely small spacings is so uniform and reliable that we are able to usefully probe gap dimensions where the classical Drude model of the conducting electrons in the metals is no longer descriptive; for gap sizes smaller than a few nanometers, either quantum or semiclassical models of the carrier response must be employed to predict the observed wavelength shifts. We find that, despite the limitations, large field enhancements and extreme sensitivity persist down to even the smallest gap sizes.

Biocorrosion of TiO2 nanoparticle coating of Ti-6Al-4V in DMEM under specific in vitro conditions

NASA Astrophysics Data System (ADS)

Höhn, Sarah; Virtanen, Sannakaisa

2015-02-01

A TiO2 nanoparticle coating was prepared on a biomedical Ti-6Al-4V alloy using "spin-coating" technique with a colloidal suspension of TiO2 nanopowders with the aim to optimize the surface morphology (e.g., roughness) for improved biocompatibility. The influence of a TiO2 nanoparticle (NP) coating on the corrosion behavior, metal ion release, and biomimetic apatite formation was studied in DMEM, at 37.5 °C with a continuous supply of 5% CO2. Electrochemical impedance spectroscopy measurements indicate a formation of a new layer on the surface of the NP-coated sample upon 28 days immersion in DMEM. Scanning electron microscopy (SEM) and X-ray spectroscopy confirm that the surface of the NP-coated Ti-6Al-4V shows a complete coverage by a Ca-phosphate layer in contrast to the non-coated Ti-6Al-4V alloy. Hence, the TiO2-NP coating strongly enhances biomimetic apatite formation on the alloy surface. In addition, the TiO2-NP coating can efficiently reduce Al-release from the alloy, for which the bare Ti-6Al-4V alloy is significant for at least 28 days of immersion in DMEM.

The energy blocker inside the power house: Mitochondria targeted delivery of 3-bromopyruvate.

PubMed

Marrache, Sean; Dhar, Shanta

2015-03-01

A key hallmark of many aggressive cancers is accelerated glucose metabolism. The enzymes that catalyze the first step of glucose metabolism are hexokinases. High levels of hexokinase 2 (HK2) are found in cancer cells, but only in a limited number of normal tissues. Metabolic reprogramming of cancer cells using the energy blocker, 3-bromopyruvate (3-BP) that inhibits HK2 has the potential to provide tumor-specific anticancer agents. However, the unique structural and functional characteristics of mitochondria prohibit selective subcellular targeting of 3-BP to modulate the function of this organelle for therapeutic gain. A mitochondria targeted gold nanoparticle (T-3-BP-AuNP) decorated with 3-BP and delocalized lipophilic triphenylphosphonium cations to target the mitochondrial membrane potential (Δ ψ m ) was developed for delivery of 3-BP to cancer cell mitochondria by taking advantage of higher Δ ψ m in cancer cells compared to normal cells. In vitro studies demonstrated enhanced anticancer activity of T-3-BP-AuNPs compared to the non-targeted construct NT-3-BP-AuNP or free 3-BP. The anticancer activity of T-3-BP-AuNP was further enhanced upon laser irradiation by exciting the surface plasmon resonance band of AuNP and thereby utilizing a combination of 3-BP chemotherapeutic and AuNP photothermal effects. The less toxic behavior of T-3-BPNPs in normal mesenchymal stem cells indicated that these NPs preferentially kill cancer cells. T-3-BP-AuNPs showed enhanced ability to modulate cancer cell metabolism by inhibiting glycolysis as well as demolishing mitochondrial oxidative phosphorylation. Our findings demonstrated that concerted chemo-photothermal treatment of glycolytic cancer cells with a single NP capable of targeting mitochondria mediating simultaneous release of a glycolytic inhibitor and photothermal ablation may have promise as a new anticancer therapy.

A smart approach to add antibacterial functionality to cellulosic pigment prints.

PubMed

Ibrahim, N A; Eid, B M; Elmaaty, T M Abou; El-Aziz, E Abd

2013-04-15

This study was devoted to enhancing the antibacterial functionality of pigment printed cotton, linen and viscose fabrics. Ag-NP's/PVP colloid, triclosan derivatives, chitosan or choline chloride was successfully incorporated into the pigment paste followed by printing and microwave curing to impart antibacterial activity to the cellulosic prints. Results obtained demonstrate that the modified pigment prints exhibit a remarkable antibacterial activity against the G+ve (Staphylococcus aureus) and G-ve (Escherichia coli) bacteria with a noticeable durability after 20 washing cycles without adversely affecting the printing and softness properties. The extent of printability and functionality of the nominated substrates are significantly governed by the type of: bio-active ingredient, binder, pigment and substrate. TEM, SEM and EDX analysis confirmed the formation of Ag-NP's/PVP colloid, of particle size range 7-14 nm, deposition of cross-linked-binder film onto the modified pigment prints, and the existence of elementary Ag and Si loaded onto fabrics surface, respectively. Copyright © 2013 Elsevier Ltd. All rights reserved.

Biodistribution of arctigenin-loaded nanoparticles designed for multimodal imaging.

PubMed

Cui, Qingxin; Hou, Yuanyuan; Wang, Yanan; Li, Xu; Liu, Yang; Ma, Xiaoyao; Wang, Zengyong; Wang, Weiya; Tao, Jin; Wang, Qian; Jiang, Min; Chen, Dongyan; Feng, Xizeng; Bai, Gang

2017-04-07

Tracking targets of natural products is one of the most challenging issues in fields ranging from pharmacognosy to biomedicine. It is widely recognized that the biocompatible nanoparticle (NP) could function as a "key" that opens the target "lock". We report a functionalized poly-lysine NP technique that can monitor the target protein of arctigenin (ATG) in vivo non-invasively. The NPs were synthesized, and their morphologies and surface chemical properties were characterized by transmission electron microscopy (TEM), laser particle size analysis and atomic force microscopy (AFM). In addition, we studied the localization of ATG at the level of the cell and the whole animal (zebrafish and mice). We demonstrated that fluorescent NPs could be ideal carriers in the development of a feasible method for target identification. The distributions of the target proteins were found to be consistent with the pharmacological action of ATG at the cellular and whole-organism levels. The results indicated that functionalized poly-lysine NPs could be valuable in the multimodal imaging of arctigenin.

Concentration Dependence of Gold Nanoparticles for Fluorescence Enhancement

NASA Astrophysics Data System (ADS)

Solomon, Joel; Wittmershaus, Bruce

Noble metal nanoparticles possess a unique property known as surface plasmon resonance in which the conduction electrons oscillate due to incoming light, dramatically increasing their absorption and scattering of light. The oscillating electrons create a varying electric field that can affect nearby molecules. The fluorescence and photostability of fluorophores can be enhanced significantly when they are near plasmonic nanoparticles. This effect is called metal enhanced fluorescence (MEF). MEF from two fluorescence organic dyes, Lucifer Yellow CH and Riboflavin, was measured with different concentrations of 50-nm colloidal gold nanoparticles (Au-NP). The concentration range of Au-NP was varied from 2.5 to 250 pM. To maximize the interaction, the dyes were chosen so their emission spectra had considerable overlap with the absorption spectra of the Au-NP, which is common in MEF studies. If the dye molecules are too close to the surface of Au-NP, fluorescence quenching can occur instead of MEF. To try to observe this difference, silica-coated Au-NP were compared to citrate-based Au-NP; however, fluorescence quenching was observed with both Au-NP. This material is based upon work supported by the National Science Foundation under Grant Number NSF-ECCS-1306157.

Citrus-Peel-Derived, Nanoporous Carbon Nanosheets Containing Redox-Active Heteroatoms for Sodium-Ion Storage.

PubMed

Kim, Na Rae; Yun, Young Soo; Song, Min Yeong; Hong, Sung Ju; Kang, Minjee; Leal, Cecilia; Park, Yung Woo; Jin, Hyoung-Joon

2016-02-10

Advanced design of nanostructured functional carbon materials for use in sustainable energy storage systems suffers from complex fabrication procedures and the use of special methods and/or expensive precursors, limiting their practical applications. In this study, nanoporous carbon nanosheets (NP-CNSs) containing numerous redox-active heteroatoms (C/O and C/N ratios of 5.5 and 34.3, respectively) were fabricated from citrus peels by simply heating the peels in the presence of potassium ions. The NP-CNSs had a 2D-like morphology with a high aspect ratio of >100, high specific surface area of 1167 m(2) g(-1), and a large amount of nanopores between 1 and 5 nm. The NP-CNSs also had an electrical conductivity of 2.6 × 10(1) s cm(-1), which is approximately 50 times higher than that of reduced graphene oxide. These unique material properties resulted in superior electrochemical performance with a high specific capacity of 140 mAh g(-1) in the cathodic potential range. In addition, symmetric full-cell devices based on the NP-CNSs showed excellent cyclic performance over 100,000 repetitive cycles.

Gold surface supported spherical liposome-gold nano-particle nano-composite for label free DNA sensing.

PubMed

Bhuvana, M; Narayanan, J Shankara; Dharuman, V; Teng, W; Hahn, J H; Jayakumar, K

2013-03-15

Immobilization of 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) liposome-gold nano-particle (DOPE-AuNP) nano-composite covalently on 3-mercaptopropionic acid (MPA) on gold surface is demonstrated for the first time for electrochemical label free DNA sensing. Spherical nature of the DOPE on the MPA monolayer is confirmed by the appearance of sigmoidal voltammetric profile, characteristic behavior of linear diffusion, for the MPA-DOPE in presence of [Fe(CN)(6)](3-/4-) and [Ru(NH(3))(6)](3+) redox probes. The DOPE liposome vesicle fusion is prevented by electroless deposition of AuNP on the hydrophilic amine head groups of the DOPE. Immobilization of single stranded DNA (ssDNA) is made via simple gold-thiol linkage for DNA hybridization sensing in the presence of [Fe(CN)(6)](3-/4-). The sensor discriminates the hybridized (complementary target hybridized), un-hybridized (non-complementary target hybridized) and single base mismatch target hybridized surfaces sensitively and selectively without signal amplification. The lowest target DNA concentration detected is 0.1×10(-12)M. Cyclic voltammetry (CV), electrochemical impedance (EIS), differential pulse voltammetry (DPV) and quartz crystal microbalance (QCM) techniques are used for DNA sensing on DOPE-AuNP nano-composite. Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Atomic Force Microscopy (AFM), Dynamic Light Scattering (DLS) and Ultraviolet-Visible (UV) spectroscopic techniques are used to understand the interactions between the DOPE, AuNP and ssDNA. The results indicate the presence of an intact and well defined spherical DOPE-AuNP nano-composite on the gold surface. The method could be applied for fabrication of the surface based liposome-AuNP-DNA composite for cell transfection studies at reduced reagents and costs. Copyright © 2012 Elsevier B.V. All rights reserved.

Colloidal behavior of aluminum oxide nanoparticles as affected by pH and natural organic matter.

PubMed

Ghosh, Saikat; Mashayekhi, Hamid; Pan, Bo; Bhowmik, Prasanta; Xing, Baoshan

2008-11-04

The colloidal behavior of aluminum oxide nanoparticles (NPs) was investigated as a function of pH and in the presence of two structurally different humic acids (HAs), Aldrich HA (AHA) and the seventh HA fraction extracted from Amherst peat soil (HA7). Dynamic light scattering (DLS) and atomic force microscopy (AFM) were employed to determine the colloidal behavior of the NPs. Influence of pH and HAs on the surface charges of the NPs was determined. zeta-Potential data clearly showed that the surface charge of the NPs decreased with increasing pH and reached the point of zero charge (ZPC) at pH 7.9. Surface charge of the NPs also decreased with the addition of HAs. The NPs tend to aggregate as the pH of the suspension approaches ZPC, where van der Waals attraction forces dominate over electrostatic repulsion. However, the NP colloidal suspension was stable in the pHs far from ZPC. Colloidal stability was strongly enhanced in the presence of HAs at the pH of ZPC or above it, but in acidic conditions NPs showed strong aggregation in the presence of HAs. AFM imaging revealed the presence of long-chain fractions in HA7, which entangled with the NPs to form large aggregates. The association of HA with the NP surface can be assumed to follow a two-step process, possibly the polar fractions of the HA7 sorbed on the NP surface followed by entanglement with the long-chain fractions. Thus, our study demonstrated that the hydrophobic nature of the HA molecules strongly influenced the aggregation of colloidal NPs, possibly through their conformational behavior in a particular solution condition. Therefore, various organic matter samples will result in different colloidal behavior of NPs, subsequently their environmental fate and transport.

Effects of a large scale nitrogen and phosphorous fertilization on the ecosystem functioning of a Mediterranean tree-grass ecosystem

NASA Astrophysics Data System (ADS)

Migliavacca, Mirco; El Madany, Tarek; Perez-Priego, Oscar; Carrara, Arnaud; Hammer, Tiana; Henkel, Kathin; Kolle, Olaf; Luo, Yunpeng; Moreno, Gerardo; Morris, Kendalynn; Nair, Richard; Schrumpf, Marion; Wutzler, Thomas; Reichstein, Markus

2017-04-01

Recent studies have shown how human induced N/P imbalances affect essential ecosystem processes, and might be particularly important in water-limited ecosystems. In this contribution we will present results from an ecosystem scale nutrient manipulation experiment on a Mediterranean tree-grass ecosystem (Majadas del Tietar, Spain). Specifically, we will show how ecosystem functioning (e.g. light use efficiency, water use efficiency - WUE, albedo) changes as consequence of N and NP fertilization. A cluster of eddy covariance (EC) flux towers has been set up beside a long-term EC site (Control site) to measured high temporal resolution C and water fluxes between the ecosystem and the atmosphere. The sites were selected in a way to have similar pre-treatment conditions. Two out of three EC footprint areas (18 Ha) were fertilized with N and NP at the beginning of 2015 and 2016. To interpret the variations in C and water fluxes measured with the EC systems we monitored spatial and temporal variations in phenology, plant traits, species richness, and tree transpiration by using sap-flow meters, digital repeat photography, as well as soil sampling. The results show a consistent increase ( 15% compared to the Control site) in net ecosystem production (NEP) observed both in the N and the NP treatments. An increase of evapotranspiration (ET) of about 15% and 10% is observed in the N and NP site, respectively, indicating an increase of WUE in the NP treatment. The partitioning of the NEP into its gross components, the gross primary production (GPP) and the total ecosystem respiration (TER), show that the fertilization stimulated more GPP rather than TER, increasing therefore the capability of the ecosystem to act as carbon sink. The effects of fertilization are pronounced in spring and autumn and negligible in summer. This indicates that grass reacted much more than trees to N and NP addition. An increase of greenness and also an earlier green-up of grass in the N and NP sites in autumn after the first rainfall are observed. In particular we observed an enhanced response of NEP and greenness to onset of precipitation in fall for the NP treatment. No systematic differences are observed in summer during the dry-out period. These results suggest that an increase of N availability can have a relevant impact on the studied tree-grass ecosystem. The attempt of compensating the N/P imbalance, by adding P, impacted marginally the C fluxes, while increased the WUE of the ecosystem. Differences in temporal variations of ecosystem level greenness also might indicate an impact of N and NP availability of the temporal variability of surface albedo.

Integrated nanoparticle-biomolecule systems for biosensing and bioelectronics.

PubMed

Willner, Itamar; Baron, Ronan; Willner, Bilha

2007-04-15

The similar dimensions of biomolecules such as enzymes, antibodies or DNA, and metallic or semiconductor nanoparticles (NPs) enable the synthesis of biomolecule-NP hybrid systems where the unique electronic, photonic and catalytic properties of NPs are combined with the specific recognition and biocatalytic properties of biomolecules. The unique functions of biomolecule-NP hybrid systems are discussed with several examples: (i) the electrical contacting of redox enzymes with electrodes is the basis for the development of enzymatic electrodes for amperometric biosensors or biofuel cell elements. The reconstitution of the apo-glucose oxidase or apo-glucose dehydrogenase on flavin adenine dinucleotide (FAD)-functionalized Au NPs (1.4 nm) associated with electrodes, or on pyrroloquinoline quinone (PQQ)-functionalized Au NPs (1.4 nm) associated with electrodes, respectively, yields electrically contacted enzyme electrodes. The aligned, reconstituted enzymes on the electrode surfaces reveal effective electrical contacting, and the glucose oxidase and glucose dehydrogenase reveal turnover rates of 5000 and 11,800 s(-1), respectively. (ii) The photoexcitation of semiconductor nanoparticles yields fluorescence with a wavelength controlled by the size of the NPs. The fluorescence functions of semiconductor NPs are used to develop a fluorescence resonance energy transfer (FRET) assay for nucleic acids, and specifically, for analyzing telomerase activity in cancer cells. CdSe-ZnS NPs are functionalized by a primer recognized by telomerase, and this is elongated by telomerase extracted from HeLa cancer cells in the presence of dNTPs and Texas-red-functionalized dUTP. The dye integrated into the telomers allows the FRET process that is intensified as telomerization proceeds. Also, the photoexcited electron-hole pair generated in semiconductor NPs is used to generate photocurrents in a CdS-DNA hybrid system associated with an electrode. A redox-active intercalator, methylene blue, was incorporated into a CdS-duplex DNA monolayer associated with a Au electrode, and this facilitated the electron transfer between the electrode and the CdS NPs. The direction of the photocurrent was controlled by the oxidation state of the intercalator. (iii) Biocatalysts grow metallic NPs, and the absorbance of the NPs provides a means to assay the biocatalytic transformations. This is exemplified with the glucose oxidase-induced growth of Au NPs and with the tyrosinase-stimulated growth of Au NPs, in the presence of glucose or tyrosine, respectively. The biocatalytic growth of the metallic NPs is used to grow nanowires on surfaces. Glucose oxidase or alkaline phosphatase functionalized with Au NPs (1.4 nm) acted as 'biocatalytic inks' for the synthesis of metallic nanowires. The deposition of the Au NP-modified glucose oxidase, or the Au NP-modified alkaline phosphatase on Si surfaces by dip-pen nanolithography led to biocatalytic templates, that after interaction with glucose/AuCl4- or p-aminophenolphosphate/Ag+, allowed the synthesis of Au nanowires or Ag nanowires, respectively.

Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation

DOE PAGES

Personick, Michelle L.; Zugic, Branko; Biener, Monika M.; ...

2015-05-28

We report a new method for facile and reproducible activation of nanoporous gold (npAu) materials of different forms for the catalytic selective partial oxidation of alcohols under ambient pressure, steady flow conditions. This method, based on the surface cleaning of npAu ingots with ozone to remove carbon documented in ultrahigh vacuum conditions, produces active npAu catalysts from ingots, foils, and shells by flowing an ozone/dioxygen mixture over the catalyst at 150 °C, followed by a temperature ramp from 50 to 150 °C in a flowing stream of 10% methanol and 20% oxygen. With this treatment, all three materials (ingots, foils,more » and shells) can be reproducibly activated, despite potential carbonaceous poisons resulting from their synthesis, and are highly active for the selective oxidation of primary alcohols over prolonged periods of time. The npAu materials activated in this manner exhibit catalytic behavior substantially different from those activated under different conditions previously reported. Once activated in this manner, they can be stored and easily reactivated by flow of reactant gases at 150 °C for a few hours. They possess improved selectivity for the coupling of higher alcohols, such as 1-butanol, and are not active for carbon monoxide oxidation. As a result, this ozone-treated npAu is a functionally new catalytic material.« less

Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Personick, Michelle L.; Zugic, Branko; Biener, Monika M.

We report a new method for facile and reproducible activation of nanoporous gold (npAu) materials of different forms for the catalytic selective partial oxidation of alcohols under ambient pressure, steady flow conditions. This method, based on the surface cleaning of npAu ingots with ozone to remove carbon documented in ultrahigh vacuum conditions, produces active npAu catalysts from ingots, foils, and shells by flowing an ozone/dioxygen mixture over the catalyst at 150 °C, followed by a temperature ramp from 50 to 150 °C in a flowing stream of 10% methanol and 20% oxygen. With this treatment, all three materials (ingots, foils,more » and shells) can be reproducibly activated, despite potential carbonaceous poisons resulting from their synthesis, and are highly active for the selective oxidation of primary alcohols over prolonged periods of time. The npAu materials activated in this manner exhibit catalytic behavior substantially different from those activated under different conditions previously reported. Once activated in this manner, they can be stored and easily reactivated by flow of reactant gases at 150 °C for a few hours. They possess improved selectivity for the coupling of higher alcohols, such as 1-butanol, and are not active for carbon monoxide oxidation. As a result, this ozone-treated npAu is a functionally new catalytic material.« less

Modeling Np and Pu transport with a surface complexation model and spatially variant sorption capacities: Implications for reactive transport modeling and performance assessments of nuclear waste disposal sites

USGS Publications Warehouse

Glynn, P.D.

2003-01-01

One-dimensional (1D) geochemical transport modeling is used to demonstrate the effects of speciation and sorption reactions on the ground-water transport of Np and Pu, two redox-sensitive elements. Earlier 1D simulations (Reardon, 1981) considered the kinetically limited dissolution of calcite and its effect on ion-exchange reactions (involving 90Sr, Ca, Na, Mg and K), and documented the spatial variation of a 90Sr partition coefficient under both transient and steady-state chemical conditions. In contrast, the simulations presented here assume local equilibrium for all reactions, and consider sorption on constant potential, rather than constant charge, surfaces. Reardon's (1981) seminal findings on the spatial and temporal variability of partitioning (of 90Sr) are reexamined and found partially caused by his assumption of a kinetically limited reaction. In the present work, sorption is assumed the predominant retardation process controlling Pu and Np transport, and is simulated using a diffuse-double-layer-surface-complexation (DDLSC) model. Transport simulations consider the infiltration of Np- and Pu-contaminated waters into an initially uncontaminated environment, followed by the cleanup of the resultant contamination with uncontaminated water. Simulations are conducted using different spatial distributions of sorption capacities (with the same total potential sorption capacity, but with different variances and spatial correlation structures). Results obtained differ markedly from those that would be obtained in transport simulations using constant Kd, Langmuir or Freundlich sorption models. When possible, simulation results (breakthrough curves) are fitted to a constant K d advection-dispersion transport model and compared. Functional differences often are great enough that they prevent a meaningful fit of the simulation results with a constant K d (or even a Langmuir or Freundlich) model, even in the case of Np, a weakly sorbed radionuclide under the simulation conditions. Functional behaviors that cannot be fit include concentration trend reversals and radionuclide desorption spikes. Other simulation results are fit successfully but the fitted parameters (Kd and dispersivity) vary significantly depending on simulation conditions (e.g. "infiltration" vs. "cleanup" conditions). Notably, an increase in the variance of the specified sorption capacities results in a marked increase in the dispersion of the radionuclides. The results presented have implications for the simulation of radionuclide migration in performance assessments of nuclear waste-disposal sites, for the future monitoring of those sites, and more generally for modeling contaminant transport in ground-water environments. ?? 2003 Published by Elsevier Science Ltd.

Single-molecule interfacial electron transfer dynamics in solar energy conversion

NASA Astrophysics Data System (ADS)

Dhital, Bharat

This dissertation work investigated the parameters affecting the interfacial electron transfer (ET) dynamics in dye-semiconductor nanoparticles (NPs) system by using single-molecule fluorescence spectroscopy and imaging combined with electrochemistry. The influence of the molecule-substrate electronic coupling, the molecular structure, binding geometry on the surface and the molecule-attachment surface chemistry on interfacial charge transfer processes was studied on zinc porphyrin-TiO2 NP systems. The fluorescence blinking measurement on TiO2 NP demonstrated that electronic coupling regulates dynamics of charge transfer processes at the interface depending on the conformation of molecule on the surface. Moreover, semiconductor surface charge induced electronic coupling of molecule which is electrostatically adsorbed on the semiconductor surface also predominantly alters the ET dynamics. Furthermore, interfacial electric field and electron accepting state density dependent ET dynamics has been dissected in zinc porphyrin-TiO2 NP system by observing the single-molecule fluorescence blinking dynamics and fluorescence lifetime with and without applied bias. The significant difference in fluorescence fluctuation and lifetime suggested the modulation of charge transfer dynamics at the interface with external electric field perturbation. Quasi-continuous distribution of fluorescence intensity with applied negative potential was attributed to the faster charge recombination due to reduced density of electron accepting states. The driving force and electron accepting state density ET dependent dynamics has also been probed in zinc porphyrin-TiO2 NP and zinc porphyrin-indium tin oxide (ITO) systems. Study of a molecule adsorbed on two different semiconductors (ITO and TiO2), with large difference in electron densities and distinct driving forces, allows us to observe the changes in rates of back electron transfer process reflected by the suppressed fluorescence blinking of molecule on ITO surface. Finally, the electric field effect on the interface properties has been probed by using surface-enhanced Raman spectroscopy and supported by density functional theory calculations in alizarin-TiO2 system. The perturbation, created by the external potential, has been observed to cause a shift and/or splitting interfacial bond vibrational mode, typical indicator of the coupling energy changes between alizarin and TiO2. Such splitting provides evidence for electric field-dependent electronic coupling changes that have a significant impact on the interfacial electron transfer dynamics.

Targeted antitumoral dehydrocrotonin nanoparticles with L-ascorbic acid 6-stearate.

PubMed

Frungillo, Lucas; Martins, Dorival; Teixeira, Sérgio; Anazetti, Maristela Conti; Melo, Patrícia da Silva; Durán, Nelson

2009-12-01

Tumoral cells are known to have a higher ascorbic acid uptake than normal cells. Therefore, the aim of this study was to obtain polymeric nanoparticles containing the antitumoral compound trans-dehydrocrotonin (DHC) functionalized with L-ascorbic acid 6-stearate (AAS) to specifically target this system tumoral cells. Nanoparticle suspensions (NP-AAS-DHC) were prepared by the nanoprecipitation method. The systems were characterized for AAS presence by thin-layer chromatography and for drug loading (81-88%) by UV-Vis spectroscopy. To further characterize these systems, in vitro release kinetics, size distribution (100-140 nm) and Zeta potential by photon-correlation spectroscopic method were used. In vitro toxicity against HL60 cells was evaluated by tetrazolium reduction and Trypan blue exclusion assays. Cell death by apoptosis was quantified and characterized by flow cytometry and caspase activity. Zeta potential analyses showed that the system has a negatively charged outer surface and also indicate that AAS is incorporated on the external surface of the nanoparticles. In vitro release kinetics assay showed that DHC loaded in nanoparticles had sustained release behavior. In vitro toxicity assays showed that NP-AAS-DHC suspension was more effective as an antitumoral than free DHC or NP-DHC and increased apoptosis induction by receptor-mediated pathway. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

Monolayer-directed Assembly and Magnetic Properties of FePt Nanoparticles on Patterned Aluminum Oxide

PubMed Central

Yildirim, Oktay; Gang, Tian; Kinge, Sachin; Reinhoudt, David N.; Blank, Dave H.A.; van der Wiel, Wilfred G.; Rijnders, Guus; Huskens, Jurriaan

2010-01-01

FePt nanoparticles (NPs) were assembled on aluminum oxide substrates, and their ferromagnetic properties were studied before and after thermal annealing. For the first time, phosph(on)ates were used as an adsorbate to form self-assembled monolayers (SAMs) on alumina to direct the assembly of NPs onto the surface. The Al2O3 substrates were functionalized with aminobutylphosphonic acid (ABP) or phosphonoundecanoic acid (PNDA) SAMs or with poly(ethyleneimine) (PEI) as a reference. FePt NPs assembled on all of these monolayers, but much less on unmodified Al2O3, which shows that ligand exchange at the NPs is the most likely mechanism of attachment. Proper modification of the Al2O3 surface and controlling the immersion time of the modified Al2O3 substrates into the FePt NP solution resulted in FePt NPs assembly with controlled NP density. Alumina substrates were patterned by microcontact printing using aminobutylphosphonic acid as the ink, allowing local NP assembly. Thermal annealing under reducing conditions (96%N2/4%H2) led to a phase change of the FePt NPs from the disordered FCC phase to the ordered FCT phase. This resulted in ferromagnetic behavior at room temperature. Such a process can potentially be applied in the fabrication of spintronic devices. PMID:20480007

[The effect of substance P on functional proteins in human neutrophil].

PubMed

Yang, Lin; Fa, Xiang-guang

2002-02-01

To explore the effect of substance P (SP) on the functional proteins on plasma membrane of neutrophil (Np). The response of Np to SP was examined by measuring the level of respiratory burst, the activities of ACP and ALP, the fluoroscopy intensity of CR3, CD45 and FM-LP. It was found that SP could increase respiratory burst of Np, decrease the activity of acid phosphatase (ACP), but had no effect on alkaline phosphatase (ALP). SP could also promote the amount of CD45, complement receptor type 3 (CR3) and N-Formyl-Met-Leu-Phe (FMLP) receptors. The results showed that the effects of SP on functional proteins in human Np membrane were universality and diversity. It implied that SP could affect various inflammation responses in Np.

Directed self-assembly of nanogold using a chemically modified nanopatterned surface

NASA Astrophysics Data System (ADS)

Nidetz, Robert; Kim, Jinsang

2012-02-01

Electron-beam lithography (EBL) was used to define an aminosilane nanopatterned surface in order to electrostatically self-assemble gold nanoparticles (Au NPs). The chemically modified nanopatterned surfaces were immersed into a Au NP solution to allow the Au NPs to self-assemble. Equilibrium self-assembly was achieved in only 20 min. The number of Au NPs that self-assembled on an aminosilane dot was controlled by manipulating the diameters of both the Au NPs and the dots. Adding salt to the Au NP solution enabled the Au NPs to self-assemble in greater numbers on the same sized dot. However, the preparation of the Au NP solution containing salt was sensitive to spikes in the salt concentration. These spikes led to aggregation of the Au NPs and non-specific deposition of Au NPs on the substrate. The Au NP patterned surfaces were immersed in a sodium hydroxide solution in order to lift-off the patterned Au NPs, but no lift-off was observed without adequate physical agitation. The van der Waals forces are too strong to allow for lift-off despite the absence of electrostatic forces.

Nanoparticle packing within block copolymer micelles prepared by the interfacial instability method.

PubMed

Nabar, Gauri M; Winter, Jessica O; Wyslouzil, Barbara E

2018-05-02

The interfacial instability method has emerged as a viable approach for encapsulating high concentrations of nanoparticles (NPs) within morphologically diverse micelles. In this method, transient interfacial instabilities at the surface of an emulsion droplet guide self-assembly of block co-polymers and NP encapsulants. Although used by many groups, there are no systematic investigations exploring the relationship between NP properties and micelle morphology. Here, the effect of quantum dot (QD) and superparamagnetic iron oxide NP (SPION) concentration on the shape, size, and surface deformation of initially spherical poly(styrene-b-ethylene oxide) (PS-b-PEO) micelles was examined. Multi-NP encapsulation and uniform dispersion within micelles was obtained even at low NP concentrations. Increasing NP concentration initially resulted in larger numbers of elongated micelles and cylinders with tightly-controlled diameters smaller than those of spherical micelles. Beyond a critical NP concentration, micelle formation was suppressed; the dominant morphology became densely-loaded NP structures that were coated with polymer and exhibited increased polydispersity. Transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) revealed that NPs in densely-loaded structures can be well-ordered, with packing volume fractions of up to 24%. These effects were enhanced in magnetic composites, possibly by dipole interactions. Mechanisms governing phase transitions triggered by NP loading in the interfacial instability process were proposed. The current study helps establish and elucidate the active role played by NPs in directing block copolymer assembly in the interfacial instability process, and provides important guiding principles for the use of this approach in generating NP-loaded block copolymer composites.

High velocity collisions of nanoparticles

NASA Astrophysics Data System (ADS)

Johnson, Donald F.; Mattson, William D.

2017-01-01

Nanoparticles (NPs) are a unique class of material with highly functionalizable surfaces and exciting applications. With a large surface-to-volume ratio and potentially high surface tension, shocked nanoparticles might display unique materials behavior. Using density functional theory, we have simulated high-velocity NP collisions under a variety of conditions. NPs composed of diamond-C, cubic-BN, and diamond-Si were considered with particle sizes up to 3.5 nm diameter. Additional simulations involved NPs that were destabilized by incorporating internal strain. The initial spherical NP structures were carved out of bulk crystals while the NPs with internal strain were constructed as a dense core (compressive strain) encompassed by a thin shell (tensile strain). Both on-axis and off-axis collisions were simulated at 10 km/s relative velocity. The amount of internal strain was artificially increased by creating a dense inner core with bond lengths compressed up to 8%. Collision dynamics, shock propagation, and fragmentation will be analyzed, but the simulation are ongoing and results are not finalized. The effect of material properties, internal strain, and collision velocity will be discussed.

Phospholipid lung surfactant and nanoparticle surface toxicity: Lessons from diesel soots and silicate dusts

NASA Astrophysics Data System (ADS)

Wallace, William E.; Keane, Michael J.; Murray, David K.; Chisholm, William P.; Maynard, Andrew D.; Ong, Tong-man

2007-01-01

Because of their small size, the specific surface areas of nanoparticulate materials (NP), described as particles having at least one dimension smaller than 100 nm, can be large compared with micrometer-sized respirable particles. This high specific surface area or nanostructural surface properties may affect NP toxicity in comparison with micrometer-sized respirable particles of the same overall composition. Respirable particles depositing on the deep lung surfaces of the respiratory bronchioles or alveoli will contact pulmonary surfactants in the surface hypophase. Diesel exhaust ultrafine particles and respirable silicate micrometer-sized insoluble particles can adsorb components of that surfactant onto the particle surfaces, conditioning the particles surfaces and affecting their in vitro expression of cytotoxicity or genotoxicity. Those effects can be particle surface composition-specific. Effects of particle surface conditioning by a primary component of phospholipid pulmonary surfactant, diacyl phosphatidyl choline, are reviewed for in vitro expression of genotoxicity by diesel exhaust particles and of cytotoxicity by respirable quartz and aluminosilicate kaolin clay particles. Those effects suggest methods and cautions for assaying and interpreting NP properties and biological activities.

Loading of chitosan - Nano metal oxide hybrids onto cotton/polyester fabrics to impart permanent and effective multifunctions.

PubMed

Ibrahim, Nabil A; Eid, Basma M; El-Aziz, Eman Abd; Elmaaty, Tarek M Abou; Ramadan, Shaimaa M

2017-12-01

New and durable multifunctional properties of cotton/polyester blended fabrics were developed through loading of chitosan (Cs) and various metal oxide nanoparticles (MONPs) namely ZnO, TiO 2 , and SiO 2 onto fabric surface using citric acid/Sodium hypophosphite for ester-crosslinking and creating new anchoring and binding sites, COOH groups, onto the ester-crosslinked fabrics surface. The surface morphology and the presence of active ingredients (Cs & MONPs) onto selected - coated fabric samples were analyzed by SEM images and confirmed by EDS spectrums. The influence of various finishing formulations on some performance and functional properties such as wettability, antibacterial activity, UV-protection, self-cleaning, resiliency and durability to wash were studied. The obtained results revealed that the extent of improvement in the imparted functional properties is governed by type of loaded-hybrid and follows the decreasing order: Cs-TiO 2 NPs>Cs-ZnONPs>SiO 2 NP s >Cs alone, as well as kind of substrate cotton/polyester (65/35)>cotton/polyester (50/50). Moreover, after 15 washing cycles, the durability of the imparted functional properties of Cs/TiO 2 NP s - loaded substrates marginally decreased indicating the strong fixation of the hybrid components onto the ester-crosslinked substrates. The obtained bioactive multifunctional textiles can be used for producing eco-friendly protective textile materials for numerous applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Antibiofilm surface functionalization of catheters by magnesium fluoride nanoparticles

PubMed Central

Lellouche, Jonathan; Friedman, Alexandra; Lahmi, Roxanne; Gedanken, Aharon; Banin, Ehud

2012-01-01

The ability of bacteria to colonize catheters is a major cause of infection. In the current study, catheters were surface-modified with MgF2 nanoparticles (NPs) using a sonochemical synthesis protocol described previously. The one-step synthesis and coating procedure yielded a homogenous MgF2 NP layer on both the inside and outside of the catheter, as analyzed by high resolution scanning electron microscopy and energy dispersive spectroscopy. The coating thickness varied from approximately 750 nm to 1000 nm on the inner walls and from approximately 450 nm to approximately 580 nm for the outer wall. The coating consisted of spherical MgF2 NPs with an average diameter of approximately 25 nm. These MgF2 NP-modified catheters were investigated for their ability to restrict bacterial biofilm formation. Two bacterial strains most commonly associated with catheter infections, Escherichia coli and Staphylococcus aureus, were cultured in tryptic soy broth, artificial urine and human plasma on the modified catheters. The MgF2 NP-coated catheters were able to significantly reduce bacterial colonization for a period of 1 week compared to the uncoated control. Finally, the potential cytotoxicity of MgF2 NPs was also evaluated using human and mammalian cell lines and no significant reduction in the mitochondrial metabolism was observed. Taken together, our results indicate that the surface modification of catheters with MgF2 NPs can be effective in preventing bacterial colonization and can provide catheters with long-lasting self-sterilizing properties. PMID:22419866

[Clinical analysis of nasal resistance and pulmonary function testing in patients with chronic nasal-sinusitis and nasal polyps].

PubMed

Liao, Hua; Shen, Ying; Wang, Pengjun

2015-05-01

To study the pulmonary function and nasal resistance characteristics of patients with chronic nose-sinusitis and nasal polyps (CRSwNP), to explore the evaluation role of nasal resistance in nasal ventilation function and the effect of endoscopic sinus surgery on pulmonary function in patients with CRSwNP. Fifty CRSwNP patients that met the study criteria were selected . The patients were performed endoscopic surgeries according to Messerklinger surgical procedures under general anesthesia. Extent of surgery was based on preoperative CT showing the range of the lesion of disease and endoscopic findings. Perioperative treatments contained intranasal corticosteroids, cephalosporin or penicillin antibiotics, nasal irrigation and other treatments. Main outcome measures included visual analog scale (VAS), endoscopic Lind-Kennedy scores, nasal resistence, pulmonary function in patientsone week before and after surgery, three months and six months after surgery. Pulmonary function includes forced expiratory volume in one second (FEV1), forced vital capacity FEV1/FVC and peak expiratory flow (PEF). The study found that there were significantly positive correlations among VAS score, Lund-Kennedy score and nasal resistance (P < 0.05) in CRSwNP patients, but there is a significantly negative correlation between VAS score, Lund-Kennedy score, nasal resistance and pulmonary function indexes of FEV1, FVC and PEF (P < 0.05). The VAS score, Lund-Kennedy score and nasal resistance values of CRSwNP patients were decreased significantly after comprehensive treatments with nasal endoscopic operation as the major one, the difference was statistically different (P < 0.05). And the pulmonary function indexs (FEV1, FVC, PEF) were significantly increased after surgery in CRSwNP patients. The nasal resistance can objectively and reliably reflect the degree of nasal congestion and the recovery of nasal function in CRSwNP patients after endoscopic sinus surgery. The detection method of nasal resistance is simple. Functional endoscopic sinus surgery can effectively improve the pulmonary ventilation function in CRSwNP patients, providing some clinical references about the prevention and treatment of CRS related lower respiratory disease.

A spectroscopic study on stability of curcumin as a function of pH in silica nanoformulations, liposome and serum protein

NASA Astrophysics Data System (ADS)

Jain, Beena

2017-02-01

The effect of pH on the stability of curcumin formulated with different carriers has been studied spectroscopically. This was investigated by monitoring the absorption and emission kinetics and fluorescence decay time of four different curcumin formulations suspended in buffer with pH varying from 5 to 8.5. The carriers were organically modified silica NP (SiNP) having 3-amino propyl and/or vinyl groups, liposome and serum protein. The results reveal that stability of curcumin formulated with SiNP functionalized with 3-amino propyl group (SiNP-VA) is significantly higher as compared to SiNP with only vinyl group (SiNP-V) and buffer but lower as compared to serum protein and liposome. However, fluorescence quantum yield (QY) is highest in SiNP-VA among all the nano formulations at pH 7.4 and below, which is attributed to the excited state interaction of curcumin with the amino groups of SiNP-VA. Results suggest that SiNP-VA could be an effective carrier for curcumin, which may have applications for imaging and drug delivery.

Nanoparticle bioconjugate for controlled cellular delivery of doxorubicin

NASA Astrophysics Data System (ADS)

Sangtani, Ajmeeta; Petryayeva, Eleonora; Wu, Miao; Susumu, Kimihiro; Oh, Eunkeu; Huston, Alan L.; Lasarte-Aragones, Guillermo; Medintz, Igor L.; Algar, W. Russ; Delehanty, James B.

2018-02-01

Nanoparticle (NP)-mediated drug delivery offers the potential to overcome limitations of systemic delivery, including the ability to specifically target cargo and control release of NP-associated drug cargo. Doxorubicin (DOX) is a widely used FDA-approved cancer therapeutic; however, multiple side effects limit its utility. Thus, there is wide interest in modulating toxicity after cell delivery. Our goal here was to realize a NP-based DOX-delivery system that can modulate drug toxicity by controlling the release kinetics of DOX from the surface of a hard NP carrier. To achieve this, we employed a quantum dot (QD) as a central scaffold which DOX was appended via three different peptidyl linkages (ester, disulfide, hydrazone) that are cleavable in response to various intracellular conditions. Attachment of a cell penetrating peptide (CPP) containing a positively charged polyarginine sequence facilitates endocytosis of the ensemble. Polyhistidine-driven metal affinity coordination was used to self-assemble both peptides to the QD surface, allowing for fine control over both the ratio of peptides attached to the QD as well as DOX dose delivered to cells. Microplate-based Förster resonance energy transfer assays confirmed the successful ratiometric assembly of the conjugates and functionality of the linkages. Cell delivery experiments and cytotoxicity assays were performed to compare the various cleavable linkages to a control peptide where DOX is attached through an amide bond. The role played by various attachment chemistries used in QD-peptide-drug assemblies and their implications for the rationale in design of NPbased constructs for drug delivery is described here.

High-density platinum nanoparticle-decorated titanium dioxide nanofiber networks for efficient capillary photocatalytic hydrogen generation

Treesearch

Zhaodong Li; Chunhua Yao; Yi-Cheng Wang; Solomon Mikael; Sundaram Gunasekaran; Zhenqiang Ma; Zhiyong Cai; Xudong Wang

2016-01-01

Aldehyde-functionalized cellulose nanofibers (CNFs) were applied to synthesize Pt nanoparticles (NPs) on CNF surfaces via on-site Pt ion reduction and achieve high concentration and uniform Pt NP loading. ALD could then selectively deposit TiO2 on CNFs and keep the Pt NPs uncovered due to their drastically different hydro-affinity properties. The...

A highly sensitive SPRi biosensing strategy for simultaneous detection of multiplex miRNAs based on strand displacement amplification and AuNP signal enhancement.

PubMed

Wei, Xiaotong; Duan, Xiaolei; Zhou, Xiaoyan; Wu, Jiangling; Xu, Hongbing; Min, Xun; Ding, Shijia

2018-06-07

Herein, a dual channel surface plasmon resonance imaging (SPRi) biosensor has been developed for the simultaneous and highly sensitive detection of multiplex miRNAs based on strand displacement amplification (SDA) and DNA-functionalized AuNP signal enhancement. In the presence of target miRNAs (miR-21 or miR-192), the miRNAs could specifically hybridize with the corresponding hairpin probes (H) and initiate the SDA, resulting in massive triggers. Subsequently, the two parts of the released triggers could hybridize with capture probes (CP) and DNA-functionalized AuNPs, assembling DNA sandwiches with great mass on the chip surface. A significantly amplified SPR signal readout was achieved. This established biosensing method was capable of simultaneously detecting multiplex miRNAs with a limit of detection down to 0.15 pM for miR-21 and 0.22 pM for miR-192. This method exhibited good specificity and acceptable reproducibility. Moreover, the developed method was applied to the determination of target miRNAs in a complex matrix. Thus, this developed SPRi biosensing method may present a potential alternative tool for miRNA detection in biomedical research and clinical diagnosis.

Protein corona – from molecular adsorption to physiological complexity

PubMed Central

Docter, Dominic; Maskos, Michael

2015-01-01

Summary In biological environments, nanoparticles are enshrouded by a layer of biomolecules, predominantly proteins, mediating its subsequent interactions with cells. Detecting this protein corona, understanding its formation with regards to nanoparticle (NP) and protein properties, and elucidating its biological implications were central aims of bio-related nano-research throughout the past years. Here, we discuss the mechanistic parameters that are involved in the protein corona formation and the consequences of this corona formation for both, the particle, and the protein. We review consequences of corona formation for colloidal stability and discuss the role of functional groups and NP surface functionalities in shaping NP–protein interactions. We also elaborate the recent advances demonstrating the strong involvement of Coulomb-type interactions between NPs and charged patches on the protein surface. Moreover, we discuss novel aspects related to the complexity of the protein corona forming under physiological conditions in full serum. Specifically, we address the relation between particle size and corona composition and the latest findings that help to shed light on temporal evolution of the full serum corona for the first time. Finally, we discuss the most recent advances regarding the molecular-scale mechanistic role of the protein corona in cellular uptake of NPs. PMID:25977856

PdNP Decoration of Halloysite Lumen via Selective Grafting of Ionic Liquid onto the Aluminol Surfaces and Catalytic Application.

PubMed

Dedzo, Gustave K; Ngnie, Gaëlle; Detellier, Christian

2016-02-01

The synthesis of selectively deposited palladium nanoparticles (PdNPs) inside tubular halloysite lumens is reported. This specific localization was directed by the selective modification of the aluminol surfaces of the clay mineral through stable Al-O-C bonds. An ionic liquid (1-(2-hydroxyethyl)-3-methylimidazolium) was grafted onto halloysite following the guest displacement method (generally used for kaolinite) using halloysite-DMSO preintercalate. The characterization of this clay nanohybrid material (XRD, NMR, TGA) showed characteristics reminiscent of similar materials synthesized from kaolinite. The grafting on halloysite lumens was also effective without using the DMSO preintercalate. The presence of these new functionalities in halloysite directs the synthesis of uniform PdNPs with size ranging between 3 and 6 nm located exclusively in the lumens. This results from the selective adsorption of PdNPs precursors in functionalized lumens through an anion exchange mechanism followed by in situ reduction. In contrast, the unmodified clay mineral displayed nanoparticles both inside and outside the tubes. These catalysts showed significant catalytic activity for the reduction of 4-nitrophenol (4-NP). The most efficient catalysts were recycled up to three times without reducing significantly the catalytic activities.

Surface functionalization of copper via oxidative graft polymerization of 2,2'-bithiophene and immobilization of silver nanoparticles for combating biocorrosion.

PubMed

Wan, Dong; Yuan, Shaojun; Neoh, K G; Kang, E T

2010-06-01

An environmentally benign approach to surface modification was developed to impart copper surface with enhanced resistance to corrosion, bacterial adhesion and biocorrosion. Oxidative graft polymerization of 2,2'-bithiophene from the copper surface with self-assembled 2,2'-bithiophene monolayer, and subsequent reduction of silver ions to silver nanoparticles (Ag NPs) on the surface, give rise to a homogeneous bithiophene polymer (PBT) film with densely coupled Ag NPs on the copper surface (Cu-g-PBT-Ag NP surface). The immobilized Ag NPs were found to significantly inhibit bacterial adhesion and enhance the antibacterial properties of the PBT modified copper surface. The corrosion inhibition performance of the functionalized copper substrates was evaluated by Tafel polarization curves and electrochemical impedance spectroscopy. Arising from the chemical affinity of thiols for the noble and coinage metals, the copper surface functionalized with both PBT brushes and Ag NPs also exhibits long-term stability, and is thus potentially useful for combating the combined problems of corrosion and biocorrosion in harsh marine and aquatic environments.

Understanding the nanoparticle-protein corona complexes using computational and experimental methods.

PubMed

Kharazian, B; Hadipour, N L; Ejtehadi, M R

2016-06-01

Nanoparticles (NP) have capability to adsorb proteins from biological fluids and form protein layer, which is called protein corona. As the cell sees corona coated NPs, the protein corona can dictate biological response to NPs. The composition of protein corona is varied by physicochemical properties of NPs including size, shape, surface chemistry. Processing of protein adsorption is dynamic phenomena; to that end, a protein may desorb or leave a surface vacancy that is rapidly filled by another protein and cause changes in the corona composition mainly by the Vroman effect. In this review, we discuss the interaction between NP and proteins and the available techniques for identification of NP-bound proteins. Also we review current developed computational methods for understanding the NP-protein complex interactions. Copyright © 2016. Published by Elsevier Ltd.

An ultrastable conjugate of silver nanoparticles and protein formed through weak interactions

NASA Astrophysics Data System (ADS)

Brahmkhatri, Varsha P.; Chandra, Kousik; Dubey, Abhinav; Atreya, Hanudatta S.

2015-07-01

In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein ubiquitin (Ubq). This involves a dynamic and reversible association and dissociation of ubiquitin from the surface of AgNP. The exchange occurs at a rate much greater than 25 s-1 implying a residence time of <40 ms for the protein. The AgNP-Ubq complex remains stable for months due to steric stabilization over a wide pH range compared to unconjugated AgNPs. NMR studies reveal that the protein molecules bind reversibly to AgNP with an approximate dissociation constant of 55 μM and undergo fast exchange. At pH > 4 the positively charged surface of the protein comes in contact with the citrate capped AgNP surface. Further, NMR relaxation-based experiments suggest that in addition to the dynamic exchange, a conformational rearrangement of the protein takes place upon binding to AgNP. The ultrastability of the AgNP-Ubq complex was found to be useful for its anti-microbial activity, which allowed the recycling of this complex multiple times without the loss of stability. Altogether, the study provides new insights into the mechanism of protein-silver nanoparticle interactions and opens up new avenues for its application in a wide range of systems.In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein ubiquitin (Ubq). This involves a dynamic and reversible association and dissociation of ubiquitin from the surface of AgNP. The exchange occurs at a rate much greater than 25 s-1 implying a residence time of <40 ms for the protein. The AgNP-Ubq complex remains stable for months due to steric stabilization over a wide pH range compared to unconjugated AgNPs. NMR studies reveal that the protein molecules bind reversibly to AgNP with an approximate dissociation constant of 55 μM and undergo fast exchange. At pH > 4 the positively charged surface of the protein comes in contact with the citrate capped AgNP surface. Further, NMR relaxation-based experiments suggest that in addition to the dynamic exchange, a conformational rearrangement of the protein takes place upon binding to AgNP. The ultrastability of the AgNP-Ubq complex was found to be useful for its anti-microbial activity, which allowed the recycling of this complex multiple times without the loss of stability. Altogether, the study provides new insights into the mechanism of protein-silver nanoparticle interactions and opens up new avenues for its application in a wide range of systems. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03047a

Elucidating the evolutionary history and expression patterns of nucleoside phosphorylase paralogs (vegetative storage proteins) in Populus and the plant kingdom

PubMed Central

2013-01-01

Background Nucleoside phosphorylases (NPs) have been extensively investigated in human and bacterial systems for their role in metabolic nucleotide salvaging and links to oncogenesis. In plants, NP-like proteins have not been comprehensively studied, likely because there is no evidence of a metabolic function in nucleoside salvage. However, in the forest trees genus Populus a family of NP-like proteins function as an important ecophysiological adaptation for inter- and intra-seasonal nitrogen storage and cycling. Results We conducted phylogenetic analyses to determine the distribution and evolution of NP-like proteins in plants. These analyses revealed two major clusters of NP-like proteins in plants. Group I proteins were encoded by genes across a wide range of plant taxa while proteins encoded by Group II genes were dominated by species belonging to the order Malpighiales and included the Populus Bark Storage Protein (BSP) and WIN4-like proteins. Additionally, we evaluated the NP-like genes in Populus by examining the transcript abundance of the 13 NP-like genes found in the Populus genome in various tissues of plants exposed to long-day (LD) and short-day (SD) photoperiods. We found that all 13 of the Populus NP-like genes belonging to either Group I or II are expressed in various tissues in both LD and SD conditions. Tests of natural selection and expression evolution analysis of the Populus genes suggests that divergence in gene expression may have occurred recently during the evolution of Populus, which supports the adaptive maintenance models. Lastly, in silico analysis of cis-regulatory elements in the promoters of the 13 NP-like genes in Populus revealed common regulatory elements known to be involved in light regulation, stress/pathogenesis and phytohormone responses. Conclusion In Populus, the evolution of the NP-like protein and gene family has been shaped by duplication events and natural selection. Expression data suggest that previously uncharacterized NP-like proteins may function in nutrient sensing and/or signaling. These proteins are members of Group I NP-like proteins, which are widely distributed in many plant taxa. We conclude that NP-like proteins may function in plants, although this function is undefined. PMID:23957885

Nanoporous Gold: Fabrication, Characterization, and Applications

PubMed Central

Seker, Erkin; Reed, Michael L.; Begley, Matthew R.

2009-01-01

Nanoporous gold (np-Au) has intriguing material properties that offer potential benefits for many applications due to its high specific surface area, well-characterized thiol-gold surface chemistry, high electrical conductivity, and reduced stiffness. The research on np-Au has taken place on various fronts, including advanced microfabrication and characterization techniques to probe unusual nanoscale properties and applications spanning from fuel cells to electrochemical sensors. Here, we provide a review of the recent advances in np-Au research, with special emphasis on microfabrication and characterization techniques. We conclude the paper with a brief outline of challenges to overcome in the study of nanoporous metals.

Hydrophilic/hydrophobic features of TiO2 nanoparticles as a function of crystal phase, surface area and coating, in relation to their potential toxicity in peripheral nervous system.

PubMed

Bolis, V; Busco, C; Ciarletta, M; Distasi, C; Erriquez, J; Fenoglio, I; Livraghi, S; Morel, S

2012-03-01

The hydrophilic/hydrophobic properties of a variety of commercial TiO(2) nanoparticles (NP), to be employed as inorganic filters in sunscreen lotions, were investigated both as such (dry powders) and dispersed in aqueous media. Water uptake and the related interaction energy have been determined by means of adsorption microcalorimetry of H(2)O vapor, whereas dispersion features in aqueous solutions were investigated by dynamic light scattering and electrokinetic measurements (zeta potential). The optimized dispersions in cell culture medium were employed to assess the possible in vitro neuro-toxicological effect on dorsal root ganglion (DRG) cells upon exposure to TiO(2)-NP, as a function of crystal phase, surface area and coating. All investigated materials, with the only exception of the uncoated rutile, were found to induce apoptosis on DRG cells; the inorganic/organic surface coating was found not to protect against the TiO(2)-induced apoptosis. The risk profile for DRG cells, which varies for the uncoated samples in the same sequence as the photo-catalytic activity of the different polymorphs: anatase-rutile>anatase>rutile, was found not to be correlated with the surface hydrophilicity of the uncoated/coated specimens. Aggregates/agglomerates hydrodynamic diameter was comprised in the ~200-400 nm range, compatible with the internalization within DRG cells. Copyright © 2011 Elsevier Inc. All rights reserved.

Charge-based characterization of nanometric cationic bifunctional maghemite/silica core/shell particles by capillary zone electrophoresis.

PubMed

d'Orlyé, Fanny; Varenne, Anne; Georgelin, Thomas; Siaugue, Jean-Michel; Teste, Bruno; Descroix, Stéphanie; Gareil, Pierre

2009-07-01

In view of employing functionalized nanoparticles (NPs) in the context of an immunodiagnostic, aminated maghemite/silica core/shell particles were synthesized so as to be further coated with an antibody or an antigen via the amino groups at their surface. Different functionalization rates were obtained by coating these maghemite/silica core/shell particles with 3-(aminopropyl)triethoxysilane and 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane at different molar ratios. Adequate analytical performances with CE coupled with UV-visible detection were obtained through semi-permanent capillary coating with didodecyldimethyl-ammonium bromide, thus preventing particle adsorption. First, the influence of experimental conditions such as electric field strength, injected particle amount as well as electrolyte ionic strength and pH, was evaluated. A charge-dependent electrophoretic mobility was evidenced and the separation selectivity was tuned according to electrolyte ionic strength and pH. The best resolutions were obtained at pH 8.0, high ionic strength (ca. 100 mM), and low total particle volume fraction (ca. 0.055%), thus eliminating interference effects between different particle populations in mixtures. A protocol derived from Kaiser's original description was performed for quantitation of the primary amino groups attached onto the NP surface. Thereafter a correlation between particle electrophoretic mobility and the density of amino groups at their surface was established. Eventually, CE proved to be an easy, fast, and reliable method for the determination of NP effective surface charge density.

Varactor with integrated micro-discharge source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elizondo-Decanini, Juan M.; Manginell, Ronald P.; Moorman, Matthew W.

2016-10-18

An apparatus that includes a varactor element and an integrated micro-discharge source is disclosed herein. In a general embodiment, the apparatus includes at least one np junction and at least one voltage source that is configured to apply voltage across the np junction. The apparatus further includes an aperture that extends through the np junction. When the voltage is applied across the np junction, gas in the aperture is ionized, forming a plasma, in turn causing a micro-discharge (of light, charge particles, and space charge) to occur. The light (charge particles, and space charge) impinges upon the surface of themore » np junction exposed in the aperture, thereby altering capacitance of the np junction. When used within an oscillator circuit, the effect of the plasma on the np-junction extends the capacitance changes of the np-junction and extends the oscillator frequency range in ways not possible by a conventional voltage controlled oscillator (VCO).« less

The functional dissection of the plasma corona of SiO₂-NPs spots histidine rich glycoprotein as a major player able to hamper nanoparticle capture by macrophages.

PubMed

Fedeli, Chiara; Segat, Daniela; Tavano, Regina; Bubacco, Luigi; De Franceschi, Giorgia; de Laureto, Patrizia Polverino; Lubian, Elisa; Selvestrel, Francesco; Mancin, Fabrizio; Papini, Emanuele

2015-11-14

A coat of strongly-bound host proteins, or hard corona, may influence the biological and pharmacological features of nanotheranostics by altering their cell-interaction selectivity and macrophage clearance. With the goal of identifying specific corona-effectors, we investigated how the capture of amorphous silica nanoparticles (SiO2-NPs; Ø = 26 nm; zeta potential = -18.3 mV) by human lymphocytes, monocytes and macrophages is modulated by the prominent proteins of their plasma corona. LC MS/MS analysis, western blotting and quantitative SDS-PAGE densitometry show that Histidine Rich Glycoprotein (HRG) is the most abundant component of the SiO2-NP hard corona in excess plasma from humans (HP) and mice (MP), together with minor amounts of the homologous Kininogen-1 (Kin-1), while it is remarkably absent in their Foetal Calf Serum (FCS)-derived corona. HRG binds with high affinity to SiO2-NPs (HRG Kd ∼2 nM) and competes with other plasma proteins for the NP surface, so forming a stable and quite homogeneous corona inhibiting nanoparticles binding to the macrophage membrane and their subsequent uptake. Conversely, in the case of lymphocytes and monocytes not only HRG but also several common plasma proteins can interchange in this inhibitory activity. The depletion of HRG and Kin-1 from HP or their plasma exhaustion by increasing NP concentration (>40 μg ml(-1) in 10% HP) lead to a heterogeneous hard corona, mostly formed by fibrinogen (Fibr), HDLs, LDLs, IgGs, Kallikrein and several minor components, allowing nanoparticle binding to macrophages. Consistently, the FCS-derived SiO2-NP hard corona, mainly formed by hemoglobin, α2 macroglobulin and HDLs but lacking HRG, permits nanoparticle uptake by macrophages. Moreover, purified HRG competes with FCS proteins for the NP surface, inhibiting their recruitment in the corona and blocking NP macrophage capture. HRG, the main component of the plasma-derived SiO2-NPs' hard corona, has antiopsonin characteristics and uniquely confers to these particles the ability to evade macrophage capture.

Nanoparticle diffusion in, and microrheology of, the bovine vitreous ex vivo

PubMed Central

Xu, Qingguo; Boylan, Nicholas J.; Suk, Jung Soo; Wang, Ying-Ying; Nance, Elizabeth; Yang, Jeh-Chang; McDonnell, Peter; Cone, Richard; Duh, Elia J.; Hanes, Justin

2013-01-01

Intravitreal injection of biodegradable nanoparticles (NP) holds promise for gene therapy and drug delivery to the back of the eye. In some cases, including gene therapy, NP need to diffuse rapidly from the site of injection in order to reach targeted cell types in the back of the eye, whereas in other cases it may be preferred for the particles to remain at the injection site and slowly release drugs that may then diffuse to the site of action. We studied the movements of polystyrene (PS) nanoparticles of various sizes and surface chemistries in fresh bovine vitreous. PS NP as large as 510 nm rapidly penetrated the vitreous gel when coated with polyethylene glycol (PEG), whereas the movements of NP 1190 nm in diameter or larger were highly restricted regardless of surface chemistry owing to steric obstruction. PS NP coated with primary amine groups (–NH2) possessed positively charged surfaces at the pH of bovine vitreous (pH = 7.2), and were immobilized within the vitreous gel. In comparison, PS NP coated with –COOH (possessing negatively charged surfaces) in the size range of 100–200 nm and at particle concentrations below 0.0025% (w/v) readily diffused through the vitreous meshwork; at higher concentrations (~0.1% w/v), these nanoparticles aggregated within vitreous. Based on the mobility of different sized PS-PEG NP, we estimated the average mesh size of fresh bovine vitreous to be ~550 ± 50 nm. The bovine vitreous behaved as an impermeable elastic barrier to objects sized 1190 nm and larger, but as a highly permeable viscoelastic liquid to non-adhesive objects smaller than 510 nm in diameter. Guided by these studies, we next sought to examine the transport of drug- and DNA-loaded nanoparticles in bovine vitreous. Biodegradable NP with diameter of 227 nm, composed of a poly(lactic-co-glycolic acid) (PLGA)-based core coated with poly(vinyl alcohol) rapidly penetrated vitreous. Rod-shaped, highly-compacted CK30PEG10k/DNA with PEG coating (neutral surface charge; diameter ~60 nm) diffused rapidly within vitreous. These findings will help guide the development of nanoparticle-based therapeutics for the treatment of vision-threatening ocular diseases. PMID:23369761

Enhancement in volatile organic compound sensitivity of aged Ag nanoparticle aggregates by plasma exposure

NASA Astrophysics Data System (ADS)

Hosomi, Kei; Ozaki, Koichi; Nishiyama, Fumitaka; Takahiro, Katsumi

2018-01-01

Silver nanoparticles (Ag NPs) tarnish easily upon exposure to ambient air, and eventually lose their ability as a plasmonic sensor via weakened localized surface plasmon resonance (LSPR). We have demonstrated the enhancement in plasmonic sensitivity of tarnished Ag NP aggregates to vapors of volatile organic compounds (VOCs) such as ethanol and butanol by Ar plasma exposure. The response of Ag NP aggregates to the VOC vapors was examined by measuring the change in optical extinction spectra before and after exposure to the vapors. The sensitivity of Ag NP aggregates decreased gradually when stored in ambient air. The performance of tarnished Ag NPs for ethanol sensing was recovered by exposure to argon (Ar) plasma for 15 s. The reduction from oxidized Ag to metallic one was recognized, while morphological change was hardly noticeable after the plasma exposure. We conclude, therefore, that a compositional change rather than a morphological change occurred on Ag NP surfaces enhances the sensing ability of tarnished Ag NP aggregates to the VOC vapors.

Surface effects on the radiation response of nanoporous Au foams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, E. G.; Caro, M.; Wang, Y. Q.

2012-11-05

We report on an experimental and simulation campaign aimed at exploring the radiation response of nanoporous Au (np-Au) foams. We find different defect accumulation behavior by varying radiation dose-rate in ion-irradiated np-Au foams. Stacking fault tetrahedra are formed when np-Au foams are irradiated at high dose-rate, but they do not seem to be formed in np-Au at low dose-rate irradiation. A model is proposed to explain the dose-rate dependent defect accumulation based on these results.

Interactions of ciprofloxacin (CIP), titanium dioxide (TiO2) nanoparticles and natural organic matter (NOM) in aqueous suspensions.

PubMed

Fries, Elke; Crouzet, Catherine; Michel, Caroline; Togola, Anne

2016-09-01

The aim of the present study was to investigate interactions of the antibiotic ciprofloxacin (CIP), titanium dioxide nanoparticles (TiO2 NP) and natural organic matter (NOM) in aqueous suspensions. The mean hydrodynamic diameter of particles of TiO2 NP and NOM in the suspensions ranged from 113 to 255nm. During batch experiments the radioactivity resulting from (14)CIP was determined in the filtrate (filter pore size 100nm) by scintillation measurements. Up to 72h, no significant sorption of NOM to TiO2 NP was observed at a TiO2 NP concentration of 5mg/L. When the concentration of TiO2 NP was increased to 500mg/L, a small amount of NOM of 9.5%±0.6% was sorbed at 72h. The low sorption affinity of NOM on TiO2 NP surfaces could be explained by the negative charge of both components in alkaline media or by the low hydrophobicity of the NOM contents. At a TiO2 NP concentration of 5mgL(-1), the sorption of CIP on TiO2 NP was insignificant (TiO2 NP/CIP ratio: 10). When the TiO2 NP/CIP ratio was increased to 1000, a significant amount of 53.6%±7.2% of CIP was sorbed on TiO2 NP under equilibrium conditions at 64h. In alkaline media, CIP is present mainly as zwitterions which have an affinity to sorb on negatively charged TiO2 NP surfaces. The sorption of CIP on TiO2 NP in the range of TiO2 NP concentrations currently estimated for municipal wastewater treatment plants is estimated to be rather low. The Freundlich sorption coefficients (KF) in the presence of NOM of 2167L(n)mgmg(-n)kg(-1) was about 10 times lower than in the absence of NOM. This is an indication that the particle fraction of NOM<100nm could play a role as a carrier for ionic organic micro-pollutants as CIP. Copyright © 2015 Elsevier B.V. All rights reserved.

Silica Encapsulated Gold Nanoparticles as SERS Labels for the Detection of Lymphoma B-Cells in Tissue Sections

NASA Astrophysics Data System (ADS)

Al-Faouri, Tamara

The surface of silica encapsulated gold nanoparticles with trans-1,2-bis (4-pyridyl) ethylene Raman active dye were utilized as SERS labels to target CD20 surface protein on lymphoma B-cells in human tissue sections with CLL or FL. SERS labels were functionalized with various antibody linkers including carboxylic, aldehyde, and heterobifunctional PEG chains with an NHS end, to permit them to bind to tissue section samples. NP samples and tissue sections were characterized through UV-Vis spectroscopy, TEM, XPS, Zeta potential measurements, Dark Field microscopy, Raman spectroscopy, NMR, and AFM. The number of SERS labels present on a tissue sample was estimated using dark field images and a particle counting software. It was found that the heterobifunctional PEG chains linker provided the most specific binding of SERS labels with an estimated NP count of 1.33x106 NPs on the whole tissue and produced the highest Raman scatter intensity of approximately 48600 counts.

Synthesis of mono-dispersed nanofluids using solution plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heo, Yong Kang, E-mail: yk@rd.numse.nagoya-u.ac.jp; Bratescu, Maria Antoaneta, E-mail: maria@rd.numse.nagoya-u.ac.jp; Knowledge Hub Aichi, Yakusa-cho, Nagakute-ku, Toyota

2014-07-14

Small-sized and well-dispersed gold nanoparticles (NPs) for nanofluidics have been synthesized by electrical discharge in liquid environment using termed solution plasma processing (SPP). Electrons and the hydrogen radicals are reducing the gold ions to the neutral form in plasma gas phase and liquid phase, respectively. The gold NPs have the smallest diameter of 4.9 nm when the solution temperature was kept at 20 °C. Nucleation and growth theory describe the evolution of the NP diameter right after the reduction reaction in function of the system temperature, NP surface energy, dispersion energy barrier, and nucleation rate. Negative charges on the NPs surface duringmore » and after SPP generate repulsive forces among the NPs avoiding their agglomeration in solution. Increasing the average energy in the SPP determines a decrease of the zeta potential and an increase of the NPs diameter. An important enhancement of the thermal conductivity of 9.4% was measured for the synthesized nanofluids containing NPs with the smallest size.« less

Impact of surface grafting density of PEG macromolecules on dually fluorescent silica nanoparticles used for the in vivo imaging of subcutaneous tumors.

PubMed

Adumeau, Laurent; Genevois, Coralie; Roudier, Lydia; Schatz, Christophe; Couillaud, Franck; Mornet, Stéphane

2017-06-01

In the context of systematically administered nanomedicines, the physicochemistry of NP surfaces must be controlled as a prerequisite to improve blood circulation time, and passive and active targeting. In particular, there is a real need to develop NP stealth and labelling for both in vivo and microscopic fluorescence imaging in a mice model. We have synthesized NIR/red dually fluorescent silica nanoparticles of 19nm covalently covered by a PEG layer of different grafting density in the brush conformational regime by using a reductive amination reaction. These particles were characterized by TEM, DRIFT, DLS, TGA, ζ potential measurements, UV-vis and fluorescence spectroscopy. Prostate tumors were generated in mice by subcutaneous injection of RM1-CMV-Fluc cells. Tumor growth was monitored by BLI after a D-luciferin injection. Four samples of PEGylated fluorescent NPs were individually intravenously injected into 6 mice (N=6, total 24 mice). Nanoparticle distribution was investigated using in vivo fluorescence reflectance imaging (FRI) over 48h and microscopy imaging was employed to localize the NPs within tumors in vitro. Fluorescent NP accumulation, due to the enhanced permeability and retention (EPR) effect, increases gradually as a function of increased PEG surface grafting density with a huge difference observed for the highest density grafting. For the highest grafting density, a blood circulation time of up to 24h was observed with a strong reduction in uptake by the liver. In vivo experimental results suggest that the biodistribution of NPs is very sensitive to slight variations in surface grafting density when the NPs present a high curvature radius. This study underlines the need to compensate a high curvature radius with a PEG-saturated NP surface to improve blood circulation and accumulation within tumors through the EPR effect. Dually fluorescent NPs PEGylated to saturation display physical properties useful for assessing the susceptibility of tumors to the EPR effect. Control of the physicochemical features of nanoparticle surfaces to improve blood circulation times and monitoring of the EPR effect. This article is part of a Special Issue entitled "Recent Advances in Bionanomaterials" Guest Editor: Dr. Marie-Louise Saboungi and Dr. Samuel D. Bader. Copyright © 2017 Elsevier B.V. All rights reserved.

An intrinsically disordered peptide from Ebola virus VP35 controls viral RNA synthesis by modulating nucleoprotein-RNA interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leung, Daisy  W.; Borek, Dominika; Luthra, Priya

During viral RNA synthesis, Ebola virus (EBOV) nucleoprotein (NP) alternates between an RNA-template-bound form and a template-free form to provide the viral polymerase access to the RNA template. In addition, newly synthesized NP must be prevented from indiscriminately binding to noncognate RNAs. Here, we investigate the molecular bases for these critical processes. We identify an intrinsically disordered peptide derived from EBOV VP35 (NPBP, residues 20–48) that binds NP with high affinity and specificity, inhibits NP oligomerization, and releases RNA from NP-RNA complexes in vitro. The structure of the NPBP/ΔNP NTD complex, solved to 3.7 Å resolution, reveals how NPBP peptidemore » occludes a large surface area that is important for NP-NP and NP-RNA interactions and for viral RNA synthesis. Together, our results identify a highly conserved viral interface that is important for EBOV replication and can be targeted for therapeutic development.« less

An intrinsically disordered peptide from Ebola virus VP35 controls viral RNA synthesis by modulating nucleoprotein-RNA interactions

DOE PAGES

Leung, Daisy  W.; Borek, Dominika; Luthra, Priya; ...

2015-04-01

During viral RNA synthesis, Ebola virus (EBOV) nucleoprotein (NP) alternates between an RNA-template-bound form and a template-free form to provide the viral polymerase access to the RNA template. In addition, newly synthesized NP must be prevented from indiscriminately binding to noncognate RNAs. Here, we investigate the molecular bases for these critical processes. We identify an intrinsically disordered peptide derived from EBOV VP35 (NPBP, residues 20–48) that binds NP with high affinity and specificity, inhibits NP oligomerization, and releases RNA from NP-RNA complexes in vitro. The structure of the NPBP/ΔNP NTD complex, solved to 3.7 Å resolution, reveals how NPBP peptidemore » occludes a large surface area that is important for NP-NP and NP-RNA interactions and for viral RNA synthesis. Together, our results identify a highly conserved viral interface that is important for EBOV replication and can be targeted for therapeutic development.« less

Sequential strand displacement beacon for detection of DNA coverage on functionalized gold nanoparticles.

PubMed

Paliwoda, Rebecca E; Li, Feng; Reid, Michael S; Lin, Yanwen; Le, X Chris

2014-06-17

Functionalizing nanomaterials for diverse analytical, biomedical, and therapeutic applications requires determination of surface coverage (or density) of DNA on nanomaterials. We describe a sequential strand displacement beacon assay that is able to quantify specific DNA sequences conjugated or coconjugated onto gold nanoparticles (AuNPs). Unlike the conventional fluorescence assay that requires the target DNA to be fluorescently labeled, the sequential strand displacement beacon method is able to quantify multiple unlabeled DNA oligonucleotides using a single (universal) strand displacement beacon. This unique feature is achieved by introducing two short unlabeled DNA probes for each specific DNA sequence and by performing sequential DNA strand displacement reactions. Varying the relative amounts of the specific DNA sequences and spacing DNA sequences during their coconjugation onto AuNPs results in different densities of the specific DNA on AuNP, ranging from 90 to 230 DNA molecules per AuNP. Results obtained from our sequential strand displacement beacon assay are consistent with those obtained from the conventional fluorescence assays. However, labeling of DNA with some fluorescent dyes, e.g., tetramethylrhodamine, alters DNA density on AuNP. The strand displacement strategy overcomes this problem by obviating direct labeling of the target DNA. This method has broad potential to facilitate more efficient design and characterization of novel multifunctional materials for diverse applications.

Biocompatibilite des complexes proteines-nanoparticules: Perspectives sur la reponse cellulaire aux nanoparticules d'oxyde de fer fonctionnalisees, revetues d'un corona

NASA Astrophysics Data System (ADS)

Mbeh, Doris Antoinette

This thesis presents the study of the biocompatibility of nanoparticles (NPs) of iron oxide (Fe3O4) candidates for targeted delivery of therapeutic molecules. We especially devoted to study the impact of the surface composition of the NPs and protein adsorption at the surface thereof on the cellular responses. To do this, we first examined the toxic potential of magnetite with various functionalizations: one that is prepared with (1) a monolayer of oleic acid (Fe3O4@OA), which is then converted to (2) an envelope silane containing an amine (Fe3O4@NH 2), (3) a coating of silica (Fe3O4@SiO 2), and (4) an envelope containing a silane coating on amine silica (Fe3O4@SiO2@NH 2). The presence of these groups at the surface of the NPs was confirmed by XPS and transmission electron microscopy (TEM) analysis. We were able to prove that the toxic potential of NPs is dose-dependent and we determine the biocompatible doses for each surface functionalization. Microscopic observation of the morphology of the cells exposed to NPs, and their proinflammatory and mitochondrial activity showed that, in addition to surface features, the cell culture medium also affect the cytotoxicity of the NPs. These results clearly show that in order to use our NPs as pharmaceutical nanocarrier safely, we need to control the surface functionalization and the dynamic interaction between the NP and the physiological environment in which it is suspended. To understand the interaction between the NP and the culture medium, as a first step, we used three different culture media namely: DMEM, F-12K and DMEM / F12 (see Appendix A) and uncoated magnetite (Fe3O 4). These media were enriched with either fetal bovine serum (see Appendix B) or with a synthetic serum (SFMS). We have proved the presence of a protein corona on NPs suspended in culture media enriched with bovine serum. We also demonstrated that the formation of the corona depends on the composition of the culture medium and that the cytotoxic potential of the NPs is influenced by NP-protein interaction. In a second step, we used one culture medium (DMEM / F12) and the magnetite with three different surface compositions: uncoated SPIONs with hydroxyl groups (OH) on the surface; coated SPIONs with an amine group (NH2) on the surface and the last one with a carboxylic group (COOH) on the surface. The results show that the composition of the corona depends on the surface composition of the NP and cellular responses are also different from one surface to another. In fact, some proteins (e.g. albumin) are adsorbed on the coatings only positively charged (NH2), while others (e.g., fibrinogen) are adsorbed on the negatively charged coatings (OH and COOH). Cell proliferation is influenced by the surface chemistry and is dose-dependent. SPIONs coated with carboxylic groups are more biocompatible while those uncoated, having hydroxyl groups on the surface are the most cytotoxic. Exploring three possible mechanisms of cytotoxicity, i.e., the production of ions by the SPIONs in the culture media, reactive oxygen species and protein adsorption, we found that in our case, protein adsorption was behind the cytotoxicity of our NPs since oxidative stress have been proved non-existent and there are not enough ions in the culture media to be detected . From these results, we can make a first correlation between the chemical composition of the surface, the identity of the adsorbed proteins and cellular responses. But we must take into account many other parameters related either to the NPs such as the charge, the agglomeration status, or related to the culture medium as the density of each protein, or finally to the experimental conditions.

Vestibular function in patients with Niemann-Pick type C disease.

PubMed

Bremova, Tatiana; Krafczyk, Siegbert; Bardins, Stanislavs; Reinke, Jörg; Strupp, Michael

2016-11-01

We investigated whether vestibular dysfunction may cause or contribute to postural imbalance and falls in patients with Niemann-Pick type C disease (NP-C). Eight patients with NP-C disease and 20 healthy controls were examined using the video-based head impulse test (vHIT) and caloric irrigation to investigate horizontal canal function as well as ocular- and cervical vestibular evoked myogenic potentials (o- and cVEMP), and binocular subjective visual vertical estimation (SVV) for otolith function, and static posturography. There were no significant differences in vestibulo-ocular gain, caloric excitability, o-/cVEMP measures or SVV between the two groups. Posturographic total sway path (tSP) and root mean square (RMS) were significantly higher in NP-C than in controls in 3 out of 4 conditions. The Romberg quotient (RQ) to assess the amount of visual stabilization was significantly lower in the NP-C than in the HC group. In contrast to other inherited metabolic disorders, such as Morbus Gaucher type 3, we did not find any evidence for an impairment of canal or otolith function in patients with NP-C as their cause of postural imbalance. Since RQ was low in NP-C patients, indicating proper sensory input, the observed increased postural sway is most likely due to a cerebellar dysfunction in NP-C, which may therefore, explain postural imbalance.

The Effect of Reduced Water Availability in the Great Ruaha River on the Vulnerable Common Hippopotamus in the Ruaha National Park, Tanzania.

PubMed

Stommel, Claudia; Hofer, Heribert; East, Marion L

2016-01-01

In semi-arid environments, 'permanent' rivers are essential sources of surface water for wildlife during 'dry' seasons when rainfall is limited or absent, particularly for species whose resilience to water scarcity is low. The hippopotamus (Hippopotamus amphibius) requires submersion in water to aid thermoregulation and prevent skin damage by solar radiation; the largest threat to its viability are human alterations of aquatic habitats. In the Ruaha National Park (NP), Tanzania, the Great Ruaha River (GRR) is the main source of surface water for wildlife during the dry season. Recent, large-scale water extraction from the GRR by people upstream of Ruaha NP is thought to be responsible for a profound decrease in dry season water-flow and the absence of surface water along large sections of the river inside the NP. We investigated the impact of decreased water flow on daytime hippo distribution using regular censuses at monitoring locations, transects and camera trap records along a 104km section of the GRR within the Ruaha NP during two dry seasons. The minimum number of hippos per monitoring location increased with the expanse of surface water as the dry seasons progressed, and was not affected by water quality. Hippo distribution significantly changed throughout the dry season, leading to the accumulation of large numbers in very few locations. If surface water loss from the GRR continues to increase in future years, this will have serious implications for the hippo population and other water dependent species in Ruaha NP.

Oriented Attachment Is a Major Control Mechanism To Form Nail-like Mn-Doped ZnO Nanocrystals.

PubMed

Patterson, Samuel; Arora, Priyanka; Price, Paige; Dittmar, Jasper W; Das, Vijay Kumar; Pink, Maren; Stein, Barry; Morgan, David Gene; Losovyj, Yaroslav; Koczkur, Kallum M; Skrabalak, Sara E; Bronstein, Lyudmila M

2017-12-26

Here, we present a controlled synthesis of Mn-doped ZnO nanoparticles (NPs) with predominantly nail-like shapes, whose formation occurs via tip-to-base-oriented attachment of initially formed nanopyramids, followed by leveling of sharp edges that lead to smooth single-crystalline "nails". This shape is prevalent in noncoordinating solvents such as octadecene and octadecane. Yet, the double bond in the former promotes oriented attachment. By contrast, Mn-doped ZnO NP synthesis in a weakly coordinating solvent, benzyl ether, results in dendritic structures because of random attachment of initial NPs. Mn-doped ZnO NPs possess a hexagonal wurtzite structure, and in the majority of cases, the NP surface is enriched with Mn, indicating a migration of Mn 2+ ions to the NP surface during the NP formation. When the NP formation is carried out without the addition of octadecyl alcohol, which serves as a surfactant and a reaction initiator, large, concave pyramid dimers are formed whose attachment takes place via basal planes. UV-vis and photoluminescence spectra of these NPs confirm the utility of controlling the NP shape to tune electro-optical properties.

Asteroidal Space Weathering: The Major Role of FeS

NASA Technical Reports Server (NTRS)

Keller, L. P.; Rahman, Z.; Hiroi, T.; Sasaki, S.; Noble, S. K.; Horz, F.; Cintala, M. J.

2013-01-01

Space weathering (SW) effects on the lunar surface are reasonably well-understood from sample analyses, remote-sensing data, and experiments, yet our knowledge of asteroidal SW effects are far less constrained. While the same SW processes are operating on asteroids and the Moon, namely solar wind irradiation, impact vaporization and condensation, and impact melting, their relative rates and efficiencies are poorly known, as are their effects on such vastly different parent materials. Asteroidal SW models based on remote-sensing data and experiments are in wide disagreement over the dominant mechanisms involved and their kinetics. Lunar space weathering effects observed in UVVIS-NIR spectra result from surface- and volume-correlated nanophase Fe metal (npFe(sup 0)) particles. In the lunar case, it is the tiny vapor-deposited npFe(sup 0) that provides much of the spectral reddening, while the coarser (largely melt-derived) npFe(sup 0) produce lowered albedos. Nanophase FeS (npFeS) particles are expected to modify reflectance spectra in much the same way as npFe(sup 0) particles. Here we report the results of experiments designed to explore the efficiency of npFeS production via the main space weathering processes operating in the asteroid belt.

Functional and pathological improvements of the hearts in diabetes model by the combined therapy of bFGF-loaded nanoparticles with ultrasound-targeted microbubble destruction.

PubMed

Zhao, Ying-Zheng; Tian, Xin-Qiao; Zhang, Ming; Cai, Lu; Ru, Ao; Shen, Xiao-Tong; Jiang, Xi; Jin, Rong-Rong; Zheng, Lei; Hawkins, Kyle; Charkrabarti, Subrata; Li, Xiao-Kun; Lin, Qian; Yu, Wen-Ze; Ge, Shuping; Lu, Cui-Tao; Wong, Ho Lun

2014-07-28

Diabetic cardiomyopathy (DCM) is the leading cause of morbidity and mortality among the diabetic patients and currently there is no effective means to reverse its pathological progress. Basic fibroblast growth factor (bFGF) has shown promise as a molecular therapy for DCM, but its delivery is inefficient and non-specific. In the present study, a therapy combining nanoparticle (NP) carrier and ultrasound-targeted microbubble destruction (UTMD) was reported the first time for bFGF delivery to the heart of diabetic rats. bFGF-loaded NP (bFGF-NP) were prepared with Poloxamer 188-grafted heparin copolymer using water-in-water technique, and the morphology, encapsulation efficiency, and bioactivity of bFGF-NP were studied. The cellular uptake and cytotoxicity of bFGF-NP were evaluated with primary cultures of the left ventricular (LV) cardiomyocytes in vitro. Therapeutic effects of bFGF-NP/UTMD on the heart of DCM rats were studied by measuring LV systolic and diastolic functions, hemodynamic characteristics and indicators of cardiac remodeling including myocardial collagen volume fraction and capillary density. Results demonstrated that bFGF-NP showed good round morphology, efficient bFGF encapsulation and stable bioactivity of bFGF in vitro. bFGF-NP/UTMD combined treatment significantly enhanced the efficiency of bFGF cellular uptake (P<0.05) without obvious cytotoxicity. Significant improvements (P<0.05) in both cardiac functions and tissue morphology in the DCM rats were observed in bFGF-NP/UTMD group. These were not achievable using free bFGF, bFGF-NP or UTMD treatment alone. Our results show that combining a non-viral vector with UTMD technique is an effective strategy to deliver bFGF to the heart, and the resulting growth factor therapy has demonstrated potential to reverse the progress of DCM by restoring the cardiac functions and even the structure of damaged cardiac tissues. Copyright © 2014 Elsevier B.V. All rights reserved.

Occurrence and distribution of bisphenol A and alkylphenols in the water of the Gulf of Gdansk (Southern Baltic).

PubMed

Staniszewska, Marta; Koniecko, Iga; Falkowska, Lucyna; Krzymyk, Ewelina

2015-02-15

In 2011-2012, the concentrations of bisphenol A (BPA), 4-tert-octylophenol (OP) and 4-nonylphenol (NP) in surface and near-bottom water of the Gulf of Gdansk, as well as inflowing rivers, were similar to those in other regions of Europe; BPA from <5.0 to 277.9 ng dm(-3), OP from <1.0 to 834.5 ng dm(-3), and NP from <4.0 to 228.6 ng dm(-3). The atmospheric transportation of phenol derivatives and their deposition into the water of the gulf was indicated by high enrichment factor values (EF) in the sea surface microlayer in relation to the sub-surface layer. The main route of BPA, OP and NP transportation into the waters of the Gulf of Gdansk is the River Vistula. In spring, significant amounts of bisphenol A and 4-nonylphenol were introduced to the coastal zone with meltwater. The main factors affecting the variability of BPA, OP and NP concentrations in surface and near-bottom water, particularly in summer, were increased tourism in the coastal region, water temperature and dissolved oxygen concentration. Copyright © 2014 Elsevier Ltd. All rights reserved.

Lanthanide luminescent displacement assays: the sensing of phosphate anions using Eu(III)-cyclen-conjugated gold nanoparticles in aqueous solution.

PubMed

Massue, Julien; Quinn, Susan J; Gunnlaugsson, Thorfinnur

2008-06-04

1.Eu, a cyclen based Eu(III)-thiol conjugate, was incorporated onto the surface of water-soluble gold nanoparticles to give AuNP-1.Eu. The self-assembly between AuNP-1.Eu and the antenna 2 resulted in the formation of the highly luminescent lanthanide system, AuNP-1.Eu-2, at pH 7.4. The sensing of flavin monophosphate 3 is demonstrated, whereby 3 displaced the antenna 2 in AuNP-1.Eu-2, resulting in the formation of AuNP-1.Eu-3 and quenching of the Eu(III) emission.

Surface-enhanced Raman spectroscopy with Au-nanoparticle substrate fabricated by using femtosecond pulse

NASA Astrophysics Data System (ADS)

Zhang, Wending; Li, Cheng; Gao, Kun; Lu, Fanfan; Liu, Min; Li, Xin; Zhang, Lu; Mao, Dong; Gao, Feng; Huang, Ligang; Mei, Ting; Zhao, Jianlin

2018-05-01

Au-nanoparticle (Au-NP) substrates for surface-enhanced Raman spectroscopy (SERS) were fabricated by grid-like scanning a Au-film using a femtosecond pulse. The Au-NPs were directly deposited on the Au-film surface due to the scanning process. The experimentally obtained Au-NPs presented local surface plasmon resonance effect in the visible spectral range, as verified by finite difference time domain simulations and measured reflection spectrum. The SERS experiment using the Au-NP substrates exhibited high activity and excellent substrate reproducibility and stability, and a clearly present Raman spectra of target analytes, e.g. Rhodamine-6G, Rhodamine-B and Malachite green, with concentrations down to 10‑9 M. This work presents an effective approach to producing Au-NP SERS substrates with advantages in activity, reproducibility and stability, which could be used in a wide variety of practical applications for trace amount detection.

Nanoporous Microsphere Assembly of Iodine-Functionalised Silver Nanoparticles as a Novel Mini-Substrate for Enriching and Sensing

NASA Astrophysics Data System (ADS)

Wu, X.-L.; Wu, H.; Wang, Z.-M.; Aizawa, H.; Guo, J.; Chu, Y.-H.

2017-04-01

Herein, debris particulates of nanoporous silver (np-Ag) were synthesised by a dealloying method, and their integration behaviour and surface-enhanced Raman scattering (SERS) properties during iodine functionalisation were examined. It was found that the dealloyed np-Ag debris particulates gradually assembled to form rigid nanoporous microspheres comprising Ag nano-ligaments due to mechanical collisions during iodine treatment. High-resolution transmission electron microscopy and X-ray photoelectron microscopy clearly showed the iodide surface of np-Ag, which was dotted with iodine or iodide ‘nanoislands’. The exceptional, and unexpected, integration and surface structures result in a highly enhanced localised surface plasmon resonance. Furthermore, the robust nanoporous microspheres can be employed individually as as-produced miniaturised electrodes to electrically enrich target molecules at parts-per-trillion levels, so as to achieve charge selectivity and superior detectability compared with the ordinary SERS effect.

Surface-enhanced Raman spectroscopy with Au-nanoparticle substrate fabricated by using femtosecond pulse.

PubMed

Zhang, Wending; Li, Cheng; Gao, Kun; Lu, Fanfan; Liu, Min; Li, Xin; Zhang, Lu; Mao, Dong; Gao, Feng; Huang, Ligang; Mei, Ting; Zhao, Jianlin

2018-05-18

Au-nanoparticle (Au-NP) substrates for surface-enhanced Raman spectroscopy (SERS) were fabricated by grid-like scanning a Au-film using a femtosecond pulse. The Au-NPs were directly deposited on the Au-film surface due to the scanning process. The experimentally obtained Au-NPs presented local surface plasmon resonance effect in the visible spectral range, as verified by finite difference time domain simulations and measured reflection spectrum. The SERS experiment using the Au-NP substrates exhibited high activity and excellent substrate reproducibility and stability, and a clearly present Raman spectra of target analytes, e.g. Rhodamine-6G, Rhodamine-B and Malachite green, with concentrations down to 10 -9 M. This work presents an effective approach to producing Au-NP SERS substrates with advantages in activity, reproducibility and stability, which could be used in a wide variety of practical applications for trace amount detection.

Biomolecule-nanoparticle interactions: Elucidation of the thermodynamics by isothermal titration calorimetry.

PubMed

Huang, Rixiang; Lau, Boris L T

2016-05-01

Nanomaterials (NMs) are often exposed to a broad range of biomolecules of different abundances. Biomolecule sorption driven by various interfacial forces determines the surface structure and composition of NMs, subsequently governs their functionality and the reactivity of the adsorbed biomolecules. Isothermal titration calorimetry (ITC) is a nondestructive technique that quantifies thermodynamic parameters through in-situ measurement of the heat absorption or release associated with an interaction. This review highlights the recent applications of ITC in understanding the thermodynamics of interactions between various nanoparticles (NPs) and biomolecules. Different aspects of a typical ITC experiment that are crucial for obtaining accurate and meaningful data, as well as the strengths, weaknesses, and challenges of ITC applications to NP research were discussed. ITC reveals the driving forces behind biomolecule-NP interactions and the effects of the physicochemical properties of both NPs and biomolecules by quantifying the crucial thermodynamics parameters (e.g., binding stoichiometry, ΔH, ΔS, and ΔG). Complimentary techniques would strengthen the interpretation of ITC results for a more holistic understanding of biomolecule-NP interactions. The thermodynamic information revealed by ITC and its complimentary characterizations is important for understanding biomolecule-NP interactions that are fundamental to the biomedical and environmental applications of NMs and their toxicological effects. Copyright © 2016 Elsevier B.V. All rights reserved.

ICAM-1 Targeting of Doxorubicin-Loaded PLGA Nanoparticles to Lung Epithelial Cells

PubMed Central

Chuda, Chittasupho; Sheng-Xue, Xie; Abdulgader, Baoum; Tatyana, Yakovleva; Teruna, Siahaan J.; Cory, Berkland

2009-01-01

Interaction of leukocyte function associated antigen-1 (LFA-1) on T-lymphoctytes and intercellular adhesion molecule-1 (ICAM-1) on epithelial cells controls leukocyte adhesion, spreading, and extravasation. This process plays an important role in leukocyte recruitment to a specific site of inflammation and has been indentified as a biomarker for certain types of carcinomas. Cyclo-(1,12)-PenITDGEATDSGC (cLABL) has been shown to inhibit LFA-1 and ICAM-1 interaction via binding to ICAM-1. In addition, cLABL has been shown to internalize after binding ICAM-1. The possibility of using cLABL conjugated nanoparticles (cLABL-NP) as a targeted and controlled release drug delivery system has been investigated in this study. The cLABL peptide was conjugated to a modified Pluronic® surfactant on poly (DL-lactic-co-glycolic acid) (PLGA) nanoparticles. The cLABL-NP showed more rapid cellular uptake by A549 lung epithelial cells compared to nanoparticles without peptide. The specificity of ICAM-1 mediated internalization was confirmed by blocking the uptake of cLABL-NP to ICAM-1 using free cLABL peptide to block the binding of cLABL-NP to ICAM-1 on the cell surface. Cell studies suggested that cLABL-NPs targeted encapsulated doxorubicin to ICAM-1 expressing cells. Cytotoxicity assay confirmed the activity of the drug incorporated in nanoparticles. Sustained release of doxorubicin afforded by PLGA nanoparticles may enable cLABL-NP as a targeted, controlled release drug delivery system. PMID:19429421

Noun-phrase anaphors and focus: the informational load hypothesis.

PubMed

Almor, A

1999-10-01

The processing of noun-phrase (NP) anaphors in discourse is argued to reflect constraints on the activation and processing of semantic information in working memory. The proposed theory views NP anaphor processing as an optimization process that is based on the principle that processing cost, defined in terms of activating semantic information, should serve some discourse function--identifying the antecedent, adding new information, or both. In a series of 5 self-paced reading experiments, anaphors' functionality was manipulated by changing the discourse focus, and their cost was manipulated by changing the semantic relation between the anaphors and their antecedents. The results show that reading times of NP anaphors reflect their functional justification: Anaphors were read faster when their cost had a better functional justification. These results are incompatible with any theory that treats NP anaphors as one homogeneous class regardless of discourse function and processing cost.

Monolayer coated gold nanoparticles for delivery applications

PubMed Central

Rana, Subinoy; Bajaj, Avinash; Mout, Rubul; Rotello, Vincent M.

2011-01-01

Gold nanoparticles (AuNPs) provide attractive vehicles for delivery of drugs, genetic materials, proteins, and small molecules. AuNPs feature low core toxicity coupled with the ability to parametrically control particle size and surface properties. In this review, we focus on engineering of the AuNP surface monolayer, highlighting recent advances in tuning monolayer structures for efficient delivery of drugs and biomolecules. This review covers two broad categories of particle functionalization, organic monolayers and biomolecule coatings, and discusses their applications in drug, DNA/RNA, protein and small molecule delivery. PMID:21925556

Acute toxicity of 353-nonylphenol and its metabolites for zebrafish embryos.

PubMed

Kammann, Ulrike; Vobach, Michael; Wosniok, Werner; Schäffer, Andreas; Telscher, Andreas

2009-03-01

Nonylphenol (NP) can be detected in the aquatic environment all over the world. It is applied as a technical mixture of isomers of which 353-NP is the most relevant both in terms of abundance (about 20% of total mass) and endocrine potential. 353-NP is metabolised in sewage sludge. The aims of the present study were to determine and to compare the acute toxicity of t-NP, 353-NP and its metabolites as well as to discuss if the toxicity of 353-NP changes during degradation. 353-NP and two of its metabolites were synthesised. The zebrafish embryo test was performed according to standard protocols. Several lethal and non-lethal endpoints during embryonal development were reported. NOEL, LOEL and EC50 were calculated. All tested compounds caused lethal as well as non-lethal malformations during embryo development. 353-NP showed a higher toxicity (EC50 for lethal endpoints 6.7 mg/L) compared to its metabolites 4-(3.5-dimethyl-3-heptyl)-2-nitrophenol (EC50 13.3 mg/L) and 4-(3,5-dimethyl-3-heptyl)-2-bromophenol (EC50 27.1 mg/L). In surface water, concentrations of NP are far below the NOEC identified by the zebrafish embryo test. However, in soils and sewage sludge, concentrations may reach or even exceed these concentrations. Therefore, sludge-treated sites close to surface waters should be analysed for NP and its metabolites in order to detect an unduly high contamination due to runoff events. The results of the present study point out that the toxicity of 353-NP probably declines during metabolisation in water, sediment and soil, but does not vanish since the major metabolites exhibit a clear toxic potential for zebrafish embryos. Metabolites of environmental pollutants should be included in the ecotoxicological test strategy for a proper risk assessment.

Portable SERS sensor for malachite green and other small dye molecules

NASA Astrophysics Data System (ADS)

Qiu, Suyan; Zhao, Fusheng; Li, Jingting; Shih, Wei-Chuan

2017-02-01

Sensitive detection of specific chemicals on site can be extremely powerful in many fields. Owing to its molecular fingerprinting capability, surface-enhanced Raman scattering has been one of the technological contenders. In this paper, we describe the novel use of DNA topological nanostructure on nanoporous gold nanoparticle (NPG-NP) array chip for chemical sensing. NPG-NP features large surface area and high-density plasmonic field enhancement known as "hotspots". Hence, NPG-NP array chip has found many applications in nanoplasmonic sensor development. This technique can provide novel label-free molecular sensing capability and enables high sensitivity and specificity detection using a portable Raman spectrometer.

The Novel Preparation of P-N Junction Mesa Diodes by Silicon-Wafer Direct Bonding (SDB)

NASA Astrophysics Data System (ADS)

Yeh, Ching-Fa; Hwangleu, Shyang

1992-05-01

The key processes of silicon-wafer direct bonding (SDB), including hydrophilic surface formation and optimal two-step heat treatment, have been developed However, H2SO4/H2O2 solution being a strong oxidized acid solution, native oxide is found to have grown on the wafer surface as soon as a wafer is treated in this solution. In the case of a wafer further treated in diluted HF solution after hydrophilic surface formation, it is shown that the wafer surface can not only be cleaned of its native oxide but also remains hydrophilic, and can provide excellent voidless bonding. The N+/P and N/P combination junction mesa diodes fabricated on the wafers prepared by these novel SDB technologies are examined. The ideality factor n of the N/P mesa diode is 2.4˜2.8 for the voltage range 0.2˜0.3 V; hence, the lowering of the ideality factor n is evidently achieved. As for the N+/P mesa diode, the ideality factor n shows a value of 1.10˜1.30 for the voltage range 0.2˜0.6 V; the low value of n is attributed to an autodoping phenomenon which has caused the junction interface to form in the P-silicon bulk. However, the fact that the sustaining voltage of the N/P mesa diode showed a value greater than 520 V reveals the effectiveness of our novel SDB processes.

A highly selective and sensitive cocaine aptasensor based on covalent attachment of the aptamer-functionalized AuNPs onto nanocomposite as the support platform.

PubMed

Roushani, Mahmoud; Shahdost-Fard, Faezeh

2015-01-01

Based on the conformational changes of the aptamer-functionalized gold nanoparticles (AuNPs) onto MWCNTs/IL/Chit nanocomposite as the support platform, we have developed a sensitive and selective electrochemical aptasensor for the detection of cocaine. The 5'-amine-3'-AuNP terminated aptamer is covalently attached to a MWCNTs/IL/Chit nanocomposite. The interaction of cocaine with the aptamer functionalized AuNP caused the aptamer to be folded and the AuNPs with negative charge at the end of the aptamer came to the near of electrode surface therefore, the electron transfer between ferricyanide (K3Fe(CN)6) as redox probe and electrode surface was inhibited. A decreased current of (K3Fe(CN)6) was monitored by differential pulse voltammetry technique. In an optimized condition the calibration curve for cocaine concentration was linear up to 11 μM with detection limit (signal-to-noise ratio of 3) of 100 pM. To test the selectivity of the prepared aptasensor sensing platform applicability, some analgesic drugs as the interferes were examined. The potential of the aptasensor was successfully applied for measuring cocaine concentration in human blood serum. Based on our experiments it can be said that the present method is absolutely beneficial in developing other electrochemical aptasensor. Copyright © 2014 Elsevier B.V. All rights reserved.

Towards hybrid biocompatible magnetic rHuman serum albumin-based nanoparticles: use of ultra-small (CeLn)3/4+ cation-doped maghemite nanoparticles as functional shell

NASA Astrophysics Data System (ADS)

Israel, Liron L.; Kovalenko, Elena I.; Boyko, Anna A.; Sapozhnikov, Alexander M.; Rosenberger, Ina; Kreuter, Jörg; Passoni, Lorena; Lellouche, Jean-Paul

2015-01-01

Human serum albumin (HSA) is a protein found in human blood. Over the last decade, HSA has been evaluated as a promising drug carrier. However, not being magnetic, HSA cannot be used for biomedical applications such as magnetic resonance imaging (MRI) and magnetic drug targeting. Therefore, subsequent composites building on iron oxide nanoparticles that are already used clinically as MRI contrast agents are extensively studied. Recently and in this context, innovative fully hydrophilic ultra-small CAN-stabilized maghemite ((CeLn)3/4+-γ-Fe2O3) nanoparticles have been readily fabricated. The present study discusses the design, fabrication, and characterization of a dual phase hybrid core (rHSA)-shell ((CeLn)3/4+-γ-Fe2O3 NPs) nanosystem. Quite importantly and in contrast to widely used encapsulation strategies, rHSA NP surface-attached (CeLn)3/4+-γ-Fe2O3 NPs enabled to exploit both rHSA (protein functionalities) and (CeLn)3/4+-γ-Fe2O3 NP surface functionalities (COOH and ligand L coordinative exchange) in addition to very effective MRI contrast capability due to optimal accessibility of H2O molecules with the outer magnetic phase. Resulting hybrid nanoparticles might be used as a platform modular system for therapeutic (drug delivery system) and MR diagnostic purposes.

Immobilized Pd-Ag bimetallic nanoparticles on polymeric nanofibers as an effective catalyst: effective loading of Ag with bimetallic functionality through Pd nucleated nanofibers.

PubMed

Ranjith, Kugalur Shanmugam; Celebioglu, Asli; Uyar, Tamer

2018-06-15

Here, we present a precise process for synthesizing Pd-Ag bimetallic nanoparticles (NPs) onto polymeric nanofibers by decorating Pd-NPs through atomic layer deposition followed by a chemical reduction process for tagging Ag nanostructures with bimetallic functionality. The results show that Pd-NPs act as a nucleation platform for tagging Ag and form Pd-Ag bimetallic NPs with a monodisperse nature with significant catalytic enhancement to the reaction rate over the bimetallic nature of the Pd-Ag ratio. A Pd-NP decorated polymeric nanofibrous web acts as an excellent platform for the encapsulation or interaction of Ag, which prevents agglomeration and promotes the interaction of Ag ions only on the surface of the Pd-NPs. We observed an effective reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by sodium borohydride (NaBH 4 ) to access the catalytic activity of Pd-Ag bimetallic NPs on a free-standing flexible polymeric nanofibrous web as a support. The captive formation of the polymeric nanofibrous web with Pd-Ag bimetallic functionality exhibited superior and stable catalytic performance with reduction rates of 0.0719, 0.1520, and 0.0871 min -1 for different loadings of Ag on Pd decorated nanofibrous webs such as Pd/Ag(0.01), Pd/Ag(0.03), and Pd/Ag(0.05), respectively. The highly faceted Pd-Ag NPs with an immobilized nature improves the catalytic functionality by enhancing the binding energy of the 4-NP adsorbate to the surface of the NPs. With the aid of bimetallic functionality, the nanofibrous web was demonstrated as a hybrid heterogeneous photocatalyst with a 3.16-fold enhancement in the reaction rate as compared with the monometallic decorative nature of NaBH 4 as a reducing agent. The effective role of the monodisperse nature of Pd ions with an ultralow content as low as 3 wt% and the tunable ratio of Ag on the nanofibrous web induced effective catalytic activity over multiple cycles.

Immobilized Pd-Ag bimetallic nanoparticles on polymeric nanofibers as an effective catalyst: effective loading of Ag with bimetallic functionality through Pd nucleated nanofibers

NASA Astrophysics Data System (ADS)

Shanmugam Ranjith, Kugalur; Celebioglu, Asli; Uyar, Tamer

2018-06-01

Here, we present a precise process for synthesizing Pd-Ag bimetallic nanoparticles (NPs) onto polymeric nanofibers by decorating Pd-NPs through atomic layer deposition followed by a chemical reduction process for tagging Ag nanostructures with bimetallic functionality. The results show that Pd-NPs act as a nucleation platform for tagging Ag and form Pd-Ag bimetallic NPs with a monodisperse nature with significant catalytic enhancement to the reaction rate over the bimetallic nature of the Pd-Ag ratio. A Pd-NP decorated polymeric nanofibrous web acts as an excellent platform for the encapsulation or interaction of Ag, which prevents agglomeration and promotes the interaction of Ag ions only on the surface of the Pd-NPs. We observed an effective reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by sodium borohydride (NaBH4) to access the catalytic activity of Pd-Ag bimetallic NPs on a free-standing flexible polymeric nanofibrous web as a support. The captive formation of the polymeric nanofibrous web with Pd-Ag bimetallic functionality exhibited superior and stable catalytic performance with reduction rates of 0.0719, 0.1520, and 0.0871 min‑1 for different loadings of Ag on Pd decorated nanofibrous webs such as Pd/Ag(0.01), Pd/Ag(0.03), and Pd/Ag(0.05), respectively. The highly faceted Pd-Ag NPs with an immobilized nature improves the catalytic functionality by enhancing the binding energy of the 4-NP adsorbate to the surface of the NPs. With the aid of bimetallic functionality, the nanofibrous web was demonstrated as a hybrid heterogeneous photocatalyst with a 3.16-fold enhancement in the reaction rate as compared with the monometallic decorative nature of NaBH4 as a reducing agent. The effective role of the monodisperse nature of Pd ions with an ultralow content as low as 3 wt% and the tunable ratio of Ag on the nanofibrous web induced effective catalytic activity over multiple cycles.

Clinical value of natriuretic peptides in chronic kidney disease.

PubMed

Santos-Araújo, Carla; Leite-Moreira, Adelino; Pestana, Manuel

2015-01-01

According to several lines of evidence, natriuretic peptides (NP) are the main components of a cardiac-renal axis that operate in clinical conditions of decreased cardiac hemodynamic tolerance to regulate sodium homeostasis, blood pressure and vascular function. Even though it is reasonable to assume that NP may exert a relevant role in the adaptive response to renal mass ablation, evidence gathered so far suggest that this contribution is probably complex and dependent on the type and degree of the functional mass loss. In the last years NP have been increasingly used to diagnose, monitor treatment and define the prognosis of several cardiovascular (CV) diseases. However, in many clinical settings, like chronic kidney disease (CKD), the predictive value of these biomarkers has been questioned. In fact, it is now well established that renal function significantly affects the plasmatic levels of NP and that renal failure is the clinical condition associated with the highest plasmatic levels of these peptides. The complexity of the relation between NP plasmatic levels and CV and renal functions has obvious consequences, as it may limit the predictive value of NP in CV assessment of CKD patients and be a demanding exercise for clinicians involved in the daily management of these patients. This review describes the role of NP in the regulatory response to renal function loss and addresses the main factors involved in the clinical valorization of the peptides in the context of significant renal failure. Copyright © 2015 The Authors. Published by Elsevier España, S.L.U. All rights reserved.

The effect of the UV photon flux on the photoelectrocatalytic degradation of endocrine-disrupting alkylphenolic chemicals.

PubMed

da Silva, Salatiel Wohlmuth; Viegas, Cheila; Ferreira, Jane Zoppas; Rodrigues, Marco Antônio Siqueira; Bernardes, Andréa Moura

2016-10-01

The photoelectrocatalytic (PEC) degradation of 4-nonylphenol ethoxylate (NP4EO) using a low, moderate, or high UV photon flux in different treatment times was investigated. The byproducts were verified using gas chromatography with flame ionization detection (GC-FID) and gas chromatography with quadrupole mass analyzer (GC-qMS). The GC results showed that the use of a low (2.89 μmol m(-2)s(-1)) or a high (36.16 μmol m(-2)s(-1)) UV photon flux reaching the anode surface was associated to the production of alcohols and the toxic byproduct nonylphenol (NP), leading to the same degradation pathway. Meanwhile, the use of a moderate UV photon flux (14.19 μmol m(-2)s(-1)) reaching the anode surface did not produce alcohols or the NP toxic byproduct. This study demonstrates that different UV photon fluxes will have an influence in the degradation of NP4EO with or without generation of toxic byproducts. Furthermore, it is concluded that, after the determination of the UV photon flux able to degrade NP4EO without NP formation, the treatment time is essential in removal of NP4EO, since increasing the treatment time of 4 to 10 h, when using the PEC best conditions (moderate UV photon flux), implies in a higher treatment efficiency.

Coordination-based gold nanoparticle layers.

PubMed

Wanunu, Meni; Popovitz-Biro, Ronit; Cohen, Hagai; Vaskevich, Alexander; Rubinstein, Israel

2005-06-29

Gold nanoparticle (NP) mono- and multilayers were constructed on gold surfaces using coordination chemistry. Hydrophilic Au NPs (6.4 nm average core diameter), capped with a monolayer of 6-mercaptohexanol, were modified by partial substitution of bishydroxamic acid disulfide ligand molecules into their capping layer. A monolayer of the ligand-modified Au NPs was assembled via coordination with Zr4+ ions onto a semitransparent Au substrate (15 nm Au, evaporated on silanized glass and annealed) precoated with a self-assembled monolayer of the bishydroxamate disulfide ligand. Layer-by-layer construction of NP multilayers was achieved by alternate binding of Zr4+ ions and ligand-modified NPs onto the first NP layer. Characterization by atomic force microscopy (AFM), ellipsometry, wettability, transmission UV-vis spectroscopy, and cross-sectional transmission electron microscopy showed regular growth of NP layers, with a similar NP density in successive layers and gradually increased roughness. The use of coordination chemistry enables convenient step-by-step assembly of different ligand-possessing components to obtain elaborate structures. This is demonstrated by introducing nanometer-scale vertical spacing between a NP layer and the gold surface, using a coordination-based organic multilayer. Electrical characterization of the NP films was carried out using conductive AFM, emphasizing the barrier properties of the organic spacer multilayer. The results exhibit the potential of coordination self-assembly in achieving highly controlled composite nanostructures comprising molecules, NPs, and other ligand-derivatized components.

Combined Subchronic Toxicity of Aluminum (III), Titanium (IV) and Silicon (IV) Oxide Nanoparticles and Its Alleviation with a Complex of Bioprotectors.

PubMed

Minigalieva, Ilzira A; Katsnelson, Boris A; Privalova, Larisa I; Sutunkova, Marina P; Gurvich, Vladimir B; Shur, Vladimir Y; Shishkina, Ekaterina V; Valamina, Irene E; Makeyev, Oleg H; Panov, Vladimir G; Varaksin, Anatoly N; Bushueva, Tatiana V; Sakhautdinova, Renata R; Klinova, Svetlana V; Solovyeva, Svetlana N; Meshtcheryakova, Ekaterina Y

2018-03-13

Stable suspensions of metal/metalloid oxide nanoparticles (MeO-NPs) obtained by laser ablation of 99.99% pure elemental aluminum, titanium or silicon under a layer of deionized water were used separately, or in three binary combinations, or in a ternary combination to induce subchronic intoxications in rats. To this end, the MeO-NPs were repeatedly injected intraperitoneally (i.p.) 18 times during 6 weeks before measuring a large number of functional, biochemical, morphological and cytological indices for the organism's status. In many respects, the Al₂O₃-NP was found to be the most toxic species alone and the most dangerous component of the combinations studied. Mathematical modeling with the help of the Response Surface Methodology showed that, as well as in the case of any other binary toxic combinations previously investigated by us, the organism's response to a simultaneous exposure to any two of the MeO-NP species under study was characterized by a complex interaction between all possible types of combined toxicity (additivity, subadditivity or superadditivity of unidirectional action and different variants of opposite effects) depending on which outcome this type was estimated for and on effect and dose levels. With any third MeO-NP species acting in the background, the type of combined toxicity displayed by the other two remained virtually the same or changed significantly, becoming either more or less unfavorable. Various harmful effects produced by the (Al₂O₃-NP + TiO₂-NP + SiO₂-NP)-combination, including its genotoxicity, were substantially attenuated by giving the rats per os during the entire exposure period a complex of innocuous bioactive substances expected to increase the organism's antitoxic resistance.

Combined Subchronic Toxicity of Aluminum (III), Titanium (IV) and Silicon (IV) Oxide Nanoparticles and Its Alleviation with a Complex of Bioprotectors

PubMed Central

Minigalieva, Ilzira A.; Katsnelson, Boris A.; Privalova, Larisa I.; Sutunkova, Marina P.; Gurvich, Vladimir B.; Shur, Vladimir Y.; Shishkina, Ekaterina V.; Valamina, Irene E.; Makeyev, Oleg H.; Panov, Vladimir G.; Varaksin, Anatoly N.; Bushueva, Tatiana V.; Sakhautdinova, Renata R.; Klinova, Svetlana V.; Solovyeva, Svetlana N.; Meshtcheryakova, Ekaterina Y.

2018-01-01

Stable suspensions of metal/metalloid oxide nanoparticles (MeO-NPs) obtained by laser ablation of 99.99% pure elemental aluminum, titanium or silicon under a layer of deionized water were used separately, or in three binary combinations, or in a ternary combination to induce subchronic intoxications in rats. To this end, the MeO-NPs were repeatedly injected intraperitoneally (i.p.) 18 times during 6 weeks before measuring a large number of functional, biochemical, morphological and cytological indices for the organism’s status. In many respects, the Al2O3-NP was found to be the most toxic species alone and the most dangerous component of the combinations studied. Mathematical modeling with the help of the Response Surface Methodology showed that, as well as in the case of any other binary toxic combinations previously investigated by us, the organism’s response to a simultaneous exposure to any two of the MeO-NP species under study was characterized by a complex interaction between all possible types of combined toxicity (additivity, subadditivity or superadditivity of unidirectional action and different variants of opposite effects) depending on which outcome this type was estimated for and on effect and dose levels. With any third MeO-NP species acting in the background, the type of combined toxicity displayed by the other two remained virtually the same or changed significantly, becoming either more or less unfavorable. Various harmful effects produced by the (Al2O3-NP + TiO2-NP + SiO2-NP)-combination, including its genotoxicity, were substantially attenuated by giving the rats per os during the entire exposure period a complex of innocuous bioactive substances expected to increase the organism’s antitoxic resistance. PMID:29534019

Mucus-penetrating nanoparticles: Promising drug delivery systems for the photodynamic therapy of intestinal cancer.

PubMed

Anderski, Juliane; Mahlert, Laura; Mulac, Dennis; Langer, Klaus

2018-05-17

Photodynamic therapy (PDT) is an auspicious therapy approach for the treatment of cancer. Despite its numerous benefits, the drug delivery of the used photosensitizer (PS) to target locations inside the human body remains a main therapy challenge, since the standard intravenous PS injection often causes systemic side-effects. To circumvent this therapy drawback, the oral application represents a promising administration alternative. Especially for the treatment of intestinal cancer it offers the possibility of a local treatment with a reduced likelihood for adverse drug reactions. To establish a suitable drug delivery system for intestinal PDT, we developed nanoparticles (NP) of the biodegradable and biocompatible polymer poly(lactic-co-glycolic) acid (PLGA), loaded with the model PS 5,10,15,20-tetrakis(m-hydroxyphenyl)porphyrin (mTHPP). By functionalizing the particle surface with either poly(ethylene glycol) (PEG) or chitosan (CS), mucus-penetrating or mucoadhesive properties were obtained. These particle characteristics are important to enable an overcoming of the intestinal mucus barrier and thus lead to a PS accumulation close to and in the target cells. In permeation studies with a biosimilar mucus and in cell culture experiments with mucus-covered Caco-2 cells, PEG-modified NP were identified as a superior drug vehicle for an intestinal PDT, compared to surface unmodified or mucoadhesive NP. Copyright © 2018. Published by Elsevier B.V.

Modification and Utilization of Nanoporous Gold for Loading and Release of Drugs

NASA Astrophysics Data System (ADS)

Al-badri, Ibtisam

Nanoporous gold (np-Au) is a sponge-like structure of gold, which can be created by removing the less noble element from the precursor alloy, most typically silver or copper, using different chemical or electrochemical methods. It consists of interconnected ligaments and gaps between the ligaments, whose width can range from a few nanometers to a few hundreds of nanometers, creating a high surface area-to-volume ratio. Due to its many important properties (e.g., conductivity, high surface area-to-volume ratio, plasmonic response, biocompatibility, chemically inertness, and physically robustness), np-Au is suitable for different types of applications, including as a transducer for biosensors, in catalysis, for biomolecule separation, as a substrate for enzyme immobilization, and in drug delivery. The widths of the ligaments and gaps of np-Au can be easily tuned by varying conditions during the pre- or post-production process, for example, time kept in an acid bath and post-annealing (e.g. thermal, chemical, and electrochemical), depending on the requirement of the study. Thermal annealing is a commonly used process for tuning the ligaments and pore size of np-Au. However, the effects of thermal annealing on modification of ligaments and gaps sizes are not completely understood and more research needs to be done. Herein, we have explored the effect of annealing time and thickness of the np-Au sample on modification of ligaments and gaps. Furthermore, we used the electroless plating method to cover the pores or gaps partially on the surface without modifying the interior of np-Au. As-prepared np-Au was then studied as a platform for molecular loading and releasing kinetics for the possible use in drug delivery. We have found that simply applying the electroless deposition for 1 to 5 min can drastically decrease the rate of release of the molecules, and flow cell-based loading is the preferred way to load the molecules inside np-Au compared to the static method. The structure of the np-Au monoliths before and after the modification was characterized using Energy-Dispersive X-ray Spectroscopy (EDS) and scanning electron microscopy (SEM), whereas the molecular loading and releasing studies were performed using UV-Vis spectrophotometer.

Composite multifunctional nanostructures based on ZnO tetrapods and superparamagnetic Fe3O4 nanoparticles.

PubMed

Villani, M; Rimoldi, T; Calestani, D; Lazzarini, L; Chiesi, V; Casoli, F; Albertini, F; Zappettini, A

2013-04-05

A nanocomposite material is obtained by coupling superparamagnetic magnetite nanoparticles (Fe3O4 NP) and vapor phase grown zinc oxide nanostructures with 'tetrapod' morphology (ZnO TP). The aim is the creation of a multifunctional material which retains the attractive features of ZnO (e.g. surface reactivity, strong UV emission, piezoelectricity) together with added magnetism. Structural, morphological, optical, magnetic and functional characterization are performed. In particular, the high saturation magnetization of Fe3O4 NP (above 50 A m(2) kg(-1)), the strong UV luminescence and the enhanced photocatalytic activity of coupled nanostructures are discussed. Thus the nanocomposite turns out to be suitable for applications in energy harvesting and conversion, gas- and bio-sensing, bio-medicine and filter-free photocatalysis.

Development of dihydrochalcone-functionalized gold nanoparticles for augmented antineoplastic activity

PubMed Central

Moolani, Harsh V; Tockstein, Sarah; Thompson, David H; Dakshinamurthy, Rajalingam

2018-01-01

Background Phloridzin, an antidiabetic and antineoplastic agent usually found in fruit trees, is a dihydrochalcone constituent that has a clinical/pharmaceutical significance as a sodium-glucose linked transport 2 (SGLT2) inhibitor. While the aglycone metabolite of phloridzin, phloretin, displays a reduced capacity of SGLT2 inhibition, this nutraceutical displays enhanced antineoplastic activity in comparison to phloridzin. Purpose The objective of this study was to develop gold nanoparticle (AuNP) mediated delivery of phloridzin and phloretin and explore their anticancer mechanism through conjugation of the dihydrochalcones and the AuNP cores. Methods Phloridzin and phloretin conjugated AuNPs (Phl-AuNP and Pht-AuNP) were synthesized in single-step, rapid, biofriendly processes. The synthesized AuNPs morphology was characterized via transmission electron microscopy and ultraviolet-visible spectroscopy. The presence of phloridzin or phloretin was confirmed using scanning electron microscopy-energy dispersive x-ray spectroscopy. The percentage of organic component (phloridzin/phloretin) onto AuNPs surface was characterized using thermogravimetric analysis. Assessment of the antineoplastic potency of the dihydrochalcones conjugated AuNPs against cancerous cell lines (HeLa) was accomplished through monitoring via flow cytometry. Results The functionalized AuNPs were synthesized via a single-step method that relied only upon the redox potential of the conjugate itself and required no toxic chemicals. The synthesized Phl-AuNPs were found to be in the size range of 15±5 nm, whereas the Pht-AuNP were found to be 8±3 nm, placing both conjugated AuNPs well within the size range necessary for successful pharmaceutical applications. These assays demonstrate a significant increase in the cancerous cell toxicities as a result of the conjugation of the drugs to AuNPs, as indicated by the 17.45-fold increase in the efficacy of Pht-AuNPs over pure phloretin, and the 4.49-fold increase in efficacy of Phl-AuNP over pure phloridzin. Conclusion We report a simple, biofriendly process using the reducing and capping potential of the dihydrochalcones, phloridzin and phloretin, to synthesize stable AuNPs that have promising futures as potential antineoplastic agents. PMID:29636609

Development of dihydrochalcone-functionalized gold nanoparticles for augmented antineoplastic activity.

PubMed

Payne, Jason N; Badwaik, Vivek D; Waghwani, Hitesh K; Moolani, Harsh V; Tockstein, Sarah; Thompson, David H; Dakshinamurthy, Rajalingam

2018-01-01

Phloridzin, an antidiabetic and antineoplastic agent usually found in fruit trees, is a dihydrochalcone constituent that has a clinical/pharmaceutical significance as a sodium-glucose linked transport 2 (SGLT2) inhibitor. While the aglycone metabolite of phloridzin, phloretin, displays a reduced capacity of SGLT2 inhibition, this nutraceutical displays enhanced antineoplastic activity in comparison to phloridzin. The objective of this study was to develop gold nanoparticle (AuNP) mediated delivery of phloridzin and phloretin and explore their anticancer mechanism through conjugation of the dihydrochalcones and the AuNP cores. Phloridzin and phloretin conjugated AuNPs (Phl-AuNP and Pht-AuNP) were synthesized in single-step, rapid, biofriendly processes. The synthesized AuNPs morphology was characterized via transmission electron microscopy and ultraviolet-visible spectroscopy. The presence of phloridzin or phloretin was confirmed using scanning electron microscopy-energy dispersive x-ray spectroscopy. The percentage of organic component (phloridzin/phloretin) onto AuNPs surface was characterized using thermogravimetric analysis. Assessment of the antineoplastic potency of the dihydrochalcones conjugated AuNPs against cancerous cell lines (HeLa) was accomplished through monitoring via flow cytometry. The functionalized AuNPs were synthesized via a single-step method that relied only upon the redox potential of the conjugate itself and required no toxic chemicals. The synthesized Phl-AuNPs were found to be in the size range of 15±5 nm, whereas the Pht-AuNP were found to be 8±3 nm, placing both conjugated AuNPs well within the size range necessary for successful pharmaceutical applications. These assays demonstrate a significant increase in the cancerous cell toxicities as a result of the conjugation of the drugs to AuNPs, as indicated by the 17.45-fold increase in the efficacy of Pht-AuNPs over pure phloretin, and the 4.49-fold increase in efficacy of Phl-AuNP over pure phloridzin. We report a simple, biofriendly process using the reducing and capping potential of the dihydrochalcones, phloridzin and phloretin, to synthesize stable AuNPs that have promising futures as potential antineoplastic agents.

Influence of the bound polymer layer on nanoparticle diffusion in polymer melts

DOE PAGES

Griffin, Philip J.; Bocharova, Vera; Middleton, L. Robert; ...

2016-09-23

We measure the center-of-mass diffusion of silica nanoparticles (NPs) in entangled poly(2-vinylpyridine) (P2VP) melts using Rutherford backscattering spectrometry. While these NPs are well within the size regime where enhanced, nonhydrodynamic NP transport is theoretically predicted and has been observed experimentally (2R NP/d tube ≈ 3, where 2R NP is the NP diameter and d tube is the tube diameter), we find that the diffusion of these NPs in P2VP is in fact well-described by the hydrodynamic Stokes–Einstein relation. The effective NP diameter 2R eff is significantly larger than 2R NP and strongly dependent on P2VP molecular weight, consistent with themore » presence of a bound polymer layer on the NP surface with thickness h eff ≈ 1.1R g. Our results show that the bound polymer layer significantly augments the NP hydrodynamic size in polymer melts with attractive polymer–NP interactions and effectively transitions the mechanism of NP diffusion from the nonhydrodynamic to hydrodynamic regime, particularly at high molecular weights where NP transport is expected to be notably enhanced. Lastly, these results provide the first experimental demonstration that hydrodynamic NP transport in polymer melts requires particles of size ≳5d tube, consistent with recent theoretical predictions.« less

Self-Assembled Layering of Magnetic Nanoparticles in a Ferrofluid on Silicon Surfaces.

PubMed

Theis-Bröhl, Katharina; Vreeland, Erika C; Gomez, Andrew; Huber, Dale L; Saini, Apurve; Wolff, Max; Maranville, Brian B; Brok, Erik; Krycka, Kathryn L; Dura, Joseph A; Borchers, Julie A

2018-02-07

This article describes the three-dimensional self-assembly of monodisperse colloidal magnetite nanoparticles (NPs) from a dilute water-based ferrofluid onto a silicon surface and the dependence of the resultant magnetic structure on the applied field. The NPs assemble into close-packed layers on the surface followed by more loosely packed ones. The magnetic field-dependent magnetization of the individual NP layers depends on both the rotational freedom of the layer and the magnetization of the adjacent layers. For layers in which the NPs are more free to rotate, the easy axis of the NP can readily orient along the field direction. In more dense packing, free rotation of the NPs is hampered, and the NP ensembles likely build up quasi-domain states to minimize energy, which leads to lower magnetization in those layers. Detailed analysis of polarized neutron reflectometry data together with model calculations of the arrangement of the NPs within the layers and input from small-angle scattering measurements provide full characterization of the core/shell NP dimensions, degree of chaining, arrangement of the NPs within the different layers, and magnetization depth profile.

Acid-base accounting to predict post-mining drainage quality on surface mines.

PubMed

Skousen, J; Simmons, J; McDonald, L M; Ziemkiewicz, P

2002-01-01

Acid-base accounting (ABA) is an analytical procedure that provides values to help assess the acid-producing and acid-neutralizing potential of overburden rocks prior to coal mining and other large-scale excavations. This procedure was developed by West Virginia University scientists during the 1960s. After the passage of laws requiring an assessment of surface mining on water quality, ABA became a preferred method to predict post-mining water quality, and permitting decisions for surface mines are largely based on the values determined by ABA. To predict the post-mining water quality, the amount of acid-producing rock is compared with the amount of acid-neutralizing rock, and a prediction of the water quality at the site (whether acid or alkaline) is obtained. We gathered geologic and geographic data for 56 mined sites in West Virginia, which allowed us to estimate total overburden amounts, and values were determined for maximum potential acidity (MPA), neutralization potential (NP), net neutralization potential (NNP), and NP to MPA ratios for each site based on ABA. These values were correlated to post-mining water quality from springs or seeps on the mined property. Overburden mass was determined by three methods, with the method used by Pennsylvania researchers showing the most accurate results for overburden mass. A poor relationship existed between MPA and post-mining water quality, NP was intermediate, and NNP and the NP to MPA ratio showed the best prediction accuracy. In this study, NNP and the NP to MPA ratio gave identical water quality prediction results. Therefore, with NP to MPA ratios, values were separated into categories: <1 should produce acid drainage, between 1 and 2 can produce either acid or alkaline water conditions, and >2 should produce alkaline water. On our 56 surface mined sites, NP to MPA ratios varied from 0.1 to 31, and six sites (11%) did not fit the expected pattern using this category approach. Two sites with ratios <1 did not produce acid drainage as predicted (the drainage was neutral), and four sites with a ratio >2 produced acid drainage when they should not have. These latter four sites were either mined very slowly, had nonrepresentative ABA data, received water from an adjacent underground mine, or had a surface mining practice that degraded the water. In general, an NP to MPA ratio of <1 produced mostly acid drainage sites, between 1 and 2 produced mostly alkaline drainage sites, while NP to MPA ratios >2 produced alkaline drainage with a few exceptions. Using these values, ABA is a good tool to assess overburden quality before surface mining and to predict post-mining drainage quality after mining. The interpretation from ABA values was correct in 50 out of 52 cases (96%), excluding the four anomalous sites, which had acid water for reasons other than overburden quality.

Synthesis, secretion, function, metabolism and application of natriuretic peptides in heart failure.

PubMed

Fu, Shihui; Ping, Ping; Wang, Fengqi; Luo, Leiming

2018-01-01

As a family of hormones with pleiotropic effects, natriuretic peptide (NP) system includes atrial NP (ANP), B-type NP (BNP), C-type NP (CNP), dendroaspis NP and urodilatin, with NP receptor-A (guanylate cyclase-A), NP receptor-B (guanylate cyclase-B) and NP receptor-C (clearance receptor). These peptides are genetically distinct, but structurally and functionally related for regulating circulatory homeostasis in vertebrates. In humans, ANP and BNP are encoded by NP precursor A (NPPA) and NPPB genes on chromosome 1, whereas CNP is encoded by NPPC on chromosome 2. NPs are synthesized and secreted through certain mechanisms by cardiomyocytes, fibroblasts, endotheliocytes, immune cells (neutrophils, T-cells and macrophages) and immature cells (embryonic stem cells, muscle satellite cells and cardiac precursor cells). They are mainly produced by cardiovascular, brain and renal tissues in response to wall stretch and other causes. NPs provide natriuresis, diuresis, vasodilation, antiproliferation, antihypertrophy, antifibrosis and other cardiometabolic protection. NPs represent body's own antihypertensive system, and provide compensatory protection to counterbalance vasoconstrictor-mitogenic-sodium retaining hormones, released by renin-angiotensin-aldosterone system (RAAS) and sympathetic nervous system (SNS). NPs play central roles in regulation of heart failure (HF), and are inactivated through not only NP receptor-C, but also neutral endopeptidase (NEP), dipeptidyl peptidase-4 and insulin degrading enzyme. Both BNP and N-terminal proBNP are useful biomarkers to not only make the diagnosis and assess the severity of HF, but also guide the therapy and predict the prognosis in patients with HF. Current NP-augmenting strategies include the synthesis of NPs or agonists to increase NP bioactivity and inhibition of NEP to reduce NP breakdown. Nesiritide has been established as an available therapy, and angiotensin receptor blocker NEP inhibitor (ARNI, LCZ696) has obtained extremely encouraging results with decreased morbidity and mortality. Novel pharmacological approaches based on NPs may promote a therapeutic shift from suppressing the RAAS and SNS to re-balancing neuroendocrine dysregulation in patients with HF. The current review discussed the synthesis, secretion, function and metabolism of NPs, and their diagnostic, therapeutic and prognostic values in HF.

The role of aqueous leaf extract of Tinospora crispa as reducing and capping agents for synthesis of gold nanoparticles

NASA Astrophysics Data System (ADS)

Apriandanu, D. O. B.; Yulizar, Y.

2017-04-01

Environmentally friendly method for green synthesis of Au nanoparticles (AuNP) using aqueous leaf extract of Tinospora crispa (TLE) was reported. TLE has the ability for reducing and capping AuNP. Identification of active compounds in aqueous leaf extract was obtained by phytochemical analysis and Fourier transform infrared spectroscopy (FTIR). The AuNP-TLE growth was characterized using UV-Vis spectrophotometer. The particle size and the distribution of AuNP were confirmed by particle size analyzer (PSA). AuNP-TLE formation was optimized by varying the extract concentration and time of the synthesis process. UV-Vis absorption spectrum of optimum AuNP formation displayed by the surface plasmon resonance at maximum wavelength of λmax 536 nm. The PSA result showed that AuNP has size distribution of 80.60 nm and stable up to 21 days. TEM images showed that the size of the AuNP is ± 25 nm.

An Intrinsically Disordered Peptide from Ebola Virus VP35 Controls Viral RNA Synthesis by Modulating Nucleoprotein-RNA Interactions.

PubMed

Leung, Daisy W; Borek, Dominika; Luthra, Priya; Binning, Jennifer M; Anantpadma, Manu; Liu, Gai; Harvey, Ian B; Su, Zhaoming; Endlich-Frazier, Ariel; Pan, Juanli; Shabman, Reed S; Chiu, Wah; Davey, Robert A; Otwinowski, Zbyszek; Basler, Christopher F; Amarasinghe, Gaya K

2015-04-21

During viral RNA synthesis, Ebola virus (EBOV) nucleoprotein (NP) alternates between an RNA-template-bound form and a template-free form to provide the viral polymerase access to the RNA template. In addition, newly synthesized NP must be prevented from indiscriminately binding to noncognate RNAs. Here, we investigate the molecular bases for these critical processes. We identify an intrinsically disordered peptide derived from EBOV VP35 (NPBP, residues 20-48) that binds NP with high affinity and specificity, inhibits NP oligomerization, and releases RNA from NP-RNA complexes in vitro. The structure of the NPBP/ΔNPNTD complex, solved to 3.7 Å resolution, reveals how NPBP peptide occludes a large surface area that is important for NP-NP and NP-RNA interactions and for viral RNA synthesis. Together, our results identify a highly conserved viral interface that is important for EBOV replication and can be targeted for therapeutic development. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Efficient Energy Transfer from Near-Infrared Emitting Gold Nanoparticles to Pendant Ytterbium(III).

PubMed

Crawford, Scott E; Andolina, Christopher M; Kaseman, Derrick C; Ryoo, Bo Hyung; Smith, Ashley M; Johnston, Kathryn A; Millstone, Jill E

2017-12-13

Here, we demonstrate efficient energy transfer from near-infrared-emitting ortho-mercaptobenzoic acid-capped gold nanoparticles (AuNPs) to pendant ytterbium(III) cations. These functional materials combine the high molar absorptivity (1.21 × 10 6 M -1 cm -1 ) and broad excitation features (throughout the UV and visible regions) of AuNPs with the narrow emissive properties of lanthanides. Interaction between the AuNP ligand shell and ytterbium is determined using both nuclear magnetic resonance and electron microscopy measurements. In order to identify the mechanism of this energy transfer process, the distance of the ytterbium(III) from the surface of the AuNPs is systematically modulated by changing the size of the ligand appended to the AuNP. By studying the energy transfer efficiency from the various AuNP conjugates to pendant ytterbium(III) cations, a Dexter-type energy transfer mechanism is suggested, which is an important consideration for applications ranging from catalysis to energy harvesting. Taken together, these experiments lay a foundation for the incorporation of emissive AuNPs in energy transfer systems.

Wetlands inform how climate extremes influence surface water expansion and contraction

NASA Astrophysics Data System (ADS)

Vanderhoof, Melanie K.; Lane, Charles R.; McManus, Michael G.; Alexander, Laurie C.; Christensen, Jay R.

2018-03-01

Effective monitoring and prediction of flood and drought events requires an improved understanding of how and why surface water expansion and contraction in response to climate varies across space. This paper sought to (1) quantify how interannual patterns of surface water expansion and contraction vary spatially across the Prairie Pothole Region (PPR) and adjacent Northern Prairie (NP) in the United States, and (2) explore how landscape characteristics influence the relationship between climate inputs and surface water dynamics. Due to differences in glacial history, the PPR and NP show distinct patterns in regards to drainage development and wetland density, together providing a diversity of conditions to examine surface water dynamics. We used Landsat imagery to characterize variability in surface water extent across 11 Landsat path/rows representing the PPR and NP (images spanned 1985-2015). The PPR not only experienced a 2.6-fold greater surface water extent under median conditions relative to the NP, but also showed a 3.4-fold greater change in surface water extent between drought and deluge conditions. The relationship between surface water extent and accumulated water availability (precipitation minus potential evapotranspiration) was quantified per watershed and statistically related to variables representing hydrology-related landscape characteristics (e.g., infiltration capacity, surface storage capacity, stream density). To investigate the influence stream connectivity has on the rate at which surface water leaves a given location, we modeled stream-connected and stream-disconnected surface water separately. Stream-connected surface water showed a greater expansion with wetter climatic conditions in landscapes with greater total wetland area, but lower total wetland density. Disconnected surface water showed a greater expansion with wetter climatic conditions in landscapes with higher wetland density, lower infiltration and less anthropogenic drainage. From these findings, we can expect that shifts in precipitation and evaporative demand will have uneven effects on surface water quantity. Accurate predictions regarding the effect of climate change on surface water quantity will require consideration of hydrology-related landscape characteristics including wetland storage and arrangement.

Improved expression of halorhodopsin for light-induced silencing of neuronal activity

PubMed Central

Zhao, Shengli; Cunha, Catarina; Zhang, Feng; Liu, Qun; Gloss, Bernd; Deisseroth, Karl; Augustine, George J.; Feng, Guoping

2011-01-01

The ability to control and manipulate neuronal activity within an intact mammalian brain is of key importance for mapping functional connectivity and for dissecting the neural circuitry underlying behaviors. We have previously generated transgenic mice that express channelrhodopsin-2 for light-induced activation of neurons and mapping of neural circuits. Here we describe transgenic mice that express halorhodopsin (NpHR), a light-driven chloride pump, that can be used to silence neuronal activity via light. Using the Thy-1 promoter to target NpHR expression to neurons, we found that neurons in these mice expressed high levels of NpHR-YFP and that illumination of cortical pyramidal neurons expressing NpHR-YFP led to rapid, reversible photoinhibition of action potential firing in these cells. However, NpHR-YFP expression led to the formation of numerous intracellular blebs, which may disrupt neuronal function. Labeling of various subcellular markers indicated that the blebs arise from retention of NpHR-YFP in the endoplasmic reticulum. By improving the signal peptide sequence and adding an ER export signal to NpHR-YFP, we eliminated the formation of blebs and dramatically increased the membrane expression of NpHR-YFP. Thus, the improved version of NpHR should serve as an excellent tool for neuronal silencing in vitro and in vivo. PMID:18931914

Proof-of-principle for SERS imaging of Aspergillus nidulans hyphae using in vivo synthesis of gold nanoparticles.

PubMed

Prusinkiewicz, Martin A; Farazkhorasani, Fatemeh; Dynes, James J; Wang, Jian; Gough, Kathleen M; Kaminskyj, Susan G W

2012-11-07

High spatial resolution methods to assess the physiology of growing cells should permit analysis of fungal biochemical composition. Whole colony methods cannot capture the details of physiology and organism-environment interaction, in part because the structure, function and composition of fungal hyphae vary within individual cells depending on their distance from the growing apex. Surface Enhanced Raman Scattering (SERS) can provide chemical information on materials that are in close contact with appropriate metal substrates, such as nanopatterned gold surfaces and gold nanoparticles (AuNPs). Since nanoparticles can be generated by living cells, we have created conditions for AuNP formation within and on the surface of Aspergillus nidulans hyphae in order to explore their potential for SERS analysis. AuNP distribution and composition have been assessed by UV-Vis spectroscopy, fluorescence light microscopy, transmission electron microscopy, and scanning transmission X-ray microscopy. AuNPs were often associated with hyphal walls, both in the peripheral cytoplasm and on the outer wall surface. Interpretation of SERS spectra is challenging, and will require validation for the diversity of organic molecules present. Here, we show proof-of-principle that it is possible to generate SERS spectra from nanoparticles grown in situ by living hyphae.

Screening metal nanoparticles using boron-doped diamond microelectrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivandini, Tribidasari A., E-mail: ivandini.tri@sci.ui.ac.id; Rangkuti, Prasmita K.; Einaga, Yasuaki

2016-04-19

Boron-doped diamond (BDD) microelectrodes were used to observe the correlation between electrocatalytic currents caused by individual Pt nanoparticle (Pt-np) collisions at the electrode. The BDD microelectrodes, ∼20 µm diameter and ∼2 µm particle size, were fabricated at the surface of tungsten wires. Pt-np with a size of 1 to 5 nm with agglomerations up to 20 nm was used for observation. The electrolytic currents were observed via catalytic reaction of 15 mM hydrazine in 50 mM phosphate buffer solution at Pt-np at 0.4 V when it collides with the surface of the microelectrodes. The low current noise and wider potential window in the measurements using BDD microelectrodemore » produced a better results, which represents a better correlation to the TEM result of the Pt-np, compared to when gold microelectrodes was used.« less

Effect of the pollution level on the functional bacterial groups aiming at degrading bisphenol A and nonylphenol in natural biofilms of an urban river.

PubMed

Cai, Wei; Li, Yi; Wang, Peifang; Niu, Lihua; Zhang, Wenlong; Wang, Chao

2016-08-01

Bisphenol A (BPA) and 4-nonylphenol (NP) are ubiquitous pollutants with estrogenic activity in aquatic environment and have attracted global concern due to their disruption of endocrine systems. This study investigated the spatial distribution characteristics of the bacterial groups involved in the degradation of BPA and NP within biofilms in an urban river using terminal restriction fragment length polymorphism based on 16S rRNA gene sequences. The effects of the pollution level and water parameters on these groups were also assessed. Hierarchical cluster analysis grouped the sampling sites into three clusters reflecting their varying nutrient pollution levels of relatively slight pollution (SP), moderate pollution (MP), and high pollution (HP) based on water quality data and Environmental Quality Standard for Surface Water of China (GB3838-2002). The BPA and NP concentration in river water ranged from 0.8 to 77.5 and 10.2 to 162.9 ng L(-1), respectively. Comamonadaceae, Pseudomonadaceae, Alcaligenaceae, Bacillaceae, Sphingomonadacea, Burkholderiaceae, and Rhizobiaceae were the dominant bacterial taxa involved in BPA and NP degradation, comprising an average of 9.8, 8.1, 7.6, 6.7, 6.2, 4.1, and 2.8 % of total sequences, respectively. The total abundance of these groups showed a slight upward trend and subsequently rapidly decreased with increasing pollution levels. The average proportion of Comamonadaceae in MP river sections was almost 1.5-2 times than that in SP or HP one. The distribution of functional groups was found related to environmental variables, especially pH, conductivity, ammonium nitrogen (NH3-N), and BPA. The abundance of Comamonadaceae and Rhizobiaceae was both closely related to higher values of pH and conductivity as well as lower concentrations of NP and BPA. Alcaligenaceae and Pseudomonadaceae were associated with higher concentrations of TP and CODMn and inversely correlated with DO concentration. This study might provide effective data on bacterial group changes in polluted urban rivers.

Phenol adsorption on surface-functionalized iron oxide nanoparticles: modeling of the kinetics, isotherm, and mechanism

NASA Astrophysics Data System (ADS)

Yoon, Soon Uk; Mahanty, Biswanath; Ha, Hun Moon; Kim, Chang Gyun

2016-06-01

Phenol adsorption from aqueous solution was carried out using uncoated and methyl acrylic acid (MAA)-coated iron oxide nanoparticles (NPs), having size <10 nm, as adsorbents. Batch adsorption studies revealed that the phenol removal efficiency of MAA-coated NPs (950 mg g-1) is significantly higher than that of uncoated NPs (550 mg g-1) under neutral to acidic conditions. However, this improvement disappears above pH 9. The adsorption data under optimized conditions (pH 7) were modeled with pseudo-first- and pseudo-second-order kinetics and subjected to Freundlich and Langmuir isotherms. The analysis determined that pseudo-second-order kinetics and the Freundlich model are appropriate for both uncoated and MAA-coated NPs (all R 2 > 0.98). X-ray photoelectron spectroscopy analysis of pristine and phenol-adsorbed NPs revealed core-level binding energy and charge for Fe(2 s) and O(1 s) on the NP surfaces. The calculations suggest that phenol adsorption onto MAA-coated NPs is a charge transfer process, where the adsorbate (phenol) acts as an electron donor and the NP surface (Fe, O) as an electron acceptor. However, a physisorption process appears to be the relevant mechanism for uncoated NPs.

Membrane mimetic surface functionalization of nanoparticles: Methods and applications

PubMed Central

Weingart, Jacob; Vabbilisetty, Pratima; Sun, Xue-Long

2013-01-01

Nanoparticles (NPs), due to their size-dependent physical and chemical properties, have shown remarkable potential for a wide range of applications over the past decades. Particularly, the biological compatibilities and functions of NPs have been extensively studied for expanding their potential in areas of biomedical application such as bioimaging, biosensing, and drug delivery. In doing so, surface functionalization of NPs by introducing synthetic ligands and/or natural biomolecules has become a critical component in regards to the overall performance of the NP system for its intended use. Among known examples of surface functionalization, the construction of an artificial cell membrane structure, based on phospholipids, has proven effective in enhancing biocompatibility and has become a viable alternative to more traditional modifications, such as direct polymer conjugation. Furthermore, certain bioactive molecules can be immobilized onto the surface of phospholipid platforms to generate displays more reminiscent of cellular surface components. Thus, NPs with membrane-mimetic displays have found use in a range of bioimaging, biosensing, and drug delivery applications. This review herein describes recent advances in the preparations and characterization of integrated functional NPs covered by artificial cell membrane structures and their use in various biomedical applications. PMID:23688632

Proteomic and Lipidomic Analysis of Nanoparticle Corona upon Contact with Lung Surfactant Reveals Differences in Protein, but Not Lipid Composition.

PubMed

Raesch, Simon Sebastian; Tenzer, Stefan; Storck, Wiebke; Rurainski, Alexander; Selzer, Dominik; Ruge, Christian Arnold; Perez-Gil, Jesus; Schaefer, Ulrich Friedrich; Lehr, Claus-Michael

2015-12-22

Pulmonary surfactant (PS) constitutes the first line of host defense in the deep lung. Because of its high content of phospholipids and surfactant specific proteins, the interaction of inhaled nanoparticles (NPs) with the pulmonary surfactant layer is likely to form a corona that is different to the one formed in plasma. Here we present a detailed lipidomic and proteomic analysis of NP corona formation using native porcine surfactant as a model. We analyzed the adsorbed biomolecules in the corona of three NP with different surface properties (PEG-, PLGA-, and Lipid-NP) after incubation with native porcine surfactant. Using label-free shotgun analysis for protein and LC-MS for lipid analysis, we quantitatively determined the corona composition. Our results show a conserved lipid composition in the coronas of all investigated NPs regardless of their surface properties, with only hydrophilic PEG-NPs adsorbing fewer lipids in total. In contrast, the analyzed NP displayed a marked difference in the protein corona, consisting of up to 417 different proteins. Among the proteins showing significant differences between the NP coronas, there was a striking prevalence of molecules with a notoriously high lipid and surface binding, such as, e.g., SP-A, SP-D, DMBT1. Our data indicate that the selective adsorption of proteins mediates the relatively similar lipid pattern in the coronas of different NPs. On the basis of our lipidomic and proteomic analysis, we provide a detailed set of quantitative data on the composition of the surfactant corona formed upon NP inhalation, which is unique and markedly different to the plasma corona.

Study of serum interaction with a cationic nanoparticle: Implications for in vitro endocytosis, cytotoxicity and genotoxicity.

PubMed

Merhi, Maysaloun; Dombu, Christophe Youta; Brient, Alizée; Chang, Jiang; Platel, Anne; Le Curieux, Frank; Marzin, Daniel; Nesslany, Fabrice; Betbeder, Didier

2012-02-14

We used well-characterized and positively charged nanoparticles (NP(+)) to investigate the importance of cell culture conditions, specifically the presence of serum and proteins, on NP(+) physicochemical characteristics, and the consequences for their endocytosis and genotoxicity in bronchial epithelial cells (16HBE14o-). NP(+) surface charge was significantly reduced, proportionally to NP(+)/serum and NP(+)/BSA ratios, while NP(+) size was not modified. Microscopy studies showed high endocytosis of NP(+) in 16HBE14o-, and serum/proteins impaired this internalization in a dose-dependent manner. Toxicity studies showed no cytotoxicity, even for very high doses of NP(+). No genotoxicity was observed with classic comet assay while primary oxidative DNA damage was observed when using the lesion-specific repair enzyme, formamidopyrimidine DNA-glycosylase (FPG). The micronucleus test showed NP(+) genotoxicity only for very high doses that cannot be attained in vivo. The low toxicity of these NP(+) might be explained by their high exocytosis from 16HBE14o- cells. Our results confirm the importance of serum and proteins on nanoparticles endocytosis and genotoxicity. Copyright © 2011 Elsevier B.V. All rights reserved.

Mutagenic activities of a chlorination by-product of butamifos, its structural isomer, and their related compounds.

PubMed

Kamoshita, Masahiro; Kosaka, Koji; Endo, Osamu; Asami, Mari; Aizawa, Takako

2010-01-01

The mutagenic activities of 5-methyl-2-nitrophenol (5M2NP), a chlorination by-product of butamifos, its structural isomer 2-methyl-5-nitrophenol (2M5NP), and related compounds were evaluated by the Ames assay. The mutagenic activities of 5M2NP and 2M5NP were negative or not particularly high. However, those of their chlorinated derivatives were increased in Salmonella typhimurium strain TA100 and the overproducer strains YG1026, and YG1029 in the absence and/or presence of a rat liver metabolic activation system (S9 mix), particularly for YG1029. The mutagenic activities of 6-chloro-2-methyl-5-nitrophenol (6C2M5NP) in YG1029 in the absence and presence of S9 mix were 70000 and 110000 revertants mg(-1), respectively. When nitro functions of 6C2M5NP and 4-chloro-5-methyl-2-nitrophenol (4C5M2NP) were reduced to amino functions, their mutagenic activities were markedly decreased. The mutagenic activities of 5M2NP and 4C5M2NP were lower than those of 2M5NP and 6C2M5NP, respectively. Thus, it was shown that substituent position is a key factor for the mutagenic activities of methylnitrophenols (MNPs) and related compounds. The mutagenic activities of the extracts of 2M5NP in chlorination increased early during the reaction time and then decreased. The main chlorination by-product contributing to the mutagenic activities of the extracts of 2M5NP in chlorination was 6C2M5NP. The results of chlorination of 2M5NP suggested that MNPs were present as their dichlorinated derivatives or further chlorination by-products in drinking water. Copyright 2009 Elsevier Ltd. All rights reserved.

Preparation of surface multiple-coated polylactide acid drug-loaded nanoparticles for intranasal delivery and evaluation on its brain-targeting efficiency.

PubMed

Bian, Junjie; Yuan, Zhixiang; Chen, Xiaoliang; Gao, Yuan; Xu, Chaoqun; Shi, Jianyou

2016-01-01

To prepare a mixture of multiple-coated aniracetam nasal polylactic-acid nanoparticles (M-C-PLA-NP) and evaluate its stability preliminarily in vitro and its brain-targeting efficiency in vivo. The solvent diffusion-evaporation combined with magnetic stirring method has been chosen for the entrapment of aniracetam. The M-C-PLA-NP was characterized with respect to its morphology, particle size, size distribution and aniracetam entrapment efficiency. The in vivo distribution was studied in male SD rats after an intranasal administration. In vitro release of M-C-PLA-NP showed two components with an initial rapid release due to the surface-associated drug and followed by a slower exponential release of aniracetam, which was dissolved in the core. The AUC0 → 30 min of M-C-PLA-NP in brain tissues resulted in a 5.19-fold increase compared with aniracetam solution. The ratios of AUC in brain to that in other tissues obtained after nasal application of M-C-PLA-NP were significantly higher than those of aniracetam solution. Therefore, it can be concluded that M-C-PLA-NP demonstrated its potential on increasing the brain-targeting efficiency of drugs and will be used as novel brain-targeting agent for nasal drug delivery.

Interactions between natural organic matter and gold nanoparticles stabilized with different organic capping agents.

PubMed

Stankus, Dylan P; Lohse, Samuel E; Hutchison, James E; Nason, Jeffrey A

2011-04-15

The adsorption of natural organic matter (NOM) to the surfaces of natural colloids and engineered nanoparticles is known to strongly influence, and in some cases control, their surface properties and aggregation behavior. As a result, the understanding of nanoparticle fate, transport, and toxicity in natural systems must include a fundamental framework for predicting such behavior. Using a suite of gold nanoparticles (AuNPs) with different capping agents, the impact of surface functionality, presence of natural organic matter, and aqueous chemical composition (pH, ionic strength, and background electrolytes) on the surface charge and colloidal stability of each AuNP type was investigated. Capping agents used in this study were as follows: anionic (citrate and tannic acid), neutral (2,2,2-[mercaptoethoxy(ethoxy)]ethanol and polyvinylpyrrolidone), and cationic (mercaptopentyl(trimethylammonium)). Each AuNP type appeared to adsorb Suwannee River Humic Acid (SRHA) as evidenced by measurable decreases in zeta potential in the presence of 5 mg C L(-1) SRHA. It was found that 5 mg C L(-1) SRHA provided a stabilizing effect at low ionic strength and in the presence of only monovalent ions while elevated concentrations of divalent cations lead to enhanced aggregation. The colloidal stability of the NPs in the absence of NOM is a function of capping agent, pH, ionic strength, and electrolyte valence. In the presence of NOM at the conditions examined in this study, the capping agent is a less important determinant of stability, and the adsorption of NOM is a controlling factor.

Sleep disturbances and cognitive decline in the Northern Manhattan Study

PubMed Central

Ramos, Alberto R.; Gardener, Hannah; Rundek, Tatjana; Elkind, Mitchell S.V.; Boden-Albala, Bernadette; Dong, Chuanhui; Cheung, Ying Kuen; Stern, Yaakov; Sacco, Ralph L.

2016-01-01

Objective: To examine frequent snoring, sleepiness, and sleep duration with baseline and longitudinal performance on neuropsychological (NP) battery. Methods: The analysis consists of 711 participants of the Northern Manhattan Study (NOMAS) with sleep data and NP assessment (age 63 ± 8 years, 62% women, 18% white, 17% black, 67% Hispanic) and 687 with repeat NP testing (at a mean of 6 ± 2 years). The main exposures were snoring, sleepiness, and sleep duration obtained during annual follow-up. Using factor analysis–derived domain-specific Z scores for episodic memory, language, executive function, and processing speed, we constructed multivariable regression models to evaluate sleep symptoms with baseline NP performance and change in performance in each NP domain. Results: In the cross-sectional analysis, adjusting for demographics and the NOMAS vascular risk score, participants with frequent snoring had worse executive function (β = −12; p = 0.04) and processing speed (β = −13; p = 0.02), but no difference in with episodic memory or language. Those with severe daytime sleepiness (β = −26; p = 0.009) had worse executive function, but no changes in the other NP domains. There was no cross-sectional association between sleep duration and NP performance. Frequent snoring (β = −29; p = 0.0007), severe daytime sleepiness (β = −29; p = 0.05), and long sleep duration (β = −29; p = 0.04) predicted decline in executive function, adjusting for demographic characteristics and NOMAS vascular risk score. Sleep symptoms did not explain change in episodic memory, language, or processing speed. Conclusions: In this race-ethnically diverse community-based cohort, sleep symptoms led to worse cognitive performance and predicted decline in executive function. PMID:27590286

Multifunctional Composite Nanofibers for Smart Structures

DTIC Science & Technology

2011-10-13

low cost. It is coated onto the surface of CNF to use as a supercapacitor cathode. The high porosity and surface area of nanofiber composite...SiNP fusion, pulverization, and capacity loss can be minimized during electrochemical cycling. Carbon is also ductile in absorbing the mechanical...b) Figure 2 Core-shell CNF/Si composite with a thin layer of carbon shell coating on SiNP (a) and the capacity of both

Mitochondria-rich cells adjustments and ionic balance in the Neotropical fish Prochilodus lineatus exposed to titanium dioxide nanoparticles.

PubMed

Carmo, Talita L L; Azevedo, Vinícius C; Siqueira, Priscila R; Galvão, Tiago D; Santos, Fabrício A; Martinez, Cláudia B R; Appoloni, Carlos R; Fernandes, Marisa N

2018-07-01

Manufactured titanium dioxide nanoparticles (TiO 2 -NP) have been intensely applied in numerous industrial products and may be a risk for aquatic systems as they are not completely removed from domestic and industrial wastes after water treatment. This study evaluated the osmo- and ionic balance, Na + /K + -ATPase, H + -ATPase and carbonic anhydrase activities and the mitochondria-rich cells (MRC) in the gills and kidney of the Neotropical fish Prochilodus lineatus after 2 (acute) and 14 (subchronic) days of exposure to nominal 0, 1, 5, 10 and 50 mg L -1 TiO 2 -NP. The nominal concentrations corresponded to 0.0, 0.6, 1.6, 2.7 and 18.1 mg L -1 suspended TiO 2 -NP, respectively, in the water column one hour after NP introduction and were maintained for at least 24 h. Acute exposure to TiO 2 -NP decreased plasma osmolality and Ca 2+ levels. Na + /K + -ATPase, H + -ATPase and carbonic anhydrase activities were inhibited in the gills, but not in the kidney. Total MRC density did not change in gills and kidneys. At gill surface, total MRC density decreased in fish exposed to 50 mg L -1 TiO 2 -NP and the total MRC fractional surface area unchanged although, there were some changes in the fractional area of MRC with apical microvilli (MRCm) and MRC with apical sponge-like structure (MRCs). MRCm was more abundant than MRCs. After subchronic exposure, there was no change in plasma osmolality, ionic balance and enzyme activities. Total gill MRC density increased in the filament epithelium and renal tubules. In the gills, MRC contacting water exhibited some adjustments. Total MRC and fractional surface area unchanged, but there was an increase of MRCs contacting water at gill surface after exposure to10 and 50 mg L -1 TiO 2 -NP. MRC proliferation in filament epithelium and in renal tubules as well as the increasing MRCs at gill surface may have contributed to avoid change in plasma osmolality, ionic balance and enzyme activities and suggested a cellular physiological and morphological response to restore and maintain osmotic and ionic homeostasis after subchronic exposure. Copyright © 2018 Elsevier B.V. All rights reserved.

Fermi surface properties of paramagnetic NpCd11 with a large unit cell

NASA Astrophysics Data System (ADS)

Homma, Yoshiya; Aoki, Dai; Haga, Yoshinori; Settai, Rikio; Sakai, Hironori; Ikeda, Shugo; Yamamoto, Etsuji; Nakamura, Akio; Shiokawa, Yoshinobu; Takeuchi, Tetsuya; Yamagami, Hiroshi; Ōnuki, Yoshichika

2010-03-01

We succeeded in growing a high-quality single crystal of NpCd11 with the cubic BaHg11-type structure by the Cd-self flux method. The lattice parameter of a = 9.2968(2) Å and crystallographic positions of the atoms were determined by x-ray single-crystal structure analysis. From the results of the magnetic susceptibility and specific heat experiments, this compound is found to be a 5f-localized paramagnet with the singlet ground state in the crystalline electric field (CEF) scheme. Fermi surface properties were measured using the de Haas-van Alphen (dHvA) technique. Long-period oscillations were observed in the dHvA frequency range of 9.1 x 105 to 1.9 x 107 Oe, indicating small cross-sectional areas of Fermi surfaces, which is consistent with a small Brillouin zone based on a large unit cell. From the results of dHvA and magnetoresistance experiments, the Fermi surface of NpCd11 is found to consist of many kinds of closed Fermi surfaces and a multiply-connected-like Fermi surface, although the result of energy band calculations based on the 5f-localized Np3+(5f4) configuration reveals the existence of only closed Fermi surfaces. The corresponding cyclotron effective mass is small, ranging from 0.1 to 0.7 m0, which is consistent with a small electronic specific heat coefficient γ ≅ 10mJ/K2·mol, revealing no hybridization between the 5f electrons and conduction electrons.

Influence of surface melting effects and availability of reagent ions on LDI-MS efficiency after UV laser irradiation of Pd nanostructures.

PubMed

Silina, Yuliya E; Koch, Marcus; Volmer, Dietrich A

2015-03-01

In this study, the influence of surface morphology, reagent ions and surface restructuring effects on atmospheric pressure laser desorption/ionization (LDI) for small molecules after laser irradiation of palladium self-assembled nanoparticular (Pd-NP) structures has been systematically studied. The dominant role of surface morphology during the LDI process, which was previously shown for silicon-based substrates, has not been investigated for metal-based substrates before. In our experiments, we demonstrated that both the presence of reagent ions and surface reorganization effects--in particular, melting--during laser irradiation was required for LDI activity of the substrate. The synthesized Pd nanostructures with diameters ranging from 60 to 180 nm started to melt at similar temperatures, viz. 890-898 K. These materials exhibited different LDI efficiencies, however, with Pd-NP materials being the most effective surface in our experiments. Pd nanostructures of diameters >400-800 nm started to melt at higher temperatures, >1000 K, making such targets more resistant to laser irradiation, with subsequent loss of LDI activity. Our data demonstrated that both melting of the surface structures and the presence of reagent ions were essential for efficient LDI of the investigated low molecular weight compounds. This dependence of LDI on melting points was exploited further to improve the performance of Pd-NP-based sampling targets. For example, adding sodium hypophosphite as reducing agent to Pd electrolyte solutions during synthesis lowered the melting points of the Pd-NP materials and subsequently gave reduced laser fluence requirements for LDI. Copyright © 2015 John Wiley & Sons, Ltd.

Altered brain functional connectivity induced by physical exercise may improve neuropsychological functions in patients with benign epilepsy.

PubMed

Koirala, Gyan Raj; Lee, Dongpyo; Eom, Soyong; Kim, Nam-Young; Kim, Heung Dong

2017-11-01

The objective of this study was to elucidate alteration in functional connectivity (FC) in patients with benign epilepsy with centrotemporal spikes (BECTS) as induced by physical exercise therapy and their correlation to the neuropsychological (NP) functions. We analyzed 115 artifact- and spike-free 2-second epochs extracted from resting state EEG recordings before and after 5weeks of physical exercise in eight patients with BECTS. The exact Low Resolution Electromagnetic Tomography (eLORETA) was used for source reconstruction. We evaluated the cortical current source density (CSD) power across five different frequency bands (delta, theta, alpha, beta, and gamma). Altered FC between 34 regions of interests (ROIs) was then examined using lagged phase synchronization (LPS) method. We further investigated the correlation between the altered FC measures and the changes in NP test scores. We observed changes in CSD power following the exercise for all frequency bands and statistically significant increases in the right temporal region for the alpha band. There were a number of altered FC between the cortical ROIs in all frequency bands of interest. Furthermore, significant correlations were observed between FC measures and NP test scores at theta and alpha bands. The increased localization power at alpha band may be an indication of the positive impact of exercise in patients with BECTS. Frequency band-specific alterations in FC among cortical regions were associated with the modulation of cognitive and NP functions. The significant correlation between FC and NP tests suggests that physical exercise may mitigate the severity of BECTS, thereby enhancing NP function. Copyright © 2017 Elsevier Inc. All rights reserved.

Distinguishing neurocognitive deficits in adult patients with NP-C from early onset Alzheimer's dementia.

PubMed

Johnen, Andreas; Pawlowski, Matthias; Duning, Thomas

2018-06-05

Niemann-Pick disease type C (NP-C) is a rare, progressive neurodegenerative disease caused by mutations in the NPC1 or the NPC2 gene. Neurocognitive deficits are common in NP-C, particularly in patients with the adolescent/adult-onset form. As a disease-specific therapy is available, it is important to distinguish clinically between the cognitive profiles in NP-C and primary dementia (e.g., early Alzheimer's disease; eAD). In a prospective observational study, we directly compared the neurocognitive profiles of patients with confirmed NP-C (n = 7) and eAD (n = 15). All patients underwent neurocognitive assessment using dementia screening tests (mini-mental status examination [MMSE] and frontal assessment battery [FAB]) and an extensive battery of tests assessing verbal memory, visuoconstructive abilities, visual memory, executive functions and verbal fluency. Overall cognitive impairment (MMSE) was significantly greater in eAD vs. NP-C (p = 0.010). The frequency of patients classified as cognitively 'impaired' was also significantly greater in eAD vs. NP-C (p = 0.025). Patients with NP-C showed relatively preserved verbal memory, but frequent impairment in visual memory, visuoconstruction, executive functions and in particular, verbal fluency. In the eAD group, a wider profile of more frequent and more severe neurocognitive deficits was seen, primarily featuring severe verbal and visual memory deficits along with major executive impairment. Delayed verbal memory recall was a particularly strong distinguishing factor between the two groups. A combination of detailed yet easy-to-apply neurocognitive tests assessing verbal memory, executive functions and verbal fluency may help distinguish NP-C cases from those with primary dementia due to eAD.

EGaIn-Assisted Room-Temperature Sintering of Silver Nanoparticles for Stretchable, Inkjet-Printed, Thin-Film Electronics.

PubMed

Tavakoli, Mahmoud; Malakooti, Mohammad H; Paisana, Hugo; Ohm, Yunsik; Marques, Daniel Green; Alhais Lopes, Pedro; Piedade, Ana P; de Almeida, Anibal T; Majidi, Carmel

2018-05-29

Coating inkjet-printed traces of silver nanoparticle (AgNP) ink with a thin layer of eutectic gallium indium (EGaIn) increases the electrical conductivity by six-orders of magnitude and significantly improves tolerance to tensile strain. This enhancement is achieved through a room-temperature "sintering" process in which the liquid-phase EGaIn alloy binds the AgNP particles (≈100 nm diameter) to form a continuous conductive trace. Ultrathin and hydrographically transferrable electronics are produced by printing traces with a composition of AgNP-Ga-In on a 5 µm-thick temporary tattoo paper. The printed circuit is flexible enough to remain functional when deformed and can support strains above 80% with modest electromechanical coupling (gauge factor ≈1). These mechanically robust thin-film circuits are well suited for transfer to highly curved and nondevelopable 3D surfaces as well as skin and other soft deformable substrates. In contrast to other stretchable tattoo-like electronics, the low-cost processing steps introduced here eliminate the need for cleanroom fabrication and instead requires only a commercial desktop printer. Most significantly, it enables functionalities like "electronic tattoos" and 3D hydrographic transfer that have not been previously reported with EGaIn or EGaIn-based biphasic electronics. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Binary metal oxide nanoparticle incorporated composite multilayer thin films for sono-photocatalytic degradation of organic pollutants

NASA Astrophysics Data System (ADS)

Gokul, Paramasivam; Vinoth, Ramalingam; Neppolian, Bernaurdshaw; Anandhakumar, Sundaramurthy

2017-10-01

We report reduced graphene oxide (rGO) supported binary metal oxide (CuO-TiO2/rGO) nanoparticle (NP) incorporated multilayer thin films based on Layer-by-Layer (LbL) assembly for enhanced sono-photocatalytic degradation of methyl orange under exposure to UV radiation. Multilayer thin films were fabricated on glass and quartz slides, and investigated using scanning electron microscopy and UV-vis spectroscopy. The loading of catalyst NPs on the film resulted in the change of morphology of the film from smooth to rough with uniformly distributed NPs on the surface. The growth of the control and NP incorporated films followed a linear regime as a function of number of layers. The%degradation of methyl orange as a function of time was investigated by UV-vis spectroscopy and total organic carbon (TOC) measurements. Complete degradation of methyl orange was achieved within 13 h. The amount of NP loading in the film significantly influenced the%degradation of methyl orange. Catalyst reusability studies revealed that the catalyst thin films could be repeatedly used for up to five times without any change in photocatalytic activity of the films. The findings of the present study support that the binary metal oxide catalyst films reported here are very useful for continuous systems, and thus, making it an option for scale up.

Gating capacitive field-effect sensors by the charge of nanoparticle/molecule hybrids.

PubMed

Poghossian, Arshak; Bäcker, Matthias; Mayer, Dirk; Schöning, Michael J

2015-01-21

The semiconductor field-effect platform is a powerful tool for chemical and biological sensing with direct electrical readout. In this work, the field-effect capacitive electrolyte-insulator-semiconductor (EIS) structure - the simplest field-effect (bio-)chemical sensor - modified with citrate-capped gold nanoparticles (AuNPs) has been applied for a label-free electrostatic detection of charged molecules by their intrinsic molecular charge. The EIS sensor detects the charge changes in AuNP/molecule inorganic/organic hybrids induced by the molecular adsorption or binding events. The feasibility of the proposed detection scheme has been exemplarily demonstrated by realizing capacitive EIS sensors consisting of an Al-p-Si-SiO2-silane-AuNP structure for the label-free detection of positively charged cytochrome c and poly-d-lysine molecules as well as for monitoring the layer-by-layer formation of polyelectrolyte multilayers of poly(allylamine hydrochloride)/poly(sodium 4-styrene sulfonate), representing typical model examples of detecting small proteins and macromolecules and the consecutive adsorption of positively/negatively charged polyelectrolytes, respectively. For comparison, EIS sensors without AuNPs have been investigated, too. The adsorption of molecules on the surface of AuNPs has been verified via the X-ray photoelectron spectroscopy method. In addition, a theoretical model of the functioning of the capacitive field-effect EIS sensor functionalized with AuNP/charged-molecule hybrids has been discussed.

Complementation for an essential ancillary nonstructural protein function across parvovirus genera

PubMed Central

Mihaylov, Ivailo S.; Cotmore, Susan F.; Tattersall, Peter

2014-01-01

Parvoviruses encode a small number of ancillary proteins that differ substantially between genera. Within the genus Protoparvovirus, minute virus of mice (MVM) encodes three isoforms of its ancillary protein NS2, while human bocavirus 1 (HBoV1), in the genus Bocaparvovirus, encodes an NP1 protein that is unrelated in primary sequence to MVM NS2. To search for functional overlap between NS2 and NP1, we generated murine A9 cell populations that inducibly express HBoV1 NP1. These were used to test whether NP1 expression could complement specific defects resulting from depletion of MVM NS2 isoforms. NP1 induction had little impact on cell viability or cell cycle progression in uninfected cells, and was unable to complement late defects in MVM virion production associated with low NS2 levels. However, NP1 did relocate to MVM replication centers, and supports both the normal expansion of these foci and overcomes the early paralysis of DNA replication in NS2-null infections. PMID:25194919

Electron cryo-microscopy structure of Ebola nucleoprotein reveals a mechanism for nucleocapsid-like assembly

PubMed Central

Su, Zhaoming; Wu, Chao; Shi, Liuqing; Luthra, Priya; Pintilie, Grigore D.; Johnson, Britney; Porter, Justin R.; Ge, Peng; Chen, Muyuan; Liu, Gai; Frederick, Thomas E.; Binning, Jennifer M.; Bowman, Gregory R.; Zhou, Z. Hong; Basler, Christopher F.; Gross, Michael L.; Leung, Daisy W.

2018-01-01

Summary Ebola virus nucleoprotein (eNP) assembles into higher-ordered structures that form the viral nucleocapsid (NC) and serve as the scaffold for viral RNA synthesis. However, molecular insights into the NC assembly process are lacking. Using a hybrid approach, we characterized the NC-like assembly of eNP, identified novel regulatory elements, and described how these elements impact function. We generated a three-dimensional structure of the eNP NC-like assembly at 5.8 Å using electron cryo-microscopy and identified a new regulatory role for eNP helices α22–α23. Biochemical, biophysical, and mutational analysis revealed inter-eNP contacts within α22–α23 are critical for viral NC-assembly and regulate viral RNA synthesis. These observations suggest that the N-terminus and α22–α23 of eNP function as context dependent regulatory modules (CDRMs). Our current study provides a framework for a structural mechanism for NC-like assembly and a new therapeutic target. PMID:29474922

Potential-based and non-potential-based cohesive zone formulations under mixed-mode separation and over-closure-Part II: Finite element applications

NASA Astrophysics Data System (ADS)

Máirtín, Éamonn Ó.; Parry, Guillaume; Beltz, Glenn E.; McGarry, J. Patrick

2014-02-01

This paper, the second of two parts, presents three novel finite element case studies to demonstrate the importance of normal-tangential coupling in cohesive zone models (CZMs) for the prediction of mixed-mode interface debonding. Specifically, four new CZMs proposed in Part I of this study are implemented, namely the potential-based MP model and the non-potential-based NP1, NP2 and SMC models. For comparison, simulations are also performed for the well established potential-based Xu-Needleman (XN) model and the non-potential-based model of van den Bosch, Schreurs and Geers (BSG model). Case study 1: Debonding and rebonding of a biological cell from a cyclically deforming silicone substrate is simulated when the mode II work of separation is higher than the mode I work of separation at the cell-substrate interface. An active formulation for the contractility and remodelling of the cell cytoskeleton is implemented. It is demonstrated that when the XN potential function is used at the cell-substrate interface repulsive normal tractions are computed, preventing rebonding of significant regions of the cell to the substrate. In contrast, the proposed MP potential function at the cell-substrate interface results in negligible repulsive normal tractions, allowing for the prediction of experimentally observed patterns of cell cytoskeletal remodelling. Case study 2: Buckling of a coating from the compressive surface of a stent is simulated. It is demonstrated that during expansion of the stent the coating is initially compressed into the stent surface, while simultaneously undergoing tangential (shear) tractions at the coating-stent interface. It is demonstrated that when either the proposed NP1 or NP2 model is implemented at the stent-coating interface mixed-mode over-closure is correctly penalised. Further expansion of the stent results in the prediction of significant buckling of the coating from the stent surface, as observed experimentally. In contrast, the BSG model does not correctly penalise mixed-mode over-closure at the stent-coating interface, significantly altering the stress state in the coating and preventing the prediction of buckling. Case study 3: Application of a displacement to the base of a bi-layered composite arch results in a symmetric sinusoidal distribution of normal and tangential traction at the arch interface. The traction defined mode mixity at the interface ranges from pure mode II at the base of the arch to pure mode I at the top of the arch. It is demonstrated that predicted debonding patterns are highly sensitive to normal-tangential coupling terms in a CZM. The NP2, XN, and BSG models exhibit a strong bias towards mode I separation at the top of the arch, while the NP1 model exhibits a bias towards mode II debonding at the base of the arch. Only the SMC model provides mode-independent behaviour in the early stages of debonding. This case study provides a practical example of the importance of the behaviour of CZMs under conditions of traction controlled mode mixity, following from the theoretical analysis presented in Part I of this study.

Functional Characterization of Adaptive Mutations during the West African Ebola Virus Outbreak.

PubMed

Dietzel, Erik; Schudt, Gordian; Krähling, Verena; Matrosovich, Mikhail; Becker, Stephan

2017-01-15

The Ebola virus (EBOV) outbreak in West Africa started in December 2013, claimed more than 11,000 lives, threatened to destabilize a whole region, and showed how easily health crises can turn into humanitarian disasters. EBOV genomic sequences of the West African outbreak revealed nonsynonymous mutations, which induced considerable public attention, but their role in virus spread and disease remains obscure. In this study, we investigated the functional significance of three nonsynonymous mutations that emerged early during the West African EBOV outbreak. Almost 90% of more than 1,000 EBOV genomes sequenced during the outbreak carried the signature of three mutations: a D759G substitution in the active center of the L polymerase, an A82V substitution in the receptor binding domain of surface glycoprotein GP, and an R111C substitution in the self-assembly domain of RNA-encapsidating nucleoprotein NP. Using a newly developed virus-like particle system and reverse genetics, we found that the mutations have an impact on the functions of the respective viral proteins and on the growth of recombinant EBOVs. The mutation in L increased viral transcription and replication, whereas the mutation in NP decreased viral transcription and replication. The mutation in the receptor binding domain of the glycoprotein GP improved the efficiency of GP-mediated viral entry into target cells. Recombinant EBOVs with combinations of the three mutations showed a growth advantage over the prototype isolate Makona C7 lacking the mutations. This study showed that virus variants with improved fitness emerged early during the West African EBOV outbreak. The dimension of the Ebola virus outbreak in West Africa was unprecedented. Amino acid substitutions in the viral L polymerase, surface glycoprotein GP, and nucleocapsid protein NP emerged, were fixed early in the outbreak, and were found in almost 90% of the sequences. Here we showed that these mutations affected the functional activity of viral proteins and improved viral growth in cell culture. Our results demonstrate emergence of adaptive changes in the Ebola virus genome during virus circulation in humans and prompt further studies on the potential role of these changes in virus transmissibility and pathogenicity. Copyright © 2017 American Society for Microbiology.

Biological Surface Coating and Molting Inhibition as Mechanisms of TiO2 Nanoparticle Toxicity in Daphnia magna

PubMed Central

Dabrunz, André; Duester, Lars; Prasse, Carsten; Seitz, Frank; Rosenfeldt, Ricki; Schilde, Carsten; Schaumann, Gabriele E.; Schulz, Ralf

2011-01-01

The production and use of nanoparticles (NP) has steadily increased within the last decade; however, knowledge about risks of NP to human health and ecosystems is still scarce. Common knowledge concerning NP effects on freshwater organisms is largely limited to standard short-term (≤48 h) toxicity tests, which lack both NP fate characterization and an understanding of the mechanisms underlying toxicity. Employing slightly longer exposure times (72 to 96 h), we found that suspensions of nanosized (∼100 nm initial mean diameter) titanium dioxide (nTiO2) led to toxicity in Daphnia magna at nominal concentrations of 3.8 (72-h EC50) and 0.73 mg/L (96-h EC50). However, nTiO2 disappeared quickly from the ISO-medium water phase, resulting in toxicity levels as low as 0.24 mg/L (96-h EC50) based on measured concentrations. Moreover, we showed that nTiO2 (∼100 nm) is significantly more toxic than non-nanosized TiO2 (∼200 nm) prepared from the same stock suspension. Most importantly, we hypothesized a mechanistic chain of events for nTiO2 toxicity in D. magna that involves the coating of the organism surface with nTiO2 combined with a molting disruption. Neonate D. magna (≤6 h) exposed to 2 mg/L nTiO2 exhibited a “biological surface coating” that disappeared within 36 h, during which the first molting was successfully managed by 100% of the exposed organisms. Continued exposure up to 96 h led to a renewed formation of the surface coating and significantly reduced the molting rate to 10%, resulting in 90% mortality. Because coating of aquatic organisms by manmade NP might be ubiquitous in nature, this form of physical NP toxicity might result in widespread negative impacts on environmental health. PMID:21647422

Diffusion and Clustering of Carbon Dioxide on Non-porous Amorphous Solid Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Jiao; Emtiaz, Shahnewaj M.; Vidali, Gianfranco

2017-03-01

Observations by ISO and Spitzer toward young stellar objects showed that CO{sub 2} segregates in the icy mantles covering dust grains. Thermal processing of the ice mixture was proposed as being responsible for the segregation. Although several laboratories studied thermally induced segregation, a satisfying quantification is still missing. We propose that the diffusion of CO{sub 2} along pores inside water ice is the key to quantify segregation. We combined Temperature Programmed Desorption and Reflection Absorption InfraRed Spectroscopy to study how CO{sub 2} molecules interact on a non-porous amorphous solid water (np-ASW) surface. We found that CO{sub 2} diffuses significantly onmore » an np-ASW surface above 65 K and clusters are formed at well below one monolayer. A simple rate equation simulation finds that the diffusion energy barrier of CO{sub 2} on np-ASW is 2150 ± 50 K, assuming a diffusion pre-exponential factor of 10{sup 12} s{sup −1}. This energy should also apply to the diffusion of CO{sub 2} on the wall of pores. The binding energy of CO{sub 2} from CO{sub 2} clusters and CO{sub 2} from H{sub 2}O ice has been found to be 2415 ± 20 K and 2250 ± 20 K, respectively, assuming the same prefactor for desorption. CO{sub 2}–CO{sub 2} interaction is stronger than CO{sub 2}–H{sub 2}O interaction, in agreement with the experimental finding that CO{sub 2} does not wet the np-ASW surface. For comparison, we carried out similar experiments with CO on np-ASW, and found that the CO–CO interaction is always weaker than CO–H{sub 2}O. As a result, CO wets the np-ASW surface. This study should be of help to uncover the thermal history of CO{sub 2} on the icy mantles of dust grains.« less

The fate of silver nanoparticles in soil solution--Sorption of solutes and aggregation.

PubMed

Klitzke, Sondra; Metreveli, George; Peters, Andre; Schaumann, Gabriele E; Lang, Friederike

2015-12-01

Nanoparticles enter soils through various pathways. In the soil, they undergo various interactions with the solution and the solid phase. We tested the following hypotheses using batch experiments: i) the colloidal stability of Ag NP increases through sorption of soil-borne dissolved organic matter (DOM) and thus inhibits aggregation; ii) the presence of DOM suppresses Ag oxidation; iii) the surface charge of Ag NP governs sorption onto soil particles. Citrate-stabilized and bare Ag NPs were equilibrated with (colloid-free) soil solution extracted from a floodplain soil for 24h. Nanoparticles were removed through centrifugation. Concentrations of free Ag ions and DOC, the specific UV absorbance at a wavelength of 254 nm, and the absorption ratio α254/α410 were determined in the supernatant. Nanoparticle aggregation was studied using time-resolved dynamic light scattering (DLS) measurement following the addition of soil solution and 1.5mM Ca(2+) solution. To study the effect of surface charge on the adsorption of Ag NP onto soil particles, bare and citrate-stabilized Ag NP, differing in the zeta potential, were equilibrated with silt at a solid-to-solution ratio of 1:10 and an initial Ag concentration range of 30 to 320 μg/L. Results showed that bare Ag NPs sorb organic matter, with short-chained organic matter being preferentially adsorbed over long-chained, aromatic organic matter. Stabilizing effects of organic matter only come into play at higher Ag NP concentrations. Soil solution inhibits the release of Ag(+) ions, presumably due to organic matter coatings. Sorption to silt particles was very similar for the two particle types, suggesting that the surface charge does not control Ag NP sorption. Besides, sorption was much lower than in comparable studies with sand and glass surfaces. Copyright © 2014. Published by Elsevier B.V.

Gene Activated Titanium Surfaces Promote In Vitro Osteogenesis

PubMed Central

Atluri, Keerthi; Lee, Joun; Seabold, Denise; Elangovan, Satheesh; Salem, Aliasger K.

2016-01-01

Commercially pure titanium (CpTi) and its alloys possess favorable mechanical and biological properties for use as implants in orthopedics and dentistry. However, failures in osseointegration still exist and are common in select individuals with risk factors such as smoking. Therefore, in this study, a proposal was made to enhance the potential of CpTi discs for osseointegration by coating their surfaces with nanoplexes comprising polyethyleneimine (PEI) and plasmid DNA encoding bone morphogenetic protein-2 (pBMP-2). The nanoplexes were characterized for size and surface charge at a range of N/P ratios. CpTi discs were surface characterized for morphology and composition before and after nanoplex coating using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD). The cytotoxicity and transfection ability of CpTi discs coated with nanoplexes of varying N/P ratios in human bone marrow derived mesenchymal stem cells (BMSCs) was measured via MTS assays and flow cytometry, respectively. The CpTi discs coated with nanoplexes prepared at an N/P ratio of 10 (N/P-10) were considered optimal, resulting in 75% cell viability and 14% transfection efficiency. ELISA results demonstrated a significant enhancement in BMP-2 protein secretion by BMSCs 7 days post-treatment with CpTi discs coated with PEI/pBMP-2 nanoplexes (N/P-10), compared to the controls. Real time PCR data demonstrated that the BMSCs treated with PEI/pBMP-2 nanoplex coated CpTi discs resulted in an enhancement of runx-2, alkaline phosphatase and osteocalcin gene expressions on day 7, post-treatment. In addition, these BMSCs demonstrated enhanced calcium deposition on day 30 post-treatment as determined by qualitative (alizarin red staining) and quantitative (atomic absorption spectroscopy) assays. Thus, from all the above data it can be concluded that PEI/pBMP-2 nanoplex (N/P-10) coated CpTi discs have the potential to induce osteogenesis and enhance osseointegration. PMID:27706263

Topical nanoparticulate formulation of drugs for ocular keratitis

NASA Astrophysics Data System (ADS)

Yang, Xiaoyan

The primary objective of this project is to develop drug-loaded polymeric nanoparticles suspended in a biocompatible gel for topical delivery of therapeutic agents commonly employed in the treatment of ocular viral/bacterial keratitis. PART 1: Poly(D,L-lactic-co-glycolic acid) (PLGA) nanoparticles (NP) of dipeptide monoester prodrugs of ganciclovir (GCV) including L-Val-L-Val-GCV (LLGCV), L-Val-D-Val-GCV (LDGCV), D-Val-L-Val-GCV (DLGCV) were formulated and dispersed in thermosensitive PLGA-PEG-PLGA polymer gel for the treatment of herpes simplex virus type 1 (HSV-1) induced viral corneal keratitis. NP containing prodrugs of GCV were prepared by a double-emulsion solvent evaporation technique using various PLGA polymers with different drug/polymer ratios. Cytotoxicity studies suggested that all NP formulations are non-toxic. In vitro release of prodrugs from NP showed a biphasic release pattern with an initial burst phase followed by a sustained phase. Such burst effect was completely eliminated when NP were suspended in thermosensitive gels with near zero-order release kinetics. Prodrugs-loaded PLGA NP dispersed in thermosensitive gels can thus serve as a promising drug delivery system for the treatment of anterior eye diseases. Maximum uptake (around 60%) was noted at 3 h for NP. Cellular uptake and intracellular accumulation of prodrugs are significantly different among three stereoisomeric dipeptide prodrugs. The microscopic images show that NP are avidly internalized by HCEC cells and distributed throughout the cytoplasm instead of being localized on the cell surface. Following cellular uptake, prodrugs released from NP gradually bioreversed into parent drug GCV. LLGCV showed the highest degradation rate, followed by LDGCV and DLGCV. LLGCV, LDGCV and DLGCV released from NP exhibited superior uptake and bioreversion in corneal cells. PART 2: PLGA NP of hydrocortisone butyrate (HB) suspended in thermosensitive PLGA-PEG-PLGA gel were developed for the treatment of bacterial corneal keratitis. Experimental designs were employed in order to investigate specific effects of independent variables during preparation of HB-loaded PLGA NP and corresponding responses in optimizing the formulation. NP containing HB were prepared by an oil-in-water (O/W) emulsion evaporation technique with different surfactants including polyvinyl alcohol (PVA), pluronic F-108 and chitosan. NP were characterized with respect to particle size, entrapment efficiency, polydispersity, drug loading, surface morphology, zeta potential and crystallinity. In vitro release of HB from NP showed a biphasic release pattern with an initial burst phase followed by a sustained phase. Such burst effect was completely eliminated when NP were suspended in thermosensitive gels and zero-order release kinetics was observed. Percentage of uptake in HCEC after 4 h was 59.09+/-6.21% for PVA-emulsified NP relative to 55.74+/-6.26% for pluronic-emulsified NP, and 62.54+/-3.30% for chitosan-emulsified NP, respectively. In HCEC cell line, chitosan-emulsified NP with chitosan showed highest cellular uptake efficiency over PVA- and pluronic-emulsified NP. However, NP with chitosan indicated significant cytotoxicity under 200 and 500 ?g/mL after 48 h, while NP with PVA and pluronic showed no significant cytotoxicity. PLGA NP dispersed in thermosensitive gels can be considered as a promising drug delivery system for the treatment of anterior eye diseases.

Nonylphenol biodegradation characterizations and bacterial composition analysis of an effective consortium NP-M2.

PubMed

Bai, Naling; Abuduaini, Rexiding; Wang, Sheng; Zhang, Meinan; Zhu, Xufen; Zhao, Yuhua

2017-01-01

Nonylphenol (NP), ubiquitously detected as the degradation product of nonionic surfactants nonylphenol polyethoxylates, has been reported as an endocrine disrupter. However, most pure microorganisms can degrade only limited species of NP with low degradation efficiencies. To establish a microbial consortium that can effectively degrade different forms of NP, in this study, we isolated a facultative microbial consortium NP-M2 and characterized the biodegradation of NP by it. NP-M2 could degrade 75.61% and 89.75% of 1000 mg/L NP within 48 h and 8 days, respectively; an efficiency higher than that of any other consortium or pure microorganism reported so far. The addition of yeast extract promoted the biodegradation more significantly than that of glucose. Moreover, surface-active compounds secreted into the extracellular environment were hypothesized to promote high-efficiency metabolism of NP. The detoxification of NP by this consortium was determined. The degradation pathway was hypothesized to be initiated by oxidization of the benzene ring, followed by step-wise side-chain biodegradation. The bacterial composition of NP-M2 was determined using 16S rDNA library, and the consortium was found to mainly comprise members of the Sphingomonas, Pseudomonas, Alicycliphilus, and Acidovorax genera, with the former two accounting for 86.86% of the consortium. The high degradation efficiency of NP-M2 indicated that it could be a promising candidate for NP bioremediation in situ. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dual-radiolabeled nanoparticle probes for depth-independent in vivo imaging of enzyme activation

NASA Astrophysics Data System (ADS)

Black, Kvar C. L.; Zhou, Mingzhou; Sarder, Pinaki; Kuchuk, Maryna; Al-Yasiri, Amal Y.; Gunsten, Sean P.; Liang, Kexian; Hennkens, Heather M.; Akers, Walter J.; Laforest, Richard; Brody, Steven L.; Cutler, Cathy S.; Achilefu, Samuel

2018-02-01

Quantitative and noninvasive measurement of protease activities has remained an imaging challenge in deep tissues such as the lungs. Here, we designed a dual-radiolabeled probe for reporting the activities of proteases such as matrix metalloproteinases (MMPs) with multispectral single photon emission computed tomography (SPECT) imaging. A gold nanoparticle (NP) was radiolabeled with 125I and 111In and functionalized with an MMP9-cleavable peptide to form a multispectral SPECT imaging contrast agent. In another design, incorporation of 199Au radionuclide into the metal crystal structure of gold NPs provided a superior and stable reference signal in lungs, and 111In was linked to the NP surface via a protease-cleavable substrate, which can serve as an enzyme activity reporter. This work reveals strategies to correlate protease activities with diverse pathologies in a tissue-depth independent manner.

Tuning Adsorption Duration To Control the Diffusion of a Nanoparticle in Adsorbing Polymers.

PubMed

Cao, Xue-Zheng; Merlitz, Holger; Wu, Chen-Xu

2017-06-15

Controlling the nanoparticle (NP) diffusion in polymers is a prerequisite to obtain polymer nanocomposites (PNCs) with desired dynamical and rheological properties and to achieve targeted delivery of nanomedicine in biological systems. Here we determine the suppression mechanism of direct NP-polymer attraction to hamper the NP mobility in adsorbing polymers and then quantify the dependence of the effective viscosity η eff felt by the NP on the adsorption duration τ ads of polymers on the NP using scaling theory analysis and molecular dynamics simulations. We propose and confirm that participation of adsorbed chains in the NP motion break up at time intervals beyond τ ads due to the rearrangement of polymer segments at the NP surface, which accounts for the onset of Fickian NP diffusion on a time scale of t ≈ τ ads . We develop a power law, η eff ∼ (τ ads ) ν , where ν is the scaling exponent of the dependence of polymer coil size on the chain length, which leads to a theoretical basis for the design of PNCs and nanomedicine with desired applications through tuning the polymer adsorption duration.

Nanoporous Metals with Structural Hierarchy: A Review

DOE PAGES

Juarez, Theresa; Biener, Juergen; Weissmüller, Jörg; ...

2017-08-09

Nanoporous (np) metals have generated much interest since they combine several desirable material characteristics, such as high surface area, mechanical size effects, and high conductivity. Most of the research has been focused on np Au due to its relatively straightforward synthesis, chemical stability, and many promising applications in the fields of catalysis and actuation. Other materials, such as np-Cu, Ag, and Pd have also been studied. Here, this review discusses recent advances in the field of np metals, focusing on new research areas that implement and leverage structural hierarchy while using np metals as their base structural constituents. First, wemore » focus on single-element porous metals that are made of np metals at the fundamental level, but synthesized with additional levels of porosity. Second, we discuss the fabrication of composite structures, which use auxiliary materials to enhance the properties of np metals. Important applications of these hierarchical materials, especially in the fields of catalysis and electrochemistry, are also reviewed. Lastly, we conclude with a discussion about future opportunities for the advancement and application of np metals.« less

Apolipoprotein E3 Mediated Targeted Brain Delivery of Reconstituted High Density Lipoprotein Bearing 3, 10, And 17 Nm Hydrophobic Core Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Chuang, Skylar T.

We have developed a high density lipoprotein (HDL)-based platform for transport and delivery of hydrophobic gold nanoparticles (AuNP). The ability of apolipoprotein E3 (apoE3) to act as a ligand for the low-density lipoprotein receptor (LDLr) was exploited to gain entry of HDL with AuNP into glioblastoma cells. AuNP of 3, 10 and 17 nm diameter, the latter two synthesized by phase transfer process, were solubilized by integration into reconstituted HDL (rHDL). Absorption spectroscopy indicated the presence of stable particles with signature surface plasmon bands, while electron microscopy revealed AuNP embedded in rHDL core. The rHDL-AuNP complexes displayed robust binding to the LDLr, were internalized by the glioblastoma cells, and appeared as aggregated AuNP in the endosomal-lysosomal compartments. The rHDL-AuNP generated little cytotoxicity and were able to cross the blood brain barrier. The findings bear significance since they offer an effective means of delivering AuNP across tumor cell membrane.

Nanoporous Metals with Structural Hierarchy: A Review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Juarez, Theresa; Biener, Juergen; Weissmüller, Jörg

Nanoporous (np) metals have generated much interest since they combine several desirable material characteristics, such as high surface area, mechanical size effects, and high conductivity. Most of the research has been focused on np Au due to its relatively straightforward synthesis, chemical stability, and many promising applications in the fields of catalysis and actuation. Other materials, such as np-Cu, Ag, and Pd have also been studied. Here, this review discusses recent advances in the field of np metals, focusing on new research areas that implement and leverage structural hierarchy while using np metals as their base structural constituents. First, wemore » focus on single-element porous metals that are made of np metals at the fundamental level, but synthesized with additional levels of porosity. Second, we discuss the fabrication of composite structures, which use auxiliary materials to enhance the properties of np metals. Important applications of these hierarchical materials, especially in the fields of catalysis and electrochemistry, are also reviewed. Lastly, we conclude with a discussion about future opportunities for the advancement and application of np metals.« less

Effects of Surface-Modified MgO Nanoparticles on Inclusion Characteristics and Microstructure in Carbon Structural Steel

NASA Astrophysics Data System (ADS)

Guo, Hao; Yang, Shufeng; Li, Jingshe; Zhao, Mengjing; Chen, Zhengyang; Zhang, Xueliang; Li, Jikang

2018-05-01

An innovative approach involving chemical modification of the surface of MgO nanoparticles (NPs) for steelmaking and application of NPs to carbon structural steel has been investigated. The results show that the inclusions in the test steels were completely converted to MgAl2O4 spinel or MnS complex inclusions. The mean inclusion size decreased with increasing NP content from 0.01% to 0.03%, but increased at 0.05% because of NP aggregation. Addition of NPs increased the amount of intragranular ferrite and prevented polygonal ferrite formation, thereby enhancing the impact toughness. Impact tests showed that the dimple fractures in steel with 0.05% NP content were deeper than those in the other samples because the MgAl2O4 inclusions were larger. The surface-modified MgO NPs had a major effect on the inclusion characteristics and microstructure of carbon structural steel.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Lei; Sun, Tao; Cai, Hua

Surface plasmon (SP)-enhanced ultraviolet and visible photocatalytic activities of SrTiO{sub 3} (STO) are observed after incorporating Ag nanoparticles (Ag-NPs) on STO surfaces. A two-step excitation model is proposed to explain the SP-enhanced photocatalysis. The point of the model is that an electron at the valence band of STO is first excited onto the Fermi level of Ag-NP by the SP field generated on the Ag-NP, and then injected into the conduction band of STO from the SP band, leaving a hole at the valence band of STO. A full redox catalytic reaction at the surface of STO is then available.more » For Ag-NP incorporated STO, up-converted and inter-band photoluminescence emissions of STO are observed, and nonlinear evolutions of photocatalytic activity with illumination light powers are found. Furthermore, near infrared photocatalysis is detected. These results support the proposed model.« less

Solution processed ZnO hybrid nanocomposite with tailored work function for improved electron transport layer in organic photovoltaic devices.

PubMed

Lee, Yun-Ju; Wang, Jian; Cheng, Samuel R; Hsu, Julia W P

2013-09-25

We demonstrate improved organic photovoltaic device performance using solution processed electron transport layers of ZnO nanoparticle (NP) films containing organic additives, poly(vinylpyrrolidone) (PVP), or diethanolamine (DEA), that do not require post processing after film deposition. Inclusion of PVP or DEA decreased the ZnO work function by 0.4 eV through interfacial dipole formation. While PVP did not change the ZnO NP shape or size, DEA modified the ZnO shape from 5 nm × 15 nm nanorods to 5 nm nanoparticles. At an optimized PVP concentration of 0.7 wt %, ZnO NP:PVP electron transport layers (ETLs) improved the efficiency of inverted P3HT:PCBM devices by 37%, primarily through higher fill factor. ZnO NP:PVP and ZnO NP:DEA ETLs increased the open circuit voltage of inverted P3HT:ICBA devices by 0.07 V due to decreasing ETL work function, leading to enhanced built-in field. The relationship between ZnO nanocomposite ETL work function, donor-acceptor energy offset, and device performance is discussed. The effects of the two additives are compared.

Density functional calculations on the effect of sulfur substitution for 2'-hydroxypropyl-p-nitrophenyl phosphate: C-O vs. P-O bond cleavage.

PubMed

Xia, Futing; Zhu, Hua

2012-02-01

Density functional theory calculations have been used to investigate the intra-molecular attack of 2'-hydroxypropyl-p-nitrophenyl phosphate (HPpNP) and its analogous compound 2-thiouridyl-p-nitrophenyl phosphate (s-2'pNP). Bulk solvent effect has been tested at the geometry optimization level with the polarized continuum model. It is found that the P-path involving the intra-molecular attack at the phosphorus atom and C-path involving the attack at the beta carbon atom proceed through the S(N)2-type mechanism for HPpNP and s-2'pNP. The calculated results indicate that the P-path with the free energy barrier of about 11 kcal/mol is more accessible than the C-path for the intra-molecular attack of HPpNP, which favors the formation of the five-membered phosphate diester. While for s-2'pNP, the C-path with the free energy barrier of about 21 kcal/mol proceeds more favorably than the P-path. The calculated energy barriers of the favorable pathways for HPpNP and s-2'pNP are both in agreement with the experimental results. Crown Copyright © 2011. Published by Elsevier Inc. All rights reserved.

ΔNp63 promotes pediatric neuroblastoma and osteosarcoma by regulating tumor angiogenesis

PubMed Central

Bid, Hemant K.; Roberts, Ryan D.; Cam, Maren; Audino, Anthony; Kurmasheva, Raushan T.; Lin, Jiayuh; Houghton, Peter J.; Cam, Hakan

2013-01-01

The tumor suppressor gene p53 and its family members p63/p73 are critical determinants of tumorigenesis. ΔNp63 is a splice variant of p63, which lacks the N-terminal transactivation domain. It is thought to antagonize p53-, p63- and p73- dependent translation, thus blocking their tumor suppressor activity. In our studies of the pediatric solid tumors neuroblastoma and osteosarcoma, we find overexpression of ΔNp63; however, there is no correlation of ΔNp63 expression with p53 mutation status. Our data suggest that ΔNp63 itself endows cells with a gain of function that leads to malignant transformation, a function independent of any p53 antagonism. Here, we demonstrate that ΔNp63 overexpression, independent of p53, increases secretion of interleukin-6 (IL-6) and interleukin-8 (IL-8), leading to elevated phosphorylation of STAT-3 (Tyr-705). We show that elevated phosphorylation of STAT-3 leads to stabilization of HIF-1α protein, resulting in VEGF secretion. We also show human clinical data, which suggests a mechanistic role for ΔNp63 in osteosarcoma metastasis. In summary, our studies reveal the mechanism by which ΔNp63, as a master transcription factor, modulates tumor angiogenesis. PMID:24154873

Carbon-coated nanoparticle superlattices for energy applications

NASA Astrophysics Data System (ADS)

Li, Jun; Yiliguma, Affa; Wang, Yifei; Zheng, Gengfeng

2016-07-01

Nanoparticle (NP) superlattices represent a unique material architecture for energy conversion and storage. Recent reports on carbon-coated NP superlattices have shown exciting electrochemical properties attributed to their rationally designed compositions and structures, fast electron transport, short diffusion length, and abundant reactive sites via enhanced coupling between close-packed NPs, which are distinctive from their isolated or disordered NP or bulk counterparts. In this minireview, we summarize the recent developments of highly-ordered and interconnected carbon-coated NP superlattices featuring high surface area, tailorable and uniform doping, high conductivity, and structure stability. We then introduce the precisely-engineered NP superlattices by tuning/studying specific aspects, including intermetallic structures, long-range ordering control, and carbon coating methods. In addition, these carbon-coated NP superlattices exhibit promising characteristics in energy-oriented applications, in particular, in the fields of lithium-ion batteries, fuel cells, and electrocatalysis. Finally, the challenges and perspectives are discussed to further explore the carbon-coated NP superlattices for optimized electrochemical performances.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loh, Jing Wen; Saunders, Martin; Lim, Lee-Yong, E-mail: lee.lim@uwa.edu.au

Published toxicology data on chitosan nanoparticles (NP) often lack direct correlation to the in situ size and surface characteristics of the nanoparticles, and the repeated NP assaults as experienced in chronic use. The aim of this paper was to breach these gaps. Chitosan nanoparticles synthesized by spinning disc processing were characterised for size and zeta potential in HBSS and EMEM at pHs 6.0 and 7.4. Cytotoxicity against the Caco-2 cells was evaluated by measuring the changes in intracellular mitochondrial dehydrogenase activity, TEER and sodium fluorescein transport data and cell morphology. Cellular uptake of NP was observed under the confocal microscope.more » Contrary to established norms, the collective data suggest that the in vitro cytotoxicity of NP against the Caco-2 cells was less influenced by positive surface charges than by the particle size. Particle size was in turn determined by the pH of the medium in which the NP was dispersed, with the mean size ranging from 25 to 333 nm. At exposure concentration of 0.1%, NP of 25 ± 7 nm (zeta potential 5.3 ± 2.8 mV) was internalised by the Caco-2 cells, and the particles were observed to inflict extensive damage to the intracellular organelles. Concurrently, the transport of materials along the paracellular pathway was significantly facilitated. The Caco-2 cells were, however, capable of recovering from such assaults 5 days following NP removal, although a repeat NP exposure was observed to produce similar effects to the 1st exposure, with the cells exhibiting comparable resiliency to the 2nd assault. -- Highlights: ► Chitosan nanoparticles reduced mitochondrial dehydrogenase activity. ► Cellular uptake of chitosan nanoparticles was observed. ► Chitosan nanoparticles inflicted extensive damage to the cell morphology. ► The transport of materials along the paracellular pathway was facilitated.« less

Surface-enhanced Raman scattering from AgNP-graphene-AgNP sandwiched nanostructures

NASA Astrophysics Data System (ADS)

Wu, Jian; Xu, Yijun; Xu, Pengyu; Pan, Zhenghui; Chen, Sheng; Shen, Qishen; Zhan, Li; Zhang, Yuegang; Ni, Weihai

2015-10-01

We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a ``hot surface'' for enhancing the Raman response of two-dimensional materials.We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a ``hot surface'' for enhancing the Raman response of two-dimensional materials. Electronic supplementary information (ESI) available: Additional SEM images, electric field enhancement profiles, Raman scattering spectra, and structure-dependent peak ratios. See DOI: 10.1039/c5nr04500b

Laser tailored nanoparticle arrays to detect molecules at dilute concentration

NASA Astrophysics Data System (ADS)

Zanchi, Chiara; Lucotti, Andrea; Tommasini, Matteo; Trusso, Sebastiano; de Grazia, Ugo; Ciusani, Emilio; Ossi, Paolo M.

2017-02-01

By nanosecond pulsed laser ablation in an ambient gas gold nanoparticles (NPs) were produced that self-assemble on a substrate resulting in increasingly elaborated architectures of growing thickness, from isolated NP arrays up to percolated films. NPs nucleate and grow in the plasma plume propagating through the gas. Process parameters including laser wavelength, laser energy density, target to substrate distance, nature and pressure of the gas affect plasma expansion, thus asymptotic NP size and kinetic energy. NP size, energy and mobility at landing determine film growth and morphology that affect the physico-chemical properties of the film. Keeping fixed the other process parameters, we discuss the sensitive dependence of film surface nanostructure on Ar pressure and on laser pulse number. The initial plume velocity and average ablated mass per pulse allow predicting the asymptotic NP size. The control of growth parameters favors fine-tuning of NP aggregation, relevant to plasmonics to get optimized substrates for surface enhanced Raman spectroscopy (SERS). Their behavior is discussed for testing conditions of interest for clinical application. Both in aqueous and in biological solutions we obtained good sensitivity and reproducibility of the SERS signals for the anti-Parkinson drug apomorphine, and for the anti-epilepsy drug carbamazepine.

Effects of surface compositional and structural heterogeneity on nanoparticle-protein interactions: different protein configurations.

PubMed

Huang, Rixiang; Carney, Randy P; Ikuma, Kaoru; Stellacci, Francesco; Lau, Boris L T

2014-06-24

As nanoparticles (NPs) enter into biological systems, they are immediately exposed to a variety and concentration of proteins. The physicochemical interactions between proteins and NPs are influenced by the surface properties of the NPs. To identify the effects of NP surface heterogeneity, the interactions between bovine serum albumin (BSA) and gold NPs (AuNPs) with similar chemical composition but different surface structures were investigated. Different interaction modes and BSA conformations were studied by dynamic light scattering, circular dichroism spectroscopy, fluorescence quenching and isothermal titration calorimetry (ITC). Depending on the surface structure of AuNPs, BSA seems to adopt either a "side-on" or an "end-on" conformation on AuNPs. ITC demonstrated that the adsorption of BSA onto AuNPs with randomly distributed polar and nonpolar groups was primarily driven by electrostatic interaction, and all BSA were adsorbed in the same process. The adsorption of BSA onto AuNPs covered with alternating domains of polar and nonpolar groups was a combination of different interactions. Overall, the results of this study point to the potential for utilizing nanoscale manipulation of NP surfaces to control the resulting NP-protein interactions.

Improved facial nerve identification during parotidectomy with fluorescently labeled peptide.

PubMed

Hussain, Timon; Nguyen, Linda T; Whitney, Michael; Hasselmann, Jonathan; Nguyen, Quyen T

2016-12-01

Additional intraoperative guidance could reduce the risk of iatrogenic injury during parotid gland cancer surgery. We evaluated the intraoperative use of fluorescently labeled nerve binding peptide NP41 to aid facial nerve identification and preservation during parotidectomy in an orthotopic model of murine parotid gland cancer. We also quantified the accuracy of intraoperative nerve detection for surface and buried nerves in the head and neck with NP41 versus white light (WL) alone. Twenty-eight mice underwent parotid gland cancer surgeries with additional fluorescence (FL) guidance versus WL reflectance (WLR) alone. Eight mice were used for additional nerve-imaging experiments. Twenty-eight parotid tumor-bearing mice underwent parotidectomy. Eight mice underwent imaging of both sides of the face after skin removal. Postoperative assessment of facial nerve function measured by automated whisker tracking were compared between FL guidance (n = 13) versus WL alone (n=15). In eight mice, nerve to surrounding tissue contrast was measured under FL versus WLR for all nerve branches detectable in the field of view. Postoperative facial nerve function after parotid gland cancer surgery tended to be better with additional FL guidance. Fluorescent labeling significantly improved nerve to surrounding tissue contrast for both large and smaller buried nerve branches compared to WLR visualization and improved detection sensitivity and specificity. NP41 FL imaging significantly aids the intraoperative identification of nerve braches otherwise nearly invisible to the naked eye. Its application in a murine model of parotid gland cancer surgery tended to improve functional preservation of the facial nerve. NA Laryngoscope, 126:2711-2717, 2016. © 2016 The American Laryngological, Rhinological and Otological Society, Inc.

Improved Facial Nerve Identification During Parotidectomy With Fluorescently Labeled Peptide

PubMed Central

Hussain, Timon; Nguyen, Linda T.; Whitney, Michael; Hasselmann, Jonathan; Nguyen, Quyen T.

2016-01-01

Objectives/Hypothesis Additional intraoperative guidance could reduce the risk of iatrogenic injury during parotid gland cancer surgery. We evaluated the intraoperative use of fluorescently labeled nerve binding peptide NP41 to aid facial nerve identification and preservation during parotidectomy in an orthotopic model of murine parotid gland cancer. We also quantified the accuracy of intraoperative nerve detection for surface and buried nerves in the head and neck with NP41 versus white light (WL) alone. Study Design Twenty-eight mice underwent parotid gland cancer surgeries with additional fluorescence (FL) guidance versus WL reflectance (WLR) alone. Eight mice were used for additional nerve-imaging experiments. Methods Twenty-eight parotid tumor-bearing mice underwent parotidectomy. Eight mice underwent imaging of both sides of the face after skin removal. Postoperative assessment of facial nerve function measured by automated whisker tracking were compared between FL guidance (n = 13) versus WL alone (n = 15). In eight mice, nerve to surrounding tissue contrast was measured under FL versus WLR for all nerve branches detectable in the field of view. Results Postoperative facial nerve function after parotid gland cancer surgery tended to be better with additional FL guidance. Fluorescent labeling significantly improved nerve to surrounding tissue contrast for both large and smaller buried nerve branches compared to WLR visualization and improved detection sensitivity and specificity. Conclusions NP41 FL imaging significantly aids the intraoperative identification of nerve braches otherwise nearly invisible to the naked eye. Its application in a murine model of parotid gland cancer surgery tended to improve functional preservation of the facial nerve. PMID:27171862

Multifunctional silver nanoparticle-doped silica for solid-phase extraction and surface-enhanced Raman scattering detection

NASA Astrophysics Data System (ADS)

Markina, Natalia E.; Markin, Alexey V.; Zakharevich, Andrey M.; Gorin, Dmitry A.; Rusanova, Tatiana Yu.; Goryacheva, Irina Yu.

2016-12-01

Multifunctional silica gel with embedded silver nanoparticles (SiO2-AgNP) is proposed for application as sorbent for solid-phase extraction (SPE) and simultaneously as substrate for surface-enhanced Raman spectroscopy (SERS) due to their high sorption properties and ability to enhance Raman signal (SERS-active sorbents). SiO2-AgNP was synthesized via alkaline hydrolysis of tetraethyl orthosilicate with simultaneous reduction of silver ions to silver nanoparticles (AgNP) within the SiO2 bulk. Synthesis of AgNP directly to the SiO2 matrix enables to exclude any additional stabilizers for the nanoparticles that educes signal-to-noise ratio during SERS measurement. Apart from Raman spectroscopy, obtained sorbents were also characterized by scanning electron microscopy and UV-visible diffuse reflectance spectroscopy. The influence of AgNO3 concentration used during the SiO2-AgNP synthesis on its gelling time, color, diffuse reflectance spectra, and enhancement of Raman signal was investigated. A Raman enhancement factor of SiO2-AgNP with optimal composition was around 105. Finally, the sorbents were applied for SPE and subsequent SERS detection of model compounds (rhodamine 6G and folic acid). It was found that SPE enables to decrease detectable concentrations by two orders. Therefore, SPE combined with SERS has high potential for further analytical investigations.

ΔNp63α induces the expression of FAT2 and Slug to promote tumor invasion

PubMed Central

Dang, Tuyen T.; Westcott, Jill M.; Maine, Erin A.; Kanchwala, Mohammed; Xing, Chao; Pearson, Gray W.

2016-01-01

Tumor invasion can be induced by changes in gene expression that alter cell phenotype. The transcription factor ΔNp63α promotes basal-like breast cancer (BLBC) migration by inducing the expression of the mesenchymal genes Slug and Axl, which confers cells with a hybrid epithelial/mesenchymal state. However, the extent of the ΔNp63α regulated genes that support invasive behavior is not known. Here, using gene expression analysis, ChIP-seq, and functional testing, we find that ΔNp63α promotes BLBC motility by inducing the expression of the atypical cadherin FAT2, the vesicular binding protein SNCA, the carbonic anhydrase CA12, the lipid binding protein CPNE8 and the kinase NEK1, along with Slug and Axl. Notably, lung squamous cell carcinoma migration also required ΔNp63α dependent FAT2 and Slug expression, demonstrating that ΔNp63α promotes migration in multiple tumor types by inducing mesenchymal and non-mesenchymal genes. ΔNp63α activation of FAT2 and Slug influenced E-cadherin localization to cell-cell contacts, which can restrict spontaneous cell movement. Moreover, live-imaging of spheroids in organotypic culture demonstrated that ΔNp63α, FAT2 and Slug were essential for the extension of cellular protrusions that initiate collective invasion. Importantly, ΔNp63α is co-expressed with FAT2 and Slug in patient tumors and the elevated expression of ΔNp63α, FAT2 and Slug correlated with poor patient outcome. Together, these results reveal how ΔNp63α promotes cell migration by directly inducing the expression of a cohort of genes with distinct cellular functions and suggest that FAT2 is a new regulator of collective invasion that may influence patient outcome. PMID:27081041

Change of microbial community structure and functional gene abundance in nonylphenol-degrading sediment.

PubMed

Wang, Zhao; Yang, Yuyin; He, Tao; Xie, Shuguang

2015-04-01

Biodegradation by autochthonous microbial community is an important way to clean up nonylphenol (NP) from contaminated river sediment. Knowledge of sediment microbial community can aid in our understanding of biological processes related to NP degradation. However, the change in sediment microbial community associated with NP biodegradation remains unclear. The present study investigated the shift in bacterial community structure and NP-degrading gene abundance in response to NP attenuation in river sediment. Sediment microcosms with different levels of 4-NP (0, 100, or 300 μg/g) were constructed. A nearly complete attenuation of NP occurred in the microcosm with 100 μg/g NP after 9 days' incubation, while a residual NP rate of 8.1 % was observed in the microcosm with 300 μg/g NP after 22 days' incubation. Illumina MiSeq sequencing analysis indicated that Gammaproteobacteria, Alphaproteobacteria, and Bacteroidetes predominated in NP-degrading river sediment. Sediment bacterial community structure varied significantly during NP biodegradation and subsequent incubation, which was affected by the level of added NP. The n-alkane biodegradation (alkB) gene abundance showed a significant variation in each NP-amended microcosm (100 or 300 μg/g), while a significant increase in the single component monooxygenase (sMO) gene abundance only occurred in the microcosm spiked with 300 μg/g NP. This study can provide some new insights toward NP-degrading microbial ecology in the environment.

Radiation resistance and comparative performance of ITO/InP and n/p InP homojunction solar cells

NASA Technical Reports Server (NTRS)

Weinberg, I.; Swartz, C. K.; Hart, R. E., Jr.; Coutts, T. J.

1988-01-01

The radiation resistance of ITO/InP cells processed by dc magnetron sputtering is compared to that of standard n/p InP and GaAs homojunction cells. After 20 MeV proton irradiations, it is found that the radiation resistance of the present ITO/InP cell is comparable to that of the n/p homojunction InP cell and that both InP cell types have radiation resistances significantly greater than GaAs. The relatively lower radiation resistance, observed at higher fluence, for the InP cell with the deepest junction depth, is attributed to losses in the cells emitter region. Diode parameters obtained from I sub sc - V sub oc plots, data from surface Raman spectrosocpy, and determinations of surface conductivity type are used to investigate the configuration of the ITO/InP cells. It is concluded that these latter cells are n/p homojunctions, the n-region consisting of a disordered layer at the oxide semiconductor.

Radiation resistance and comparative performance of ITO/InP and n/p InP homojunction solar cells

NASA Technical Reports Server (NTRS)

Weinberg, I.; Swartz, C. K.; Hart, R. E., Jr.; Coutts, T. J.

1988-01-01

The radiation resistance of ITO/InP cells processed by DC magnetron sputtering is compared to that of standard n/p InP and GaAs homojunction cells. After 20 MeV proton irradiations, it is found that the radiation resistance of the present ITO/InP cell is comparable to that of the n/p homojunction InP cell and that both InP cell types have radiation resistance significantly greater than GaAs. The relatively lower radiation resistance, observed at higher fluence, for the InP cell with the deepest junction depth, is attributed to losses in the cells emitter region. Diode parameters obtained from I sub sc - V sub oc plots, data from surface Raman spectroscopy, and determinations of surface conductivity types are used to investigate the configuration of the ITO/InP cells. It is concluded that thesee latter cells are n/p homojunctions, the n-region consisting of a disordered layer at the oxide semiconductor.

Nanoparticles as potential new generation broad spectrum antimicrobial agents.

PubMed

Yah, Clarence S; Simate, Geoffrey S

2015-09-02

The rapid emergence of antimicrobial resistant strains to conventional antimicrobial agents has complicated and prolonged infection treatment and increased mortality risk globally. Furthermore, some of the conventional antimicrobial agents are unable to cross certain cell membranes thus, restricting treatment of intracellular pathogens. Therefore, the disease-causing-organisms tend to persist in these cells. However, the emergence of nanoparticle (NP) technology has come with the promising broad spectrum NP-antimicrobial agents due to their vast physiochemical and functionalization properties. In fact, NP-antimicrobial agents are able to unlock the restrictions experienced by conventional antimicrobial agents. This review discusses the status quo of NP-antimicrobial agents as potent broad spectrum antimicrobial agents, sterilization and wound healing agents, and sustained inhibitors of intracellular pathogens. Indeed, the perspective of developing potent NP-antimicrobial agents that carry multiple-functionality will revolutionize clinical medicine and play a significant role in alleviating disease burden.

Mass or total surface area with aerosol size distribution as exposure metrics for inflammatory, cytotoxic and oxidative lung responses in rats exposed to titanium dioxide nanoparticles.

PubMed

Noël, A; Truchon, G; Cloutier, Y; Charbonneau, M; Maghni, K; Tardif, R

2017-04-01

There is currently no consensus on the best exposure metric(s) for expressing nanoparticle (NP) dose. Although surface area has been extensively studied for inflammatory responses, it has not been as thoroughly validated for cytotoxicity or oxidative stress effects. Since inhaled NPs deposit and interact with lung cells based on agglomerate size, we hypothesize that mass concentration combined with aerosol size distribution is suitable for NP risk assessment. The objective of this study was to evaluate different exposure metrics for inhaled 5 nm titanium dioxide aerosols composed of small (SA < 100 nm) or large (LA > 100 nm) agglomerates at 2, 7, and 20 mg/m 3 on rat lung inflammatory, cytotoxicity, and oxidative stress responses. We found a significant positive correlation ( r = 0.98, p < 0.01) with the inflammatory reaction, measured by the number of neutrophils and the mass concentration when considering all six (SA + LA) aerosols. This correlation was similar ( r = 0.87) for total surface area. Regarding cytotoxicity and oxidative stress responses, measured by lactate dehydrogenase and 8-isoprostane, respectively, and mass or total surface area as an exposure metric, we observed significant positive correlations only with SA aerosols for both the mass concentration and size distribution ( r > 0.91, p < 0.01), as well as for the total surface area ( r > 0.97, p < 0.01). These data show that mass or total surface area concentrations alone are insufficient to adequately predict oxidant and cytotoxic pulmonary effects. Overall, our study indicates that considering NP size distribution along with mass or total surface area concentrations contributes to a more mechanistic discrimination of pulmonary responses to NP exposure.

Magnetite nanoparticle-induced fluorescence quenching of adenosine triphosphate-BODIPY Conjugates: application to adenosine triphosphate and pyrophosphate sensing.

PubMed

Yu, Cheng-Ju; Wu, Su-Mei; Tseng, Wei-Lung

2013-09-17

We report that magnetite nanoparticles (Fe3O4 NPs) act as an efficient quencher for boron dipyrromethene-conjugated adenosine 5'-triphosphate (BODIPY-ATP) that is highly fluorescent in bulk solution. BODIPY-ATP molecules attached to the surface of Fe3O4 NPs through the coordination between the triphosphate group of BODIPY-ATP and Fe(3+)/Fe(2+) on the NP surface. The formed complexes induced an apparent reduction in the BODIPY-ATP fluorescence resulting from an oxidative-photoinduced electron transfer (PET) from the BODIPY-ATP excited state to an unfilled d shell of Fe(3+)/Fe(2+) on the NP surface. A comparison of the Stern-Volmer quenching constant between Fe(3+) and Fe(2+) suggests that Fe(3+) on the NP surface dominantly controls this quenching process. The efficiency for Fe3O4 NP-induced fluorescence quenching of the BODIPY-ATP was enhanced by increasing the concentration of Fe3O4 NPs and lowering the pH of the solution to below 6.0. We found that pyrophosphate and ATP compete with BODIPY-ATP for binding to Fe3O4 NPs. Thus, we amplified BODIPY-ATP fluorescence in the presence of increasing the pyrophosphate and ATP concentration; the detection limits at a signal-to-noise ratio of 3 for pyrophosphate and ATP were determined to be 7 and 30 nM, respectively. The Fe3O4 NP-based competitive binding assay detected ATP and pyrophosphate in only 5 min. The selectivity of this assay for ATP over metal ions, amino acids, and adenosine analogues is particularly high. The practicality of using the developed method to determine ATP in a single drop of blood is also validated.

Impact Characteristics of Different Rocks in a Pulsed Laser Irradiation Experiment: Simulation of Micrometeorite Bombardment on the Moon

NASA Astrophysics Data System (ADS)

Wu, Yanxue; Li, Xiongyao; Yao, Wenqing; Wang, Shijie

2017-10-01

Without the protection of the atmosphere, the soils on lunar surfaces undergo a series of optical, physical, and chemical changes during micrometeorite bombardment. To simulate the micrometeorite bombardment process and analyze the impact characteristics, four types of rocks, including terrestrial basalt and anorthosite supposed to represent lunar rock, an H-type chondrite (the Huaxi ordinary chondrite), and an iron meteorite (the Gebel Kamil iron meteorite) supposed to represent micrometeorite impactors, are irradiated by a nanosecond pulse laser in a high vacuum chamber. Based on laser irradiation experiments, the laser pits are found to be of different shapes and sizes which vary with the rock type. Many melt and vapor deposits are found on the mineral surfaces of all the samples, and nanophase iron (npFe) or Fe-Ni alloy particles are typically distributed on the surfaces of ilmenite, kamacite, or other minerals near kamacite. By analyzing the focused ion beam ultrathin slices of laser pits with a transmission electron microscope, the results show that the subsurface structures can be divided into three classes and that npFe can be easily found in Fe-bearing minerals. These differences in impact characteristics will help determine the source material of npFe and infer the type of micrometeorite impactors. During micrometeorite bombardment, in the mare regions, the npFe are probably produced simultaneously from lunar basalt and micrometeorites with iron-rich minerals, while the npFe in the highlands regions mainly come from micrometeorites.

Non-specific binding and steric hindrance thresholds for penetration of particulate drug carriers within tumor tissue

PubMed Central

Dancy, Jimena G.; Wadajkar, Aniket S.; Schneider, Craig S.; Mauban, Joseph R.H.; Woodworth, Graeme F.; Winkles, Jeffrey A.; Kim, Anthony J.

2017-01-01

Therapeutic nanoparticles (NPs) approved for clinical use in solid tumor therapy provide only modest improvements in patient survival, in part due to physiological barriers that limit delivery of the particles throughout the entire tumor. Here, we explore the thresholds for NP size and surface poly(ethylene glycol) (PEG) density for penetration within tumor tissue extracellular matrix (ECM). We found that NPs as large as 62 nm, but less than 110 nm in diameter, diffused rapidly within a tumor ECM preparation (Matrigel) and breast tumor xenograft slices ex vivo. Studies of PEG-density revealed that increasing PEG density enhanced NP diffusion and that PEG density below a critical value led to adhesion of NP to ECM. Non-specific binding of NPs to tumor ECM components was assessed by surface plasmon resonance (SPR), which revealed excellent correlation with the particle diffusion results. Intravital microscopy of NP spread in breast tumor tissue confirmed a significant difference in tumor tissue penetration between the 62 and 110 nm PEG-PS NPs, as well as between PEG-coated and uncoated NPs. SPR assays also revealed that Abraxane, an FDA-approved non-PEGylated NP formulation used for cancer therapy, binds to tumor ECM. Our results establish limitations on the size and surface PEG density parameters required to achieve uniform and broad dispersion within tumor tissue and highlight the utility of SPR as a high throughput method to screen NPs for tumor penetration. PMID:27460683

Wetlands inform how climate extremes influence surface water expansion and contraction

USGS Publications Warehouse

Vanderhoof, Melanie; Lane, Charles R.; McManus, Michael L.; Alexander, Laurie C.; Christensen, Jay R.

2018-01-01

Effective monitoring and prediction of flood and drought events requires an improved understanding of how and why surface water expansion and contraction in response to climate varies across space. This paper sought to (1) quantify how interannual patterns of surface water expansion and contraction vary spatially across the Prairie Pothole Region (PPR) and adjacent Northern Prairie (NP) in the United States, and (2) explore how landscape characteristics influence the relationship between climate inputs and surface water dynamics. Due to differences in glacial history, the PPR and NP show distinct patterns in regards to drainage development and wetland density, together providing a diversity of conditions to examine surface water dynamics. We used Landsat imagery to characterize variability in surface water extent across 11 Landsat path/rows representing the PPR and NP (images spanned 1985–2015). The PPR not only experienced a 2.6-fold greater surface water extent under median conditions relative to the NP, but also showed a 3.4-fold greater change in surface water extent between drought and deluge conditions. The relationship between surface water extent and accumulated water availability (precipitation minus potential evapotranspiration) was quantified per watershed and statistically related to variables representing hydrology-related landscape characteristics (e.g., infiltration capacity, surface storage capacity, stream density). To investigate the influence stream connectivity has on the rate at which surface water leaves a given location, we modeled stream-connected and stream-disconnected surface water separately. Stream-connected surface water showed a greater expansion with wetter climatic conditions in landscapes with greater total wetland area, but lower total wetland density. Disconnected surface water showed a greater expansion with wetter climatic conditions in landscapes with higher wetland density, lower infiltration and less anthropogenic drainage. From these findings, we can expect that shifts in precipitation and evaporative demand will have uneven effects on surface water quantity. Accurate predictions regarding the effect of climate change on surface water quantity will require consideration of hydrology-related landscape characteristics including wetland storage and arrangement.

Stacking InAs quantum dots over ErAs semimetal nanoparticles on GaAs (0 0 1) using molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Zhang, Yuanchang; Eyink, Kurt G.; Grazulis, Lawrence; Hill, Madelyn; Peoples, Joseph; Mahalingam, Krishnamurthy

2017-11-01

Hybrid nanostructures are known to elicit an enhanced optical response. We study the directed alignment of ErAs metal nanoparticle (NP) and InAs quantum dot (QD) using molecular beam eptaxy (MBE) in a GaAs matrix. Due to high surface free energy caused by the crystal structure difference, overgrowth of an ErAs NP with GaAs forms a depression that condenses subsequent InAs adatoms to form an inverted QD self-aligned to the underlying ErAs NP. The ErAs NP growth, GaAs overgrowth, and InAs QD deposition were carefully controlled and studied with transmission electron microscopy (TEM) and atomic force microscopy (AFM) to investigate their effects on the QD-NP alignment.

Chitosan Nanoparticles for Nuclear Targeting: The Effect of Nanoparticle Size and Nuclear Localization Sequence Density.

PubMed

Tammam, Salma N; Azzazy, Hassan M E; Breitinger, Hans G; Lamprecht, Alf

2015-12-07

Many recently discovered therapeutic proteins exert their main function in the nucleus, thus requiring both efficient uptake and correct intracellular targeting. Chitosan nanoparticles (NPs) have attracted interest as protein delivery vehicles due to their biocompatibility and ability to escape the endosomes offering high potential for nuclear delivery. Molecular entry into the nucleus occurs through the nuclear pore complexes, the efficiency of which is dependent on NP size and the presence of nuclear localization sequence (NLS). Chitosan nanoparticles of different sizes (S-NPs ≈ 25 nm; L-NP ≈ 150 nm) were formulated, and they were modified with different densities of the octapeptide NLS CPKKKRKV (S-NPs, 0.25, 0.5, 2.0 NLS/nm(2); L-NPs, 0.6, 0.9, 2 NLS/nm(2)). Unmodified and NLS-tagged NPs were evaluated for their protein loading capacity, extent of cell association, cell uptake, cell surface binding, and finally nuclear delivery efficiency in L929 fibroblasts. To avoid errors generated with cell fractionation and nuclear isolation protocols, nuclear delivery was assessed in intact cells utilizing Förster resonance energy transfer (FRET) fluorometry and microscopy. Although L-NPs showed ≈10-fold increase in protein loading per NP when compared to S-NPs, due to higher cell association and uptake S-NPs showed superior protein delivery. NLS exerts a size and density dependent effect on nanoparticle uptake and surface binding, with a general reduction in NP cell surface binding and an increase in cell uptake with the increase in NLS density (up to 8.4-fold increase in uptake of High-NLS-L-NPs (2 NLS/nm(2)) compared to unmodified L-NPs). However, for nuclear delivery, unmodified S-NPs show higher nuclear localization rates when compared to NLS modified NPs (up to 5-fold by FRET microscopy). For L-NPs an intermediate NLS density (0.9 NLS/nm(2)) seems to provide highest nuclear localization (3.7-fold increase in nuclear delivery compared to High-NLS-L-NPs). Results indicate that a higher NLS density does not result in maximum protein nuclear localization and that a universal optimal density for NPs of different sizes does not exist.

AHAPS-functionalized silica nanoparticles do not modulate allergic contact dermatitis in mice

NASA Astrophysics Data System (ADS)

Ostrowski, Anja; Nordmeyer, Daniel; Mundhenk, Lars; Fluhr, Joachim W.; Lademann, Jürgen; Graf, Christina; Rühl, Eckart; Gruber, Achim D.

2014-09-01

Allergic contact dermatitis (ACD) is a common skin disease in people and may become a potential site of exposure to nanoparticles (NP). Silica nanoparticles (SiO2-NP) possess a promising potential for various medical and non-medical applications, including normal and diseased skin as target organs. However, it has been shown that negatively charged SiO2-NP may act as proinflammatory adjuvant in allergic diseases. The effect of topical SiO2-NP exposure on preexisting ACD has not been studied to date although this reflects a common in vivo situation. Of particular interest are the potential effects of positively charged N-(6-aminohexyl)-aminopropyltrimethoxysilane (AHAPS)-functionalized SiO2-NP which are promising candidates for delivery systems, including gene delivery into the skin. Here, the effects of such AHAPS-functionalized SiO2-NP (55 ± 6 nm in diameter) were studied in an oxazolone-induced ACD model in SKH1 mice and compared to ACD mice treated with vehicle only. The clinical course of the disease was assessed by monitoring of the transepidermal water loss (TEWL) and the erythema. In histologic and morphometric analyses, the distribution of particles, the degree of inflammation, epidermal thickness, and the inflammatory infiltrate were characterized and quantified by standard and special histological stains as well as immunohistochemistry for CD3+ lymphocytes. To assess possible systemic effects, serum immunoglobulin E (IgE) was determined by enzyme-linked immunosorbent assay. Following administration of AHAPS-SiO2-NP for five consecutive days, no effects were observed in all clinical, histologic, morphometric, and molecular parameters investigated. In conclusion, positively charged AHAPS-SiO2-NP seem not to affect the course of ACD during exposure for 5 days.

SiN sub x passivation of silicon surfaces

NASA Technical Reports Server (NTRS)

Olsen, L. C.

1986-01-01

The objectives were to perform surface characterization of high efficiency n+/p and p+/n silicon cells, to relate surface density to substrate dopant concentration, and to identify dominant current loss mechanisms in high efficiency cells. The approach was to measure density of states on homogeneously doped substrates with high frequency C-V and Al/SiN sub x/Si structures; to investigate density of states and photoresponse of high efficiency N+/P and P+/N cells; and to conduct I-V-T studies to identify current loss nechanisms in high efficiency cells. Results are given in tables and graphs.

An ultrasensitive hollow-silica-based biosensor for pathogenic Escherichia coli DNA detection.

PubMed

Ariffin, Eda Yuhana; Lee, Yook Heng; Futra, Dedi; Tan, Ling Ling; Karim, Nurul Huda Abd; Ibrahim, Nik Nuraznida Nik; Ahmad, Asmat

2018-03-01

A novel electrochemical DNA biosensor for ultrasensitive and selective quantitation of Escherichia coli DNA based on aminated hollow silica spheres (HSiSs) has been successfully developed. The HSiSs were synthesized with facile sonication and heating techniques. The HSiSs have an inner and an outer surface for DNA immobilization sites after they have been functionalized with 3-aminopropyltriethoxysilane. From field emission scanning electron microscopy images, the presence of pores was confirmed in the functionalized HSiSs. Furthermore, Brunauer-Emmett-Teller (BET) analysis indicated that the HSiSs have four times more surface area than silica spheres that have no pores. These aminated HSiSs were deposited onto a screen-printed carbon paste electrode containing a layer of gold nanoparticles (AuNPs) to form a AuNP/HSiS hybrid sensor membrane matrix. Aminated DNA probes were grafted onto the AuNP/HSiS-modified screen-printed electrode via imine covalent bonds with use of glutaraldehyde cross-linker. The DNA hybridization reaction was studied by differential pulse voltammetry using an anthraquinone redox intercalator as the electroactive DNA hybridization label. The DNA biosensor demonstrated a linear response over a wide target sequence concentration range of 1.0×10 -12 -1.0×10 -2 μM, with a low detection limit of 8.17×10 -14 μM (R 2 = 0.99). The improved performance of the DNA biosensor appeared to be due to the hollow structure and rough surface morphology of the hollow silica particles, which greatly increased the total binding surface area for high DNA loading capacity. The HSiSs also facilitated molecule diffusion through the silica hollow structure, and substantially improved the overall DNA hybridization assay. Graphical abstract Step-by-step DNA biosensor fabrication based on aminated hollow silica spheres.

Complementation for an essential ancillary non-structural protein function across parvovirus genera.

PubMed

Mihaylov, Ivailo S; Cotmore, Susan F; Tattersall, Peter

2014-11-01

Parvoviruses encode a small number of ancillary proteins that differ substantially between genera. Within the genus Protoparvovirus, minute virus of mice (MVM) encodes three isoforms of its ancillary protein NS2, while human bocavirus 1 (HBoV1), in the genus Bocaparvovirus, encodes an NP1 protein that is unrelated in primary sequence to MVM NS2. To search for functional overlap between NS2 and NP1, we generated murine A9 cell populations that inducibly express HBoV1 NP1. These were used to test whether NP1 expression could complement specific defects resulting from depletion of MVM NS2 isoforms. NP1 induction had little impact on cell viability or cell cycle progression in uninfected cells, and was unable to complement late defects in MVM virion production associated with low NS2 levels. However, NP1 did relocate to MVM replication centers, and supports both the normal expansion of these foci and overcomes the early paralysis of DNA replication in NS2-null infections. Copyright © 2014 Elsevier Inc. All rights reserved.

Presence and distribution of organic wastewater compounds in wastewater, surface, ground, and drinking waters, Minnesota, 2000-02

USGS Publications Warehouse

Lee, Kathy E.; Barber, Larry B.; Furlong, Edward T.; Cahill, Jeffery D.; Kolpin, Dana W.; Meyer, Michael T.; Zaugg, Steven D.

2004-01-01

Results of this study indicate ubiquitous distribution of measured OWCs in the environment that originate from numerous sources and pathways. During this reconnaissance of OWCs in Minnesota it was not possible to determine the specific sources of OWCs to surface, ground, or drinking waters. The data indicate WWTP effluent is a major pathway of OWCs to surface waters and that landfill leachate at selected facilities is a potential source of OWCs to WWTPs. Aquatic organism or human exposure to some OWCs is likely based on OWC distribution. Few aquatic or human health standards or criteria exist for the OWCs analyzed, and the risks to humans or aquatic wildlife are not known. Some OWCs detected in this study are endocrine disrupters and have been found to disrupt or influence endocrine function in fish. Thirteen endocrine disrupters, 3-tert-butyl-4-hydoxyanisole (BHA), 4- cumylphenol, 4-normal-octylphenol, 4-tert-octylphenol, acetyl-hexamethyl-tetrahydro-naphthalene (AHTN), benzo[α]pyrene, beta-sitosterol, bisphenol-A, diazinon, nonylphenol diethoxylate (NP2EO), octyphenol diethoxylate (OP2EO), octylphenol monoethoxylate (OP1EO), and total para-nonylphenol (NP) were detected. Results of reconnaissance studies may help regulators who set water-quality standards begin to prioritize which OWCs to focus upon for given categories of water use.

Toxicological and pharmacokinetic properties of chemically modified siRNAs targeting p53 RNA following intravenous administration.

PubMed

Thompson, James D; Kornbrust, Douglas J; Foy, Jeffrey W-D; Solano, Elisabeth C R; Schneider, David J; Feinstein, Elena; Molitoris, Bruce A; Erlich, Shai

2012-08-01

We report the toxicological and pharmacokinetic properties of the synthetic, small interfering RNA I5NP following intravenous administration in rodents and nonhuman primates. I5NP is designed to act via the RNA interference (RNAi) pathway to temporarily inhibit expression of the pro-apoptotic protein p53 and is being developed to protect cells from acute ischemia/reperfusion injuries such as acute kidney injury that can occur during major cardiac surgery and delayed graft function that can occur following renal transplantation. Following intravenous administration, I5NP was very rapidly cleared from plasma was distributed predominantly to the kidney, with very low levels in liver and other tissues. Doses of 800 mg/kg I5NP in rodents, and 1,000 mg/kg I5NP in nonhuman primates, were required to elicit adverse effects, which in the monkey were isolated to direct effects on the blood that included a sub-clinical activation of complement and slightly increased clotting times. In the rat, no additional adverse effects were observed with a rat analogue of I5NP, indicating that the effects likely represent class effects of synthetic RNA duplexes rather than toxicity related to the intended pharmacologic activity of I5NP. Taken together, these data support clinical testing of intravenous administration of I5NP for the preservation of renal function following acute ischemia/reperfusion injury.

Sequence analysis of the lactococcal plasmid pNP40: a mobile replicon for coping with environmental hazards.

PubMed

O'Driscoll, Jonathan; Glynn, Frances; Fitzgerald, Gerald F; van Sinderen, Douwe

2006-09-01

The conjugative lactococcal plasmid pNP40, identified in Lactococcus lactis subsp. diacetylactis DRC3, possesses a potent complement of bacteriophage resistance systems, which has stimulated its application as a fitness-improving, food-grade genetic element for industrial starter cultures. The complete sequence of this plasmid allowed the mapping of previously known functions including replication, conjugation, bacteriocin resistance, heavy metal tolerance, and bacteriophage resistance. In addition, functions for cold shock adaptation and DNA damage repair were identified, further confirming pNP40's contribution to environmental stress protection. A plasmid cointegration event appears to have been part of the evolution of pNP40, resulting in a "stockpiling" of bacteriophage resistance systems.

[Expression and analysis of the nucleoprotein of paramyxovirus Tianjin strain].

PubMed

Wang, Qing; Li, Mei; Shi, Li-Ying; Yuan, Li-Jun; Wang, Wen-Xiu

2008-05-01

Paramyxovirus Tianjin strain is a novel strain of virus causing common cotton-eared marmoset fatal infection. To investigate the relationship between the gene structure and function of nucleoprotein (NP) of Tianjin strain, NP gene of paramyxovirus Tianjin strain was cloned and three domains of NP were expressed. The homologous and phylogenetic analysis of NP sequences among the paramyxovirus Tianjin strain and eight strains of Sendai viruses from GenBank were performed. The results indicated the recombinant proteins NP1, NP2 and NP3 showed the native antigenicity to the polyclonal antiserum of paramyxovirus Tianjin strain, ranking as NP3>NP1>NP2 (precedence order). The homology of NP nucleotide and the deduced amino acid sequences between paramyxovirus Tianjin strain and Sendai virus BB1 strain were 94.5%, 96.2%, respectively, whereas the identity were 85.1% - 88.7% and 92.4% - 94.7% among Tianjin strain and the 7 strains of Sendai viruses from GenBank respectively. There were 15 unique amino acid substitutions in Tianjin strain NP protein and 11 common amino acid substitutions same with BB1 strain. This research confirmed that paramyxovirus Tianjin strain might be a new genotype of Sendai virus and can be helpful in the establishment of detection assay applying recombinant NP as antigen instead of the whole virions.

Loss of HIF-1α in the notochord results in cell death and complete disappearance of the nucleus pulposus.

PubMed

Merceron, Christophe; Mangiavini, Laura; Robling, Alexander; Wilson, Tremika LeShan; Giaccia, Amato J; Shapiro, Irving M; Schipani, Ernestina; Risbud, Makarand V

2014-01-01

The intervertebral disc (IVD) is one of the largest avascular organs in vertebrates. The nucleus pulposus (NP), a highly hydrated and proteoglycan-enriched tissue, forms the inner portion of the IVD. The NP is surrounded by a multi-lamellar fibrocartilaginous structure, the annulus fibrosus (AF). This structure is covered superior and inferior side by cartilaginous endplates (CEP). The NP is a unique tissue within the IVD as it results from the differentiation of notochordal cells, whereas, AF and CEP derive from the sclerotome. The hypoxia inducible factor-1α (HIF-1α) is expressed in NP cells but its function in NP development and homeostasis is largely unknown. We thus conditionally deleted HIF-1α in notochordal cells and investigated how loss of this transcription factor impacts NP formation and homeostasis at E15.5, birth, 1 and 4 months of age, respectively. Histological analysis, cell lineage studies, and TUNEL assay were performed. Morphologic changes of the mutant NP cells were identified as early as E15.5, followed, postnatally, by the progressive disappearance and replacement of the NP with a novel tissue that resembles fibrocartilage. Notably, lineage studies and TUNEL assay unequivocally proved that NP cells did not transdifferentiate into chondrocyte-like cells but they rather underwent massive cell death, and were completely replaced by a cell population belonging to a lineage distinct from the notochordal one. Finally, to evaluate the functional consequences of HIF-1α deletion in the NP, biomechanical testing of mutant IVD was performed. Loss of the NP in mutant mice significantly reduced the IVD biomechanical properties by decreasing its ability to absorb mechanical stress. These findings are similar to the changes usually observed during human IVD degeneration. Our study thus demonstrates that HIF-1α is essential for NP development and homeostasis, and it raises the intriguing possibility that this transcription factor could be involved in IVD degeneration in humans.

Colloidal stability of carbonate-coated silver nanoparticles in synthetic and natural freshwater.

PubMed

Piccapietra, Flavio; Sigg, Laura; Behra, Renata

2012-01-17

To gain important information on fate, mobility, and bioavailability of silver nanoparticles (AgNP) in aquatic systems, the influence of pH, ionic strength, and humic substances on the stability of carbonate-coated AgNP (average diameter 29 nm) was systematically investigated in 10 mM carbonate and 10 mM MOPS buffer, and in filtered natural freshwater. Changes in the physicochemical properties of AgNP were measured using nanoparticle tracking analysis, dynamic light scattering, and ultraviolet-visible spectroscopy. According to the pH-dependent carbonate speciation, below pH 4 the negatively charged surface of AgNP became positive and increased agglomeration was observed. Electrolyte concentrations above 2 mM Ca(2+) and 100 mM Na(+) enhanced AgNP agglomeration in the synthetic media. In the considered concentration range of humic substances, no relevant changes in the AgNP agglomeration state were measured. Agglomeration of AgNP exposed in filtered natural freshwater was observed to be primarily controlled by the electrolyte type and concentration. Moreover, agglomerated AgNP were still detected after 7 days of exposure. Consequently, slow sedimentation and high mobility of agglomerated AgNP could be expected under the considered natural conditions. A critical evaluation of the different methods used is presented as well.

Dysregulation of major functional genes in frontal cortex by maternal exposure to carbon black nanoparticle is not ameliorated by ascorbic acid pretreatment.

PubMed

Onoda, Atsuto; Takeda, Ken; Umezawa, Masakazu

2018-09-01

Recent cohort studies have revealed that perinatal exposure to particulate air pollution, including carbon-based nanoparticles, increases the risk of brain disorders. Although developmental neurotoxicity is currently a major issue in the toxicology of nanoparticles, critical information for understanding the mechanisms underlying the developmental neurotoxicity of airway exposure to carbon black nanoparticle (CB-NP) is still lacking. In order to investigate these mechanisms, we comprehensively analyzed fluctuations in the gene expression profile of the frontal cortex of offspring mice exposed maternally to CB-NP, using microarray analysis combined with Gene Ontology information. We also analyzed differences in the enriched function of genes dysregulated by maternal CB-NP exposure with and without ascorbic acid pretreatment to refine specific alterations in gene expression induced by CB-NP. Total of 652 and 775 genes were dysregulated by CB-NP in the frontal cortex of 6- and 12-week-old offspring mice, respectively. Among the genes dysregulated by CB-NP, those related to extracellular matrix structural constituent, cellular response to interferon-beta, muscle organ development, and cysteine-type endopeptidase inhibitor activity were ameliorated by ascorbic acid pretreatment. A large proportion of the dysregulated genes, categorized in hemostasis, growth factor, chemotaxis, cell proliferation, blood vessel, and dopaminergic neurotransmission, were, however, not ameliorated by ascorbic acid pretreatment. The lack of effects of ascorbic acid on the dysregulation of genes following maternal CB-NP exposure suggests that the contribution of oxidative stress to the effects of CB-NP on these biological functions, i.e., cell migration and proliferation, blood vessel maintenance, and dopaminergic neuron system, may be limited. At least, ascorbic acid pretreatment is hardly likely to be able to protect the brain of offspring from developmental neurotoxicity of CB-NP. The present study provides insight into the mechanisms underlying developmental neurotoxicity following maternal nanoparticle exposure. Copyright © 2018 Elsevier B.V. All rights reserved.

Expression and functional roles of estrogen receptor GPR30 in human intervertebral disc.

PubMed

Wei, Aiqun; Shen, Bojiang; Williams, Lisa A; Bhargav, Divya; Yan, Feng; Chong, Beng H; Diwan, Ashish D

2016-04-01

Estrogen withdrawal, a characteristic of female aging, is associated with age-related intervertebral disc (IVD) degeneration. The function of estrogen is mediated by two classic nuclear receptors, estrogen receptor (ER)-α and -β, and a membrane bound G-protein-coupled receptor 30 (GPR30). To date, the expression and function of GPR30 in human spine is poorly understood. This study aimed to evaluate GPR30 expression in IVD, and its role in estrogen-related regulation of proliferation and apoptosis of disc nucleus pulposus (NP) cells. GPR30 expression was examined in 30 human adult NP and 9 fetal IVD. Results showed that GPR30 was expressed in NP cells at both mRNA and protein levels. In human fetal IVD, GPR30 protein was expressed in the NP at 12-14 weeks gestation, but was undetectable at 8-11 weeks. The effect of 17β-estradiol (E2) on GPR30-mediated proliferation and interleukin-1β (IL-1β)-induced apoptosis of NP cells was investigated. Cultured NP cells were treated with or without E2, GPR30 antagonist G36, and ER antagonist ICI 182,780. NP cell viability was tested by MTS assay. Apoptosis was determined by flow cytometry using fluorescence labeled annexin-V, TUNEL assay and immumnocytochemical staining of activated caspase-3. E2 enhanced cell proliferation and prevented IL-1β-induced cell death, but the effect was partially blocked by G36 and completely abrogated by a combination of ICI 182,780 and G36. This study demonstrates that GPR30 is expressed in human IVD to transmit signals triggering E2-induced NP cell proliferation and protecting against IL-1β-induced apoptosis. The effects of E2 on NP cells require both GPR30 and classic estrogen receptors. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Controls on the Fate and Speciation of Np(V) During Iron (Oxyhydr)oxide Crystallization.

PubMed

Bots, Pieter; Shaw, Samuel; Law, Gareth T W; Marshall, Timothy A; Mosselmans, J Frederick W; Morris, Katherine

2016-04-05

The speciation and fate of neptunium as Np(V)O2(+) during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2(+) to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.

Sulfur Effect on the Space Weathering of Airless Bodies: Laboratory Simulation

NASA Astrophysics Data System (ADS)

Sasaki, S.; Okazaki, M.; Tanaka, H.; Hiroi, T.

2017-12-01

Space weathering is the main process that should control the change of brightness and color of the surface of airless silicate bodies such and the Moon, Mercury and asteroids. S-type asteroids show more overall depletion and reddening of the spectra, and more weakening of absorption bands than ordinary chondrites. Vapor-deposition through at high-velocity dust impacts as well as implantation of intensive solar wind ions may produce the space weathering rims bearing nano-iron particles (npFe0), responsible for spectral change. Simulation experiments using nanosecond pulse laser successfully produced vapor-deposition type npFe0 to change the optical properties [1]. A small (500m) asteroid Itokawa has a weathered surface, although its surface is rocky (rough terrain) or pebble-rich (smooth terrain). In 2011, HAYABUSA returned the particulate samples from the smooth terrain. The most notable discoveries in Itokawa particles are amorphous space-weathering rims containing npFe0. Sulfur and magnesium abundances suggest the presence of nanophase FeS (and MgS) in addition to npFe0 [2]. The presence of npFeS in asteroidal regolith is compatible with the observation of regolith breccia meteorites. On Mercury, MESSENGER revealed a high sulfur abundance (2wt% on average up to 4wt%), which can account for all of Fe by FeS. Both npFeS and npMgS may play an important role also on the surface of Mercury by lowering albedo. In our laboratory simulation using pulsed laser, spectral changes of olivine samples are facilitated when FeS is mixed (5-10wt%) (Fig.1). Nanophase Fe is confirmed by TEM. The darkening feature is reduced by additional heading at 150C, which would suggest the presence of volatile residue. Mixing of pure sulfur particles showed some, but not significant changes after laser irradiation. We acknowledge A. Miyake and A. Tsuchiyama at Kyoto U. for TEM observation. Ref: [1] S. Sasaki et al.: Nature 410 (2001) 555; [2] T. Noguchi et al.: Science 333 (2011) 1121 Fig. 1. Spectral change after pulse laser irradiation. The vertical axis shows normalized reflectance at 2500 nm-infrared darkening, whereas the horizontal axis shows the spectral slope of reflectance ratio of 1600 nm to 560 nm that would show reddening. Size range of fine FeS is smaller than 45 micron.

Mutagenicity of silver nanoparticles in CHO cells dependent on particle surface functionalization and metabolic activation

NASA Astrophysics Data System (ADS)

Guigas, Claudia; Walz, Elke; Gräf, Volker; Heller, Knut J.; Greiner, Ralf

2017-06-01

The potential of engineered nanomaterials to induce genotoxic effects is an important aspect of hazard identification. In this study, cytotoxicity and mutagenicity as a function of metabolic activation of three silver nanoparticle (AgNP) preparations differing in surface coating were determined in Chinese hamster ovary (CHO) subclone K1 cells. Three silver nanoparticle preparations ( x 90,0 <30 nm) stabilized with polyoxyethylene glycerol trioleate and polyoxyethylene sorbitan monolaurate (AgPure™), citrate (Citrate-Ag), and polyvinylpyrrolidone (PVP-Ag) were used for the experiments. The cytotoxic effect of AgNPs was assessed with the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazoliumbromide) test using different concentrations of nanoparticles, while the mutagenicity was evaluated using the hypoxanthine-guanine phosphoribosyltransferase (HPRT) gene mutation assay. The cytotoxicity of all three AgNPs was lower in a cell culture medium containing 10% fetal calf serum (FCS) than in medium without FCS. The HPRT test without metabolic activation system S9 revealed that compared to the other AgNP formulations, citrate-coated Ag showed a lower genotoxic effect. However, addition of S9 increased the mutation frequency of all AgNPs and especially influenced the genotoxicity of Citrate-Ag. The results showed that exogenous metabolic activation of nanosilver is crucial even if interactions of the metabolic activation system, nanosilver, and cells are not really understood up to now.

Toxicity of organic and inorganic nanoparticles to four species of white-rot fungi.

PubMed

Galindo, T P S; Pereira, R; Freitas, A C; Santos-Rocha, T A P; Rasteiro, M G; Antunes, F; Rodrigues, D; Soares, A M V M; Gonçalves, F; Duarte, A C; Lopes, I

2013-08-01

The rapid development of nanoparticles (NP) for industrial applications and large-volume manufacturing, with its subsequent release into the environment, raised the need to understand and characterize the potential effects of NP to biota. Accordingly, this work aimed to assess sublethal effects of five NP to the white-rot fungi species Trametes versicolor, Lentinus sajor caju, Pleurotus ostreatus, and Phanerochaete chrysosporium. Each species was exposed to serial dilutions of the following NP: organic-vesicles of SDS/DDAB and of Mo/NaO; gold-NP, quantum dot CdSe/ZnS, and Fe/Co. Fungi growth rate was monitored every day, and at the end of assay the mycelium from each replicate was collected to evaluate possible changes in its chemical composition. For all NP-suspensions the following parameters were characterized: hydrodynamic diameter, surface charge, aggregation index, zeta potential, and conductivity. All tested NP tended to aggregate when suspended in aqueous media. The obtained results showed that gold-NP, CdSe/ZnS, Mo/NaO, and SDS/DDAB significantly inhibited the growth of fungi with effects on the mycelium chemical composition. Among the tested NP, gold-NP and CdSe/ZnS were the ones exerting a higher effect on the four fungi. Finally to our knowledge, this is the first study reporting that different types of NP induce changes in the chemical composition of fungi mycelium. Copyright © 2013 Elsevier B.V. All rights reserved.

Surface plasmon coupling for suppressing p-GaN absorption and TM-polarized emission in a deep-UV light-emitting diode.

PubMed

Kuo, Yang; Su, Chia-Ying; Hsieh, Chieh; Chang, Wen-Yen; Huang, Chu-An; Kiang, Yean-Woei; Yang, C C

2015-09-15

The radiated power enhancement (suppression) of an in- (out-of-) plane-oriented radiating dipole at a desired emission wavelength in the deep-ultraviolet (UV) range when it is coupled with a surface plasmon (SP) resonance mode induced on a nearby Al nanoparticle (NP) is demonstrated. Also, it is found that the enhanced radiated power propagates mainly in the direction from the Al NP toward the dipole. Such SP coupling behaviors can be used for suppressing the transverse-magnetic (TM)-polarized emission, enhancing the transverse-electric-polarized emission, and reducing the UV absorption of the p-GaN layer in an AlGaN-based deep-UV light-emitting diode by embedding a sphere-like Al NP in its p-AlGaN layer.

Communication: Diverse nanoscale cluster dynamics: Diffusion of 2D epitaxial clusters

NASA Astrophysics Data System (ADS)

Lai, King C.; Evans, James W.; Liu, Da-Jiang

2017-11-01

The dynamics of nanoscale clusters can be distinct from macroscale behavior described by continuum formalisms. For diffusion of 2D clusters of N atoms in homoepitaxial systems mediated by edge atom hopping, macroscale theory predicts simple monotonic size scaling of the diffusion coefficient, DN ˜ N-β, with β = 3/2. However, modeling for nanoclusters on metal(100) surfaces reveals that slow nucleation-mediated diffusion displaying weak size scaling β < 1 occurs for "perfect" sizes Np = L2 and L(L+1) for integer L = 3,4,… (with unique square or near-square ground state shapes), and also for Np+3, Np+4,…. In contrast, fast facile nucleation-free diffusion displaying strong size scaling β ≈ 2.5 occurs for sizes Np+1 and Np+2. DN versus N oscillates strongly between the slowest branch (for Np+3) and the fastest branch (for Np+1). All branches merge for N = O(102), but macroscale behavior is only achieved for much larger N = O(103). This analysis reveals the unprecedented diversity of behavior on the nanoscale.

T Tank Farm Interim Surface Barrier Demonstration - Vadose Zone Monitoring FY09 Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Z. F.; Strickland, Christopher E.; Field, Jim G.

2010-01-01

DOE’s Office of River Protection constructed a temporary surface barrier over a portion of the T Tank Farm as part of the T Farm Interim Surface Barrier Demonstration Project. As part of the demonstration effort, vadose zone moisture is being monitored to assess the effectiveness of the barrier at reducing soil moisture. A solar-powered system was installed to continuously monitor soil water conditions at four locations (i.e., instrument Nests A, B, C, and D) beneath the barrier and outside the barrier footprint as well as site meteorological conditions. Nest A is placed in the area outside the barrier footprint andmore » serves as a control, providing subsurface conditions outside the influence of the surface barrier. Nest B provides subsurface measurements to assess surface-barrier edge effects. Nests C and D are used to assess changes in soil-moisture conditions beneath the interim surface barrier. Each instrument nest is composed of a capacitance probe (CP) with multiple sensors, multiple heat-dissipation units (HDUs), and a neutron probe (NP) access tube. The monitoring results in FY09 are summarized below. The solar panels functioned normally and could provide sufficient power to the instruments. The CP in Nest C after September 20, 2009, was not functional. The CP sensors in Nest B after July 13 and the 0.9-m CP sensor in Nest D before June 10 gave noisy data. Other CPs were functional normally. All the HDUs were functional normally but some pressure-head values measured by HDUs were greater than the upper measurement-limit. The higher-than-upper-limit values might be due to the very wet soil condition and/or measurement error but do not imply the malfunction of the sensors. Similar to FY07 and FY08, in FY09, the soil under natural conditions (Nest A) was generally recharged during the winter period (October-March) and discharged during the summer period (April-September). Soil water conditions above about 1.5-m to 2-m depth from all three types of measurements (i.e., CP, NP and HDU) showed relatively large variation during the seasonal wetting-drying cycle. For the soil below 2-m depth, the seasonal variation of soil water content was relatively small. The construction of the surface barrier was completed in April 2008. In the soil below the surface barrier (Nests C and D), the CP measurements showed that water content at the soil between 0.6-m and 2.3-m depths was very stable, indicating no climatic impacts on soil water condition beneath the barrier. The NP-measured water content showed that soil water drainage seemed occurring in the soil between about 3.4 m (11 ft) and 9.1 m (30 ft) in FY09. The HDU-measured water pressure decreased consistently in the soil above 5-m depth, indicating soil water drainage at these depths of the soil. In the soil below the edge of the surface barrier (Nest B), the CP-measured water content was relatively stable through the year except at the 0.9-m depth; the NP-measured water content showed that soil water drainage was occurring in the soil between about 3.4 m (11 ft) and 9.1 m (30 ft) but at a slightly smaller magnitude than those in Nests C and D; the HDU-measurements show that the pressure head changes in FY09 in Nest B were less than those for C and D but more than those for A. The soil-water-pressure head was more sensitive to soil water regime changes under dry conditions. In the soil beneath the barrier, the theoretical steady-state values of pressure head is equal to the negative of the distance to groundwater table. Hence, it is expected that, in the future, while the water content become stable, the pressure head will keep decreasing for a long time (e.g., many years). These results indicate that the T Tank Farm surface barrier was performing as expected by intercepting the meteoric water from infiltrating into the soil and the soil was becoming drier gradually. The barrier also has some effects on the soil below the barrier edge but at a reduced magnitude.« less

Detection of urinary creatinine using gold nanoparticles after solid phase extraction

NASA Astrophysics Data System (ADS)

Sittiwong, Jarinya; Unob, Fuangfa

2015-03-01

Label-free gold nanoparticles (AuNPs) were utilized in the detection of creatinine in human urine after a sample preparation by extraction of creatinine on sulfonic acid functionalized silica gel. With the proposed sample preparation method, the interfering effects of the urine matrix on creatinine detection by AuNPs were eliminated. Parameters affecting creatinine extraction were investigated. The aggregation of AuNPs induced by creatinine resulted in a change in the surface plasmon resonance signal with a concomitant color change that could be observed by the naked eye and quantified spectrometrically. The effect of AuNP concentration and reaction time on AuNP aggregation was investigated. The method described herein provides a determination of creatinine in a range of 15-40 mg L-1 with a detection limit of 13.7 mg L-1 and it was successfully used in the detection of creatinine in human urine samples.

Virus-Based Nanoparticles of Simian Virus 40 in the Field of Nanobiotechnology.

PubMed

Zhang, Wenjing; Zhang, Xian-En; Li, Feng

2017-12-26

Biomolecular nanostructures derived from living organisms, such as protein cages, fibers, and layers are drawing increasing interests as natural biomaterials. The virus-based nanoparticles (VNPs) of simian virus 40 (SV40), with a cage-like structure assembled from the major capsid protein of SV40, have been developed as a platform for nanobiotechnology in the recent decade. Foreign nanomaterials (e.g., quantum dots (QDs) and gold nanoparticles (AuNPs)) can be positioned in the inner cavity or on the outer surface of SV40 VNPs, through self-assembly by engineering the nanoparticle (NP)-protein interfacial interactions. Construction of these hybrid nanostructures has enabled integration of different functionalities. This review briefly summarizes the applications of SV40 VNPs in this multidisciplinary field, including NP encapsulation, templated assembly of nanoarchitectures, nanophotonics, and fluorescence imaging. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exposure to Silver Nanospheres Leads to Altered Respiratory Mechanics and Delayed Immune Response in an in Vivo Murine Model

PubMed Central

Botelho, Danielle; Leo, Bey F.; Massa, Christopher; Sarkar, Srijata; Tetley, Terry; Chung, Kian F.; Chen, Shu; Ryan, Mary P.; Porter, Alexandra; Atochina-Vasserman, Elena N.; Zhang, Junfeng; Schwander, Stephan; Gow, Andrew J.

2018-01-01

Here we examine the organ level toxicology of both carbon black (CB) and silver nanoparticles (AgNP). We aim to determine metal-specific effects to respiratory function, inflammation and potential interactions with lung lining fluid (LLF). C57Bl6/J male mice were intratracheally instilled with saline (control), low (0.05 μg/g) or high (0.5 μg/g) doses of either AgNP or CB 15 nm nanospheres. Lung histology, cytology, surfactant composition and function, inflammatory gene expression, and pulmonary function were measured at 1, 3, and 7 days post-exposure. Acutely, high dose CB resulted in an inflammatory response, increased neutrophilia and cytokine production, without alteration in surfactant composition or respiratory mechanics. Low dose CB had no effect. Neither low nor high dose AgNPs resulted in an acute inflammatory response, but there was an increase in work of breathing. Three days post-exposure with CB, a persistent neutrophilia was noted. High dose AgNP resulted in an elevated number of macrophages and invasion of lymphocytes. Additionally, AgNP treated mice displayed increased expression of IL1B, IL6, CCL2, and IL10. However, there were no significant changes in respiratory mechanics. At day 7, inflammation had resolved in AgNP-treated mice, but tissue stiffness and resistance were significantly decreased, which was accompanied by an increase in surfactant protein D (SP-D) content. These data demonstrate that the presence of metal alters the response of the lung to nanoparticle exposure. AgNP-surfactant interactions may alter respiratory function and result in a delayed immune response, potentially due to modified airway epithelial cell function. PMID:29632485

Study of crystallization mechanisms of Fe nanoparticle

NASA Astrophysics Data System (ADS)

Kien, P. H.; Trang, G. T. T.; Hung, P. K.

2017-06-01

In this paper, the nanoparticle (NP) Fe was investigated by means of molecular dynamics simulation. The crystallization mechanism was studied through the time evolution of crystal cluster and potential energies of different atom types. The simulation shows that the NP was crystallized into bcc crystal structure when it was annealed at 900 K for long times. At early stage of the annealing, small nuclei form in different places of NP and dissolve for short times. After long times some nuclei form and gather nearby which create the stable clusters in the core of NP. After that the crystal clusters grow in the direction to cover the core and then to spread into the surface of NP. Analyzing the energies of different type atoms, we found that the crystal growth is originated from specific atomic arrangement in the boundary region of crystal clusters.

An optical microplate biosensor for the detection of methyl parathion pesticide using a biohybrid of Sphingomonas sp. cells-silica nanoparticles.

PubMed

Mishra, Archana; Kumar, Jitendra; Melo, Jose Savio

2017-01-15

The previously developed Sphingomonas sp. based optical microplate biosensor for methyl parathion (MP) was good as it detected multiple samples but had poor stability and low sensitivity. The present study aims to overcome these limitations. Silica nanoparticles (Si NP) were thus functionalized with polyethyleneimine (PEI) and the functionalized silica nanoparticles ( f Si NP) were then integrated with Sphingomonas sp. cells. The process was optimized for hydrolysis of MP into p-nitrophenol (PNP). Integration of f Si NP with cells was confirmed by FT-IR analysis. Biohybrid of Sphingomonas sp.- f Si NP was immobilized on the wells of microplate and associated directly with the optical transducer of microplate reader. Immobilized biohybrid of Sphingomonas sp.- f Si NP was characterized using SEM. A detection range of 0.1-1ppm MP was achieved from the linear range of calibration plot. After integration with f Si NP the storage stability of biohybrid was enhanced ten times from 18 to 180 days. This study proves that after interaction of cells with f Si NP, improved the sensitivity and stability of the biosensor. Spiked samples were also analyzed and correlated using this biohybrid based biosensor. Copyright © 2016 Elsevier B.V. All rights reserved.

Cognitive Reserve as a Protective Factor in Older HIV-Positive Patients at Risk for Cognitive Decline

PubMed Central

Foley, Jessica M.; Ettenhofer, Mark L.; Kim, Michelle S.; Behdin, Nina; Castellon, Steven A.; Hinkin, Charles H.

2013-01-01

The present study examined the impact of cognitive reserve in maintaining intact neuropsychological (NP) function among older HIV-positive individuals, a uniquely at-risk subgroup. Participants included 129 individuals classified by HIV serostatus, age group, and NP impairment. A three-way analysis of variance (ANOVA) followed by a series of within-group ANOVA and multiple regression analyses were conducted to investigate the pattern of cognitive reserve (vs. other protective) influence among groups with varying risks of NP impairment. Results indicated a significant age ×HIV status interaction, with older HIV-positive individuals demonstrating higher cognitive reserve than subgroups with less risk for NP compromise (younger age and/or HIV-negative). Results demonstrated higher cognitive reserve specific to NP-intact older HIV-positive individuals. Within this group, the interaction of younger age and higher cognitive reserve independently contributed to cognitive status when controlling for psychiatric, immunological, and psychosocial protective mechanisms, suggesting the importance of cognitive reserve beyond other protective mechanisms in maintaining optimal NP functioning in those individuals most at risk. Alongside younger age, factors contributing to cognitive reserve (i.e., education and estimated premorbid intelligence) may provide substantial benefit for older HIV-positive adults who are at high risk for NP compromise. PMID:22385375

Sensitive determination of dopamine levels via surface-enhanced Raman scattering of Ag nanoparticle dimers.

PubMed

Yu, Xiantong; He, XiaoXiao; Yang, Taiqun; Zhao, Litao; Chen, Qichen; Zhang, Sanjun; Chen, Jinquan; Xu, Jianhua

2018-01-01

Dopamine (DA) is an important neurotransmitter in the hypothalamus and pituitary gland, which can produce a direct influence on mammals' emotions in midbrain. Additionally, the level of DA is highly related with some important neurologic diseases such as schizophrenia, Parkinson, and Huntington's diseases, etc. In light of the important roles that DA plays in the disease modulation, it is of considerable significance to develop a sensitive and reproducible approach for monitoring DA. The objective of this study was to develop an efficient approach to quantitatively monitor the level of DA using Ag nanoparticle (NP) dimers and enhanced Raman spectroscopy. Ag NP dimers were synthesized for the sensitive detection of DA via surface-enhanced Raman scattering (SERS). Citrate was used as both the capping agent of NPs and sensing agent to DA, which is self-assembled on the surface of Ag NP dimers by reacting with the surface carboxyl group to form a stable amide bond. To improve accuracy and precision, the multiplicative effects model for surface-enhanced Raman spectroscopy was utilized to analyze the SERS assays. A low limits of detection (LOD) of 20 pM and a wide linear response range from 30 pM to 300 nM were obtained for DA quantitative detection. The SERS enhancement factor was theoretically valued at approximately 10 7 by discrete dipole approximation. DA was self-assembled on the citrate capped surface of Ag NPs dimers through the amide bond. The adsorption energy was estimated to be 256 KJ/mol using the Langmuir isotherm model. The density functional theory was used to simulate the spectral characteristics of SERS during the adsorption of DA on the surface of the Ag dimers. Furthermore, to improve the accuracy and precision of quantitative analysis of SERS assays with a multiplicative effects model for surface-enhanced Raman spectroscopy. A LOD of 20 pM DA-level was obtained, and the linear response ranged from 30 pM to 300 nM for quantitative DA detection. The absolute relative percentage error was 4.22% between the real and predicted DA concentrations. This detection scheme is expected to have good applications in the prevention and diagnosis of certain diseases caused by disorders in the DA level.

Sensitive determination of dopamine levels via surface-enhanced Raman scattering of Ag nanoparticle dimers

PubMed Central

Yu, Xiantong; He, XiaoXiao; Yang, Taiqun; Zhao, Litao; Chen, Qichen; Zhang, Sanjun; Chen, Jinquan; Xu, Jianhua

2018-01-01

Background Dopamine (DA) is an important neurotransmitter in the hypothalamus and pituitary gland, which can produce a direct influence on mammals’ emotions in midbrain. Additionally, the level of DA is highly related with some important neurologic diseases such as schizophrenia, Parkinson, and Huntington’s diseases, etc. In light of the important roles that DA plays in the disease modulation, it is of considerable significance to develop a sensitive and reproducible approach for monitoring DA. Purpose The objective of this study was to develop an efficient approach to quantitatively monitor the level of DA using Ag nanoparticle (NP) dimers and enhanced Raman spectroscopy. Methods Ag NP dimers were synthesized for the sensitive detection of DA via surface-enhanced Raman scattering (SERS). Citrate was used as both the capping agent of NPs and sensing agent to DA, which is self-assembled on the surface of Ag NP dimers by reacting with the surface carboxyl group to form a stable amide bond. To improve accuracy and precision, the multiplicative effects model for surface-enhanced Raman spectroscopy was utilized to analyze the SERS assays. Results A low limits of detection (LOD) of 20 pM and a wide linear response range from 30 pM to 300 nM were obtained for DA quantitative detection. The SERS enhancement factor was theoretically valued at approximately 107 by discrete dipole approximation. DA was self-assembled on the citrate capped surface of Ag NPs dimers through the amide bond. The adsorption energy was estimated to be 256 KJ/mol using the Langmuir isotherm model. The density functional theory was used to simulate the spectral characteristics of SERS during the adsorption of DA on the surface of the Ag dimers. Furthermore, to improve the accuracy and precision of quantitative analysis of SERS assays with a multiplicative effects model for surface-enhanced Raman spectroscopy. Conclusion A LOD of 20 pM DA-level was obtained, and the linear response ranged from 30 pM to 300 nM for quantitative DA detection. The absolute relative percentage error was 4.22% between the real and predicted DA concentrations. This detection scheme is expected to have good applications in the prevention and diagnosis of certain diseases caused by disorders in the DA level. PMID:29713165

In situ characterization of catalytic activity of graphene stabilized small-sized Pd nanoparticles for CO oxidation

NASA Astrophysics Data System (ADS)

Mao, Bao-Hua; Liu, Chang-Hai; Gao, Xu; Chang, Rui; Liu, Zhi; Wang, Sui-Dong

2013-10-01

The room-temperature ionic liquid assisted sputtering method is utilized to achieve the Pd-nanoparticle (NP)-graphene hybrid. The supported Pd NPs possess uniformly small sizes of 1-2 nm, which create huge surface area with ultralow Pd consumption and high NP stability. The Pd-NP-graphene hybrid is in situ characterized by the ambient pressure X-ray photoelectron spectroscopy using synchrotron radiation, and the results demonstrate high catalytic activity of the hybrid for CO oxidation. The catalytic behavior is reproducible for several catalytic cycles. The present simple and clean approach is promising to produce metal-NP-based high-efficiency catalysts for CO oxidation.

Thermally annealed gold nanoparticles for surface-assisted laser desorption ionisation-mass spectrometry of low molecular weight analytes.

PubMed

Pilolli, Rosa; Ditaranto, Nicoletta; Di Franco, Cinzia; Palmisano, Francesco; Cioffi, Nicola

2012-10-01

Metal nanomaterials have an emerging role in surface-assisted laser desorption ionisation-mass spectrometry (SALDI-MS) providing a useful tool to overcome some limitations intrinsically related to the use of conventional organic matrices in matrix-assisted LDI-MS. In this contribution, the possibility to use a stainless-steel-supported gold nanoparticle (AuNP) film as a versatile platform for SALDI-MS was assessed. A sacrificial anode electrosynthetic route was chosen in order to obtain morphologically controlled core-shell AuNPs; the colloidal AuNPs were, thereafter, drop cast onto a stainless-steel sample plate and the resulting AuNP film was thermally annealed in order to improve its effectiveness as LDI-MS promoter. Spectroscopic characterization of the nanostructured film by X-ray photoelectron spectroscopy was crucial for understanding how annealing induced changes in the surface chemistry and influenced the performance of AuNPs as desorption/ionisation promoter. In particular, it was demonstrated that the post-deposition treatments were essential to enhance the AuNP core/analyte interaction, thus resulting in SALDI-MS spectra of significantly improved quality. The AuNP films were applied to the detection of three different classes of low molecular weight (LMW) analytes, i.e. amino acids, peptides and LMW polymers, in order to demonstrate the versatility of this nanostructured material.

Nanoporous-Gold-Based Electrode Morphology Libraries for Investigating Structure-Property Relationships in Nucleic Acid Based Electrochemical Biosensors.

PubMed

Matharu, Zimple; Daggumati, Pallavi; Wang, Ling; Dorofeeva, Tatiana S; Li, Zidong; Seker, Erkin

2017-04-19

Nanoporous gold (np-Au) electrode coatings significantly enhance the performance of electrochemical nucleic acid biosensors because of their three-dimensional nanoscale network, high electrical conductivity, facile surface functionalization, and biocompatibility. Contrary to planar electrodes, the np-Au electrodes also exhibit sensitive detection in the presence of common biofouling media due to their porous structure. However, the pore size of the nanomatrix plays a critical role in dictating the extent of biomolecular capture and transport. Small pores perform better in the case of target detection in complex samples by filtering out the large nonspecific proteins. On the other hand, larger pores increase the accessibility of target nucleic acids in the nanoporous structure, enhancing the detection limits of the sensor at the expense of more interference from biofouling molecules. Here, we report a microfabricated np-Au multiple electrode array that displays a range of electrode morphologies on the same chip for identifying feature sizes that reduce the nonspecific adsorption of proteins but facilitate the permeation of target DNA molecules into the pores. We demonstrate the utility of the electrode morphology library in studying DNA functionalization and target detection in complex biological media with a special emphasis on revealing ranges of electrode morphologies that mutually enhance the limit of detection and biofouling resilience. We expect this technique to assist in the development of high-performance biosensors for point-of-care diagnostics and facilitate studies on the electrode structure-property relationships in potential applications ranging from neural electrodes to catalysts.

A nanohybrid of platinum nanoparticles-porous ZnO-hemin with electrocatalytic activity to construct an amplified immunosensor for detection of influenza.

PubMed

Yang, Zhe-Han; Zhuo, Ying; Yuan, Ruo; Chai, Ya-Qin

2016-04-15

In this work, a nanohybrid of platinum nanoparticles-porous ZnO spheres-hemin (Pt-pZnO-hemin) was synthesized for construction of alkaline phosphatase-based immunosensor for detection of influenza. Briefly, porous ZnO spheres (pZnO) were prepared using soluble starches as the capping agent, followed by surface functionalization of platinum nanoparticles via a hydrothermal method (Pt-pZnO). Then, hemin with carboxylic functionality was spontaneously adsorbed onto Pt-pZnO by ester-like binding between carboxylic group of hemin and ZnO. Compared with platinum nanoparticles and hemin, the resulting Pt-pZnO-hemin nanohybrid showed more excellent electrocatalysis activity toward 1-naphthol (1-NP). Taking advantage of the Pt-pZnO-hemin, we have developed an amplified electrochemical immunosensor based on in situ generation of redox probe by alkaline phosphatase (ALP) and Pt-pZnO-hemin as signal enhancer. Herein, electrochemically active 1-NP was generated by enzymatic hydrolysis of inactive 1-naphthyl phosphate by ALP, then Pt-pZnO-hemin was used as catalyst to catalytically oxidize 1-NP, resulting in electrochemical signal amplification. Furthermore, in comparison with other nanomaterials including Au-pZnO, Pt-pZnO and Au-pZnO-hemin, the excellent catalytical property of Pt-pZnO-hemin make it a promising nanohybrid material for ALP-based immunosensor for signal amplification. Copyright © 2015. Published by Elsevier B.V.

RbsB (NTHI_0632) mediates quorum signal uptake in nontypeable Haemophilus influenzae strain 86-028NP

PubMed Central

Armbruster, Chelsie E.; Pang, Bing; Murrah, Kyle; Juneau, Richard A.; Perez, Antonia C.; Weimer, Kristin E.D.; Swords, W. Edward

2011-01-01

Summary Nontypeable Haemophilus influenzae (NTHI) is a respiratory commensal and opportunistic pathogen, which persists within biofilms on airway mucosal surfaces. For many species, biofilm formation is impacted by quorum signaling. Our prior work shows that production of autoinducer-2 (AI-2) promotes biofilm development and persistence for NTHI 86-028NP. NTHI 86-028NP encodes an ABC transporter annotated as a ribose transport system that includes a protein (RbsB) with similarity to the Escherichia coli LsrB and Aggregatibacter actinomycetemcomitans RbsB proteins that bind AI-2. In this study, inactivation of rbsB significantly reduced uptake of AI-2 and the AI-2 precursor dihydroxypentanedione (DPD) by NTHI 86-028NP. Moreover, DPD uptake was not competitively inhibited by ribose or other pentose sugars. Transcript levels of rbsB increased in response to DPD and as bacteria approached stationary-phase growth. The NTHI 86-028NP rbsB mutant also formed biofilms with significantly reduced thickness and total biomass and reduced surface phosphorylcholine, similar to a luxS mutant. Infection studies revealed that loss of rbsB impaired bacterial persistence in the chinchilla middle-ear, similar to our previous results with luxS mutants. Based on these data, we conclude that in NTHI 86-028NP, RbsB is a LuxS/AI-2 regulated protein that is required for uptake of and response to AI-2. PMID:21923771

RbsB (NTHI_0632) mediates quorum signal uptake in nontypeable Haemophilus influenzae strain 86-028NP.

PubMed

Armbruster, Chelsie E; Pang, Bing; Murrah, Kyle; Juneau, Richard A; Perez, Antonia C; Weimer, Kristin E D; Swords, W Edward

2011-11-01

Nontypeable Haemophilus influenzae (NTHI) is a respiratory commensal and opportunistic pathogen, which persists within biofilms on airway mucosal surfaces. For many species, biofilm formation is impacted by quorum signalling. Our prior work shows that production of autoinducer-2 (AI-2) promotes biofilm development and persistence for NTHI 86-028NP. NTHI 86-028NP encodes an ABC transporter annotated as a ribose transport system that includes a protein (RbsB) with similarity to the Escherichia coli LsrB and Aggregatibacter actinomycetemcomitans RbsB proteins that bind AI-2. In this study, inactivation of rbsB significantly reduced uptake of AI-2 and the AI-2 precursor dihydroxypentanedione (DPD) by NTHI 86-028NP. Moreover, DPD uptake was not competitively inhibited by ribose or other pentose sugars. Transcript levels of rbsB increased in response to DPD and as bacteria approached stationary-phase growth. The NTHI 86-028NP rbsB mutant also formed biofilms with significantly reduced thickness and total biomass and reduced surface phosphorylcholine, similar to a luxS mutant. Infection studies revealed that loss of rbsB impaired bacterial persistence in the chinchilla middle ear, similar to our previous results with luxS mutants. Based on these data, we conclude that in NTHI 86-028NP, RbsB is a LuxS/AI-2 regulated protein that is required for uptake of and response to AI-2. © 2011 Blackwell Publishing Ltd.

The use of kernel density estimators in breakthrough curve reconstruction and advantages in risk analysis

NASA Astrophysics Data System (ADS)

Siirila, E. R.; Fernandez-Garcia, D.; Sanchez-Vila, X.

2014-12-01

Particle tracking (PT) techniques, often considered favorable over Eulerian techniques due to artificial smoothening in breakthrough curves (BTCs), are evaluated in a risk-driven framework. Recent work has shown that given a relatively few number of particles (np), PT methods can yield well-constructed BTCs with kernel density estimators (KDEs). This work compares KDE and non-KDE BTCs simulated as a function of np (102-108) and averaged as a function of the exposure duration, ED. Results show that regardless of BTC shape complexity, un-averaged PT BTCs show a large bias over several orders of magnitude in concentration (C) when compared to the KDE results, remarkably even when np is as low as 102. With the KDE, several orders of magnitude less np are required to obtain the same global error in BTC shape as the PT technique. PT and KDE BTCs are averaged as a function of the ED with standard and new methods incorporating the optimal h (ANA). The lowest error curve is obtained through the ANA method, especially for smaller EDs. Percent error of peak of averaged-BTCs, important in a risk framework, is approximately zero for all scenarios and all methods for np ≥105, but vary between the ANA and PT methods, when np is lower. For fewer np, the ANA solution provides a lower error fit except when C oscillations are present during a short time frame. We show that obtaining a representative average exposure concentration is reliant on an accurate representation of the BTC, especially when data is scarce.

Spatial distribution and migration of nonylphenol in groundwater following long-term wastewater irrigation.

PubMed

Wang, Shiyu; Wu, Wenyong; Liu, Fei; Yin, Shiyang; Bao, Zhe; Liu, Honglu

2015-01-01

Seen as a solution to water shortages, wastewater reuse for crop irrigation does however poses a risk owing to the potential release of organic contaminants into soil and water. The frequency of detection (FOD), concentration, and migration of nonylphenol (NP) isomers in reclaimed water (FODRW), surface water (FODSW), and groundwater (FODGW) were investigated in a long-term wastewater irrigation area in Beijing. The FODRW, FODSW and FODGW of any or all of 12 NP isomers were 66.7% to 100%, 76.9% to 100% and 13.3% to 60%, respectively. The mean (±standard deviation) NP concentrations of the reclaimed water, surface water, and groundwater (NPRW, NPSW, NPGW, repectively) were 469.4±73.4 ng L(-1), 694.6±248.7 ng(-1) and 244.4±230.8 ng(-1), respectively. The existence of external pollution sources during water transmission and distribution resulted in NPSW exceeding NPRW. NP distribution in groundwater was related to the duration and quantity of wastewater irrigation, the sources of aquifer recharge, and was seen to decrease with increasing aquifer depth. Higher riverside infiltration rate nearby leads to higher FODGW values. The migration rate of NP isomers was classified as high, moderate or low. Copyright © 2015 Elsevier B.V. All rights reserved.

Impact of nonconductive powder on electrostatic separation for recycling crushed waste printed circuit board.

PubMed

Wu, Jiang; Qin, Yufei; Zhou, Quan; Xu, Zhenming

2009-05-30

The electrostatic separation is an effective and environmentally friendly method for recycling metals and nonmetals from crushed printed circuit board (PCB) wastes. However, it still confronts some problems brought by nonconductive powder (NP). Firstly, the NP is fine and liable to aggregate. This leads to an increase of middling products and loss of metals. Secondly, the stability of separation process is influenced by NP. Finally, some NPs accumulate on the surface of the corona and electrostatic electrodes during the process. These problems lead to an inefficient separation. In the present research, the impacts of NP on electrostatic separation are investigated. The experimental results show that: the separation is notably influenced when the NP content is more than 10%. With the increase of NP content, the middling products sharply increase from 1.4 g to 4.3g (increase 207.1%), while the conductive products decrease from 24.0 g to 19.1g (decrease 20.4%), and the separation process become more instable.

Dispersion Morphology of Poly(methyl acrylate)/Silica Nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

D Janes; J Moll; S Harton

Nearly monodisperse poly(methyl acrylate) (PMA) and spherical SiO{sub 2} nanoparticles (NP, d = 14 {+-} 4 nm) were co-cast from 2-butanone, a mutually good solvent and a displacer of adsorbed PMA from silica. The effects of NP content and post-casting sample history on the dispersion morphology were found by small-angle X-ray scattering supplemented by transmission electron microscopy. Analysis of the X-ray results show that cast and thermally annealed samples exhibited a nearly random particle dispersion. That the same samples, prior to annealing, were not well-dispersed is indicative of thermodynamic miscibility during thermal annealing over the range of NP loadings studied.more » A simple mean-field thermodynamic model suggests that miscibility results primarily from favorable polymer segment/NP surface interactions. The model also indicates, and experiments confirm, that subsequent exposure of the composites to the likely displacer ethyl acetate results in entropic destabilization and demixing into NP-rich and NP-lean phases.« less

CeO2 nanoparticles alter the outcome of species interactions.

PubMed

Peng, Cheng; Chen, Ying; Pu, Zhichao; Zhao, Qing; Tong, Xin; Chen, Yongsheng; Jiang, Lin

2017-06-01

Despite considerable research on the environmental impacts of nanomaterials, we know little about how they influence interactions between species. Here, we investigated the acute (12 d) and chronic (64 d) toxicities of cerium oxide nanoparticles (CeO 2 NPs) and bulk particles (0-200 mg/L) to three ciliated protist species (Loxocephalus sp., Paramecium aurelia, and Tetrahymena pyriformis) in single-, bi-, and multispecies microcosms. The results show that CeO 2 NPs strongly affected the interactions between ciliated protozoan species. When exposed to the highest CeO 2 NPs (200 mg/L), the intrinsic growth rates of Loxocephalus and Paramecium were significantly decreased by 18.87% and 88.27%, respectively, while their carrying capacities declined by more than 90%. However, CeO 2 NP exposure made it difficult to predict outcomes of interspecific competition between species. At higher NP exposure (100 and 200 mg/L), competition led to the extinction of both species in the Loxocephalus and Paramecium microcosms that survived in the absence of competitors or CeO 2 NPs. Further, the presence of potential competitors improved the survival of Loxocephalus to hundreds of individuals per milliliter in microcosms with Tetrahymena where Loxocephalus would otherwise not be able to tolerate high levels of NP exposure. This result could be attributed to weakened NP adsorption on the cell surface due to competitor-caused reduction of NP surface charge (from -18.52 to -25.17 mV) and intensified NP aggregation via phagocytosis of NPs by ciliate cells. Our results emphasize the need to explicitly consider species interactions for a more comprehensive understanding of the ecological consequences of NP exposure.

Stability and Biodistribution of Thiol-Functionalized and (177)Lu-Labeled Metal Chelating Polymers Bound to Gold Nanoparticles.

PubMed

Yook, Simmyung; Lu, Yijie; Jeong, Jenny Jooyoung; Cai, Zhongli; Tong, Lemuel; Alwarda, Ramina; Pignol, Jean-Philippe; Winnik, Mitchell A; Reilly, Raymond M

2016-04-11

We are studying a novel radiation nanomedicine approach to treatment of breast cancer using 30 nm gold nanoparticles (AuNP) modified with polyethylene glycol (PEG) metal-chelating polymers (MCP) that incorporate 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelators for complexing the β-particle emitter, (177)Lu. Our objective was to compare the stability of AuNP conjugated to MCP via a single thiol [DOTA-PEG-ortho-pyridyl disulfide (OPSS)], a dithiol [DOTA-PEG-lipoic acid (LA)] or multithiol end-group [PEG-pGlu(DOTA)8-LA4] and determine the elimination and biodistribution of these (177)Lu-labeled MCP-AuNP in mice. Stability to aggregation in the presence of thiol-containing dithiothreitol (DTT), L-cysteine or glutathione was assessed and dissociation of (177)Lu-MCP from AuNP in human plasma measured. Elimination of radioactivity from the body of athymic mice and excretion into the urine and feces was measured up to 168 h post-intravenous (i.v.) injection of (177)Lu-MCP-AuNP and normal tissue uptake was determined. ICP-AES was used to quantify Au in the liver and spleen and these were compared to (177)Lu. Our results showed that PEG-pGlu(DOTA)8-LA4-AuNP were more stable to aggregation in vitro than DOTA-PEG-LA-AuNP and both forms of AuNP were more stable to thiol challenge than DOTA-PEG-OPSS-AuNP. PEG-pGlu((177)Lu-DOTA)8-LA4 was the most stable in plasma. Whole body elimination of (177)Lu was most rapid for mice injected with (177)Lu-DOTA-PEG-OPSS-AuNP. Urinary excretion accounted for >90% of eliminated (177)Lu. All (177)Lu-MCP-AuNP accumulated in the liver and spleen. Liver uptake was lowest for PEG-pGlu((177)Lu-DOTA)8-LA4-AuNP but these AuNP exhibited the greatest spleen uptake. There were differences in Au and (177)Lu in the liver for PEG-pGlu((177)Lu-DOTA)8-LA4-AuNP. These differences were not correlated with in vitro stability of the (177)Lu-MCP-AuNP. We conclude that conjugation of AuNP with PEG-pGlu((177)Lu-DOTA)8-LA4 via a multithiol functional group provided the greatest stability in vitro and lowest liver uptake in vivo and is, therefore, the most promising for constructing (177)Lu-MCP-AuNP for radiation treatment of breast cancer.

Experimental investigations of quantum confined silicon nanoparticle light emitting devices

NASA Astrophysics Data System (ADS)

Ligman, Rebekah Kristine

2007-12-01

As the demands on our world's energy resources continue to grow, alternative high efficiency materials such as quantum confined silicon nanoparticles (Si nps) are desirable for their potential low cost application in white light illumination, in optical displays, and in on-chip optical interconnects. Many fabrication and passivation techniques exist that produce Si nps with high photogenerated quantum yield. However, high electrically generated Si np quantum efficiency has eluded our society. Predominantly due to the lack of a stable surface passivation and a device fabrication technique that preserves the Si np optical properties. To amend these deficiencies, the passivation of nonthermal plasma fabricated Si nps with a surface oxide grown under UV exposure was first investigated. Control over the surface oxidized Si np (Si/SiO2) passivation growth was demonstrated and the optical stability of Si/SiO2 nps was suitable for demonstrating Si np electroluminescence (EL). Two approaches for constructing hybrid organic light emitting diode (OLED) devices around nonthermal plasma fabricated Si nps were then investigated. Multilayer devices, composed of a nonthermal plasma fabricated Si np layer embedded within an OLED, were first studied. However, no EL from Si nps was obtained using the multilayer device architecture due to poor control over the Si np film thickness. Single layer polymer(Si/SiO2) hybrid devices, composed of nps randomly dispersed within an extrinsic conductive polymer, were then studied and EL from Si/SiO2 nps was obtained. The hybrid device optical and electrical response was enhanced over the control devices, possibly due to morphology changes induced by the Si/SiO2 nps. The energy transfer (ET) processes in single layer polymer(Si/SiO 2) hybrid devices were then investigated by imposing known spatial separations between the intrinsic conductive polymers and Si/SiO2 nps. No measurable Si/SiO2 np emission was observed from the intrinsic hybrid devices independent of the spatial separation, implying no ET occurs between the intrinsic polymers and Si/SiO2 nps. These results suggest the observed Si/SiO 2 np emission from extrinsic polymer(Si/SiO2) hybrid devices may be produced by direct carrier injection, Forster or Dexter ET mechanisms.

Antibacterial and antibiofilm properties of yttrium fluoride nanoparticles

PubMed Central

Lellouche, Jonathan; Friedman, Alexandra; Gedanken, Aharon; Banin, Ehud

2012-01-01

Antibiotic resistance has prompted the search for new agents that can inhibit bacterial growth. Moreover, colonization of abiotic surfaces by microorganisms and the formation of biofilms is a major cause of infections associated with medical implants, resulting in prolonged hospitalization periods and patient mortality. In this study we describe a water-based synthesis of yttrium fluoride (YF3) nanoparticles (NPs) using sonochemistry. The sonochemical irradiation of an aqueous solution of yttrium (III) acetate tetrahydrate [Y(Ac)3 · (H2O)4], containing acidic HF as the fluorine ion source, yielded nanocrystalline needle-shaped YF3 particles. The obtained NPs were characterized by scanning electron microscopy and X-ray elemental analysis. NP crystallinity was confirmed by electron and powder X-ray diffractions. YF3 NPs showed antibacterial properties against two common bacterial pathogens (Escherichia coli and Staphylococcus aureus) at a μg/mL range. We were also able to demonstrate that antimicrobial activity was dependent on NP size. In addition, catheters were surface modified with YF3 NPs using a one-step synthesis and coating process. The coating procedure yielded a homogeneous YF3 NP layer on the catheter, as analyzed by scanning electron microscopy and energy dispersive spectroscopy. These YF3 NP-modified catheters were investigated for their ability to restrict bacterial biofilm formation. The YF3 NP-coated catheters were able to significantly reduce bacterial colonization compared to the uncoated surface. Taken together, our results highlight the potential to further develop the concept of utilizing these metal fluoride NPs as novel antimicrobial and antibiofilm agents, taking advantage of their low solubility and providing extended protection. PMID:23152681

A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO 2·M] 4+ Cation–Cation Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Freiderich, John W.; Burn, Adam G.; Martin, Leigh R.

The equilibrium constants for [NpO 2M∙] 4+ (M = Al 3+, In 3+, Sc 3+, Fe 3+) in μ = 10 M nitric acid and [NpO 2∙Ga] 4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe 3+ > Sc 3+ In 3+ > Ga 3+ Al 3+. These equilibrium constants are compared to those of previously reported values for NpO 2 + complexes with Cr 3+ and Rh 3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicatingmore » that the NpO 2 + dioxocation acts as a -donor with transition-metal cations and a sigma donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.« less

A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO 2·M] 4+ Cation–Cation Complexes

DOE PAGES

Freiderich, John W.; Burn, Adam G.; Martin, Leigh R.; ...

2017-04-14

The equilibrium constants for [NpO 2M∙] 4+ (M = Al 3+, In 3+, Sc 3+, Fe 3+) in μ = 10 M nitric acid and [NpO 2∙Ga] 4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe 3+ > Sc 3+ In 3+ > Ga 3+ Al 3+. These equilibrium constants are compared to those of previously reported values for NpO 2 + complexes with Cr 3+ and Rh 3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicatingmore » that the NpO 2 + dioxocation acts as a -donor with transition-metal cations and a sigma donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.« less

Targeted delivery of cisplatin to prostate cancer cells by aptamer functionalized Pt(IV) prodrug-PLGA-PEG nanoparticles.

PubMed

Dhar, Shanta; Gu, Frank X; Langer, Robert; Farokhzad, Omid C; Lippard, Stephen J

2008-11-11

Cisplatin is used to treat a variety of tumors, but dose limiting toxicities or intrinsic and acquired resistance limit its application in many types of cancer including prostate. We report a unique strategy to deliver cisplatin to prostate cancer cells by constructing Pt(IV)-encapsulated prostate-specific membrane antigen (PSMA) targeted nanoparticles (NPs) of poly(D,L-lactic-co-glycolic acid) (PLGA)-poly(ethylene glycol) (PEG)-functionalized controlled release polymers. By using PLGA-b-PEG nanoparticles with PSMA targeting aptamers (Apt) on the surface as a vehicle for the platinum(IV) compound c,t,c-[Pt(NH(3))(2)(O(2)CCH(2)CH(2)CH(2)CH(2)CH(3))(2)Cl(2)] (1), a lethal dose of cisplatin was delivered specifically to prostate cancer cells. PSMA aptamer targeted delivery of Pt(IV) cargos to PSMA(+) LNCaP prostate cancer cells by endocytosis of the nanoparticle vehicles was demonstrated using fluorescence microscopy by colocalization of green fluorescent labeled cholesterol-encapsulated NPs and early endosome marker EEA-1. The choice of linear hexyl chains in 1 was the result of a systematic study to optimize encapsulation and controlled release from the polymer without compromising either feature. Release of cisplatin from the polymeric nanoparticles after reduction of 1 and formation of cisplatin 1,2-intrastrand d(GpG) cross-links on nuclear DNA was confirmed by using a monoclonal antibody for the adduct. A comparison between the cytotoxic activities of Pt(IV)-encapsulated PLGA-b-PEG NPs with the PSMA aptamer on the surface (Pt-NP-Apt), cisplatin, and the nontargeted Pt(IV)-encapsulated NPs (Pt-NP) against human prostate PSMA-overexpressing LNCaP and PSMA(-) PC3 cancer cells revealed significant differences. The effectiveness of PSMA targeted Pt-NP-Apt nanoparticles against the PSMA(+) LNCaP cells is approximately an order of magnitude greater than that of free cisplatin.

Direct Metal Writing and Precise Positioning of Gold Nanoparticles within Microfluidic Channels for SERS Sensing of Gaseous Analytes.

PubMed

Lee, Mian Rong; Lee, Hiang Kwee; Yang, Yijie; Koh, Charlynn Sher Lin; Lay, Chee Leng; Lee, Yih Hong; Phang, In Yee; Ling, Xing Yi

2017-11-15

We demonstrate a one-step precise direct metal writing of well-defined and densely packed gold nanoparticle (AuNP) patterns with tunable physical and optical properties. We achieve this by using two-photon lithography on a Au precursor comprising poly(vinylpyrrolidone) (PVP) and ethylene glycol (EG), where EG promotes higher reduction rates of Au(III) salt via polyol reduction. Hence, clusters of monodisperse AuNP are generated along raster scanning of the laser, forming high-particle-density, well-defined structures. By varying the PVP concentration, we tune the AuNP size from 27.3 to 65.0 nm and the density from 172 to 965 particles/μm 2 , corresponding to a surface roughness of 12.9 to 67.1 nm, which is important for surface-based applications such as surface-enhanced Raman scattering (SERS). We find that the microstructures exhibit an SERS enhancement factor of >10 5 and demonstrate remote writing of well-defined Au microstructures within a microfluidic channel for the SERS detection of gaseous molecules. We showcase in situ SERS monitoring of gaseous 4-methylbenzenethiol and real-time detection of multiple small gaseous species with no specific affinity to Au. This one-step, laser-induced fabrication of AuNP microstructures ignites a plethora of possibilities to position desired patterns directly onto or within most surfaces for the future creation of multifunctional lab-on-a-chip devices.

Determination of Cancer Cell-Based pH-Sensitive Fluorescent Carbon Nanoparticles of Cross-Linked Polydopamine by Fluorescence Sensing of Alkaline Phosphatase Activity on Coated Surfaces and Aqueous Solution.

PubMed

Kang, Eun Bi; Choi, Cheong A; Mazrad, Zihnil Adha Islamy; Kim, Sung Han; In, Insik; Park, Sung Young

2017-12-19

The tumor-specific sensitive fluorescence sensing of cellular alkaline phosphatase (ALP) activity on the basis of host-guest specific and pH sensitivity was conducted on coated surfaces and aqueous states. Cross-linked fluorescent nanoparticles (C-FNP) consisting of β-cyclodextrin (β-CD)/boronic acid (BA) and fluorescent hyaluronic acid [FNP(HA)] were conjugated to fluorescent polydopamine [FNP(pDA)]. To determine the quenching effect of this system, hydrolysis of 4-nitrophenyl phosphate (NPP) to 4-nitrophenol (NP) was performed in the cavity of β-CD in the presence of ALP activated photoinduced electron transfer (PET) between NP and C-FNP. At an ALP level of 30-1000 U/L, NP caused off-emission of C-FNP because of their specific host-guest recognition. Fluorescence can be recovered under pH shock due to cleavage of the diol bond between β-CD and BA, resulting in release of NP from the fluorescent system. Sensitivity of the assays was assessed by confocal imaging not only in aqueous states, but also for the first time on coated surfaces in MDAMB-231 and MDCK cells. This novel system demonstrated high sensitivity to ALP through generation of good electron donor/acceptor pair during the PET process. Therefore, this fluorescence sensor system can be used to enhance ALP monitoring and cancer diagnosis on both coated surfaces and in aqueous states in clinical settings.

A multimodal assessment of driving performance in HIV infection.

PubMed

Marcotte, T D; Wolfson, T; Rosenthal, T J; Heaton, R K; Gonzalez, R; Ellis, R J; Grant, I

2004-10-26

To examine if HIV-seropositive (HIV+) individuals are at risk for impaired driving. Sixty licensed drivers (40 HIV+, 20 HIV-) completed a neuropsychological (NP) test battery and driving assessments. Eleven HIV+ subjects were NP-impaired. Driving-related skills were assessed using 1) two driving simulations (examining accident avoidance and navigational abilities), 2) the Useful Field of View (UFOV) test, and 3) an on-road evaluation. HIV+ NP-impaired subjects had greater difficulty than cognitively intact subjects on all driving measures, whereas the HIV- and HIV+ NP-normal groups performed similarly. On the UFOV, the HIV+ NP-impaired group had worse performance on Visual Processing and Divided Attention tasks but not in overall risk classification. They also had a higher number of simulator accidents (1.3 vs 2.0; p = 0.03), were less efficient at completing the navigation task (3.2 vs 9.2 blocks; p = 0.001), and were more likely to fail the on-road evaluation (6 vs 36%; p = 0.02). Impairment in Executive Functioning was the strongest NP predictor of failing the on-road drive test. NP performance and both simulations independently contributed to a model predicting 48% of the variance in on-road performance. HIV+ NP-impaired individuals are at increased risk for on-road driving impairments, whereas HIV+ individuals with normal cognition are not at a significantly higher risk than HIV- subjects. Executive Functioning is most strongly associated with impaired on-road performance. Cognitive and simulator testing may each provide data in identifying driving-impaired individuals.

Diffusion of two-dimensional epitaxial clusters on metal (100) surfaces: Facile versus nucleation-mediated behavior and their merging for larger sizes

NASA Astrophysics Data System (ADS)

Lai, King C.; Liu, Da-Jiang; Evans, James W.

2017-12-01

For diffusion of two-dimensional homoepitaxial clusters of N atoms on metal (100) surfaces mediated by edge atom hopping, macroscale continuum theory suggests that the diffusion coefficient scales like DN˜ N-β with β =3 /2 . However, we find quite different and diverse behavior in multiple size regimes. These include: (i) facile diffusion for small sizes N <9 ; (ii) slow nucleation-mediated diffusion with small β <1 for "perfect" sizes N = Np= L2 or L (L +1 ) , for L =3 ,4 , ... having unique ground-state shapes, for moderate sizes 9 ≤N ≤O (102) ; the same also applies for N =Np+3 , Np+ 4 , ... (iii) facile diffusion but with large β >2 for N =Np+1 and Np+2 also for moderate sizes 9 ≤N ≤O (102) ; (iv) merging of the above distinct branches and subsequent anomalous scaling with 1 ≲β <3 /2 , reflecting the quasifacetted structure of clusters, for larger N =O (102) to N =O (103) ; (v) classic scaling with β =3 /2 for very large N =O (103) and above. The specified size ranges apply for typical model parameters. We focus on the moderate size regime where we show that diffusivity cycles quasiperiodically from the slowest branch for Np+3 (not Np) to the fastest branch for Np+1 . Behavior is quantified by kinetic Monte Carlo simulation of an appropriate stochastic lattice-gas model. However, precise analysis must account for a strong enhancement of diffusivity for short time increments due to back correlation in the cluster motion. Further understanding of this enhancement, of anomalous size scaling behavior, and of the merging of various branches, is facilitated by combinatorial analysis of the number of the ground-state and low-lying excited state cluster configurations, and also of kink populations.

Formation of mixed organic layers by stepwise electrochemical reduction of diazonium compounds.

PubMed

Santos, Luis; Ghilane, Jalal; Lacroix, Jean Christophe

2012-03-28

This work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (β-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by β-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

Adsorption of doxorubicin on citrate-capped gold nanoparticles: insights into engineering potent chemotherapeutic delivery systems

NASA Astrophysics Data System (ADS)

Curry, Dennis; Cameron, Amanda; MacDonald, Bruce; Nganou, Collins; Scheller, Hope; Marsh, James; Beale, Stefanie; Lu, Mingsheng; Shan, Zhi; Kaliaperumal, Rajendran; Xu, Heping; Servos, Mark; Bennett, Craig; Macquarrie, Stephanie; Oakes, Ken D.; Mkandawire, Martin; Zhang, Xu

2015-11-01

Gold nanomaterials have received great interest for their use in cancer theranostic applications over the past two decades. Many gold nanoparticle-based drug delivery system designs rely on adsorbed ligands such as DNA or cleavable linkers to load therapeutic cargo. The heightened research interest was recently demonstrated in the simple design of nanoparticle-drug conjugates wherein drug molecules are directly adsorbed onto the as-synthesized nanoparticle surface. The potent chemotherapeutic, doxorubicin often serves as a model drug for gold nanoparticle-based delivery platforms; however, the specific interaction facilitating adsorption in this system remains understudied. Here, for the first time, we propose empirical and theoretical evidence suggestive of the main adsorption process where (1) hydrophobic forces drive doxorubicin towards the gold nanoparticle surface before (2) cation-π interactions and gold-carbonyl coordination between the drug molecule and the cations on AuNP surface facilitate DOX adsorption. In addition, biologically relevant compounds, such as serum albumin and glutathione, were shown to enhance desorption of loaded drug molecules from AuNP at physiologically relevant concentrations, providing insight into the drug release and in vivo stability of such drug conjugates.Gold nanomaterials have received great interest for their use in cancer theranostic applications over the past two decades. Many gold nanoparticle-based drug delivery system designs rely on adsorbed ligands such as DNA or cleavable linkers to load therapeutic cargo. The heightened research interest was recently demonstrated in the simple design of nanoparticle-drug conjugates wherein drug molecules are directly adsorbed onto the as-synthesized nanoparticle surface. The potent chemotherapeutic, doxorubicin often serves as a model drug for gold nanoparticle-based delivery platforms; however, the specific interaction facilitating adsorption in this system remains understudied. Here, for the first time, we propose empirical and theoretical evidence suggestive of the main adsorption process where (1) hydrophobic forces drive doxorubicin towards the gold nanoparticle surface before (2) cation-π interactions and gold-carbonyl coordination between the drug molecule and the cations on AuNP surface facilitate DOX adsorption. In addition, biologically relevant compounds, such as serum albumin and glutathione, were shown to enhance desorption of loaded drug molecules from AuNP at physiologically relevant concentrations, providing insight into the drug release and in vivo stability of such drug conjugates. Electronic supplementary information (ESI) available: DOX-AuNP absorption spectra and colored solution images, citrate displacement data, original DOX-AuNP loading isotherm, XPS data and TEM micrographs, modelling data. See DOI: 10.1039/c5nr05826k

Immunosensing platform based on gallium nanoparticle arrays on silicon substrates.

PubMed

García Marín, Antonio; Hernández, María Jesús; Ruiz, Eduardo; Abad, Jose María; Lorenzo, Encarnación; Piqueras, Juan; Pau, Jose Luis

2015-12-15

Gallium nanoparticles (GaNPs) of different sizes are deposited on Si(100) substrates by thermal evaporation. Through ellipsometric analysis, it is possible to investigate the plasmonic effects in the GaNPs and exploit them to develop biosensors. The excitation of the resonant modes for certain incidence angles leads to negative values of the imaginary part of the pseudodielectric function (<εi>) obtained in ellipsometry. Furthermore, there is an abrupt sign change when the difference between the phase shifts of p- and s-polarization components reaches 180° at an energy of around 3.15 eV. At that energy, reversal of the polarization handedness (RPH) occurs for an elliptically-polarized input beam. The energy of the RPH condition reduces as the evaporation time increases. The slope of <εi> at the RPH condition is extremely sensitive to changes in the surrounding medium of the NP surface and prompts the use of the GaNP/Si system as sensor platform. Fourier transformed infrared spectroscopy (FTIR) is used before and after functionalization with 3,3'-dithiodipropionic acid di(N-succinimidyl ester) and a glutathione-specific antibody to confirm the chemical modification of the sample surface. The developed immunosensor is exposed to different concentrations of glutathione (GSH) showing a linear relationship between the slope of the pseudodielectric function at the RPH condition and the GSH concentration. The immunosensor shows a limit of detection of 10nM enabling its use for the detection of low GSH levels in different medical conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

HLA-B27, but not HLA-B7, immunodominance to influenza is ERAP dependent.

PubMed

Akram, Ali; Lin, Aifeng; Gracey, Eric; Streutker, Catherine J; Inman, Robert D

2014-06-15

Endoplasmic reticulum-associated aminopeptidase-1 (ERAP1) plays a critical role in the processing of peptides prior to binding to MHC class I molecules. In this article, we show for the first time, to our knowledge, that the HLA-B27 immunodominant influenza nucleoprotein (NP) 383-391 epitope is made as an N-terminally extended 14-mer before it is trimmed by ERAP. In the absence of ERAP, there is a significant reduction in the CTL response to the B27/NP383-391 epitope in influenza A (flu)-infected B27/ERAP(-/-) mice. With the use of tetramer staining, the number of naive CD8(+) T cells expressing TCR Vβ8.1 in B27/ERAP(-/-) transgenic mice is significantly lower than that seen in B27/ERAP(+/+) mice. HLA-B27 surface expression in naive and flu-infected B27/ERAP(-/-) mice is also lower than the expression seen for the same allele in naive and flu-infected B27/ERAP(+/+) mice. In contrast, surface expression of HLA-B7 was unaffected by the absence of ERAP in B7/ERAP(-/-) transgenic mice. The B7-restricted NP418-426 CTL response in flu-infected B7/ERAP(-/-) and B7/ERAP(+/+) mice was also similar. These results provide, to our knowledge, the first in vivo demonstration of ERAP functionally influencing host immune response in an HLA allele-specific manner. This principle has relevance to diseases such as ankylosing spondylitis, in which HLA-B27 and ERAP jointly contribute to disease predisposition. Copyright © 2014 by The American Association of Immunologists, Inc.

Deciphering the mechanisms of cellular uptake of engineered nanoparticles by accurate evaluation of internalization using imaging flow cytometry

PubMed Central

2013-01-01

Background The uptake of nanoparticles (NPs) by cells remains to be better characterized in order to understand the mechanisms of potential NP toxicity as well as for a reliable risk assessment. Real NP uptake is still difficult to evaluate because of the adsorption of NPs on the cellular surface. Results Here we used two approaches to distinguish adsorbed fluorescently labeled NPs from the internalized ones. The extracellular fluorescence was either quenched by Trypan Blue or the uptake was analyzed using imaging flow cytometry. We used this novel technique to define the inside of the cell to accurately study the uptake of fluorescently labeled (SiO2) and even non fluorescent but light diffracting NPs (TiO2). Time course, dose-dependence as well as the influence of surface charges on the uptake were shown in the pulmonary epithelial cell line NCI-H292. By setting up an integrative approach combining these flow cytometric analyses with confocal microscopy we deciphered the endocytic pathway involved in SiO2 NP uptake. Functional studies using energy depletion, pharmacological inhibitors, siRNA-clathrin heavy chain induced gene silencing and colocalization of NPs with proteins specific for different endocytic vesicles allowed us to determine macropinocytosis as the internalization pathway for SiO2 NPs in NCI-H292 cells. Conclusion The integrative approach we propose here using the innovative imaging flow cytometry combined with confocal microscopy could be used to identify the physico-chemical characteristics of NPs involved in their uptake in view to redesign safe NPs. PMID:23388071

Rice No Pollen 1 (NP1) is required for anther cuticle formation and pollen exine patterning.

PubMed

Liu, Ze; Lin, Sen; Shi, Jianxin; Yu, Jing; Zhu, Lu; Yang, Xiujuan; Zhang, Dabing; Liang, Wanqi

2017-07-01

Angiosperm male reproductive organs (anthers and pollen grains) have complex and interesting morphological features, but mechanisms that underlie their patterning are poorly understood. Here we report the isolation and characterization of a male sterile mutant of No Pollen 1 (NP1) in rice (Oryza sativa). The np1-4 mutant exhibited smaller anthers with a smooth cuticle surface, abnormal Ubisch bodies, and aborted pollen grains covered with irregular exine. Wild-type exine has two continuous layers; but np1-4 exine showed a discontinuous structure with large granules of varying size. Chemical analysis revealed reduction in most of the cutin monomers in np1-4 anthers, and less cuticular wax. Map-based cloning suggested that NP1 encodes a putative glucose-methanol-choline oxidoreductase; and expression analyses found NP1 preferentially expressed in the tapetal layer from stage 8 to stage 10 of anther development. Additionally, the expression of several genes involved in biosynthesis and in the transport of lipid monomers of sporopollenin and cutin was decreased in np1-4 mutant anthers. Taken together, these observations suggest that NP1 is required for anther cuticle formation, and for patterning of Ubisch bodies and the exine. We propose that products of NP1 are likely important metabolites in the development of Ubisch bodies and pollen exine, necessary for polymerization, assembly, or both. © 2017 The Authors The Plant Journal © 2017 John Wiley & Sons Ltd.

Investigation into the feasibility of black carbon for remediation of nonylphenol polluted sediment through desorption kinetics after different order spiking.

PubMed

Cheng, Guanghuan; Sun, Mingyang; Yao, Lingdan; Wang, Lixiao; Sorial, George A; Xu, Xinhua; Lou, Liping

2015-11-01

The binding order of sorbent, sediment and organic compounds, as well as binding time is important factors determining the potential success of sorbent amendment, which should be considered when the practicability of sorbents was assessed. But until now, relevant research was rare. In this study, desorption in three practical conditions were simulated, by three mixing spiking orders among nonylphenol (NP), rice straw black carbon (RC) and sediment (the order of mixing spiking is (RC+Sediment)+NP, (Sediment+NP)+RC and (RC+NP)+Sediment, for situation I, II and III, respectively), to discuss the feasibility of using RC to remedy NP pollution. Results demonstrated that amendment of RC into sediment decreased desorption fractions of NP, and increased the resistant desorption fraction (Fr), implying strong affinity of NP to RC and efficient sequestration by RC. No significant differences were observed for desorption among the three fresh situations, meaning NP may be adsorbed on RC exterior surface sites and inter-phase diffusion is faster than desorption. However, Fr for three aged situations was in the order: situation I0.5, suggesting RC is an effective sorbent for remedying NP pollution in the aquatic environment. Overall, we proposed a practical and analytical method for properly assessing the validity of a sorbent. Copyright © 2015. Published by Elsevier Ltd.

Toxicity of nonylphenol diethoxylate in lab-scale anaerobic digesters.

PubMed

Bozkurt, Hande; Sanin, F Dilek

2014-06-01

Nonylphenol compounds have high commercial, industrial and domestic uses owing to their surface active properties. In addition to their toxic, carcinogenic and persistent characteristics; they have drawn the attention of scientists lately due to their endocrine disrupting properties. Their widespread use and disposal cause them to enter wastewater treatment systems at high concentrations. Since they are highly persistent and hydrophobic, they accumulate mostly on sludge. In this study using Anaerobic Toxicity Assay (ATA) tests, the toxicity of a model nonylphenol compound, nonylphenol diethoxylate (NP2EO), for anaerobic digestion of sludge was determined. The test bottles were dosed with NP2EO in acetone, with concentrations ranging from 1 mg L(-1) to 30 mg L(-1). During the tests, gas productions and compositions in terms of methane and carbon dioxide were monitored. To be able to judge about the fate, the target compounds were extracted from water and sludge and analyzed using GC/MS. The sludge samples used for assembling the reactors were found to contain NP and NP1EO but no NP2EO. After the assay was completed, all the NP2EO spiked into the live reactors was found to disappear. The increase seen in NP1EO and NP and further accumulation of NP in the system, indicated the conversion of NP2EO to these metabolites. On the other hand, no conversion was observed in abiotic reactors. Inhibition of NP2EO for anaerobic microorganisms was not observed throughout the tests considering the biogas production of the test reactors in comparison to the control reactors. Copyright © 2013 Elsevier Ltd. All rights reserved.

Nanoparticle-Based Topical Ophthalmic Gel Formulation for Sustained Release of Hydrocortisone Butyrate.

PubMed

Yang, Xiaoyan; Trinh, Hoang M; Agrahari, Vibhuti; Sheng, Ye; Pal, Dhananjay; Mitra, Ashim K

2016-04-01

This study was conducted to develop formulations of hydrocortisone butyrate (HB)-loaded poly(D,L-lactic-co-glycolic acid) nanoparticles (PLGA NP) suspended in thermosensitive gel to improve ocular bioavailability of HB for the treatment of bacterial corneal keratitis. PLGA NP with different surfactants such as polyvinyl alcohol (PVA), pluronic F-108, and chitosan were prepared using oil-in-water (O/W) emulsion evaporation technique. NP were characterized with respect to particle size, entrapment efficiency, polydispersity, drug loading, surface morphology, zeta potential, and crystallinity. In vitro release of HB from NP showed a biphasic release pattern with an initial burst phase followed by a sustained phase. Such burst effect was completely eliminated when nanoparticles were suspended in thermosensitive gels and zero-order release kinetics was observed. In HCEC cell line, chitosan-emulsified NP showed the highest cellular uptake efficiency over PVA- and pluronic-emulsified NP (59.09 ± 6.21%, 55.74 ± 6.26%, and 62.54 ± 3.30%, respectively) after 4 h. However, chitosan-emulsified NP indicated significant cytotoxicity of 200 and 500 μg/mL after 48 h, while PVA- and pluronic-emulsified NP exhibited no significant cytotoxicity. PLGA NP dispersed in thermosensitive gels can be considered as a promising drug delivery system for the treatment of anterior eye diseases.

Development of a functional cell-based assay that probes the specific interaction between influenza A virus NP and its packaging signal sequence RNA.

PubMed

Woo, Jiwon; Yu, Kyung Lee; Lee, Sun Hee; You, Ji Chang

2015-02-06

Although cis-acting packaging signal RNA sequences for the influenza virus NP encoding vRNA have been identified recently though genetic studies, little is known about the interaction between NP and the vRNA packaging signals either in vivo or in vitro. Here, we provide evidence that NP is able to interact specifically with the vRNA packaging sequence RNA within living cells and that the specific RNA binding activity of NP in vivo requires both the N-terminal and central region of the protein. This assay established would be a valuable tool for further detailed studies of the NP-packaging signal RNA interaction in living cells. Copyright © 2014 Elsevier Inc. All rights reserved.

Silver Nanoparticles: Technological Advances, Societal Impacts, and Metrological Challenges

PubMed Central

Calderón-Jiménez, Bryan; Johnson, Monique E.; Montoro Bustos, Antonio R.; Murphy, Karen E.; Winchester, Michael R.; Vega Baudrit, José R.

2017-01-01

Silver nanoparticles (AgNPs) show different physical and chemical properties compared to their macroscale analogs. This is primarily due to their small size and, consequently, the exceptional surface area of these materials. Presently, advances in the synthesis, stabilization, and production of AgNPs have fostered a new generation of commercial products and intensified scientific investigation within the nanotechnology field. The use of AgNPs in commercial products is increasing and impacts on the environment and human health are largely unknown. This article discusses advances in AgNP production and presents an overview of the commercial, societal, and environmental impacts of this emerging nanoparticle (NP), and nanomaterials in general. Finally, we examine the challenges associated with AgNP characterization, discuss the importance of the development of NP reference materials (RMs) and explore their role as a metrological mechanism to improve the quality and comparability of NP measurements. PMID:28271059

Silver nanoparticles: technological advances, societal impacts, and metrological challenges

NASA Astrophysics Data System (ADS)

Calderón-Jiménez, Bryan; Johnson, Monique E.; Montoro Bustos, Antonio R.; Murphy, Karen E.; Winchester, Michael R.; Vega Baudrit, José R.

2017-02-01

Silver nanoparticles (AgNPs) show different physical and chemical properties compared to their macroscale analogs. This is primarily due to their small size and, consequently, the exceptional surface area of these materials. Presently, advances in the synthesis, stabilization, and production of AgNPs have fostered a new generation of commercial products and intensified scientific investigation within the nanotechnology field. The use of AgNPs in commercial products is increasing and impacts on the environment and human health are largely unknown. This article discusses advances in AgNP production and presents an overview of the commercial, societal, and environmental impacts of this emerging nanoparticle (NP), and nanomaterials in general. Finally, we examine the challenges associated with AgNP characterization, discuss the importance of the development of NP reference materials (RMs) and explore their role as a metrological mechanism to improve the quality and comparability of NP measurements.

Investigation on the adsorption characteristics of sodium benzoate and taurine on gold nanoparticle film by ATR-FTIR spectroscopy

NASA Astrophysics Data System (ADS)

Kumar, Naveen; Thomas, S.; Tokas, R. B.; Kshirsagar, R. J.

2014-01-01

Fourier transform infrared (FTIR) spectroscopic studies of sodium benzoate and taurine adsorbed on gold nanoparticle (AuNp) film on silanised glass slides have been studied by attenuated total reflection technique (ATR). The surface morphology of the AuNp films has been measured by Atomic Force Microscopy. The ATR spectra of sodium benzoate and taurine deposited on AuNp film are compared with ATR spectra of their powdered bulk samples. A new red-shifted band appeared along with the symmetric and asymmetric stretches of carboxylate group of sodium benzoate leading to a broadening of the above peaks. Similar behavior is also seen in the case of symmetric and asymmetric stretches of sulphonate group of taurine. The results indicate presence of both chemisorbed and physisorbed layers of both sodium benzoate and taurine on the AuNp film with bottom layer chemically bound to AuNp through carboxylate and sulphonate groups respectively.

Silver Nanoparticles: Technological Advances, Societal Impacts, and Metrological Challenges.

PubMed

Calderón-Jiménez, Bryan; Johnson, Monique E; Montoro Bustos, Antonio R; Murphy, Karen E; Winchester, Michael R; Vega Baudrit, José R

2017-01-01

Silver nanoparticles (AgNPs) show different physical and chemical properties compared to their macroscale analogs. This is primarily due to their small size and, consequently, the exceptional surface area of these materials. Presently, advances in the synthesis, stabilization, and production of AgNPs have fostered a new generation of commercial products and intensified scientific investigation within the nanotechnology field. The use of AgNPs in commercial products is increasing and impacts on the environment and human health are largely unknown. This article discusses advances in AgNP production and presents an overview of the commercial, societal, and environmental impacts of this emerging nanoparticle (NP), and nanomaterials in general. Finally, we examine the challenges associated with AgNP characterization, discuss the importance of the development of NP reference materials (RMs) and explore their role as a metrological mechanism to improve the quality and comparability of NP measurements.

The importance of selecting a proper biological milieu for protein corona analysis in vitro: Human plasma versus human serum.

PubMed

Mirshafiee, Vahid; Kim, Raehyun; Mahmoudi, Morteza; Kraft, Mary L

2016-06-01

Nanoparticle (NP) exposure to biological fluids in the body results in protein binding to the NP surface, which forms a protein coating that is called the "protein corona". To simplify studies of protein-NP interactions and protein corona formation, NPs are incubated with biological solutions, such as human serum or human plasma, and the effects of this exposure are characterized in vitro. Yet, how NP exposure to these two different biological milieus affects protein corona composition and cell response has not been investigated. Here, we explore the differences between the protein coronas that form when NPs are incubated in human serum versus human plasma. NP characterization indicated that NPs that were exposed to human plasma had higher amounts of proteins bound to their surfaces, and were slightly larger in size than those exposed to human serum. In addition, significant differences in corona composition were also detected with gel electrophoresis and liquid chromatography-mass spectrometry/mass spectrometry, where a higher fraction of coagulation proteins and complement factors were found on the plasma-exposed NPs. Flow cytometry and confocal microscopy showed that the uptake of plasma-exposed NPs was higher than that of serum-exposed NPs by RAW 264.7 macrophage immune cells, but not by NIH 3T3 fibroblast cells. This difference is likely due to the elevated amounts of opsonins, such as fibrinogen, on the surfaces of the NPs exposed to plasma, but not serum, because these components trigger NP internalization by immune cells. As the human plasma better mimics the composition of the in vivo environment, namely blood, in vitro protein corona studies should employ human plasma, and not human serum, so the biological phenomena that is observed is more similar to that occurring in vivo. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reactive Capture of Gold Nanoparticles by Strongly Physisorbed Monolayers on Graphite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Xiaoliang; Tong, Wenjun; Fidler, Vlastimil

2012-12-01

Anthracene Diels Alder adducts (DAa) bearing two long side chains (H-(CH2)22O(CH2)6OCH2-) at the 1- and 5-positions form self-assembled monolayers (SAMs) at the phenyloctane - highly oriented pyrolytic graphite (HOPG) interface. The long DAa side chains promote strong physisorption of the monolayer to HOPG and maintain the monolayer morphology upon rinsing or incubation in ethanol and air-drying of the substrate. Incorporating a carboxylic acid group on the DAa core enables capture of 1 - 4 nm diameter gold nanoparticles (AuNP) provided (i) the monolayer containing DAa-carboxylic acids is treated with Cu2+ ions and (ii) the organic coating on the AuNP containsmore » carboxylic acids (11-mercaptoundecanoic acid, MUA-AuNP). AuNP capture by the monolayer proceeds with formation of Cu2+ - carboxylate coordination complexes. The captured AuNP appear as mono- and multi-layered clusters at high coverage on HOPG. The surface density of the captured AuNPs can be adjusted from AuNP multi-layers to isolated AuNPs by varying incubation times, MUA-AuNP concentration, the number density of carboxylic acids in the monolayer, the number of MUA per AuNP, and the post-incubation treatments.« less

Environmental alkylphenols modulate cytokine expression in plasmacytoid dendritic cells.

PubMed

Hung, Chih-Hsing; Yang, San-Nan; Wang, Ya-Fang; Liao, Wei-Ting; Kuo, Po-Lin; Tsai, Eing-Mei; Lee, Chin-Lai; Chao, Yu-Shen; Yu, Hsin-Su; Huang, Shau-Ku; Suen, Jau-Ling

2013-01-01

Alkylphenols, such as nonylphenol (NP) and 4-octylphenol (4-OP), have the potential to disturb immune system due to their weak estrogen-like activity, an effect with potential serious public health impact due to the worldwide distribution of these substances. Plasmacytoid dendritic cells (PDCs) can secrete large amounts of type I IFNs and are critical in immune regulation. However, there has been limited study about the influence of alkylphenols on the function of pDCs. The aim of this study was to examine the effect of alkylphenols on pDC functions in vitro and in vivo and then further explored the involved signaling pathways and epigenetic changes. Circulating pDCs from human peripheral blood mononuclear cells were treated with alkylphenols with or without CpG stimulation. Alkylphenol-associated cytokine responses, signaling events, histone modifications and viral activity were further examined. In NP-exposed mice, the effect of NP on splenic pDC function and allergic lung inflammation were also assessed. The results showed that NP increased the expression of TNF-α, but suppressed IL-10 production in the range of physiological doses, concomitant with activation of the MKK3/6-p38 signaling pathway and enhanced levels of acetylated histone 3 as well as histone 4 at the TNFA gene locus. Further, in CpG-stimulated pDCs, NP suppressed type I IFNs production, associated with down-regulation of IRF-7 and MKK1/2-ERK-Elk-1 pathways and led to the impaired anti-enterovirus 71 activity in vitro. Additionally, splenic pDCs from NP-exposed mice showed similar cytokine changes upon CpG stimulation under conditions relevant to route and level of exposure in humans. NP treatment also enhanced allergic lung inflammation in vivo. Alkylphenols may influence pDCs' functions via their abilities to induce expression of a pro-inflammatory cytokine, TNF-α, and to suppress regulatory cytokines, including IL-10, IFN-α and IFN-β, suggesting the potential impact of endocrine disrupting chemicals on immune regulation.

On the work function and the charging of small ( r ≤ 5 nm) nanoparticles in plasmas

NASA Astrophysics Data System (ADS)

Kalered, E.; Brenning, N.; Pilch, I.; Caillault, L.; Minéa, T.; Ojamäe, L.

2017-01-01

The growth of nanoparticles (NPs) in plasmas is an attractive technique where improved theoretical understanding is needed for quantitative modeling. The variation of the work function W with size for small NPs, rN P≤ 5 nm, is a key quantity for modeling of three NP charging processes that become increasingly important at a smaller size: electron field emission, thermionic electron emission, and electron impact detachment. Here we report the theoretical values of the work function in this size range. Density functional theory is used to calculate the work functions for a set of NP charge numbers, sizes, and shapes, using copper for a case study. An analytical approximation is shown to give quite accurate work functions provided that rN P > 0.4 nm, i.e., consisting of about >20 atoms, and provided also that the NPs have relaxed close to spherical shape. For smaller sizes, W deviates from the approximation, and also depends on the charge number. Some consequences of these results for nanoparticle charging are outlined. In particular, a decrease in W for NP radius below about 1 nm has fundamental consequences for their charge in a plasma environment, and thereby on the important processes of NP nucleation, early growth, and agglomeration.

[Construction of injectable tissue engineered nucleus pulposus in vitro].

PubMed

Tian, Huake; Wang, Jian; Chen, Chao; Liu, Jie; Zhou, Yue

2009-02-01

To investigate the feasibility of using thermo-sensitive chitosan hydrogen as a scaffold to construct tissue engineered injectable nucleus pulposus (NP). Three-month-old neonatal New Zealand rabbits (male or female) weighing 150-200 g were selected to isolate and culture NP cells. The thermo-sensitive chitosan hydrogel scaffold was made of chitosan, disodium beta-glycerophosphate and hydroxyethyl cellulose. Its physical properties and gross condition were observed. The tissue engineered NP was constructed by compounding the scaffold and rabbit NP cells. Then, the viability of NP cells in the chitosan hydrogel was observed 2 days after compound culture and the growth condition of NP cells on the scaffold was observed by SEM 7 days after compound culture. NP cells went through histology and immunohistochemistry detection and their secretion of aggrecan and expression of Col II mRNA were analyzed by RT-PCR 21 days after compound culture. The thermo-sensitive chitosan hydrogel was liquid at room temperature and solidified into gel at 37 degrees C (15 minutes) due to crosslinking reaction. Acridine orange-propidium iodide staining showed that the viability rate of NP cells in chitosan hydrogel was above 90%. Scanning electron microscope observation demonstrated that the NP cells were distributed in the reticulate scaffold, with ECM on their surfaces. The results of HE, toluidine blue, safranin O and histology and immunohistochemistry staining confirmed that the NP cells in chitosan hydrogel were capable of producing ECM. RT-PCR results showed that the secretion of Col II and aggrecan mRNA in NP cells cultured three-dimensionally by chitosan hydrogen scaffold were 0.631 +/- 0.064 and 0.832 +/- 0.052, respectively, showing more strengths of producing matrix than that of monolayer culture (0.528 +/- 0.039, 0.773 +/- 0.046) with a significant difference (P < 0.05). With good cellular compatibilities, the thermo-sensitive chitosan hydrogel makes it possible for NP cells to maintain their normal morphology and secretion after compound culture, and may be a potential NP cells carrier for tissue engineered NP.

Ag nanoparticle decorated molybdenum oxide structures: growth, characterization, DFT studies and their application to enhanced field emission

NASA Astrophysics Data System (ADS)

Guha, Puspendu; Ghosh, Arnab; Thapa, Ranjit; Mathan Kumar, E.; Kirishwaran, Sabari; Singh, Ranveer; Satyam, Parlapalli V.

2017-10-01

We report a simple single step growth of α-MoO3 structures and energetically suitable site specific Ag nanoparticle (NP) decorated α-MoO3 structures on varied substrates, having almost similar morphologies and oxygen vacancies. We elucidate possible growth mechanisms in light of experimental findings and density functional theory (DFT) calculations. We experimentally establish and verified by DFT calculations that the MoO3(010) surface is a weakly interacting and stable surface compared to other orientations. From DFT study, the binding energy is found to be higher for (100) and (001) surfaces (˜-0.98 eV), compared to the (010) surface (˜-0.15 eV) and thus it is likely that Ag NP formation is not favorable on the MoO3(010) surface. The Ag decorated MoO3 (Ag-MoO3) nanostructured sample shows enhanced field emission properties with an approimately 2.1 times lower turn-on voltage of 1.67 V μm-1 and one order higher field enhancement factor (β) of 8.6 × 104 compared to the MoO3 sample without Ag incorporation. From Kelvin probe force microscopy measurements, the average local work function (Φ) is found to be approximately 0.47 eV smaller for the Ag-MoO3 sample (˜5.70 ± 0.05 eV) compared to the MoO3 sample (˜6.17 ± 0.05 eV) and the reduction in Φ can be attributed to the shifting Fermi level of MoO3 toward vacuum via electron injection from Ag NPs to MoO3. The presence of oxygen vacancies together with Ag NPs lead to the highest β and lowest turn-on field among the reported values under the MoO3 emitter category.

Plant and soil nutrient stoichiometry along primary ecological successions: Is there any link?

PubMed Central

Di Palo, Francesca

2017-01-01

Ecological stoichiometry suggests that plant Nitrogen (N)-to-Phosphorus (P) ratios respond to changes in both soil N:P stoichiometry and soil N and P availability. Thus we would expect that soil and plant N:P ratios be significantly related along natural gradients of soil development such as those associated with primary ecological successions. Here we explicitly search for linkages between plant and soil N:P stoichiometry along four primary successions distributed across Europe. We measured N and P content in soils and plant compartments (leaf, stem and root) of 72 wild plant species distributed along two sand dune and two glacier successions where soil age ranges from few to thousand years old. Overall we found that soil N:P ratios strongly increased along successional stages, however, plant N:P ratios were neither related to soil N:P stoichiometry nor to changes in soil N and P availability. Instead changes in plant nutrient stoichiometry were “driven” by plant-functional-group identity. Not only N:P ratios differed between legumes, grasses and forbs but each of these plant functional groups maintained N:P ratios relatively constant across pioneer, middle and advanced successional stages. Our evidence is that soil nutrient stoichiometry may not be a good predictor of changes in plant N:P stoichiometry along natural primary ecological successions, which have not reached yet a retrogressive stage. This could be because wild-plants rely on mechanisms of internal nutrient regulation, which make them less dependent to changes in soil nutrient availability under unpredictable environmental conditions. Further studies need to clarify what underlying evolutionary and eco-physiological mechanisms determine changes in nutrient stoichiometry in plant species distributed across natural environmental gradients. PMID:28787437

Thermal desorption of formamide and methylamine from graphite and amorphous water ice surfaces

NASA Astrophysics Data System (ADS)

Chaabouni, H.; Diana, S.; Nguyen, T.; Dulieu, F.

2018-04-01

Context. Formamide (NH2CHO) and methylamine (CH3NH2) are known to be the most abundant amine-containing molecules in many astrophysical environments. The presence of these molecules in the gas phase may result from thermal desorption of interstellar ices. Aims: The aim of this work is to determine the values of the desorption energies of formamide and methylamine from analogues of interstellar dust grain surfaces and to understand their interaction with water ice. Methods: Temperature programmed desorption (TPD) experiments of formamide and methylamine ices were performed in the sub-monolayer and monolayer regimes on graphite (HOPG) and non-porous amorphous solid water (np-ASW) ice surfaces at temperatures 40-240 K. The desorption energy distributions of these two molecules were calculated from TPD measurements using a set of independent Polanyi-Wigner equations. Results: The maximum of the desorption of formamide from both graphite and ASW ice surfaces occurs at 176 K after the desorption of H2O molecules, whereas the desorption profile of methylamine depends strongly on the substrate. Solid methylamine starts to desorb below 100 K from the graphite surface. Its desorption from the water ice surface occurs after 120 K and stops during the water ice sublimation around 150 K. It continues to desorb from the graphite surface at temperatures higher than160 K. Conclusions: More than 95% of solid NH2CHO diffuses through the np-ASW ice surface towards the graphitic substrate and is released into the gas phase with a desorption energy distribution Edes = 7460-9380 K, which is measured with the best-fit pre-exponential factor A = 1018 s-1. However, the desorption energy distribution of methylamine from the np-ASW ice surface (Edes = 3850-8420 K) is measured with the best-fit pre-exponential factor A = 1012 s-1. A fraction of solid methylamine monolayer of roughly 0.15 diffuses through the water ice surface towards the HOPG substrate. This small amount of methylamine desorbs later with higher binding energies (5050-8420 K) that exceed that of the crystalline water ice (Edes = 4930 K), which is calculated with the same pre-exponential factor A = 1012 s-1. The best wetting ability of methylamine compared to H2O molecules makes CH3NH2 molecules a refractory species for low coverage. Other binding energies of astrophysical relevant molecules are gathered and compared, but we could not link the chemical functional groups (amino, methyl, hydroxyl, and carbonyl) with the binding energy properties. Implications of these high binding energies are discussed.

The assessment of changes in cognitive functioning: age-, education-, and gender-specific reliable change indices for older adults tested on the CERAD-NP battery: results of the German Study on Ageing, Cognition, and Dementia in Primary Care Patients (AgeCoDe).

PubMed

Stein, Janine; Luppa, Melanie; Luck, Tobias; Maier, Wolfgang; Wagner, Michael; Daerr, Moritz; van den Bussche, Hendrik; Zimmermann, Thomas; Köhler, Mirjam; Bickel, Horst; Mösch, Edelgard; Weyerer, Siegfried; Kaufeler, Teresa; Pentzek, Michael; Wiese, Birgitt; Wollny, Anja; König, Hans-Helmut; Riedel-Heller, Steffi G

2012-01-01

The Consortium to Establish a Registry for Alzheimer's Disease-Neuropsychological (CERAD-NP) battery represents a commonly used neuropsychological instrument to measure cognitive functioning in the elderly. This study provides normative data for changes in cognitive function that normally occur in cognitively healthy individuals to interpret changes in CERAD-NP test scores over longer time periods. Longitudinal cohort study with three assessments at 1.5-year intervals over a period of 3 years. : Primary care medical record registry sample. As part of the German Study on Ageing, Cognition, and Dementia in Primary Care Patients, a sample of 1,450 cognitively healthy general practitioner patients, age 75 years and older, was assessed. Age-, education-, and gender-specific Reliable Change Indices (RCIs) were computed for a 90% confidence interval for selected subtests of the CERAD-NP battery. Across different age, education, and gender subgroups, changes from at least six to nine points in Verbal Fluency, four to eight points in Word List Memory, two to four points in Word List Recall, and one to four points in Word List Recognition indicated significant (i.e. reliable) changes in CERAD-NP test scores at the 90% confidence level. Furthermore, the calculation of RCIs for individual patients is demonstrated. Smaller changes in CERAD-NP test scores can be interpreted with only high uncertainty because of probable measurement error, practice effects, and normal age-related cognitive decline. This study, for the first time, provides age-, education-, and gender-specific CERAD-NP reference values on the basis of RCI methods for the interpretation of cognitive changes in older-age groups.

Cognitive Complaints After Breast Cancer Treatments: Examining the Relationship With Neuropsychological Test Performance

PubMed Central

2013-01-01

Background Cognitive complaints are reported frequently after breast cancer treatments. Their association with neuropsychological (NP) test performance is not well-established. Methods Early-stage, posttreatment breast cancer patients were enrolled in a prospective, longitudinal, cohort study prior to starting endocrine therapy. Evaluation included an NP test battery and self-report questionnaires assessing symptoms, including cognitive complaints. Multivariable regression models assessed associations among cognitive complaints, mood, treatment exposures, and NP test performance. Results One hundred eighty-nine breast cancer patients, aged 21–65 years, completed the evaluation; 23.3% endorsed higher memory complaints and 19.0% reported higher executive function complaints (>1 SD above the mean for healthy control sample). Regression modeling demonstrated a statistically significant association of higher memory complaints with combined chemotherapy and radiation treatments (P = .01), poorer NP verbal memory performance (P = .02), and higher depressive symptoms (P < .001), controlling for age and IQ. For executive functioning complaints, multivariable modeling controlling for age, IQ, and other confounds demonstrated statistically significant associations with better NP visual memory performance (P = .03) and higher depressive symptoms (P < .001), whereas combined chemotherapy and radiation treatment (P = .05) approached statistical significance. Conclusions About one in five post–adjuvant treatment breast cancer patients had elevated memory and/or executive function complaints that were statistically significantly associated with domain-specific NP test performances and depressive symptoms; combined chemotherapy and radiation treatment was also statistically significantly associated with memory complaints. These results and other emerging studies suggest that subjective cognitive complaints in part reflect objective NP performance, although their etiology and biology appear to be multifactorial, motivating further transdisciplinary research. PMID:23606729

Long-term neuropsychological follow-up of young children with medulloblastoma treated with sequential high-dose chemotherapy and irradiation sparing approach.

PubMed

Fay-McClymont, Taryn B; Ploetz, Danielle M; Mabbott, Don; Walsh, Karin; Smith, Amy; Chi, Susan N; Wells, Elizabeth; Madden, Jennifer; Margol, Ashley; Finlay, Jonathan; Kieran, Mark W; Strother, Douglas; Dhall, Girish; Packer, Roger J; Foreman, Nicholas K; Bouffet, E; Lafay-Cousin, Lucie

2017-05-01

High-dose chemotherapy (HDC) strategies were developed in brain tumor protocols for young children to prevent neuropsychological (NP) impairments associated with radiotherapy. However, comprehensive NP evaluations of these children treated with such strategies remain limited. We examined the long-term neurocognitive outcomes of young children (<6 years) with medulloblastoma, treated similarly, with a HDC strategy "according to" the chemotherapy regimen of the protocol CCG 99703. This retrospective study included young children less than 6 years of age at diagnosis of medulloblastoma treated from 1998 to 2011 at 7 North American institutions. Twenty-four patients who had at least one NP assessment post-treatment are the focus of the current study. Of 24 patients in this review, 15 (63%) were male and the mean age at diagnosis was 29.4 months (SD = 13.5). Posterior fossa syndrome (PFs) was reported in five patients (21%). Nine (37.5%) received radiotherapy (5 focal, 4 craniospinal). On average, children were assessed 3.5 years (SD = 1.8) post-diagnosis, and full-scale intellectual quotient (FSIQ) scores ranged from 56 to 119 ([Formula: see text]= 92; SD = 16.8). The majority of children (74%) had low-average to average NP functioning. Very young children treated with radiotherapy, who needed hearing support or with PFs had worse neurocognitive outcomes. Clinically significant deficits (<10th percentile) in at least one area of NP functioning were found in 25% of the children. NP data obtained from this sample of survivors of medulloblastoma in early childhood, all treated with sequential HDC and 1/3 with radiotherapy, describe NP functioning within average normal limits overall. However, almost 25% of children had significant deficits in specific domains.

Cognitive function after the initiation of adjuvant endocrine therapy in early-stage breast cancer: an observational cohort study.

PubMed

Ganz, Patricia A; Petersen, Laura; Castellon, Steven A; Bower, Julienne E; Silverman, Daniel H S; Cole, Steven W; Irwin, Michael R; Belin, Thomas R

2014-11-01

This report examines cognitive complaints and neuropsychological (NP) testing outcomes in patients with early-stage breast cancer after the initiation of endocrine therapy (ET) to determine whether this therapy plays any role in post-treatment cognitive complaints. One hundred seventy-three participants from the Mind Body Study (MBS) observational cohort provided data from self-report questionnaires and NP testing obtained at enrollment (T1, before initiation of ET), and 6 months later (T2). Bivariate analyses compared demographic and treatment variables, cognitive complaints, depressive symptoms, quality of life, and NP functioning between those who received ET versus not. Multivariable linear regression models examined predictors of cognitive complaints at T2, including selected demographic variables, depressive symptoms, ET use, and other medical variables, along with NP domains that were identified in bivariate analyses. Seventy percent of the 173 MBS participants initiated ET, evenly distributed between tamoxifen or aromatase inhibitors. ET-treated participants reported significantly increased language and communication (LC) cognitive complaints at T2 (P = .003), but no significant differences in NP test performance. Multivariable regression on LC at T2 found higher LC complaints significantly associated with T1 LC score (P < .001), ET at T2 (P = .004), interaction between ET and past hormone therapy (HT) (P < .001), and diminished improvement in NP psychomotor function (P = .05). Depressive symptoms were not significant (P = .10). Higher LC complaints are significantly associated with ET 6 months after starting treatment and reflect diminished improvements in some NP tests. Past HT is a significant predictor of higher LC complaints after initiation of ET. © 2014 by American Society of Clinical Oncology.

Cognitive Function After the Initiation of Adjuvant Endocrine Therapy in Early-Stage Breast Cancer: An Observational Cohort Study

PubMed Central

Ganz, Patricia A.; Petersen, Laura; Castellon, Steven A.; Bower, Julienne E.; Silverman, Daniel H.S.; Cole, Steven W.; Irwin, Michael R.; Belin, Thomas R.

2014-01-01

Purpose This report examines cognitive complaints and neuropsychological (NP) testing outcomes in patients with early-stage breast cancer after the initiation of endocrine therapy (ET) to determine whether this therapy plays any role in post-treatment cognitive complaints. Patients and Methods One hundred seventy-three participants from the Mind Body Study (MBS) observational cohort provided data from self-report questionnaires and NP testing obtained at enrollment (T1, before initiation of ET), and 6 months later (T2). Bivariate analyses compared demographic and treatment variables, cognitive complaints, depressive symptoms, quality of life, and NP functioning between those who received ET versus not. Multivariable linear regression models examined predictors of cognitive complaints at T2, including selected demographic variables, depressive symptoms, ET use, and other medical variables, along with NP domains that were identified in bivariate analyses. Results Seventy percent of the 173 MBS participants initiated ET, evenly distributed between tamoxifen or aromatase inhibitors. ET-treated participants reported significantly increased language and communication (LC) cognitive complaints at T2 (P = .003), but no significant differences in NP test performance. Multivariable regression on LC at T2 found higher LC complaints significantly associated with T1 LC score (P < .001), ET at T2 (P = .004), interaction between ET and past hormone therapy (HT) (P < .001), and diminished improvement in NP psychomotor function (P = .05). Depressive symptoms were not significant (P = .10). Conclusion Higher LC complaints are significantly associated with ET 6 months after starting treatment and reflect diminished improvements in some NP tests. Past HT is a significant predictor of higher LC complaints after initiation of ET. PMID:25267747

The gene responsible for borate cross-linking of pectin Rhamnogalacturonan-II is required for plant reproductive tissue development and fertilization

PubMed Central

Iwai, Hiroaki; Hokura, Akiko; Oishi, Masahiro; Chida, Hiroshi; Ishii, Tadashi; Sakai, Shingo; Satoh, Shinobu

2006-01-01

Deficiencies in boron, a microelement that is essential for the growth and development of higher plants, often cause problems in reproductive growth. Rhamnogalacturonan-II (RG-II) in cell wall pectin acts as the sole receptor for boron in plant cells, forming a borate cross-linked RG-II dimer (dRG-II-B), but the physiological functions of dRG-II-B remain unknown. We have previously shown that the pectin glucuronyltransferase 1 gene NpGUT1, which is involved in the biosynthesis of RG-II sugar chains, is essential for the formation of the RG-II-B complex, resulting in tight intercellular attachment in meristematic tissues. Because NpGUT1 expression was found to be abundant in reproductive organs in addition to meristematic tissues, we analyzed the expression and functions of NpGUT1 in more detail in tobacco reproductive tissues. Specific NpGUT1 expression was detected in the tapetum of flower buds and in the pollen, pollen tube tips, and transmitting tissue of the pistils of flowers. Dexamethasone-induced expression of the NpGUT1 antisense gene in flower buds resulted in the formation of sterile flowers with aberrant development of pollen and transmitting tissue. Pollen tubes could not pass through pistils with aborted transmitting tissue, and expression of an NpGUT1 antisense gene in germinating pollen inhibited pollen tube elongation, accompanied by the absence of pectin RG-II and boron in the pollen tube tip. These results indicate that expression of NpGUT1 is required for the development and functions of male and female tissues. PMID:17053077

Interaction with culture medium components, cellular uptake and intracellular distribution of cobalt nanoparticles, microparticles and ions in Balb/3T3 mouse fibroblasts.

PubMed

Sabbioni, Enrico; Fortaner, Salvador; Farina, Massimo; Del Torchio, Riccardo; Petrarca, Claudia; Bernardini, Giovanni; Mariani-Costantini, Renato; Perconti, Silvia; Di Giampaolo, Luca; Gornati, Rosalba; Di Gioacchino, Mario

2014-02-01

The mechanistic understanding of nanotoxicity requires the physico-chemical characterisation of nanoparticles (NP), and their comparative investigation relative to the corresponding ions and microparticles (MP). Following this approach, the authors studied the dissolution, interaction with medium components, bioavailability in culture medium, uptake and intracellular distribution of radiolabelled Co forms (CoNP, CoMP and Co(2+)) in Balb/3T3 mouse fibroblasts. Co(2+) first saturates the binding sites of molecules in the extracellular milieu (e.g., albumin and histidine) and on the cell surface. Only after saturation, Co(2+) is actively uptaken. CoNP, instead, are predicted to be internalised by endocytosis. Dissolution of Co particles allows the formation of Co compounds (CoNP-rel), whose mechanism of cellular internalisation is unknown. Co uptake (ranking CoMP > CoNP > Co(2+)) reached maximum at 4 h. Once inside the cell, CoNP spread into the cytosol and organelles. Consequently, massive amounts of Co ions and CoNP-rel can reach subcellular compartments normally unexposed to Co(2+). This could explain the fact that the nuclear and mitochondrial Co concentrations resulted significantly higher than those obtained with Co(2+).

A nanoporous PdCo alloy as a highly active electrocatalyst for the oxygen-reduction reaction and formic acid electrooxidation.

PubMed

Xu, Caixia; Liu, Yunqing; Zhang, Huan; Geng, Haoran

2013-11-01

A nanoporous (NP) PdCo alloy with uniform structure size and controllable bimetallic ratio was fabricated simply by one-step mild dealloying of a PdCoAl precursor alloy. The as-made alloy consists of a nanoscaled bicontinuous network skeleton with interconnected hollow channels that extend in all three dimensions. With a narrow ligament size distribution around 5 nm, the NP PdCo alloy exhibits much higher electrocatalytic activity towards the oxygen-reduction reaction (ORR) with enhanced specific and mass activities relative to NP Pd and commercial Pt/C catalysts. A long-term stability test demonstrated that NP PdCo has comparable catalytic durability with less loss of ORR activity and electrochemical surface area than Pt/C. The NP PdCo alloy also shows dramatically enhanced catalytic activity towards formic acid electrooxidation relative to NP Pd and Pd/C catalysts. The as-made NP PdCo holds great application potential as a promising cathode as well as an anode electrocatalyst in fuel cells with the advantages of superior catalytic performance and easy preparation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modulating the activity of protein conjugated to gold nanoparticles by site-directed orientation and surface density of bound protein.

PubMed

Liu, Feng; Wang, Lei; Wang, Hongwei; Yuan, Lin; Li, Jingwen; Brash, John Law; Chen, Hong

2015-02-18

The key property of protein-nanoparticle conjugates is the bioactivity of the protein. The ability to accurately modulate the activity of protein on the nanoparticles at the interfaces is important in many applications. In the work reported here, modulation of the activity of protein-gold nanoparticle (AuNP) conjugates by specifically orienting the protein and by varying the surface density of the protein was investigated. Different orientations were achieved by introducing cysteine (Cys) residues at specific sites for binding to gold. We chose Escherichia coli inorganic pyrophosphatase (PPase) as a model protein and used site-directed mutagenesis to generate two mutant types (MTs) with a single Cys residue on the surface: MT1 with Cys near the active center and MT2 with Cys far from the active center. The relative activities of AuNP conjugates with wild type (WT), MT1, and MT2 were found to be 44.8%, 68.8%, and 91.2% of native PPase in aqueous solution. Site-directed orientation with the binding site far from the active center thus allowed almost complete preservation of the protein activity. The relative activity of WT and MT2 conjugates did not change with the surface density of the protein, while that of MT1 increased significantly with increasing surface density. These results demonstrate that site-directed orientation and surface density can both modulate the activity of proteins conjugated to AuNP and that orientation has a greater effect than density. Furthermore, increasing the surface density of the specifically oriented protein MT2, while having no significant effect on the specific activity of the protein, still allowed increased protein loading on the AuNP and thus increased the total protein activity. This is of great importance in the study on the interface of protein and nanoparticle and the applications for enzyme immobilization, drug delivery, and biocatalysis.

Segregation Phenomena in Size-Selected Bimetallic CuNi Nanoparticle Catalysts

DOE PAGES

Pielsticker, Lukas; Zegkinoglou, Ioannis; Divins, Nuria J.; ...

2017-10-25

Surface segregation, restructuring, and sintering phenomena in size-selected copper–nickel nanoparticles (NPs) supported on silicon dioxide substrates were systematically investigated as a function of temperature, chemical state, and reactive gas environment. Using near-ambient pressure (NAP-XPS) and ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), we showed that nickel tends to segregate to the surface of the NPs at elevated temperatures in oxygen- or hydrogen-containing atmospheres. It was found that the NP pretreatment, gaseous environment, and oxide formation free energy are the main driving forces of the restructuring and segregation trends observed, overshadowing the role of the surface free energy. The depth profile ofmore » the elemental composition of the particles was determined under operando CO 2 hydrogenation conditions by varying the energy of the X-ray beam. The temperature dependence of the chemical state of the two metals was systematically studied, revealing the high stability of nickel oxides on the NPs and the important role of high valence oxidation states in the segregation behavior. Atomic force microscopy (AFM) studies revealed a remarkable stability of the NPs against sintering at temperatures as high as 700 °C. The results provide new insights into the complex interplay of the various factors which affect alloy formation and segregation phenomena in bimetallic NP systems, often in ways different from those previously known for their bulk counterparts. In conclusion, this leads to new routes for tuning the surface composition of nanocatalysts, for example, through plasma and annealing pretreatments.« less

Polymer Brush Grafted Nanoparticles and Their Impact on the Morphology Evolution of Polymer Blend Films

NASA Astrophysics Data System (ADS)

Chung, Hyun-Joong; Ohno, Kohji; Composto, Russell

2013-03-01

We present an novel pathway to control the location of nanoparticles (NPs) in phase-separating polymer blend films containing poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN). Because hydrophobic polymer phases have a small interfacial energy, ~1 mJ/m2, subtle changes in the NP surface functionality can be used to guide NPs to either the interface between immiscible polymers or into one of the phases. Based on this idea, we designed a class of NPs grafted with PMMA brushes. These PMMA brushes were grown from the NP surface by atom transfer radical polymerization (ATRP), which results in chains terminated with chlorine atoms. The chain end can be substituted with protons (H) by dehalogenation. As a result, the NPs are strongly segregated at the interface when grafted PMMA chains are short (Mn =1.8K) and the end group is Cl, whereas NPs partition into PMMA-rich phase when chains are long (Mn =160K) and/or when chains are terminated with hydrogen. The Cl end groups and shorter chain length cause an increase in surface energy for the NPs. The increase in surface energy of short-chained NPs can be attributed to (i) an extended brush conformation (entropic) and/or (ii) a high density of ``unfavorable'' end groups (enthalpic). Finally, the impact of NPs on the morphological evolution of the polymer blend films will be discussed. Ref: H.-J.Chung et al., ACS Macro Lett. 1(1), 252-256 (2012).

An overview of the characterization of occupational exposure to nanoaerosols in workplaces

NASA Astrophysics Data System (ADS)

Castellano, Paola; Ferrante, Riccardo; Curini, Roberta; Canepari, Silvia

2009-05-01

Currently, there is a lack of standardized sampling and metric methods that can be applied to measure the level of exposure to nanosized aerosols. Therefore, any attempt to characterize exposure to nanoparticles (NP) in a workplace must involve a multifaceted approach characterized by different sampling and analytical techniques to measure all relevant characteristics of NP exposure. Furthermore, as NP aerosols are always complex mixtures of multiple origins, sampling and analytical methods need to be improved to selectively evaluate the apportionment from specific sources to the final nanomaterials. An open question at the world's level is how to relate specific toxic effects of NP with one or more among several different parameters (such as particle size, mass, composition, surface area, number concentration, aggregation or agglomeration state, water solubility and surface chemistry). As the evaluation of occupational exposure to NP in workplaces needs dimensional and chemical characterization, the main problem is the choice of the sampling and dimensional separation techniques. Therefore a convenient approach to allow a satisfactory risk assessment could be the contemporary use of different sampling and measuring techniques for particles with known toxicity in selected workplaces. Despite the lack of specific NP exposure limit values, exposure metrics, appropriate to nanoaerosols, are discussed in the Technical Report ISO/TR 27628:2007 with the aim to enable occupational hygienists to characterize and monitor nanoaerosols in workplaces. Moreover, NIOSH has developed the Document Approaches to Safe Nanotechnology (intended to be an information exchange with NIOSH) in order to address current and future research needs to understanding the potential risks that nanotechnology may have to workers.

Easy Preparation and Photoelectrochemical Properties of CdS Nanoparticle/Graphene Nanosheet Nanocomposites Using Supercritical Carbon Dioxide.

PubMed

Yan, Shancheng; Xu, Xin; Jiang, Chao; Pan, Lijia; Shi, Yi; Hu, Dong; Cao, Zhenglin

2016-03-01

Graphene nanosheets (GNSs) were modified with CdS nanoparticles (NPs) using supercritical CO2 (SC CO2), which has gas-like diffusivity, low viscosity, and near-zero surface tension. The resulting CdS NP/GNS nanocomposites were characterized by field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and photoluminescence spectroscopy. Distinct morphologies of CdS NP/GNS nanocomposites decorated on the GNS surface were obtained at different SC CO2 pressures, temperatures, and durations and in different sources. Results showed that the sources and SC CO2 significantly influenced the aggregation or assembly behavior of the CdS NP/GNS nanocomposites on the GNSs. The formation mechanism of the distinct nanohybrid structures was studied by Raman mapping. A difference was noted between the Raman spectra of pristine graphene nanosheets and CdS NP/GNS nanocomposites. This result can be ascribed to the CdS NPs anchored onto the GNS defects and to the improved quality of the GNSs under SC CO2. The photo-current densities of CdS NP/GNS nanocomposites were at least three times higher than that of the pristine CdS NPs at the same applied voltage for photoelectrochemical water splitting. The findings suggested that highly efficient graphene-supported NP photoelectrocatalysts can be fabricated by the supercritical fluid method and that graphene can serve as a favorable photoelectrocatalytic carrier, with promising potential applications in environmental and energy fields. Keywords: Graphene Nanosheets, Cadmium Sulfide, Raman Spectroscopy, Photoelectrochemical.

Functional genomics reveals the induction of inflammatory response and metalloproteinase gene expression during lethal Ebola virus infection.

PubMed

Cilloniz, Cristian; Ebihara, Hideki; Ni, Chester; Neumann, Gabriele; Korth, Marcus J; Kelly, Sara M; Kawaoka, Yoshihiro; Feldmann, Heinz; Katze, Michael G

2011-09-01

Ebola virus is the etiologic agent of a lethal hemorrhagic fever in humans and nonhuman primates with mortality rates of up to 90%. Previous studies with Zaire Ebola virus (ZEBOV), mouse-adapted virus (MA-ZEBOV), and mutant viruses (ZEBOV-NP(ma), ZEBOV-VP24(ma), and ZEBOV-NP/VP24(ma)) allowed us to identify the mutations in viral protein 24 (VP24) and nucleoprotein (NP) responsible for acquisition of high virulence in mice. To elucidate specific molecular signatures associated with lethality, we compared global gene expression profiles in spleen samples from mice infected with these viruses and performed an extensive functional analysis. Our analysis showed that the lethal viruses (MA-ZEBOV and ZEBOV-NP/VP24(ma)) elicited a strong expression of genes 72 h after infection. In addition, we found that although the host transcriptional response to ZEBOV-VP24(ma) was nearly the same as that to ZEBOV-NP/VP24(ma), the contribution of a mutation in the NP gene was required for a lethal phenotype. Further analysis indicated that one of the most relevant biological functions differentially regulated by the lethal viruses was the inflammatory response, as was the induction of specific metalloproteinases, which were present in our newly identify functional network that was associated with Ebola virus lethality. Our results suggest that this dysregulated proinflammatory response increased the severity of disease. Consequently, the newly discovered molecular signature could be used as the starting point for the development of new drugs and therapeutics. To our knowledge, this is the first study that clearly defines unique molecular signatures associated with Ebola virus lethality.

Iodide-induced organothiol desorption and photochemical reaction, gold nanoparticle (AuNP) fusion, and SERS signal reduction in organothiol-containing AuNP aggregates

USDA-ARS?s Scientific Manuscript database

Gold nanoparticles (AuNPs) have been used extensively as surface-enhanced Raman spectroscopic (SERS) substrates for their large SERS enhancements and widely believed chemical stability. Presented is the finding that iodide can rapidly reduce the SERS intensity of the ligands, including organothiols ...

Betavoltaic p--n+-structure simulation

NASA Astrophysics Data System (ADS)

Urchuk, S. U.; Murashev, V. N.; Legotin, S. A.; Krasnov, A. A.; Rabinovich, O. I.; Kuzmina, K. A.; Omel'chenko, Y. K.; Osipov, U. V.; Didenko, S. I.

2016-08-01

In order to increase the betavoltaic batteries efficiency output characteristics of the p--n+ (n--p+) - structures were simulated. Replacing the p+-n-structures on the p-n+ and n-p+ -structures enables the space-charge expansion to the crystal surface and thus to reduce the recombination loss in the heavy doped p+-layer and improve conversion of betavoltaic elements efficiency.

Au nanoparticle arrays produced by Pulsed Laser Deposition for Surface Enhanced Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Agarwal, N. R.; Neri, F.; Trusso, S.; Lucotti, A.; Ossi, P. M.

2012-09-01

Using UV pulses from KrF excimer laser, Au targets were ablated in varying pressures of argon to deposit Au nanoparticle (NP) arrays. The morphology of these films from island structures to isolated NPs, observed by SEM and TEM, depends on the gas pressure (10-100 Pa) and pulse number keeping other deposition parameters constant. By fast imaging of the plasma with an iCCD camera at different time delays with respect to the arrival of the laser pulse, we study the plasma propagation regime and we measured its initial velocity. These data and the measured average ablated mass per pulse were introduced to the mixed propagation model to calculate the average asymptotic size of clusters grown in the plume which were compared with NP sizes from TEM measurements. UV-visible Spectroscopy revealed changes of surface plasmon resonance with respect to NP size and spatial density and distribution on the surface. Suitable wavelength to excite the localized surface plasmon was chosen to detect ultra-low concentrations of Rhodamine and Apomorphine as an application to biomedical sensors, using Surface Enhanced Raman Spectroscopy (SERS). A comparison of SERS spectra taken under identical conditions from commercial substrates and from PLD substrates show that the latter have superior performances.

Systemic delivery of blood-brain barrier-targeted polymeric nanoparticles enhances delivery to brain tissue.

PubMed

Saucier-Sawyer, Jennifer K; Deng, Yang; Seo, Young-Eun; Cheng, Christopher J; Zhang, Junwei; Quijano, Elias; Saltzman, W Mark

2015-01-01

Delivery of therapeutic agents to the central nervous system is a significant challenge, hindering progress in the treatment of diseases such as glioblastoma. Due to the presence of the blood-brain barrier (BBB), therapeutic agents do not readily transverse the brain endothelium to enter the parenchyma. Previous reports suggest that surface modification of polymer nanoparticles (NPs) can improve their ability to cross the BBB, but it is unclear whether the observed enhancements in transport are large enough to enhance therapy. In this study, we synthesized two degradable polymer NP systems surface-modified with ligands previously suggested to improve BBB transport, and tested their ability to cross the BBB after intravenous injection in mice. All the NP preparations were able to cross the BBB, although generally in low amounts (<0.5% of the injected dose), which was consistent with prior reports. One NP produced significantly higher brain uptake (∼0.8% of the injected dose): a block copolymer of polylactic acid and hyperbranched polyglycerol, surface modified with adenosine (PLA-HPG-Ad). PLA-HPG-Ad NPs provided controlled release of camptothecin, killing U87 glioma cells in culture. When administered intravenously in mice with intracranial U87 tumors, they failed to increase survival. These results suggest that enhancing NP transport across the BBB does not necessarily yield proportional pharmacological effects.

Study on aggregation behavior of Cytochrome C-conjugated silver nanoparticles using asymmetrical flow field-flow fractionation.

PubMed

Kim, Sun Tae; Lee, Yong-Ju; Hwang, Yu-Sik; Lee, Seungho

2015-01-01

In this study, 40 nm silver nanoparticles (AgNPs) were synthesized using the citrate reduction method and then the surface of AgNPs was modified by conjugating Cytochrome C (Cyto C) to improve stability and to enhance bioactivity and biocompatibility of AgNPs. It is known that Cyto C may undergo conformational changes under various conditions of pH, temperature, ionic strength, etc., resulting in aggregation of the particles. These parameters also affect the size and size distribution of Cyto C-conjugated AgNPs (Cyto C-AgNP). ζ-potential measurement revealed that the adsorption of Cyto C on the surface of AgNPs is saturated at the molar ratio [Cyto C]/[AgNPs] above about 300. Asymmetrical flow field-flow fractionation (AsFlFFF) analysis showed that hydrodynamic diameter of AgNPs increases by about 4 nm when the particle is saturated by Cyto C. The aggregation behavior of Cyto C-AgNP at various conditions of pH, temperature and ionic strength were investigated using AsFlFFF and UV-vis spectroscopy. It was found that the aggregation of Cyto C-AgNP increases with decreasing pH, increasing temperature and ionic strength due to denaturation of Cyto C on AgNPs and reduction in the thickness of electrostatic double layer on the surface of Cyto C-AgNP. Copyright © 2014 Elsevier B.V. All rights reserved.

Space Weathering of Silicates Simulated by Successive Laser Irradiation: In Situ Reflectance Measurements of Fo90, Fo99+, and Sio2

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Dukes, C. A.; Christoffersen, R.; Baragiola, R. A.

2016-01-01

Pulsed-laser irradiation causes the visible-near-infrared spectral slope of olivine (Fo90 and Fo99+) and SiO2 to increase (redden), while the olivine samples darken and the SiO2 samples brighten slightly. XPS analysis shows that irradiation of Fo90 produces metallic Fe. Analytical SEM and TEM measurements confirm that reddening in the Fo90 olivine samples correlates with the production of nanophase metallic Fe (npFe0) grains, 2050 nm in size. The reddening observed in the SiO2 sample is consistent with the formation of SiO or other SiOx species that absorb in the visible. The weak spectral brightening induced by laser irradiation of SiO2 is consistent with a change in surface topography of the sample. The darkening observed in the olivine samples is likely caused by the formation of larger npFe0 particles, such as the 100400 nm diameter npFe0 identified during our TEM analysis of Fo90 samples. The Fo90 reflectance spectra are qualitatively similar to those in previous experiments suggesting that in all cases formation of npFe0 is causing the spectral alteration. Finally, we find that the accumulation of successive laserpulses cause continued sample darkening in the Vis-NIR, which suggests that repeated surface impacts are an efficient way to darken airless body surfaces.

Grand-canonical solution of semiflexible self-avoiding trails on the Bethe lattice.

PubMed

Dantas, W G; Oliveira, Tiago J; Stilck, Jürgen F; Prellberg, Thomas

2017-02-01

We consider a model of semiflexible interacting self-avoiding trails (sISATs) on a lattice, where the walks are constrained to visit each lattice edge at most once. Such models have been studied as an alternative to the self-attracting self-avoiding walks (SASAWs) to investigate the collapse transition of polymers, with the attractive interactions being on site as opposed to nearest-neighbor interactions in SASAWs. The grand-canonical version of the sISAT model is solved on a four-coordinated Bethe lattice, and four phases appear: non-polymerized (NP), regular polymerized (P), dense polymerized (DP), and anisotropic nematic (AN), the last one present in the phase diagram only for sufficiently stiff chains. The last two phases are dense, in the sense that all lattice sites are visited once in the AN phase and twice in the DP phase. In general, critical NP-P and DP-P transition surfaces meet with a NP-DP coexistence surface at a line of bicritical points. The region in which the AN phase is stable is limited by a discontinuous critical transition to the P phase, and we study this somewhat unusual transition in some detail. In the limit of rods, where the chains are totally rigid, the P phase is absent and the three coexistence lines (NP-AN, AN-DP, and NP-DP) meet at a triple point, which is the endpoint of the bicritical line.

Direct visual observations of nanoparticles in the Celtic Sea

NASA Astrophysics Data System (ADS)

Rusiecka, D.; Gledhill, M.; Achterberg, E. P.; Elgy, C.; Connelly, D.

2016-02-01

Shelf seas are a substantial source of dissolved iron and other biologically essential dissolved trace metals (dTM) to the open ocean. The concentration of dTM in seawater is strongly influenced by their physico-chemical forms. The role of submicron colloids on the stabilization and transport of dTM in the soil porewaters has already been recognized. However, the influence of nanoparticles (NP) on dTM stabilization in marine systems and consequently on their long range off-shelf transport is still very poorly constrained. The characterization of marine NP is fundamental to understand their chemical behaviour. Here, we report the first direct visual investigation into the formation, water column size distribution and seasonal variation of NP in the Celtic Sea with supportive examination of particle morphology. Samples were collected from surface (depth range), intermediate (depth range) and deep (depth range) waters in December 2014, April 2015 and July 2015. Nanoparticles (>3 KDa) were concentrated by stirred cell ultrafiltration and imaged using Atomic Force Microscopy and Transmission Electron Microscopy. NP size distributions from the spring cruise showed that they mainly existed in the smallest 0.4-1 nm fraction in surface- and bottom-waters, whereas the summer season was dominated by 0.4-1 nm fraction at all depths. In winter NP in bottom-waters were found predominantly in bigger 1-2 nm fraction.

Enhancing the photoelectrochemical response of TiO2 nanotubes through their nanodecoration by pulsed-laser-deposited Ag nanoparticles

NASA Astrophysics Data System (ADS)

Trabelsi, K.; Hajjaji, A.; Gaidi, M.; Bessais, B.; El Khakani, M. A.

2017-08-01

We report on the pulsed laser deposition (PLD) based nanodecoration of titanium dioxide (TiO2) nanotube arrays (NTAs) by Ag nanoparticles (NPs). We focus here on the investigation of the effect of the number of laser ablation pulses (NLP) of the silver target on both the average size of the Ag-NPs and the photoelectrochemical conversion efficiency of the Ag-NP decorated TiO2-NT based photoanodes. By varying the NLP, we were able to not only control the size of the PLD-deposited Ag nanoparticles from 20 to ˜50 nm, but also to increase concomitantly the surface coverage of the TiO2 NTAs by Ag-NPs. The red-shifting of the surface plasmon resonance peak of the PLD-deposited Ag-NPs deposited onto quartz substrates confirmed the increase of their size as the NLP is increased from 500 to 10 000. By investigating the photo-electrochemical properties of Ag-NP decorated TiO2-NTAs, by means of linear sweep cyclic voltammetry under UV-Vis illumination, we found that the generated photocurrent is sensitive to the size of the Ag-NPs and reaches a maximum value at NLP =500 (i.e.,; Ag-NP size of ˜20 nm). For NLP = 500, the photoconversion efficiency of the Ag-NP decorated TiO2-NTAs is shown to reach a maximum of 4.5% (at 0.5 V vs Ag/AgCl). The photocurrent enhancement of Ag-NP decorated TiO2-NTAs is believed to result from the additional light harvesting enabled by the ability of Ag-NPs to absorb visible irradiation caused by various localized surface plasmon resonances, which in turn depend on the size and interdistance of the Ag nanoparticles.

pH-Switchable Interaction of a Carboxybetaine Ester-Based SAM with DNA and Gold Nanoparticles.

PubMed

Filip, Jaroslav; Popelka, Anton; Bertok, Tomas; Holazova, Alena; Osicka, Josef; Kollar, Jozef; Ilcikova, Marketa; Tkac, Jan; Kasak, Peter

2017-07-11

We describe a self-assembled monolayer (SAM) on a gold surface with a carboxybetaine ester functionality to control the interaction between DNA and gold nanoparticles via pH. The negatively charged phosphate backbone of DNA interacts with and adsorbs to the positively charged carboxybetaine esters on the SAM. DNA release can be achieved by the hydrolysis of carboxybetaine ester (CBE) to a zwitterionic carboxybetaine state. Furthermore, the adsorption of negatively charged citrate-capped gold nanoparticles to a SAM-modified plain gold surface can be controlled by the pH. The SAM based on carboxybetaine ester allows for the homogeneous adsorption of particles, whereas the SAM after hydrolysis at high pH repels AuNP adsorption. The antifouling surface properties of the surface modified with carboxybetaine were investigated with protein samples.

Ammonia-modified graphene sheets decorated with magnetic Fe3O4 nanoparticles for the photocatalytic and photo-Fenton degradation of phenolic compounds under sunlight irradiation.

PubMed

Boruah, Purna K; Sharma, Bhagyasmeeta; Karbhal, Indrapal; Shelke, Manjusha V; Das, Manash R

2017-03-05

Synthesis of easily separable and eco-friendly efficient catalyst with both photocatalytic and photo-Fenton degradation properties is of great importance for environment remediation application. Herein, ammonia-modified graphene (AG) sheets decorated with Fe 3 O 4 nanoparticles (AG/Fe 3 O 4 ) as a magnetically recoverable photocatalyst by a simple in situ solution chemistry approach. First, we have functionalized graphene oxide (GO) sheets by amide functional group and then Fe 3 O 4 nanoparticles (NPs) are doped onto the functionalized GO surface. The AG/Fe 3 O 4 nanocomposite showed efficient photocatalytic activity towards degradation of phenol (92.43%), 2-nitrophenol (2-NP) (98%) and 2-chlorophenol (2-CP) (97.15%) within 70-120min. Consequently, in case of photo-Fenton degradation phenomenon, 93.56% phenol, 98.76% 2-NP and 98.06% of 2-CP degradation were achieved within 50-80min using AG/Fe 3 O 4 nanocomposite under sunlight irradiation. The synergistic effect between amide functionalized graphene and Fe 3 O 4 nanoparticles (NPs) enhances the photocatalytic activity by preventing the recombination rate of electron-hole-pair in Fe 3 O 4 NPs. Furthermore, the remarkable reusability of the AG/Fe 3 O 4 nanocomposite was observed up to ten cycles during the photocatalytic degradation of these phenolic compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Environmental concentration of nonylphenol alters the development of urogenital and visceral organs in avian model.

PubMed

Roig, Benoit; Cadiere, Axelle; Bressieux, Stephanie; Biau, Sandrine; Faure, Sandrine; de Santa Barbara, Pascal

2014-01-01

Nonylphenol (NP) is an endocrine disruptor with harmful effects including feminization and carcinogenesis on various organisms. This substance is a degradation product of nonylphenol ethoxylates (NPEO) that is used in several industrial and agricultural processes. In this paper, we examined the assessment of NP exposure on chick embryo development, using a concentration consistent with the environmental concentrations of NP. With this aim, NP (between 0.1 and 50 μg/egg) was injected into the yolk of egg through a small needle hole in the shell. We report the effect of NP on chick reproductive system development although the effect we observed is lower than those observed by exposition to other endocrine disruptors. However, histological analysis highlighted a decrease of intraluminal seminiferous surface area in 64.12% of case (P=0.0086) and an heterogeneous organization of the renal tubules when 10 μg/egg were injected. Moreover, an impairment of liver development with an abnormal bile spillage was observed when higher concentration of NP was injected (50 μg/egg). © 2013.

An Overview of Chitosan Nanoparticles and Its Application in Non-Parenteral Drug Delivery

PubMed Central

Mohammed, Munawar A.; Syeda, Jaweria T. M.; Wasan, Kishor M.; Wasan, Ellen K.

2017-01-01

The focus of this review is to provide an overview of the chitosan based nanoparticles for various non-parenteral applications and also to put a spotlight on current research including sustained release and mucoadhesive chitosan dosage forms. Chitosan is a biodegradable, biocompatible polymer regarded as safe for human dietary use and approved for wound dressing applications. Chitosan has been used as a carrier in polymeric nanoparticles for drug delivery through various routes of administration. Chitosan has chemical functional groups that can be modified to achieve specific goals, making it a polymer with a tremendous range of potential applications. Nanoparticles (NP) prepared with chitosan and chitosan derivatives typically possess a positive surface charge and mucoadhesive properties such that can adhere to mucus membranes and release the drug payload in a sustained release manner. Chitosan-based NP have various applications in non-parenteral drug delivery for the treatment of cancer, gastrointestinal diseases, pulmonary diseases, drug delivery to the brain and ocular infections which will be exemplified in this review. Chitosan shows low toxicity both in vitro and some in vivo models. This review explores recent research on chitosan based NP for non-parenteral drug delivery, chitosan properties, modification, toxicity, pharmacokinetics and preclinical studies. PMID:29156634

SEM and TEM Observation of the Surfaces of the Fine-Grained Particles Retrieved from the Muses-C Regio on the Asteroid 25413 Itokawa

NASA Technical Reports Server (NTRS)

Noguchi, T.; Nakamura, T.; Zolensky, Michael E.; Tanaka, M.; Hashimoto, T.; Konno, M.; Nakato, A.; Ogami, T.; Fujimura, A.; Abe, M.;

Asymmetric flow field-flow fractionation of manufactured silver nanoparticles spiked into soil solution.

PubMed

Koopmans, G F; Hiemstra, T; Regelink, I C; Molleman, B; Comans, R N J

2015-05-01

Manufactured metallic silver nanoparticles (AgNP) are intensively utilized in consumer products and this will inevitably lead to their release to soils. To assess the environmental risks of AgNP in soils, quantification of both their concentration and size in soil solution is essential. We developed a methodology consisting of asymmetric flow field-flow fractionation (AF4) in combination with on-line detection by UV-vis spectroscopy and off-line HR-ICP-MS measurements to quantify the concentration and size of AgNP, coated with either citrate or polyvinylpyrrolidone (PVP), in water extracts of three different soils. The type of mobile phase was a critical factor in the fractionation of AgNP by AF4. In synthetic systems, fractionation of a series of virgin citrate- and PVP-coated AgNP (10-90 nm) with reasonably high recoveries could only be achieved with ultrahigh purity water as a mobile phase. For the soil water extracts, 0.01% (w:v) sodium dodecyl sulfate (SDS) at pH 8 was the key to a successful fractionation of the AgNP. With SDS, the primary size of AgNP in all soil water extracts could be determined by AF4, except for PVP-coated AgNP when clay colloids were present. The PVP-coated AgNP interacted with colloidal clay minerals, leading to an overestimation of their primary size. Similar interactions between PVP-coated AgNP and clay colloids can take place in the environment and facilitate their transport in soils, aquifers, and surface waters. In conclusion, AF4 in combination with UV-vis spectroscopy and HR-ICP-MS measurements is a powerful tool to characterize AgNP in soil solution if the appropriate mobile phase is used. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigation of silicon surface passivation by silicon nitride film deposition

NASA Technical Reports Server (NTRS)

Olsen, L. C.

1984-01-01

The use of Sin sub x grown by plasma enhanced chemical vapor deposition (PECVO) for passivating silicon surfaces was studied. The application of PECVO SiN sub x films for passivations of silicon N+/P or P+/N solar cells is of particular interest. This program has involved the following areas of investigation: (1) Establishment of PECVO system and development of procedures for growth of SiN sub x; (2) Optical characterization of SiN sub x films; (3) Characterization of the SiN sub x/Si interface; (4) Surface recombination velocity deduced from photoresponse; (5) Current-Voltage analyses of silicon N+/P cells; and (6) Gated diode device studies.

Impairment of the reproductive potential of male fathead minnows by environmentally relevant exposures to 4-nonylphenolf

USGS Publications Warehouse

Schoenfuss, H.L.; Bartell, S.E.; Bistodeau, T.B.; Cediel, R.A.; Grove, K.J.; Zintek, Larry; Lee, K.E.; Barber, L.B.

2008-01-01

The synthetic organic compound 4-nonylphenol (NP) has been detected in many human-impacted surface waters in North America. In this study, we examined the ability of NP to alter reproductive competence in male fathead minnows after a 28 day flow-through exposure in a range of environmentally relevant concentrations bracketing the U.S. Environmental Protection Agency toxicity-based NP chronic exposure criterion of 6.1 ??g NP/L. Exposure to NP at and above the EPA chronic exposure criterion resulted in an induction of plasma vitellogenin (VTG) within 14 days. However, 7 days after the cessation of exposure, VTG concentrations had dropped more than 50% and few males expressed VTG above the detection threshold. All of the morphological endpoints, including gonadosomatic index, hepatosomatic index, secondary sexual characters, and histopathology, were unaltered by all NP treatments. However, when NP-exposed male fish were allowed to compete with control males for access to nest sites and females, most treatments altered the reproductive competence of exposed males. At lower NP concentrations, exposed males out-competed control males, possibly by being primed through the estrogenic NP exposure in a fashion similar to priming by pheromones released from female fathead minnows. At higher NP exposure concentrations, this priming effect was negated by the adverse effects of the exposure and control males out-competed treated males. Results of this study indicate the complexity of endocrine disrupting effects and the need for multiple analysis levels to assess the effects of these compounds on aquatic organisms. ?? 2007 Elsevier B.V. All rights reserved.

Abbreviated neuropsychological assessment in schizophrenia

PubMed Central

Harvey, Philip D.; Keefe, Richard S. E.; Patterson, Thomas L.; Heaton, Robert K.; Bowie, Christopher R.

2008-01-01

The aim of this study was to identify the best subset of neuropsychological tests for prediction of several different aspects of functioning in a large (n = 236) sample of older people with schizophrenia. While the validity of abbreviated assessment methods has been examined before, there has never been a comparative study of the prediction of different elements of cognitive impairment, real-world outcomes, and performance-based measures of functional capacity. Scores on 10 different tests from a neuropsychological assessment battery were used to predict global neuropsychological (NP) performance (indexed with averaged scores or calculated general deficit scores), performance-based indices of everyday-living skills and social competence, and case-manager ratings of real-world functioning. Forward entry stepwise regression analyses were used to identify the best predictors for each of the outcomes measures. Then, the analyses were adjusted for estimated premorbid IQ, which reduced the magnitude, but not the structure, of the correlations. Substantial amounts (over 70%) of the variance in overall NP performance were accounted for by a limited number of NP tests. Considerable variance in measures of functional capacity was also accounted for by a limited number of tests. Different tests constituted the best predictor set for each outcome measure. A substantial proportion of the variance in several different NP and functional outcomes can be accounted for by a small number of NP tests that can be completed in a few minutes, although there is considerable unexplained variance. However, the abbreviated assessments that best predict different outcomes vary across outcomes. Future studies should determine whether responses to pharmacological and remediation treatments can be captured with brief assessments as well. PMID:18720182

Photoelectrochemical response of GaN, InGaN, and GaNP nanowire ensembles

NASA Astrophysics Data System (ADS)

Philipps, Jan M.; Hölzel, Sara; Hille, Pascal; Schörmann, Jörg; Chatterjee, Sangam; Buyanova, Irina A.; Eickhoff, Martin; Hofmann, Detlev M.

2018-05-01

The photoelectrochemical responses of GaN, GaNP, and InGaN nanowire ensembles are investigated by the electrical bias dependent photoluminescence, photocurrent, and spin trapping experiments. The results are explained in the frame of the surface band bending model. The model is sufficient for InGaN nanowires, but for GaN nanowires the electrochemical etching processes in the anodic regime have to be considered additionally. These processes lead to oxygen rich surface (GaxOy) conditions as evident from energy dispersive X-ray fluorescence. For the GaNP nanowires, a bias dependence of the carrier transfer to the electrolyte is not reflected in the photoluminescence response, which is tentatively ascribed to a different origin of radiative recombination in this material as compared to (In)GaN. The corresponding consequences for the applications of the materials for water splitting or pH-sensing will be discussed.

Polymerizable-group capped ZnS nanoparticle for high refractive index inorganic-organic hydrogel contact lens.

PubMed

Zhao, Peili; Xu, Jinku; Zhang, Yongchun; Zhu, Weiyue; Cui, Yuezhi

2018-09-01

Refractive index (RI) is an important parameter for contact lens biomaterials. In this paper, a novel polymerizable-group capped ZnS nanoparticle (NP) was synthesized by chemical link between hydroxyl group on the surface of ZnS (ME-capped) and isocyanate group of polymerizable molecule of 2-isocyanatoethyl methacrylate. Then the ZnS NP copolymerized with monomer of 2-hydroxyethyl methacrylate (HEMA) and N,N-dimethylacrylamide (DMA) to prepare high refractive index hydrogel contact lens with high content of inorganic ZnS NP. Increasing polymerizable-group capped ZnS content in the hydrogels improved its RI value and mechanical properties, however decreased slightly its transmittance, equilibrium (ESR) and lysozyme deposition on the hydrogel surface. The ZnS-containing hydrogels possessed good cytocompatibility and in vivo biocompatibility in rabbit eyes, demonstrating a potential application as high RI ocular refractive correction biomaterial. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrochemical and in vitro neuronal recording characteristics of multi-electrode arrays surface-modified with electro-co-deposited gold-platinum nanoparticles.

PubMed

Kim, Yong Hee; Kim, Ah Young; Kim, Gook Hwa; Han, Young Hwan; Chung, Myung-Ae; Jung, Sang-Don

2016-02-01

In order to complement the high impedance electrical property of gold nanoparticles (Au NPs) we have performed electro-co-deposition of gold-platinum nanoparticles (Au-Pt NPs) onto the Au multi-electrode array (MEA) and modified the Au-Pt NPs surface with cell adhesive poly-D-lysine via thiol chemistry based covalent binding. The Au-Pt NPs were analyzed to have bimetallic nature not the mixture of Au NPs and Pt NPs by X-ray diffraction analysis and to have impedance value (4.0 × 10(4) Ω (at 1 kHz)) comparable to that of Pt NPs. The performance of Au-Pt NP-modified MEAs was also checked in relation to neuronal signal recording. The noise level in Au-Pt NP-modified MEAs was lower than in that of Au NP-modified MEA.

Local Schottky contacts of embedded Ag nanoparticles in Al2O3/SiNx:H stacks on Si: a design to enhance field effect passivation of Si junctions.

PubMed

Ibrahim Elmi, Omar; Cristini-Robbe, Odile; Chen, Minyu; Wei, Bin; Bernard, Rémy; Okada, Etienne; Yarekha, Dmitri A; Ouendi, Saliha; Portier, Xavier; Gourbilleau, Fabrice; Xu, Tao; Stievenard, Didier

2018-04-26

This paper describes an original design leading to the field effect passivation of Si n+-p junctions. Ordered Ag nanoparticle (Ag-NP) arrays with optimal size and coverage fabricated by means of nanosphere lithography and thermal evaporation, were embedded in ultrathin-Al2O3/SiNx:H stacks on the top of implanted Si n+-p junctions, to achieve effective surface passivation. One way to characterize surface passivation is to use photocurrent, sensitive to recombination centers. We evidenced an improvement of photocurrent by a factor of 5 with the presence of Ag nanoparticles. Finite-difference time-domain (FDTD) simulations combining with semi-quantitative calculations demonstrated that such gain was mainly due to the enhanced field effect passivation through the depleted region associated with the Ag-NPs/Si Schottky contacts. © 2018 IOP Publishing Ltd.

Terahertz transmission properties of a triadic-Cantor-set photonic crystal containing a semiconductor

NASA Astrophysics Data System (ADS)

King, Tzu-Chyang; Liu, Chi-Chung; Huang, Chih-Hsi; Wu, Chien-Jang

2016-08-01

Terahertz transmission properties of a stage 3 triadic-Cantor-set photonic crystal (S3 TCS PC) containing a semiconductor of n-InSb are theoretically investigated. With the resonant frequency in the permittivity function of n-InSb, transmission responses can be classified as three regions. In the two regions with frequencies well above and below the resonant frequency, the permittivity functions are nearly a positive constant and n-InSb is dielectric-like. For these two regions, transmittance response of S3 TCS PC at a given number of periods Np reveals that, within a photonic band gap, there are two groups of defect modes with numbers of Np and Np-1, respectively. Defect modes are shown to be blue-shifted as the angle of incidence increases for both TE and TM waves. Additionally, adjusting the layer thickness enables us to control mode positions for the group of (Np-1)-mode, but the one with Np-mode is not able to be controlled. In a region of 5.1-6.2 THz, where the loss is large, there also are many transmission modes.

FRET enhancement close to gold nanoparticles positioned in DNA origami constructs.

PubMed

Aissaoui, Nesrine; Moth-Poulsen, Kasper; Käll, Mikael; Johansson, Peter; Wilhelmsson, L Marcus; Albinsson, Bo

2017-01-05

Here we investigate the energy transfer rates of a Förster resonance energy transfer (FRET) pair positioned in close proximity to a 5 nm gold nanoparticle (AuNP) on a DNA origami construct. We study the distance dependence of the FRET rate by varying the location of the donor molecule, D, relative to the AuNP while maintaining a fixed location of the acceptor molecule, A. The presence of the AuNP induces an alteration in the spontaneous emission of the donor (including radiative and non-radiative rates) which is strongly dependent on the distance between the donor and AuNP surface. Simultaneously, the energy transfer rates are enhanced at shorter D-A (and D-AuNP) distances. Overall, in addition to the direct influence of the acceptor and AuNP on the donor decay there is also a significant increase in decay rate not explained by the sum of the two interactions. This leads to enhanced energy transfer between donor and acceptor in the presence of a 5 nm AuNP. We also demonstrate that the transfer rate in the three "particle" geometry (D + A + AuNP) depends approximately linearly on the transfer rate in the donor-AuNP system, suggesting the possibility to control FRET process with electric field induced by 5 nm AuNPs close to the donor fluorophore. It is concluded that DNA origami is a very versatile platform for studying interactions between molecules and plasmonic nanoparticles in general and FRET enhancement in particular.

[Preparation of ASODN-protamine-HSA-PLGA nanoparticles and initial evaluation of their nucleus targeting property in vitro].

PubMed

Zhang, Yi; Yuan, Li; Yan, Xiao-ling; Gong, Tao; Liu, Jie; Zhang, Zhi-rong; Sun, Xun

2009-05-01

To develop a novel non-viral gene delivery system-SODN-Protamine-HSA-PLGA (ASODN-P/H-PLGA-NP) and investigate its nucleus targeting potential in vitro. ASODN-P/H-PLGA-NP was prepared by mixing the protamine sulfate and HSA. Then the PLGA nanoparticles were prepared using double-emulsion evaporation technique, followed by addition of ASODN to the prepared P/H complex. The morphology of ASODN-P/H-PLGA-NP was observed by transmission electron microscopy. The diameter, PDI, and surface charge of ASODN-P/H-PLGA-NP were measured by photo correlation spectroscopy (PCS). The encapsulation efficiency of ASODN was determined by double step method. The cytotoxicity of ASODN-P/H-PLGA-NP was investigated by MTT assays. The ability to enter the squamouse carcinoma: Hep-2 cell line and its nucleus targeting property were observed by confocal laser scanning microscope. The average diameter, PDI, zeta potential, and encapsulation efficiency of ASODN-P/H-PLGA-NP were 128 nm, 0.234, -23.3 mV, and 78.45%, respectively. ASODN-P/H-PLGA-NP could protect the ASODN from the shear force in the ultrasound process during preparation. ASODN-P/H-PLGA-NP couldenter Hep-2 cells and have certain level of nucleus targeting property. ASODN-P/H-PLGA-NP can be prepared easily with small particle sizes and low cytotoxicity, which might be employed as a good non-viral vector for applications in ASODN delivery to nucleus.

Cholera Toxin Subunit B Enabled Multifunctional Glioma-Targeted Drug Delivery.

PubMed

Guan, Juan; Zhang, Zui; Hu, Xuefeng; Yang, Yang; Chai, Zhilan; Liu, Xiaoqin; Liu, Jican; Gao, Bo; Lu, Weiyue; Qian, Jun; Zhan, Changyou

2017-12-01

Glioma is among the most formidable brain cancers due to location in the brain. Cholera toxin subunit B (CTB) is investigated to facilitate multifunctional glioma-targeted drug delivery by targeting the glycosphingolipid GM1 expressed in the blood-brain barrier (BBB), neovasulature, and glioma cells. When modified on the surface of poly(lactic-co-glycolic acid) (PLGA) nanoparticles (CTB-NPs), CTB fully retains its bioactivity after 24 h incubation in the fresh mouse plasma. The formed protein corona (PC) of CTB-NP and plain PLGA nanoparticles (NP) after incubation in plasma is analyzed using liquid chromatography tandem massspectrometry (nano-LC-MS/MS). CTB modification does not alter the protein components of the formed PC, macrophage phagocytosis, or pharmacokinetic profiles. CTB-NP can efficiently penetrate the in vitro BBB model and target glioma cells and human umbilical vascular endothelial cells. Paclitaxel is loaded in NP (NP/PTX) and CTB-NP (CTB-NP/PTX), and their antiglioma effects are assessed in nude mice bearing intracranial glioma. CTB-NP/PTX can efficiently induce apoptosis of intracranial glioma cells and ablate neovasulature in vivo, resulting in significant prolongation of survival of nude mice bearing intracranial glioma (34 d) in comparison to those treated with NP/PTX (29 d), Taxol (24 d), and saline (21 d). The present study suggests a potential multifunctional glioma-targeted drug delivery system enabled by cholera toxin subunit B. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoparticle Assemblies at Fluid Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Russell, Thomas P.

2015-03-10

A systematic study of the structure and dynamics of nanoparticles (NP) and NP-surfactants was performed. The ligands attached to both the NPs and NP-surfactants dictate the manner in which the nanoscopic materials assemble at fluid interfaces. Studies have shown that a single layer of the nanoscpic materials form at the interface to reduce the interactions between the two immiscible fluids. The shape of the NP is, also, important, where for spherical particles, a disordered, liquid-like monolayer forms, and, for nanorods, ordered domains at the interface is found and, if the monolayers are compressed, the orientation of the nanorods with respectmore » to the interface can change. By associating end-functionalized polymers to the NPs assembled at the interface, NP-surfactants are formed that increase the energetic gain in segregating each NP at the interface which allows the NP-surfactants to jam at the interface when compressed. This has opened the possibility of structuring the two liquids by freezing in shape changes of the liquids.« less

An analysis of noun definition in Cantonese.

PubMed

To, Carol Kit Sum; Stokes, Stephanie; Man, Yonnie; T'sou, Benjamin

2013-03-01

This study investigated the noun definitions given by Cantonese speakers at different ages. Definitional responses on six concrete nouns from 1075 children aged 4;10 to 12;01 and 15 adults were analyzed with reference to the semantic content and the syntactic form. Results showed that conventional definitions produced by Cantonese adult speakers were realized with specific superordinates and more perceptual than functional attributes. The content was carried by a syntactic frame, "NP1, is NP2", where relative clause was not the predominant form of NP2 as in the English definition forms. Core attributes signifying the defining properties increased significantly with age while non-core attributes were observed relatively evenly throughout all groups. Preschoolers tended to drop the sentential-subject (i.e., NP1) and the copula is, and produce more functional than perceptual attributes. By Primary-2 (P2) (about 7;0), the taxonomic relation was coded with the frame of "NP1 is NP2". Beginning at P4 (about 9;0), children included a superordinate but the specificity of the adult-like superordinate was not achieved even by P6 (about 11;0). In general, developmental trends accorded with the trends observed in other languages, but typological features played a role in framing the development of the syntactic form.

Targeted silver nanoparticles for ratiometric cell phenotyping

NASA Astrophysics Data System (ADS)

Willmore, Anne-Mari A.; Simón-Gracia, Lorena; Toome, Kadri; Paiste, Päärn; Kotamraju, Venkata Ramana; Mölder, Tarmo; Sugahara, Kazuki N.; Ruoslahti, Erkki; Braun, Gary B.; Teesalu, Tambet

2016-04-01

Affinity targeting is used to deliver nanoparticles to cells and tissues. For efficient targeting, it is critical to consider the expression and accessibility of the relevant receptors in the target cells. Here, we describe isotopically barcoded silver nanoparticles (AgNPs) as a tool for auditing affinity ligand receptors in cells. Tumor penetrating peptide RPARPAR (receptor: NRP-1) and tumor homing peptide GKRK (receptor: p32) were used as affinity ligands on the AgNPs. The binding and uptake of the peptide-functionalized AgNPs by cultured PPC-1 prostate cancer and M21 melanoma cells was dependent on the cell surface expression of the cognate peptide receptors. Barcoded peptide-functionalized AgNPs were synthesized from silver and palladium isotopes. The cells were incubated with a cocktail of the barcoded nanoparticles [RPARPAR (R), GKRK (K), and control], and cellular binding and internalization of each type of nanoparticle was assessed by inductively coupled plasma mass spectrometry. The results of isotopic analysis were in agreement with data obtained using optical methods. Using ratiometric measurements, we were able to classify the PPC-1 cell line as mainly NRP-1-positive, with 75 +/- 5% R-AgNP uptake, and the M21 cell line as only p32-positive, with 89 +/- 9% K-AgNP uptake. The isotopically barcoded multiplexed AgNPs are useful as an in vitro ratiometric phenotyping tool and have potential uses in functional evaluation of the expression of accessible homing peptide receptors in vivo.Affinity targeting is used to deliver nanoparticles to cells and tissues. For efficient targeting, it is critical to consider the expression and accessibility of the relevant receptors in the target cells. Here, we describe isotopically barcoded silver nanoparticles (AgNPs) as a tool for auditing affinity ligand receptors in cells. Tumor penetrating peptide RPARPAR (receptor: NRP-1) and tumor homing peptide GKRK (receptor: p32) were used as affinity ligands on the AgNPs. The binding and uptake of the peptide-functionalized AgNPs by cultured PPC-1 prostate cancer and M21 melanoma cells was dependent on the cell surface expression of the cognate peptide receptors. Barcoded peptide-functionalized AgNPs were synthesized from silver and palladium isotopes. The cells were incubated with a cocktail of the barcoded nanoparticles [RPARPAR (R), GKRK (K), and control], and cellular binding and internalization of each type of nanoparticle was assessed by inductively coupled plasma mass spectrometry. The results of isotopic analysis were in agreement with data obtained using optical methods. Using ratiometric measurements, we were able to classify the PPC-1 cell line as mainly NRP-1-positive, with 75 +/- 5% R-AgNP uptake, and the M21 cell line as only p32-positive, with 89 +/- 9% K-AgNP uptake. The isotopically barcoded multiplexed AgNPs are useful as an in vitro ratiometric phenotyping tool and have potential uses in functional evaluation of the expression of accessible homing peptide receptors in vivo. Electronic supplementary information (ESI) available: TEM images of isotopic AgNPs, cell antibody staining, coadministration ICP-MS data, and biotin control particle ICP-MS data. See DOI: 10.1039/C5NR07928D

Neptunium carbonato complexes in aqueous solution: an electrochemical, spectroscopic, and quantum chemical study.

PubMed

Ikeda-Ohno, Atsushi; Tsushima, Satoru; Takao, Koichiro; Rossberg, André; Funke, Harald; Scheinost, Andreas C; Bernhard, Gert; Yaita, Tsuyoshi; Hennig, Christoph

2009-12-21

The electrochemical behavior and complex structure of Np carbonato complexes, which are of major concern for the geological disposal of radioactive wastes, have been investigated in aqueous Na(2)CO(3) and Na(2)CO(3)/NaOH solutions at different oxidation states by using cyclic voltammetry, X-ray absorption spectroscopy, and density functional theory calculations. The end-member complexes of penta- and hexavalent Np in 1.5 M Na(2)CO(3) with pH = 11.7 have been determined as a transdioxo neptunyl tricarbonato complex, [NpO(2)(CO(3))(3)](n-) (n = 5 for Np(V), and 4 for Np(VI)). Hence, the electrochemical reaction of the Np(V/VI) redox couple merely results in the shortening/lengthening of bond distances mainly because of the change of the cationic charge of Np, without any structural rearrangement. This explains the observed reversible-like feature on their cyclic voltammograms. In contrast, the electrochemical oxidation of Np(V) in a highly basic carbonate solution of 2.0 M Na(2)CO(3)/1.0 M NaOH (pH > 13) yielded a stable heptavalent Np complex of [Np(VII)O(4)(OH)(2)](3-), indicating that the oxidation reaction from Np(V) to Np(VII) in the carbonate solution involves a drastic structural rearrangement from the transdioxo configuration to a square-planar-tetraoxo configuration, as well as exchanging the coordinating anions from carbonate ions (CO(3)(2-)) to hydroxide ions (OH(-)).

Modulation of porphyrin photoluminescence by nanoscale spacers on silicon substrates

NASA Astrophysics Data System (ADS)

Fang, Y. C.; Zhang, Y.; Gao, H. Y.; Chen, L. G.; Gao, B.; He, W. Z.; Meng, Q. S.; Zhang, C.; Dong, Z. C.

2013-11-01

We investigate photoluminescence (PL) properties of quasi-monolayered tetraphenyl porphyrin (TPP) molecules on silicon substrates modulated by three different nanoscale spacers: native oxide layer (NOL), hydrogen (H)-passivated layer, and Ag nanoparticle (AgNP) thin film, respectively. In comparison with the PL intensity from the TPP molecules on the NOL-covered silicon, the fluorescence intensity from the molecules on the AgNP-covered surface was greatly enhanced while that for the H-passivated surface was found dramatically suppressed. Time-resolved fluorescence spectra indicated shortened lifetimes for TPP molecules in both cases, but the decay kinetics is believed to be different. The suppressed emission for the H-passivated sample was attributed to the weaker decoupling effect of the monolayer of hydrogen atoms as compared to the NOL, leading to increased nonradiative decay rate; whereas the enhanced fluorescence with shortened lifetime for the AgNP-covered sample is attributed not only to the resonant excitation by local surface plasmons, but also to the increased radiative decay rate originating from the emission enhancement in plasmonic "hot-spots".

Modification of Patterned Nanoporous Gold Thin Film Electrodes via Electro-annealing and Electrochemical Etching

NASA Astrophysics Data System (ADS)

Dorofeeva, Tatiana

Nanostructured materials have had a major impact on various fields, including medicine, catalysis, and energy storage, for the major part due to unique phenomena that arise at nanoscale. For this reason, there is a sustained need for new nanostructured materials, techniques to pattern them, and methods to precisely control their nanostructure. To that end, the primary focus of this dissertation is to demonstrate novel techniques to fabricate and tailor the morphology of a class of nanoporous metals, obtained by a process known as dealloying. In this process, while the less noble constituent of an alloy is chemically dissolved, surface-diffusion of the more noble constituent leads to self-assembly of a bicontinuous ligament network with characteristic porosity of ˜70% and ligament diameter of 10s of nanometers. As a model material produced by dealloying, this work employ nanoporous gold (np-Au), which has attracted significant attention of desirable features, such as high effective surface area, electrical conductivity, well-defined thiol-based surface modification strategies, microfabrication-compatibility, and biocompatibility. The most commonly method used to modify the morphology of np-Au is thermal treatment, where the enhanced diffusivity of the surface atoms leads to ligament (and consequently pore) coarsening. This method, however, is not conducive to modifying the morphology of thin films at specific locations on the film, which is necessary for creating devices that may need to contain different morphologies on a single device. In addition, coarsening attained by thermal treatment also leads to an undesirable reduction in effective surface area. In response to these challenges, this work demonstrates two different techniques that enables in situ modification of np-Au thin film electrodes obtained by sputter-deposition of a precursors silver-rich gold-silver alloy. The first method, referred to as electro-annealing, is achieved by injecting electrical current to np-Au electrodes, which leads coarsening due to a combination of Joule heating and other mechanisms. This method offers the capability to anneal different electrodes to varying degrees of coarsening in one step, by employing electrodes patterns with different cross-sectional areas - easily attained since np-Au can be patterned into arbitrary shapes via photolithography - to control electrode resistivity, thus current density and the amount of electro-annealing of an electrode. A surprising finding was that electro-annealing lead to electrode coarsening at much lower temperatures than conventional thermal treatment, which was attributed to augmented electron-surface atom interactions at high current densities that may in turn enhance surface atom diffusivity. A major advantage of electro-annealing is the ability to monitor the resistance change of the electrode (surrogate for electrode morphology) in real-time and vary the electro-annealing current accordingly to establish a closed-loop electro-annealing configuration. In nanostructured materials, the electrical resistance is often a function of nanostructure, thus changes in resistance can be directly linked to morphological changes of the electrode. Examination of the underlying mechanisms of nanostructure-dependent resistance change revealed that both ligament diameter and grain size play a role in dictating the observed electrode resistance change. The second method relies on electrochemical etching of ligaments to modify electrode morphology in order to maintain both a high effective surface area and large pores for unhindered transport of molecules to/from the ligament surfaces - an important consideration for many physico-chemical processes, such fuel cells, electrochemical sensors, and drug delivery platforms. The advantage of this method over purely chemical approach is that while an entire sample in exposed to the chemical reagent, the etching process does not occur until the necessary electrochemical potential is applied. Similar to the electro-annealing methods, electrical addressability allows for differentially modifying the morphology individual electrodes on a single substrate. The results of this study also revealed that electrochemical etching is a combination of coarsening and etching processes, where the optimization of etching parameters makes it possible precisely control the etching by favoring one process over the other. In summary, the two techniques, taken together in combination with np-Au's compatibility with microfabrication processes, can be extended to create multiple electrode arrays that display different morphologies for studying structure?property relationships and tuning catalysts/sensors for optimal performance.

Periodically Aligned Si Nanopillar Arrays as Efficient Antireflection Layers for Solar Cell Applications

PubMed Central

2010-01-01

Periodically aligned Si nanopillar (PASiNP) arrays were fabricated on Si substrate via a silver-catalyzed chemical etching process using the diameter-reduced polystyrene spheres as mask. The typical sub-wavelength structure of PASiNP arrays had excellent antireflection property with a low reflection loss of 2.84% for incident light within the wavelength range of 200–1,000 nm. The solar cell incorporated with the PASiNP arrays exhibited a power conversion efficiency (PCE) of ~9.24% with a short circuit current density (JSC) of ~29.5 mA/cm2 without using any extra surface passivation technique. The high PCE of PASiNP array-based solar cell was attributed to the excellent antireflection property of the special periodical Si nanostructure. PMID:21124636

Monitor for detecting and assessing exposure to airborne nanoparticles

NASA Astrophysics Data System (ADS)

Marra, Johan; Voetz, Matthias; Kiesling, Heinz-Jürgen

2010-01-01

An important safety aspect of the workplace environment concerns the severity of its air pollution with nanoparticles (NP; <100 nm) and ultrafine particles (UFP; <300 nm). Depending on their size and chemical nature, exposure to these particles through inhalation can be hazardous because of their intrinsic ability to deposit in the deep lung regions and the possibility to subsequently pass into the blood stream. Recommended safety measures in the nanomaterials industry are pragmatic, aiming at exposure minimization in general, and advocating continuous control by monitoring both the workplace air pollution level and the personal exposure to airborne NPs. This article describes the design and operation of the Aerasense NP monitor that enables intelligence gathering in particular with respect to airborne particles in the 10-300 nm size range. The NP monitor provides real time information about their number concentration, average size, and surface areas per unit volume of inhaled air that deposit in the various compartments of the respiratory tract. The monitor's functionality relies on electrical charging of airborne particles and subsequent measurements of the total particle charge concentration under various conditions. Information obtained with the NP monitor in a typical workplace environment has been compared with simultaneously recorded data from a Scanning Mobility Particle Sizer (SMPS) capable of measuring the particle size distribution in the 11-1086 nm size range. When the toxicological properties of the engineered and/or released particles in the workplace are known, personal exposure monitoring allows a risk assessment to be made for a worker during each workday, when the workplace-produced particles can be distinguished from other (ambient) particles.

A distance-dependent metal-enhanced fluorescence sensing platform based on molecular beacon design.

PubMed

Zhou, Zhenpeng; Huang, Hongduan; Chen, Yang; Liu, Feng; Huang, Cheng Zhi; Li, Na

2014-02-15

A new metal-enhanced fluorescence (MEF) based platform was developed on the basis of distance-dependent fluorescence quenching-enhancement effect, which combined the easiness of Ag-thiol chemistry with the MEF property of noble-metal structures as well as the molecular beacon design. For the given sized AgNPs, the fluorescence enhancement factor was found to increase with a d(6) dependency in agreement with fluorescence resonance energy transfer mechanism at shorter distance and decrease with a d(-3) dependency in agreement with plasmonic enhancement mechanism at longer distance between the fluorophore and the AgNP surface. As a proof of concept, the platform was demonstrated by a sensitive detection of mercuric ions, using thymine-containing molecular beacon to tune silver nanoparticle (AgNP)-enhanced fluorescence. Mercuric ions were detected via formation of a thymine-mercuric-thymine structure to open the hairpin, facilitating fluorescence recovery and AgNP enhancement to yield a limit of detection of 1 nM, which is well below the U.S. Environmental Protection Agency regulation of the Maximum Contaminant Level Goal (10nM) in drinking water. Since the AgNP functioned as not only a quencher to reduce the reagent blank signal but also an enhancement substrate to increase fluorescence of the open hairpin when target mercuric ions were present, the quenching-enhancement strategy can greatly improve the detection sensitivity and can in principle be a universal approach for various targets when combined with molecular beacon design. © 2013 Elsevier B.V. All rights reserved.

Influence of Gas Adsorption and Gold Nanoparticles on the Electrical Properties of CVD-Grown MoS2 Thin Films.

PubMed

Cho, Yunae; Sohn, Ahrum; Kim, Sujung; Hahm, Myung Gwan; Kim, Dong-Ho; Cho, Byungjin; Kim, Dong-Wook

2016-08-24

Molybdenum disulfide (MoS2) has increasingly attracted attention from researchers and is now one of the most intensively explored atomic-layered two-dimensional semiconductors. Control of the carrier concentration and doping type of MoS2 is crucial for its application in electronic and optoelectronic devices. Because the MoS2 layers are atomically thin, their transport characteristics may be very sensitive to ambient gas adsorption and the resulting charge transfer. We investigated the influence of the ambient gas (N2, H2/N2, and O2) choice on the resistance (R) and surface work function (WF) of trilayer MoS2 thin films grown via chemical vapor deposition. We also studied the electrical properties of gold (Au)-nanoparticle (NP)-coated MoS2 thin films; their R value was found to be 2 orders of magnitude smaller than that for bare samples. While the WF largely varied for each gas, R was almost invariant for both the bare and Au-NP-coated samples regardless of which gas was used. Temperature-dependent transport suggests that variable range hopping is the dominant mechanism for electrical conduction for bare and Au-NP-coated MoS2 thin films. The charges transferred from the gas adsorbates might be insufficient to induce measurable R change and/or be trapped in the defect states. The smaller WF and larger localization length of the Au-NP-coated sample, compared with the bare sample, suggest that more carriers and less defects enhanced conduction in MoS2.

Ultrastructural and Functional Analyses of Recombinant Influenza Virus Ribonucleoproteins Suggest Dimerization of Nucleoprotein during Virus Amplification

PubMed Central

Ortega, Joaquín; Martín-Benito, Jaime; Zürcher, Thomas; Valpuesta, José M.; Carrascosa, José L.; Ortín, Juan

2000-01-01

Influenza virus ribonucleoproteins (RNPs) were reconstituted in vivo from cloned cDNAs expressing the three polymerase subunits, the nucleoprotein (NP), and short template RNAs. The structure of purified RNPs was studied by electron microscopy and image processing. Circular and elliptic structures were obtained in which the NP and the polymerase complex could be defined. Comparison of the structure of RNPs of various lengths indicated that each NP monomer interacts with approximately 24 nucleotides. The analysis of the amplification of RNPs with different lengths showed that those with the highest replication efficiency contained an even number of NP monomers, suggesting that the NP is incorporated as dimers into newly synthesized RNPs. PMID:10590102

On the application potential of gold nanoparticles in nanoelectronics and biomedicine.

PubMed

Homberger, Melanie; Simon, Ulrich

2010-03-28

Ligand-stabilized gold nanoparticles (AuNPs) are of high interest to research dedicated to future technologies such as nanoelectronics or biomedical applications. This research interest arises from the unique size-dependent properties such as surface plasmon resonance or Coulomb charging effects. It is shown here how the unique properties of individual AuNPs and AuNP assemblies can be used to create new functional materials for applications in a technical or biological environment. While the term technical environment focuses on the potential use of AuNPs as subunits in nanoelectronic devices, the term biological environment addresses issues of toxicity and novel concepts of controlling biomolecular reactions on the surface of AuNPs.

Nanoparticles That "Remember" Temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klajn, Rafal; Browne, Kevin P.; Siowling, Soh

2010-06-02

Photoresponsive gold nanoparticles dispersed in a solid/frozen matrix provide a basis for sensors that “remember” whether the sample has ever exceeded the melting temperature of the matrix. The operation of these sensors rests on the ability to photoinduce metastable electric dipoles on NP surfaces – upon melting, these dipoles drive NP aggregation, precipitation, and crosslinking. These events are manifested by a pronounced color change.

Ligand Exchange Kinetics of Environmentally Relevant Metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Panasci, Adele Frances

2014-07-15

The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb tomore » mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237Np is a radioactive transuranic element with a half-life of 2 million years.« less

Paleogene-Neogene calcareous nannofossil biostratigraphy and paleoecological inferences from northern Campos Basin, Brazil (well Campos-01)

NASA Astrophysics Data System (ADS)

Alves, Thamara Daniel; Cooper, Maurice Kevin Edward; Rios-Netto, Aristóteles de Moraes

2016-11-01

Quantitative analyses of calcareous nannofossils were performed on 50 ditch-cuttings samples from a well drilled in the northern Campos Basin, Brazil. Nine zones and two subzones were recognised in the Paleogene-Neogene section. The absence of zones NN9-NN7 (earliest late-latest middle Miocene), NP25-NP21 (Oligocene) and NP18-NP1 (earliest late Eocene-Paleocene) implies the occurrence of three stratigraphic breaks/unconformities within the studied interval. Nannofossil assemblages present suggest an open-ocean depositional environment under oligotrophic-surface water conditions for the Miocene section of the well. Hughesius spp. and Umbilicosphaera spp., here named the "small dark" group, were recognised as an index of high nutrient concentration. We suggest that small coccolith/nannolith size is a better indicator of eutrophic condition than taxonomic affinity. Morphometric analysis of specimens of Sphenolithus belemnos and Sphenolithus disbelemnos showed that size tends to decrease within the highstand system tract. The influx of nutrients associated with the highstand could explain this size reduction and may also support our hypothesis that small specimens are indicative of high nutrient concentrations in the surface water.

Biological synthesis of nanoparticles in biofilms.

PubMed

Tanzil, Abid H; Sultana, Sujala T; Saunders, Steven R; Shi, Liang; Marsili, Enrico; Beyenal, Haluk

2016-12-01

The biological synthesis of nanoparticles (NPs) by bacteria and biofilms via extracellular redox reactions has received attention because of the minimization of harmful chemicals, low cost, and ease of culturing and downstream processing. Bioreduction mechanisms vary across bacteria and growth conditions, which leads to various sizes and shapes of biosynthesized NPs. NP synthesis in biofilms offers additional advantages, such as higher biomass concentrations and larger surface areas, which can lead to more efficient and scalable biosynthesis. Although biofilms have been used to produce NPs, the mechanistic details of NP formation are not well understood. In this review, we identify three critical areas of research and development needed to advance our understanding of NP production by biofilms: 1) synthesis, 2) mechanism and 3) stabilization. Advancement in these areas could result in the biosynthesis of NPs that are suitable for practical applications, especially in drug delivery and biocatalysis. Specifically, the current status of methods and mechanisms of nanoparticle synthesis and surface stabilization using planktonic bacteria and biofilms is discussed. We conclude that the use of biofilms to synthesize and stabilize NPs is underappreciated and could provide a new direction in biofilm-based NP production. Copyright © 2016 Elsevier Inc. All rights reserved.

Ag-NP@Ge-nanotaper/Si-micropillar ordered arrays as ultrasensitive and uniform surface enhanced Raman scattering substrates.

PubMed

Liu, Jing; Meng, Guowen; Li, Zhongbo; Huang, Zhulin; Li, Xiangdong

2015-11-21

Surface-enhanced Raman scattering (SERS) is considered to be an excellent candidate for analytical detection schemes, because of its molecular specificity, rapid response and high sensitivity. Here, SERS-substrates of Ag-nanoparticle (Ag-NP) decorated Ge-nanotapers grafted on hexagonally ordered Si-micropillar (denoted as Ag-NP@Ge-nanotaper/Si-micropillar) arrays are fabricated via a combinatorial process of two-step etching to achieve hexagonal Si-micropillar arrays, chemical vapor deposition of flocky Ge-nanotapers on each Si-micropillar and decoration of Ag-NPs onto the Ge-nanotapers through galvanic displacement. With high density three-dimensional (3D) "hot spots" created from the large quantities of the neighboring Ag-NPs and large-scale uniform morphology, the hierarchical Ag-NP@Ge-nanotaper/Si-micropillar arrays exhibit strong and reproducible SERS activity. Using our hierarchical 3D SERS-substrates, both methyl parathion (a commonly used pesticide) and PCB-2 (one congener of highly toxic polychlorinated biphenyls) with concentrations down to 10(-7) M and 10(-5) M have been detected respectively, showing great potential in SERS-based rapid trace-level detection of toxic organic pollutants in the environment.

Quantitative investigation on the critical thickness of the dielectric shell for metallic nanoparticles determined by the plasmon decay length.

PubMed

Li, Anran; Lim, Xinyi; Guo, Lin; Li, Shuzhou

2018-04-20

Inert dielectric shells coating the surface of metallic nanoparticles (NPs) are important for enhancing the NPs' stability, biocompatibility, and realizing targeting detection, but they impair NPs' sensing ability due to the electric fields damping. The dielectric shell not only determines the distance of the analyte from the NP surface, but also affects the field decay. From a practical point of view, it is extremely important to investigate the critical thickness of the shell, beyond which the NPs are no longer able to effectively detect the analytes. The plasmon decay length of the shell-coated NPs determines the critical thickness of the coating layer. Extracting from the exponential fitting results, we quantitatively demonstrate that the critical thickness of the shell exhibits a linear dependence on the NP volume and the dielectric constants of the shell and the surrounding medium, but only with a small variation influenced by the NP shape where the dipole resonance is dominated. We show the critical thickness increases with enlarging the NP sizes, or increasing the dielectric constant differences between the shell and surrounding medium. The findings are essential for applications of shell-coated NPs in plasmonic sensing.

Quantitative investigation on the critical thickness of the dielectric shell for metallic nanoparticles determined by the plasmon decay length

NASA Astrophysics Data System (ADS)

Li, Anran; Lim, Xinyi; Guo, Lin; Li, Shuzhou

2018-04-01

Inert dielectric shells coating the surface of metallic nanoparticles (NPs) are important for enhancing the NPs’ stability, biocompatibility, and realizing targeting detection, but they impair NPs’ sensing ability due to the electric fields damping. The dielectric shell not only determines the distance of the analyte from the NP surface, but also affects the field decay. From a practical point of view, it is extremely important to investigate the critical thickness of the shell, beyond which the NPs are no longer able to effectively detect the analytes. The plasmon decay length of the shell-coated NPs determines the critical thickness of the coating layer. Extracting from the exponential fitting results, we quantitatively demonstrate that the critical thickness of the shell exhibits a linear dependence on the NP volume and the dielectric constants of the shell and the surrounding medium, but only with a small variation influenced by the NP shape where the dipole resonance is dominated. We show the critical thickness increases with enlarging the NP sizes, or increasing the dielectric constant differences between the shell and surrounding medium. The findings are essential for applications of shell-coated NPs in plasmonic sensing.

Alkylphenols in Surface Sediments of the Gulf of Gdansk (Baltic Sea).

PubMed

Koniecko, Iga; Staniszewska, Marta; Falkowska, Lucyna; Burska, Dorota; Kielczewska, Joanna; Jasinska, Anita

2014-01-01

The widespread use of alkylphenols in European industry has led to their presence in the environment and the living organisms of the Baltic Sea. The present study (2011-2012) was designed to determine the concentrations of alkylphenols, 4-nonylphenol (NP) and 4- tert -octylphenol (OP), in surface sediments of the Gulf of Gdansk, a section of the Baltic that lies in close proximity to industrial and agricultural areas and borders with an agglomeration of nearly one million inhabitants. It is also where the Vistula, the largest Polish river, ends its course. In spring, large concentrations of 4-nonylphenol and 4- tert -octylphenol were washed off into the coastal zone with meltwater. In summertime, sediments near the beach had the highest alkylphenol concentrations (NP-2.31 ng g -1 dw, OP-13.09 ng g -1 dw), which was related to tourism and recreational activity. In silt sediments located off the coast, the highest NP (1.46 ng g -1 dw) and OP (6.56 ng g -1 dw) amounts were observed in autumn. The origin of OP and NP at those test stations was linked to atmospheric transport of black carbon along with adsorbed alkylphenols.

The Molecular Basis of Inactivation of Metronidazole-Resistant Helicobacter pylori Using Polyethyleneimine Functionalized Zinc Oxide Nanoparticles

PubMed Central

Chowdhury, Rukhsana; Chakrabarti, Pinak

2013-01-01

In view of the world wide prevalence of Helicobacter pylori infection, its potentially serious consequences, and the increasing emergence of antibiotic resistant H. pylori strains there is an urgent need for the development of alternative strategies to combat the infection. In this study it has been demonstrated that polyethyleneimine (PEI) functionalized zinc oxide (ZnO) nanoparticles (NPs) inhibit the growth of a metronidazole-resistant strain of H. pylori and the molecular basis of the anti-bacterial activity of ZnO-PEI NP has been investigated. The ZnO-PEI NP was synthesized using a wet chemical method with a core size of approximately 3–7 nm. Internalization and distribution of ZnO-PEI NP without agglomeration was observed in H. pylori cytosol by electron microscopy. Several lines of evidence including scanning electron microscopy, propidium iodide uptake and ATP assay indicate severe membrane damage in ZnO-PEI NP treated H. pylori. Intracellular ROS generation increased rapidly following the treatment of H. pylori with ZnO-PEI NP and extensive degradation of 16S and 23S rRNA was observed by quantitative reverse-transcriptase PCR. Finally, considerable synergy between ZnO-PEI NP and antibiotics was observed and it has been demonstrated that the concentration of ZnO-PEI NP (20 µg/ml) that is non-toxic to human cells could be used in combination with sub-inhibitory concentrations of antibiotics for the inhibition of H. pylori growth. PMID:23951006

Behavioral Impairment and Oxidative Damage Induced by Chronic Application of Nonylphenol

PubMed Central

Mao, Zhen; Zheng, Yuan-Lin; Zhang, Yan-Qiu

2011-01-01

Nonylphenol (NP) is a degradation product of nonylphenol polyethoxylates, which are widely used in the production of industrial and consumer surfactants. The aim of the present study was to evaluate the effect of NP on the antioxidant capacity and cognitive ability of mice. NP was given orally by gavages at doses of 0, 50, 100, and 200 mg kg−1 d−1 for 90 days. The results showed that NP significantly decreased the activity of superoxide dismutases (SOD), catalase (CAT), glutathione peroxidase (GPx), and glutathione reductase (GR) and at the same time increased malondialdehyde (MDA) levels in mice brains. Exploration, memory function and ability to learn a novel task were significantly decreased in NP fed mice. These results indicate that chronic high dose of NP exposure has the potential to generate oxidative stress and induce the cognitive impairment in male mice. PMID:21339980

Genipin cross-linked type II collagen/chondroitin sulfate composite hydrogel-like cell delivery system induces differentiation of adipose-derived stem cells and regenerates degenerated nucleus pulposus.

PubMed

Zhou, Xiaopeng; Wang, Jingkai; Fang, Weijing; Tao, Yiqing; Zhao, Tengfei; Xia, Kaishun; Liang, Chengzhen; Hua, Jianming; Li, Fangcai; Chen, Qixin

2018-04-15

Nucleus pulposus (NP) degeneration is usually the origin of intervertebral disc degeneration and consequent lower back pain. Although adipose-derived stem cell (ADSC)-based therapy is regarded to be promising for the treatment of degenerated NP, there is a lack of viable cell carriers to transplant ADSCs into the NP while maintaining cell function. In this study, we developed a type II collagen/chondroitin sulfate (CS) composite hydrogel-like ADSC (CCSA) delivery system with genipin as the cross-linking agent. The induction effect of the scaffold on ADSC differentiation was studied in vitro, and a rat coccygeal vertebrae degeneration model was used to investigate the regenerative effect of the CCSA system on the degenerated NP in vivo. The results showed that the CCSA delivery system cross-linked with 0.02% genipin was biocompatible and promoted the expressions of NP-specific genes. After the injection of the CCSA system, the disc height, water content, extracellular matrix synthesis, and structure of the degenerated NP were partly restored. Our CCSA delivery system uses minimally invasive approaches to promote the regeneration of degenerated NP and provides an exciting new avenue for the treatment of degenerative disc disease. Nucleus pulposus (NP) degeneration is usually the origin of intervertebral disc degeneration and consequent lower back pain. Stem cell-based tissue engineering is a promising method in NP regeneration, but there is a lack of viable cell carriers to transplant ADSCs into the NP while maintaining cell function. In this study, we developed a type II collagen/chondroitin sulfate (CS) composite hydrogel-like ADSC (CCSA) delivery system with genipin as the cross-linking agent. Although several research groups have studied the fabrication of injectable hydrogel with biological matrix, our study differs from other works. We chose type II collagen and CS, the two primary native components in the NP, as the main materials and combined them according to the natural ratio of collagen and sGAG in the NP. The delivery system is preloaded with ADSCs and can be injected into the NP with a needle, followed by in situ gelation. Genipin is used as a cross-linker to improve the bio-stability of the scaffold, with low cytotoxicity. We investigated the stimulatory effects of our scaffold on the differentiation of ADSCs in vitro and the regenerative effect of the CCSA delivery system on degenerated NP in vivo. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Surface functionalities of gold nanoparticles impact embryonic gene expression responses

PubMed Central

Truong, Lisa; Tilton, Susan C.; Zaikova, Tatiana; Richman, Erik; Waters, Katrina M.; Hutchison, James E.; Tanguay, Robert L.

2012-01-01

Incorporation of gold nanoparticles (AuNPs) into consumer products is increasing; however, there is a gap in available toxicological data to determine the safety of AuNPs. In this study, we utilised the embryonic zebrafish to investigate how surface functionalisation and charge influence molecular responses. Precisely engineered AuNPs with 1.5 nm cores were synthesised and functionalized with three ligands: 2-mercaptoethanesulfonic acid (MES), N,N,N-trimethylammoniumethanethiol (TMAT), or 2-(2-(2-mercaptoethoxy)ethoxy)ethanol. Developmental assessments revealed differential biological responses when embryos were exposed to the functionalised AuNPs at the same concentration. Using inductively coupled plasma–mass spectrometry, AuNP uptake was confirmed in exposed embryos. Following exposure to MES- and TMAT-AuNPs from 6 to 24 or 6 to 48 h post fertilisation, pathways involved in inflammation and immune response were perturbed. Additionally, transport mechanisms were misregulated after exposure to TMAT and MES-AuNPs, demonstrating that surface functionalisation influences many molecular pathways. PMID:22263968

Ag-NP@Ge-nanotaper/Si-micropillar ordered arrays as ultrasensitive and uniform surface enhanced Raman scattering substrates

NASA Astrophysics Data System (ADS)

Liu, Jing; Meng, Guowen; Li, Zhongbo; Huang, Zhulin; Li, Xiangdong

2015-10-01

Surface-enhanced Raman scattering (SERS) is considered to be an excellent candidate for analytical detection schemes, because of its molecular specificity, rapid response and high sensitivity. Here, SERS-substrates of Ag-nanoparticle (Ag-NP) decorated Ge-nanotapers grafted on hexagonally ordered Si-micropillar (denoted as Ag-NP@Ge-nanotaper/Si-micropillar) arrays are fabricated via a combinatorial process of two-step etching to achieve hexagonal Si-micropillar arrays, chemical vapor deposition of flocky Ge-nanotapers on each Si-micropillar and decoration of Ag-NPs onto the Ge-nanotapers through galvanic displacement. With high density three-dimensional (3D) ``hot spots'' created from the large quantities of the neighboring Ag-NPs and large-scale uniform morphology, the hierarchical Ag-NP@Ge-nanotaper/Si-micropillar arrays exhibit strong and reproducible SERS activity. Using our hierarchical 3D SERS-substrates, both methyl parathion (a commonly used pesticide) and PCB-2 (one congener of highly toxic polychlorinated biphenyls) with concentrations down to 10-7 M and 10-5 M have been detected respectively, showing great potential in SERS-based rapid trace-level detection of toxic organic pollutants in the environment.Surface-enhanced Raman scattering (SERS) is considered to be an excellent candidate for analytical detection schemes, because of its molecular specificity, rapid response and high sensitivity. Here, SERS-substrates of Ag-nanoparticle (Ag-NP) decorated Ge-nanotapers grafted on hexagonally ordered Si-micropillar (denoted as Ag-NP@Ge-nanotaper/Si-micropillar) arrays are fabricated via a combinatorial process of two-step etching to achieve hexagonal Si-micropillar arrays, chemical vapor deposition of flocky Ge-nanotapers on each Si-micropillar and decoration of Ag-NPs onto the Ge-nanotapers through galvanic displacement. With high density three-dimensional (3D) ``hot spots'' created from the large quantities of the neighboring Ag-NPs and large-scale uniform morphology, the hierarchical Ag-NP@Ge-nanotaper/Si-micropillar arrays exhibit strong and reproducible SERS activity. Using our hierarchical 3D SERS-substrates, both methyl parathion (a commonly used pesticide) and PCB-2 (one congener of highly toxic polychlorinated biphenyls) with concentrations down to 10-7 M and 10-5 M have been detected respectively, showing great potential in SERS-based rapid trace-level detection of toxic organic pollutants in the environment. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06001j

A Mechanism of Male Germ Cell Apoptosis Induced by Bisphenol-A and Nonylphenol Involving ADAM17 and p38 MAPK Activation

PubMed Central

Moreno, Ricardo D.

2014-01-01

Germ cell apoptosis regulation is pivotal in order to maintain proper daily sperm production. Several reports have shown that endocrine disruptors such as Bisphenol-A (BPA) and Nonylphenol (NP) induce germ cell apoptosis along with a decrease in sperm production. Given their ubiquitous distribution in plastic products used by humans it is important to clarify their mechanism of action. TACE/ADAM17 is a widely distributed extracellular metalloprotease and participates in the physiological apoptosis of germ cells during spermatogenesis. The aims of this work were: 1) to determine whether BPA and NP induce ADAM17 activation; and 2) to study whether ADAM17 and/or ADAM10 are involved in germ cell apoptosis induced by BPA and NP in the pubertal rat testis. A single dose of BPA or NP (50 mg/kg) induces germ cell apoptosis in 21-day-old male rats, which was prevented by a pharmacological inhibitor of ADAM17, but not by an inhibitor of ADAM10. In vitro, we showed that BPA and NP, at similar concentrations to those found in human samples, induce the shedding of exogenous and endogenous (TNF-α) ADAM17 substrates in primary rat Sertoli cell cultures and TM4 cell line. In addition, pharmacological inhibitors of metalloproteases and genetic silencing of ADAM17 prevent the shedding induced in vitro by BPA and NP. Finally, we showed that in vivo BPA and NP induced early activation (phosphorylation) of p38 MAPK and translocation of ADAM17 to the cell surface. Interestingly, the inhibition of p38 MAPK prevents germ cell apoptosis and translocation of ADAM17 to the cell surface. These results show for the first time that xenoestrogens can induce activation of ADAM17 at concentrations similar to those found in human samples, suggesting a mechanism by which they could imbalance para/juxtacrine cell-to-cell-communication and induce germ cell apoptosis. PMID:25474107

Formation of Fe nanoparticles on water-washed coal fly ash for enhanced reduction of p-nitrophenol.

PubMed

Park, Jaehyeong; Bae, Sungjun

2018-07-01

The catalytic reduction of p-nitrophenol (p-NP) by coal fly ash (FA) washed with water was investigated in this study. A significant increase in pH (from 7.0 to 10.1) was observed in the suspension of raw fly ash (RFA), while water-washed fly ash (WFA) showed a relatively lower increase in pH (7.2), which was caused by the dissolution of Ca species during the water-washing process. Almost 33.4% of p-NP reduction was observed in the RFA suspension with NaBH 4 in 1 h, while the enhanced reduction of p-NP (87.2%) was observed in the WFA suspension. The catalytic reduction of p-NP was inhibited by addition of CaO and Ca(OH) 2 , indicating that higher amount of CaO dissolved from RFA resulted in the inhibition effect. Similar experiments using different oxides (i.e., Al 2 O 3 , SiO 2 , CaO and MgO) revealed no significant reduction of p-NP, which was comparable with Fe 2 O 3 (75.8%). Results from various surface analyses revealed that iron oxides on the surface of WFA can be reduced to elemental Fe nanoparticles, which can effectively reduce p-NP with NaBH 4 . No significant leaching of heavy metals such as Cr, Pb, and As was observed during the catalytic reduction of p-NP and in the suspension of WFA after reaction at pH 3, 5, 7, and 9 for 24 h, which can solve the toxic effect when the FA is used for environmental applications. We also observed a good reusability of WFA during the recycling test, indicating the potential use of WFA for the treatment of wastewater containing reductively degradable pollutants. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mucosal immunization with PspA (Pneumococcal surface protein A)-adsorbed nanoparticles targeting the lungs for protection against pneumococcal infection

PubMed Central

Rodrigues, Tasson C.; Oliveira, Maria Leonor S.; Soares-Schanoski, Alessandra; Chavez-Rico, Stefanni L.; Figueiredo, Douglas B.; Gonçalves, Viviane M.; Ferreira, Daniela M.; Kunda, Nitesh K.; Saleem, Imran Y.

2018-01-01

Burden of pneumonia caused by Streptococcus pneumoniae remains high despite the availability of conjugate vaccines. Mucosal immunization targeting the lungs is an attractive alternative for the induction of local immune responses to improve protection against pneumonia. Our group had previously described the development of poly(glycerol adipate-co-ω-pentadecalactone) (PGA-co-PDL) polymeric nanoparticles (NPs) adsorbed with Pneumococcal surface protein A from clade 4 (PspA4Pro) within L-leucine microcarriers (nanocomposite microparticles—NCMPs) for mucosal delivery targeting the lungs (NP/NCMP PspA4Pro). NP/NCMP PspA4Pro was now used for immunization of mice. Inoculation of this formulation induced anti-PspA4Pro IgG antibodies in serum and lungs. Analysis of binding of serum IgG to intact bacteria showed efficient binding to bacteria expressing PspA from clades 3, 4 and 5 (family 2), but no binding to bacteria expressing PspA from clades 1 and 2 (family 1) was observed. Both mucosal immunization with NP/NCMP PspA4Pro and subcutaneous injection of the protein elicited partial protection against intranasal lethal pneumococcal challenge with a serotype 3 strain expressing PspA from clade 5 (PspA5). Although similar survival levels were observed for mucosal immunization with NP/NCMP PspA4Pro and subcutaneous immunization with purified protein, NP/NCMP PspA4Pro induced earlier control of the infection. Conversely, neither immunization with NP/NCMP PspA4Pro nor subcutaneous immunization with purified protein reduced bacterial burden in the lungs after challenge with a serotype 19F strain expressing PspA from clade 1 (PspA1). Mucosal immunization with NP/NCMP PspA4Pro targeting the lungs is thus able to induce local and systemic antibodies, conferring protection only against a strain expressing PspA from the homologous family 2. PMID:29360883

Effect of environmentally-relevant concentrations of nonylphenol on sexual differentiation in zebrafish: a multi-generational study

NASA Astrophysics Data System (ADS)

Sun, Dong; Chen, Qi; He, Ning; Diao, Pan-Pan; Jia, Li-Xing; Duan, Shun-Shan

2017-02-01

Nonylphenol (NP) is a persistent environmental chemical that can disrupt the organism’s endocrine system, and is detected in the surface water and sea. In this study, we investigated whether NP can alter transcriptional expression of sexual differentiation-related genes. Three generations of zebrafish were exposed to 0, 2, 20 and 200 μg·L-1 of NP, and transcriptional expression of sexual differentiation genes were assessed in 10, 20 and 40 dpf in the F1 and F2 generations. Growth of zebrafish exposed to 200 μg·L-1 of NP was inhibited at 125 dpf in the F1 generation. 20 μg·L-1 of NP resulted in 80% females in the F1 generation, but had no effect on the F2 generation. In terms of the sexual differentiation genes, the transcriptional expression of cyp19a1a and esr1 genes were upregulated in 20 μg·L-1 of NP in the F1 generation. But expression of the sexual differentiation genes were not affected in the F2 generation. Overall, NP could affect sexual differentiation and gene transcriptional expression in the F1 generation. The tolerance of contaminant in the offsprings was improved at low concentration.

Preparation of nanodispersions by solvent displacement using the Venturi tube.

PubMed

García-Salazar, Gilberto; de la Luz Zambrano-Zaragoza, María; Quintanar-Guerrero, David

2018-05-02

The Venturi tube (VT) is an apparatus that produces turbulence which is taken advantage of to produce nanoparticles (NP) by solvent displacement. The objective of this study was to evaluate the potential of this device for preparing NP of poly-ε-caprolactone. Response Surface Methodology was used to determine the effect of the operating conditions and optimization. The NP produced by VT were characterized by Dynamic Light-Scattering to determine their particle size distribution (PS) and polydispersity index (PDI). Results showed that the Reynolds number (Re) has a strong effect on both PS and process yield (PY).The turbulence regime is key to the efficient formation of NP. The optimal conditions for obtaining NP were a polymer concentration of 1.6 w/v, a recirculation rate of 4.8 L/min, and a stabilizer concentration of 1.1 w/v. The predicted response of the PY was 99.7%, with a PS of 333 nm, and a PDI of 0.2. Maintaining the same preparation conditions will make it possible to obtain NP using other polymers with similar properties. Our results show that VT is a reproducible and versatile method for manufacturing NP, and so may be a feasible method for industrial-scale nanoprecipitation production. Copyright © 2018 Elsevier B.V. All rights reserved.

Anodization Mechanism on SiC Nanoparticle Reinforced Al Matrix Composites Produced by Power Metallurgy.

PubMed

Ferreira, Sonia C; Conde, Ana; Arenas, María A; Rocha, Luis A; Velhinho, Alexandre

2014-12-19

Specimens of aluminum-based composites reinforced by silicon carbide nanoparticles (Al/SiC np ) produced by powder metallurgy (PM) were anodized under voltage control in tartaric-sulfuric acid (TSA). In this work, the influence of the amount of SiC np on the film growth during anodizing was investigated. The current density versus time response and the morphology of the porous alumina film formed at the composite surface are compared to those concerning a commercial aluminum alloy (AA1050) anodized under the same conditions. The processing method of the aluminum alloys influences the efficiency of the anodizing process, leading to a lower thicknesses for the unreinforced Al-PM alloy regarding the AA1050. The current density versus time response is strongly dependent on the amount of SiC np . The current peaks and the steady-state current density recorded at each voltage step increases with the SiC np volume fraction due to the oxidation of the SiC np . The formation mechanism of the anodic film on Al/SiC np composites is different from that occurring in AA1050, partly due the heterogeneous distribution of the reinforcement particles in the metallic matrix, but also to the entrapment of SiC np in the anodic film.

Divergent Mechanisms for Passive Pneumococcal Resistance to β-Lactam Antibiotics in the Presence of Haemophilus influenzae

PubMed Central

Weimer, Kristin E.D.; Juneau, Richard A.; Murrah, Kyle A.; Pang, Bing; Armbruster, Chelsie E.; Richardson, Stephen H.

2011-01-01

Background. Otitis media, for which antibiotic treatment failure is increasingly common, is a leading pediatric public health problem. Methods. In vitro and in vivo studies using the chinchilla model of otitis media were performed using a β-lactamase-producing strain of nontypeable Haemophilus influenzae (NTHi 86-028NP) and an isogenic mutant deficient in β-lactamase production (NTHi 86-028NP bla) to define the roles of biofilm formation and β-lactamase production in antibiotic resistance. Coinfection studies were done with Streptococcus pneumoniae to determine if NTHi provides passive protection by means of β-lactamase production, biofilm formation, or both. Results. NTHi 86-028NP bla was resistant to amoxicillin killing in biofilm studies in vitro; however, it was cleared by amoxicillin treatment in vivo, whereas NTHi 86-028NP was unaffected in either system. NTHi 86-028NP protected pneumococcus in vivo in both the effusion fluid and bullar homogenate. NTHi 86-028NP bla and pneumococcus were both recovered from the surface-associated bacteria of amoxicillin-treated animals; only NTHi 86-028NP bla was recovered from effusion. Conclusions. Based on these studies, we conclude that NTHi provides passive protection for S. pneumoniae in vivo through 2 distinct mechanisms: production of β-lactamase and formation of biofilm communities. PMID:21220774

Divergent mechanisms for passive pneumococcal resistance to β-lactam antibiotics in the presence of Haemophilus influenzae.

PubMed

Weimer, Kristin E D; Juneau, Richard A; Murrah, Kyle A; Pang, Bing; Armbruster, Chelsie E; Richardson, Stephen H; Swords, W Edward

2011-02-15

Otitis media, for which antibiotic treatment failure is increasingly common, is a leading pediatric public health problem. In vitro and in vivo studies using the chinchilla model of otitis media were performed using a β-lactamase-producing strain of nontypeable Haemophilus influenzae (NTHi 86-028NP) and an isogenic mutant deficient in β-lactamase production (NTHi 86-028NP bla) to define the roles of biofilm formation and β-lactamase production in antibiotic resistance. Coinfection studies were done with Streptococcus pneumoniae to determine if NTHi provides passive protection by means of β-lactamase production, biofilm formation, or both. NTHi 86-028NP bla was resistant to amoxicillin killing in biofilm studies in vitro; however, it was cleared by amoxicillin treatment in vivo, whereas NTHi 86-028NP was unaffected in either system. NTHi 86-028NP protected pneumococcus in vivo in both the effusion fluid and bullar homogenate. NTHi 86-028NP bla and pneumococcus were both recovered from the surface-associated bacteria of amoxicillin-treated animals; only NTHi 86-028NP bla was recovered from effusion. Based on these studies, we conclude that NTHi provides passive protection for S. pneumoniae in vivo through 2 distinct mechanisms: production of β-lactamase and formation of biofilm communities.

Investigation on the adsorption characteristics of sodium benzoate and taurine on gold nanoparticle film by ATR-FTIR spectroscopy.

PubMed

Kumar, Naveen; Thomas, S; Tokas, R B; Kshirsagar, R J

2014-01-24

Fourier transform infrared (FTIR) spectroscopic studies of sodium benzoate and taurine adsorbed on gold nanoparticle (AuNp) film on silanised glass slides have been studied by attenuated total reflection technique (ATR). The surface morphology of the AuNp films has been measured by Atomic Force Microscopy. The ATR spectra of sodium benzoate and taurine deposited on AuNp film are compared with ATR spectra of their powdered bulk samples. A new red-shifted band appeared along with the symmetric and asymmetric stretches of carboxylate group of sodium benzoate leading to a broadening of the above peaks. Similar behavior is also seen in the case of symmetric and asymmetric stretches of sulphonate group of taurine. The results indicate presence of both chemisorbed and physisorbed layers of both sodium benzoate and taurine on the AuNp film with bottom layer chemically bound to AuNp through carboxylate and sulphonate groups respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

Toward a molecular understanding of nanoparticle-protein interactions.

PubMed

Treuel, Lennart; Nienhaus, Gerd Ulrich

2012-06-01

Wherever nanoparticles (NPs) come in contact with a living organism, physical and chemical interactions take place between the surfaces of the NPs and biomatter, in particular proteins. When NP are exposed to biological fluids, an adsorption layer of proteins, a "protein corona" forms around the NPs. Consequently, living systems interact with the protein-coated NP rather than with a bare NP. To anticipate biological responses to NPs, we thus require comprehensive knowledge of the interactions at the bio-nano interface. In recent years, a wide variety of biophysical techniques have been employed to elucidate mechanistic aspects of NP-protein interactions. In this brief review, we present the latest findings regarding the composition of the protein corona as it forms on NPs in the blood stream. We also discuss molecular aspects of this adsorption layer and its time evolution. The current state of knowledge is summarized, and issues that still need to be addressed to further advance our understanding of NP-protein interactions are identified.

Comprehensive characterizations of nanoparticle biodistribution following systemic injection in mice

NASA Astrophysics Data System (ADS)

Liao, Wei-Yin; Li, Hui-Jing; Chang, Ming-Yao; Tang, Alan C. L.; Hoffman, Allan S.; Hsieh, Patrick C. H.

2013-10-01

Various nanoparticle (NP) properties such as shape and surface charge have been studied in an attempt to enhance the efficacy of NPs in biomedical applications. When trying to undermine the precise biodistribution of NPs within the target organs, the analytical method becomes the determining factor in measuring the precise quantity of distributed NPs. High performance liquid chromatography (HPLC) represents a more powerful tool in quantifying NP biodistribution compared to conventional analytical methods such as an in vivo imaging system (IVIS). This, in part, is due to better curve linearity offered by HPLC than IVIS. Furthermore, HPLC enables us to fully analyze each gram of NPs present in the organs without compromising the signals and the depth-related sensitivity as is the case in IVIS measurements. In addition, we found that changing physiological conditions improved large NP (200-500 nm) distribution in brain tissue. These results reveal the importance of selecting analytic tools and physiological environment when characterizing NP biodistribution for future nanoscale toxicology, therapeutics and diagnostics.Various nanoparticle (NP) properties such as shape and surface charge have been studied in an attempt to enhance the efficacy of NPs in biomedical applications. When trying to undermine the precise biodistribution of NPs within the target organs, the analytical method becomes the determining factor in measuring the precise quantity of distributed NPs. High performance liquid chromatography (HPLC) represents a more powerful tool in quantifying NP biodistribution compared to conventional analytical methods such as an in vivo imaging system (IVIS). This, in part, is due to better curve linearity offered by HPLC than IVIS. Furthermore, HPLC enables us to fully analyze each gram of NPs present in the organs without compromising the signals and the depth-related sensitivity as is the case in IVIS measurements. In addition, we found that changing physiological conditions improved large NP (200-500 nm) distribution in brain tissue. These results reveal the importance of selecting analytic tools and physiological environment when characterizing NP biodistribution for future nanoscale toxicology, therapeutics and diagnostics. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03954d

Healing of burn wounds by topical treatment: A randomized controlled comparison between silver sulfadiazine and nano-crystalline silver

PubMed Central

Adhya, Abhishek; Bain, Jayanta; Ray, Oindri; Hazra, Avijit; Adhikari, Souvik; Dutta, Gouranga; Ray, Sudhin; Majumdar, Bijay Kumar

2014-01-01

Background: Silver sulfadiazine (SSD) has been the standard topical antimicrobial for burn wounds for decades. Recently, nanometer-sized silver particles are available which have high surface to volume ratio and remain effective even at a very low concentration and minimizes the chance for tissue toxicity due to silver. Hence, we conducted a randomized controlled trial to compare the effectiveness of topical SSD and nano-crystalline silver (AgNP) hydrogel in burn wounds management. Materials and Methods: Study was conducted in the Burn Unit of IPGME&R & SSKM Hospital Calcutta, from January 2011 to August 2012. Patients with 2° burn injury were randomly allocated to SSD and AgNP treatment group. Clinical assessments of burn wound were done on every week till 4th week and on completion of treatment. Results: Data for evaluation were obtained for 54 patients on SSD (2° deep-dermal cases 27) and 52 (2° deep-dermal cases 31) on AgNP treatment. Healing status of 2° deep-dermal burns was more satisfactory for AgNP group than SSD treatment at 4 weeks. Among patients receiving AgNP, 80.6% showed at least 50% healing of 2° deep-dermal wounds compared to 48.1% on SSD at 4 weeks (P = 0.001). The figures for complete healing at 4 weeks were, respectively, 4% and 0% (P = 0.116). Conclusions: AgNP can be an effective and superior alternative to SSD for burn wounds, particularly 2° deep-dermal burns. Healing can be expected, in general, in 6 to 8 weeks time, depending upon the extent of body surface involvement. PMID:25538469

Impact and oxidation of single silver nanoparticles at electrode surfaces: one shot versus multiple events† †Electronic supplementary information (ESI) available: Summary of previous studies; Ag NP characterization: TEM and DLS; event duration histogram; maximum current histogram. See DOI: 10.1039/c6sc04483b Click here for additional data file.

PubMed Central

Kang, Minkyung; Bullions, Erin

2017-01-01

Single nanoparticle (NP) electrochemical impacts is a rapidly expanding field of fundamental electrochemistry, with applications from electrocatalysis to electroanalysis. These studies, which involve monitoring the electrochemical (usually current–time, I–t) response when a NP from solution impacts with a collector electrode, have the scope to provide considerable information on the properties of individual NPs. Taking the widely studied oxidative dissolution of individual silver nanoparticles (Ag NPs) as an important example, we present measurements with unprecedented noise (< 5 pA) and time resolution (time constant 100 μs) that are highly revealing of Ag NP dissolution dynamics. Whereas Ag NPs of diameter, d = 10 nm are mostly dissolved in a single event (on the timescale of the measurements), a wide variety of complex processes operate for NPs of larger diameter (d ≥ 20 nm). Detailed quantitative analysis of the I–t features, consumed charge, event duration and impact frequency leads to a major conclusion: Ag NPs undergo sequential partial stripping (oxidative dissolution) events, where a fraction of a NP is electrochemically oxidized, followed by the NP drifting away and back to the tunnelling region before the next partial stripping event. As a consequence, analysis of the charge consumed by single events (so-called “impact coulometry”) cannot be used as a general method to determine the size of colloidal NPs. However, a proper analysis of the I–t responses provides highly valuable information on the transient physicochemical interactions between NPs and polarized surfaces. PMID:28553474

Fabrication of doxorubicin nanoparticles by controlled antisolvent precipitation for enhanced intracellular delivery.

PubMed

Tam, Yu Tong; To, Kenneth Kin Wah; Chow, Albert Hee Lum

2016-03-01

Over-expression of ATP-binding cassette transporters is one of the most important mechanisms responsible for multidrug resistance. Here, we aimed to develop a stable polymeric nanoparticle system by flash nanoprecipitation (FNP) for enhanced anticancer drug delivery into drug resistant cancer cells. As an antisolvent precipitation process, FNP works best for highly lipophilic solutes (logP>6). Thus we also aimed to evaluate the applicability of FNP to drugs with relatively low lipophilicity (logP=1-2). To this end, doxorubicin (DOX), an anthracycline anticancer agent and a P-gp substrate with a logP of 1.3, was selected as a model drug for the assessment. DOX was successfully incorporated into the amphiphilic diblock copolymer, polyethylene glycol-b-polylactic acid (PEG-b-PLA), by FNP using a four-stream multi-inlet vortex mixer. Optimization of key processing parameters and co-formulation with the co-stabilizer, polyvinylpyrrolidone, yielded highly stable, roughly spherical DOX-loaded PEG-b-PLA nanoparticles (DOX.NP) with mean particle size below 100nm, drug loading up to 14%, and drug encapsulation efficiency up to 49%. DOX.NP exhibited a pH-dependent drug release profile with higher cumulative release rate at acidic pHs. Surface analysis of DOX.NP by XPS revealed an absence of DOX on the particle surface, indicative of complete drug encapsulation. While there were no significant differences in cytotoxic effect on P-gp over-expressing LCC6/MDR cell line between DOX.NP and free DOX in buffered aqueous media, DOX.NP exhibited a considerably higher cellular uptake and intracellular retention after efflux. The apparent lack of cytotoxicity enhancement with DOX.NP may be attributable to its slow DOX release inside the cells. Copyright © 2015 Elsevier B.V. All rights reserved.