Simulation studies on structural and thermal properties of alkane thiol capped gold nanoparticles.

PubMed

Devi, J Meena

2017-06-01

The structural and thermal properties of the passivated gold nanoparticles were explored employing molecular dynamics simulation for the different surface coverage densities of the self-assembled monolayer (SAM) of alkane thiol. The structural properties of the monolayer protected gold nanoparticles such us overall shape, organization and conformation of the capping alkane thiol chains were found to be influenced by the capping density. The structural order of the thiol capped gold nanoparticles enhances with the increase in the surface coverage density. The specific heat capacity of the alkane thiol capped gold nanoparticles was found to increase linearly with the thiol coverage density. This may be attributed to the enhancement in the lattice vibrational energy. The present simulation results suggest, that the structural and thermal properties of the alkane thiol capped gold nanoparticles may be modified by the suitable selection of the SAM coverage density. Copyright © 2017 Elsevier Inc. All rights reserved.

Effect of Nanoparticle Surface on the HPLC Elution Profile of Liposomal Nanoparticles.

PubMed

Itoh, Naoki; Yamamoto, Eiichi; Santa, Tomofumi; Funatsu, Takashi; Kato, Masaru

2016-06-01

Nanoparticles have been used in diverse areas, and even broader applications are expected in the future. Since surface modification can influence the configuration and toxicity of nanoparticles, a rapid screening method is important to ensure nanoparticle quality. We examined the effect of the nanoparticle surface morphology on the HPLC elution profile using two types of 100-nm liposomal nanoparticles (AmBisome(Ⓡ) and DOXIL(Ⓡ)). These 100-nm-sized nanoparticles eluted before the holdup time (about 4 min), even when a column packed with particles with a relatively large pore size (30 nm) was used. The elution time of the nanoparticles increased with pegylation of the nanoparticles and protein adsorption to the nanoparticles; however, the nanoparticles still eluted before the holdup time. The results of this study indicate that HPLC is a suitable tool for rapid evaluation of the surface of liposomal nanoparticles.

Dispersion of ceria nanoparticles on γ-alumina surface functionalized using long chain carboxylic acids

NASA Astrophysics Data System (ADS)

Ledwa, Karolina Anna; Kępiński, Leszek

2017-04-01

Dispersion and stability of nanoparticles on a support is determined by the interaction between these phases. In case of hydrophobic nanoparticles (e.g. synthesized by reverse microemulsion method) the interaction with hydrophilic support (e.g. γ-Al2O3) is weak and agglomeration as well as poor resistance to sintering may cause problems. The bonding of the particles to the support may be effectively strengthened by proper modification of the support, e.g. by adsorption of hydrophobic compounds on its surface. In this work decanoic, myristic, stearic and oleic acid were used for the first time to cover γ-Al2O3 surface in order to enhance the dispersion of ceria nanoparticles deposited afterward by impregnation on such support. TGA and FTIR methods revealed that at monolayer coverage (1.1-2.5 molecules per nm2) the acid molecules are firmly bounded to the alumina surface. Morphology, textural properties, phase composition and reducibility of the CeO2/γ-Al2O3 samples were investigated using TEM, SEM, BET, XRD and H2-TPR methods. It has been shown that deposition of CeO2 nanoparticles on γ-Al2O3 surface covered with all studied acids enhances its dispersion, stability and reducibility. The most effective modification of the γ-Al2O3 surface was obtained at loading of 2.3 molecules of decanoic acid per nm2 of the support.

Phosphonic Acids on an Atomically Defined Oxide Surface: The Binding Motif Changes with Surface Coverage.

PubMed

Schuschke, Christian; Schwarz, Matthias; Hohner, Chantal; Silva, Thais N; Fromm, Lukas; Döpper, Tibor; Görling, Andreas; Libuda, Jörg

2018-04-19

We have studied the anchoring mechanism of a phosphonic acid on an atomically defined oxide surface. Using time-resolved infrared reflection absorption spectroscopy, we investigated the reaction of deuterated phenylphosphonic acid (DPPA, C 6 H 5 PO 3 D 2 ) with an atomically defined Co 3 O 4 (111) surface in situ during film growth by physical vapor deposition. We show that the binding motif of the phosphonate anchor group changes as a function of coverage. At low coverage, DPPA binds in the form of a chelating tridentate phosphonate, while a transition to a chelating bidentate occurs close to monolayer saturation coverage. However, the coverage-dependent change in the binding motif is not associated with a major change of the molecular orientation, suggesting that the rigid phosphonate linker always maintains the DPPA in a strongly tilted orientation irrespective of the surface coverage.

Influence of particle size and water coverage on the thermodynamic properties of water confined on the surface of SnO2 cassiterite nanoparticles

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

Spencer, Elinor; Ross, Dr. Nancy; Parker, Stewart F.

2011-01-01

Inelastic neutron scattering (INS) data for SnO2 nanoparticles of three different sizes and varying hydration levels are presented. Data were recorded on five nanoparticle samples that had the following compositions: 2 nm SnO2*0.82H2O, 6 nm SnO2*0.055H2O, 6 nm SnO2*0.095H2O, 20 nm SnO2*0.072H2O, and 20 nm SnO2*0.092H2O. The isochoric heat capacity and vibrational entropy values at 298 K for the water confined on the surface of these nanoparticles were calculated from the vibrational density of states that were extracted from the INS data. This study has shown that the hydration level of the SnO2 nanoparticles influences the thermodynamic properties of themore » water layers and, most importantly, that there appears to be a critical size limit for SnO2 between 2 and 6 nm below which the particle size also affects these properties and above which it does not. These results have been compared with those for isostructural rutile-TiO2 nanoparticles [TiO2*0.22H2O and TiO2*0.37H2O], which indicated that water on the surface of TiO2 nanoparticles is more tightly bound and experiences a greater degree of restricted motion with respect to water on the surface of SnO2 nanoparticles. This is believed to be a consequence of the difference in chemical composition, and hence surface properties, of these metal oxide nanoparticles.« less

SERS-activating effect of chlorides on borate-stabilized silver nanoparticles: formation of new reduced adsorption sites and induced nanoparticle fusion.

PubMed

Sloufová, Ivana; Sisková, Karolína; Vlcková, Blanka; Stepánek, Josef

2008-04-28

Changes in morphology, surface reactivity and surface-enhancement of Raman scattering induced by modification of borate-stabilized Ag nanoparticles by adsorbed chlorides have been explored using TEM, EDX analysis and SERS spectra of probing adsorbate 2,2'-bipyridine (bpy) excited at 514.5 nm and evaluated by factor analysis. At fractional coverages of the parent Ag nanoparticles by adsorbed chlorides <0.6, the Ag colloid/Cl(-)/bpy systems were found to be constituted by fractal aggregates of Ag nanoparticles fairly uniform in size (10 +/- 2 nm) and SERS spectra of Ag(+)-bpy surface species were detected. The latter result was interpreted in terms of the presence of oxidized Ag(+) and/or Ag(n)(+) adsorption sites, which have been encountered also in systems with the chemically untreated Ag nanoparticles. At chloride coverages >0.6, a fusion of fractal aggregates into the compact aggregates of touching and/or interpenetrating Ag nanoparticles has been observed and found to be accompanied by the formation of another surface species, Ag-bpy, as well as by the increase of the overall SERS enhancement of bpy by factor of 40. The same Ag-bpy surface species has been detected under the strongly reducing conditions of reduction of silver nitrate by sodium borohydride in the presence of bpy. The formation of Ag-bpy is thus interpreted in terms of the stabilization of reduced Ag(0) adsorption sites by adsorbed bpy. The formation of reduced adsorption sites on Ag nanoparticle surfaces at chloride coverages >0.6 is discussed in terms of local changes in the work function of Ag. Finally, the SERS spectral detection of Ag-bpy species is proposed as a tool for probing the presence of reduced Ag(0) adsorption sites in systems with chemically modified Ag nanoparticles.

Diamond-coated ATR prism for infrared absorption spectroscopy of surface-modified diamond nanoparticles

NASA Astrophysics Data System (ADS)

Remes, Z.; Kozak, H.; Rezek, B.; Ukraintsev, E.; Babchenko, O.; Kromka, A.; Girard, H. A.; Arnault, J.-C.; Bergonzo, P.

2013-04-01

Linear antenna microwave chemical vapor deposition process was used to homogeneously coat a 7 cm long silicon prism by 85 nm thin nanocrystalline diamond (NCD) layer. To show the advantages of the NCD-coated prism for attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) of nanoparticles, we apply diamond nanoparticles (DNPs) of 5 nm nominal size with various surface modifications by a drop-casting of their methanol dispersions. ATR-FTIR spectra of as-received, air-annealed, plasma-oxidized, and plasma-hydrogenated DNPs were measured in the 4000-1500 cm-1 spectral range. The spectra show high spectral resolution, high sensitivity to specific DNP surface moieties, and repeatability. The NCD coating provides mechanical protection against scratching and chemical stability of the surface. Moreover, unlike on bare Si surface, NCD hydrophilic properties enable optically homogeneous coverage by DNPs with some aggregation on submicron scale as evidenced by scanning electron microscopy and atomic force microscopy. Compared to transmission FTIR regime with KBr pellets, direct and uniform deposition of DNPs on NCD-ATR prism significantly simplifies and speeds up the analysis (from days to minutes). We discuss prospects for in situ monitoring of surface modifications and molecular grafting.

Surface patterning of nanoparticles with polymer patches

NASA Astrophysics Data System (ADS)

Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse; Klinkova, Anna; Larin, Egor M.; Querejeta-Fernández, Ana; Han, Lili; Xin, Huolin L.; Gang, Oleg; Zhulina, Ekaterina B.; Rubinstein, Michael; Kumacheva, Eugenia

2016-10-01

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules, serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient, but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties. At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles, and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. Here we demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. These patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.

Surface patterning of nanoparticles with polymer patches

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

Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties.more » At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. We demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. Furthermore, these patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.« less

Surface patterning of nanoparticles with polymer patches

DOE PAGES

Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse; ...

2016-08-24

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties.more » At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. We demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. Furthermore, these patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.« less

Correlation of surface enhanced Raman spectroscopy and nanoparticle aggregation with rhodamine 6G

NASA Astrophysics Data System (ADS)

Hoff, Christopher A.

Surface enhanced Raman spectroscopy (SERS) has fascinated the analytical chemistry field for decades. The SERS phenomenon has progressively leveraged the inherently insensitive Raman phenomenon from a novelty vibrational spectroscopy method into one capable of single molecule detection, with attendant molecular level selectivity and information. Yet, even after 40 years since its discovery, the core mechanism behind this phenomenon is still debated. This thesis presents results from a series of photometric titrations wherein solutions of 30 nm Au@Ag nanoparticles (NPs) were titrated with rhodamine 6G (R6G), spanning five orders of magnitude in R6G concentration, and which elucidate the conditions required for the onset of SERS by R6G in this system. The experiments illustrated the correlation between the Raman response and the plasmonic (via UV-Vis spectroscopy) properties of the nanoparticle solutions. It was found that the onset of R6G SERS was related much more closely to the aggregation of the nanoparticles in solution than to their R6G adsorbed surface coverage. However, triggering aggregation with sodium chloride appeared to enhance SERS by an independent mechanism, which is operative only at low, i.e., [NaCl] > 100 mM concentration.

Surface Coverage and Metallicity of ZnO Surfaces from First-Principles Calculations

NASA Astrophysics Data System (ADS)

Zhang, Xiao; Schleife, Andre; The Schleife research Group Team

Zinc oxide (ZnO) surfaces are widely used in different applications such as catalysis, biosensing, and solar cells. These surfaces are, in many cases, chemically terminated by hydroxyl groups. In experiment, a transition of the ZnO surface electronic properties from semiconducting to metallic was reported upon increasing the hydroxyl coverage to more than approximately 80 %. The reason for this transition is not well understood yet. We report on first-principles calculations based on density functional theory for the ZnO [ 10 1 0 ] surface, taking different amounts of hydroxyl coverage into account. We calculated band structures for fully relaxed configurations and verified the existence of this transition. However, we only find the fully covered surface to be metallic. We thus explore the possibility for clustering of the surface-terminating hydroxyl groups based on total-energy calculations. We also found that the valence band maximum consists of oxygen p states from both the surface hydroxyl groups and the surface oxygen atoms of the material. The main contribution to the metallicity is found to be from the hydroxyl groups.

Toward rational nanoparticle synthesis: predicting surface intermixing in bimetallic alloy nanocatalysts

DOE PAGES

Roling, Luke T.; Mavrikakis, Manos

2017-09-19

In this paper, we present a database of first-principles calculated activation energy barriers for two competitive processes involving bimetallic adatom-surface permutations of ten transition metals: (i) adatom “hopping” diffusion and (ii) adatom substitution into the surface. We consider the surface structure sensitivity of these events as well as coverage effects. We find that surface hopping mechanisms are facile and always preferred to substitution events on close-packed fcc(111) and hcp(0001) surfaces. However, surface atom substitution is more facile on the more open fcc(100) surfaces and is competitive with adatom surface hopping, which is more difficult than on the close-packed surfaces. Finally,more » by comparing the absolute and relative magnitudes of the energetics of hopping and substitution, our calculations can offer qualitative predictions of intermixing and other phenomena relevant to nanocrystal growth, such as the tendency to form intermixed alloys or core–shell structures during layer-by-layer nanoparticle synthesis involving a given bimetallic pair, and thereby inform the rational design and synthesis of novel bimetallic nanomaterials.« less

Adsorption of bovine serum albumin on silicon dioxide nanoparticles: Impact of pH on nanoparticle-protein interactions.

PubMed

Givens, Brittany E; Diklich, Nina D; Fiegel, Jennifer; Grassian, Vicki H

2017-05-03

Bovine serum albumin (BSA) adsorbed on amorphous silicon dioxide (SiO 2 ) nanoparticles was studied as a function of pH across the range of 2 to 8. Aggregation, surface charge, surface coverage, and protein structure were investigated over this entire pH range. SiO 2 nanoparticle aggregation is found to depend upon pH and differs in the presence of adsorbed BSA. For SiO 2 nanoparticles truncated with hydroxyl groups, the largest aggregates were observed at pH 3, close to the isoelectric point of SiO 2 nanoparticles, whereas for SiO 2 nanoparticles with adsorbed BSA, the aggregate size was the greatest at pH 3.7, close to the isoelectric point of the BSA-SiO 2 complex. Surface coverage of BSA was also the greatest at the isoelectric point of the BSA-SiO 2 complex with a value of ca. 3 ±   1 × 10 11 molecules cm -2 . Furthermore, the secondary protein structure was modified when compared to the solution phase at all pH values, but the most significant differences were seen at pH 7.4 and below. It is concluded that protein-nanoparticle interactions vary with solution pH, which may have implications for nanoparticles in different biological fluids (e.g., blood, stomach, and lungs).

Effect of the size of silver nanoparticles on SERS signal enhancement

NASA Astrophysics Data System (ADS)

He, Rui Xiu; Liang, Robert; Peng, Peng; Norman Zhou, Y.

2017-08-01

The localized surface plasmon resonance arising from plasmonic materials is beneficial in solution-based and thin-film sensing applications, which increase the sensitivity of the analyte being tested. Silver nanoparticles from 35 to 65 nm in diameter were synthesized using a low-temperature method and deposited in a monolayer on a (3-aminopropyl)triethoxysilane (APTES)-functionalized glass slide. The effect of particle size on monolayer structure, optical behavior, and surface-enhanced Raman scattering (SERS) is studied. While increasing particle size decreases particle coverage, it also changes the localized surface plasmon resonance and thus the SERS activity of individual nanoparticles. Using a laser excitation wavelength of 633 nm, the stronger localized surface plasmon resonance coupling to this excitation wavelength at larger particle sizes trumps the loss in surface coverage, and greater SERS signals are observed. The SERS signal enhancement accounts for the higher SERS signal, which was verified using a finite element model of a silver nanoparticle dimer with various nanoparticle sizes and separation distances.

Development of a highly transparent superamphiphobic plastic sheet by nanoparticle and chemical coating.

PubMed

Wong, Ten It; Wang, Hao; Wang, Fuke; Sin, Sau Leng; Quan, Cheng Gen; Wang, Shi Jie; Zhou, Xiaodong

2016-04-01

A highly transparent superamphiphobic plastic sheet was developed. The plastic sheet polymethyl methacrylate (PMMA) was spin-coated on a glass substrate. Synthesized silica nanoparticles were sprayed on PMMA, followed by fluorosilane drop-coating. The results of contact angle measurements show that the developed PMMA sheet has superamphiphobic properties with high advancing contact angles for water (154°), toluene (139°), and silicone oil (132.9°). The amphiphobicity of the plastic sheet can be tuned by the surface coverage of the silica nanoparticles distributed on the PMMA surface. The surface coverage of the nanoparticles on our PMMA sheet is about 20%, and it agrees with our contact angle calculations for the sheet with and without nanoparticles. Copyright © 2016 Elsevier Inc. All rights reserved.

Understanding electric field-enhanced transport for the measurement of nanoparticles and their assembly on surfaces

NASA Astrophysics Data System (ADS)

Tsai, De-Hao

The goal of this dissertation is to understand the synthesis, characterization, and integration of nanoparticles and nanoparticle-based devices by electric field-enhanced transport of nanoparticles. Chapter I describes the factors used for determining particle trajectories and found that electric fields provide the directional electrostatic force to overcome other non-directional influences on particle trajectories. This idea is widely applied in the nanoparticle classification, characterization, and assembly onto substrate surfaces as investigated in the following chapters. Chapter 2 presents a new assembly method to position metal nanoparticles delivered from the gas phase onto surfaces using the electrostatic force generated by biased p-n junction patterned substrates. Aligned deposition patterns of metal nanoparticles were observed, and the patterning selectivity quantified. A simple model accounting for the generated electric field, and the electrostatic, van der Waals, and image forces was used to explain the observed results. Chapter 2.2 describes a data set for particle size resolved deposition, from which a Brownian dynamics model for the process can be evaluated. Brownian motion and fluid convection of nanoparticles, as well as the interactions between the charged nanoparticles and the patterned substrate, including electrostatic force, image force and van der Waals force, are accounted for in the simulation. Using both experiment and simulation the effects of the particle size, electric field intensity, and the convective flow on coverage selectivity have been investigated. Coverage selectivity is most sensitive to electric field, which is controlled by the applied reverse bias voltage across the p-n junction. A non-dimensional analysis of the competition between the electrostatic and diffusion force is found to provide a means to collapse a wide range of process operating conditions and an effective indicator or process performance. Directed assembly of

EEG source localization: Sensor density and head surface coverage.

PubMed

Song, Jasmine; Davey, Colin; Poulsen, Catherine; Luu, Phan; Turovets, Sergei; Anderson, Erik; Li, Kai; Tucker, Don

2015-12-30

The accuracy of EEG source localization depends on a sufficient sampling of the surface potential field, an accurate conducting volume estimation (head model), and a suitable and well-understood inverse technique. The goal of the present study is to examine the effect of sampling density and coverage on the ability to accurately localize sources, using common linear inverse weight techniques, at different depths. Several inverse methods are examined, using the popular head conductivity. Simulation studies were employed to examine the effect of spatial sampling of the potential field at the head surface, in terms of sensor density and coverage of the inferior and superior head regions. In addition, the effects of sensor density and coverage are investigated in the source localization of epileptiform EEG. Greater sensor density improves source localization accuracy. Moreover, across all sampling density and inverse methods, adding samples on the inferior surface improves the accuracy of source estimates at all depths. More accurate source localization of EEG data can be achieved with high spatial sampling of the head surface electrodes. The most accurate source localization is obtained when the voltage surface is densely sampled over both the superior and inferior surfaces. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Quantitation of Surface Coating on Nanoparticles Using Thermogravimetric Analysis.

PubMed

Dongargaonkar, Alpana A; Clogston, Jeffrey D

2018-01-01

Nanoparticles are critical components in nanomedicine and nanotherapeutic applications. Some nanoparticles, such as metallic nanoparticles, consist of a surface coating or surface modification to aid in its dispersion and stability. This surface coating may affect the behavior of nanoparticles in a biological environment, thus it is important to measure. Thermogravimetric analysis (TGA) can be used to determine the amount of coating on the surface of the nanoparticle. TGA experiments run under inert atmosphere can also be used to determine residual metal content present in the sample. In this chapter, the TGA technique and experimental method are described.

Influence of surface coverage on the chemical desorption process

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

Minissale, M.; Dulieu, F., E-mail: francois.dulieu@obspm.fr

2014-07-07

In cold astrophysical environments, some molecules are observed in the gas phase whereas they should have been depleted, frozen on dust grains. In order to solve this problem, astrochemists have proposed that a fraction of molecules synthesized on the surface of dust grains could desorb just after their formation. Recently the chemical desorption process has been demonstrated experimentally, but the key parameters at play have not yet been fully understood. In this article, we propose a new procedure to analyze the ratio of di-oxygen and ozone synthesized after O atoms adsorption on oxidized graphite. We demonstrate that the chemical desorptionmore » efficiency of the two reaction paths (O+O and O+O{sub 2}) is different by one order of magnitude. We show the importance of the surface coverage: for the O+O reaction, the chemical desorption efficiency is close to 80% at zero coverage and tends to zero at one monolayer coverage. The coverage dependence of O+O chemical desorption is proved by varying the amount of pre-adsorbed N{sub 2} on the substrate from 0 to 1.5 ML. Finally, we discuss the relevance of the different physical parameters that could play a role in the chemical desorption process: binding energy, enthalpy of formation, and energy transfer from the new molecule to the surface or to other adsorbates.« less

The impacts of surface polarity on the solubility of nanoparticle

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

Zhu, Jianzhuo; Su, Jiguo, E-mail: jiguosu@ysu.edu.cn; Ou, Xinwen

In order to study the dependence of water solubility and hydration behavior of nanoparticles on their surface polarity, we designed polar nanoparticles with varying surface polarity by assigning atomic partial charge to the surface of C60. The water solubility of the nanoparticle is enhanced by several orders of magnitude after the introduction of surface polarity. Nevertheless, when the atomic partial charge grows beyond a certain value (q{sub M}), the solubility continuously decreases to the level of nonpolar nanoparticle. It should be noted that such q{sub M} is comparable with atomic partial charge of a variety of functional groups. The hydrationmore » behaviors of nanoparticles were then studied to investigate the non-monotonic dependence of solubility on the surface polarity. The interaction between the polar nanoparticle and the hydration water is stronger than the nonpolar counterpart, which should facilitate the dissolution of the nanoparticles. On the other hand, the surface polarity also reduces the interaction of hydration water with the other water molecules and enhances the interaction between the nanoparticles which may hinder their dispersion. Besides, the introduction of surface polarity disturbs and even rearranges the hydration structure of nonpolar nanoparticle. Interestingly, the polar nanoparticle with less ordered hydration structure tends to have higher water solubility.« less

Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeO x–TiO 2(110) surfaces: Effects of high ceria coverage

DOE PAGES

Grinter, D. C.; Park, J. B.; Agnoli, S.; ...

2016-08-01

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO 2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO 2(110)-(1 × 1). For the other half of the surface, it comprised CeO x nanoparticles and reconstructed TiOx supported on TiO 2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film andmore » TiO 2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeO x/TiO 2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO 2(110) and Au/CeO 2(111) systems. Finally, for Au/CeO x/TiO 2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce 3 + formed during WGS reaction conditions.« less

Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeO x–TiO 2(110) surfaces: Effects of high ceria coverage

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

Grinter, D. C.; Park, J. B.; Agnoli, S.

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO 2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO 2(110)-(1 × 1). For the other half of the surface, it comprised CeO x nanoparticles and reconstructed TiOx supported on TiO 2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film andmore » TiO 2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeO x/TiO 2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO 2(110) and Au/CeO 2(111) systems. Finally, for Au/CeO x/TiO 2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce 3 + formed during WGS reaction conditions.« less

A single-step aerosol process for in-situ surface modification of nanoparticles: Preparation of stable aqueous nanoparticle suspensions.

PubMed

Sapra, Mahak; Pawar, Amol Ashok; Venkataraman, Chandra

2016-02-15

Surface modification of nanoparticles during aerosol or gas-phase synthesis, followed by direct transfer into liquid media can be used to produce stable water-dispersed nanoparticle suspensions. This work investigates a single-step, aerosol process for in-situ surface-modification of nanoparticles. Previous studies have used a two-step sublimation-condensation mechanism following droplet drying, for surface modification, while the present process uses a liquid precursor containing two solutes, a matrix lipid and a surface modifying agent. A precursor solution in chloroform, of stearic acid lipid, with 4 %w/w of surface-active, physiological molecules [1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol)-sodium salt (DPPG) or 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy (polyethylene glycol) 2000]-ammonium salt (DPPE-PEG)] was processed in an aerosol reactor at a low gas temperatures. The surface modified nanoparticles were characterized for morphology, surface composition and suspension properties. Spherical, surface-modified lipid nanoparticles with median mobility diameters in the range of 105-150nm and unimodal size distributions were obtained. Fourier transform infra-red spectroscopy (FTIR) measurements confirmed the presence of surface-active molecules on external surfaces of modified lipid nanoparticles. Surface modified nanoparticles exhibited improved suspension stability, compared to that of pure lipid nanoparticles for a period of 30days. Lowest aggregation was observed in DPPE-PEG modified nanoparticles from combined electrostatic and steric effects. The study provides a single-step aerosol method for in-situ surface modification of nanoparticles, using minimal amounts of surface active agents, to make stable, aqueous nanoparticle suspensions. Copyright © 2015 Elsevier Inc. All rights reserved.

Surface functionalization of WS2 fullerene-like nanoparticles.

PubMed

Shahar, Chen; Zbaida, David; Rapoport, Lev; Cohen, Hagai; Bendikov, Tatyana; Tannous, Johny; Dassenoy, Fabrice; Tenne, Reshef

2010-03-16

WS(2) belongs to a family of layered metal dichalcogenide compounds that are known to form cylindrical (inorganic nanotubes-INT) and polyhedral nanostructures--onion or nested fullerene-like (IF) particles. The outermost layers of these IF nanoparticles can be peeled under shear stress, thus IF nanoparticles have been studied for their use as solid lubricants. However, the IF nanoparticles tend to agglomerate, presumably because of surface structural defects induced by elastic strain and curvature, a fact that has a deleterious effect on their tribological properties. In the present work, chemical modification of the IF-WS(2) surface with alkyl-silane molecules is reported. The surface-modified IF nanoparticles display improved dispersion in oil-based suspensions. The alkyl-silane coating reduces the IF-WS(2) nanoparticles' tendency to agglomerate and consequently improves the long-term tribological behavior of oil formulated with the IF additive.

Surface plasmon resonances in liquid metal nanoparticles

NASA Astrophysics Data System (ADS)

Ershov, A. E.; Gerasimov, V. S.; Gavrilyuk, A. P.; Karpov, S. V.

2017-06-01

We have shown significant suppression of resonant properties of metallic nanoparticles at the surface plasmon frequency during the phase transition "solid-liquid" in the basic materials of nanoplasmonics (Ag, Au). Using experimental values of the optical constants of liquid and solid metals, we have calculated nanoparticle plasmonic absorption spectra. The effect was demonstrated for single particles, dimers and trimers, as well as for the large multiparticle colloidal aggregates. Experimental verification was performed for single Au nanoparticles heated to the melting temperature and above up to full suppression of the surface plasmon resonance. It is emphasized that this effect may underlie the nonlinear optical response of composite materials containing plasmonic nanoparticles and their aggregates.

Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

2012-02-01

The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).

Small nanoparticles, surface geometry and contact forces.

PubMed

Takato, Yoichi; Benson, Michael E; Sen, Surajit

2018-03-01

In this molecular dynamics study, we examine the local surface geometric effects of the normal impact force between two approximately spherical nanoparticles that collide in a vacuum. Three types of surface geometries-(i) crystal facets, (ii) sharp edges, and (iii) amorphous surfaces of small nanoparticles with radii R <10 nm-are considered. The impact forces are compared with their macroscopic counterparts described by nonlinear contact forces based on Hertz contact mechanics. In our simulations, edge and amorphous surface contacts with weak surface energy reveal that the average impact forces are in excellent agreement with the Hertz contact force. On the other hand, facet collisions show a linearly increasing force with increasing compression. Our results suggest that the nearly spherical nanoparticles are likely to enable some nonlinear dynamic phenomena, such as breathers and solitary waves observed in granular materials, both originating from the nonlinear contact force.

In situ assessment of the contact angles of nanoparticles adsorbed at fluid interfaces by multiple angle of incidence ellipsometry.

PubMed

Stocco, Antonio; Su, Ge; Nobili, Maurizio; In, Martin; Wang, Dayang

2014-09-28

Here multiple angle of incidence ellipsometry was successfully applied to in situ assess the contact angle and surface coverage of gold nanoparticles as small as 18 nm, coated with stimuli-responsive polymers, at water-oil and water-air interfaces in the presence of NaCl and NaOH, respectively. The interfacial adsorption of the nanoparticles was found to be very slow and took days to reach a fairly low surface coverage. For water-oil interfaces, in situ nanoparticle contact angles agree with the macroscopic equilibrium contact angles of planar gold surfaces with the same polymer coatings, whilst for water-air interfaces, significant differences have been observed.

Controlling the Nanoscale Patterning of AuNPs on Silicon Surfaces

PubMed Central

Williams, Sophie E.; Davies, Philip R.; Bowen, Jenna L.; Allender, Chris J.

2013-01-01

This study evaluates the effectiveness of vapour-phase deposition for creating sub-monolayer coverage of aminopropyl triethoxysilane (APTES) on silicon in order to exert control over subsequent gold nanoparticle deposition. Surface coverage was evaluated indirectly by observing the extent to which gold nanoparticles (AuNPs) deposited onto the modified silicon surface. By varying the distance of the silicon wafer from the APTES source and concentration of APTES in the evaporating media, control over subsequent gold nanoparticle deposition was achievable to an extent. Fine control over AuNP deposition (AuNPs/μm2) however, was best achieved by adjusting the ionic concentration of the AuNP-depositing solution. Furthermore it was demonstrated that although APTES was fully removed from the silicon surface following four hours incubation in water, the gold nanoparticle-amino surface complex was stable under the same conditions. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) were used to study these affects. PMID:28348330

Formation of positively charged gold nanoparticle monolayers on silica sensors.

PubMed

Oćwieja, Magdalena; Maciejewska-Prończuk, Julia; Adamczyk, Zbigniew; Roman, Maciej

2017-09-01

Formation of positively charged gold nanoparticle monolayers on the Si/SiO 2 was studied under in situ conditions using quartz microbalance (QCM). The gold nanoparticles were synthesized in a chemical reduction method using sodium borohydride as reducing agent. Cysteamine hydrochloride was applied to generate a positive surface charge of nanoparticles. The micrographs obtained from transmission electron microscopy (TEM) revealed that the average size of nanoparticles was equal to 12±3nm. The stability of nanoparticle suspensions under controlled pH and ionic strength was determined by dynamic light scattering (DLS). The electrophoretic mobility measurements showed that the zeta potential of nanoparticles was positive, decreasing with ionic strength and pH from 56mV at pH 4.2 and I=10 -4 M to 22mV at pH 8.3 and I=3×10 -3 M. The surface enhanced Raman spectroscopy (SERS) confirmed chemisorption of cysteamine on nanoparticles and the contribution of amine moieties in the generation of nanoparticle charge. The influence of suspension concentration, ionic strength and flow rate on the kinetics of nanoparticle deposition on the sensors was quantitatively determined. It was confirmed that the deposition for the low coverage regime is governed by the bulk mass transfer that results in a linear increase of the coverage with time. The significant increase in the maximum coverage of gold monolayers with ionic strength was interpreted as due to the decreasing range of the electrostatic interactions among deposited particles. Moreover, the hydratation of formed monolayers, their structure and the stability were determined by the comparison of the QCM results with those obtained by AFM and SEM. The experimental data were adequately interpreted in terms of the extended random sequential adsorption (eRSA) model that considers the bulk and surface transfer steps in a rigorous way. The obtained results are useful for a facile fabrication of gold nanoparticle-based biosensors

Corrosion Prevention of Aluminum Nanoparticles by a Polyurethane Coating.

PubMed

Nishimura, Toshiyasu; Raman, Vedarajan

2014-06-19

In order to prevent corrosion, aluminum nanoparticles were coated with a polyurethane polymer. The coverage of the polyurethane polymer was controlled from 0 to 100%, which changed the corrosion rate of the nanoparticles quantitatively. The surface of the polymer coating was investigated by Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM), and the corrosion resistance of the nanoparticles was estimated by a wet/dry corrosion test on a Pt plate with a NaCl solution. From a TEM with EDAX analysis, the 10 mass% polymer coated Al particles in the synthesis were almost 100% covered on the surface by a polymer film of 10 nm thick. On the other hand, the 3 mass% polymer coated Al was almost 40% covered by a film. In the AFM, the potential around the Al particles had a relatively low value with the polymer coating, which indicated that the conductivity of the Al was isolated from the Pt plate by the polymer. Both the corrosion and H₂ evolution reaction rates were quantitatively reduced by the mass% of polymer coating. In the case of the 10 mass% coated sample, there was no corrosion of Al nanoparticles. This fact suggested that the electrochemical reaction was suppressed by the polymer coating. Moreover, the reaction rate of Al nanoparticles was suppressed in proportion to the coverage percentage of the coating. Thus, to conclude, it was found that the corrosion rate of Al nanoparticles could be quantitatively suppressed by the coverage percentage of the polymer coating.

Surface functionalized magnetic nanoparticles for cancer therapy applications

NASA Astrophysics Data System (ADS)

Wydra, Robert John

Despite recent advances, cancer remains the second leading cause of deaths in the United States. Magnetic nanoparticles have found various applications in cancer research as drug delivery platforms, enhanced contrast agents for improved diagnostic imaging, and the delivery of thermal energy as standalone therapy. Iron oxide nanoparticles absorb the energy from an alternating magnetic field and convert it into heat through Brownian and Neel relaxations. To better utilize magnetic nanoparticles for cancer therapy, surface functionalization is essential for such factors as decreasing cytotoxicity of healthy tissue, extending circulation time, specific targeting of cancer cells, and manage the controlled delivery of therapeutics. In the first study, iron oxide nanoparticles were coated with a poly(ethylene glycol) (PEG) based polymer shell. The PEG coating was selected to prevent protein adsorption and thus improve circulation time and minimize host response to the nanoparticles. Thermal therapy application feasibility was demonstrated in vitro with a thermoablation study on lung carcinoma cells. Building on the thermal therapy demonstration with iron oxide nanoparticles, the second area of work focused on intracellular delivery. Nanoparticles can be appropriately tailored to enter the cell and deliver energy on the nanoscale eliminating individual cancer cells. The underlying mechanism of action is still under study, and we were interested in determining the role of reactive oxygen species (ROS) catalytically generated from the surface of iron oxide nanoparticles in this measured cytotoxicity. When exposed to an AMF, the nanoscale heating effects are capable of enhancing the Fenton-like generation of ROS determined through a methylene blue degradation assay. To deliver this enhanced ROS effect to cells, monosaccharide coated nanoparticles were developed and successfully internalized by colon cancer cell lines. Upon AMF exposure, there was a measured increase in

Molecular effective coverage surface area of optical clearing agents for predicting optical clearing potential

NASA Astrophysics Data System (ADS)

Feng, Wei; Ma, Ning; Zhu, Dan

2015-03-01

The improvement of methods for optical clearing agent prediction exerts an important impact on tissue optical clearing technique. The molecular dynamic simulation is one of the most convincing and simplest approaches to predict the optical clearing potential of agents by analyzing the hydrogen bonds, hydrogen bridges and hydrogen bridges type forming between agents and collagen. However, the above analysis methods still suffer from some problem such as analysis of cyclic molecule by reason of molecular conformation. In this study, a molecular effective coverage surface area based on the molecular dynamic simulation was proposed to predict the potential of optical clearing agents. Several typical cyclic molecules, fructose, glucose and chain molecules, sorbitol, xylitol were analyzed by calculating their molecular effective coverage surface area, hydrogen bonds, hydrogen bridges and hydrogen bridges type, respectively. In order to verify this analysis methods, in vitro skin samples optical clearing efficacy were measured after 25 min immersing in the solutions, fructose, glucose, sorbitol and xylitol at concentration of 3.5 M using 1951 USAF resolution test target. The experimental results show accordance with prediction of molecular effective coverage surface area. Further to compare molecular effective coverage surface area with other parameters, it can show that molecular effective coverage surface area has a better performance in predicting OCP of agents.

Surface modification of protein enhances encapsulation in chitosan nanoparticles

NASA Astrophysics Data System (ADS)

Koyani, Rina D.; Andrade, Mariana; Quester, Katrin; Gaytán, Paul; Huerta-Saquero, Alejandro; Vazquez-Duhalt, Rafael

2018-04-01

Chitosan nanoparticles have a huge potential as nanocarriers for environmental and biomedical purposes. Protein encapsulation in nano-sized chitosan provides protection against inactivation, proteolysis, and other alterations due to environmental conditions, as well as the possibility to be targeted to specific tissues by ligand functionalization. In this work, we demonstrate that the chemical modification of the protein surface enhances the protein loading in chitosan nanocarriers. Encapsulation of green fluorescent protein and the cytochrome P450 was studied. The increase of electrostatic interactions between the free amino groups of chitosan and the increased number of free carboxylic groups in the protein surface enhance the protein loading, protein retention, and, thus, the enzymatic activity of chitosan nanoparticles. The chemical modification of protein surface with malonic acid moieties reduced drastically the protein isoelectric point increasing the protein interaction with the polycationic biomaterial and chitosan. The chemical modification of protein does not alter the morphology of chitosan nanoparticles that showed an average diameter of 18 nm, spheroidal in shape, and smooth surfaced. The strategy of chemical modification of protein surface, shown here, is a simple and efficient technique to enhance the protein loading in chitosan nanoparticles. This technique could be used for other nanoparticles based on polycationic or polyanionic materials. The increase of protein loading improves, doubtless, the performance of protein-loaded chitosan nanoparticles for biotechnological and biomedical applications.

Immobilization of magnetic nanoparticles onto conductive surfaces modified by diazonium chemistry.

PubMed

Ktari, Nadia; Quinson, Jonathan; Teste, Bruno; Siaugue, Jean-Michel; Kanoufi, Frédéric; Combellas, Catherine

2012-08-28

Core-shell γ-Fe(2)O(3)@SiO(2) nanoparticles (NPs) substituted by PEG and NH(2) groups may be immobilized on metal surfaces (glassy carbon or gold) substituted by 4-carboxyphenyl groups through electrostatic interactions. Such immobilization is evidenced by (i) IRRAS owing to the Si-O band, (ii) SEM images, which show that the surface coverage by the NPs is nearly 100%, and (iii) the NPs film thickness measured by ellipsometry or AFM, which corresponds to about one NPs monolayer. Such NPs film is permeable to redox probes, which allows us to propose electrochemical methods based on direct or local measurements as a way to inspect the NPs assembly steps through their ability to alter mass and charge transfer. This process also applies to patterned polystyrene surfaces, and selective immobilization of NPs substituted by amino groups was carried out onto submillimeter patterns obtained by local oxidation. Biological applications are then expected for hyperthermia activation of the NPs to trigger cellular death. Finally, some tests were performed to further derivatize the immobilized NPs onto surfaces through either a covalent bond or electrostatic interactions. Future work will be dedicated to the recovery of such Janus NPs from the substrate surface.

Surface-independent antibacterial coating using silver nanoparticle-generating engineered mussel glue.

PubMed

Jo, Yun Kee; Seo, Jeong Hyun; Choi, Bong-Hyuk; Kim, Bum Jin; Shin, Hwa Hui; Hwang, Byeong Hee; Cha, Hyung Joon

2014-11-26

During implant surgeries, antibacterial agents are needed to prevent bacterial infections, which can cause the formation of biofilms between implanted materials and tissue. Mussel adhesive proteins (MAPs) derived from marine mussels are bioadhesives that show strong adhesion and coating ability on various surfaces even in wet environment. Here, we proposed a novel surface-independent antibacterial coating strategy based on the fusion of MAP to a silver-binding peptide, which can synthesize silver nanoparticles having broad antibacterial activity. This sticky recombinant fusion protein enabled the efficient coating on target surface and the easy generation of silver nanoparticles on the coated-surface under mild condition. The biosynthesized silver nanoparticles showed excellent antibacterial efficacy against both Gram-positive and Gram-negative bacteria and also revealed good cytocompatibility with mammalian cells. In this coating strategy, MAP-silver binding peptide fusion proteins provide hybrid environment incorporating inorganic silver nanoparticle and simultaneously mediate the interaction of silver nanoparticle with surroundings. Moreover, the silver nanoparticles were fully synthesized on various surfaces including metal, plastic, and glass by a simple, surface-independent coating manner, and they were also successfully synthesized on a nanofiber surface fabricated by electrospinning of the fusion protein. Thus, this facile surface-independent silver nanoparticle-generating antibacterial coating has great potential to be used for the prevention of bacterial infection in diverse biomedical fields.

PEG-Stabilized Core–Shell Surface-Imprinted Nanoparticles

PubMed Central

Moczko, Ewa; Guerreiro, Antonio; Piletska, Elena; Piletsky, Sergey

2016-01-01

Here we present a simple technique to produce target-specific molecularly imprinted polymeric nanoparticles (MIP NPs) and their surface modification in order to prevent the aggregation process that is ever-present in most nanomaterial suspensions/dispersions. Specifically, we studied the influence of surface modification of MIP NPs with polymerizable poly(ethylene glycol) on their degree of stability in water, in phosphate buffer, and in the presence of serum proteins. Grafting a polymer shell on the surface of nanoparticles decreases the surface energy, enhances the polarity, and as a result improves the dispersibility, storage, and colloidal stability as compared to those of core (unmodified) particles. Because of the unique solid-phase approach used for synthesis, the binding sites of MIP NPs are protected during grafting, and the recognition properties of nanoparticles are not affected. These results are significant for developing nanomaterials with selective molecular recognition, increased biocompatibility, and stability in solution. Materials synthesized this way have the potential to be used in a variety of technological fields, including in vivo applications such as drug delivery and imaging. PMID:23855734

PEG-stabilized core-shell surface-imprinted nanoparticles.

PubMed

Moczko, Ewa; Guerreiro, Antonio; Piletska, Elena; Piletsky, Sergey

2013-08-06

Here we present a simple technique to produce target-specific molecularly imprinted polymeric nanoparticles (MIP NPs) and their surface modification in order to prevent the aggregation process that is ever-present in most nanomaterial suspensions/dispersions. Specifically, we studied the influence of surface modification of MIP NPs with polymerizable poly(ethylene glycol) on their degree of stability in water, in phosphate buffer, and in the presence of serum proteins. Grafting a polymer shell on the surface of nanoparticles decreases the surface energy, enhances the polarity, and as a result improves the dispersibility, storage, and colloidal stability as compared to those of core (unmodified) particles. Because of the unique solid-phase approach used for synthesis, the binding sites of MIP NPs are protected during grafting, and the recognition properties of nanoparticles are not affected. These results are significant for developing nanomaterials with selective molecular recognition, increased biocompatibility, and stability in solution. Materials synthesized this way have the potential to be used in a variety of technological fields, including in vivo applications such as drug delivery and imaging.

Facile preparation of superhydrophobic surfaces based on metal oxide nanoparticles

NASA Astrophysics Data System (ADS)

Bao, Xue-Mei; Cui, Jin-Feng; Sun, Han-Xue; Liang, Wei-Dong; Zhu, Zhao-Qi; An, Jin; Yang, Bao-Ping; La, Pei-Qing; Li, An

2014-06-01

A novel method for fabrication of superhydrophobic surfaces was developed by facile coating various metal oxide nanoparticles, including ZnO, Al2O3 and Fe3O4, on various substrates followed by treatment with polydimethylsiloxane (PDMS) via chemical vapor deposition (CVD) method. Using ZnO nanoparticles as a model, the changes in the surface chemical composition and crystalline structures of the metal oxide nanoparticles by PDMS treatment were investigated by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) analysis. The results show that the combination of the improved surface roughness generated from of the nanoparticles aggregation with the low surface-energy of silicon-coating originated from the thermal pyrolysis of PDMS would be responsible for the surface superhydrophobicity. By a simple dip-coating method, we show that the metal oxide nanoparticles can be easily coated onto the surfaces of various textural and dimensional substrates, including glass slide, paper, fabric or sponge, for preparation of superhydrophobic surfaces for different purpose. The present strategy may provide an inexpensive and new route to surperhydrophobic surfaces, which would be of technological significance for various practical applications especially for separation of oils or organic contaminates from water.

Surface-functionalized nanoparticles for biosensing and imaging-guided therapeutics

NASA Astrophysics Data System (ADS)

Jiang, Shan; Win, Khin Yin; Liu, Shuhua; Teng, Choon Peng; Zheng, Yuangang; Han, Ming-Yong

2013-03-01

In this article, the very recent progress of various functional inorganic nanomaterials is reviewed including their unique properties, surface functionalization strategies, and applications in biosensing and imaging-guided therapeutics. The proper surface functionalization renders them with stability, biocompatibility and functionality in physiological environments, and further enables their targeted use in bioapplications after bioconjugation via selective and specific recognition. The surface-functionalized nanoprobes using the most actively studied nanoparticles (i.e., gold nanoparticles, quantum dots, upconversion nanoparticles, and magnetic nanoparticles) make them an excellent platform for a wide range of bioapplications. With more efforts in recent years, they have been widely developed as labeling probes to detect various biological species such as proteins, nucleic acids and ions, and extensively employed as imaging probes to guide therapeutics such as drug/gene delivery and photothermal/photodynamic therapy.

Surface-mode-assisted amplification of radiative heat transfer between nanoparticles

NASA Astrophysics Data System (ADS)

Messina, Riccardo; Biehs, Svend-Age; Ben-Abdallah, Philippe

2018-04-01

We show that the radiative heat flux between two nanoparticles can be significantly amplified when they are placed in proximity of a planar substrate supporting a surface resonance. The amplification factor goes beyond two orders of magnitude in the case of dielectric nanoparticles, whereas it is lower in the case of metallic nanoparticles. We analyze how this effect depends on the frequency and on the particle-surface distance by clearly identifying the signature of the surface mode producing the amplification. Finally, we show how the presence of a graphene sheet on top of the substrate can modify the effect by making an amplification of two orders of magnitude possible also in the case of metallic nanoparticles. This long-range amplification effect should play an important role in the thermal relaxation dynamics of nanoparticle networks.

Surface spins disorder in uncoated and SiO2 coated maghemite nanoparticles

NASA Astrophysics Data System (ADS)

Zeb, F.; Nadeem, K.; Shah, S. Kamran Ali; Kamran, M.; Gul, I. Hussain; Ali, L.

2017-05-01

We studied the surface spins disorder in uncoated and silica (SiO2) coated maghemite (γ-Fe2O3) nanoparticles using temperature and time dependent magnetization. The average crystallite size for SiO2 coated and uncoated nanoparticles was about 12 and 29 nm, respectively. Scanning electron microscopy (SEM) showed that the nanoparticles are spherical in shape and well separated. Temperature scans of zero field cooled (ZFC)/field cooled (FC) magnetization measurements showed lower average blocking temperature (TB) for SiO2 coated maghemite nanoparticles as compared to uncoated nanoparticles. The saturation magnetization (Ms) of SiO2 coated maghemite nanoparticles was also lower than the uncoated nanoparticles and is attributed to smaller average crystallite size of SiO2 coated nanoparticles. For saturation magnetization vs. temperature data, Bloch's law (M(T)= M(0).(1- BTb)) was fitted well for both uncoated and SiO2 coated nanoparticles and yields: B =3×10-7 K-b, b=2.22 and B=0.0127 K-b, b=0.57 for uncoated and SiO2 coated nanoparticles, respectively. Higher value of B for SiO2 coated nanoparticles depicts decrease in exchange coupling due to enhanced surface spins disorder (broken surface bonds) as compared to uncoated nanoparticles. The Bloch's exponent b was decreased for SiO2 coated nanoparticles which is due to their smaller average crystallite size or finite size effects. Furthermore, a sharp increase of coercivity at low temperatures (<25 K) was observed for SiO2 coated nanoparticles which is also due to contribution of increased surface anisotropy or frozen surface spins in these smaller nanoparticles. The FC magnetic relaxation data was fitted to stretched exponential law which revealed slower magnetic relaxation for SiO2 coated nanoparticles. All these measurements revealed smaller average crystallite size and enhanced surface spins disorder in SiO2 coated nanoparticles than in uncoated γ-Fe2O3 nanoparticles.

Size-Dependent Surface Energy Density of Spherical Face-Centered-Cubic Metallic Nanoparticles.

PubMed

Wei, Yaochi; Chen, Shaohua

2015-12-01

The surface energy density of nano-sized elements exhibits a significantly size-dependent behavior. Spherical nanoparticle, as an important element in nano-devices and nano-composites, has attracted many interesting studies on size effect, most of which are molecular dynamics (MD) simulations. However, the existing MD calculations yield two opposite size-dependent trends of surface energy density of nanoparticles. In order to clarify such a real underlying problem, atomistic calculations are carried out in the present paper for various spherical face-centered-cubic (fcc) metallic nanoparticles. Both the embedded atom method (EAM) potential and the modified embedded atom method (MEAM) one are adopted. It is found that the size-dependent trend of surface energy density of nanoparticles is not governed by the chosen potential function or variation trend of surface energy, but by the defined radius of spherical nanoparticles in MD models. The finding in the present paper should be helpful for further theoretical studies on surface/interface effect of nanoparticles and nanoparticle-reinforced composites.

Importance of ion bombardment during coverage of Au nanoparticles on their structural features and optical response

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

Resta, V.; Peláez, R. J.; Afonso, C. N.

2014-03-28

This work studies the changes in the optical response and morphological features of 6 ± 1 nm diameter Au nanoparticles (NPs) when covered by a layer of a-Al{sub 2}O{sub 3} by pulsed laser deposition (PLD). The laser fluence used for ablating the Al{sub 2}O{sub 3} target is varied in order to modify the kinetic energy (KE) of the species bombarding the NPs during their coverage. When the ion KE < 200 eV, the structural features and optical properties of the NPs are close to those of uncovered ones. Otherwise, a shift to the blue and a strong damping of the surface plasmon resonance is observed asmore » fluence is increased. There are two processes responsible for these changes, both related to aluminum ions arriving to the substrate during the coverage process, i.e., sputtering of the metal and implantation of aluminum species in the metal. Both processes have been simulated using standard models for ion bombardment, the calculated effective implanted depths allow explaining the observed changes in the optical response, and the use of a size-dependent sputtering coefficient for the Au NPs predicts the experimental sputtering fractions. In spite of the work is based on PLD, the concepts investigated and conclusions can straightforwardly be extrapolated to other physical vapor deposition techniques or processes involving ion bombardment of metal NPs by ions having KE > 200 eV.« less

Local modification of the surface state properties at dilute coverages: CO/Cu(111)

NASA Astrophysics Data System (ADS)

Zaum, Ch.; Meyer-auf-der-Heide, K. M.; Morgenstern, K.

2018-04-01

We follow the diffusion of CO molecules on Cu(111) by time-lapsed low-temperature scanning tunneling microscopy. The diffusivity of individual CO molecules oscillates with the distance to its nearest neighbor due to the long-range interaction mediated by the surface state electrons. The markedly different wavelengths of the oscillation at a coverage of 0.6% ML as compared to the one at 6% ML coverage correspond to two different wavelengths of the surface state electrons, consistent with a shift of the surface state by 340 meV. This surprisingly large shift as compared to results of averaging methods suggests a local modification of the surface state properties.

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.

The Impact of Nanoparticle Surface Chemistry on Biological Systems

NASA Astrophysics Data System (ADS)

Thorn, Angie Sue Morris

The unique properties of nanomaterials, such as their small size and large surface area-to-volume ratios, have attracted tremendous interest in the scientific community over the last few decades. Thus, the synthesis and characterization of many different types of nanoparticles has been well defined and reported on in the literature. Current research efforts have redirected from the basic study of nanomaterial synthesis and their properties to more application-based studies where the development of functionally active materials is necessary. Today such nanoparticle-based systems exist for a range of biomedical applications including imaging, drug delivery and sensors. The inherent properties of the nanomaterial, although important, aren't always ideal for specific applications. In order to optimize nanoparticles for biomedical applications it is often desirable to tune their surface properties. Researchers have shown that these surface properties (such as charge, hydrophobicity, or reactivity) play a direct role in the interactions between nanoparticles and biological systems can be altered by attaching molecules to the surface of nanoparticles. In this work, the effects of physicochemical properties of a wide variety of nanoparticles was investigated using in vitro and in vivo models. For example, copper oxide (CuO) nanoparticles were of interest due to their instability in biological media. These nanoparticles undergo dissolution when in an aqueous environment and tend to aggregate. Therefore, the cytotoxicity of two sizes of CuO NPs was evaluated in cultured cells to develop a better understanding of how these propertied effect toxicity outcomes in biological systems. From these studies, it was determined that CuO NPs are cytotoxic to lung cells in a size-dependent manner and that dissolved copper ions contribute to the cytotoxicity however it is not solely responsible for cell death. Moreover, silica nanoparticles are one of the most commonly used nanomaterials

Creating surfactant nanoparticles for block copolymer composites through surface chemistry.

PubMed

Kim, Bumjoon J; Bang, Joona; Hawker, Craig J; Chiu, Julia J; Pine, David J; Jang, Se Gyu; Yang, Seung-Man; Kramer, Edward J

2007-12-04

A simple strategy to tailor the surface of nanoparticles for their specific adsorption to and localization at block copolymer interfaces was explored. Gold nanoparticles coated by a mixture of low molecular weight thiol end-functional polystyrene (PS-SH) (Mn = 1.5 and 3.4 kg/mol) and poly(2-vinylpyridine) homopolymers (P2VP-SH) (Mn = 1.5 and 3.0 kg/mol) were incorporated into a lamellar poly(styrene-b-2-vinylpyridine) diblock copolymer (PS-b-P2VP) (Mn = 196 kg/mol). A library of nanoparticles with varying PS and P2VP surface compositions (FPS) and high polymer ligand areal chain densities was synthesized. The location of the nanoparticles in the PS-b-P2VP block copolymer was determined by transmission electron microscopy. Sharp transitions in particle location from the PS domain to the PS/P2VP interface, and subsequently to the P2VP domain, were observed at FPS = 0.9 and 0.1, respectively. This extremely wide window of FPS values where the polymer-coated gold nanoparticles adsorb to the interface suggests a redistribution of PS and P2VP polymers on the Au surface, inducing the formation of amphiphilic nanoparticles at the PS/P2VP interface. In a second and synthetically more challenging approach, gold nanoparticles were covered with a thiol terminated random copolymer of styrene and 2-vinylpyridine synthesized by RAFT polymerization. Two different random copolymers were considered, where the molecular weight was fixed at 3.5 kg/mol and the relative incorporation of styrene and 2-vinylpyridine repeat units varied (FPS = 0.52 and 0.40). The areal chain density of these random copolymers on Au is unfortunately not high enough to preclude any contact between the P2VP block of the block copolymer and the Au surface. Interestingly, gold nanoparticles coated by the random copolymer with FPS = 0.4 were dispersed in the P2VP domain, while those with FPS = 0.52 were located at the interface. A simple calculation for the adsorption energy to the interface of the nanoparticles

Generation of metal nanoparticles from silver and copper objects: nanoparticle dynamics on surfaces and potential sources of nanoparticles in the environment.

PubMed

Glover, Richard D; Miller, John M; Hutchison, James E

2011-11-22

The use of silver nanoparticles (AgNPs) in antimicrobial applications, including a wide range of consumer goods and apparel, has attracted attention because of the unknown health and environmental risks associated with these emerging materials. Of particular concern is whether there are new risks that are a direct consequence of their nanoscale size. Identifying those risks associated with nanoscale structure has been difficult due to the fundamental challenge of detecting and monitoring nanoparticles in products or the environment. Here, we introduce a new strategy to directly monitor nanoparticles and their transformations under a variety of environmental conditions. These studies reveal unprecedented dynamic behavior of AgNPs on surfaces. Most notably, under ambient conditions at relative humidities greater than 50%, new silver nanoparticles form in the vicinity of the parent particles. This humidity-dependent formation of new particles was broadly observed for a variety of AgNPs and substrate surface coatings. We hypothesize that nanoparticle production occurs through a process involving three stages: (i) oxidation and dissolution of silver from the surface of the particle, (ii) diffusion of silver ion across the surface in an adsorbed water layer, and (iii) formation of new, smaller particles by chemical and/or photoreduction. Guided by these findings, we investigated non-nanoscale sources of silver such as wire, jewelry, and eating utensils that are placed in contact with surfaces and found that they also formed new nanoparticles. Copper objects display similar reactivity, suggesting that this phenomenon may be more general. These findings challenge conventional thinking about nanoparticle reactivity and imply that the production of new nanoparticles is an intrinsic property of the material that is not strongly size dependent. The discovery that AgNPs and CuNPs are generated spontaneously from manmade objects implies that humans have long been in direct

Indium nanoparticles for ultraviolet surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Das, Rupali; Soni, R. K.

2018-05-01

Ultraviolet Surface-enhanced Raman spectroscopy (UVSERS) has emerged as an efficient molecular spectroscopy technique for ultra-sensitive and ultra-low detection of analyte concentration. The generic SERS substrates based on gold and silver nanostructures have been extensively explored for high local electric field enhancement only in visible-NIR region of the electromagnetic spectrum. The template synthesis of controlled nanoscale size metallic nanostructures supporting localized surface plasmon resonance (LSPR) in the UV region have been recently explored due to their ease of synthesis and potential applications in optoelectronic, catalysis and magnetism. Indium (In0) nanoparticles exhibit active surface plasmon resonance (SPR) in ultraviolet (UV) and deep-ultaviolet (DUV) region with optimal absorption losses. This extended accessibility makes indium a promising material for UV plasmonic, chemical sensing and more recently in UV-SERS. In this work, spherical indium nanoparticles (In NPs) were synthesized by modified polyol reduction method using NaBH4 having local surface plasmon resonance near 280 nm. The as-synthesized spherical In0 nanoparticles were then coated with thin silica shells of thickness ˜ 5nm by a modified Stober method protecting the nanoparticles from agglomeration, direct contact with the probed molecules as well as prevent oxidation of the nanoparticles. Morphological evolution of In0 nanoparticles and SiO2 coating were characterized by transmission electron microscope (TEM). An enhanced near resonant shell-isolated SERS activity from thin film of tryptophan (Tryp) molecules deposited on indium coated substrates under 325nm UV excitation was observed. Finite difference time domain (FDTD) method is employed to comprehend the experimental results and simulate the electric field contours which showed amplified electromagnetic field localized around the nanostructures. The comprehensive analysis indicates that indium is a promising alternate

Theoretical aspects of studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.

2010-10-01

The study of adsorption of oxygen on transition metal surface is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. The structures formed on transition metal surfaces vary from simple adlayers of chemisorbed oxygen to oxygen diffusion into the sub-surface region and the formation of oxides. In this work we present the results of an ab-initio investigation of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. Calculations are also performed for the on-surface adsorption of oxygen on the unreconstructed Cu(001) surface for coverages up to one monolayer to use for comparison. The geometry of the surfaces with adsorbed oxygen is fully optimized. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy.

Immobilization of biomolecules on the surface of inorganic nanoparticles for biomedical applications

PubMed Central

Xing, Zhi-Cai; Chang, Yongmin; Kang, Inn-Kyu

2010-01-01

Various inorganic nanoparticles have been used for drug delivery, magnetic resonance and fluorescence imaging, and cell targeting owing to their unique properties, such as large surface area and efficient contrasting effect. In this review, we focus on the surface functionalization of inorganic nanoparticles via immobilization of biomolecules and the corresponding surface interactions with biocomponents. Applications of surface-modified inorganic nanoparticles in biomedical fields are also outlined. PMID:27877316

Advanced wide-field surface plasmon microscopy of single adsorbing nanoparticles

NASA Astrophysics Data System (ADS)

Nizamov, Shavkat; Scherbahn, Vitali; Mirsky, Vladimir M.

2017-05-01

In-situ detection and characterization of nanoparticles in biological media as well as in food or other complex samples is still a big challenge for existing analytical methods. Here we describe a label-free and cost-effective analytical method for detection of nanoparticles in the concentration range 106 -1010 NPs/ml. The proposed method is based on the surface plasmon resonance microscopy (SPRM) with a large field of view ( 1.3mm2 ). It is able to detect and count adsorbing nanoparticles individually, totally up to the hundreds of thousands of NPs on the sensor surface. At constant diffusion conditions the detection rate is proportional to the number concentration of NPs, this provides an approach to determine the NPs concentration. The adsorption of nanoparticle can be manipulated by the surface functionalization, pH and electrolyte concentration of suspensions. Images of detected nanoparticles can be quantified in order to characterize them individually. The image intensity grows quasi-linearly with nanoparticle size for the given material. However, the size and material of nanoparticle cannot be resolved directly from the image. For determination of chemical composition, SPRM can be assisted by electrochemical analysis. In this case, the gold sensor surface is used both as a resonant media for plasmon microscopy and as a working electrode. Under potential sweep, the adsorbed NPs can be subjected to electrochemical dissolution, which is detected optically. The potential of this conversion characterizes the material of NPs.

Nanoparticle flotation collectors: mechanisms behind a new technology.

PubMed

Yang, Songtao; Pelton, Robert; Raegen, Adam; Montgomery, Miles; Dalnoki-Veress, Kari

2011-09-06

This is the first report describing a new technology where hydrophobic nanoparticles adsorb onto much larger, hydrophilic mineral particle surfaces to facilitate attachment to air bubbles in flotation. The adsorption of 46 nm cationic polystyrene nanoparticles onto 43 μm diameter glass beads, a mineral model, facilitates virtually complete removal of the beads by flotation. As little as 5% coverage of the bead surfaces with nanoparticles promotes high flotation efficiencies. The maximum force required to pull a glass bead from an air bubble interface into the aqueous phase was measured by micromechanics. The pull-off force was 1.9 μN for glass beads coated with nanoparticles, compared to 0.0086 μN for clean beads. The pull-off forces were modeled using Scheludko's classical expression. We propose that the bubble/bead contact area may not be dry (completely dewetted). Instead, for hydrophobic nanoparticles sitting on a hydrophilic surface, it is possible that only the nanoparticles penetrate the air/water interface to form a three-phase contact line. We present a new model for pull-off forces for such a wet contact patch between the bead and the air bubble. Contact angle measurements of both nanoparticle coated glass and smooth films from dissolved nanoparticles were performed to support the modeling. © 2011 American Chemical Society

Fluorescent proteins as efficient tools for evaluating the surface PEGylation of silica nanoparticles

NASA Astrophysics Data System (ADS)

Zhang, Wei; Ma, Minyan; Zhang, Xiao-ai; Zhang, Ze-yu; Saleh, Sayed M.; Wang, Xu-dong

2017-06-01

Surface PEGylation is essential for preventing non-specific binding of biomolecules when silica nanoparticles are utilized for in vivo applications. Methods for installing poly(ethylene glycol) on a silica surface have been widely explored but varies from study to study. Because there is a lack of a satisfactory method for evaluating the properties of silica surface after PEGylation, the prepared nanoparticles are not fully characterized before use. In some cases, even non-PEGylated silica nanoparticles were produced, which is unfortunately not recognized by the end-user. In this work, a fluorescent protein was employed, which acts as a sensitive material for evaluating the surface protein adsorption properties of silica nanoparticles. Eleven different methods were systematically investigated for their reaction efficiency towards surface PEGylation. Results showed that both reaction conditions (including pH, catalyst) and surface functional groups of parent silica nanoparticles play critical roles in producing fully PEGylated silica nanoparticles. Great care needs to be taken in choosing the proper coupling chemistry for surface PEGylation. The data and method shown here will guarantee high-quality PEGylated silica nanoparticles to be produced and guide their applications in biology, chemistry, industry and medicine.

Immobilization of gold nanoparticles on cell culture surfaces for safe and enhanced gold nanoparticle-mediated laser transfection.

PubMed

Kalies, Stefan; Heinemann, Dag; Schomaker, Markus; Gentemann, Lara; Meyer, Heiko; Ripken, Tammo

2014-01-01

In comparison to standard transfection methods, gold nanoparticle-mediated laser transfection has proven to be a versatile alternative. This is based on its minor influence on cell viability and its high efficiency, especially for the delivery of small molecules like small interfering RNA. However, in order to transfer it to routine usage, a safety aspect is of major concern: The avoidance of nanoparticle uptake by the cells is desired. The immobilization of the gold nanoparticles on cell culture surfaces can address this issue. In this study, we achieved this by silanization of the appropriate surfaces and the binding of gold nanoparticles to them. Comparable perforation efficiencies to the previous approaches of gold nanoparticle-mediated laser transfection with free gold nanoparticles are demonstrated. The uptake of the immobilized particles by the cells is unlikely. Consequently, these investigations offer the possibility of bringing gold nanoparticle-mediated laser transfection closer to routine usage.

Nanoparticle-wetted surfaces for relays and energy transmission contacts.

PubMed

Voevodin, Andrey A; Vaia, Richard A; Patton, Steven T; Diamanti, Steven; Pender, Mark; Yoonessi, Mitra; Brubaker, Jennifer; Hu, Jian-Jun; Sanders, Jeffrey H; Phillips, Benjamin S; MacCuspie, Robert I

2007-11-01

Submonolayer coatings of noble-metal nanoparticle liquids (NPLs) are shown to provide replenishable surfaces with robust asperities and metallic conductivity that extends the durability of electrical relays by 10 to 100 times (depending on the current driven through the contact) as compared to alternative approaches. NPLs are single-component materials consisting of a metal nanoparticle core (5-20 nm Au or Pt nanoparticles) surrounded by a covalently tethered ionic-liquid corona of 1.5 to 2 nm. Common relay failure modes, such as stiction, surface distortion, and contact shorting, are suppressed with the addition of a submonolayer of NPLs to the contact surfaces. This distribution of NPLs results in a force profile for a contact-retraction cycle that is distinct from bare Au contacts and thicker, multilayer coatings of NPLs. Postmortem examination reveals a substantial decrease in topological change of the electrode surface relative to bare contacts, as well as an indication of lateral migration of the nanoparticles from the periphery towards the contact. A general extension of this concept to dynamic physical interfaces experiencing impact, sliding, or rolling affords alternatives to increase reliability and reduced losses for transmittance of electrical and mechanical energy.

Deposition of gold nanoparticles from colloid on TiO2 surface

NASA Astrophysics Data System (ADS)

Rehacek, Vlastimil; Hotovy, Ivan

2017-11-01

In this paper, experimental results are presented on the deposition of colloidal gold nanoparticles on the surfaces of TiO2 prepared on silicon/silicon dioxide. Important procedures, such as titanium dioxide surface hydrophilization as well as functionalization by an organosilane coupling agent (3-aminopropyl) trimethoxysilane and (3-mercaptopropyl) trimethoxysilane were investigated in order to obtain a metal oxide surface with the most convenient properties for immobilization of gold nanoparticles having a dense and uniform distribution. TiO2 nanotips prepared by reactive ion etching of oxide surface covered with self-mask gold nanoparticles are demonstrated.

Nanopatterning of magnetic domains: Fe coverage of self-assembled alumina nanostructure

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

Wu, Qibin; Wang, Bo -Yao; Lin, Wen -Chin

2015-08-19

Nanosized ultrathin magnetic films were prepared by controlling the deposition of Fe onto an oxidized NiAl(001) surface with an alumina nanostructure on it. Because the ultrathin ferromagnetic Fe films on the bare NiAl(001) surface are separated by paramagnetic Fe nanoparticles on the alumina stripes, as determined by scanning electron microscopy with spin analysis, they form rectangular domains with sizes ranging from tens of nanometer to larger than a micrometer. Furthermore, magnetic domain patterning can thus be achieved by controlling the Fe coverage and nanostructured template.

Covalent Coupling of Nanoparticles with Low-Density Functional Ligands to Surfaces via Click Chemistry

PubMed Central

Rianasari, Ina; de Jong, Michel P.; Huskens, Jurriaan; van der Wiel, Wilfred G.

2013-01-01

We demonstrate the application of the 1,3-dipolar cycloaddition (“click” reaction) to couple gold nanoparticles (Au NPs) functionalized with low densities of functional ligands. The ligand coverage on the citrate-stabilized Au NPs was adjusted by the ligand:Au surface atom ratio, while maintaining the colloidal stability of the Au NPs in aqueous solution. A procedure was developed to determine the driving forces governing the selectivity and reactivity of citrate-stabilized and ligand-functionalized Au NPs on patterned self-assembled monolayers. We observed selective and remarkably stable chemical bonding of the Au NPs to the complimentarily functionalized substrate areas, even when estimating that only 1–2 chemical bonds are formed between the particles and the substrate. PMID:23434666

Silica coating of nanoparticles by the sonogel process.

PubMed

Chen, Quan; Boothroyd, Chris; Tan, Gim Hong; Sutanto, Nelvi; Soutar, Andrew McIntosh; Zeng, Xian Ting

2008-02-05

A modified aqueous sol-gel route was developed using ultrasonic power for the silica coating of indium tin oxide (ITO) nanoparticles. In this approach, organosilane with an amino functional group was first used to cover the surface of as-received nanoparticles. Subsequent silica coating was initiated and sustained under power ultrasound irradiation in an aqueous mixture of surface-treated particles and epoxy silane. This process resulted in a thin but homogeneous coverage of silica on the particle surface. Particles coated with a layer of silica show better dispersability in aqueous and organic media compared with the untreated powder. Samples were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and the zeta potential.

Nanostructured medical device coatings based on self-assembled poly(lactic-co-glycolic acid) nanoparticles.

PubMed

Dayyoub, Eyas; Hobler, Christian; Nonnweiler, Pierina; Keusgen, Michael; Bakowsky, Udo

2013-07-01

Here we present a new method for providing nanostructured drug-loaded polymer films which enable control of film surface morphology and delivery of therapeutic agents. Silicon wafers were employed as models for implanted biomaterials and poly(lactic-co-glycolic acid) (PLGA) nanoparticles were assembled onto the silicon surface by electrostatic interaction. Monolayers of the PLGA particles were deposited onto the silicon surface upon incubation in an aqueous particle suspension. Particle density and surface coverage of the silicon wafers were varied by altering particle concentration, incubation time in nanoparticle suspension and ionic strength of the suspension. Dye loaded nanoparticles were prepared and assembled to silicon surface to form nanoparticle films. Fluorescence intensity measurements showed diffusion-controlled release of the dye over two weeks and atomic force microscopy (AFM) analysis revealed that these particles remained attached to the surface during the incubation time. This work suggests that coating implants with PLGA nanoparticles is a versatile technique which allows drug release from the implant surface and modulation of surface morphology. Copyright © 2013 Elsevier B.V. All rights reserved.

Vegetation Coverage and Impervious Surface Area Estimated Based on the Estarfm Model and Remote Sensing Monitoring

NASA Astrophysics Data System (ADS)

Hu, Rongming; Wang, Shu; Guo, Jiao; Guo, Liankun

2018-04-01

Impervious surface area and vegetation coverage are important biophysical indicators of urban surface features which can be derived from medium-resolution images. However, remote sensing data obtained by a single sensor are easily affected by many factors such as weather conditions, and the spatial and temporal resolution can not meet the needs for soil erosion estimation. Therefore, the integrated multi-source remote sensing data are needed to carry out high spatio-temporal resolution vegetation coverage estimation. Two spatial and temporal vegetation coverage data and impervious data were obtained from MODIS and Landsat 8 remote sensing images. Based on the Enhanced Spatial and Temporal Adaptive Reflectance Fusion Model (ESTARFM), the vegetation coverage data of two scales were fused and the data of vegetation coverage fusion (ESTARFM FVC) and impervious layer with high spatiotemporal resolution (30 m, 8 day) were obtained. On this basis, the spatial variability of the seepage-free surface and the vegetation cover landscape in the study area was measured by means of statistics and spatial autocorrelation analysis. The results showed that: 1) ESTARFM FVC and impermeable surface have higher accuracy and can characterize the characteristics of the biophysical components covered by the earth's surface; 2) The average impervious surface proportion and the spatial configuration of each area are different, which are affected by natural conditions and urbanization. In the urban area of Xi'an, which has typical characteristics of spontaneous urbanization, landscapes are fragmented and have less spatial dependence.

Magnetic Nanoparticles: Surface Effects and Properties Related to Biomedicine Applications

PubMed Central

Issa, Bashar; Obaidat, Ihab M.; Albiss, Borhan A.; Haik, Yousef

2013-01-01

Due to finite size effects, such as the high surface-to-volume ratio and different crystal structures, magnetic nanoparticles are found to exhibit interesting and considerably different magnetic properties than those found in their corresponding bulk materials. These nanoparticles can be synthesized in several ways (e.g., chemical and physical) with controllable sizes enabling their comparison to biological organisms from cells (10–100 μm), viruses, genes, down to proteins (3–50 nm). The optimization of the nanoparticles’ size, size distribution, agglomeration, coating, and shapes along with their unique magnetic properties prompted the application of nanoparticles of this type in diverse fields. Biomedicine is one of these fields where intensive research is currently being conducted. In this review, we will discuss the magnetic properties of nanoparticles which are directly related to their applications in biomedicine. We will focus mainly on surface effects and ferrite nanoparticles, and on one diagnostic application of magnetic nanoparticles as magnetic resonance imaging contrast agents. PMID:24232575

Protection of surface states in topological nanoparticles

NASA Astrophysics Data System (ADS)

Siroki, Gleb; Haynes, Peter D.; Lee, Derek K. K.; Giannini, Vincenzo

2017-07-01

Topological insulators host protected electronic states at their surface. These states show little sensitivity to disorder. For miniaturization one wants to exploit their robustness at the smallest sizes possible. This is also beneficial for optical applications and catalysis, which favor large surface-to-volume ratios. However, it is not known whether discrete states in particles share the protection of their continuous counterparts in large crystals. Here we study the protection of the states hosted by topological insulator nanoparticles. Using both analytical and tight-binding simulations, we show that the states benefit from the same level of protection as those on a planar surface. The results hold for many shapes and sustain surface roughness which may be useful in photonics, spectroscopy, and chemistry. They complement past studies of large crystals—at the other end of possible length scales. The protection of the nanoparticles suggests that samples of all intermediate sizes also possess protected states.

Surface plasmon resonances of protein-conjugated gold nanoparticles on graphitic substrates

NASA Astrophysics Data System (ADS)

Phan, Anh D.; Hoang, Trinh X.; Nghiem, Thi H. L.; Woods, Lilia M.

2013-10-01

We present theoretical calculations for the absorption properties of protein-coated gold nanoparticles on graphene and graphite substrates. As the substrate is far away from nanoparticles, numerical results show that the number of protein bovine serum molecules aggregating on gold surfaces can be quantitatively determined for gold nanoparticles with arbitrary size by means of the Mie theory and the absorption spectra. The presence of a graphene substrate near the protein-conjugated gold nanoparticles results in a red shift of the surface plasmon resonances of the nanoparticles. This effect can be modulated upon changing the graphene chemical potential. Our findings show that the graphene and graphite affect the absorption spectra in a similar way.

Reactive wetting properties of TiO2 nanoparticles predicted by ab initio molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Brandt, Erik G.; Agosta, Lorenzo; Lyubartsev, Alexander P.

2016-07-01

Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity.Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity. Electronic supplementary information (ESI) available: Simulation data on equilibration of energies and structures (root-mean-square-deviations and

Shape-dependent surface magnetism of Co-Pt and Fe-Pt nanoparticles from first principles

NASA Astrophysics Data System (ADS)

Liu, Zhenyu; Wang, Guofeng

2017-12-01

In this paper, we have performed the first-principles density functional theory calculations to predict the magnetic properties of the CoPt and FePt nanoparticles in cuboctahedral, decahedral, and icosahedral shapes. The modeled alloy nanoparticles have a diameter of 1.1 nm and consist of 31 5 d Pt atoms and 24 3 d Co (or Fe) atoms. For both CoPt and FePt, we found that the decahedral nanoparticles had appreciably lower surface magnetic moments than the cuboctahedral and icosahedral nanoparticles. Our analysis indicated that this reduction in the surface magnetism was related to a large contraction of atomic spacing and high local Co (or Fe) concentration in the surface of the decahedral nanoparticles. More interestingly, we predicted that the CoPt and FePt cuboctahedral nanoparticles exhibited dramatically different surface spin structures when noncollinear magnetism was taken into account. Our calculation results revealed that surface anisotropy energy decided the fashion of surface spin canting in the CoPt and FePt nanoparticles, confirming previous predictions from atomistic Monte Carlo simulations.

Formation of aggregated nanoparticle spheres through femtosecond laser surface processing

NASA Astrophysics Data System (ADS)

Tsubaki, Alfred T.; Koten, Mark A.; Lucis, Michael J.; Zuhlke, Craig; Ianno, Natale; Shield, Jeffrey E.; Alexander, Dennis R.

2017-10-01

A detailed structural and chemical analysis of a class of self-organized surface structures, termed aggregated nanoparticle spheres (AN-spheres), created using femtosecond laser surface processing (FLSP) on silicon, silicon carbide, and aluminum is reported in this paper. AN-spheres are spherical microstructures that are 20-100 μm in diameter and are composed entirely of nanoparticles produced during femtosecond laser ablation of material. AN-spheres have an onion-like layered morphology resulting from the build-up of nanoparticle layers over multiple passes of the laser beam. The material properties and chemical composition of the AN-spheres are presented in this paper based on scanning electron microscopy (SEM), focused ion beam (FIB) milling, transmission electron microscopy (TEM), and energy dispersive x-ray spectroscopy (EDX) analysis. There is a distinct difference in the density of nanoparticles between concentric rings of the onion-like morphology of the AN-sphere. Layers of high-density form when the laser sinters nanoparticles together and low-density layers form when nanoparticles redeposit while the laser ablates areas surrounding the AN-sphere. The dynamic nature of femtosecond laser ablation creates a variety of nanoparticles that make-up the AN-spheres including Si/C core-shell, nanoparticles that directly fragmented from the base material, nanoparticles with carbon shells that retarded oxidation, and amorphous, fully oxidized nanoparticles.

Role of nanoparticle size, shape and surface chemistry in oral drug delivery.

PubMed

Banerjee, Amrita; Qi, Jianping; Gogoi, Rohan; Wong, Jessica; Mitragotri, Samir

2016-09-28

Nanoparticles find intriguing applications in oral drug delivery since they present a large surface area for interactions with the gastrointestinal tract and can be modified in various ways to address the barriers associated with oral delivery. The size, shape and surface chemistry of nanoparticles can greatly impact cellular uptake and efficacy of the treatment. However, the interplay between particle size, shape and surface chemistry has not been well investigated especially for oral drug delivery. To this end, we prepared sphere-, rod- and disc-shaped nanoparticles and conjugated them with targeting ligands to study the influence of size, shape and surface chemistry on their uptake and transport across intestinal cells. A triple co-culture model of intestinal cells was utilized to more closely mimic the intestinal epithelium. Results demonstrated higher cellular uptake of rod-shaped nanoparticles in the co-culture compared to spheres regardless of the presence of active targeting moieties. Transport of nanorods across the intestinal co-culture was also significantly higher than spheres. The findings indicate that nanoparticle-mediated oral drug delivery can be potentially improved with departure from spherical shape which has been traditionally utilized for the design of nanoparticles. We believe that understanding the role of nanoparticle geometry in intestinal uptake and transport will bring forth a paradigm shift in nanoparticle engineering for oral delivery and non-spherical nanoparticles should be further investigated and considered for oral delivery of therapeutic drugs and diagnostic materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Nanoparticle-based etching of silicon surfaces

DOEpatents

Branz, Howard [Boulder, CO; Duda, Anna [Denver, CO; Ginley, David S [Evergreen, CO; Yost, Vernon [Littleton, CO; Meier, Daniel [Atlanta, GA; Ward, James S [Golden, CO

2011-12-13

A method (300) of texturing silicon surfaces (116) such to reduce reflectivity of a silicon wafer (110) for use in solar cells. The method (300) includes filling (330, 340) a vessel (122) with a volume of an etching solution (124) so as to cover the silicon surface 116) of a wafer or substrate (112). The etching solution (124) is made up of a catalytic nanomaterial (140) and an oxidant-etchant solution (146). The catalytic nanomaterial (140) may include gold or silver nanoparticles or noble metal nanoparticles, each of which may be a colloidal solution. The oxidant-etchant solution (146) includes an etching agent (142), such as hydrofluoric acid, and an oxidizing agent (144), such as hydrogen peroxide. Etching (350) is performed for a period of time including agitating or stirring the etching solution (124). The etch time may be selected such that the etched silicon surface (116) has a reflectivity of less than about 15 percent such as 1 to 10 percent in a 350 to 1000 nanometer wavelength range.

Coverage dependent non-adiabaticity of CO on a copper surface

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

Omiya, Takuma; Surface and Interface Science Laboratory, RIKEN, Wako 351-0198; Arnolds, Heike

2014-12-07

We have studied the coverage-dependent energy transfer dynamics between hot electrons and CO on Cu(110) with femtosecond visible pump, sum frequency probe spectroscopy. We find that transients of the C–O stretch frequency display a red shift, which increases from 3 cm{sup −1} at 0.1 ML to 9 cm{sup −1} at 0.77 ML. Analysis of the transients reveals that the non-adiabatic coupling between the adsorbate vibrational motion and the electrons becomes stronger with increasing coverage. This trend requires the frustrated rotational mode to be the cause of the non-adiabatic behavior, even for relatively weak laser excitation of the adsorbate. We attributemore » the coverage dependence to both an increase in the adsorbate electronic density of states and an increasingly anharmonic potential energy surface caused by repulsive interactions between neighboring CO adsorbates. This work thus reveals adsorbate-adsorbate interactions as a new way to control adsorbate non-adiabaticity.« less

Using Amphiphilic Copolymers and Nanoparticles to Organize Charged Biopolymers

NASA Astrophysics Data System (ADS)

Park, Jung Hyun; McConnell, Marla; Sun, Yujie; Goldman, Yale; Composto, Russell

2009-03-01

Nanoparticles (NPs) on amphiphilic random copolymers control filamentous actin (F-actin) attachment. 3-aminopropyltriethoxysilane (APTES) coated silica NPs are selectively bonded to acrylic acid groups on the surface of a poly(styrene-r-acrylic acid) (PS-r-PAA) film. By changing the concentration of NPs in the medium, the surface density of positively charged anchors is tuned. Using total internal reflection fluorescence (TIRF) microscopy, immobilization of F-actin is observed via electrostatic interaction with NPs at high NP coverages. Below a critical coverage, F-actin is weakly attached and undergoes thermal fluctuations near the surface. Another method to tune F-actin attachment is to use APTES to cross-link and create positive charge in PAA films. Here, the surface coverage of F-actin decreases as APTES concentration increases. This observation is attributed to an increase in surface roughness and hydrophobicity that reduces the effective surface sites that attract F-actin. In addition, in-situ G-actin polymerization to F-actin is observed on both the NP and cross-linked PAA templates.

Characterization of QCM sensor surfaces coated with molecularly imprinted nanoparticles.

PubMed

Reimhult, Kristina; Yoshimatsu, Keiichi; Risveden, Klas; Chen, Si; Ye, Lei; Krozer, Anatol

2008-07-15

Molecularly imprinted polymers (MIPs) are gaining great interest as tailor-made recognition materials for the development of biomimetic sensors. Various approaches have been adopted to interface MIPs with different transducers, including the use of pre-made imprinted particles and the in situ preparation of thin polymer layers directly on transducer surfaces. In this work we functionalized quartz crystal microbalance (QCM) sensor crystals by coating the sensing surfaces with pre-made molecularly imprinted nanoparticles. The nanoparticles were immobilized on the QCM transducers by physical entrapment in a thin poly(ethylene terephthalate) (PET) layer that was spin-coated on the transducer surface. By controlling the deposition conditions, it was possible to gain a high nanoparticle loading in a stable PET layer, allowing the recognition sites in nanoparticles to be easily accessed by the test analytes. In this work, different sensor surfaces were studied by micro-profilometry and atomic force microscopy and the functionality was evaluated using quartz crystal microbalance with dissipation (QCM-D). The molecular recognition capability of the sensors were also confirmed using radioligand binding analysis by testing their response to the presence of the test compounds, (R)- and (S)-propranolol in aqueous buffer.

Surface-charge-dependent cell localization and cytotoxicity of cerium oxide nanoparticles.

PubMed

Asati, Atul; Santra, Santimukul; Kaittanis, Charalambos; Perez, J Manuel

2010-09-28

Cerium oxide nanoparticles (nanoceria) have shown great potential as antioxidant and radioprotective agents for applications in cancer therapy. Recently, various polymer-coated nanoceria preparations have been developed to improve their aqueous solubility and allow for surface functionalization of these nanoparticles. However, the interaction of polymer-coated nanoceria with cells, their uptake mechanism, and subcellular localization are poorly understood. Herein, we engineered polymer-coated cerium oxide nanoparticles with different surface charges (positive, negative, and neutral) and studied their internalization and toxicity in normal and cancer cell lines. The results showed that nanoceria with a positive or neutral charge enters most of the cell lines studied, while nanoceria with a negative charge internalizes mostly in the cancer cell lines. Moreover, upon entry into the cells, nanoceria is localized to different cell compartments (e.g., cytoplasm and lysosomes) depending on the nanoparticle's surface charge. The internalization and subcellular localization of nanoceria plays a key role in the nanoparticles' cytotoxicity profile, exhibiting significant toxicity when they localize in the lysosomes of the cancer cells. In contrast, minimal toxicity is observed when they localize into the cytoplasm or do not enter the cells. Taken together, these results indicate that the differential surface-charge-dependent localization of nanoceria in normal and cancer cells plays a critical role in the nanoparticles' toxicity profile.

Surface elastic properties in silicon nanoparticles

NASA Astrophysics Data System (ADS)

Melis, Claudio; Giordano, Stefano; Colombo, Luciano

2017-09-01

The elastic behavior of the external surface of a solid body plays a key role in nanomechanical phenomena. While bulk elasticity enjoys the benefits of a robust theoretical understanding, many surface elasticity features remain unexplored: some of them are here addressed by blending together continuum elasticity and atomistic simulations. A suitable readdressing of the surface elasticity theory allows to write the balance equations in arbitrary curvilinear coordinates and to investigate the dependence of the surface elastic parameters on the mean and Gaussian curvatures of the surface. In particular, we predict the radial strain induced by surface effects in spherical and cylindrical silicon nanoparticles and provide evidence that the surface parameters are nearly independent of curvatures and, therefore, of the surface conformation.

Effect of fullerenol surface chemistry on nanoparticle binding-induced protein misfolding

NASA Astrophysics Data System (ADS)

Radic, Slaven; Nedumpully-Govindan, Praveen; Chen, Ran; Salonen, Emppu; Brown, Jared M.; Ke, Pu Chun; Ding, Feng

2014-06-01

Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and dynamics of ubiquitin. We found that all derivatives bound to the model protein. Specifically, the more hydrophilic nanoparticles with a higher number of hydroxyl groups bound to the surface of the protein via hydrogen bonds, which stabilized the protein without inducing large conformational changes in the protein structure. In contrast, fullerene derivatives with a smaller number of hydroxyl groups buried their hydrophobic surface inside the protein, thereby causing protein denaturation. Overall, our results revealed a distinct role of surface chemistry on nanoparticle-protein binding and binding-induced protein misfolding.Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and

Water adsorbate phases on ZnO and impact of vapor pressure on the equilibrium shape of nanoparticles

NASA Astrophysics Data System (ADS)

Kenmoe, Stephane; Biedermann, P. Ulrich

2018-02-01

ZnO nanoparticles are used as catalysts and have potential applications in gas-sensing and solar energy conversion. A fundamental understanding of the exposed crystal facets, their surface chemistry, and stability as a function of environmental conditions is essential for rational design and improvement of synthesis and properties. We study the stability of water adsorbate phases on the non-polar low-index (10 1 ¯ 0 ) and (11 2 ¯ 0 ) surfaces from low coverage to multilayers using ab initio thermodynamics. We show that phonon contributions and the entropies due to a 2D lattice gas at low coverage and multiple adsorbate configurations at higher coverage have an important impact on the stability range of water adsorbate phases in the (T,p) phase diagram. Based on this insight, we compute and analyze the possible growth mode of water films for pressures ranging from UHV via ambient conditions to high pressures and the impact of water adsorption on the equilibrium shape of nanoparticles in a humid environment. A 2D variant of the Wulff construction shows that the (10 1 ¯ 0 ) and (11 2 ¯ 0 ) surfaces coexist on 12-faceted prismatic ZnO nanoparticles in dry conditions, while in humid environment, the (10 1 ¯ 0 ) surface is selectively stabilized by water adsorption resulting in hexagonal prisms.

Nanosensors based on functionalized nanoparticles and surface enhanced raman scattering

DOEpatents

Talley, Chad E.; Huser, Thomas R.; Hollars, Christopher W.; Lane, Stephen M.; Satcher, Jr., Joe H.; Hart, Bradley R.; Laurence, Ted A.

2007-11-27

Surface-Enhanced Raman Spectroscopy (SERS) is a vibrational spectroscopic technique that utilizes metal surfaces to provide enhanced signals of several orders of magnitude. When molecules of interest are attached to designed metal nanoparticles, a SERS signal is attainable with single molecule detection limits. This provides an ultrasensitive means of detecting the presence of molecules. By using selective chemistries, metal nanoparticles can be functionalized to provide a unique signal upon analyte binding. Moreover, by using measurement techniques, such as, ratiometric received SERS spectra, such metal nanoparticles can be used to monitor dynamic processes in addition to static binding events. Accordingly, such nanoparticles can be used as nanosensors for a wide range of chemicals in fluid, gaseous and solid form, environmental sensors for pH, ion concentration, temperature, etc., and biological sensors for proteins, DNA, RNA, etc.

Facile synthesis of biocompatible gold nanoparticles with organosilicone-coated surface properties

NASA Astrophysics Data System (ADS)

Xia, Lijin; Yi, Sijia; Lenaghan, Scott C.; Zhang, Mingjun

2012-07-01

In this study, a simple method for one-step synthesis of gold nanoparticles has been developed using an organosilicone surfactant, Silwet L-77, as both a reducing and capping agent. Synthesis of gold nanoparticles using this method is rapid and can be conducted conveniently at ambient temperature. Further refinement of the method, through the addition of sodium hydroxide and/or silver nitrate, allowed fine control over the size of spherical nanoparticles produced. Coated on the surface with organosilicone, the as-prepared gold nanoparticles were biocompatible and stable over the pH range from 5 to 12, and have been proven effective at transportation into MC3T3 osteoblast cells. The proposed method is simple, fast, and can produce size-controlled gold nanoparticles with unique surface properties for biomedical applications.

Surface modified PLGA nanoparticles for brain targeting of Bacoside-A.

PubMed

Jose, S; Sowmya, S; Cinu, T A; Aleykutty, N A; Thomas, S; Souto, E B

2014-10-15

The present paper focuses on the development and in vitro/in vivo characterization of nanoparticles composed of poly-(D,L)-Lactide-co-Glycolide (PLGA) loading Bacoside-A, as a new approach for the brain delivery of the neuroprotective drug for the treatment of neurodegenerative disorders (e.g. Alzheimer Disease). Bacoside-A-loaded PLGA nanoparticles were prepared via o/w emulsion solvent evaporation technique. Surface of the nanoparticles were modified by coating with polysorbate 80 to facilitate the crossing of the blood brain barrier (BBB), and the processing parameters (i.e. sonication time, the concentration of polymer (PLGA) and surfactant (polysorbate 80), and drug-polymer ratio) were optimized with the aim to achieve a high production yield. Brain targeting potential of the nanoparticles was evaluated by in vivo studies using Wistar albino rats. The nanoparticles produced by optimal formulation were within the nanosized range (70-200 nm) with relatively low polydispersity index (0.391 ± 1.2). The encapsulation efficiency of Bacoside-A in PLGA nanoparticles was 57.11 ± 7.11%, with a drug loading capacity of 20.5 ± 1.98%. SEM images showed the spherical shape of the PLGA nanoparticles, whereas their low crystallinity was demonstrated by X-ray studies, which also confirmed no chemical interactions between the drug and polymer molecules. The in vitro release of Bacoside-A from the PLGA nanoparticles followed a sustained release pattern with a maximum release of up to 83.04 ± 2.55% in 48 h. When compared to pure drug solution (2.56 ± 1.23 μg/g tissue), in vivo study demonstrated higher brain concentration of Bacoside-A (23.94 ± 1.74 μg/g tissue) suggesting a significant role of surface coated nanoparticles on brain targeting. The results indicate the potential of surface modified PLGA nanoparticles for the delivery of Bacoside-A to the brain. Copyright © 2014 Elsevier B.V. All rights reserved.

Surface modification of the TiO2 nanoparticle surface enables fluorescence monitoring of aggregation and enhanced photoreactivity.

PubMed

Kamps, Kara; Leek, Rachael; Luebke, Lanette; Price, Race; Nelson, Megan; Simonet, Stephanie; Eggert, David Joeseph; Ateşin, Tülay Aygan; Brown, Eric Michael Bratsolias

2013-01-01

Chemically and biologically modified nanoparticles are increasingly considered as viable and multifunctional tools to be used in cancer theranostics. Herein, we demonstrate that coordination of alizarin blue black B (ABBB) to the TiO(2) nanoparticle surface enhances the resulting nanoparticles by (1) creating distinct fluorescence emission spectra that differentiate smaller TiO(2) nanoparticles from larger TiO(2) nanoparticle aggregates (both in vitro and intracellular) and (2) enhancing visible light activation of TiO(2) nanoparticles above previously described methods to induce in vitro and intracellular damage to DNA and other targets. ABBB-TiO(2) nanoparticles are characterized through sedimentation, spectral absorbance, and gel electrophoresis. The possible coordination modes of ABBB to the TiO(2) nanoparticle surface are modeled by computational methods. Fluorescence emission spectroscopy studies indicate that ABBB coordination on TiO(2) nanoparticles enables discernment between nanoparticles and nanoparticle aggregates both in vitro and intracellular through fluorescence confocal microscopy. Visible light activated ABBB-TiO(2) nanoparticles are capable of inflicting increased DNA cleavage through localized production of reactive oxygen species as visualized by plasmid DNA damage detected through gel electrophoresis and atomic force microscopy. Finally, visible light excited ABBB-TiO(2) nanoparticles are capable of inflicting damage upon HeLa (cervical cancer) cells by inducing alterations in DNA structure and membrane associated proteins. The multifunctional abilities of these ABBB-TiO(2) nanoparticles to visualize and monitor aggregation in real time, as well as inflict visible light triggered damage upon cancer targets will enhance the use of TiO(2) nanoparticles in cancer theranostics.

Influence of surface charge on the potential toxicity of PLGA nanoparticles towards Calu-3 cells

PubMed Central

Mura, Simona; Hillaireau, Herve; Nicolas, Julien; Le Droumaguet, Benjamin; Gueutin, Claire; Zanna, Sandrine; Tsapis, Nicolas; Fattal, Elias

2011-01-01

Background Because of the described hazards related to inhalation of manufactured nanoparticles, we investigated the lung toxicity of biodegradable poly (lactide-co-glycolide) (PLGA) nanoparticles displaying various surface properties on human bronchial Calu-3 cells. Methods Positively and negatively charged as well as neutral nanoparticles were tailored by coating their surface with chitosan, Poloxamer, or poly (vinyl alcohol), respectively. Nanoparticles were characterized in terms of size, zeta potential, and surface chemical composition, confirming modifications provided by hydrophilic polymers. Results Although nanoparticle internalization by lung cells was clearly demonstrated, the cytotoxicity of the nanoparticles was very limited, with an absence of inflammatory response, regardless of the surface properties of the PLGA nanoparticles. Conclusion These in vitro results highlight the safety of biodegradable PLGA nanoparticles in the bronchial epithelium and provide initial data on their potential effects and the risks associated with their use as nanomedicines. PMID:22114491

Modification of surfaces of silver nanoparticles for controlled deposition of silicon, manganese, and titanium dioxides

NASA Astrophysics Data System (ADS)

Apostolova, Tzveta; Obreshkov, B. D.; Ionin, A. A.; Kudryashov, S. I.; Makarov, S. V.; Mel'nik, N. N.; Rudenko, A. A.

2018-01-01

In this work we show that nanometric-thick layers of SiO2, MnO2, and TiO2 may be effectively deposited on various silver nanoparticles (including cubic Ag nanoparticles) covered by a very thin (below 0.4 nm) layer of silver sulphide. The background in Raman measurements generated by sulphide-protected Ag nanoparticles is significantly smaller than that for analogous Ag nanoparticles protected by a monolayer formed from alkanethiols - depositing alkanethiols on a surface of anisotropic silver nanoparticles is the current standard method used for protecting a surface of Ag nanoparticles before depositing a layer of silica. Because of significantly smaller generated Raman background, Ag@SiO2 nanostructures with an Ag2S linkage layer between the silver core and the silica shell are very promising low-background electromagnetic nanoresonators for carrying out Raman analysis of various surfaces - especially using what is known as shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Sample SHINERS analyses of various surfaces (including pesticide-contaminated surfaces of tomatoes) using cubic-Ag@SiO2 nanoparticles as electromagnetic nanoresonators are also presented.

Growth of well-defined metal and oxide nanoparticles on biological surfaces

NASA Astrophysics Data System (ADS)

Tsukruk, Vladimir

2009-03-01

We present a brief overview of our recent studies in the field of bio-enabled surface-mediated growth of inorganic nanoparticles at room temperature and ambient conditions. We demonstrate that all titania, gold, and silver nanoparticles can be grown with relatively monodisperse diameter within 4-6 nm surrounded by biological shells of 1-2 nm thick. As biological templates we utilized ultrathin, molecular uniform and micropatterned surface layers of two different proteins: silk fibroin (for growth of gold and silver nanoparticles) and silaffin (for growth of titania nanoparticles). To identify the grown nanophases and chemical composition/secondary structure of biological templates we applied combined AFM, SEM, TEM, XPS, SERS, UV-vis, and ATR-FTIR techniques.

Theoretical analyses of localized surface plasmon resonance spectrum with nanoparticles imprinted polymers

NASA Astrophysics Data System (ADS)

Li, Hong; Peng, Wei; Wang, Yanjie; Hu, Lingling; Liang, Yuzhang; Zhang, Xinpu; Yao, Wenjuan; Yu, Qi; Zhou, Xinlei

2011-12-01

Optical sensors based on nanoparticles induced Localized Surface Plasmon Resonance are more sensitive to real-time chemical and biological sensing, which have attracted intensive attentions in many fields. In this paper, we establish a simulation model based on nanoparticles imprinted polymer to increase sensitivity of the LSPR sensor by detecting the changes of Surface Plasmon Resonance signals. Theoretical analysis and numerical simulation of parameters effects to absorption peak and light field distribution are highlighted. Two-dimensional simulated color maps show that LSPR lead to centralization of the light energy around the gold nanoparticles, Transverse Magnetic wave and total reflection become the important factors to enhance the light field in our simulated structure. Fast Fourier Transfer analysis shows that the absorption peak of the surface plasmon resonance signal resulted from gold nanoparticles is sharper while its wavelength is bigger by comparing with silver nanoparticles; a double chain structure make the amplitude of the signals smaller, and make absorption wavelength longer; the absorption peak of enhancement resulted from nanopore arrays has smaller wavelength and weaker amplitude in contrast with nanoparticles. These simulation results of the Localized Surface Plasmon Resonance can be used as an enhanced transduction mechanism for enhancement of sensitivity in recognition and sensing of target analytes in accordance with different requirements.

Theoretical aspects of studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Reed, J. A.

2011-03-01

The study of adsorption of oxygen on transition metal surface is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. The structures formed on transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which results from diffusion of oxygen into the sub-surface regions. In this work we present the results of an ab-initio investigation of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the Cu(100) missing row reconstructed surface under conditions of high oxygen coverage. Calculations are performed for various surface and subsurface oxygen coverages ranging from 0.50 to 1.50 monolayers. Calculations are also performed for the on-surface adsorption of oxygen on the unreconstructed Cu(001) surface for coverages up to one monolayer to use for comparison. Estimates of the positron binding energy, positron work function, and annihilation characteristics reveal their sensitivity to atomic structure of the topmost layers of the surface and charge transfer. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy.

Au Nanoparticle Sub-Monolayers Sandwiched between Sol-Gel Oxide Thin Films

PubMed Central

Della Gaspera, Enrico; Menin, Enrico; Sada, Cinzia

2018-01-01

Sub-monolayers of monodisperse Au colloids with different surface coverage have been embedded in between two different metal oxide thin films, combining sol-gel depositions and proper substrates functionalization processes. The synthetized films were TiO2, ZnO, and NiO. X-ray diffraction shows the crystallinity of all the oxides and verifies the nominal surface coverage of Au colloids. The surface plasmon resonance (SPR) of the metal nanoparticles is affected by both bottom and top oxides: in fact, the SPR peak of Au that is sandwiched between two different oxides is centered between the SPR frequencies of Au sub-monolayers covered with only one oxide, suggesting that Au colloids effectively lay in between the two oxide layers. The desired organization of Au nanoparticles and the morphological structure of the prepared multi-layered structures has been confirmed by Rutherford backscattering spectrometry (RBS), Secondary Ion Mass Spectrometry (SIMS), and Scanning Electron Microscopy (SEM) analyses that show a high quality sandwich structure. The multi-layered structures have been also tested as optical gas sensors. PMID:29538338

Enhanced visible light-induced photocatalytic activity of surface-modified BiOBr with Pd nanoparticles

NASA Astrophysics Data System (ADS)

Meng, Xiangchao; Li, Zizhen; Chen, Jie; Xie, Hongwei; Zhang, Zisheng

2018-03-01

Palladium nanoparticles well-dispersed on BiOBr surfaces were successfully prepared via a two-step process, namely hydrothermal synthesis of BiOBr followed by photodeposition of palladium. Surface-exposed palladium nanoparticles may improve the harvesting capacity of visible light photons via the surface plasmonic resonance effect to produce extra electrons. Palladium is an excellent electron acceptor, and therefore favours the separation of photogenerated electron/hole pairs. As a result, palladium significantly improves the photocatalytic activity of BiOBr in the removal of organic pollutants (phenol) under visible light irradiation. In addition to as-prepared samples which were comprehensively characterized, the mechanism for the enhancement via the deposition of palladium nanoparticles was also proposed based on results. This work may serve as solid evidence to confirm that surface-deposited palladium nanoparticles are capable of improving photocatalytic activity, and that photodeposition may be an effective approach to load metal nanoparticles onto a surface.

Influence of Polyoxometalate Protecting Ligands on Catalytic Aerobic Oxidation at the Surfaces of Gold Nanoparticles in Water.

PubMed

Zhang, Mingfu; Hao, Jingcheng; Neyman, Alevtina; Wang, Yifeng; Weinstock, Ira A

2017-03-06

Metal oxide cluster-anion (polyoxometalate, or POM) protecting ligands, [α-PW 11 O 39 ] 7- (1), modify the rates at which 14 nm gold nanoparticles (Au NPs) catalyze an important model reaction, the aerobic (O 2 ) oxidation of CO to CO 2 in water. At 20 °C and pH 6.2, the following stoichiometry was observed: CO + O 2 + H 2 O = CO 2 + H 2 O 2 . After control experiments verified that the H 2 O 2 product was sufficiently stable and did not react with 1 under turnover conditions, quantitative analysis of H 2 O 2 was used to monitor the rates of CO oxidation, which increased linearly with the percent coverage of the Au NPs by 1 (0-64% coverage, with the latter value corresponding to 211 ± 19 surface-bound molecules of 1). X-ray photoelectron spectroscopy of Au NPs protected by a series of POM ligands (K + salts): 1, the Wells-Dawson ion [α-P 2 W 18 O 62 ] 6- (2) and the monodefect Keggin anion [α-SiW 11 O 39 ] 8- (3) revealed that binding energies of electrons in the Au 4f 7/2 and 4f 5/2 atomic orbitals decreased as a linear function of the POM charge and percent coverage of Au NPs, providing a direct correlation between the electronic effects of the POMs bound to the surfaces of the Au NPs and the rates of CO oxidation by O 2 . Additional data show that this effect is not limited to POMs but occurs, albeit to a lesser extent, when common anions capable of binding to Au-NP surfaces, such as citrate or phosphate, are present.

Platinum nanoparticles on gallium nitride surfaces: effect of semiconductor doping on nanoparticle reactivity.

PubMed

Schäfer, Susanne; Wyrzgol, Sonja A; Caterino, Roberta; Jentys, Andreas; Schoell, Sebastian J; Hävecker, Michael; Knop-Gericke, Axel; Lercher, Johannes A; Sharp, Ian D; Stutzmann, Martin

2012-08-01

Platinum nanoparticles supported on n- and p-type gallium nitride (GaN) are investigated as novel hybrid systems for the electronic control of catalytic activity via electronic interactions with the semiconductor support. In situ oxidation and reduction were studied with high pressure photoemission spectroscopy. The experiments revealed that the underlying wide-band-gap semiconductor has a large influence on the chemical composition and oxygen affinity of supported nanoparticles under X-ray irradiation. For as-deposited Pt cuboctahedra supported on n-type GaN, a higher fraction of oxidized surface atoms was observed compared to cuboctahedral particles supported on p-type GaN. Under an oxygen atmosphere, immediate oxidation was recorded for nanoparticles on n-type GaN, whereas little oxidation was observed for nanoparticles on p-type GaN. Together, these results indicate that changes in the Pt chemical state under X-ray irradiation depend on the type of GaN doping. The strong interaction between the nanoparticles and the support is consistent with charge transfer of X-ray photogenerated free carriers at the semiconductor-nanoparticle interface and suggests that GaN is a promising wide-band-gap support material for photocatalysis and electronic control of catalysis.

Surface engineering of macrophages with nanoparticles to generate a cell-nanoparticle hybrid vehicle for hypoxia-targeted drug delivery.

PubMed

Holden, Christopher A; Yuan, Quan; Yeudall, W Andrew; Lebman, Deborah A; Yang, Hu

2010-02-02

Tumors frequently contain hypoxic regions that result from a shortage of oxygen due to poorly organized tumor vasculature. Cancer cells in these areas are resistant to radiation- and chemotherapy, limiting the treatment efficacy. Macrophages have inherent hypoxia-targeting ability and hold great advantages for targeted delivery of anticancer therapeutics to cancer cells in hypoxic areas. However, most anticancer drugs cannot be directly loaded into macrophages because of their toxicity. In this work, we designed a novel drug delivery vehicle by hybridizing macrophages with nanoparticles through cell surface modification. Nanoparticles immobilized on the cell surface provide numerous new sites for anticancer drug loading, hence potentially minimizing the toxic effect of anticancer drugs on the viability and hypoxia-targeting ability of the macrophage vehicles. In particular, quantum dots and 5-(aminoacetamido) fluorescein-labeled polyamidoamine dendrimer G4.5, both of which were coated with amine-derivatized polyethylene glycol, were immobilized to the sodium periodate-treated surface of RAW264.7 macrophages through a transient Schiff base linkage. Further, a reducing agent, sodium cyanoborohydride, was applied to reduce Schiff bases to stable secondary amine linkages. The distribution of nanoparticles on the cell surface was confirmed by fluorescence imaging, and it was found to be dependent on the stability of the linkages coupling nanoparticles to the cell surface.

Poly(organo phosphazene) nanoparticles surface modified with poly(ethylene oxide).

PubMed

Vandorpe, J; Schacht, E; Stolnik, S; Garnett, M C; Davies, M C; Illum, L; Davis, S S

1996-10-05

The use of biodegradable derivatives of poly(organo phosphazenes) for the preparation of nanoparticles and their surface modification with the novel poly(ethylene oxide) derivative of poly(organo phosphazene) has been assessed using a range of in vitro characterization methods. The nanoparticles were produced by the precipitation solvent evaporation method from the derivative co-substituted with phenylalanine and glycine ethyl ester side groups. A reduction in particle size to less than 200 nm was achieved by an increase in pH of the preparation medium. The formation (and colloidal stability) of these nanoparticles seems to be controlled by two opposite effects: attractive hydrophobic interactions between phenylalanine ester groups and electrostatic repulsions arising from the carboxyl groups formed due to (partial) hydrolysis of the ester bond(s) at the high pH of the preparation medium. The poly[(glycine ethyl ester)phosphazene] derivative containing 5000-Da poly(ethylene oxide) as 5% of the side groups was used for the surface modification of nanoparticles. Adsorbed onto the particles, the polymer produced a thick coating layer of approximately 35 nm. The coated nanoparticles exhibited reduced surface negative potential and improved colloidal stability toward electrolyte-induced flocculation, relative to the uncoated system. However, the steric stabilization provided was less effective than that of a Poloxamine 908 coating. This difference in effectiveness of the steric stabilization might indicate that, although both the stabilizing polymers possess a 5000-Da poly(ethylene oxide) moiety, there is a difference in the arrangements of these poly(ethylene oxide) chains at the particle surface. (c) 1996 John Wiley & Sons, Inc.

Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

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

Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

2012-11-29

The ionic charge state of monodisperse cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine in the presence of 1,3-bis(diphenylphosphino)propane. The polydisperse gold clusters were introduced into the gas phase by electrospray ionization and mass selection was employed to select a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at coverages of 1011 and 1012 clusters/mm2.more » Employing the spatial profiling capabilities of in-situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano, 2012, 6, 573) the coverage of cationic gold clusters on the surface may be used to control the distribution of ionic charge states of the soft-landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol SAM (FSAM) almost complete retention of charge by the deposited Au11L53+ clusters was observed at a lower coverage of 1011 clusters/mm2. In contrast, at a higher coverage of 1012 clusters/mm2, pronounced reduction of charge to Au11L52+ and Au11L5+ was observed on the FSAM. When soft landed onto 16- and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au11L53+ clusters exhibited partial reduction of charge to Au11L52+ at lower coverage and additional reduction of charge to both Au11L52+ and Au11L5+ at higher coverage. The reduction of charge was found to be more pronounced on the surface of the shorter (thinner) C11 than the longer (thicker) C16-COOH-SAM. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge

The role of surface charge on the uptake and biocompatibility of hydroxyapatite nanoparticles with osteoblast cells

PubMed Central

Chen, Liang; Mccrate, Joseph M.; Lee, James C-M.; Li, Hao

2011-01-01

The objective of this study is to evaluate the effect of hydroxyapatite (HAP) nanoparticles with different surface charges on the cellular uptake behavior and in vitro cell viability and proliferation of MC3T3-E1 cell lines (osteoblast). The nanoparticles surface charge was varied by the surface modification with two carboxylic acids: 12-aminododecanoic acid (positive) and dodecanedioic acid (negative). The untreated HAP nanoparticles and dodecanoic acid modified HAP nanoparticles (neutral) were used as the control. X-ray diffraction (XRD) revealed that surface modifications by the three carboxylic acids did not change the crystal structure of HAP nanoparticles; Fourier transform infrared spectroscopy (FTIR) confirmed the adsorption and binding of the carboxylic acids on HAP nanoparticle surface; and zeta potential measurement confirmed that the chemicals successfully modified the surface charge of HAP nanoparticles in water based solution. Transmission electron microscopy (TEM) images showed that positively charged, negatively charged and untreated HAP nanoparticles, with similar size and shape, all penetrated into the cells and cells had more uptake of HAP nanoparticles with positive charge compared to those with negative charge, which might be attributed to the attractive or repulsive interaction between the negatively charged cell membrane and positively/negatively charged HAP nanoparticles. The neutral HAP nanoparticles could not penetrate cell membrane due to the larger size. MTT assay and LDH assay results indicated that as compared with the polystyrene control, greater cell viability and cell proliferation were measured on MC3T3-E1 cells treated with the three kinds of the HAP nanoparticles (neutral, positive, and untreated), among which positively charged HAP nanoparticles shows strongest improvement for cell viability and cell proliferation. In summary, the surface charge of HAP nanoparticles can be modified to influence the cellular uptake of HAP

Acellular assessments of engineered-manufactured nanoparticle biological surface reactivity

EPA Science Inventory

It is critical to assess the surface properties and reactivity of engineered-manufactured nanoparticles (NPs) as these will influence their interactions with biological systems, biokinetics and toxicity. We examined the physicochemical properties and surface reactivity of metal o...

Near-field Light Scattering Techniques for Measuring Nanoparticle-Surface Interaction Energies and Forces.

PubMed

Schein, Perry; Ashcroft, Colby K; O'Dell, Dakota; Adam, Ian S; DiPaolo, Brian; Sabharwal, Manit; Shi, Ce; Hart, Robert; Earhart, Christopher; Erickson, David

2015-08-15

Nanoparticles are quickly becoming commonplace in many commercial and industrial products, ranging from cosmetics to pharmaceuticals to medical diagnostics. Predicting the stability of the engineered nanoparticles within these products a priori remains an important and difficult challenge. Here we describe our techniques for measuring the mechanical interactions between nanoparticles and surfaces using near-field light scattering. Particle-surface interfacial forces are measured by optically "pushing" a particle against a reference surface and observing its motion using scattered near-field light. Unlike atomic force microscopy, this technique is not limited by thermal noise, but instead takes advantage of it. The integrated waveguide and microfluidic architecture allow for high-throughput measurements of about 1000 particles per hour. We characterize the reproducibility of and experimental uncertainty in the measurements made using the NanoTweezer surface instrument. We report surface interaction studies on gold nanoparticles with 50 nm diameters, smaller than previously reported in the literature using similar techniques.

Surface-modified silk hydrogel containing hydroxyapatite nanoparticle with hyaluronic acid-dopamine conjugate.

PubMed

Kim, Hyung Hwan; Park, Jong Bo; Kang, Min Ji; Park, Young Hwan

2014-09-01

Silk fibroin/hydroxyapatite (SF/HAp) composite hydrogels were fabricated in this study, having different HAp contents (0-33 wt%) in SF matrix hydrogel. Surface modification of HAp nanoparticle with hyaluronic acid (HA)-dopamine (DA) conjugate improved a dispersibility of HAp in aqueous SF solution due to its negatively charged surface and therefore, fabrication of the SF composite hydrogel having HAp nanoparticles inside could be possible. Zeta potential of surface-modified HAP was examined by ELS. It demonstrates that surface of HAp was well modified to a negative charge with HA-DA. Morphological structure of SF hydrogel containing surface-modified HAp was examined by FE-SEM for analyzing pore structure of hydrogel and deposition of HAp nanoparticle in SF hydrogel. It was found that HAp nanoparticles were uniformly deposited on the pore wall of SF hydrogel. Structural characteristics of SF/HAp composite hydrogel was performed using X-ray diffraction and FT-IR analysis. It was found that β-sheet crystal conformation of SF was significantly influenced by the HAp content during gelation of a mixture of SF and HAp. As a result of MTT assay, the SF/HAp composite hydrogel showed excellent cell proliferation ability. Therefore, it is expected that SF hydrogel containing HAp nanoparticles has a high potential as bone regeneration scaffold. Copyright © 2014 Elsevier B.V. All rights reserved.

Single-electron induced surface plasmons on a topological nanoparticle

PubMed Central

Siroki, G.; Lee, D.K.K.; Haynes, P. D.; Giannini, V.

2016-01-01

It is rarely the case that a single electron affects the behaviour of several hundred thousands of atoms. Here we demonstrate a phenomenon where this happens. The key role is played by topological insulators—materials that have surface states protected by time-reversal symmetry. Such states are delocalized over the surface and are immune to its imperfections in contrast to ordinary insulators. For topological insulators, the effects of these surface states will be more strongly pronounced in the case of nanoparticles. Here we show that under the influence of light a single electron in a topologically protected surface state creates a surface charge density similar to a plasmon in a metallic nanoparticle. Such an electron can act as a screening layer, which suppresses absorption inside the particle. In addition, it can couple phonons and light, giving rise to a previously unreported topological particle polariton mode. These effects may be useful in the areas of plasmonics, cavity electrodynamics and quantum information. PMID:27491515

Adsorption of Small Cationic Nanoparticles onto Large Anionic Particles from Aqueous Solution: A Model System for Understanding Pigment Dispersion and the Problem of Effective Particle Density.

PubMed

North, S M; Jones, E R; Smith, G N; Mykhaylyk, O O; Annable, T; Armes, S P

2017-02-07

The present study focuses on the use of copolymer nanoparticles as a dispersant for a model pigment (silica). Reversible addition-fragmentation chain transfer (RAFT) alcoholic dispersion polymerization was used to synthesize sterically stabilized diblock copolymer nanoparticles. The steric stabilizer block was poly(2-(dimethylamino)ethyl methacrylate) (PDMA) and the core-forming block was poly(benzyl methacrylate) (PBzMA). The mean degrees of polymerization for the PDMA and PBzMA blocks were 71 and 100, respectively. Transmission electron microscopy (TEM) studies confirmed a near-monodisperse spherical morphology, while dynamic light scattering (DLS) studies indicated an intensity-average diameter of 30 nm. Small-angle X-ray scattering (SAXS) reported a volume-average diameter of 29 ± 0.5 nm and a mean aggregation number of 154. Aqueous electrophoresis measurements confirmed that these PDMA 71 -PBzMA 100 nanoparticles acquired cationic character when transferred from ethanol to water as a result of protonation of the weakly basic PDMA chains. Electrostatic adsorption of these nanoparticles from aqueous solution onto 470 nm silica particles led to either flocculation at submonolayer coverage or steric stabilization at or above monolayer coverage, as judged by DLS. This technique indicated that saturation coverage was achieved on addition of approximately 465 copolymer nanoparticles per silica particle, which corresponds to a fractional surface coverage of around 0.42. These adsorption data were corroborated using thermogravimetry, UV spectroscopy and X-ray photoelectron spectroscopy. TEM studies indicated that the cationic nanoparticles remained intact on the silica surface after electrostatic adsorption, while aqueous electrophoresis confirmed that surface charge reversal occurred below pH 7. The relatively thick layer of adsorbed nanoparticles led to a significant reduction in the effective particle density of the silica particles from 1.99 g cm -3 to

Surface modification of PLGA nanoparticles via human serum albumin conjugation for controlled delivery of docetaxel

PubMed Central

2013-01-01

Background Poly lactic-co-glycolic acid (PLGA) based nanoparticles are considered to be a promising drug carrier in tumor targeting but suffer from the high level of opsonization by reticuloendothelial system due to their hydrophobic structure. As a result surface modification of these nanoparticles has been widely studied as an essential step in their development. Among various surface modifications, human serum albumin (HSA) possesses advantages including small size, hydrophilic surface and accumulation in leaky vasculature of tumors through passive targeting and a probable active transport into tumor tissues. Methods PLGA nanoparticles of docetaxel were prepared by emulsification evaporation method and were surface conjugated with human serum albumin. Fourier transform infrared spectrum was used to confirm the conjugation reaction where nuclear magnetic resonance was utilized for conjugation ratio determination. In addition, transmission electron microscopy showed two different contrast media in conjugated nanoparticles. Furthermore, cytotoxicity of free docetaxel, unconjugated and conjugated PLGA nanoparticles was studied in HepG2 cells. Results Size, zeta potential and drug loading of PLGA nanoparticles were about 199 nm, −11.07 mV, and 4%, respectively where size, zeta potential and drug loading of conjugated nanoparticles were found to be 204 nm, −5.6 mV and 3.6% respectively. Conjugated nanoparticles represented a three-phasic release pattern with a 20% burst effect for docetaxel on the first day. Cytotoxicity experiment showed that the IC50 of HSA conjugated PLGA nanoparticles (5.4 μg) was significantly lower than both free docetaxel (20.2 μg) and unconjugated PLGA nanoparticles (6.2 μg). Conclusion In conclusion surface modification of PLGA nanoparticles through HSA conjugation results in more cytotoxicity against tumor cell lines compared with free docetaxel and unconjugated PLGA nanoparticles. Albumin conjugated PLGA nanoparticles may

Surface-modified multifunctional MIP nanoparticles

NASA Astrophysics Data System (ADS)

Moczko, Ewa; Poma, Alessandro; Guerreiro, Antonio; Perez de Vargas Sansalvador, Isabel; Caygill, Sarah; Canfarotta, Francesco; Whitcombe, Michael J.; Piletsky, Sergey

2013-04-01

The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as a protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity (PEG methacrylate); electro-activity (vinylferrocene); fluorescence (eosin acrylate); thiol groups (pentaerythritol tetrakis(3-mercaptopropionate)). The method has broad applicability and can be used to produce multifunctional imprinted nanoparticles with potential for further application in the biosensors, diagnostics and biomedical fields and as an alternative to natural receptors.The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as a protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity

Modified surface of titanium dioxide nanoparticles-based biosensor for DNA detection

NASA Astrophysics Data System (ADS)

Nadzirah, Sh.; Hashim, U.; Rusop, M.

2018-05-01

A new technique was used to develop a simple and selective picoammeter DNA biosensor for identification of E. coli O157:H7. This biosensor was fabricated from titanium dioxide nanoparticles that was synthesized by sol-gel method and spin-coated on silicon dioxide substrate via spinner. 3-Aminopropyl triethoxy silane (APTES) was used to modify the surface of TiO2. Simple surface modification approach has been applied; which is single dropping of APTES onto the TiO2 nanoparticles surface. Carboxyl modified probe DNA has been bind onto the surface of APTES/TiO2 without any amplifier element. Electrical signal has been used as the indicator to differentiate each step (surface modification of TiO2 and probe DNA immobilization). The I-V measurements indicate extremely low current (pico-ampere) flow through the device which is 2.8138E-10 A for pure TiO2 nanoparticles, 2.8124E-10 A after APTES modification and 3.5949E-10 A after probe DNA immobilization.

Molecular dynamics study of oil adsorption on the rock surface in presence of silica nanoparticles

NASA Astrophysics Data System (ADS)

Salehzadeh, Jamal; Tohidi, Zahra; Jafari, Arezou

2018-01-01

Despite the increasing applications of nanoparticles in enhanced oil recovery (EOR), there is not enough information about the mechanisms and microscopic aspects of nanoparticles' effects. Therefore, in this research, molecular dynamics simulation is used to provide the molecular-scale insight for investigation of the silica nanoparticles effects on the oil adsorption on calcite surface for the first time. The surface interacts with the mixture of heptane and decane as the oil phase with mole ratio of 1/2 and silica nanoparticles are dispersed in distilled water with concentration of 7000 ppm. Based on the simulation results, by using nanoparticles surface adsorption behavior have been changed to hydrophilic and the oil molecules departed from the calcite. This result is based on the oil-calcite binding energy calculation which is decreased from 5224 kcal/mol to 3278 kcal/mol by using silica nanoparticles. In addition, calculation of radial distribution functions showed that after adding silica nanoparticles, the picks fall which means increasing in average distance between oil and calcite surface.

Catalytic Properties of Unsupported Palladium Nanoparticle Surfaces Capped with Small Organic Ligands

PubMed Central

Gavia, Diego J.

2015-01-01

This Minireview summarizes a variety of intriguing catalytic studies accomplished by employing unsupported, either solubilized or freely mobilized, and small organic ligand-capped palladium nanoparticles as catalysts. Small organic ligands are gaining more attention as nanoparticle stabilizers and alternates to larger organic supports, such as polymers and dendrimers, owing to their tremendous potential for a well-defined system with spatial control in surrounding environments of reactive surfaces. The nanoparticle catalysts are grouped depending on the type of surface stabilizers with reactive head groups, which include thiolate, phosphine, amine, and alkyl azide. Applications for the reactions such as hydrogenation, alkene isomerization, oxidation, and carbon-carbon cross coupling reactions are extensively discussed. The systems defined as “ligandless” Pd nanoparticle catalysts and solvent (e.g. ionic liquid)-stabilized Pd nanoparticle catalysts are not discussed in this review. PMID:25937846

Improving the Yule-Nielsen modified Neugebauer model by dot surface coverages depending on the ink superposition conditions

NASA Astrophysics Data System (ADS)

Hersch, Roger David; Crété, Frédérique

2004-12-01

Dot gain is different when dots are printed alone, printed in superposition with one ink or printed in superposition with two inks. In addition, the dot gain may also differ depending on which solid ink the considered halftone layer is superposed. In a previous research project, we developed a model for computing the effective surface coverage of a dot according to its superposition conditions. In the present contribution, we improve the Yule-Nielsen modified Neugebauer model by integrating into it our effective dot surface coverage computation model. Calibration of the reproduction curves mapping nominal to effective surface coverages in every superposition condition is carried out by fitting effective dot surfaces which minimize the sum of square differences between the measured reflection density spectra and reflection density spectra predicted according to the Yule-Nielsen modified Neugebauer model. In order to predict the reflection spectrum of a patch, its known nominal surface coverage values are converted into effective coverage values by weighting the contributions from different reproduction curves according to the weights of the contributing superposition conditions. We analyze the colorimetric prediction improvement brought by our extended dot surface coverage model for clustered-dot offset prints, thermal transfer prints and ink-jet prints. The color differences induced by the differences between measured reflection spectra and reflection spectra predicted according to the new dot surface estimation model are quantified on 729 different cyan, magenta, yellow patches covering the full color gamut. As a reference, these differences are also computed for the classical Yule-Nielsen modified spectral Neugebauer model incorporating a single halftone reproduction curve for each ink. Taking into account dot surface coverages according to different superposition conditions considerably improves the predictions of the Yule-Nielsen modified Neugebauer model. In

Improving the Yule-Nielsen modified Neugebauer model by dot surface coverages depending on the ink superposition conditions

NASA Astrophysics Data System (ADS)

Hersch, Roger David; Crete, Frederique

2005-01-01

Dot gain is different when dots are printed alone, printed in superposition with one ink or printed in superposition with two inks. In addition, the dot gain may also differ depending on which solid ink the considered halftone layer is superposed. In a previous research project, we developed a model for computing the effective surface coverage of a dot according to its superposition conditions. In the present contribution, we improve the Yule-Nielsen modified Neugebauer model by integrating into it our effective dot surface coverage computation model. Calibration of the reproduction curves mapping nominal to effective surface coverages in every superposition condition is carried out by fitting effective dot surfaces which minimize the sum of square differences between the measured reflection density spectra and reflection density spectra predicted according to the Yule-Nielsen modified Neugebauer model. In order to predict the reflection spectrum of a patch, its known nominal surface coverage values are converted into effective coverage values by weighting the contributions from different reproduction curves according to the weights of the contributing superposition conditions. We analyze the colorimetric prediction improvement brought by our extended dot surface coverage model for clustered-dot offset prints, thermal transfer prints and ink-jet prints. The color differences induced by the differences between measured reflection spectra and reflection spectra predicted according to the new dot surface estimation model are quantified on 729 different cyan, magenta, yellow patches covering the full color gamut. As a reference, these differences are also computed for the classical Yule-Nielsen modified spectral Neugebauer model incorporating a single halftone reproduction curve for each ink. Taking into account dot surface coverages according to different superposition conditions considerably improves the predictions of the Yule-Nielsen modified Neugebauer model. In

Molecular dynamic simulations of the high-speed copper nanoparticles collision with the aluminum surface

NASA Astrophysics Data System (ADS)

Pogorelko, V. V.; Mayer, A. E.

2016-11-01

With the use of the molecular dynamic simulations, we investigated the effect of the high-speed (500 m/s, 1000 m/s) copper nanoparticle impact on the mechanical properties of an aluminum surface. Dislocation analysis shows that a large number of dislocations are formed in the impact area; the total length of dislocations is determined not only by the speed and size of the incoming copper nanoparticle (kinetic energy of the nanoparticle), but by a temperature of the system as well. The dislocations occupy the whole area of the aluminum single crystal at high kinetic energy of the nanoparticle. With the decrease of the nanoparticle kinetic energy, the dislocation structures are formed in the near-surface layer; formation of the dislocation loops takes place. Temperature rise of the system (aluminum substrate + nanoparticle) reduces the total dislocation length in the single crystal of aluminum; there is deeper penetration of the copper atoms in the aluminum at high temperatures. Average energy of the nanoparticles and room temperature of the system are optimal for production of high-quality layers of copper on the aluminum surface.

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Devetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

2015-05-01

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this

Physicochemical properties of surface charge-modified ZnO nanoparticles with different particle sizes

PubMed Central

Kim, Kyoung-Min; Choi, Mun-Hyoung; Lee, Jong-Kwon; Jeong, Jayoung; Kim, Yu-Ri; Kim, Meyoung-Kon; Paek, Seung-Min; Oh, Jae-Min

2014-01-01

In this study, four types of standardized ZnO nanoparticles were prepared for assessment of their potential biological risk. Powder-phased ZnO nanoparticles with different particle sizes (20 nm and 100 nm) were coated with citrate or L-serine to induce a negative or positive surface charge, respectively. The four types of coated ZnO nanoparticles were subjected to physicochemical evaluation according to the guidelines published by the Organisation for Economic Cooperation and Development. All four samples had a well crystallized Wurtzite phase, with particle sizes of ∼30 nm and ∼70 nm after coating with organic molecules. The coating agents were determined to have attached to the ZnO surfaces through either electrostatic interaction or partial coordination bonding. Electrokinetic measurements showed that the surface charges of the ZnO nanoparticles were successfully modified to be negative (about −40 mV) or positive (about +25 mV). Although all the four types of ZnO nanoparticles showed some agglomeration when suspended in water according to dynamic light scattering analysis, they had clearly distinguishable particle size and surface charge parameters and well defined physicochemical properties. PMID:25565825

Mechanochemical activation and patterning of an adhesive surface toward nanoparticle deposition.

PubMed

Baytekin, H Tarik; Baytekin, Bilge; Huda, Sabil; Yavuz, Zelal; Grzybowski, Bartosz A

2015-02-11

Mechanical pulling of adhesive tape creates radicals on the tape's surface. These radicals are capable of reducing metal salts to the corresponding metal nanoparticles. In this way, the mechanically activated tape can be decorated with various types of nanoparticles, including Au, Ag, Pd, or Cu. While retaining their mechanical properties and remaining "sticky," the tapes can exhibit new properties derived from the presence of metal nanoparticles (e.g., bacteriostaticity, increased electrical conductivity). They can also be patterned with nanoparticles only at selective locations of mechanical activation.

Colloidal aluminum nanoparticles with tunable localized surface plasmon resonances for energy applications

NASA Astrophysics Data System (ADS)

Cheng, Yan; Smith, Kenneth; Arinze, Ebuka; Nyirjesy, Gabrielle; Bragg, Arthur; Thon, Susanna

Localized surface plasmon resonances (LSPRs) of noble metal nanoparticles are of interest for energy applications due to their visible and near infrared wavelength sensitivity. However, application of these materials in optoelectronic devices is limited by their rarity and high cost. Earth-abundant, inexpensive and non-toxic aluminum is a promising alternative material with a plasmon resonance that can also be tuned via size-, shape- and surface-oxide-control. Here, we employ solution-processed methods to synthesize stable colloidal aluminum nanoparticles. We systematically investigate parameters in the synthesis that control size, shape and oxidation of the aluminum nanoparticles and tune their LSPRs over the ultraviolet and visible spectral regions. We optically characterize the nanoparticle solutions and evaluate their potential for future integration into photovoltaic, photocatalytic and photosensing systems.

Characterization and electrochemical response of DNA functionalized 2nm gold nanoparticles confined in a nanochannel array.

PubMed

Peinetti, Ana S; Ceretti, Helena; Mizrahi, Martín; González, Graciela A; Ramírez, Silvana A; Requejo, Félix G; Montserrat, Javier M; Battaglini, Fernando

2018-06-01

Polyvalent gold nanoparticle oligonucleotide conjugates are subject of intense research. Even though 2nm diameter AuNPs have been previously modified with DNA, little is known about their structure and electrochemical behavior. In this work, we examine the influence of different surface modification strategies on the interplay between the meso-organization and the molecular recognition properties of a 27-mer DNA strand. This DNA strand is functionalized with different sulfur-containing moieties and immobilized on 2nm gold nanoparticles confined on a nanoporous alumina, working the whole system as an electrode array. Surface coverages were determined by EXAFS and the performance as recognition elements for impedance-based sensors is evaluated. Our results prove that low DNA coverages on the confined nanoparticles prompt to a more sensitive response, showing the relevance in avoiding the DNA strand overcrowding. The system was able to determine a concentration as low as 100pM of the complementary strand, thus introducing the foundations for the construction of label-free genosensors at the nanometer scale. Copyright © 2018 Elsevier B.V. All rights reserved.

Gold Nanoparticles with Externally Controlled, Reversible Shifts of Local Surface Plasmon Resonance Bands

PubMed Central

Yavuz, Mustafa S.; Jensen, Gary C.; Penaloza, David P.; Seery, Thomas A. P.; Pendergraph, Samuel A.; Rusling, James F.; Sotzing, Gregory A.

2010-01-01

We have achieved reversible tunability of local surface plasmon resonance in conjugated polymer functionalized gold nanoparticles. This property was facilitated by the preparation of 3,4-ethylenedioxythiophene (EDOT) containing polynorbornene brushes on gold nanoparticles via surface-initiated ring-opening metathesis polymerization. Reversible tuning of the surface plasmon band was achieved by electrochemically switching the EDOT polymer between its reduced and oxidized states. PMID:19839619

Surface-modified multifunctional MIP nanoparticles

PubMed Central

Moczko, Ewa; Poma, Alessandro; Guerreiro, Antonio; de Vargas Sansalvador, Isabel Perez; Caygill, Sarah; Canfarotta, Francesco; Whitcombe, Michael J.; Piletsky, Sergey

2015-01-01

The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly-sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity (PEG methacrylate); electro-activity (vinyl ferrocene); fluorescence (eosin acrylate); thiol groups (pentaerythritol tetrakis(3-mercaptopropionate)). The method has broad applicability and can be used to produce multifunctional imprinted nanoparticles with potential for further application in the biosensors, diagnostics and biomedical fields and as an alternative to natural receptors. PMID:23503559

Surface-modified multifunctional MIP nanoparticles.

PubMed

Moczko, Ewa; Poma, Alessandro; Guerreiro, Antonio; Perez de Vargas Sansalvador, Isabel; Caygill, Sarah; Canfarotta, Francesco; Whitcombe, Michael J; Piletsky, Sergey

2013-05-07

The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as a protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity (PEG methacrylate); electro-activity (vinylferrocene); fluorescence (eosin acrylate); thiol groups (pentaerythritol tetrakis(3-mercaptopropionate)). The method has broad applicability and can be used to produce multifunctional imprinted nanoparticles with potential for further application in the biosensors, diagnostics and biomedical fields and as an alternative to natural receptors.

Reversible Regulation of Catalytic Activity of Gold Nanoparticles with DNA Nanomachines

NASA Astrophysics Data System (ADS)

Zhou, Peipei; Jia, Sisi; Pan, Dun; Wang, Lihua; Gao, Jimin; Lu, Jianxin; Shi, Jiye; Tang, Zisheng; Liu, Huajie

2015-09-01

Reversible catalysis regulation has gained much attention and traditional strategies utilized reversible ligand coordination for switching catalyst’s conformations. However, it remains challenging to regulate the catalytic activity of metal nanoparticle-based catalysts. Herein, we report a new DNA nanomachine-driven reversible nano-shield strategy for circumventing this problem. The basic idea is based on the fact that the conformational change of surface-attached DNA nanomachines will cause the variation of the exposed surface active area on metal nanoparticles. As a proof-of-concept study, we immobilized G-rich DNA strands on gold nanoparticles (AuNPs) which have glucose oxidase (GOx) like activity. Through the reversible conformational change of the G-rich DNA between a flexible single-stranded form and a compact G-quadruplex form, the catalytic activity of AuNPs has been regulated reversibly for several cycles. This strategy is reliable and robust, which demonstrated the possibility of reversibly adjusting catalytic activity with external surface coverage switching, rather than coordination interactions.

Vortex generating flow passage design for increased film-cooling effectiveness and surface coverage

NASA Astrophysics Data System (ADS)

Papell, S. S.

The fluid mechanics of the basic discrete hole film cooling process is described as an inclined jet in crossflow and a cusp shaped coolant flow channel contour that increases the efficiency of the film cooling process is hypothesized. The design concept requires the channel to generate a counter rotating vortex pair secondary flow within the jet stream by virture of flow passage geometry. The interaction of the vortex structures generated by both geometry and crossflow was examined in terms of film cooling effectiveness and surface coverage. Comparative data obtained with this vortex generating coolant passage showed up to factors of four increases in both effectiveness and surface coverage over that obtained with a standard round cross section flow passage. A streakline flow visualization technique was used to support the concept of the counter rotating vortex pair generating capability of the flow passage design.

Enhanced conductivity of tunnel junctions employing semimetallic nanoparticles through variation in growth temperature and deposition

NASA Astrophysics Data System (ADS)

Nair, Hari P.; Crook, Adam M.; Bank, Seth R.

2010-05-01

We report ErAs nanoparticle-enhanced tunnel junctions grown on GaAs with low specific resistances (<2×10-4 Ω cm-2), approximately tenfold lower than previous reports. A reduction in specific resistance was achieved by modifying the ErAs nanoparticle morphology through the molecular beam epitaxial growth conditions, particularly lower growth temperatures. A further investigation of the variation in tunnel junction resistance with the amount of ErAs deposited and growth temperature shows that nanoparticle surface coverage may not be the only factor determining tunnel junction resistance.

Guided selective deposition of nanoparticles by tuning of the surface potential

NASA Astrophysics Data System (ADS)

Eklöf, J.; Stolaś, A.; Herzberg, M.; Pekkari, A.; Tebikachew, B.; Gschneidtner, T.; Lara-Avila, S.; Hassenkam, T.; Moth-Poulsen, K.

2017-07-01

Guided deposition of nanoparticles onto different substrates is of great importance for a variety of applications such as biosensing, targeted cancer therapy, anti-bacterial coatings and single molecular electronics. It is therefore important to gain an understanding of what parameters are involved in the deposition of nanoparticles. In this work we have deposited 60 nm, negatively charged, citrate stabilized gold nanoparticles onto microstructures consisting of six different materials, (vanadium (V), silicon dioxide (SiO2), gold (Au), aluminum (Al), copper (Cu) and nickel (Ni)). The samples have then been investigated by scanning electron microscopy to extract the particle density. The surface potential was calculated from the measured surface charge density maps measured by atomic force microscopy while the samples were submerged in a KCl water solution. These values were compared with literature values of the isoelectric points (IEP) of different oxides formed on the metals in an ambient environment. According to measurements, Al had the highest surface potential followed by Ni and Cu. The same trend was observed for the nanoparticle densities. No particles were found on V, SiO2 and Au. The literature values of the IEP showed a different trend compared to the surface potential measurements concluding that IEP is not a reliable parameter for the prediction of NP deposition. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

Surface-Directed Synthesis of Erbium-Doped Yttrium Oxide Nanoparticles within Organosilane Zeptoliter Containers

PubMed Central

2015-01-01

We introduce an approach to synthesize rare earth oxide nanoparticles using high temperature without aggregation of the nanoparticles. The dispersity of the nanoparticles is controlled at the nanoscale by using small organosilane molds as reaction containers. Zeptoliter reaction vessels prepared from organosilane self-assembled monolayers (SAMs) were used for the surface-directed synthesis of rare earth oxide (REO) nanoparticles. Nanopores of octadecyltrichlorosilane were prepared on Si(111) using particle lithography with immersion steps. The nanopores were filled with a precursor solution of erbium and yttrium salts to confine the crystallization step to occur within individual zeptoliter-sized organosilane reaction vessels. Areas between the nanopores were separated by a matrix film of octadecyltrichlorosilane. With heating, the organosilane template was removed by calcination to generate a surface array of erbium-doped yttria nanoparticles. Nanoparticles synthesized by the surface-directed approach retain the periodic arrangement of the nanopores formed from mesoparticle masks. While bulk rare earth oxides can be readily prepared by solid state methods at high temperature (>900 °C), approaches for preparing REO nanoparticles are limited. Conventional wet chemistry methods are limited to low temperatures according to the boiling points of the solvents used for synthesis. To achieve crystallinity of REO nanoparticles requires steps for high-temperature processing of samples, which can cause self-aggregation and dispersity in sample diameters. The facile steps for particle lithography address the problems of aggregation and the requirement for high-temperature synthesis. PMID:25163977

Synthesis of water soluble glycine capped silver nanoparticles and their surface selective interaction

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

Agasti, Nityananda, E-mail: nnagasti@gmail.com; Singh, Vinay K.; Kaushik, N.K.

Highlights: • Synthesis of water soluble silver nanoparticles at ambient reaction conditions. • Glycine as stabilizing agent for silver nanoparticles. • Surface selective interaction of glycine with silver nanoparticles. • Glycine concentration influences crystalinity and optical property of silver nanoparticles. - Abstract: Synthesis of biocompatible metal nanoparticles has been an area of significant interest because of their wide range of applications. In the present study, we have successfully synthesized water soluble silver nanoparticles assisted by small amino acid glycine. The method is primarily based on reduction of AgNO{sub 3} with NaBH{sub 4} in aqueous solution under atmospheric air in themore » presence of glycine. UV–vis spectroscopy, transmission electron microscopy (TEM), X–ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TG) and differential thermal analysis (DTA) techniques used for characterization of resulting silver nanoparticles demonstrated that, glycine is an effective capping agent to stabilize silver nanoparticles. Surface selective interaction of glycine on (1 1 1) face of silver nanoparticles has been investigated. The optical property and crystalline behavior of silver nanoparticles were found to be sensitive to concentration of glycine. X–ray diffraction studies ascertained the phase specific interaction of glycine on silver nanoparticles. Silver nanoparticles synthesized were of diameter 60 nm. We thus demonstrated an efficient synthetic method for synthesis of water soluble silver nanoparticles capped by amino acid under mild reaction conditions with excellent reproducibility.« less

A variable pressure method for characterizing nanoparticle surface charge using pore sensors.

PubMed

Vogel, Robert; Anderson, Will; Eldridge, James; Glossop, Ben; Willmott, Geoff

2012-04-03

A novel method using resistive pulse sensors for electrokinetic surface charge measurements of nanoparticles is presented. This method involves recording the particle blockade rate while the pressure applied across a pore sensor is varied. This applied pressure acts in a direction which opposes transport due to the combination of electro-osmosis, electrophoresis, and inherent pressure. The blockade rate reaches a minimum when the velocity of nanoparticles in the vicinity of the pore approaches zero, and the forces on typical nanoparticles are in equilibrium. The pressure applied at this minimum rate can be used to calculate the zeta potential of the nanoparticles. The efficacy of this variable pressure method was demonstrated for a range of carboxylated 200 nm polystyrene nanoparticles with different surface charge densities. Results were of the same order as phase analysis light scattering (PALS) measurements. Unlike PALS results, the sequence of increasing zeta potential for different particle types agreed with conductometric titration.

Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

NASA Astrophysics Data System (ADS)

Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-Dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

2015-12-01

Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest--and more attractive--systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination--without nanoparticle aggregation and without complex dissociation--of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude.

Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

PubMed Central

Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

2015-01-01

Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest—and more attractive—systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination—without nanoparticle aggregation and without complex dissociation—of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude. PMID:26634987

Preparation of transition metal nanoparticles and surfaces modified with (CO)polymers synthesized by RAFT

DOEpatents

McCormick, III., Charles L.; Lowe, Andrew B.; Sumerlin, Brent S.

2006-11-21

A new, facile, general one-phase method of generating thio-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the stops of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Preparation of transition metal nanoparticles and surfaces modified with (co)polymers synthesized by RAFT

DOEpatents

McCormick, III, Charles L.; Lowe, Andrew B [Hattiesburg, MS; Sumerlin, Brent S [Pittsburgh, PA

2011-12-27

A new, facile, general one-phase method of generating thiol-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the steps of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Mapping Titan Cloud Coverage

NASA Image and Video Library

2010-09-21

This graphic, constructed from data obtained by NASA Cassini spacecraft, shows the percentage of cloud coverage across the surface of Saturn moon Titan. The color scale from black to yellow signifies no cloud coverage to complete cloud coverage.

Significance of surface charge and shell material of superparamagnetic iron oxide nanoparticle (SPION) based core/shell nanoparticles on the composition of the protein corona.

PubMed

Sakulkhu, Usawadee; Mahmoudi, Morteza; Maurizi, Lionel; Coullerez, Geraldine; Hofmann-Amtenbrink, Margarethe; Vries, Marcel; Motazacker, Mahdi; Rezaee, Farhad; Hofmann, Heinrich

2015-02-01

As nanoparticles (NPs) are increasingly used in many applications their safety and efficient applications in nanomedicine have become concerns. Protein coronas on nanomaterials' surfaces can influence how the cell "recognizes" nanoparticles, as well as the in vitro and in vivo NPs' behaviors. The SuperParamagnetic Iron Oxide Nanoparticle (SPION) is one of the most prominent agents because of its superparamagnetic properties, which is useful for separation applications. To mimic surface properties of different types of NPs, a core-shell SPION library was prepared by coating with different surfaces: polyvinyl alcohol polymer (PVA) (positive, neutral and negative), SiO2 (positive and negative), titanium dioxide and metal gold. The SPIONs with different surfaces were incubated at a fixed serum : nanoparticle surface ratio, magnetically trapped and washed. The tightly bound proteins were quantified and identified. The surface charge has a great impact on protein adsorption, especially on PVA and silica where proteins preferred binding to the neutral and positively charged surfaces. The importance of surface material on protein adsorption was also revealed by preferential binding on TiO2 and gold coated SPION, even negatively charged. There is no correlation between the protein net charge and the nanoparticle surface charge on protein binding, nor direct correlation between the serum proteins' concentration and the proteins detected in the coronas.

A surface phase transition of supported gold nanoparticles.

PubMed

Plech, Anton; Cerna, Roland; Kotaidis, Vassilios; Hudert, Florian; Bartels, Albrecht; Dekorsy, Thomas

2007-04-01

A thermal phase transition has been resolved in gold nanoparticles supported on a surface. By use of asynchronous optical sampling with coupled femtosecond oscillators, the Lamb vibrational modes could be resolved as a function of annealing temperature. At a temperature of 104 degrees C the damping rate and phase changes abruptly, indicating a structural transition in the particle, which is explained as the onset of surface melting.

Solubility studies of inorganic-organic hybrid nanoparticle photoresists with different surface functional groups

NASA Astrophysics Data System (ADS)

Li, Li; Chakrabarty, Souvik; Jiang, Jing; Zhang, Ben; Ober, Christopher; Giannelis, Emmanuel P.

2016-01-01

The solubility behavior of Hf and Zr based hybrid nanoparticles with different surface ligands in different concentrations of photoacid generator as potential EUV photoresists was investigated in detail. The nanoparticles regardless of core or ligand chemistry have a hydrodynamic diameter of 2-3 nm and a very narrow size distribution in organic solvents. The Hansen solubility parameters for nanoparticles functionalized with IBA and 2MBA have the highest contribution from the dispersion interaction than those with tDMA and MAA, which show more polar character. The nanoparticles functionalized with unsaturated surface ligands showed more apparent solubility changes after exposure to DUV than those with saturated ones. The solubility differences after exposure are more pronounced for films containing a higher amount of photoacid generator. The work reported here provides material selection criteria and processing strategies for the design of high performance EUV photoresists.The solubility behavior of Hf and Zr based hybrid nanoparticles with different surface ligands in different concentrations of photoacid generator as potential EUV photoresists was investigated in detail. The nanoparticles regardless of core or ligand chemistry have a hydrodynamic diameter of 2-3 nm and a very narrow size distribution in organic solvents. The Hansen solubility parameters for nanoparticles functionalized with IBA and 2MBA have the highest contribution from the dispersion interaction than those with tDMA and MAA, which show more polar character. The nanoparticles functionalized with unsaturated surface ligands showed more apparent solubility changes after exposure to DUV than those with saturated ones. The solubility differences after exposure are more pronounced for films containing a higher amount of photoacid generator. The work reported here provides material selection criteria and processing strategies for the design of high performance EUV photoresists. Electronic supplementary

Enhanced Cyanate Ester Nanocomposites through Improved Nanoparticle Surface Interactions

DTIC Science & Technology

2013-05-01

and a chemically active 3- aminopropyl surface. The cure behavior and thermal properties of the cyanate ester/modified silica nanocomposites were...area of 150 m 2 /g. Nanoparticles with a chemically active 3- aminopropyl surface were prepared by treating Aerosil 200 particles with 3...however, was visibly observed to severely undercure the nanocomposites with octyl and 3- aminopropyl surface moieties, providing a good initial

Single quantum dot tracking reveals the impact of nanoparticle surface on intracellular state.

PubMed

Zahid, Mohammad U; Ma, Liang; Lim, Sung Jun; Smith, Andrew M

2018-05-08

Inefficient delivery of macromolecules and nanoparticles to intracellular targets is a major bottleneck in drug delivery, genetic engineering, and molecular imaging. Here we apply live-cell single-quantum-dot imaging and tracking to analyze and classify nanoparticle states after intracellular delivery. By merging trajectory diffusion parameters with brightness measurements, multidimensional analysis reveals distinct and heterogeneous populations that are indistinguishable using single parameters alone. We derive new quantitative metrics of particle loading, cluster distribution, and vesicular release in single cells, and evaluate intracellular nanoparticles with diverse surfaces following osmotic delivery. Surface properties have a major impact on cell uptake, but little impact on the absolute cytoplasmic numbers. A key outcome is that stable zwitterionic surfaces yield uniform cytosolic behavior, ideal for imaging agents. We anticipate that this combination of quantum dots and single-particle tracking can be widely applied to design and optimize next-generation imaging probes, nanoparticle therapeutics, and biologics.

Surface chemistry governs cellular tropism of nanoparticles in the brain

NASA Astrophysics Data System (ADS)

Song, Eric; Gaudin, Alice; King, Amanda R.; Seo, Young-Eun; Suh, Hee-Won; Deng, Yang; Cui, Jiajia; Tietjen, Gregory T.; Huttner, Anita; Saltzman, W. Mark

2017-05-01

Nanoparticles are of long-standing interest for the treatment of neurological diseases such as glioblastoma. Most past work focused on methods to introduce nanoparticles into the brain, suggesting that reaching the brain interstitium will be sufficient to ensure therapeutic efficacy. However, optimized nanoparticle design for drug delivery to the central nervous system is limited by our understanding of their cellular deposition in the brain. Here, we investigated the cellular fate of poly(lactic acid) nanoparticles presenting different surface chemistries, after administration by convection-enhanced delivery. We demonstrate that nanoparticles with `stealth' properties mostly avoid internalization by all cell types, but internalization can be enhanced by functionalization with bio-adhesive end-groups. We also show that association rates measured in cultured cells predict the extent of internalization of nanoparticles in cell populations. Finally, evaluating therapeutic efficacy in an orthotopic model of glioblastoma highlights the need to balance significant uptake without inducing adverse toxicity.

Cytotoxicity of gold nanoparticles with different structures and surface-anchored chiral polymers.

PubMed

Deng, Jun; Yao, Mengyun; Gao, Changyou

2017-04-15

Nanoparticles (NPs) can have profound effects on cell biology. However, the potential adverse effects of gold nanoparticles (AuNPs) with different surface chirality and structures have not been elucidated. In this study, monolayers of poly(acryloyl-l(d)-valine (l(d)-PAV) chiral molecules were anchored on the surfaces of gold nanocubes (AuNCs) and nanooctahedras (AuNOs), respectively. The l-PAV-AuNCs and d-PAV-AuNCs, or the l-PAV-AuNOs and d-PAV-AuNOs, had identical physicochemical properties in terms of size, morphology and ligand density except of the reverse molecular chirality on the particle surfaces, respectively. The l-PAV capped AuNCs and AuNOs exhibited larger cytotoxicity to A549 cells than the D-PAV coated ones, and the PAV-AuNOs had larger cytotoxicity than PAV-AuNCs when being capped with the same type of enantiomers, respectively. The cytotoxicity was positively correlated with the cellular uptake amount, and thereby the production of intracellular reactive oxygen species (ROS). • Gold nanoparticles with different structure and surface chirality are fabricated. • The structure and surface chirality at the nanoscale can influence cytotoxicity and genotoxicity. • A new perspective on designing nanoparticles for drug delivery, bioimaging and diagnosis. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Demonstration of surface-enhanced Raman scattering by tunable, plasmonic gallium nanoparticles.

PubMed

Wu, Pae C; Khoury, Christopher G; Kim, Tong-Ho; Yang, Yang; Losurdo, Maria; Bianco, Giuseppe V; Vo-Dinh, Tuan; Brown, April S; Everitt, Henry O

2009-09-02

Size-controlled gallium nanoparticles deposited on sapphire were explored as alternative substrates to enhance Raman spectral signatures. Gallium's resilience following oxidation is inherently advantageous in comparison with silver for practical ex vacuo nonsolution applications. Ga nanoparticles were grown using a simple molecular beam epitaxy-based fabrication protocol, and monitoring their corresponding surface plasmon resonance energy through in situ spectroscopic ellipsometry allowed the nanoparticles to be easily controlled for size. The Raman spectra obtained from cresyl fast violet (CFV) deposited on substrates with differing mean nanoparticle sizes represent the first demonstration of enhanced Raman signals from reproducibly tunable self-assembled Ga nanoparticles. Nonoptimized aggregate enhancement factors of approximately 80 were observed from the substrate with the smallest Ga nanoparticles for CFV dye solutions down to a dilution of 10 ppm.

Demonstration of surface-enhanced Raman scattering by tunable, plasmonic gallium nanoparticles

PubMed Central

Wu, Pae C; Khoury, Christopher G.; Kim, Tong-Ho; Yang, Yang; Losurdo, Maria; Bianco, Giuseppe V.; Vo-Dinh, Tuan; Brown, April S.; Everitt, Henry O.

2009-01-01

Size-controlled gallium nanoparticles deposited on sapphire are explored as alternative substrates to enhance Raman spectral signatures. Gallium’s resilience following oxidation is inherently advantageous compared to silver for practical ex vacuo, non-solution applications. Ga nanoparticles are grown using a simple, molecular beam epitaxy-based fabrication protocol, and by monitoring their corresponding surface plasmon resonance energy through in situ spectroscopic ellipsometry, the nanoparticles are easily controlled for size. Raman spectroscopy performed on cresyl fast violet (CFV) deposited on substrates of differing mean nanoparticle size represents the first demonstration of enhanced Raman signals from reproducibly tunable self-assembled Ga nanoparticles. Non-optimized aggregate enhancement factors of ~80 were observed from the substrate with the smallest Ga nanoparticles for CFV dye solutions down to a dilution of 10 ppm. PMID:19655747

Geometry and surface controlled formation of nanoparticle helical ribbons

NASA Astrophysics Data System (ADS)

Pham, Jonathan; Lawrence, Jimmy; Lee, Dong; Grason, Gregory; Emrick, Todd; Crosby, Alfred

2013-03-01

Helical structures are interesting because of their space efficiency, mechanical tunability and everyday uses in both the synthetic and natural world. In general, the mechanisms governing helix formation are limited to bilayer material systems and chiral molecular structures. However, in a special range of dimensions where surface energy dominates (i.e. high surface to volume ratio), geometry rather than specific materials can drive helical formation of thin asymmetric ribbons. In an evaporative assembly technique called flow coating, based from the commonly observed coffee ring effect, we create nanoparticle ribbons possessing non-rectangular nanoscale cross-sections. When released into a liquid medium of water, interfacial tension between the asymmetric ribbon and water balances with the elastic cost of bending to form helices with a preferred radius of curvature and a minimum pitch. We demonstrate that this is a universal mechanism that can be used with a wide range of materials, such as quantum dots, metallic nanoparticles, or polymers. Nanoparticle helical ribbons display excellent structural integrity with spring-like characteristics and can be extended high strains.

Surface-Initiated Polymerization with Poly(n-hexylisocyanate) to Covalently Functionalize Silica Nanoparticles.

PubMed

Vatansever, Fatma; Hamblin, Michael R

2017-02-01

New methods are needed for covalent functionalization of nanoparticles-surface with organic polymer coronas to generate polymeric nanocomposite in a controlled manner. Here we report the use of a surface-initiated polymerization approach, mediated by titanium (IV) catalysis, to grow poly( n -hexylisocyanate) chains from silica surface. Two pathways were used to generate the interfacing in these nano-hybrids. In the first one, the nanoparticles was "seeded" with SiCl4, followed by reaction with 1,6-hexanediol to form hydroxyl groups attached directly to the surface via O-Si-O bonding. In the second pathway, the nanoparticles were initially exposed to a 9:1 mixture of trimethyl silyl chloride and chlorodimethyl octenyl silane which was then followed by hydroboration of the double bonds, to afford hydroxyl groups with a spatially controlled density and surface-attachment via O-Si-C bonding. These functionalized surfaces were then activated with the titanium tetrachloride catalyst. In our approach, thus surface tethered catalyst provided the sites for n -hexyl isocyanate monomer insertion, to "build up" the surface-grown polymer layers from the "bottom-up". A final end-capping, to seal off the chain ends, was done via acetyl chloride. Compounds were characterized by FT-IR, 1H-NMR, GC-MS, GPC, and thermogravimetric analyses.

Surface-Initiated Polymerization with Poly(n-hexylisocyanate) to Covalently Functionalize Silica Nanoparticles

PubMed Central

Vatansever, Fatma; Hamblin, Michael R.

2017-01-01

New methods are needed for covalent functionalization of nanoparticles-surface with organic polymer coronas to generate polymeric nanocomposite in a controlled manner. Here we report the use of a surface-initiated polymerization approach, mediated by titanium (IV) catalysis, to grow poly(n-hexylisocyanate) chains from silica surface. Two pathways were used to generate the interfacing in these nano-hybrids. In the first one, the nanoparticles was “seeded” with SiCl4, followed by reaction with 1,6-hexanediol to form hydroxyl groups attached directly to the surface via O-Si-O bonding. In the second pathway, the nanoparticles were initially exposed to a 9:1 mixture of trimethyl silyl chloride and chlorodimethyl octenyl silane which was then followed by hydroboration of the double bonds, to afford hydroxyl groups with a spatially controlled density and surface-attachment via O-Si-C bonding. These functionalized surfaces were then activated with the titanium tetrachloride catalyst. In our approach, thus surface tethered catalyst provided the sites for n-hexyl isocyanate monomer insertion, to “build up” the surface-grown polymer layers from the “bottom-up”. A final end-capping, to seal off the chain ends, was done via acetyl chloride. Compounds were characterized by FT-IR, 1H-NMR, GC-MS, GPC, and thermogravimetric analyses. PMID:28989336

Fabrication of highly hydrophobic two-component thermosetting polyurethane surfaces with silica nanoparticles

NASA Astrophysics Data System (ADS)

Yang, Guang; Song, Jialu; Hou, Xianghui

2018-05-01

Highly hydrophobic thermosetting polyurethane (TSU) surfaces with micro-nano hierarchical structures were developed by a simple process combined with sandpaper templates and nano-silica embellishment. Sandpapers with grit sizes varying from 240 to 7000 grit were used to obtain micro-scale roughness on an intrinsic hydrophilic TSU surface. The surface wettability was investigated by contact angle measurement. It was found that the largest contact angle of the TSU surface without nanoparticles at 102 ± 3° was obtained when the template was 240-grit sandpaper and the molding progress started after 45 min curing of TSU. Silica nanoparticles modified with polydimethylsiloxane were scattered onto the surfaces of both the polymer and the template to construct the desirable nanostructures. The influences of the morphology, surface composition and the silica content on the TSU surface wettability were studied by scanning electron microscopy (SEM), attenuated total reflection (ATR) infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The surface of the TSU/SiO2 nanocomposites containing 4 wt% silica nanoparticles exhibited a distinctive dual-scale structure and excellent hydrophobicity with the contact angle above 150°. The mechanism of wettability was also discussed by Wenzel model and Cassie-Baxter model.

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy.

PubMed

DeVetter, Brent M; Mukherjee, Prabuddha; Murphy, Catherine J; Bhargava, Rohit

2015-05-21

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min(-1). This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

PubMed Central

DeVetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

2015-01-01

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min 1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes. PMID:25905515

Atomistic Simulations of Hydrodynamic and Interaction Forces on Functionalized Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Lane, J. Matthew D.; Ismail, Ahmed E.; Chandross, Michael; Lorenz, Christian D.; Grest, Gary S.

2009-03-01

It is often desired to prevent the flocculation and phase separation of nanoparticles in solution. This can be accomplished either by manipulating the solvent or by tailoring the surface chemistry of the nanoparticles through functionalization with a monolayer of oligomer chains. Since it is not known how these functionalized coatings affect the interactions between nanoparticles and with the surrounding solvent, we present results from a series of molecular dynamics simulations of polyethylene oxide (PEO) coated silica nanoparticles of varying size (5 to 20 nm diameter) in water. For a single nanoparticle we determined the Stokes drag on the nanoparticle as it moves through the solvent and as it approaches a wall. Due to hydrodynamic interactions there are large finite size effects which we estimate by varying the size of the simulation cell. We also determined both solvent-mediated (velocity-independent) and lubrication (velocity-dependent) forces between two nanoparticles as a function of the coverage and chain length of the PEO chains.

Does seed size and surface anatomy play role in combating phytotoxicity of nanoparticles?

PubMed

Jain, Navin; Bhargava, Arpit; Pareek, Vikram; Sayeed Akhtar, Mohd; Panwar, Jitendra

2017-03-01

Rapid utilization of nano-based products will inevitably release nanoparticles into the environment with unidentified consequences. Plants, being an integral part of ecosystem play a vital role in the incorporation of nanoparticles in food chain and thus, need to be critically assessed. The present study assesses the comparative phytotoxicity of nanoparticle, bulk and ionic forms of zinc at different concentrations on selected plant species with varying seed size and surface anatomy. ZnO nanoparticles were chosen in view of their wide spread use in cosmetics and health care products, which allow their direct release in the environment. The impact on germination rate, shoot & root length and vigour index were evaluated. A concentration dependent inhibition of seed germination as well as seedling length was observed in all the tested plants. Due to the presence of thick cuticle on testa and root, pearl millet (xerophytic plant) was found to be relatively less sensitive to ZnO nanoparticles as compared to wheat and tomato (mesophytic plants) with normal cuticle layer. No correlation was observed between nanoparticles toxicity and seed size. The results indicated that variations in surface anatomy of seeds play a crucial role in determining the phytotoxicity of nanoparticles. The present findings significantly contribute to assess potential consequences of nanoparticle release in environment particularly with major emphasis on plant systems. It is the first report which suggests that variations observed in phytotoxicity of nanoparticles is mainly due to the predominant differences in size and surface anatomy of tested plant seeds and root architecture. Effect of various concentrations of nano ZnO, bulk ZnO and zinc sulphate on the growth of pearl millet (A), tomato (B) and wheat (C) seedlings.

Surface functionalization of titanium dioxide nanoparticles: Photo-stability and reactive oxygen species (ROS) generation

NASA Astrophysics Data System (ADS)

Louis, Kacie M.

Metal oxide nanoparticles are becoming increasingly prevalent in society for applications of sunscreens, cosmetics, paints, biomedical imaging, and photovoltaics. Due to the increased surface area to volume ratio of nanoparticles compared to bulk materials, it is important to know the health and safety impacts of these materials. One mechanism of toxicity of nominally "safe" materials such as TiO 2 is through the photocatalytic generation of reactive oxygen species (ROS). ROS production and ligand degradation can affect the bioavailability of these particles in aqueous organisms. We have investigated ROS generation by functionalized TiO2 nanoparticles and its influence on aggregation and bioavailability and toxicity to zebrafish embryos/larvae. For these studies we investigated anatase TiO2 nanoparticles. For application purposes and solution stability, the TiO2 nanoparticles were functionalized with a variety of ligands such as citrate, 3,4-dihydroxybenzaldehyde, and ascorbate. We quantitatively examined the amount of ROS produced in aqueous solution using fluorescent probes and see that more ROS is produced under UV light than in the dark control. Our measurements show that TiO2 toxicity reaches a maximum for nanoparticles with smaller diameters, and is correlated with surface area dependent changes in ROS generation. In an effort to reduce toxicity through control of the surface and surface ligands, we synthesized anatase nanoparticles of different sizes, functionalized them with different ligands, and examined the resulting ROS generation and ligand stability. Using a modular ligand containing a hydrophobic inner region and a hydrophilic outer region, we synthesized water-stable nanoparticles, via two different chemical reactions, having much-reduced ROS generation and thus reduced toxicity. These results suggest new strategies for making safer nanoparticles while still retaining their desired properties. We also examine the degradation of the different ligands

Cryo-electron tomography investigation of serum albumin-camouflaged tobacco mosaic virus nanoparticles.

PubMed

Gulati, Neetu M; Pitek, Andrzej S; Steinmetz, Nicole F; Stewart, Phoebe L

2017-03-09

Nanoparticles offer great potential in drug delivery and imaging, but shielding strategies are necessary to increase circulation time and performance. Structure-function studies are required to define the design rules to achieve effective shielding. With several formulations reaching clinical testing and approval, the ability to assess and detail nanoparticle formulations at the single particle level is becoming increasingly important. To address this need, we use cryo-electron tomography (cryo-ET) to investigate stealth-coated nanoparticles. As a model system, we studied the soft matter nanotubes formed by tobacco mosaic virus (TMV) coated with human serum albumin (SA) stealth proteins. Cryo-ET and subtomogram averaging allow for visualization of individual SA molecules and determination of their orientations relative to the TMV surface, and also for measurement of the surface coverage provided by added stealth proteins. This information fills a critical gap in the understanding of the structural morphology of stealth-coated nanoparticles, and therefore cryo-ET may play an important role in guiding the development of future nanoparticle-based therapeutics.

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles

DOE PAGES

Jia, Qingying; Zhao, Zipeng; Cao, Liang; ...

2017-12-22

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo–PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shapemore » enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable Pt 3Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Lastly, our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.« less

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles

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

Jia, Qingying; Zhao, Zipeng; Cao, Liang

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo–PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shapemore » enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable Pt 3Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Lastly, our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.« less

Surface modification of zinc oxide nanoparticle by PMAA and its dispersion in aqueous system

NASA Astrophysics Data System (ADS)

Tang, Erjun; Cheng, Guoxiang; Ma, Xiaolu; Pang, Xingshou; Zhao, Qiang

2006-05-01

Commercial zinc oxide nanoparticles were modified by polymethacrylic acid (PMAA) in aqueous system. The hydroxyl groups of nano-ZnO particle surface can interact with carboxyl groups (COO-) of PMAA and form poly(zinc methacrylate) complex on the surface of nano-ZnO. The formation of poly(zinc methacrylate) complex was testified by Fourier-transform infrared spectra (FT-IR). Thermogravimetric analysis (TGA) indicated that PMAA molecules were absorbed or anchored on the surface of nano-ZnO particle, which facilitated to hinder the aggregation of nano-ZnO particles. Through particle size analysis and transmission electron micrograph (TEM) observation, it was found that PMAA enhanced the dispersibility of nano-ZnO particles in water. The dispersion stabilization of modified ZnO nanoparticles in aqueous system was significantly improved due to the introduction of grafted polymer on the surface of nanoparticles. The modification did not alter the crystalline structure of the ZnO nanoparticles according to the X-ray diffraction patterns.

Gold nanoparticles with patterned surface monolayers for nanomedicine: current perspectives.

PubMed

Pengo, Paolo; Şologan, Maria; Pasquato, Lucia; Guida, Filomena; Pacor, Sabrina; Tossi, Alessandro; Stellacci, Francesco; Marson, Domenico; Boccardo, Silvia; Pricl, Sabrina; Posocco, Paola

2017-12-01

Molecular self-assembly is a topic attracting intense scientific interest. Various strategies have been developed for construction of molecular aggregates with rationally designed properties, geometries, and dimensions that promise to provide solutions to both theoretical and practical problems in areas such as drug delivery, medical diagnostics, and biosensors, to name but a few. In this respect, gold nanoparticles covered with self-assembled monolayers presenting nanoscale surface patterns-typically patched, striped or Janus-like domains-represent an emerging field. These systems are particularly intriguing for use in bio-nanotechnology applications, as presence of such monolayers with three-dimensional (3D) morphology provides nanoparticles with surface-dependent properties that, in turn, affect their biological behavior. Comprehensive understanding of the physicochemical interactions occurring at the interface between these versatile nanomaterials and biological systems is therefore crucial to fully exploit their potential. This review aims to explore the current state of development of such patterned, self-assembled monolayer-protected gold nanoparticles, through step-by-step analysis of their conceptual design, synthetic procedures, predicted and determined surface characteristics, interactions with and performance in biological environments, and experimental and computational methods currently employed for their investigation.

Gold nanoparticles-decorated electrospun poly(N-vinyl-2-pyrrolidone) nanofibers with tunable size and coverage density for nanomolar detection of single and binary component dyes by surface-enhanced raman spectroscopy

NASA Astrophysics Data System (ADS)

Kurniawan, Alfin; Wang, Meng-Jiy

2017-09-01

The application of the electrospun nanomaterials to surface-enhanced Raman spectroscopy (SERS) is a rapidly evolving field which holds potential for future developments in the generation of portable plasmonic-based detection platforms. In this study, a simple approach to fabricate electrospun poly(N-vinylpyrrolidone) (PVP) mats decorated with gold nanoparticles (AuNPs) by combining electrospinning and calcination was presented. AuNPs were decorated on the fiber mat surface through electrostatic interactions between positively charged aminosilane groups and negatively charged AuNPs. The size and coverage density of AuNPs on the fiber mats could be tuned by varying the calcination temperature. Calcination of AuNPs-decorated PVP fibers at 500 °C-700 °C resulted in the uniform decoration of high density AuNPs with very narrow gaps on every single fiber, which in turn contribute to strong electromagnetic SERS enhancement. The robust free-standing AuNPs-decorated mat which calcined at 500 °C (500/AuNPs-F) exhibited high SERS activity toward cationic (methylene blue, MB) and anionic (methyl orange, MO) dyes in single and binary systems with a detection range from tens of nM to a few hundred μM. The fabricated SERS substrate demonstrated high reproducibility with the spot-to-spot variation in SERS signal intensities was ±10% and ±12% for single and binary dye systems, respectively. The determination of MB and MO in spiked river water and tap water with 500/AuNPs-F substrate gave satisfactory results in terms of the percent spike recoveries (ranging from 92.6%-96.6%) and reproducibility (%RSD values less than 15 for all samples).

pH-Responsive Mercaptoundecanoic Acid Functionalized Gold Nanoparticles and Applications in Catalysis

PubMed Central

Ansar, Siyam M.; Chakraborty, Saptarshi

2018-01-01

Mercaptoundecanoic acid (MUA) functionalized gold nanoparticles (AuNP-MUA) were synthesized and demonstrated to possess pH-triggered aggregation and re-dispersion, as well as the capability of phase transfer between aqueous and organic phases in response to changes in pH. The pH of aggregation for AuNP-MUA is consistent with the pKa of MUA (pH ~4) in solution, while AuNP-MUA phase transition between aqueous and organic phases occurs at pH ~9. The ion pair formation between the amine group in octadecylamine (ODA), the carboxylate group in MUA, and the hydrophobic alkyl chain of ODA facilitates the phase transfer of AuNP-MUA into an organic medium. The AuNP-MUA were investigated as a reusable catalyst in the catalytic reduction of 4-nitrophenol by borohydride—a model reaction for AuNPs. It was determined that 100% MUA surface coverage completely inhibits the catalytic activity of AuNPs. Decreasing the surface coverage was shown to increase catalytic activity, but this decrease also leads to decreased colloidal stability, recoverability, and reusability in subsequent reactions. At 60% MUA surface coverage, colloidal stability and catalytic activity were achieved, but the surface coverage was insufficient to enable redispersion following pH-induced recovery. A balance between AuNP colloidal stability, recoverability, and catalytic activity with reusability was achieved at 90% MUA surface coverage. The AuNP-MUA catalyst can also be recovered at different pH ranges depending on the recovery method employed. At pH ~4, protonation of the MUA results in reduced surface charge and aggregation. At pH ~9, ODA will form an ion-pair with the MUA and induce phase transfer into an immiscible organic phase. Both the pH-triggered aggregation/re-dispersion and aqueous/organic phase transfer methods were employed for catalyst recovery and reuse in subsequent reactions. The ability to recover and reuse the AuNP-MUA catalyst by two different methods and different pH regimes is

Nanoparticle image velocimetry at topologically structured surfaces

PubMed Central

Parikesit, Gea O. F.; Guasto, Jeffrey S.; Girardo, Salvatore; Mele, Elisa; Stabile, Ripalta; Pisignano, Dario; Lindken, Ralph; Westerweel, Jerry

2009-01-01

Nanoparticle image velocimetry (nano-PIV), based on total internal reflection fluorescent microscopy, is very useful to investigate fluid flows within ∼100 nm from a surface; but so far it has only been applied to flow over smooth surfaces. Here we show that it can also be applied to flow over a topologically structured surface, provided that the surface structures can be carefully configured not to disrupt the evanescent-wave illumination. We apply nano-PIV to quantify the flow velocity distribution over a polydimethylsiloxane surface, with a periodic gratinglike structure (with 215 nm height and 2 μm period) fabricated using our customized multilevel lithography method. The measured tracer displacement data are in good agreement with the computed theoretical values. These results demonstrate new possibilities to study the interactions between fluid flow and topologically structured surfaces. PMID:20216973

Kinetically controlled indium surface coverage effects on PAMBE-growth of InN/GaN(0001) quantum well structures

NASA Astrophysics Data System (ADS)

Li, Chen; Maidaniuk, Yurii; Kuchuk, Andrian V.; Shetty, Satish; Ghosh, Pijush; White, Thomas P.; Morgan, Timothy Al.; Hu, Xian; Wu, Yang; Ware, Morgan E.; Mazur, Yuriy I.; Salamo, Gregory J.

2018-05-01

We report the effects of nitrogen (N) plasma and indium (In) flux on the In adatom adsorption/desorption kinetics on a GaN(0001) surface at the relatively high plasma-assisted molecular beam epitaxy-growth temperature of 680 °C. We experimentally demonstrate that under an active N flux, the (√{3 }×√{3 })R 30 ° surface reconstruction containing In and N quickly appears and the dynamically stable In adlayers sitting on this surface exhibit a continuous change from 0 to 2 MLs as a function of In flux. Compared to the bare GaN 1 ×1 surface which is stable during In exposure without an active N flux, we observed a much faster desorption for the bottom In adlayer and the absence of an In flux window corresponding to an In coverage of 1 ML. Moreover, when the In coverage exceeds 2 MLs, the desorption rates become identical for both surfaces. Finally, the importance of In surface coverage before GaN capping was shown by growing a series of InN/GaN multiple quantum well samples. The photoluminescence data show that a consistent quantum well structure is only formed if the surface is covered by excess In droplets before GaN capping.

Preparation, Surface Properties, and Therapeutic Applications of Gold Nanoparticles in Biomedicine.

PubMed

Panahi, Yunes; Mohammadhosseini, Majid; Nejati-Koshki, Kazem; Abadi, Azam Jafari Najaf; Moafi, Hadi Fallah; Akbarzadeh, Abolfazl; Farshbaf, Masoud

2017-02-01

Gold nanoparticles (AuNPs) due to their unique properties and manifold surface functionalities have been applied in bio-nanotechnology. The application of GNPs in recent medical and biological research is very extensive. Especially it involves applications such as detection and photothermalysis of microorganisms and cancer stem cells, biosensors; optical bio-imaging and observing of cells and these nanostructures also serve as practical platforms for therapeutic agents. In this review we studied all therapeutic applications of gold nanoparticles in biomedicine, synthesis methods, and surface properties. © Georg Thieme Verlag KG Stuttgart · New York.

Volume versus surface-mediated recombination in anatase TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Cavigli, Lucia; Bogani, Franco; Vinattieri, Anna; Faso, Valentina; Baldi, Giovanni

2009-09-01

We present an experimental study of the radiative recombination dynamics in size-controlled anatase TiO2 nanoparticles in the range 20-130 nm. From time-integrated photoluminescence spectra and picosecond time-resolved experiments as a function of the nanoparticle size, excitation density, and temperature, we show that photoluminescence comes out from a bulk and a surface radiative recombination. The spectral shift and the different time dynamics provide a clear distinction between them. Moreover, the intrinsic nature of the emission is also proven, providing a quantitative evaluation of volume and surface contributions.

Research on the effect of coverage rate on the surface quality in laser direct writing process

NASA Astrophysics Data System (ADS)

Pan, Xuetao; Tu, Dawei

2017-07-01

Direct writing technique is usually used in femtosecond laser two-photon micromachining. The size of the scanning step is an important factor affecting the surface quality and machining efficiency of micro devices. According to the mechanism of two-photon polymerization, combining the distribution function of light intensity and the free radical concentration theory, we establish the mathematical model of coverage of solidification unit, then analyze the effect of coverage on the machining quality and efficiency. Using the principle of exposure equivalence, we also obtained the analytic expressions of the relationship among the surface quality characteristic parameters of microdevices and the scanning step, and carried out the numerical simulation and experiment. The results show that the scanning step has little influence on the surface quality of the line when it is much smaller than the size of the solidification unit. However, with increasing scanning step, the smoothness of line surface is reduced rapidly, and the surface quality becomes much worse.

Hematite/silica nanoparticle bilayers on mica: AFM and electrokinetic characterization.

PubMed

Morga, Maria; Adamczyk, Zbigniew; Kosior, Dominik; Oćwieja, Magdalena

2018-06-06

Quantitative studies on self-assembled hematite/silica nanoparticle (NP) bilayers on mica were performed by applying scanning electron microscopy (SEM), atomic force microscopy (AFM), and streaming potential measurements. The coverage of the supporting hematite layers was adjusted by changing the bulk concentration of the suspension and the deposition time. The coverage was determined by direct enumeration of deposited particles from AFM images and SEM micrographs. Afterward, silica nanoparticle monolayers were assembled under diffusion-controlled transport. A unique functional relationship was derived connecting the silica coverage with the hematite precursor layer coverage. The formation of the hematite monolayer and the hematite/silica bilayer was also monitored in situ by streaming potential measurements. It was confirmed that the zeta potential of the bilayers was independent of the supporting layer coverage, exceeding 0.15. These measurements were theoretically interpreted in terms of the general electrokinetic model that allowed for deriving a formula for calculating nanoparticle coverage in the bilayers. Additionally, from desorption experiments, the interactions among hematite/silica particles in the bilayers were determined using DLVO theory. These results facilitate the development of a robust method of preparing nanoparticle bilayers with controlled properties, with potential applications in catalytic processes.

Facile electrocatalytic redox of hemoglobin by flower-like gold nanoparticles on boron-doped diamond surface.

PubMed

Li, Mingfang; Zhao, Guohua; Geng, Rong; Hu, Huikang

2008-11-01

The flower-like gold nanoparticles together with spherical and convex polyhedron gold nanoparticles were fabricated on boron-doped diamond (BDD) surface by one-step and simple electrochemical method through easily controlling the applied potential and the concentration of HAuCl(4). The recorded X-ray diffraction (XRD) patterns confirmed that these three shapes of gold nanoparticles were dominated by different crystal facets. The cyclic voltammetric results indicated that the morphology of gold nanoparticles plays big role in their electrochemical behaviors. The direct electrochemistry of hemoglobin (Hb) was realized on all the three different shapes of nanogold-attached BDD surface without the aid of any electron mediator. In pH 4.5 acetate buffer solutions (ABS), Hb showed a pair of well defined and quasi-reversible redox peaks. However, the results obtained demonstrated that the redox peak potential, the average surface concentration of electroactive heme, and the electron transfer rates of Hb are greatly dependent upon the surface morphology of gold nanoparticles. The electron transfer rate constant of hemoglobin over flower-like nanogold/BDD electrode was more than two times higher than that over spherical and convex polyhedron nanogold. The observed differences may be ascribed to the difference in gold particle characteristics including surface roughness, exposed surface area, and crystal structure.

Cancer imaging using Surface-Enhanced Resonance Raman Scattering (SERRS) nanoparticles

PubMed Central

Harmsen, Stefan; Wall, Matthew A.; Huang, Ruimin

2017-01-01

The unique spectral signatures and biologically inert compositions of surface-enhanced (resonance) Raman scattering (SE(R)RS) nanoparticles make them promising contrast agents for in vivo cancer imaging. Subtle aspects of their preparation can shift their limit of detection by orders of magnitude. In this protocol, we present the optimized, step-by-step procedure for generating reproducible SERRS nanoparticles with femtomolar (10−15 M) limits of detection. We introduce several applications of these nanoprobes for biomedical research, with a focus on intraoperative cancer imaging via Raman imaging. A detailed account is provided for successful intravenous administration of SERRS nanoparticles such that delineation of cancerous lesions may be achieved without the need for specific biomarker targeting. The time estimate for this straightforward, yet comprehensive protocol from initial de novo gold nanoparticle synthesis to SE(R)RS nanoparticle contrast-enhanced preclinical Raman imaging in animal models is ~96 h. PMID:28686581

Modulating interactions between ligand-coated nanoparticles and phase-separated lipid bilayers by varying the ligand density and the surface charge.

PubMed

Chen, Xiaojie; Tieleman, D Peter; Liang, Qing

2018-02-01

The interactions between nanoparticles and lipid bilayers are critical in applications of nanoparticles in nanomedicine, cell imaging, toxicology, and elsewhere. Here, we investigate the interactions between nanoparticles coated with neutral and/or charged ligands and phase-separated lipid bilayers using coarse-grained molecular dynamics simulation. Both penetration and adsorption processes as well as the final distribution of the nanoparticles can be readily modulated by varying the ligand density and the surface charge of the nanoparticles. Completely hydrophobic (neutral) nanoparticles with larger size initially preferentially penetrate into the liquid-disordered region of the lipid bilayer and finally transfer into the liquid-ordered region; partially hydrophilic nanoparticles with low or moderate surface charge tend to either distribute in the liquid-disordered region or be adsorbed on the surface of the lipid bilayer, while strongly hydrophilic nanoparticles with high surface charge always reside on the surface of the lipid bilayer. Interactions of the nanoparticles with the lipid bilayers are affected by the surface charge of nanoparticles, hydrophobic mismatch, bending of the ligands, and the packing state of the lipids. Insight in these factors can be used to improve the efficiency of designing nanoparticles for specific applications.

Highly-branched anisotropic hybrid nanoparticles at surfaces.

NASA Astrophysics Data System (ADS)

Tsukruk, Vladimir

2009-03-01

We present a brief overview of our recent studies on combined hybrid anisotropic structures composed of inorganic nanoparticles and highly branched molecules such as modified silsesquioxanes polyhedra cores (POSS) with mixed hydrophobic-hydrophilic tails and silver nanowires with functionalized star block copolymer with embedded gold nanoparticles (nanocobs). We demonstrate two-stage melting of that branched POSS and their ability to form monolayer and multilayered LB structures. On the other hand, we observed that silver-BCP-gold nanocobs display extremely bright Raman scattering caused by surface enhanced Raman effect with very different longitudinal and transversal optical properties as revealed by high-resolution confocal Raman microscopy. To study these hybrid nanostructures we applied combined AFM, SEM, TEM, XPS, SERS, UV-vis, and XR techniques.

Ordered CdSe nanoparticles within self-assembled block copolymer domains on surfaces.

PubMed

Zou, Shan; Hong, Rui; Emrick, Todd; Walker, Gilbert C

2007-02-13

Hierarchical, high-density, ordered patterns were fabricated on Si substrates by self-assembly of CdSe nanoparticles within approximately 20-nm-thick diblock copolymer films in a controlled manner. Surface-modified CdSe nanoparticles formed well-defined structures within microphase-separated polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) domains. Trioctylphosphine oxide (TOPO)-coated CdSe nanoparticles were incorporated into PS domains and polyethylene glycol-coated CdSe nanoparticles were located primarily in the P2VP domains. Nearly close-packed CdSe nanoparticles were clearly identified within the highly ordered patterns on Si substrates by scanning electron microscopy (SEM). Contact angle measurements together with SEM results indicate that TOPO-CdSe nanoparticles were partially placed at the air/copolymer interface.

The detection of HBV DNA with gold-coated iron oxide nanoparticle gene probes

NASA Astrophysics Data System (ADS)

Xi, Dong; Luo, XiaoPing; Lu, QiangHua; Yao, KaiLun; Liu, ZuLi; Ning, Qin

2008-03-01

Gold-coated iron oxide nanoparticle Hepatitis B virus (HBV) DNA probes were prepared, and their application for HBV DNA measurement was studied. Gold-coated iron oxide nanoparticles were prepared by the citrate reduction of tetra-chloroauric acid in the presence of iron oxide nanoparticles which were added as seeds. With a fluorescence-based method, the maximal surface coverage of hexaethiol 30-mer oligonucleotides and the maximal percentage of hybridization strands on gold-coated iron oxide nanoparticles were (120 ± 8) oligonucleotides per nanoparticle, and (14 ± 2%), respectively, which were comparable with those of (132 ± 10) and (22 ± 3%) in Au nanoparticle groups. Large network aggregates were formed when gold-coated iron oxide nanoparticle HBV DNA gene probe was applied to detect HBV DNA molecules as evidenced by transmission electron microscopy and the high specificity was verified by blot hybridization. Our results further suggested that detecting DNA with iron oxide nanoparticles and magnetic separator was feasible and might be an alternative effective method.

Effects of oleic acid surface coating on the properties of nickel ferrite nanoparticles/PLA composites.

PubMed

Yin, Hong; Chow, Gan-Moog

2009-11-01

Nickel ferrite nanoparticles with or without oleic acid surface coating were mixed with poly(D,L-lactide) (PLA) by double emulsion method. If the nanoparticles were prepared without oleic acid coating, they adsorbed on the PLA surface. If the nanoparticles were coated with oleic acid, they could be readily encapsulated within the PLA microspheres. A slight depression in glass transition temperature was found in all composites and it could be related to the interfacial energies between nanoparticles and PLA. Optimum mixed composite was achieved by reducing interfacial energy. However, loading capacity was limited in this composite. Increasing the amount of nickel ferrite nanoparticles was not useful to increase loading capacity. Cytotoxicity of the composite decreased significantly when nickel ferrite nanoparticles were effectively encapsulated in PLA microspheres. (c) 2008 Wiley Periodicals, Inc.

Surface faceting and elemental diffusion behaviour at atomic scale for alloy nanoparticles during in situ annealing

PubMed Central

Chi, Miaofang; Wang, Chao; Lei, Yinkai; Wang, Guofeng; Li, Dongguo; More, Karren L.; Lupini, Andrew; Allard, Lawrence F.; Markovic, Nenad M.; Stamenkovic, Vojislav R.

2015-01-01

The catalytic performance of nanoparticles is primarily determined by the precise nature of the surface and near-surface atomic configurations, which can be tailored by post-synthesis annealing effectively and straightforwardly. Understanding the complete dynamic response of surface structure and chemistry to thermal treatments at the atomic scale is imperative for the rational design of catalyst nanoparticles. Here, by tracking the same individual Pt3Co nanoparticles during in situ annealing in a scanning transmission electron microscope, we directly discern five distinct stages of surface elemental rearrangements in Pt3Co nanoparticles at the atomic scale: initial random (alloy) elemental distribution; surface platinum-skin-layer formation; nucleation of structurally ordered domains; ordered framework development and, finally, initiation of amorphization. Furthermore, a comprehensive interplay among phase evolution, surface faceting and elemental inter-diffusion is revealed, and supported by atomistic simulations. This work may pave the way towards designing catalysts through post-synthesis annealing for optimized catalytic performance. PMID:26576477

Surface faceting and elemental diffusion behaviour at atomic scale for alloy nanoparticles during in situ annealing

DOE PAGES

Chi, Miaofang; Wang, Chao; Lei, Yinkai; ...

2015-11-18

The catalytic performance of nanoparticles is primarily determined by the precise nature of the surface and near-surface atomic configurations, which can be tailored by post-synthesis annealing effectively and straightforwardly. Understanding the complete dynamic response of surface structure and chemistry to thermal treatments at the atomic scale is imperative for the rational design of catalyst nanoparticles. Here, by tracking the same individual Pt 3Co nanoparticles during in situ annealing in a scanning transmission electron microscope, we directly discern five distinct stages of surface elemental rearrangements in Pt 3Co nanoparticles at the atomic scale: initial random (alloy) elemental distribution; surface platinum-skin-layer formation;more » nucleation of structurally ordered domains; ordered framework development and, finally, initiation of amorphization. Furthermore, a comprehensive interplay among phase evolution, surface faceting and elemental inter-diffusion is revealed, and supported by atomistic simulations. In conlcusion, this work may pave the way towards designing catalysts through post-synthesis annealing for optimized catalytic performance.« less

Sustained release and permeation of timolol from surface-modified solid lipid nanoparticles through bioengineered human cornea.

PubMed

Attama, A A; Reichl, S; Müller-Goymann, C C

2009-08-01

The aim of the study was to formulate and evaluate surface-modified solid lipid nanoparticles sustained delivery system of timolol hydrogen maleate, a prototype ocular drug using a human cornea construct. Surface-modified solid lipid nanoparticles containing timolol with and without phospholipid were formulated by melt emulsification with high-pressure homogenization and characterized by particle size, wide-angle X-ray diffraction, encapsulation efficiency, and in vitro drug release. Drug transport studies through cornea bioengineered from human donor cornea cells were carried out using a modified Franz diffusion cell and drug concentration analyzed by high-performance liquid chromatography. Results show that surface-modified solid lipid nanoparticles possessed very small particles (42.9 +/- 0.3 nm, 47.2 +/- 0.3 nm, 42.7 +/- 0.7 nm, and 37.7 +/- 0.3 nm, respectively for SM-SLN 1, SM-SLN 2, SM-SLN 3, and SM-SLN 4) with low polydispersity indices, increased encapsulation efficiency (> 44%), and sustained in vitro release compared with unmodified lipid nanoparticles whose particles were greater than 160 nm. Permeation of timolol hydrogen maleate from the surface-modified lipid nanoparticles across the cornea construct was sustained compared with timolol hydrogen maleate solution in distilled water. Surface-modified solid lipid nanoparticles could provide an efficient way of improving ocular bioavailability of timolol hydrogen maleate.

Surface modification by metal ion implantation forming metallic nanoparticles in an insulating matrix

NASA Astrophysics Data System (ADS)

Salvadori, M. C.; Teixeira, F. S.; Sgubin, L. G.; Cattani, M.; Brown, I. G.

2014-08-01

There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We have investigated nanocomposites produced by metal ion implantation into insulating substrates, where the implanted metal self-assembles into nanoparticles. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), which can be estimated by computer simulation using the TRIDYN code. TRIDYN is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study show that the nanoparticles form a bidimentional array buried a few nanometers below the substrate surface. We have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples show that metallic nanoparticles form in the insulating matrix. These nanocomposites have been characterized by measuring the resistivity of the composite layer as a function of the implantation dose. The experimental results are compared with a model based on percolation theory, in which electron transport through the composite is explained by conduction through a random resistor network formed by the metallic nanoparticles. Excellent agreement is found between the experimental results and the predictions of the theory. We conclude in that the conductivity process is due only to percolation (when the conducting elements are in geometric contact) and that the contribution from tunneling conduction is negligible.

Effect of surfactant in mitigating cadmium oxide nanoparticle toxicity: Implications for mitigating cadmium toxicity in environment

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

Balmuri, Sricharani Rao

Cadmium (Cd), classified as human carcinogen, is an extremely toxic heavy metal pollutant, and there is an increasing environmental concern for cadmium exposure through anthropogenic sources including cigarette smoke. Though Cd based nanoparticles such as cadmium oxide (CdO) are being widely used in a variety of clinical and industrial applications, the toxicity of CdO nanoparticles has not been well characterized. Herein we report the toxicity of CdO nanoparticles employing zebrafish as a model. Two different CdO nanoparticles were prepared, calcination of Cd(OH){sub 2} without any organic molecule (CdO-1) and calcination of Cd-citrate coordination polymer (CdO-2), to evaluate and compare themore » toxicity of these two different CdO nanoparticles. Results show that zebrafish exposed to CdO-2 nanoparticles expressed reduced toxicity as judged by lower oxidative stress levels, rescue of liver carboxylesterases and reduction in metallothionein activity compared to CdO-1 nanoparticles. Histopathological observations also support our contention that CdO-1 nanoparticles showed higher toxicity relative to CdO-2 nanoparticles. The organic unit of Cd-citrate coordination polymer might have converted into carbon during calcination that might have covered the surface of CdO nanoparticles. This carbon surface coverage can control the release of Cd{sup 2+} ions in CdO-2 compared to non-covered CdO-1 nanoparticles and hence mitigate the toxicity in the case of CdO-2. This was supported by atomic absorption spectrophotometer analyses of Cd{sup 2+} ions release from CdO-1 and CdO-2 nanoparticles. Thus the present study clearly demonstrates the toxicity of CdO nanoparticles in an aquatic animal and also indicates that the toxicity could be substantially reduced by carbon coverage. This could have important implications in terms of anthropogenic release and environmental pollution caused by Cd and human exposure to Cd{sup 2+} from sources such as cigarette smoke. - Highlights: �

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.

Enteric trimethyl chitosan nanoparticles containing hepatitis B surface antigen for oral delivery.

PubMed

Farhadian, Asma; Dounighi, Naser Mohammadpour; Avadi, Mohammadreza

2015-01-01

Oral vaccination is the preferred route of immunization. However, the degradative condition of the gastrointestinal tract and the higher molecular size of peptides pose major challenges in developing an effective oral vaccination system. One of the most excellent methods used in the development of oral vaccine delivery system relies on the entrapment of the antigen in polymeric nanoparticles. In this work, trimethyl chitosan (TMC) nanoparticles were fabricated using ionic gelation teqnique by interaction hydroxypropyl methylcellulose phthalate (HPMCP), a pH-sensitive polymer, with TMC and the utility of the particles in the oral delivery of hepatitis B surface antigen (HBsAg) was evaluated employing solutions that simulated gastric and intestinal conditions. The particle size, morphology, zeta potential, loading capacity, loading efficiency, in vitro release behavior, structure, and morphology of nanoparticles were evaluated, and the activity of the loaded antigen was assessed. Size of the optimized TMC/HPMCP nanoparticles and that of the antigen-loaded nanoparticles were 85 nm and 158 nm, respectively. Optimum loading capacity (76.75%) and loading efficiency (86.29%) were achieved at 300 µg/mL concentration of the antigen. SEM images revealed a spherical shape as well as a smooth and near-homogenous surface of nanoparticles. Results of the in vitro release studies showed that formulation with HPMCP improved the acid stability of the TMC nanoparticles as well as their capability to preserve the loaded HBsAg from gastric destruction. The antigen showed good activity both before and after loading. The results suggest that TMC/HPMCP nanoparticles could be used in the oral delivery of HBsAg vaccine.

Volume Labeling with Alexa-Fluor Dyes and Surface Functionalization of Highly Sensitive Fluorescent SiO2 Nanoparticles

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

Wang, Wei; Foster, Carmen M; Morrell-Falvey, Jennifer L

2013-01-01

A new synthesis approach is described that allows the direct incorporation of fluorescent labels into the volume or body of SiO2 nanoparticles. In this process, fluorescent Alexa Fluor dyes with different emission wavelengths were covalently incorporated into the SiO2 nanoparticles during their formation by the hydrolysis of tetraethoxysilane. The dye molecules were homogeneously distributed throughout the SiO2 nanoparticles. The quantum yields of the Alexa Fluor volume-labeled SiO2 nanoparticles were much higher than nanoparticles labeled using conventional organic dyes. The size of the resulting nanoparticles was controlled using microemulsion reaction media with sizes in the range of 20-100 nm and amore » polydispersity of <15%. In comparison with conventional surface tagged particles created by post-synthesis modification, this process maintains the physical and surface chemical properties that have the most pronounced effect on colloidal stability and interactions with their surroundings. These volume-labeled nanoparticles have proven to be extremely robust, showing excellent signal strength, negligible photobleaching, and minimal loss of functional organic components. The native or free surface of the volume-labeled particles can be altered to achieve a specific surface functionality without altering fluorescence. Their utility was demonstrated for visualizing the association of surface modified fluorescent particles with cultured macrophages. Differences in particle agglomeration and cell association were clearly associated with differences in observed nanoparticle toxicity. The capacity to maintain particle fluorescence while making significant changes to surface chemistry makes these particles extremely versatile and useful for studies of particle agglomeration, uptake, and transport in environmental and biological systems.« less

Effect of surface roughness on substrate-tuned gold nanoparticle gap plasmon resonances.

PubMed

Lumdee, Chatdanai; Yun, Binfeng; Kik, Pieter G

2015-03-07

The effect of nanoscale surface roughness on the gap plasmon resonance of gold nanoparticles on thermally evaporated gold films is investigated experimentally and numerically. Single-particle scattering spectra obtained from 80 nm diameter gold particles on a gold film show significant particle-to-particle variation of the peak scattering wavelength of ±28 nm. The experimental results are compared with numerical simulations of gold nanoparticles positioned on representative rough gold surfaces, modeled based on atomic force microscopy measurements. The predicted spectral variation and average resonance wavelength show good agreement with the measured data. The study shows that nanometer scale surface roughness can significantly affect the performance of gap plasmon-based devices.

Electrodeposition of gold nanoparticles on aryl diazonium monolayer functionalized HOPG surfaces.

PubMed

González, M C R; Orive, A G; Salvarezza, R C; Creus, A H

2016-01-21

Gold nanoparticle electrodeposition on a modified HOPG surface with a monolayer organic film based on aryl diazonium chemistry has been studied. This organic monolayer is electrochemically grown with the use of 2,2-diphenyl-1-picrylhydrazyl (DPPH), a radical scavenger. The electrodeposition of gold on this modified surface is highly favored resulting in an AuNP surface density comparable to that found on glassy carbon. AuNPs grow only in the areas covered by the organic monolayer leaving free clean HOPG zones. A progressive mechanism for the nucleation and growth is followed giving hemispherical AuNPs, homogeneously distributed on the surface and their sizes can be well controlled by the applied electrodeposition potential. By using AFM, C-AFM and electrochemical measurements with the aid of two redox probes, namely Fe(CN)6(4-)/Fe(CN)6(3-) and dopamine, relevant results about the electrochemical modified surface as well as the gold nanoparticles electrodeposited on them are obtained.

Surface enhanced Raman scattering, antibacterial and antifungal active triangular gold nanoparticles

NASA Astrophysics Data System (ADS)

Smitha, S. L.; Gopchandran, K. G.

2013-02-01

Shape controlled syntheses of gold nanoparticles have attracted a great deal of attention as their optical, electronic, magnetic and biological properties are strongly dependent on the size and shape of the particles. Here is a report on the surface enhanced Raman scattering (SERS) activity of Cinnamomum zeylanicum leaf broth reduced gold nanoparticles consisting of triangular and spherical like particles, using 2-aminothiophenol (2-ATP) and crystal violet (CV) as probe molecules. Nanoparticles prepared with a minimum leaf broth concentration, having a greater number of triangular like particles exhibit a SERS activity of the order of 107. The synthesized nanoparticles exhibit efficient antibacterial activity against the tested gram negative bacterium Escherichia coli and gram positive bacterium Staphylococcus aureus. Investigations on the antifungal activity of the synthesized nanoparticles against Aspergillus niger and Fusarium oxysporum positive is also discussed.

Mobility and Oxidation of Adsorbed CO on Shape-Controlled Pt Nanoparticles in Acidic Medium.

PubMed

Farias, Manuel J S; Busó-Rogero, Carlos; Vidal-Iglesias, Francisco J; Solla-Gullón, José; Camara, Giuseppe A; Feliu, Juan M

2017-01-31

The knowledge about how CO occupies and detaches from specific surface sites on well-structured Pt surfaces provides outstanding information on both dynamics/mobility of CO ads and oxidation of this molecule under electrochemical conditions. This work reports how the potentiostatic growth of different coverage CO adlayers evolves with time on both cubic and octahedral Pt nanoparticles in acidic medium. Data suggest that during the growth of the CO adlayer, CO ads molecules slightly shift toward low coordination sites only on octahedral Pt nanoparticles, so that these undercoordinated sites are the first filled on octahedral Pt nanoparticles. Conversely, on cubic Pt nanoparticles, adsorbed CO behaves as an immobile species, and low coordinated sites as well as (100) terraces are apparently filled uniformly and simultaneously. However, once the adlayer is complete, irrespectively of whether the CO is oxidized in a single step or in a sequence of different potential steps, results suggest that CO ads behaves as an immobile species during its oxidation on both octahedral and cubic Pt nanoparticles.

Nanoparticle monolayers under stress: mechanically forced desorption from a fluid-fluid interface

NASA Astrophysics Data System (ADS)

Garbin, Valeria; Crocker, John C.; Stebe, Kathleen J.

2011-11-01

Nanoparticle-laden interfaces are studied for applications to materials with tunable electronic and optical properties, as emulsion stabilizers, and in catalysis. The mechanical response of nanoparticle monolayers under applied stress is of emerging interest since it impacts the success of these applications. Here we focus on the response of nanoparticle-laden interfaces to compression. A monolayer of nanoparticles is allowed to spontaneously form by adsorption from an aqueous suspension onto a pendant drop of oil. The effective surface pressure Π of the composite interface is monitored by pendant drop tensiometry. As the drop is compressed, the nanoparticles are mechanically forced out of the interface into the aqueous phase. A new optical method is developed to measure the nanoparticle area density in situ. We show that desorption occurs at a coverage that corresponds to close packing of the ligand-capped particles, suggesting that ligand-induced repulsion plays a crucial role in the desorption process.

Design of water-repellant coating using dual scale size of hybrid silica nanoparticles on polymer surface

NASA Astrophysics Data System (ADS)

Conti, J.; De Coninck, J.; Ghazzal, M. N.

2018-04-01

The dual-scale size of the silica nanoparticles is commonly aimed at producing dual-scale roughness, also called hierarchical roughness (Lotus effect). In this study, we describe a method to build a stable water-repellant coating with controlled roughness. Hybrid silica nanoparticles are self-assembled over a polymeric surface by alternating consecutive layers. Each one uses homogenously distributed silica nanoparticles of a particular size. The effect of the nanoparticle size of the first layer on the final roughness of the coating is studied. The first layer enables to adjust the distance between the silica nanoparticles of the upper layer, leading to a tuneable and controlled final roughness. An optimal size nanoparticle has been found for higher water-repellency. Furthermore, the stability of the coating on polymeric surface (Polycarbonate substrate) is ensured by photopolymerization of hybridized silica nanoparticles using Vinyl functional groups.

Elastomeric nanoparticle composites covalently bound to Al2O3/GaAs surfaces.

PubMed

Song, Hyon Min; Ye, Peide D; Ivanisevic, Albena

2007-08-28

This article reports the modification of Al2O3/GaAs surfaces with multifunctional soft materials. Siloxane elastomers were covalently bound to dopamine-modified Al2O3/GaAs semiconductor surfaces using MPt (M = Fe, Ni) nanoparticles. The sizes of the monodisperse FePt and NiPt nanoparticles were less than 5 nm. The surfaces of the nanoparticles as well as the Al2O3/GaAs substrates were modified with allyl-functionalized dopamine that utilized a dihydroxy group as a strong ligand. The immobilization of the elastomers was performed via a hydrosilation reaction of the allyl-functionalized dopamines with the siloxane backbones. X-ray photoelectron spectroscopy (XPS) experiments confirmed the covalent bonding of the siloxane elastomers to the oxide layer on the semiconductor surface. Fourier transform-infrared reflection absorption spectroscopy (FT-IRRAS) measurements revealed that the allyl functional groups are bonded to the siloxane backbones. The FT-IRRAS data also showed that the density of the allyl groups on the surface was lower than that of the siloxane backbones. The mechanical properties of the surface-bound nanocomposites were tested using nanoindentation experiments. The nanoindentation data showed that the soft matrix composed of the elastomeric coating on the surfaces behaves differently from the inner, hard Al2O3/GaAs substrate.

High reactive sulphide chemically supported on silica surface to prepare functional nanoparticle

NASA Astrophysics Data System (ADS)

Chen, Lijuan; Guo, Xiaohui; Jia, Zhixin; Tang, Yuhan; Wu, Lianghui; Luo, Yuanfang; Jia, Demin

2018-06-01

A solid-phase preparation method was applied to obtain a novel, green and effective functional nanoparticle, silica-supported sulfur monochloride (silica-s-S2Cl2), by the chemical reaction between chlorine atom and silicon hydroxyl on the silica surface. Through this chemical reaction, silica surface supported with high content of sulfur, and the functional nanoparticles can not only vulcanize the rubber instead of sulfur or other vulcanizing agent with high performance, but also improve the filler-rubber interaction as a modifier due to the improved modification effect. 29Si NMR, Raman spectroscopy, Element analysis and TGA confirm that the sulfur monochloride is chemically bonded on the silica surface. Cure properties measurement, morphology of filler dispersion, mechanical properties measurement, immobilized polymer layer and oxidation induction time increment together show that the novel vulcanizing agent silica-s-S2Cl2 instead of sulfur in rubber vulcanization gives rise to significant improvement in the crosslinking density and the interfacial adhesion between silica particles and the rubber matrix, which is on account of the promoted vulcanizing on the functional silica nanoparticles surface with the supported sulfur.

Effect of Cu Alloying on S Poisoning of Ni Surfaces and Nanoparticle Morphologies Using Ab-Initio Thermodynamics Calculations.

PubMed

Kim, Ji-Su; Kim, Byung-Kook; Kim, Yeong-Cheol

2015-10-01

We investigated the effect of Cu alloying on S poisoning of Ni surfaces and nanoparticle morphologies using ab-initio thermodynamics calculations. Based on the Cu segregation energy and the S adsorption energy, the surface energy and nanoparticle morphology of pure Ni, pure Cu, and NiCu alloys were evaluated as functions of the chemical potential of S and the surface orientations of (100), (110), and (111). The constructed nanoparticle morphology was varied as a function of chemical potential of S. We find that the Cu added to Ni for NiCu alloys is strongly segregated into the top surface, and increases the S tolerance of the NiCu nanoparticles.

Surface plasmon-enhanced light-emitting diodes using silver nanoparticles embedded in p-GaN.

PubMed

Cho, Chu-Young; Kwon, Min-Ki; Lee, Sang-Jun; Han, Sang-Heon; Kang, Jang-Won; Kang, Se-Eun; Lee, Dong-Yul; Park, Seong-Ju

2010-05-21

We demonstrate the surface plasmon-enhanced blue light-emitting diodes (LEDs) using Ag nanoparticles embedded in p-GaN. A large increase in optical output power of 38% is achieved at an injection current of 20 mA due to an improved internal quantum efficiency of the LEDs. The enhancement of optical output power is dependent on the density of the Ag nanoparticles. This improvement can be attributed to an increase in the spontaneous emission rate through resonance coupling between the excitons in multiple quantum wells and localized surface plasmons in Ag nanoparticles embedded in p-GaN.

Why CO bonds side-on at low coverage and both side-on and upright at high coverage on the Cr(110) surface

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, A. B.

1985-01-01

An atom superposition and electron delocalization molecular orbital study of CO adsorption on the Cr(110) surface shows a high coordinate lying down orientation is favored. This is a result of the large number of empty d-band energy levels in chromium, which allows the antibonding counterparts to sigma and pi donation bonds to the surface to be empty. When lying down, backbonding to CO pi sup * orbitals is enhanced. Repulsive interactions cause additional CO to stand upright at 1/4 monolyer coverage. The results confirm the recent experimental study of Shinn and Madey.

Volume labeling with Alexa Fluor dyes and surface functionalization of highly sensitive fluorescent silica (SiO2) nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Wei; Nallathamby, Prakash D.; Foster, Carmen M.; Morrell-Falvey, Jennifer L.; Mortensen, Ninell P.; Doktycz, Mitchel J.; Gu, Baohua; Retterer, Scott T.

2013-10-01

A new synthesis approach is described that allows the direct incorporation of fluorescent labels into the volume or body of SiO2 nanoparticles. In this process, fluorescent Alexa Fluor dyes with different emission wavelengths were covalently incorporated into the SiO2 nanoparticles during their formation by the hydrolysis of tetraethoxysilane. The dye molecules were homogeneously distributed throughout the SiO2 nanoparticles. The quantum yields of the Alexa Fluor volume-labeled SiO2 nanoparticles were much higher than nanoparticles labeled using conventional organic dyes. The size of the resulting nanoparticles was controlled using microemulsion reaction media with sizes in the range of 20-100 nm and a polydispersity of <15%. In comparison with conventional surface tagged particles created by post-synthesis modification, this process maintains the physical and surface chemical properties that have the most pronounced effect on colloidal stability and interactions with their surroundings. These volume-labeled nanoparticles have proven to be extremely robust, showing excellent signal strength, negligible photobleaching, and minimal loss of functional organic components. The native or ``free'' surface of the volume-labeled particles can be altered to achieve a specific surface functionality without altering fluorescence. Their utility was demonstrated for visualizing the association of surface-modified fluorescent particles with cultured macrophages. Differences in particle agglomeration and cell association were clearly associated with differences in observed nanoparticle toxicity. The capacity to maintain particle fluorescence while making significant changes to surface chemistry makes these particles extremely versatile and useful for studies of particle agglomeration, uptake, and transport in environmental and biological systems.A new synthesis approach is described that allows the direct incorporation of fluorescent labels into the volume or body of SiO2

Martensitic and austenitic transformations in core-surface cubic nanoparticles

NASA Astrophysics Data System (ADS)

Özüm, S.; Yalçın, O.; Erdem, R.; Bayrakdar, H.; Eker, H. N.

2015-01-01

As a continuation of our recently published work, we have used the pair approximation in Kikuchi version to investigate martensitic and austenitic transformations in homogeneous (HM) and composite (CM) cubic nanoparticles (CNPs) based on the Blume-Emery-Griffiths model. A single cubic nanoparticle made of a core surrounded by a surface is considered as shaped in two dimensional (2D) square arrays instead of hexagonal array. From the phase diagrams of HM and CM-CNPs it has been observed that the martensitic-austenitic transformations (MT-AT) occurred. The influence of the exchange coupling and single-ion anisotropy parameters in the model Hamiltonian on the MT-AT is studied and analyzed in comparison with the results for hexagonal nanoparticles. Significant changes of the phase transition points and hysteresis behaviours depending upon the particle structure have been discussed.

Sodium hydroxide catalyzed monodispersed high surface area silica nanoparticles.

PubMed

Bhakta, Snehasis; Dixit, Chandra K; Bist, Itti; Jalil, Karim Abdel; Suib, Steven L; Rusling, James F

2016-07-01

Understanding of the synthesis kinetics and our ability to modulate medium conditions allowed us to generate nanoparticles via an ultra-fast process. The synthesis medium is kept quite simple with tetraethyl orthosilicate (TEOS) as precursor and 50% ethanol and sodium hydroxide catalyst. Synthesis is performed under gentle conditions at 20 °C for 20 min Long synthesis time and catalyst-associated drawbacks are most crucial in silica nanoparticle synthesis. We have addressed both these bottlenecks by replacing the conventional Stober catalyst, ammonium hydroxide, with sodium hydroxide. We have reduced the overall synthesis time from 20 to 1/3 h, ~60-fold decrease, and obtained highly monodispersed nanoparticles with 5-fold higher surface area than Stober particles. We have demonstrated that the developed NPs with ~3-fold higher silane can be used as efficient probes for biosensor applications.

Nanoparticle surface characterization and clustering through concentration-dependent surface adsorption modeling.

PubMed

Chen, Ran; Zhang, Yuntao; Sahneh, Faryad Darabi; Scoglio, Caterina M; Wohlleben, Wendel; Haase, Andrea; Monteiro-Riviere, Nancy A; Riviere, Jim E

2014-09-23

Quantitative characterization of nanoparticle interactions with their surrounding environment is vital for safe nanotechnological development and standardization. A recent quantitative measure, the biological surface adsorption index (BSAI), has demonstrated promising applications in nanomaterial surface characterization and biological/environmental prediction. This paper further advances the approach beyond the application of five descriptors in the original BSAI to address the concentration dependence of the descriptors, enabling better prediction of the adsorption profile and more accurate categorization of nanomaterials based on their surface properties. Statistical analysis on the obtained adsorption data was performed based on three different models: the original BSAI, a concentration-dependent polynomial model, and an infinite dilution model. These advancements in BSAI modeling showed a promising development in the application of quantitative predictive modeling in biological applications, nanomedicine, and environmental safety assessment of nanomaterials.

High-energy x-ray diffraction from surfaces and nanoparticles

NASA Astrophysics Data System (ADS)

Hejral, U.; Müller, P.; Shipilin, M.; Gustafson, J.; Franz, D.; Shayduk, R.; Rütt, U.; Zhang, C.; Merte, L. R.; Lundgren, E.; Vonk, V.; Stierle, A.

2017-11-01

High-energy surface-sensitive x-ray diffraction (HESXRD) is a powerful high-energy photon technique (E > 70 keV) that has in recent years proven to allow a fast data acquisition for the 3D structure determination of surfaces and nanoparticles under in situ and operando conditions. The use of a large-area detector facilitates the direct collection of nearly distortion-free diffraction patterns over a wide q range, including crystal truncation rods perpendicular to the surface and large-area reciprocal space maps from epitaxial nanoparticles, which is not possible in the conventional low-photon energy approach (E =10 -20 keV ). Here, we present a comprehensive mathematical approach, explaining the working principle of HESXRD for both single-crystal surfaces and epitaxial nanostructures on single-crystal supports. The angular calculations used in conventional crystal truncation rod measurements at low-photon energies are adopted for the high-photon-energy regime, illustrating why and to which extent large reciprocal-space areas can be probed in stationary geometry with fixed sample rotation. We discuss how imperfections such as mosaicity and finite domain size aid in sampling a substantial part of reciprocal space without the need of rotating the sample. An exact account is given of the area probed in reciprocal space using such a stationary mode, which is essential for in situ or operando time-resolved experiments on surfaces and nanostructures.

From well-defined Pt(II) surface species to the controlled growth of silica supported Pt nanoparticles.

PubMed

Laurent, Pierre; Veyre, Laurent; Thieuleux, Chloé; Donet, Sébastien; Copéret, Christophe

2013-01-07

Silica-supported Pt nanoparticles were prepared from well-defined surface platinum(II) surface species, obtained by grafting of well-defined Pt(II) molecular precursors with specific ligands (Cl, Me, N(SiMe(3))(2), OSi(OtBu)(3)) onto silica partially dehydroxylated at 200 and 700 °C yielding well-defined platinum(II) surface species. This approach allowed for testing the effect of Pt density and ligands on nanoparticle size. Higher grafting densities are achieved on silica partially dehydroxylated at 200 °C due to its initially higher surface silanol density. Surface species have been synthesized from symmetrical and dissymmetrical complexes, namely (COD)Pt(Me)(2), (COD)Pt(OSi(OtBu)(3))(2), (COD)Pt(Me)(OSi(OtBu)(3)), (COD)Pt(Me)(N(SiMe(3))(2)), (COD)Pt(Cl)(N(SiMe(3))(2)) and (COD)Pt(N(SiMe(3))(2))(OSi(OtBu)(3)) yielding mono-grafted complexes of general formula (COD)Pt(R)(OSi≡) according to elemental analyses, diffuse reflectance infrared fourier transform (DRIFT) and carbon-13 solid-state nuclear magnetic resonance (NMR) spectroscopies. While the dimethyl-complex shows low reactivity towards grafting, bis-siloxy and dissymmetric complexes demonstrate better reactivity yielding platinum loadings up to 7.4 wt%. Upon grafting amido complexes, the surface passivation yielding Me(3)SiOSi≡ surface species is demonstrated. Nanoparticles have been synthesized from these well-defined surface species by reduction under H(2) at 300 °C, under static or flow conditions. This process yields nanoparticles with sizes ranging from 2 to 3.3 nm and narrow size dispersion from 0.5 to 1.2 nm. Interestingly, the chloride complex yields large nanoparticles from 5 to 40 nm demonstrating the strong influence of chloride over the nanoparticles growth.

Synthesis methods of gold nanoparticles for Localized Surface Plasmon Resonance (LSPR) sensor applications

NASA Astrophysics Data System (ADS)

Diyanah Samsuri, Nurul; Maisarah Mukhtar, Wan; Rashid, Affa Rozana Abdul; Dasuki, Karsono Ahmad; Awangku Yussuf, Awangku Abdul Rahman Hj.

2017-11-01

Gold nanoparticles (GNPs) have been known as an excellent characteristic for Local Surface Plasmon Resonance (LSPR) sensors due to their sensitive spectral response to the local environment of the nanoparticle surface and ease of monitoring the light signal due to their strong scattering or absorption. Prior the technologies, GNPs based LSPR has been commercialized and have become a central tool for characterizing and quantifying in various field. In this review, we presented a brief introduction on the history of surface plasmon, the theory behind the surface plasmon resonance (SPR) and the principles of LSPR. We also reported on the synthetization as well of the properties of the GNPs and the applications in current LSPR sensors.

Porous polymer monolithic columns with gold nanoparticles as an intermediate ligand for the separation of proteins in reverse phase-ion exchange mixed mode

DOE PAGES

Terborg, Lydia; Masini, Jorge C.; Lin, Michelle; ...

2014-11-04

A new approach has been developed for the preparation of mixed-mode stationary phases to separate proteins. The pore surface of monolithic poly(glycidyl methacrylate- co-ethylene dimethacrylate) capillary columns was functionalized with thiols and coated with gold nanoparticles. The final mixed mode surface chemistry was formed by attaching, in a single step, alkanethiols, mercaptoalkanoic acids, and their mixtures on the free surface of attached gold nanoparticles. Use of these mixtures allowed fine tuning of the hydrophobic/hydrophilic balance. The amount of attached gold nanoparticles according to thermal gravimetric analysis was 44.8 wt.%. This value together with results of frontal elution enabled calculation ofmore » surface coverage with the alkanethiol and mercaptoalkanoic acid ligands. Interestingly, alkanethiols coverage in a range of 4.46–4.51 molecules/nm 2 significantly exceeded that of mercaptoalkanoic acids with 2.39–2.45 molecules/nm 2. The mixed mode character of these monolithic stationary phases was for the first time demonstrated in the separations of proteins that could be achieved in the same column using gradient elution conditions typical of reverse phase (using gradient of acetonitrile in water) and ion exchange chromatographic modes (applying gradient of salt in water), respectively.« less

Enhancing performance and surface antifouling properties of polysulfone ultrafiltration membranes with salicylate-alumoxane nanoparticles

NASA Astrophysics Data System (ADS)

Mokhtari, Samaneh; Rahimpour, Ahmad; Shamsabadi, Ahmad Arabi; Habibzadeh, Setareh; Soroush, Masoud

2017-01-01

To improve the hydrophilicity and antifouling properties of polysulfone (PS) ultrafiltration membranes, we studied the use of salicylate-alumoxane (SA) nanoparticles as a novel hydrophilic additive. The effects of SA nanoparticles on the membrane characteristics and performance were investigated in terms of membrane structure, permeation flux, solute rejection, hydrophilicity, and antifouling ability. The new mixed-matrix membranes (MMMs) possess asymmetric structures. They have smaller finger-like pores and smoother surfaces than the neat PS membranes. The embedment of SA nanoparticles in the polymer matrix and the improvement of surface hydrophilicity were investigated. Ultrafiltration experiments indicated that the pure-water flux of the new MMMs initially increases with SA nanoparticles loading followed by a decrease at high loadings. Higher BSA solution flux was achieved for the MMMs compared to the neat PS membranes. Membranes with 1 wt.% SA nanoparticles exhibit the highest flux recovery ratio of 87% and the lowest irreversible fouling of 13%.

Surface structure and structural point defects of liquid and amorphous aluminosilicate nanoparticles.

PubMed

Linh, Nguyen Ngoc; Hoang, Vo Van

2008-07-02

The surface structure of liquid and amorphous aluminosilicate nanoparticles of composition Al(2)O(3)·2SiO(2) has been investigated in a model of different sizes ranging from 2.0 to 5.0 nm with the Born-Mayer type pair potential under non-periodic boundary conditions. Models have been obtained by cooling from the melts at a constant density of 2.6 g cm(-3) via molecular dynamics (MD) simulation. The surface structure has been investigated via the coordination number, bond-angle distributions and structural point defects. Calculations show that surface effects on surface static and thermodynamic properties of models are significant according to the change in the number of Al atoms in the surface layers. Evolution of the local environment of oxygen in the surface shell of nanoparticles upon cooling from the melt toward the glassy state was also found and discussed. In addition, the nanosize dependence of the glass transition temperature was presented.

Surface structure and structural point defects of liquid and amorphous aluminosilicate nanoparticles

NASA Astrophysics Data System (ADS)

Linh, Nguyen Ngoc; Van Hoang, Vo

2008-07-01

The surface structure of liquid and amorphous aluminosilicate nanoparticles of composition Al2O3·2SiO2 has been investigated in a model of different sizes ranging from 2.0 to 5.0 nm with the Born-Mayer type pair potential under non-periodic boundary conditions. Models have been obtained by cooling from the melts at a constant density of 2.6 g cm-3 via molecular dynamics (MD) simulation. The surface structure has been investigated via the coordination number, bond-angle distributions and structural point defects. Calculations show that surface effects on surface static and thermodynamic properties of models are significant according to the change in the number of Al atoms in the surface layers. Evolution of the local environment of oxygen in the surface shell of nanoparticles upon cooling from the melt toward the glassy state was also found and discussed. In addition, the nanosize dependence of the glass transition temperature was presented.

Nano-particle dynamics during capillary suction.

PubMed

Kuijpers, C J; Huinink, H P; Tomozeiu, N; Erich, S J F; Adan, O C G

2018-07-01

Due to the increased use of nanoparticles in everyday applications, there is a need for theoretical descriptions of particle transport and attachment in porous media. It should be possible to develop a one dimensional model to describe nanoparticle retention during capillary transport of liquid mixtures in porous media. Water-glycerol-nanoparticle mixtures were prepared and the penetration process in porous Al 2 O 3 samples of varying pore size is measured using NMR imaging. The liquid and particle front can be measured by utilizing T 2 relaxation effects from the paramagnetic nanoparticles. A good agreement between experimental data and the predicted particle retention by the developed theory is found. Using the model, the binding constant for Fe 2 O 3 nanoparticles on sintered Al 2 O 3 samples and the maximum surface coverage are determined. Furthermore, we show that the penetrating liquid front follows a square root of time behavior as predicted by Darcy's law. However, scaling with the liquid parameters is no longer sufficient to map different liquid mixtures onto a single master curve. The Darcy model should be extended to address the two formed domains (with and without particles) and their interaction, to give an accurate prediction for the penetrating liquid front. Copyright © 2018 Elsevier Inc. All rights reserved.

Surface-enhanced Raman scattering on tunable plasmonic nanoparticle substrates

PubMed Central

Jackson, J. B.; Halas, N. J.

2004-01-01

Au and Ag nanoshells are investigated as substrates for surface-enhanced Raman scattering (SERS). We find that SERS enhancements on nanoshell films are dramatically different from those observed on colloidal aggregates, specifically that the Raman enhancement follows the plasmon resonance of the individual nanoparticles. Comparative finite difference time domain calculations of fields at the surface of smooth and roughened nanoshells reveal that surface roughness contributes only slightly to the total enhancement. SERS enhancements as large as 2.5 × 1010 on Ag nanoshell films for the nonresonant molecule p-mercaptoaniline are measured. PMID:15608058

Nanoparticles Affect PCR Primarily via Surface Interactions with PCR Components: Using Amino-Modified Silica-Coated Magnetic Nanoparticles as a Main Model.

PubMed

Bai, Yalong; Cui, Yan; Paoli, George C; Shi, Chunlei; Wang, Dapeng; Shi, Xianming

2015-06-24

Nanomaterials have been widely reported to affect the polymerase chain reaction (PCR). However, many studies in which these effects were observed were not comprehensive, and many of the proposed mechanisms have been primarily speculative. In this work, we used amino-modified silica-coated magnetic nanoparticles (ASMNPs, which can be collected very easily using an external magnetic field) as a model and compared them with gold nanoparticles (AuNPs, which have been studied extensively) to reveal the mechanisms by which nanoparticles affect PCR. We found that nanoparticles affect PCR primarily by binding to PCR components: (1) inhibition, (2) specifity, and (3) efficiency and yield of PCR are impacted. (1) Excess nanomaterials inhibit PCR by adsorbing to DNA polymerase, Mg(2+), oligonucleotide primers, or DNA templates. Nanoparticle surface-active groups are particularly important to this effect. (2, a) Nanomaterials do not inhibit nonspecific amplification products caused by false priming as previously surmised. It was shown that relatively low concentrations of nanoparticles inhibited the amplification of long amplicons, and increasing the amount of nanoparticles inhibited the amplification of short amplicons. This concentration phenomenon appears to be the result of the formation of "joints" upon the adsorption of ASMNPs to DNA templates. (b) Nanomaterials are able to inhibit nonspecific amplification products due to incomplete amplification by preferably adsorbing single-stranded incomplete amplification products. (3) Some types of nanomaterials, such as AuNPs, enhance the efficiency and yield of PCR because these types of nanoparticles can adsorb to single-stranded DNA more strongly than to double-stranded DNA. This behavior assists in the rapid and thorough denaturation of double-stranded DNA templates. Therefore, the interaction between the surface of nanoparticles and PCR components is sufficient to explain most of the effects of nanoparticles on PCR.

Regulating the surface poly(ethylene glycol) density of polymeric nanoparticles and evaluating its role in drug delivery in vivo.

PubMed

Du, Xiao-Jiao; Wang, Ji-Long; Liu, Wei-Wei; Yang, Jin-Xian; Sun, Chun-Yang; Sun, Rong; Li, Hong-Jun; Shen, Song; Luo, Ying-Li; Ye, Xiao-Dong; Zhu, Yan-Hua; Yang, Xian-Zhu; Wang, Jun

2015-11-01

Poly(ethylene glycol) (PEG) is usually used to protect nanoparticles from rapid clearance in blood. The effects are highly dependent on the surface PEG density of nanoparticles. However, there lacks a detailed and informative study in PEG density and in vivo drug delivery due to the critical techniques to precisely control the surface PEG density when maintaining other nano-properties. Here, we regulated the polymeric nanoparticles' size and surface PEG density by incorporating poly(ε-caprolactone) (PCL) homopolymer into poly(ethylene glycol)-block-poly(ε-caprolactone) (PEG-PCL) and adjusting the mass ratio of PCL to PEG-PCL during the nanoparticles preparation. We further developed a library of polymeric nanoparticles with different but controllable sizes and surface PEG densities by changing the molecular weight of the PCL block in PEG-PCL and tuning the molar ratio of repeating units of PCL (CL) to that of PEG (EG). We thus obtained a group of nanoparticles with variable surface PEG densities but with other nano-properties identical, and investigated the effects of surface PEG densities on the biological behaviors of nanoparticles in mice. We found that, high surface PEG density made the nanoparticles resistant to absorption of serum protein and uptake by macrophages, leading to a greater accumulation of nanoparticles in tumor tissue, which recuperated the defects of decreased internalization by tumor cells, resulting in superior antitumor efficacy when carrying docetaxel. Copyright © 2015 Elsevier Ltd. All rights reserved.

Novel anti-reflection technology for GaAs single-junction solar cells using surface patterning and Au nanoparticles.

PubMed

Kim, Youngjo; Lam, Nguyen Dinh; Kim, Kangho; Kim, Sangin; Rotermund, Fabian; Lim, Hanjo; Lee, Jaejin

2012-07-01

Single-junction GaAs solar cell structures were grown by low-pressure MOCVD on GaAs (100) substrates. Micro-rod arrays with diameters of 2 microm, 5 microm, and 10 microm were fabricated on the surfaces of the GaAs solar cells via photolithography and wet chemical etching. The patterned surfaces were coated with Au nanoparticles using an Au colloidal solution. Characteristics of the GaAs solar cells with and without the micro-rod arrays and Au nanoparticles were investigated. The short-circuit current density of the GaAs solar cell with 2 microm rod arrays and Au nanoparticles increased up to 34.9% compared to that of the reference cell without micro-rod arrays and Au nanoparticles. The conversion efficiency of the GaAs solar cell that was coated with Au nanoparticles on the patterned surface with micro-rod arrays can be improved from 14.1% to 19.9% under 1 sun AM 1.5G illumination. These results show that micro-rod arrays and Au nanoparticle coating can be applied together in surface patterning to achieve a novel cost-effective anti-reflection technology.

Characterization of the disassembly and reassembly of the HBV glycoprotein surface antigen, a pliable nanoparticle vaccine platform

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

Gallagher, John R.; Torian, Udana; McCraw, Dustin

While nanoparticle vaccine technology is gaining interest due to the success of vaccines like those for the human papillomavirus that is based on viral capsid nanoparticles, little information is available on the disassembly and reassembly of viral surface glycoprotein-based nanoparticles. One such particle is the hepatitis B virus surface antigen (sAg) that exists as nanoparticles. Here we show, using biochemical analysis coupled with electron microscopy, that sAg nanoparticle disassembly requires both reducing agent to disrupt intermolecular disulfide bonds, and detergent to disrupt hydrophobic interactions that stabilize the nanoparticle. Particles were otherwise resistant to salt and urea, suggesting the driving mechanismmore » of particle formation involves hydrophobic interactions. We reassembled isolated sAg protein into nanoparticles by detergent removal and reassembly resulted in a wider distribution of particle diameters. Knowledge of these driving forces of nanoparticle assembly and stability should facilitate construction of epitope-displaying nanoparticles that can be used as immunogens in vaccines.« less

Characterization of the disassembly and reassembly of the HBV glycoprotein surface antigen, a pliable nanoparticle vaccine platform.

PubMed

Gallagher, John R; Torian, Udana; McCraw, Dustin M; Harris, Audray K

2017-02-01

While nanoparticle vaccine technology is gaining interest due to the success of vaccines like those for the human papillomavirus that is based on viral capsid nanoparticles, little information is available on the disassembly and reassembly of viral surface glycoprotein-based nanoparticles. One such particle is the hepatitis B virus surface antigen (sAg) that exists as nanoparticles. Here we show, using biochemical analysis coupled with electron microscopy, that sAg nanoparticle disassembly requires both reducing agent to disrupt intermolecular disulfide bonds, and detergent to disrupt hydrophobic interactions that stabilize the nanoparticle. Particles were otherwise resistant to salt and urea, suggesting the driving mechanism of particle formation involves hydrophobic interactions. We reassembled isolated sAg protein into nanoparticles by detergent removal and reassembly resulted in a wider distribution of particle diameters. Knowledge of these driving forces of nanoparticle assembly and stability should facilitate construction of epitope-displaying nanoparticles that can be used as immunogens in vaccines. Published by Elsevier Inc.

Radiative heat pumping from the Earth using surface phonon resonant nanoparticles.

PubMed

Gentle, A R; Smith, G B

2010-02-10

Nanoparticles that have narrow absorption bands that lie entirely within the atmosphere's transparent window from 7.9 to 13 mum can be used to radiatively cool to temperatures that are well below ambient. Heating from incoming atmospheric radiation in the remainder of the Planck radiation spectrum, where the atmosphere is nearly "black", is reduced if the particles are dopants in infrared transmitting polymers, or in transmitting coatings on low emittance substrates. Crystalline SiC nanoparticles stand out with a surface phonon resonance from 10.5 to 13 mum clear of the atmospheric ozone band. Resonant SiO(2) nanoparticles are complementary, absorbing from 8 to 10 mum, which includes atmospheric ozone emissions. Their spectral location has made SiC nanoparticles in space dust a feature in ground-based IR astronomy. Optical properties are presented and subambient cooling performance analyzed for doped polyethylene on aluminum. A mixture of SiC and SiO(2) nanoparticles yields high performance cooling at low cost within a practical cooling rig.

Enhancement of the thermo-optical response of silver nanoparticles due to surface plasmon resonance

NASA Astrophysics Data System (ADS)

Hashemi Zadeh, Sakineh; Rashidi-Huyeh, Majid; Palpant, Bruno

2017-10-01

Owing to their remarkable optical properties, noble metals' nanoparticles are proposed for many applications. Controlling the temperature dependence of these properties may then appear to be of great relevance. In this paper, we investigate the thermo-optical properties of silver nanoparticles. Different silver nanocolloids were prepared with different surface plasmon resonance modes. The thermo-extinction spectra of the colloidal solutions were then evaluated by measuring the extinction spectra at different temperatures. This reveals a typical peak-valley profile around each surface plasmon resonance mode. Mie theory was used to study theoretically the impact of nanoparticle size on the thermo-optical properties. The results allow us to interpret properly the experimental findings.

High-speed collision of copper nanoparticle with aluminum surface: Molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Pogorelko, Victor V.; Mayer, Alexander E.; Krasnikov, Vasiliy S.

2016-12-01

We investigate the effect of the high-speed collision of copper nanoparticles with aluminum surface by means of molecular dynamic simulations. Studied diameter of nanoparticles is varied within the range 7.2-22 nm and the velocity of impact is equal to 500 or 1000 m/s. Dislocation analysis shows that a large quantity of dislocations is formed within the impact area. Overall length of dislocations is determined, first of all, by the impact velocity and by the size of incident copper nanoparticle, in other words, by the kinetic energy of the nanoparticle. Dislocations occupy the total volume of the impacted aluminum single crystal layer (40.5 nm in thickness) in the form of intertwined structure in the case of large kinetic energy of the incident nanoparticle. Decrease in the initial kinetic energy or increase in the layer thickness lead to restriction of the penetration depth of the dislocation net; formation of separate dislocation loops is observed in this case. Increase in the initial system temperature slightly raises the dislocation density inside the bombarded layer and considerably decreases the dislocation density inside the nanoparticle. The temperature increase also leads to a deeper penetration of the copper atoms inside the aluminum. Additional molecular dynamic simulations show that the deposited particles demonstrate a very good adhesion even in the case of the considered relatively large nanoparticles. Medium energy of the nanoparticles corresponding to velocity of about 500 m/s and elevated temperature of the system about 700-900 K are optimal parameters for production of high-quality layers of copper on the aluminum surface. These conditions provide both a good adhesion and a less degree of the plastic deformation. At the same time, higher impact velocities can be used for combined treatment consisting of both the plastic deformation and the coating.

Au nanoparticle monolayers covered with sol-gel oxide thin films: optical and morphological study.

PubMed

Della Gaspera, Enrico; Karg, Matthias; Baldauf, Julia; Jasieniak, Jacek; Maggioni, Gianluigi; Martucci, Alessandro

2011-11-15

In this work, we provide a detailed study of the influence of thermal annealing on submonolayer Au nanoparticle deposited on functionalized surfaces as standalone films and those that are coated with sol-gel NiO and TiO(2) thin films. The systems are characterized through the use of UV-vis absorption, X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and spectroscopic ellipsometry. The surface plasmon resonance peak of the Au nanoparticles was found to red-shift and increase in intensity with increasing surface coverage, an observation that is directly correlated to the complex refractive index properties of Au nanoparticle layers. The standalone Au nanoparticles sinter at 200 °C, and a relationship between the optical properties and the annealing temperature is presented. When overcoated with sol-gel metal oxide films (NiO, TiO(2)), the optical properties of the Au nanoparticles are strongly affected by the metal oxide, resulting in an intense red shift and broadening of the plasmon band; moreover, the temperature-driven sintering is strongly limited by the metal oxide layer. Optical sensing tests for ethanol vapor are presented as one possible application, showing reversible sensing dynamics and confirming the effect of Au nanoparticles in increasing the sensitivity and in providing a wavelength dependent response, thus confirming the potential use of such materials as optical probes.

Fluorescent silica nanoparticles with chemically reactive surface: Controlling spatial distribution in one-step synthesis.

PubMed

Vera, María L; Cánneva, Antonela; Huck-Iriart, Cristián; Requejo, Felix G; Gonzalez, Mónica C; Dell'Arciprete, María L; Calvo, Alejandra

2017-06-15

The encapsulation of fluorescent dyes inside silica nanoparticles is advantageous to improve their quality as probes. Inside the particle, the fluorophore is protected from the external conditions and its main emission parameters remains unchanged even in the presence of quenchers. On the other hand, the amine-functionalized nanoparticle surface enables a wide range of applications, as amino groups could be easily linked with different biomolecules for targeting purposes. This kind of nanoparticle is regularly synthesized by methods that employ templates, additional nanoparticle formation or multiple pathway process. However, a one-step synthesis will be an efficient approach in this sort of bifunctional hybrid nanoparticles. A co-condensation sol-gel synthesis of hybrid fluorescent silica nanoparticle where developed. The chemical and morphological characterization of the particles where investigated by DRIFTS, XPS, SEM and SAXS. The nanoparticle fluorescent properties were also assessed by excitation-emission matrices and time resolved experiments. We have developed a one-pot synthesis method that enables the simultaneous incorporation of functionalities, the fluorescent molecule and the amino group, by controlling co-condensation process. An exhaustive characterization allows the definition of the spatial distribution of the fluorescent probe, fluorescein isothiocyanate, inside the particle and reactive amino groups on the surface of the nanoparticle with diameter about 100nm. Copyright © 2017 Elsevier Inc. All rights reserved.

Surface-enhanced Raman scattering of the adsorption of pesticide endosulfan on gold nanoparticles.

PubMed

Hernández-Castillo, M I; Zaca-Morán, O; Zaca-Morán, P; Orduña-Diaz, A; Delgado-Macuil, R; Rojas-López, M

2015-01-01

The absorption of pesticide endosulfan on the surface of gold nanoparticles results from the formation of micrometric structures (1-10 μm) with irregular shape because of the aggregation of individual particles. Such aggregation of gold nanoparticles after absorption of pesticide shows a surface-enhanced Raman scattering (SERS) spectrum, whose intensity depends on the concentration of endosulfan. In addition, the discoloration of the colloidal solution and a diminishing of the intensity of the surface plasmon resonance absorption from individual particles were observed by UV-visible spectroscopy. At the same time, a second band between 638 and 700 nm confirms the formation of aggregates of gold nanoparticles as the concentration of endosulfan increases. Finally, we used the SERS intensity of the S-O stretching vibration at 1239 cm(-1) from the SO3 group as a measure of concentration of pesticide endosulfan. This method could be used to estimate the level of pollution in water by endosulfan in a simple and practical form.

XAFS studies of surface structures of TiO{sub 2} nanoparticles and photocatalytic reduction of metal ions.

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

Chen, L. X.; Rajh, T.; Wang, Z.

1997-01-01

To probe the origin of the unique functions of titanium dioxide (TiO{sub 2}) nanoparticles observed in photocatalytic reactions, structures of Ti atom sites in titanium dioxide (TiO{sub 2}) nanoparticles with different sizes were studied by Ti K-edge XAFS (X-ray absorption fine structure). Compared to the bulk TiO{sub 2} structure, a shorter Ti-O distance from surface TiO{sub 2} resulting from Ti-OH bonding was observed. The XAFS spectra also revealed an increasing disorder of the lattice with decreasing sizes of the nanoparticles based on a coordination number decrease for the third-shell O atoms as well as changes in relative intensities of pre-edgemore » peaks A1, A2, and A3. However, the Ti sites largely remain octahedral even in the 30 Angstrom diameter particles. These results imply that the increasing number of surface Ti sites as well as possible corner defects in small nanoparticles may be the main cause of the unique surface chemistry exhibited by nanoparticles of TiO{sub 2}. XAFS was also used in monitoring the photoreduction reaction products of Cu{sup 2+} and Hg{sup 2+} on TiO{sub 2} nanoparticle surfaces, with or without surface adsorbers, alanine (Ala) and thiolactic acid (TLA). Ala dramatically enhanced photoreduction of Cu{sup 2+} on TiO{sub 2} nanoparticle surfaces, whereas thiolactic acid did not affect or even hindered Hg{sup 2+} photoreduction. Although both surface adsorbers chelated with the metal ions in the absence of TiO{sub 2} nanoparticles, this chelation was drastically changed in the Cu-Ala complex but was largely retained in the Hg-TLA complex when TiO{sub 2} was present. This may correlate with the different effects of the adsorbers on the photoreduction of the metal. Our experimental results suggest that a proper balance between the affinities of the adsorber to the metal ions and to the surface Ti atoms of TiO{sub 2} may be one of the keys in selecting a surface adsorber for enhanced photoreduction efficiency.« less

[Three-dimensional vertically aligned CNTs coated by Ag nanoparticles for surface-enhanced Raman scattering].

PubMed

Zhang, Xiao-Lei; Zhang, Jie; Fan, Tuo; Ren, Wen-Jie; Lai, Chun-Hong

2014-09-01

In order to make surface-enhanced Raman scattering (SERS) substrates contained more "hot spots" in a three-dimensional (3D) focal volume, and can be adsorbed more probe molecules and metal nanoparticles, to obtain stronger Raman spectral signal, a new structure based on vertically aligned carbon nanotubes (CNTs) coated by Ag nanoparticles for surface Raman enhancement is presented. The vertically aligned CNTs are synthesized by chemical vapor deposition (CVD). A silver film is first deposited on the vertically aligned CNTs by magnetron sputtering. The samples are then annealed at different temperature to cause the different size silver nanoparticles to coat on the surface and sidewalls of vertically aligned CNTs. The result of scanning electron microscopy(SEM) shows that Ag nanoparticles are attached onto the sidewalls and tips of the vertically aligned CNTs, as the annealing temperature is different , pitch size, morphology and space between the silver nanoparticles is vary. Rhodamine 6G is served as the probe analyte. Raman spectrum measurement indicates that: the higher the concentration of R6G, the stronger the Raman intensity, but R6G concentration increase with the enhanced Raman intensity varies nonlinearly; when annealing temperature is 450 °C, the average size of silver nanoparticles is about 100 to 120 nm, while annealing temperature is 400 °C, the average size is about 70 nm, and the Raman intensity of 450 °C is superior to the annealing temperature that of 400 °C and 350 °C.

Surface-enhanced Raman spectroscopy of double-shell hollow nanoparticles: electromagnetic and chemical enhancements.

PubMed

Mahmoud, Mahmoud A

2013-05-28

Enhancements of the Raman signal by the newly prepared gold-palladium and gold-platinum double-shell hollow nanoparticles were examined and compared with those using gold nanocages (AuNCs). The surface-enhanced Raman spectra (SERS) of thiophenol adsorbed on the surface of AuNCs assembled into a Langmuir-Blodgett monolayer were 10-fold stronger than AuNCs with an inner Pt or Pd shell. The chemical and electromagnetic enhancement mechanisms for these hollow nanoparticles were further proved by comparing the Raman enhancement of nitrothiophenol and nitrotoulene. Nitrothiophenol binds to the surface of the nanoparticles by covalent interaction, and Raman enhancement by both the two mechanisms is possible, while nitrotoulene does not form any chemical bond with the surface of the nanoparticles and hence no chemical enhancement is expected. Based on discrete dipole approximation (DDA) calculations and the experimental SERS results, AuNCs introduced a high electromagnetic enhancement, while the nanocages with inner Pt or Pd shell have a strong chemical enhancement. The optical measurements of the localized surface plasmon resonance (LSPR) of the nanocages with an outer Au shell and an inner Pt or Pd shell were found, experimentally and theoretically, to be broad compared with AuNCs. The possible reason could be due to the decrease of the coherence time of Au oscillated free electrons and fast damping of the plasmon energy. This agreed well with the fact that a Pt or Pd inner nanoshell decreases the electromagnetic field of the outer Au nanoshell while increasing the SERS chemical enhancement.

Surface modification of PLGA nanoparticles by carbopol to enhance mucoadhesion and cell internalization.

PubMed

Surassmo, Suvimol; Saengkrit, Nattika; Ruktanonchai, Uracha Rungsardthong; Suktham, Kunat; Woramongkolchai, Noppawan; Wutikhun, Tuksadon; Puttipipatkhachorn, Satit

2015-06-01

Mucoadhesive poly (lactic-co-glycolic acid) (PLGA) nanoparticles having a modified shell-matrix derived from polyvinyl alcohol (PVA) and Carbopol (CP), a biodegradable polymer coating, to improve the adhesion and cell transfection properties were developed. The optimum formulations utilized a CP concentration in the range of 0.05-0.2%w/v, and were formed using modified emulsion-solvent evaporation technique. The resulting CP-PLGA nanoparticles were characterized in terms of their physical and chemical properties. The absorbed CP on the PLGA shell-matrix was found to affect the particle size and surface charge, with 0.05% CP giving rise to smooth spherical particles (0.05CP-PLGA) with the smallest size (285.90 nm), and strong negative surface charge (-25.70 mV). The introduction of CP results in an enhancement of the mucoadhesion between CP-PLGA nanoparticles and mucin particles. In vitro cell internalization studies highlighted the potential of 0.05CP-PLGA nanoparticles for transfection into SiHa cells, with uptake being time dependent. Additionally, cytotoxicity studies of CP-PLGA nanoparticles against SiHa cancer cells indicated that low concentrations of the nanoparticles were non-toxic to cells (cell viability >80%). From the various formulations studied, 0.05CP-PLGA nanoparticles proved to be the optimum model carrier having the required mucoadhesive profile and could be an alternative therapeutic efficacy carrier for targeted mucosal drug delivery systems with biodegradable polymer. Copyright © 2015 Elsevier B.V. All rights reserved.

Strong catalytic activity of iron nanoparticles on the surfaces of reduced olivine

NASA Astrophysics Data System (ADS)

Tucker, William C.; Quadery, Abrar H.; Schulte, Alfons; Blair, Richard G.; Kaden, William E.; Schelling, Patrick K.; Britt, Daniel T.

2018-01-01

It is demonstrated that olivine powders heated to subsolidus temperatures in reducing conditions can develop significant concentrations of 10-50 nm diameter Fe nanoparticles on grain surfaces and that these display strong catalytic activity not observed in powders without Fe nanoparticles. Reduced surfaces were exposed to NH3, CO, and H2, volatiles that may be present on the surfaces of comet and volatile-rich asteroids. In the case of NH3 exposure, rapid decomposition was observed. When exposed to a mixture of CO and H2, significant coking of the mineral surfaces occurred. Analysis of the mineral grains after reaction indicated primarily the presence of graphene or graphitic carbon. The results demonstrate that strong chemical activity can be expected at powders that contain nanophase Fe particles. This suggests space-weathered mineral surfaces may play an important role in the synthesis and processing of organic species. This processing may be part of the weathering processes of volatile-rich but atmosphereless solar-system bodies.

Quantitative Transmission Electron Microscopy of Nanoparticles and Thin-Film Formation in Electroless Metallization of Polymeric Surfaces

NASA Astrophysics Data System (ADS)

Dutta, Aniruddha; Heinrich, Helge; Kuebler, Stephen; Grabill, Chris; Bhattacharya, Aniket

2011-03-01

Gold nanoparticles(Au-NPs) act as nucleation sites for electroless deposition of silver on functionalized SU8 polymeric surfaces. Here we report the nanoscale morphology of Au and Ag nanoparticles as studied by Transmission Electron Microscopy (TEM). Scanning TEM with a high-angle annular dark-field detector is used to obtain atomic number contrast. From the intensity-calibrated plan-view scanning TEM images we determine the mean thickness and the volume distribution of the Au-NPs on the surface of the functionalized polymer. We also report the height and the radius distribution of the gold nanoparticles obtained from STEM images taking into consideration the experimental errors. The cross sectional TEM images yield the density and the average distance of the Au and Ag nanoparticles on the surface of the polymer. Supported by grant NSF, Chemistry Division.

Cutaneous exposure scenarios for engineered nanoparticles used in semiconductor fabrication: a preliminary investigation of workplace surface contamination.

PubMed

Shepard, Michele; Brenner, Sara

2014-01-01

Numerous studies are ongoing in the fields of nanotoxicology and exposure science; however, gaps remain in identifying and evaluating potential exposures from skin contact with engineered nanoparticles in occupational settings. The aim of this study was to identify potential cutaneous exposure scenarios at a workplace using engineered nanoparticles (alumina, ceria, amorphous silica) and evaluate the presence of these materials on workplace surfaces. Process review, workplace observations, and preliminary surface sampling were conducted using microvacuum and wipe sample collection methods and transmission electron microscopy with elemental analysis. Exposure scenarios were identified with potential for incidental contact. Nanoparticles of silica or silica and/or alumina agglomerates (or aggregates) were identified in surface samples from work areas where engineered nanoparticles were used or handled. Additional data are needed to evaluate occupational exposures from skin contact with engineered nanoparticles; precautionary measures should be used to minimize potential cutaneous exposures in the workplace.

Structural and electronic properties of AlN(0001) surface under partial N coverage as determined by ab initio approach

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

Strak, Pawel; Sakowski, Konrad; Kempisty, Pawel

2015-09-07

Properties of bare and nitrogen-covered Al-terminated AlN(0001) surface were determined using density functional theory (DFT) calculations. At a low nitrogen coverage, the Fermi level is pinned by Al broken bond states located below conduction band minimum. Adsorption of nitrogen is dissociative with an energy gain of 6.05 eV/molecule at a H3 site creating an overlap with states of three neighboring Al surface atoms. During this adsorption, electrons are transferred from Al broken bond to topmost N adatom states. Accompanying charge transfer depends on the Fermi level. In accordance with electron counting rule (ECR), the DFT results confirm the Fermi levelmore » is not pinned at the critical value of nitrogen coverage θ{sub N}(1) = 1/4 monolayer (ML), but it is shifted from an Al-broken bond state to Np{sub z} state. The equilibrium thermodynamic potential of nitrogen in vapor depends drastically on the Fermi level pinning being shifted by about 4 eV for an ECR state at 1/4 ML coverage. For coverage above 1/4 ML, adsorption is molecular with an energy gain of 1.5 eV at a skewed on-top position above an Al surface atom. Electronic states of the admolecule are occupied as in the free molecule, no electron transfer occurs and adsorption of a N{sub 2} molecule does not depend on the Fermi level. The equilibrium pressure of molecular nitrogen above an AlN(0001) surface depends critically on the Fermi level position, being very low and very high for low and high coverage, respectively. From this fact, one can conclude that at typical growth conditions, the Fermi level is not pinned, and the adsorption and incorporation of impurities depend on the position of Fermi level in the bulk.« less

Extracellular polymeric substances govern the surface charge of biogenic elemental selenium nanoparticles.

PubMed

Jain, Rohan; Jordan, Norbert; Weiss, Stephan; Foerstendorf, Harald; Heim, Karsten; Kacker, Rohit; Hübner, René; Kramer, Herman; van Hullebusch, Eric D; Farges, François; Lens, Piet N L

2015-02-03

The origin of the organic layer covering colloidal biogenic elemental selenium nanoparticles (BioSeNPs) is not known, particularly in the case when they are synthesized by complex microbial communities. This study investigated the presence of extracellular polymeric substances (EPS) on BioSeNPs. The role of EPS in capping the extracellularly available BioSeNPs was also examined. Fourier transform infrared (FT-IR) spectroscopy and colorimetric measurements confirmed the presence of functional groups characteristic of proteins and carbohydrates on the BioSeNPs, suggesting the presence of EPS. Chemical synthesis of elemental selenium nanoparticles in the presence of EPS, extracted from selenite fed anaerobic granular sludge, yielded stable colloidal spherical selenium nanoparticles. Furthermore, extracted EPS, BioSeNPs, and chemically synthesized EPS-capped selenium nanoparticles had similar surface properties, as shown by ζ-potential versus pH profiles and isoelectric point measurements. This study shows that the EPS of anaerobic granular sludge form the organic layer present on the BioSeNPs synthesized by these granules. The EPS also govern the surface charge of these BioSeNPs, thereby contributing to their colloidal properties, hence affecting their fate in the environment and the efficiency of bioremediation technologies.

Nature of peptide wrapping onto metal nanoparticle catalysts and driving forces for size control.

PubMed

Ramezani-Dakhel, Hadi; Bedford, Nicholas M; Woehl, Taylor J; Knecht, Marc R; Naik, Rajesh R; Heinz, Hendrik

2017-06-22

Colloidal metal nanocrystals find many applications in catalysis, energy conversion devices, and therapeutics. However, the nature of ligand interactions and implications on shape control have remained uncertain at the atomic scale. Large differences in peptide adsorption strength and facet specificity were found on flat palladium surfaces versus surfaces of nanoparticles of 2 to 3 nm size using accurate atomistic simulations with the Interface force field. Folding of longer peptides across many facets explains the formation of near-spherical particles with local surface disorder, in contrast to the possibility of nanostructures of higher symmetry with shorter ligands. The average particle size in TEM correlates inversely with the surface coverage with a given ligand and with the strength of ligand adsorption. The role of specific amino acids and sequence mutations on the nanoparticle size and facet composition is discussed, as well as the origin of local surface disorder that leads to large differences in catalytic reactivity.

Positronic probe of vacancy defects on surfaces of Au nanoparticles embedded in MgO

NASA Astrophysics Data System (ADS)

Xu, Jun; Moxom, J.; Somieski, B.; White, C. W.; Mills, A. P., Jr.; Suzuki, R.; Ishibashi, S.

2001-09-01

Clusters of four atomic vacancies were found in Au nanoparticle-embedded MgO by positron lifetime spectroscopy [Phys. Rev. Lett. 83, 4586 (1999)]. These clusters were also suggested to locate at the surface of Au nanoparticles by one-detector measurements of Doppler broadening of annihilation radiation. In this work we provide evidence, using two-detector coincidence experiments of Doppler broadening (2D-DBAR), to clarify that these vacancy clusters reside on the surfaces of Au nanoparticles. This work also demonstrates a method for identifying defects at nanomaterials interfaces: a combination of both positron lifetime spectroscopy, which tells the type of the defects, and 2D-DBAR measurements, which reveals chemical environment of the defects.

Altering Iron Oxide Nanoparticle Surface Properties Induce Cortical Neuron Cytotoxicity

PubMed Central

Rivet, Christopher J.; Yuan, Yuan; Borca-Tasciuc, Diana-Andra; Gilbert, Ryan J.

2014-01-01

Superparamagnetic iron oxide nanoparticles, with diameters in the range of a few tens of nanometers, display the ability to cross the blood-brain barrier and are envisioned as diagnostic and therapeutic tools in neuro-medicine. However, despite the numerous applications being explored, insufficient information is available on their potential toxic effect on neurons. While iron oxide has been shown to pose a decreased risk of toxicity, surface functionalization, often employed for targeted delivery, can significantly alter the biological response. This aspect is addressed in the present study, which investigates the response of primary cortical neurons to iron oxide nanoparticles with coatings frequently used in biomedical applications: aminosilane, dextran, and polydimethylamine. Prior to administering the particles to neuronal cultures, each particle type was thoroughly characterized to assess the (1) size of individual nanoparticles, (2) concentration of the particles in solution and (3) agglomeration size and morphology. Culture results show that polydimethylamine functionalized nanoparticles induce cell death at all concentrations tested by swift and complete removal of the plasma membrane. Aminosilane coated particles affected metabolic activity only at higher concentrations while leaving the membrane intact and dextran-coated nanoparticles partially altered viability at higher concentrations. These findings suggest that nanoparticle characterization and primary cell-based cytotoxicity evaluation should be completed prior to applying nanomaterials to the nervous system. PMID:22111864

Bidisperse silica nanoparticles close-packed monolayer on silicon substrate by three step spin method

NASA Astrophysics Data System (ADS)

Khanna, Sakshum; Marathey, Priyanka; Utsav, Chaliawala, Harsh; Mukhopadhyay, Indrajit

2018-05-01

We present the studies on the structural properties of monolayer Bidisperse silica (SiO2) nanoparticles (BDS) on Silicon (Si-100) substrate using spin coating technique. The Bidisperse silica nanoparticle was synthesised by the modified sol-gel process. Nanoparticles on the substrate are generally assembled in non-close/close-packed monolayer (CPM) form. The CPM form is obtained by depositing the colloidal suspension onto the silicon substrate using complex techniques. Here we report an effective method for forming a monolayer of bidisperse silica nanoparticle by three step spin coating technique. The samples were prepared by mixing the monodisperse solutions of different particles size 40 and 100 nm diameters. The bidisperse silica nanoparticles were self-assembled on the silicon substrate forming a close-packed monolayer film. The scanning electron microscope images of bidisperse films provided in-depth film structure of the film. The maximum surface coverage obtained was around 70-80%.

Surface impact on nanoparticle-based magnetic resonance imaging contrast agents

PubMed Central

Zhang, Weizhong; Liu, Lin; Chen, Hongmin; Hu, Kai; Delahunty, Ian; Gao, Shi; Xie, Jin

2018-01-01

Magnetic resonance imaging (MRI) is one of the most widely used diagnostic tools in the clinic. To improve imaging quality, MRI contrast agents, which can modulate local T1 and T2 relaxation times, are often injected prior to or during MRI scans. However, clinically used contrast agents, including Gd3+-based chelates and iron oxide nanoparticles (IONPs), afford mediocre contrast abilities. To address this issue, there has been extensive research on developing alternative MRI contrast agents with superior r1 and r2 relaxivities. These efforts are facilitated by the fast progress in nanotechnology, which allows for preparation of magnetic nanoparticles (NPs) with varied size, shape, crystallinity, and composition. Studies suggest that surface coatings can also largely affect T1 and T2 relaxations and can be tailored in favor of a high r1 or r2. However, the surface impact of NPs has been less emphasized. Herein, we review recent progress on developing NP-based T1 and T2 contrast agents, with a focus on the surface impact. PMID:29721097

Au-Ag-Au double shell nanoparticles-based localized surface plasmon resonance and surface-enhanced Raman scattering biosensor for sensitive detection of 2-mercapto-1-methylimidazole.

PubMed

Liao, Xue; Chen, Yanhua; Qin, Meihong; Chen, Yang; Yang, Lei; Zhang, Hanqi; Tian, Yuan

2013-12-15

In this paper, Au-Ag-Au double shell nanoparticles were prepared based on the reduction of the metal salts HAuCl4 and AgNO3 at the surface of seed particles. Due to the synergistic effect between Au and Ag, the hybrid nanoparticles are particularly stable and show excellent performances on the detection of 2-mercapto-1-methylimidazole (methimazole). The binding of target molecule at the surface of Au-Ag-Au double shell nanoparticles was demonstrated based on both localized surface plasmon resonance (LSPR) and surface-enhanced Raman scattering (SERS) spectra. The LSPR intensity is directly proportional to the methimazole concentration in the range of 0.10-3.00×10(-7) mol L(-1). The SERS spectrum can be applied in identification of methimazole molecule. The LSPR coupled with SERS based on the Au-Ag-Au double shell nanoparticles would be very attractive for the quantitative determination and qualitative analysis of the analytes in medicines. © 2013 Elsevier B.V. All rights reserved.

Cutaneous exposure scenarios for engineered nanoparticles used in semiconductor fabrication: a preliminary investigation of workplace surface contamination

PubMed Central

Shepard, Michele; Brenner, Sara

2014-01-01

Background: Numerous studies are ongoing in the fields of nanotoxicology and exposure science; however, gaps remain in identifying and evaluating potential exposures from skin contact with engineered nanoparticles in occupational settings. Objectives: The aim of this study was to identify potential cutaneous exposure scenarios at a workplace using engineered nanoparticles (alumina, ceria, amorphous silica) and evaluate the presence of these materials on workplace surfaces. Methods: Process review, workplace observations, and preliminary surface sampling were conducted using microvacuum and wipe sample collection methods and transmission electron microscopy with elemental analysis. Results: Exposure scenarios were identified with potential for incidental contact. Nanoparticles of silica or silica and/or alumina agglomerates (or aggregates) were identified in surface samples from work areas where engineered nanoparticles were used or handled. Conclusions: Additional data are needed to evaluate occupational exposures from skin contact with engineered nanoparticles; precautionary measures should be used to minimize potential cutaneous exposures in the workplace. PMID:25000112

Occlusion of Sulfate-Based Diblock Copolymer Nanoparticles within Calcite: Effect of Varying the Surface Density of Anionic Stabilizer Chains.

PubMed

Ning, Yin; Fielding, Lee A; Ratcliffe, Liam P D; Wang, Yun-Wei; Meldrum, Fiona C; Armes, Steven P

2016-09-14

Polymerization-induced self-assembly (PISA) offers a highly versatile and efficient route to a wide range of organic nanoparticles. In this article, we demonstrate for the first time that poly(ammonium 2-sulfatoethyl methacrylate)-poly(benzyl methacrylate) [PSEM-PBzMA] diblock copolymer nanoparticles can be prepared with either a high or low PSEM stabilizer surface density using either RAFT dispersion polymerization in a 2:1 v/v ethanol/water mixture or RAFT aqueous emulsion polymerization, respectively. We then use these model nanoparticles to gain new insight into a key topic in materials chemistry: the occlusion of organic additives into inorganic crystals. Substantial differences are observed for the extent of occlusion of these two types of anionic nanoparticles into calcite (CaCO3), which serves as a suitable model host crystal. A low PSEM stabilizer surface density leads to uniform nanoparticle occlusion within calcite at up to 7.5% w/w (16% v/v), while minimal occlusion occurs when using nanoparticles with a high PSEM stabilizer surface density. This counter-intuitive observation suggests that an optimum anionic surface density is required for efficient occlusion, which provides a hitherto unexpected design rule for the incorporation of nanoparticles within crystals.

Synthesis of polymer-stabilized monometallic Cu and bimetallic Cu/Ag nanoparticles and their surface-enhanced Raman scattering properties

NASA Astrophysics Data System (ADS)

Zhang, Danhui; Liu, Xiaoheng

2013-03-01

The present study demonstrates a facile process for the production of spherical-shaped Cu and Ag nanoparticles synthesized and stabilized by hydrazine and gelatin, respectively. Advantages of the synthetic method include its production of water dispersible copper and copper/silver nanoparticles at room temperature under no inert atmosphere. The resulting nanoparticles (copper or copper/silver) are investigated by X-ray diffraction (XRD), UV-vis spectroscopy, and transmission electron microscopy (TEM). The nanometallic dispersions were characterized by surface plasmon absorbance measuring at 420 and 572 nm for Ag and Cu nanoparticles, respectively. Transmission electron microscopy showed the formation of nanoparticles in the range of ˜10 nm (silver), and ˜30 nm (copper). The results also demonstrate that the reducing order of Cu2+/Ag+ is important for the formation of the bimetallic nanoparticles. The surface-enhanced Raman scattering effects of copper and copper/silver nanoparticles were also displayed. It was found that the enhancement ability of copper/silver nanoparticles was little higher than the copper nanoparticles.

Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions

NASA Astrophysics Data System (ADS)

Hejral, U.; Franz, D.; Volkov, S.; Francoual, S.; Strempfer, J.; Stierle, A.

2018-03-01

Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.

Streaming current for particle-covered surfaces: simulations and experiments

NASA Astrophysics Data System (ADS)

Blawzdziewicz, Jerzy; Adamczyk, Zbigniew; Ekiel-Jezewska, Maria L.

2017-11-01

Developing in situ methods for assessment of surface coverage by adsorbed nanoparticles is crucial for numerous technological processes, including controlling protein deposition and fabricating diverse microstructured materials (e.g., antibacterial coatings, catalytic surfaces, and particle-based optical systems). For charged surfaces and particles, promising techniques for evaluating surface coverage are based on measurements of the electrokinetic streaming current associated with ion convection in the double-layer region. We have investigated the dependence of the streaming current on the area fraction of adsorbed particles for equilibrium and random-sequential-adsorption (RSA) distributions of spherical particles, and for periodic square and hexagonal sphere arrays. The RSA results have been verified experimentally. Our numerical results indicate that the streaming current weakly depends on the microstructure of the particle monolayer. Combining simulations with the virial expansion, we provide convenient fitting formulas for the particle and surface contributions to the streaming current as functions of area fractions. For particles that have the same ζ-potential as the surface, we find that surface roughness reduces the streaming current. Supported by NSF Award No. 1603627.

Surface-modified nanoparticles as anti-biofilm filler for dental polymers

PubMed Central

Zaltsman, Nathan; Ionescu, Andrei C.; Weiss, Ervin I.; Brambilla, Eugenio; Beyth, Shaul

2017-01-01

The objective of the study was to synthesis silica nanoparticles modified with (i) a tertiary amine bearing two t-cinnamaldehyde substituents or (ii) dimethyl-octyl ammonium, alongside the well-studied quaternary ammonium polyethyleneimine nanoparticles. These were to be evaluated for their chemical and mechanical properties, as well for antibacterial and antibiofilm activity. Samples were incorporated in commercial dental resin material and the degree of monomer conversion, mechanical strength, and water contact angle were tested to characterize the effect of the nanoparticles on resin material. Antibacterial activity was evaluated with the direct contact test and the biofilm inhibition test against Streptococcus mutans. Addition of cinnamaldehyde-modified particles preserved the degree of conversion and compressive strength of the base material and increased surface hydrophobicity. Quaternary ammonium functional groups led to a decrease in the degree of conversion and to low compressive strength, without altering the hydrophilic nature of the base material. In the direct contact test and the anti-biofilm test, the polyethyleneimine particles exhibited the strongest antibacterial effect. The cinnamaldehyde-modified particles displayed antibiofilm activity, silica particles with quaternary ammonium were ineffective. Immobilization of t-cinnamaldehyde onto a solid surface via amine linkers provided a better alternative to the well-known quaternary ammonium bactericides. PMID:29244848

Studies on surface morphology and electrical conductivity of PEDOT:PSS thin films in presence of gold nanoparticles

NASA Astrophysics Data System (ADS)

Bhowal, Ashim Chandra; Kundu, Sarathi

2018-04-01

PEDOT:PSS is a water soluble conducting polymer consists of positively charged PEDOT and negatively charged PSS. However, this polymer suffers low conductivity problem which restrict its use. In this paper, electrical conductivity of PEDOT:PSS thin films is improved by using charged gold nanoparticles. The nanoparticles used are synthesized using lysozyme protein. The nanoparticles coated with lysozyme protein possess positive zeta potential. In the presence of gold nanoparticles due to electrostatic interaction between positively charged nanoparticles and negatively charged PSS chains, modification takes place in the surface morphology and electrical behaviors of PEDOT:PSS thin films. The changes in the polymer matrix conformations in the presence of nanoparticles are studied by Fourier transformed Infra-red (FTIR) spectroscopy, whereas the surface morphology of prepared thin films before and after interaction with nanoparticles is investigated through atomic force microscopy (AFM). Four probe method is used to measure the variation of electrical conductivity from I-V characteristics curves.

Individual and collective modes of surface magnetoplasmon in thiolate-protected silver nanoparticles studied by MCD spectroscopy.

PubMed

Yao, Hiroshi; Shiratsu, Taisuke

2016-06-07

Large magneto-optical (MO) responses at the energy of localized surface plasmon resonance (LSPR), namely, surface magnetoplasmons, are demonstrated for the first time in thiolate-protected silver nanoparticles with magnetic circular dichroism (MCD) spectroscopy. The samples examined are decanethiol (DT)-, azobenzenethiol (ABT)-, and ABT/DT mixed-monolayer-protected Ag nanoparticles. ABT-protected Ag nanoparticles are somewhat aggregated and thus exhibit a broad, collective mode of plasmonic absorption, whereas other samples with highly-dispersed nanoparticles show an individual mode of LSPR absorption. In all Ag nanoparticles, a derivative-like MCD signal is observed under an applied magnetic field of 1.6 T, which can be explained in terms of two circular modes of magnetoplasmon caused by the increase (or decrease) in the Lorentz force imparted on the free electrons that oscillate in the left (or right) circular orbits in the nanosphere. For the Ag nanoparticles exhibiting an individual LSPR mode, in particular, simultaneous deconvolution analysis of UV-vis absorption and MCD spectra reveal that (i) the amplitude of the magnetoplasmonic component with lower frequency (ω-), resulting from the reduction in the confinement strength of collective electrons by the Lorentz force, is stronger than that with a higher frequency (ω+); (ii) the accurate shift or cyclotron frequency between two magnetoplasmonic modes (ωc = ω+-ω-) is size-dependent, and presents a very large value with implications for the apparent enhancement of the local magnetic-field in the Ag nanoparticles. These results strongly suggest that the Ag-thiolate layer or Ag-S bonding on the nanoparticle surface plays a significant role in the MO enhancement.

Surface functionalization of microwave plasma-synthesized silica nanoparticles for enhancing the stability of dispersions

NASA Astrophysics Data System (ADS)

Sehlleier, Yee Hwa; Abdali, Ali; Schnurre, Sophie Marie; Wiggers, Hartmut; Schulz, Christof

2014-08-01

Gas phase-synthesized silica nanoparticles were functionalized with three different silane coupling agents (SCAs) including amine, amine/phosphonate and octyltriethoxy functional groups and the stability of dispersions in polar and non-polar dispersing media such as water, ethanol, methanol, chloroform, benzene, and toluene was studied. Fourier transform infrared spectroscopy showed that all three SCAs are chemically attached to the surface of silica nanoparticles. Amine-functionalized particles using steric dispersion stabilization alone showed limited stability. Thus, an additional SCA with sufficiently long hydrocarbon chains and strong positively charged phosphonate groups was introduced in order to achieve electrosteric stabilization. Steric stabilization was successful with hydrophobic octyltriethoxy-functionalized silica nanoparticles in non-polar solvents. The results from dynamic light scattering measurements showed that in dispersions of amine/phosphonate- and octyltriethoxy-functionalized silica particles are dispersed on a primary particle level. Stable dispersions were successfully prepared from initially agglomerated nanoparticles synthesized in a microwave plasma reactor by designing the surface functionalization.

Surface spin tunneling and heat dissipation in magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Palakkal, Jasnamol P.; Obula Reddy, Chinna; Paulose, Ajeesh P.; Sankar, Cheriyedath Raj

2018-03-01

Quantum superparamagnetic state is observed in ultra-fine magnetic particles, which is often experimentally identified by a significant hike in magnetization towards low temperatures much below the superparamagnetic blocking temperature. Here, we report experimentally observed surface spin relaxation at low temperatures in hydrated magnesium ferrite nanoparticles of size range of about 5 nm. We observed time dependent oscillatory magnetization of the sample below 2.5 K, which is attributed to surface spin tunneling. Interestingly, we observed heat dissipation during the process by using an external thermometer.

Silver nanoparticles-incorporated Nb2O5 surface passivation layer for efficiency enhancement in dye-sensitized solar cells.

PubMed

Suresh, S; Unni, Gautam E; Satyanarayana, M; Sreekumaran Nair, A; Mahadevan Pillai, V P

2018-08-15

Guiding and capturing photons at the nanoscale by means of metal nanoparticles and interfacial engineering for preventing back-electron transfer are well documented techniques for performance enhancement in excitonic solar cells. Drifting from the conventional route, we propose a simple one-step process to integrate both metal nanoparticles and surface passivation layer in the porous photoanode matrix of a dye-sensitized solar cell. Silver nanoparticles and Nb 2 O 5 surface passivation layer are simultaneously deposited on the surface of a highly porous nanocrystalline TiO 2 photoanode, facilitating an absorption enhancement in the 465 nm and 570 nm wavelength region and a reduction in back-electron transfer in the fabricated dye-sensitized solar cells together. The TiO 2 photoanodes were prepared by spray pyrolysis deposition method from a colloidal solution of TiO 2 nanoparticles. An impressive 43% enhancement in device performance was accomplished in photoanodes having an Ag-incorporated Nb 2 O 5 passivation layer as against a cell without Ag nanoparticles. By introducing this idea, we were able to record two benefits - the metal nanoparticles function as the absorption enhancement agent, and the Nb 2 O 5 layer as surface passivation for TiO 2 nanoparticles and as an energy barrier layer for preventing back-electron transfer - in a single step. Copyright © 2018 Elsevier Inc. All rights reserved.

Metabolism, survival, and gene expression of Pseudomonas putida to hematite nanoparticles mediated by surface-bound humic acid

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

Ouyang, Kai; Walker, Sharon L.; Yu, Xiao-Ying

Natural organic matter (NOM) is likely to coat naturally occurring nanoparticles (NNPs) in the soil environment and poses distinct effects on the interaction between NPs and soil microorganisms, however such topic has not been well investigated. This study explored the influence of nanoparticle surface-bound humic acid (HA, as a model NOM) on the toxicity of hematite NPs (i.e., nano-Fe2O3) to Pseudomonas putida (P. putida). Results showed that nano-Fe2O3 could inhibit the bacterial growth with an IC50 of 23.58 mg L-1, while nanoparticle surface-bound HA could significantly alleviate the P. putida toxicity of nano-Fe2O3. IC50 of nano-Fe2O3 increased to 4774.23 mgmore » L-1 as a result of surface-saturation by HA. Co-precipitation experiment and transmission electron microscopy observation revealed that nanoparticle surface-bound HA prevented the adhesion of nano-Fe2O3 to the cells as well as limited cell internalization of nanoparticles due to the increased electrostatic repulsion. The generation of intracellular reactive oxygen species (ROS) was significantly limited by the nanoparticle surface-bound HA. The prevention of adhesion and inhibition of ROS generation could account for the HA-mitigated nanotoxicity. Interfacial interactions between hematite NPs and cell membrane were also evaluated on the basis of the Derjaguin–Landau–Verwey–Overbeek (DLVO) theory, and the magnitude of interaction energy barrier correlated well with the 48 h LC50 data of hematite NPs to P. putida. This result implies that metal oxide NPs with strong association with the cell surface might induce more severe cytotoxicity in microorganisms.« less

Surface Plasmon Resonance of Counterions coated Charged Silver Nanoparticles and Application in Bio-interaction

NASA Astrophysics Data System (ADS)

Ghosh, Goutam; Panicker, Lata; Naveen Kumar, N.; Mallick, Vivek

2018-05-01

Silver nanoparticles (SNPs) play very significant roles in biomedical applications, e.g., biosensors in numerous assays for quantitative detection, and the surface chemistry adds an important factor in that. In this investigation, we coated SNPs either by anionic citrates, like tri-lithium citrate (TLC) or tri-potassium citrate (TKC) which are associated with Li+ or K+ counterions, respectively; or by cationic surfactants, like cetylpyridinium chloride (CPC) or cetylpyridinium iodide (CPI) which are associated with Cl‑ or I‑ counterions, respectively, at the surface of nanoparticles. Our aim was to study (i) how the counterions affect the optical property of SNPs and (ii) the interaction of coated SNPs with a protein, hen egg white lysozyme (HEWL). Transmission electron microscopy (TEM) and dynamic light scattering (DLS) techniques were used to measure the size, and UV absorption spectroscopy was used to characterize the surface plasmon resonance (SPR) band of SNPs. ζ-potential, fluorescence quenching and circular dichroism (CD) spectroscopy techniques were used for characterizing the protein-nanoparticles interaction.

Direct Measurement of the Surface Energy of Bimetallic Nanoparticles: Evidence of Vegard's Rulelike Dependence.

PubMed

Chmielewski, Adrian; Nelayah, Jaysen; Amara, Hakim; Creuze, Jérôme; Alloyeau, Damien; Wang, Guillaume; Ricolleau, Christian

2018-01-12

We use in situ transmission electron microscopy to monitor in real time the evaporation of gold, copper, and bimetallic copper-gold nanoparticles at high temperature. Besides, we extend the Kelvin equation to two-component systems to predict the evaporation rates of spherical liquid mono- and bimetallic nanoparticles. By linking this macroscopic model to experimental TEM data, we determine the surface energies of pure gold, pure copper, Cu_{50}Au_{50}, and Cu_{25}Au_{75} nanoparticles in the liquid state. Our model suggests that the surface energy varies linearly with the composition in the liquid Cu-Au nanoalloy; i.e., it follows a Vegard's rulelike dependence. To get atomic-scale insights into the thermodynamic properties of Cu-Au alloys on the whole composition range, we perform Monte Carlo simulations employing N-body interatomic potentials. These simulations at a microscopic level confirm the Vegard's rulelike behavior of the surface energy obtained from experiments combined with macroscopic modeling.

Direct Measurement of the Surface Energy of Bimetallic Nanoparticles: Evidence of Vegard's Rulelike Dependence

NASA Astrophysics Data System (ADS)

Chmielewski, Adrian; Nelayah, Jaysen; Amara, Hakim; Creuze, Jérôme; Alloyeau, Damien; Wang, Guillaume; Ricolleau, Christian

2018-01-01

We use in situ transmission electron microscopy to monitor in real time the evaporation of gold, copper, and bimetallic copper-gold nanoparticles at high temperature. Besides, we extend the Kelvin equation to two-component systems to predict the evaporation rates of spherical liquid mono- and bimetallic nanoparticles. By linking this macroscopic model to experimental TEM data, we determine the surface energies of pure gold, pure copper, Cu50 Au50 , and Cu25 Au75 nanoparticles in the liquid state. Our model suggests that the surface energy varies linearly with the composition in the liquid Cu-Au nanoalloy; i.e., it follows a Vegard's rulelike dependence. To get atomic-scale insights into the thermodynamic properties of Cu-Au alloys on the whole composition range, we perform Monte Carlo simulations employing N -body interatomic potentials. These simulations at a microscopic level confirm the Vegard's rulelike behavior of the surface energy obtained from experiments combined with macroscopic modeling.

Individual and collective modes of surface magnetoplasmon in thiolate-protected silver nanoparticles studied by MCD spectroscopy

NASA Astrophysics Data System (ADS)

Yao, Hiroshi; Shiratsu, Taisuke

2016-05-01

Large magneto-optical (MO) responses at the energy of localized surface plasmon resonance (LSPR), namely, surface magnetoplasmons, are demonstrated for the first time in thiolate-protected silver nanoparticles with magnetic circular dichroism (MCD) spectroscopy. The samples examined are decanethiol (DT)-, azobenzenethiol (ABT)-, and ABT/DT mixed-monolayer-protected Ag nanoparticles. ABT-protected Ag nanoparticles are somewhat aggregated and thus exhibit a broad, collective mode of plasmonic absorption, whereas other samples with highly-dispersed nanoparticles show an individual mode of LSPR absorption. In all Ag nanoparticles, a derivative-like MCD signal is observed under an applied magnetic field of 1.6 T, which can be explained in terms of two circular modes of magnetoplasmon caused by the increase (or decrease) in the Lorentz force imparted on the free electrons that oscillate in the left (or right) circular orbits in the nanosphere. For the Ag nanoparticles exhibiting an individual LSPR mode, in particular, simultaneous deconvolution analysis of UV-vis absorption and MCD spectra reveal that (i) the amplitude of the magnetoplasmonic component with lower frequency (ω-), resulting from the reduction in the confinement strength of collective electrons by the Lorentz force, is stronger than that with a higher frequency (ω+) (ii) the accurate shift or cyclotron frequency between two magnetoplasmonic modes (ωc = ω+ - ω-) is size-dependent, and presents a very large value with implications for the apparent enhancement of the local magnetic-field in the Ag nanoparticles. These results strongly suggest that the Ag-thiolate layer or Ag-S bonding on the nanoparticle surface plays a significant role in the MO enhancement.Large magneto-optical (MO) responses at the energy of localized surface plasmon resonance (LSPR), namely, surface magnetoplasmons, are demonstrated for the first time in thiolate-protected silver nanoparticles with magnetic circular dichroism (MCD

Formation of silver nanoparticle at phospholipid template using Langmuir-Blodgett technique and its Surface-enhanced Raman Spectroscopy application

NASA Astrophysics Data System (ADS)

Mahato, M.; Sarkar, R.; Pal, P.; Talapatra, G. B.

2015-10-01

The biosynthesis of metal nanoparticle and their suitable assembly has recently gained tremendous interest for its application in biomedical arena such as substrates for surface-enhanced Raman scattering and others. In this article, an easy, low-cost, fast, bio-friendly and toxic-reducing agent free protocol has been described for the preparation of silver nanoparticle film using biocompatible 1,2-dipalmitoyl-sn-glycero-3-phosphocholine phospholipid Langmuir monolayer template. Interactions, docking and attachment of silver ions to the above-mentioned phospholipid monolayer have been studied by surface pressure-area isotherm and compressibility analysis at the air-water interface. We have deposited the Langmuir-Blodgett monolayer/multilayer containing silver nanoparticle onto glass/SiO2/quartz substrates. The formation of phospholipid-silver nanoparticle complex in Langmuir-Blodgett film has been characterized by field emission-scanning electron microscopy and high-resolution tunneling electron microscopy images. We have applied this deposited film as a substrate for surface-enhanced Raman scattering application using rhodamine 123 to understand the existence of the surface plasmon activity of silver nanoparticle.

Immobilization of Ag nanoparticles/FGF-2 on a modified titanium implant surface and improved human gingival fibroblasts behavior.

PubMed

Ma, Qianli; Mei, Shenglin; Ji, Kun; Zhang, Yumei; Chu, Paul K

2011-08-01

The objective of this study was to form a rapid and firm soft tissue sealing around dental implants that resists bacterial invasion. We present a novel approach to modify Ti surface by immobilizing Ag nanoparticles/FGF-2 compound bioactive factors onto a titania nanotubular surface. The titanium samples were anodized to form vertically organized TiO(2) nanotube arrays and Ag nanoparticles were electrodeposited onto the nanotubular surface, on which FGF-2 was immobilized with repeated lyophilization. A uniform distribution of Ag nanoparticles/FGF-2 was observed on the TiO(2) nanotubular surface. The L929 cell line was used for cytotoxicity assessment. Human gingival fibroblasts (HGFs) were cultured on the modified surface for cytocompatibility determination. The Ag/FGF-2 immobilized samples displayed excellent cytocompatibility, negligible cytotoxicity, and enhanced HGF functions such as cell attachment, proliferation, and ECM-related gene expression. The Ag nanoparticles also exhibit some bioactivity. In conclusion, this modified TiO(2) nanotubular surface has a large potential for use in dental implant abutment. Copyright © 2011 Wiley Periodicals, Inc.

Surface functionalization of magnetic nanoparticles formed by self-associating hydrophobized oxidized dextrans

NASA Astrophysics Data System (ADS)

Farber, Shimon; Ickowicz, Diana E.; Melnik, Kristie; Yudovin-Farber, Ira; Recko, Daniel; Rampersaud, Arfaan; Domb, Abraham J.

2014-06-01

Magnetic iron oxide nanoparticles surface covered with oleic acid layer followed by a second layer of hydrophobized oxidized dextran aldehyde were prepared and tested for physico-chemical properties and ligand- and cell-specific binding. It was demonstrated that oleic acid-iron oxide nanoparticles coated with an additional layer of hydrophobized oxidized dextran were dispersible in buffer solutions and possess surface aldehyde active groups available for further binding of ligands or markers via imine or amine bond formation. Hydrophobized dextrans were synthesized by periodate oxidation and conjugation of various alkanamines to oxidized dextran by imination. Physico-chemical properties, as separation using magnetic field, magnetite concentration, and particle diameter, of the prepared magnetic samples are reported. The biotin-binding protein, neutravidin, was coupled to the particle surface by a simple reductive amination procedure. The particles were used for specific cell separation with high specificity.

Differential effect of hydroxyapatite nano-particle versus nano-rod decorated titanium micro-surface on osseointegration.

PubMed

Bai, Long; Liu, Yanlian; Du, Zhibin; Weng, Zeming; Yao, Wei; Zhang, Xiangyu; Huang, Xiaobo; Yao, Xiaohong; Crawford, Ross; Hang, Ruiqiang; Huang, Di; Tang, Bin; Xiao, Yin

2018-06-15

Coating materials applied for intraosseous implants must be optimized to stimulate osseointegration. Osseointegration is a temporal and spatial physiological process that not only requires interactions between osteogenesis and angiogenesis but also necessitates a favorable immune microenvironment. It is now well-documented that hierarchical nano-micro surface structures promote the long-term stability of implants, the interactions between nano-micro structure and the immune response are largely unknown. Here, we report the effects of microporous titanium (Ti) surfaces coated with nano-hydroxyapatite (HA) produced by micro-arc oxidation and steam-hydrothermal treatment (SHT) on multiple cell behavior and osseointegration. By altering the processing time of SHT it was possible to shift HA structures from nano-particles to nano-rods on the microporous Ti surfaces. Ti surfaces coated with HA nano-particles were found to modulate the inflammatory response resulting in an osteoimmune microenvironment more favorable for osteo-/angio-genesis, most likely via the activation of certain key signaling pathways (TGF-β, OPG/RANKL, and VEGF). By contrast, Ti surfaces coated with nano-rod shaped HA particles had a negative impact on osteo-/angio-genesis and osteoimmunomodulation. In vivo results further demonstrated that Ti implant surfaces decorated with HA nano-particles can stimulate new bone formation and osseointegration with enhanced interaction between osteocytes and implant surfaces. This study demonstrated that Ti implants with micro-surfaces coated with nano-particle shaped HA have a positive impact on osseointegration. Osteo-/angio-genesis are of importance during osteointegration of the implants. Recent advances unravel that immune response of macrophages and its manipulated osteoimmunomodulation also exerts a pivotal role to determine the fate of the implant. Surface nano-micro modification has evidenced to be efficient to influence osteogenesis, however, little is

Adsorption differences between low coverage enantiomers of alanine on the chiral Cu{421}R surface.

PubMed

Gladys, Michael J; Han, Jeong Woo; Pedersen, Therese S; Tadich, Anton; O'Donnell, Kane M; Thomsen, Lars

2017-05-31

Chiral separation using heterogeneous methods has long been sought after. Chiral metal surfaces have the potential to make it possible to model these systems using small amino acids, the building blocks for proteins. A comparison of submonolayer concentrations of alanine enantiomers adsorbed onto Cu{421} R has revealed a large geometrical differences between the two molecules as compared to the saturated coverage. Large differences were observed in HR-XPS and NEXAFS and complemented by theoretical DFT calculations. At approximately one third of a monolayer a comparison of the C1s XPS signal showed a shift in the methyl group of more than 300 meV indicating that the two enantiomers are in different chemical environments. NEXAFS spectroscopy confirmed the XPS variations and showed large differences in the orientation of the adsorbed molecules. Our DFT results show that the l-enantiomer is energetically the most stable in the {311} microfacet configuration. In contrast to the full monolayer coverage, these lower coverages showed enhanced selectivity.

Wide-range tuning of the surface plasmon resonance of silver/gold core shell and alloyed nanoparticles

NASA Astrophysics Data System (ADS)

Hubenthal, Frank; Ziegler, Torsten; Hendrich, Christian; Träger, Frank

2004-03-01

For many applications like surface enhanced Raman scattering in which the optical field enhancement associated with surface plasmon excitation is exploited, tunability of this collective resonance over a wide range is required. For this purpose we have prepared Ag/Au core shell and Ag/Au alloyed nanoparticles with different shell thicknesses and different percentages of the two metals. The nanoparticles were made by subsequent deposition of Ag and Au atoms on dielectric substrates followed by diffusion and nucleation or heat treatment. Depending on the Au shell thickness the plasmon frequency can be tuned, e.g. from 2.8 eV (442 nm) to 2.1 eV (590 nm). Annealing of the core-shell nanoparticles causes a shift of the resonance frequency to 2.6 eV. Theoretical modelling allows us to attribute this observation to the production of alloyed nanoparticles. Possible application of the Ag/Au nanoparticles will be discussed.

Orthogonal Clickable Iron Oxide Nanoparticle Platform for Targeting, Imaging, and On-Demand Release.

PubMed

Guldris, Noelia; Gallo, Juan; García-Hevia, Lorena; Rivas, José; Bañobre-López, Manuel; Salonen, Laura M

2018-04-12

A versatile iron oxide nanoparticle platform is reported that can be orthogonally functionalized to obtain highly derivatized nanomaterials required for a wide variety of applications, such as drug delivery, targeted therapy, or imaging. Facile functionalization of the nanoparticles with two ligands containing isocyanate moieties allows for high coverage of the surface with maleimide and alkyne groups. As a proof-of-principle, the nanoparticles were subsequently functionalized with a fluorophore as a drug model and with biotin as a targeting ligand towards tumor cells through Diels-Alder and azide-alkyne cycloaddition reactions, respectively. The thermoreversibility of the Diels-Alder product was exploited to induce the on-demand release of the loaded molecules by magnetic hyperthermia. Additionally, the nanoparticles were shown to target cancer cells through in vitro experiments, as analyzed by magnetic resonance imaging. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fine-Tuning the Antimicrobial Profile of Biocompatible Gold Nanoparticles by Sequential Surface Functionalization Using Polyoxometalates and Lysine

PubMed Central

Daima, Hemant K.; Selvakannan, P. R.; Shukla, Ravi; Bhargava, Suresh K.; Bansal, Vipul

2013-01-01

Antimicrobial action of nanomaterials is typically assigned to the nanomaterial composition, size and/or shape, whereas influence of complex corona stabilizing the nanoparticle surface is often neglected. We demonstrate sequential surface functionalization of tyrosine-reduced gold nanoparticles (AuNPsTyr) with polyoxometalates (POMs) and lysine to explore controlled chemical functionality-driven antimicrobial activity. Our investigations reveal that highly biocompatible gold nanoparticles can be tuned to be a strong antibacterial agent by fine-tuning their surface properties in a controllable manner. The observation from the antimicrobial studies on a gram negative bacterium Escherichia coli were further validated by investigating the anticancer properties of these step-wise surface-controlled materials against A549 human lung carcinoma cells, which showed a similar toxicity pattern. These studies highlight that the nanomaterial toxicity and biological applicability are strongly governed by their surface corona. PMID:24147146

Fine-tuning the antimicrobial profile of biocompatible gold nanoparticles by sequential surface functionalization using polyoxometalates and lysine.

PubMed

Daima, Hemant K; Selvakannan, P R; Shukla, Ravi; Bhargava, Suresh K; Bansal, Vipul

2013-01-01

Antimicrobial action of nanomaterials is typically assigned to the nanomaterial composition, size and/or shape, whereas influence of complex corona stabilizing the nanoparticle surface is often neglected. We demonstrate sequential surface functionalization of tyrosine-reduced gold nanoparticles (AuNPs(Tyr)) with polyoxometalates (POMs) and lysine to explore controlled chemical functionality-driven antimicrobial activity. Our investigations reveal that highly biocompatible gold nanoparticles can be tuned to be a strong antibacterial agent by fine-tuning their surface properties in a controllable manner. The observation from the antimicrobial studies on a gram negative bacterium Escherichia coli were further validated by investigating the anticancer properties of these step-wise surface-controlled materials against A549 human lung carcinoma cells, which showed a similar toxicity pattern. These studies highlight that the nanomaterial toxicity and biological applicability are strongly governed by their surface corona.

News coverage of controversial emerging technologies. Evidence for the issue attention cycle in print and online media.

PubMed

Anderson, Ashley A; Brossard, Dominique; Scheufele, Dietram A

2012-01-01

This study analyzes the issue attention cycle for print and online media coverage of a scientific publication examining the deaths of Chinese factory workers due to lung damage from chronic exposure to nanoparticles. The results of the nanoparticle study, published in 2009, embody news values that would make the study a prime candidate for press coverage, namely, novelty, negativity, controversy, and potential widespread impact. Nevertheless, mentions of the event in traditional English-language print media were nearly nonexistent. Online media, on the other hand, gave the story greater coverage. This case study exemplifies why online media may not be bound to the same issue attention cycle that print media are for controversial scientific events.

Identification of the functional groups on the surface of nanoparticles formed in photonucleation of aldehydes generated during forest fire events

NASA Astrophysics Data System (ADS)

Dultsev, Fedor N.; Mik, Ivan A.; Dubtsov, Sergei N.; Dultseva, Galina G.

2014-11-01

We describe the new procedure developed to determine the functional groups on the surface of nanoparticles formed in photonucleation of furfural, one of the aldehydes generated during forest fire events. The procedure is based on the detection of nanoparticle rupture from chemically modified surface of the quartz crystal microbalance oscillating in the thickness shear mode under voltage sweep. The rupture force is determined from the voltage at which the rupture occurs. It depends on particle mass and on the affinity of the surface functional groups of the particle to the groups that are present on the modified QCM surface. It was demonstrated with the amine modification of the surface that the nanoparticles formed in furfural photonucleation contain carbonyl and carboxyl groups. The applicability of the method for the investigation of functional groups on the surface of the nanoparticles of atmospheric aerosol is demonstrated.

Ambiance-dependent agglomeration and surface-enhanced Raman spectroscopy response of self-assembled silver nanoparticles for plasmonic photovoltaic devices

NASA Astrophysics Data System (ADS)

Gwamuri, Jephias; Venkatesan, Ragavendran; Sadatgol, Mehdi; Mayandi, Jeyanthinath; Guney, Durdu O.; Pearce, Joshua M.

2017-07-01

The agglomeration/dewetting process of thin silver films provides a scalable method of obtaining self-assembled nanoparticles (SANPs) for plasmonics-based thin-film solar photovoltaic (PV) devices. We show the effect of annealing ambiance on silver SANP average size, particle/cluster finite shape, substrate area coverage/particle distribution, and how these physical parameters influence optical properties and surface-enhanced Raman scattering (SERS) responses of SANPs. Statistical analysis performed indicates that generally Ag SANPs processed in the presence of a gas (argon and nitrogen) ambiance tend to have smaller average size particles compared to those processed under vacuum. Optical properties are observed to be highly dependent on particle size, separation distance, and finite shape. The greatest SERS enhancement was observed for the argon-processed samples. There is a correlation between simulation and experimental data that indicate argon-processed AgNPs have a great potential to enhance light coupling when integrated to thin-film PV.

Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles

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

Zhang, Honghu; Nayak, Srikanth; Wang, Wenjie

Here, we report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor–liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor–liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to themore » protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl 2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar to that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.« less

Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles

DOE PAGES

Zhang, Honghu; Nayak, Srikanth; Wang, Wenjie; ...

2017-10-06

Here, we report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor–liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor–liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to themore » protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl 2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar to that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.« less

Thiol-reactive amphiphilic block copolymer for coating gold nanoparticles with neutral and functionable surfaces

PubMed Central

Chen, Hongwei; Zou, Hao; Paholak, Hayley J.; Ito, Masayuki; Qian, Wei; Che, Yong; Sun, Duxin

2014-01-01

Nanoparticles designed for biomedical applications are often coated with polymers containing reactive functional groups, such as –COOH and –NH2, to conjugate targeting ligands or drugs. However, introducing highly charged surfaces promotes binding of the nanoparticles to biomolecules in biological systems through ionic interactions, causing the nanoparticles to aggregate in biological environments and consequently undergo strong non-specific binding to off-target cells and tissues. Developing a unique polymer with neutral surfaces that can be further functionalized directly would be critical to develop suitable nanomaterials for nanomedicine. Here, we report a thiol-reactive amphiphilic block copolymer poly(ethylene oxide)-block-poly(pyridyldisulfide ethylmeth acrylate) (PEO-b-PPDSM) for coating gold nanoparticles (AuNPs). The resultant polymer-coated AuNPs have almost neutral surfaces with slightly negative zeta potentials from -10 to 0 mV over a wide pH range from 2 to 12. Although the zeta potential is close to zero we show that the PEO-b-PPDSM copolymer-coated AuNPs have both good stability in various physiological conditions and reduced non-specific adsorption of proteins/biomolecules. Because of the multiple pyridyldisulfide groups on the PPDSM block, these individually dispersed nanocomplexes with an overall hydrodynamic size around 43.8 nm can be directly functionalized via disulfide-thiol exchange chemistry. PMID:24729795

Effect of organic fuels on surface area and photocatalytic activity of scheelite CaWO4 nanoparticles

NASA Astrophysics Data System (ADS)

Manjunath, Kusuma; Gujjarahalli Thimmanna, Chandrappa

2018-03-01

Discrete nanoscale calcium tungstate (CaWO4) nanoparticles with exquisite photocatalytic activities were synthesized through ultra-rapid solution combustion route. Here, we aim to study the effect of different fuels on the synthesis of CaWO4 nanoparticles which lead to improve the characteristic properties and morphological evolution of the powders. From BET surface area measurement, it is observed that CaWO4 nanoparticles synthesized by using citric acid as fuel exhibits relatively large surface area (31.78 m2 g‑1) as compared to other fuels. The powder x-ray diffraction (PXRD) studies reveal that CaWO4 nanoparticles belong to scheelite type tetragonal system. The morphology of CaWO4 nanoparticles investigated using scanning electron microscopy (SEM) reveals that the powders are highly porous and agglomerated. Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) images of the CaWO4 nanoparticles show that a well-dispersed nearly oval-shaped nanoparticles with variable dimensions and lattice spacing that depends on the type of fuels used in the synthesis. The selected area electron diffraction (SAED) patterns of CaWO4 nanoparticles exhibit several concentric rings with bright spots indicating the polycrystalline nature of the powders. Investigation on photocatalytic activity of CaWO4 nanoparticles synthesized using citric acid shows highest (∼93%) degradation of methylene blue (MB).

Dispersion and surface functionalization of oxide nanoparticles for transparent photocatalytic and UV-protecting coatings and sunscreens

NASA Astrophysics Data System (ADS)

Faure, Bertrand; Salazar-Alvarez, German; Ahniyaz, Anwar; Villaluenga, Irune; Berriozabal, Gemma; De Miguel, Yolanda R.; Bergström, Lennart

2013-04-01

This review describes recent efforts on the synthesis, dispersion and surface functionalization of the three dominating oxide nanoparticles used for photocatalytic, UV-blocking and sunscreen applications: titania, zinc oxide, and ceria. The gas phase and liquid phase synthesis is described briefly and examples are given of how weakly aggregated photocatalytic or UV-absorbing oxide nanoparticles with different composition, morphology and size can be generated. The principles of deagglomeration are reviewed and the specific challenges for nanoparticles highlighted. The stabilization of oxide nanoparticles in both aqueous and non-aqueous media requires a good understanding of the magnitude of the interparticle forces and the surface chemistry of the materials. Quantitative estimates of the Hamaker constants in various media and measurements of the isoelectric points for the different oxide nanoparticles are presented together with an overview of different additives used to prepare stable dispersions. The structural and chemical requirements and the various routes to produce transparent photocatalytic and nanoparticle-based UV-protecting coatings, and UV-blocking sunscreens are described and discussed.

Dispersion and surface functionalization of oxide nanoparticles for transparent photocatalytic and UV-protecting coatings and sunscreens

PubMed Central

Faure, Bertrand; Salazar-Alvarez, German; Ahniyaz, Anwar; Villaluenga, Irune; Berriozabal, Gemma; De Miguel, Yolanda R; Bergström, Lennart

2013-01-01

This review describes recent efforts on the synthesis, dispersion and surface functionalization of the three dominating oxide nanoparticles used for photocatalytic, UV-blocking and sunscreen applications: titania, zinc oxide, and ceria. The gas phase and liquid phase synthesis is described briefly and examples are given of how weakly aggregated photocatalytic or UV-absorbing oxide nanoparticles with different composition, morphology and size can be generated. The principles of deagglomeration are reviewed and the specific challenges for nanoparticles highlighted. The stabilization of oxide nanoparticles in both aqueous and non-aqueous media requires a good understanding of the magnitude of the interparticle forces and the surface chemistry of the materials. Quantitative estimates of the Hamaker constants in various media and measurements of the isoelectric points for the different oxide nanoparticles are presented together with an overview of different additives used to prepare stable dispersions. The structural and chemical requirements and the various routes to produce transparent photocatalytic and nanoparticle-based UV-protecting coatings, and UV-blocking sunscreens are described and discussed. PMID:27877568

Electrodeposition of Highly Porous Pt Nanoparticles Studied by Quantitative 3D Electron Tomography: Influence of Growth Mechanisms and Potential Cycling on the Active Surface Area.

PubMed

Ustarroz, Jon; Geboes, Bart; Vanrompay, Hans; Sentosun, Kadir; Bals, Sara; Breugelmans, Tom; Hubin, Annick

2017-05-17

Nanoporous Pt nanoparticles (NPs) are promising fuel cell catalysts due to their large surface area and increased electrocatalytic activity toward the oxygen reduction reaction (ORR). Herein, we report on the influence of the growth mechanisms on the surface properties of electrodeposited Pt dendritic NPs with large surface areas. The electrochemically active surface was studied by hydrogen underpotential deposition (H UPD) and compared for the first time to high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) quantitative 3D electron tomography of individual nanoparticles. Large nucleation overpotential leads to a large surface coverage of roughened spheroids, which provide a large roughness factor (R f ) but low mass-specific electrochemically active surface area (EASA). Lowering the nucleation overpotential leads to highly porous Pt NPs with pores stretching to the center of the structure. At the expense of smaller R f , the obtained EASA values of these structures are in the range of those of large surface area supported fuel cell catalysts. The active surface area of the Pt dendritic NPs was measured by electron tomography, and it was found that the potential cycling in the H adsorption/desorption and Pt oxidation/reduction region, which is generally performed to determine the EASA, leads to a significant reduction of that surface area due to a partial collapse of their dendritic and porous morphology. Interestingly, the extrapolation of the microscopic tomography results in macroscopic electrochemical parameters indicates that the surface properties measured by H UPD are comparable to the values measured on individual NPs by electron tomography after the degradation caused by the H UPD measurement. These results highlight that the combination of electrochemical and quantitative 3D surface analysis techniques is essential to provide insights into the surface properties, the electrochemical stability, and, hence, the

Synthesis, surface modifications, and size-sorting of mixed nickel-zinc ferrite colloidal magnetic nanoparticles.

PubMed

Majewski, P; Krysiński, P

2008-01-01

We report on the spontaneous covalent growth of monomolecular adlayers on mixed nickel-zinc nanoferrite colloidal suspensions (ferrofluids). Synthesized nanoparticles were subjected to surface modification by means of acid chloride chemistry, leading to the formation of covalent bonds between the hydroxy groups at the nanoparticle surface and the acid chloride molecules. This procedure can be easily tailored to allow for the formation of adlayers containing both hydrophobic and hydrophilic regions stacked at predetermined distances from the magnetic core, and also providing the nanoferrites with functional carboxy groups capable of further modifications with, for example, drug molecules. Here, fluorophore aminopyrene molecules were bound to such modified nanoferrites through amide bonds. We also used the same chemistry to modify the surface with covalently bound long-chain palmitoyl moieties, and for comparison we also modified the nanoferrite surface by simple adsorption of oleic acid. Both procedures made the surface highly hydrophobic. These hydrophobic colloids were subsequently spread on an aqueous surface to form Langmuir monolayers with different characteristics. Moreover, since uniformity of size is crucial in a number of applications, we propose an efficient way of sorting the magnetic nanoparticles by size in their colloidal suspension. The suspension is centrifuged at increasing rotational speed and the fractions are collected after each run. The mean size of nanoferrite in each fraction was measured by the powder X-ray diffraction (PXRD) technique.

Polymer-coated surface enhanced Raman scattering (SERS) gold nanoparticles for multiplexed labeling of chronic lymphocytic leukemia cells

NASA Astrophysics Data System (ADS)

MacLaughlin, Christina M.; Parker, Edward P. K.; Walker, Gilbert C.; Wang, Chen

2012-01-01

The ease and flexibility of functionalization and inherent light scattering properties of plasmonic nanoparticles make them suitable contrast agents for measurement of cell surface markers. Immunophenotyping of lymphoproliferative disorders is traditionally undertaken using fluorescence detection methods which have a number of limitations. Herein, surface-enhanced Raman scattering (SERS) gold nanoparticles conjugated to monoclonal antibodies are used for the selective targeting of CD molecules on the surface of chronic lymphocytic leukemia (CLL) cells. Raman-active reporters were physisorbed on to the surface of 60 nm spherical Au nanoparticles, the particles were coated with 5kDa polyethylene glycol (PEG) including functionalities for conjugation to monoclonal IgG1 antibodies. A novel method for quantifying the number of antibodies bound to SERS probes on an individual basis as opposed to obtaining averages from solution was demonstrated using metal dots in transmission electron microscopy (TEM). The specificity of the interaction between SERS probes and surface CD molecules of CLL cells was assessed using Raman spectroscopy and dark field microscopy. An in-depth study of SERS probe targeting to B lymphocyte marker CD20 was undertaken, and proof-of-concept targeting using different SERS nanoparticle dyes specific for cell surface CD19, CD45 and CD5 demonstrated using SERS spectroscopy.

Surface-Enhanced Raman Spectroscopy Study of 4-ATP on Gold Nanoparticles for Basal Cell Carcinoma Fingerprint Detection

NASA Astrophysics Data System (ADS)

Quynh, Luu Manh; Nam, Nguyen Hoang; Kong, K.; Nhung, Nguyen Thi; Notingher, I.; Henini, M.; Luong, Nguyen Hoang

2016-05-01

The surface-enhanced Raman signals of 4-aminothiophenol (4-ATP) attached to the surface of colloidal gold nanoparticles with size distribution of 2 to 5 nm were used as a labeling agent to detect basal cell carcinoma (BCC) of the skin. The enhanced Raman band at 1075 cm-1 corresponding to the C-S stretching vibration in 4-ATP was observed during attachment to the surface of the gold nanoparticles. The frequency and intensity of this band did not change when the colloids were conjugated with BerEP4 antibody, which specifically binds to BCC. We show the feasibility of imaging BCC by surface-enhanced Raman spectroscopy, scanning the 1075 cm-1 band to detect the distribution of 4-ATP-coated gold nanoparticles attached to skin tissue ex vivo.

Self-Assembly of Magnetic Nanoparticles at the Surface and Within Block Copolymer Films

NASA Astrophysics Data System (ADS)

Xu, Chen; Ohno, Kohji; Composto, Russell

2007-03-01

We investigate the self-assembly of magnetic Fe3O4 nanoparticles in thin films of a symmetric block copolymer of poly(styrene-b-methyl methacrylate), PS-b-PMMA (75 kg/mol). The Fe3O4 nanoparticles (4nm) are grafted by poly(methyl methacrylate) (PMMA) (2.7 kg/mol) brushes to improve their compatibility. The weight percent of Fe3O4 in PS-b-PMMA is 1, 4 and 10. The Fe3O4 reside at the intermaterial dividing surface and also form small disk-like aggregates within the PMMA phase. The addition of Fe3O4 slows down the transition from perpendicular to parallel lamellae morphology at the surface and slowing down increases as weight percent Fe3O4 increases. Using cross-sectional TEM, nanoparticles are found to be rejected from the parallel lamellae and gather preferentially within the perpendicular lamellae. These studies demonstrate that the Fe3O4 particles influence thin film morphology and visa versa. Because of widespread interest in nanodevices, this study shows that arrays of functional nanoparticles can be formed using block copolymer templates.

Novel color additive for chlorine disinfectants corrects deficiencies in spray surface coverage and wet-contact time and checks for correct chlorine concentration.

PubMed

Tyan, Kevin; Jin, Katherine; Kang, Jason; Kyle, Aaron M

2018-04-18

Bleach sprays suffer from poor surface coverage, dry out before reaching proper contact time, and can be inadvertently over-diluted to ineffective concentrations. Highlight ® , a novel color additive for bleach that fades to indicate elapsed contact time, maintained >99.9% surface coverage over full contact time and checked for correct chlorine concentration. Copyright © 2018 Association for Professionals in Infection Control and Epidemiology, Inc. Published by Elsevier Inc. All rights reserved.

Studies of Positrons Trapped at Quantum-Dot Like Particles Embedded in Metal Surfaces

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Nadesalingam, M. P.; Weiss, A. H.

2009-03-01

Experimental studies of the positron annihilation induced Auger electron (PAES) spectra from the Fe-Cu alloy surfaces with quantum-dot like Cu nanoparticles embedded in Fe show that the PAES signal from Cu increase rapidly as the concentration of Cu is enhanced by vacuum annealing. These measurements indicate that almost 75% of positrons that annihilate with core electrons due so with Cu even though the surface concentration of Cu as measured by EAES is only 6%. This result suggests that positrons become localized at sites at the surface containing high concentration of Cu atoms before annihilation. These experimental results are investigated theoretically by performing calculations of the "image-potential" positron surface states and annihilation characteristics of the surface trapped positrons with relevant Fe and Cu core-level electrons for the clean Fe(100) and Cu(100) surfaces and for the Fe(100) surface with quantum-dot like Cu nanoparticles embedded in the top atomic layers of the host substrate. Estimates of the positron binding energy and positron annihilation characteristics reveal their strong sensitivity to the nanoparticle coverage. Computed core annihilation probabilities are compared with experimental ones estimated from the measured Auger peak intensities. The observed behavior of the Fe and Cu PAES signal intensities is explained by theoretical calculations as being due to trapping of positrons in the regions of Cu nanoparticles embedded in the top atomic layers of Fe.

Measuring melittin uptake into hydrogel nanoparticles with near-infrared single nanoparticle surface plasmon resonance microscopy.

PubMed

Cho, Kyunghee; Fasoli, Jennifer B; Yoshimatsu, Keiichi; Shea, Kenneth J; Corn, Robert M

2015-01-01

This paper describes how changes in the refractive index of single hydrogel nanoparticles (HNPs) detected with near-infrared surface plasmon resonance microscopy (SPRM) can be used to monitor the uptake of therapeutic compounds for potential drug delivery applications. As a first example, SPRM is used to measure the specific uptake of the bioactive peptide melittin into N-isopropylacrylamide (NIPAm)-based HNPs. Point diffraction patterns in sequential real-time SPRM differential reflectivity images are counted to create digital adsorption binding curves of single 220 nm HNPs from picomolar nanoparticle solutions onto hydrophobic alkanethiol-modified gold surfaces. For each digital adsorption binding curve, the average single nanoparticle SPRM reflectivity response, ⟨Δ%RNP⟩, was measured. The value of ⟨Δ%RNP⟩ increased linearly from 1.04 ± 0.04 to 2.10 ± 0.10% when the melittin concentration in the HNP solution varied from zero to 2.5 μM. No change in the average HNP size in the presence of melittin is observed with dynamic light scattering measurements, and no increase in ⟨Δ%RNP⟩ is observed in the presence of either FLAG octapeptide or bovine serum albumin. Additional bulk fluorescence measurements of melittin uptake into HNPs are used to estimate that a 1% increase in ⟨Δ%RNP⟩ observed in SPRM corresponds to the incorporation of approximately 65000 molecules into each 220 nm HNP, corresponding to roughly 4% of its volume. The lowest detected amount of melittin loading into the 220 nm HNPs was an increase in ⟨Δ%RNP⟩ of 0.15%, corresponding to the absorption of 10000 molecules.

One-step Melt Synthesis of Water Soluble, Photoluminescent, Surface-Oxidized Silicon Nanoparticles for Cellular Imaging Applications

PubMed Central

Manhat, Beth A.; Brown, Anna L.; Black, Labe A.; Ross, J.B. Alexander; Fichter, Katye; Vu, Tania; Richman, Erik

2012-01-01

We have developed a versatile, one-step melt synthesis of water-soluble, highly emissive silicon nanoparticles using bi-functional, low-melting solids (such as glutaric acid) as reaction media. Characterization through transmission electron microscopy, selected area electron diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy shows that the one-step melt synthesis produces nanoscale Si cores surrounded by a silicon oxide shell. Analysis of the nanoparticle surface using FT-IR, zeta potential, and gel electrophoresis indicates that the bi-functional ligand used in the one-step synthesis is grafted onto the nanoparticle, which allows for tuning of the particle surface charge, solubility, and functionality. Photoluminescence spectra of the as-prepared glutaric acid-synthesized silicon nanoparticles show an intense blue-green emission with a short (ns) lifetime suitable for biological imaging. These nanoparticles are found to be stable in biological media and have been used to examine cellular uptake and distribution in live N2a cells. PMID:23139440

Label-free DNA biosensor based on resistance change of platinum nanoparticles assemblies.

PubMed

Skotadis, Evangelos; Voutyras, Konstantinos; Chatzipetrou, Marianneza; Tsekenis, Georgios; Patsiouras, Lampros; Madianos, Leonidas; Chatzandroulis, Stavros; Zergioti, Ioanna; Tsoukalas, Dimitris

2016-07-15

A novel nanoparticle based biosensor for the fast and simple detection of DNA hybridization events is presented. The sensor utilizes hybridized DNA's charge transport properties, combining them with metallic nanoparticle networks that act as nano-gapped electrodes. The DNA hybridization events can be detected by a significant reduction in the sensor's resistance due to the conductive bridging offered by hybridized DNA. By modifying the nanoparticle surface coverage, which can be controlled experimentally being a function of deposition time, and the structural properties of the electrodes, an optimized biosensor for the in situ detection of DNA hybridization events is ultimately fabricated. The fabricated biosensor exhibits a wide response range, covering four orders of magnitude, a limit of detection of 1nM and can detect a single base pair mismatch between probe and complementary DNA. Copyright © 2016 Elsevier B.V. All rights reserved.

Highly monodisperse multiple twinned AuCu-Pt trimetallic nanoparticles with high index surfaces.

PubMed

Khanal, Subarna; Bhattarai, Nabraj; McMaster, David; Bahena, Daniel; Velazquez-Salazar, J Jesus; Jose-Yacaman, Miguel

2014-08-14

Trimetallic nanoparticles possess different properties than their mono- and bi-metallic counterparts, opening a wide range of possibilities for diverse potential applications with the notion to study possible morphology, atomic ordering, reduce precious metal consumption and many others. In this paper, we present a comprehensive experimental study on AuCu-Pt trimetallic nanoparticles with an average diameter of 15 ± 1.0 nm, synthesized in a one-pot synthesis method and characterized by the Cs-corrected scanning transmission electron microscopy technique that allowed us to probe the structure at the atomic level resolution. A new way to control the nanoparticle morphology by the presence of third metal (Pt) is also discussed by the overgrowth of Pt on the as prepared AuCu core by Frank-van der Merwe (FM) layer-by-layer and Stranski-Krastanov (SK) island-on-wetting-layer growth modes. With the application of this research, we are now a step closer to produce optimum catalysts in which the active phase forms only surface monolayers. In addition, the nanoalloy exhibits high index facet surfaces with {211} and {321} families that are highly open-structure surfaces and are interesting for the catalytic applications.

Highly Monodisperse Multiple Twinned AuCu/Pt Trimetallic Nanoparticles with High Index Surfaces

PubMed Central

Khanal, Subarna; Bhattarai, Nabraj; McMaster, David; Bahena, Daniel; Velazquez-Salazar, J. Jesus

2014-01-01

Trimetallic nanoparticles present different properties than their mono- and bi-metallic counterparts, opening a wide range of possibilities for diverse potential applications with the notion to study possible morphology, atomic ordering, reduce precious metal consumption and many others. In this paper, we are presenting a comprehensive experimental study on AuCu/Pt trimetallic nanoparticles with an average diameter 15 ± 1.0 nm, synthesized in one-pot synthesis method and characterized by Cs-corrected scanning transmission electron microscopy technique that allowed us to probe the structure at the atomic level resolution. A new way to control the nanoparticle morphology by the presence of third metal (Pt) is also discussed by the overgrowth of Pt on as prepared AuCu core by Frank–van der Merwe (FM) layer-by-layer and Stranski–Krastanov (SK) island-on-wetting-layer growth modes. With the application of this research, we are now a step closer to produce optimum catalysts in which the active phase forms only surface monolayers. In addition, the nanoalloy presents high index facet surfaces with {211} and {321} families, that are highly open-structure surfaces and are interesting for the catalytic applications. PMID:24975090

Gold nanoparticles as markers for fluorinated surfaces containing embedded amide groups

NASA Astrophysics Data System (ADS)

Ballarin, Barbara; Barreca, Davide; Bertola, Maurizio; Cristina Cassani, Maria; Carraro, Giorgio; Maccato, Chiara; Mignani, Adriana; Nanni, Daniele; Parise, Chiara; Ranieri, Silvia

2018-05-01

Indium tin oxide (ITO) substrates were functionalized with fluoroalkylsilanes (FAS) having formula RFC(O)N(R)(CH2)3Si(OMe)3 (1, R = H, RF = C5F11; 2, R = CH3, RF = C5F11;3, R = H, RF = C3F7) and containing embedded amide moieties between the perfluoroalkyl chain and the syloxanic moiety. Subsequently, Au nanoparticle deposition (AuNP) onto the ITO-FAS functionalized surfaces was carried out by immersion into a solution of citrate-stabilized AuNP. The ITO-FAS and AuNP/ITO-FAS modified systems were characterized by various complementary techniques and compared with AuNP/ITO modified with RF(CH2)2Si(OEt)3 (4, RF = C6F13), free from functional groups between the fluorinated tail and the syloxanic moiety. The results showed that only ITO glasses modified with 1, 2 and 3 displayed an oleophobic, as well as hydrophobic, behaviour and that the AuNP Surface Coverage (SC %) directly depended on the fluoroalkylsilane nature with the following trend: 60% ITO-2 > 16% ITO-3 > 9% ITO-1 > 3% ITO-4. The obtained results revealed that, in organosilane 2, the presence of a methyl group on the amide nitrogen increases the steric hindrance in the rotation around the Nsbnd CO bond, resulting in the co-presence of two stable conformers in comparable amounts. Their co-presence in solution, combined with the lack of intermolecular Nsbnd H⋯OCsbnd N hydrogen bonds among the anchored molecules, has dramatic influences on the functionalized ITO, yielding a disorderedly packed coating able to accommodate a large quantity of AuNP. These results indicate that AuNP can act as excellent probes to evaluate the coating layer quality but, at the same time, it is possible to tune the gold loading on electroactive surfaces depending on the chemical structure of the used fluorinated silane.

All-optical patterning of Au nanoparticles on surfaces using optical traps.

PubMed

Guffey, Mason J; Scherer, Norbert F

2010-11-10

The fabrication of nanoscale devices would be greatly enhanced by "nanomanipulators" that can position single and few objects rapidly with nanometer precision and without mechanical damage. Here, we demonstrate the feasibility and precision of an optical laser tweezer, or optical trap, approach to place single gold (Au) nanoparticles on surfaces with high precision (approximately 100 nm standard deviation). The error in the deposition process is rather small but is determined to be larger than the thermal fluctuations of single nanoparticles within the optical trap. Furthermore, areas of tens of square micrometers could be patterned in a matter of minutes. Since the method does not rely on lithography, scanning probes or a specialized surface, it is versatile and compatible with a variety of systems. We discuss active feedback methods to improve positioning accuracy and the potential for multiplexing and automation.

Size and surface effects on the magnetism of magnetite and maghemite nanoparticles

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

Nikiforov, V. N., E-mail: pppnvn@yandex.ru; Ignatenko, A. N.; Irkhin, V. Yu.

2017-02-15

The size effects of magnetite and maghemite nanoparticles on their magnetic properties (magnetic moment, Curie temperature, blocking temperature, etc.) have been investigated. Magnetic separation and centrifugation of an aqueous solution of nanoparticles were used for their separation into fractions; their sizes were measured by atomic force microscopy, dynamic light scattering, and electron microscopy. A change in the size leads to a change in the Curie temperature and magnetic moment per formula unit. Both native nanoparticles and those covered with a bioresorbable layer have been considered. The magnetic properties have been calculated by the Monte Carlo method for the classical Heisenbergmore » model with various bulk and surface magnetic moments.« less

Effect of the addition of Al2O3 nanoparticles on the magnetic properties of Fe soft magnetic composites

NASA Astrophysics Data System (ADS)

Peng, Yuandong; Nie, Junwu; Zhang, Wenjun; Ma, Jian; Bao, Chongxi; Cao, Yang

2016-02-01

We investigated the effect of the addition of Al2O3 nanoparticles on the permeability and core loss of Fe soft magnetic composites coated with silicone. Fourier transform infra-red spectroscopy, scanning electron microscopy and energy-dispersive X-ray spectroscopy analysis revealed that the surface layer of the powder particles consisted of a thin insulating Al2O3 layer with uniform surface coverage. The permeability and core loss of the composite with the Al2O3 addition annealed at 650 °C were excellent. The results indicated that the Al2O3 nanoparticle addition increases the permeability stablility with changing frequency and decreases the core loss over a wide range of frequencies.

Silver-nanoparticles-modified biomaterial surface resistant to staphylococcus: new insight into the antimicrobial action of silver

PubMed Central

Wang, Jiaxing; Li, Jinhua; Guo, Geyong; Wang, Qiaojie; Tang, Jin; Zhao, Yaochao; Qin, Hui; Wahafu, Tuerhongjiang; Shen, Hao; Liu, Xuanyong; Zhang, Xianlong

2016-01-01

Titanium implants are widely used clinically, but postoperative implant infection remains a potential severe complication. The purpose of this study was to investigate the antibacterial activity of nano-silver(Ag)-functionalized Ti surfaces against epidemic Staphylococcus from the perspective of the regulation of biofilm-related genes and based on a bacteria-cell co-culture study. To achieve this goal, two representative epidemic Staphylococcus strains, Staphylococcus epidermidis (S. epidermidis, RP62A) and Staphylococcus aureus (S. aureus, USA 300), were used, and it was found that an Ag-nanoparticle-modified Ti surface could regulate the expression levels of biofilm-related genes (icaA and icaR for S. epidermidis; fnbA and fnbB for S. aureus) to inhibit bacterial adhesion and biofilm formation. Moreover, a novel bacteria-fibroblast co-culture study revealed that the incorporation of Ag nanoparticles on such a surface can help mammalian cells to survive, adhere and spread more successfully than Staphylococcus. Therefore, the modified surface was demonstrated to possess a good anti-infective capability against both sessile bacteria and planktonic bacteria through synergy between the effects of Ag nanoparticles and ion release. This work provides new insight into the antimicrobial action and mechanism of Ag-nanoparticle-functionalized Ti surfaces with bacteria-killing and cell-assisting capabilities and paves the way towards better satisfying the clinical needs. PMID:27599568

Gold nanoparticles protected by mixed hydrogenated/fluorinated monolayers: controlling and exploring the surface features

NASA Astrophysics Data System (ADS)

Şologan, Maria; Gentilini, Cristina; Bidoggia, Silvia; Boccalon, Mariangela; Pace, Alice; Pengo, Paolo; Pasquato, Lucia

2018-06-01

Harnessing the reciprocal phobicity of hydrogenated and fluorinated thiolates proved to be a valuable strategy in preparing gold nanoparticles displaying mixed monolayers with a well-defined and pre-determined morphology. Our studies display that the organisation of the fluorinated ligands in phase-separated domains takes place even when these represent a small fraction of the ligands grafted on the gold surface. Using simple model ligands and by combining 19F NMR or ESR spectroscopies, and multiscale molecular simulations, we could demonstrate how the monolayer morphology responds in a predictable manner to structural differences between the thiolates. This enables a straightforward preparation of gold nanoparticles with monolayers displaying stripe-like, Janus, patchy, and random morphologies. Additionally, solubility properties may be tuned as function of the nature of the ligands and of the monolayer morphology obtaining gold nanoparticles soluble in organic solvents or in aqueous solutions. Most importantly, this rich diversity can be achieved not by resorting to ad hoc developed fabrication techniques, but rather relying on the spontaneous self-sorting of the ligands upon assembly on the nanoparticle surface. Besides enabling control over the monolayer morphology, fluorinated ligands endow the nanoparticles with several properties that can be exploited in the development of novel materials with applications, for instance in drug delivery and diagnostic imaging.

Vortex generating flow passage design for increased film-cooling effectiveness and surface coverage. [aircraft engine blade cooling

NASA Technical Reports Server (NTRS)

Papell, S. S.

1984-01-01

The fluid mechanics of the basic discrete hole film cooling process is described as an inclined jet in crossflow and a cusp shaped coolant flow channel contour that increases the efficiency of the film cooling process is hypothesized. The design concept requires the channel to generate a counter rotating vortex pair secondary flow within the jet stream by virture of flow passage geometry. The interaction of the vortex structures generated by both geometry and crossflow was examined in terms of film cooling effectiveness and surface coverage. Comparative data obtained with this vortex generating coolant passage showed up to factors of four increases in both effectiveness and surface coverage over that obtained with a standard round cross section flow passage. A streakline flow visualization technique was used to support the concept of the counter rotating vortex pair generating capability of the flow passage design.

Thrombolysis based on magnetically-controlled surface-functionalized Fe3O4 nanoparticle

PubMed Central

Chang, Ming; Lin, Yu-Hao; Gabayno, Jacque Lynn; Li, Qian; Liu, Xiaojun

2017-01-01

ABSTRACT In this study, the control of magnetic fields to manipulate surface-functionalized Fe3O4 nanoparticles by urokinase coating is investigated for thrombolysis in a microfluidic channel. The urokinase-coated Fe3O4 nanoparticles are characterized using particle size distribution, zeta potential measurement and spectroscopic data. Thrombolytic ratio tests reveal that the efficiency for thrombus cleaning is significantly improved when using magnetically-controlled urokinase-coated Fe3O4 nanoparticles than pure urokinase solution. The average increase in the rate of thrombolysis with the use of urokinase-coated Fe3O4 nanoparticles is about 50%. In vitro thrombolysis test in a microfluidic channel using the coated nanoparticles shows nearly complete removal of thrombus, a result that can be attributed to the clot busting effect of the urokinase as it inhibits the possible formation of blood bolus during the magnetically-activated microablation process. The experiment further demonstrates that a thrombus mass of 10.32 mg in the microchannel is fully removed in about 180 s. PMID:27689864

Acute and subchronic toxicity analysis of surface modified paclitaxel attached hydroxyapatite and titanium dioxide nanoparticles.

PubMed

Venkatasubbu, Gopinath Devanand; Ramasamy, S; Gaddam, Pramod Reddy; Kumar, J

2015-01-01

Nanoparticles are widely used for targeted drug delivery applications. Surface modification with appropriate polymer and ligands is carried out to target the drug to the affected area. Toxicity analysis is carried out to evaluate the safety of the surface modified nanoparticles. In this study, paclitaxel attached, folic acid functionalized, polyethylene glycol modified hydroxyapatite and titanium dioxide nanoparticles were used for targeted drug delivery system. The toxicological behavior of the system was studied in vivo in rats and mice. Acute and subchronic studies were carried out. Biochemical, hematological, and histopathological analysis was also done. There were no significant alterations in the biochemical parameters at a low dosage. There was a small change in alkaline phosphatase (ALP) level at a high dosage. The results indicate a safe toxicological profile.

Driving CO2 to a Quasi-Condensed Phase at the Interface between a Nanoparticle Surface and a Metal-Organic Framework at 1 bar and 298 K.

PubMed

Lee, Hiang Kwee; Lee, Yih Hong; Morabito, Joseph V; Liu, Yejing; Koh, Charlynn Sher Lin; Phang, In Yee; Pedireddy, Srikanth; Han, Xuemei; Chou, Lien-Yang; Tsung, Chia-Kuang; Ling, Xing Yi

2017-08-23

We demonstrate a molecular-level observation of driving CO 2 molecules into a quasi-condensed phase on the solid surface of metal nanoparticles (NP) under ambient conditions of 1 bar and 298 K. This is achieved via a CO 2 accumulation in the interface between a metal-organic framework (MOF) and a metal NP surface formed by coating NPs with a MOF. Using real-time surface-enhanced Raman scattering spectroscopy, a >18-fold enhancement of surface coverage of CO 2 is observed at the interface. The high surface concentration leads CO 2 molecules to be in close proximity with the probe molecules on the metal surface (4-methylbenzenethiol), and transforms CO 2 molecules into a bent conformation without the formation of chemical bonds. Such linear-to-bent transition of CO 2 is unprecedented at ambient conditions in the absence of chemical bond formation, and is commonly observed only in pressurized systems (>10 5 bar). The molecular-level observation of a quasi-condensed phase induced by MOF coating could impact the future design of hybrid materials in diverse applications, including catalytic CO 2 conversion and ambient solid-gas operation.

The mechanisms for nanoparticle surface diffusion and chain self-assembly determined from real-time nanoscale kinetics in liquid

DOE PAGES

Woehl, Taylor J.; Prozorov, Tanya

2015-08-20

The mechanisms for nanoparticle self-assembly are often inferred from the morphology of the final nanostructures in terms of attractive and repulsive interparticle interactions. Understanding how nanoparticle building blocks are pieced together during self-assembly is a key missing component needed to unlock new strategies and mechanistic understanding of this process. Here we use real-time nanoscale kinetics derived from liquid cell transmission electron microscopy investigation of nanoparticle self-assembly to show that nanoparticle mobility dictates the pathway for self-assembly and final nanostructure morphology. We describe a new method for modulating nanoparticle diffusion in a liquid cell, which we employ to systematically investigate themore » effect of mobility on self-assembly of nanoparticles. We interpret the observed diffusion in terms of electrostatically induced surface diffusion resulting from nanoparticle hopping on the liquid cell window surface. Slow-moving nanoparticles self-assemble predominantly into linear 1D chains by sequential attachment of nanoparticles to existing chains, while highly mobile nanoparticles self-assemble into chains and branched structures by chain–chain attachments. Self-assembly kinetics are consistent with a diffusion-driven mechanism; we attribute the change in self-assembly pathway to the increased self-assembly rate of highly mobile nanoparticles. Furthermore, these results indicate that nanoparticle mobility can dictate the self-assembly mechanism and final nanostructure morphology in a manner similar to interparticle interactions.« less

RMS roughness-independent tuning of surface wettability by tailoring silver nanoparticles with a fluorocarbon plasma polymer.

PubMed

Choukourov, A; Kylián, O; Petr, M; Vaidulych, M; Nikitin, D; Hanuš, J; Artemenko, A; Shelemin, A; Gordeev, I; Kolská, Z; Solař, P; Khalakhan, I; Ryabov, A; Májek, J; Slavínská, D; Biederman, H

2017-02-16

A layer of 14 nm-sized Ag nanoparticles undergoes complex transformation when overcoated by thin films of a fluorocarbon plasma polymer. Two regimes of surface evolution are identified, both with invariable RMS roughness. In the early regime, the plasma polymer penetrates between and beneath the nanoparticles, raising them above the substrate and maintaining the multivalued character of the surface roughness. The growth (β) and the dynamic (1/z) exponents are close to zero and the interface bears the features of self-affinity. The presence of inter-particle voids leads to heterogeneous wetting with an apparent water contact angle θ a = 135°. The multivalued nanotopography results in two possible positions for the water droplet meniscus, yet strong water adhesion indicates that the meniscus is located at the lower part of the spherical nanofeatures. In the late regime, the inter-particle voids become filled and the interface acquires a single valued character. The plasma polymer proceeds to grow on the thus-roughened surface whereas the nanoparticles keep emerging away from the substrate. The RMS roughness remains invariable and lateral correlations propagate with 1/z = 0.27. The surface features multiaffinity which is given by different evolution of length scales associated with the nanoparticles and with the plasma polymer. The wettability turns to the homogeneous wetting state.

Development of Surface-Variable Polymeric Nanoparticles for Drug Delivery to Tumors.

PubMed

Han, Ning; Pang, Liang; Xu, Jun; Hyun, Hyesun; Park, Jinho; Yeo, Yoon

2017-05-01

To develop nanoparticle drug carriers that interact with cells specifically in the mildly acidic tumor microenvironment, we produced polymeric nanoparticles modified with amidated TAT peptide via a simple surface modification method. Two types of core poly(lactic-co-glycolic acid) nanoparticles (NL and NP) were prepared with a phospholipid shell as an optional feature and covered with polydopamine that enabled the conjugation of TAT peptide on the surface. Subsequent treatment with acid anhydrides such as cis-aconitic anhydride (CA) and succinic anhydride (SA) converted amines of lysine residues in TAT peptide to β-carboxylic amides, introducing carboxylic groups that undergo pH-dependent protonation and deprotonation. The nanoparticles modified with amidated TAT peptide (NLpT-CA and NPpT-CA) avoided interactions with LS174T colon cancer cells and J774A.1 macrophages at pH 7.4 but restored the ability to interact with LS174T cells at pH 6.5, delivering paclitaxel efficiently to the cells following a brief contact time. In LS174T tumor-bearing nude mice, NPpT-CA showed less accumulation in the lung than NPpT, reflecting the shielding effect of amidation, but tumor accumulation of NPpT and NPpT-CA was equally minimal. Comparison of particle stability and protein corona formation in media containing sera from different species suggests that NPpT-CA has been activated and opsonized in mouse blood to a greater extent than those in bovine serum-containing medium, thus losing the benefits of pH-sensitivity expected from in vitro experiments.

Plasmonic reflectance anisotropy spectroscopy of metal nanoparticles on a semiconductor surface

NASA Astrophysics Data System (ADS)

Kosobukin, V. A.; Korotchenkov, A. V.

2016-12-01

A theory of plasmonic differential anisotropic reflection of light from nanoparticles located near the interface between media is developed. The model of a monolayer consisting of identical ellipsoidal metal particles occupying sites of a rectangular lattice is investigated. Effective plasmonic polarizabilities of nanoparticles in the layer are calculated self-consistently using the Green's function technique in the quasipoint dipole approximation. The local-field effect caused by anisotropic dipole plasmons of particles in the layer and their image dipoles is taken into account. The lately observed resonant reflectance anisotropy spectra of indium nanoclusters on InAs surface are explained by the difference between frequencies of plasmons with the orthogonal polarizations in the surface plane. The difference between the plasmon frequencies is attributed to anisotropy of the particles shape or/and the layer structure; the signs of frequency difference for the two types of anisotropy being different.

Using the Localized Surface Plasmon Resonance of Gold Nanoparticles to Monitor Lipid Membrane Assembly and Protein Binding.

PubMed

Messersmith, Reid E; Nusz, Greg J; Reed, Scott M

2013-12-19

Gold nanoparticles provide a template for preparing supported lipid layers with well-defined curvature. Here, we utilize the localized surface plasmon resonance (LSPR) of gold nanoparticles as a sensor for monitoring the preparation of lipid layers on nanoparticles. The LSPR is very sensitive to the immediate surroundings of the nanoparticle surface and it is used to monitor the coating of lipids and subsequent conversion of a supported bilayer to a hybrid membrane with an outer lipid leaflet and an inner leaflet containing hydrophobic alkanethiol. We demonstrate that both decanethiol and propanethiol are able to form hybrid membranes and that the membrane created over the shorter thiol can be stripped from the gold along with the lipid leaflet using β-mercaptoethanol. The sensitivity of the nanoparticle LSPR to the refractive index (RI) of its surroundings is greater when the shorter thiol is used (37.8 ± 1.5 nm per RI unit) than when the longer thiol is used (27.5 ± 0.5 nm per RI unit). Finally, C-reactive protein binding to the membrane is measured using this sensor allowing observation of both protein-membrane and nanoparticle-nanoparticle interactions without chemical labeling of protein or lipids.

Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands.

PubMed

Mori, Taizo; Sharma, Anshul; Hegmann, Torsten

2016-01-26

Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle

Stability, surface features, and atom leaching of palladium nanoparticles: toward prediction of catalytic functionality.

PubMed

Ramezani-Dakhel, Hadi; Mirau, Peter A; Naik, Rajesh R; Knecht, Marc R; Heinz, Hendrik

2013-04-21

Surfactant-stabilized metal nanoparticles have shown promise as catalysts although specific surface features and their influence on catalytic performance have not been well understood. We quantify the thermodynamic stability, the facet composition of the surface, and distinct atom types that affect rates of atom leaching for a series of twenty near-spherical Pd nanoparticles of 1.8 to 3.1 nm size using computational models. Cohesive energies indicate higher stability of certain particles that feature an approximate 60/20/20 ratio of {111}, {100}, and {110} facets while less stable particles exhibit widely variable facet composition. Unique patterns of atom types on the surface cause apparent differences in binding energies and changes in reactivity. Estimates of the relative rate of atom leaching as a function of particle size were obtained by the summation of Boltzmann-weighted binding energies over all surface atoms. Computed leaching rates are in good qualitative correlation with the measured catalytic activity of peptide-stabilized Pd nanoparticles of the same shape and size in Stille coupling reactions. The agreement supports rate-controlling contributions by atom leaching in the presence of reactive substrates. The computational approach provides a pathway to estimate the catalytic activity of metal nanostructures of engineered shape and size, and possible further refinements are described.

The use of surface enhanced absorption, scattering and catalytic properties of gold nanoparticles in some bio- and biomedical applications

NASA Astrophysics Data System (ADS)

Huang, Xiaohua; El-Sayed, Ivan H.; El-Sayed, Mostafa A.

2005-08-01

Gold nanoparticles with unique optical properties offer useful applications in biotechnology. In this article two applications that we have developed are summarized, in one they are used in cancer cell diagnostics and in the other they are found to have catalytic property for the NADH oxidation reaction which is important in ATP formations. By conjugation with anti-EGFR antibodies which specifically target EGFR that are usually overexpressed on most cancer cells, gold nanoparticles are used as a molecular contrast agent for cancer cell diagnostics using their both strong surface plasmon absorption and efficient Mie scattering properties. Au nanoparticles are also good catalysts for many reactions due to their high surface to volume ratio. Au nanoparticles are found to be the catalyst for the NADH oxidation reaction. This was studied by monitoring the effect of the nanoparticles on NADH fluorescence intensity and lifetime as well as the change of the surface plasmon absorption band during the reaction.

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.

The influence of dissolved and surface-bound humic acid on the toxicity of TiO₂ nanoparticles to Chlorella sp.

PubMed

Lin, Daohui; Ji, Jing; Long, Zhifeng; Yang, Kun; Wu, Fengchang

2012-09-15

NOM is likely to coat TiO₂ nanoparticles (nano-TiO₂) discharged into the aquatic environment and influence the nanotoxicity to aquatic organisms, which however has not been well investigated. This study explored the influence of nanoparticle surface-bound humic acid (HA, as a model NOM) as well as dissolved HA on the toxicity of nano-TiO₂ to Chlorella sp., with a specific focus on adhesion of the nanoparticles to the algae. Results showed that nano-TiO₂ and the dissolved HA could inhibit the algal growth with an IC₅₀ of 4.9 and 8.4 mg L⁻¹, respectively, while both dissolved and nanoparticle surface-bound HA could significantly alleviate the algal toxicity of nano-TiO₂. IC₅₀ of nano-TiO₂ increased to 18 mg L⁻¹ in the presence of 5 mg L⁻¹ of the dissolved HA and to 48 mg L⁻¹ as the result of surface-saturation by HA. Co-precipitation experiment and transmission electron microscopy observation revealed that both dissolved and nanoparticle surface-bound HA prevented the adhesion of nano-TiO₂ to the algal cells due to the increased electrosteric repulsion. The generation of intracellular reactive oxygen species (ROS) was significantly limited by the dissolved and nanoparticle surface-bound HA. The prevention of adhesion and inhibition of ROS generation could account for the HA-mitigated nanotoxicity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Fabrication of superhydrophobic and antibacterial surface on cotton fabric by doped silica-based sols with nanoparticles of copper

PubMed Central

2011-01-01

The study discussed the synthesis of silica sol using the sol-gel method, doped with two different amounts of Cu nanoparticles. Cotton fabric samples were impregnated by the prepared sols and then dried and cured. To block hydroxyl groups, some samples were also treated with hexadecyltrimethoxysilane. The average particle size of colloidal silica nanoparticles were measured by the particle size analyzer. The morphology, roughness, and hydrophobic properties of the surface fabricated on cotton samples were analyzed and compared via the scanning electron microscopy, the transmission electron microscopy, the scanning probe microscopy, with static water contact angle (SWC), and water shedding angle measurements. Furthermore, the antibacterial efficiency of samples was quantitatively evaluated using AATCC 100 method. The addition of 0.5% (wt/wt) Cu into silica sol caused the silica nanoparticles to agglomerate in more grape-like clusters on cotton fabrics. Such fabricated surface revealed the highest value of SWC (155° for a 10-μl droplet) due to air trapping capability of its inclined structure. However, the presence of higher amounts of Cu nanoparticles (2% wt/wt) in silica sol resulted in the most slippery smooth surface on cotton fabrics. All fabricated surfaces containing Cu nanoparticles showed the perfect antibacterial activity against both of gram-negative and gram-positive bacteria. PMID:22085594

Development of a nanoparticle-based surface-modified fluorescence assay for the detection of prion proteins.

PubMed

Henry, James; Anand, Ashish; Chowdhury, Mustafa; Coté, Gerard; Moreira, Rosana; Good, Theresa

2004-11-01

A nanoparticle-based immunoassay for the detection of recombinant bovine prion protein (PrP) was developed as a step in the development of screening tools for the prevention of the spread of transmissible spongiform encephalopathies. The assay is based on the competitive binding between PrP and a peptide-fluorophore to a nanoparticle-labeled antibody which is specific for a conserved prion sequence. The fluorophore, when bound to the antibody, is subject to surfaced-modified fluorescence, enabling detection of changes in the concentration of bound fluorophore in the presence of prion protein. Important factors considered during the development of the assay were ease of use, robustness, and detection level. The effects of pH and nanoparticle conjugation chemistry on surface-modified fluorescence observed in the assay were explored. Effects of concentrations of antibody and fluorophore on reproducibility and detection limits were examined. At present, the detection limits of the system are approximately equal to the antibody-peptide fluorophore equilibrium dissociation constant, which is near one nanomolar concentration. Improved assay performance could be obtained by optimization of the nanoparticle surface resonance effects. The simplicity of the assay and ease of use may make the type of assay described in this report attractive for screening purposes in the food industry.

Effect of surface properties of NiFe2O4 nanoparticles synthesized by dc thermal plasma route on antimicrobial activity

NASA Astrophysics Data System (ADS)

Bhosale, S. V.; Ekambe, P. S.; Bhoraskar, S. V.; Mathe, V. L.

2018-05-01

The present work reports the role of surface properties of NiFe2O4 nanoparticles on the antimicrobial activity. The NiFe2O4 nanoparticles were synthesized by gas phase condensation and chemical co-precipitation route. These nanoparticles were extensively investigated using X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and electro-kinetic property measurements. The HRTEM was used to analyze surface morphology of nickel ferrite nanoparticles obtained by two different routes. Electro-kinetic properties of the nanoparticles under investigation were recorded, analyzed and correlated with the antimicrobial properties. It was observed that nickel ferrite nanoparticles synthesized by thermal plasma route (NFOTP) formed highly stable colloidal solution as compared to chemically synthesized (NFOCP), as the later tends to agglomerate due to low surface charge. The antimicrobial activity of NiFe2O4 nanoparticles were investigated on two Gram positive bacteria Staphylococcus aureus and Streptococcus pyogenes, two Gram negative bacteria Escherichia coli and Salmonella typhimurium and one fungal species Candida albicans. It was noted that the surface properties of NiFe2O4 particles have revealing effect on the antimicrobial activity. The NFOTP nanoparticles showed significant activity for gram negative E. coli bacteria however no activity was observed for other bacteria's and fungi under study. Moreover NFOCP particles did not show any significant activity for both bacteria's and fungi. Further, antimicrobial activity of nickel ferrite nanoparticles were studied even for different concentration to obtain the minimum inhibition concentration (MIC).

Diffusion of hydrogen interstitials in the near-surface region of Pd(111) under the influence of surface coverage and external static electric fields

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

Blanco-Rey, M.; Donostia International Physics Center; Tremblay, J. C.

2015-04-21

Past scanning tunneling microscopy (STM) experiments of H manipulation on Pd(111), at low temperature, have shown that it is possible to induce diffusion of surface species as well as of those deeply buried under the surface. Several questions remain open regarding the role of subsurface site occupancies. In the present work, the interaction potential of H atoms with Pd(111) under various H coverage conditions is determined by means of density functional theory calculations in order to provide an answer to two of these questions: (i) whether subsurface sites are the final locations for the H impurities that attempt to emergemore » from bulk regions, and (ii) whether penetration of the surface is a competing route of on-surface diffusion during depletion of surface H on densely covered Pd(111). We find that a high H coverage has the effect of blocking resurfacing of H atoms travelling from below, which would otherwise reach the surface fcc sites, but it hardly alters deeper diffusion energy barriers. Penetration is unlikely and restricted to high occupancies of hcp hollows. In agreement with experiments, the Pd lattice expands vertically as a consequence of H atoms being blocked at subsurface sites, and surface H enhances this expansion. STM tip effects are included in the calculations self-consistently as an external static electric field. The main contribution to the induced surface electric dipoles originates from the Pd substrate polarisability. We find that the electric field has a non-negligible effect on the H-Pd potential in the vicinity of the topmost Pd atomic layer, yet typical STM intensities of 1-2 VÅ{sup −1} are insufficient to invert the stabilities of the surface and subsurface equilibrium sites.« less

Finite-size effects in surface-enhanced Raman scattering in noble-metal nanoparticles: a semiclassical approach.

PubMed

Pustovit, Vitaliy N; Shahbazyan, Tigran V

2006-06-01

We study finite-size effects in surface-enhanced Raman scattering (SERS) from molecules adsorbed on small metal particles. Within an electromagnetic description of SERS, the enhancement of the Raman signal originates from the local field of the surface plasmon resonance in a nanoparticle. With decreasing particle sizes, this enhancement is reduced due to the size-dependent Landau damping of the surface plasmon. We show that, in small noble-metal particles, the reduction of interband screening in the surface layer leads to an additional increase in the local field acting on a molecule close to the metal surface. The overall size dependence of Raman signal enhancement is determined by the interplay between Landau damping and underscreening effects. Our calculations, based on a two-region model, show that the role of the surface layer increases for smaller nanoparticle sizes due to a larger volume fraction of the underscreened region.

Pretargeting with bispecific fusion proteins facilitates delivery of nanoparticles to tumor cells with distinct surface antigens.

PubMed

Yang, Qi; Parker, Christina L; Lin, Yukang; Press, Oliver W; Park, Steven I; Lai, Samuel K

2017-06-10

Tumor heterogeneity, which describes the genetically and phenotypically distinct subpopulations of tumor cells present within the same tumor or patient, presents a major challenge to targeted delivery of diagnostic and/or therapeutic agents. An ideal targeting strategy should deliver a given nanocarrier to the full diversity of cancer cells, which is difficult to achieve with conventional ligand-conjugated nanoparticles. We evaluated pretargeting (i.e., multistep targeting) as a strategy to facilitate nanoparticle delivery to multiple target cells by measuring the uptake of biotinylated nanoparticles by lymphoma cells with distinct surface antigens pretreated with different bispecific streptavidin-scFv fusion proteins. Fusion proteins targeting CD20 or tumor-associated glycoprotein 72 (TAG-72) mediated the specific in vitro uptake of 100nm biotin-functionalized nanoparticles by Raji and Jurkat lymphoma cells (CD20-positive and TAG-72-positive cells, respectively). Greater uptake was observed for pretargeted nanoparticles with increasing amounts of surface biotin, with 6- to 18-fold higher uptake vs. non-biotinylated nanoparticle and fusion protein controls. Fully biotin-modified particles remained resistant to cultured macrophage cell uptake, although they were still quickly cleared from systemic circulation in vivo (t 1/2 <1h). For single Raji tumor-bearing mice, pretargeting with CD20-specific FP significantly increased nanoparticle tumor targeting. In mice bearing both Raji and Jurkat tumors, pretargeting with both fusion proteins markedly increased nanoparticle targeting to both tumor types, compared to animals dosed with nanoparticles alone. These in vitro and in vivo observations support further evaluations of pretargeting fusion protein cocktails as a strategy to enhance nanoparticle delivery to a diverse array of molecularly distinct target cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Acute and subchronic toxicity analysis of surface modified paclitaxel attached hydroxyapatite and titanium dioxide nanoparticles

PubMed Central

Venkatasubbu, Gopinath Devanand; Ramasamy, S; Gaddam, Pramod Reddy; Kumar, J

2015-01-01

Nanoparticles are widely used for targeted drug delivery applications. Surface modification with appropriate polymer and ligands is carried out to target the drug to the affected area. Toxicity analysis is carried out to evaluate the safety of the surface modified nanoparticles. In this study, paclitaxel attached, folic acid functionalized, polyethylene glycol modified hydroxyapatite and titanium dioxide nanoparticles were used for targeted drug delivery system. The toxicological behavior of the system was studied in vivo in rats and mice. Acute and subchronic studies were carried out. Biochemical, hematological, and histopathological analysis was also done. There were no significant alterations in the biochemical parameters at a low dosage. There was a small change in alkaline phosphatase (ALP) level at a high dosage. The results indicate a safe toxicological profile. PMID:26491315

Aminolysis of polyethylene terephthalate surface along with in situ synthesis and stabilizing ZnO nanoparticles using triethanolamine optimized with response surface methodology.

PubMed

Poortavasoly, Hajar; Montazer, Majid; Harifi, Tina

2016-01-01

This research concerned the simultaneous polyester surface modification and synthesis of zinc oxide nano-reactors to develop durable photo-bio-active fabric with variable hydrophobicity/hydrophilicity under sunlight. For this purpose, triethanolamine (TEA) was applied as a stabilizer and pH adjusting chemical for the aminolysis of polyester surface and enhancing the surface reactivity along with synthesis and deposition of ZnO nanoparticles on the fabric. Therefore, TEA played a crucial role in providing the alkaline condition for the preparation of zinc oxide nanoparticles and acting as stabilizer controlling the size of the prepared nanoparticles. The stain-photodegradability regarded as self-cleaning efficiency, wettability and weight change under the process was optimized based on zinc acetate and TEA concentrations, using central composite design (CCD). Findings also suggested the potential of the prepared fabric in inhibiting Staphylococcus aureus and Escherichia coli bacteria growth with greater than 99.99% antibacterial efficiency. Besides, the proposed treatment had no detrimental effect on tensile strength and hand feeling of the polyester fabric. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of a Planet: Dependence on Coverage Fraction

NASA Astrophysics Data System (ADS)

Lorenz, R. D.

1996-03-01

I investigate, by means of numerical experiments and a real-time quiz of colleagues (to be repeated at the poster presentation associated with this abstract), how well-characterized a planet may be considered, as a function of how much of its surface has been studied. Most measures seem to indicate that characterization quality increases steeply up to about 30% coverage. Beyond 30%, additional coverage has a lower marginal value as a 'complete' knowledge of the surface is asymptotically reached. These studies are pertinent where tradeoffs of coverage against other scientific objectives exist, for example the orbital tour design of the Cassini mission. The tour design affects how much of Titan's surface (after the Galileo mission, Titan's surface becomes the largest mappable, but unmapped, area in the solar system) may be covered by the Cassini radar. The mission has too few flybys to cover all of Titan's surface: the Radar team aims to have 30% coverage at 1km resolution or better. I also find that long, thin swaths sample a planet better than square blocks of equivalent area.

Investigation of the structure and stability of SnO2 nanocrystal and its surface-bound water

NASA Astrophysics Data System (ADS)

Wang, H.; Wesolowski, D. J.; Proffen, T. E.; Kolesnikov, A. I.; Vlcek, L.; Wang, W.; Feygenson, M.; Sofo, J. O.; Anovitz, L.

2012-12-01

by our previous molecular dynamic (MD) simulations, perhaps because this outermost hydration layer is not laterally-ordered parallel to the oxide surface and thus contributes a much weaker G(r) signal than the first two layers. Additionally, due to the relatively broad distribution of D-D distances and Fourier termination ripples, NPDF results cannot provide unambiguous evidence about the formation of hydroxylated surfaces, even though the dissociative MD model gives a better fitted result. Upon heating to 250 °C (at 10-7 bar), SnO2 nanoparticles start to show surface transformation and increased crystallinity before completion of dehydration. This likely corresponds to the minimum concentration of surface-bound groups required to stabilize the nanoparticles (i.e., < 0.7 monolayer coverage). Attempts to remove D2O/OD- groups below this threshold lead to rapidly increase of crystallinity. INS experiments on SnO2 nanoparticles with a minimum threshold coverage and with those from a fully hydrated sample clearly suggested dissociated water configurations with no observations of H2O bending modes in the sample with a minimum threshold coverage. Corresponding ab initio MD simulation on SnO2 (110) surface for a comparison with INS results is underway to provide a complete picture of SnO2-water surface dynamics.

Surface plasmon mediated Raman scattering in metal nanoparticles

NASA Astrophysics Data System (ADS)

Bachelier, G.; Mlayah, A.

2004-05-01

The Raman scattering due to confined acoustic vibrations in metal particles is studied theoretically. Various coupling mechanisms between the surface plasmon polaritons and the confined vibrations are investigated. Their relative contribution to the light scattering is discussed. We found that two mechanisms play an important role: (i) modulation of the interband dielectric susceptibility via deformation potential due to pure radial vibrations and (ii) modulation of the surface polarization charges by quadripolar vibrations. The dependence of the Raman spectra on the nanoparticles size and size distribution and on the excitation energy is studied in connection with the nature of the excited plasmon-polariton states. We found a good agreement between calculated line shapes and relatives intensities of the Raman bands and the experimental spectra reported in the literature.

Synthesis and characterization of WO3 nanowires and metal nanoparticle-WO3 nanowire composites

NASA Astrophysics Data System (ADS)

Szabó, Mária; Pusztai, Péter; Leino, Anne-Riikka; Kordás, Krisztián; Kónya, Zoltán; Kukovecz, Ákos

2013-07-01

Tungsten-trioxide nanowire bundles were prepared using a simple hydrothermal method. Sodium-tungstate was used as precursor and sodium-sulfate as structure directing agent. All the reflections of the X-ray diffractogram of the synthesized wires belong to the hexagonal phase of the tungsten trioxide. The nanowires were successfully decorated with metal nanoparticles by wet impregnation. The TEM investigation showed that using different metal precursors resulted in different particle sizes and coverage on the surface.

The Chameleon Effect: characterization challenges due to the variability of nanoparticles and their surfaces of nanoparticles and their surfaces

NASA Astrophysics Data System (ADS)

Baer, Donald R.

2018-05-01

Nanoparticles in a variety of forms are increasing important in fundamental research, technological and medical applications, and environmental or toxicology studies. Physical and chemical drivers that lead to multiple types of particle instabilities complicate both the ability to produce, appropriately characterize, and consistently deliver well-defined particles, frequently leading to inconsistencies and conflicts in the published literature. This perspective suggests that provenance information, beyond that often recorded or reported, and application of a set of core characterization methods, including a surface sensitive technique, consistently applied at critical times can serve as tools in the effort minimize reproducibility issues.

Effect of surface charge on the colloidal stability and in vitro uptake of carboxymethyl dextran-coated iron oxide nanoparticles

PubMed Central

Ayala, Vanessa; Herrera, Adriana P.; Latorre-Esteves, Magda; Torres-Lugo, Madeline

2013-01-01

Nanoparticle physicochemical properties such as surface charge are considered to play an important role in cellular uptake and particle–cell interactions. In order to systematically evaluate the role of surface charge on the uptake of iron oxide nanoparticles, we prepared carboxymethyl-substituted dextrans with different degrees of substitution, ranging from 38 to 5 groups per chain, and reacted them using carbodiimide chemistry with amine–silane-coated iron oxide nanoparticles with narrow size distributions in the range of 33–45 nm. Surface charge of carboxymethyl-substituted dextran-coated nano-particles ranged from −50 to 5 mV as determined by zeta potential measurements, and was dependent on the number of carboxymethyl groups incorporated in the dextran chains. Nanoparticles were incubated with CaCo-2 human colon cancer cells. Nanoparticle–cell interactions were observed by confocal laser scanning microscopy and uptake was quantified by elemental analysis using inductively coupled plasma mass spectroscopy. Mechanisms of internalization were inferred using pharmacological inhibitors for fluid-phase, clathrin-mediated, and caveola-mediated endocytosis. Results showed increased uptake for nanoparticles with greater negative charge. Internalization patterns suggest that uptake of the most negatively charged particles occurs via non-specific interactions. PMID:24470787

Nanoparticle-density-dependent field emission of surface-decorated SiC nanowires

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

Dong, Qizheng; School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo City 315016; State Key Lab of New Fine Ceramics and Fine Processing, Tsinghua University, Beijing City 100084

2016-08-22

Increasing the electron emission site density of nanostructured emitters with limited field screening effects is one of the key issues for improving the field emission (FE) properties. In this work, we reported the Au-nanoparticles-density-dependent field emission behaviors of surface-decorated SiC nanowires. The Au nanoparticles (AuNPs) decorated around the surface of the SiC nanowires were achieved via an ion sputtering technique, by which the densities of the isolated AuNPs could be adjusted by controlling the fixed sputtering times. The measured FE characteristics demonstrated that the turn-on fields of the SiC nanowires were tuned to be of 2.06, 1.14, and 3.35 V/μm withmore » the increase of the decorated AuNPs densities, suggesting that a suitable decorated AuNPs density could render the SiC nanowires with totally excellent FE performances by increasing the emission sites and limiting the field screening effects.« less

Effect of silica nanoparticles with variable size and surface functionalization on human endothelial cell viability and angiogenic activity

NASA Astrophysics Data System (ADS)

Guarnieri, Daniela; Malvindi, Maria Ada; Belli, Valentina; Pompa, Pier Paolo; Netti, Paolo

2014-02-01

Silica nanoparticles could be promising delivery vehicles for drug targeting or gene therapy. However, few studies have been undertaken to determine the biological behavior effects of silica nanoparticles on primary endothelial cells. Here we investigated uptake, cytotoxicity and angiogenic properties of silica nanoparticle with positive and negative surface charge and sizes ranging from 25 to 115 nm in primary human umbilical vein endothelial cells. Dynamic light scattering measurements and nanoparticle tracking analysis were used to estimate the dispersion status of nanoparticles in cell culture media, which was a key aspect to understand the results of the in vitro cellular uptake experiments. Nanoparticles were taken up by primary endothelial cells in a size-dependent manner according to their degree of agglomeration occurring after transfer in cell culture media. Functionalization of the particle surface with positively charged groups enhanced the in vitro cellular uptake, compared to negatively charged nanoparticles. However, this effect was contrasted by the tendency of particles to form agglomerates, leading to lower internalization efficiency. Silica nanoparticle uptake did not affect cell viability and cell membrane integrity. More interestingly, positively and negatively charged 25 nm nanoparticles did not influence capillary-like tube formation and angiogenic sprouting, compared to controls. Considering the increasing interest in nanomaterials for several biomedical applications, a careful study of nanoparticle-endothelial cells interactions is of high relevance to assess possible risks associated to silica nanoparticle exposure and their possible applications in nanomedicine as safe and effective nanocarriers for vascular transport of therapeutic agents.

Tuning the structure of thermosensitive gold nanoparticle monolayers.

PubMed

Rezende, Camila A; Shan, Jun; Lee, Lay-Theng; Zalczer, Gilbert; Tenhu, Heikki

2009-07-23

Gold nanoparticles grafted with poly(N-isopropylacrylamide) (PNIPAM) are rendered amphiphilic and thermosensitive. When spread on the surface of water, they form stable Langmuir monolayers that exhibit surface plasmon resonance. Using Langmuir balance and contrast-matched neutron reflectivity, the detailed structural properties of these nanocomposite monolayers are revealed. At low surface coverage, the gold nanoparticles are anchored to the interface by an adsorbed PNIPAM layer that forms a thin and compact pancake structure. Upon isothermal compression (T=20 degrees C), the adsorbed layer thickens with partial desorption of polymer chains to form brush structures. Two distinct polymer conformations thus coexist: an adsorbed conformation that assures stability of the monolayer, and brush structures that dangle in the subphase. An increase in temperature to 30 degrees C results in contractions of both adsorbed and brush layers with a concomitant decrease in interparticle distance, indicating vertical as well as lateral contractions of the graft polymer layer. The reversibility of this thermal response is also shown by the contraction-expansion of the polymer layers in heating-cooling cycles. The structure of the monolayer can thus be tuned by compression and reversibly by temperature. These compression and thermally induced conformational changes are discussed in relation to optical properties.

Bifunctional nanoparticles for surface-enhanced Raman spectroscopy-based leukemia biomarker detection

NASA Astrophysics Data System (ADS)

Mehn, Dora; Morasso, Carlo; Vanna, Renzo; Schiumarini, Domitilla; Bedoni, Marzia; Ciceri, Fabio; Gramatica, Furio

2014-03-01

The Wilms tumor gene (WT1) is a biomarker overexpressed in more than 90% of acute myeloid leukemia patients. Fast and sensitive detection of the WT1 in blood samples would allow monitoring of the minimal residual disease during clinical remission and would permit early detection of a potential relapse in acute myeloid leukemia. In this work, Surface Enhanced Raman Spectroscopy (SERS) based detection of the WT1 sequence using bifunctional, magnetic core - gold shell nanoparticles is presented. The classical co-precipitation method was applied to generate magnetic nanoparticles which were coated with a gold shell after modification with aminopropyltriethoxy silane and subsequent deposition of gold nanoparticle seeds. Simple hydroquinone based reduction procedure was applied for the shell growing in water based reaction mixture at room temperature. Thiolated ssDNA probes of the WT1 sequence were immobilized as capture oligonucleotides on the gold surface. Malachite green was applied both for testing the amplification performance of the core-shell colloidal SERS substrate and also as label dye of the target DNA sequence. The SERS enhancer efficacy of the core-shell nanomaterial was compared with the efficacy of classical spherical gold particles produced using the conventional citrate reduction method. The core-shell particles were found not only to provide an opportunity for facile separation in a heterogeneous reaction system but also to be superior regarding robustness as SERS enhancers.

Surface active gold nanoparticles biosynthesis by new approach for bionanocatalytic activity.

PubMed

Vasantharaj, S; Sripriya, N; Shanmugavel, M; Manikandan, E; Gnanamani, A; Senthilkumar, P

2018-02-01

In the present day, nanotechnology is one of the most promising leading scientific and potentials areas in modern key technology development toward to the humankind. The synthesis of noble metal nanoparticles (NPs) is an expanding research area due to the possible applications for the development of bio-medical applications. Eco-friendly approach for the biosynthesis of gold nanoparticles (AuNPs) using the aqueous extract from Ruellia tuberosa and Phyllanthus acidus (leaf and twig) for the first time. Surface active AuNPs were characterized by UV-Vis spectroscopy, FTIR (Fourier transform infrared) spectroscopy, DSC (differential scanning colorimetry), DLS (dynamic light scattering) and environmental SEM (scanning electron microscope) analysis at room temperature (RT). Enhanced surface plasmon resonance (SPR) absorbance UV visible optical spectra were detected in the range of 552, 548, 558 and 536 nm. SEM and DLS (transmission mode) analysis confirmed the morphology of the nanoparticles to be spherical with the average size in the range of 88.37, 94.31, 82.23 and 81.36 nm. Further they have enhanced the enzyme activity on α-amylase, cellulase, and xylanase. The results suggest that the phyto-fabricated AuNPs from R. tuberosa and P. acidus is simple, less expensive, eco-friendly, green synthesis and also can be exploited for the potential future industrial and bio-medical applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Noninvasive noble metal nanoparticle arrays for surface-enhanced Raman spectroscopy of proteins

NASA Astrophysics Data System (ADS)

Inya-Agha, Obianuju; Forster, Robert J.; Keyes, Tia E.

2007-02-01

Noble metal nanoparticles arrays are well established substrates for surface enhanced Raman spectroscopy (SERS). Their ability to enhance optical fields is based on the interaction of their surface valence electrons with incident electromagnetic radiation. In the array configuration, noble metal nanoparticles have been used to produce SER spectral enhancements of up to 10 8 orders of magnitude, making them useful for the trace analysis of physiologically relevant analytes such as proteins and peptides. Electrostatic interactions between proteins and metal surfaces result in the preferential adsorption of positively charged protein domains onto metal surfaces. This preferential interaction has the effect of disrupting the native conformation of the protein fold, with a concomitant loss of protein function. A major historic advantage of Raman microspectroscopy has been is its non-invasive nature; protein denaturation on the metal surfaces required for SER spectroscopy renders it a much more invasive technique. Further, part of the analytical power of Raman spectroscopy lies in its use as a secondary conformation probe. The protein structural loss which occurs on the metal surface results in secondary conformation readings which are not true to the actual native state of the analyte. This work presents a method for chemical fabrication of noble metal SERS arrays with surface immobilized layers which can protect protein native conformation without excessively mitigating the electromagnetic enhancements of spectra. Peptide analytes are used as model systems for proteins. Raman spectra of alpha lactalbumin on surfaces and when immobilized on these novel arrays are compared. We discuss the ability of the surface layer to protect protein structure whilst improving signal intensity.

Anisotropic noble metal nanoparticles: Synthesis, surface functionalization and applications in biosensing, bioimaging, drug delivery and theranostics.

PubMed

Paramasivam, Gokul; Kayambu, Namitharan; Rabel, Arul Maximus; Sundramoorthy, Ashok K; Sundaramurthy, Anandhakumar

2017-02-01

Anisotropic nanoparticles have fascinated scientists and engineering communities for over a century because of their unique physical and chemical properties. In recent years, continuous advances in design and fabrication of anisotropic nanoparticles have opened new avenues for application in various areas of biology, chemistry and physics. Anisotropic nanoparticles have the plasmon absorption in the visible as well as near-infrared (NIR) region, which enables them to be used for crucial applications such as biological imaging, medical diagnostics and therapy ("theranostics"). Here, we describe the progress in anisotropic nanoparticles achieved since the millennium in the area of preparation including various shapes and modification of the particle surface, and in areas of application by providing examples of applications in biosensing, bio-imaging, drug delivery and theranostics. Furthermore, we also explain various mechanisms involved in cellular uptake of anisotropic nanoparticles, and conclude with our opinion on various obstacles that limit their applications in biomedical field. Anisotropy at the molecular level has always fascinated scientists and engineering communities for over a century, however, the research on novel methods through which shape and size of nanoparticles can be precisely controlled has opened new avenues for anisotropic nanoparticles in various areas of biology, chemistry and physics. In this manuscript, we describe progress achieved since the millennium in the areas of preparation of various shapes of anisotropic nanoparticles, investigate various methods involved in modifying the surface of these NPs, and provide examples of applications in biosensing and bio-imaging, drug delivery and theranostics. We also present mechanisms involved in cellular uptake of nanoparticles, describe different methods of preparation of anisotropic nanoparticles including biomimetic and photochemical synthesis, and conclude with our opinion on various

Surface plasmon resonance enhanced light absorption and wavelength tuneable in gold-coated iron oxide spherical nanoparticle

NASA Astrophysics Data System (ADS)

Dasri, Thananchai; Chingsungnoen, Artit

2018-06-01

Surface plasmon in nano-sized particles, such as gold, silver, copper and their composites, has recently attracted a great deal of attention due to its possible uses in many applications, especially in life sciences. It is desirable for application devices with a tenability of surface plasmon wavelength and optical properties enhancement. This article presents enhanced optical light absorption and tunable wavelength in gold-coated magnetite (Fe3O4@Au core-shell) nanoparticles embedded in water using the theoretical method of discrete dipole approximation (DDA). The absorption spectra in the wavelengths from 350 to 900 nm were found to be the spectra obtained from Fe3O4@Au core-shell nanoparticles, and when compared with pure Fe3O4 nanoparticles, the surface plasmon resonance can be enhanced and tuned over the entire visible spectrum (viz. 350-800 nm) of the electromagnetic spectrum by varying the Au shell thickness (2-5 nm). Similarly, the Faraday rotation spectra can also be obtained.

Various nanoparticle morphologies and surface properties of waterborne polyurethane controlled by water

PubMed Central

Zhou, Xing; Fang, Changqing; Lei, Wanqing; Du, Jie; Huang, Tingyi; Li, Yan; Cheng, Youliang

2016-01-01

Water plays important roles in organic reactions such as polyurethane synthesis, and the aqueous solution environment affects polymer morphology and other properties. This paper focuses on the morphology and surface properties of waterborne polyurethane resulting from the organic reaction in water involving different forms (solid and liquid), temperatures and aqueous solutions. We provide evidence from TEM observations that the appearance of polyurethane nanoparticles in aqueous solutions presents diverse forms, including imperfect spheres, perfect spheres, perfect and homogenous spheres and tubes. Based on the results on FTIR, GPC, AFM and XRD experiments, we suggest that the shape of the nanoparticles may be decided by the crimp degree (i.e., the degree of polyurethane chains intertangling in the water environment) and order degree, which are determined by the molecular weight (Mn) and hydrogen bonds. Meanwhile, solid water and high-temperature water can both reduce hard segments that gather on the polyurethane film surface to reduce hydrophilic groups and produce a soft surface. Our findings show that water may play key roles in aqueous polymer formation and bring order to molecular chains. PMID:27687001

Role of Surface Charge Density in Nanoparticle-templated Assembly of Bromovirus Protein Cages

PubMed Central

Daniel, Marie-Christine; Tsvetkova, Irina B.; Quinkert, Zachary T.; Murali, Ayaluru; De, Mrinmoy; Rotello, Vincent M.; Kao, C. Cheng; Dragnea, Bogdan

2010-01-01

Self-assembling icosahedral protein cages have potencially useful physical and chemical characteristics for a variety of nanotechnology applications, ranging from therapeutic or diagnostic vectors to building blocks for hierarchical materials. For application-specific functional control of protein cage assemblies, a deeper understanding of the interaction between the protein cage and its payload is necessary. Protein-cage encapsulated nanoparticles, with their well-defined surface chemistry, allow for systematic control over key parameters of encapsulation such as the surface charge, hydrophobicity, and size. Independent control over these variables allows experimental testing of different assembly mechanism models. Previous studies done with Brome mosaic virus capsids and negatively-charged gold nanoparticles indicated that the result of the self-assembly process depends on the diameter of the particle. However, in these experiments, the surface-ligand density was maintained at saturation levels, while the total charge and the radius of curvature remained coupled variables, making the interpretation of the observed dependence on the core size difficult. The current work furnishes evidence of a critical surface charge density for assembly through an analysis aimed at decoupling the surface charge the core size. PMID:20575505

Chemical changes in carbon Nanotube-Nickel/Nickel Oxide Core/Shell nanoparticle heterostructures treated at high temperatures

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

Chopra, Nitin, E-mail: nchopra@eng.ua.edu; McWhinney, Hylton G.; Shi Wenwu

2011-06-15

Heterostructures composed of carbon nanotube (CNT) coated with Ni/NiO core/shell nanoparticles (denoted as CNC heterostructures) were synthesized in a wet-chemistry and single-step synthesis route involving direct nucleation of nanoparticles on CNT surface. Two different aspects of CNC heterostructures were studied here. First, it was observed that the nanoparticle coatings were more uniform on the as-produced and non-purified CNTs compared to purified (or acid treated) CNTs. These heterostructures were characterized using electron microscopy, Raman spectroscopy, and energy dispersive spectroscopy. Second, thermal stability of CNC heterostructures was studied by annealing them in N{sub 2}-rich (O{sub 2}-lean) environment between 125 and 750 deg.more » C for 1 h. A detailed X-ray photoelectron spectroscopy and Raman spectroscopy analysis was performed to evaluate the effects of annealing temperatures on chemical composition, phases, and stability of the heterostructures. It was observed that the CNTs present in the heterostructures completely decomposed and core Ni nanoparticle oxidized significantly between 600 and 750 deg. C. - Research Highlights: {yields} Heterostructures composed of CNTs coated with Ni/NiO core/shell nanoparticles. {yields} Poor nanoparticle coverage on purified CNT surface compared to non-purified CNTs. {yields} CNTs in heterostructures decompose between 600 and 750 deg. C in N{sub 2}-rich atmosphere. {yields} Metallic species in heterostructures were oxidized at higher temperatures.« less

Adsorption energies of poly(ethylene oxide)-based surfactants and nanoparticles on an air-water surface.

PubMed

Zell, Zachary A; Isa, Lucio; Ilg, Patrick; Leal, L Gary; Squires, Todd M

2014-01-14

The self-assembly of polymer-based surfactants and nanoparticles on fluid-fluid interfaces is central to many applications, including dispersion stabilization, creation of novel 2D materials, and surface patterning. Very often these processes involve compressing interfacial monolayers of particles or polymers to obtain a desired material microstructure. At high surface pressures, however, even highly interfacially active objects can desorb from the interface. Methods of directly measuring the energy which keeps the polymer or particles bound to the interface (adsorption/desorption energies) are therefore of high interest for these processes. Moreover, though a geometric description linking adsorption energy and wetting properties through the definition of a contact angle can be established for rigid nano- or microparticles, such a description breaks down for deformable or aggregating objects. Here, we demonstrate a technique to quantify desorption energies directly, by comparing surface pressure-density compression measurements using a Wilhelmy plate and a custom-microfabricated deflection tensiometer. We focus on poly(ethylene oxide)-based polymers and nanoparticles. For PEO-based homo- and copolymers, the adsorption energy of PEO chains scales linearly with molecular weight and can be tuned by changing the subphase composition. Moreover, the desorption surface pressure of PEO-stabilized nanoparticles corresponds to the saturation surface pressure for spontaneously adsorbed monolayers, yielding trapping energies of ∼10(3) k(B)T.

Clathrin to Lipid Raft-Endocytosis via Controlled Surface Chemistry and Efficient Perinuclear Targeting of Nanoparticle.

PubMed

Chakraborty, Atanu; Jana, Nikhil R

2015-09-17

Nanoparticle interacts with live cells depending on their surface chemistry, enters into cell via endocytosis, and is commonly trafficked to an endosome/lysozome that restricts subcellular targeting options. Here we show that nanoparticle surface chemistry can be tuned to alter their cell uptake mechanism and subcellular trafficking. Quantum dot based nanoprobes of 20-30 nm hydrodynamic diameters have been synthesized with tunable surface charge (between +15 mV to -25 mV) and lipophilicity to influence their cellular uptake processes and subcellular trafficking. It is observed that cationic nanoprobe electrostatically interacts with cell membrane and enters into cell via clathrin-mediated endocytosis. At lower surface charge (between +10 mV to -10 mV), the electrostatic interaction with cell membrane becomes weaker, and additional lipid raft endocytosis is initiated. If a lipophilic functional group is introduced on a weakly anionic nanoparticle surface, the uptake mechanism shifts to predominant lipid raft-mediated endocytosis. In particular, the zwitterionic-lipophilic nanoprobe has the unique advantage as it weakly interacts with anionic cell membrane, migrates toward lipid rafts for interaction through lipophilic functional group, and induces lipid raft-mediated endocytosis. While predominate or partial clathrin-mediated entry traffics most of the nanoprobes to lysozome, predominate lipid raft-mediated entry traffics them to perinuclear region, particularly to the Golgi apparatus. This finding would guide in designing appropriate nanoprobe for subcellular targeting and delivery.

Silica-covered star-shaped Au-Ag nanoparticles as new electromagnetic nanoresonators for Raman characterisation of surfaces

NASA Astrophysics Data System (ADS)

Krajczewski, Jan; Kołątaj, Karol; Pietrasik, Sylwia; Kudelski, Andrzej

2018-03-01

One of the tools used for determining the composition of surfaces of various materials is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). SHINERS is a modification of "standard" surface-enhanced Raman spectroscopy (SERS), in which, before Raman spectra are recorded, the surfaces analysed are covered with a layer of plasmonic nanoparticles protected by a very thin layer of a transparent dielectric. The plasmonic cores of the core-shell nanoparticles used in SHINERS measurements generate a local enhancement of the electric field of the incident electromagnetic radiation, whereas the transparent coatings prevent the metal cores from coming into direct contact with the material being analysed. In this contribution, we propose a new type of SHINERS nanoresonators that contain spiky, star-shaped metal cores (produced from a gold/silver alloy). These spiky, star-shaped Au-Ag nanoparticles have been covered by a layer of silica. The small radii of the ends of the tips of the spikes of these plasmonic nanostructures make it possible to generate a very large enhancement of the electromagnetic field there, with the result that such SHINERS nanoresonators are significantly more efficient than the standard semi-spherical nanostructures. The Au-Ag alloy nanoparticles were synthesised by the reduction of a solution containing silver nitrate and chloroauric acid by ascorbic acid. The final geometry of the nanostructures thus formed was controlled by changing the ratio between the concentrations of AuCl4- and Ag+ ions. The shape of the synthesised star-shaped Au-Ag nanoparticles does not change significantly during the two standard procedures for depositing a layer of silica (by the decomposition of sodium silicate or the decomposition of tetraethyl orthosilicate).

Adenosine monophosphate is elevated in the bronchoalveolar lavage fluid of mice with acute respiratory toxicity induced by nanoparticles with high surface hydrophobicity.

PubMed

Dailey, Lea Ann; Hernández-Prieto, Raquel; Casas-Ferreira, Ana Maria; Jones, Marie-Christine; Riffo-Vasquez, Yanira; Rodríguez-Gonzalo, Encarnación; Spina, Domenico; Jones, Stuart A; Smith, Norman W; Forbes, Ben; Page, Clive; Legido-Quigley, Cristina

2015-02-01

Inhaled nanomaterials present a challenge to traditional methods and understanding of respiratory toxicology. In this study, a non-targeted metabolomics approach was used to investigate relationships between nanoparticle hydrophobicity, inflammatory outcomes and the metabolic fingerprint in bronchoalveolar fluid. Measures of acute lung toxicity were assessed following single-dose intratracheal administration of nanoparticles with varying surface hydrophobicity (i.e. pegylated lipid nanocapsules, polyvinyl acetate nanoparticles and polystyrene beads; listed in order of increasing hydrophobicity). Broncho-alveolar lavage (BAL) fluid was collected from mice exposed to nanoparticles at a surface area dose of 220 cm(2) and metabolite fingerprints were acquired via ultra pressure liquid chromatography-mass spectrometry-based metabolomics. Particles with high surface hydrophobicity were pro-inflammatory. Multivariate analysis of the resultant small molecule fingerprints revealed clear discrimination between the vehicle control and polystyrene beads (p < 0.05), as well as between nanoparticles of different surface hydrophobicity (p < 0.0001). Further investigation of the metabolic fingerprints revealed that adenosine monophosphate (AMP) concentration in BAL correlated with neutrophilia (p < 0.01), CXCL1 levels (p < 0.05) and nanoparticle surface hydrophobicity (p < 0.001). Our results suggest that extracellular AMP is an intermediary metabolite involved in adenine nucleotide-regulated neutrophilic inflammation as well as tissue damage, and could potentially be used to monitor nanoparticle-induced responses in the lung following pulmonary administration.

New surface radiolabeling schemes of super paramagnetic iron oxide nanoparticles (SPIONs) for biodistribution studies

NASA Astrophysics Data System (ADS)

Nallathamby, Prakash D.; Mortensen, Ninell P.; Palko, Heather A.; Malfatti, Mike; Smith, Catherine; Sonnett, James; Doktycz, Mitchel J.; Gu, Baohua; Roeder, Ryan K.; Wang, Wei; Retterer, Scott T.

2015-04-01

Nanomaterial based drug delivery systems allow for the independent tuning of the surface chemical and physical properties that affect their biodistribution in vivo and the therapeutic payloads that they are intended to deliver. Additionally, the added therapeutic and diagnostic value of their inherent material properties often provides extra functionality. Iron based nanomaterials with their magnetic properties and easily tailorable surface chemistry are of particular interest as model systems. In this study the core radius of the iron oxide nanoparticles (NPs) was 14.08 +/- 3.92 nm while the hydrodynamic radius of the NPs, as determined by Dynamic Light Scattering (DLS), was between 90-110 nm. In this study, different approaches were explored to create radiolabeled NPs that are stable in solution. The NPs were functionalized with polycarboxylate or polyamine surface functional groups. Polycarboxylate functionalized NPs had a zeta potential of -35 mV and polyamine functionalized NPs had a zeta potential of +40 mV. The polycarboxylate functionalized NPs were chosen for in vivo biodistribution studies and hence were radiolabeled with 14C, with a final activity of 0.097 nCi mg-1 of NPs. In chronic studies, the biodistribution profile is tracked using low level radiolabeled proxies of the nanoparticles of interest. Conventionally, these radiolabeled proxies are chemically similar but not chemically identical to the non-radiolabeled NPs of interest. This study is novel as different approaches were explored to create radiolabeled NPs that are stable, possess a hydrodynamic radius of <100 nm and most importantly they exhibit an identical surface chemical functionality as their non-radiolabeled counterparts. Identical chemical functionality of the radiolabeled probes to the non-radiolabeled probes was an important consideration to generate statistically similar biodistribution data sets using multiple imaging and detection techniques. The radiolabeling approach described

Programmed Nanoparticle-Loaded Nanoparticles for Deep-Penetrating 3D Cancer Therapy.

PubMed

Kim, Jinhwan; Jo, Changshin; Lim, Won-Gwang; Jung, Sungjin; Lee, Yeong Mi; Lim, Jun; Lee, Haeshin; Lee, Jinwoo; Kim, Won Jong

2018-05-18

Tumors are 3D, composed of cellular agglomerations and blood vessels. Therapies involving nanoparticles utilize specific accumulations due to the leaky vascular structures. However, systemically injected nanoparticles are mostly uptaken by cells located on the surfaces of cancer tissues, lacking deep penetration into the core cancer regions. Herein, an unprecedented strategy, described as injecting "nanoparticle-loaded nanoparticles" to address the long-lasting problem is reported for effective surface-to-core drug delivery in entire 3D tumors. The "nanoparticle-loaded nanoparticle" is a silica nanoparticle (≈150 nm) with well-developed, interconnected channels (diameter of ≈30 nm), in which small gold nanoparticles (AuNPs) (≈15 nm) with programmable DNA are located. The nanoparticle (AuNPs)-loaded nanoparticles (silica): (1) can accumulate in tumors through leaky vascular structures by protecting the inner therapeutic AuNPs during blood circulation, and then (2) allow diffusion of the AuNPs for penetration into the entire surface-to-core tumor tissues, and finally (3) release a drug triggered by cancer-characteristic pH gradients. The hierarchical "nanoparticle-loaded nanoparticle" can be a rational design for cancer therapies because the outer large nanoparticles are effective in blood circulation and in protection of the therapeutic nanoparticles inside, allowing the loaded small nanoparticles to penetrate deeply into 3D tumors with anticancer drugs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of para-substituents of styrene derivatives on their chemical reactivity on platinum nanoparticle surfaces

NASA Astrophysics Data System (ADS)

Hu, Peiguang; Chen, Limei; Deming, Christopher P.; Lu, Jia-En; Bonny, Lewis W.; Chen, Shaowei

2016-06-01

Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 +/- 0.3 nm, 1.3 +/- 0.2 nm, and 1.1 +/- 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species.Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent

In Vivo Neural Recording and Electrochemical Performance of Microelectrode Arrays Modified by Rough-Surfaced AuPt Alloy Nanoparticles with Nanoporosity

PubMed Central

Zhao, Zongya; Gong, Ruxue; Zheng, Liang; Wang, Jue

2016-01-01

In order to reduce the impedance and improve in vivo neural recording performance of our developed Michigan type silicon electrodes, rough-surfaced AuPt alloy nanoparticles with nanoporosity were deposited on gold microelectrode sites through electro-co-deposition of Au-Pt-Cu alloy nanoparticles, followed by chemical dealloying Cu. The AuPt alloy nanoparticles modified gold microelectrode sites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and in vivo neural recording experiment. The SEM images showed that the prepared AuPt alloy nanoparticles exhibited cauliflower-like shapes and possessed very rough surfaces with many different sizes of pores. Average impedance of rough-surfaced AuPt alloy nanoparticles modified sites was 0.23 MΩ at 1 kHz, which was only 4.7% of that of bare gold microelectrode sites (4.9 MΩ), and corresponding in vitro background noise in the range of 1 Hz to 7500 Hz decreased to 7.5 μVrms from 34.1 μVrms at bare gold microelectrode sites. Spontaneous spike signal recording was used to evaluate in vivo neural recording performance of modified microelectrode sites, and results showed that rough-surfaced AuPt alloy nanoparticles modified microelectrode sites exhibited higher average spike signal-to-noise ratio (SNR) of 4.8 in lateral globus pallidus (GPe) due to lower background noise compared to control microelectrodes. Electro-co-deposition of Au-Pt-Cu alloy nanoparticles combined with chemical dealloying Cu was a convenient way for increasing the effective surface area of microelectrode sites, which could reduce electrode impedance and improve the quality of in vivo spike signal recording. PMID:27827893

Synthesis and surface modification of magnetic nanoparticles for potential applications in sarcomas

NASA Astrophysics Data System (ADS)

Shahbazi, S.; Wang, X.; Yang, J.-L.; Jiang, X. C.; Ryan, R.; Yu, A. B.

2015-06-01

The application of nano-science in cancer therapy has become one of the most attractive tools in scientific research because of its versatility in diagnosis and treatment. Among the different types of nanoparticles, iron oxide nanoparticles (IONPs) are renowned for their low toxicity and suitability for therapeutic and diagnostic, or `theragnostic,' approach against different types of cancers. Research investigating the effect of IONPs with different physiochemical characteristics in sarcoma is limited. In this study, we initially prepared IONPs of different sizes (200, 100, 20, and 10 nm) and modified their surface with different types of coatings (polyethylene glycol, d-glucose, and silica) under mild conditions. Various methods were used to illustrate and quantify cellular uptake of magnetic nanoparticles in sarcoma cell lines. Finally, the safety of the uptaken nanoparticles on diverse human sarcoma cell lines was investigated and found that the readily available IONPs can be taken up by synovial sarcoma and liposarcoma cell lines in the selective histological tumor types; however, they seem highly toxic for fibrous histiocytoma and fibrosarcoma.

Surface analysis of gold nanoparticles functionalized with thiol-modified glucose SAMs for biosensor applications.

NASA Astrophysics Data System (ADS)

Spampinato, Valentina; Parracino, Mariaantonietta; La Spina, Rita; Rossi, Francois; Ceccone, Giacomo

2016-02-01

In this work, Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS), Principal Component Analysis (PCA) and X-ray Photoelectron Spectroscopy (XPS) have been used to characterize the surface chemistry of gold substrates before and after functionalization with thiol-modified glucose self-assembled monolayers and subsequent biochemical specific recognition of maltose binding protein (MBP). The results indicate that the surface functionalization is achieved both on flat and nanoparticles gold substrates thus showing the potential of the developed system as biodetection platform. Moreover, the method presented here has been found to be a sound and valid approach to characterize the surface chemistry of nanoparticles functionalized with large molecules. Both techniques were proved to be very useful tools for monitoring all the functionalization steps, including the investigation of the biological behaviour of the glucose-modified particles in presence of the maltose binding protein.

Surface modification of nanoparticles enables selective evasion of phagocytic clearance by distinct macrophage phenotypes

NASA Astrophysics Data System (ADS)

Qie, Yaqing; Yuan, Hengfeng; von Roemeling, Christina A.; Chen, Yuanxin; Liu, Xiujie; Shih, Kevin D.; Knight, Joshua A.; Tun, Han W.; Wharen, Robert E.; Jiang, Wen; Kim, Betty Y. S.

2016-05-01

Nanomedicine is a burgeoning industry but an understanding of the interaction of nanomaterials with the immune system is critical for clinical translation. Macrophages play a fundamental role in the immune system by engulfing foreign particulates such as nanoparticles. When activated, macrophages form distinct phenotypic populations with unique immune functions, however the mechanism by which these polarized macrophages react to nanoparticles is unclear. Furthermore, strategies to selectively evade activated macrophage subpopulations are lacking. Here we demonstrate that stimulated macrophages possess higher phagocytic activities and that classically activated (M1) macrophages exhibit greater phagocytic capacity than alternatively activated (M2) macrophages. We show that modification of nanoparticles with polyethylene-glycol results in decreased clearance by all macrophage phenotypes, but importantly, coating nanoparticles with CD47 preferentially lowers phagocytic activity by the M1 phenotype. These results suggest that bio-inspired nanoparticle surface design may enable evasion of specific components of the immune system and provide a rational approach for developing immune tolerant nanomedicines.

Magnetic circular dichroism of thiolate-protected plasmonic gold nanoparticles: separating the effects of interband transitions and surface magnetoplasmon resonance

NASA Astrophysics Data System (ADS)

Shiratsu, Taisuke; Yao, Hiroshi

2016-10-01

Magneto-optical activity is demonstrated in thiolate-protected Au nanoparticles with magnetic circular dichroism (MCD) spectroscopy. The samples examined are decanethiolate-protected Au nanoparticles with the mean diameters ranging from 2.0 to 4.7 nm. The nanoparticles larger than 2.4 nm in diameter exhibit a derivative-like MCD signal, indicating the presence of two circular modes of surface magnetoplasmon, but the spectral shape is so asymmetric that its identification is rather difficult. This is due to the contribution of interband transitions occurring at around the localized surface plasmon resonance (LSPR) frequency. We then develop an efficient method to phenomenologically separate the effects of magnetoplasmonic intraband (= Drude) and interband transitions in the measured MCD spectra using an approximation that the optical response of the Au nanoparticle with a critical size (˜2.0 nm) for the disappearance of LSPR, which is also experimentally obtainable, is substantially dominated by the interband transitions. The consistency of the method is ensured for tiopronin-protected Au nanoparticles, and a very small bisignate magnetoplasmonic response hidden in the total MCD spectrum can be extracted. The practical advantage of the proposed method is that we can intuitively and effectively evaluate the characteristic features of the surface magnetoplasmon of thiolate-protected Au nanoparticles without performing complicated Mie or quasielectrostatic calculations.

Triggering nanoparticle surface ligand rearrangement via external stimuli: light-based actuation of biointerfaces

NASA Astrophysics Data System (ADS)

Tang, Zhenghua; Lim, Chang-Keun; Palafox-Hernandez, J. Pablo; Drew, Kurt L. M.; Li, Yue; Swihart, Mark T.; Prasad, Paras N.; Walsh, Tiffany R.; Knecht, Marc R.

2015-08-01

Bio-molecular non-covalent interactions provide a powerful platform for material-specific self-organization in aqueous media. Here, we introduce a strategy that integrates a synthetic optically-responsive motif with a materials-binding peptide to enable remote actuation. Specifically, we linked a photoswitchable azobenzene moiety to either terminus of a Au-binding peptide. We employed these hybrid molecules as capping agents for synthesis of Au nanoparticles. Integrated experiments and molecular simulations showed that the hybrid molecules maintained both of their functions, i.e. binding to Au and optically-triggered reconfiguration. The azobenzene unit was optically switched reversibly between trans and cis states while adsorbed on the particle surface. Upon switching, the conformation of the peptide component of the molecule also changed. This highlights the interplay between the surface adsorption and conformational switching that will be pivotal to the creation of actuatable nanoparticle bio-interfaces, and paves the way toward multifunctional peptide hybrids that can produce stimuli responsive nanoassemblies.Bio-molecular non-covalent interactions provide a powerful platform for material-specific self-organization in aqueous media. Here, we introduce a strategy that integrates a synthetic optically-responsive motif with a materials-binding peptide to enable remote actuation. Specifically, we linked a photoswitchable azobenzene moiety to either terminus of a Au-binding peptide. We employed these hybrid molecules as capping agents for synthesis of Au nanoparticles. Integrated experiments and molecular simulations showed that the hybrid molecules maintained both of their functions, i.e. binding to Au and optically-triggered reconfiguration. The azobenzene unit was optically switched reversibly between trans and cis states while adsorbed on the particle surface. Upon switching, the conformation of the peptide component of the molecule also changed. This highlights

Resveratrol stabilized gold nanoparticles enable surface loading of doxorubicin and anticancer activity.

PubMed

Mohanty, Ranjeet Kumar; Thennarasu, Sathiah; Mandal, Asit Baran

2014-02-01

The green synthesis of gold nanoparticles was achieved by exploiting the antioxidant property of resveratrol (R). The formation of resveratrol stabilized gold nanoparticles (R-GNPs) was confirmed by the observation of the surface plasmon resonance band at 537 nm. The average size of R-GNPs produced in resveratrol medium was ~35nm. The geometrical shape and zeta potential of the gold nanoparticles were spherical and -21.2 mV, respectively. R-GNPs showed excellent stability in saline and other buffers mimicking the physiological pH. The MTT assay using fibroblast cells from explants tissue revealed the biocompatibility of R-GNPs. The cytotoxic activity of doxorubicin loaded R-GNPs against glioma carcinoma cell line (LN 229), showed the suitability of R-GNPs as a carrier for anticancer drugs. Copyright © 2013 Elsevier B.V. All rights reserved.

Effect of Surface-Modified TiO2 Nanoparticles on the Anti-Ultraviolet Aging Performance of Foamed Wheat Straw Fiber/Polypropylene Composites

PubMed Central

Xuan, Lihui; Han, Guangping; Wang, Dong; Cheng, Wanli; Gao, Xun; Chen, Feng; Li, Qingde

2017-01-01

Surface modification and characterization of titanium dioxide (TiO2) nanoparticles and their roles in thermal, mechanical, and accelerated aging behavior of foamed wheat straw fiber/polypropylene (PP) composites are investigated. To improve the dispersion of nanoparticles and increase the possible interactions between wheat straw fiber and the PP matrix, the surface of the TiO2 nanoparticles was modified with ethenyltrimethoxy silane (A171), a silane coupling agent. The grafting of A171 on the TiO2 nanoparticles’ surface was characterized by Fourier transform infrared spectroscopy (FTIR). The wheat straw fibers treated with A171 and modified TiO2 nanoparticles were characterized by FTIR and thermogravimetric analysis (TGA). FTIR spectra confirmed that the organic functional groups of A171 were successfully grafted onto the TiO2 nanoparticles and wheat straw fibers, and the modified TiO2 nanoparticles were adsorbed onto the wheat straw fibers. Thermogravimetric analysis showed that a higher thermal stability of the wheat straw fiber was obtained with the modified TiO2 nanoparticles. The flexural, tensile, and impact properties were improved. A higher ultraviolet (UV) stability of the samples treated with modified TiO2 nanoparticles was exhibited by the study of the color change and loss in mechanical properties. PMID:28772816

Comprehensive study of the drug delivery properties of poly(l-lactide)-poly(ethylene glycol) nanoparticles in rats and tumor-bearing mice.

PubMed

Shalgunov, Vladimir; Zaytseva-Zotova, Daria; Zintchenko, Arkadi; Levada, Tatiana; Shilov, Yuri; Andreyev, Dmitry; Dzhumashev, Dzhangar; Metelkin, Evgeny; Urusova, Alexandra; Demin, Oleg; McDonnell, Kevin; Troiano, Greg; Zale, Stephen; Safarovа, Elmira

2017-09-10

Nanoparticles made of polylactide-poly(ethylene glycol) block-copolymer (PLA-PEG) are promising vehicles for drug delivery due to their biodegradability and controllable payload release. However, published data on the drug delivery properties of PLA-PEG nanoparticles are heterogeneous in terms of nanoparticle characteristics and mostly refer to low injected doses (a few mg nanoparticles per kg body weight). We have performed a comprehensive study of the biodistribution of nanoparticle formulations based on PLA-PEG nanoparticles of ~100nm size at injected doses of 30 to 140mg/kg body weight in healthy rats and nude tumor-bearing mice. Nanoparticle formulations differed by surface PEG coverage and by release kinetics of the encapsulated model active pharmaceutical ingredient (API). Increase in PEG coverage prolonged nanoparticle circulation half-life up to ~20h in rats and ~10h in mice and decreased retention in liver, spleen and lungs. Circulation half-life of the encapsulated API grew monotonously as the release rate slowed down. Plasma and tissue pharmacokinetics was dose-linear for inactive nanoparticles, but markedly dose-dependent for the model therapeutic formulation, presumably because of the toxic effects of released API. A mathematical model of API distribution calibrated on the data for inactive nanoparticles and conventional API form correctly predicted the distribution of the model therapeutic formulation at the lowest investigated dose, but for higher doses the toxic action of the released API had to be explicitly modelled. Our results provide a coherent illustration of the ability of controllable-release PLA-PEG nanoparticles to serve as an effective drug delivery platform to alter API biodistribution. They also underscore the importance of physiological effects of released drug in determining the biodistribution of therapeutic drug formulations at doses approaching tolerability limits. Copyright © 2017 The Authors. Published by Elsevier B.V. All

Surface-enhanced Raman scattering on molecular self-assembly in nanoparticle-hydrogel composite.

PubMed

Miljanić, Snezana; Frkanec, Leo; Biljan, Tomislav; Meić, Zlatko; Zinić, Mladen

2006-10-24

Surface-enhanced Raman scattering has been applied to study weak intermolecular interactions between small organic gelling molecules involved in the silver nanoparticle-hydrogel composite formation. Assembly and disassembly of the gelator molecules in close vicinity to embedded silver nanoparticles were followed by changes in Raman intensity of the amide II and carboxyl vibrational bands, whereas the strength of the bands related to benzene modes remained constant. This implied that the gelator molecules were strongly attached to the silver particles through the benzene units, while participating in gel structure organization by intermolecular hydrogen bonding between oxalyl amide and carboxyl groups.

Role of nanoparticles generation in the formation of femtosecond laser-induced periodic surface structures on silicon.

PubMed

Xue, Hongyan; Deng, Guoliang; Feng, Guoying; Chen, Lin; Li, Jiaqi; Yang, Chao; Zhou, Shouhuan

2017-09-01

An initial roughness is assumed in the most accepted Sipe-Drude model to analyze laser-induced periodic surface structures (LIPSS). However, the direct experimental observation for the crucial parameters is still lacking. The generation of nanoparticles and low-spatial frequency LIPSS (LSFL) (LIPSS with a periodicity close to laser wavelength) on a silicon surface upon a single pulse and subsequent pulses irradiation, respectively, is observed experimentally. Finite-difference time-domain (FDTD) simulation indicates that the nanoparticles generated with the first pulse enhance the local electric field greatly. Based on the experimental extrapolated parameters, FDTD-η maps have been calculated. The results show that the inhomogeneous energy deposition, which leads to the formation of LSFL, is mainly from the modulation of the nanoparticles with a radius of around 100 nm.

Durability improvements of two-dimensional metal nanoparticle sheets by molecular cross-linked structures between nanoparticles

NASA Astrophysics Data System (ADS)

Saito, Noboru; Ryuzaki, Sou; Wang, Pangpang; Park, Susie; Sakai, Nobuyuki; Tatsuma, Tetsu; Okamoto, Koichi; Tamada, Kaoru

2018-03-01

The durability of two-dimensional metal nanoparticle sheets is a crucial factor for realizing next-generation optoelectronic devices based on plasmonics such as organic light-emitting diodes. Here, we report improvements in the durability of Ag nanoparticle sheets by forming alkanedithiol (DT16) cross-linked structures between the nanoparticles. The cross-linked structures in a sheet were fabricated by the self-assembly of DT16-capped Ag nanoparticles with 10% coverage (AgDT16). The durabilities for thermal, organic solvent, and oxidation reactions of AgDT16 sheets were found to be improved owing to the cross-linked structures by comparing Ag nanoparticle sheets without the cross-linked structures. The absorbance spectra revealed that the Ag nanoparticle sheets without the structure are markedly damaged by each durability test, whereas the AgDT16 sheets remain. The molecular cross-linked structures between nanoparticles in two-dimansional metal nanoparticle sheets were found to have the potential to play a key role in the realization of plasmonic optoelectronic devices including metal nanoparticles.

Prediction of Surface and pH-Specific Binding of Peptides to Metal and Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Heinz, Hendrik; Lin, Tzu-Jen; Emami, Fateme Sadat; Ramezani-Dakhel, Hadi; Naik, Rajesh; Knecht, Marc; Perry, Carole C.; Huang, Yu

2015-03-01

The mechanism of specific peptide adsorption onto metallic and oxidic nanostructures has been elucidated in atomic resolution using novel force fields and surface models in comparison to measurements. As an example, variations in peptide adsorption on Pd and Pt nanoparticles depending on shape, size, and location of peptides on specific bounding facets are explained. Accurate computational predictions of reaction rates in C-C coupling reactions using particle models derived from HE-XRD and PDF data illustrate the utility of computational methods for the rational design of new catalysts. On oxidic nanoparticles such as silica and apatites, it is revealed how changes in pH lead to similarity scores of attracted peptides lower than 20%, supported by appropriate model surfaces and data from adsorption isotherms. The results demonstrate how new computational methods can support the design of nanoparticle carriers for drug release and the understanding of calcification mechanisms in the human body.

Surface and exchange-bias effects in compacted CaMnO3-δ nanoparticles

NASA Astrophysics Data System (ADS)

Markovich, V.; Fita, I.; Wisniewski, A.; Puzniak, R.; Mogilyansky, D.; Titelman, L.; Vradman, L.; Herskowitz, M.; Gorodetsky, G.

2008-02-01

Magnetic properties of compacted 50nm CaMnO3-δ (CMO) nanoparticles have been investigated. Measurements of ac-susceptibility exhibit upon cooling two magnetic transitions at Ttilde 270K accompanied by a small spontaneous magnetic moment and a para-antiferromagnetic (AFM) transition at TN˜120K , observed previously in bulk CMO. Asymmetric magnetization hysteresis loops observed in applied magnetic fields H≤90kOe are attributed to an exchange coupling between the antiferromagnetic core and the ferromagnetic (FM) shell of the CMO nanoparticles. This work provides the observation of exchange bias effect in manganite nanoparticles with inverted AFM-core-FM-shell structure, as compared to the typical FM-core-AFM-shell. Effects of surface and exchange anisotropy are also discussed.

Synthesis of surface bound silver nanoparticles on cellulose fibers using lignin as multi-functional agent.

PubMed

Hu, Sixiao; Hsieh, You-Lo

2015-10-20

Lignin has proven to be highly effective "green" multi-functional binding, complexing and reducing agents for silver cations as well as capping agents for the synthesis of silver nanoparticles on ultra-fine cellulose fibrous membranes. Silver nanoparticles could be synthesized in 10min to be densely distributed and stably bound on the cellulose fiber surfaces at up to 2.9% in mass. Silver nanoparticle increased in sizes from 5 to 100nm and became more polydispersed in size distribution on larger fibers and with longer synthesis time. These cellulose fiber bound silver nanoparticles did not agglomerate under elevated temperatures and showed improved thermal stability. The presence of alkali lignin conferred moderate UV absorbing ability in both UV-B and UV-C regions whereas the bound silver nanoparticles exhibited excellent antibacterial activities toward Escherichia coli. Copyright © 2015 Elsevier Ltd. All rights reserved.

Surface charge-specific interactions between polymer nanoparticles and ABC transporters in Caco-2 cells

NASA Astrophysics Data System (ADS)

Bhattacharjee, Sourav; van Opstal, Edward J.; Alink, Gerrit M.; Marcelis, Antonius T. M.; Zuilhof, Han; Rietjens, Ivonne M. C. M.

2013-06-01

The surface charge-dependent transport of polymeric nanoparticles (PNPs) across Caco-2 monolayers grown on transwell culture systems as an in vitro model for intestinal transport was tested. The transport of well-characterized, monodisperse, and fluorescent tri-block copolymer nanoparticles (TCNPs/size 45 nm) and polystyrene nanoparticles (PSNPs/size 50 nm), with different surface charges (positive and negative), was quantified. The positive PNPs showed a higher intracellular uptake and flux across the Caco-2 monolayers than the negative PNPs. Multidrug resistance/P-glycoprotein (MDR1/P-gp), a specific ATP-binding cassette (ABC) transporter, was found to play a major role in the cellular efflux of positive PNPs, whereas the multidrug resistance protein 1 took part in the efflux of negative PNPs from Caco-2 cells. The positive PNPs also caused an increased cellular uptake and apical to basolateral transport of the carcinogen PhIP across the Caco-2 monolayer. The flavonoid quercetin, which is known to interact with ABC transporters, promoted the intracellular uptake of different PNPs and interfered with the normal distribution patterns of PNPs in the transwell system. These results indicate that PNPs display surface charge-specific interactions with ABC transporters and can even affect the bioavailability of toxic food-borne compounds (like pro-carcinogens).

Revisiting 30 years of biofunctionalization and surface chemistry of inorganic nanoparticles for nanomedicine

PubMed Central

Conde, João; Dias, Jorge T.; Grazú, Valeria; Moros, Maria; Baptista, Pedro V.; de la Fuente, Jesus M.

2014-01-01

In the last 30 years we have assisted to a massive advance of nanomaterials in material science. Nanomaterials and structures, in addition to their small size, have properties that differ from those of larger bulk materials, making them ideal for a host of novel applications. The spread of nanotechnology in the last years has been due to the improvement of synthesis and characterization methods on the nanoscale, a field rich in new physical phenomena and synthetic opportunities. In fact, the development of functional nanoparticles has progressed exponentially over the past two decades. This work aims to extensively review 30 years of different strategies of surface modification and functionalization of noble metal (gold) nanoparticles, magnetic nanocrystals and semiconductor nanoparticles, such as quantum dots. The aim of this review is not only to provide in-depth insights into the different biofunctionalization and characterization methods, but also to give an overview of possibilities and limitations of the available nanoparticles. PMID:25077142

Coverage dependent molecular assembly of anthraquinone on Au(111)

NASA Astrophysics Data System (ADS)

DeLoach, Andrew S.; Conrad, Brad R.; Einstein, T. L.; Dougherty, Daniel B.

2017-11-01

A scanning tunneling microscopy study of anthraquinone (AQ) on the Au(111) surface shows that the molecules self-assemble into several structures depending on the local surface coverage. At high coverages, a close-packed saturated monolayer is observed, while at low coverages, mobile surface molecules coexist with stable chiral hexamer clusters. At intermediate coverages, a disordered 2D porous network interlinking close-packed islands is observed in contrast to the giant honeycomb networks observed for the same molecule on Cu(111). This difference verifies the predicted extreme sensitivity [J. Wyrick et al., Nano Lett. 11, 2944 (2011)] of the pore network to small changes in the surface electronic structure. Quantitative analysis of the 2D pore network reveals that the areas of the vacancy islands are distributed log-normally. Log-normal distributions are typically associated with the product of random variables (multiplicative noise), and we propose that the distribution of pore sizes for AQ on Au(111) originates from random linear rate constants for molecules to either desorb from the surface or detach from the region of a nucleated pore.

Coverage dependent molecular assembly of anthraquinone on Au(111).

PubMed

DeLoach, Andrew S; Conrad, Brad R; Einstein, T L; Dougherty, Daniel B

2017-11-14

A scanning tunneling microscopy study of anthraquinone (AQ) on the Au(111) surface shows that the molecules self-assemble into several structures depending on the local surface coverage. At high coverages, a close-packed saturated monolayer is observed, while at low coverages, mobile surface molecules coexist with stable chiral hexamer clusters. At intermediate coverages, a disordered 2D porous network interlinking close-packed islands is observed in contrast to the giant honeycomb networks observed for the same molecule on Cu(111). This difference verifies the predicted extreme sensitivity [J. Wyrick et al., Nano Lett. 11, 2944 (2011)] of the pore network to small changes in the surface electronic structure. Quantitative analysis of the 2D pore network reveals that the areas of the vacancy islands are distributed log-normally. Log-normal distributions are typically associated with the product of random variables (multiplicative noise), and we propose that the distribution of pore sizes for AQ on Au(111) originates from random linear rate constants for molecules to either desorb from the surface or detach from the region of a nucleated pore.

Visualization of nanoconstructions with DNA-Aptamers for targeted molecules binding on the surface of screen-printed electrodes

NASA Astrophysics Data System (ADS)

Lapin, Ivan N.; Shabalina, Anastasiia V.; Svetlichyi, Valery A.; Kolovskaya, Olga S.

2018-04-01

Nanoconstructions of gold nanoparticles (NPs) obtained via pulsed laser ablation in liquid with DNA-aptamer specific to protein tumor marker were visualized on the surface of screen-printed electrode using scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). AuNPs/aptamer nanoconstuctions distribution on the solid surface was studied. More uniform coverage of the carbon electrode surface with the nanoconstuctions was showed in comparison with DNA-aptamer alone on the golden electrode surface. Targeted binding of the tumor marker molecules with the AuNPs/DNA-aptamer nanoconstuctions was approved.

Gold surfaces and nanoparticles are protected by Au(0)-thiyl species and are destroyed when Au(I)-thiolates form.

PubMed

Reimers, Jeffrey R; Ford, Michael J; Halder, Arnab; Ulstrup, Jens; Hush, Noel S

2016-03-15

The synthetic chemistry and spectroscopy of sulfur-protected gold surfaces and nanoparticles is analyzed, indicating that the electronic structure of the interface is Au(0)-thiyl, with Au(I)-thiolates identified as high-energy excited surface states. Density-functional theory indicates that it is the noble character of gold and nanoparticle surfaces that destabilizes Au(I)-thiolates. Bonding results from large van der Waals forces, influenced by covalent bonding induced through s-d hybridization and charge polarization effects that perturbatively mix in some Au(I)-thiolate character. A simple method for quantifying these contributions is presented, revealing that a driving force for nanoparticle growth is nobleization, minimizing Au(I)-thiolate involvement. Predictions that Brust-Schiffrin reactions involve thiolate anion intermediates are verified spectroscopically, establishing a key feature needed to understand nanoparticle growth. Mixing of preprepared Au(I) and thiolate reactants always produces Au(I)-thiolate thin films or compounds rather than monolayers. Smooth links to O, Se, Te, C, and N linker chemistry are established.

Oxidative dissolution of silver nanoparticles: A new theoretical approach.

PubMed

Adamczyk, Zbigniew; Oćwieja, Magdalena; Mrowiec, Halina; Walas, Stanisław; Lupa, Dawid

2016-05-01

A general model of an oxidative dissolution of silver particle suspensions was developed that rigorously considers the bulk and surface solute transport. A two-step surface reaction scheme was proposed that comprises the formation of the silver oxide phase by direct oxidation and the acidic dissolution of this phase leading to silver ion release. By considering this, a complete set of equations is formulated describing oxygen and silver ion transport to and from particles' surfaces. These equations are solved in some limiting cases of nanoparticle dissolution in dilute suspensions. The obtained kinetic equations were used for the interpretation of experimental data pertinent to the dissolution kinetics of citrate-stabilized silver nanoparticles. In these kinetic measurements the role of pH and bulk suspension concentration was quantitatively evaluated by using the atomic absorption spectrometry (AAS). It was shown that the theoretical model adequately reflects the main features of the experimental results, especially the significant increase in the dissolution rate for lower pH. Also the presence of two kinetic regimes was quantitatively explained in terms of the decrease in the coverage of the fast dissolving oxide layer. The overall silver dissolution rate constants characterizing these two regimes were determined. Copyright © 2015 Elsevier Inc. All rights reserved.

Appropriate salt concentration of nanodiamond colloids for electrostatic self-assembly seeding of monosized individual diamond nanoparticles on silicon dioxide surfaces.

PubMed

Yoshikawa, Taro; Zuerbig, Verena; Gao, Fang; Hoffmann, René; Nebel, Christoph E; Ambacher, Oliver; Lebedev, Vadim

2015-05-19

Monosized (∼4 nm) diamond nanoparticles arranged on substrate surfaces are exciting candidates for single-photon sources and nucleation sites for ultrathin nanocrystalline diamond film growth. The most commonly used technique to obtain substrate-supported diamond nanoparticles is electrostatic self-assembly seeding using nanodiamond colloidal suspensions. Currently, monodisperse nanodiamond colloids, which have a narrow distribution of particle sizes centering on the core particle size (∼4 nm), are available for the seeding technique on different substrate materials such as Si, SiO2, Cu, and AlN. However, the self-assembled nanoparticles tend to form small (typically a few tens of nanometers or even larger) aggregates on all of those substrate materials. In this study, this major weakness of self-assembled diamond nanoparticles was solved by modifying the salt concentration of nanodiamond colloidal suspensions. Several salt concentrations of colloidal suspensions were prepared using potassium chloride as an inserted electrolyte and were examined with respect to seeding on SiO2 surfaces. The colloidal suspensions and the seeded surfaces were characterized by dynamic light scattering and atomic force microscopy, respectively. Also, the interaction energies between diamond nanoparticles in each of the examined colloidal suspensions were compared on the basis of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. From these investigations, it became clear that the appropriate salt concentration suppresses the formation of small aggregates during the seeding process owing to the modified electrostatic repulsive interaction between nanoparticles. Finally, monosized (<10 nm) individual diamond nanoparticles arranged on SiO2 surfaces have been successfully obtained.