Single Nanoparticle Translocation Through Chemically Modified Solid Nanopore

NASA Astrophysics Data System (ADS)

Tan, Shengwei; Wang, Lei; Liu, Hang; Wu, Hongwen; Liu, Quanjun

2016-02-01

The nanopore sensor as a high-throughput and low-cost technology can detect single nanoparticle in solution. In the present study, the silicon nitride nanopores were fabricated by focused Ga ion beam (FIB), and the surface was functionalized with 3-aminopropyltriethoxysilane to change its surface charge density. The positively charged nanopore surface attracted negatively charged nanoparticles when they were in the vicinity of the nanopore. And, nanoparticle translocation speed was slowed down to obtain a clear and deterministic signal. Compared with previous studied small nanoparticles, the electrophoretic translocation of negatively charged polystyrene (PS) nanoparticles (diameter ~100 nm) was investigated in solution using the Coulter counter principle in which the time-dependent nanopore current was recorded as the nanoparticles were driven across the nanopore. A linear dependence was found between current drop and biased voltage. An exponentially decaying function ( t d ~ e -v/v0 ) was found between the duration time and biased voltage. The interaction between the amine-functionalized nanopore wall and PS microspheres was discussed while translating PS microspheres. We explored also translocations of PS microspheres through amine-functionalized solid-state nanopores by varying the solution pH (5.4, 7.0, and 10.0) with 0.02 M potassium chloride (KCl). Surface functionalization showed to provide a useful step to fine-tune the surface property, which can selectively transport molecules or particles. This approach is likely to be applied to gene sequencing.

Controlled functionalization of nanoparticles & practical applications

NASA Astrophysics Data System (ADS)

Rashwan, Khaled

With the increasing use of nanoparticles in both science and industry, their chemical modification became a significant part of nanotechnology. Unfortunately, most commonly used procedures provide just randomly functionalized materials. The long-term objective of our work is site- and stoichiometrically-controlled functionalization of nanoparticles with the utilization of solid supports and other nanostructures. On the examples of silica nanoparticles and titanium dioxide nanorods, we have obtained results on the solid-phase chemistry, method development, and modeling, which advanced us toward this goal. At the same time, we explored several applications of nanoparticles that will benefit from the controlled functionalization: imaging of titanium-dioxide-based photocatalysts, bioimaging by fluorescent nanoparticles, drug delivery, assembling of bone implants, and dental compositions. Titanium dioxide-based catalysts are known for their catalytic activity and their application in solar energy utilization such as photosplitting of water. Functionalization of titanium dioxide is essential for enhancing bone-titanium dioxide nanotube adhesion, and, therefore, for its application as an interface between titanium implants and bones. Controlled functionalization of nanoparticles should enhance sensitivity and selectivity of nanoassemblies for imaging and drug delivery applications. Along those lines, we studied the relationship between morphology and surface chemistry of nanoparticles, and their affinity to organic molecules (salicylic and caffeic acid) using Langmuir adsorption isotherms, and toward material surfaces using SEM- and TEM-imaging. We focused on commercial samples of titanium dioxide, titanium dioxide nanorods with and without oleic acid ligands, and differently functionalized silica nanoparticles. My work included synthesis, functionalization, and characterization of several types of nanoparticles, exploring their application in imaging, dentistry, and bone implant construction. Significant part of my experimental efforts was devoted to the solid-phase method development using model organic molecules, as well as affinity of nanoparticles to the functional groups and surfaces that can be used as linkages for constructing functional nanodevices.

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

NASA Astrophysics Data System (ADS)

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

2009-01-01

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

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.

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

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.

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.

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 information (ESI) available. See DOI: 10.1039/c5nr07334k

Aliphatic hyperbranched polyester: A new building block in the construction of multifunctional nanoparticles and nanocomposites**

PubMed Central

Santra, Santimukul; Kaittanis, Charalambos; Perez, J. Manuel

2009-01-01

Herein we report the design and synthesis of multifunctional hyperbranched polyester-based nanoparticles and nanocomposites with properties ranging from magnetic, fluorescence, antioxidant and X-ray contrast. The fabrication of these nanostructures was achieved using a novel aliphatic and biodegradable hyperbranched polyester (HBPE) synthesized from readily available diethylmalonate. The polymer’s globular structure with functional surface carboxylic groups and hydrophobic cavities residing in the polymer’s interior allows for the formation of multifunctional polymeric nanoparticles, which are able to encapsulate a diversity of hydrophobic cargos. Via simple surface chemistry modifications, the surface carboxylic acid groups were modified to yield nanoparticles with a variety of surface functionalizations, such as amino, azide and propargyl groups, which mediated the conjugation of small molecules. This capability achieved the engineering of the HBPE nanoparticle surface for specific cell internalization studies and the formation of nanoparticle assemblies for the creation of novel nanocomposites that retained, and in some cases enhanced, the properties of the parental nanoparticle building blocks. Considering these results, the HBPE polymer, nanoparticles and composites should be ideal for biomedical, pharmaceutical, nanophotonics and material applications. PMID:19957939

Erythrocyte membrane-camouflaged polymeric nanoparticles as a biomimetic delivery platform

PubMed Central

Hu, Che-Ming J.; Zhang, Li; Aryal, Santosh; Cheung, Connie; Fang, Ronnie H.; Zhang, Liangfang

2011-01-01

Efforts to extend nanoparticle residence time in vivo have inspired many strategies in particle surface modifications to bypass macrophage uptake and systemic clearance. Here we report a top-down biomimetic approach in particle functionalization by coating biodegradable polymeric nanoparticles with natural erythrocyte membranes, including both membrane lipids and associated membrane proteins for long-circulating cargo delivery. The structure, size and surface zeta potential, and protein contents of the erythrocyte membrane-coated nanoparticles were verified using transmission electron microscopy, dynamic light scattering, and gel electrophoresis, respectively. Mice injections with fluorophore-loaded nanoparticles revealed superior circulation half-life by the erythrocyte-mimicking nanoparticles as compared to control particles coated with the state-of-the-art synthetic stealth materials. Biodistribution study revealed significant particle retention in the blood 72 h following the particle injection. The translocation of natural cellular membranes, their associated proteins, and the corresponding functionalities to the surface of synthetic particles represents a unique approach in nanoparticle functionalization. PMID:21690347

Influence of functionalized nanoparticles on conformational stability of type I collagen for possible biomedical applications.

PubMed

Kandamchira, Aswathy; Selvam, Sangeetha; Marimuthu, Nidhin; Janardhanan, Sreeram Kalarical; Fathima, Nishter Nishad

2013-12-01

Collagen-nanoparticle interactions are vital for many biomedical applications including drug delivery and tissue engineering applications. Iron oxide nanoparticles synthesized using starch template according to our earlier reported procedures were functionalized by treating them with Gum Arabic (GA), a biocompatible polysaccharide, so as to enhance the interaction between nanoparticle surfaces and collagen. Viscosity, circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR) techniques have been used to study the collagen-nanoparticle interactions. The relative viscosity for collagen-nanoparticle conjugate was found to increase with increase in concentration of the nanoparticle within the concentration range investigated, which is due to the aggregation of protein onto the surface of nanoparticle. The CD spectra for the collagen-nanoparticle at different concentration ratios do not have much variation in the Rpn values (ratio of positive peak intensity over negative peak intensity) after functionalization with GA. The variation of molar ellipticity values for collagen-nanoparticle is due to the glycoprotein present in GA. The collagen triple helical structure is maintained after interaction with nanoparticles. The FTIR spectra of native collagen, Coll-Fs (nanoparticle without functionalization) and Coll-FsG (nanoparticle functionalized with GA) show clearly the amide I, II, III bands, with respect to collagen. The ability of polysaccharide stabilized/functionalized nanoparticles to maintain the collagen properties would help in its biomedical applications. © 2013.

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 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. Electronic supplementary information (ESI) available: Cell culture preparation for dose/response imaging experiments. See DOI: 10.1039/c3nr02639f

Computational design of nanoparticle drug delivery systems for selective targeting

NASA Astrophysics Data System (ADS)

Duncan, Gregg A.; Bevan, Michael A.

2015-09-01

Ligand-functionalized nanoparticles capable of selectively binding to diseased versus healthy cell populations are attractive for improved efficacy of nanoparticle-based drug and gene therapies. However, nanoparticles functionalized with high affinity targeting ligands may lead to undesired off-target binding to healthy cells. In this work, Monte Carlo simulations were used to quantitatively determine net surface interactions, binding valency, and selectivity between targeted nanoparticles and cell surfaces. Dissociation constant, KD, and target membrane protein density, ρR, are explored over a range representative of healthy and cancerous cell surfaces. Our findings show highly selective binding to diseased cell surfaces can be achieved with multiple, weaker affinity targeting ligands that can be further optimized by varying the targeting ligand density, ρL. Using the approach developed in this work, nanomedicines can be optimally designed for exclusively targeting diseased cells and tissues.Ligand-functionalized nanoparticles capable of selectively binding to diseased versus healthy cell populations are attractive for improved efficacy of nanoparticle-based drug and gene therapies. However, nanoparticles functionalized with high affinity targeting ligands may lead to undesired off-target binding to healthy cells. In this work, Monte Carlo simulations were used to quantitatively determine net surface interactions, binding valency, and selectivity between targeted nanoparticles and cell surfaces. Dissociation constant, KD, and target membrane protein density, ρR, are explored over a range representative of healthy and cancerous cell surfaces. Our findings show highly selective binding to diseased cell surfaces can be achieved with multiple, weaker affinity targeting ligands that can be further optimized by varying the targeting ligand density, ρL. Using the approach developed in this work, nanomedicines can be optimally designed for exclusively targeting diseased cells and tissues. Electronic supplementary information (ESI) available: Movie showing simulation renderings of targeted (ρL = 1820/μm2, KD = 120 μM) nanoparticle selective binding to cancer (ρR = 256/μm2) vs. healthy (ρR = 64/μm2) cell surfaces. Target membrane proteins have linear color scale depending on binding energy ranging from white when unbound (URL = 0) to red when tightly bound (URL = UM). See DOI: 10.1039/c5nr03691g

Functionalizable and ultra stable nanoparticles coated with zwitterionic poly(carboxybetaine) in undiluted blood serum.

PubMed

Yang, Wei; Zhang, Lei; Wang, Shanlin; White, Andrew D; Jiang, Shaoyi

2009-10-01

A new surface chemistry presenting an abundance of functional groups for ligand immobilization in an ultra-low fouling background all in one material for nanoparticles was introduced. This surface platform, as demonstrated by zwitterionic poly(carboxybetaine acrylamide) (polyCBAA) coated nanoparticles, is not only ultra stable in undiluted human blood serum, but also can be conjugated to biomolecules conveniently and effectively. Thus, this surface chemistry is ideal to create multi-functional nanoparticles for targeted delivery and diagnostics. In addition, this work clearly shows that 10% blood serum commonly used to evaluate the stability of nanoparticles is insufficient and a new evaluation criterion with undiluted blood serum is recommended.

Gum ghatti mediated, one pot green synthesis of optimized gold nanoparticles: Investigation of process-variables impact using Box-Behnken based statistical design.

PubMed

Alam, Md Sabir; Garg, Arun; Pottoo, Faheem Hyder; Saifullah, Mohammad Khalid; Tareq, Abu Izneid; Manzoor, Ovais; Mohsin, Mohd; Javed, Md Noushad

2017-11-01

Due to unique inherent catalytic characteristics of different size, shape and surface functionalized gold nanoparticles, their potential applications, are being explored in various fields such as drug delivery, biosensor, diagnosis and theranostics. However conventional process for synthesis of these metallic nanoparticles utilizes toxic reagents as reducing agents, additional capping agent for stability as well as surface functionalization for drug delivery purposes. Hence, in this work suitability of gum Ghatti for reducing, capping and surface functionalization during the synthesis of stable Gold nanoparticles were duly explored. Role and impact of key process variables i.e. volume of chloroauric acid solution, gum solution and temperature at their respective three different levels, as well as mechanism of formation of optimized gold nanoparticles were also investigated using Box- Behnken design. These novel synthesized optimized Gold nanoparticles were further characterized by UV spectrophotometer for its surface plasmon resonance (SPR) at around ∼530nm, dynamic light scattering (DLS) for its hydrodynamic size (112.5nm), PDI (0.222) and zeta potential (-21.3mV) while, transmission electron microscopy (TEM) further revealed surface geometry of these nanoparticles being spherical in shape. Copyright © 2017 Elsevier B.V. All rights reserved.

Specific effects of surface carboxyl groups on anionic polystyrene particles in their interactions with mesenchymal stem cells

NASA Astrophysics Data System (ADS)

Jiang, Xiue; Musyanovych, Anna; Röcker, Carlheinz; Landfester, Katharina; Mailänder, Volker; Nienhaus, G. Ulrich

2011-05-01

Nanoparticle uptake by living cells is governed by chemical interactions between functional groups on the nanoparticle as well as the receptors on cell surfaces. Here we have investigated the uptake of anionic polystyrene (PS) nanoparticles of ~100 nm diameter by mesenchymal stem cells (MSCs) using spinning-disk confocal optical microscopy combined with a quantitative analysis of the fluorescence images. Two types of anionic PS nanoparticles with essentially identical sizes and ζ-potentials were employed in this study, carboxyl-functionalized nanoparticles (CPS) and plain PS nanoparticles, both coated with anionic detergent for stabilization. CPS nanoparticles were observed to internalize more rapidly and accumulate to a much higher level than plain PS nanoparticles. The relative importance of different uptake mechanisms for the two types of nanoparticles was investigated by using specific inhibitors. CPS nanoparticles were internalized mainly via the clathrin-mediated mechanism, whereas plain PS nanoparticles mainly utilized the macropinocytosis pathway. The pronounced difference in the internalization behavior of CPS and plain PS nanoparticles points to a specific interaction of the carboxyl group with receptors on the cell surface.

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

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 on the surface of the particles using XPS and FTIR. The combination of ROS production and ligand degradation can affect the bioavailability of these particles in aqueous species.

Characterization of the modified nickel-zinc ferrite nanoparticles coated with APTES by salinization reaction

NASA Astrophysics Data System (ADS)

Zainal, Israa G.; Al-Shammari, Ahmed Majeed; Kachi, Wjeah

2018-05-01

Surface functionalization of magnetic iron oxide nanoparticles (NPs) is a kind of functional materials, which have been widely used in the biotechnology and catalysis. In this study, Nickel-Zinc ferrite nanoparticles was functionalized with amino propyl triethoxy silane (APTES) by silanization reaction and both non coated and organosilane-coated magnetite characterized by energy-dispersive X-ray spectroscopy (EDX), X-ray diffractometry, Fourier transformed infrared spectroscopy (FTIR) and atomic force microscopy. Basic groups of amino anchored on the external surface of the coated magnetite were observed. Our study procedure nanoparticles which have surface with free - NH2 groups which can carry out ionic interaction with carboxylic groups and act as a carrier of biological molecules, drugs and metals.

Controlling Surface Termination and Facet Orientation in Cu2O Nanoparticles for High Photocatalytic Activity: A Combined Experimental and Density Functional Theory Study.

PubMed

Su, Yang; Li, Hongfei; Ma, Hanbin; Robertson, John; Nathan, Arokia

2017-03-08

Cu 2 O nanoparticles with controllable facets are of great significance for photocatalysis. In this work, the surface termination and facet orientation of Cu 2 O nanoparticles are accurately tuned by adjusting the amount of hydroxylamine hydrochloride and surfactant. It is found that Cu 2 O nanoparticles with Cu-terminated (110) or (111) surfaces show high photocatalytic activity, while other exposed facets show poor reactivity. Density functional theory simulations confirm that sodium dodecyl sulfate surfactant can lower the surface free energy of Cu-terminated surfaces, increase the density of exposed Cu atoms at the surfaces and thus benefit the photocatalytic activity. It also shows that the poor reactivity of the Cu-terminated Cu 2 O (100) surface is due to the high energy barrier of holes at the surface region.

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

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

Nanoparticles for Biomedical Imaging

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

Nune, Satish K.; Gunda, Padmaja; Thallapally, Praveen K.

2009-11-01

Background: Synthetic nanoparticles are emerging as versatile tools in biomedical applications, particularly in the area of biomedical imaging. Nanoparticles 1 to 100 nm in diameter possess dimensions comparable to biological functional units. Diverse surface chemistries, unique magnetic properties, tunable absorption and emission properties, and recent advances in the synthesis and engineering of various nanoparticles suggest their potential as probes for early detection of diseases such as cancer. Surface functionalization has further expanded the potential of nanoparticles as probes for molecular imaging. Objective: To summarize emerging research of nanoparticles for biomedical imaging with increased selectivity and reduced non-specific uptake with increasedmore » spatial resolution containing stabilizers conjugated with targeting ligands. Methods: This review summarizes recent technological advances in the synthesis of various nanoparticle probes, and surveys methods to improve the targeting of nanoparticles for their applications in biomedical imaging. Conclusion: Structural design of nanomaterials for biomedical imaging continues to expand and diversify. Synthetic methods have aimed to control the size and surface characteristics of nanoparticles to control distribution, half-life and elimination. Although molecular imaging applications using nanoparticles are advancing into clinical applications, challenges such as storage stability and long-term toxicology should continue to be addressed. Keywords: nanoparticle synthesis, surface modification, targeting, molecular imaging, and biomedical imaging.« less

Preferential Interaction of Na+ over K+ to Carboxylate-functionalized Silver Nanoparticles

EPA Science Inventory

Elucidating mechanistic interactions between specific ions (Na+/ K+) and nanoparticle surfaces to alter particle stability in polar media has received little attention. We investigated relative preferential binding of Na+ and K+ to carboxylate-functionalized silver nanoparticles ...

Functionalization of Mechanochemically Passivated Germanium Nanoparticles via "Click" Chemistry

NASA Astrophysics Data System (ADS)

Purkait, Tapas Kumar

Germanium nanoparticles (Ge NPs) may be fascinating for their electronic and optoelectronic properties, as the band gap of Ge NPs can be tuned from the infrared into the visible range of solar spectru. Further functionalization of those nanoparticles may potentially lead to numerous applications ranging from surface attachment, bioimaging, drug delivery and nanoparticles based devices. Blue luminescent germanium nanoparticles were synthesized from a novel top-down mechanochemical process using high energy ball milling (HEBM) of bulk germanium. Various reactive organic molecules (such as, alkynes, nitriles, azides) were used in this process to react with fresh surface and passivate the surface through Ge-C or Ge-N bond. Various purification process, such as gel permeation chromatography (GPC), Soxhlet dailysis etc. were introduced to purify nanoparticles from molecular impurities. A size separation technique was developed using GPC. The size separated Ge NPs were characterize by TEM, small angle X-ray scattering (SAXS), UV-vis absorption and photoluminescence (PL) emission spectroscopy to investigate their size selective properties. Germanium nanoparticles with alkyne termini group were prepared by HEBM of germanium with a mixture of n-alkynes and alpha, o-diynes. Additional functionalization of those nanoparticles was achieved by copper(I) catalyzed azide-alkyne "click" reaction. A variety of organic and organometallic azides including biologically important glucals have been reacted in this manner resulting in nanopartilces adorned with ferrocenyl, trimethylsilyl, and glucal groups. Additional functionalization of those nanoparticles was achieved by reactions with various azides via a Cu(I) catalyzed azide-alkyne "click" reaction. Various azides, including PEG derivatives and cylcodextrin moiety, were grafted to the initially formed surface. Globular nanoparticle arrays were formed through interparticle linking via "click" chemistry or "host-guest" chemistry. Copper(I) catalyzed "click" chemistry also can be explored with azido-terminated Ge NPs which were synthesized by azidation of chloro-terminated Ge NPs. Water soluble PEGylated Ge NPs were synthesized by "click" reaction for biological application. PEGylated Ge NP clusters were prepared using alpha, o-bis alkyno or bis-azido polyethylene glycol (PEG) derivatives by copper catalyzed "click" reaction via inter-particle linking. These nanoparticles were further functionalized by azido beta-cyclodextrin (beta-CD) and azido adamantane via alkyne-azide "click" reactions. Nanoparticle clusters were made from the functionalized Ge NPs by "host-guest" chemistry of beta-CD functionalized Ge NPs either with adamantane functionalized Ge NPs or fullerene, C60.

Fabrication of phosphonic acid films on nitinol nanoparticles by dynamic covalent assembly

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

Quinones, Rosalynn; Garretson, Samantha; Behnke, Grayce

Nitinol (NiTi) nanoparticles are a valuable metal alloy due to many unique properties that allow for medical applications. NiTi nanoparticles have the potential to form nanofluids, which can advance the thermal conductivity of fluids by controlling the surface functionalization through chemical attachment of organic acids to the surface to form self-assembled alkylphosphonate films. In this study, phosphonic functional head groups such as 16-phosphonohexadecanoic acid, octadecylphosphonic acid, and 12-aminododecylphosphonic acid were used to form an ordered and strongly chemically bounded film on the NiTi nanopowder. The surface of the NiTi nanoparticles was modified in order to tailor the chemical and physicalmore » properties to the desired application. The modified NiTi nanoparticles were characterized using infrared spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and 31P solid-state nuclear magnetic resonance. The interfacial bonding was identified by spectroscopic data suggesting the phosphonic head group adsorbs in a mixed bidentate/monodentate binding motif on the NiTi nanoparticles. Dynamic light scattering and scanning electron microscopy-energy dispersive X-ray spectroscopy revealed the particle sizes. Differential scanning calorimetry was used to examine the phase transitions. Zeta potential determination as a function of pH was examined to investigate the surface properties of charged nanoparticles. In conclusion, the influence of environmental stability of the surface modifications was also assessed.« less

Fabrication of phosphonic acid films on nitinol nanoparticles by dynamic covalent assembly

DOE PAGES

Quinones, Rosalynn; Garretson, Samantha; Behnke, Grayce; ...

2017-09-25

Nitinol (NiTi) nanoparticles are a valuable metal alloy due to many unique properties that allow for medical applications. NiTi nanoparticles have the potential to form nanofluids, which can advance the thermal conductivity of fluids by controlling the surface functionalization through chemical attachment of organic acids to the surface to form self-assembled alkylphosphonate films. In this study, phosphonic functional head groups such as 16-phosphonohexadecanoic acid, octadecylphosphonic acid, and 12-aminododecylphosphonic acid were used to form an ordered and strongly chemically bounded film on the NiTi nanopowder. The surface of the NiTi nanoparticles was modified in order to tailor the chemical and physicalmore » properties to the desired application. The modified NiTi nanoparticles were characterized using infrared spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and 31P solid-state nuclear magnetic resonance. The interfacial bonding was identified by spectroscopic data suggesting the phosphonic head group adsorbs in a mixed bidentate/monodentate binding motif on the NiTi nanoparticles. Dynamic light scattering and scanning electron microscopy-energy dispersive X-ray spectroscopy revealed the particle sizes. Differential scanning calorimetry was used to examine the phase transitions. Zeta potential determination as a function of pH was examined to investigate the surface properties of charged nanoparticles. In conclusion, the influence of environmental stability of the surface modifications was also assessed.« less

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.

Carbodiimide versus click chemistry for nanoparticle surface functionalization: a comparative study for the elaboration of multimodal superparamagnetic nanoparticles targeting αvβ3 integrins.

PubMed

Bolley, Julie; Guenin, Erwann; Lievre, Nicole; Lecouvey, Marc; Soussan, Michael; Lalatonne, Yoann; Motte, Laurence

2013-11-26

Superparamagnetic fluorescent nanoparticles targeting αvβ3 integrins were elaborated using two methodologies: carbodiimide coupling and click chemistries (CuACC and thiol-yne). The nanoparticles are first functionalized with hydroxymethylenebisphonates (HMBP) bearing carboxylic acid or alkyne functions. Then, a large number of these reactives functions were used for the covalent coupling of dyes, poly(ethylene glycol) (PEG), and cyclic RGD. Several methods were used to characterize the nanoparticle surface functionalization, and the magnetic properties of these contrast agents were studied using a 1.5 T clinical MRI. The affinity toward integrins was evidenced by solid-phase receptor-binding assay. In addition to their chemoselective natures, click reactions were shown to be far more efficient than the carbodiimide coupling. The grafting increase was shown to enhance targeting affinity to integrin without imparing MRI and fluorescent properties.

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.

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

QCM-D study of nanoparticle interactions.

PubMed

Chen, Qian; Xu, Shengming; Liu, Qingxia; Masliyah, Jacob; Xu, Zhenghe

2016-07-01

Quartz crystal microbalance with dissipation monitoring (QCM-D) has been proven to be a powerful research tool to investigate in situ interactions between nanoparticles and different functionalized surfaces in liquids. QCM-D can also be used to quantitatively determine adsorption kinetics of polymers, DNA and proteins from solutions on various substrate surfaces while providing insights into conformations of adsorbed molecules. This review aims to provide a comprehensive overview on various important applications of QCM-D, focusing on deposition of nanoparticles and attachment-detachment of nanoparticles on model membranes in complex fluid systems. We will first describe the working principle of QCM-D and DLVO theory pertinent to understanding nanoparticle deposition phenomena. The interactions between different nanoparticles and functionalized surfaces for different application areas are then critically reviewed. Finally, the potential applications of QCM-D in other important fields are proposed and knowledge gaps are identified. Copyright © 2015 Elsevier B.V. All rights reserved.

An improved, non-functionalized route to plasmonic nanoparticle based cellular probing through osmolyte mediation (Conference Presentation)

NASA Astrophysics Data System (ADS)

Siddhanta, Soumik; Barman, Ishan

2017-02-01

Engineering nanostructured probes for ultra-sensitive detection of specific molecular species, our research seeks to capture the complex changes in cells and tissues that can predict disease progression in an individual. While such nanoparticle-based platforms are rapidly gaining a foothold in cancer diagnostics, one of the most concerning factors is the vulnerability of cells to the interaction with functional nanoparticles thereby raising the specter of systemic toxicity. The nanoparticles end up damaging the cells and disrupting cellular functions thereby impeding their imaging aim. Furthermore, PEGylation, and similar routes, force a tradeoff between desired nanoparticle properties (recognition, uptake, and reduced toxicity) and sensitivity of plasmon-enhanced spectroscopic sensing methods, such as surface-enhanced Raman spectroscopy (SERS) where the proximal presence of noble metal NP and the organic molecule of interest is key. In this work, we report a trehalose-mediated, non-surface functionalized route for cell-nanoparticle interactions that maintains cell viability while allowing selective interaction of the nanoparticle with the cell surface receptors and subsequent internalization. Through careful electron microscopy of nanoparticle-prostate cancer cells interactions, we elucidated that there exists a dynamic equilibrium between "free" cytosolic diffusion of the nanoparticles and endocytosis through vesicle formation - and trehalose tilts the scale in favor of the latter to mask the toxic effects of the nanoparticles. The precise molecular interpretation of this behavior was further probed through SERS, which directly points towards the protein stabilization properties of trehalose mediation during interaction of the nanoparticles with the plasma membrane components.

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 Analysis of Gold Nanoparticles Functionalized with Thiol-Modified Glucose SAMs for Biosensor Applications

PubMed Central

Spampinato, Valentina; Parracino, Maria Antonietta; La Spina, Rita; Rossi, Francois; Ceccone, Giacomo

2016-01-01

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 behavior of the glucose-modified particles in the presence of the maltose binding protein. PMID:26973830

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.

Fabrication, Light Emission, and Magnetism of Silica Nanoparticles Hybridized with AIE Luminogens and Inorganic Nanostructures

NASA Astrophysics Data System (ADS)

Faisal, Mahtab

Much research efforts have been devoted in developing new synthetic approaches for fluorescent silica nanoparticles (FSNPs) due to their potential high-technological applications. However, light emissions from most of the FSNPs prepared so far have been rather weak. This is due to the emission quenching caused by the aggregation of fluorophores in the solid state. We have observed a novel phenomenon of aggregation-induced emission (AIE): a series of propeller-shaped molecules such as tetraphenylethene (TPE) and silole are induced to emit efficiently by aggregate formation. Thus, they are ideal fluorophors for the construction of FSNPs and my thesis work focuses on the synthesis of silica nanoparticles containing these luminogens and magnetic nanostructures. Highly emissive FSNPs with core-shell structures are fabricated by surfactant-free sol-gel reactions of tetraphenylethene- (TPE) and silole-functionalized siloxanes followed by the reactions with tetraethoxysilane. The FSNPs are uniformly sized, surface-charged and colloidally stable. The diameters of the FSNPs are tunable in the range of 45--295 nm by changing the reaction conditions. Whereas their TPE and silole precursors are non-emissive, the FSNPs emit strong visible lights, thanks to the novel aggregation-induced emission characteristics of the TPE and silole aggregates in the hybrid nanoparticles. The FSNPs pose no toxicity to living cells and can be utilized to selectively image cytoplasm of HeLa cells. Applying the same tool in the presence of citrate-coated magnetite nanoparticles, uniform magnetic fluorescent silica nanoparticles (MFSNPs) with smooth surfaces are fabricated. These particles exhibit appreciable surface charges and hence good colloidal stability. They are superparamagnetic, exhibiting no hysteresis at room temperature. UV irradiation of a suspension of MFSNPs in ethanol gives strong blue and green emissions. The MFSNPs can selectively stain the cytoplasmic regions of the living cells. Sol-gel reaction in the presence of (3-aminopropyl)triethoxysilane has generated MFSNP-NH2 with numerous amino functionalities decorated on the surfaces, enabling them to immobilize bovine serum albumin efficiently. FSNPs with strong light emissions are facilely fabricated by thio-click chemistry, Cu(I)-catalyzed 1,3-dipolar cycloaddition, and sol-gel reaction. The FSNPs are characterized by SEM, TEM, IR, PL, and zeta potential analyses. They are uniformly sized with smooth surfaces. Upon photoexcitation, the FSNPs emit strong visible lights with fluorescence quantum yields up to 25.5%. Sugar-functionalized fluorescent silica nanoparticles are facilely fabricated by click reaction of azide-modified FSNPs with sugar- containing phenylacetylene catalyzed by Cu(PPh3)3Br in THF. The nanoparticles are uniformly sized and emit efficient light upon photoexcitation. They can function as fluorescent visualizers for intracellular imaging and can target specific cancer cells. Folic acid-functionalized fluorescent silica nanoparticles are facilely fabricated by surface functionalization of FSNPs with folic acid. The nanoparticles are spherical in shape. They possess high zeta potentials and hence exhibit excellent colloidal stability. UV irradiation of suspensions of the nanoparticles in ethanol gives strong blue and green emissions at 465 and 490 nm with absolute fluorescence quantum yields up to 47%. Carboxylic acid and thiol-functionalized fluorescent silica nanoparticles (FSNP-COOH and FSNP-SH) with uniform particle sizes, narrow size distributions, and smooth surface morphologies are fabricated. The nanoparticles possess high surface charges and exhibit strong light emissions upon photoexcitation. They can adsorb lysozyme strongly on their surfaces and for 5 mg of FSNP-COOH and FSNP-SH, they can take 209 and 86 mug of lysozyme. Thus, they are potential carriers for protein and fluorescent probes or biosensors for an array of biological applications.

Surface functionalization of gold nanoparticles using hetero-bifunctional poly(ethylene glycol) spacer for intracellular tracking and delivery

PubMed Central

Shenoy, Dinesh; Fu, Wei; Li, Jane; Crasto, Curtis; Jones, Graham; DiMarzio, Charles; Sridhar, Srinivas; Amiji, Mansoor

2006-01-01

For the development of surface-functionalized gold nanoparticles as cellular probes and delivery agents, we have synthesized hetero-bifunctional poly(ethylene glycol) (PEG, MW 1500) having a thiol group on one terminus and a reactive functional group on the other for use as a flexible spacer. Coumarin, a model fluorescent dye, was conjugated to one end of the PEG spacer and gold nanoparticles were modified with coumarin-PEG-thiol. Surface attachment of coumarin through the PEG spacer decreased the fluorescence quenching effect of gold nanoparticles. The results of cellular cytotoxicity and fluorescence confocal analyses showed that the PEG spacer-modified nanoparticles were essentially non-toxic and could be efficiently internalized in the cells within 1 hour of incubation. Intracellular particle tracking using a Keck 3-D Fusion Microscope System showed that the functionalized gold nanoparticles were rapidly internalized in the cells and localized in the peri-nuclear region. Using the PEG spacer, the gold nano-platform can be conjugated with a variety of biologically relevant ligands such as fluorescent dyes, antibodies, etc in order to target, probe, and induce a stimulus at the target site. PMID:16467923

Multifunctional Surface Modification of Nanodiamonds Based on Dopamine Polymerization.

PubMed

Zeng, Yun; Liu, Wenyan; Wang, Zheyu; Singamaneni, Srikanth; Wang, Risheng

2018-04-03

Surface functionalization of nanodiamonds (NDs), which is of great interest in advanced material and therapeutic applications, requires the immobilization of functional species, such as nucleic acids, bioprobes, drugs, and metal nanoparticles, onto NDs' surfaces to form stable nanoconjugates. However, it is still challenging to modify the surface of NDs due to the complexity of their surface chemistry and the low density of each functional group on the surfaces of NDs. In this work, we demonstrate a general applicable surface functionalization approach for the preparation of ND-based core-shell nanoconjugates using dopamine polymerization. By taking advantage of the universal adhesion and versatile reactivity of polydopamine, we have effectively conjugated DNA and silver nanoparticles onto NDs. Moreover, the catalytic activity of ND-supported silver nanoparticle was characterized by the reduction of 4-nitrophenol, and the addressability of NDs was tested through DNA hybridization that formed satellite ND-gold nanorod conjugation. This simple and robust method we have presented may significantly improve the capability for attaching various functionalities onto NDs and open up new platforms for applications of NDs.

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.

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

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 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. Electronic supplementary information (ESI) is available: Fluorescence spectra, ITC, CD spectra and other data as described in the text. See DOI: 10.1039/c4nr01544d

EDTA functionalized magnetic nanoparticle as a multifunctional adsorbent for Congo red dye from contaminated water

NASA Astrophysics Data System (ADS)

Sahoo, Jitendra Kumar; Rath, Juhi; Dash, Priyabrat; Sahoo, Harekrushna

2017-05-01

The present work reports the applicability of magnetite iron nanoparticles (Fe3O4) functionalized with ethylenediaminetetraacetic acid (EDTA) as an efficient adsorbent for the removal of Congo red (CR) dye from contaminated water. Magnetic nanoparticles (Fe3O4) are prepared by chemical precipitation method in which Fe2+ and Fe3+ salt from aqueous solution were reacted in presence of ammonia solution. The surface of Fe3O4 nanoparticle was first coated with (3-aminopropyl) triethoxy silane (APTES) by a salinization reaction and then linked with EDTA via reaction between -NH2 and -COOH to form well dispersed surface functionalised biocompatible magnetic nanoparticles. The obtained EDTA functionalized magnetic nanoparticles are characterized in terms of their morphological, XRD, BET surface area analysis, Fourier transform infrared spectroscopy (FT-IR) and Vibrating sample magnetometer (VSM). The adsorption of CR on Fe3O4-APTES-EDTA nanocomposite corresponds well to the Langmuir model and the Freundlich model respectively. The adsorption processes for CR followed the pseudo-second-order model.

Quantitative Characterization of Magnetic Mobility of Nanoparticle in Solution-Based Condition.

PubMed

Rodoplu, Didem; Boyaci, Ismail H; Bozkurt, Akif G; Eksi, Haslet; Zengin, Adem; Tamer, Ugur; Aydogan, Nihal; Ozcan, Sadan; Tugcu-Demiröz, Fatmanur

2015-01-01

Magnetic nanoparticles are considered as the ideal substrate to selectively isolate target molecules or organisms from sample solutions in a wide variety of applications including bioassays, bioimaging and environmental chemistry. The broad array of these applications in fields requires the accurate magnetic characterization of nanoparticles for a variety of solution based-conditions. Because the freshly synthesized magnetic nanoparticles demonstrated a perfect magnetization value in solid form, they exhibited a different magnetic behavior in solution. Here, we present simple quantitative method for the measurement of magnetic mobility of nanoparticles in solution-based condition. Magnetic mobility of the nanoparticles was quantified with initial mobility of the particles using UV-vis absorbance spectroscopy in water, ethanol and MES buffer. We demonstrated the efficacy of this method through a systematic characterization of four different core-shell structures magnetic nanoparticles over three different surface modifications. The solid nanoparticles were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD) and saturation magnetization (Ms). The surfaces of the nanoparticles were functionalized with 11-mercaptoundecanoic acid and bovine serum albumin BSA was selected as biomaterial. The effect of the surface modification and solution media on the stability of the nanoparticles was monitored by zeta potentials and hydrodynamic diameters of the nanoparticles. Results obtained from the mobility experiments indicate that the initial mobility was altered with solution media, surface functionalization, size and shape of the magnetic nanoparticle. The proposed method easily determines the interactions between the magnetic nanoparticles and their surrounding biological media, the magnetophoretic responsiveness of nanoparticles and the initial mobilities of the nanoparticles.

Synthesis of antibacterial surfaces by plasma grafting of zinc oxide based nanocomposites onto polypropylene.

PubMed

de Rancourt, Yoann; Couturaud, Benoit; Mas, André; Robin, Jean Jacques

2013-07-15

Antibacterial polymer surfaces were designed using ZnO nanoparticles as a bactericide. Mineral encapsulated nanoparticles were grafted onto activated polymer surfaces through their shells. Polypropylene (PP) surfaces were treated using an innovative process coupling core-shell technology and plasma grafting, well-known techniques commonly used to obtain active surfaces for biomedical applications. First, ZnO nanoparticles were encapsulated by (co)polymers: poly(acrylic acid) (PAA) or a poly(methyl methacrylate-co-methacrylic acid) copolymer [P(MMA-MA)]. Second, PP substrates were activated using plasma treatment. Finally, plasma-treated surfaces were immersed in solutions containing the encapsulated nanoparticles dispersed in an organic solvent and allowed to graft onto it. The presence of nanoparticles on the substrates was demonstrated using Fourier-Transform Infrared Spectroscopy (FTIR) analysis, Scanning Electron Microspcopy (SEM)/Energy-Dispersive X-ray (EDX), and Atomic Force Microscopy (AFM) studies. Indeed, the ZnO-functionalized substrates exhibited an antibacterial response in Escherichia coli adhesion tests. Moreover, this study revealed that, surprisingly, native ZnO nanoparticles without any previous functionalization could be directly grafted onto polymeric surfaces through plasma activation. The antibacterial activity of the resulting sample was shown to be comparable to that of the other samples. Copyright © 2013 Elsevier Inc. All rights reserved.

Study of magnetic nanoparticles and overcoatings for biological applications including a sensor device

NASA Astrophysics Data System (ADS)

Grancharov, Stephanie G.

I. A general introduction to the field of nanomaterials is presented, highlighting their special attributes and characteristics. Nanoparticles in general are discussed with respect to their structure, form and properties. Magnetic particles in particular are highlighted, especially the iron oxides. The importance and interest of integrating these materials with biological media is discussed, with emphasis on transferring particles from one medium to another, and subsequent modification of surfaces with different types of materials. II. A general route to making magnetic iron oxide nanoparticles is explained, both as maghemite and magnetite, including properties of the particles and characterization. A novel method of producing magnetite particles without a ligand is then presented, with subsequent characterization and properties described. III. Attempts to coat iron oxide nanoparticles with a view to creating biofunctional magnetic nanoparticles are presented, using a gold overcoating method. Methods of synthesis and characterization are examined, with unique problems to core-shell structures analyzed. IV. Solubility of nanoparticles in both aqueous and organic media is discussed and examined. The subsequent functionalization of the surface of maghemite and magnetite nanoparticles with a variety of biomaterials including block copolypeptides, phospholipids and carboxydextran is then presented. These methods are integral to the use of magnetic nanoparticles in biological applications, and therefore their properties are examined once tailored with these molecules. V. A new type of magnetic nanoparticle sensor-type device is described. This device integrates bio-and DNA-functionalized nanoparticles with conjugate functionalized silicon dioxide surfaces. These techniques to pattern particles to a surface are then incorporated into a device with a magnetic tunnel junction, which measures magnetoresistance in the presence of an external magnetic field. This configuration thereby introduces a new way to detect magnetic nanoparticles via their magnetic properties after conjugation via biological entities.

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.

Evaluation of the influence of sulfur-based functional groups on the embedding of silver nanoparticles into the pores of MCM-41

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

Oliveira, Roselaine da S.; Camilo, Fernanda F.; Bizeto, Marcos A., E-mail: mabizeto@unifesp.br

The incorporation of noble metals in the pores of mesoporous silicas might produce materials with interesting catalytic and sensing capabilities, but the proper control of pore filling and the avoidance of nanoparticles migration to outside the pores are processes not yet completely understood. In this work, we evaluated the role of –SH and –SO{sub 3}H groups post-grafted into MCM-41 on the production of silver nanoparticles by using 1-butanol as reducing agent. Thiol groups were the most efficient on promoting the formation of nanoparticles within the pores. Conversely, sulfonic groups establish electrostatic interactions with silver cations that preclude the formation ofmore » nanoparticle in yields comparable to thiol groups. MCM-41 without functional groups did not have good affinity to silver and the nanoparticles are produced outside the pores. This study showed the importance on selecting an adequate surface functional group in order to obtain silver nanoparticles filling the pores of MCM-41. - Graphical abstract: Silver nanoparticles formation inside the pores of sulfur-groups functionalized mesoporous silica. - Highlights: • Silver nanoparticles formation inside the pores of mesoporous silica. • n-butanol as reducing agent of impregnated silver cations. • Tuning the silica surface properties by grafting sulfur-based functional groups. • Influence on the loading and distribution of the nanoparticles through the pores.« less

Split of surface plasmon resonance of gold nanoparticles on silicon substrate: a study of dielectric functions.

PubMed

Zhu, S; Chen, T P; Cen, Z H; Goh, E S M; Yu, S F; Liu, Y C; Liu, Y

2010-10-11

The split of surface plasmon resonance of self-assembled gold nanoparticles on Si substrate is observed from the dielectric functions of the nanoparticles. The split plasmon resonances are modeled with two Lorentz oscillators: one oscillator at ~1 eV models the polarization parallel to the substrate while the other at ~2 eV represents the polarization perpendicular to the substrate. Both parallel and perpendicular resonances are red-shifted when the nanoparticle size increases. The red shifts in both resonances are explained by the image charge effect of the Si substrate.

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.

Direct work function measurement by gas phase photoelectron spectroscopy and its application on PbS nanoparticles.

PubMed

Axnanda, Stephanus; Scheele, Marcus; Crumlin, Ethan; Mao, Baohua; Chang, Rui; Rani, Sana; Faiz, Mohamed; Wang, Suidong; Alivisatos, A Paul; Liu, Zhi

2013-01-01

Work function is a fundamental property of a material's surface. It is playing an ever more important role in engineering new energy materials and efficient energy devices, especially in the field of photovoltaic devices, catalysis, semiconductor heterojunctions, nanotechnology, and electrochemistry. Using ambient pressure X-ray photoelectron spectroscopy (APXPS), we have measured the binding energies of core level photoelectrons of Ar gas in the vicinity of several reference materials with known work functions (Au(111), Pt(111), graphite) and PbS nanoparticles. We demonstrate an unambiguously negative correlation between the work functions of reference samples and the binding energies of Ar 2p core level photoelectrons detected from the Ar gas near the sample surface region. Using this experimentally determined linear relationship between the surface work function and Ar gas core level photoelectron binding energy, we can measure the surface work function of different materials under different gas environments. To demonstrate the potential applications of this ambient pressure XPS technique in nanotechnology and solar energy research, we investigate the work functions of PbS nanoparticles with various capping ligands: methoxide, mercaptopropionic acid, and ethanedithiol. Significant Fermi level position changes are observed for PbS nanoparticles when the nanoparticle size and capping ligands are varied. The corresponding changes in the valence band maximum illustrate that an efficient quantum dot solar cell design has to take into account the electrochemical effect of the capping ligand as well.

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

General and Direct Method for Preparing Oligonucleotide-Functionalized Metal-Organic Framework Nanoparticles.

PubMed

Wang, Shunzhi; McGuirk, C Michael; Ross, Michael B; Wang, Shuya; Chen, Pengcheng; Xing, Hang; Liu, Yuan; Mirkin, Chad A

2017-07-26

Metal-organic frameworks (MOFs) are a class of modular, crystalline, and porous materials that hold promise for storage and transport of chemical cargoes. Though MOFs have been studied in bulk forms, ways of deliberately manipulating the external surface functionality of MOF nanoparticles are less developed. A generalizable approach to modify their surfaces would allow one to impart chemical functionality onto the particle surface that is independent of the bulk MOF structure. Moreover, the use of a chemically programmable ligand, such as DNA, would allow for the manipulation of interparticle interactions. Herein, we report a coordination chemistry-based strategy for the surface functionalization of the external metal nodes of MOF nanoparticles with terminal phosphate-modified oligonucleotides. The external surfaces of nine distinct archetypical MOF particles containing four different metal species (Zr, Cr, Fe, and Al) were successfully functionalized with oligonucleotides, illustrating the generality of this strategy. By taking advantage of the programmable and specific interactions of DNA, 11 distinct MOF particle-inorganic particle core-satellite clusters were synthesized. In these hybrid nanoclusters, the relative stoichiometry, size, shape, and composition of the building blocks can all be independently controlled. This work provides access to a new set of nucleic acid-nanoparticle conjugates, which may be useful as programmable material building blocks and as probes for measuring and manipulating intracellular processes.

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

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.

XPS and NRA investigations during the fabrication of gold nanostructured functionalized screen-printed sensors for the detection of metallic pollutants

NASA Astrophysics Data System (ADS)

Jasmin, Jean-Philippe; Miserque, Frédéric; Dumas, Eddy; Vickridge, Ian; Ganem, Jean-Jacques; Cannizzo, Caroline; Chaussé, Annie

2017-03-01

An all covalent nanostructured lead sensor was built by the successive grafting of gold nanoparticles and carboxylic ligands at the surface of self-adhesive carbon screen-printed electrodes (SPEs). Surface analysis techniques were used in each step in order to investigate the structuration of this sensor. The self-adhesive surfaces were made from the electrochemical grafting of p-phenylenediamine at the surface of the SPEs via diazonium salts chemistry. The quantity of grafted aniline functions, estimated by Nuclear Reaction Analysis (NRA) performed with p-phenylenediamine labelled with 15N isotope, is in agreement with an almost complete coverage of the electrode surface. The subsequent diazotization of the aniline functions at the surface of the SPEs was performed; X-ray Photoelectron Spectroscopy (XPS) allowed us to consider a quantitative conversion of the aniline functions into diazonium moieties. The spontaneous grafting of gold nanoparticles on the as-obtained reactive surfaces ensures the nanostructuration of the material, and XPS studies showed that the covalent bonding of the gold nanoparticles at the surface of the SPEs induces a change both in the Au-4f (gold nanoparticles) and Cl-2p (carbon ink) core level signals. These unusual observations are explained by an interaction between the carbon ink constituting the substrate and the gold nanoparticles. Heavy and toxic metals are considered of major environmental concern because of their non-biodegradability. In a final step, the grafting of the carboxylic ligands at the surface of the SPEs and an accumulation step in the presence of lead(II) cations allowed us to evidence the interest of nanostructured materials as metallic pollutants sensors.

Biomembrane disruption by silica-core nanoparticles: effect of surface functional group measured using a tethered bilayer lipid membrane

PubMed Central

Liu, Ying; Zhang, Zhen; Zhang, Quanxuan; Baker, Gregory L.; Worden, R. Mark

2013-01-01

Engineered nanomaterials (ENM) have desirable properties that make them well suited for many commercial applications. However, a limited understanding of how ENM’s properties influence their molecular interactions with biomembranes hampers efforts to design ENM that are both safe and effective. This paper describes the use of a tethered bilayer lipid membrane (tBLM) to characterize biomembrane disruption by functionalized silica-core nanoparticles. Electrochemical impedance spectroscopy was used to measure the time trajectory of tBLM resistance following nanoparticle exposure. Statistical analysis of parameters from an exponential resistance decay model was then used to quantify and analyze differences between the impedance profiles of nanoparticles that were unfunctionalized, amine-functionalized, or carboxyl-functionalized. All of the nanoparticles triggered a decrease in membrane resistance, indicating nanoparticle-induced disruption of the tBLM. Hierarchical clustering allowed the potency of nanoparticles for reducing tBLM resistance to be ranked in the order amine > carboxyl ~ bare silica. Dynamic light scattering analysis revealed that tBLM exposure triggered minor coalescence for bare and amine-functionalized silica nanoparticles but not for carboxyl-functionalized silica nanoparticles. These results indicate that the tBLM method can reproducibly characterize ENM-induced biomembrane disruption and can distinguish the BLM-disruption patterns of nanoparticles that are identical except for their surface functional groups. The method provides insight into mechanisms of molecular interaction involving biomembranes and is suitable for miniaturization and automation for high-throughput applications to help assess the health risk of nanomaterial exposure or identify ENM having a desired mode of interaction with biomembranes. PMID:24060565

Covalent immobilization of molecularly imprinted polymer nanoparticles using an epoxy silane.

PubMed

Kamra, Tripta; Chaudhary, Shilpi; Xu, Changgang; Johansson, Niclas; Montelius, Lars; Schnadt, Joachim; Ye, Lei

2015-05-01

Molecularly imprinted polymers (MIPs) can be used as antibody mimics to develop robust chemical sensors. One challenging problem in using MIPs for sensor development is the lack of reliable conjugation chemistry that allows MIPs to be fixed on transducer surface. In this work, we study the use of epoxy silane to immobilize MIP nanoparticles on model transducer surfaces without impairing the function of the immobilized nanoparticles. The MIP nanoparticles with a core-shell structure have selective molecular binding sites in the core and multiple amino groups in the shell. The model transducer surface is functionalized with a self-assembled monolayer of epoxy silane, which reacts with the core-shell MIP particles to enable straightforward immobilization. The whole process is characterized by studying the treated surfaces after each preparation step using atomic force microscopy, scanning electron microscopy, fluorescence microscopy, contact angle measurements and X-ray photoelectron spectroscopy. The microscopy results show that the MIP particles are immobilized uniformly on surface. The photoelectron spectroscopy results further confirm the action of each functionalization step. The molecular selectivity of the MIP-functionalized surface is verified by radioligand binding analysis. The particle immobilization approach described here has a general applicability for constructing selective chemical sensors in different formats. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Electrokinetic pump

DOEpatents

Patel, Kamlesh D.

2007-11-20

A method for altering the surface properties of a particle bed. In application, the method pertains particularly to an electrokinetic pump configuration where nanoparticles are bonded to the surface of the stationary phase to alter the surface properties of the stationary phase including the surface area and/or the zeta potential and thus improve the efficiency and operating range of these pumps. By functionalizing the nanoparticles to change the zeta potential the electrokinetic pump is rendered capable of operating with working fluids having pH values that can range from 2-10 generally and acidic working fluids in particular. For applications in which the pump is intended to handle highly acidic solutions latex nanoparticles that are quaternary amine functionalized can be used.

Non-specific cellular uptake of surface-functionalized quantum dots

NASA Astrophysics Data System (ADS)

Kelf, T. A.; Sreenivasan, V. K. A.; Sun, J.; Kim, E. J.; Goldys, E. M.; Zvyagin, A. V.

2010-07-01

We report a systematic empirical study of nanoparticle internalization into cells via non-specific pathways. The nanoparticles were comprised of commercial quantum dots (QDs) that were highly visible under a fluorescence confocal microscope. Surface-modified QDs with basic biologically significant moieties, e.g. carboxyl, amino, and streptavidin, were used, in combination with surface derivatization with polyethylene glycol (PEG) for a range of immortalized cell lines. Internalization rates were derived from image analysis and a detailed discussion about the effect of nanoparticle size, charge and surface groups is presented. We find that PEG derivatization dramatically suppresses the non-specific uptake while PEG-free carboxyl and amine functional groups promote QD internalization. These uptake variations displayed a remarkable consistency across different cell types. The reported results are important for experiments concerned with cellular uptake of surface-functionalized nanomaterials, both when non-specific internalization is undesirable and when it is intended for material to be internalized as efficiently as possible.

Functionalized ZnO Nanoparticles with Gallic Acid for Antioxidant and Antibacterial Activity against Methicillin-Resistant S. aureus

PubMed Central

Lee, Joo Min; Choi, Kyong-Hoon; Min, Jeeeun; Kim, Ho-Joong; Jee, Jun-Pil; Park, Bong Joo

2017-01-01

In this study, we report a new multifunctional nanoparticle with antioxidative and antibacterial activities in vitro. ZnO@GA nanoparticles were fabricated by coordinated covalent bonding of the antioxidant gallic acid (GA) on the surface of ZnO nanoparticles. This addition imparts both antioxidant activity and high affinity for the bacterial cell membrane. Antioxidative activities at various concentrations were evaluated using a 2,2′-azino-bis(ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging method. Antibacterial activities were evaluated against Gram-positive bacteria (Staphylococcus aureus: S. aureus), including several strains of methicillin-resistant S. aureus (MRSA), and Gram-negative bacteria (Escherichia coli). The functionalized ZnO@GA nanoparticles showed good antioxidative activity (69.71%), and the bactericidal activity of these nanoparticles was also increased compared to that of non-functionalized ZnO nanoparticles, with particularly effective inhibition and high selectivity for MRSA strains. The results indicate that multifunctional ZnO nanoparticles conjugated to GA molecules via a simple surface modification process displaying both antioxidant and antibacterial activity, suggesting a possibility to use it as an antibacterial agent for removing MRSA. PMID:29099064

Density functional theoretical modeling, electrostatic surface potential and surface enhanced Raman spectroscopic studies on biosynthesized silver nanoparticles: observation of 400 PM sensitivity to explosives.

PubMed

Sil, Sanchita; Chaturvedi, Deepika; Krishnappa, Keerthi B; Kumar, Srividya; Asthana, S N; Umapathy, Siva

2014-04-24

Interaction of adsorbate on charged surfaces, orientation of the analyte on the surface, and surface enhancement aspects have been studied. These aspects have been explored in details to explain the surface-enhanced Raman spectroscopic (SERS) spectra of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW or CL-20), a well-known explosive, and 2,4,6-trinitrotoluene (TNT) using one-pot synthesis of silver nanoparticles via biosynthetic route using natural precursor extracts of clove and pepper. The biosynthesized silver nanoparticles (bio Ag Nps) have been characterized using UV-vis spectroscopy, scanning electron microscopy and atomic force microscopy. SERS studies conducted using bio Ag Nps on different water insoluble analytes, such as CL-20 and TNT, lead to SERS signals at concentration levels of 400 pM. The experimental findings have been corroborated with density functional computational results, electrostatic surface potential calculations, Fukui functions and ζ potential measurements.

Iron oxide nanoparticles stabilized with dendritic polyglycerols as selective MRI contrast agents

NASA Astrophysics Data System (ADS)

Nordmeyer, Daniel; Stumpf, Patrick; Gröger, Dominic; Hofmann, Andreas; Enders, Sven; Riese, Sebastian B.; Dernedde, Jens; Taupitz, Matthias; Rauch, Ursula; Haag, Rainer; Rühl, Eckart; Graf, Christina

2014-07-01

Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 +/- 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI.Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 +/- 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI. Electronic supplementary information (ESI) available: A detailed description of the synthesis of the ligands as well as the preparation and functionalization of the iron oxide nanoparticles including their physico-chemical characterization are presented. Further, details of the cell experiments and the SPR experiments are given. Two representative movies are provided showing leukocyte rolling on the ligand coated surface of the flow chamber. See DOI: 10.1039/c3nr04793h

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.

Recent advances in chemical functionalization of nanoparticles with biomolecules for analytical applications.

PubMed

Oh, Ju-Hwan; Park, Do Hyun; Joo, Jang Ho; Lee, Jae-Seung

2015-11-01

The recent synthetic development of a variety of nanoparticles has led to their widespread application in diagnostics and therapeutics. In particular, the controlled size and shape of nanoparticles precisely determine their unique chemical and physical properties, which is highly attractive for accurate analysis of given systems. In addition to efforts toward controlling the synthesis and properties of nanoparticles, the surface functionalization of nanoparticles with biomolecules has been intensively investigated since the mid-1990s. The complicated yet programmable properties of biomolecules have proved to substantially enhance and enrich the novel functions of nanoparticles to achieve "smart" nanoparticle materials. In this review, the advances in chemical functionalization of four types of representative nanoparticle with DNA and protein molecules in the past five years are critically reviewed, and their future trends are predicted.

Surface functionalization of PLGA nanoparticles by non-covalent insertion of a homo-bifunctional spacer for active targeting in cancer therapy.

PubMed

Thamake, S I; Raut, S L; Ranjan, A P; Gryczynski, Z; Vishwanatha, J K

2011-01-21

This work reports the surface functionalization of polymeric PLGA nanoparticles by non-covalent insertion of a homo-bifunctional chemical crosslinker, bis(sulfosuccinimidyl) suberate (BS3) for targeted cancer therapy. We dissolved BS3 in aqueous solution of PVA during formulation of nanoparticles by a modified solid/oil/water emulsion solvent evaporation method. The non-covalent insertion of BS3 was confirmed by Fourier transform infrared (FTIR) spectroscopy. Curcumin and annexin A2 were used as a model drug and a cell specific target, respectively. Nanoparticles were characterized for particle size, zeta potential and surface morphology. The qualitative assessment of antibody attachment was performed by transmission electron microscopy (TEM) as well as confocal microscopy. The optimized formulation showed antibody attachment of 86%. However, antibody attachment was abolished upon blocking the functional groups of BS3. The availability of functional antibodies was evaluated by the presence of a light chain fraction after gel electrophoresis. We further evaluated the in vitro release kinetics of curcumin from antibody coated and uncoated nanoparticles. The release of curcumin is enhanced upon antibody attachment and followed an anomalous release pattern. We also observed that the cellular uptake of nanoparticles was significantly higher in annexin A2 positive cells than in negative cells. Therefore, these results demonstrate the potential use of this method for functionalization as well as to deliver chemotherapeutic agents for treating cancer.

Surface functionalization of PLGA nanoparticles by non-covalent insertion of a homo-bifunctional spacer for active targeting in cancer therapy

NASA Astrophysics Data System (ADS)

Thamake, S. I.; Raut, S. L.; Ranjan, A. P.; Gryczynski, Z.; Vishwanatha, J. K.

2011-01-01

This work reports the surface functionalization of polymeric PLGA nanoparticles by non-covalent insertion of a homo-bifunctional chemical crosslinker, bis(sulfosuccinimidyl) suberate (BS3) for targeted cancer therapy. We dissolved BS3 in aqueous solution of PVA during formulation of nanoparticles by a modified solid/oil/water emulsion solvent evaporation method. The non-covalent insertion of BS3 was confirmed by Fourier transform infrared (FTIR) spectroscopy. Curcumin and annexin A2 were used as a model drug and a cell specific target, respectively. Nanoparticles were characterized for particle size, zeta potential and surface morphology. The qualitative assessment of antibody attachment was performed by transmission electron microscopy (TEM) as well as confocal microscopy. The optimized formulation showed antibody attachment of 86%. However, antibody attachment was abolished upon blocking the functional groups of BS3. The availability of functional antibodies was evaluated by the presence of a light chain fraction after gel electrophoresis. We further evaluated the in vitro release kinetics of curcumin from antibody coated and uncoated nanoparticles. The release of curcumin is enhanced upon antibody attachment and followed an anomalous release pattern. We also observed that the cellular uptake of nanoparticles was significantly higher in annexin A2 positive cells than in negative cells. Therefore, these results demonstrate the potential use of this method for functionalization as well as to deliver chemotherapeutic agents for treating cancer.

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.

Polarized Optical Scattering Measurements of Metallic Nanoparticles on a Thin Film Silicon Wafer

NASA Astrophysics Data System (ADS)

Liu, Cheng-Yang; Liu, Tze-An; Fu, Wei-En

2009-09-01

Light scattering has shown its powerful diagnostic capability to characterize optical quality surfaces. In this study, the theory of bidirectional reflectance distribution function (BRDF) was used to analyze the metallic nanoparticles' sizes on wafer surfaces. The BRDF of a surface is defined as the angular distribution of radiance scattered by the surface normalized by the irradiance incident on the surface. A goniometric optical scatter instrument has been developed to perform the BRDF measurements on polarized light scattering on wafer surfaces for the diameter and distribution measurements of metallic nanoparticles. The designed optical scatter instrument is capable of distinguishing various types of optical scattering characteristics, which are corresponding to the diameters of the metallic nanoparticles, near surfaces by using the Mueller matrix calculation. The metallic nanoparticle diameter of measurement is 60 nm on 2 inch thin film wafers. These measurement results demonstrate that the polarization of light scattered by metallic particles can be used to determine the size of metallic nanoparticles on silicon wafers.

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

Lattice-patterned LC-polymer composites containing various nanoparticles as additives

PubMed Central

2012-01-01

In this study, we show the effect of various nanoparticle additives on phase separation behavior of a lattice-patterned liquid crystal [LC]-polymer composite system and on interfacial properties between the LC and polymer. Lattice-patterned LC-polymer composites were fabricated by exposing to UV light a mixture of a prepolymer, an LC, and SiO2 nanoparticles positioned under a patterned photomask. This resulted in the formation of an LC and prepolymer region through phase separation. We found that the incorporation of SiO2 nanoparticles significantly affected the electro-optical properties of the lattice-patterned LC-polymer composites. This effect is a fundamental characteristic of flexible displays. The electro-optical properties depend on the size and surface functional groups of the SiO2 nanoparticles. Compared with untreated pristine SiO2 nanoparticles, which adversely affect the performance of LC molecules surrounded by polymer walls, SiO2 nanoparticles with surface functional groups were found to improve the electro-optical properties of the lattice-patterned LC-polymer composites by increasing the quantity of SiO2 nanoparticles. The surface functional groups of the SiO2 nanoparticles were closely related to the distribution of SiO2 nanoparticles in the LC-polymer composites, and they influenced the electro-optical properties of the LC molecules. It is clear from our work that the introduction of nanoparticles into a lattice-patterned LC-polymer composite provides a method for controlling and improving the composite's electro-optical properties. This technique can be used to produce flexible substrates for various flexible electronic devices. PMID:22222011

In situ reduction of antibacterial silver ions to metallic silver nanoparticles on bioactive glasses functionalized with polyphenols

NASA Astrophysics Data System (ADS)

Ferraris, S.; Miola, M.; Cochis, A.; Azzimonti, B.; Rimondini, L.; Prenesti, E.; Vernè, E.

2017-02-01

The realization of surfaces with antibacterial properties due to silver nanoparticles loaded through a green approach is a promising research challenge of the biomaterial field. In this research work, two bioactive glasses have been doubly surface functionalized with polyphenols (gallic acid or natural polyphenols extracted from red grape skins and green tea leaves) and silver nanoparticles deposited by in situ reduction from a silver nitrate aqueous solution. The presence of biomolecules - showing reducing ability to directly obtain in situ metallic silver - and silver nanoparticles was investigated by means of UV-vis spectroscopy, X-Ray Photoelectron Spectroscopy (XPS) and Field Emission Scanning Electron Microscopy (FESEM). The antibacterial activity of the modified surfaces was tested against a multidrug resistant Staphylococcus aureus bacterial strain.

High efficiency protein separation with organosilane assembled silica coated magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Chang, Jeong Ho; Kang, Ki Ho; Choi, Jinsub; Jeong, Young Keun

2008-10-01

This work describes the development of high efficiency protein separation with functionalized organosilanes on the surface of silica coated magnetic nanoparticles. The magnetic nanoparticles were synthesized with average particle size of 9 nm and silica coated magnetic nanoparticles were obtained by controlling the coating thicknesses on magnetic nanoparticles. The silica coating thickness could be uniformly sized with a diameter of 10-40 nm by a sol-gel approach. The surface modification was performed with four kinds of functionalized organosilanes such as carboxyl, aldehyde, amine, and thiol groups. The protein separation work with organosilane assembled silica coated magnetic nanoparticles was achieved for model proteins such as bovine serum albumin (BSA) and lysozyme (LSZ) at different pH conditions. Among the various functionalities, the thiol group showed good separation efficiency due to the change of electrostatic interactions and protein conformational structure. The adsorption efficiency of BSA and LSZ was up to 74% and 90% corresponding pH 4.65 and pH 11.

Protein-functionalized magnetic iron oxide nanoparticles: time efficient potential-water treatment

NASA Astrophysics Data System (ADS)

Okoli, Chuka; Boutonnet, Magali; Järås, Sven; Rajarao-Kuttuva, Gunaratna

2012-10-01

Recent advances in nanoscience suggest that the existing issues involving water quality could be resolved or greatly improved using nanomaterials, especially magnetic iron oxide nanoparticles. Magnetic nanoparticles have been synthesized for the development and use, in association with natural coagulant protein for water treatment. The nanoparticles size, morphology, structure, and magnetic properties were characterized by transmission electron microscope, X-ray diffraction, and superconducting quantum interference device magnetometry. Purified Moringa oleifera protein was attached onto microemulsions-prepared magnetic iron oxide nanoparticles (ME-MION) to form stable protein-functionalized magnetic nanoparticles (PMO+ME-MION). The turbidity removal efficiency in both synthetic and surface water samples were investigated and compared with the commonly used synthetic coagulant (alum) as well as PMO. More than 90 % turbidity could be removed from the surface waters within 12 min by magnetic separation of PMO+ME-MION; whereas gravimetrically, 70 % removal in high and low turbid waters can be achieved within 60 min. In contrast, alum requires 180 min to reduce the turbidity of low turbid water sample. These data support the advantage of separation with external magnetic field (magnetophoresis) over gravitational force. Time kinetics studies show a significant enhancement in ME-MION efficiency after binding with PMO implying the availability of large surface of the ME-MION. The coagulated particles (impurities) can be removed from PMO+ME-MION by washing with mild detergent or cleaning solution. To our knowledge, this is the first report on surface water turbidity removal using protein-functionalized magnetic nanoparticle.

In vitro cytotoxicity of iron oxide nanoparticles: effects of chitosan and polyvinyl alcohol as stabilizing agents

NASA Astrophysics Data System (ADS)

Tran, Phong A.; Nguyen, Hiep T.; Fox, Kate; Tran, Nhiem

2018-03-01

Iron oxide magnetic nanoparticles have significant potential in biomedical applications such as in diagnosis, imaging and therapeutic agent delivery. The choice of stabilizers and surface functionalization is important as it is known to strongly influence the cytotoxicity of the nanoparticles. The present study aimed at investigating the effects of surface charges on the cytotoxicity of iron oxide nanoparticles. We used a co-precipitation method to synthesize iron oxide nanoparticles which were then stabilized with either chitosan (CS) or polyvinyl alcohol (PVA) which have net positive charge and zero charge at physiological pH, respectively. The nanoparticles were characterized in terms of size, charges and chemical oxidation state. Cytotoxicity of the nanoparticles was assessed using mouse fibroblast cells and was correlated with surface charges of the nanoparticles and their aggregation.

Aging and behavior of functional TiO2 nanoparticles in aqueous environment.

PubMed

Lu, Huiting; Dong, Haifeng; Fan, Wenhong; Zuo, Jinxing; Li, Xiaomin

2017-03-05

Nanoparticles are usually functionalized with various surface capping moieties in practical applications. Understand the behavior and fate of them is critical to evaluate or even predict their risk to environment. However, little attention has been denoted on this issue until now. Using three commercial TiO 2 nanoparticles with different capping moieties, their aging procedures and corresponding change as well as their byproducts were systematically studied. Comprehensive microscopic and spectrometric measurements demonstrated a capping agent-dependent with the aging procedure. All the aging agents exhibited sharp change in morphologies compared to the fresh counterparts. The degraded degree and surface properties including surface charge and hydrophobicity of the functional TiO 2 nanoparticles were varied depended on the capping moieties. Furthermore, the behaviors of these byproducts in various background media had also been investigated. Contrastively, environment factors such as pH, electrolyte valence, and humic acid regardless of capping moieties govern the behavior of these byproducts, despite of the capping moieties slightly affect the point of zero charge. This study highlights the influence of the capping moieties and environmental factors to the transformation progress of functional nanomaterials in environment exposure, which contributes to design and assess the environmental risk of other analogous functional nanoparticles in practical application. Copyright © 2016 Elsevier B.V. All rights reserved.

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 cellular ROS and apoptosis that was attributed to lysosomal disruption since the surface functionalization selected inhibited the Fenton-like surface chemistry. To overcome this surface inhibition, a biodegradable poly(beta-amino ester) (PBAE) polymer coating was synthesized to deliver bare iron oxide to intracellular components. Delivering enhanced ROS to cancer cells is a promising new route of therapy that deserves future studies.

Surface water retardation around single-chain polymeric nanoparticles: critical for catalytic function?

PubMed

Stals, Patrick J M; Cheng, Chi-Yuan; van Beek, Lotte; Wauters, Annelies C; Palmans, Anja R A; Han, Songi; Meijer, E W

2016-03-01

A library of water-soluble dynamic single-chain polymeric nanoparticles (SCPN) was prepared using a controlled radical polymerisation technique followed by the introduction of functional groups, including probes at targeted positions. The combined tools of electron paramagnetic resonance (EPR) and Overhauser dynamic nuclear polarization (ODNP) reveal that these SCPNs have structural and surface hydration properties resembling that of enzymes.

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.

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.

Towards potential nanoparticle contrast agents: Synthesis of new functionalized PEG bisphosphonates.

PubMed

Kachbi-Khelfallah, Souad; Monteil, Maelle; Cortes-Clerget, Margery; Migianu-Griffoni, Evelyne; Pirat, Jean-Luc; Gager, Olivier; Deschamp, Julia; Lecouvey, Marc

2016-01-01

The use of nanotechnologies for biomedical applications took a real development during these last years. To allow an effective targeting for biomedical imaging applications, the adsorption of plasmatic proteins on the surface of nanoparticles must be prevented to reduce the hepatic capture and increase the plasmatic time life. In biologic media, metal oxide nanoparticles are not stable and must be coated by biocompatible organic ligands. The use of phosphonate ligands to modify the nanoparticle surface drew a lot of attention in the last years for the design of highly functional hybrid materials. Here, we report a methodology to synthesize bisphosphonates having functionalized PEG side chains with different lengths. The key step is a procedure developed in our laboratory to introduce the bisphosphonate from acyl chloride and tris(trimethylsilyl)phosphite in one step.

DNA-length-dependent quenching of fluorescently labeled iron oxide nanoparticles with gold, graphene oxide and MoS2 nanostructures.

PubMed

Balcioglu, Mustafa; Rana, Muhit; Robertson, Neil; Yigit, Mehmet V

2014-08-13

We controlled the fluorescence emission of a fluorescently labeled iron oxide nanoparticle using three different nanomaterials with ultraefficient quenching capabilities. The control over the fluorescence emission was investigated via spacing introduced by the surface-functionalized single-stranded DNA molecules. DNA molecules were conjugated on different templates, either on the surface of the fluorescently labeled iron oxide nanoparticles or gold and nanographene oxide. The efficiency of the quenching was determined and compared with various fluorescently labeled iron oxide nanoparticle and nanoquencher combinations using DNA molecules with three different lengths. We have found that the template for DNA conjugation plays significant role on quenching the fluorescence emission of the fluorescently labeled iron oxide nanoparticles. We have observed that the size of the DNA controls the quenching efficiency when conjugated only on the fluorescently labeled iron oxide nanoparticles by setting a spacer between the surfaces and resulting change in the hydrodynamic size. The quenching efficiency with 12mer, 23mer and 36mer oligonucleotides decreased to 56%, 54% and 53% with gold nanoparticles, 58%, 38% and 32% with nanographene oxide, 46%, 38% and 35% with MoS2, respectively. On the other hand, the presence, not the size, of the DNA molecules on the other surfaces quenched the fluorescence significantly with different degrees. To understand the effect of the mobility of the DNA molecules on the nanoparticle surface, DNA molecules were attached to the surface with two different approaches. Covalently immobilized oligonucleotides decreased the quenching efficiency of nanographene oxide and gold nanoparticles to ∼22% and ∼21%, respectively, whereas noncovalently adsorbed oligonucleotides decreased it to ∼25% and ∼55%, respectively. As a result, we have found that each nanoquencher has a powerful quenching capability against a fluorescent nanoparticle, which can be tuned with surface functionalized DNA molecules.

General and Direct Method for Preparing Oligonucleotide-Functionalized Metal–Organic Framework Nanoparticles

PubMed Central

2017-01-01

Metal–organic frameworks (MOFs) are a class of modular, crystalline, and porous materials that hold promise for storage and transport of chemical cargoes. Though MOFs have been studied in bulk forms, ways of deliberately manipulating the external surface functionality of MOF nanoparticles are less developed. A generalizable approach to modify their surfaces would allow one to impart chemical functionality onto the particle surface that is independent of the bulk MOF structure. Moreover, the use of a chemically programmable ligand, such as DNA, would allow for the manipulation of interparticle interactions. Herein, we report a coordination chemistry-based strategy for the surface functionalization of the external metal nodes of MOF nanoparticles with terminal phosphate-modified oligonucleotides. The external surfaces of nine distinct archetypical MOF particles containing four different metal species (Zr, Cr, Fe, and Al) were successfully functionalized with oligonucleotides, illustrating the generality of this strategy. By taking advantage of the programmable and specific interactions of DNA, 11 distinct MOF particle–inorganic particle core–satellite clusters were synthesized. In these hybrid nanoclusters, the relative stoichiometry, size, shape, and composition of the building blocks can all be independently controlled. This work provides access to a new set of nucleic acid–nanoparticle conjugates, which may be useful as programmable material building blocks and as probes for measuring and manipulating intracellular processes. PMID:28718644

Recent progress on magnetic iron oxide nanoparticles: synthesis, surface functional strategies and biomedical applications

PubMed Central

Wu, Wei; Wu, Zhaohui; Yu, Taekyung; Jiang, Changzhong; Kim, Woo-Sik

2015-01-01

This review focuses on the recent development and various strategies in the preparation, microstructure, and magnetic properties of bare and surface functionalized iron oxide nanoparticles (IONPs); their corresponding biological application was also discussed. In order to implement the practical in vivo or in vitro applications, the IONPs must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of IONPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The new functionalized strategies, problems and major challenges, along with the current directions for the synthesis, surface functionalization and bioapplication of IONPs, are considered. Finally, some future trends and the prospects in these research areas are also discussed. PMID:27877761

The toxicity of plastic nanoparticles to green algae as influenced by surface modification, medium hardness and cellular adsorption.

PubMed

Nolte, Tom M; Hartmann, Nanna B; Kleijn, J Mieke; Garnæs, Jørgen; van de Meent, Dik; Jan Hendriks, A; Baun, Anders

2017-02-01

To investigate processes possibly underlying accumulation and ecological effects of plastic nano-particles we have characterized their interaction with the cell wall of green algae. More specifically, we have investigated the influence of particle surface functionality and water hardness (Ca 2+ concentration) on particle adsorption to algae cell walls. Polystyrene nanoparticles with different functional groups (non-functionalized, -COOH and -NH 2 ) as well as coated (starch and PEG) gold nanoparticles were applied in these studies. Depletion measurements and atomic force microscopy (AFM) showed that adsorption of neutral and positively charged plastic nanoparticles onto the cell wall of P. subcapitata was stronger than that of negatively charged plastic particles. Results indicated that binding affinity is a function of both inter-particle and particle-cell wall interactions which are in turn influenced by the medium hardness and particle concentration. Physicochemical modelling using DLVO theory was used to interpret the experimental data, using also values for interfacial surface free energies. Our study shows that material properties and medium conditions play a crucial role in the rate and state of nanoparticle bio-adsorption for green algae. The results show that the toxicity of nanoparticles can be better described and assessed by using appropriate dose metrics including material properties, complexation/agglomeration behavior and cellular attachment and adsorption. The applied methodology provides an efficient and feasible approach for evaluating potential accumulation and hazardous effects of nanoparticles to algae caused by particle interactions with the algae cell walls. Copyright © 2016 Elsevier B.V. All rights reserved.

A technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates.

PubMed

Fontana, Jake; Spillmann, Christopher; Naciri, Jawad; Ratna, Banahalli R

2014-05-09

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface. This drives the ligand-capped nanoparticles to form monolayer domains at the air-fluid interface. The use of water-miscible organic solvents is important as it enables the transport of the nanoparticles from the interface onto template-free substrates. The flow is mediated by a surface tension gradient and creates macroscopic, high-density, monolayer nanoparticle-ligand films. This self-assembly technique may be generalized to include the use of particles of different compositions, size, and shape and may lead to an efficient assembly method to produce low-cost, macroscopic, high-density, monolayer nanoparticle films for wide-spread applications.

In situ spectroscopy of ligand exchange reactions at the surface of colloidal gold and silver nanoparticles

NASA Astrophysics Data System (ADS)

Dinkel, Rebecca; Peukert, Wolfgang; Braunschweig, Björn

2017-04-01

Gold and silver nanoparticles with their tunable optical and electronic properties are of great interest for a wide range of applications. Often the ligands at the surface of the nanoparticles have to be exchanged in a second step after particle formation in order to obtain a desired surface functionalization. For many techniques, this process is not accessible in situ. In this review, we present second-harmonic scattering (SHS) as an inherently surface sensitive and label-free optical technique to probe the ligand exchange at the surface of colloidal gold and silver nanoparticles in situ and in real time. First, a brief introduction to SHS and basic features of the SHS of nanoparticles are given. After that, we demonstrate how the SHS intensity decrease can be correlated to the thiol coverage which allows for the determination of the Gibbs free energy of adsorption and the surface coverage.

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.

Nanoparticles modified with multiple organic acids

NASA Technical Reports Server (NTRS)

Luebben, Silvia DeVito (Inventor); Cook, Ronald Lee (Inventor); Wilson, Carolina (Inventor); Meiser, Manfred (Inventor); Myers, Andrew William (Inventor); Smith, Bryan Matthew (Inventor); Elliott, Brian John (Inventor); Kreutzer, Cory (Inventor)

2007-01-01

Surface-modified nanoparticles of boehmite, and methods for preparing the same. Aluminum oxyhydroxide nanoparticles are surface modified by reaction with selected amounts of organic acids. In particular, the nanoparticle surface is modified by reactions with two or more different carboxylic acids, at least one of which is an organic carboxylic acid. The product is a surface modified boehmite nanoparticle that has an inorganic aluminum oxyhydroxide core, or part aluminum oxyhydroxide core and a surface-bonded organic shell. Organic carboxylic acids of this invention contain at least one carboxylic acid group and one carbon-hydrogen bond. One embodiment of this invention provides boehmite nanoparticles that have been surface modified with two or more acids one of which additional carries at least one reactive functional group. Another embodiment of this invention provides boehmite nanoparticles that have been surface modified with multiple acids one of which has molecular weight or average molecular weight greater than or equal to 500 Daltons. Yet, another embodiment of this invention provides boehmite nanoparticles that are surface modified with two or more acids one of which is hydrophobic in nature and has solubility in water of less than 15 by weight. The products of the methods of this invention have specific useful properties when used in mixture with liquids, as filler in solids, or as stand-alone entities.

Nanoparticles modified with multiple organic acids

DOEpatents

Cook, Ronald Lee [Lakewood, CO; Luebben, Silvia DeVito [Golden, CO; Myers, Andrew William [Arvada, CO; Smith, Bryan Matthew [Boulder, CO; Elliott, Brian John [Superior, CO; Kreutzer, Cory [Brighton, CO; Wilson, Carolina [Arvada, CO; Meiser, Manfred [Aurora, CO

2007-07-17

Surface-modified nanoparticles of boehmite, and methods for preparing the same. Aluminum oxyhydroxide nanoparticles are surface modified by reaction with selected amounts of organic acids. In particular, the nanoparticle surface is modified by reactions with two or more different carboxylic acids, at least one of which is an organic carboxylic acid. The product is a surface modified boehmite nanoparticle that has an inorganic aluminum oxyhydroxide core, or part aluminum oxyhydroxide core and a surface-bonded organic shell. Organic carboxylic acids of this invention contain at least one carboxylic acid group and one carbon-hydrogen bond. One embodiment of this invention provides boehmite nanoparticles that have been surface modified with two or more acids one of which additional carries at least one reactive functional group. Another embodiment of this invention provides boehmite nanoparticles that have been surface modified with multiple acids one of which has molecular weight or average molecular weight greater than or equal to 500 Daltons. Yet, another embodiment of this invention provides boehmite nanoparticles that are surface modified with two or more acids one of which is hydrophobic in nature and has solubility in water of less than 15 by weight. The products of the methods of this invention have specific useful properties when used in mixture with liquids, as filler in solids, or as stand-alone entities.

The electrokinetic characterization of gold nanoparticles, functionalized with cationic functional groups, and its' interaction with DNA.

PubMed

Lazarus, Geraldine Genevive; Revaprasadu, Neerish; López-Viota, Julián; Singh, Moganavelli

2014-09-01

Gold nanoparticles have attracted strong biomedical interest for drug delivery due to their low toxic nature, surface plasmon resonance and capability of increasing the stability of the payload. However, gene transfection represents another important biological application. Considering that cellular barriers keep enclosed their secret to deliver genes using nanoparticles, an important step can be achieved by studying the functionalization of nanoparticles with DNA. In the present contribution the synthesis of nanoparticles consisting of a gold core coated with one or more layers of amino acid (l-lysine), and cationic polyelectrolytes (poly-ethyleneimine and poly-l-lysine) is reported. All nanoparticles were subjected to dynamic light scattering, electrophoretic mobility measurements, UV-vis optical spectrophotometry analysis and transmission electron microscopy imaging. In addition, the adsorption of DNA plasmid (pSGS) with linear and supercoiled configurations was studied for those gold nanoparticles under the most suitable surface modifications. Preliminary results showed that the gold nanoparticles functionalized with poly-ethyleneimine and poly-l-lysine, respectively, and bound to linear DNA configurations, present in absolute value a higher electrophoretic mobility irrespective of the pH of the media, compared to the supercoiled and nicked configuration. The findings from this study suggest that poly-ethyleneimine and poly-l-lysine functionalized gold nanoparticles are biocompatible and may be promising in the chemical design and future optimization of nanostructures for biomedical applications such as gene and drug delivery. Copyright © 2014 Elsevier B.V. All rights reserved.

Silver nanoparticles with tunable work functions

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

Wang, Pangpang, E-mail: pangpang@molecular-device.kyushu-u.ac.jp; Tanaka, Daisuke; Ryuzaki, Sou

To improve the efficiencies of electronic devices, materials with variable work functions are required to decrease the energy level differences at the interfaces between working layers. Here, we report a method to obtain silver nanoparticles with tunable work functions, which have the same silver core of 5 nm in diameter and are capped by myristates and 1-octanethoilates self-assembled monolayers, respectively. The silver nanoparticles capped by organic molecules can form a uniform two-dimensional sheet at air-water interface, and the sheet can be transferred on various hydrophobic substrates. The surface potential of the two-dimensional nanoparticle sheet was measured in terms of Kelvin probemore » force microscopy, and the work function of the sheet was then calculated from the surface potential value by comparing with a reference material. The exchange of the capping molecules results in a work function change of approximately 150–250 meV without affecting their hydrophobicity. We systematically discussed the origin of the work function difference and found it should come mainly from the anchor groups of the ligand molecules. The organic molecule capped nanoparticles with tunable work functions have a potential for the applications in organic electronic devices.« less

Functionalization of surfactant wrapped graphenenanosheets with alkylazides for enhanced dispersibility

NASA Astrophysics Data System (ADS)

Vadukumpully, Sajini; Gupta, Jhinuk; Zhang, Yongping; Xu, Guo Qin; Valiyaveettil, Suresh

2011-01-01

A facile and simple approach for the covalent functionalization of surfactant wrapped graphene sheets is described. The approach involves functionalization of dispersible graphene sheets with various alkylazides and 11-azidoundecanoic acid proved the best azide for enhanced dispersibility. The functionalization was confirmed by infrared spectroscopy and scanning tunneling microscopy. The free carboxylic acidgroups can bind to gold nanoparticles, which were introduced as markers for the reactive sites. The interaction between gold nanoparticles and the graphene sheets was followed by UV-vis spectroscopy. The gold nanoparticle-graphene composite was characterized by transmission electron microscopy and atomic force microscopy, demonstrating the uniform distribution of gold nanoparticles all over the surface. Our results open the possibility to control the functionalization on graphene in the construction of composite nanomaterials.A facile and simple approach for the covalent functionalization of surfactant wrapped graphene sheets is described. The approach involves functionalization of dispersible graphene sheets with various alkylazides and 11-azidoundecanoic acid proved the best azide for enhanced dispersibility. The functionalization was confirmed by infrared spectroscopy and scanning tunneling microscopy. The free carboxylic acidgroups can bind to gold nanoparticles, which were introduced as markers for the reactive sites. The interaction between gold nanoparticles and the graphene sheets was followed by UV-vis spectroscopy. The gold nanoparticle-graphene composite was characterized by transmission electron microscopy and atomic force microscopy, demonstrating the uniform distribution of gold nanoparticles all over the surface. Our results open the possibility to control the functionalization on graphene in the construction of composite nanomaterials. Electronic Supplementary Information (ESI) available: Synthesis and characterization details of dodecylazide, hexylazide, 11-azidoundecanol (AUO), micrographs (SEM and TEM images) of the various azide functionalized samples and the statistical analysis of the graphene thickness. See 10.1039/c0nr00547a.

Nano-functionalization of protein microspheres

NASA Astrophysics Data System (ADS)

Yoon, Sungkwon; Nichols, William T.

2014-08-01

Protein microspheres are promising building blocks for the assembly of complex functional materials. Here we demonstrate a set of three techniques that add functionality to the surface of protein microspheres. In the first technique, a positive surface charge on the protein spheres is deposited by electrostatic adsorption. Negatively charged silica and gold nanoparticle colloids can then electrostatically bind reversibly to the microsphere surface. In the second technique, nanoparticles are covalently anchored to the protein shell using a simple one-pot process. The strong covalent bond between sulfur groups in cysteine in the protein shell irreversibly binds to the gold nanoparticles. In the third technique, surface morphology of the protein microsphere is tuned through hydrodynamic instability at the water-oil interface. This is accomplished through the degree of solubility of the oil phase in water. Taken together these three techniques form a platform to create nano-functionalized protein microspheres, which can then be used as building blocks for the assembly of more complex macroscopic materials.

Surface enhanced Raman spectral studies of 2-bromo-1,4-naphthoquinone.

PubMed

Geetha, K; Umadevi, M; Sathe, G V; Vanelle, P; Terme, T; Khoumeri, O

2015-03-05

Silver nanoparticles have been synthesized by a simple and inexpensive solution combustion method with urea as fuel. The structural and morphology of the silver nanoparticles were investigated through X-ray powder diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) and Energy Dispersion Spectra (EDS) techniques. Structural and morphological results confirmed the nanocrystalline nature of the silver nanoparticles. Density Functional Theory (DFT) calculations were also performed to study the ground and excited state behavior of 2-bromo-1,4-naphthoquinone (2-BrNQ) and 2-BrNQ on silver nanoparticles. Surface-Enhanced Raman Scattering (SERS) spectra of 2-BrNQ adsorbed on silver nanoparticles were investigated. The CO, CH in-plane bending and CBr stretching modes were enhanced in SERS spectrum with respect to normal Raman spectrum. The spectral analysis reveals that the 2-BrNQ adsorbed 'stand-on' orientation on the silver surface. Density Functional Theory (DFT) calculations are also performed to study the vibrational features of 2-BrNQ molecule and 2-BrNQ molecule on silver surface. Copyright © 2014 Elsevier B.V. All rights reserved.

Magnetic imaging of cyanide-bridged co-ordination nanoparticles grafted on FIB-patterned Si substrates.

PubMed

Ghirri, Alberto; Candini, Andrea; Evangelisti, Marco; Gazzadi, Gian Carlo; Volatron, Florence; Fleury, Benoit; Catala, Laure; David, Christophe; Mallah, Talal; Affronte, Marco

2008-12-01

Prussian blue CsNiCr nanoparticles are used to decorate selected portions of a Si substrate. For successful grafting to take place, the Si surface needs first to be chemically functionalized. Low-dose focused ion beam patterning on uniformly functionalized surfaces selects those portions that will not participate in the grafting process. Step-by-step control is assured by atomic force and high-resolution scanning electron microscopy, revealing a submonolayer distribution of the grafted nanoparticles. By novel scanning Hall-probe microscopy, an in-depth investigation of the magnetic response of the nanoparticles to varying temperature and applied magnetic field is provided. The magnetic images acquired suggest that low-temperature canted ferromagnetism is found in the grafted nanoparticles, similar to what is observed in the equivalent bulk material.

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.

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.

Synthesis and Characterization of Superhydrophobic, Self-cleaning NIR-reflective Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Sriramulu, Deepa; Reed, Ella Louise; Annamalai, Meenakshi; Venkatesan, Thirumalai Venky; Valiyaveettil, Suresh

2016-11-01

Multifunctional coatings offer many advantages towards protecting various surfaces. Here we apply aggregation induced segregation of perylene diimide (PDI) to control the surface morphology and properties of silica nanoparticles. Differentially functionalized PDI was incorporated on the surface of silica nanoparticles through Si-O-Si bonds. The absorption and emission spectra of the resultant functionalised nanoparticles showed monomeric or excimeric peaks based on the amounts of perylene molecules present on the surface of silica nanoparticles. Contact angle measurements on thin films prepared from nanoparticles showed that unfunctionalised nanoparticles were superhydrophilic with a contact angle (CA) of 0°, whereas perylene functionalised silica particles were hydrophobic (CA > 130°) and nanoparticles functionalised with PDI and trimethoxy(octadecyl)silane (TMODS) in an equimolar ratio were superhydrophobic with static CA > 150° and sliding angle (SA) < 10°. In addition, the near infrared (NIR) reflectance properties of PDI incorporated silica nanoparticles can be used to protect various heat sensitive substrates. The concept developed in this paper offers a unique combination of super hydrophobicity, interesting optical properties and NIR reflectance in nanosilica, which could be used for interesting applications such as surface coatings with self-cleaning and NIR reflection properties.

Plasmonic properties and enhanced fluorescence of gold and dye-doped silica nanoparticle aggregates

NASA Astrophysics Data System (ADS)

Green, Nathaniel Scott

The development of metal-enhanced fluorescence has prompted a great interest in augmenting the photophysical properties of fluorescent molecules with noble metal nanostructures. Our research efforts, outlined in this dissertation, focus on augmenting properties of fluorophores by conjugation with gold nanostructures. The project goals are split into two separate efforts; the enhancement in brightness of fluorophores and long distance non-radiative energy transfer between fluorophores. We believe that interacting dye-doped silica nanoparticles with gold nanoparticles can facilitate both of these phenomena. Our primary research interest is focused on optimizing brightness, as this goal should open a path to studying the second goal of non-radiative energy transfer. The two major challenges to this are constructing suitable nanomaterials and functionalizing them to promote plasmonically active complexes. The synthesis of dye-doped layered silica nanoparticles allows for control over the discrete location of the dye and a substrate that can be surface functionalized. Controlling the exact location of the dye is important to create a silica spacer, which promotes productive interactions with metal nanostructures. Furthermore, the synthesis of silica nanoparticles allows for various fluorophores to be studied in similar environments (removing solvent and other chemo-sensitive issues). Functionalizing the surface of silica nanoparticles allows control over the degree of silica and gold nanoparticle aggregation in solution. Heteroaggregation in solution is useful for producing well-aggregated clusters of many gold around a single silica nanoparticle. The dye-doped surface functionalized silica nanoparticles can than be mixed efficiently with gold nanomaterials. Aggregating multiple gold nanospheres around a single dye-doped silica nanoparticle can dramatically increase the fluorescent brightness of the sample via metal-enhanced fluorescence due to increase plasmonic scattering. Our aim is to promote heteroaggregation with functionalized silica nanoparticles while minimizing homoaggregation of silica-silica or gold-gold species. Reproducible production of multiple gold nanospheres about a dye-doped silica nanoparticle should lead to dramatic fluorescence brightness enhancements in solution. Gold nanorods can potentially be used to establish radiationless energy transfer between hetero dye-doped silica nanoparticles via gold nanorod plasmon mediated FRET by aggregating two different dye-doped silica nanoparticles preferentially at opposite ends of the nanorod. End-cap binding is accomplished by tuning the strength of gold binding ligands that functionalize the surface of the silica nanoparticles. The gold nanorod can then theoretically serve as a waveguide by employing the longitudinal plasmon as a non-radiative energy transfer agent between the two different fluorophores, giving rise to a new ultrafast signaling paradigm. Heteroaggregation of dye-doped silica nanoparticles and gold nanorods can be potentially employed to as nano waveguides. Construction and aggregation of functionalized silica and gold nano-materials provides an opportunity to advance the field of fluorescence. The synthesis of gold nano-particles allows control over their size and shape, which give rise to useful optical and electronic properties. Silica nanoparticles provide a framework allowing control over a requisite distance for increasing beneficial and deceasing non-radiative dye-metal interactions as well fluorophore protection. Our aim is to take advantage of fine-tuned synthetic control of functionalized nanomaterials to realize the great potential of solution based metal-enhanced fluorescence for future applications.

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.

Bare laser-synthesized Si nanoparticles as functional elements for chitosan nanofiber-based tissue engineering platforms

NASA Astrophysics Data System (ADS)

Popov, Anton A.; Al-Kattan, Ahmed; Nirwan, Viraj P.; Munnier, Emilie; Tselikov, Gleb I.; Ryabchikov, Yury V.; Chourpa, Igor; Fahmi, Amir; Kabashin, A. V.

2018-02-01

Methods of femtosecond laser ablation were used to fabricate bare (ligand-free) silicon (Si) nanoparticles in deionized water. The nanoparticles were round in shape, crystalline, free of any impurities, and water-dissolvable, while the dissolution rate depended on the concentration of oxygen defects in their composition. The nanoparticles were then eletrospun with chitosan to form nanoparticle decorated nanofibrous matrices. We found that the functionalization of nanofibers by the nanoparticles can affect the morphology and physico-chemical characteristics of resulting nanostructures. In particular, the presence of Si nanoparticles led to the reduction of fibers thickness, suggesting a potential improvement of fiber's surface reactivity. We also observed the improvement of thermal stability of hybrid nanofibers. We believe that the incorporated Si nanoparticles can serve as functional elements to improve characteristics of chitosan-based matrices for cellular growth, as well as to enable novel imaging or therapeutic functionalities for tissue engineering applications.

Forces between functionalized silica nanoparticles in solution

NASA Astrophysics Data System (ADS)

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

2009-05-01

To prevent the flocculation and phase separation of nanoparticles in solution, nanoparticles are often functionalized with short chain surfactants. Here we present fully atomistic molecular dynamics simulations which characterize how these functional coatings affect the interactions between nanoparticles and with the surrounding solvent. For 5-nm-diameter silica nanoparticles coated with poly(ethylene oxide) (PEO) oligomers in water, we determined the hydrodynamic drag on two approaching nanoparticles moving through solvent and on a single nanoparticle as it approaches a planar surface. In most circumstances, macroscale fluid theory accurately predicts the drag on these nanoscale particles. Good agreement is seen with Brenner’s analytical solutions for wall separations larger than the soft nanoparticle radius. For two approaching coated nanoparticles, the solvent-mediated (velocity independent) and lubrication (velocity-dependent) forces are purely repulsive and do not exhibit force oscillations that are typical of uncoated rigid spheres.

Metagenomic analysis of microbial communities yields insight into impacts of nanoparticle design

NASA Astrophysics Data System (ADS)

Metch, Jacob W.; Burrows, Nathan D.; Murphy, Catherine J.; Pruden, Amy; Vikesland, Peter J.

2018-01-01

Next-generation DNA sequencing and metagenomic analysis provide powerful tools for the environmentally friendly design of nanoparticles. Herein we demonstrate this approach using a model community of environmental microbes (that is, wastewater-activated sludge) dosed with gold nanoparticles of varying surface coatings and morphologies. Metagenomic analysis was highly sensitive in detecting the microbial community response to gold nanospheres and nanorods with either cetyltrimethylammonium bromide or polyacrylic acid surface coatings. We observed that the gold-nanoparticle morphology imposes a stronger force in shaping the microbial community structure than does the surface coating. Trends were consistent in terms of the compositions of both taxonomic and functional genes, which include antibiotic resistance genes, metal resistance genes and gene-transfer elements associated with cell stress that are relevant to public health. Given that nanoparticle morphology remained constant, the potential influence of gold dissolution was minimal. Surface coating governed the nanoparticle partitioning between the bioparticulate and aqueous phases.

Synthesis of amino-silane modified superparamagnetic Fe{sub 3}O{sub 4} nanoparticles and its application in immobilization of lipase from Pseudomonas fluorescens Lp1

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

Kanimozhi, S., E-mail: skanimo@gmail.com; Perinbam, K.

2013-05-15

Highlights: ► Magnetic nanoparticles were synthesized by chemical co-precipitation method. ► Surface was functionalized with amino-silane and used for lipase immobilization. ► Characterized through TEM, SEM, XRD, FT-IR and VSM analysis. ► The functionalization and immobilization did not affect the magnetite properties. ► The immobilized lipase showed greater functional property than free lipase. - Abstract: Superparamagnetic nanoparticles (Fe{sub 3}O{sub 4}–magnetite) were prepared by chemical co-precipitation method and their surface was functionalized with 3-aminopropyltriethoxysilane via silanization reaction to obtain amino functionalized magnetic nanoparticles. The purified lipase from Pseudomonas fluorescens Lp1 was immobilized onto functionalized magnetite using glutaraldehyde as the coupling agent.more » The characterization of the nanoparticles was done by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, vibrating sample magnetometry and Fourier transformed infrared spectroscopy. The size of the magnetite was measured about 10–30 nm. The results of characterization study revealed the successful immobilization of lipase on to functionalized magnetite. The saturation magnetization of magnetic nanoparticles was found to be 28.34 emu/g whereas the immobilized magnetic nanoparticle was 17.074 emu/g. The immobilized lipase had greater activity at 50 °C and thermal stability upto 70 °C. It exhibited excellent reusability for 4 cycles and storage stability upto 15 days by retaining 75% of its initial activity.« less

Immunogold Nanoparticles for Rapid Plasmonic Detection of C. sakazakii.

PubMed

Aly, Mohamed A; Domig, Konrad J; Kneifel, Wolfgang; Reimhult, Erik

2018-06-25

Cronobacter sakazakii is a foodborne pathogen that can cause a rare, septicemia, life-threatening meningitis, and necrotizing enterocolitis in infants. In general, standard methods for pathogen detection rely on culture, plating, colony counting and polymerase chain reaction DNA-sequencing for identification, which are time, equipment and skill demanding. Recently, nanoparticle- and surface-based immunoassays have increasingly been explored for pathogen detection. We investigate the functionalization of gold nanoparticles optimized for irreversible and specific binding to C. sakazakii and their use for spectroscopic detection of the pathogen. We demonstrate how 40-nm gold nanoparticles grafted with a poly(ethylene glycol) brush and functionalized with polyclonal antibodies raised against C. sakazakii can be used to specifically target C. sakazakii . The strong extinction peak of the Au nanoparticle plasmon polariton resonance in the optical range is used as a label for detection of the pathogens. Individual binding of the nanoparticles to the C. sakazakii surface is also verified by transmission electron microscopy. We show that a high degree of surface functionalization with anti- C. sakazakii optimizes the detection and leads to a detection limit as low as 10 CFU/mL within 2 h using a simple cuvette-based UV-Vis spectrometric readout that has great potential for further optimization.

Incorporating functionalized polyethylene glycol lipids into reprecipitated conjugated polymer nanoparticles for bioconjugation and targeted labeling of cells

NASA Astrophysics Data System (ADS)

Kandel, Prakash K.; Fernando, Lawrence P.; Ackroyd, P. Christine; Christensen, Kenneth A.

2011-03-01

We report a simple and rapid method to prepare extremely bright, functionalized, stable, and biocompatible conjugated polymer nanoparticles incorporating functionalized polyethylene glycol (PEG) lipids by reprecipitation. These nanoparticles retain the fundamental spectroscopic properties of conjugated polymer nanoparticles prepared without PEG lipid, but demonstrate greater hydrophilicity and quantum yield compared to unmodified conjugated polymer nanoparticles. The sizes of these nanoparticles, as determined by TEM, were 21-26 nm. Notably, these nanoparticles were prepared with several PEG lipid functional end groups, including biotin and carboxy moieties that can be easily conjugated to biomolecules. We have demonstrated the availability of these end groups for functionalization using the interaction of biotin PEG lipid conjugated polymer nanoparticles with streptavidin. Biotinylated PEG lipid conjugated polymer nanoparticles bound streptavidin-linked magnetic beads, while carboxy and methoxy PEG lipid modified nanoparticles did not. Similarly, biotinylated PEG lipid conjugated polymer nanoparticles bound streptavidin-coated glass slides and could be visualized as diffraction-limited spots, while nanoparticles without PEG lipid or with non-biotin PEG lipid end groups were not bound. To demonstrate that nanoparticle functionalization could be used for targeted labelling of specific cellular proteins, biotinylated PEG lipid conjugated polymer nanoparticles were bound to biotinylated anti-CD16/32 antibodies on J774A.1 cell surface receptors, using streptavidin as a linker. This work represents the first demonstration of targeted delivery of conjugated polymer nanoparticles and demonstrates the utility of these new nanoparticles for fluorescence based imaging and sensing.We report a simple and rapid method to prepare extremely bright, functionalized, stable, and biocompatible conjugated polymer nanoparticles incorporating functionalized polyethylene glycol (PEG) lipids by reprecipitation. These nanoparticles retain the fundamental spectroscopic properties of conjugated polymer nanoparticles prepared without PEG lipid, but demonstrate greater hydrophilicity and quantum yield compared to unmodified conjugated polymer nanoparticles. The sizes of these nanoparticles, as determined by TEM, were 21-26 nm. Notably, these nanoparticles were prepared with several PEG lipid functional end groups, including biotin and carboxy moieties that can be easily conjugated to biomolecules. We have demonstrated the availability of these end groups for functionalization using the interaction of biotin PEG lipid conjugated polymer nanoparticles with streptavidin. Biotinylated PEG lipid conjugated polymer nanoparticles bound streptavidin-linked magnetic beads, while carboxy and methoxy PEG lipid modified nanoparticles did not. Similarly, biotinylated PEG lipid conjugated polymer nanoparticles bound streptavidin-coated glass slides and could be visualized as diffraction-limited spots, while nanoparticles without PEG lipid or with non-biotin PEG lipid end groups were not bound. To demonstrate that nanoparticle functionalization could be used for targeted labelling of specific cellular proteins, biotinylated PEG lipid conjugated polymer nanoparticles were bound to biotinylated anti-CD16/32 antibodies on J774A.1 cell surface receptors, using streptavidin as a linker. This work represents the first demonstration of targeted delivery of conjugated polymer nanoparticles and demonstrates the utility of these new nanoparticles for fluorescence based imaging and sensing. Electronic supplementary information (ESI) available: Additional TEM data, supplemental light scattering measurements, absorbance and fluorescence emission spectra, and photostability measurements. See DOI: 10.1039/c0nr00746c

Surface Functionalization of Polymeric Nanoparticles with Umbilical Cord-Derived Mesenchymal Stem Cell Membrane for Tumor-Targeted Therapy.

PubMed

Yang, Na; Ding, Yanping; Zhang, Yinlong; Wang, Bin; Zhao, Xiao; Cheng, Keman; Huang, Yixin; Taleb, Mohammad; Zhao, Jing; Dong, Wen-Fei; Zhang, Lirong; Nie, Guangjun

2018-06-15

Multiple cell plasma membranes have been utilized for surface functionalization of synthetic nanomaterials and construction of biomimetic drug delivery systems for cancer treatment. The natural characters and facile isolation of original cells facilitate the biomedical applications of plasma membranes in functionalizing nanocarriers. Human umbilical cord-derived mesenchymal stem cells (MSC) have been identified to show tropism towards malignant lesions and have great advantages in ease of acquisition, low immunogenicity, and high proliferative ability. Here we developed a poly(lactic-co-glycolic acid) (PLGA) nanoparticle with a layer of plasma membrane from umbilical cord MSC coating on the surface for tumor-targeted delivery of chemotherapy. Functionalization of MSC plasma membrane significantly enhanced the cellular uptake efficiency of PLGA nanoparticles, the tumor cell killing efficacy of PLGA-encapsulated doxorubicin, and most importantly the tumor-targeting and accumulation of the nanoparticles. As a result, this MSC-mimicking nanoformulation led to remarkable tumor growth inhibition and induced obvious apoptosis within tumor lesions. This study for the first time demonstrated the great potential of umbilical cord MSC plasma membranes in functionalizing nanocarriers with inherent tumor-homing features, and the high feasibility of such biomimetic nanoformulations in cancer therapy.

Electrochemically induced actuation of liquid metal marbles

NASA Astrophysics Data System (ADS)

Tang, Shi-Yang; Sivan, Vijay; Khoshmanesh, Khashayar; O'Mullane, Anthony P.; Tang, Xinke; Gol, Berrak; Eshtiaghi, Nicky; Lieder, Felix; Petersen, Phred; Mitchell, Arnan; Kalantar-Zadeh, Kourosh

2013-06-01

Controlled actuation of soft objects with functional surfaces in aqueous environments presents opportunities for liquid phase electronics, novel assembled super-structures and unusual mechanical properties. We show the extraordinary electrochemically induced actuation of liquid metal droplets coated with nanoparticles, so-called ``liquid metal marbles''. We demonstrate that nanoparticle coatings of these marbles offer an extra dimension for affecting the bipolar electrochemically induced actuation. The nanoparticles can readily migrate along the surface of liquid metals, upon the application of electric fields, altering the capacitive behaviour and surface tension in a highly asymmetric fashion. Surprising actuation behaviours are observed illustrating that nanoparticle coatings can have a strong effect on the movement of these marbles. This significant novel phenomenon, combined with unique properties of liquid metal marbles, represents an exciting platform for enabling diverse applications that cannot be achieved using rigid metal beads.Controlled actuation of soft objects with functional surfaces in aqueous environments presents opportunities for liquid phase electronics, novel assembled super-structures and unusual mechanical properties. We show the extraordinary electrochemically induced actuation of liquid metal droplets coated with nanoparticles, so-called ``liquid metal marbles''. We demonstrate that nanoparticle coatings of these marbles offer an extra dimension for affecting the bipolar electrochemically induced actuation. The nanoparticles can readily migrate along the surface of liquid metals, upon the application of electric fields, altering the capacitive behaviour and surface tension in a highly asymmetric fashion. Surprising actuation behaviours are observed illustrating that nanoparticle coatings can have a strong effect on the movement of these marbles. This significant novel phenomenon, combined with unique properties of liquid metal marbles, represents an exciting platform for enabling diverse applications that cannot be achieved using rigid metal beads. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00185g

Towards potential nanoparticle contrast agents: Synthesis of new functionalized PEG bisphosphonates

PubMed Central

Kachbi-Khelfallah, Souad; Monteil, Maelle; Cortes-Clerget, Margery; Migianu-Griffoni, Evelyne; Pirat, Jean-Luc; Gager, Olivier; Deschamp, Julia

2016-01-01

Summary The use of nanotechnologies for biomedical applications took a real development during these last years. To allow an effective targeting for biomedical imaging applications, the adsorption of plasmatic proteins on the surface of nanoparticles must be prevented to reduce the hepatic capture and increase the plasmatic time life. In biologic media, metal oxide nanoparticles are not stable and must be coated by biocompatible organic ligands. The use of phosphonate ligands to modify the nanoparticle surface drew a lot of attention in the last years for the design of highly functional hybrid materials. Here, we report a methodology to synthesize bisphosphonates having functionalized PEG side chains with different lengths. The key step is a procedure developed in our laboratory to introduce the bisphosphonate from acyl chloride and tris(trimethylsilyl)phosphite in one step. PMID:27559386

Proton NMR studies of functionalized nanoparticles in aqueous environments

NASA Astrophysics Data System (ADS)

Tataurova, Yulia Nikolaevna

Nanoscience is an emerging field that can provide potential routes towards addressing critical issues such as clean and sustainable energy, environmental remediation and human health. Specifically, porous nanomaterials, such as zeolites and mesoporous silica, are found in a wide range of applications including catalysis, drug delivery, imaging, environmental protection, and sensing. The characterization of the physical and chemical properties of nanocrystalline materials is essential to the realization of these innovative applications. The great advantage of porous nanocrystals is their increased external surface area that can control their biological, chemical and catalytic activities. Specific functional groups synthesized on the surface of nanoparticles are able to absorb heavy metals from the solution or target disease cells, such as cancer cells. In these studies, three main issues related to functionalized nanomaterials will be addressed through the application of nuclear magnetic resonance (NMR) techniques including: 1) surface composition and structure of functionalized nanocrystalline particles; 2) chemical properties of the guest molecules on the surface of nanomaterials, and 3) adsorption and reactivity of surface bound functional groups. Nuclear magnetic resonance (NMR) is one of the major spectroscopic techniques available for the characterization of molecular structure and conformational dynamics with atomic level detail. This thesis deals with the application of 1H solution state NMR to porous nanomaterial in an aqueous environment. Understanding the aqueous phase behavior of functionalized nanomaterials is a key factor in the design and development of safe nanomaterials because their interactions with living systems are always mediated through the aqueous phase. This is often due to a lack of fundamental knowledge in interfacial chemical and physical phenomena that occur on the surface of nanoparticles. The use of solution NMR spectroscopy results in high-resolution NMR spectra. This technique is selective for protons on the surface organic functional groups due to their motional averaging in solution. In this study, 1H solution NMR spectroscopy was used to investigate the interface of the organic functional groups in D2O. The pKa for these functional groups covalently bound to the surface of nanoparticles was determined using an NMR-pH titration method based on the variation in the proton chemical shift for the alkyl group protons closest to the amine group with pH. The adsorption of toxic contaminants (chromate and arsenate anions) on the surface of functionalized silicalite-1 and mesoporous silica nanoparticles has been studied by 1H solution NMR spectroscopy. With this method, the surface bound contaminants are detected. The analysis of the intensity and position of these peaks allows quantitative assessment of the relative amounts of functional groups with adsorbed metal ions. These results demonstrate the sensitivity of solution NMR spectroscopy to the electronic environment and structure of the surface functional groups on porous nanomaterials.

The Role of Dextran Coatings on the Cytotoxicity Properties of Ceria Nanoparticles Toward Bone Cancer Cells

NASA Astrophysics Data System (ADS)

Yazici, Hilal; Alpaslan, Ece; Webster, Thomas J.

2015-04-01

Cerium oxide nanoparticles have demonstrated great potential as antioxidant and radioprotective agents for nanomedicine applications especially for cancer therapy. The surface chemistry of nanoparticles is an important property that has a significant effect on their performance in biological applications including cancer diagnosis, cancer treatment, and bacterial infection. Recently, various nanosized cerium oxide particles with different types of polymer coatings have been developed to improve aqueous solubility and allow for surface functionalization for distinct applications. In this study, the role of ceria nanoparticles coated with dextran on the cytotoxicity properties of bone cancer cells was shown. Specifically, 0.1 M and 0.01 M dextran-coated, <5-nm ceria nanoparticles, were synthesized. The cytotoxicity of 0.1 M and 0.01 M dextran-coated ceria nanoparticles was evaluated against osteosarcoma cells. A change in cell viability was observed when treating osteosarcoma cells with 0.1 M dextran-coated ceria nanoparticles in the 250 -1000 μg/mL concentration range. In contrast, minimal toxicity to bone cancer cells was observed for the 0.01 M dextran coating after 3 days compared with the 0.1 M dextran coating. These results indicated that surface dextran functionalization had a positive impact on the cytotoxicity of cerium oxide nanoparticles against osteosarcoma cells.

Dual immobilization and magnetic manipulation of magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Yang, S. Y.; Jian, Z. F.; Horng, H. E.; Hong, Chin-Yih; Yang, H. C.; Wu, C. C.; Lee, Y. H.

By suitably bio-functionalizing the surfaces, magnetic nanoparticles are able to bind specific biomolecules, and may serve as vectors for delivering bio-entities to target tissues. In this work, the synthesis of bio-functionalized magnetic nanoparticles with two kinds of bio-probes is developed. Here, the stem cell is selected as a to-be-delivered bio-entity and infarcted myocardium is the target issue. Thus, cluster designation-34 (CD-34) on stem cell and creatine kinase-MB (CK-MB) (or troponin I) on infarcted myocardium are the specific biomolecules to be bound with bio-functionalized magnetic nanoparticles. In addition to demonstrating the co-coating of two kinds of bio-probes on a magnetic nanoparticle, the feasibility of manipulation on bio-functionalized magnetic nanoparticles by external magnetic fields is investigated.

Exploring the influence of Diels-Alder linker length on photothermal molecule release from gold nanorods.

PubMed

Vetterlein, Claudia; Vásquez, Rodrigo; Bolaños, Karen; Acosta, Gerardo A; Guzman, Fanny; Albericio, Fernando; Celis, Freddy; Campos, Marcelo; Kogan, Marcelo J; Araya, Eyleen

2018-06-01

We studied the photothermal release of carboxyfluorescein (CF) linked to the gold surface of gold nanorods (GNRs) by two Diels-Alder adducts of different lengths (n = 4 and n = 9). The functionalized GNRs were irradiated with infrared light to produce photothermal release of CF by a retro-Diels-Alder reaction. The adducts were chemisorbed on the GNRs and the functionalized nanoparticles were characterized by UV-vis, DLS, zeta potential and Raman and surface-enhanced Raman spectroscopy (SERS). On the basis of the degree of nanoparticle functionalization and the SERS results, we inferred the orientation of CF on the surface of the gold nanoparticle. Moreover, we determined the photothermal release profiles of CF from the gold surface by laser irradiation. The release was faster for the longer linker (n = 9). SERS revealed that, for the shorter linker (n = 4), molecules are oriented perpendicularly with respect to the gold surface, thereby maintaining the CF far from the surface. In contrast, the longer linker was observed to be tilted, thus maintaining CF close to the gold surface and therefore potentially favoring the photothermal transfer of energy. These results are relevant for the future development of the spatial and temporal controlled release of drugs by means of gold nanoparticles. Copyright © 2018 Elsevier B.V. All rights reserved.

The Role of Structural Enthalpy in Spherical Nucleic Acid Hybridization.

PubMed

Fong, Lam-Kiu; Wang, Ziwei; Schatz, George C; Luijten, Erik; Mirkin, Chad A

2018-05-23

DNA hybridization onto DNA-functionalized nanoparticle surfaces (e.g., in the form of a spherical nucleic acid (SNA)) is known to be enhanced relative to hybridization free in solution. Surprisingly, via isothermal titration calorimetry, we reveal that this enhancement is enthalpically, as opposed to entropically, dominated by ∼20 kcal/mol. Coarse-grained molecular dynamics simulations suggest that the observed enthalpic enhancement results from structurally confining the DNA on the nanoparticle surface and preventing it from adopting enthalpically unfavorable conformations like those observed in the solution case. The idea that structural confinement leads to the formation of energetically more stable duplexes is evaluated by decreasing the degree of confinement a duplex experiences on the nanoparticle surface. Both experiment and simulation confirm that when the surface-bound duplex is less confined, i.e., at lower DNA surface density or at greater distance from the nanoparticle surface, its enthalpy of formation approaches the less favorable enthalpy of duplex formation for the linear strand in solution. This work provides insight into one of the most important and enabling properties of SNAs and will inform the design of materials that rely on the thermodynamics of hybridization onto DNA-functionalized surfaces, including diagnostic probes and therapeutic agents.

Removal of heavy metals from aqueous systems with thiol functionalized superparamagnetic nanoparticles.

PubMed

Yantasee, Wassana; Warner, Cynthia L; Sangvanich, Thanapon; Addleman, R Shane; Carter, Timothy G; Wiacek, Robert J; Fryxell, Glen E; Timchalk, Charles; Warner, Marvin G

2007-07-15

We have shown that superparamagnetic iron oxide (Fe3O4) nanoparticles with a surface functionalization of dimercaptosuccinic acid (DMSA) are an effective sorbent material for toxic soft metals such as Hg, Ag, Pb, Cd, and Tl, which effectively bind to the DMSA ligands and for As, which binds to the iron oxide lattices. The nanoparticles are highly dispersible and stable in solutions, have a large surface area (114 m2/g), and have a high functional group content (1.8 mmol thiols/g). They are attracted to a magnetic field and can be separated from solution within a minute with a 1.2 T magnet. The chemical affinity, capacity, kinetics, and stability of the magnetic nanoparticles were compared to those of conventional resin based sorbents (GT-73), activated carbon, and nanoporous silica (SAMMS) of similar surface chemistries in river water, groundwater, seawater, and human blood and plasma. DMSA-Fe3O4 had a capacity of 227 mg of Hg/g, a 30-fold larger value than GT-73. The nanoparticles removed 99 wt% of 1 mg/L Pb within a minute, while it took over 10 and 120 min for Chelex-100 and GT-73 to remove 96% of Pb.

Nanoparticle flotation collectors--the influence of particle softness.

PubMed

Yang, Songtao; Razavizadeh, Bi Bi Marzieh; Pelton, Robert; Bruin, Gerard

2013-06-12

The ability of polymeric nanoparticles to promote glass bead and pentlandite (Pn, nickel sulfide mineral) attachment to air bubbles in flotation was measured as a function of the nanoparticle glass transition temperature using six types of nanoparticles based on styrene/N-butylacrylate copolymers. Nanoparticle size, surface charge density, and hydrophobicity were approximately constant over the series. The ability of the nanoparticles to promote air bubble attachment and perform as flotation collectors was significantly greater for softer nanoparticles. We propose that softer nanoparticles were more firmly attached to the glass beads or mineral surface because the softer particles had a greater glass/polymer contact areas and thus stronger overall adhesion. The diameters of the contact areas between polymeric nanoparticles and glass surfaces were estimated with the Young-Laplace equation for soft, liquidlike particles, whereas JKR adhesion theory was applied to the harder polystyrene particles. The diameters of the contact areas were estimated to be more than an order of magnitude greater for the soft particles compared to harder polystyrene particles.

Carbon nanotubes decorated with Pt nanoparticles via electrostatic self-assembly: a highly active oxygen reduction electrocatalyst

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

Zhang, Sheng; Shao, Yuyan; Yin, Geping

2010-03-20

Carbon nanotubes (CNTs) are noncovalently functionalized with poly(allylamine hydrochloride) (PAH) and then employed as the support of Pt nanoparticles. X-Ray photoelectron spectroscopy confirms the successful functionalization of CNTs with PAH. The negatively charged Pt precursors are adsorbed on positively charged PAH-wrapping CNTs surface via electrostatic self-assembly and then in situ reduced in ethylene glycol. X-Ray diffraction and transmission electron microscope images reveal that Pt nanoparticles with an average size of 2.6 nm are uniformly dispersed on CNT surface. Pt/PAH-CNTs exhibit unexpectedly high activity towards oxygen reduction reaction, which can be attributed to the large electrochemical surface area of Pt nanoparticles.more » It also shows enhanced electrochemical stability due to the structural integrity of PAH-CNTs. This provides a facile approach to synthesize CNTs-based nanoelectrocatalysts.« less

Tyrosine- and tryptophan-coated gold nanoparticles inhibit amyloid aggregation of insulin.

PubMed

Dubey, Kriti; Anand, Bibin G; Badhwar, Rahul; Bagler, Ganesh; Navya, P N; Daima, Hemant Kumar; Kar, Karunakar

2015-12-01

Here, we have strategically synthesized stable gold (AuNPs(Tyr), AuNPs(Trp)) and silver (AgNPs(Tyr)) nanoparticles which are surface functionalized with either tyrosine or tryptophan residues and have examined their potential to inhibit amyloid aggregation of insulin. Inhibition of both spontaneous and seed-induced aggregation of insulin was observed in the presence of AuNPs(Tyr), AgNPs(Tyr), and AuNPs(Trp) nanoparticles. These nanoparticles also triggered the disassembly of insulin amyloid fibrils. Surface functionalization of amino acids appears to be important for the inhibition effect since isolated tryptophan and tyrosine molecules did not prevent insulin aggregation. Bioinformatics analysis predicts involvement of tyrosine in H-bonding interactions mediated by its C=O, -NH2, and aromatic moiety. These results offer significant opportunities for developing nanoparticle-based therapeutics against diseases related to protein aggregation.

Synthesis and characterization of (3-Aminopropyl)trimethoxy-silane (APTMS) functionalized Gd2O3:Eu(3+) red phosphor with enhanced quantum yield.

PubMed

Jain, Akhil; Hirata, G A; Farías, M H; Castillón, F F

2016-02-12

We report the surface modification of nanocrystalline Gd2O3:Eu(3+) phosphor by (3-Aminopropyl)trimethoxysilane (APTMS). The nanoparticles were first coated with silica using the Stöber process, and then annealed at 650 °C for 2 h. Afterwards, APTMS was functionalized onto the silica layer to obtain Gd2O3:Eu(3+) nanoparticles bearing amine groups on the surface. The effect of silica coating, and the subsequent annealing process on the crystallization of the nanophosphor were analyzed by x-ray diffraction (XRD). High-resolution transmission electron microscopy (HR-TEM) confirmed the presence of a silica layer of ∼45 nm thickness. X-ray photoelectron (XPS) and Fourier transform infrared (FTIR) spectroscopy confirmed the presence of silica and the amine groups. Photoluminescence (PL) analysis demonstrated an increased emission after functionalization of nanoparticles. Absolute quantum yield (QY) measurements revealed an 18% enhancement in QY in functionalized nanoparticles compared with unmodified nanoparticles, which is of great importance for their biomedical applications.

Synthesis and characterization of (3-Aminopropyl)trimethoxy-silane (APTMS) functionalized Gd2O3:Eu3+ red phosphor with enhanced quantum yield

NASA Astrophysics Data System (ADS)

Jain, Akhil; Hirata, G. A.; Farías, M. H.; Castillón, F. F.

2016-02-01

We report the surface modification of nanocrystalline Gd2O3:Eu3+ phosphor by (3-Aminopropyl)trimethoxysilane (APTMS). The nanoparticles were first coated with silica using the Stöber process, and then annealed at 650 °C for 2 h. Afterwards, APTMS was functionalized onto the silica layer to obtain Gd2O3:Eu3+ nanoparticles bearing amine groups on the surface. The effect of silica coating, and the subsequent annealing process on the crystallization of the nanophosphor were analyzed by x-ray diffraction (XRD). High-resolution transmission electron microscopy (HR-TEM) confirmed the presence of a silica layer of ∼45 nm thickness. X-ray photoelectron (XPS) and Fourier transform infrared (FTIR) spectroscopy confirmed the presence of silica and the amine groups. Photoluminescence (PL) analysis demonstrated an increased emission after functionalization of nanoparticles. Absolute quantum yield (QY) measurements revealed an 18% enhancement in QY in functionalized nanoparticles compared with unmodified nanoparticles, which is of great importance for their biomedical applications.

Functionalized magnetic nanoparticles for the decontamination of water polluted with cesium

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

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

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.

Functionalized gold nanoparticles manifested as potent carriers for nucleolar targeting

NASA Astrophysics Data System (ADS)

Shahbazi, Reza; Ozcicek, Ilyas; Ozturk, Gurkan; Ulubayram, Kezban

2017-01-01

It is generally known that gold nanoparticles are localised in the cytoplasm and, if synthesised in small sizes or functionalized with specific proteins, they enter the cell nucleus. However, there is no report emphasising the importance of surface functionalization in their accumulation in the nucleolus. Here, for the first time in the literature, it is proposed that functionalization of gold nanoparticles with a thin layer of polyethyleneimine (PEI) spearheads them to the nucleolus of hard-to-transfect post-mitotic dorsal root ganglion neurones in a size-independent manner. As a potential for theranostic applications, it was found that functionalization with a thin layer of PEI affected the emission signal intensity of gold nanoparticles so that the cellular biodistribution of nanoparticles was visualised clearly under both confocal and two-photon microscopes.

Rapid, Efficient and Versatile Strategies for Functionally Sophisticated Polymers and Nanoparticles: Degradable Polyphosphoesters and Anisotropic Distribution of Chemical Functionalities

NASA Astrophysics Data System (ADS)

Zhang, Shiyi

The overall emphasis of this dissertation research included two kinds of asymmetrically-functionalized nanoparticles with anisotropic distributions of chemical functionalities, three degradable polymers synthesized by organocatalyzed ring-opening polymerizations, and two polyphosphoester-based nanoparticle systems for various biomedical applications. Inspired by the many hierarchical assembly processes that afford complex materials in Nature, the construction of asymmetrically-functionalized nanoparticles with efficient surface chemistries and the directional organization of those building blocks into complex structures have attracted much attention. The first method generated a Janus-faced polymer nanoparticle that presented two orthogonally click-reactive surface chemistries, thiol and azido. This robust method involved reactive functional group transfer by templating against gold nanoparticle substrates. The second method produced nanoparticles with sandwich-like distribution of crown ether functionalities through a stepwise self-assembly process that utilized crown ether-ammonium supramolecular interactions to mediate inter-particle association and the local intra-particle phase separation of unlike hydrophobic polymers. With the goal to improve the efficiency of the production of degradable polymers with tunable chemical and physical properties, a new type of reactive polyphosphoester was synthesized bearing alkynyl groups by an organocatalyzed ring-opening polymerization, the chemical availability of the alkyne groups was investigated by employing "click" type azide-alkyne Huisgen cycloaddition and thiol-yne radical-mediated reactions. Based on this alkyne-functionalized polyphosphoester polymer and its two available "click" type reactions, two degradable nanoparticle systems were developed. To develop the first system, the well defined poly(ethylene oxide)-block-polyphosphester diblock copolymer was transformed into a multifunctional Paclitaxel drug conjugate by densely attaching the polyphosphoester block with azide-functionalized Paclitaxel by azide-alkyne Huisgen cycloaddition. This Paclitaxel drug conjugate provides a powerful platform for combinational cancer therapy and bioimaging due to its ultra-high Paclitaxel loading (> 65 wt%), high water solubility (>6.2 mg/mL for PTX) and easy functionalization. Another polyphosphoester-based nanoparticle system has been developed by a programmable process for the rapid and facile preparation of a family of nanoparticles with different surface charges and functionalities. The non-ionic, anionic, cationic and zwitterionic nanoparticles with hydrodynamic diameters between 13 nm to 21 nm and great size uniformity could be rapidly prepared from small molecules in 6 h or 2 days. The anionic and zwitterionic nanoparticles were designed to load silver ions to treat pulmonary infections, while the cationic nanoparticles are being applied to regulate lung injuries by serving as a degradable iNOS inhibitor conjugates. In addition, a direct synthesis of acid-labile polyphosphoramidate by organobase-catalyzed ring-opening polymerization and an improved two-step preparation of polyphosphoester ionomer by acid-assisted cleavage of phosphoramidate bonds on polyphosphoramidate were developed. Polyphosphoramidate and polyphosphoester ionomers may be applied to many applications, due to their unique chemical and physical properties.

Development of Multifunctional Nanoparticles for Cancer Therapy Applications

NASA Astrophysics Data System (ADS)

Huth, Christopher

The focus of this thesis is the functionalization and tailoring of nanoparticle surfaces to perform specific objectives in a biological environment. The nanoparticles examined include carbon nanotubes (CNTs), superparamagnetic iron oxide nanoparticles and superparamagnetic iron oxide nanocomposites. The unique nanomaterials have been developed to address continued issues in cancer therapy, including cancer diagnosis and efficient drug delivery. CNT surfaces were modified by plasma polymerization, providing functional groups for conjugation. Luminescent amine labeled quantum dots were fixed to the surface of the CNTs to aid in cancer diagnosis by in vivo imaging. Mice, injected with the quantum dot functionalized carbon nanotubes, were imaged displaying the in vivo imaging capability. In addition, the drug loading and drug release capabilities were examined by incorporating the drug paclitaxel into PLGA-coated CNTs, which showed much higher cytotoxicity to PC-3MM2 human prostate carcinoma cells compared to CNTs without paclitaxel. Paclitaxel was loaded at 112.5 microg/mg of PLGA-coated CNTs. Iron oxide nanocomposites were functionalized with quantum dots for diagnosis applications. Because the nanocomposites contain iron oxide, the nanoparticle provides the opportunity for magnetic hyperthermia, creating a unique material for diagnosis and therapy. Mice, injected with the quantum dot functionalized iron oxide nanocomposites, were imaged displaying the in vivo imaging capability. The magnetic hyperthermic property of the quantum dot functionalized nanocomposites was observed with the attainment of temperatures above 50°C during exposure to an alternating magnetic field. Thermoresponsive nanoparticles were prepared by immobilizing a 2 - 3 nm thick phospholipid layer on the surface of superparamagnetic Fe3O 4 nanoparticles via high affinity avidin/biotin interactions. Morphological and physicochemical surface properties were assessed using TEM, confocal laser scanning microscopy, differential scanning calorimetry, and ATR-FTIR. The zeta potential of Fe3O4 colloids in phosphate buffered saline (PBS) decreased from -23.6 to -5.0 mV as a consequence of phospholipid immobilization. Hyperthermia-relevant temperatures greater than 40°C were achieved within 10--15 min using a 7-mT magnetic field alternating at a frequency of 1MHz. Loading of the surface-associated phospholipid layer with the hydrophobic dye dansylcadaverine was accomplished at an efficiency of 479 ng/mg Fe3O4. Release of this drug surrogate was temperature-dependent, resulting in a 2.5-fold greater release rate when nanoparticles were exposed to temperatures above the experimentally determined melting temperature of 39.7°C. In vitro cytotoxicity studies by release of the cytotoxic drug, doxorubicin, from the thermoresponsive nanoparticles was lastly intended. However, colloidal stability became an issue, prompting a thorough review of nanoparticle stabilization. Factors affecting stabilization, including dispersant, the nanoparticle, and the thermoresponsive coating, were characterized by dynamic light scattering and zeta potential. PBS was compared to two dispersants containing lower ionic concentrations, HBSS and HEPES, using the original iron oxide nanoparticles compared to an iron oxide nanocomposite. The nanocomposite in the HEPES buffer displayed the greatest stability with a zeta potential of -30.47 mV and particle size of 155.4 nm. Stabilization of the immobilized phospholipid bilayer was examined with and without incorporation of the cationic lipid stearylamine. Zeta potential (33.6 mV) and size (315 nm) data indicate that stearylamine incorporated DPPC coated nanoparticles provide better stability.

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.

Regulation of Macrophage Recognition through the Interplay of Nanoparticle Surface Functionality and Protein Corona.

PubMed

Saha, Krishnendu; Rahimi, Mehran; Yazdani, Mahdieh; Kim, Sung Tae; Moyano, Daniel F; Hou, Singyuk; Das, Ridhha; Mout, Rubul; Rezaee, Farhad; Mahmoudi, Morteza; Rotello, Vincent M

2016-04-26

Using a family of cationic gold nanoparticles (NPs) with similar size and charge, we demonstrate that proper surface engineering can control the nature and identity of protein corona in physiological serum conditions. The protein coronas were highly dependent on the hydrophobicity and arrangement of chemical motifs on NP surface. The NPs were uptaken in macrophages in a corona-dependent manner, predominantly through recognition of specific complement proteins in the NP corona. Taken together, this study shows that surface functionality can be used to tune the protein corona formed on NP surface, dictating the interaction of NPs with macrophages.

Probing nanoparticles and nanoparticle-conjugated biomolecules using time-of-flight secondary ion mass spectrometry.

PubMed

Kim, Young-Pil; Shon, Hyun Kyong; Shin, Seung Koo; Lee, Tae Geol

2015-01-01

Bio-conjugated nanoparticles have emerged as novel molecular probes in nano-biotechnology and nanomedicine and chemical analyses of their surfaces have become challenges. The time-of-flight (TOF) secondary ion mass spectrometry (SIMS) has been one of the most powerful surface characterization techniques for both nanoparticles and biomolecules. When combined with various nanoparticle-based signal enhancing strategies, TOF-SIMS can probe the functionalization of nanoparticles as well as their locations and interactions in biological systems. Especially, nanoparticle-based SIMS is an attractive approach for label-free drug screening because signal-enhancing nanoparticles can be designed to directly measure the enzyme activity. The chemical-specific imaging analysis using SIMS is also well suited to screen nanoparticles and nanoparticle-biomolecule conjugates in complex environments. This review presents some recent applications of nanoparticle-based TOF-SIMS to the chemical analysis of complex biological systems. © 2014 Wiley Periodicals, Inc.

Synthesis and fabrication of sized-controlled nanoparticles: Using surface self-assemblies as building blocks for developing supralattices on nanocomposite materials

NASA Astrophysics Data System (ADS)

Yee, Chanel Kitmon

2001-10-01

A general one-phase synthesis for self-assembling thiols onto gold, platinum, palladium and iridium nanoparticles using tetrahydrofuran (THF) as the solvent, and lithium triethylborohydride (superhydride) as the reducing agent, is presented. Using the same synthetic procedure gold nanoparticles functionalized with 11-hydroxyundecane-1-thiol and 4'-bromo-4-mercaptobiphenyl were prepared to show that the availability and reflexibility of this method could lead to surface fabrication with various type of facial moieties. Alkyl selenide- and alkyl thiolate-functionalized gold nanoparticles were also prepared by the same method at 6°C. The properties were compared to their counterparts made at 25°C. The formation of the Se-Au bond and S-Au bonds was investigated by transmission Fourier transform infrared spectroscopy (FTIR), while the bond nature in each case was examined by x-ray photoelectron spectroscopy (XPS). Particle size was determined by Transmission Electron Microscopy (TEM), and further confirmed by ultraviolet spectroscopy (UV). Superparamagnetic Fe and Fe2O3 nanoparticles were synthesized by ultrasound irradiation and post-fabricated with alkyl sulfonic acids of various chain lengths and octadecyl phosphonic acid. TEM reveals nanoparticles of 5--10 mn in diameter. FTIR spectra suggest that the alkyl chains are packed in a solid-like assembly with packing disorder increasing with the decreasing chain length. The octadecyl sulfonic acid coating displays the lowest magnetization within the sulfonic acid series, which may be explained by the high packing and ordering of the alkyl chains on the particle surface. The smallest value of magnetization in the OPA case suggests that the spin-state of surface Fe3+ ions is affected by the bonded surfactant, and that the phosphonate empty d-orbitals increase magnetic interactions between neighboring Fe3+ spins. To build superstructures beyond the monolayer level, a general route for the attachment of amino-terminated biomolecules to nanoparticles was proposed. Thiophene thiolate-functionalized platinum nanoparticles were prepared and reacted with nitrosonium tetrafluoroborate to provide the nitroso-functionalized nanoparticles. The reaction of the nitroso group with primary amines to yield strong N=N bonds might provide a general route for the attachment of amino-terminated biomolecules to nanoparticles. The attachment of two cytidine molecules to platinum nanoparticles was accomplished, and experimental data were provided to demonstrate the intended grafting reaction.

Supramolecular domains in mixed peptide self-assembled monolayers on gold nanoparticles.

PubMed

Duchesne, Laurence; Wells, Geoff; Fernig, David G; Harris, Sarah A; Lévy, Raphaël

2008-09-01

Self-organization in mixed self-assembled monolayers of small molecules provides a route towards nanoparticles with complex molecular structures. Inspired by structural biology, a strategy based on chemical cross-linking is introduced to probe proximity between functional peptides embedded in a mixed self-assembled monolayer at the surface of a nanoparticle. The physical basis of the proximity measurement is a transition from intramolecular to intermolecular cross-linking as the functional peptides get closer. Experimental investigations of a binary peptide self-assembled monolayer show that this transition happens at an extremely low molar ratio of the functional versus matrix peptide. Molecular dynamics simulations of the peptide self-assembled monolayer are used to calculate the volume explored by the reactive groups. Comparison of the experimental results with a probabilistic model demonstrates that the peptides are not randomly distributed at the surface of the nanoparticle, but rather self-organize into supramolecular domains.

Facile synthesis of microporous SiO2/triangular Ag composite nanostructures for photocatalysis

NASA Astrophysics Data System (ADS)

Sirohi, Sidhharth; Singh, Anandpreet; Dagar, Chakit; Saini, Gajender; Pani, Balaram; Nain, Ratyakshi

2017-11-01

In this article, we present a novel fabrication of microporous SiO2/triangular Ag nanoparticles for dye (methylene blue) adsorption and plasmon-mediated degradation. Microporous SiO2 nanoparticles with pore size <2 nm were synthesized using cetyltrimethylammonium bromide as a structure-directing agent and functionalized with APTMS ((3-aminopropyl) trimethoxysilane) to introduce amine groups. Amine-functionalized microporous silica was used for adsorption of triangular silver (Ag) nanoparticles. The synthesized microporous SiO2 nanostructures were investigated for adsorption of different dyes including methylene blue, congo red, direct green 26 and curcumin crystalline. Amine-functionalized microporous SiO2/triangular Ag nanostructures were used for plasmon-mediated photocatalysis of methylene blue. The experimental results revealed that the large surface area of microporous silica facilitated adsorption of dye. Triangular Ag nanoparticles, due to their better charge carrier generation and enhanced surface plasmon resonance, further enhanced the photocatalysis performance.

pH dependent conjugation of Ibuprofen to PEGylated nanoparticles

NASA Astrophysics Data System (ADS)

Bharti, Shivani; Jain, Shikshita; Kaur, Gurvir; Gupta, Shikha; Tripathi, S. K.

2018-04-01

In this paper, Ibuprofen, a water insoluble drug was covalently attached to PEGylated nanoparticles. Firstly, Surface functionalization of water dispersed core/shell nanoparticles had been done using hydrophilic polymer PEG-diamine. Therefore, PEGylated nanoparticles contain NH2 groups over the surface of nanoparticles and can be used for the further attachment of biomolecules. Ibuprofen was covalently loaded on the PEGylated core/shell nanoparticles using carbodiimide reaction. The synthesis had been carried out under two different pH environments, as the solubility of Ibuprofen is pH dependent. The resultant samples were characterized using UV-Vis absorption and FT-IR spectroscopy. The results strongly suggest the successful chemical conjugation of Ibuprofen to PEGylated nanoparticles in aqueous media and they could be further used for drug delivery applications.

Creation of hydrophobic surfaces using a paint containing functionalized oxide particles

NASA Astrophysics Data System (ADS)

Sino, Paul Albert L.; Herrera, Marvin U.; Balela, Mary Donnabelle L.

2017-05-01

Hydrophobic surfaces were created by coating various substrates (aluminum sheet, soda-lime glass, silicon carbide polishing paper, glass with double-sided adhesive) with paint containing functionalized oxide particles. The paint was created by functionalizing oxide particles (ground ZnO, TiO2 nanoparticles, or TiO2 microparticles) with fluorosilane molecules in absolute ethanol. Water contact angle of samples shows that the coated substrate becomes hydrophobic (water contact angle ≥ 90°). Among the oxides that were used, ground ZnO yielded contact angle exemplifying superhydrophobicity (water contact angle ≥ 150°). Scanning electron micrograph of paint-containing TiO2 nanoparticles shows rough functionalized oxides structures which probably increase the hydrophobicity of the surface.

Curvature dependence of the effect of ionic functionalization on the attraction among nanoparticles in dispersion

NASA Astrophysics Data System (ADS)

Jabes, B. Shadrack; Bratko, Dusan; Luzar, Alenka

2018-06-01

Solubilization of nanoparticles facilitates nanomaterial processing and enables new applications. An effective method to improve dispersibility in water is provided by ionic functionalization. We explore how the necessary extent of functionalization depends on the particle geometry. Using molecular dynamics/umbrella sampling simulations, we determine the effect of the solute curvature on solvent-averaged interactions among ionizing graphitic nanoparticles in aqueous dispersion. We tune the hydrophilicity of molecular-brush coated fullerenes, carbon nanotubes, and graphane platelets by gradually replacing a fraction of the methyl end groups of the alkyl coating by the ionizing -COOK or -NH3Cl groups. To assess the change in nanoparticles' dispersibility in water, we determine the potential-of-mean-force profiles at varied degrees of ionization. When the coating comprises only propyl groups, the attraction between the hydrophobic particles intensifies from spherical to cylindrical to planar geometry. This is explained by the increasing fraction of surface groups that can be brought into contact and the reduced access to water molecules, both following the above sequence. When ionic groups are added, however, the dispersibility increases in the opposite order, with the biggest effect in the planar geometry and the smallest in the spherical geometry. These results highlight the important role of geometry in nanoparticle solubilization by ionic functionalities, with about twice higher threshold surface charge necessary to stabilize a dispersion of spherical than planar particles. At 25%-50% ionization, the potential of mean force reaches a plateau because of the counterion condensation and saturated brush hydration. Moreover, the increase in the fraction of ionic groups can weaken the repulsion through counterion correlations between adjacent nanoparticles. High degrees of ionization and concomitant ionic screening gradually reduce the differences among surface interactions in distinct geometries until an essentially curvature-independent dispersion environment is created. Insights into tuning nanoparticle interactions can guide the synthesis of a broad class of nonpolar nanoparticles, where solubility is achieved by ionic functionalization.

Superparamagnetic nanoparticles for cancer diagnostics and therapeutics

NASA Astrophysics Data System (ADS)

Kohler, Nathan

2005-11-01

This dissertation describes the development of a magnetic nanoparticle conjugate that can potentially serve as both a contrast enhancement agent in magnetic resonance imaging (MRI) and as a drug carrier in controlled drug release, targeted for cancer diagnostics and therapeutics. In this work, we developed a unique method to synthesize well-dispersed 10-nm superparamagnetic iron oxide nanoparticles (SPION) without using chemical surfactants. This approach is especially advantageous for subsequent surface modification of nanoparticles with functional coatings. To target the SPION for cancer cells in vivo to facilitate MRI contrast enhancement of tumors, we immobilized folic acid on the particle surface. Folic acid is a low molecular weight growth factor over-expressed on many forms of cancer. The covalent immobilization of folic acid to the nanoparticle surface was characterized with FTIR and the intracellular uptake of the folic acid nanoparticles was visualized with scanning confocal microscopy. To use SPION for controlled drug release, we immobilized methotrexate (MTX), a chemotherapeutic drug, to the nanoparticle surface. MTX-modified nanoparticles have several combined advantages including real-time monitoring of drug delivery using MRI, higher intracellular concentrations of methotrexate that increase cellular cytotoxicity, and reduced non-specific uptake by healthy cells within the body. We successfully conducted drug release experiments demonstrating that MTX was released under low pH conditions that mimic the intracellular conditions in the lysozome. To assess cellular cytotoxicity, we tested MTX-nanoparticle conjugates in human breast cancer cells (MCF-7), human cervical cancer cells (HeLa), and glioma cells (9L), and showed that the drug efficacy of MTX-nanoparticle conjugates was similar to that of free MTX. To improve nanoparticle circulation time and intracellular uptake, we developed a novel bifunctional poly(ethylene glycol) (PEG) SAM capable of reducing protein adsorption and particle agglomeration in vivo. The trifluoroethylester-terminal PEG SAM is compatible with oxide surfaces through silanization and ligand functionalization of the chain terminus through amidation. The structure of the silane was characterized by FTIR and NMR. Immobilization of the SAM on the particle surface and ligand grafting of folic acid was confirmed by FTIR and visualized with TEM.

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.

Immobilization of functional oxide nanoparticles on silicon surfaces via Si-C bonded polymer brushes.

PubMed

Xu, F J; Wuang, S C; Zong, B Y; Kang, E T; Neoh, K G

2006-05-01

A method for immobilizing and mediating the spatial distribution of functional oxide (such as SiO2 and Fe3O4) nanoparticles (NPs) on (100)-oriented single crystal silicon surface, via Si-C bonded poly(3-(trimethoxysilyl)propyl methacrylate) (P(TMSPM)) brushes from surface-initiated atom transfer radical polymerization (ATRP) of (3-(trimethoxysilyl)propyl methacrylate) (TMSPM), was described. The ATRP initiator was covalently immobilized via UV-induced hydrosilylation of 4-vinylbenzyl chloride (VBC) with the hydrogen-terminated Si(100) surface (Si-H surface). The surface-immobilized Fe3O4 NPs retained their superparamagnetic characteristics and their magnetization intensity could be mediated by adjusting the thickness of the P(TMSPM) brushes.

Comparative study of three magnetic nano-particles (FeSO4, FeSO4/SiO2, FeSO4/SiO2/TiO2) in plasmid DNA extraction.

PubMed

Rahnama, H; Sattarzadeh, A; Kazemi, F; Ahmadi, N; Sanjarian, F; Zand, Z

2016-11-15

Recent updates on Magnetic Nano-Particles (MNPs) based separation of nucleic acids have received more attention due to their easy manipulation, simplicity, ease of automation and cost-effectiveness. It has been indicated that DNA molecules absorb on solid surfaces via hydrogen-bonding, and hydrophobic and electrostatic interactions. These properties highly depend on the surface condition of the solid support. Therefore, surface modification of MNPs may enhance their functionality and specification. In the present study, we functionalized Fe3O4 nano-particle surface utilizing SiO2 and TiO2 layer as Fe3O4/SiO2 and Fe3O4/SiO2/TiO2 and then compare their functionality in the adsorption of plasmid DNA molecules with the naked Fe3O4 nano-particles. The result obtained showed that the purity and amount of DNA extracted by Fe3O4 coated by SiO2 or SiO2/TiO2 were higher than the naked Fe3O4 nano-particles. Furthermore, we obtained pH 8 and 1.5 M NaCl as an optimal condition for desorption of DNA from MNPs. The result further showed that, 0.2 mg nano-particle and 10 min at 55 °C are the optimal conditions for DNA desorption from nano-particles. In conclusion, we recommended Fe3O4/SiO2/TiO2 as a new MNP for separation of DNA molecules from biological sources. Copyright © 2016 Elsevier Inc. All rights reserved.

Functionalized nanoparticle probes for protein detection

NASA Astrophysics Data System (ADS)

Park, Do Hyun; Lee, Jae-Seung

2015-05-01

In this Review, we discuss representative studies of recent advances in the development of nanoparticle-based protein detection methods, with a focus on the properties and functionalization of nanoparticle probes, as well as their use in detection schemes. We have focused on functionalized nanoparticle probes because they offer a number of advantages over conventional assays and because their use for detecting protein targets for diagnostic purposed has been demonstrated. In this report, we discuss nanoparticle probes classified by material type (gold, silver, silica, semiconductor, carbon, and virus) and surface functionality (antibody, aptamer, and DNA), which play a critical role in enhancing the sensitivity, selectivity, and efficiency of the detection systems. In particular, the synergistic function of each component of the nanoparticle probe is emphasized in terms of specific chemical and physical properties. This research area is in its early stages with many milestones to reach before nanoparticle probes are successfully applied in the field; however, the substantial ongoing efforts of researchers underline the great promise offered by nanoparticlebased probes for future applications. [Figure not available: see fulltext.

Artificial receptor-functionalized nanoshell: facile preparation, fast separation and specific protein recognition

NASA Astrophysics Data System (ADS)

Ouyang, Ruizhuo; Lei, Jianping; Ju, Huangxian

2010-05-01

This work combined molecular imprinting technology with superparamagnetic nanospheres as the core to prepare artificial receptor-functionalized magnetic nanoparticles for separation of homologous proteins. Using dopamine as a functional monomer, novel surface protein-imprinted superparamagnetic polydopamine (PDA) core-shell nanoparticles were successfully prepared in physiological conditions, which could maintain the natural structure of a protein template and achieved the development of molecularly imprinted polymers (MIPs) from one dimension to zero dimension for efficient recognition towards large biomolecules. The resultant nanoparticles could be used for convenient magnetic separation of homologous proteins with high specificity. The nanoparticles possessed good monodispersibility, uniform surface morphology and high saturation magnetization value. The bound amounts of template proteins measured by both indirect and direct methods were in good agreement. The maximum number of imprinted cavities on the surface of the bovine hemoglobin (Hb)-imprinted nanoshell was 2.21 × 1018 g - 1, which well matched their maximum binding capacity toward bovine Hb. Both the simple method for preparation of MIPs and the magnetic nanospheres showed good application potential in fast separation, effective concentration and selective biosensing of large protein molecules.

Revealing the Atomic Restructuring of Pt–Co Nanoparticles

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

Xin, Huolin L.; Alayoglu, Selim; Tao, Runzhe

2014-06-11

We studied Pt-Co bimetallic nanoparticles during oxidation in O2 and reduction in H2 atmospheres using an aberration corrected environmental transmission electron microscope. During oxidation Co migrates to the nanoparticle surface forming a strained epitaxial CoO film. It subsequently forms islands via strain relaxation. The atomic restructuring is captured as a function of time. During reduction cobalt migrates back to the bulk, leaving a monolayer of platinum on the surface.

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

Simultaneous size control and surface functionalization of titania nanoparticles through bioadhesion-assisted bio-inspired mineralization

NASA Astrophysics Data System (ADS)

Shi, Jiafu; Yang, Dong; Jiang, Zhongyi; Jiang, Yanjun; Liang, Yanpeng; Zhu, Yuanyuan; Wang, Xiaoli; Wang, Huihui

2012-09-01

Simultaneous size control and surface functionalization of inorganic nanoparticles (NPs) are often desired for their efficient applications in (bio)catalysis, drug and/or DNA delivery, and photonics, etc. In this study, a novel strategy "bioadhesion-assisted bio-inspired mineralization (BABM)" was put forward to prepare titania nanoparticles (TiNPs) with tunable particle size and multiple surface functionality. Specifically, the initial formation and subsequent growth of TiNPs were enabled by arginine via bio-inspired mineralization, while the mineralization process was terminated through the addition of the pre-polymerized dopa (oligodopa). By adjusting the addition time of oligodopa, the size of TiNPs could be facilely tailored from ca. 30-350 nm; meanwhile, the surface of TiNPs could be functionalized by oligodopa through metal-catechol coordination interaction (a typical bioadhesion phenomenon). In other words, oligodopa coating could not only exquisitely control the size of TiNPs, but also render TiNPs surface multifunctional groups for secondary treatment such as conjugating proteins through amine-catechol adduct formation. Hopefully, this BABM approach will construct a versatile platform for green and facile synthesis of inorganic NPs, in particular transition metal oxide NPs.

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.

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

Vörös, Márton; Brawand, Nicholas P.; Galli, Giulia

Lead chalcogenide (PbX) nanoparticles are promising materials for solar energy conversion. However, the presence of trap states in their electronic gap limits their usability, and developing a universal strategy to remove trap states is a persistent challenge. Using calculations based on density functional theory, we show that hydrogen acts as an amphoteric impurity on PbX nanoparticle surfaces; hydrogen atoms may passivate defects arising from ligand imbalance or off-stoichiometric surface terminations irrespective of whether they originate from cation or anion excess. In addition, we show, using constrained density functional theory calculations, that hydrogen treatment of defective nanoparticles is also beneficial formore » charge transport in films. We also find that hydrogen adsorption on stoichiometric nanoparticles leads to electronic doping, preferentially n-type. Lastly, our findings suggest that postsynthesis hydrogen treatment of lead chalcogenide nanoparticle films is a viable approach to reduce electronic trap states or to dope well-passivated films.« less

Nanoparticles in ionic liquids: interactions and organization.

PubMed

He, Zhiqi; Alexandridis, Paschalis

2015-07-28

Ionic liquids (ILs), defined as low-melting organic salts, are a novel class of compounds with unique properties and a combinatorially great chemical diversity. Ionic liquids are utilized as synthesis and dispersion media for nanoparticles as well as for surface functionalization. Ionic liquid and nanoparticle hybrid systems are governed by a combined effect of several intermolecular interactions between their constituents. For each interaction, including van der Waals, electrostatic, structural, solvophobic, steric, and hydrogen bonding, the characterization and quantitative calculation methods together with factors affecting these interactions are reviewed here. Various self-organized structures based on nanoparticles in ionic liquids are generated as a result of a balance of these intermolecular interactions. These structures, including colloidal glasses and gels, lyotropic liquid crystals, nanoparticle-stabilized ionic liquid-containing emulsions, ionic liquid surface-functionalized nanoparticles, and nanoscale ionic materials, possess properties of both ionic liquids and nanoparticles, which render them useful as novel materials especially in electrochemical and catalysis applications. This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic liquid-based materials, enabling applications in broad areas.

Interfacial functionalization and engineering of nanoparticles

NASA Astrophysics Data System (ADS)

Song, Yang

The intense research interest in nanoscience and nanotechnology is largely fueled by the unique properties of nanoscale materials. In this dissertation, the research efforts are focused on surface functionalization and interfacial engineering of functional nanoparticles in the preparation of patchy nanoparticles (e.g., Janus nanoparticles and Neapolitan nanoparticles) such that the nanoparticle structures and properties may be manipulated to an unprecedented level of sophistication. Experimentally, Janus nanoparticles were prepared by an interfacial engineering method where one hemisphere of the originally hydrophobic nanoparticles was replaced with hydrophilic ligands at the air|liquid or solid|liquid interface. The amphiphilic surface characters of the Janus nanoparticles were verified by contact angle measurements, as compared to those of the bulk-exchange counterparts where the two types of ligands were distributed rather homogeneously on the nanoparticle surface. In a further study, a mercapto derivative of diacetylene was used as the hydrophilic ligands to prepare Janus nanoparticles by using hydrophobic hexanethiolate-protected gold nanoparticles as the starting materials. Exposure to UV irradiation led to effective covalent cross-linking between the diacetylene moieties of neighboring ligands and hence marked enhancement of the structural integrity of the Janus nanoparticles, which was attributable to the impeded surface diffusion of the thiol ligands on the nanoparticle surface, as manifested in fluorescence measurements of aged nanoparticles. More complicated bimetallic AgAu Janus nanoparticles were prepared by interfacial galvanic exchange reactions of a Langmuir-Blodgett monolayer of 1-hexanethiolate-passivated silver nanoparticles on a glass slide with gold(I)-mercaptopropanediol complex in a water/ethanol solution. The resulting nanoparticles exhibited an asymmetrical distribution not only of the organic capping ligands on the nanoparticle surface but also of the metal elements in the nanoparticle cores, in contrast to the bulk-exchange counterparts where these distributions were homogeneous within the nanoparticles, as manifested in contact angle, UV--vis, XPS, and TEM measurements. More interestingly, the electrocatalytic performance of the Janus nanoparticles was markedly better than the bulk-exchange ones, suggesting that the segregated distribution of the polar ligands from the apolar ones might further facilitate charge transfer from Ag to Au in the nanoparticle cores, leading to additional improvement of the adsorption and reduction of oxygen. This interfacial protocol was then adopted to prepare trimetallic Ag AuPt Neapolitan nanoparticles by two sequential galvanic exchange reactions of 1-hexanethiolate-capped silver nanoparticles with gold(I)-thiomalic acid and platinum(II)-hexanethiolate complexes. As both reactions were confined to an interface, the Au and Pt elements were situated on two opposite poles of the original Ag nanoparticles, which was clearly manifested in elemental mapping of the nanoparticles, and consistent with the damping and red-shift of the nanoparticle surface plasmon resonance. As nanoscale analogs to conventional amphiphilic molecules, the resulting Janus nanoparticles were found to form oil-in-water micelle-like or water-in-oil reverse micelle-like superparticulate structures depending on the solvent media. These unique characteristics were exploited for the effective transfer of diverse guest nanoparticles between organic and water phase. The transfer of hydrophobic nanoparticles from organic to water media or water-soluble nanoparticles to the organic phase was evidenced by TEM, DLS, UV-Vis, and PL measurements. In particular, line scans based on EDS analysis showed that the vesicle-like structures consisted of multiple layers of the Janus nanoparticles, which encapsulated the guest nanoparticles in the cores. The results highlight the unique effectiveness of using Janus nanoparticles in the formation of functional nanocomposites. Part of the dissertation research was also devoted to graphene quantum dots (GQDs)-supported platinum (Pt/G) nanoparticles and their electrocatalytic activity in oxygen reduction reaction. These Pt/G nanocomposites were prepared by a hydrothermal procedure at controlled temperatures. Spectroscopic measurements based on FTIR, Raman and XPS confirmed the formation of various oxygenated structural defects on GQDs and the variation of their concentrations with the hydrothermal conditions. Interestingly, electrocatalytic activity of GQD/Pt composites exhibited a volcano-shaped variation with the GQD structural defects, with the best identified as the samples prepared at 160 °C for 6 h where the mass activity was found to meet the DOE target for 2015. This remarkable performance was accounted for by the deliberate manipulation of the adsorption of oxygen and reaction intermediates on platinum by the GQD structural defects through partial charge transfer. The strategy presented herein may offer a new paradigm in the design and engineering of nanoparticle catalysts for fuel cell electrochemistry. In addition, studies were also carried out to study intervalence charge transfer between ferrocenyl moieties bonded on carbon nanoparticle surfaces by diazonium reaction. Electrochemical studies exhibited two pairs of voltammetric waves with a difference of their formal potentials at about 78 mV, suggesting nanoparticle-mediated intraparticle charge delocalization at mixed valence as a result of the strong core-ligand covalent bonds and the conductive sp 2 carbon matrix of the graphitic cores. Consistent behaviors were observed in near-infrared measurements, indicating that the particles behaved analogously to a Class I/II mixed-valence compound.

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 here is applicable to the synthesis of a large class of nanomaterials with multiple core and surface functionalities. This work combined with the biodistribution data suggests that the radiolabeling schemes carried out in this study have broad implications for use in pharmacokinetic studies for a variety of nanomaterials.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 here is applicable to the synthesis of a large class of nanomaterials with multiple core and surface functionalities. This work combined with the biodistribution data suggests that the radiolabeling schemes carried out in this study have broad implications for use in pharmacokinetic studies for a variety of nanomaterials. Electronic supplementary information (ESI) available: (S1) High-Resolution Transmission Electron Microscopy (HRTEM) image of iron oxide nanoparticles, (S2) Superconducting Quantum Interference Device (SQUID) measurement of magnetization of super paramagnetic iron oxide nanoparticles, (S3) Fourier Transform Infrared Spectroscopy (FT-IR) spectra of Fe-Si-COO- synthesised using Grignard reagents (S4) FT-IR spectra of iron oxide nanoparticles silanized with commercially available N-[(3-Trimethoxysilyl)propyl]ethylenediamine triacetic acid tripotassium salt, (S5) Synthesis of hyperbranched amine functionalized iron oxide nanoparticles from amino propyl triethyl silane functionalized iron nanoparticles using ethyleneimine as an initiator and polymerizing agent. See DOI: 10.1039/c4nr06441k

Electrochemical analysis of gold-coated magnetic nanoparticles for detecting immunological interaction

NASA Astrophysics Data System (ADS)

Pham, Thao Thi-Hien; Sim, Sang Jun

2010-01-01

An electrochemical impedance immunosensor was developed for detecting the immunological interaction between human immunoglobulin (IgG) and protein A from Staphylococcus aureus based on the immobilization of human IgG on the surface of modified gold-coated magnetic nanoparticles. The nanoparticles with an Au shell and Fe oxide cores were functionalized by a self-assembled monolayer of 11-mercaptoundecanoic acid. The electrochemical analysis was conducted on the modified magnetic carbon paste electrodes with the nanoparticles. The magnetic nanoparticles were attached to the surface of the magnetic carbon paste electrodes via magnetic force. The cyclic voltammetry technique and electrochemical impedance spectroscopy measurements of the magnetic carbon paste electrodes coated with magnetic nanoparticles-human IgG complex showed changes in its alternating current (AC) response both after the modification of the surface of the electrode and the addition of protein A. The immunological interaction between human IgG on the surface of the modified magnetic carbon paste electrodes and protein A in the solution could be successfully monitored.

Deactivation of photocatalytically active ZnO nanoparticle and enhancement of its compatibility with organic compounds by surface-capping with organically modified silica

NASA Astrophysics Data System (ADS)

Cao, Zhi; Zhang, Zhijun

2011-02-01

Tetraethyl orthosilicate (TEOS) and dimethyldiethoxysilane (DEDMS) were used as co-precursors to prepare organically modified silica (ormosil) via sol-gel process. The resultant ormosil was adopted for surface-capping of ZnO nanoparticle, where methyl (organic functional group) and silica (inorganic component) were simultaneously introduced onto the surface of the nanoparticles for realizing dual surface-modification. The ormosil-capped ZnO nanoparticle showed strong hydrophobicity and good compatibility with organic phases, as well as effectively decreased photocatalytic activity and almost unchanged ultraviolet (UV)-shielding ability. More importantly, the comprehensive properties of ormosil-capped ZnO nanoparticle could be manipulated by adjusting the molar ratio of TEOS to DEDMS during sol-gel process. This should help to open a wider window to better utilizing the unique and highly attractive properties such as high UV-shielding ability and high-visible light transparency of ZnO nanoparticle in sunscreen cosmetics.

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

Hydrogen treatment as a detergent of electronic trap states in lead chalcogenide nanoparticles

DOE PAGES

Vörös, Márton; Brawand, Nicholas P.; Galli, Giulia

2016-11-15

Lead chalcogenide (PbX) nanoparticles are promising materials for solar energy conversion. However, the presence of trap states in their electronic gap limits their usability, and developing a universal strategy to remove trap states is a persistent challenge. Using calculations based on density functional theory, we show that hydrogen acts as an amphoteric impurity on PbX nanoparticle surfaces; hydrogen atoms may passivate defects arising from ligand imbalance or off-stoichiometric surface terminations irrespective of whether they originate from cation or anion excess. In addition, we show, using constrained density functional theory calculations, that hydrogen treatment of defective nanoparticles is also beneficial formore » charge transport in films. We also find that hydrogen adsorption on stoichiometric nanoparticles leads to electronic doping, preferentially n-type. Lastly, our findings suggest that postsynthesis hydrogen treatment of lead chalcogenide nanoparticle films is a viable approach to reduce electronic trap states or to dope well-passivated films.« less

Targeted therapy of hepatocellular carcinoma with aptamer-functionalized biodegradable nanoparticles

NASA Astrophysics Data System (ADS)

Weigum, Shannon; McIvor, Elizabeth; Munoz, Christopher; Feng, Richard; Cantu, Travis; Walsh, Kyle; Betancourt, Tania

2016-11-01

Hepatocellular carcinoma (HCC) is the most common form of liver cancer, occurring primarily in regions where viral hepatitis infections are common. Unfortunately, most HCC cases remain undiagnosed until late stages of the disease when patient outcome is poor, typically limiting survival from a few months to a year after initial diagnosis. In order to better care for HCC patients, new target-specific approaches are needed to improve early detection and therapeutic intervention. In this work, polymeric nanoparticles functionalized with a HCC-specific aptamer were examined as potential targeted drug delivery vehicles. Specifically, doxorubicin-loaded nanoparticles were prepared via nanoprecipitation of blends of poly(lactic-co-glycolic acid)- b-poly(ethylene glycol). These particles were further functionalized with the HCC-specific TLS11a aptamer. The in vitro interaction and therapeutic efficacy of the aptamer and aptamer-functionalized nanoparticles were characterized in a hepatoma cell line. Nanoparticles were found to be spherical in shape, roughly 100-125 nm in diameter, with a low polydispersity (≤0.2) and slightly negative surface potential. Doxorubicin was encapsulated within the particles at 40 % efficiency. Drug release was found to occur through anomalous transport influenced by diffusion and polymer relaxation, releasing 50 % doxorubicin in the first 10 h and full release occurring within 36 h. Confocal microscopy confirmed binding and attachment of aptamer-targeted nanoparticles to the cell surface of cultured HCC cells. Efficacy studies demonstrated a significant improvement in doxorubicin delivery and cell-killing capacity using the aptamer-functionalized, drug-loaded nanoparticles versus controls further supporting use of aptamer nanoparticles as a targeted drug delivery system for HCC tumors.

Oil-soluble hairy nanoparticles as lubricant additives

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

Zhao, Bin

Oil-soluble polymer brush-grafted nanoparticles (hairy NPs) were synthesized by surface-initiated atom transfer radical polymerization of lauryl methacrylate from initiator-functionalized silica nanoparticles and used as an additive for polyalphaolefin (PAO) for friction and wear reduction. Addition of 1 wt% hairy nanoparticles into PAO led to significant friction and wear reduction compared with PAO base oil.

Nanoparticle decoration with surfactants: Molecular interactions, assembly, and applications

NASA Astrophysics Data System (ADS)

Heinz, Hendrik; Pramanik, Chandrani; Heinz, Ozge; Ding, Yifu; Mishra, Ratan K.; Marchon, Delphine; Flatt, Robert J.; Estrela-Lopis, Irina; Llop, Jordi; Moya, Sergio; Ziolo, Ronald F.

2017-02-01

Nanostructures of diverse chemical nature are used as biomarkers, therapeutics, catalysts, and structural reinforcements. The decoration with surfactants has a long history and is essential to introduce specific functions. The definition of surfactants in this review is very broad, following its lexical meaning ;surface active agents;, and therefore includes traditional alkyl modifiers, biological ligands, polymers, and other surface active molecules. The review systematically covers covalent and non-covalent interactions of such surfactants with various types of nanomaterials, including metals, oxides, layered materials, and polymers as well as their applications. The major themes are (i) molecular recognition and noncovalent assembly mechanisms of surfactants on the nanoparticle and nanocrystal surfaces, (ii) covalent grafting techniques and multi-step surface modification, (iii) dispersion properties and surface reactions, (iv) the use of surfactants to influence crystal growth, as well as (v) the incorporation of biorecognition and other material-targeting functionality. For the diverse materials classes, similarities and differences in surfactant assembly, function, as well as materials performance in specific applications are described in a comparative way. Major factors that lead to differentiation are the surface energy, surface chemistry and pH sensitivity, as well as the degree of surface regularity and defects in the nanoparticle cores and in the surfactant shell. The review covers a broad range of surface modifications and applications in biological recognition and therapeutics, sensors, nanomaterials for catalysis, energy conversion and storage, the dispersion properties of nanoparticles in structural composites and cement, as well as purification systems and classical detergents. Design principles for surfactants to optimize the performance of specific nanostructures are discussed. The review concludes with challenges and opportunities.

Surface functionalization of chitosan-coated magnetic nanoparticles for covalent immobilization of yeast alcohol dehydrogenase from Saccharomyces cerevisiae

NASA Astrophysics Data System (ADS)

Li, Gui-yin; Zhou, Zhi-de; Li, Yuan-jian; Huang, Ke-long; Zhong, Ming

2010-12-01

A novel and efficient immobilization of yeast alcohol dehydrogenase (YADH, EC1.1.1.1) from Saccharomyces cerevisiae has been developed by using the surface functionalization of chitosan-coated magnetic nanoparticles (Fe 3O 4/KCTS) as support. The magnetic Fe 3O 4/KCTS nanoparticles were prepared by binding chitosan alpha-ketoglutaric acid (KCTS) onto the surface of magnetic Fe 3O 4 nanoparticles. Later, covalent immobilization of YADH was attempted onto the Fe 3O 4/KCTS nanoparticles. The effect of various preparation conditions on the immobilized YADH process such as immobilization time, enzyme concentration and pH was investigated. The influence of pH and temperature on the activity of the free and immobilized YADH using phenylglyoxylic acid as substrate has also been studied. The optimum reaction temperature and pH value for the enzymatic conversion catalyzed by the immobilized YADH were 30 °C and 7.4, respectively. Compared to the free enzyme, the immobilized YADH retained 65% of its original activity and exhibited significant thermal stability and good durability.

Bio-inspired formation of functional calcite/metal oxide nanoparticle composites.

PubMed

Kim, Yi-Yeoun; Schenk, Anna S; Walsh, Dominic; Kulak, Alexander N; Cespedes, Oscar; Meldrum, Fiona C

2014-01-21

Biominerals are invariably composite materials, where occlusion of organic macromolecules within single crystals can significantly modify their properties. In this article, we take inspiration from this biogenic strategy to generate composite crystals in which magnetite (Fe3O4) and zincite (ZnO) nanoparticles are embedded within a calcite single crystal host, thereby endowing it with new magnetic or optical properties. While growth of crystals in the presence of small molecules, macromolecules and particles can lead to their occlusion within the crystal host, this approach requires particles with specific surface chemistries. Overcoming this limitation, we here precipitate crystals within a nanoparticle-functionalised xyloglucan gel, where gels can also be incorporated within single crystals, according to their rigidity. This method is independent of the nanoparticle surface chemistry and as the gel maintains its overall structure when occluded within the crystal, the nanoparticles are maintained throughout the crystal, preventing, for example, their movement and accumulation at the crystal surface during crystal growth. This methodology is expected to be quite general, and could be used to endow a wide range of crystals with new functionalities.

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.

Fabrication of nanoscale heterostructures comprised of graphene-encapsulated gold nanoparticles and semiconducting quantum dots for photocatalysis.

PubMed

Li, Yuan; Chopra, Nitin

2015-05-21

Patterned growth of multilayer graphene shell encapsulated gold nanoparticles (GNPs) and their covalent linking with inorganic quantum dots are demonstrated. GNPs were grown using a xylene chemical vapor deposition process, where the surface oxidized gold nanoparticles catalyze the multilayer graphene shell growth in a single step process. The graphene shell encapsulating gold nanoparticles could be further functionalized with carboxylic groups, which were covalently linked to amine-terminated quantum dots resulting in GNP-quantum dot heterostructures. The compositions, morphologies, crystallinity, and surface functionalization of GNPs and their heterostructures with quantum dots were evaluated using microscopic, spectroscopic, and analytical methods. Furthermore, optical properties of the derived architectures were studied using both experimental methods and simulations. Finally, GNP-quantum dot heterostructures were studied for photocatalytic degradation of phenol.

Correlating structural dynamics and catalytic activity of AgAu nanoparticles with ultrafast spectroscopy and all-atom molecular dynamics simulations.

PubMed

Ferbonink, G F; Rodrigues, T S; Dos Santos, D P; Camargo, P H C; Albuquerque, R Q; Nome, R A

2018-05-29

In this study, we investigated hollow AgAu nanoparticles with the goal of improving our understanding of the composition-dependent catalytic activity of these nanoparticles. AgAu nanoparticles were synthesized via the galvanic replacement method with controlled size and nanoparticle compositions. We studied extinction spectra with UV-Vis spectroscopy and simulations based on Mie theory and the boundary element method, and ultrafast spectroscopy measurements to characterize decay constants and the overall energy transfer dynamics as a function of AgAu composition. Electron-phonon coupling times for each composition were obtained from pump-power dependent pump-probe transients. These spectroscopic studies showed how nanoscale surface segregation, hollow interiors and porosity affect the surface plasmon resonance wavelength and fundamental electron-phonon coupling times. Analysis of the spectroscopic data was used to correlate electron-phonon coupling times to AgAu composition, and thus to surface segregation and catalytic activity. We have performed all-atom molecular dynamics simulations of model hollow AgAu core-shell nanoparticles to characterize nanoparticle stability and equilibrium structures, besides providing atomic level views of nanoparticle surface segregation. Overall, the basic atomistic and electron-lattice dynamics of core-shell AgAu nanoparticles characterized here thus aid the mechanistic understanding and performance optimization of AgAu nanoparticle catalysts.

The internalization of fluorescence-labeled PLA nanoparticles by macrophages.

PubMed

Li, Fengjuan; Zhu, Aiping; Song, Xiaoli; Ji, Lijun; Wang, Juan

2013-09-10

Rhodamine B (RhB)-labeled PLA nanoparticles were prepared through surface grafting copolymerization of glycidyl methacrylate (GMA) onto PLA nanoparticles during the emulsion/evaporation process. RhB firstly interacts with sodium dodecyl sulfate (SDS) through electrostatic interaction to form hydrophobic complex (SDS-RhB). Due to the high-affinity of SDS-RhB with GMA, hydrophilic RhB can be successfully combined into PLA nanoparticles. The internalization of RhB-labeled PLA nanoparticles by macrophages was investigated with fluorescence microscope technology. The effects of the PLA nanoparticle surface nature and size on the internalization were investigated. The results indicate that the PLA particles smaller than 200 nm can avoid the uptake of phagocytosis. The bigger PLA particles (300 nm) with polyethylene glycol (PEG) surface showed less internalization by macrophage compared with those with poly(ethylene oxide-propylene oxide) copolymer (F127) or poly(vinyl alcohol) (PVA) surface. The "stealth" function of PEG on the PLA nanoparticles from internalization of macrophages due to the low protein adsorption is revealed by electrochemical impedance technology. Copyright © 2013 Elsevier B.V. All rights reserved.

Activation of Osteoblastic Function on Titanium Surface with Titanium-Doped Hydroxyapatite Nanoparticle Coating: An In Vitro Study.

PubMed

Nakazawa, Masahiro; Yamada, Masahiro; Wakamura, Masato; Egusa, Hiroshi; Sakurai, Kaoru

Titanium-doped hydroxyapatite (TiHA) nanoparticles contain titanium atoms in the hydroxyapatite lattice, which can physicochemically functionalize the titanium surface without modification of the surface topography. This study aimed to evaluate the physicochemical properties of machined or microroughened titanium surfaces coated with TiHA nanoparticles and the functions of osteoblasts cultured on them. Titanium disks with commercially available surface topography, such as machined or sandblasted, large-grit, and acid-etched (SLA) surfaces, were coated with TiHA. The disks with original or TiHA-coated surfaces were evaluated in topography, wettability, and chemical composition. Osteoblastic cells from rat femurs were cultured on the disks and evaluated in proliferation and differentiation. TiHA coating changed from hydrophobicity to hydrophilicity on both machined and SLA surfaces. Calcium and phosphate atoms were detected all over the surface with TiHA coating regardless of the surface topography. However, the considerable change in the inherent surface topographies was not observed on both types of surfaces after TiHA coating. Osteoblastic proliferative activity at day 4 was increased by TiHA coating on both types of surfaces. TiHA coating did not enhance expressions of bone matrix-related genes such as osteocalcin, osteopontin, bone sialoprotein, alkaline phosphatase, and collagen I. However, depositions of collagen, osteocalcin, and calcium in the culture at days 7 and 20 were increased on both types of surface topographies with TiHA coating. TiHA coating enhanced extracellular matrix formation on smooth and microroughened titanium surfaces by increasing osteoblastic proliferative activity without the deterioration of differentiation through hydrophilic and chemical functionalization.

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.

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.

Polymer Nanocomposite Film with Metal Rich Surface Prepared by In Situ Single-Step Formation of Palladium Nanoparticles: An Interesting Way to Combine Specific Functional Properties.

PubMed

Thompson, David; Kranbuehl, David; Espuche, Eliane

2016-10-18

This paper presents a continuous single-step route that permits preparation of a thermostable polymer/metal nanocomposite film and to combine different functional properties in a unique material. More precisely, palladium nanoparticles are in situ generated in a polyimide matrix thanks to a designed curing cycle which is applied to a polyamic acid/metal precursor solution cast on a glass plate. A metal-rich surface layer which is strongly bonded to the bulk film is formed in addition to homogeneously dispersed metal nanoparticles. This specific morphology leads to obtaining an optically reflective film. The metal nanoparticles act as gas diffusion barriers for helium, oxygen, and carbon dioxide; they induce a tortuosity effect which allows dividing the gas permeation coefficients by a factor near to 2 with respect to the neat polyimide matrix. Moreover, the ability of the in situ synthesized palladium nanoparticles to entrap hydrogen is evidenced. The nanocomposite film properties can be modulated as a function of the location of the film metal-rich surface with respect to the hydrogen feed. The synthesized nanocomposite could represent a major interest for a wide variety of applications, from specific coatings for aerospace or automotive industry, to catalysis applications or sensors.

The effect of concentration ratio and type of functional group on synthesis of CNT-ZnO hybrid nanomaterial by an in situ sol-gel process

NASA Astrophysics Data System (ADS)

Hosseini Largani, Sekineh; Akbarzadeh Pasha, Mohammad

2017-12-01

In this research, MWCNT-ZnO hybrid nanomaterials were synthesized by a simple sol-gel process using Zn(CH3COO)2·2H2O and functionalized MWCNT with carboxyl(COOH) and hydroxyl(OH) groups. Three different mass ratios of MWCNT:ZnO = 3:1, 1:1 and 1:3 were examined. The prepared nanomaterials were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR). Successful growth of MWCNT-ZnO hybrids for both COOH and OH functional groups and all the three mass ratios were obtained. The ZnO nanoparticles attached on the surfaces of CNTs have rather spherical shapes and hexagonal crystal structure. By increasing the concentration of ZnO, the number and average size of ZnO nanoparticles decorated the body of CNTs in hybrid structures increase. By increasing the ZnO precursor, the distribution of ZnO nanoparticles that appeared on the surface of CNTs becomes more uniform. The SEM observation beside EDX analysis revealed that at the same concentration ratio the amount of ZnO loading on the surface of MWCNT-COOH is more than MWCNT-OH. Moreover, the average size of ZnO nanoparticles attached on the surface of COOH functionalized CNTs is relatively smaller than that of OH functionalized ones.

Polymer Nanocomposites: Insights from Theory and Molecular Simulations

NASA Astrophysics Data System (ADS)

Pani, Rakhee

Advantages of polymer nanocomposites have attracted great industrial attention due to their multifunctionality and innovative technological properties. Addition of small amount of nanoparticle (nanospheres, nanotubes, nanorods, nanoplatelets, or sheets) to polymer matrix cause dramatic improvement in structural and functional properties, which is difficult to attain from those of individual components. The interaction between polymer and nanoparticle create bulk materials dominated by solid state physics at the nanoscale. Furthermore, morphology of nanocomposites depends on structural arrangements of nanoparticles. Thus, for achievement of optimized functionality like electrical, optical, mechanical and thermal properties control over the dispersion of the nanoparticle is essential. However, properties of polymer nanocomposites depend on morphology control and nature of interfacial interactions. In order to control the morphology it is necessary to understand how the processing conditions, shape and size of nanoparticle influence the structure of composite. Molecular simulations can help us to predict the parameters that control the structural changes and we could design polymer nanocomposite entailing their end-use. In this work, we addressed the following research questions: (1) the dependence of nanoparticle ligand corona structure on solvent quality and (2) the role of interfacial energy and interactions on the dispersion of molecules and nanoparticles. Specifically, this research assessed the effect of solvent interactions on the structure of nanoparticles on the example of redox core encapsulating dendrimer and ligand functionalized gold nanoparticles, role of chemical interaction on solubility of glucose in ionic liquids, diffusion of fullerene nanoparticles in polymer matrix and influence of solubility parameters on the compatibility of gold nanoparticles with diblock copolymers. Computational methods allow quantifying the structure and flexibility of the polymer chains, how energetics and surface tension change with chemical composition of the polymer/dendrimer blocks, influence of nanoparticle on structural properties of polymer and factors which may contribute to the phase separation of the polymer from nanoparticle. Interfacial characteristics are not only determined by the size-induced properties, but also the surface chemistry of the particles. Presence of solvent and the resultant interactions with the solvent are known to influence the morphology and prevent or induce aggregation of nanoparticles in polymers. We found that surface chemistry can induce change in the structure of dendrimers encapsulating a redox active core and change the solubility of the nanoparticles. The interactions between nanoparticles and polymers can also influence the morphology. We performed investigation on the role of orientation of fullerene derivatives and surface energy of polymer surface which may induce the aggregation of the fullerene nanoparticles. Furthermore, we used quantitative measurements like cluster analysis to understand the most probable orientation of the fullerene derivative with respect to the polymer chains and the diffusion of the fullerene nanoparticle, which is related to the efficiency of solar cells, can change on presence of regiorandom and regioregular polymer chains. Furthermore, we have also used different solvents based on their Hildebrand solubility parameters to investigate factors governing the morphology of polymer nanocomposite via solvent interactions. We showed that change in solvent interactions affect the compatibility, aggregation/dispersion of the gold nanoparticles, which will directly affect the morphology of polymer matrix and structural aspects which can impact their functionality. Overall, our research indicated that solvent interaction play a role in controlling the morphology of polymer nanocomposite and solubility parameter can help us to predict the resulting morphology.

Dual-Function Au@Y2O3:Eu3+ Smart Film for Enhanced Power Conversion Efficiency and Long-Term Stability of Perovskite Solar Cells.

PubMed

Kim, Chang Woo; Eom, Tae Young; Yang, In Seok; Kim, Byung Su; Lee, Wan In; Kang, Yong Soo; Kang, Young Soo

2017-07-28

In the present study, a dual-functional smart film combining the effects of wavelength conversion and amplification of the converted wave by the localized surface plasmon resonance has been investigated for a perovskite solar cell. This dual-functional film, composed of Au nanoparticles coated on the surface of Y 2 O 3 :Eu 3+ phosphor (Au@Y 2 O 3 :Eu 3+ ) nanoparticle monolayer, enhances the solar energy conversion efficiency to electrical energy and long-term stability of photovoltaic cells. Coupling between the Y 2 O 3 :Eu 3+ phosphor monolayer and ultraviolet solar light induces the latter to be converted into visible light with a quantum yield above 80%. Concurrently, the Au nanoparticle monolayer on the phosphor nanoparticle monolayer amplifies the converted visible light by up to 170%. This synergy leads to an increased solar light energy conversion efficiency of perovskite solar cells. Simultaneously, the dual-function film suppresses the photodegradation of perovskite by UV light, resulting in long-term stability. Introducing the hybrid smart Au@Y 2 O 3 :Eu 3+ film in perovskite solar cells increases their overall solar-to-electrical energy conversion efficiency to 16.1% and enhances long-term stability, as compared to the value of 15.2% for standard perovskite solar cells. The synergism between the wavelength conversion effect of the phosphor nanoparticle monolayer and the wave amplification by the localized surface plasmon resonance of the Au nanoparticle monolayer in a perovskite solar cell is comparatively investigated, providing a viable strategy of broadening the solar spectrum utilization.

Surface modification of ZnO nanorods with Hamilton receptors.

PubMed

Zeininger, Lukas; Klaumünzer, Martin; Peukert, Wolfgang; Hirsch, Andreas

2015-04-13

A new prototype of a Hamilton receptor suitable for the functionalization of inorganic nanoparticles was synthesized and characterized. The hydrogen bonding receptor was coupled to a catechol moiety, which served as anchor group for the functionalization of metal oxides, in particular zinc oxide. Synthesized zinc oxide nanorods [ZnO] were used for surface functionalization. The wet-chemical functionalization procedure towards monolayer-grafted particles [ZnO-HR] is described and a detailed characterization study is presented. In addition, the detection of specific cyanurate molecules is demonstrated. The hybrid structures [ZnO-HR-CA] were stable towards agglomeration and exhibited enhanced dispersability in apolar solvents. This observation, in combination with several spectroscopic experiments gave evidence of the highly directional supramolecular recognition at the surface of nanoparticles.

Fabrication of high flux and antifouling mixed matrix fumarate-alumoxane/PAN membranes via electrospinning for application in membrane bioreactors

NASA Astrophysics Data System (ADS)

Moradi, Golshan; Zinadini, Sirus; Rajabi, Laleh; Dadari, Soheil

2018-01-01

The nanofibrous Polyacrylonitrile (PAN) membranes embedded with fumarate-alumoxane (Fum-A) nanoparticles were prepared via electrospinning technique as high flux and antifouling membranes for membrane bioreactor (MBR) applications. The effect of Fum-A nanoparticles on membrane morphology, surface hydrophilicity, pure water flux, effluent turbidity and the antifouling property was investigated. Fum-A is a carboxylate-alumoxane nanoparticle covered by extra hydroxyl and carboxylate groups on its surface. By embedding Fum-A nanoparticles into the spinning solution, the surface hydrophilicity and pure water flux of the resulted membranes were improved. The smooth surface of fibers at the low amount of nanoparticles and the agglomeration of nanoparticles at their high concentration were shown in SEM images of the membranes surface. The energy dispersive spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) analysis of the prepared Fum-A/PAN membrane confirmed the presence of carboxylate and hydroxyl functional groups of Fum-A nanoparticles on the surface of the Fum-A nanoparticles containing membrane. The results obtained from the filtration of activated sludge suspension revealed that by addition of a low amount of Fum-A nanoparticles, the irreversible fouling was significantly decreased due to the higher hydrophilicity. The Fum-A/PAN membranes showed superior permeate flux and antifouling properties compared to bare electrospun PAN membrane. Finally, 2 wt.% Fum-A/PAN membrane exhibited the highest FRR of 96% and the lowest irreversible fouling of 4% with excellent durability of antifouling property during twenty repeated activated sludge filtrations.

Nanoparticle mediated micromotor motion

NASA Astrophysics Data System (ADS)

Liu, Mei; Liu, Limei; Gao, Wenlong; Su, Miaoda; Ge, Ya; Shi, Lili; Zhang, Hui; Dong, Bin; Li, Christopher Y.

2015-03-01

In this paper, we report the utilization of nanoparticles to mediate the motion of a polymer single crystal catalytic micromotor. Micromotors have been fabricated by directly self-assembling functional nanoparticles (platinum and iron oxide nanoparticles) onto one or both sides of two-dimensional polymer single crystals. We show that the moving velocity of these micromotors in fluids can be readily tuned by controlling the nanoparticles' surface wettability and catalytic activity. A 3 times velocity increase has been achieved for a hydrophobic micromotor as opposed to the hydrophilic ones. Furthermore, we demonstrate that the catalytic activity of platinum nanoparticles inside the micromotor can be enhanced by their synergetic interactions with iron oxide nanoparticles and an electric field. Both strategies lead to dramatically increased moving velocities, with the highest value reaching ~200 μm s-1. By decreasing the nanoparticles' surface wettability and increasing their catalytic activity, a maximum of a ~10-fold increase in the moving speed of the nanoparticle based micromotor can be achieved. Our results demonstrate the advantages of using nanoparticles in micromotor systems.In this paper, we report the utilization of nanoparticles to mediate the motion of a polymer single crystal catalytic micromotor. Micromotors have been fabricated by directly self-assembling functional nanoparticles (platinum and iron oxide nanoparticles) onto one or both sides of two-dimensional polymer single crystals. We show that the moving velocity of these micromotors in fluids can be readily tuned by controlling the nanoparticles' surface wettability and catalytic activity. A 3 times velocity increase has been achieved for a hydrophobic micromotor as opposed to the hydrophilic ones. Furthermore, we demonstrate that the catalytic activity of platinum nanoparticles inside the micromotor can be enhanced by their synergetic interactions with iron oxide nanoparticles and an electric field. Both strategies lead to dramatically increased moving velocities, with the highest value reaching ~200 μm s-1. By decreasing the nanoparticles' surface wettability and increasing their catalytic activity, a maximum of a ~10-fold increase in the moving speed of the nanoparticle based micromotor can be achieved. Our results demonstrate the advantages of using nanoparticles in micromotor systems. Electronic supplementary information (ESI) available: Fig. S1-S5 and Video S1-S3. See DOI: 10.1039/c4nr07558g

Studies on the biodistribution of dextrin nanoparticles

NASA Astrophysics Data System (ADS)

Gonçalves, C.; Ferreira, M. F. M.; Santos, A. C.; Prata, M. I. M.; Geraldes, C. F. G. C.; Martins, J. A.; Gama, F. M.

2010-07-01

The characterization of biodistribution is a central requirement in the development of biomedical applications based on the use of nanoparticles, in particular for controlled drug delivery. The blood circulation time, organ biodistribution and rate of excretion must be well characterized in the process of product development. In this work, the biodistribution of recently developed self-assembled dextrin nanoparticles is addressed. Functionalization of the dextrin nanoparticles with a DOTA-monoamide-type metal chelator, via click chemistry, is described. The metal chelator functionalized nanoparticles were labelled with a γ-emitting 153Sm3 + radioisotope and the blood clearance rate and organ biodistribution of the nanoparticles were obtained. The effect of PEG surface coating on the blood clearance rate and organ biodistribution of the nanoparticles was also studied.

Preparation of surface plasmon resonance biosensor based on magnetic core/shell Fe3O4/SiO2 and Fe3O4/Ag/SiO2 nanoparticles.

PubMed

Wang, Liying; Sun, Ying; Wang, Jing; Wang, Jian; Yu, Aimin; Zhang, Hanqi; Song, Daqian

2011-06-01

In this paper, surface plasmon resonance biosensors based on magnetic core/shell Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were developed for immunoassay. With Fe(3)O(4) and Fe(3)O(4)/Ag nanoparticles being used as seeding materials, Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were formed by hydrolysis of tetraethyl orthosilicate. The aldehyde group functionalized magnetic nanoparticles provide organic functionality for bioconjugation. The products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), FTIR and UV-vis absorption spectrometry. The magnetic nanoparticles possess the unique superparamagnetism property, exceptional optical properties and good compatibilities, and could be used as immobilization matrix for goat anti-rabbit IgG. The magnetic nanoparticles can be easily immobilized on the surface of SPR biosensor chip by a magnetic pillar. The effects of Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles on the sensitivity of SPR biosensors were also investigated. As a result, the SPR biosensors based on Fe(3)O(4)/SiO(2) nanoparticles and Fe(3)O(4)/Ag/SiO(2) nanoparticles exhibit a response for rabbit IgG in the concentration range of 1.25-20.00 μg ml(-1) and 0.30-20.00 μg ml(-1), respectively. Copyright © 2011 Elsevier B.V. All rights reserved.

Acid monolayer functionalized iron oxide nanoparticle catalysts

NASA Astrophysics Data System (ADS)

Ikenberry, Myles

Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide nanoparticle syntheses and functionalizations for biomedical and catalytic applications, affecting understandings of surface charge and other material properties.

Glyconanoparticles: types, synthesis and applications in glycoscience, biomedicine and material science.

PubMed

de la Fuente, Jesús M; Penadés, Soledad

2006-04-01

Nanoparticles are the subject of numerous papers and reports and are full of promises for electronic, optical, magnetic and biomedical applications. Although metallic nanoparticles have been functionalized with peptides, proteins and DNA during the last 20 years, carbohydrates have not been used with this purpose until 2001. Since the first synthesis of gold nanoparticles functionalized with carbohydrates (glyconanoparticles) was reported, the number of published articles has considerably increased. This article reviews progress in the development of nanoparticles functionalized with biological relevant oligosaccharides. The glyconanoparticles constitute a good bio-mimetic model of carbohydrate presentation at the cell surface, and maybe, excellent tools for Glycobiology, Biomedicine and Material Science investigations.

Avidin-conjugated calcium phosphate nanoparticles as a modular targeting system for the attachment of biotinylated molecules in vitro and in vivo.

PubMed

van der Meer, Selina Beatrice; Knuschke, Torben; Frede, Annika; Schulze, Nina; Westendorf, Astrid M; Epple, Matthias

2017-07-15

Avidin was covalently conjugated to the surface of calcium phosphate nanoparticles, coated with a thin silica shell and terminated by sulfhydryl groups (diameter of the solid core about 50nm), with a bifunctional crosslinker connecting the amino groups of avidin to the sulfhydryl group on the nanoparticle surface. This led to a versatile nanoparticle system where all kinds of biotinylated (bio-)molecules can be easily attached to the surface by the non-covalent avidin-biotin-complex formation. It also permits the attachment of different biomolecules on the same nanoparticle (heteroavidity), creating a modular system for specific applications in medicine and biology. The variability of the binding to the nanoparticle surface of the was demonstrated with various biotinylated molecules, i.e. fluorescent dyes and antibodies. The accessibility of the conjugated avidin was demonstrated by a fluorescence-quenching assay. About 2.6 binding sites for biotin were accessible on each avidin tetramer. Together with a number of about 240 avidin tetramer units per nanoparticle, this offers about 600 binding sites for biotin on each nanoparticle. The uptake of fluorescently labelled avidin-conjugated calcium phosphate nanoparticles by HeLa cells showed the co-localization of fluorescent avidin and fluorescent biotin, indicating the stability of the complex under cell culture conditions. CD11c-antibody functionalized nanoparticles specifically targeted antigen-presenting immune cells (dendritic cells; DCs) in vitro and in vivo (mice) with high efficiency. Calcium phosphate nanoparticles have turned out to be very useful transporters for biomolecules into cells, both in vitro and in vivo. However, their covalent surface functionalization with antibodies, fluorescent dyes, or proteins requires a separate chemical synthesis for each kind of surface molecule. We have therefore developed avidin-terminated calcium phosphate nanoparticles to which all kinds of biotinylated molecules can be easily attached, also as a mixture of two or more molecules. This non-covalent bond is stable both in cell culture and after injection into mice in vivo. Thus, we have created a highly versatile system for many applications, from the delivery of biomolecules over the targeting of cells and tissue to in vivo imaging. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Polymer-encapsulated organic nanoparticles for fluorescence and photoacoustic imaging.

PubMed

Li, Kai; Liu, Bin

2014-09-21

Polymer encapsulated organic nanoparticles have recently attracted increasing attention in the biomedical field because of their unique optical properties, easy fabrication and outstanding performance as imaging and therapeutic agents. Of particular importance is the polymer encapsulated nanoparticles containing conjugated polymers (CP) or fluorogens with aggregation induced emission (AIE) characteristics as the core, which have shown significant advantages in terms of tunable brightness, superb photo- and physical stability, good biocompatibility, potential biodegradability and facile surface functionalization. In this review, we summarize the latest advances in the development of polymer encapsulated CP and AIE fluorogen nanoparticles, including preparation methods, material design and matrix selection, nanoparticle fabrication and surface functionalization for fluorescence and photoacoustic imaging. We also discuss their specific applications in cell labeling, targeted in vitro and in vivo imaging, blood vessel imaging, cell tracing, inflammation monitoring and molecular imaging. We specially focus on strategies to fine-tune the nanoparticle property (e.g. size and fluorescence quantum yield) through precise engineering of the organic cores and careful selection of polymer matrices. The review also highlights the merits and limitations of these nanoparticles as well as strategies used to overcome the limitations. The challenges and perspectives for the future development of polymer encapsulated organic nanoparticles are also discussed.

Fabrication and characterisation of ligand-functionalised ultrapure monodispersed metal nanoparticle nanoassemblies employing advanced gas deposition technique

NASA Astrophysics Data System (ADS)

Geremariam Welearegay, Tesfalem; Cindemir, Umut; Österlund, Lars; Ionescu, Radu

2018-02-01

Here, we report for the first time the fabrication of ligand-functionalised ultrapure monodispersed metal nanoparticles (Au, Cu, and Pt) from their pure metal precursors using the advanced gas deposition technique. The experimental conditions during nanoparticle formation were adjusted in order to obtain ultrafine isolated nanoparticles on different substrates. The morphology and surface analysis of the as-deposited metal nanoparticles were investigated using scanning electron microscopy, x-ray diffraction and Fourier transform infra-red spectroscopy, which demonstrated the formation of highly ordered pure crystalline nanoparticles with a relatively uniform size distribution of ∼10 nm (Au), ∼4 nm (Cu) and ∼3 nm (Pt), respectively. A broad range of organic ligands containing thiol or amine functional groups were attached to the nanoparticles to form continuous networks of nanoparticle-ligand nanoassemblies, which were characterised by scanning electron microscopy and x-ray photoelectron spectroscopy. The electrical resistance of the functional nanoassemblies deposited in the gap spacing of two microfabricated parallel Au electrodes patterned on silicon substrates ranged between tens of kΩ and tens of MΩ, which is suitable for use in many applications including (bio)chemical sensors, surface-enhanced Raman spectroscopy and molecular electronic rectifiers.

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.

Functionalized multimodal ZnO@Gd2O3 nanosystems to use as perspective contrast agent for MRI

NASA Astrophysics Data System (ADS)

Babayevska, Nataliya; Florczak, Patryk; Woźniak-Budych, Marta; Jarek, Marcin; Nowaczyk, Grzegorz; Zalewski, Tomasz; Jurga, Stefan

2017-05-01

The main aim of this research was the synthesis of the multimodal hybrid ZnO@Gd2O3 nanostructures as prospective contrast agent for Magnetic Resonance Imaging (MRI) for bio-medical applications. The nanoparticles surface was functionalized by organosilicon compounds (OSC) then, by folic acid (FA) as targeting agent and doxorubicin (Dox) as chemotherapeutic agent. Doxorubicin and folic acid were attached to the nanoparticles surface by amino groups as well as due to attractive physical interactions. The morphology and crystallography of the nanostructures were studied by HRTEM and SAXS techniques. After ZnO nanoparticles surface modification by Gd3+ and annealing at 900 °C, ZnO@Gd2O3 nanostructures are polydispersed with size 30-100 nm. NMR (Nuclear Magnetic Resonance) studies of ZnO@Gd2O3 were performed on fractionated particles with size up to 50 nm. Fourier transform infrared spectroscopy (FTIR), UV-vis spectroscopy, zeta-potential measurements and energy dispersive X-ray analysis (EDX) showed that functional groups have been effectively bonded onto the nanoparticles surface. The high adsorption capacity of folic acid (up to 20%) and doxorubicin (up to 40%) on nanoparticles was reached upon 15 min of adsorption process in a temperature-dependent manner. The nuclear magnetic resonance (NMR) relaxation measurements confirmed that the obtained ZnO@Gd2O3 nanostructures could be good contrast agents, useful for magnetic resonance imaging.

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

Examining changes in cellular communication in neuroendocrine cells after noble metal nanoparticle exposure.

PubMed

Love, Sara A; Liu, Zhen; Haynes, Christy L

2012-07-07

As nanoparticles enjoy increasingly widespread use in commercial applications, the potential for unintentional exposure has become much more likely during any given day. Researchers in the field of nanotoxicity are working to determine the physicochemical nanoparticle properties that lead to toxicity in an effort to establish safe design rules. This work explores the effects of noble metal nanoparticle exposure in murine chromaffin cells, focusing on examining the effects of size and surface functionality (coating) in silver and gold, respectively. Carbon-fibre microelectrode amperometry was utilized to examine the effect of exposure on exocytosis function, at the single cell level, and provided new insights into the compromised functions of cells. Silver nanoparticles of varied size, between 15 and 60 nm diameter, were exposed to cells and found to alter the release kinetics of exocytosis for those cells exposed to the smallest examined size. Effects of gold were examined after modification with two commonly used 'bio-friendly' polymers, either heparin or poly (ethylene glycol), and gold nanoparticles were found to induce altered cellular adhesion or the number of chemical messenger molecules released, respectively. These results support the body of work suggesting that noble metal nanoparticles perturb exocytosis, typically altering the number of molecules and kinetics of release, and supports a direct disruption of the vesicle matrix by the nanoparticle. Overall, it is clear that various nanoparticle physicochemical properties, including size and surface coating, do modulate changes in cellular communication via exocytosis.

Efficient self-assembly of DNA-functionalized fluorophores and gold nanoparticles with DNA functionalized silicon surfaces: the effect of oligomer spacers

PubMed Central

Milton, James A.; Patole, Samson; Yin, Huabing; Xiao, Qiang; Brown, Tom; Melvin, Tracy

2013-01-01

Although strategies for the immobilization of DNA oligonucleotides onto surfaces for bioanalytical and top-down bio-inspired nanobiofabrication approaches are well developed, the effect of introducing spacer molecules between the surface and the DNA oligonucleotide for the hybridization of nanoparticle–DNA conjugates has not been previously assessed in a quantitative manner. The hybridization efficiency of DNA oligonucleotides end-labelled with gold nanoparticles (1.4 or 10 nm diameter) with DNA sequences conjugated to silicon surfaces via hexaethylene glycol phosphate diester oligomer spacers (0, 1, 2, 6 oligomers) was found to be independent of spacer length. To quantify both the density of DNA strands attached to the surfaces and hybridization with the surface-attached DNA, new methodologies have been developed. Firstly, a simple approach based on fluorescence has been developed for determination of the immobilization density of DNA oligonucleotides. Secondly, an approach using mass spectrometry has been created to establish (i) the mean number of DNA oligonucleotides attached to the gold nanoparticles and (ii) the hybridization density of nanoparticle–oligonucleotide conjugates with the silicon surface–attached complementary sequence. These methods and results will be useful for application with nanosensors, the self-assembly of nanoelectronic devices and the attachment of nanoparticles to biomolecules for single-molecule biophysical studies. PMID:23361467

PVA and PEG functionalised LSMO nanoparticles for magnetic fluid hyperthermia application

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

Jadhav, S.V.; Nikam, D.S.; Khot, V.M.

2015-04-15

La{sub 0.7}Sr{sub 0.3}MnO{sub 3} magnetic nanoparticles are synthesized by a solution combustion method and functionalised with polyvinyl alcohol and polyethylene glycol. The induction heating characteristics of coated magnetic nanoparticles (42 °C) were observed at a reasonably low concentration (5 mg/mL). Remarkably, coated magnetic nanoparticles exhibited a promisingly high specific absorption rate with varying magnetic field and constant frequency. The surface analysis is carried out by X-ray photoelectron spectroscopy. A reduction in the agglomeration of the particles was observed when the magnetic nanoparticles were functionalised with polyvinyl alcohol or polyethylene glycol and can be confirmed by transmission electron microscopy and dynamicmore » light scattering studies. Vibrating sample magnetometer measurements indicate superparamagnetic behaviour at room temperature before and after coating. Colloidal stability revealed a considerably higher zeta potential value for coated system. In vitro cytotoxicity test of the magnetic nanoparticles indicates that coated nanoparticles have no significant effect on cell viability within the tested concentrations (1–5 mg mL{sup -1}) as compared to uncoated La{sub 0.7}Sr{sub 0.3}MnO{sub 3}. All these findings explore the potentiality of La{sub 0.7}Sr{sub 0.3}MnO{sub 3} nanoparticles for magnetic fluid hyperthermia. - Highlights: • Surface functionalization of LSMO nanoparticles — first time with PVA • Surface functionalization of LSMO nanoparticles — first time with PEG • BSA protein — first time used as dispersion medium for stability of LSMO nanoparticles • The heating ability observed at low concentration • Improved efficiency of magnetic fluid hyperthermia treatment with surfactants.« less

How surface functional groups influence fracturation in nanofluids droplets dry-outs

NASA Astrophysics Data System (ADS)

Brutin, David; Carle, Florian

2012-11-01

We report an experimental investigation of the drying of a deposited droplets of nanofluids with different surface functional groups. For identical nano-particles diameter, material and concentration, identical drying conditions, the substrate and the functional groups at the nano-particles surface are changed. Both flow motion, adhesion, gelation and fracturation occur during the evaporation of this complex matter leading to different final typical patterns. The differences in between the patterns are explained based on the surface chemical potential. Crack shapes and wavelengths are globally proportional to the electrical charges carried at the nano- particles surface which is a new parameter to implement in existing predicting models. Presently only the colloid concentration and softness and the deposit thickness are used (Allain and Limat, 1995). The authors gratefully acknowledge the help and the fruitful discussions raised with J.B. Lang.

Colorimetric-Based Detection of TNT Explosives Using Functionalized Silica Nanoparticles

PubMed Central

Idros, Noorhayati; Ho, Man Yi; Pivnenko, Mike; Qasim, Malik M.; Xu, Hua; Gu, Zhongze; Chu, Daping

2015-01-01

This proof-of-concept study proposes a novel sensing mechanism for selective and label-free detection of 2,4,6-trinitrotoluene (TNT). It is realized by surface chemistry functionalization of silica nanoparticles (NPs) with 3-aminopropyl-triethoxysilane (APTES). The primary amine anchored to the surface of the silica nanoparticles (SiO2-NH2) acts as a capturing probe for TNT target binding to form Meisenheimer amine–TNT complexes. A colorimetric change of the self-assembled (SAM) NP samples from the initial green of a SiO2-NH2 nanoparticle film towards red was observed after successful attachment of TNT, which was confirmed as a result of the increased separation between the nanoparticles. The shift in the peak wavelength of the reflected light normal to the film surface (λpeak) and the associated change of the peak width were measured, and a merit function taking into account their combined effect was proposed for the detection of TNT concentrations from 10−12 to 10−4 molar. The selectivity of our sensing approach is confirmed by using TNT-bound nanoparticles incubated in AptamerX, with 2,4-dinitrotoluene (DNT) and toluene used as control and baseline, respectively. Our results show the repeatable systematic color change with the TNT concentration and the possibility to develop a robust, easy-to-use, and low-cost TNT detection method for performing a sensitive, reliable, and semi-quantitative detection in a wide detection range. PMID:26046595

Ion-ion correlation, solvent excluded volume and pH effects on physicochemical properties of spherical oxide nanoparticles.

PubMed

Ovanesyan, Zaven; Aljzmi, Amal; Almusaynid, Manal; Khan, Asrar; Valderrama, Esteban; Nash, Kelly L; Marucho, Marcelo

2016-01-15

One major source of complexity in the implementation of nanoparticles in aqueous electrolytes arises from the strong influence that biological environments has on their physicochemical properties. A key parameter for understanding the molecular mechanisms governing the physicochemical properties of nanoparticles is the formation of the surface charge density. In this article, we present an efficient and accurate approach that combines a recently introduced classical solvation density functional theory for spherical electrical double layers with a surface complexation model to account for ion-ion correlation and excluded volume effects on the surface titration of spherical nanoparticles. We apply the proposed computational approach to account for the charge-regulated mechanisms on the surface chemistry of spherical silica (SiO2) nanoparticles. We analyze the effects of the nanoparticle size, as well as pH level and electrolyte concentration of the aqueous solution on the nanoparticle's surface charge density and Zeta potential. We validate our predictions for 580Å and 200Å nanoparticles immersed in acid, neutral and alkaline mono-valent aqueous electrolyte solutions against experimental data. Our results on mono-valent electrolyte show that the excluded volume and ion-ion correlations contribute significantly to the surface charge density and Zeta potential of the nanoparticle at high electrolyte concentration and pH levels, where the solvent crowding effects and electrostatic screening have shown a profound influence on the protonation/deprotonation reactions at the liquid/solute interface. The success of this approach in describing physicochemical properties of silica nanoparticles supports its broader application to study other spherical metal oxide nanoparticles. Copyright © 2015 Elsevier Inc. All rights reserved.

Gentamicin coated iron oxide nanoparticles as novel antibacterial agents

NASA Astrophysics Data System (ADS)

Bhattacharya, Proma; Neogi, Sudarsan

2017-09-01

Applications of different types of magnetic nanoparticles for biomedical purposes started a long time back. The concept of surface functionalization of the iron oxide nanoparticles with antibiotics is a novel technique which paves the path for further application of these nanoparticles by virtue of their property of superparamagnetism. In this paper, we have synthesized novel iron oxide nanoparticles surface functionalized with Gentamicin. The average size of the particles, concluded from the HR-TEM images, came to be around 14 nm and 10 nm for unmodified and modified nanoparticles, respectively. The magnetization curve M(H) obtained for these nanoparticles are typical of superparamagnetic nature and having almost zero values of coercivity and remanance. The release properties of the drug coated nanoparticles were studied; obtaining an S shaped profile, indicating the initial burst effect followed by gradual sustained release. In vitro investigations against various gram positive and gram negative strains viz Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and Bacillus subtilis indicated significant antibacterial efficiency of the drug-nanoparticle conjugate. The MIC values indicated that a small amount like 0.2 mg ml-1 of drug capped particles induce about 98% bacterial death. The novelty of the work lies in the drug capping of the nanoparticles, which retains the superparamagnetic nature of the iron oxide nanoparticles and the medical properties of the drug simultaneously, which is found to extremely blood compatible.

Silica nanoparticles with a substrate switchable luminescence

NASA Astrophysics Data System (ADS)

Bochkova, O. D.; Mustafina, A. R.; Fedorenko, S. V.; Konovalov, A. I.

2011-04-01

Silica nanoparticles with visible (Tb and Ru doped), near IR (Yb doped) and dual visible-near IR luminescence (Ru-Yb doped) were obtained by reverse w/o microemulsion procedure. Plenty of luminescent complexes (from 4900 to 10000) encapsulated into each nanoparticle ensures the intensive luminescence of nanoparticles and their applicability as biomarkers. The silica surface decoration by definite anchor groups is the required step for the gaining to these nanoparticles marking and sensing functions. Thus covalent and non-covalent surface modification of these nanoparticles was developed to provide the binding with biotargets and sensing of anions. The dicationic surfactant coating of negatively charged Tb(III)-TCAS doped silica nanoparticles was chosen as the basis for the anion responsible system. The reversible insertion of the quenching anions (namely phenol red) into the surfactant based layer at the surface of luminescent nanoparticles switches off the Tb-centered luminescence. In turn the reversible reestablishment of the luminescence results from the competitive insertion of the non-quenching anions into the surfactant layer at the silica/water interface. The hydrophobic anions exemplified by dodecylsulfates versus hydrophilic ones (hydrophosphates) are preferable in the competition with phenol red anions.

A novel DNA nanosensor based on CdSe/ZnS quantum dots and synthesized Fe3O4 magnetic nanoparticles.

PubMed

Hushiarian, Roozbeh; Yusof, Nor Azah; Abdullah, Abdul Halim; Ahmad, Shahrul Ainliah Alang; Dutse, Sabo Wada

2014-04-09

Although nanoparticle-enhanced biosensors have been extensively researched, few studies have systematically characterized the roles of nanoparticles in enhancing biosensor functionality. This paper describes a successful new method in which DNA binds directly to iron oxide nanoparticles for use in an optical biosensor. A wide variety of nanoparticles with different properties have found broad application in biosensors because their small physical size presents unique chemical, physical, and electronic properties that are different from those of bulk materials. Of all nanoparticles, magnetic nanoparticles are proving to be a versatile tool, an excellent case in point being in DNA bioassays, where magnetic nanoparticles are often used for optimization of the hybridization and separation of target DNA. A critical step in the successful construction of a DNA biosensor is the efficient attachment of biomolecules to the surface of magnetic nanoparticles. To date, most methods of synthesizing these nanoparticles have led to the formation of hydrophobic particles that require additional surface modifications. As a result, the surface to volume ratio decreases and nonspecific bindings may occur so that the sensitivity and efficiency of the device deteriorates. A new method of large-scale synthesis of iron oxide (Fe3O4) nanoparticles which results in the magnetite particles being in aqueous phase, was employed in this study. Small modifications were applied to design an optical DNA nanosensor based on sandwich hybridization. Characterization of the synthesized particles was carried out using a variety of techniques and CdSe/ZnS core-shell quantum dots were used as the reporter markers in a spectrofluorophotometer. We showed conclusively that DNA binds to the surface of ironoxide nanoparticles without further surface modifications and that these magnetic nanoparticles can be efficiently utilized as biomolecule carriers in biosensing devices.

Influence of Collector Surface Composition and Water Chemistry on the Deposition of Cerium Dioxide Nanoparticles: QCM-D and Column Experiment Approaches

EPA Science Inventory

The deposition behavior of cerium dioxide (CeO2) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied ...

Immune response to functionalized mesoporous silica nanoparticles for targeted drug delivery

NASA Astrophysics Data System (ADS)

Heidegger, Simon; Gößl, Dorothée; Schmidt, Alexandra; Niedermayer, Stefan; Argyo, Christian; Endres, Stefan; Bein, Thomas; Bourquin, Carole

2015-12-01

Multifunctional mesoporous silica nanoparticles (MSN) have attracted substantial attention with regard to their high potential for targeted drug delivery. For future clinical applications it is crucial to address safety concerns and understand the potential immunotoxicity of these nanoparticles. In this study, we assess the biocompatibility and functionality of multifunctional MSN in freshly isolated, primary murine immune cells. We show that the functionalized silica nanoparticles are rapidly and efficiently taken up into the endosomal compartment by specialized antigen-presenting cells such as dendritic cells. The silica nanoparticles showed a favorable toxicity profile and did not affect the viability of primary immune cells from the spleen in relevant concentrations. Cargo-free MSN induced only very low immune responses in primary cells as determined by surface expression of activation markers and release of pro-inflammatory cytokines such as Interleukin-6, -12 and -1β. In contrast, when surface-functionalized MSN with a pH-responsive polymer capping were loaded with an immune-activating drug, the synthetic Toll-like receptor 7 agonist R848, a strong immune response was provoked. We thus demonstrate that MSN represent an efficient drug delivery vehicle to primary immune cells that is both non-toxic and non-inflammagenic, which is a prerequisite for the use of these particles in biomedical applications.Multifunctional mesoporous silica nanoparticles (MSN) have attracted substantial attention with regard to their high potential for targeted drug delivery. For future clinical applications it is crucial to address safety concerns and understand the potential immunotoxicity of these nanoparticles. In this study, we assess the biocompatibility and functionality of multifunctional MSN in freshly isolated, primary murine immune cells. We show that the functionalized silica nanoparticles are rapidly and efficiently taken up into the endosomal compartment by specialized antigen-presenting cells such as dendritic cells. The silica nanoparticles showed a favorable toxicity profile and did not affect the viability of primary immune cells from the spleen in relevant concentrations. Cargo-free MSN induced only very low immune responses in primary cells as determined by surface expression of activation markers and release of pro-inflammatory cytokines such as Interleukin-6, -12 and -1β. In contrast, when surface-functionalized MSN with a pH-responsive polymer capping were loaded with an immune-activating drug, the synthetic Toll-like receptor 7 agonist R848, a strong immune response was provoked. We thus demonstrate that MSN represent an efficient drug delivery vehicle to primary immune cells that is both non-toxic and non-inflammagenic, which is a prerequisite for the use of these particles in biomedical applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06122a

Long-circulating Janus nanoparticles made by electrohydrodynamic co-jetting for systemic drug delivery applications.

PubMed

Rahmani, Sahar; Villa, Carlos H; Dishman, Acacia F; Grabowski, Marika E; Pan, Daniel C; Durmaz, Hakan; Misra, Asish C; Colón-Meléndez, Laura; Solomon, Michael J; Muzykantov, Vladimir R; Lahann, Joerg

2015-01-01

Nanoparticles with controlled physical properties have been widely used for controlled release applications. In addition to shape, the anisotropic nature of the particles can be an important design criterion to ensure selective surface modification or independent release of combinations of drugs. Electrohydrodynamic (EHD) co-jetting is used for the fabrication of uniform anisotropic nanoparticles with individual compartments and initial physicochemical and biological characterization is reported. EHD co-jetting is used to create nanoparticles, which are characterized at each stage with scanning electron microscopy (SEM), structured illumination microscopy (SIM), dynamic light scattering (DLS) and nanoparticle tracking analysis (NTA). Surface immobilization techniques are used to incorporate polyethylene glycol (PEG) and I(125) radiolabels into the nanoparticles. Particles are injected in mice and the particle distribution after 1, 4 and 24 hours is assessed. Nanoparticles with an average diameter of 105.7 nm are prepared by EHD co-jetting. The particles contain functional chemical groups for further surface modification and radiolabeling. The density of PEG molecules attached to the surface of nanoparticles is determined to range between 0.02 and 6.04 ligands per square nanometer. A significant fraction of the nanoparticles (1.2% injected dose per mass of organ) circulates in the blood after 24 h. EHD co-jetting is a versatile method for the fabrication of nanoparticles for drug delivery. Circulation of the nanoparticles for 24 h is a pre-requisite for subsequent studies to explore defined targeting of the nanoparticles to a specific anatomic site.

Iron oxide magnetic nanoparticles with versatile surface functions based on dopamine anchors

NASA Astrophysics Data System (ADS)

Mazur, Mykola; Barras, Alexandre; Kuncser, Victor; Galatanu, Andrei; Zaitzev, Vladimir; Turcheniuk, Kostiantyn V.; Woisel, Patrice; Lyskawa, Joel; Laure, William; Siriwardena, Aloysius; Boukherroub, Rabah; Szunerits, Sabine

2013-03-01

The synthesis of multifunctional magnetic nanoparticles (MF-MPs) is one of the most active research areas in advanced materials as their multifunctional surfaces allow conjugation of biological and chemical molecules, thus making it possible to achieve target-specific diagnostic in parallel to therapeutics. We report here a simple strategy to integrate in a one-step reaction several reactive sites onto the particles. The preparation of MF-MPs is based on their simultaneous modification with differently functionalized dopamine derivatives using simple solution chemistry. The formed MF-MPs show comparable magnetic properties to those of naked nanoparticles with almost unaltered particle size of around 25 nm. The different termini, amine, azide and maleimide functions, enable further functionalization of MF-MPs by the grafting-on approach. Michael addition, Cu(i) catalyzed « click » chemistry and amidation reactions are performed on the MF-MPs integrating subsequently 6-(ferrocenyl)-hexanethiol, horseradish peroxidase (HRP) and mannose.

Cellular membrane trafficking of mesoporous silica nanoparticles

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

Fang, I-Ju

This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulfmore » some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine the specific organelle that mesoporous silica nanoparticles could approach via the identification of harvested proteins from exocytosis process. Based on the study of endo- and exocytosis behavior of mesoporous silica nanoparticle materials, we can design smarter drug delivery vehicles for cancer therapy that can be effectively controlled. The destination, uptake efficiency and the cellular distribution of mesoporous silica nanoparticle materials can be programmable. As a result, release mechanism and release rate of drug delivery systems can be a well-controlled process. The deep investigation of an endo- and exocytosis study of mesoporous silica nanoparticle materials promotes the development of drug delivery applications.« less

Polymer-functionalized nanoparticles for improving oil displacement

NASA Astrophysics Data System (ADS)

Fossati, Ana B.; Martins Alho, Miriam; Jacobo, Silvia E.

2018-03-01

This work focuses on the synthesis, functionalization, and characterization of magnetic nanoparticles to be used for improving the oil recovery in the oil exploitation industry. In this manuscript we explore three different types of hydrophobic/hydrophilic functionalization through a silanized particle: with styrene, with acrylic acid and with a copolymer of styrene and maleic acid. Further application of such nanoparticles dispersions (nanofluid) are discussed as the wetting and spreading behaviour of liquids on the solid surfaces change if the wettability of solid surface is altered. In order to investigate the influence of wettability alternation on enhancing oil recovery after nanofluid treatment, flushing oil experiment and contact angle measurement were conducted in our laboratory. The results indicated that nanofluid can produce a better flushing efficiency compared with brine solution, and the contact angles of oil phase increased from 13° to 37° after nanofluid treatment (0.005% w/w). We focus on the synthesis of magnetic iron oxide nanoparticles considering recovering possibility.

Electrochemical synthesis of elongated noble metal nanoparticles, such as nanowires and nanorods, on high-surface area carbon supports

DOEpatents

Adzic, Radoslav; Blyznakov, Stoyan; Vukmirovic, Miomir

2015-08-04

Elongated noble-metal nanoparticles and methods for their manufacture are disclosed. The method involves the formation of a plurality of elongated noble-metal nanoparticles by electrochemical deposition of the noble metal on a high surface area carbon support, such as carbon nanoparticles. Prior to electrochemical deposition, the carbon support may be functionalized by oxidation, thus making the manufacturing process simple and cost-effective. The generated elongated nanoparticles are covalently bound to the carbon support and can be used directly in electrocatalysis. The process provides elongated noble-metal nanoparticles with high catalytic activities and improved durability in combination with high catalyst utilization since the nanoparticles are deposited and covalently bound to the carbon support in their final position and will not change in forming an electrode assembly.

TiO2 Nanoparticle-Induced Oxidation of the Plasma Membrane: Importance of the Protein Corona.

PubMed

Runa, Sabiha; Lakadamyali, Melike; Kemp, Melissa L; Payne, Christine K

2017-09-21

Titanium dioxide (TiO 2 ) nanoparticles, used as pigments and photocatalysts, are widely present in modern society. Inhalation or ingestion of these nanoparticles can lead to cellular-level interactions. We examined the very first step in this cellular interaction, the effect of TiO 2 nanoparticles on the lipids of the plasma membrane. Within 12 h of TiO 2 nanoparticle exposure, the lipids of the plasma membrane were oxidized, determined with a malondialdehyde assay. Lipid peroxidation was inhibited by surface passivation of the TiO 2 nanoparticles, incubation with an antioxidant (Trolox), and the presence of serum proteins in solution. Subsequent experiments determined that serum proteins adsorbed on the surface of the TiO 2 nanoparticles, forming a protein corona, inhibit lipid peroxidation. Super-resolution fluorescence microscopy showed that these serum proteins were clustered on the nanoparticle surface. These protein clusters slow lipid peroxidation, but by 24 h, the level of lipid peroxidation is similar, independent of the protein corona or free serum proteins. Additionally, over 24 h, this corona of proteins was displaced from the nanoparticle surface by free proteins in solution. Overall, these experiments provide the first mechanistic investigation of plasma membrane oxidation by TiO 2 nanoparticles, in the absence of UV light and as a function of the protein corona, approximating a physiological environment.

The effect of nanoparticle size on in vivo pharmacokinetics and cellular interaction

PubMed Central

Hoshyar, Nazanin; Gray, Samantha; Han, Hongbin; Bao, Gang

2016-01-01

Nanoparticle-based technologies offer exciting new approaches to disease diagnostics and therapeutics. To take advantage of unique properties of nanoscale materials and structures, the size, shape and/or surface chemistry of nanoparticles need to be optimized, allowing their functionalities to be tailored for different biomedical applications. Here we review the effects of nanoparticle size on cellular interaction and in vivo pharmacokinetics, including cellular uptake, biodistribution and circulation half-life of nanoparticles. Important features of nanoparticle probes for molecular imaging and modeling of nanoparticle size effects are also discussed. PMID:27003448

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.

Mean-field and linear regime approach to magnetic hyperthermia of core-shell nanoparticles: can tiny nanostructures fight cancer?

NASA Astrophysics Data System (ADS)

Carrião, Marcus S.; Bakuzis, Andris F.

2016-04-01

The phenomenon of heat dissipation by magnetic materials interacting with an alternating magnetic field, known as magnetic hyperthermia, is an emergent and promising therapy for many diseases, mainly cancer. Here, a magnetic hyperthermia model for core-shell nanoparticles is developed. The theoretical calculation, different from previous models, highlights the importance of heterogeneity by identifying the role of surface and core spins on nanoparticle heat generation. We found that the most efficient nanoparticles should be obtained by selecting materials to reduce the surface to core damping factor ratio, increasing the interface exchange parameter and tuning the surface to core anisotropy ratio for each material combination. From our results we propose a novel heat-based hyperthermia strategy with the focus on improving the heating efficiency of small sized nanoparticles instead of larger ones. This approach might have important implications for cancer treatment and could help improving clinical efficacy.The phenomenon of heat dissipation by magnetic materials interacting with an alternating magnetic field, known as magnetic hyperthermia, is an emergent and promising therapy for many diseases, mainly cancer. Here, a magnetic hyperthermia model for core-shell nanoparticles is developed. The theoretical calculation, different from previous models, highlights the importance of heterogeneity by identifying the role of surface and core spins on nanoparticle heat generation. We found that the most efficient nanoparticles should be obtained by selecting materials to reduce the surface to core damping factor ratio, increasing the interface exchange parameter and tuning the surface to core anisotropy ratio for each material combination. From our results we propose a novel heat-based hyperthermia strategy with the focus on improving the heating efficiency of small sized nanoparticles instead of larger ones. This approach might have important implications for cancer treatment and could help improving clinical efficacy. Electronic supplementary information (ESI) available: Unit cells per region calculation; core-shell Hamiltonian; magnetisation description functions; energy argument of Brillouin function; polydisperse models; details of experimental procedure; LRT versus core-shell model; model calculation software; and shell thickness study. See DOI: 10.1039/C5NR09093H

Assembly of Functional Porous Solids in Complex Hybrid Composites

DTIC Science & Technology

2004-03-19

synthesis … 30 7.1.2 Grafting … 34 7.2 Surface functionalization of 3DOM oxide supports with polyelectrolytes and nanoparticles of another oxide … 34...incorporating hydrothermally prepared rutile/anatase nanoparticles (᝿ nm) within the walls of 3DOM silica, varying the titania content from ca. 0.5-20 wt... nanoparticles showing the bright colors that can be obtained and varied through synthesis parameters. 5.7 Effects of 3DOM particle sizes on optical

Nanoparticle mediated micromotor motion.

PubMed

Liu, Mei; Liu, Limei; Gao, Wenlong; Su, Miaoda; Ge, Ya; Shi, Lili; Zhang, Hui; Dong, Bin; Li, Christopher Y

2015-03-21

In this paper, we report the utilization of nanoparticles to mediate the motion of a polymer single crystal catalytic micromotor. Micromotors have been fabricated by directly self-assembling functional nanoparticles (platinum and iron oxide nanoparticles) onto one or both sides of two-dimensional polymer single crystals. We show that the moving velocity of these micromotors in fluids can be readily tuned by controlling the nanoparticles' surface wettability and catalytic activity. A 3 times velocity increase has been achieved for a hydrophobic micromotor as opposed to the hydrophilic ones. Furthermore, we demonstrate that the catalytic activity of platinum nanoparticles inside the micromotor can be enhanced by their synergetic interactions with iron oxide nanoparticles and an electric field. Both strategies lead to dramatically increased moving velocities, with the highest value reaching ∼200 μm s(-1). By decreasing the nanoparticles' surface wettability and increasing their catalytic activity, a maximum of a ∼10-fold increase in the moving speed of the nanoparticle based micromotor can be achieved. Our results demonstrate the advantages of using nanoparticles in micromotor systems.

A comparative analysis of localized and propagating surface plasmon resonance sensors: the binding of concanavalin a to a monosaccharide functionalized self-assembled monolayer.

PubMed

Yonzon, Chanda Ranjit; Jeoung, Eunhee; Zou, Shengli; Schatz, George C; Mrksich, Milan; Van Duyne, Richard P

2004-10-06

A comparative analysis of the properties of two optical biosensor platforms: (1) the propagating surface plasmon resonance (SPR) sensor based on a planar, thin film gold surface and (2) the localized surface plasmon resonance (LSPR) sensor based on surface confined Ag nanoparticles fabricated by nanosphere lithography (NSL) are presented. The binding of Concanavalin A (ConA) to mannose-functionalized self-assembled monolayers (SAMs) was chosen to highlight the similarities and differences between the responses of the real-time angle shift SPR and wavelength shift LSPR biosensors. During the association phase in the real-time binding studies, both SPR and LSPR sensors exhibited qualitatively similar signal vs time curves. However, in the dissociation phase, the SPR sensor showed an approximately 5 times greater loss of signal than the LSPR sensor. A comprehensive set of nonspecific binding studies demonstrated that this signal difference was not the consequence of greater nonspecific binding to the LSPR sensor but rather a systematic function of the Ag nanoparticle's nanoscale structure. Ag nanoparticles with larger aspect ratios showed larger dissociation phase responses than those with smaller aspect ratios. A theoretical analysis based on finite element electrodynamics demonstrates that this results from the characteristic decay length of the electromagnetic fields surrounding Ag nanoparticles being of comparable dimensions to the ConA molecules. Finally, an elementary (2 x 1) multiplexed version of an LSPR carbohydrate sensing chip to probe the simultaneous binding of ConA to mannose and galactose-functionalized SAMs has been demonstrated.

Synthesis of D-mannose capped silicon nanoparticles and their interactions with MCF-7 human breast cancerous cells.

PubMed

Ahire, Jayshree H; Chambrier, Isabelle; Mueller, Anja; Bao, Yongping; Chao, Yimin

2013-08-14

Silicon nanoparticles (SiNPs) hold prominent interest in various aspects of biomedical applications. For this purpose, surface functionalization of the NPs is essential to stabilize them, target them to specific disease area, and allow them to selectively bind to the cells or the bio-molecules present on the surface of the cells. However, no such functionalization has been explored with Si nanoparticles. Carbohydrates play a critical role in cell recognition. Here, we report the first synthesis of silicon nanoparticles functionalized with carbohydrates. In this study, stable and brightly luminescent d-Mannose (Man) capped SiNPs have been synthesized from amine terminated SiNPs and d-mannopyranoside acid. The surface functionalization is confirmed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), and energy dispersive X-ray spectroscopy (EDX) studies. The mean diameter of the crystal core is 5.5 nm, as measured by transmission electron microscopy (TEM), while the hydrodynamic diameter obtained by dynamic light scattering (DLS) is 16 nm. The quantum yield (QY) of photoluminescence emission is found to be 11.5%, and the nanoparticles exhibit an exceptional stability over two weeks. The Man-capped SiNPs may prove to be valuable tools for further investigating glycobiological, biomedical, and material science fields. Experiments are carried out using Concanavalin A (ConA) as a target protein in order to prove the hypothesis. When Man functionalized SiNPs are treated with ConA, cross-linked aggregates are formed, as shown in TEM images as well as monitored by photoluminescence spectroscopy (PL). Man functionalized SiNPs can target cancerous cells. Visualization imaging of SiNPs in MCF-7 human breast cancer cells shows the fluorescence is distributed throughout the cytoplasm of these cells.

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.

Surface grafting of zwitterionic polymers onto dye doped AIE-active luminescent silica nanoparticles through surface-initiated ATRP for biological imaging applications

NASA Astrophysics Data System (ADS)

Mao, Liucheng; Liu, Xinhua; Liu, Meiying; Huang, Long; Xu, Dazhuang; Jiang, Ruming; Huang, Qiang; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2017-10-01

Aggregation-induced emission (AIE) dyes have recently been intensively explored for biological imaging applications owing to their outstanding optical feature as compared with conventional organic dyes. The AIE-active luminescent silica nanoparticles (LSNPs) are expected to combine the advantages both of silica nanoparticles and AIE-active dyes. Although the AIE-active LSNPs have been prepared previously, surface modification of these AIE-active LSNPs with functional polymers has not been reported thus far. In this work, we reported a rather facile and general strategy for preparation of polymers functionalized AIE-active LSNPs through the surface-initiated atom transfer radical polymerization (ATRP). The AIE-active LSNPs were fabricated via direct encapsulation of AIE-active dye into silica nanoparticles through a non-covalent modified Stöber method. The ATRP initiator was subsequently immobilized onto these AIE-active LSNPs through amidation reaction between 3-aminopropyl-triethoxy-silane and 2-bromoisobutyryl bromide. Finally, the zwitterionic 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) was selected as model monomer and grafted onto MSNs through ATRP. The characterization results suggested that LSNPs can be successfully modified with poly(MPC) through surface-initiated ATRP. The biological evaluation results demonstrated that the final SNPs-AIE-pMPC composites possess low cytotoxicity, desirable optical properties and great potential for biological imaging. Taken together, we demonstrated that AIE-active LSNPs can be fabricated and surface modified with functional polymers to endow novel functions and better performance for biomedical applications. More importantly, this strategy developed in this work could also be extended for fabrication of many other LSNPs polymer composites owing to the good monomer adoptability of ATRP.

The role of ROS generation from magnetic nanoparticles in an alternating magnetic field on cytotoxicity

PubMed Central

Wydra, Robert J.; Rychahou, Piotr G.; Evers, B. Mark; Anderson, Kimberly W.; Dziubla, Thomas D.; Hilt, J. Zach

2015-01-01

Monosaccharide coated iron oxide nanoparticles were developed to selectively target colon cancer cell lines for magnetically mediated energy delivery therapy. The nanoparticles were prepared using a coupling reaction to attach the glucose functional group to the iron oxide core, and functionality was confirmed with physicochemical characterization techniques. The targeted nanoparticles were internalized into CT26 cells at a greater extent than non-targeted nanoparticles, and the nanoparticles were shown to be localized within lysosomes. Cells with internalized nanoparticles were exposed to an AMF to determine the potential to delivery therapy. Cellular ROS generation and apoptotic cell death was enhanced with field exposure. The nanoparticle coatings inhibit the Fenton-like surface generation of ROS suggesting a thermal or mechanical effect is more likely the source of the intracellular effect. PMID:26143604

Final Report: “Energetics of Nanomaterials”

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

Woodfield, Brian F.; navrotsky, alexandra; Ross, Nancy

2016-08-30

Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of compositionmore » and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.« less

Final Report: "Energetics of Nanomaterials

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

Navrotsky, Alexandra; Ross, Nancy; Woodfield, Brian

2015-02-14

Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of compositionmore » and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.« less

Enhanced chemiluminescence-based detection on gold substrate after electrografting of diazonium precursor-coated gold nanoparticles.

PubMed

Houmed Adabo, Ali; Zeggari, Rabah; Mohamed Saïd, Nasser; Bazzi, Rana; Elie-Caille, Céline; Marquette, Christophe; Martini, Matteo; Tillement, Olivier; Perriat, Pascal; Chaix, Carole; Boireau, Wilfrid; Roux, Stéphane

2016-04-01

Since it was demonstrated that nanostructured surfaces are more efficient for the detection based on the specific capture of analytes, there is a real need to develop strategies for grafting nanoparticles onto flat surfaces. Among the different routes for the functionalization of a surface, the reduction of diazonium salts appears very attractive for the covalent immobilization of nanoparticles because this method does not require a pre-treatment of the surface. For achieving this goal, gold nanoparticles coated by precursor of diazonium salts were synthesized by reduction of gold salt in presence of mercaptoaniline. These mercaptoaniline-coated gold nanoparticles (Au@MA) were successfully immobilized onto various conducting substrates (indium tin oxide (ITO), glassy carbon (GC) and gold electrodes with flat terraces) after addition of sodium nitrite at fixed potential. When applied onto the gold electrodes, such a grafting strategy led to an obvious enhancement of the luminescence of luminol used for the biodetection. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

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

Interfacing superhydrophobic silica nanoparticle films with graphene and thermoplastic polyurethane for wear/abrasion resistance.

PubMed

Naderizadeh, Sara; Athanassiou, Athanassia; Bayer, Ilker S

2018-06-01

Nanoparticle films are one of the most suitable platforms for obtaining sub-micrometer and nanometer dual-scale surface texture required for liquid repellency. The assembly of superhydrophobic nanoparticles into conformal and strongly adherent films having abrasion-induced wear resistance still poses a significant challenge. Various techniques have been developed over the years to render nanoparticle films with good liquid repellent properties and transparency. However, forming abrasion resistant superhydrophobic nanoparticle films on hard surfaces is challenging. One possibility is to partially embed or weld nanoparticles in thin thermoplastic primers applied over metals. Hexamethyldisilazane-functionalized fumed silica nanoparticle films spray deposited on aluminum surfaces were rendered abrasion resistant by thermally welding them into thermoplastic polyurethane (TPU) primer applied a priori over aluminum. Different solvents, nanoparticle concentrations and annealing temperatures were studied to optimize nanoparticle film morphology and hydrophobicity. Thermal annealing at 150 °C enhanced stability and wear resistance of nanoparticle films. A thin thermal interface layer of graphene nanoplatelets (GnPs) between the primer and the nanoparticle film significantly improved superhydrophobic wear resistance after annealing. As such, superhydrophobic nanocomposite films with the GnPs thermal interface layer displayed superior abrasion-induced wear resistance under 20 kPa compared to films having no GnPs-based thermal interface. Copyright © 2018 Elsevier Inc. All rights reserved.

Interfacing Nanoparticles and Biology: New Strategies for Biomedicine

PubMed Central

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

2014-01-01

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

Spherical Nucleic Acids: A New Form of DNA

NASA Astrophysics Data System (ADS)

Cutler, Joshua Isaac

Spherical Nucleic Acids (SNAs) are a new class of nucleic acid-based nanomaterials that exhibit unique properties currently being explored in the contexts of gene-based cancer therapies and in the design of programmable nanoparticle-based materials. The properties of SNAs differ from canonical, linear nucleic acids by virtue of their dense packing into an oriented 3-dimensional array. SNAs can be synthesized from a number of useful nanoparticle templates, such as plasmonic gold and silver, magnetic oxides, luminescent semi-conductor quantum dots, and silica. In addition, by crosslinking the oligonucleotides and dissolving the core, they can be made in a hollow form as well. This dissertation describes the evolution of SNAs from initial studies of inorganic nanoparticle-based materials densely functionalized with oligonucleotides to the proving of a hypothesis that their unique properties can be observed in a core-less structure if the nucleic acids are densely packed and highly oriented. Chapter two describes the synthesis of densely functionalized polyvalent oligonucleotide superparamagnetic iron oxide nanoparticles using the copper-catalyzed azide-alkyne cycloaddition reaction. These particles are shown to exhibit cooperative binding in a density- and salt concentration-dependent fashion, with nearly identical behaviors to those of SNA-functionalized gold nanoparticles. Importantly, these particles are the first non-gold particles shown to be capable of entering cells in high numbers via the SNA-mediated cellular uptake pathway, and provided the first evidence that SNA-mediated cellular uptake is core-independent. In the third chapter, a gold nanoparticle catalyzed alkyne cross-linking reaction is described that is capable of forming hollow organic nanoparticles using polymers with alkyne-functionalized backbones. With this method, the alkyne-modified polymers adsorb to the particle surfaces, cross-link on the surface, allowing the gold nanoparticle to be subsequently dissolved oxidatively with KCN or Iodine. The reaction pathway is analyzed through characterization of the reaction progression and resulting products, and a mechanistic pathway is proposed. This is the first report of a gold nanoparticle catalyzed reaction involving the conversion of propargyl ethers to terminal alcohols, which can subsequently cross-link if densely arranged on a gold nanoparticle surface. Importantly, these structures can be synthesized using gold nanoparticles of a range of sizes, thereby providing control over the size and properties of the resulting crosslinked particle. Chapter four returns to the topic of SNAs and builds upon the chemistry of chapter three culminating in the synthesis of cross-linked hollow SNA nanoparticles. These structures are formed by the cross-linking of synthetically modified alkyne-bearing oligonucleotides through the pathway described in chapter three. When the gold core is dissolved, the resulting hollow SNAs exhibit nearly identical binding, nuclease resistance, cellular uptake, and gene regulation properties of SNA-gold nanoparticle conjugates. Indeed, this chapter demonstrates that the unique properties of SNA-nanoparticle conjugates are core-independent and stem solely from the dense ensemble of oligonucleotides arranged on their surfaces. The fifth chapter further asserts the synthetic achievements made in chapter four by showing how hollow SNAs can be substituted for SNA-gold nanoparticles in the context of DNA-programmable assembly. In this case, they can be used as building blocks within binary synthetic schemes to synthesize unique nanoparticle superlattices. It bolsters the design rules of DNA-programmable assembly by showing that the predicted structures form based on the behavior of SNA hybridization, and are universal for any SNA-functionalized nanoparticle.

The interplay of nanointerface curvature and calcium binding in weak polyelectrolyte-coated nanoparticles.

PubMed

Nap, Rikkert J; Gonzalez Solveyra, Estefania; Szleifer, Igal

2018-05-01

When engineering nanomaterials for application in biological systems, it is important to understand how multivalent ions, such as calcium, affect the structural and chemical properties of polymer-modified nanoconstructs. In this work, a recently developed molecular theory was employed to study the effect of surface curvature on the calcium-induced collapse of end-tethered weak polyelectrolytes. In particular, we focused on cylindrical and spherical nanoparticles coated with poly(acrylic acid) in the presence of different amounts of Ca2+ ions. We describe the structural changes that grafted polyelectrolytes undergo as a function of calcium concentration, surface curvature, and morphology. The polymer layers collapse in aqueous solutions that contain sufficient amounts of Ca2+ ions. This collapse, due to the formation of calcium bridges, is not only controlled by the calcium ion concentration but also strongly influenced by the curvature of the tethering surface. The transition from a swollen to a collapsed layer as a function of calcium concentration broadens and shifts to lower amounts of calcium ions as a function of the radius of cylindrical and spherical nanoparticles. The results show how the interplay between calcium binding and surface curvature governs the structural and functional properties of the polymer molecules. This would directly impact the fate of weak polyelectrolyte-coated nanoparticles in biological environments, in which calcium levels are tightly regulated. Understanding such interplay would also contribute to the rational design and optimization of smart interfaces with applications in, e.g., salt-sensitive and ion-responsive materials and devices.

Ultraviolet radiation and nanoparticle induced intracellular free radicals generation measured in human keratinocytes by electron paramagnetic resonance spectroscopy.

PubMed

Rancan, F; Nazemi, B; Rautenberg, S; Ryll, M; Hadam, S; Gao, Q; Hackbarth, S; Haag, S F; Graf, C; Rühl, E; Blume-Peytavi, U; Lademann, J; Vogt, A; Meinke, M C

2014-05-01

Several nanoparticle-based formulations used in cosmetics and dermatology are exposed to sunlight once applied to the skin. Therefore, it is important to study possible synergistic effects of nanoparticles and ultraviolet radiation. Electron paramagnetic resonance spectroscopy (EPR) was used to detect intracellular free radicals induced by ultraviolet B (UVB) radiation and amorphous silica nanoparticle and to evaluate the influence of nanoparticle surface chemistry on particle cytotoxicity toward HaCaT cells. Uncoated titanium dioxide nanoparticles served as positive control. In addition, particle intracellular uptake, viability, and induction of interleukin-6 were measured. We found that photo-activated titanium dioxide particles induced a significant amount of intracellular free radicals. On the contrary, no intracellular free radicals were generated by the investigated silica nanoparticles in the dark as well as under UVB radiation. However, under UVB exposure, the non-functionalized silica nanoparticles altered the release of IL-6. At the same concentrations, the amino-functionalized silica nanoparticles had no influence on UVB-induced IL-6 release. EPR spectroscopy is a useful technique to measure nanoparticle-induced intracellular free radicals. Non-toxic concentrations of silica particles enhanced the toxicity of UVB radiation. This synergistic effect was not mediated by particle-generated free radicals and correlated with particle surface charge and intracellular distribution. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Applications of functional polymer brushes for nanoparticle uptake and prevention of protein adsorption

NASA Astrophysics Data System (ADS)

Arifuzzaman, Shafi M.

The central theme of this Ph.D. dissertation is to develop novel multifunctional polymer coatings for understanding partition of proteins and nanoparticles on polymers grafted to flat surfaces (so-called brushes). Systematic investigation of the adsorption phenomena is accomplished by utilizing surface-anchored assemblies comprising grafted polymers with variation in physical properties (i.e., length or/and grafting density) and chemical functionality. The chemical composition of the brush is tailored by either "chemical coloring" of a parent homopolymer brush with selective chemical moieties or by sequential growth of two chemically dissimilar polymer blocks. We present preparation of two types of tailor-made, surface-grafted copolymers: (1) those composed of hydrophilic and hydrophobic blocks (so-called amphiphilic polymer brushes), and (2) those comprising of anionic and cationic polymer segments (so-called polyampholyte brushes). We describe the organization of functionality in the grafted polymer brushes and the partitioning of proteins and nanoparticles using a battery of complementary analytical probes. Specifically, we address how varying the molecular weight, grafting density, and chemical composition of the brush affects adsorbtion and desorbtion of model proteins and gold nanoparticles. Our observations indicate densely-populated responsive amphiphilic polymers are very efficient in suppressing protein adsorption. In addition, we have established that the length of poly(ethylene glycol) spacers attached to a parent homopolymer brush is a key factor governing uptake of gold nanoparticles. Both grafting density and molecular weight of the coating are important in controlling the kinetics and thermodynamics of protein adsorption on surfaces. Our findings and methodologies can lead to the development of next generation environmentally friendly antifouling surfaces and will find application in medical devices, antifouling coatings and anti reflection finishes.

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

Petkov, Valeri; Hessel, Colin M.; Ovtchinnikoff, Justine

High-energy synchrotron X-ray diffraction coupled to atomic pair distribution function analysis and computer simulations is used to determine the atomic-scale structure of silicon (Si) nanoparticles obtained by two different synthetic routes. Results show that Si nanoparticles may have significant structural differences depending on the synthesis route and surface chemistry. In this case, one method produced Si nanoparticles that are highly crystalline but surface oxidized, whereas a different method yields organic ligand-passivated nanoparticles without surface oxide but that are structurally distorted at the atomic scale. Particular structural features of the oxide-free Si nanoparticles such as average first coordination numbers, length ofmore » structural coherence, and degree of local distortions are compared to their optical properties such as photoluminescence emission energy, quantum yield, and Raman spectra. A clear structure–properties correlation is observed indicating that the former may need to be taken into account when considering the latter.« less

Silver Nanoparticle Oligonucleotide Conjugates Based on DNA with Triple Cyclic Disulfide Moieties

PubMed Central

Lee, Jae-Seung; Lytton-Jean, Abigail K. R.; Hurst, Sarah J.; Mirkin, Chad A.

2011-01-01

We report a new strategy for preparing silver nanoparticle oligonucleotide conjugates that are based upon DNA with cyclic disulfide-anchoring groups. These particles are extremely stable and can withstand NaCl concentrations up to 1.0 M. When silver nanoparticles functionalized with complementary sequences are combined, they assemble to form DNA-linked nanoparticle networks. This assembly process is reversible with heating and is associated with a red-shifting of the particle surface plasmon resonance and a concomitant color change from yellow to pale red. Analogous to the oligonucleotide-functionalized gold nanoparticles, these particles also exhibit highly cooperative binding properties with extremely sharp melting transitions. This work is an important step towards being able to use silver nanoparticle oligonucleotide conjugates for a variety of purposes, including molecular diagnostic labels, synthons in programmable materials synthesis approaches, and functional components for nanoelectronic and plasmonic devices. PMID:17571909

In Situ Generation of Two-Dimensional Au–Pt Core–Shell Nanoparticle Assemblies

PubMed Central

2010-01-01

Two-dimensional assemblies of Au–Pt bimetallic nanoparticles are generated in situ on polyethyleneimmine (PEI) silane functionalized silicon and indium tin oxide (ITO) coated glass surfaces. Atomic force microscopy (AFM), UV–Visible spectroscopy, and electrochemical measurements reveal the formation of core–shell structure with Au as core and Pt as shell. The core–shell structure is further supported by comparing with the corresponding data of Au nanoparticle assemblies. Static contact angle measurements with water show an increase in hydrophilic character due to bimetallic nanoparticle generation on different surfaces. It is further observed that these Au–Pt core–shell bimetallic nanoparticle assemblies are catalytically active towards methanol electro-oxidation, which is the key reaction for direct methanol fuel cells (DMFCs). PMID:20651923

Formulation/preparation of functionalized nanoparticles for in vivo targeted drug delivery.

PubMed

Gu, Frank; Langer, Robert; Farokhzad, Omid C

2009-01-01

Targeted cancer therapy allows the delivery of therapeutic agents to cancer cells without incurring undesirable side effects on the neighboring healthy tissues. Over the past decade, there has been an increasing interest in the development of advanced cancer therapeutics using targeted nanoparticles. Here we describe the preparation of drug-encapsulated nanoparticles formulated with biocompatible and biodegradable poly(D: ,L: -lactic-co-glycolic acid)-block-poly(ethylene glycol) (PLGA-b-PEG) copolymer and surface functionalized with the A10 2-fluoropyrimidine ribonucleic acid aptamers that recognize the extracellular domain of prostate-specific membrane antigen (PSMA), a well-characterized antigen expressed on the surface of prostate cancer cells. We show that the self-assembled nanoparticles can selectively bind to PSMA-targeted prostate cancer cells in vitro and in vivo. This formulation method may contribute to the development of highly selective and effective cancer therapeutic and diagnostic devices.

Cyborg cells: functionalisation of living cells with polymers and nanomaterials.

PubMed

Fakhrullin, Rawil F; Zamaleeva, Alsu I; Minullina, Renata T; Konnova, Svetlana A; Paunov, Vesselin N

2012-06-07

Living cells interfaced with a range of polyelectrolyte coatings, magnetic and noble metal nanoparticles, hard mineral shells and other complex nanomaterials can perform functions often completely different from their original specialisation. Such "cyborg cells" are already finding a range of novel applications in areas like whole cell biosensors, bioelectronics, toxicity microscreening, tissue engineering, cell implant protection and bioanalytical chemistry. In this tutorial review, we describe the development of novel methods for functionalisation of cells with polymers and nanoparticles and comment on future advances in this technology in the light of other literature approaches. We review recent studies on the cell viability and function upon direct deposition of nanoparticles, coating with polyelectrolytes, polymer assisted assembly of nanomaterials and hard shells on the cell surface. The cell toxicity issues are considered for many practical applications in terms of possible adverse effects of the deposited polymers, polyelectrolytes and nanoparticles on the cell surface.

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.

Surface engineering of nanoparticles in suspension for particle based bio-sensing

PubMed Central

Sen, Tapas; Bruce, Ian J.

2012-01-01

Surface activation of nanoparticles in suspension using amino organosilane has been carried out via strict control of a particle surface ad-layer of water using a simple but efficient protocol ‘Tri-phasic Reverse Emulsion’ (TPRE). This approach produced thin and ordered layers of particle surface functional groups which allowed the efficient conjugation of biomolecules. When used in bio-sensing applications, the resultant conjugates were highly efficient in the hybrid capture of complementary oligonucleotides and the detection of food borne microorganism. TPRE overcomes a number of fundamental problems associated with the surface modification of particles in aqueous suspension viz. particle aggregation, density and organization of resultant surface functional groups by controlling surface condensation of the aminosilane. The approach has potential for application in areas as diverse as nanomedicine, to food technology and industrial catalysis. PMID:22872809

The effects of bacteria-nanoparticles interface on the antibacterial activity of green synthesized silver nanoparticles.

PubMed

Ahmad, Aftab; Wei, Yun; Syed, Fatima; Tahir, Kamran; Rehman, Aziz Ur; Khan, Arifullah; Ullah, Sadeeq; Yuan, Qipeng

2017-01-01

Neutralization of bacterial cell surface potential using nanoscale materials is an effective strategy to alter membrane permeability, cytoplasmic leakage, and ultimate cell death. In the present study, an attempt was made to prepare biogenic silver nanoparticles using biomolecules from the aqueous rhizome extract of Coptis Chinensis. The biosynthesized silver nanoparticles were surface modified with chitosan biopolymer. The prepared silver nanoparticles and chitosan modified silver nanoparticles were cubic crystalline structures (XRD) with an average particle size of 15 and 20 nm respectively (TEM, DLS). The biosynthesized silver nanoparticles were surface stabilized by polyphenolic compounds (FTIR). Coptis Chinensis mediated silver nanoparticles displayed significant activity against E. coli and Bacillus subtilus with a zone of inhibition 12 ± 1.2 (MIC = 25 μg/mL) and 18 ± 1.6 mm (MIC = 12.50 μg/mL) respectively. The bactericidal efficacy of these nanoparticles was considerably increased upon surface modification with chitosan biopolymer. The chitosan modified biogenic silver nanoparticles exhibited promising activity against E. coli (MIC = 6.25 μg/mL) and Bacillus subtilus (MIC = 12.50 μg/mL). Our results indicated that the chitosan modified silver nanoparticles were promising agents in damaging bacterial membrane potential and induction of high level of intracellular reactive oxygen species (ROS). In addition, these nanoparticles were observed to induce the release of the high level of cytoplasmic materials especially protein and nucleic acids into the media. All these findings suggest that the chitosan functionalized silver nanoparticles are efficient agents in disrupting bacterial membrane and induction of ROS leading to cytoplasmic leakage and cell death. These findings further conclude that the bacterial-nanoparticles surface potential modulation is an effective strategy in enhancing the antibacterial potency of silver nanoparticles. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Perspective on nanoparticle technology for biomedical use

PubMed Central

Raliya, Ramesh; Chadha, Tandeep Singh; Hadad, Kelsey; Biswas, Pratim

2016-01-01

This review gives a short overview on the widespread use of nanostructured and nanocomposite materials for disease diagnostics, drug delivery, imaging and biomedical sensing applications. Nanoparticle interaction with a biological matrix/entity is greatly influenced by its morphology, crystal phase, surface chemistry, functionalization, physicochemical and electronic properties of the particle. Various nanoparticle synthesis routes, characteristization, and functionalization methodologies to be used for biomedical applications ranging from drug delivery to molecular probing of underlying mechanisms and concepts are described with several examples (150 references). PMID:26951098

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.

Boron-based nanostructures: Synthesis, functionalization, and characterization

NASA Astrophysics Data System (ADS)

Bedasso, Eyrusalam Kifyalew

Boron-based nanostructures have not been explored in detail; however, these structures have the potential to revolutionize many fields including electronics and biomedicine. The research discussed in this dissertation focuses on synthesis, functionalization, and characterization of boron-based zero-dimensional nanostructures (core/shell and nanoparticles) and one-dimensional nanostructures (nanorods). The first project investigates the synthesis and functionalization of boron-based core/shell nanoparticles. Two boron-containing core/shell nanoparticles, namely boron/iron oxide and boron/silica, were synthesized. Initially, boron nanoparticles with a diameter between 10-100 nm were prepared by decomposition of nido-decaborane (B10H14) followed by formation of a core/shell structure. The core/shell structures were prepared using the appropriate precursor, iron source and silica source, for the shell in the presence of boron nanoparticles. The formation of core/shell nanostructures was confirmed using high resolution TEM. Then, the core/shell nanoparticles underwent a surface modification. Boron/iron oxide core/shell nanoparticles were functionalized with oleic acid, citric acid, amine-terminated polyethylene glycol, folic acid, and dopamine, and boron/silica core/shell nanoparticles were modified with 3-(amino propyl) triethoxy silane, 3-(2-aminoethyleamino)propyltrimethoxysilane), citric acid, folic acid, amine-terminated polyethylene glycol, and O-(2-Carboxyethyl)polyethylene glycol. A UV-Vis and ATR-FTIR analysis established the success of surface modification. The cytotoxicity of water-soluble core/shell nanoparticles was studied in triple negative breast cancer cell line MDA-MB-231 and the result showed the compounds are not toxic. The second project highlights optimization of reaction conditions for the synthesis of boron nanorods. This synthesis, done via reduction of boron oxide with molten lithium, was studied to produce boron nanorods without any contamination and with a uniform size distribution. Various reaction parameters such as temperature, reaction time, and sonication were altered to find the optimal reaction conditions. Once these conditions were determined, boron nanorods were produced then functionalized with amine-terminated polyethylene glycol.

Supported Silver Nanoparticle and Near-Interface Solution Dynamics in a Deep Eutectic Solvent

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

Hammons, Joshua A.; Ustarroz, Jon; Muselle, Thibault

2016-01-28

Type III deep eutectic solvents (DES) have attracted significant interest as both environmentally friendly and functional solvents that are, in some ways, advantageous to traditional aqueous systems. While these solvents continue to produce remarkable thin films and nanoparticle assemblies, their interactions with metallic surfaces are complex and difficult to manipulate. In this study, the near-surface region (2–600 nm) of a carbon surface is investigated immediately following silver nanoparticle nucleation and growth. This is accomplished, in situ, using a novel grazing transmission small-angle X-ray scattering approach with simultaneous voltammetry and electrochemical impedance spectroscopy. With this physical and electrochemical approach, the timemore » evolution of three distinct surface interaction phenomena is observed: aggregation and coalescence of Ag nanoparticles, multilayer perturbations induced by nonaggregated Ag nanoparticles, and a stepwise transport of dissolved Ag species from the carbon surface. The multilayer perturbations contain charge-separated regions of positively charged choline-ethylene and negatively charged Ag and Cl species. Both aggregation-coalescence and the stepwise decrease in Ag precursor near the surface are observed to be very slow (~2 h) processes, as both ion and particle transport are significantly impeded in a DES as compared to aqueous electrolytes. Finally, altogether, this study shows how the unique chemistry of the DES changes near the surface and in the presence of nanoparticles that adsorb the constituent species.« less

Green Synthesis, Characterization and Application of Proanthocyanidins-Functionalized Gold Nanoparticles

PubMed Central

Biao, Linhai; Tan, Shengnan; Meng, Qinghuan; Gao, Jing; Zhang, Xuewei; Liu, Zhiguo; Fu, Yujie

2018-01-01

Green synthesis of gold nanoparticles using plant extracts is one of the more promising approaches for obtaining environmentally friendly nanomaterials for biological applications and environmental remediation. In this study, proanthocyanidins-functionalized gold nanoparticles were synthesized via a hydrothermal method. The obtained gold nanoparticles were characterized by ultraviolet and visible spectrophotometry (UV-Vis), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and X-ray diffraction (XRD) measurements. UV-Vis and FTIR results indicated that the obtained products were mainly spherical in shape, and that the phenolic hydroxyl of proanthocyanidins had strong interactions with the gold surface. TEM and XRD determination revealed that the synthesized gold nanoparticles had a highly crystalline structure and good monodispersity. The application of proanthocyanidins-functionalized gold nanoparticles for the removal of dyes and heavy metal ions Ni2+, Cu2+, Cd2+ and Pb2+ in an aqueous solution was investigated. The primary results indicate that proanthocyanidins-functionalized gold nanoparticles had high removal rates for the heavy metal ions and dye, which implies that they have potential applications as a new kind of adsorbent for the removal of contaminants in aqueous solution. PMID:29361727

Long-circulating Janus nanoparticles made by electrohydrodynamic co-jetting for systemic drug delivery applications

PubMed Central

Rahmani, Sahar; Villa, Carlos H.; Dishman, Acacia F.; Grabowski, Marika E.; Pan, Daniel C.; Durmaz, Hakan; Misra, Asish C; Colón-Meléndez, Laura; Solomon, Michael J.; Muzykantov, Vladimir R.; Lahann, Joerg

2016-01-01

Background Nanoparticles with controlled physical properties have been widely used for controlled release applications. In addition to shape, the anisotropic nature of the particles can be an important design criterion to ensure selective surface modification or independent release of combinations of drugs. Purpose Electrohydrodynamic (EHD) co-jetting is used for the fabrication of uniform anisotropic nanoparticles with individual compartments and initial physicochemical and biological characterization is reported. Methods EHD co-jetting is used to create nanoparticles, which are characterized at each stage with scanning electron microscopy (SEM), structured illumination microscopy (SIM), dynamic light scattering (DLS) and nanoparticle tracking analysis (NTA). Surface immobilization techniques are used to incorporate polyethylene glycol (PEG) and I125 radiolabels into the nanoparticles. Particles are injected in mice and the particle distribution after 1, 4 and 24 hours is assessed. Results and discussion Nanoparticles with an average diameter of 105.7 nm are prepared by EHD co-jetting. The particles contain functional chemical groups for further surface modification and radiolabeling. The density of PEG molecules attached to the surface of nanoparticles is determined to range between 0.02 and 6.04 ligands per square nanometer. A significant fraction of the nanoparticles (1.2% injected dose per mass of organ) circulates in the blood after 24 h. Conclusion EHD co-jetting is a versatile method for the fabrication of nanoparticles for drug delivery. Circulation of the nanoparticles for 24 h is a pre-requisite for subsequent studies to explore defined targeting of the nanoparticles to a specific anatomic site. PMID:26453170

Enzymes immobilization on Fe 3O 4-gold nanoparticles

NASA Astrophysics Data System (ADS)

Kalska-Szostko, B.; Rogowska, M.; Dubis, A.; Szymański, K.

2012-01-01

In the present study Fe3O4 magnetic nanoparticles were synthesized by coprecipitation of Fe2+ and Fe3+ from chlorides. In the next step magnetite-gold core-shell nanoparticles were synthesized from HAuCl4 using an ethanol as a reducing agent. Finally, magnetic nanoparticles were functionalized by hexadecanethiol. The immobilization of biological molecules (trypsin and glucose oxidase) to the thiol-modified and unmodified magnetite-gold nanoparticles surface was tested. The resulting nanoparticles were characterized by infrared spectroscopy, differential scanning calorimetry, Mössbauer spectroscopy and transmission electron microscopy.

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.

Enhanced antibactericidal function of W4+-doped titania-coated nickel ferrite composite nanoparticles: a biomaterial system.

PubMed

Sunkara, B K; Misra, R D K

2008-03-01

The study demonstrates a distinct enhancement of antimicrobial activity of W4+-doped titania that is coated on nickel ferrite nanoparticles in comparison to undoped titania. The composite nanoparticles were synthesized by uniquely combining reverse micelle and chemical hydrolysis synthesis methods [Rana S, Rawat J, Misra RDK, Acta Biomater 2005;1:691]. The superior antimicrobial activity of W4+-doped titania is related to the inhibition of electron-hole recombination and decrease in the band gap energy of titania. The function of the ferrite is to facilitate the removal of nanoparticles from the sprayed surface using a small magnetic field. The coating of ferrite nanoparticles with titania retains superparamagnetic character and magnetic strength of composite nanoparticles signifying non-deterioration of magnetic properties and promoting their use as removable antimicrobial photocatalyst nanoparticles.

Hybrid Nanomaterials with Single-Site Catalysts by Spatially Controllable Immobilization of Nickel Complexes via Photoclick Chemistry for Alkene Epoxidation.

PubMed

Ghosh, Dwaipayan; Febriansyah, Benny; Gupta, Disha; Ng, Leonard Kia-Sheun; Xi, Shibo; Du, Yonghua; Baikie, Tom; Dong, ZhiLi; Soo, Han Sen

2018-05-22

Catalyst deactivation is a persistent problem not only for the scientific community but also in industry. Isolated single-site heterogeneous catalysts have shown great promise to overcome these problems. Here, a versatile anchoring strategy for molecular complex immobilization on a broad range of semiconducting or insulating metal oxide ( e. g., titanium dioxide, mesoporous silica, cerium oxide, and tungsten oxide) nanoparticles to synthesize isolated single-site catalysts has been studied systematically. An oxidatively stable anchoring group, maleimide, is shown to form covalent linkages with surface hydroxyl functionalities of metal oxide nanoparticles by photoclick chemistry. The nanocomposites have been thoroughly characterized by techniques including UV-visible diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy (XAS). The IR spectroscopic studies confirm the covalent linkages between the maleimide group and surface hydroxyl functionalities of the oxide nanoparticles. The hybrid nanomaterials function as highly efficient catalysts for essentially quantitative oxidations of terminal and internal alkenes and show molecular catalyst product selectivities even in more eco-friendly solvents. XAS studies verify the robustness of the catalysts after several catalytic cycles. We have applied the photoclick anchoring methodology to precisely control the deposition of a luminescent variant of our catalyst on the metal oxide nanoparticles. Overall, we demonstrate a general approach to use irradiation to anchor molecular complexes on oxide nanoparticles to create recyclable, hybrid, single-site catalysts that function with high selectivity in a broad range of solvents. We have achieved a facile, spatially and temporally controllable photoclick method that can potentially be extended to other ligands, catalysts, functional molecules, and surfaces.

Optical Limiting Materials Based on Gold Nanoparticles

DTIC Science & Technology

2014-04-30

of the electromagnetic spectrum. 2. Functionalization of the surface of the gold nanoparticles with selected organic and inorganic materials, with...F. A Review of Optical Limiting Mechanisms and Devices Using Organics, Fullerenes , Semiconductors and Other Materials. Prog. Quant. Electr. 1993

Molecular dynamics simulation of the local concentration and structure in multicomponent aerosol nanoparticles under atmospheric conditions.

PubMed

Karadima, Katerina S; Mavrantzas, Vlasis G; Pandis, Spyros N

2017-06-28

Molecular dynamics (MD) simulations were employed to investigate the local structure and local concentration in atmospheric nanoparticles consisting of an organic compound (cis-pinonic acid or n-C 30 H 62 ), sulfate and ammonium ions, and water. Simulations in the isothermal-isobaric (NPT) statistical ensemble under atmospheric conditions with a prespecified number of molecules of the abovementioned compounds led to the formation of a nanoparticle. Calculations of the density profiles of all the chemical species in the nanoparticle, the corresponding radial pair distribution functions, and their mobility inside the nanoparticle revealed strong interactions developing between sulfate and ammonium ions. However, sulfate and ammonium ions prefer to populate the central part of the nanoparticle under the simulated conditions, whereas organic molecules like to reside at its outer surface. Sulfate and ammonium ions were practically immobile; in contrast, the organic molecules exhibited appreciable mobility at the outer surface of the nanoparticle. When the organic compound was a normal alkane (e.g. n-C 30 H 62 ), a well-organized (crystalline-like) phase was rapidly formed at the free surface of the nanoparticle and remained separate from the rest of the species.

Silicon surface passivation by PEDOT: PSS functionalized by SnO2 and TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

García-Tecedor, M.; Karazhanov, S. Zh; Vásquez, G. C.; Haug, H.; Maestre, D.; Cremades, A.; Taeño, M.; Ramírez-Castellanos, J.; González-Calbet, J. M.; Piqueras, J.; You, C. C.; Marstein, E. S.

2018-01-01

In this paper, we present a study of silicon surface passivation based on the use of spin-coated hybrid composite layers. We investigate both undoped poly(3,4-ethylenedioxythiophene)/poly-(styrenesulfonate) (PEDOT:PSS), as well as PEDOT:PSS functionalized with semiconducting oxide nanomaterials (TiO2 and SnO2). The hybrid compound was deposited at room temperature by spin coating—a potentially lower cost, lower processing time and higher throughput alternative compared with the commonly used vacuum-based techniques. Photoluminescence imaging was used to characterize the electronic properties of the Si/PEDOT:PSS interface. Good surface passivation was achieved by PEDOT:PSS functionalized by semiconducting oxides. We show that control of the concentration of semiconducting oxide nanoparticles in the polymer is crucial in determining the passivation performance. A charge carrier lifetime of about 275 μs has been achieved when using SnO2 nanoparticles at a concentration of 0.5 wt.% as a filler in the composite film. X-ray diffraction (XRD), scanning electron microscopy, high resolution transmission electron microscopy (HRTEM), energy dispersive x-ray in an SEM, and μ-Raman spectroscopy have been used for the morphological, chemical and structural characterization. Finally, a simple model of a photovoltaic device based on PEDOT:PSS functionalized with semiconducting oxide nanoparticles has been fabricated and electrically characterized.

Enantioselective separation of chiral aromatic amino acids with surface functionalized magnetic nanoparticles.

PubMed

Ghosh, Sudipa; Fang, Tan Hui; Uddin, M S; Hidajat, K

2013-05-01

Chiral resolution aromatic amino acids, DL-tryptophan (DL-Trp), DL-phenylalanine (DL-Phe), DL-tyrosine (DL-Tyr) from phosphate buffer solution was achieved in present study employing the concept of selective adsorption by surface functionalized magnetic nanoparticles (MNPs). Surfaces of magnetic nanoparticles were functionalized with silica and carboxymethyl-β-cyclodextrin (CMCD) to investigate their adsorption resolution characteristics. Resolution of enantiomers from racemic mixture was quantified in terms of enantiomeric excess using chromatographic method. The MNPs selectively adsorbed L-enantiomers of DL-Trp, DL-Phe, and DL-Tyr from racemic mixture and enantiomeric excesses (e.e.) were determined as 94%, 73% and 58%, respectively. FTIR studies demonstrated that hydrophobic portion of enantiomer penetrated into hydrophobic cavity of cyclodextrin molecules to form inclusion complex. Furthermore, adsorption site was explored using XPS and it was revealed that amino group at chiral center of the amino acid molecule formed hydrogen bond with secondary hydroxyl group of CMCD molecule and favorability of hydrogen bond formation resulted in selective adsorption of L-enantiomer. Finally, stability constant (K) and Gibbs free energy change (-ΔG°) for inclusion complexation of CMCD with L-/D-enantiomers of amino acids were determined using spectroflurometry in aqueous buffer solution. Higher binding constants were obtained for inclusion complexation of CMCD with L-enantiomers compared to D-enantiomers which stimulated enantioselective properties of CMCD functionalized magnetite silica nanoparticles. Copyright © 2013 Elsevier B.V. All rights reserved.

Silicon surface passivation by PEDOT: PSS functionalized by SnO2 and TiO2 nanoparticles.

PubMed

García-Tecedor, M; Karazhanov, S Zh; Vásquez, G C; Haug, H; Maestre, D; Cremades, A; Taeño, M; Ramírez-Castellanos, J; González-Calbet, J M; Piqueras, J; You, C C; Marstein, E S

2018-01-19

In this paper, we present a study of silicon surface passivation based on the use of spin-coated hybrid composite layers. We investigate both undoped poly(3,4-ethylenedioxythiophene)/poly-(styrenesulfonate) (PEDOT:PSS), as well as PEDOT:PSS functionalized with semiconducting oxide nanomaterials (TiO 2 and SnO 2 ). The hybrid compound was deposited at room temperature by spin coating-a potentially lower cost, lower processing time and higher throughput alternative compared with the commonly used vacuum-based techniques. Photoluminescence imaging was used to characterize the electronic properties of the Si/PEDOT:PSS interface. Good surface passivation was achieved by PEDOT:PSS functionalized by semiconducting oxides. We show that control of the concentration of semiconducting oxide nanoparticles in the polymer is crucial in determining the passivation performance. A charge carrier lifetime of about 275 μs has been achieved when using SnO 2 nanoparticles at a concentration of 0.5 wt.% as a filler in the composite film. X-ray diffraction (XRD), scanning electron microscopy, high resolution transmission electron microscopy (HRTEM), energy dispersive x-ray in an SEM, and μ-Raman spectroscopy have been used for the morphological, chemical and structural characterization. Finally, a simple model of a photovoltaic device based on PEDOT:PSS functionalized with semiconducting oxide nanoparticles has been fabricated and electrically characterized.

Functional surface engineering of C-dots for fluorescent biosensing and in vivo bioimaging.

PubMed

Ding, Changqin; Zhu, Anwei; Tian, Yang

2014-01-21

Nanoparticles are promising scaffolds for applications such as imaging, chemical sensors and biosensors, diagnostics, drug delivery, catalysis, energy, photonics, medicine, and more. Surface functionalization of nanoparticles introduces an additional dimension in controlling nanoparticle interfacial properties and provides an effective bridge to connect nanoparticles to biological systems. With fascinating photoluminescence properties, carbon dots (C-dots), carbon-containing nanoparticles that are attracting considerable attention as a new type of quantum dot, are becoming both an important class of imaging probes and a versatile platform for engineering multifunctional nanosensors. In order to transfer C-dots from proof-of-concept studies toward real world applications such as in vivo bioimaging and biosensing, careful design and engineering of C-dot probes is becoming increasingly important. A comprehensive knowledge of how C-dot surfaces with various properties behave is essential for engineering C-dots with useful imaging properties such as high quantum yield, stability, and low toxicity, and with desirable biosensing properties such as high selectivity, sensitivity, and accuracy. Several reviews in recent years have reported preparation methods and properties of C-dots and described their application in biosensors, catalysis, photovoltatic cells, and more. However, no one has yet systematically summarized the surface engineering of C-dots, nor the use of C-dots as fluorescent nanosensors or probes for in vivo imaging in cells, tissues, and living organisms. In this Account, we discuss the major design principles and criteria for engineering the surface functionality of C-dots for biological applications. These criteria include brightness, long-term stability, and good biocompatibility. We review recent developments in designing C-dot surfaces with various functionalities for use as nanosensors or as fluorescent probes with fascinating analytical performance, and we emphasize applications in bioimaging and biosensing in live cells, tissues, and animals. In addition, we highlight our work on the design and synthesis of a C-dot ratiometric biosensor for intracellular Cu(2+) detection, and a twophoton fluorescent probe for pH measurement in live cells and tissues. We conclude this Account by outlining future directions in engineering the functional surface of C-dots for a variety of in vivo imaging applications, including dots with combined targeting, imaging and therapeutic-delivery capabilities, or high-resolution multiplexed vascular imaging. With each application C-dots should open new horizons of multiplexed quantitative detection, high-resolution fluorescence imaging, and long-term, real-time monitoring of their target.

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

Enrichment of peptides in serum by C(8)-functionalized magnetic nanoparticles for direct matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis.

PubMed

Yao, Ning; Chen, Hemei; Lin, Huaqing; Deng, Chunhui; Zhang, Xiangmin

2008-03-21

Human serum contains a complex array of proteolytically derived peptides (serum peptidome), which contain biomarkers of preclinical screening and disease diagnosis. Recently, commercial C(8)-functionalized magnetic beads (1-10 microm) were widely applied to the separation and enrichment of peptides in human serum, prior to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis. In this work, laboratory-prepared C(8)-functionalized magnetic nanoparticles (about 50 nm) were prepared and applied to the fast separation and the enrichment of peptides from serum. At first, the C(8)-magnetic nanoparticles were synthesized by modifying amine-functionalized magnetic nanoparticles with chlorodimethyloctylsilane. These synthesized C(8)-amine-functionalized magnetic particles have excellent magnetic responsibility, high dispersibility and large surface area. Finally, the C(8)-magnetic nanoparticles were successfully applied to fast and efficient enrichment of low-abundance peptides from protein tryptic digestion and human serum followed by MALDI-TOF-MS analysis.

New insights into the adsorption of 3-(trimethoxysilyl)propylmethacrylate on hydroxylated ZnO nanopowders.

PubMed

Bressy, Christine; Ngo, Van Giang; Ziarelli, Fabio; Margaillan, André

2012-02-14

Functionalization of zinc oxide (ZnO) nano-objects by silane grafting is an attractive method to provide nanostructured materials with a variety of surface properties. Active hydroxyl groups on the oxide surface are one of the causes governing the interfacial bond strength in nanohybrid particles. Here, "as-prepared" and commercially available zinc oxide nanopowders with a wide range of surface hydroxyl density were functionalized by a well-known polymerizable silane coupling agent, i.e., 3-(trimethoxysilyl)propylmethacrylate (MPS). Fourier transform infrared (FTIR) and solid-state (13)C and (29)Si nuclear magnetic resonance (NMR) spectroscopic investigations demonstrated that the silane coupling agent was fully hydrolyzed and linked to the hydroxyl groups already present on the particle surface through covalent and hydrogen bonds. Due to a basic catalyzed condensation of MPS with water, a siloxane layer was shown to be anchored to the nanoparticles through mono- and tridentate structures. Quantitative investigations were performed by thermogravimetric (TGA) and elemental analyses. The amount of silane linked to ZnO particles was shown to be affected by the amount of isolated hydroxyl groups available to react on the particle surface. For as-prepared ZnO nanoparticles, the number of isolated and available hydroxyl groups per square nanometer was up to 3 times higher than the one found on commercially available ZnO nanoparticles, leading to higher amounts of polymerizable silane agent linked to the surface. The MPS molecules were shown to be mainly oriented perpendicular to the oxide surface for all the as-prepared ZnO nanoparticles, whereas a parallel orientation was found for the preheated commercially ZnO nanopowders. In addition, ZnO nanoparticles were shown to be hydrophobized by the MPS treatment with water contact angles higher than 60°.

Preparation of silica coated cobalt ferrite magnetic nanoparticles for the purification of histidine-tagged proteins

NASA Astrophysics Data System (ADS)

Aygar, Gülfem; Kaya, Murat; Özkan, Necati; Kocabıyık, Semra; Volkan, Mürvet

2015-12-01

Surface modified cobalt ferrite (CoFe2O4) nanoparticles containing Ni-NTA affinity group were synthesized and used for the separation of histidine tag proteins from the complex matrices through the use of imidazole side chains of histidine molecules. Firstly, CoFe2O4 nanoparticles with a narrow size distribution were prepared in an aqueous solution using the controlled co-precipitation method. In order to obtain small CoFe2O4 agglomerates, oleic acid and sodium chloride were used as dispersants. The CoFe2O4 particles were coated with silica and subsequently the surface of these silica coated particles (SiO2-CoFe2O4) was modified by amine (NH2) groups in order to add further functional groups on the silica shell. Then, carboxyl (-COOH) functional groups were added to the SiO2-CoFe2O4 magnetic nanoparticles through the NH2 groups. After that Nα,Nα-Bis(carboxymethyl)-L-lysine hydrate (NTA) was attached to carboxyl ends of the structure. Finally, the surface modified nanoparticles were labeled with nickel (Ni) (II) ions. Furthermore, the modified SiO2-CoFe2O4 magnetic nanoparticles were utilized as a new system that allows purification of the N-terminal His-tagged recombinant small heat shock protein, Tpv-sHSP 14.3.

Non-aqueous synthesis of water-dispersible Fe3O4-Ca3(PO4)2 core-shell nanoparticles

NASA Astrophysics Data System (ADS)

Liu, HongLing; Wu, JunHua; Min, Ji Hyun; Hou, Peng; Song, Ah-Young; Kim, Young Keun

2011-02-01

The Fe3O4-Ca3(PO4)2 core-shell nanoparticles were prepared by one-pot non-aqueous nanoemulsion with the assistance of a biocompatible triblock copolymer, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO), integrating the magnetic properties of Fe3O4 and the bioactive functions of Ca3(PO4)2 into single entities. The Fe3O4 nanoparticles were pre-formed first by thermal reduction of Fe(acac)3 and then the Ca3(PO4)2 layer was coated by simultaneous deposition of Ca2 + and PO43 - . The characterization shows that the combination of the two materials into a core-shell nanostructure retains the magnetic properties and the Ca3(PO4)2 shell forms an hcp phase (a = 7.490 Å, c = 9.534 Å) on the Fe3O4 surface. The magnetic hysteresis curves of the nanoparticles were further elucidated by the Langevin equation, giving an estimation of the effective magnetic dimension of the nanoparticles and reflecting the enhanced susceptibility response as a result of the surface covering. Fourier transform infrared (FTIR) analysis provides the characteristic vibrations of Ca3(PO4)2 and the presence of the polymer surfactant on the nanoparticle surface. Moreover, the nanoparticles could be directly transferred to water and the aqueous dispersion-collection process of the nanoparticles was demonstrated for application readiness of such core-shell nanostructures in an aqueous medium. Thus, the construction of Fe3O4 and Ca3(PO4)2 in the core-shell nanostructure has conspicuously led to enhanced performance and multi-functionalities, offering various possible applications of the nanoparticles.

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.

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.

On the design of composite protein-quantum dot biomaterials via self-assembly.

PubMed

Majithia, Ravish; Patterson, Jan; Bondos, Sarah E; Meissner, Kenith E

2011-10-10

Incorporation of nanoparticles during the hierarchical self-assembly of protein-based materials can impart function to the resulting composite materials. Herein we demonstrate that the structure and nanoparticle distribution of composite fibers are sensitive to the method of nanoparticle addition and the physicochemical properties of both the nanoparticle and the protein. Our model system consists of a recombinant enhanced green fluorescent protein-Ultrabithorax (EGFP-Ubx) fusion protein and luminescent CdSe-ZnS core-shell quantum dots (QDs), allowing us to optically assess the distribution of both the protein and nanoparticle components within the composite material. Although QDs favorably interact with EGFP-Ubx monomers, the relatively rough surface morphology of composite fibers suggests EGFP-Ubx-QD conjugates impact self-assembly. Indeed, QDs templated onto EGFP-Ubx film post-self-assembly can be subsequently drawn into smooth composite fibers. Additionally, the QD surface charge impacts QD distribution within the composite material, indicating that surface charge plays an important role in self-assembly. QDs with either positively or negatively charged coatings significantly enhance fiber extensibility. Conversely, QDs coated with hydrophobic moieties and suspended in toluene produce composite fibers with a heterogeneous distribution of QDs and severely altered fiber morphology, indicating that toluene severely disrupts Ubx self-assembly. Understanding factors that impact the protein-nanoparticle interaction enables manipulation of the structure and mechanical properties of composite materials. Since proteins interact with nanoparticle surface coatings, these results should be applicable to other types of nanoparticles with similar chemical groups on the surface.

Stress relaxation in quasi-two-dimensional self-assembled nanoparticle monolayers

NASA Astrophysics Data System (ADS)

Boucheron, Leandra S.; Stanley, Jacob T.; Dai, Yeling; You, Siheng Sean; Parzyck, Christopher T.; Narayanan, Suresh; Sandy, Alec R.; Jiang, Zhang; Meron, Mati; Lin, Binhua; Shpyrko, Oleg G.

2018-05-01

We experimentally probed the stress relaxation of a monolayer of iron oxide nanoparticles at the water-air interface. Upon drop-casting onto a water surface, the nanoparticles self-assembled into islands of two-dimensional hexagonally close packed crystalline domains surrounded by large voids. When compressed laterally, the voids gradually disappeared as the surface pressure increased. After the compression was stopped, the surface pressure (as measured by a Wilhelmy plate) evolved as a function of the film aging time with three distinct timescales. These aging dynamics were intrinsic to the stressed state built up during the non-equilibrium compression of the film. Utilizing x-ray photon correlation spectroscopy, we measured the characteristic relaxation time (τ ) of in-plane nanoparticle motion as a function of the aging time through both second-order and two-time autocorrelation analysis. Compressed and stretched exponential fitting of the intermediate scattering function yielded exponents (β ) indicating different relaxation mechanisms of the films under different compression stresses. For a monolayer compressed to a lower surface pressure (between 20 mN/m and 30 mN/m), the relaxation time (τ ) decreased continuously as a function of the aging time, as did the fitted exponent, which transitioned from being compressed (>1 ) to stretched (<1 ), indicating that the monolayer underwent a stress release through crystalline domain reorganization. However, for a monolayer compressed to a higher surface pressure (around 40 mN/m), the relaxation time increased continuously and the compressed exponent varied very little from a value of 1.6, suggesting that the system may have been highly stressed and jammed. Despite the interesting stress relaxation signatures seen in these samples, the structural ordering of the monolayer remained the same over the sample lifetime, as revealed by grazing incidence x-ray diffraction.

Lanthanide sorbent based on magnetite nanoparticles functionalized with organophosphorus extractants

PubMed Central

Basualto, Carlos; Gaete, José; Molina, Lorena; Valenzuela, Fernando; Yañez, Claudia; Marco, Jose F

2015-01-01

In this work, an adsorbent was prepared based on the attachment of organophosphorus acid extractants, namely, D2EHPA, CYANEX 272, and CYANEX 301, to the surface of superparamagnetic magnetite (Fe3O4) nanoparticles. The synthesized nanoparticles were coated with oleic acid, first by a chemisorption mechanism and later by the respective extractant via physical adsorption. The obtained core–shell functionalized magnetite nanoparticle composites were characterized by dynamic light scattering, scanning electron microscopy, transmission electron microscopy, thermogravimetry, infrared absorption and vibrating sample magnetometry. All the prepared nanoparticles exhibited a high saturation magnetization capacity that varied between 72 and 46 emu g−1 and decreased as the magnetite nanoparticle was coated with oleic acid and functionalized. The scope of this study also included adsorption tests for lanthanum, cerium, praseodymium, and neodymium and the corresponding analysis of their results. Sorption tests indicated that the functionalized nanoparticles were able to extract the four studied lanthanide metal ions, although the best extraction performance was observed when the sorbent was functionalized with CYANEX 272, which resulted in a loading capacity of approximately 12–14 mgLa/gMNP. The magnetization of the synthesized nanoparticles was verified during the separation of the lanthanide-loaded sorbent from the raffinate by using a conventional magnet. PMID:27877811

Multifunctional iron oxide nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Magnetic nanoparticles: synthesis, functionalization, and applications in bioimaging and magnetic energy storage.

PubMed

Frey, Natalie A; Peng, Sheng; Cheng, Kai; Sun, Shouheng

2009-09-01

This tutorial review summarizes the recent advances in the chemical synthesis and potential applications of monodisperse magnetic nanoparticles. After a brief introduction to nanomagnetism, the review focuses on recent developments in solution phase syntheses of monodisperse MFe(2)O(4), Co, Fe, CoFe, FePt and SmCo(5) nanoparticles. The review further outlines the surface, structural, and magnetic properties of these nanoparticles for biomedicine and magnetic energy storage applications.

Light sensitive polymer obtained by dispersion of azo-functionalized POSS nanoparticles

NASA Astrophysics Data System (ADS)

Miniewicz, A.; Tomkowicz, M.; Karpinski, P.; Sznitko, L.; Mossety-Leszczak, B.; Dutkiewicz, M.

2015-07-01

Hybrid inorganic-organic nanoparticles based on cubic siloxane cage (RSiO3/2)8, known as polyhedral oligosilsesquioxane (POSS), have been functionalized by eight groups of azo-benzene mesogens and dispersed in poly(methyl methacrylate) PMMA matrix. Presence of azo-benzene units adds an important light-driven functionality to the system due to their photoisomerization resulting in refractive index and/or absorption changes of the whole system. The polymer films containing various concentrations of azo-POSS nanoparticles show remarkable changes of surface morphology being either transparent (at low POSS concentration) or highly scattering (at high POSS concentration) for visible light. Surface structures were examined by optical microscopy as well as by atomic force microscopy (AFM). Results of photoinduced alignment are discussed in the framework of light-induced modification of the aliphatic chains containing azo-benzene photoisomerizing moieties and self-organization process.

Synthesis, characterization and functionalization of silicon nanoparticle based hybrid nanomaterials for photovoltaic and biological applications

NASA Astrophysics Data System (ADS)

Xu, Zejing

Silicon nanoparticles are attractive candidates for biological, photovoltaic and energy storage applications due to their size dependent optoelectronic properties. These include tunable light emission, high brightness, and stability against photo-bleaching relative to organic dyes (see Chapter 1). The preparation and characterization of silicon nanoparticle based hybrid nanomaterials and their relevance to photovoltaic and biological applications are described. The surface-passivated silicon nanoparticles were produced in one step from the reactive high-energy ball milling (RHEBM) of silicon wafers with various organic ligands. The surface structure and optical properties of the passivated silicon nanoparticles were systematically characterized. Fast approaches for purifying and at the same time size separating the silicon nanoparticles using a gravity GPC column were developed. The hydrodynamic diameter and size distribution of these size-separated silicon nanoparticles were determined using GPC and Diffusion Ordered NMR Spectroscopy (DOSY) as fast, reliable alternative approaches to TEM. Water soluble silicon nanoparticles were synthesized by grafting PEG polymers onto functionalized silicon nanoparticles with distal alkyne or azide moieties. The surface-functionalized silicon nanoparticles were produced from the reactive high-energy ball milling (RHEBM) of silicon wafers with a mixture of either 5-chloro-1-pentyne in 1-pentyne or 1,7 octadiyne in 1-hexyne to afford air and water stable chloroalkyl or alkynyl terminated nanoparticles, respectively. Nanoparticles with the ω-chloroalkyl substituents were easily converted to ω-azidoalkyl groups through the reaction of the silicon nanoparticles with sodium azide in DMF. The azido terminated nanoparticles were then grafted with monoalkynyl-PEG polymers using a copper catalyzed alkyne-azide cycloaddition (CuAAC) reaction to afford core-shell silicon nanoparticles with a covalently attached PEG shell. Covalently linked silicon nanoparticle clusters were synthesized via the CuAAC "click" reaction of functional silicon nanoparticles with α,ω-functional PEG polymers of various lengths. Dynamic light scattering studies show that the flexible globular nanoparticle arrays undergo a solvent dependent change in volume (ethanol> dichloromethane> toluene) similar in behavior to hydrogel nanocomposites. A novel light-harvesting complex and artificial photosynthetic material based on silicon nanoparticles was designed and synthesized. Silicon nanoparticles were used as nanoscaffolds for organizing the porphyrins to form light-harvesting complexes thereby enhancing the light absorption of the system. The energy transfer from silicon nanoparticles to porphyrin acceptors was investigated by both steady-state and time-resolved fluorescence spectroscopy. The energy transfer efficiency depended on the donor-acceptor ratio and the distance between the nanoparticle and the porphyrin ring. The addition of C60 resulted in the formation of silicon nanoparticle-porphyrin-fullerene nanoclusters which led to charge separation upon irradiation of the porphyrin ring. The electron-transfer process between the porphyrin and fullerene was investigated by femto-second transient absorption spectroscopy. Finally, the water soluble silicon nanoparticles were used as nanocarriers in photodynamic therapeutic application, in which can selectively deliver porphyrins into human embryonic kidney 293T (HEK293T) cells. In particular, the PEGylated alkynyl-porphyrins were conjugated onto the azido-terminated silicon nanoparticles via a CuAAC "click" reaction. The resultant PEGylated porphyrin grafted silicon nanoparticles have diameters around 13.5 +/- 3.8 nm. The cryo-TEM and conventional TEM analysis proved that the PEGylated porphyrin grafted silicon nanoparticle could form the micelle-like structures at higher concentration in water via self-assembly. The UV-Vis absorption analysis demonstrated that the silicon nanoparticle could reduce the porphyrin aggregation in water which can reduce the photophysical activity of porphyrin. In addition, the nanoparticle complex was capable of producing singlet oxygen when the porphyrin units were excited by light. The cell studies demonstrated that the silicon nanoparticle could deliver the porphyrin drugs into HEK293T cells and accumulate in the mitochondria where the porphyrin could serve as an efficient photosensitizer to kill the cells via mitochondrial apoptotic pathway.

On the relationship between the specific heat enhancement of salt-based nanofluids and the ionic exchange capacity of nanoparticles.

PubMed

Mondragón, Rosa; Juliá, J Enrique; Cabedo, Luis; Navarrete, Nuria

2018-05-14

Nanoparticles have been used in thermal applications to increase the specific heat of the molten salts used in Concentrated Solar Power plants for thermal energy storage. Although several mechanisms for abnormal enhancement have been proposed, they are still being investigated and more research is necessary. However, this nanoparticle-salt interaction can also be found in chemical applications in which nanoparticles have proved suitable to be used as an adsorbent for nitrate removal given their high specific surface, reactivity and ionic exchange capacity. In this work, the ionic exchange capacity mechanism for the nanoparticles functionalization phenomenon was evaluated. The ionic exchange capacity of silica and alumina nanoparticles dispersed in lithium, sodium and potassium nitrates was measured. Fourier-transform infrared spectroscopy tests confirmed the adsorption of nitrate ions on the nanoparticle surface. A relationship between the ionic exchange capacity of nanoparticles and the specific heat enhancement of doped molten salts was proposed for the first time.

Spontaneous formation of nanoparticle stripe patterns through dewetting

NASA Astrophysics Data System (ADS)

Huang, Jiaxing; Kim, Franklin; Tao, Andrea R.; Connor, Stephen; Yang, Peidong

2005-12-01

Significant advancement has been made in nanoparticle research, with synthetic techniques extending over a wide range of materials with good control over particle size and shape. A grand challenge is assembling and positioning the nanoparticles in desired locations to construct complex, higher-order functional structures. Controlled positioning of nanoparticles has been achieved in pre-defined templates fabricated by top-down approaches. A self-assembly method, however, is highly desirable because of its simplicity and compatibility with heterogeneous integration processes. Here we report on the spontaneous formation of ordered gold and silver nanoparticle stripe patterns on dewetting a dilute film of polymer-coated nanoparticles floating on a water surface. Well-aligned stripe patterns with tunable orientation, thickness and periodicity at the micrometre scale were obtained by transferring nanoparticles from a floating film onto a substrate in a dip-coating fashion. This facile technique opens up a new avenue for lithography-free patterning of nanoparticle arrays for various applications including, for example, multiplexed surface-enhanced Raman substrates and templated fabrication of higher-order nanostructures.

Docetaxel immunonanocarriers as targeted delivery systems for HER 2-positive tumor cells: preparation, characterization, and cytotoxicity studies.

PubMed

Koopaei, Mona Noori; Dinarvand, Rassoul; Amini, Mohsen; Rabbani, Hojatollah; Emami, Shaghayegh; Ostad, Seyed Nasser; Atyabi, Fatemeh

2011-01-01

The objective of this study was to develop pegylated poly lactide-co-glycolide acid (PLGA) immunonanocarriers for targeting delivery of docetaxel to human breast cancer cells. The polyethylene glycol (PEG) groups on the surface of the PLGA nanoparticles were functionalized using maleimide groups. Trastuzumab, a monoclonal antibody against human epidermal growth factor receptor 2 (HER2) antigens of cancer cells, used as the targeting moiety, was attached to the maleimide groups on the surface of pegylated PLGA nanoparticles. Nanoparticles prepared by a nanoprecipitation method were characterized for their size, size distribution, surface charge, surface morphology, drug-loading, and in vitro drug release profile. The average size of the trastuzumab-decorated nanoparticles was 254 ± 16.4 nm and their zeta potential was -11.5 ± 1.4 mV. The average size of the nontargeted PLGA nanoparticles was 183 ± 22 nm and their zeta potential was -2.6 ± 0.34 mV. The cellular uptake of nanoparticles was studied using both HER2-positive (SKBR3 and BT-474) and HER2-negative (Calu-6) cell lines. The cytotoxicity of the immunonanocarriers against HER2-positive cell lines was significantly higher than that of nontargeted PLGA nanoparticles and free docetaxel.

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

Xue, Teng; Lin, Zhaoyang; Chiu, Chin-Yi

Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts tomore » date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less

Surfactant adsorption and aggregate structure of silica nanoparticles: a versatile stratagem for the regulation of particle size and surface modification

NASA Astrophysics Data System (ADS)

Chaudhary, Savita; Rohilla, Deepak; Mehta, S. K.

2014-03-01

The area of silica nanoparticles is incredibly polygonal. Silica particles have aroused exceptional deliberation in bio-analysis due to great progress in particular arenas, for instance, biocompatibility, unique properties of modifiable pore size and organization, huge facade areas and pore volumes, manageable morphology and amendable surfaces, elevated chemical and thermal stability. Currently, silica nanoparticles participate in crucial utilities in daily trade rationales such as power storage, chemical and genetic sensors, groceries dispensation and catalysis. Herein, the size-dependent interfacial relation of anionic silica nanoparticles with twelve altered categories of cationic surfactants has been carried out in terms of the physical chemical facets of colloid and interface science. The current analysis endeavours to investigate the virtual consequences of different surfactants through the development of the objective composite materials. The nanoparticle size controls, the surface-to-volume ratio and surface bend relating to its interaction with surfactant will also be addressed in this work. More importantly, the simulated stratagem developed in this work can be lengthened to formulate core-shell nanostructures with functional nanoparticles encapsulated in silica particles, making this approach valuable and extensively pertinent for employing sophisticated materials for catalysis and drug delivery.

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

PubMed

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

2010-06-01

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

Modulation of hydrogel nanoparticle intracellular trafficking by multivalent surface engineering with tumor targeting peptide

NASA Astrophysics Data System (ADS)

Karamchand, Leshern; Kim, Gwangseong; Wang, Shouyan; Hah, Hoe Jin; Ray, Aniruddha; Jiddou, Ruba; Koo Lee, Yong-Eun; Philbert, Martin A.; Kopelman, Raoul

2013-10-01

Surface engineering of a hydrogel nanoparticle (NP) with the tumor-targeting ligand, F3 peptide, enhances both the NP's binding affinity for, and internalization by, nucleolin overexpressing tumor cells. Remarkably, the F3-functionalized NPs consistently exhibited significantly lower trafficking to the degradative lysosomes than the non-functionalized NPs, in the tumor cells, after internalization. This is attributed to the non-functionalized NPs, but not the F3-functionalized NPs, being co-internalized with Lysosome-associated Membrane Protein-1 (LAMP1) from the surface of the tumor cells. Furthermore, it is shown that the intracellular trafficking of the F3-functionalized NPs differs significantly from that of the molecular F3 peptides (untethered to NPs). This has important implications for designing effective, chemically-responsive, controlled-release and multifunctional nanodrugs for multi-drug-resistant cancers.Surface engineering of a hydrogel nanoparticle (NP) with the tumor-targeting ligand, F3 peptide, enhances both the NP's binding affinity for, and internalization by, nucleolin overexpressing tumor cells. Remarkably, the F3-functionalized NPs consistently exhibited significantly lower trafficking to the degradative lysosomes than the non-functionalized NPs, in the tumor cells, after internalization. This is attributed to the non-functionalized NPs, but not the F3-functionalized NPs, being co-internalized with Lysosome-associated Membrane Protein-1 (LAMP1) from the surface of the tumor cells. Furthermore, it is shown that the intracellular trafficking of the F3-functionalized NPs differs significantly from that of the molecular F3 peptides (untethered to NPs). This has important implications for designing effective, chemically-responsive, controlled-release and multifunctional nanodrugs for multi-drug-resistant cancers. Electronic supplementary information (ESI) available: Effect of Potassium depletion on F3 peptide subcellular localization, MTT cytotoxicity data for endocytic inhibitors, size and morphology characterizations of hydrogel PAA nanocarriers, and optimization data for nanocarrier surface functionalization with PEG molecules and F3 peptides. See DOI: 10.1039/c3nr00908d

Selective adsorption of bovine hemoglobin on functional TiO2 nano-adsorbents: surface physic-chemical properties determined adsorption activity

NASA Astrophysics Data System (ADS)

Guo, Shiguang; Zhang, Jianghua; Shao, Mingxue; Zhang, Xia; Liu, Yufeng; Xu, Junli; Meng, Hao; Han, Yide

2015-04-01

Surface functionalized nanoparticles are efficient adsorbents which have shown good potential for protein separation. In this work, we chose two different types of organic molecules, oleic acid (OA) and 3-glycidoxypropyltrimethoxy silane (GPTMS), to functionalize the surface of TiO2 nanoparticles, and we studied the effects of this modification on their surface physicochemical properties in correlation with their selective adsorption of proteins. The results showed that the surface zeta potential and the surface water wettability of the modified TiO2 were significantly changed in comparison with the original TiO2 nanoparticles. The adsorption activities of bovine hemoglobin (BHb) and bovine serum albumin (BSA) on these functionalized TiO2 samples were investigated under different conditions, including pH values, contact time, ion strength, and initial protein concentration. In comparison with the non-specific adsorption of original TiO2, however, both the OA-TiO2 and GPTMS-TiO2 exhibited increased BHb adsorption and decreased BSA adsorption at the same time. Using a binary protein mixture as the adsorption object, a higher separation factor (SF) was obtained for OA-TiO2 under optimum conditions. The different adsorption activities of BHb and BSA on the modified TiO2 were correlated with different interactions at the protein/solid interface, and the chemical force as well as the electrostatic force played an important role in the selective adsorption process.

Multidentate oligomeric ligands to enhance the biocompatibility of iron oxide and other metal nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Wentao; Palui, Goutam; Ji, Xin; Aldeek, Fadi; Mattoussi, Hedi

2014-03-01

We prepared a set of multi-coordinating and reactive amphiphilic polymer ligands and used them for surface-functionalizing magnetic iron oxide nanoparticles. The amphiphilic oligomers were prepared by coupling (via one step nucleophilic addition) several dopamine anchoring groups, polyethylene glycol moieties and reactive groups onto a poly(isobutylene-alt-maleic anhydride) chain. The availability of several anchoring groups in the same ligand greatly enhances the ligand affinity to the nanoparticle surfaces, via multiplecoordination, while the hydrophilic and reactive groups promote colloidal stability in buffer media and allow subsequent conjugation to target biomolecules. The hydrophilic nanoparticles capped with these polymers maintain compact size and exhibit great long term colloidal stability.

Silica-based mesoporous nanoparticles for controlled drug delivery

PubMed Central

Kwon, Sooyeon; Singh, Rajendra K; Perez, Roman A; Abou Neel, Ensanya A

2013-01-01

Drug molecules with lack of specificity and solubility lead patients to take high doses of the drug to achieve sufficient therapeutic effects. This is a leading cause of adverse drug reactions, particularly for drugs with narrow therapeutic window or cytotoxic chemotherapeutics. To address these problems, there are various functional biocompatible drug carriers available in the market, which can deliver therapeutic agents to the target site in a controlled manner. Among the carriers developed thus far, mesoporous materials emerged as a promising candidate that can deliver a variety of drug molecules in a controllable and sustainable manner. In particular, mesoporous silica nanoparticles are widely used as a delivery reagent because silica possesses favourable chemical properties, thermal stability and biocompatibility. Currently, sol-gel-derived mesoporous silica nanoparticles in soft conditions are of main interest due to simplicity in production and modification and the capacity to maintain function of bioactive agents. The unique mesoporous structure of silica facilitates effective loading of drugs and their subsequent controlled release. The properties of mesopores, including pore size and porosity as well as the surface properties, can be altered depending on additives used to fabricate mesoporous silica nanoparticles. Active surface enables functionalisation to modify surface properties and link therapeutic molecules. The tuneable mesopore structure and modifiable surface of mesoporous silica nanoparticle allow incorporation of various classes of drug molecules and controlled delivery to the target sites. This review aims to present the state of knowledge of currently available drug delivery system and identify properties of an ideal drug carrier for specific application, focusing on mesoporous silica nanoparticles. PMID:24020012

Design and preparation of bi-functionalized short-chain modified zwitterionic nanoparticles.

PubMed

Hu, Fenglin; Chen, Kaimin; Xu, Hong; Gu, Hongchen

2018-05-01

An ideal nanomaterial for use in the bio-medical field should have a distinctive surface capable of effectively preventing nonspecific protein adsorption and identifying target bio-molecules. Recently, the short-chain zwitterion strategy has been suggested as a simple and novel approach to create outstanding anti-fouling surfaces. In this paper, the carboxyl end group of short-chain zwitterion-coated silica nanoparticles (SiO 2 -ZWS) was found to be difficult to functionalize via a conventional EDC/NHS strategy due to its rapid hydrolysis side-reactions. Hence, a series of bi-functionalized silica nanoparticles (SiO 2 -ZWS/COOH) were designed and prepared by controlling the molar ratio of 3-aminopropyltriethoxysilane (APTES) to short-chain zwitterionic organosiloxane (ZWS) in order to achieve above goal. The synthesized SiO 2 -ZWS/COOH had similar excellent anti-fouling properties compared with SiO 2 -ZWS, even in 50% fetal bovine serum characterized by DLS and turbidimetric titration. Subsequently, SiO 2 -ZWS/COOH 5/1 was chosen as a representative and then demonstrated higher detection signal intensity and more superior signal-to-noise ratios compare with the pure SiO 2 -COOH when they were used as a bio-carrier for chemiluminescence enzyme immunoassay (CLEIA). These unique bi-functionalized silica nanoparticles have many potential applications in the diagnostic and therapeutic fields. Reducing nonspecific protein adsorption and enhancing the immobilized efficiency of specific bio-probes are two of the most important issues for bio-carriers, particularly for a nanoparticle based bio-carrier. Herein, we designed and prepared a bi-functional nanoparticle with anti-fouling property and bio conjugation capacity for further bioassay by improving the short-chain zwitterionic modification strategy we have proposed previously. The heterogeneous surface of this nanoparticle showed effective anti-fouling properties both in model protein solutions and fetal bovine serum (FBS). The modified nanoparticles can also be successfully functionalized with a specific antibody for CLEIA assay with a prominent bio-detection performance even in 50% FBS. In this paper, we also investigated an unexpectedly fast hydrolysis behavior of NHS-activated carboxylic groups within the pure short-chain zwitterionic molecule that led to no protein binding in the short-chain zwitterion modified nanoparticle. Our findings pave a new way for the designing of high performance bio-carriers, demonstrating their strong potential as a robust platform for diagnosis and therapy. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Functionalization of γ-alumina cores by polyvinylpirrolidone: properties of the resulting biocompatible nanoparticles in aqueous suspension

NASA Astrophysics Data System (ADS)

Fernández, L.; Arranz, G.; Palacio, L.; Soria, C.; Sánchez, M.; Pérez, G.; Lozano, A. E.; Hernández, A.; Prádanos, P.

2009-02-01

A biocompatible polymer has been used to functionalize 45-50 nm diameter γ-alumina nanoparticles. Because the target was to use these systems in real applications, polyvinylpirrolidone (PVP) was chosen due to the characteristics of non-toxicity, biocompatibility, and feasibility of this polymer to form complexes with many cations and chemical species. This approach allows the use of these materials in medicine and food, textile, or pharmaceutical industry. The functionalization process required a previous attachment of an active group on the surface of the nanoparticles. Subsequently, a polymer chain was generated in situ, using vinyltrimethoxysilane (VTMS) and 1-vinyl-2-pyrrolidone (VP) as reactives. The morphology and topology of the nanocompound has been characterized in aqueous suspensions, attending to possible applications in this medium. The results obtained from the different techniques show that the polymer chain was successfully grafted to the nanoparticle surface, and allow an estimation of the size of the modified particle. Their electrical and conformational behavior have also been studied in different aqueous chemical environments.

Interfacially Optimized, High Energy Density Nanoparticle-Polymer Composites for Capacitive Energy Storage

NASA Astrophysics Data System (ADS)

Shipman, Joshua; Riggs, Brian; Luo, Sijun; Adireddy, Shiva; Chrisey, Douglas

Energy storage is a green energy technology, however it must be cost effective and scalable to meet future energy demands. Polymer-nanoparticle composites are low cost and potentially offer high energy storage. This is based on the high breakdown strength of polymers and the high dielectric constant of ceramic nanoparticles, but the incoherent nature of the interface between the two components prevents the realization of their combined full potential. We have created inkjet printable nanoparticle-polymer composites that have mitigated many of these interface effects, guided by first principle modelling of the interface. We detail density functional theory modelling of the interface and how it has guided our use in in specific surface functionalizations and other inorganic layers. We have validated our approach by using finite element analysis of the interface. By choosing the correct surface functionalization we are able to create dipole traps which further increase the breakdown strength of our composites. Our nano-scale understanding has allowed us to create the highest energy density composites currently available (>40 J/cm3).

Biosafety evaluations of well-dispersed mesoporous silica nanoparticles: towards in vivo-relevant conditions

NASA Astrophysics Data System (ADS)

Liu, Tsang-Pai; Wu, Si-Han; Chen, Yi-Ping; Chou, Chih-Ming; Chen, Chien-Tsu

2015-04-01

This study aimed to investigate how mesoporous silica nanoparticles (MSNs), especially focussing on their surface functional groups, interacted with Raw 264.7 macrophages, as well as with zebrafish embryos. Upon introducing nanoparticles into a biological milieu, adsorption of proteins and biomolecules onto the nanoparticle surface usually progresses rapidly. Nanoparticles bound with proteins can result in physiological and pathological changes, but the mechanisms remain to be elucidated. In order to evaluate how protein corona affected MSNs and the subsequent cellular immune responses, we experimented in both serum and serum-deprived conditions. Our findings indicated that the level of p-p38 was significantly elevated by the positively charged MSNs, whereas negatively charged MSNs resulted in marked ROS production. Most significantly, our experiments demonstrated that the presence of protein efficiently mitigated the potential nano-hazard. On the other hand, strongly positively charged MSNs caused 94% of the zebrafish embryos to die. In that case, the toxicity caused by the quaternary ammonium ligands on the surface of those nanoparticles was exerted in a dose-dependent manner. In summary, these fundamental studies here provide valuable insights into the design of better biocompatible nanomaterials in the future.This study aimed to investigate how mesoporous silica nanoparticles (MSNs), especially focussing on their surface functional groups, interacted with Raw 264.7 macrophages, as well as with zebrafish embryos. Upon introducing nanoparticles into a biological milieu, adsorption of proteins and biomolecules onto the nanoparticle surface usually progresses rapidly. Nanoparticles bound with proteins can result in physiological and pathological changes, but the mechanisms remain to be elucidated. In order to evaluate how protein corona affected MSNs and the subsequent cellular immune responses, we experimented in both serum and serum-deprived conditions. Our findings indicated that the level of p-p38 was significantly elevated by the positively charged MSNs, whereas negatively charged MSNs resulted in marked ROS production. Most significantly, our experiments demonstrated that the presence of protein efficiently mitigated the potential nano-hazard. On the other hand, strongly positively charged MSNs caused 94% of the zebrafish embryos to die. In that case, the toxicity caused by the quaternary ammonium ligands on the surface of those nanoparticles was exerted in a dose-dependent manner. In summary, these fundamental studies here provide valuable insights into the design of better biocompatible nanomaterials in the future. Electronic supplementary information (ESI) available: TEM image, size distribution histogram of as-synthesized wn-R-MSN@PEG. TGA measurements. Cellular uptake efficiency. WST-1 analysis. Western blot assays. Confocal images and zebrafish mortality. See DOI: 10.1039/c4nr07421a

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

Characterization of Platinum Nanoparticles Deposited on Functionalized Graphene Sheets

PubMed Central

Chiang, Yu-Chun; Liang, Chia-Chun; Chung, Chun-Ping

2015-01-01

Due to its special electronic and ballistic transport properties, graphene has attracted much interest from researchers. In this study, platinum (Pt) nanoparticles were deposited on oxidized graphene sheets (cG). The graphene sheets were applied to overcome the corrosion problems of carbon black at operating conditions of proton exchange membrane fuel cells. To enhance the interfacial interactions between the graphene sheets and the Pt nanoparticles, the oxygen-containing functional groups were introduced onto the surface of graphene sheets. The results showed the Pt nanoparticles were uniformly dispersed on the surface of graphene sheets with a mean Pt particle size of 2.08 nm. The Pt nanoparticles deposited on graphene sheets exhibited better crystallinity and higher oxygen resistance. The metal Pt was the predominant Pt chemical state on Pt/cG (60.4%). The results from the cyclic voltammetry analysis showed the value of the electrochemical surface area (ECSA) was 88 m2/g (Pt/cG), much higher than that of Pt/C (46 m2/g). The long-term test illustrated the degradation in ECSA exhibited the order of Pt/C (33%) > Pt/cG (7%). The values of the utilization efficiency were calculated to be 64% for Pt/cG and 32% for Pt/C. PMID:28793577

Targeting hepatocellular carcinoma with aptamer-functionalized PLGA/PLA-PEG nanoparticles

NASA Astrophysics Data System (ADS)

Weigum, Shannon E.; Sutton, Melissa; Barnes, Eugenia; Miller, Sarah; Betancourt, Tania

2014-08-01

Hepatocellular carcinoma (HCC) is one of the leading causes of cancer-related death worldwide, particularly in regions where chronic Hepatitis B and C infections are common. Nanoparticle assemblies that incorporate high-affinity aptamers which specifically bind malignant hepatocellular carcinoma cells could be useful for targeted drug delivery or enhancing contrast with existing ablation therapies. The in vitro interactions of a tumor-specific aptamer, TLS11a, were characterized in a hepatoma cell line via live-cell fluorescence imaging, SDS-PAGE and Western Blotting techniques. Cell surface binding of the aptamer-AlexaFluor®546 conjugate was found to occur within 20 minutes of initial exposure, followed by internalization and localization to late endosomes or lysosomes using a pH-sensitive LysoSensor™ Green dye and confocal microscopy. Aptamer-functionalized polymer nanoparticles containing poly(lactic-co-glycolic acid) (PLGA) and poly(lactide)-b-poly(ethylene glycol) (PLA-PEG) were then prepared by nanoprecipitation and passively loaded with the chemotherapeutic agent, doxorubicin, yielding spherical nanoparticles approximately 50 nm in diameter. Targeted drug delivery and cytotoxicity was assessed using live/dead fluorescent dyes and a MTT colorimetric viability assay with elevated levels of cell death found in cultures treated with either the aptamer-coated and uncoated polymer nanoparticles. Identification and characterization of the cell surface protein epitope(s) recognized by the TLS11a aptamer are ongoing along with nanoparticle optimization, but these preliminary studies support continued investigation of this aptamer and functionalized nanoparticle conjugates for targeted labeling and drug delivery within malignant hepatocellular carcinomas.

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.

Hydrogen treatment as a detergent of electronic trap states in lead chalcogenide nanoparticles

NASA Astrophysics Data System (ADS)

Voros, Marton; Brawand, Nicholas; Galli, Giulia

Lead chalcogenide (PbX) nanoparticles are promising materials for solar energy conversion. However, the presence of trap states in their electronic gap limits their usability, and developing a universal strategy to remove trap states is a persistent challenge. Using calculations based on density functional theory, we show that hydrogen acts as an amphoteric impurity on PbX nanoparticle surfaces; hydrogen atoms may passivate defects arising from ligand imbalance or off-stoichiometric surface terminations, irrespective of whether they originate from cation or anion excess. In addition, we show, using constrained density functional theory calculations, that hydrogen treatment of defective nanoparticles is also beneficial for charge transport in films. We also find that hydrogen adsorption on stoichiometric nanoparticles leads to electronic doping, preferentially n-type. Our findings suggest that post-synthesis hydrogen treatment of lead chalcogenide nanoparticle films is a viable approach to reduce electronic trap states or to dope well-passivated films. Work supported by the Center for Advanced Solar Photophysics, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (NB) and U.S. DOE under Contract No. DE-AC02-06CH11357 (MV).

Hybrid Nanoparticles for Detection and Treatment of Cancer

PubMed Central

Sailor, Michael J.; Park, Ji-Ho

2012-01-01

There is currently considerable effort to incorporate both diagnostic and therapeutic functions into a single nanoscale system for the more effective treatment of cancer. Nanoparticles have great potential to achieve such dual functions, particularly if more than one type of nanostructure can be incorporated in a nanoassembly—referred to in this review as a hybrid nanoparticle. Here we review recent developments in the synthesis and evaluation of such hybrid nanoparticles based on two design strategies (barge vs. tanker), in which liposomal, micellar, porous silica, polymeric, viral, noble metal, and nanotube systems are incorporated either within (barge) or at the surface of (tanker) a nanoparticle. We highlight the design factors that should be considered to obtain effective nanodevices for cancer detection and treatment. PMID:22610698

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.

Gold surfaces and nanoparticles are protected by Au(0)–thiyl species and are destroyed when Au(I)–thiolates form

PubMed Central

Reimers, Jeffrey R.; Ford, Michael J.; Halder, Arnab; Ulstrup, Jens; Hush, Noel S.

2016-01-01

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. PMID:26929334

The Optoelectronic Properties of Nanoparticles from First Principles Calculations

NASA Astrophysics Data System (ADS)

Brawand, Nicholas Peter

The tunable optoelectronic properties of nanoparticles through the modification of their size, shape, and surface chemistry, make them promising platforms for numerous applications, including electronic and solar conversion devices. However, the rational design and optimization of nanostructured materials remain open challenges, e.g. due to difficulties in controlling and reproducing synthetic processes and in precise atomic-scale characterization. Hence, the need for accurate theoretical predictions, which can complement and help interpret experiments and provide insight into the underlying physical properties of nanostructured materials. This dissertation focuses on the development and application of first principles calculations to predict the optoelectronic properties of nanoparticles. Novel methods based on density functional theory are developed, implemented, and applied to predict both optical and charge transport properties. In particular, the generalization of dielectric dependent hybrid functionals to finite systems is introduced and shown to yield highly accurate electronic structure properties of molecules and nanoparticles, including photoemission and absorption properties. In addition, an implementation of constrained density functional theory is discussed, for the calculation of hopping transport in nanoparticle systems. The implementation was verified against literature results and compared against other methods used to compute transport properties, showing that some methods used in the literature give unphysical results for thermally disordered systems. Furthermore, the constrained density functional theory implementation was coupled to the self-consistent image charge method, making it possible to include image charge effects self-consistently when predicting charge transport properties of nanoparticles near interfaces. The methods developed in this dissertation were then applied to study the optoelectronic and transport properties of specific systems, in particular, silicon and lead chalcogenide nanoparticles. In the case of Si, blinking in oxidized Si nanoparticles was addressed. Si dangling bonds at the surface were found to introduce defect states which, depending on their charge and local stress conditions, may give rise to ON and OFF states responsible for exponential blinking statistics. We also investigated, engineering of band edge positions of nanoparticles through post-synthetic surface chemistry modification, with a focus on lead chalcogenides. In collaboration with experiment, we demonstrated how band edge positions of lead sulfide nanoparticles can be tuned by over 2.0 eV. We established a clear relationship between ligand dipole moments and nanoparticle band edge shifts which can be used to engineer nanoparticles for optoelectronic applications. Calculations of transport properties focused on charge transfer in silicon and lead chalcogenide nanoparticles. Si nanoparticles with deep defects and shallow impurities were investigated, showing that shallow defects may be more detrimental to charge transport than previously assumed. In the case of lead chalcogenide nanoparticles, hydrogen was found to form complexes with defects which can be used to remove potentially detrimental charge traps in nanoparticle solids. The methods and results presented in this dissertation are expected to help guide engineering of nanoparticles for future device applications.

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

Predicting the Oxygen-Binding Properties of Platinum Nanoparticle Ensembles by Combining High-Precision Electron Microscopy and Density Functional Theory.

PubMed

Aarons, Jolyon; Jones, Lewys; Varambhia, Aakash; MacArthur, Katherine E; Ozkaya, Dogan; Sarwar, Misbah; Skylaris, Chris-Kriton; Nellist, Peter D

2017-07-12

Many studies of heterogeneous catalysis, both experimental and computational, make use of idealized structures such as extended surfaces or regular polyhedral nanoparticles. This simplification neglects the morphological diversity in real commercial oxygen reduction reaction (ORR) catalysts used in fuel-cell cathodes. Here we introduce an approach that combines 3D nanoparticle structures obtained from high-throughput high-precision electron microscopy with density functional theory. Discrepancies between experimental observations and cuboctahedral/truncated-octahedral particles are revealed and discussed using a range of widely used descriptors, such as electron-density, d-band centers, and generalized coordination numbers. We use this new approach to determine the optimum particle size for which both detrimental surface roughness and particle shape effects are minimized.

Surface modification of titanium substrates with silver nanoparticles embedded sulfhydrylated chitosan/gelatin polyelectrolyte multilayer films for antibacterial application.

PubMed

Li, Wen; Xu, Dawei; Hu, Yan; Cai, Kaiyong; Lin, Yingcheng

2014-06-01

To develop Ti implants with potent antibacterial activity, a novel "sandwich-type" structure of sulfhydrylated chitosan (Chi-SH)/gelatin (Gel) polyelectrolyte multilayer films embedding silver (Ag) nanoparticles was coated onto titanium substrate using a spin-assisted layer-by-layer assembly technique. Ag ions would be enriched in the polyelectrolyte multilayer films via the specific interactions between Ag ions and -HS groups in Chi-HS, thus leading to the formation of Ag nanoparticles in situ by photo-catalytic reaction (ultraviolet irradiation). Contact angle measurement and field emission scanning electron microscopy equipped with energy dispersive X-ray spectroscopy were employed to monitor the construction of Ag-containing multilayer on titanium surface, respectively. The functional multilayered films on titanium substrate [Ti/PEI/(Gel/Chi-SH/Ag) n /Gel] could efficiently inhibit the growth and activity of Bacillus subtitles and Escherichia coli onto titanium surface. Moreover, studies in vitro confirmed that Ti substrates coating with functional multilayer films remained the biological functions of osteoblasts, which was reflected by cell morphology, cell viability and ALP activity measurements. This study provides a simple, versatile and generalized methodology to design functional titanium implants with good cyto-compatibility and antibacterial activity for potential clinical applications.

Magnetically driven floating foams for the removal of oil contaminants from water.

PubMed

Calcagnile, Paola; Fragouli, Despina; Bayer, Ilker S; Anyfantis, George C; Martiradonna, Luigi; Cozzoli, P Davide; Cingolani, Roberto; Athanassiou, Athanassia

2012-06-26

In this study, we present a novel composite material based on commercially available polyurethane foams functionalized with colloidal superparamagnetic iron oxide nanoparticles and submicrometer polytetrafluoroethylene particles, which can efficiently separate oil from water. Untreated foam surfaces are inherently hydrophobic and oleophobic, but they can be rendered water-repellent and oil-absorbing by a solvent-free, electrostatic polytetrafluoroethylene particle deposition technique. It was found that combined functionalization of the polytetrafluoroethylene-treated foam surfaces with colloidal iron oxide nanoparticles significantly increases the speed of oil absorption. Detailed microscopic and wettability studies reveal that the combined effects of the surface morphology and of the chemistry of the functionalized foams greatly affect the oil-absorption dynamics. In particular, nanoparticle capping molecules are found to play a major role in this mechanism. In addition to the water-repellent and oil-absorbing capabilities, the functionalized foams exhibit also magnetic responsivity. Finally, due to their light weight, they float easily on water. Hence, by simply moving them around oil-polluted waters using a magnet, they can absorb the floating oil from the polluted regions, thereby purifying the water underneath. This low-cost process can easily be scaled up to clean large-area oil spills in water.

Optically transparent and environmentally durable superhydrophobic coating based on functionalized SiO 2 nanoparticles

DOE PAGES

Schaeffer, Daniel A.; Polizos, Georgios; Smith, D. Barton; ...

2015-01-09

Optical surfaces such as mirrors and windows that are exposed to outdoor environmental conditions are susceptible to dust buildup and water condensation. The application of transparent superhydrophobic coatings on optical surfaces can improve outdoor performance via a self-cleaning effect similar to the Lotus effect. The contact angle (CA) of water droplets on a typical hydrophobic flat surface varies from 100° to 120°. Adding roughness or microtexture to a hydrophobic surface leads to an enhancement of hydrophobicity and the CA can be increased to a value in the range of 16≥0° to 175°. This result is remarkable because such behavior cannotmore » be explained using surface chemistry alone. When surface features are on the order of 100 nm or smaller, surfaces exhibit superhydrophobic behavior and maintain their optical transparency. In this work we discuss our results on transparent superhydrophobic coatings that can be applied across large surface areas. We have used functionalized silica nanoparticles to coat various optical elements and have measured the contact angle and optical transmission between 190 to 1100 nm on these elements. The functionalized silica nanoparticles were dissolved in a solution of the solvents isopropyl alcohol and 4-chlorobenzotrifluoride (PCBTF) and a proprietary ceramic binder (Cerakote ). Finally, this solution was spin-coated onto a variety of test glass substrates, and following a curing period of about 30 minutes, these coatings exhibited superhydrophobic behavior with a static CA ≥160°.« less

Magnet-induced temporary superhydrophobic coatings from one-pot synthesized hydrophobic magnetic nanoparticles.

PubMed

Fang, Jian; Wang, Hongxia; Xue, Yuhua; Wang, Xungai; Lin, Tong

2010-05-01

In this paper, we report on the production of superhydrophobic coatings on various substrates (e.g., glass slide, silicon wafer, aluminum foil, plastic film, nanofiber mat, textile fabrics) using hydrophobic magnetic nanoparticles and a magnet-assembly technique. Fe(3)O(4) magnetic nanoparticles functionalized with a thin layer of fluoroalkyl silica on the surface were synthesized by one-step coprecipitation of Fe(2+)/Fe(3+) under an alkaline condition in the presence of a fluorinated alkyl silane. Under a magnetic field, the magnetic nanoparticles can be easily deposited on any solid substrate to form a thin superhydrophobic coating with water contact angle as high as 172 degrees , and the surface superhydrophobicity showed very little dependence on the substrate type. The particulate coating showed reasonable durability because of strong aggregation effect of nanoparticles, but the coating layer can be removed (e.g., by ultrasonication) to restore the original surface feature of the substrates. By comparison, the thin particle layer deposited under no magnetic field showed much lower hydrophobicity. The main reason for magnet-induced superhydrophobic surfaces is the formation of nano- and microstructured surface features. Such a magnet-induced temporary superhydrophobic coating may have wide applications in electronic, biomedical, and defense-related areas.

Method of producing catalytic material for fabricating nanostructures

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

Seals, Roland D.; Menchhofer, Paul A.; Howe, Jane Y.

Methods of fabricating nano-catalysts are described. In some embodiments the nano-catalyst is formed from a powder-based substrate material and is some embodiments the nano-catalyst is formed from a solid-based substrate material. In some embodiments the substrate material may include metal, ceramic, or silicon or another metalloid. The nano-catalysts typically have metal nanoparticles disposed adjacent the surface of the substrate material. The methods typically include functionalizing the surface of the substrate material with a chelating agent, such as a chemical having dissociated carboxyl functional groups (--COO), that provides an enhanced affinity for metal ions. The functionalized substrate surface may then bemore » exposed to a chemical solution that contains metal ions. The metal ions are then bound to the substrate material and may then be reduced, such as by a stream of gas that includes hydrogen, to form metal nanoparticles adjacent the surface of the substrate.« less

Method of producing catalytic materials for fabricating nanostructures

DOEpatents

Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

2013-02-19

Methods of fabricating nano-catalysts are described. In some embodiments the nano-catalyst is formed from a powder-based substrate material and is some embodiments the nano-catalyst is formed from a solid-based substrate material. In some embodiments the substrate material may include metal, ceramic, or silicon or another metalloid. The nano-catalysts typically have metal nanoparticles disposed adjacent the surface of the substrate material. The methods typically include functionalizing the surface of the substrate material with a chelating agent, such as a chemical having dissociated carboxyl functional groups (--COO), that provides an enhanced affinity for metal ions. The functionalized substrate surface may then be exposed to a chemical solution that contains metal ions. The metal ions are then bound to the substrate material and may then be reduced, such as by a stream of gas that includes hydrogen, to form metal nanoparticles adjacent the surface of the substrate.

Powering the programmed nanostructure and function of gold nanoparticles with catenated DNA machines

NASA Astrophysics Data System (ADS)

Elbaz, Johann; Cecconello, Alessandro; Fan, Zhiyuan; Govorov, Alexander O.; Willner, Itamar

2013-06-01

DNA nanotechnology is a rapidly developing research area in nanoscience. It includes the development of DNA machines, tailoring of DNA nanostructures, application of DNA nanostructures for computing, and more. Different DNA machines were reported in the past and DNA-guided assembly of nanoparticles represents an active research effort in DNA nanotechnology. Several DNA-dictated nanoparticle structures were reported, including a tetrahedron, a triangle or linear nanoengineered nanoparticle structures; however, the programmed, dynamic reversible switching of nanoparticle structures and, particularly, the dictated switchable functions emerging from the nanostructures, are missing elements in DNA nanotechnology. Here we introduce DNA catenane systems (interlocked DNA rings) as molecular DNA machines for the programmed, reversible and switchable arrangement of different-sized gold nanoparticles. We further demonstrate that the machine-powered gold nanoparticle structures reveal unique emerging switchable spectroscopic features, such as plasmonic coupling or surface-enhanced fluorescence.

In Vivo Delivery of Nanoparticles into Plant Leaves.

PubMed

Wu, Honghong; Santana, Israel; Dansie, Joshua; Giraldo, Juan P

2017-12-14

Plant nanobiotechnology is an interdisciplinary field at the interface of nanotechnology and plant biology that aims to utilize nanomaterials as tools to study, augment or impart novel plant functions. The delivery of nanoparticles to plants in vivo is a key initial step to investigate plant nanoparticle interactions and the impact of nanoparticles on plant function. Quantum dots are smaller than plant cell wall pores, have versatile surface chemistry, bright fluorescence and do not photobleach, making them ideal for the study of nanoparticle uptake, transport, and distribution in plants by widely available confocal microscopy tools. Herein, we describe three different methods for quantum dot delivery into leaves of living plants: leaf lamina infiltration, whole shoot vacuum infiltration, and root to leaf translocation. These methods can be potentially extended to other nanoparticles, including nanosensors and drug delivery nanoparticles. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

Optical properties of BaTiO3 nanoparticles and silver nanoprisms in polymer host matrices

NASA Astrophysics Data System (ADS)

Requena, Sebastian

Nanocomposites are materials comprised of a host matrix, such as glass or polymer, with embedded nanoparticles. Embedding nanoparticles into the host makes it possible to create materials with properties that are distinctly unique from those of their host and nanoparticle constituents. Nanocomposites can have superior mechanical, thermal, and optical properties compared to their host materials. We characterized the photoluminescent properties of BaTiO3 polymer nanocomposites and the effects of chemically modifying the nanoparticles surface on said properties. BaTiO3 nanopowders of average grain sizes 50 nm and 100 nm were functionalized by (3-aminopropyl)triethoxysilane (3APTS) and mixed with poly(methyl methacrylate)/toluene solution. The nanocomposites films morphology and chemical structure were studied via AFM and FTIR. The photoluminescence spectrum of the pure nanoparticles was composed of an emission at ˜3.0 eV and multiple bands centered at ˜2.5 eV. Surface functionalization of the BaTiO3 nanoparticles via 3APTS increased overall luminescence at room temperature while only enhancing the ˜3.0 eV emission at low-temperature. On the other hand, polymer coating of the functionalized nanoparticles significantly enhances ˜3.0 eV emissions while decreasing emissions associated with near-surface lattice distortions at ˜2.5 eV. Chemical modification of the surface with 3APTS and PMMA presents a pathway to tune and control the photoluminescent properties of BTO nanoparticles. We also present optical studies of two different size distributions of silver triangular nanoprisms, one with a dipole resonance at ˜520 nm and the other with a dipole resonance at ˜650 nm, placed in different media. The silver nanoprisms were embedded in a polyvinyl alcohol (PVA) polymer matrix and oriented by stretching the polymer/nanoprism nanocomposite films. We observe significantly increased linear dichroism in the region associated with the plasmonic in-plane dipole mode upon stretching. Additionally, there is a weaker linear dichroism in the region associated with out-of-plane modes, which vanish in the extinction spectrum of the stretched nanocomposite film. Our results show that these silver nanoprisms are promising as key components in wavelength-specific depolarizers and depolarization-based assays.

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

PubMed

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

2016-03-01

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

Nanoparticle-Based Receptors Mimic Protein-Ligand Recognition.

PubMed

Riccardi, Laura; Gabrielli, Luca; Sun, Xiaohuan; De Biasi, Federico; Rastrelli, Federico; Mancin, Fabrizio; De Vivo, Marco

2017-07-13

The self-assembly of a monolayer of ligands on the surface of noble-metal nanoparticles dictates the fundamental nanoparticle's behavior and its functionality. In this combined computational-experimental study, we analyze the structure, organization, and dynamics of functionalized coating thiols in monolayer-protected gold nanoparticles (AuNPs). We explain how functionalized coating thiols self-organize through a delicate and somehow counterintuitive balance of interactions within the monolayer itself and with the solvent. We further describe how the nature and plasticity of these interactions modulate nanoparticle-based chemosensing. Importantly, we found that self-organization of coating thiols can induce the formation of binding pockets in AuNPs. These transient cavities can accommodate small molecules, mimicking protein-ligand recognition, which could explain the selectivity and sensitivity observed for different organic analytes in NMR chemosensing experiments. Thus, our findings advocate for the rational design of tailored coating groups to form specific recognition binding sites on monolayer-protected AuNPs.

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.

Optical tracking of organically modified silica nanoparticles as DNA carriers: A nonviral, nanomedicine approach for gene delivery

NASA Astrophysics Data System (ADS)

Roy, Indrajit; Ohulchanskyy, Tymish Y.; Bharali, Dhruba J.; Pudavar, Haridas E.; Mistretta, Ruth A.; Kaur, Navjot; Prasad, Paras N.

2005-01-01

This article reports a multidisciplinary approach to produce fluorescently labeled organically modified silica nanoparticles as a nonviral vector for gene delivery and biophotonics methods to optically monitor intracellular trafficking and gene transfection. Highly monodispersed, stable aqueous suspensions of organically modified silica nanoparticles, encapsulating fluorescent dyes and surface functionalized by cationic-amino groups, are produced by micellar nanochemistry. Gel-electrophoresis studies reveal that the particles efficiently complex with DNA and protect it from enzymatic digestion of DNase 1. The electrostatic binding of DNA onto the surface of the nanoparticles, due to positively charged amino groups, is also shown by intercalating an appropriate dye into the DNA and observing the Förster (fluorescence) resonance energy transfer between the dye (energy donor) intercalated in DNA on the surface of nanoparticles and a second dye (energy acceptor) inside the nanoparticles. Imaging by fluorescence confocal microscopy shows that cells efficiently take up the nanoparticles in vitro in the cytoplasm, and the nanoparticles deliver DNA to the nucleus. The use of plasmid encoding enhanced GFP allowed us to demonstrate the process of gene transfection in cultured cells. Our work shows that the nanomedicine approach, with nanoparticles acting as a drug-delivery platform combining multiple optical and other types of probes, provides a promising direction for targeted therapy with enhanced efficacy as well as for real-time monitoring of drug action. nonviral vector | ORMOSIL nanoparticles | confocal microscopy

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

Studies of drag on the nanocomposite superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Brassard, Jean-Denis; Sarkar, D. K.; Perron, Jean

2015-01-01

The nanocomposite thin films of stearic acid (SA)-functionalized ZnO nanoparticles incorporated in epoxy polymer matrix have been achieved. The X-ray diffraction (XRD) studies show the formation of zinc stearate on ZnO nanoparticles as the confirmation of SA-functionalization of ZnO nanoparticles in the thin films. Morphological analyses reveal the presence of micro-holes with the presence of irregular nanoparticles. The measured root mean square (rms) roughness of the thin film is found to be 12 ± 1 μm with the adhesion of 5B on both glass and aluminum substrates. The wetting property shows that the surface of the film is superhydrophobic with the contact angle of water of 156 ± 4° having contact angle hysteresis (CAH) of 4 ± 2°. The average terminal velocity in the water of the as-received glass spheres and superhydrophobic spheres were found to be 0.66 ± 0.01 m/s and 0.72 ± 0.01 m/s respectively. Consequently, the calculated average coefficients of the surface drag of the as-received glass sphere and superhydrophobic glass sphere were 2.30 ± 0.01 and 1.93 ± 0.03, respectively. Hence, the drag reduction on the surface of superhydrophobic glass sphere is found to be approximately 16% lower than as-received glass sphere.

Reflectometric measurement of n-hexane adsorption on ZnO2 nanohybrid film modified by hydrophobic gold nanoparticles

NASA Astrophysics Data System (ADS)

Sebők, Dániel; Csapó, Edit; Ábrahám, Nóra; Dékány, Imre

2015-04-01

Zinc-peroxide/poly(styrenesulfonate) nanohybrid thin films (containing 20 bilayers: [ZnO2/PSS]20, d ∼ 500 nm) were prepared using layer-by-layer (LbL) method. The thin film surface was functionalized by different surface modifying agents (silanes, alkylthiols and hydrophobized nanoparticles). Based on the experimental results of quartz crystal microbalance (QCM) and contact angle measurements (as prequalifications) the octanethiol covered gold nanoparticles (OT-AuNPs) were selected for further vapour adsorption studies. Reflectometric interference spectroscopy (RIfS) was used to measure n-hexane vapour adsorption on the original and modified nanohybrid films in a gas flow platform. The thin film provides only the principle of the measurement (by interference phenomenon), the selectivity and hydrophobicity is controlled and enhanced by surface functionalization (by dispersion interaction between the alkyl chains). The interference pattern shift (Δλ) caused by the increase of the optical thickness of the thin film due to vapour adsorption was investigated. It was found that due to the surface functionalization by hydrophobic nanoparticles the effect of water vapour adsorption decreased significantly, while for n-hexane opposite tendency was observed (the effective refractive index and thus the interference pattern shift increased drastically). The correlation between QCM technique and optical method (RIfS) was specified: linear specific adsorbed amount vs. wavelength shift calibration curves were determined in the pr = 0-0.4 relative vapour pressure range. The thin film is suitable for sensorial application (e.g. volatile organic compound/VOC sensor).

Kinetics of Spontaneous Bimetallization between Silver and Noble Metal Nanoparticles.

PubMed

Hirakawa, Kazutaka; Kaneko, Tetsuya; Toshima, Naoki

2018-06-05

A physical mixture of polymer-protected Ag nanoparticles and Rh, Pd, or Pt nanoparticles spontaneously forms Ag-core bimetallic nanoparticles. The formed nanoparticles were smaller than the parent Ag nanoparticles. In the initial process of this reaction, the surface plasmon absorption of Ag nanoparticles diminished and then almost ceased within one hour. Within several minutes, the decrease in Ag surface plasmon absorption could be analyzed by second-order reaction. This reaction was accelerated with an increase of temperature and the energy gap in the Fermi level between Ag and the other metals. The activation energy (E a ) of this reaction could be determined. An electron transfer reaction from Ag to other metal nanoparticles was proposed as the initial interaction between these metal nanoparticles because the Fermi level of Ag is relatively high, and the electron transfer is possible in terms of energy. The Marcus plot between the rate constant and the driving force, roughly estimated from the work function of metals, and the observed E a values reasonably explained the proposed electron transfer mechanism. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical properties of MgF2 nano-composite films dispersed with noble metal nanoparticles synthesized by sol-gel method

NASA Astrophysics Data System (ADS)

Wakaki, Moriaki; Soujima, Nobuaki; Shibuya, Takehisa

2015-03-01

Porous MgF2 films synthesized by a sol-gel method exhibit the lowest refractive index among the dielectric optical materials and are the most useful materials for the anti-reflection coatings. On the other hand, surface plasmon resonance (SPR) absorptions of noble metal nanoparticles in various solid matrices have been extensively studied. New functional materials like a SERS (Surface Enhanced Raman Spectroscopy) tips are expected by synthesizing composite materials between porous MgF2 films featured by the network of MgF2 nanoparticles and noble metal nanoparticles introduced within the network. In this study, fundamental physical properties including morphology and optical properties are characterized for these materials to make clear the potential of the composite system. Composite materials of MgF2 films dispersed with noble metal (Ag, Au) nanoparticles were prepared using the sol-gel technique with various annealing temperatures and densities of noble metal nanoparticles. The structural morphology was analyzed by an X-ray diffractometer (XRD) and a scanning electron microscope (SEM). The size and shape distributions of the metal nanoparticles were observed using a transmission electron microscope (TEM). The optical properties of fabricated composite films were characterized by UV-Vis-NIR and FT-IR spectrophotometers. The absorption spectra due to the surface plasmon resonance (SPR) of the metal nanoparticles were analyzed using the dielectric function considering the effective medium approximation, typically Maxwell-Garnett model. The Raman scattering spectra were also studied to check the enhancement effect of specimen dropped on the MgF2: Ag nano-composite films deposited on Si substrate. Enhancement of the Raman intensity of pyridine solution specimen was observed.

Increased cellular uptake of peptide-modified PEGylated gold nanoparticles.

PubMed

He, Bo; Yang, Dan; Qin, Mengmeng; Zhang, Yuan; He, Bing; Dai, Wenbing; Wang, Xueqing; Zhang, Qiang; Zhang, Hua; Yin, Changcheng

2017-12-09

Gold nanoparticles are promising drug delivery vehicles for nucleic acids, small molecules, and proteins, allowing various modifications on the particle surface. However, the instability and low bioavailability of gold nanoparticles compromise their clinical application. Here, we functionalized gold nanoparticles with CPP fragments (CALNNPFVYLI, CALRRRRRRRR) through sulfhydryl PEG to increase their stability and bioavailability. The resulting gold nanoparticles were characterized with transmission electron microscopy (TEM), dynamic light scattering (DLS), UV-visible spectrometry and X-ray photoelectron spectroscopy (XPS), and the stability in biological solutions was evaluated. Comparing to PEGylated gold nanoparticles, CPP (CALNNPFVYLI, CALRRRRRRRR)-modified gold nanoparticles showed 46 folds increase in cellular uptake in A549 and B16 cell lines, as evidenced by the inductively coupled plasma atomic emission spectroscopy (ICP-AES). The interactions between gold nanoparticles and liposomes indicated CPP-modified gold nanoparticles bind to cell membrane more effectively than PEGylated gold nanoparticles. Surface plasmon resonance (SPR) was used to measure interactions between nanoparticles and the membrane. TEM and uptake inhibitor experiments indicated that the cellular entry of gold nanoparticles was mediated by clathrin and macropinocytosis. Other energy independent endocytosis pathways were also identified. Our work revealed a new strategy to modify gold nanoparticles with CPP and illustrated the cellular uptake pathway of CPP-modified gold nanoparticles. Copyright © 2017 Elsevier Inc. All rights reserved.

Interaction of PM2.5 airborne particulates with ZnO and TiO2 nanoparticles and their effect on bacteria.

PubMed

Baysal, Asli; Saygin, Hasan; Ustabasi, Gul Sirin

2017-12-21

A significant knowledge gap in nanotechnology is the absence of standardized protocols for examining and comparison the effect of metal oxide nanoparticles on different environment media. Despite the large number of studies on ecotoxicity of nanoparticles, most of them disregard the particles physicochemical transformation under real exposure conditions and interaction with different environmental components like air, soil, water, etc. While one of the main exposure ways is inhalation and/or atmosphere for human and environment, there is no investigation between airborne particulates and nanoparticles. In this study, some metal oxide nanoparticle (ZnO and TiO 2 ) transformation and behavior in PM2.5 air particulate media were examined and evaluated by the influence on nanoparticle physicochemical properties (size, surface charge, surface functionalization) and on bacterium (Gram-positive Bacillus subtilis, Staphylococcus aureus/Gram-negative Escherichia coli, Pseudomonas aeruginosa bacteria) by testing in various concentrations of PM2.5 airborne particulate media to contribute to their environmental hazard and risk assessment in atmosphere. PM2.5 airborne particulate media affected their toxicity and physicochemical properties when compared the results obtained in controlled conditions. ZnO and TiO 2 surfaces were functionalized mainly with sulfoxide groups in PM2.5 air particulates. In addition, tested particles were not observed to be toxic in controlled conditions. However, these were observed inhibition in PM2.5 airborne particulates media by the exposure concentration. These observations and dependence of the bacteria viability ratio explain the importance of particulate matter-nanoparticle interaction.

Precisely Size-Tunable Monodisperse Hairy Plasmonic Nanoparticles via Amphiphilic Star-Like Block Copolymers.

PubMed

Chen, Yihuang; Yoon, Young Jun; Pang, Xinchang; He, Yanjie; Jung, Jaehan; Feng, Chaowei; Zhang, Guangzhao; Lin, Zhiqun

2016-12-01

In situ precision synthesis of monodisperse hairy plasmonic nanoparticles with tailored dimensions and compositions by capitalizing on amphiphilic star-like diblock copolymers as nanoreactors are reported. Such hairy plasmonic nanoparticles comprise uniform noble metal nanoparticles intimately and perpetually capped by hydrophobic polymer chains (i.e., "hairs") with even length. Interestingly, amphiphilic star-like diblock copolymer nanoreactors retain the spherical shape under reaction conditions, and the diameter of the resulting plasmonic nanoparticles and the thickness of polymer chains situated on the surface of the nanoparticle can be readily and precisely tailored. These hairy nanoparticles can be regarded as hard/soft core/shell nanoparticles. Notably, the polymer "hairs" are directly and permanently tethered to the noble metal nanoparticle surface, thereby preventing the aggregation of nanoparticles and rendering their dissolution in nonpolar solvents and the homogeneous distribution in polymer matrices with long-term stability. This amphiphilic star-like block copolymer nanoreactor-based strategy is viable and robust and conceptually enables the design and synthesis of a rich variety of hairy functional nanoparticles with new horizons for fundamental research on self-assembly and technological applications in plasmonics, catalysis, energy conversion and storage, bioimaging, and biosensors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface chemistry and morphology in single particle optical imaging

NASA Astrophysics Data System (ADS)

Ekiz-Kanik, Fulya; Sevenler, Derin Deniz; Ünlü, Neşe Lortlar; Chiari, Marcella; Ünlü, M. Selim

2017-05-01

Biological nanoparticles such as viruses and exosomes are important biomarkers for a range of medical conditions, from infectious diseases to cancer. Biological sensors that detect whole viruses and exosomes with high specificity, yet without additional labeling, are promising because they reduce the complexity of sample preparation and may improve measurement quality by retaining information about nanoscale physical structure of the bio-nanoparticle (BNP). Towards this end, a variety of BNP biosensor technologies have been developed, several of which are capable of enumerating the precise number of detected viruses or exosomes and analyzing physical properties of each individual particle. Optical imaging techniques are promising candidates among broad range of label-free nanoparticle detectors. These imaging BNP sensors detect the binding of single nanoparticles on a flat surface functionalized with a specific capture molecule or an array of multiplexed capture probes. The functionalization step confers all molecular specificity for the sensor's target but can introduce an unforeseen problem; a rough and inhomogeneous surface coating can be a source of noise, as these sensors detect small local changes in optical refractive index. In this paper, we review several optical technologies for label-free BNP detectors with a focus on imaging systems. We compare the surface-imaging methods including dark-field, surface plasmon resonance imaging and interference reflectance imaging. We discuss the importance of ensuring consistently uniform and smooth surface coatings of capture molecules for these types of biosensors and finally summarize several methods that have been developed towards addressing this challenge.

Recent Advances on Inorganic Nanoparticle-Based Cancer Therapeutic Agents

PubMed Central

Wang, Fenglin; Li, Chengyao; Cheng, Jing; Yuan, Zhiqin

2016-01-01

Inorganic nanoparticles have been widely investigated as therapeutic agents for cancer treatments in biomedical fields due to their unique physical/chemical properties, versatile synthetic strategies, easy surface functionalization and excellent biocompatibility. This review focuses on the discussion of several types of inorganic nanoparticle-based cancer therapeutic agents, including gold nanoparticles, magnetic nanoparticles, upconversion nanoparticles and mesoporous silica nanoparticles. Several cancer therapy techniques are briefly introduced at the beginning. Emphasis is placed on how these inorganic nanoparticles can provide enhanced therapeutic efficacy in cancer treatment through site-specific accumulation, targeted drug delivery and stimulated drug release, with elaborations on several examples to highlight the respective strategies adopted. Finally, a brief summary and future challenges are included. PMID:27898016

Targeting Strategies for Multifunctional Nanoparticles in Cancer Imaging and Therapy

PubMed Central

Yu, Mi Kyung; Park, Jinho; Jon, Sangyong

2012-01-01

Nanomaterials offer new opportunities for cancer diagnosis and treatment. Multifunctional nanoparticles harboring various functions including targeting, imaging, therapy, and etc have been intensively studied aiming to overcome limitations associated with conventional cancer diagnosis and therapy. Of various nanoparticles, magnetic iron oxide nanoparticles with superparamagnetic property have shown potential as multifunctional nanoparticles for clinical translation because they have been used asmagnetic resonance imaging (MRI) constrast agents in clinic and their features could be easily tailored by including targeting moieties, fluorescence dyes, or therapeutic agents. This review summarizes targeting strategies for construction of multifunctional nanoparticles including magnetic nanoparticles-based theranostic systems, and the various surface engineering strategies of nanoparticles for in vivo applications. PMID:22272217

Recent Advances on Inorganic Nanoparticle-Based Cancer Therapeutic Agents.

PubMed

Wang, Fenglin; Li, Chengyao; Cheng, Jing; Yuan, Zhiqin

2016-11-25

Inorganic nanoparticles have been widely investigated as therapeutic agents for cancer treatments in biomedical fields due to their unique physical/chemical properties, versatile synthetic strategies, easy surface functionalization and excellent biocompatibility. This review focuses on the discussion of several types of inorganic nanoparticle-based cancer therapeutic agents, including gold nanoparticles, magnetic nanoparticles, upconversion nanoparticles and mesoporous silica nanoparticles. Several cancer therapy techniques are briefly introduced at the beginning. Emphasis is placed on how these inorganic nanoparticles can provide enhanced therapeutic efficacy in cancer treatment through site-specific accumulation, targeted drug delivery and stimulated drug release, with elaborations on several examples to highlight the respective strategies adopted. Finally, a brief summary and future challenges are included.

Underwater superoleophobicity, anti-oil and ultra-broadband enhanced absorption of metallic surfaces produced by a femtosecond laser inspired by fish and chameleons

NASA Astrophysics Data System (ADS)

Yin, K.; Song, Y. X.; Dong, X. R.; Wang, C.; Duan, J. A.

2016-11-01

Reported here is the bio-inspired and robust function of underwater superoleophobic, anti-oil metallic surfaces with ultra-broadband enhanced optical absorption obtained through femtosecond laser micromachining. Three distinct surface structures are fabricated using a wide variety of processing parameters. Underwater superoleophobic and anti-oil surfaces containing coral-like microstructures with nanoparticles and mount-like microstructures are achieved. These properties of the as-prepared surfaces exhibit good chemical stability when exposed to various types of oils and when immersed in water with a wide range of pH values. Moreover, coral-like microstructures with nanoparticle surfaces show strongly enhanced optical absorption over a broadband wavelength range from 0.2-25 μm. The potential mechanism for the excellent performance of the coral-like microstructures with a nanoparticle surface is also discussed. This multifunctional surface has potential applications in military submarines, amphibious military aircraft and tanks, and underwater anti-oil optical counter-reconnaissance devices.

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

Mitra, Arijit; Barick, Barun; Sharma, H.

We have observed large tunneling Magnetoresistance (TMR) in amine functionalized octahedral nanoparticle assemblies. Amine monolayer on the surface of nanoparticles acts as an insulating barrier between the semimetal Fe{sub 3}O{sub 4} nanoparticles and provides multiple tunnel junctions where inter-granular tunneling is plausible. The tunneling magnetoresistance recorded at room temperature is 38% which increases to 69% at 180 K. When the temperature drops below 150 K, coulomb staircase is observed in the current versus voltage characteristics as the charging energy exceeds the thermal energy. A similar study is also carried out with spherical nanoparticles. A 24% TMR is recorded at roommore » temperature which increases to 41% at 180 K for spherical particles. Mössbauer spectra reveal better stoichiometry for octahedral particles which is attainable due to lesser surface disorder and strong amine coupling at the <111> facets of octahedral Fe{sub 3}O{sub 4} nanoparticles. Less stoichiometric defect in octahedral nanoparticles leads to a higher value of spin polarization and therefore larger TMR in octahedral nanoparticles.« less

Direct isolation of flavonoids from plants using ultra-small anatase TiO2 nanoparticles

PubMed Central

Kurepa, Jasmina; Nakabayashi, Ryo; Paunesku, Tatjana; Suzuki, Makoto; Saito, Kazuki; Woloschak, Gayle E.; Smalle, Jan A.

2013-01-01

Summary Surface functionalization of nanoparticles has become an important tool for the in vivo delivery of bioactive agents to their target sites. Here we describe the reverse strategy, nanoharvesting, in which nanoparticles are used as a tool to isolate and enrich bioactive compounds from living cells. Anatase TiO2 nanoparticles smaller than 20 nm form strong bonds with molecules carrying enediol and especially catechol groups. We show that these nanoparticles can enter plant cells, conjugate enediol and catechol group-rich flavonoids in situ, and exit plant cells as flavonoid-nanoparticle conjugates. The source plant tissues remain viable after treatment. As predicted by the surface chemistry of anatase TiO2 nanoparticles, the quercetin-based flavonoids were enriched amongst the nanoharvested flavonoid species. Nanoharvesting eliminates the use of organic solvents, allows spectral identification of the isolated compounds, and offers a new avenue for the use of nanomaterials for the coupled isolation and testing of bioactive properties of plant-made compounds. PMID:24147867

Green synthesis of metal nanoparticles: biodegradable polymers and enzymes in stabilization and surface functionalization

EPA Science Inventory

Current breakthroughs in green nanotechnology are capable to transform many of the existing processes and products that enhance environmental quality, reduce pollution, and conserve natural and non-renewable resources. Noteworthy, successful use of metal nanoparticles and 10 nano...

Gelatin Nanoparticles with Enhanced Affinity for Calcium Phosphate.

PubMed

Farbod, Kambiz; Diba, Mani; Zinkevich, Tatiana; Schmidt, Stephan; Harrington, Matthew J; Kentgens, Arno P M; Leeuwenburgh, Sander C G

2016-05-01

Gelatin nanoparticles can be tuned with respect to their drug loading efficiency, degradation rate, and release kinetics, which renders these drug carriers highly suitable for a wide variety of biomedical applications. The ease of functionalization has rendered gelatin an interesting candidate material to introduce specific motifs for selective targeting to specific organs, but gelatin nanoparticles have not yet been modified to increase their affinity to mineralized tissue. By means of conjugating bone-targeting alendronate to biocompatible gelatin nanoparticles, a simple method is developed for the preparation of gelatin nanoparticles which exhibit strong affinity to mineralized surfaces. It has been shown that the degree of alendronate functionalization can be tuned by controlling the glutaraldehyde crosslinking density, the molar ratio between alendronate and glutaraldehyde, as well as the pH of the conjugation reaction. Moreover, it has been shown that the affinity of gelatin nanoparticles to calcium phosphate increases considerably upon functionalization with alendronate. In summary, gelatin nanoparticles have been developed, which exhibit great potential for use in bone-specific drug delivery and regenerative medicine. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of gold nanoparticles as crosslink agent to form chitosan nanocapsules: study of the direct interaction in aqueous solutions.

PubMed

Prado-Gotor, R; López-Pérez, G; Martín, M J; Cabrera-Escribano, F; Franconetti, A

2014-06-01

A systematic study of the interaction between free anionic gold nanoparticles and chitosan in a solution is presented. A spectroscopic study of the interaction between 10nm gold nanoparticles and low molecular weight chitosan is reported as a function of the concentration and pH of the polymer in a solution. Zeta potential measurements and TEM images indicate the effective aggregation of the nanoparticles in the presence of chitosan. At the same time, anionic gold nanoparticles act as crosslink agents to form chitosan nanocapsules with an average molecular size of 260nm. The changes of the surface plasmon band due to the adsorption of the polymer on the nanoparticle surface allow using of the citrate gold nanoparticles as sensors of the polymer for analytical purposes. The limit of detection for chitosan biopolymer is 69nM. The optimum pH for the interaction between the biopolymer and the nanoparticles is found at a value of 6.4, obtained from spectrophotometric measurements and applying a deconvolution analysis of the experimental data. A simple model based on molecular surface electrostatic interactions is proposed to understand the pH dependence of the investigated system. Copyright © 2014 Elsevier Inc. All rights reserved.

Supercritical fluid attachment of palladium nanoparticles on aligned carbon nanotubes.

PubMed

Ye, Xiang-Rong; Lin, Yuehe; Wai, Chien M; Talbot, Jan B; Jin, Sungho

2005-06-01

Nanocomposite materials consisting of Pd nanoparticles deposited on aligned multi-walled carbon nanotubes have been fabricated through hydrogen reduction of palladium-beta-diketone precursor in supercritical carbon dioxide. The supercritical fluid processing allowed deposition of high-density Pd nanoparticles (approximately 5-10 nm) on both as-grown (unfunctionalized) and functionalized (using HNO3 oxidation) nanotubes. However, the wet processing for functionalization results in pre-agglomerated, bundle-shaped nanotubes, thus significantly reducing the effective surface area for Pd particle deposition, although the bundling provides more secure, lock-in-place positioning of nanotubes and Pd catalyst particles. The nanotube bundling is substantially mitigated by Pd nanoparticle deposition on the unfunctionalized and geometrically separated nanotubes, which provides much higher catalyst surface area. Such nanocomposite materials utilizing geometrically secured and aligned nanotubes can be useful for providing much enhanced catalytic activities to chemical and electrochemical reactions (e.g., fuel cell reactions), and eliminate the need for tedious catalyst recovery process after the reaction is completed.

Peptide-functionalized iron oxide magnetic nanoparticle for gold mining

NASA Astrophysics Data System (ADS)

Shen, Wei-Zheng; Cetinel, Sibel; Sharma, Kumakshi; Borujeny, Elham Rafie; Montemagno, Carlo

2017-02-01

Here, we present our work on preparing a novel nanomaterial composed of inorganic binding peptides and magnetic nanoparticles for inorganic mining. Two previously selected and well-characterized gold-binding peptides from cell surface display, AuBP1 and AuBP2, were exploited. This nanomaterial (AuBP-MNP) was designed to fulfill the following two significant functions: the surface conjugated gold-binding peptide will recognize and selectively bind to gold, while the magnetic nano-sized core will respond and migrate according to the applied external magnetic field. This will allow the smart nanomaterial to mine an individual material (gold) from a pool of mixture, without excessive solvent extraction, filtration, and concentration steps. The working efficiency of AuBP-MNP was determined by showing a dramatic reduction of gold nanoparticle colloid concentration, monitored by spectroscopy. The binding kinetics of AuBP-MNP onto the gold surface was determined using surface plasmon resonance (SPR) spectroscopy, which exhibits around 100 times higher binding kinetics than peptides alone. The binding capacity of AuBP-MNP was demonstrated by a bench-top mining test with gold microparticles.

Alizarin Dye based ultrasensitive plasmonic SERS probe for trace level Cadmium detection in drinking water

PubMed Central

Dasary, Samuel S.R.; Zones, Yolanda K.; Barnes, Sandra L.; Ray, P. C.; Singh, Anant K.

2015-01-01

Alizarin functionalized on plasmonic gold nanoparticle displays strong surface enhanced Raman scattering from the various Raman modes of Alizarin, which can be exploited in multiple ways for heavy metal sensing purposes. The present article reports a surface enhanced Raman spectroscopy (SERS) probe for trace level Cadmium in water samples. Alizarin, a highly Raman active dye was functionalized on plasmonic gold surface as a Raman reporter, and then 3-mercaptopropionic acid, 2,6-Pyridinedicarboxylic acid at pH 8.5 was immobilized on the surface of the nanoparticle for the selective coordination of the Cd (II). Upon addition of Cadmium, gold nanoparticle provide an excellent hotspot for Alizarin dye and Raman signal enhancement. This plasmonic SERS assay provided an excellent sensitivity for Cadmium detection from the drinking water samples. We achieved as low as 10 ppt sensitivity from various drinking water sources against other Alkali and heavy metal ions. The developed SERS probe is quite simple and rapid with excellent repeatability and has great potential for prototype scale up for field application. PMID:26770012

Interaction of amino acid-functionalized silver nanoparticles and Candida albicans polymorphs: A deep-UV fluorescence imaging study.

PubMed

Dojčilović, Radovan; Pajović, Jelena D; Božanić, Dušan K; Bogdanović, Una; Vodnik, Vesna V; Dimitrijević-Branković, Suzana; Miljković, Miona G; Kaščaková, Slavka; Réfrégiers, Matthieu; Djoković, Vladimir

2017-07-01

The interaction of the tryptophan functionalized Ag nanoparticles and live Candida albicans cells was studied by synchrotron excitation deep-ultraviolet (DUV) fluorescence imaging at the DISCO beamline of Synchrotron SOLEIL. DUV imaging showed that incubation of the fungus with functionalized nanoparticles results in significant increase in the fluorescence signal. The analysis of the images revealed that the interaction of the nanoparticles with (pseudo)hyphae polymorphs of the diploid fungus was less pronounced than in the case of yeast cells or budding spores. The changes in the intensity of the fluorescence signals of the cells after incubation were followed in [327-353nm] and [370-410nm] spectral ranges that correspond to the fluorescence of tryptophan in non-polar and polar environment, respectively. As a consequence of the environmental sensitivity of the silver-tryptophan fluorescent nanoprobe, we were able to determine the possible accumulation sites of the nanoparticles. The analysis of the intensity decay kinetics showed that the photobleaching effects were more pronounced in the case of the functionalized nanoparticle treated cells. The results of time-integrated emission in the mentioned spectral ranges suggested that the nanoparticles penetrate the cells, but that the majority of the nanoparticles attach to the cells' surfaces. Copyright © 2017 Elsevier B.V. All rights reserved.

Adsorption of surfactant protein D from human respiratory secretions by carbon nanotubes and polystyrene nanoparticles depends on nanomaterial surface modification and size

PubMed Central

Marchetti, Magda; Shaffer, Milo S. P.; Zambianchi, Martina; Chen, Shu; Superti, Fabiana; Schwander, Stephan; Gow, Andrew; Zhang, Junfeng (Jim); Chung, Kian Fan; Ryan, Mary P.; Porter, Alexandra E.; Tetley, Teresa D.

2015-01-01

The alveolar respiratory unit constitutes one of the main targets of inhaled nanoparticles; the effect of engineered nanomaterials (NMs) on human health is largely unknown. Surfactant protein D (SP-D) is synthesized by alveolar type II epithelial cells and released into respiratory secretions; its main function is in immune defence, notably against inhaled microbes. SP-D also plays an important role in modulating an appropriate inflammatory response in the lung, and reduced SP-D is associated with a number of inflammatory lung diseases. Adsorption of SP-D to inhaled NMs may facilitate their removal via macrophage phagocytosis. This study addresses the hypothesis that the chemistry, size and surface modification of engineered NMs will impact on their interaction with, and adsorption of, SP-D. To this purpose, we have examined the interactions between SP-D in human lung lavage and two NMs, carbon nanotubes and polystyrene nanoparticles, with different surface functionalization. We have demonstrated that particle size, functionalization and concentration affect the adsorption of SP-D from human lung lavage. Functionalization with negatively charged groups enhanced the amount of SP-D binding. While SP-D binding would be expected to enhance macrophage phagocytosis, these results suggest that the degree of binding is markedly affected by the physicochemistry of the NM and that deposition of high levels of some nanoparticles within the alveolar unit might deplete SP-D levels and affect alveolar immune defence mechanisms. PMID:25533095

When Anatase Nanoparticles Become Bulklike: Properties of Realistic TiO2 Nanoparticles in the 1-6 nm Size Range from All Electron Relativistic Density Functional Theory Based Calculations.

PubMed

Lamiel-Garcia, Oriol; Ko, Kyoung Chul; Lee, Jin Yong; Bromley, Stefan T; Illas, Francesc

2017-04-11

All electron relativistic density functional theory (DFT) based calculations using numerical atom-centered orbitals have been carried out to explore the relative stability, atomic, and electronic structure of a series of stoichiometric TiO 2 anatase nanoparticles explicitly containing up to 1365 atoms as a function of size and morphology. The nanoparticles under scrutiny exhibit octahedral or truncated octahedral structures and span the 1-6 nm diameter size range. Initial structures were obtained using the Wulff construction, thus exhibiting the most stable (101) and (001) anatase surfaces. Final structures were obtained from geometry optimization with full relaxation of all structural parameters using both generalized gradient approximation (GGA) and hybrid density functionals. Results show that, for nanoparticles of a similar size, octahedral and truncated octahedral morphologies have comparable energetic stabilities. The electronic structure properties exhibit a clear trend converging to the bulk values as the size of the nanoparticles increases but with a marked influence of the density functional employed. Our results suggest that electronic structure properties, and hence reactivity, for the largest anatase nanoparticles considered in this study will be similar to those exhibited by even larger mesoscale particles or by bulk systems. Finally, we present compelling evidence that anatase nanoparticles become effectively bulklike when reaching a size of ∼20 nm diameter.

Biodegradable bisphosphonate nanoparticles for imaging and therapeutic applications in osteosarcoma

NASA Astrophysics Data System (ADS)

Rudnick-Glick, S.; Corem-Salkmon, E.; Grinberg, I.; Gluz, E.; Margel, S.

2015-08-01

Osteosarcoma (OS) is amongst the most commonly diagnosed bone tumors occurring in adolescence, young adults and adults over the age of 65. Current treatment is based on a combination of surgery and chemotherapy. Chemotherapy has improved the survival rate, however it is associated with severe side effects due to the use of high dosages, nonspecific uptake and poor bone blood supply. At present bisphosphonates (BP) are widely used in the treatment of bone disorders including OS. We have engineered a unique biodegradable BP nanoparticle that possesses a dual functionality: 1) covalent attachment of a dye (e.g., NIR dye) or drug to the nanoparticles through the primary amine groups on the surface of the nanoparticle; 2) chelation to the bone mineral hydroxyapatite through the BP on the surface of the nanoparticle. Due to a high concentration of PEG in the BP nanoparticles they possess a relatively long plasma half-life time. Therefore, the nanoparticle has potential for use both in diagnosis and therapy of OS. Doxorubicin was conjugated to the free amine on the surface of the BP nanoparticles. In vitro experiments on osteosarcoma cells demonstrated that the doxorubicin-conjugated BP nanoparticles possess a higher efficacy than the free doxorubicin. Further investigation in vivo in a chicken embryo model confirmed that the doxorubicin-conjugated nanoparticle was significantly more effective in inhibiting tumor growth compared to free doxorubicin at a similar concentration. Additionally, we have shown that these BP nanoparticles preferentially target OS tumor tissue, thus increasing anti-cancer drug bioavailability at targeted site.

Multienzyme-nanoparticles amplification for sensitive virus genotyping in microfluidic microbeads array using Au nanoparticle probes and quantum dots as labels.

PubMed

Zhang, He; Liu, Lian; Li, Cheuk-Wing; Fu, Huayang; Chen, Yao; Yang, Mengsu

2011-11-15

A novel microfluidic device with microbeads array was developed and sensitive genotyping of human papillomavirus was demonstrated using a multiple-enzyme labeled oligonucleotide-Au nanoparticle bioconjugate as the detection tool. This method utilizes microbeads as sensing platform that was functionalized with the capture probes and modified electron rich proteins, and uses the horseradish peroxidase (HRP)-functionalized gold nanoparticles as label with a secondary DNA probe. The functionalized microbeads were independently introduced into the arrayed chambers using the loading chip slab. A single channel was used to generate weir structures to confine the microbeads and make the beads array accessible by microfluidics. Through "sandwich" hybridization, the enzyme-functionalized Au nanoparticles labels were brought close to the surface of microbeads. The oxidation of biotin-tyramine by hydrogen peroxide resulted in the deposition of multiple biotin moieties onto the surface of beads. This deposition is markedly increased in the presence of immobilized electron rich proteins. Streptavidin-labeled quantum dots were then allowed to bind to the deposited biotin moieties and displayed the signal. Enhanced detection sensitivity was achieved where the large surface area of Au nanoparticle carriers increased the amount HRP bound per sandwiched hybridization. The on-chip genotyping method could discriminate as low as 1fmol/L (10zmol/chip, SNR>3) synthesized HPV oligonucleotides DNA. The chip-based signal enhancement of the amplified assay resulted in 1000 times higher sensitivity than that of off-chip test. In addition, this on-chip format could discriminate and genotype 10copies/μL HPV genomic DNA using the PCR products. These results demonstrated that this on-chip approach can achieve highly sensitive detection and genotyping of target DNA and can be further developed for detection of disease-related biomolecules at the lowest level at their earliest incidence. Copyright © 2011 Elsevier B.V. All rights reserved.

Hydrogel, aerogel and film of cellulose nanofibrils functionalized with silver nanoparticles.

PubMed

Dong, Hong; Snyder, James F; Tran, Dat T; Leadore, Julia L

2013-06-20

In this work, we describe hydrogels, aerogels and films of nanofibrillated cellulose (NFC) functionalized with metal nanoparticles using silver as an example. The TEMPO process used to produce NFC generates negatively charged surface carboxylate groups that provide high binding capability to transition metal species such as Ag(+). The gelation of NFC triggered by transition monovalent metal ions was revealed for the first time. The interaction was utilized to bind Ag(+) on the NFC surface and simultaneously induce formation of NFC-Ag(+) hydrogels, where Ag(+) was slowly reduced to Ag nanoparticles by hydroxyl groups on NFC without additional reducing agent. The NFC-Ag(+) hydrogel was initiated by strong association of carboxylate groups on NFC with Ag(+) and sufficient NFC surface charge reduction. The stiff hydrogel has a storage modulus leveled off at a plateau value of ~6800Pa. Porous aerogels and flat thin films comprising a continuous matrix of NFC were decorated with Ag nanoparticles through freeze-drying or solution-casting of NFC-Ag(+) dispersions with low contents of Ag(+), respectively, followed by UV reduction. The presence of Ag species on NFC reduced coalescence of nanofibrils in the film formation as revealed from AFM phase images. Copyright © 2013 Elsevier Ltd. All rights reserved.

Simultaneous surface display and cargo loading of encapsulin nanocompartments and their use for rational vaccine design.

PubMed

Lagoutte, Priscillia; Mignon, Charlotte; Stadthagen, Gustavo; Potisopon, Supanee; Donnat, Stéphanie; Mast, Jan; Lugari, Adrien; Werle, Bettina

2018-05-11

In the past decades protein nanoparticles have successfully been used for vaccine applications. Their particulate nature and dense repetitive subunit organization makes them perfect carriers for antigen surface display and confers high immunogenicity. Nanoparticles have emerged as excellent candidates for vectorization of biological and immunostimulating molecules. Nanoparticles and biomolecular nanostructures such as ferritins or virus like particles have been used as diagnostic and therapeutic delivery systems, in vaccine development, as nanoreactors, etc. Recently, a new class of bacterial protein compartment has been discovered referred to as encapsulin nanocompartment. These compartments have been used for targeted diagnostics, as therapeutic delivery systems and as nanoreactors. Their biological origin makes them conveniently biocompatible and allows genetic functionalization. The aim of our study was to implement encapsulin nanocompartements for simultaneous epitope surface display and heterologous protein loading for rational vaccine design. For this proof-of-concept-study, we produced Thermotoga maritima encapsulin nanoparticles in E. coli. We demonstrated the ability of simultaneous display in our system by inserting Matrix protein 2 ectodomain (M2e) of influenza A virus at the nanoparticle surface and by packaging of a fluorescent reporter protein (GFP) into the internal cavity. Characterization of the nanoparticles by electronic microscopy confirmed homogenously shaped particles of 24 nm diameter in average. The results further show that engineering of the particle surface improved the loading capacity of the heterologous reporter protein suggesting that surface display may induce a critical elastic deformation resulting in improved stiffness. In Balb/c mice, nanoparticle immunization elicited antibody responses against both the surface epitope and the loaded cargo protein. These results confirm the potential of encapsulin nanocompartments for customized vaccine design and antigen delivery. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ag nanoparticle-functionalized ZnO micro-flowers for enhanced photodegradation of herbicide derivatives

NASA Astrophysics Data System (ADS)

Xu, Yan; Wu, Shumin; Li, Xianliang; Meng, Hao; Zhang, Xia; Wang, Zhuopeng; Han, Yide

2017-07-01

We demonstrate a general strategy to design step by step the Ag nanoparticle-functionalized ZnO micro-flowers (Ag/ZnO composites). XRD patterns confirmed the presence of Ag nanoparticles in ZnO/Ag composites, and the SEM and TEM results further demonstrated that Ag nanoparticles were highly dispersed and anchored onto the surface of each ZnO nanosheets. By using the ZnO/Ag composites, the photodegradation of two herbicide derivatives, metamitron and metribuzin, were studied. The enhanced photocatalytic performance was ascribed to the fact that the Ag deposition could reduce the recombination probability of electron-hole pairs, and the photocatalytic mechanism were also investigated in this paper.

Carboxylated SiO2-coated α-Fe nanoparticles: towards a versatile platform for biomedical applications.

PubMed

Kohara, Kaori; Yamamoto, Shinpei; Seinberg, Liis; Murakami, Tatsuya; Tsujimoto, Masahiko; Ogawa, Tetsuya; Kurata, Hiroki; Kageyama, Hiroshi; Takano, Mikio

2013-03-28

Carboxylated SiO2-coated α-Fe nanoparticles have been successfully prepared via CaH2-mediated reduction of SiO2-coated Fe3O4 nanoparticles followed by surface carboxylation. These α-Fe-based nanoparticles, which are characterized by ease of coating with additional functional groups, a large magnetization of 154 emu per g-Fe, enhanced corrosion resistivity, excellent aqueous dispersibility, and low cytotoxicity, have potential to be a versatile platform in biomedical applications.

Silicon nanoparticles: applications in cell biology and medicine

PubMed Central

O’Farrell, Norah; Houlton, Andrew; Horrocks, Benjamin R

2006-01-01

In this review, we describe the synthesis, physical properties, surface functionalization, and biological applications of silicon nanoparticles (also known as quantum dots). We compare them against current technologies, such as fluorescent organic dyes and heavy metal chalcogenide-based quantum dots. In particular, we examine the many different methods that can be used to both create and modify these nanoparticles and the advantages they may have over current technologies that have stimulated research into designing silicon nanoparticles for in vitro and in vivo applications. PMID:17722279

Novel functionalized fluorescent polymeric nanoparticles for immobilization of biomolecules

NASA Astrophysics Data System (ADS)

Jain, Swati; Chattopadhyay, Sruti; Jackeray, Richa; Abid, C. K. V. Zainul; Singh, Harpal

2013-07-01

Novel, size controlled fluorescent polymeric nanoparticles (FPNP) were synthesized having acetoacetoxy functionality on the surface for immobilization of biomolecules which can be utilized as biomarkers and labels in fluoroimmunoassays. Core-shell nanoparticles of poly(styrene, St-methyl methacrylate, MMA-acetoacetoxy ethyl methacrylate, AAEM), stabilized by various concentrations of surfactant, sodium lauryl sulphate (SLS), were obtained by facile miniemulsion co-polymerization encapsulated with pyrene molecules in their hydrophobic core. Analytical, spectroscopic and imaging characterization techniques revealed the formation of stable, monodisperse, spherical nano sized particles exhibiting high luminescence properties. Particles with 1% SLS (S1) showed good dispersion stability and fluorescence intensity and were chosen as ideal candidates for further immobilization studies. Steady state fluorescence studies showed 10 times higher fluorescence intensity of S1 nanoparticles than that of pyrene solution in solvent-toluene at the same concentration. Environmental factors such as pH, ionic strength and time were found to have no effect on fluorescence intensity of FPNPs. Surface β-di-ketone groups were utilized for the covalent immobilization of enzyme conjugated antibodies without any activation or pre-treatment of nanoparticles.Novel, size controlled fluorescent polymeric nanoparticles (FPNP) were synthesized having acetoacetoxy functionality on the surface for immobilization of biomolecules which can be utilized as biomarkers and labels in fluoroimmunoassays. Core-shell nanoparticles of poly(styrene, St-methyl methacrylate, MMA-acetoacetoxy ethyl methacrylate, AAEM), stabilized by various concentrations of surfactant, sodium lauryl sulphate (SLS), were obtained by facile miniemulsion co-polymerization encapsulated with pyrene molecules in their hydrophobic core. Analytical, spectroscopic and imaging characterization techniques revealed the formation of stable, monodisperse, spherical nano sized particles exhibiting high luminescence properties. Particles with 1% SLS (S1) showed good dispersion stability and fluorescence intensity and were chosen as ideal candidates for further immobilization studies. Steady state fluorescence studies showed 10 times higher fluorescence intensity of S1 nanoparticles than that of pyrene solution in solvent-toluene at the same concentration. Environmental factors such as pH, ionic strength and time were found to have no effect on fluorescence intensity of FPNPs. Surface β-di-ketone groups were utilized for the covalent immobilization of enzyme conjugated antibodies without any activation or pre-treatment of nanoparticles. Electronic supplementary information (ESI) available: Resulting ATR-FTIR spectrum and procedure to study fluorescence of nanoparticles, effect of particle size, concentration, pH, ionic strength and time on Fl intensity of FPNP. See DOI: 10.1039/c3nr34100c

Hydrothermal synthesis of histidine-functionalized single-crystalline gold nanoparticles and their pH-dependent UV absorption characteristic.

PubMed

Liu, Zhiguo; Zu, Yuangang; Fu, Yujie; Meng, Ronghua; Guo, Songling; Xing, Zhimin; Tan, Shengnan

2010-03-01

L-Histidine capped single-crystalline gold nanoparticles have been synthesized by a hydrothermal process under a basic condition at temperature between 65 and 150 degrees C. The produced gold nanoparticles were spherical with average diameter of 11.5+/-2.9nm. The synthesized gold colloidal solution was very stable and can be stored at room temperature for more than 6 months. The color of the colloidal solution can change from wine red to mauve, purple and blue during the acidifying process. This color changing phenomenon is attributed to the aggregation of gold nanoparticles resulted from hydrogen bond formation between the histidines adsorbed on the gold nanoparticles surfaces. This hydrothermal synthetic method is expected to be used for synthesizing some other amino acid functionalized gold nanomaterials.

Molecular ligand modulation of palladium nanocatalysts for highly efficient and robust heterogeneous oxidation of cyclohexenone to phenol

DOE PAGES

Xue, Teng; Lin, Zhaoyang; Chiu, Chin-Yi; ...

2017-01-06

Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts tomore » date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less

Conjugating folate on superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles using click chemistry

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

Shen, Xiaofang, E-mail: xfshen@jiangnan.edu.cn; Ge, Zhaoqiang; Pang, Yuehong

2015-02-15

Gold-coated magnetic core@shell nanoparticles, which exhibit magneto-optical properties, not only enhance the chemical stability of core and biocompatibility of surface, but also provide a combination of multimodal imaging and therapeutics. The conjugation of these tiny nanoparticles with specific biomolecules allows researchers to target the desired location. In this paper, superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles were synthesized and functionalized with the azide group on the surface by formation of self-assembled monolayers. Folate (FA) molecules, non-immunogenic target ligands for cancer cells, are conjugated with alkyne and then immobilized on the azide-terminated Fe{sub 3}O{sub 4}@Au nanoparticles through copper(I)-catalyzed azide-alkyne cycloaddition (click reaction). Myelogenousmore » leukemia K562 cells were used as a folate receptor (FR) model, which can be targeted and extracted by magnetic field after interaction with the Fe{sub 3}O{sub 4}@Au–FA nanoparticles. - Graphical abstract: Self-assembled azide-terminated group on superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles followed by click reaction with alkyne-functionalized folate, allowing the nanoparticles target folate receptor of cancer cells. - Highlights: • Azidoundecanethiol was coated on the superparamagnetic Fe{sub 3}O{sub 4}@Au nanoparticles by forming self-assembled monolayers. • Alkyne-terminated folate was synthesized from a reaction between the amine and the carboxylic acid. • Conjugation of Fe{sub 3}O{sub 4}@Au nanoparticles with folate was made by copper-catalyzed azide-alkyne cycloaddition click chemistry.« less

Shape-Controllable Gold Nanoparticle-MoS2 Hybrids Prepared by Tuning Edge-Active Sites and Surface Structures of MoS2 via Temporally Shaped Femtosecond Pulses.

PubMed

Zuo, Pei; Jiang, Lan; Li, Xin; Li, Bo; Xu, Yongda; Shi, Xuesong; Ran, Peng; Ma, Tianbao; Li, Dawei; Qu, Liangti; Lu, Yongfeng; Grigoropoulos, Costas P

2017-03-01

Edge-active site control of MoS 2 is crucial for applications such as chemical catalysis, synthesis of functional composites, and biochemical sensing. This work presents a novel nonthermal method to simultaneously tune surface chemical (edge-active sites) and physical (surface periodic micro/nano structures) properties of MoS 2 using temporally shaped femtosecond pulses, through which shape-controlled gold nanoparticles are in situ and self-assembly grown on MoS 2 surfaces to form Au-MoS 2 hybrids. The edge-active sites with unbound sulfurs of laser-treated MoS 2 drive the reduction of gold nanoparticles, while the surface periodic structures of laser-treated MoS 2 assist the shape-controllable growth of gold nanoparticles. The proposed novel method highlights the broad application potential of MoS 2 ; for example, these Au-MoS 2 hybrids exhibit tunable and highly sensitive SERS activity with an enhancement factor up to 1.2 × 10 7 , indicating the marked potential of MoS 2 in future chemical and biological sensing applications.

Iron oxide and gold nanoparticles in cancer therapy

NASA Astrophysics Data System (ADS)

Gotman, Irena; Psakhie, Sergey G.; Lozhkomoev, Aleksandr S.; Gutmanas, Elazar Y.

2016-08-01

Continuous research activities in the field of nanomedicine in the past decade have, to a great extent, been focused on nanoparticle technologies for cancer therapy. Gold and iron oxide nanoparticles (NP) are two of the most studied inorganic nanomaterials due to their unique optical and magnetic properties. Both types of NPs are emerging as promising systems for anti-tumor drug delivery and for nanoparticle-mediated thermal therapy of cancer. In thermal therapy, localized heating inside tumors or in proximity of tumor cells can be induced, for example, with Au NPs by radiofrequency ablation heating or conversion of photon energy (photothermal therapy) and in iron oxide magnetic NPs by heat generation through relaxation in an alternating magnetic field (magnetic hyperthermia). Furthermore, the superparamagnetic properties of iron oxide nanoparticles have led to their use as potent MRI (magnetic resonance imaging) contrast agents. Surface modification/coating can produce NPs with tailored and desired properties, such as enhanced blood circulation time, stability, biocompatibility and water solubility. To target nanoparticles to specific tumor cells, NPs should be conjugated with targeting moieties on the surface which bind to receptors or other molecular structures on the cell surface. The article presents several approaches to enhancing the specificity of Au and iron oxide nanoparticles for tumor tissue by appropriate surface modification/functionalization, as well as the effect of these treatments on the saturation magnetization value of iron oxide NPs. The use of other nanoparticles and nanostructures in cancer treatment is also briefly reviewed.

Roughening of Pt nanoparticles induced by surface-oxide formation.

PubMed

Zhu, Tianwei; Hensen, Emiel J M; van Santen, Rutger A; Tian, Na; Sun, Shi-Gang; Kaghazchi, Payam; Jacob, Timo

2013-02-21

Using density functional theory (DFT) and thermodynamic considerations we studied the equilibrium shape of Pt nanoparticles (NPs) under electrochemical conditions. We found that at very high oxygen coverage, obtained at high electrode potentials, the experimentally-observed tetrahexahedral (THH) NPs consist of high-index (520) faces. Since high-index surfaces often show higher (electro-)chemical activity in comparison to their close-packed counterparts, the THH NPs can be promising candidates for various (electro-)catalytic applications.

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).

Modeling the atomistic growth behavior of gold nanoparticles in solution

NASA Astrophysics Data System (ADS)

Turner, C. Heath; Lei, Yu; Bao, Yuping

2016-04-01

The properties of gold nanoparticles strongly depend on their three-dimensional atomic structure, leading to an increased emphasis on controlling and predicting nanoparticle structural evolution during the synthesis process. In order to provide this atomistic-level insight and establish a link to the experimentally-observed growth behavior, a kinetic Monte Carlo simulation (KMC) approach is developed for capturing Au nanoparticle growth characteristics. The advantage of this approach is that, compared to traditional molecular dynamics simulations, the atomistic nanoparticle structural evolution can be tracked on time scales that approach the actual experiments. This has enabled several different comparisons against experimental benchmarks, and it has helped transition the KMC simulations from a hypothetical toy model into a more experimentally-relevant test-bed. The model is initially parameterized by performing a series of automated comparisons of Au nanoparticle growth curves versus the experimental observations, and then the refined model allows for detailed structural analysis of the nanoparticle growth behavior. Although the Au nanoparticles are roughly spherical, the maximum/minimum dimensions deviate from the average by approximately 12.5%, which is consistent with the corresponding experiments. Also, a surface texture analysis highlights the changes in the surface structure as a function of time. While the nanoparticles show similar surface structures throughout the growth process, there can be some significant differences during the initial growth at different synthesis conditions.

The Morphology of Silver Layers on SU8 polymers prepared by Electroless Deposition

NASA Astrophysics Data System (ADS)

Dutta, Aniruddha; Yuan, Biao; Heinrich, Helge; Grabill, Chris; Williams, Henry; Kuebler, Stephen; Bhattacharya, Aniket

2010-03-01

Silver was deposited onto the functionalized surface of polymeric SU-8 where gold nanoparticles (Au-NPs) act as nucleation sites using electroless metallization chemistry. Here we report on the evolution of the nanoscale morphology of deposited Ag studied by Transmission Electron Microscopy (TEM). In TEM of sample cross sections correlations between the original gold and the silver nanoparticles were obtained while plan-view TEM results showed the distribution of nanoparticles on the surface. Scanning TEM with a high-angle annular dark field detector was used to obtain atomic number contrast. The morphology of the deposited Ag was controlled through the presence and absence of gum Arabic. The thickness and height fluctuations of the Ag layer were determined as a function of time and a statistical analysis of the growth process was conducted for the initial deposition periods.

Nanoparticle-Functionalized Porous Polymer Monolith Detection Elements for Surface-Enhanced Raman Scattering

PubMed Central

Liu, Jikun; White, Ian; DeVoe, Don L.

2011-01-01

The use of porous polymer monoliths functionalized with silver nanoparticles is introduced in this work for high-sensitivity surface-enhanced Raman scattering (SERS) detection. Preparation of the SERS detection elements is a simple process comprising the synthesis of a discrete polymer monolith section within a silica capillary, followed by physically trapping silver nanoparticle aggregates within the monolith matrix. A SERS detection limit of 220 fmol for Rhodamine 6G (R6G) is demonstrated, with excellent signal stability over a 24 h period. The capability of the SERS-active monolith for label-free detection of biomolecules was demonstrated by measurements of bradykinin and cyctochrome c. The SERS-active monoliths can be readily integrated into miniaturized micro-total-analysis systems for on-line and label-free detection for a variety of biosensing, bioanalytical, and biomedical applications. PMID:21322579

Gold and silver nanoparticles for biomolecule immobilization and enzymatic catalysis

PubMed Central

2012-01-01

In this work, a simple method for alcohol synthesis with high enantiomeric purity was proposed. For this, colloidal gold and silver surface modifications with 3-mercaptopropanoic acid and cysteamine were used to generate carboxyl and amine functionalized gold and silver nanoparticles of 15 and 45 nm, respectively. Alcohol dehydrogenase from Thermoanaerobium brockii (TbADH) and its cofactor (NADPH) were physical and covalent (through direct adsorption and using cross-linker) immobilized on nanoparticles' surface. In contrast to the physical and covalent immobilizations that led to a loss of 90% of the initial enzyme activity and 98% immobilization, the use of a cross-linker in immobilization process promoted a loss to 30% of the initial enzyme activity and >92% immobilization. The yield of NADPH immobilization was about 80%. The best results in terms of activity were obtained with Ag-citr nanoparticle functionalized with carboxyl groups (Ag-COOH), Au-COOH(CTAB), and Au-citr functionalized with amine groups and stabilized with CTAB (Au-NH2(CTAB)) nanoparticles treated with 0.7% and 1.0% glutaraldehyde. Enzyme conformation upon immobilization was studied using fluorescence and circular dichroism spectroscopies. Shift in ellipticity at 222 nm with about 4 to 7 nm and significant decreasing in fluorescence emission for all bioconjugates were observed by binding of TbADH to silver/gold nanoparticles. Emission redshifting of 5 nm only for Ag-COOH-TbADH bioconjugate demonstrated change in the microenvironment of TbADH. Enzyme immobilization on glutaraldehyde-treated Au-NH2(CTAB) nanoparticles promotes an additional stabilization preserving about 50% of enzyme activity after 15 days storage. Nanoparticles attached-TbADH-NADPH systems were used for enantioselective (ee > 99%) synthesis of (S)-7-hydroxy-2-tetralol. PMID:22655978

Gold and silver nanoparticles for biomolecule immobilization and enzymatic catalysis.

PubMed

Petkova, Galina A; Záruba, Capital Ka Cyrillicamil; Zvátora, Pavel; Král, Vladimír

2012-06-01

In this work, a simple method for alcohol synthesis with high enantiomeric purity was proposed. For this, colloidal gold and silver surface modifications with 3-mercaptopropanoic acid and cysteamine were used to generate carboxyl and amine functionalized gold and silver nanoparticles of 15 and 45 nm, respectively. Alcohol dehydrogenase from Thermoanaerobium brockii (TbADH) and its cofactor (NADPH) were physical and covalent (through direct adsorption and using cross-linker) immobilized on nanoparticles' surface. In contrast to the physical and covalent immobilizations that led to a loss of 90% of the initial enzyme activity and 98% immobilization, the use of a cross-linker in immobilization process promoted a loss to 30% of the initial enzyme activity and >92% immobilization. The yield of NADPH immobilization was about 80%. The best results in terms of activity were obtained with Ag-citr nanoparticle functionalized with carboxyl groups (Ag-COOH), Au-COOH(CTAB), and Au-citr functionalized with amine groups and stabilized with CTAB (Au-NH2(CTAB)) nanoparticles treated with 0.7% and 1.0% glutaraldehyde. Enzyme conformation upon immobilization was studied using fluorescence and circular dichroism spectroscopies. Shift in ellipticity at 222 nm with about 4 to 7 nm and significant decreasing in fluorescence emission for all bioconjugates were observed by binding of TbADH to silver/gold nanoparticles. Emission redshifting of 5 nm only for Ag-COOH-TbADH bioconjugate demonstrated change in the microenvironment of TbADH. Enzyme immobilization on glutaraldehyde-treated Au-NH2(CTAB) nanoparticles promotes an additional stabilization preserving about 50% of enzyme activity after 15 days storage. Nanoparticles attached-TbADH-NADPH systems were used for enantioselective (ee > 99%) synthesis of (S)-7-hydroxy-2-tetralol.

Highly labeled methylene blue-ds DNA silica nanoparticles for signal enhancement of immunoassays: application to the sensitive detection of bacteria in human platelet concentrates.

PubMed

Bonnet, Romaric; Farre, Carole; Valera, Lionel; Vossier, Ludivine; Léon, Fanny; Dagland, Typhaine; Pouzet, Agnès; Jaffrézic-Renault, Nicole; Fareh, Jeannette; Fournier-Wirth, Chantal; Chaix, Carole

2018-05-15

A nanoparticle-based electrochemical sandwich immunoassay was developed for bacteria detection in platelet concentrates. For the assay, magnetic beads were functionalized with antibodies to allow the specific capture of bacteria from the complex matrix, and innovative methylene blue-DNA/nanoparticle assemblies provided the electrochemical response for amplified detection. This nanoparticular system was designed as a temperature-sensitive nano-tool for electrochemical detection. First, oligonucleotide-functionalized nanoparticles were obtained by direct synthesis of the DNA strands on the nanoparticle surface using an automated oligonucleotide synthesizer. Densely packed DNA coverage was thus obtained. Then, DNA duplexes were constructed on the NP surface with a complementary strand bearing a 3 methylene blue tag. This strategy ultimately produced highly functionalized nanoparticles with electrochemical markers. These assemblies enabled amplification of the electrochemical signal, resulting in a very good sensitivity. A proof-of-concept was carried out for E. coli detection in human platelet concentrates. Bacterial contamination of this complex biological matrix is the highest residual infectious risk in blood transfusion. The development of a rapid assay that could reach 10-102 CFU mL-1 sensitivity is a great challenge. The nanoparticle-based electrochemical sandwich immunoassay carried out on a boron doped diamond electrode proved to be sensitive for E. coli detection in human platelets. Two antibody pairs were used to develop either a generic assay against certain Gram negative strains or a specific assay for E. coli. The methylene blue-DNA/nanoparticles amplify sensitivity ×1000 compared with the assay run without NPs for electrochemical detection. A limit of detection of 10 CFU mL-1 in a biological matrix was achieved for E. coli using the highly specific antibody pair.

Electrokinetic Properties of Fullerene nC60 Nanoparticles: Role of Co-ions and pH

EPA Science Inventory

Environmental exposure, bioavailability, and mobility of nanoparticles (NPs) in part depend on their aggregated state and their surface charge. These fundamental characteristics are functions of the aqueous media in which the particles are suspended. For example, inorganic ions p...

Enhanced Column Filtration for Arsenic Removal from Water: Polymer-Templated Iron Oxide Nanoparticles Immobilized on Sand via Layer-by-Layer Deposition

NASA Astrophysics Data System (ADS)

Cheng, Calvin Chia-Hung

Arsenic is ubiquitous in water sources around the world and is highly toxic. While precipitation and membrane filtration techniques are successfully implemented in developed cities, they are unsuitable for rural and low-resource settings lacking centralized facilities. This thesis presents the use of ultra-small iron oxide (Fe2O3) nanoparticles functionalized on sand granules for use as a house-hold scale adsorption filter. Water-stable alpha-Fe2O3 (hematite) nanoparticles (<10 nm) were synthesized via a collapsed-polymer approach using poly(acrylic acid) and Fe3+ ions. The nanoparticles exhibited high arsenic adsorption, with 147 +/- 2 mg As(III) per g Fe2O3 and 91 +/- 10 mg As(V) per g Fe2O3. The platform was also used to synthesize iron-based composites, including magnetite (Fe 3O4) and Fe-Cu oxide nanoparticles. For use as a column filter, Fe2O3-PAA nanoparticles were functionalized on sand granules using a layer-by-layer deposition method, with the nanoparticles embedded in the negative layer. The removal of As(III) by the Fe2O 3-PAA functionalized column was described by reversible 1st order kinetics where the forward and reverse rate constants were 0.31 hr -1 and 0.097 hr-1, respectively. Implemented as a passive water filter with 30 x 30 x 50 cm3 dimensions, the filter has an expected lifetime in the order of many years. By controlling the flow rate of the column depending on contamination levels, the filter effectively removes arsenic down to the safety limit of 0.01 mg/L. In a parallel project, the layer-by-layer deposition of Poly(diallydimethyl ammonium chloride) (PDDA) and poly(sodium 5-styrenesulfonate) (PSS) was exploited for a highly practical synthesis of discrete gradient surfaces. By independently controlling the concentration of NaCl in PDDA and PSS deposition solutions, a 2-dimensional matrix of surfaces was created in 96-well microtiter plates. Distinct non-monotonic dye adsorption patterns on the gradient surfaces was observed. Practical knowledge from this project was also used to enhance the nanoparticle surface functionalization described above. In all, a practical, no expertise-needed passive water filtration unit was described in this thesis. The unit makes use of hardware available in existing sand-based water filters, and is designed to address the unmet need of arsenic removal from drinking water in low-resource or rural settings.

pH-Switchable Interaction of a Carboxybetaine Ester-Based SAM with DNA and Gold Nanoparticles.

PubMed

Filip, Jaroslav; Popelka, Anton; Bertok, Tomas; Holazova, Alena; Osicka, Josef; Kollar, Jozef; Ilcikova, Marketa; Tkac, Jan; Kasak, Peter

2017-07-11

We describe a self-assembled monolayer (SAM) on a gold surface with a carboxybetaine ester functionality to control the interaction between DNA and gold nanoparticles via pH. The negatively charged phosphate backbone of DNA interacts with and adsorbs to the positively charged carboxybetaine esters on the SAM. DNA release can be achieved by the hydrolysis of carboxybetaine ester (CBE) to a zwitterionic carboxybetaine state. Furthermore, the adsorption of negatively charged citrate-capped gold nanoparticles to a SAM-modified plain gold surface can be controlled by the pH. The SAM based on carboxybetaine ester allows for the homogeneous adsorption of particles, whereas the SAM after hydrolysis at high pH repels AuNP adsorption. The antifouling surface properties of the surface modified with carboxybetaine were investigated with protein samples.

Synthesis and catalytic activity of the metastable phase of gold phosphide

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

Fernando, Deshani; Nigro, Toni A.E.; Dyer, I.D.

Recently, transition metal phosphides have found new applications as catalysts for the hydrogen evolution reaction that has generated an impetus to synthesize these materials at the nanoscale. In this work, Au{sub 2}P{sub 3} was synthesized utilizing the high temperature decomposition of tri-n-octylphosphine as a source of elemental phosphorous. Gold nanorods were used as morphological templates with the aim of controlling the shape and size of the resulting gold phosphide particles. We demonstrate that the surface capping ligand of the gold nanoparticle precursors can influence the purity and extent to which the gold phosphide phase will form. Gold nanorods functionalized withmore » 1-dodecanethiol undergo digestive ripening to produce discrete spherical particles that exhibit reduced reactivity towards phosphorous, resulting in low yields of the gold phosphide. In contrast, gold phosphide was obtained as a phase pure product when cetyltrimethylammonium bromide functionalized gold nanorods are used instead. The Au{sub 2}P{sub 3} nanoparticles exhibited higher activity than polycrystalline gold towards the hydrogen evolution reaction. - Graphical abstract: Au{sub 2}P{sub 3} was synthesized utilizing the high temperature decomposition of tri-n-octylphosphine as a source of elemental phosphorous and gold nanoparticles as reactants. We demonstrate that the surface capping ligand of the gold nanoparticle precursors influence the purity and extent to which the Au{sub 2}P{sub 3} phase will form. Gold nanorods functionalized with 1-dodecanethiol undergo digestive ripening to produce discrete spherical particles that exhibit reduced reactivity towards phosphorous, resulting in low yields of the gold phosphide. In contrast, gold phosphide was obtained as a phase pure product when cetyltrimethylammonium bromide functionalized gold nanoparticles are used instead. The Au{sub 2}P{sub 3} nanoparticles exhibited higher activity than polycrystalline gold towards the hydrogen evolution reaction. - Highlights: • The surface chemistry of gold affects the synthetic yields of Au{sub 2}P{sub 3}. • Imaging of Au{sub 2}P{sub 3} with transmission electron microscopy results in decomposition. • Au{sub 2}P{sub 3} nanoparticles exhibit activity towards the hydrogen evolution reaction.« less

In situ growth of capping-free magnetic iron oxide nanoparticles on liquid-phase exfoliated graphene

NASA Astrophysics Data System (ADS)

Tsoufis, T.; Syrgiannis, Z.; Akhtar, N.; Prato, M.; Katsaros, F.; Sideratou, Z.; Kouloumpis, A.; Gournis, D.; Rudolf, P.

2015-05-01

We report a facile approach for the in situ synthesis of very small iron oxide nanoparticles on the surface of high-quality graphene sheets. Our synthetic strategy involved the direct, liquid-phase exfoliation of highly crystalline graphite (avoiding any oxidation treatment) and the subsequent chemical functionalization of the graphene sheets via the well-established 1,3-dipolar cycloaddition reaction. The resulting graphene derivatives were employed for the immobilization of the nanoparticle precursor (Fe cations) at the introduced organic groups by a modified wet-impregnation method, followed by interaction with acetic acid vapours. The final graphene-iron oxide hybrid material was achieved by heating (calcination) in an inert atmosphere. Characterization by X-ray diffraction, transmission electron and atomic force microscopy, Raman and X-ray photoelectron spectroscopy gave evidence for the formation of rather small (<12 nm), spherical, magnetite-rich nanoparticles which were evenly distributed on the surface of few-layer (<1.2 nm thick) graphene. Due to the presence of the iron oxide nanoparticles, the hybrid material showed a superparamagnetic behaviour at room temperature.We report a facile approach for the in situ synthesis of very small iron oxide nanoparticles on the surface of high-quality graphene sheets. Our synthetic strategy involved the direct, liquid-phase exfoliation of highly crystalline graphite (avoiding any oxidation treatment) and the subsequent chemical functionalization of the graphene sheets via the well-established 1,3-dipolar cycloaddition reaction. The resulting graphene derivatives were employed for the immobilization of the nanoparticle precursor (Fe cations) at the introduced organic groups by a modified wet-impregnation method, followed by interaction with acetic acid vapours. The final graphene-iron oxide hybrid material was achieved by heating (calcination) in an inert atmosphere. Characterization by X-ray diffraction, transmission electron and atomic force microscopy, Raman and X-ray photoelectron spectroscopy gave evidence for the formation of rather small (<12 nm), spherical, magnetite-rich nanoparticles which were evenly distributed on the surface of few-layer (<1.2 nm thick) graphene. Due to the presence of the iron oxide nanoparticles, the hybrid material showed a superparamagnetic behaviour at room temperature. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00765h

Optical properties of medium size noble and transition metal nanoparticles

NASA Astrophysics Data System (ADS)

Idrobo, Juan C.; Pantelides, Sokrates T.

2009-03-01

Using first-principles methods within time dependent density functional theory and the local density approximation (TDLDA) the absorption spectra of medium size (˜20-80 atoms) silver, gold and copper nanoparticles have been calculated. The nanoparticles are fcc fragments with different aspect ratios. We find that in the case of Ag nanoparticles is well reproduced by classical electrodynamics theory based in Mie's formalism, using the dielectric function of bulk Ag and taking into account the nanoparticle shape. For the case of Cu and Au, there is a similarity in the overall features of the quantum mechanical and classical spectra, but no detailed agreement. We will discuss the role that the d-electrons among all the different elements and the surface states play in controlling the optical properties of the nanoparticles. This work was supported by GOALI NSF grant (DMR-0513048), DOE, the Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, and Alcoa Inc.

Multifunctional nanocomposite hollow fiber membranes by solvent transfer induced phase separation.

PubMed

Haase, Martin F; Jeon, Harim; Hough, Noah; Kim, Jong Hak; Stebe, Kathleen J; Lee, Daeyeon

2017-11-01

The decoration of porous membranes with a dense layer of nanoparticles imparts useful functionality and can enhance membrane separation and anti-fouling properties. However, manufacturing of nanoparticle-coated membranes requires multiple steps and tedious processing. Here, we introduce a facile single-step method in which bicontinuous interfacially jammed emulsions are used to form nanoparticle-functionalized hollow fiber membranes. The resulting nanocomposite membranes prepared via solvent transfer-induced phase separation and photopolymerization have exceptionally high nanoparticle loadings (up to 50 wt% silica nanoparticles) and feature densely packed nanoparticles uniformly distributed over the entire membrane surfaces. These structurally well-defined, asymmetric membranes facilitate control over membrane flux and selectivity, enable the formation of stimuli responsive hydrogel nanocomposite membranes, and can be easily modified to introduce antifouling features. This approach forms a foundation for the formation of advanced nanocomposite membranes comprising diverse building blocks with potential applications in water treatment, industrial separations and as catalytic membrane reactors.

Plasma Amino Acid Coatings for a Conformal Growth of Titania Nanoparticles

DTIC Science & Technology

2010-04-01

of dry nitrogen. Periodic porous polymer SU8 templates fabricated using multi-beam IL according to published procedures have been supplied by Thomas...3D periodic polymer structures via plasma enhanced chemical vapor deposition. We demonstrate the efficient utilization of this functional amino acid...nanoparticles were grown directly on histidine-functionalized planar and 3D polymer substrates by a wet-chemistry method that showed uniform surface

Membrane mimetic surface functionalization of nanoparticles: Methods and applications

PubMed Central

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

2013-01-01

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

Fluorescent nanoparticles based on AIE fluorogens for bioimaging.

PubMed

Yan, Lulin; Zhang, Yan; Xu, Bin; Tian, Wenjing

2016-02-07

Fluorescent nanoparticles (FNPs) have recently attracted increasing attention in the biomedical field because of their unique optical properties, easy fabrication and outstanding performance in imaging. Compared with conventional molecular probes including small organic dyes and fluorescent proteins, FNPs based on aggregation-induced emission (AIE) fluorogens have shown significant advantages in tunable emission and brightness, good biocompatibility, superb photo- and physical stability, potential biodegradability and facile surface functionalization. In this review, we summarize the latest advances in the development of fluorescent nanoparticles based on AIE fluorogens including polymer nanoparticles and silica nanoparticles over the past few years, and the various biomedical applications based on these fluorescent nanoparticles are also elaborated.

Endocytosis and exocytosis of nanoparticles in mammalian cells

PubMed Central

Oh, Nuri; Park, Ji-Ho

2014-01-01

Engineered nanoparticles that can be injected into the human body hold tremendous potential to detect and treat complex diseases. Understanding of the endocytosis and exocytosis mechanisms of nanoparticles is essential for safe and efficient therapeutic application. In particular, exocytosis is of significance in the removal of nanoparticles with drugs and contrast agents from the body, while endocytosis is of great importance for the targeting of nanoparticles in disease sites. Here, we review the recent research on the endocytosis and exocytosis of functionalized nanoparticles based on various sizes, shapes, and surface chemistries. We believe that this review contributes to the design of safe nanoparticles that can efficiently enter and leave human cells and tissues. PMID:24872703

Spectroscopic exploration of interaction between PEG-functionalized Ag2S nanoparticles with bovine serum albumin

NASA Astrophysics Data System (ADS)

Prasanth, S.; RitheshRaj, D.; Vineeshkumar, T. V.; Sudarsanakumar, C.

2018-05-01

The introduction of nanoparticles into biological fluids often leads to the formation of biocorona over the surface of nanoparticles. For the effective use of nanoparticles in biological applications it is very essential to understand their interactions with proteins. Herein, we investigated the interactions of Poly ethylene glycol capped Ag2S nanoparticles with Bovine Serum Albumin by spectroscopic techniques. By the addition of Ag2S nanoparticles, a ground state complex is formed. The CD spectroscopy reveals that the secondary structure of BSA is altered by complexation with PEG-Ag2S nanoparticles, while the overall tertiary structure remains closer to that of native BSA.

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

Fabrication and functionalization of carbon nanotube field effect transistors for bio-sensing applications

NASA Astrophysics Data System (ADS)

Zhou, Jianyun

Single walled carbon nanotube based field effect transistors are fabricated using photolithography and electron beam lithography techniques. First catalyst islands are deposited onto the substrate using standard optical lithographic techniques, and the nanotubes are grown by catalytic chemical vapor deposition from the pre-patterned catalyst islands. After imaging the grown nanotubes, the metal contact electrodes are patterned using lithography, followed by metal deposition using a sputtering technique. Both single nanotube devices and nanotube film devices are fabricated using this method. The single nanotube devices can be semiconducting, ambipolar, or metallic, with the resistance ranging from tens of kilo ohms to a few mega ohms, while the film devices are generally metallic, with only a few kilo ohms of resistance. Semiconducting single nanotube devices are functionalized for sensor applications. An electrodeposition technique was developed to functionalize the nanotube with a few materials, including avidin, chitosan, and metal nanoparticles. Among them, metal nanoparticle deposition is the most successful, and both gold and silver nanoparticles have been successfully deposited onto the sidewalls of the nanotubes from an "in situ" sacrificial electrode. The size and density of the nanoparticles, to some extent, can be tailored by controlling the deposition voltage. The gold nanoparticles are generally spherical, while the silver nanoparticles have branching snowflake shapes. These nanoparticles change the ON-state conductance of the nanotube while maintaining its semiconducting characteristics. The gold nanoparticles on the nanotube sidewalls can serve as anchoring sites for thiol-terminated biomolecules to functionalize the device for biosensing purposes. Results have shown that the thiol-terminated molecules can bind to the Au nanoparticles; however, nonspecific binding to the SiO2 surface is still abundant. Therefore, a self assembled monolayer (SAM) of protein-resistant polyethylene glycol (PEG) is deposited onto the SiO 2 surface to provide protein resistance, which results in selective immobilization of bio-receptors to the gold nanoparticles on the nanotube only. This reduces possible noise signals from the nonspecific substrate binding, and is expected to improve the device sensitivity.

Biocompatibility, endocytosis, and intracellular trafficking of mesoporous silica and polystyrene nanoparticles in ovarian cancer cells: effects of size and surface charge groups

PubMed Central

Ekkapongpisit, Maneerat; Giovia, Antonino; Follo, Carlo; Caputo, Giuseppe; Isidoro, Ciro

2012-01-01

Background and methods Nanoparticles engineered to carry both a chemotherapeutic drug and a sensitive imaging probe are valid tools for early detection of cancer cells and to monitor the cytotoxic effects of anticancer treatment simultaneously. Here we report on the effect of size (10–30 nm versus 50 nm), type of material (mesoporous silica versus polystyrene), and surface charge functionalization (none, amine groups, or carboxyl groups) on biocompatibility, uptake, compartmentalization, and intracellular retention of fluorescently labeled nanoparticles in cultured human ovarian cancer cells. We also investigated the involvement of caveolae in the mechanism of uptake of nanoparticles. Results We found that mesoporous silica nanoparticles entered via caveolae-mediated endocytosis and reached the lysosomes; however, while the 50 nm nanoparticles permanently resided within these organelles, the 10 nm nanoparticles soon relocated in the cytoplasm. Naked 10 nm mesoporous silica nanoparticles showed the highest and 50 nm carboxyl-modified mesoporous silica nanoparticles the lowest uptake rates, respectively. Polystyrene nanoparticle uptake also occurred via a caveolae-independent pathway, and was negatively affected by serum. The 30 nm carboxyl-modified polystyrene nanoparticles did not localize in lysosomes and were not toxic, while the 50 nm amine-modified polystyrene nanoparticles accumulated within lysosomes and eventually caused cell death. Ovarian cancer cells expressing caveolin-1 were more likely to endocytose these nanoparticles. Conclusion These data highlight the importance of considering both the physicochemical characteristics (ie, material, size and surface charge on chemical groups) of nanoparticles and the biochemical composition of the cell membrane when choosing the most suitable nanotheranostics for targeting cancer cells. PMID:22904626

Modulating the physicochemical and structural properties of gold-functionalized protein nanotubes through thiol surface modification.

PubMed

Carreño-Fuentes, Liliana; Plascencia-Villa, Germán; Palomares, Laura A; Moya, Sergio E; Ramírez, Octavio T

2014-12-16

Biomolecules are advantageous scaffolds for the synthesis and ordering of metallic nanoparticles. Rotavirus VP6 nanotubes possess intrinsic affinity to metal ions, a property that has been exploited to synthesize gold nanoparticles over them. The resulting nanobiomaterials have unique properties useful for novel applications. However, the formed nanobiomaterials lack of colloidal stability and flocculate, limiting their functionality. Here we demonstrate that it is possible to synthesize thiol-protected gold nanoparticles over VP6 nanotubes, which resulted in soluble nanobiomaterials. With this strategy, it was possible to modulate the size, colloidal stability, and surface plasmon resonance of the synthesized nanoparticles by controlling the content of the thiolated ligands. Two types of water-soluble ligands were tested, a small linear ligand, sodium 3-mercapto-1-propanesulfonate (MPS), and a bulky ligand, 5-mercaptopentyl β-D-glucopyranoside (GlcC5SH). The synthesized nanobiomaterials had a higher stability in suspension, as determined by Z-potential measurements. To the extent of our knowledge, this is the first time that a rational strategy is developed to modulate the particular properties of metal nanoparticles in situ synthesized over a protein bioscaffold through thiol coating, achieving a high spatial and structural organization of nanoparticles in a single integrative hybrid structure.

Bio-inspired engineering of cell- and virus-like nanoparticles for drug delivery.

PubMed

Parodi, Alessandro; Molinaro, Roberto; Sushnitha, Manuela; Evangelopoulos, Michael; Martinez, Jonathan O; Arrighetti, Noemi; Corbo, Claudia; Tasciotti, Ennio

2017-12-01

The engineering of future generations of nanodelivery systems aims at the creation of multifunctional vectors endowed with improved circulation, enhanced targeting and responsiveness to the biological environment. Moving past purely bio-inert systems, researchers have begun to create nanoparticles capable of proactively interacting with the biology of the body. Nature offers a wide-range of sources of inspiration for the synthesis of more effective drug delivery platforms. Because the nano-bio-interface is the key driver of nanoparticle behavior and function, the modification of nanoparticles' surfaces allows the transfer of biological properties to synthetic carriers by imparting them with a biological identity. Modulation of these surface characteristics governs nanoparticle interactions with the biological barriers they encounter. Building off these observations, we provide here an overview of virus- and cell-derived biomimetic delivery systems that combine the intrinsic hallmarks of biological membranes with the delivery capabilities of synthetic carriers. We describe the features and properties of biomimetic delivery systems, recapitulating the distinctive traits and functions of viruses, exosomes, platelets, red and white blood cells. By mimicking these biological entities, we will learn how to more efficiently interact with the human body and refine our ability to negotiate with the biological barriers that impair the therapeutic efficacy of nanoparticles. Copyright © 2017. Published by Elsevier Ltd.

Biosynthesis and characterization of zinc, magnesium and titanium nanoparticles: an eco-friendly approach

NASA Astrophysics Data System (ADS)

Raliya, Ramesh; Tarafdar, J. C.

2014-02-01

In the present study, zinc (Zn), magnesium (Mg) and titanium (Ti) nanoparticles synthesized using fungus by employing various precursor salts of sulfate salts, nitrate salts, chloride salts and oxide salts. To access the nanoparticle production potential, over a hundreds of fungi were isolated from the soil and tested with precursor salts of the Zn, Mg and Ti. Out of which, only 14 fungal isolates were identified, having potential to reduce metal salt into metal nanoparticles. Upon molecular identification, six were identified as Aspergillus flavus, two each as Aspergillus terreus and Aspergillus tubingensis and one each as Aspergillus niger, Rhizoctonia bataticola, Aspergillus fumigatus, and Aspergillus oryzae. Factors responsible for more production of monodispersed Zn, Mg and Ti nanoparticles were optimized. It was concluded that 0.01 mM precursor salt concentration, 72 h of incubation at pH 5.5 and temperature 28 °C resulted smaller nanoparticles obtained. The biosynthesized functional Zn and Ti nanoparticles can be stored up to 90 days and Mg nanoparticles up to 105 days in its nanoform. Bio-transformed products were analyzed using valid characterization technique i.e. dynamic light scattering, transmission electron microscopy, atomic force microscopy, energy dispersive X-ray spectroscopy to confirm size, shape, surface morphology and elemental composition. It was found that the average size of developed nano Zn was 8.2 nm, with surface charge of -5.70 mV and 98 % particles were of Zn metal only. Similarly, the average size of Mg nanoparticles was 6.4 nm with surface charge of -6.66 and 97.4 % Mg metal yield, whereas, Ti nanoparticles size were found in the ranges between 1.5 and 30 nm with surface charge of -6.25 mV and 98.6 % Ti metal yield.

Preparation and characterization of chemically functionalized silica-coated magnetic nanoparticles as a DNA separator.

PubMed

Kang, Kiho; Choi, Jinsub; Nam, Joong Hee; Lee, Sang Cheon; Kim, Kyung Ja; Lee, Sang-Won; Chang, Jeong Ho

2009-01-15

The work describes a simple and convenient process for highly efficient and direct DNA separation with functionalized silica-coated magnetic nanoparticles. Iron oxide magnetic nanoparticles and silica-coated magnetic nanoparticles were prepared uniformly, and the silica coating thickness could be easily controlled in a range from 10 to 50 nm by changing the concentration of silica precursor (TEOS) including controlled magnetic strength and particle size. A change in the surface modification on the nanoparticles was introduced by aminosilanization to enhance the selective DNA separation resulting from electrostatic interaction. The efficiency of the DNA separation was explored via the function of the amino-group numbers, particle size, the amount of the nanoparticles used, and the concentration of NaCl salt. The DNA adsorption yields were high in terms of the amount of triamino-functionalized nanoparticles used, and the average particle size was 25 nm. The adsorption efficiency of aminofunctionalized nanoparticles was the 4-5 times (80-100%) higher compared to silica-coated nanoparticles only (10-20%). DNA desorption efficiency showed an optimum level of over 0.7 M of the NaCl concentration. To elucidate the agglomeration of nanoparticles after electrostatic DNA binding, the Guinier plots were calculated from small-angle X-ray diffractions in a comparison of the results of energy diffraction TEM and confocal laser scanning microscopy. Additionally, the direct separation of human genomic DNA was achieved from human saliva and whole blood with high efficiency.

Succinate Functionalization of Hyperbranched Polyglycerol-Coated Magnetic Nanoparticles as a Draw Solute During Forward Osmosis.

PubMed

Yang, Hee-Man; Choi, Hye Min; Jang, Sung-Chan; Han, Myeong Jin; Seo, Bum-Kyoung; Moon, Jei-Kwon; Lee, Kune-Woo

2015-10-01

Hyperbranched polyglycerol-coated magnetic nanoparticles (SHPG-MNPs) were functionalized with succinate groups to form a draw solute for use in a forward osmosis (FO). After the one-step synthesis of hyperbranched polyglycerol-coated magnetic nanoparticles (HPG-MNPs), the polyglycerol groups on the surfaces of the HPG-MNPs were functionalized with succinic anhydride moieties. The resulting SHPG-MNPs showed no change of size and magnetic property compared with HPG-MNPs and displayed excellent dispersibility in water up to the concentration of 400 g/L. SHPG-MNPs solution showed higher osmotic pressure than that of HPG-MNPs solution due to the presence of surface carboxyl groups in SHPG-MNPs and could draw water from a feed solution across an FO membrane without any reverse draw solute leakage during FO process. Moreover, the water flux remained nearly constant over several SHPG-MNP darw solute regeneration cycles applied to the ultrafiltration (UF) process. The SHPG-MNPs demonstrate strong potential for use as a draw solute in FO processes.

MWCNT-MnFe2O4 nanocomposite for efficient hyperthermia applications

NASA Astrophysics Data System (ADS)

Seal, Papori; Hazarika, Monalisa; Paul, Nibedita; Borah, J. P.

2018-04-01

In this work we present synthesis of multi-walled carbon nanotube (MWCNT)-Manganese ferrite (MnFe2O4) nanocomposite and its probable application in hyperthermia. MnFe2O4 nanoparticles were synthesized by co-precipitation method. X ray diffractogram (XRD) confirms the formation of cubic phase of MnFe2O4 with preferred crystallographic orientation along (311) plane. High resolution electron microscope (HRTEM) image of the composites confirms the presence of MnFe2O4 spherical nanoparticles on the surface of CNT which are bound strongly to the surface. MWCNT-MnFe2O4 nanocomposite were prepared after acid functionalization of MWCNT. Vibrational features of the synthesized samples were confirmed through Fourier transformed infra-red spectroscopy (FTIR). FTIR spectra of acid functionalized MWCNT shows a peak positioned at ˜1620cm-1 which corresponds to C=O functional group of carboxylic acid. Prepared MnFe2O4 nanoparticles and MWCNT-MnFe2O4 nanocomposites were subjected to hyperthermia studies.

An efficient polymeric micromotor doped with Pt nanoparticle@carbon nanotubes for complex bio-media.

PubMed

Li, Yana; Wu, Jie; Xie, Yuzhe; Ju, Huangxian

2015-04-14

A highly efficient polymeric tubular micromotor doped with Pt nanoparticle@carbon nanotubes is fabricated by template-assisted electrochemical growth. The micromotors preserve good navigation in multi-media and surface modification, along with simple synthesis, easy functionalization and good biocompatibility, displaying great promise in biological applications.

Nano-magnetite (Fe3O4)as a support for recyclable catalysts in the development of sustainable methodologies

EPA Science Inventory

Surface functionalization of magnetic nanoparticles is a well-designed way to bridge the gap between heterogeneous and homogeneous catalysis. The introduction of magnetic nanoparticles (MNPs) in a variety of solid matrices allows the combination of well-known procedures for catal...

Recent advances in surface chemistry strategies for the fabrication of functional iron oxide based magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Turcheniuk, Kostiantyn; Tarasevych, Arkadii V.; Kukhar, Valeriy P.; Boukherroub, Rabah; Szunerits, Sabine

2013-10-01

The synthesis of superparamagnetic nanostructures, especially iron-oxide based nanoparticles (IONPs), with appropriate surface functional groups has been intensively researched for many high-technological applications, including high density data storage, biosensing and biomedicine. In medicine, IONPs are nowadays widely used as contrast agents for magnetic resonance imaging (MRI), in hyperthermia therapy, but are also exploited for drug and gene delivery, detoxification of biological fluids or immunoassays, as they are relatively non-toxic. The use of magnetic particles in vivo requires IONPs to have high magnetization values, diameters below 100 nm with overall narrow size distribution and long time stability in biological fluids. Due to the high surface energies of IONPs agglomeration over time is often encountered. It is thus of prime importance to modify their surface to prevent aggregation and to limit non-specific adsorption of biomolecules onto their surface. Such chemical modifications result in IONPs being well-dispersed and biocompatible, and allow for targeted delivery and specific interactions. The chemical nature of IONPs thus determines not only the overall size of the colloid, but also plays a significant role for in vivo and in vitro applications. This review discusses the different concepts currently used for the surface functionalization and coating of iron oxide nanoparticles. The diverse strategies for the covalent linking of drugs, proteins, enzymes, antibodies, and nucleotides will be discussed and the chemically relevant steps will be explained in detail.

Preparation and characterization of polymeric nanocomposite films for application as protective coatings

NASA Astrophysics Data System (ADS)

Gagliardi, S.; Rondino, F.; D'Erme, C.; Persia, F.; Menchini, F.; Santarelli, M. L.; Paulke, B.-R.; Enayati, A. L.; Falconieri, M.

2017-08-01

Addiction of ceramic nanoparticles to acrylic polymers provides a simple and effective means to produce paints with important properties, such as mechanical resistance and tailored wettability, even though for optimal performances, an engineered nanoparticle distribution would be desirable. In this paper we report on the realization and on the morphological and functional characterization of nanocomposites where the nanophase is distributed on the surface of acrylic polymer films, in order to enhance the expression of surface-related properties. To this aim, commercial titanium oxide and silicon oxide nanopowders were dispersed in water and the suspensions were air-sprayed on polymeric films prepared by paint brushing, thus producing a nanostructured ceramic surface coating. Control of the pH of suspensions and acrylic acid functionalization of the surface of titania were used together with high power ultrasonic treatments in order to control dimension of the aggregates in the sprayed suspensions. Optical microscopy, mechanical profilometry, and atomic force microscopy were used to characterize the nanocomposite surface morphology and correlate it to the coating functional properties, evaluated through mechanical abrasion tests and contact angle measurements; also, colorimetry on coated stones was performed in order to test the impact of the coatings on the aesthetical appearance and their photostability under UV irradiation. Results show that the nanostructured ceramic layer slightly improves the resistance of coatings to mechanical abrasion in case of polymer films prepared from latexes. The nanocomposite surface layer does not affect the wettability of the polymer, which remained slightly hydrophilic; this behavior is likely due to inadequate distribution of the nanophase. On the other hand UV-induced superhydrophilicity was observed when the concentration of surface titania nanoparticles is about 0.6 mg/cm2. Colorimetric analysis on historical and Carrara marbles before and after coating evidenced the good transparency of the nanocomposites. Accelerated aging tests permitted to demonstrate that, on the historical marbles, the presence of the nanoparticles has a protective action against UV-induced damage of the underlying polymer film, preventing photodegradation.

Magnetic nanoparticle detection method employing non-linear magnetoimpedance effects

NASA Astrophysics Data System (ADS)

Beato-López, J. J.; Pérez-Landazábal, J. I.; Gómez-Polo, C.

2017-04-01

In this work, a sensitive tool to detect magnetic nanoparticles (Fe3O4) based on a non-linear Giant Magnetoimpedance (GMI) effect is presented. The GMI sensor is designed with four nearly zero magnetostrictive ribbons connected in series and was analysed as a function of a constant external magnetic field and exciting frequency. The influence of the magnetic nanoparticles deposited on the ribbon surface was characterized using the first (fundamental) and second (non-linear) harmonics of the magnetoinductive voltage. The results show a clear enhancement of the sensor response in the high magnetic field region (H = 1.5 kA/m) as a consequence of the stray field generated by the magnetic nanoparticles on the GMI ribbons' surface. The highest sensitivity ratios are obtained for the non-linear component in comparison with the fundamental response. The results open a new research strategy in magnetic nanoparticle detection.

Nanoparticles as biochemical sensors

PubMed Central

El-Ansary, Afaf; Faddah, Layla M

2010-01-01

There is little doubt that nanoparticles offer real and new opportunities in many fields, such as biomedicine and materials science. Such particles are small enough to enter almost all areas of the body, including cells and organelles, potentially leading to new approaches in nanomedicine. Sensors for small molecules of biochemical interest are of critical importance. This review is an attempt to trace the use of nanomaterials in biochemical sensor design. The possibility of using nanoparticles functionalized with antibodies as markers for proteins will be elucidated. Moreover, capabilities and applications for nanoparticles based on gold, silver, magnetic, and semiconductor materials (quantum dots), used in optical (absorbance, luminescence, surface enhanced Raman spectroscopy, surface plasmon resonance), electrochemical, and mass-sensitive sensors will be highlighted. The unique ability of nanosensors to improve the analysis of biochemical fluids is discussed either through considering the use of nanoparticles for in vitro molecular diagnosis, or in the biological/biochemical analysis for in vivo interaction with the human body. PMID:24198472

Fe 2O 3-Au hybrid nanoparticles for sensing applications via sers analysis

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

Murph, Simona Hunyadi; Searles, Emily

2017-06-25

Nanoparticles with large amounts of surface area and unique characteristics that are distinct from their bulk material provide an interesting application in the enhancement of inelastic scattering signal. Surface Enhanced Raman Spectroscopy (SERS) strives to increase the Raman scattering effect when chemical species of interest are in the close proximity of metallic nnaostructures. Gold nanoparticles of various shapes have been used for sensing applications via SERS as they demonstrate the greatest effect of plasmonic behavior in the visible-near IR region of the spectrum. When coupled with other nanoparticles, namely iron oxide nanoparticles, hybrid structures with increased functionality were produced. Multifunctionalmore » iron oxide-gold hybrid nanostructures have been created via solution chemistries and investigated for analyte detection of a model analyte. By exploiting their magnetic properties, nanogaps or “hot spots” were rationally created and evaluated for SERS enhancement studies.« less

Fe 2O 3-Au hybrid nanoparticles for sensing applications via SERS analysis

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

Searles, Emily; Murph, Simona Hunyadi

Multifunctional iron oxide-gold hybrid nanostructures have been produced via solution chemistries and investigated for analyte detection. Gold nanoparticles of various shapes have been used for probing surface-enhanced Raman scattering (SERS) effects as they display unique optical properties in the visible-near IR region of the spectrum. When coupled with other nanoparticles, namely iron oxide nanoparticles, hybrid structures with increased functionality were produced. By exploiting their magnetic properties, nanogaps or “hot spots” were rationally created and evaluated for SERS enhancement studies. The “hot spots” were created by using a seeded reaction to increase the gold loading on the iron oxide support bymore » 43% by weight. SERS Nanomaterials were evaluated for their ability to promote surface-enhanced Raman scattering of a model analyte, 4-mercaptophenol. The data shows an enhancement effect of the model analyte on gold decorated iron oxide nanoparticles.« less

Carbon composites with metal nanoparticles for Alcohol fuel cells

NASA Astrophysics Data System (ADS)

Ventrapragada, Lakshman; Siddhardha, R. S.; Podilla, Ramakrishna; Muthukumar, V. S.; Creager, Stephen; Rao, A. M.; Ramamurthy, Sai Sathish

2015-03-01

Graphene due to its high surface area and superior conductivity has attracted wide attention from both industrial and scientific communities. We chose graphene as a substrate for metal nanoparticle deposition for fuel cell applications. There are many chemical routes for fabrication of metal-graphene composites, but they have an inherent disadvantage of low performance due to the usage of surfactants, that adsorb on their surface. Here we present a design for one pot synthesis of gold nanoparticles and simultaneous deposition on graphene with laser ablation of gold strip and functionalized graphene. In this process there are two natural advantages, the nanoparticles are synthesized without any surfactants, therefore they are pristine and subsequent impregnation on graphene is linker free. These materials are well characterized with electron microscopy to find their morphology and spectroscopic techniques like Raman, UV-Vis. for functionality. This gold nanoparticle decorated graphene composite has been tested for its electrocatalytic oxidation of alcohols for alkaline fuel cell applications. An electrode made of this composite showed good stability for more than 200 cycles of operation and reported a low onset potential of 100 mV more negative, an important factor for direct ethanol fuel cells.

Linker-free conjugation and specific cell targeting of antibody functionalized iron-oxide nanoparticles

PubMed Central

Xu, Yaolin; Baiu, Dana C.; Sherwood, Jennifer A.; McElreath, Meghan R.; Qin, Ying; Lackey, Kimberly H.; Otto, Mario; Bao, Yuping

2015-01-01

Specific targeting is a key step to realize the full potential of iron oxide nanoparticles in biomedical applications, especially tumor-associated diagnosis and therapy. Here, we developed anti-GD2 antibody conjugated iron oxide nanoparticles for highly efficient neuroblastoma cell targeting. The antibody conjugation was achieved through an easy, linker-free method based on catechol reactions. The targeting efficiency and specificity of the antibody-conjugated nanoparticles to GD2-positive neuroblastoma cells were confirmed by flow cytometry, fluorescence microscopy, Prussian blue staining and transmission electron microscopy. These detailed studies indicated that the receptor-recognition capability of the antibody was fully retained after conjugation and the conjugated nanoparticles quickly attached to GD2-positive cells within four hours. Interestingly, longer treatment (12 h) led the cell membrane-bound nanoparticles to be internalized into cytosol, either by directly penetrating the cell membrane or escaping from the endosomes. Last but importantly, the uniquely designed functional surfaces of the nanoparticles allow easy conjugation of other bioactive molecules. PMID:26660881

Structural, surface wettability and antibacterial properties of HPMC-ZnO nanocomposite

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

Rao, B. Lakshmeesha; Asha, S.; Madhukumar, R.

The developed hydroxypropyl methylcellulose (HPMC)/Zinc oxide (ZnO) nanocomposite films were examined for structural property and surface wettability using X-ray diffraction and contact angle measurement. Antibacterial activity of these films was evaluated as a function of ZnO concentration. The microstructuralline parameters ( and (g in %)) decreased with increasing concentration of ZnO nanoparticles and there was increase in hydrophilicity. Addition of ZnO nanoparticles in films resulted in antimicrobial activity against tested microorganisms.

Peptide-Directed PdAu Nanoscale Surface Segregation: Toward Controlled Bimetallic Architecture for Catalytic Materials

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

Bedford, Nicholas M.; Showalter, Allison R.; Woehl, Taylor J.

Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when mixing two different metallic species at the nanoscale. This is particularly prevalent in catalysis, where bimetallic nanoparticles often exhibit improved catalytic activity and durability over their monometallic counterparts. Yet despite intense research efforts, little is understood regarding how to optimize bimetallic surface composition and structure synthetically using rational design principles. Recently, it has been demonstrated that peptide-enabled routes for nanoparticle synthesis result in materials with sequence-dependent catalytic properties, providing an opportunity for rational design through sequence manipulation. In this study, bimetallic PdAu nanoparticles are synthesizedmore » with a small set of peptides containing known Pd and Au binding motifs. The resulting nanoparticles were extensively characterized using high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy and high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Structural information obtained from synchrotron radiation methods were then used to generate model nanoparticle configurations using reverse Monte Carlo simulations, which illustrate sequence-dependence in both surface structure and surface composition. Replica exchange solute tempering molecular dynamic simulations were also used to predict the modes of peptide binding on monometallic surfaces, indicating that different sequences bind to the metal interfaces via different mechanisms. As a testbed reaction, electrocatalytic methanol oxidation experiments were performed, wherein differences in catalytic activity are clearly observed in materials with identical bimetallic composition. Finally, taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be leveraged for rational bimetallic nanoparticle design using peptide-enabled approaches.« less

Peptide-Directed PdAu Nanoscale Surface Segregation: Toward Controlled Bimetallic Architecture for Catalytic Materials

DOE PAGES

Bedford, Nicholas M.; Showalter, Allison R.; Woehl, Taylor J.; ...

2016-09-01

Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when mixing two different metallic species at the nanoscale. This is particularly prevalent in catalysis, where bimetallic nanoparticles often exhibit improved catalytic activity and durability over their monometallic counterparts. Yet despite intense research efforts, little is understood regarding how to optimize bimetallic surface composition and structure synthetically using rational design principles. Recently, it has been demonstrated that peptide-enabled routes for nanoparticle synthesis result in materials with sequence-dependent catalytic properties, providing an opportunity for rational design through sequence manipulation. In this study, bimetallic PdAu nanoparticles are synthesizedmore » with a small set of peptides containing known Pd and Au binding motifs. The resulting nanoparticles were extensively characterized using high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy and high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Structural information obtained from synchrotron radiation methods were then used to generate model nanoparticle configurations using reverse Monte Carlo simulations, which illustrate sequence-dependence in both surface structure and surface composition. Replica exchange solute tempering molecular dynamic simulations were also used to predict the modes of peptide binding on monometallic surfaces, indicating that different sequences bind to the metal interfaces via different mechanisms. As a testbed reaction, electrocatalytic methanol oxidation experiments were performed, wherein differences in catalytic activity are clearly observed in materials with identical bimetallic composition. Finally, taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be leveraged for rational bimetallic nanoparticle design using peptide-enabled approaches.« less

Stimuli-Responsive Polymeric Nanoparticles.

PubMed

Liu, Xiaolin; Yang, Ying; Urban, Marek W

2017-07-01

There is increasing evidence that stimuli-responsive nanomaterials have become significantly critical components of modern materials design and technological developments. Recent advances in synthesis and fabrication of stimuli-responsive polymeric nanoparticles with built-in stimuli-responsive components (Part A) and surface modifications of functional nanoparticles that facilitate responsiveness (Part B) are outlined here. The synthesis and construction of stimuli-responsive spherical, core-shell, concentric, hollow, Janus, gibbous/inverse gibbous, and cocklebur morphologies are discussed in Part A, with the focus on shape, color, or size changes resulting from external stimuli. Although inorganic/metallic nanoparticles exhibit many useful properties, including thermal or electrical conductivity, catalytic activity, or magnetic properties, their assemblies and formation of higher order constructs are often enhanced by surface modifications. Section B focuses on selected surface reactions that lead to responsiveness achieved by decorating nanoparticles with stimuli-responsive polymers. Although grafting-to and grafting-from dominate these synthetic efforts, there are opportunities for developing novel synthetic approaches facilitating controllable recognition, signaling, or sequential responses. Many nanotechnologies utilize a combination of organic and inorganic phases to produce ceramic or metallic nanoparticles. One can envision the development of new properties by combining inorganic (metals, metal oxides) and organic (polymer) phases into one nanoparticle designated as "ceramers" (inorganics) and "metamers" (metallic). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physico-chemical changes of ZnO nanoparticles with different size and surface chemistry under physiological pH conditions.

PubMed

Gwak, Gyeong-Hyeon; Lee, Won-Jae; Paek, Seung-Min; Oh, Jae-Min

2015-03-01

We studied the physico-chemical properties of ZnO nanoparticles under physiological pH conditions (gastric, intestinal and plasma) as functions of their size (20 and 70 nm) and surface chemistry (pristine, L-serine, or citrate coating). ZnO nanoparticles were dispersed in phosphate buffered saline under physiological pH conditions and aliquots were collected at specific time points (0.5, 1, 4, 10 and 24 h) for further characterization. The pH values of the aqueous ZnO colloids at each condition were in the neutral to slightly basic range and showed different patterns depending on the original size and surface chemistry of the ZnO nanoparticles. The gastric pH condition was found to significantly dissolve ZnO nanoparticles up to 18-30 wt%, while the intestinal or plasma pH conditions resulted in much lower dissolution amounts than expected. Based on the X-ray diffraction patterns and X-ray absorption spectra, we identified partial phase transition of the ZnO nanoparticles from wurtzite to Zn(OH)2 under the intestinal and plasma pH conditions. Using scanning electron microscopy, we verified that the overall particle size and morphology of all ZnO nanoparticles were maintained regardless of the pH. Copyright © 2015 Elsevier B.V. All rights reserved.

Transparent, Flexible, Conformal Capacitive Pressure Sensors with Nanoparticles.

PubMed

Kim, Hyeohn; Kim, Gwangmook; Kim, Taehoon; Lee, Sangwoo; Kang, Donyoung; Hwang, Min-Soo; Chae, Youngcheol; Kang, Shinill; Lee, Hyungsuk; Park, Hong-Gyu; Shim, Wooyoung

2018-02-01

The fundamental challenge in designing transparent pressure sensors is the ideal combination of high optical transparency and high pressure sensitivity. Satisfying these competing demands is commonly achieved by a compromise between the transparency and usage of a patterned dielectric surface, which increases pressure sensitivity, but decreases transparency. Herein, a design strategy for fabricating high-transparency and high-sensitivity capacitive pressure sensors is proposed, which relies on the multiple states of nanoparticle dispersity resulting in enhanced surface roughness and light transmittance. We utilize two nanoparticle dispersion states on a surface: (i) homogeneous dispersion, where each nanoparticle (≈500 nm) with a size comparable to the visible light wavelength has low light scattering; and (ii) heterogeneous dispersion, where aggregated nanoparticles form a micrometer-sized feature, increasing pressure sensitivity. This approach is experimentally verified using a nanoparticle-dispersed polymer composite, which has high pressure sensitivity (1.0 kPa -1 ), and demonstrates excellent transparency (>95%). We demonstrate that the integration of nanoparticle-dispersed capacitor elements into an array readily yields a real-time pressure monitoring application and a fully functional touch device capable of acting as a pressure sensor-based input device, thereby opening up new avenues to establish processing techniques that are effective on the nanoscale yet applicable to macroscopic processing. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determining the composition of gold nanoparticles: a compilation of shapes, sizes, and calculations using geometric considerations.

PubMed

Mori, Taizo; Hegmann, Torsten

2016-01-01

Size, shape, overall composition, and surface functionality largely determine the properties and applications of metal nanoparticles. Aside from well-defined metal clusters, their composition is often estimated assuming a quasi-spherical shape of the nanoparticle core. With decreasing diameter of the assumed circumscribed sphere, particularly in the range of only a few nanometers, the estimated nanoparticle composition increasingly deviates from the real composition, leading to significant discrepancies between anticipated and experimentally observed composition, properties, and characteristics. We here assembled a compendium of tables, models, and equations for thiol-protected gold nanoparticles that will allow experimental scientists to more accurately estimate the composition of their gold nanoparticles using TEM image analysis data. The estimates obtained from following the routines described here will then serve as a guide for further analytical characterization of as-synthesized gold nanoparticles by other bulk (thermal, structural, chemical, and compositional) and surface characterization techniques. While the tables, models, and equations are dedicated to gold nanoparticles, the composition of other metal nanoparticle cores with face-centered cubic lattices can easily be estimated simply by substituting the value for the radius of the metal atom of interest.

Palladium nanoparticle deposition via precipitation: a new method to functionalize macroporous silicon

PubMed Central

Scheen, Gilles; Bassu, Margherita; Douchamps, Antoine; Zhang, Chao; Debliquy, Marc; Francis, Laurent A

2014-01-01

We present an original two-step method for the deposition via precipitation of Pd nanoparticles into macroporous silicon. The method consists in immersing a macroporous silicon sample in a PdCl2/DMSO solution and then in annealing the sample at a high temperature. The impact of composition and concentration of the solution and annealing time on the nanoparticle characteristics is investigated. This method is compared to electroless plating, which is a standard method for the deposition of Pd nanoparticles. Scanning electron microscopy and computerized image processing are used to evaluate size, shape, surface density and deposition homogeneity of the Pd nanoparticles on the pore walls. Energy-dispersive x-ray spectroscopy (EDX) and x-ray photoelectron spectroscopy (XPS) analyses are used to evaluate the composition of the deposited nanoparticles. In contrast to electroless plating, the proposed method leads to homogeneously distributed Pd nanoparticles along the macropores depth with a surface density that increases proportionally with the PdCl2 concentration. Moreover EDX and XPS analysis showed that the nanoparticles are composed of Pd in its metallic state, while nanoparticles deposited by electroless plating are composed of both metallic Pd and PdOx. PMID:27877732

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.

Toxicity of silver nanoparticles towards tumoral human cell lines U-937 and HL-60.

PubMed

Barbasz, Anna; Oćwieja, Magdalena; Roman, Maciej

2017-08-01

The toxicity of three types of silver nanoparticles towards histiocytic lymphoma (U-937) and human promyelocytic cells (HL-60) was studied. The nanoparticles were synthesized in a chemical reduction method using sodium borohydride. Trisodium citrate and cysteamine hydrochloride were used to generate a negative and positive nanoparticle surface charge. The evaluation of cell viability, membrane integrity, antioxidant activity and the induction of inflammation were used to evaluate the difference in cellular response to the nanoparticle treatment. The results revealed that the cysteamine-stabilized (positively charged) nanoparticles (SBATE) were the least toxic although they exhibited a similar ion release profile as the unmodified (negatively charged) nanoparticles obtained using sodium borohydride (SBNM). Citrate-stabilized nanoparticles (SBTC) induced superoxide dismutase (SOD) activity in the HL-60 cells and total antioxidant activity in the U-937 cells despite their resistance to oxidative dissolution. The toxicity of SBNM nanoparticles was manifested in the disruption of membrane integrity, decrease in the mitochondrial functions of cells and the induction of inflammation. These findings allowed to conclude that mechanism of silver nanoparticle cytotoxicity is the combination of effects coming from the surface charge of nanoparticles, released silver ions and biological activity of stabilizing agent molecules. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

Chemical synthesis and characterization of hollow dopamine coated, pentagonal and flower shaped magnetic iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Riasat, Rabia; Kaynat, Sumbal

2018-04-01

Iron oxide nanoparticles have gained attention recently in the field of nanoscience and technology due to their unique physicochemical properties. We hereby chemically synthesized novel pentagonal flower shaped iron oxide nanoparticles by thermal decomposition of iron penta-carbonyl in a two way annealing process. Controlled oxidation by acid etching was performed for these nanoparticles. At first 13 nm core shell nanoparticles of iron oxide (Fe/Fe3O4) were synthesized at 120°C annealing temperature that act as template material. The core shell nanoparticles then converted into porous hollow core shell nanoparticles (PH Fe/ Fe3O4) in a two way annealing process of heating, first at 100°C then at 250°C and heating rate of 5°C was kept constant throughout the reaction time. X-Ray diffraction (XRD) was done for the phase confirmation of as synthesized nanoparticles. Transmission electron microscopy (TEM) and higher resolution transmission electron microscopy (HRTEM) clearly shows the flower like nanoparticles that are approx. 16 nm-18 nm in size having the 4-5 nm core of Fe and 1-2 nm of the pores in the shell while the cavity between the shell and core is about 2 nm and the shell is 4-5 nm in diameter according to the TEM micrographs. The as prepared nanoparticles were then surface functionalized by dopamine polymer to make them water dispersible. Fourier transform Infrared spectroscopy confirmed the dopamine coating on the nanoparticles and the magnetic saturation of 38 emu/g of nanoparticles was analyzed by vibrating sample magnetometer (VSM). Magnetic saturation persists in the dopamine coated nanoparticles. These nanoparticles were surface functionalized with dopamine and show dispersity in the aqueous media and can further be exploited in many nano-biotechnological applications including target specific therapeutic applications for several diseases.

Plasmonic resonances of nanoparticles from large-scale quantum mechanical simulations

NASA Astrophysics Data System (ADS)

Zhang, Xu; Xiang, Hongping; Zhang, Mingliang; Lu, Gang

2017-09-01

Plasmonic resonance of metallic nanoparticles results from coherent motion of its conduction electrons, driven by incident light. For the nanoparticles less than 10 nm in diameter, localized surface plasmonic resonances become sensitive to the quantum nature of the conduction electrons. Unfortunately, quantum mechanical simulations based on time-dependent Kohn-Sham density functional theory are computationally too expensive to tackle metal particles larger than 2 nm. Herein, we introduce the recently developed time-dependent orbital-free density functional theory (TD-OFDFT) approach which enables large-scale quantum mechanical simulations of plasmonic responses of metallic nanostructures. Using TD-OFDFT, we have performed quantum mechanical simulations to understand size-dependent plasmonic response of Na nanoparticles and plasmonic responses in Na nanoparticle dimers and trimers. An outlook of future development of the TD-OFDFT method is also presented.

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

NASA Astrophysics Data System (ADS)

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

2015-01-01

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

Diatom frustules decorated with zinc oxide nanoparticles for enhanced optical properties

NASA Astrophysics Data System (ADS)

Lamastra, F. R.; Grilli, M. L.; Leahu, G.; Belardini, A.; Li Voti, R.; Sibilia, C.; Salvatori, D.; Cacciotti, I.; Nanni, F.

2017-09-01

Zinc oxide (ZnO) nanoparticles were synthesized on diatomite (DE) surface by a low temperature sol gel technique, starting from zinc acetate dihydrate (Zn(CH3COO)2 · 2H2O) solution in water/ethyl alcohol, in presence of triethanolamine (TEA) with functions of Zn2+ chelating agent, catalyst and mediator of nanoparticle growth on DE surface. Microstructural features were investigated by field emission scanning electron microscopy and x-ray diffraction. ZnO crystalline nanoparticles, well distributed both on the surface and into the porous architecture of diatomite, were obtained just after the synthesis carried out at 80 °C without the need of calcination treatments. The optical properties of ZnO/DE hybrid powders were measured for the first time by means of photoacoustic spectroscopy (PAS). A new method to retrieve both the optical absorption and scattering coefficients from PAS is here discussed for powder aggregates. The fingerprint of the zinc oxide nanoparticles has been highlighted in the Mie scattering resonance in the UV-Vis range, and in the enhancement of the optical absorption with respect to diatomite.

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.

Quantum dot-doped silica nanoparticles as probes for targeting of T-lymphocytes.

PubMed

Bottini, Massimo; D'Annibale, Federica; Magrini, Andrea; Cerignoli, Fabio; Arimura, Yutaka; Dawson, Marcia I; Bergamaschi, Enrico; Rosato, Nicola; Bergamaschi, Antonio; Mustelin, Tomas

2007-01-01

To enhance diagnostic or therapeutic efficacy, novel nanomaterials must be engineered to function in biologically relevant environments, be visible by conventional fluorescent microscopy, and have multivalent loading capacity for easy detection or effective drug delivery. Here we report the fabrication of silica nanoparticles doped with quantum dots and superficially functionalized with amino and phosphonate groups. The amino groups were acylated with a water-soluble biotin-labeling reagent. The biotinylated nanoparticles were subsequently decorated with neutravidin by exploiting the strong affinity between neutravidin and biotin. The resultant neutravidin-decorated fluorescent silica nanoparticles stably dispersed under physiological conditions, were visible by conventional optical and confocal fluorescent microscopy, and could be further functionalized with macromolecules, nucleic acids, and polymers. We also coated the surface of the nanoparticles with biotinylated mouse anti-human CD3 (alphaCD3). The resultant fluorescent nanoassembly was taken up by Jurkat T cells through receptor-mediated endocytosis and was partially released to lysosomes. Thus, quantum dot-doped silica nanoparticles decorated with neutravidin represent a potentially excellent scaffold for constructing specific intracellular nanoprobes and transporters.

Development of multifunctional nanoparticles towards applications in non-invasive magnetic resonance imaging and axonal tracing.

PubMed

Du, Yan; Qin, Yubo; Li, Zizhen; Yang, Xiuying; Zhang, Jingchang; Westwick, Harrison; Tsai, Eve; Cao, Xudong

2017-12-01

A multifunctional nanobiomaterial has been developed by deliberately combining functions of superparamagnetism, fluorescence, and axonal tracing into one material. Superparamagnetic iron oxide nanoparticles were first synthesized and coated with a silica layer to prevent emission quenching through core-dye interactions; a fluorescent molecule, fluorescein isothiocyanate, was doped inside second layer of silica shell to improve photo-stability and to enable further thiol functionalization. Subsequently, biotinylated dextran amine, a sensitive axonal tracing reagent, was immobilized on the thiol-functionalized nanoparticle surfaces. The resulting nanoparticles were characterized by transmission electron microscopy, dynamic light scattering, X-ray diffraction, X-ray photoelectron spectroscopy, UV-Vis spectroscopy, magnetic resonance imaging and fluorescence confocal microscopy. In vitro cell experiments using both undifferentiated and differentiated Neuro-2a cells showed that the cells were able to take up the nanoparticles intracellularly and that the nanoparticles showed good biocompatibilities. In summary, this new material demonstrated promising performances for both optical and magnetic resonance imaging modalities, suggesting its promising potentials in applications such as in non-invasive imaging, particularly in neuronal tracing.

Antimicrobial function of Nd3+-doped anatase titania-coated nickel ferrite composite nanoparticles: a biomaterial system.

PubMed

Rana, S; Rawat, J; Sorensson, M M; Misra, R D K

2006-07-01

The present study describes and makes a relative comparison of the antimicrobial function of undoped and neodymium-doped titania coated-nickel ferrite composite nanoparticles processed by uniquely combining the reverse micelle and chemical hydrolysis approaches. This methodology facilitates the formation of undoped and doped photocatalytic titania shells and a magnetic ferrite core. The ferrite core is needed to help in the removal of particles from the sprayed surface using a small magnetic field. Doping of the titania shell with neodymium significantly enhances the photocatalytic and anti-microbial function of the core-shell composite nanoparticles without influencing the magnetic characteristics of the nickel ferrite core. The increased performance is believed to be related to the inhibition of electron-hole recombination and a decrease in the band gap energy of titania. The retention of magnetic strength ensures controlled movement of the composite nanoparticles by the magnetic field, facilitating their application as removable anti-microbial photocatalyst nanoparticles. The consistent behavior of the composite nanoparticles points to the viability of the synthesis process adopted.

Impact of protein modification on the protein corona on nanoparticles and nanoparticle-cell interactions.

PubMed

Treuel, Lennart; Brandholt, Stefan; Maffre, Pauline; Wiegele, Sarah; Shang, Li; Nienhaus, G Ulrich

2014-01-28

Recent studies have firmly established that cellular uptake of nanoparticles is strongly affected by the presence and the physicochemical properties of a protein adsorption layer around these nanoparticles. Here, we have modified human serum albumin (HSA), a serum protein often used in model studies of protein adsorption onto nanoparticles, to alter its surface charge distribution and investigated the consequences for protein corona formation around small (radius ∼5 nm), dihydrolipoic acid-coated quantum dots (DHLA-QDs) by using fluorescence correlation spectroscopy. HSA modified by succinic anhydride (HSAsuc) to generate additional carboxyl groups on the protein surface showed a 3-fold decreased binding affinity toward the nanoparticles. A 1000-fold enhanced affinity was observed for HSA modified by ethylenediamine (HSAam) to increase the number of amino functions on the protein surface. Remarkably, HSAsuc formed a much thicker protein adsorption layer (8.1 nm) than native HSA (3.3 nm), indicating that it binds in a distinctly different orientation on the nanoparticle, whereas the HSAam corona (4.6 nm) is only slightly thicker. Notably, protein binding to DHLA-QDs was found to be entirely reversible, independent of the modification. We have also measured the extent and kinetics of internalization of these nanoparticles without and with adsorbed native and modified HSA by HeLa cells. Pronounced variations were observed, indicating that even small physicochemical changes of the protein corona may affect biological responses.

Novel Synthesis of Core-Shell Silica Nanoparticles for the Capture of Low Molecular Weight Proteins and Peptides.

PubMed

Hernandez-Leon, Sergio G; Sarabia-Sainz, Jose Andre-I; Montfort, Gabriela Ramos-Clamont; Guzman-Partida, Ana M; Robles-Burgueño, Maria Del Refugio; Vazquez-Moreno, Luz

2017-10-12

Silica nanoparticles were functionalized with immobilized molecular bait, Cibacron Blue, and a porous polymeric bis-acrylamide shell. These nanoparticles represent a new alternative to capture low molecular weight (LMW) proteins/peptides, that might be potential biomarkers. Functionalized core-shell silica nanoparticles (FCSNP) presented a size distribution of 243.9 ± 11.6 nm and an estimated surface charge of -38.1 ± 0.9 mV. The successful attachment of compounds at every stage of synthesis was evidenced by ATR-FTIR. The capture of model peptides was determined by mass spectrometry, indicating that only the peptide with a long sequence of hydrophobic amino acids (alpha zein 34-mer) interacted with the molecular bait. FCSNP excluded the high molecular weight protein (HMW), BSA, and captured LMW proteins (myoglobin and aprotinin), as evidenced by SDS-PAGE. Functionalization of nanoparticles with Cibacron Blue was crucial to capture these molecules. FCSNP were stable after twelve months of storage and maintained a capacity of 3.1-3.4 µg/mg.

Polymeric Janus Nanoparticles: Recent Advances in Synthetic Strategies, Materials Properties, and Applications.

PubMed

Fan, Xiaoshan; Yang, Jing; Loh, Xian Jun; Li, Zibiao

2018-06-13

Polymeric Janus nanoparticles with two sides of incompatible chemistry have received increasing attention due to their tunable asymmetric structure and unique material characteristics. Recently, with the rapid progress in controlled polymerization combined with novel fabrication techniques, a large array of functional polymeric Janus particles are diversified with sophisticated architecture and applications. In this review, the most recently developed strategies for controlled synthesis of polymeric Janus nanoparticles with well-defined size and complex superstructures are summarized. In addition, the pros and cons of each approach in mediating the anisotropic shapes of polymeric Janus particles as well as their asymmetric spatial distribution of chemical compositions and functionalities are discussed and compared. Finally, these newly developed structural nanoparticles with specific shapes and surface functions orientated applications in different domains are also discussed, followed by the perspectives and challenges faced in the further advancement of polymeric Janus nanoparticles as high performance materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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 surface is diminished as the size of the particle is reduced. However, in comparison to the free ligands, per chiral molecule all tested gold nanoparticles induce helical distortions in a 10- to 50-fold larger number of liquid crystal host molecules surrounding each particle, indicating a significantly enhanced chiral correlation length. We propose that both the helicity and the chirality transfer efficiency of axially chiral binaphthyl derivatives can be controlled at metal nanoparticle surfaces by adjusting the particle size and curvature as well as the number and density of the chiral ligands to ultimately measure and tune the chiral correlation length.

Application of Novel Amino-Functionalized NZVI@SiO2 Nanoparticles to Enhance Anaerobic Granular Sludge Removal of 2,4,6-Trichlorophenol.

PubMed

Guan, Zeyu; Wan, Jinquan; Ma, Yongwen; Wang, Yan; Shu, Yajie

2015-01-01

A novel amino-functionalized silica-coated nanoscale zerovalent iron (NZVI@SiO2-NH2) was successfully synthesized by using one-step liquid-phase method with the surface functionalization of nanoscale zerovalent iron (NZVI) to enhance degradation of chlorinated organic contaminants from anaerobic microbial system. NZVI@SiO2-NH2 nanoparticles were synthesized under optimal conditions with the uniform core-shell structure (80-100 nm), high loading of amino functionality (~0.9 wt%), and relatively large specific surface area (126.3 m(2)/g). The result demonstrated that well-dispersed NZVI@SiO2-NH2 nanoparticle with nFe(0)-core and amino-functional silicon shell can effectively remove 2,4,6-trichlorophenol (2,4,6-TCP) in the neutral condition, much higher than that of NZVI. Besides, the surface-modified nanoparticles (NZVI@SiO2-NH2) in anaerobic granule sludge system also showed a positive effect to promote anaerobic biodechlorination system. More than 94.6% of 2,4,6-TCP was removed from the combined NZVI@SiO2-NH2-anaerobic granular sludge system during the anaerobic dechlorination processes. Moreover, adding the appropriate concentration of NZVI@SiO2-NH2 in anaerobic granular sludge treatment system can decrease the toxicity of 2,4,6-TCP to anaerobic microorganisms and improved the cumulative amount of methane production and electron transport system activity. The results from this study clearly demonstrated that the NZVI@SiO2-NH2/anaerobic granular sludge system could become an effective and promising technology for the removal of chlorophenols in industrial wastewater.

Application of Novel Amino-Functionalized NZVI@SiO2 Nanoparticles to Enhance Anaerobic Granular Sludge Removal of 2,4,6-Trichlorophenol

PubMed Central

Guan, Zeyu; Wan, Jinquan; Ma, Yongwen; Wang, Yan; Shu, Yajie

2015-01-01

A novel amino-functionalized silica-coated nanoscale zerovalent iron (NZVI@SiO2-NH2) was successfully synthesized by using one-step liquid-phase method with the surface functionalization of nanoscale zerovalent iron (NZVI) to enhance degradation of chlorinated organic contaminants from anaerobic microbial system. NZVI@SiO2-NH2 nanoparticles were synthesized under optimal conditions with the uniform core-shell structure (80–100 nm), high loading of amino functionality (~0.9 wt%), and relatively large specific surface area (126.3 m2/g). The result demonstrated that well-dispersed NZVI@SiO2-NH2 nanoparticle with nFe0-core and amino-functional silicon shell can effectively remove 2,4,6-trichlorophenol (2,4,6-TCP) in the neutral condition, much higher than that of NZVI. Besides, the surface-modified nanoparticles (NZVI@SiO2-NH2) in anaerobic granule sludge system also showed a positive effect to promote anaerobic biodechlorination system. More than 94.6% of 2,4,6-TCP was removed from the combined NZVI@SiO2-NH2-anaerobic granular sludge system during the anaerobic dechlorination processes. Moreover, adding the appropriate concentration of NZVI@SiO2-NH2 in anaerobic granular sludge treatment system can decrease the toxicity of 2,4,6-TCP to anaerobic microorganisms and improved the cumulative amount of methane production and electron transport system activity. The results from this study clearly demonstrated that the NZVI@SiO2-NH2/anaerobic granular sludge system could become an effective and promising technology for the removal of chlorophenols in industrial wastewater. PMID:26060427

Chitosan magnetic nanoparticles for drug delivery systems.

PubMed

Assa, Farnaz; Jafarizadeh-Malmiri, Hoda; Ajamein, Hossein; Vaghari, Hamideh; Anarjan, Navideh; Ahmadi, Omid; Berenjian, Aydin

2017-06-01

The potential of magnetic nanoparticles (MNPs) in drug delivery systems (DDSs) is mainly related to its magnetic core and surface coating. These coatings can eliminate or minimize their aggregation under physiological conditions. Also, they can provide functional groups for bioconjugation to anticancer drugs and/or targeted ligands. Chitosan, as a derivative of chitin, is an attractive natural biopolymer from renewable resources with the presence of reactive amino and hydroxyl functional groups in its structure. Chitosan nanoparticles (NPs), due to their huge surface to volume ratio as compared to the chitosan in its bulk form, have outstanding physico-chemical, antimicrobial and biological properties. These unique properties make chitosan NPs a promising biopolymer for the application of DDSs. In this review, the current state and challenges for the application magnetic chitosan NPs in drug delivery systems were investigated. The present review also revisits the limitations and commercial impediments to provide insight for future works.

Enhanced vapour sensing using silicon nanowire devices coated with Pt nanoparticle functionalized porous organic frameworks.

PubMed

Cao, Anping; Shan, Meixia; Paltrinieri, Laura; Evers, Wiel H; Chu, Liangyong; Poltorak, Lukasz; Klootwijk, Johan H; Seoane, Beatriz; Gascon, Jorge; Sudhölter, Ernst J R; de Smet, Louis C P M

2018-04-19

Recently various porous organic frameworks (POFs, crystalline or amorphous materials) have been discovered, and used for a wide range of applications, including molecular separations and catalysis. Silicon nanowires (SiNWs) have been extensively studied for diverse applications, including as transistors, solar cells, lithium ion batteries and sensors. Here we demonstrate the functionalization of SiNW surfaces with POFs and explore its effect on the electrical sensing properties of SiNW-based devices. The surface modification by POFs was easily achieved by polycondensation on amine-modified SiNWs. Platinum nanoparticles were formed in these POFs by impregnation with chloroplatinic acid followed by chemical reduction. The final hybrid system showed highly enhanced sensitivity for methanol vapour detection. We envisage that the integration of SiNWs with POF selector layers, loaded with different metal nanoparticles will open up new avenues, not only in chemical and biosensing, but also in separations and catalysis.

Lipid nanoparticle interactions and assemblies

NASA Astrophysics Data System (ADS)

Preiss, Matthew Ryan

Novel liposome-nanoparticle assemblies (LNAs) provide a biologically inspired route for designing multifunctional bionanotheranostics. LNAs combine the benefits of lipids and liposomes to encapsulate, transport, and protect hydrophilic and hydrophobic therapeutics with functional nanoparticles. Functional nanoparticles endow LNAs with additional capabilities, including the ability to target diseases, triggered drug release, controlled therapeutic output, and diagnostic capabilities to produce a drug delivery system that can effectively and efficiently deliver therapeutics while reducing side effects. Not only could LNAs make existing drugs better, they could also provide an avenue to allow once promising non-approved drugs (rejected due to harmful side effects, inadequate pharmacokinetics, and poor efficacy) to be safely used through targeted and controlled delivery directly to the diseased site. LNAs have the potential to be stimuli responsive, delivering drugs on command by external (ultrasound, RF heating, etc.) or internal (pH, blood sugar, heart rate, etc.) stimuli. Individually, lipids and nanoparticles have been clinically approved for therapy, such as Doxil (a liposomal doxorubicin for cancer treatment), and diagnosis, such as Feridex (an iron oxide nanoparticle an MRI contrast enhancement agent for liver tumors). In order to engineer these multifunctional LNAs for theranostic applications, the interactions between nanoparticles and lipids must be better understood. This research sought to explore the formation, design, structures, characteristics, and functions of LNAs. To achieve this goal, different types of LNAs were formed, specifically magnetoliposomes, bilayer decorated LNAs (DLNAs), and lipid-coated magnetic nanoparticles (LMNPs). A fluorescent probe was embedded in the lipid bilayer of magnetoliposomes allowing the local temperature and membrane fluidity to be observed. When subjected to an electromagnetic field that heated the encapsulated iron oxide nanoparticles encapsulated in the lipid bilayer, the local temperature and membrane fluidity could be observed. DLNAs were encapsulated with different sized nanoparticles and concentrations in order to observe the effect of the bilayer nanoparticles on the lipid bilayer's phase behavior and leakage. Two different sized nanoparticles were used, a 2 nm gold nanoparticle (GNP) much smaller than the thickness of the bilayer and a 4 nm GNP near the thickness of the lipid bilayer. The 2 nm GNPs were shown to affect the lipid bilayer differently than the 4 nm GNP. Specifically, the two nanoparticles altered the phase behavior and leakage differently in a temperature dependent fashion, demonstrating that embedded nanoparticle size can be used induce or inhibit bilayer leakage. A dual solvent exchange method was used to control the lipid surface composition of an iron oxide nanoparticle with a cationic lipid and a polyethylene glycol (PEG) lipid to produce lipid coated magnetic nanoparticles (LMNPs). PEG is well known for its ability to enhance the pharmacokinetics of nanostructures by preventing uptake by the immune system. By controlling the lipid surface composition, the surface charge and PEG conformation can be controlled which allowed the LMNPs to be used as an MRI contrast agent and a delivery system for siRNA that could be triggered with temperature.

Metal nanostructures with complex surface morphology: The case of supported lumpy Pd and Pt nanoparticles produced by laser processing of metal films

NASA Astrophysics Data System (ADS)

Ruffino, F.; Maugeri, P.; Cacciato, G.; Zimbone, M.; Grimaldi, M. G.

2016-09-01

In this work we report on the formation of lumpy Pd and Pt nanoparticles on fluorine-doped tin oxide/glass (FTO/glass) substrate by a laser-based approach. In general, complex-surface morphology metal nanoparticles can be used in several technological applications exploiting the peculiarities of their physical properties as modulated by nanoscale morphology. For example plasmonic metal nanoparticles presenting a lumpy morphology (i.e. larger particles coated on the surface by smaller particles) can be used in plasmonic solar cell devices providing broadband scattering enhancement over the smooth nanoparticles leading, so, to the increase of the device efficiency. However, the use of plasmonic lumpy nanoparticles remains largely unexplored due to the lack of simply, versatile, low-cost and high-throughput methods for the controllable production of such nanostructures. Starting from these considerations, we report on the observation that nanoscale-thick Pd and Pt films (17.6 and 27.9 nm, 12.1 and 19.5 nm, respectively) deposited on FTO/glass surface irradiated by nanosecond pulsed laser at fluences E in the 0.5-1.5 J/cm2 range, produce Pd and Pt lumpy nanoparticles on the FTO surface. In addition, using scanning electron microscopy analyses, we report on the observation that starting from each metal film of fixed thickness h, the fraction F of lumpy nanoparticles increases with the laser fluence E and saturates at the higher fluences. For each fixed fluence, F was found higher starting from the Pt films (at each starting film thickness h) with respect to the Pd films. For each fixed metal and fluence, F was found to be higher decreasing the starting thickness of the deposited film. To explain the formation of the lumpy Pd and Pt nanoparticles and the behavior of F as a function of E and h both for Pd and Pt, the thermodynamic behavior of the Pd and Pt films and nanoparticles due to the interaction with the nanosecond laser is discussed. In particular, the photothermal vaporization and Coulomb explosion processes of the Pd and Pt nanoparticles are invoked as possible mechanisms for the lumpy nanoparticles formation.

In-situ small-angle x-ray scattering study of nanoparticles in the plasma plume induced by pulsed laser irradiation of metallic targets

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

Lavisse, L.; Jouvard, J.-M.; Girault, M.

2012-04-16

Small angle x-ray scattering was used to probe in-situ the formation of nanoparticles in the plasma plume generated by pulsed laser irradiation of a titanium metal surface under atmospheric conditions. The size and morphology of the nanoparticles were characterized as function of laser irradiance. Two families of nanoparticles were identified with sizes on the order of 10 and 70 nm, respectively. These results were confirmed by ex-situ transmission electron microscopy experiments.

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.

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

Gotman, Irena, E-mail: gotman@technion.ac.il; Gutmanas, Elazar Y., E-mail: gutmanas@technion.ac.il; Tomsk Polytechnic University, Tomsk, 634050

Continuous research activities in the field of nanomedicine in the past decade have, to a great extent, been focused on nanoparticle technologies for cancer therapy. Gold and iron oxide nanoparticles (NP) are two of the most studied inorganic nanomaterials due to their unique optical and magnetic properties. Both types of NPs are emerging as promising systems for anti-tumor drug delivery and for nanoparticle-mediated thermal therapy of cancer. In thermal therapy, localized heating inside tumors or in proximity of tumor cells can be induced, for example, with Au NPs by radiofrequency ablation heating or conversion of photon energy (photothermal therapy) andmore » in iron oxide magnetic NPs by heat generation through relaxation in an alternating magnetic field (magnetic hyperthermia). Furthermore, the superparamagnetic properties of iron oxide nanoparticles have led to their use as potent MRI (magnetic resonance imaging) contrast agents. Surface modification/coating can produce NPs with tailored and desired properties, such as enhanced blood circulation time, stability, biocompatibility and water solubility. To target nanoparticles to specific tumor cells, NPs should be conjugated with targeting moieties on the surface which bind to receptors or other molecular structures on the cell surface. The article presents several approaches to enhancing the specificity of Au and iron oxide nanoparticles for tumor tissue by appropriate surface modification/functionalization, as well as the effect of these treatments on the saturation magnetization value of iron oxide NPs. The use of other nanoparticles and nanostructures in cancer treatment is also briefly reviewed.« less

Effects of nanoparticle shape on the morphology and properties of porous CdSe assemblies (aerogels).

PubMed

Yu, Hongtao; Brock, Stephanie L

2008-08-01

We demonstrate the effect of differently shaped CdSe nanoscale building blocks (dots, rods, branched nanoparticles, and hyperbranched nanoparticles) on the morphologies, surface characteristics, and optical properties of resultant porous CdSe nanostructured aerogels. Monolithic CdSe aerogels were produced by controlled oxidative removal of surface thiolate ligands from differently shaped CdSe nanoparticles to yield a wet gel, followed by CO(2) supercritical drying. The X-ray diffraction data show that the resultant CdSe aerogels maintain the crystalline phase of the building blocks without significant grain growth. However, the transmission electron microscopy images indicate that the morphology of CdSe aerogels changes from a colloid-type morphology to a polymer-type morphology when the building block changes from dot to rod or the branched nanoparticle. The morphology of the CdSe aerogel assembled from hyperbranched nanoparticles appears to be intermediate between the colloid-type and the polymer-type. Nitrogen physisorption measurements suggest that the surface areas and porosity are a direct function of the shape of the primary building blocks, with aerogels formed from rods or branched particles exhibiting the greatest surface areas (>200 m(2)/g) and those prepared from hyperbranched nanoparticles exhibiting the least (<100 m(2)/g). Band gap measurements and photoluminescence studies show that the as-prepared CdSe aerogels retain to a large extent the intrinsic quantum confinement of the differently shaped building blocks, despite being connected into a 3D network.

Enzyme-Mediated Individual Nanoparticle Release Assay

PubMed Central

Glass, James R.; Dickerson, Janet C.; Schultz, David A.

2007-01-01

Numerous methods have been developed to measure the presence of macromolecular species in a sample, however methods that detect functional activity, or modulators of that activity are more limited. To address this limitation, an approach was developed that utilizes the optical detection of nanoparticles as a measure of enzyme activity. Nanoparticles are increasingly being used as biological labels in static binding assays; here we describe their use in a release assay format where the enzyme-mediated liberation of individual nanoparticles from a surface is measured. A double stranded fragment of DNA is used as the initial tether to bind the nanoparticles to a solid surface. The nanoparticle spatial distribution and number are determined using dark-field optical microscopy and digital image capture. Site specific cleavage of the DNA tether results in nanoparticle release. The methodology and validation of this approach for measuring enzyme-mediated, individual DNA cleavage events, rapidly, with high specificity, and in real-time is described. This approach was used to detect and discriminate between non-methylated and methylated DNA, and demonstrates a novel platform for high-throughput screening of modulators of enzyme activity. PMID:16620746

Mercury adsorption to gold nanoparticle and thin film surfaces

NASA Astrophysics Data System (ADS)

Morris, Todd Ashley

Mercury adsorption to gold nanoparticle and thin film surfaces was monitored by spectroscopic techniques. Adsorption of elemental mercury to colloidal gold nanoparticles causes a color change from wine-red to orange that was quantified by UV-Vis absorption spectroscopy. The wavelength of the surface plasmon mode of 5, 12, and 31 nm gold particles blue-shifts 17, 14, and 7.5 nm, respectively, after a saturation exposure of mercury vapor. Colorimetric detection of inorganic mercury was demonstrated by employing 2.5 nm gold nanoparticles. The addition of low microgram quantities of Hg 2+ to these nanoparticles induces a color change from yellow to peach or blue. It is postulated that Hg2+ is reduced to elemental mercury by SCN- before and/or during adsorption to the nanoparticle surface. It has been demonstrated that surface plasmon resonance spectroscopy (SPRS) is sensitive to mercury adsorption to gold and silver surfaces. By monitoring the maximum change in reflectivity as a function of amount of mercury adsorbed to the surface, 50 nm Ag films were shown to be 2--3 times more sensitive than 50 nm Au films and bimetallic 15 nm Au/35 nm Ag films. In addition, a surface coverage of ˜40 ng Hg/cm2 on the gold surface results in a 0.03° decrease in the SPR angle of minimum reflectivity. SPRS was employed to follow Hg exposure to self-assembled monolayers (SAMs) on Au. The data indicate that the hydrophilic or hydrophobic character of the SAM has a significant effect on the efficiency of Hg penetration. Water adsorbed to carboxylic acid end group of the hydrophilic SAMs is believed to slow the penetration of Hg compared to methyl terminated SAMs. Finally, two protocols were followed to remove mercury from gold films: immersion in concentrated nitric acid and thermal annealing up to 200°C. The latter protocol is preferred because it removes all of the adsorbed mercury from the gold surface and does not affect the morphology of the gold surface.

Cytocompatibility of polyethylene grafted with triethylenetetramine functionalized carbon nanoparticles

NASA Astrophysics Data System (ADS)

Žáková, Pavlína; Slepičková Kasálková, Nikola; Slepička, Petr; Kolská, Zdeňka; Karpíšková, Jana; Stibor, Ivan; Švorčík, Václav

2017-11-01

Various carbon nanostructures are widely researched as scaffolds for tissue engineering. We evaluated the surface properties and cell-substrate interactions of carbon nanoparticles functionalized with triethylenetetramine (CNPs) grafted polymer film. Two forms of polyethylene (HDPE, LDPE) were treated in an inert argon plasma discharge and, subsequently, grafted with CNPs. The surface properties were studied using multiple methods, including Raman spectroscopy, goniometry, atomic force microscopy, X-ray photoelectron spectroscopy and electrokinetic analysis. Cell-substrate interactions were determined in vitro by studying adhesion, proliferation and viability of vascular smooth muscle cells (VSMCs) from the aorta of a rat. Cell-substrate interactions on pristine and modified substrates were compared to standard tissue culture polystyrene. Our results show that CNPs affect surface morphology and wettability and therefore adhesion, proliferation and viability of cultured muscle cells.

Effect of different hardness nanoparticles on friction properties of magnetorheological fluids

NASA Astrophysics Data System (ADS)

Zhao, Mingmei; Zhang, Jinqiu; Yao, Jun

2017-10-01

Magnetorheological fluids (MRFs) exhibit different wear performance when nanoparticles with different hardness are added. In this study, three solid particles with different hardness are considered to study the variation in MRF performance. The friction and wear properties of the MRF are measured by using a four-ball friction and wear tester, and the surface of the steel ball was observed using a three-dimensional white light interferometer. Also, the rheological properties of MRF are tested by using an Anton-Paar rheometer. The results show that the addition of graphite yields a stable friction process and does not degrade the rheological properties of MRF. Nano-diamond increases the shear yield strength and reduces the wall slip to a greater extent. However, the wear is more serious in this case. Copper particles are unstable, and their surface activity is too high to get adsorbed on the surface of iron powder aggravating the settlement rate. The above three MRFs with different kinds of nano-particles present a more regular grinding spot, and the nano-particles have a certain repair function to the surface.

Chain Conformation near the Buried Interface in Nanoparticle-Stabilized Polymer Thin Films

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

Barkley, Deborah A.; Jiang, Naisheng; Sen, Mani

It is known that when nanoparticles are added to polymer thin films, they often migrate to the film-substrate interface and form an “immobile interfacial layer”, which has been believed as the origin of suppression of dewetting. We here report an alternative mechanism of dewetting suppression from the structural aspect of a polymer. Dodecane thiol-functionalized gold (Au) nanoparticles embedded in PS thin films prepared on Si substrates were used as a model. It was found that thermal annealing promotes irreversible polymer adsorption onto the substrate surface along with the surface migration of the nanoparticles. We also revealed that the surface migrationmore » causes additional nanoconfined space for the adsorbed polymer chains. As a result, the self-organization process of the strongly adsorbed polymer chains on the solid surface was so hindered that the chain conformations were randomized and expanded in the film normal direction. Here, the resultant chain conformation allows the interpenetration between free chains and the adsorbed chains, promoting adhesion and hence stabilizing the thin film.« less

Metal oxide nanoparticle mediated enhanced Raman scattering and its use in direct monitoring of interfacial chemical reactions.

PubMed

Li, Li; Hutter, Tanya; Finnemore, Alexander S; Huang, Fu Min; Baumberg, Jeremy J; Elliott, Stephen R; Steiner, Ullrich; Mahajan, Sumeet

2012-08-08

Metal oxide nanoparticles (MONPs) have widespread usage across many disciplines, but monitoring molecular processes at their surfaces in situ has not been possible. Here we demonstrate that MONPs give highly enhanced (×10(4)) Raman scattering signals from molecules at the interface permitting direct monitoring of their reactions, when placed on top of flat metallic surfaces. Experiments with different metal oxide materials and molecules indicate that the enhancement is generic and operates at the single nanoparticle level. Simulations confirm that the amplification is principally electromagnetic and is a result of optical modulation of the underlying plasmonic metallic surface by MONPs, which act as scattering antennae and couple light into the confined region sandwiched by the underlying surface. Because of additional functionalities of metal oxides as magnetic, photoelectrochemical and catalytic materials, enhanced Raman scattering mediated by MONPs opens up significant opportunities in fundamental science, allowing direct tracking and understanding of application-specific transformations at such interfaces. We show a first example by monitoring the MONP-assisted photocatalytic decomposition reaction of an organic dye by individual nanoparticles.

Chain Conformation near the Buried Interface in Nanoparticle-Stabilized Polymer Thin Films

DOE PAGES

Barkley, Deborah A.; Jiang, Naisheng; Sen, Mani; ...

2017-09-26

It is known that when nanoparticles are added to polymer thin films, they often migrate to the film-substrate interface and form an “immobile interfacial layer”, which has been believed as the origin of suppression of dewetting. We here report an alternative mechanism of dewetting suppression from the structural aspect of a polymer. Dodecane thiol-functionalized gold (Au) nanoparticles embedded in PS thin films prepared on Si substrates were used as a model. It was found that thermal annealing promotes irreversible polymer adsorption onto the substrate surface along with the surface migration of the nanoparticles. We also revealed that the surface migrationmore » causes additional nanoconfined space for the adsorbed polymer chains. As a result, the self-organization process of the strongly adsorbed polymer chains on the solid surface was so hindered that the chain conformations were randomized and expanded in the film normal direction. Here, the resultant chain conformation allows the interpenetration between free chains and the adsorbed chains, promoting adhesion and hence stabilizing the thin film.« less

Thermal, optical and vibrational studies of tyrosine doped LaF3:Ce nanoparticles for bioimaging and biotagging

NASA Astrophysics Data System (ADS)

Singh, Amit T.

2018-05-01

Upconversion quantum dots of tyrosine doped LaF3:Ce nanoparticles have been synthesized by wet chemical route. The thermal studies (TGA/DTA) confirm the crystallinity and stability of different phases of synthesized nanoparticles. The UV-Visible spectra show multiple absorption edges at 215.60 nm and 243.10 nm indicating quantum dot nature of the synthesized nanoparticles. The PL spectra showed upconversion with sharp emission peak at 615 nm (red colour). The FT-RAMAN spectra of the synthesized nanoparticles show the modification of the surface of the nanoparticles in the form of functional groups and skeletal groups. Upconversion nature of the synthesized nanoparticles indicates their potential application in bioimaging and biotagging.

Multiscale study of metal nanoparticles

NASA Astrophysics Data System (ADS)

Lee, Byeongchan

Extremely small structures with reduced dimensionality have emerged as a scientific motif for their interesting properties. In particular, metal nanoparticles have been identified as a fundamental material in many catalytic activities; as a consequence, a better understanding of structure-function relationship of nanoparticles has become crucial. The functional analysis of nanoparticles, reactivity for example, requires an accurate method at the electronic structure level, whereas the structural analysis to find energetically stable local minima is beyond the scope of quantum mechanical methods as the computational cost becomes prohibitingly high. The challenge is that the inherent length scale and accuracy associated with any single method hardly covers the broad scale range spanned by both structural and functional analyses. In order to address this, and effectively explore the energetics and reactivity of metal nanoparticles, a hierarchical multiscale modeling is developed, where methodologies of different length scales, i.e. first principles density functional theory, atomistic calculations, and continuum modeling, are utilized in a sequential fashion. This work has focused on identifying the essential information that bridges two different methods so that a successive use of different methods is seamless. The bond characteristics of low coordination systems have been obtained with first principles calculations, and incorporated into the atomistic simulation. This also rectifies the deficiency of conventional interatomic potentials fitted to bulk properties, and improves the accuracy of atomistic calculations for nanoparticles. For the systematic shape selection of nanoparticles, we have improved the Wulff-type construction using a semi-continuum approach, in which atomistic surface energetics and crystallinity of materials are added on to the continuum framework. The developed multiscale modeling scheme is applied to the rational design of platinum nanoparticles in the range of 2.4 nm to 3.1 nm: energetically favorable structures have been determined in terms of semi-continuum binding energy, and the reactivity of the selected nanoparticle has been investigated based on local density of states from first principles calculations. The calculation suggests that the reactivity landscape of particles is more complex than the simple reactivity of clean surfaces, and the reactivity towards a particular reactant can be predicted for a given structure.

Concepts and practices used to develop functional PLGA-based nanoparticulate systems.

PubMed

Sah, Hongkee; Thoma, Laura A; Desu, Hari R; Sah, Edel; Wood, George C

2013-01-01

The functionality of bare polylactide-co-glycolide (PLGA) nanoparticles is limited to drug depot or drug solubilization in their hard cores. They have inherent weaknesses as a drug-delivery system. For instance, when administered intravenously, the nanoparticles undergo rapid clearance from systemic circulation before reaching the site of action. Furthermore, plain PLGA nanoparticles cannot distinguish between different cell types. Recent research shows that surface functionalization of nanoparticles and development of new nanoparticulate dosage forms help overcome these delivery challenges and improve in vivo performance. Immense research efforts have propelled the development of diverse functional PLGA-based nanoparticulate delivery systems. Representative examples include PEGylated micelles/nanoparticles (PEG, polyethylene glycol), polyplexes, polymersomes, core-shell-type lipid-PLGA hybrids, cell-PLGA hybrids, receptor-specific ligand-PLGA conjugates, and theranostics. Each PLGA-based nanoparticulate dosage form has specific features that distinguish it from other nanoparticulate systems. This review focuses on fundamental concepts and practices that are used in the development of various functional nanoparticulate dosage forms. We describe how the attributes of these functional nanoparticulate forms might contribute to achievement of desired therapeutic effects that are not attainable using conventional therapies. Functional PLGA-based nanoparticulate systems are expected to deliver chemotherapeutic, diagnostic, and imaging agents in a highly selective and effective manner.

Concepts and practices used to develop functional PLGA-based nanoparticulate systems

PubMed Central

Sah, Hongkee; Thoma, Laura A; Desu, Hari R; Sah, Edel; Wood, George C

2013-01-01

The functionality of bare polylactide-co-glycolide (PLGA) nanoparticles is limited to drug depot or drug solubilization in their hard cores. They have inherent weaknesses as a drug-delivery system. For instance, when administered intravenously, the nanoparticles undergo rapid clearance from systemic circulation before reaching the site of action. Furthermore, plain PLGA nanoparticles cannot distinguish between different cell types. Recent research shows that surface functionalization of nanoparticles and development of new nanoparticulate dosage forms help overcome these delivery challenges and improve in vivo performance. Immense research efforts have propelled the development of diverse functional PLGA-based nanoparticulate delivery systems. Representative examples include PEGylated micelles/nanoparticles (PEG, polyethylene glycol), polyplexes, polymersomes, core-shell–type lipid-PLGA hybrids, cell-PLGA hybrids, receptor-specific ligand-PLGA conjugates, and theranostics. Each PLGA-based nanoparticulate dosage form has specific features that distinguish it from other nanoparticulate systems. This review focuses on fundamental concepts and practices that are used in the development of various functional nanoparticulate dosage forms. We describe how the attributes of these functional nanoparticulate forms might contribute to achievement of desired therapeutic effects that are not attainable using conventional therapies. Functional PLGA-based nanoparticulate systems are expected to deliver chemotherapeutic, diagnostic, and imaging agents in a highly selective and effective manner. PMID:23459088

Thrombin-inhibiting perfluorocarbon nanoparticles provide a novel strategy for treatment and magnetic resonance imaging of acute thrombosis

PubMed Central

Myerson, J.; He, L.; Lanza, G.; Tollefsen, D.; Wickline, S.

2013-01-01

Background As a regulator of the penultimate step in the coagulation cascade, thrombin represents a principal target of direct and specific anticoagulants. Objective A potent thrombin inhibitor complexed with a colloidal nanoparticle was devised as a first-in-class anticoagulant with prolonged and highly localized therapeutic impact conferred by its multivalent thrombin-absorbing particle surface. Methods PPACK (Phe(D)-Pro-Arg-Chloromethylketone) was secured covalently to the surface of perfluorocarbon-core nanoparticle structures. PPACK and PPACK nanoparticle inhibition of thrombin were assessed in vitro via thrombin activity against a chromogenic substrate. In vivo antithrombotic activity of PPACK, heparin, non-functionalized nanoparticles, and PPACK nanoparticles was assessed through IV administration prior to acute photochemical injury of the common carotid artery. Perfluorocarbon particle retention in extracted carotid arteries from injured mice was assessed via 19F magnetic resonance spectroscopy (MRS) and imaging (MRI) at 11.7 T. APTT measurements determined the systemic effects of the PPACK nanoparticles at various times after injection. Results Optical assay verified that PPACK nanoparticles exceeded PPACK’s intrinsic activity against thrombin. Application of the an in vivo acute arterial thrombosis model demonstrated that PPACK nanoparticles outperformed both heparin (p=.001) and uncomplexed PPACK (p=.0006) in inhibiting thrombosis. 19F MRS confirmed that PPACK nanoparticles specifically bound to sites of acute thrombotic injury. APTT normalized within twenty minutes of PPACK nanoparticles injection. Conclusions PPACK nanoparticles present thrombin-inhibiting surfaces at sites of acutely forming thrombi that continue to manifest local clot inhibition even as systemic effects rapidly diminish and thus represent a new platform for localized control of acute thrombosis. PMID:21605330

Thermoswitchable Janus Gold Nanoparticles with Stimuli-Responsive Hydrophilic Polymer Brushes.

PubMed

Niu, Xiaoqin; Ran, Fen; Chen, Limei; Lu, Gabriella Jia-En; Hu, Peiguang; Deming, Christopher P; Peng, Yi; Rojas-Andrade, Mauricio D; Chen, Shaowei

2016-05-03

Well-defined thermoswitchable Janus gold nanoparticles with stimuli-responsive hydrophilic polymer brushes were fabricated by combining ligand exchange reactions and the Langmuir technique. Stimuli-responsive polydi(ethylene glycol) methyl ether methacrylate was prepared by addition-fragmentation chain-transfer polymerization. The polymer brushes were then anchored onto the nanoparticle surface by interfacial ligand exchange reactions with hexanethiolate-protected gold nanoparticles, leading to the formation of a hydrophilic (polymer) hemisphere and a hydrophobic (hexanethiolate) one. The resulting Janus nanoparticles showed temperature-switchable wettability, hydrophobicity at high temperatures, and hydrophilicity at low temperatures, due to thermally induced conformational transition of the polymer ligands. The results further highlight the importance of interfacial engineering in the deliberate functionalization of nanoparticle materials.

Surface and finite size effect on fluctuations dynamics in nanoparticles with long-range order

NASA Astrophysics Data System (ADS)

Morozovska, A. N.; Eliseev, E. A.

2010-02-01

The influence of surface and finite size on the dynamics of the order parameter fluctuations and critical phenomena in the three-dimensional (3D)-confined systems with long-range order was not considered theoretically. In this paper, we study the influence of surface and finite size on the dynamics of the order parameter fluctuations in the particles of arbitrary shape. We consider concrete examples of the spherical and cylindrical ferroic nanoparticles within Landau-Ginzburg-Devonshire phenomenological approach. Allowing for the strong surface energy contribution in micro and nanoparticles, the analytical expressions derived for the Ornstein-Zernike correlator of the long-range order parameter spatial-temporal fluctuations, dynamic generalized susceptibility, relaxation times, and correlation radii discrete spectra are different from those known for bulk systems. Obtained analytical expressions for the correlation function of the order parameter spatial-temporal fluctuations in micro and nanosized systems can be useful for the quantitative analysis of the dynamical structural factors determined from magnetic resonance diffraction and scattering spectra. Besides the practical importance of the correlation function for the analysis of the experimental data, derived expressions for the fluctuations strength determine the fundamental limits of phenomenological theories applicability for 3D-confined systems.

Heteroaggregation of Silver Nanoparticles with Clay Minerals in Aqueous System

NASA Astrophysics Data System (ADS)

Liu, J.; Burrow, E.; Hwang, Y.; Lenhart, J.

2013-12-01

Nanoparticles are increasingly being used in industrial processes and consumer products that exploit their beneficial properties and improve our daily lives. Nevertheless, they also attract attention when released into natural environment due to their potential for causing adverse effects. The fate and transport of nanoparticles in aqueous systems have been the focus of intense study. However, their interactions with other natural particles have received only limited attention. Clay minerals are ubiquitous in most aquatic systems and their variably charged surfaces can act as deposition sites that can alter the fate and transport of nanoparticles in natural aqueous environments. In this study, we investigated the homoaggregation of silver nanoparticles with different coating layers and their heteroaggregation behavior with clay minerals (illite, kaolinite, montmorillonite) in neutral pH solutions. Silver nanoparticles with a nominal diameter of 80 nm were synthesized with three different surface coating layers: uncoated, citrate-coated and Tween-coated. Illite (IMt-2), kaolinite (KGa-2), and montmorillonite (SWy-2) were purchased from the Clay Mineral Society (Indiana) and pretreated to obtain monocationic (Na-clay) and dicationic (Ca-clay) suspensions before the experiments. The change in hydrodynamic diameter as a function of time was monitored using dynamic light scattering (DLS) measurements in order to evaluate early stage aggregation as a function of electrolyte concentration in both the homo- and heteroaggregation scenarios. A shift in the critical coagulation concentration (CCC) values to lower electrolyte concentrations was observed in binary systems, compared to single silver nanoparticle and clay systems. The results also suggest more rapid aggregation in binary system during the early aggregation stage when compared to the single-particle systems. The behavior of citrate-coated silver nanoparticles was similar to that of the bare particles, while the Tween-coated silver nanoparticles showed high stability in both single and binary systems. There were no significant differences in early stage aggregation kinetics observed inthe Na-clay-nanoparticle or Ca-clay-nanoparticle systems, which suggested that the CCC values of the single Na- or Ca-clay suspensions depend only on the electrolyte concentration, not the original cations on the clay surface. These results provide a basic idea for understanding the heteroaggregation of different silver nanoparticles and clays, which can be utilized in further study of fate and transport of engineered nanoparticles in natural aqueous system.

Multitasking mesoporous nanomaterials for biorefinery applications

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

Kandel, Kapil

2013-01-01

Mesoporous silica nanoparticles (MSNs) have attracted great interest for last two decades due to their unique and advantageous structural properties, such as high surface area, pore volume, stable mesostructure, tunable pore size and controllable particle morphology. The robust silica framework provides sites for organic modifications, making MSNs ideal platforms for adsorbents and supported organocatalysts. In addition, the pores of MSNs provide cavities/ channels for incorporation of metal and metal oxide nanoparticle catalysts. These supported metal nanoparticle catalysts benefit from confined local environments to enhance their activity and selectivity for various reactions. Biomass is considered as a sustainable feedstock with potentialmore » to replace diminishing fossil fuels for the production of biofuels. Among several strategies, one of the promising methods of biofuel production from biomass is to reduce the oxygen content of the feedstock in order to improve the energy density. This can be achieved by creating C-C bonds between biomass derived intermediates to increase the molecular weight of the final hydrocarbon molecules. In this context, pore size and organic functionality of MSNs are varied to obtain the ideal catalyst for a C-C bond forming reaction: the aldol condensation. The mechanistic aspects of this reaction in supported heterogeneous catalysts are explored. The modification of supported organocatalyst and the effect of solvent on the reaction are rationalized. The significance of two functional surfaces of MSNs is exploited by enzyme immobilization on the external surface and organo catalyst functionalization on the internal surface. Using this bifunctional catalyst, the tandem conversion of small chain alcohols into longer chain hydrocarbon molecules is demonstrated. The ability to incorporate metal and metal oxide nanoparticles in the pores and subsequent functionalization led to develop organic modified magnetic MSNs (OM-MSNs) for applications in microalgae biorefinery. Two different integrated biorefinery systems are highlighted. (i) OM-MSNs are used to harvest microalgae and selectively sequester free fatty acids (FFAs). (ii) OM-MSNs are shown to selectively sequester FFAs and convert them into diesel-range liquid hydrocarbon fuels. A similar MSN supported metal nanoparticle catalyst is demonstrated to transform FFAs into green diesel with even greater activity and selectivity. The incorporation of a different organic functional group into MSN provides a selective adsorbent for separation and purification of α-tocopherol from microalgae oil. The functional group with electron deficient aromatic rings demonstrated high sequestration capacity and selectivity of {alpha}-tocopherol.« less

Reductive surface synthesis of gold nanoparticles on silicate glass and their biochemical sensor applicationsa

PubMed Central

Li, M.; Kim, D.-P.; Jeong, G.-Y.; Seo, D.-K.; Park, C.-P.

2012-01-01

Gold nanoparticles (Au NPs) were directly synthesized on the surface of polyvinylsilazane (PVSZ, -[(vinyl)SiH-NH2]-) without use of extra reductive additives. The reductive Si-H functional groups on the surface of cured PVSZ acted as surface bound reducing agents to form gold metal when contacted with an aqueous Au precursor (HAuCl4) solution, leading to formation of Au NPs adhered to silicate glass surface. The Au NPs-silicate platforms were preliminarily tested to detect Rhodamine B (1 μM) by surface enhanced Raman scattering. Furthermore, gold microelectrode obtained by post-chemical plating was used as an integrated amperometric detection element in the polydimethylsilane-glass hybrid microfluidic chip. PMID:24324531

Introducing Students to Surface Modification and Phase Transfer of Nanoparticles with a Laboratory Experiment

ERIC Educational Resources Information Center

Alkilany, Alaaldin M.; Mansour, Sara; Amro, Hamza M.; Pelaz, Beatriz; Soliman, Mahmoud G.; Hinman, Joshua G.; Dennison, Jordan M.; Parak, Wolfgang J.; Murphy, Catherine J.

2017-01-01

A simple, reliable, and cost-effective experiment is presented in which students synthesized citrate-capped gold nanoparticles (GNPs), functionalized them with poly(ethylene glycol) (PEG), and transferred the PEG-GNPs from water to the organic phase dichloromethane. The experiment introduces students to nanotechnology with foci on important…

Photosensitizer conjugated iron oxide nanoparticles for simultaneous in vitro magneto-fluorescent imaging guided photodynamic therapy.

PubMed

Nafiujjaman, Md; Revuri, Vishnu; Nurunnabi, Md; Cho, Kwang Jae; Lee, Yong-Kyu

2015-04-04

In this study, photosensitizer conjugated iron oxide nanoparticles were strategically designed and prepared for simultaneous PDT and dual-mode fluorescence/MR imaging. The MRI contrast agent Fe3O4 was modified by APTES to functionalize the surface and further to link with heparin-pheophorbide-A conjugates.

Deposition of functional nanoparticle thin films by resonant infrared laser ablation.

NASA Astrophysics Data System (ADS)

Haglund, Richard; Johnson, Stephen; Park, Hee K.; Appavoo, Kannatessen

2008-03-01

We have deposited thin films containing functional nanoparticles, using tunable infrared light from a picosecond free-electron laser (FEL). Thin films of the green light-emitting molecule Alq3 were first deposited by resonant infrared laser ablation at 6.68 μm, targeting the C=C ring mode of the Alq3. TiO2 nanoparticles 50-100 nm diameter were then suspended in a water matrix, frozen, and transferred by resonant infrared laser ablation at 2.94 μm through a shadow mask onto the Alq3 film. Photoluminescence was substantially enhanced in the regions of the film covered by the TiO2 nanoparticles. In a second experiment, gold nanoparticles with diameters in the range of 50-100 nm were suspended in the conducting polymer and anti-static coating material PEDOT:PSS, which was diluted by mixing with N-methyl pyrrolidinone (NMP). The gold nanoparticle concentration was 8-10% by weight. The mixture was frozen and then ablated by tuning the FEL to 3.47 μm, the C-H stretch mode of NMP. Optical spectroscopy of the thin film deposited by resonant infrared laser ablation exhibited the surface-plasmon resonance characteristic of the Au nanoparticles. These experiments illustrate the versatility of matrix-assisted resonant infrared laser ablation as a technique for depositing thin films containing functionalized nanoparticles.

Theoretical characterization of the surface composition of ruthenium nanoparticles in equilibrium with syngas

NASA Astrophysics Data System (ADS)

Cusinato, Lucy; Martínez-Prieto, Luis M.; Chaudret, Bruno; Del Rosal, Iker; Poteau, Romuald

2016-05-01

A deeper understanding of the relationship between experimental reaction conditions and the surface composition of nanoparticles is crucial in order to elucidate mechanisms involved in nanocatalysis. In the framework of the Fischer-Tropsch synthesis, a resolution of this complex puzzle requires a detailed understanding of the interaction of CO and H with the surface of the catalyst. In this context, the single- and co-adsorption of CO and H to the surface of a 1 nm ruthenium nanoparticle has been investigated with density functional theory. Using several indexes (d-band center, crystal overlap Hamilton population, density of states), a systematic analysis of the bond properties and of the electronic states has also been done, in order to bring an understanding of structure/property relationships at the nanoscale. The H : CO surface composition of this ruthenium nanoparticle exposed to syngas has been evaluated according to a thermodynamic model fed with DFT energies. Such ab initio thermodynamic calculations give access to the optimal H : CO coverage values under a wide range of experimental conditions, through the construction of free energy phase diagrams. Surprisingly, under the Fischer-Tropsch synthesis experimental conditions, and in agreement with new experiments, only CO species are adsorbed at the surface of the nanoparticle. These findings shed new light on the possible reaction pathways underlying the Fischer-Tropsch synthesis, and specifically the initiation of the reaction. It is finally shown that the joint knowledge of the surface composition and energy descriptors can help to identify possible reaction intermediates.A deeper understanding of the relationship between experimental reaction conditions and the surface composition of nanoparticles is crucial in order to elucidate mechanisms involved in nanocatalysis. In the framework of the Fischer-Tropsch synthesis, a resolution of this complex puzzle requires a detailed understanding of the interaction of CO and H with the surface of the catalyst. In this context, the single- and co-adsorption of CO and H to the surface of a 1 nm ruthenium nanoparticle has been investigated with density functional theory. Using several indexes (d-band center, crystal overlap Hamilton population, density of states), a systematic analysis of the bond properties and of the electronic states has also been done, in order to bring an understanding of structure/property relationships at the nanoscale. The H : CO surface composition of this ruthenium nanoparticle exposed to syngas has been evaluated according to a thermodynamic model fed with DFT energies. Such ab initio thermodynamic calculations give access to the optimal H : CO coverage values under a wide range of experimental conditions, through the construction of free energy phase diagrams. Surprisingly, under the Fischer-Tropsch synthesis experimental conditions, and in agreement with new experiments, only CO species are adsorbed at the surface of the nanoparticle. These findings shed new light on the possible reaction pathways underlying the Fischer-Tropsch synthesis, and specifically the initiation of the reaction. It is finally shown that the joint knowledge of the surface composition and energy descriptors can help to identify possible reaction intermediates. Electronic supplementary information (ESI) available: Energies, detailed description of the hapticity and of the bridging character of the surface ligands and geometries for isomers; additional phase diagrams (without ZPE corrections). See DOI: 10.1039/C6NR01191H

Impact of silica nanoparticle surface chemistry on protein corona formation and consequential interactions with biological cells.

PubMed

Kurtz-Chalot, Andréa; Villiers, Christian; Pourchez, Jérémie; Boudard, Delphine; Martini, Matteo; Marche, Patrice N; Cottier, Michèle; Forest, Valérie

2017-06-01

Nanoparticles (NP) physico-chemical features greatly influence NP/cell interactions. NP surface functionalization is often used to improve NP biocompatibility or to enhance cellular uptake. But in biological media, the formation of a protein corona adds a level of complexity. The aim of this study was to investigate in vitro the influence of NP surface functionalization on their cellular uptake and the biological response induced. 50nm fluorescent silica NP were functionalized either with amine or carboxylic groups, in presence or in absence of polyethylene glycol (PEG). NP were incubated with macrophages, cellular uptake and cellular response were assessed in terms of cytotoxicity, pro-inflammatory response and oxidative stress. The NP protein corona was also characterized by protein mass spectroscopy. Results showed that NP uptake was enhanced in absence of PEG, while NP adsorption at the cell membrane was fostered by an initial positively charged NP surface. NP toxicity was not correlated with NP uptake. NP surface functionalization also influenced the formation of the protein corona as the profile of protein binding differed among the NP types. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Sensing of contaminants in potable water using TiO{sub 2} functional film

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

Akshatha, N.; Poonia, Monika; Gupta, R. K., E-mail: raj@pilani.bits-pilani.ac.in

2016-04-13

The piezoelectric based quartz crystal microbalance is employed for sensing contaminants in potable water. A spin coated thin layer of TiO{sub 2} nanoparticles was formed at the sensing area of a 5 MHz AT-cut quartz wafer. The thin film of TiO{sub 2} nanoparticles forms a mesoporous functional layer for the trapping of water borne contaminants. The morphology of the thin film of TiO{sub 2} nanoparticles was studied using field emission scanning electron microscope (FESEM). The surface morphology of the TiO{sub 2} nanoparticles reveals the mesoporous structures indicating large number of defects and porous sites. Such film was employed for the detectionmore » of water borne contaminants by detecting the piezoelectric response from a quartz crystal microbalance. We found the film to be very sensitive to the contaminants. The minimum detection limit was found to be 330 ppb. The effect of surface recharging was also studied by altering the physical conditions so that the film can be used for repetitive usage.« less

Functionalized TiO2 nanoparticles labelled with 225Ac for targeted alpha radionuclide therapy.

PubMed

Cędrowska, Edyta; Pruszynski, Marek; Majkowska-Pilip, Agnieszka; Męczyńska-Wielgosz, Sylwia; Bruchertseifer, Frank; Morgenstern, Alfred; Bilewicz, Aleksander

2018-01-01

The 225 Ac radioisotope exhibits very attractive nuclear properties for application in radionuclide therapy. Unfortunately, the major challenge for radioconjugates labelled with 225 Ac is that traditional chelating moieties are unable to sequester the radioactive daughters in the bioconjugate which is critical to minimize toxicity to healthy, non-targeted tissues. In the present work, we propose to apply TiO 2 nanoparticles (NPs) as carrier for 225 Ac and its decay products. The surface of TiO 2 nanoparticles with 25 nm diameter was modified with Substance P (5-11), a peptide fragment which targets NK1 receptors on the glioma cells, through the silan-PEG-NHS linker. Nanoparticles functionalized with Substance P (5-11) were synthesized with high yield in a two-step procedure, and the products were characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS) and thermogravimetric analysis (TGA). The obtained results show that one TiO 2 -bioconjugate nanoparticle contains in average 80 peptide molecules on its surface. The synthesized TiO 2 -PEG-SP(5-11) conjugates were labelled with 225 Ac by ion-exchange reaction on hydroxyl (OH) functional groups on the TiO 2 surface. The labelled bioconjugates almost quantitatively retain 225 Ac in phosphate-buffered saline (PBS), physiological salt and cerebrospinal fluid (CSF) for up to 10 days. The leaching of 221 Fr, a first decay daughter of 225 Ac, in an amount of 30% was observed only in CSF after 10 days. The synthesized 225 Ac-TiO 2 -PEG-SP(5-11) has shown high cytotoxic effect in vitro in T98G glioma cells; therefore, it is a promising new radioconjugate for targeted radionuclide therapy of brain tumours.

Functionalized TiO2 nanoparticles labelled with 225Ac for targeted alpha radionuclide therapy

NASA Astrophysics Data System (ADS)

Cędrowska, Edyta; Pruszynski, Marek; Majkowska-Pilip, Agnieszka; Męczyńska-Wielgosz, Sylwia; Bruchertseifer, Frank; Morgenstern, Alfred; Bilewicz, Aleksander

2018-03-01

The 225Ac radioisotope exhibits very attractive nuclear properties for application in radionuclide therapy. Unfortunately, the major challenge for radioconjugates labelled with 225Ac is that traditional chelating moieties are unable to sequester the radioactive daughters in the bioconjugate which is critical to minimize toxicity to healthy, non-targeted tissues. In the present work, we propose to apply TiO2 nanoparticles (NPs) as carrier for 225Ac and its decay products. The surface of TiO2 nanoparticles with 25 nm diameter was modified with Substance P (5-11), a peptide fragment which targets NK1 receptors on the glioma cells, through the silan-PEG-NHS linker. Nanoparticles functionalized with Substance P (5-11) were synthesized with high yield in a two-step procedure, and the products were characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS) and thermogravimetric analysis (TGA). The obtained results show that one TiO2-bioconjugate nanoparticle contains in average 80 peptide molecules on its surface. The synthesized TiO2-PEG-SP(5-11) conjugates were labelled with 225Ac by ion-exchange reaction on hydroxyl (OH) functional groups on the TiO2 surface. The labelled bioconjugates almost quantitatively retain 225Ac in phosphate-buffered saline (PBS), physiological salt and cerebrospinal fluid (CSF) for up to 10 days. The leaching of 221Fr, a first decay daughter of 225Ac, in an amount of 30% was observed only in CSF after 10 days. The synthesized 225Ac-TiO2-PEG-SP(5-11) has shown high cytotoxic effect in vitro in T98G glioma cells; therefore, it is a promising new radioconjugate for targeted radionuclide therapy of brain tumours.

Polythioether Particles Armored with Modifiable Graphene Oxide Nanosheets.

PubMed

Rodier, Bradley J; Mosher, Eric P; Burton, Spencer T; Matthews, Rachael; Pentzer, Emily

2016-06-01

Facile and scalable fabrication methods are attractive to prepare materials for diverse applications. Herein, a method is presented to prepare cross-linked polymeric nanoparticles with graphene oxide (GO) nanosheets covalently attached to the surface. Alkene-modified GO serves as a surfactant in a miniemulsion polymerization, and the alkene functionalities of GO exposed to the oil-phase are incorporated into the polymer particle through thiol-ene reactions, leaving the unreacted alkene functional groups of the other face of GO available for further functionalization. The surface of GO-armored polymer particles is then modified with a small molecule fluorophore or carboxylic acid functional groups that bind to Fe2 O3 and TiO2 nanoparticles. This methodology provides a facile route to preparing complex hybrid composite materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Control of DNA-Functionalized Nanoparticle Assembly

NASA Astrophysics Data System (ADS)

Olvera de La Cruz, Monica

Directed crystallization of a large variety of nanoparticles, including proteins, via DNA hybridization kinetics has led to unique materials with a broad range of crystal symmetries. The nanoparticles are functionalized with DNA chains that link neighboring functionalized units. The shape of the nanoparticle, the DNA length, the sequence of the hybridizing DNA linker and the grafting density determine the crystal symmetries and lattice spacing. By carefully selecting these parameters one can, in principle, achieve all the symmetries found for both atomic and colloidal crystals of asymmetric shapes as well as new symmetries, and drive transitions between them. A scale-accurate coarse-grained model with explicit DNA chains provides the design parameters, including degree of hybridization, to achieve specific crystal structures. The model also provides surface energy values to determine the shape of defect-free single crystals with macroscopic anisotropic properties, as well as the parameters to develop colloidal models that reproduce both the shape of single crystals and their growth kinetics.

Assessment of carbon nanoparticle exposure on murine macrophage function

NASA Astrophysics Data System (ADS)

Suro-Maldonado, Raquel M.

There is growing concern about the potential cytotoxicity of nanoparticles. Exposure to respirable ultrafine particles (2.5uM) can adversely affect human health and have been implicated with episodes of increased respiratory diseases such as asthma and allergies. Nanoparticles are of particular interest because of their ability to penetrate into the lung and potentially elicit health effects triggering immune responses. Nanoparticles are structures and devises with length scales in the 1 to 100-nanometer range. Black carbon (BC) nanoparticles have been observed to be products of combustion, especially flame combustion and multi-walled carbon nanotubes (MWCNT) have been shown to be found in both indoor and outdoor air. Furthermore, asbestos, which have been known to cause mesothelioma as well as lung cancer, have been shown to be structurally identical to MWCNTs. The aims of these studies were to examine the effects of carbon nanoparticles on murine macrophage function and clearance mechanisms. Macrophages are immune cells that function as the first line of defense against invading pathogens and are likely to be amongst the first cells affected by nanoparticles. Our research focused on two manufactured nanoparticles, MWCNT and BC. The two were tested against murine-derived macrophages in a chronic contact model. We hypothesized that long-term chronic exposure to carbon nanoparticles would decrease macrophages ability to effectively respond to immunological challenge. Production of nitric oxide (NO), tumor necrosis factor alpha (TNF-alpha), cell surface macrophage; activation markers, reactive oxygen species formation (ROS), and antigen processing and presentation were examined in response to lipopolysaccharide (LPS) following a 144hr exposure to the particulates. Data demonstrated an increase in TNF-alpha, and NO production; a decrease in phagocytosis and antigen processing and presentation; and a decrease in the expression levels of cell surface macrophage activation markers. The data suggests that carbon nanoparticle exposure alters macrophage responses to LPS marked by increased inflammation while potentially limiting clearance and ability to interact with effector T-cells. Thus, physiological exposure to carbon nanoparticles could potentially lead to ineffective pulmonary immunity.

Nano-catalysts: Bridging the gap between homogeneous and heterogeneous catalysis

EPA Science Inventory

Functionalized nanoparticles have emerged as sustainable alternatives to conventional materials, as robust, high-surface-area heterogeneous catalyst supports. We envisioned a catalyst system, which can bridge the homogenous and heterogeneous system. Postsynthetic surface modifica...

Adjusting the surface areal density of click-reactive azide groups by kinetic control of the azide substitution reaction on bromine-functional SAMs.

PubMed

Zhang, Shuo; Maidenberg, Yanir; Luo, Kai; Koberstein, Jeffrey T

2014-06-03

Azide-alkyne click chemistry has emerged as an important and versatile means for tethering a wide variety of guest molecules to virtually any substrate. In many of these applications, it is important to exercise control over the areal density of surface functional groups to achieve a desired areal density of the tethered guest molecule of interest. We demonstrate herein that the areal density of surface azide groups on flat germanium surfaces and nanoparticle substrates (silica and iron oxide) can be controlled kinetically by appropriately timed quenching of the S(N)2 substitution reaction of bromo-alkane-silane monolayers induced by the addition of sodium azide. The kinetics of the azide substitution reaction on monolayers formed on flat Ge substrates, determined by attenuated total reflection infrared spectroscopy (ATR-IR), are found to be identical to those for monolayers formed on both silica and iron oxide nanoparticles, the latter determined by transmission infrared spectroscopy. To validate the method, the percentages of surface bromine groups converted to azide groups after various reaction times were measured by quenching the S(N)2 reaction followed by analysis with ATR-IR (for Ge) and thermogravimetric analysis (after a subsequent click reaction with an alkyne-terminal polymer) for the nanoparticle substrates. The conversions found after quenching agree well with those expected from the standard kinetic curves. The latter result suggests that the kinetic method for the control of azide group areal density is a versatile means for functionalizing substrates with a prescribed areal density of azide groups for subsequent click reactions, and that the method is universal for any substrate, flat or nanoparticle, that can be modified with bromo-alkane-silane monolayers. Regardless of the surface geometry, we find that the azide substitution reaction is complete within 2-3 h, in sharp contrast to previous reports that indicate times of 48-60 h required for completion of the reaction.

Development of DNA biosensor based on TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

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

2018-05-01

A novel technique of DNA hybridization on the TiO2 nanoparticles film was developed by dropping a single droplet of target DNA onto the surface of TiO2 for the study of various concentrations of target DNA. The surface of TiO2 nanoparticle film was functionalized with APTES and covalently immobilized with 1 µM probe DNA on the silanized TiO2 nanoparticles surface. The effect of silanization, immobilization and hybridization were quantitatively measured by the output current signal obtained using a picoammeter. The 1 µM target DNA was found to be the most effective target towards the 1 µM probe DNA as the output current signal was within range; while the output current signal of the 10 µM target DNA was observed to beyond the range of the probe DNA control due to the excessive concentration as compared to the probe DNA. This approach has several advantages such as rapid, simple, low cost, and sensitive current signal during detection of different target DNA concentrations.

A Hybrid Density Functional Theory/Molecular Mechanics Approach for Linear Response Properties in Heterogeneous Environments.

PubMed

Rinkevicius, Zilvinas; Li, Xin; Sandberg, Jaime A R; Mikkelsen, Kurt V; Ågren, Hans

2014-03-11

We introduce a density functional theory/molecular mechanical approach for computation of linear response properties of molecules in heterogeneous environments, such as metal surfaces or nanoparticles embedded in solvents. The heterogeneous embedding environment, consisting from metallic and nonmetallic parts, is described by combined force fields, where conventional force fields are used for the nonmetallic part and capacitance-polarization-based force fields are used for the metallic part. The presented approach enables studies of properties and spectra of systems embedded in or placed at arbitrary shaped metallic surfaces, clusters, or nanoparticles. The capability and performance of the proposed approach is illustrated by sample calculations of optical absorption spectra of thymidine absorbed on gold surfaces in an aqueous environment, where we study how different organizations of the gold surface and how the combined, nonadditive effect of the two environments is reflected in the optical absorption spectrum.

Application of functionalized nanofluid in thermosyphon

PubMed Central

2011-01-01

A water-based functionalized nanofluid was made by surface functionalizing the ordinary silica nanoparticles. The functionalized nanofluid can keep long-term stability. and no sedimentation was observed. The functionalized nanofluid as the working fluid is applied in a thermosyphon to understand the effect of this special nanofluid on the thermal performance of the thermosyphon. The experiment was carried out under steady operating pressures. The same work was also explored for traditional nanofluid (consisting of water and the same silica nanoparticles without functionalization) for comparison. Results indicate that a porous deposition layer exists on the heated surface of the evaporator during the operating process using traditional nanofluid; however, no coating layer exists for functionalized nanofluid. Functionalized nanofluid can enhance the evaporating heat transfer coefficient, while it has generally no effect on the maximum heat flux. Traditional nanofluid deteriorates the evaporating heat transfer coefficient but enhances the maximum heat flux. The existence of the deposition layer affects mainly the thermal performance, and no meaningful nanofluid effect is found in the present study. PMID:21846362

Kinetics of laser irradiated nanoparticles cloud

NASA Astrophysics Data System (ADS)

Mishra, S. K.; Upadhyay Kahaly, M.; Misra, Shikha

2018-02-01

A comprehensive kinetic model describing the complex kinetics of a laser irradiated nanoparticle ensemble has been developed. The absorbed laser radiation here serves dual purpose, viz., photoenhanced thermionic emission via rise in its temperature and direct photoemission of electrons. On the basis of mean charge theory along with the equations for particle (electron) and energy flux balance over the nanoparticles, the transient processes of charge/temperature evolution over its surface and mass diminution on account of the sublimation (phase change) process have been elucidated. Using this formulation phenomenon of nanoparticle charging, its temperature rise to the sublimation point, mass ablation, and cloud disintegration have been investigated; afterwards, typical timescales of disintegration, sublimation and complete evaporation in reference to a graphite nanoparticle cloud (as an illustrative case) have been parametrically investigated. Based on a numerical analysis, an adequate parameter space describing the nanoparticle operation below the sublimation temperature, in terms of laser intensity, wavelength and nanoparticle material work function, has been identified. The cloud disintegration is found to be sensitive to the nanoparticle charging through photoemission; as a consequence, it illustrates that radiation operating below the photoemission threshold causes disintegration in the phase change state, while above the threshold, it occurs with the onset of surface heating.

Solid phase monofunctionalization of gold nanoparticles using ionic exchange resin as polymer support.

PubMed

Zou, Jianhua; Dai, Qiu; Wang, Jinhai; Liu, Xiong; Huo, Qun

2007-07-01

A solid phase modification method using anionic exchange resin as polymer support was developed for the synthesis of monofunctional gold nanoparticles. Based on a "catch and release" mechanism to control the number of functional groups attached to the nanoparticle surface, bifunctional thiol ligands with a carboxylic acid end group were first immobilized at a controlled density on anionic exchange resin through electrostatic interactions. Gold nanoparticles were then immobilized to the anionic exchange resin by a one-to-one place exchange reaction between resin-bound thiol ligands and butanethiol-protected gold nanoparticles in solution. After cleaving off from the resin under mild conditions, gold nanoparticles with a single carboxyl group attached to the surface were obtained as the major product. Experimental conditions such as the solvents used for ligand loading and solid phase place exchange reaction, and the loading density of the ligands, were found to play a critical role towards the successful synthesis of monofunctional nanoparticles. Overall, the noncovalent bond-based ligand immobilization technique reported here greatly simplified the process of solid phase monofunctionalization of nanoparticles compared to a previously reported covalent bond-based ligand immobilization technique.

Functionalization of a long period grating coated with gold nanoparticles for glyphosate detection

NASA Astrophysics Data System (ADS)

Heidemann, Bárbara R.; Pereira, Júlia C.; Chiamenti, Ismael; Oliveira, Marcela M.; Muller, Marcia; Fabris, José L.

2017-04-01

This work describes a method for producing a nanostructured fiber optic device for sensing of pesticides in water environment. The device consists of a long period grating with a coating of gold nanoparticles functionalized with cysteamine. The LPG shows attenuation bands near the phase matching turning point at the visible spectral range. A bottom-up production route was used to deposit gold nanoparticles on the fiber surface. Sensitivity to the refractive index of the external medium was measured before and after the layer deposition. Cysteamine was used as a ligand for glyphosate present in water at a concentration of 100 μM.

Synthesis and Characterization of Hyaluronic Acid Modified Colloidal Mesoporous Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Zhang, Wenbiao; Wang, Yu; Li, Zhen; Wang, Wanxia; Sun, Honghao; Liu, Mingxing

2017-12-01

The colloidal mesoporous silica nanoparticles functionalized with hyaluronic acid (CMS-HA) were successfully synthesized by grafting hyaluronic acid onto the external surface of the amino-functionalized mesoporous silica nanoparticles (CMS-NH2). Moreover, the paticle properties of CMS-HA were characterized by fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS) and transmission electron microscopy (TEM). The nanomaterials were negatively charged and had a relatively uniform spherical morphology with about 100 nm in diameter, which could make it more compatible with blood. So the results suggested that the CMS-HA might be a critical nanomaterial for applying in target drug delivery system.

New surface radiolabeling schemes of super paramagnetic iron oxide nanoparticles (SPIONs) for biodistribution studies.

PubMed

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

2015-04-21

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 (14)C, 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 here is applicable to the synthesis of a large class of nanomaterials with multiple core and surface functionalities. This work combined with the biodistribution data suggests that the radiolabeling schemes carried out in this study have broad implications for use in pharmacokinetic studies for a variety of nanomaterials.

New surface radiolabeling schemes of super paramagnetic iron oxide nanoparticles (SPIONs) for biodistribution studies†

PubMed Central

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.

2016-01-01

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 here is applicable to the synthesis of a large class of nanomaterials with multiple core and surface functionalities. This work combined with the biodistribution data suggests that the radiolabeling schemes carried out in this study have broad implications for use in pharmacokinetic studies for a variety of nanomaterials. PMID:25790032

New Surface Radiolabeling Schemes of Super Paramagnetic Iron Oxide Nanoparticles (SPIONs) for Biodistribution Studies

DOE PAGES

Nallathamby, Prakash D.; Mortensen, Ninell P.; Palko, Heather A.; ...

2015-03-02

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 10 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), wasmore » 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 15 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-20 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 25 detection techniques. The radiolabeling approach described here is applicable to the synthesis of a large class of nanomaterials with multiple core and surface functionalities. This work combined with the biodistribution data suggests that the radiolabeling schemes carried out in this study have broad implications for use in pharmacokinetic studies for a variety of nanomaterials.« less

Molecular imaging with targeted perfluorocarbon nanoparticles: Quantification of the concentration dependence of contrast enhancement for binding to sparse cellular epitopes

PubMed Central

Marsh, Jon N.; Partlow, Kathryn C.; Abendschein, Dana R.; Scott, Michael J.; Lanza, Gregory M.; Wickline, Samuel A.

2007-01-01

Targeted, liquid perfluorocarbon nanoparticles are effective agents for acoustic contrast enhancement of abundant cellular epitopes (e.g. fibrin in thrombi) and for lower prevalence binding sites, such as integrins associated with tumor neovasculature. In this study we sought to delineate the quantitative relationship between the extent of contrast enhancement of targeted surfaces and the density (and concentration) of bound perfluorocarbon (PFC) nanoparticles. Two dramatically different substrates were utilized for targeting. In one set of experiments, the surfaces of smooth, flat, avidin-coated agar disks were exposed to biotinylated nanoparticles to yield a thin layer of targeted contrast. For the second set of measurements, we targeted PFC nanoparticles applied in thicker layers to cultured smooth muscle cells expressing the transmembrane glycoprotein “tissue factor” at the cell surface. An acoustic microscope was used to characterize reflectivity for all samples as a function of bound PFC (determined via gas chromatography). We utilized a formulation of low-scattering nanoparticles having oil-based cores to compete against high-scattering PFC nanoparticles for binding, to elucidate the dependence of contrast enhancement on PFC concentration. The relationship between reflectivity enhancement and bound PFC content varied in a curvilinear fashion, and exhibited an apparent asymptote (approximately 16 dB and 9 dB enhancement for agar and cell samples, respectively) at the maximum concentrations (~150 μg and ~1000 μg PFOB for agar and cell samples, respectively). Samples targeted with only oil-based nanoparticles exhibited mean backscatter values that were nearly identical to untreated samples (<1 dB difference), confirming the oil particles’ low-scattering behavior. The results of this study indicate that substantial contrast enhancement with liquid perfluorocarbon nanoparticles can be realized even in cases of partial surface coverage (as might be encountered when targeting sparsely populated epitopes), or when targeting surfaces with locally irregular topography. Furthermore, it may be possible to assess the quantity of bound cellular epitopes through acoustic means. PMID:17434667

Surface-Engineered Multifunctional Eu:Gd2O3 Nanoplates for Targeted and pH-Responsive Drug Delivery and Imaging Applications.

PubMed

Saha, Arindam; Mohanta, Subas Chandra; Deka, Kashmiri; Deb, Pritam; Devi, Parukuttyamma Sujatha

2017-02-01

In this paper, we report the synthesis of surface-engineered multifunctional Eu:Gd 2 O 3 triangular nanoplates with small size and uniform shape via a high-temperature solvothermal technique. Surface engineering has been performed by a one-step polyacrylate coating, followed by controlled conjugation chemistry. This creates the desired number of surface functional groups that can be used to attach folic acid as a targeting ligand on the nanoparticle surface. To specifically deliver the drug molecules in the nucleus, the folate density on the nanoparticle surface has been kept low. We have also modified the drug molecules with terminal double bond and ester linkage for the easy conjugation of nanoparticles. The nanoparticle surface was further modified with free thiols to specifically attach the modified drug molecules with a pH-responsive feature. High drug loading has been encountered for both hydrophilic drug daunorubicin (∼69% loading) and hydrophobic drug curcumin (∼75% loading) with excellent pH-responsive drug release. These nanoparticles have also been used as imaging probes in fluorescence imaging. Some preliminary experiments to evaluate their application in magnetic resonance imaging have also been explored. A detailed fluorescence imaging study has confirmed the efficient delivery of drugs to the nuclei of cancer cells with a high cytotoxic effect. Synthesized surface-engineered nanomaterials having small hydrodynamic size, excellent colloidal stability, and high drug-loading capacity, along with targeted and pH-responsive delivery of dual drugs to the cancer cells, will be potential nanobiomaterials for various biomedical applications.

Enhanced Fluorescence Properties of Carbon Dots in Polymer Films

PubMed Central

Liu, Yamin; Wang, Ping; Shiral Fernando, K. A.; LeCroy, Gregory E.; Maimaiti, Halidan; Harruff-Miller, Barbara A.; Lewis, William K.; Bunker, Christopher E.; Hou, Zhi-Ling; Sun, Ya-Ping

2016-01-01

Carbon dots of small carbon nanoparticles surface-functionalized with 2,2′-(ethylenedioxy)bis(ethylamine) (EDA) were synthesized, and the as-synthesized sample was separated on an aqueous gel column to obtain fractions of the EDA-carbon dots with different fluorescence quantum yields. As already discussed in the literature, the variations in fluorescence performance among the fractions were attributed to the different levels and/or effectiveness of the surface functionalization-passivation in the carbon dots. These fractions, as well as carbon nanoparticles without any deliberate surface functionalization, were dispersed into poly(vinyl alcohol) (PVA) for composite films. In the PVA film matrix, the carbon dots and nanoparticles exhibited much enhanced fluorescence emissions in comparison with their corresponding aqueous solutions. The increased fluorescence quantum yields in the films were determined quantitatively by using a specifically designed and constructed film sample holder in the emission spectrometer. The observed fluorescence decays of the EDA-carbon dots in film and in solution were essentially the same, suggesting that the significant enhancement in fluorescence quantum yields from solution to film is static in nature. Mechanistic implications of the results, including a rationalization in terms of the compression effect on the surface passivation layer (similar to a soft corona) in carbon dots when embedded in the more restrictive film environment resulting in more favorable radiative recombinations of the carbon particle surface-trapped electrons and holes, and also potential technological applications of the brightly fluorescent composite films are highlighted and discussed. PMID:28133537

Coarse grained modeling of directed assembly to form functional nanoporous films

NASA Astrophysics Data System (ADS)

Al Khatib, Amir

A coarse-grained (CG) simulation of polyethylene glycol (PEG) and Polymethylsilsesquixane nanoparticle (PMSSQ) referred to as (NP) at different sizes and concentrations were done using the Martini coarse-grained (CG) force field. The interactions between CG PEG and CG NP were parameterized from the chemical compound of each molecule and based on Martini force field. NP particles migrates to the surface of the substrate in an agreement with the experimental output at high temperature of 800K. This demonstration of nanoparticles-polymer film to direct it to self-assemble a systematically spatial pattern using the substrate surface energy as the key gating parameter. Validation of the model comparing molecular dynamics simulations with experimental data collected from previous study. NP interaction with the substrate at low interactions energy using Lennard-Johns potential were able to direct the NP to self-assemble in a hexagonal shape up to 4 layers above the substrate. This thesis established that substrate surface energy is a key gating parameter to direct the collective behavior of functional nanoparticles to form thin nanoporous films with spatially predetermined optical/dielectric constants.

Nanomaterials for Functional Textiles and Fibers

NASA Astrophysics Data System (ADS)

Rivero, Pedro J.; Urrutia, Aitor; Goicoechea, Javier; Arregui, Francisco J.

2015-12-01

Nanoparticles are very interesting because of their surface properties, different from bulk materials. Such properties make possible to endow ordinary products with new functionalities. Their relatively low cost with respect to other nano-additives make them a promising choice for industrial mass-production systems. Nanoparticles of different kind of materials such as silver, titania, and zinc oxide have been used in the functionalization of fibers and fabrics achieving significantly improved products with new macroscopic properties. This article reviews the most relevant approaches for incorporating such nanoparticles into synthetic fibers used traditionally in the textile industry allowing to give a solution to traditional problems for textiles such as the microorganism growth onto fibers, flammability, robustness against ultraviolet radiation, and many others. In addition, the incorporation of such nanoparticles into special ultrathin fibers is also analyzed. In this field, electrospinning is a very promising technique that allows the fabrication of ultrathin fiber mats with an extraordinary control of their structure and properties, being an ideal alternative for applications such as wound healing or even functional membranes.

Nanomaterials for Functional Textiles and Fibers.

PubMed

Rivero, Pedro J; Urrutia, Aitor; Goicoechea, Javier; Arregui, Francisco J

2015-12-01

Nanoparticles are very interesting because of their surface properties, different from bulk materials. Such properties make possible to endow ordinary products with new functionalities. Their relatively low cost with respect to other nano-additives make them a promising choice for industrial mass-production systems. Nanoparticles of different kind of materials such as silver, titania, and zinc oxide have been used in the functionalization of fibers and fabrics achieving significantly improved products with new macroscopic properties. This article reviews the most relevant approaches for incorporating such nanoparticles into synthetic fibers used traditionally in the textile industry allowing to give a solution to traditional problems for textiles such as the microorganism growth onto fibers, flammability, robustness against ultraviolet radiation, and many others. In addition, the incorporation of such nanoparticles into special ultrathin fibers is also analyzed. In this field, electrospinning is a very promising technique that allows the fabrication of ultrathin fiber mats with an extraordinary control of their structure and properties, being an ideal alternative for applications such as wound healing or even functional membranes.

Nanosized Building Blocks for Customizing Novel Antibiofilm Approaches

PubMed Central

Paula, A.J.; Koo, H.

2016-01-01

Recent advances in nanotechnology provide unparalleled flexibility to control the composition, size, shape, surface chemistry, and functionality of materials. Currently available engineering approaches allow precise synthesis of nanocompounds (e.g., nanoparticles, nanostructures, nanocrystals) with both top-down and bottom-up design principles at the submicron level. In this context, these “nanoelements” (NEs) or “nanosized building blocks” can 1) generate new nanocomposites with antibiofilm properties or 2) be used to coat existing surfaces (e.g., teeth) and exogenously introduced surfaces (e.g., restorative or implant materials) for prevention of bacterial adhesion and biofilm formation. Furthermore, functionalized NEs 3) can be conceived as nanoparticles to carry and selectively release antimicrobial agents after attachment or within oral biofilms, resulting in their disruption. The latter mechanism includes “smart release” of agents when triggered by pathogenic microenvironments (e.g., acidic pH or low oxygen levels) for localized and controlled drug delivery to simultaneously kill bacteria and dismantle the biofilm matrix. Here we discuss inorganic, metallic, polymeric, and carbon-based NEs for their outstanding chemical flexibility, stability, and antibiofilm properties manifested when converted into bioactive materials, assembled on-site or delivered at biofilm-surface interfaces. Details are provided on the emerging concept of the rational design of NEs and recent technological breakthroughs for the development of a new generation of nanocoatings or functional nanoparticles for biofilm control in the oral cavity. PMID:27856967

Nanosized Building Blocks for Customizing Novel Antibiofilm Approaches.

PubMed

Paula, A J; Koo, H

2017-02-01

Recent advances in nanotechnology provide unparalleled flexibility to control the composition, size, shape, surface chemistry, and functionality of materials. Currently available engineering approaches allow precise synthesis of nanocompounds (e.g., nanoparticles, nanostructures, nanocrystals) with both top-down and bottom-up design principles at the submicron level. In this context, these "nanoelements" (NEs) or "nanosized building blocks" can 1) generate new nanocomposites with antibiofilm properties or 2) be used to coat existing surfaces (e.g., teeth) and exogenously introduced surfaces (e.g., restorative or implant materials) for prevention of bacterial adhesion and biofilm formation. Furthermore, functionalized NEs 3) can be conceived as nanoparticles to carry and selectively release antimicrobial agents after attachment or within oral biofilms, resulting in their disruption. The latter mechanism includes "smart release" of agents when triggered by pathogenic microenvironments (e.g., acidic pH or low oxygen levels) for localized and controlled drug delivery to simultaneously kill bacteria and dismantle the biofilm matrix. Here we discuss inorganic, metallic, polymeric, and carbon-based NEs for their outstanding chemical flexibility, stability, and antibiofilm properties manifested when converted into bioactive materials, assembled on-site or delivered at biofilm-surface interfaces. Details are provided on the emerging concept of the rational design of NEs and recent technological breakthroughs for the development of a new generation of nanocoatings or functional nanoparticles for biofilm control in the oral cavity.

A review of molecular phase separation in binary self-assembled monolayers of thiols on gold surfaces

NASA Astrophysics Data System (ADS)

Ong, Quy; Nianias, Nikolaos; Stellacci, Francesco

2017-09-01

Binary self-assembled monolayers (SAMs) on gold surfaces have been known to undergo molecular phase separation to various degrees and have been subject to both experimental and theoretical studies. On gold nanoparticles in particular, binary SAMs ligand shells display intriguing morphologies. Consequently, unexpected behaviors of the nanoparticles with respect to their biological, chemical, and interfacial properties have been observed. It is critical that the phase separation of binary SAMs be understood at both molecular and macroscopic level to create, and then manipulate, the useful properties of the functionalized surfaces. We look into the current understanding of molecular phase separation of binary SAMs on gold surfaces, represented by Au(111) flat surfaces and Au nanoparticles, from both theoretical and experimental aspects. We point out shortcomings and describe several research strategies that will address them in the future. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Pule Pileni.

Dissecting the structure of surface stabilizer on the dispersion of inorganic nanoparticles in aqueous medium

NASA Astrophysics Data System (ADS)

Ding, Yong; Yu, Zongzhi; Zheng, Junping

2017-03-01

Dispersing inorganic nanoparticles in aqueous solutions is a key requirement for a great variety of products and processes, including carriers in drug delivery or fillers in polymers. To be highly functional in the final product, inorganic particles are required to be finely dispersed in nanoscale. In this study, silica was selected as a representative inorganic particle. Surface stabilizers with different chain length and charged group were designed to reveal the influence of electrostatic and van der Waals forces between silica and stabilizer on the dispersion of silica particles in aqueous medium. Results showed surface stabilizer with longer alkyl chain and charged group exerted best ability to deaggregate silica, leading to a hydrodynamic size of 51.1 nm. Surface stabilizer designing with rational structure is a promising solution for deagglomerating and reducing process time and energy. Giving the designability and adaptability of surface stabilizer, this method is of potential for dispersion of other inorganic nanoparticles.

Polymer- and dendrimer-coated magnetic nanoparticles as versatile supports for catalysts, scavengers, and reagents.

PubMed

Kainz, Quirin M; Reiser, Oliver

2014-02-18

The work-up of chemical reactions by standard techniques is often time consuming and energy demanding, especially when chemists have to guarantee low levels of metal contamination in the products. Therefore, scientists need new ideas to rapidly purify reaction mixtures that are both economically and environmentally benign. One intriguing approach is to tether functionalities that are required to perform organic reactions to magnetic nanoparticles, for example, catalysts, reagents, scavengers, or chelators. This strategy allows researchers to quickly separate active agents from reaction mixtures by exploiting the magnetic properties of the support. In this Account, we discuss the main attributes of magnetic supports and describe how we can make the different nanomagnets accessible by surface functionalization. Arguably the most prominent magnetic nanoparticles are superparamagnetic iron oxide nanoparticles (SPIONs) due to their biologically well-accepted constituents, their established size-selective synthesis methods, and their diminished agglomeration (no residual magnetic attraction in the absence of an external magnetic field). However, nanoparticles made of pure metal have a considerably higher magnetization level that is useful in applications where high loadings are needed. A few layers of carbon can efficiently shield such highly reactive metal nanoparticles and, equally important, enable facile covalent functionalization via diazonium chemistry or non-covalent functionalization through π-π interactions. We highlight carbon-coated cobalt (Co/C) and iron (Fe/C) nanoparticles in this Account and compare them to SPIONs stabilized with surfactants or silica shells. The graphene-like coating of these nanoparticles offers only low loadings with functional groups via direct surface modification, and the resulting nanomagnets are prone to agglomeration without effective steric stabilization. To overcome these restrictions and to tune the dispersibility of the magnetic supports in different solvents, we can introduce dendrimers and polymers on Co/C and Fe/C platforms by various synthetic strategies. While dendrimers have the advantage of being able to array all functional groups on the surface, polymers need fewer synthetic steps and higher molecular weight analogues are easily accessible. We present the application of these promising hybrid materials for the extraction of analytes or contaminates from complex aqueous solutions (e.g. waste water treatments or blood analytics), for metal-, organo-, and biocatalysis, and in organic synthesis. In addition, we describe advanced concepts like magnetic protecting groups, a multistep synthesis solely applying magnetic reagents and scavengers, and thermoresponsive self-separating magnetic catalysts. We also discuss the first examples of the use of magnetic scaffolds manipulated by external magnetic fields in flow reactors on the laboratory scale. These hold promise for future applications of magnetic hybrid materials in continuous flow or highly parallelized syntheses with rapid magnetic separation of the applied resins.

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 with different surface arrangements of PS and P2VP ligands supports evidence for the rearrangement of thiol terminated homopolymers. An upper limit estimate of the adsorption energy of nanoparticles uniformly coated with a random arrangement of PS and P2VP ligands where a 10% surface area was occupied by P2VP -mers or chains was approximately 1 kBT, which indicates that such nanoparticles are unlikely to be segregated along the interface, in contrast to the experimental results for nanoparticles with mixed ligand-coated surfaces.

Interaction of PLGA and trimethyl chitosan modified PLGA nanoparticles with mixed anionic/zwitterionic phospholipid bilayers studied using molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Novak, Brian; Astete, Carlos; Sabliov, Cristina; Moldovan, Dorel

2012-02-01

Poly(lactic-co-glycolic acid) (PLGA) is a biodegradable polymer. Nanoparticles of PLGA are commonly used for drug delivery applications. The interaction of the nanoparticles with the cell membrane may influence the rate of their uptake by cells. Both PLGA and cell membranes are negatively charged, so adding positively charged polymers such as trimethyl chitosan (TMC) which adheres to the PLGA particles improves their cellular uptake. The interaction of 3 nm PLGA and TMC-modified-PLGA nanoparticles with lipid bilayers composed of mixtures of phosphatidylcholine and phosphatidylserine lipids was studied using molecular dynamics simulations. The free energy profiles as function of nanoparticles position along the normal direction to the bilayers were calculated, the distribution of phosphatidylserine lipids as a function of distance of the particle from the bilayer was calculated, and the time scale for particle motion in the directions parallel to the bilayer surface was estimated.

Hierarchical nanoparticle assemblies formed by decorating breath figures.

PubMed

Böker, Alexander; Lin, Yao; Chiapperini, Kristen; Horowitz, Reina; Thompson, Mike; Carreon, Vincent; Xu, Ting; Abetz, Clarissa; Skaff, Habib; Dinsmore, A D; Emrick, Todd; Russell, Thomas P

2004-05-01

The combination of two self-assembly processes on different length scales leads to the formation of hierarchically structured nanoparticle arrays. Here, the formation of spherical cavities, or 'breath figures'-made by the condensation of micrometre-sized water droplets on the surface of a polymer solution-that self-assemble into a well-ordered hexagonal array, is combined with the self-assembly of CdSe nanoparticles at the polymer solution-water droplet interface. Complete evaporation of the solvent and water confines the particle assembly to an array of spherical cavities and allows for ex situ investigation. Fluorescence confocal, transmission electron and scanning electron microscope images show the preferential segregation of the CdSe nanoparticles to the polymer solution-water interface where they form a 5-7-nm-thick layer, thus functionalizing the walls of the holes. This process opens a new route to fabricating highly functionalized ordered microarrays of nanoparticles, potentially useful in sensory, separation membrane or catalytic applications.

Heteroaggregation of titanium dioxide nanoparticles with natural clay colloids.

PubMed

Labille, Jérôme; Harns, Carrie; Bottero, Jean-Yves; Brant, Jonathan

2015-06-02

To better understand and predict the fate of engineered nanoparticles in the water column, we assessed the heteroaggregation of TiO2 nanoparticles with a smectite clay as analogues for natural colloids. Heteroaggregation was evaluated as a function of water salinity (10(-3) and 10(-1) M NaCl), pH (5 and 8), and selected nanoparticle concentration (0-4 mg/L). Time-resolved laser diffraction was used, coupled to an aggregation model, to identify the key mechanisms and variables that drive the heteroaggregation of the nanoparticles with colloids. Our data show that, at a relevant concentration, nanoparticle behavior is mainly driven by heteroaggregation with colloids, while homoaggregation remains negligible. The affinity of TiO2 nanoparticles for clay is driven by electrostatic interactions. Opposite surface charges and/or high ionic strength favored the formation of primary heteroaggregates via the attachment of nanoparticles to the clay. The initial shape and dispersion state of the clay as well as the nanoparticle/clay concentration ratio also affected the nature of the heteroaggregation mechanism. With dispersed clay platelets (10(-3) M NaCl), secondary heteroaggregation driven by bridging nanoparticles occurred at a nanoparticle/clay number ratio of greater than 0.5. In 10(-1) M NaCl, the clay was preaggregated into larger and more spherical units. This favored secondary heteroaggregation at lower nanoparticle concentration that correlated to the nanoparticle/clay surface area ratio. In this latter case, a nanoparticle to clay sticking efficiency could be determined.

Long Distance Enhancement of Nonlinear Optical Properties Using Low Concentration of Plasmonic Nanostructures in Dye Doped Monolithic SolGel Materials (Postprint)

DTIC Science & Technology

2016-05-31

www.MaterialsViews.com Synthesis of the Gold Nanoparticles : The Au nanospheres were prepared according to previously reported procedure using the...Au Nanoparticles Using Specifi c Silicone : The synthesis of the functional silicone was previously reported as well as the surface modifi cation of...types of gold nanoparticles (AuNPs) are prepared and polished to high optical quality. Their photophysical properties are investigated. The glass

Preparation of poly-L-lysine functionalized magnetic nanoparticles and their influence on viability of cancer cells

NASA Astrophysics Data System (ADS)

Khmara, I.; Koneracka, M.; Kubovcikova, M.; Zavisova, V.; Antal, I.; Csach, K.; Kopcansky, P.; Vidlickova, I.; Csaderova, L.; Pastorekova, S.; Zatovicova, M.

2017-04-01

This study was aimed at development of biocompatible amino-functionalized magnetic nanoparticles as carriers of specific antibodies able to detect and/or target cancer cells. Poly-L-lysine (PLL)-modified magnetic nanoparticle samples with different PLL/Fe3O4 content were prepared and tested to define the optimal PLL/Fe3O4 weight ratio. The samples were characterized for particle size and morphology (SEM, TEM and DLS), and surface properties (zeta potential measurements). The optimal PLL/Fe3O4 weight ratio of 1.0 based on both zeta potential and DLS measurements was in agreement with the UV/VIS measurements. Magnetic nanoparticles with the optimal PLL content were conjugated with antibody specific for the cancer biomarker carbonic anhydrase IX (CA IX), which is induced by hypoxia, a physiologic stress present in solid tumors and linked with aggressive tumor behavior. CA IX is localized on the cell surface with the antibody-binding epitope facing the extracellular space and is therefore suitable for antibody-based targeting of tumor cells. Here we showed that PLL/Fe3O4 magnetic nanoparticles exhibit cytotoxic activities in a cell type-dependent manner and bind to cells expressing CA IX when conjugated with the CA IX-specific antibody. These data support further investigations of the CA IX antibody-conjugated, magnetic field-guided/activated nanoparticles as tools in anticancer strategies.

Spatial distribution of organic functional groups supported on mesoporous silica nanoparticles: A study by conventional and DNP-enhanced 29Si solid-state NMR

DOE PAGES

Kobayashi, Takeshi; Singappuli-Arachchige, Dilini; Wang, Zhuoran; ...

2016-12-23

Solid-state NMR spectroscopy, both conventional and dynamic nuclear polarization (DNP)-enhanced, was employed to study the spatial distribution of organic functional groups attached to the surface of mesoporous silica nanoparticles via co-condensation and grafting. The most revealing information was provided by DNP-enhanced two-dimensional 29Si– 29Si correlation measurements, which unambiguously showed that post-synthesis grafting leads to a more homogeneous dispersion of propyl and mercaptopropyl functionalities than co-condensation. Furthermore, during the anhydrous grafting process, the organosilane precursors do not self-condense and are unlikely to bond to the silica surface in close proximity (less than 4 Å) due to the limited availability of suitablymore » arranged hydroxyl groups.« less

Switchable host-guest systems on surfaces.

PubMed

Yang, Ying-Wei; Sun, Yu-Long; Song, Nan

2014-07-15

CONSPECTUS: For device miniaturization, nanotechnology follows either the "top-down" approach scaling down existing larger-scale devices or the "bottom-up' approach assembling the smallest possible building blocks to functional nanoscale entities. For synthetic nanodevices, self-assembly on surfaces is a superb method to achieve useful functions and enable their interactions with the surrounding world. Consequently, adaptability and responsiveness to external stimuli are other prerequisites for their successful operation. Mechanically interlocked molecules such as rotaxanes and catenanes, and their precursors, that is, molecular switches and supramolecular switches including pseudorotaxanes, are molecular machines or prototypes of machines capable of mechanical motion induced by chemical signals, biological inputs, light or redox processes as the external stimuli. Switching of these functional host-guest systems on surfaces becomes a fundamental requirement for artificial molecular machines to work, mimicking the molecular machines in nature, such as proteins and their assemblies operating at dynamic interfaces such as the surfaces of cell membranes. Current research endeavors in material science and technology are focused on developing either a new class of materials or materials with novel/multiple functionalities by shifting host-guest chemistry from solution phase to surfaces. In this Account, we present our most recent attempts of building monolayers of rotaxanes/pseudorotaxanes on surfaces, providing stimuli-induced macroscopic effects and further understanding on the switchable host-guest systems at interfaces. Biocompatible versions of molecular machines based on synthetic macrocycles, such as cucurbiturils, pillararenes, calixarenes, and cyclodextrins, have been employed to form self-assembled monolayers of gates on the surfaces of mesoporous silica nanoparticles to regulate the controlled release of cargo/drug molecules under a range of external stimuli, such as light, pH variations, competitive binding, and enzyme. Rotaxanes have also been assembled onto the surfaces of gold nanodisks and microcantilevers to realize active molecular plasmonics and synthetic molecular actuators for device fabrication and function. Pillararenes have been successfully used to control and aid the synthesis of gold nanoparticles, semiconducting quantum dots, and magnetic nanoparticles. The resulting organic-inorganic hydrid nanomaterials have been successfully used for controlled self-assembly, herbicide sensing and detection, pesticide removal, and so forth, taking advantage of the selective binding of pillarenes toward target molecules. Cyclodextrins have also been successfully functionalized onto the surface of gold nanoparticles to serve as recycling extractors for C60. Many interesting prototypes of nanodevices based on synthetic macrocycles and their host-guest chemistry have been constructed and served for different potential applications. This Account will be a summary of the efforts made mainly by us, and others, on the host-guest chemistry of synthetic macrocyclic compounds on the surfaces of different solid supports.

Self-organization of gold nanoparticles on silanated surfaces.

PubMed

Kyaw, Htet H; Al-Harthi, Salim H; Sellai, Azzouz; Dutta, Joydeep

2015-01-01

The self-organization of monolayer gold nanoparticles (AuNPs) on 3-aminopropyltriethoxysilane (APTES)-functionalized glass substrate is reported. The orientation of APTES molecules on glass substrates plays an important role in the interaction between AuNPs and APTES molecules on the glass substrates. Different orientations of APTES affect the self-organization of AuNps on APTES-functionalized glass substrates. The as grown monolayers and films annealed in ultrahigh vacuum and air (600 °C) were studied by water contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, UV-visible spectroscopy and ultraviolet photoelectron spectroscopy. Results of this study are fundamentally important and also can be applied for designing and modelling of surface plasmon resonance based sensor applications.

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.

Thermoacoustic molecular tomography with magnetic nanoparticle contrast agents for targeted tumor detection.

PubMed

Nie, Liming; Ou, Zhongmin; Yang, Sihua; Xing, Da

2010-08-01

The primary feasibility steps of demonstrating the ability of microwave-induced thermoacoustic (TA) in phantoms have been previously reported. However, none were shown to target a diseased site in living subjects in thermoacoustic tomography (TAT) field so far. To determine the expressions of oncogenic surface molecules, it is quite necessary to image tumor lesions and acquire pathogenic status on them via TAT. Compared to biological tissues, iron oxide nanoparticles have a much higher microwave absorbance. Fe3O4/polyaniline (PANI) nanoparticles were prepared via polymerization of aniline in the Fe304 superparamagnetic fluids. Then Fe3O4/PANI was conjugated to folic acid (FA), which can bind specifically to the surface of the folate receptor used as a tumor marker. FA-Fe3O4/PANI targeted tumor was irradiated by pulsed microwave at 6 GHz for thermoacoustic detection and imaging. The effect of the Fe3O4/PANI superparamagnetic nanoparticles for enhancing TAT images was successfully investigated in ex vivo human blood and in vivo mouse tail. Intravenous administration of the targeted nanoparticles to mice bearing tumors showed fivefold greater thermoacoustic signal and much longer elimination time than that of mice injected with nontargeted nanoparticles in the tumor. The specific targeting ability of FA-Fe3O4/PANI to tumor was also verified on fluorescence microscopy. Fabricated iron oxide nanoparticles conjugated with tumor ligands for targeted TAT tumor detection at the molecular level was reported for the first time. The results indicate that thermoacoustic molecular imaging with functionalized iron oxide nanoparticles may contribute to targeted and functional early cancer imaging. Also, the modified iron oxide nanoparticles combined with suitable tumor markers may also be used as novel nanomaterials for targeted and guided cancer thermal therapy.

Graphene-bonded and -encapsulated si nanoparticles for lithium ion battery anodes.

PubMed

Wen, Yang; Zhu, Yujie; Langrock, Alex; Manivannan, Ayyakkannu; Ehrman, Sheryl H; Wang, Chunsheng

2013-08-26

Silicon (Si) has been considered a very promising anode material for lithium ion batteries due to its high theoretical capacity. However, high-capacity Si nanoparticles usually suffer from low electronic conductivity, large volume change, and severe aggregation problems during lithiation and delithiation. In this paper, a unique nanostructured anode with Si nanoparticles bonded and wrapped by graphene is synthesized by a one-step aerosol spraying of surface-modified Si nanoparticles and graphene oxide suspension. The functional groups on the surface of Si nanoparticles (50-100 nm) not only react with graphene oxide and bind Si nanoparticles to the graphene oxide shell, but also prevent Si nanoparticles from aggregation, thus contributing to a uniform Si suspension. A homogeneous graphene-encapsulated Si nanoparticle morphology forms during the aerosol spraying process. The open-ended graphene shell with defects allows fast electrochemical lithiation/delithiation, and the void space inside the graphene shell accompanied by its strong mechanical strength can effectively accommodate the volume expansion of Si upon lithiation. The graphene shell provides good electronic conductivity for Si nanoparticles and prevents them from aggregating during charge/discharge cycles. The functionalized Si encapsulated by graphene sample exhibits a capacity of 2250 mAh g⁻¹ (based on the total mass of graphene and Si) at 0.1C and 1000 mAh g⁻¹ at 10C, and retains 85% of its initial capacity even after 120 charge/discharge cycles. The exceptional performance of graphene-encapsulated Si anodes combined with the scalable and one-step aerosol synthesis technique makes this material very promising for lithium ion batteries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of Immunolabeled Plasmonic Nanoparticles for Cell Surface Receptor Analysis

PubMed Central

Seekell, Kevin; Price, Hillel; Marinakos, Stella; Wax, Adam

2011-01-01

Noble metal nanoparticles hold great potential as optical contrast agents due to a unique feature, known as the plasmon resonance, which produces enhanced scattering and absorption at specific frequencies. The plasmon resonance also provides a spectral tunability that is not often found in organic fluorophores or other labeling methods. The ability to functionalize these nanoparticles with antibodies has led to their development as contrast agents for molecular optical imaging. In this review article, we present methods for optimizing the spectral agility of these labels. We discuss synthesis of gold nanorods, a plasmonic nanoparticle in which the plasmonic resonance can be tuned during synthesis to provide imaging within the spectral window commonly utilized in biomedical applications. We describe recent advances in our group to functionalize gold and silver nanoparticles using distinct antibodies, including EGFR, HER-2 and IGF-1, selected for their relevance to tumor imaging. Finally, we present characterization of these nanoparticle labels to verify their spectral properties and molecular specificity. PMID:21911063

Unusual reactivity of a silver mineralizing peptide.

PubMed

Carter, Carly Jo; Ackerson, Christopher J; Feldheim, Daniel L

2010-07-27

The ability of peptides selected via phage display to mediate the formation of inorganic nanoparticles is now well established. The atomic-level interactions between the selected peptides and the metal ion precursors are in most instances, however, largely obscure. We identified a new peptide sequence that is capable of mediating the formation of Ag nanoparticles. Surprisingly, nanoparticle formation requires the presence of peptide, HEPES buffer, and light; the absence of any one of these compromises nanoparticle formation. Electrochemical experiments revealed that the peptide binds Ag+ in a 3 Ag+:1 peptide ratio and significantly alters the Ag+ reduction potential. Alanine replacement studies yielded insight into the sequence-function relationships of Ag nanoparticle formation, including the Ag+ coordination sites and the residues necessary for Ag synthesis. In addition, the peptide was found to function when immobilized onto surfaces, and the specific immobilizing concentration could be adjusted to yield either spherical Ag nanoparticles or high aspect ratio nanowires. These studies further illustrate the range of interesting new solid-state chemistries possible using biomolecules.