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At least 19 recordsLinked to original sources

Using solution-phase nanoparticles, surface-confined nanoparticle arrays and single nanoparticles as biological sensing platforms.

The intense colors of noble metal nanoparticles have inspired artists and fascinated scientists for hundreds of years. In this review, we describe three sensing platforms based on the tunability of the localized surface plasmon resonance (LSPR) of gold and silver nanoparticles. Specifically, the color associated with solution-phase nanoparticles, surface-confined nanoparticle arrays, and single nanoparticles will be shown to be tunable and useful as platforms for biological sensing.

Algorithms↗

Effect of catalysis on the stability of metallic nanoparticles: Suzuki reaction catalyzed by PVP-palladium nanoparticles.

The small size of nanoparticles makes them attractive in catalysis due to their large surface-to-volume ratio. However, being small raises questions about their stability in the harsh chemical environment in which these nanoparticles find themselves during their catalytic function. In the present work, we studied the Suzuki reaction between phenylboronic acid and iodobenzene catalyzed by PVP-Pd nanoparticles to investigate the effect of catalysis, recycling, and the different individual chemicals on the stability and catalytic activity of the nanoparticles during this harsh reaction. The stability of the nanoparticles to the different perturbations is assessed using TEM, and the changes in the catalytic activity are assessed using HPLC analysis of the product yield. It was found that the process of refluxing the nanoparticles for 12 h during the Suzuki catalytic reaction increases the average size and the width of the distribution of the nanoparticles. This was attributed to Ostwald ripening in which the small nanoparticles dissolve to form larger nanoparticles. The kinetics of the change in the nanoparticle size during the 12 h period show that the nanoparticles increase in size during the beginning of the reaction and level off toward the end of the first cycle. When the nanoparticles are recycled for the second cycle, the average size decreases. This could be due to the larger nanoparticles aggregating and precipitating out of solution. This process could also explain the observed loss of the catalytic efficiency of the nanoparticles during the second cycle. It is also found that the addition of biphenyl to the reaction mixture results in it poisoning the active sites and giving rise to a low product yield. The addition of excess PVP stabilizer to the reaction mixture seems to lead to the stability of the nanoparticle surface and size, perhaps due to the inhibition of the Ostwald ripening process. This also decreases the catalytic efficiency of the nanoparticles due to capping of the nanoparticle surface. The addition of phenylboronic acid is found to lead to the stability of the size distribution as it binds to the particle surface through the O(-) of the OH group and acts as a stabilizer. Iodobenzene is found to have no effect and thus probably does not bind strongly to the surface during the catalytic process. These two results might have an implication on the catalytic mechanism of this reaction.

Journal Article↗

Comparison of the magnetic properties of metastable hexagonal close-packed Ni nanoparticles with those of the stable face-centered cubic Ni nanoparticles.

We report the first magnetic study of pure and metastable hexagonal close-packed (hcp) Ni nanoparticles (sample 1). We also produced stable face-centered cubic (fcc) Ni nanoparticles, as mixtures with the hcp Ni nanoparticles (samples 2 and 3). We compared the magnetic properties of the hcp Ni nanoparticles with those of the fcc Ni nanoparticles by observing the evolution of magnetic properties from those of the hcp Ni nanoparticles to those of the fcc Ni nanoparticles as the number of fcc Ni nanoparticles increased from sample 1 to sample 3. The blocking temperature (T(B)) of the hcp Ni nanoparticles is approximately 12 K for particle diameters ranging between 8.5 and 18 nm, whereas those of the fcc Ni nanoparticles are 250 and 270 K for average particle diameters of 18 and 26 nm, respectively. The hcp Ni nanoparticles seem to be antiferromagnetic for T < T(B) and paramagnetic for T > T(B). This is very different from the fcc Ni nanoparticles, which are ferromagnetic for T < T(B) and superparamagnetic for T > T(B). This unusual magnetic state of the metastable hcp Ni nanoparticles is likely related to their increased bond distance (2.665 angstroms), compared to that (2.499 angstroms) of the stable fcc Ni nanoparticles.

Journal Article↗

Effect of poly(ethylene glycol)-block-polylactide nanoparticles on hepatic cells of mouse: low cytotoxicity, but efflux of the nanoparticles by ATP-binding cassette transporters.

The objective of this paper is to study the effects of poly(ethylene glycol)-block-polylactide (PLA-PEG) nanoparticles on hepatic cells of mouse. Blank PLA-PEG nanoparticles have been successfully prepared and MTT assay suggested that the nanoparticles with HepG2 cell co-culture model did not cause significant changes in membrane integrity in controlled concentration range (0.001-0.1 mg/ml). Immunohistochemical analysis demonstrated that large dose of PLA-PEG nanoparticles injection (42.04 mg/kg, i.v.) did not induce hepatic cell apoptosis. From biochemical assay experiments, although the levels of SOD decreased and those of MDA, NOS increased after treatment with large dose of PLA-PEG nanoparticles injection (42.04 mg/kg, i.v.), they were all not significant (p>0.05). Then Kunming mice were treated with large dose of PLA-PEG nanoparticles (42.04 mg/kg, i.v.) and after 4 days total RNA was isolated to elucidate patterns of gene expression using a mouse cDNA-microarray (SuperArray). Treatment with nanoparticles resulted in over-expression of a lot of ATP-binding cassette (ABC) transporters, especially two ABC transporters (ABCA8 and ABCC5/MRP5), and down-regulation of GSTP1, in comparison with the control. ABCA8 could extrude low molecular weight polymers after PLA-PEG nanoparticles hydrolysis outside the cells. We also discovered that ABCC5 expressed multidrug resistance protein 5 (MRP5) to pump out conjugate (GS-X) of PLA-PEG nanoparticles with GSH. The results were confirmed by RT-PCR. Results of in vitro accumulation and efflux experiments indicated that about 51-52% (51.5% and 52.0%) intracellular PLA-PEG nanoparticles was expulsed after mouse primary hepatocytes reached a saturation uptake of nanoparticles during the concentration range of 750-1000 microg/ml. The results suggested that ABC transporters (especially ABCA8) pump out the polymers after hydrolysis from mouse hepatic cells and large dose of PLA-PEG nanoparticles make mouse hepatic cells gain drug resistance to PLA-PEG nanoparticles.

ATP-Binding Cassette Transporters↗

Nebulization of biodegradable nanoparticles: impact of nebulizer technology and nanoparticle characteristics on aerosol features.

Nanoparticles may be effective drug delivery systems for use in various pulmonary therapeutic schemes. This study investigated the effect of nebulization technology and nanoparticle characteristics on the features of aerosol generation. Suspensions of biodegradable nanoparticles consisting of commercially available poly(lactide-co-glycolide) and novel comb polymers were nebulized with a jet, ultrasonic, and piezo-electric crystal nebulizer. The effects of the nanoparticle suspensions on the aerosol droplet size, as well as the nanoparticle size before and after nebulization, were characterized via laser diffraction. While the individual nanoparticle suspensions showed no clinically relevant influence on aerosol droplet size, as compared to control experiments, an enhanced nanoparticle aggregation within the droplets was observed. This aggregation was further characterized by fluorescence and scanning electron microscopy. Dependency of aggregation on nebulizer technology and nanoparticle characteristics was noted. Nanoparticles exhibiting the highest surface hydrophobicity were particularly susceptible to aggregation when nebulized with a jet nebulizer. Aggregation was reduced with nanoparticles exhibiting a more hydrophilic surface or when using ultrasonic nebulizers. We conclude that the biodegradable nanoparticles contained in the suspensions did not affect the aerosol droplet size in a clinically relevant manner; however, both the nanoparticle characteristics and the technique of aerosol generation influence nanoparticle aggregation occurring during aerosolization.

Aerosols↗

PLGA-mPEG nanoparticles of cisplatin: in vitro nanoparticle degradation, in vitro drug release and in vivo drug residence in blood properties.

The in vitro nanoparticle degradation, in vitro drug release and in vivo drug residence in blood properties of PLGA-mPEG nanoparticles of cisplatin were investigated. The nanoparticles were prepared by a double emulsion method and characterized with regard to their morphology, size, zeta potential and drug loading. The rate of in vitro degradation of the PLGA-mPEG nanoparticles in PBS (pH 7.4) depended on their composition, increasing when the mPEG content (mPEG:PLGA ratio) of the nanoparticles increased. Sustained cisplatin release over several hours from the PLGA-mPEG nanoparticles in vitro (PBS) was observed. The composition of the nanoparticles affected drug release: the rate of release increased when the mPEG content of the nanoparticles increased. Within the range of drug loadings investigated, the drug loading of the nanoparticles did not have any significant effect on drug release. The loading efficiency was low and needs improvement in order to obtain PLGA-mPEG nanoparticles with a satisfactory cisplatin content for therapeutic application. The i.v. administration of PLGA-mPEG nanoparticles of cisplatin in BALB/c mice resulted in prolonged cisplatin residence in systemic blood circulation. The results appear to justify further investigation of the suitability of the PLGA-mPEG nanoparticles for the controlled i.v. delivery and/or targeting of cisplatin.

Animals↗

Formation of gold nanoparticles catalyzed by platinum nanoparticles: assessment of the catalytic mechanism.

The understanding of how the formation of metal nanoparticles in aqueous solutions is influenced by the presence of presynthesized nanoparticles is important for precise control over size, shape, and composition of nanoparticles. New insights into the catalytic mechanism of Pt nanoparticles are gained by studying the formation of gold nanoparticles from the reduction of AuCl(4)(-) in aqueous solution in the presence of presynthesized Pt nanoparticles as a model system. The measurement of changes of the surface plasmon resonance band of gold nanoparticles, along with TEM analysis of particle size and morphology, provided an important means for assessing the reaction kinetics. The reductive mediation of Pt-H species on the Pt nanocrystal surface is believed to play an important role in the Pt-catalyzed formation of gold nanoparticles. This important physical insight is evidenced by comparison of the rates of the Pt-catalyzed formation of gold nanoparticles in the presence and in the absence of hydrogen (H(2)), which adsorb dissociatively on a Pt nanocrystal surface forming Pt-H species. Pt-H effectively mediates the reduction of AuCl(4)(-) toward the formation of gold nanoparticles. Implications of the findings to the controllability over size, composition, and morphology of metal nanoparticles in the aqueous synthesis environment are also discussed.

Journal Article↗

Adsorption of cyanine dyes on gold nanoparticles and formation of J-aggregates in the nanoparticle assembly.

This paper describes the results of an investigation of the interparticle interactions and reactivities in the assembly of gold nanoparticles mediated by cyanine dyes. The combination of the positively charged indolenine cyanine dyes and the negatively charged gold nanoparticles is shown to form a J-aggregate bridged assembly of nanoparticles, in addition to hydrophobic interparticle and electrostatic dye-particle interactions. Such interparticle interactions and reactivities are studied by probing the absorption of J-aggregates and fluorescence from the dyes and the surface plasmon resonance absorption from the nanoparticles. The J-aggregation of the dyes adsorbed on the nanoparticles is shown to play an important role in the assembly of nanoparticles. The spectral evolution of the J-band of the dyes and the surface plasmon resonance band of the nanoparticles was found to be sensitive to the nature of the charge and the structure of the dyes. The fluorescence quenching for the dyes was shown to be quantitatively related to the surface coverage of the dyes on the nanocrystal surfaces. These findings have provided important information for assessing a two-step process involving a rapid adsorption of the dyes on the nanoparticles and a subsequent assembly of the nanoparticles involving a combination of interparticle J-aggregation and hydrophobic interactions of the adsorbed dyes. The results are discussed in terms of the structural effects of the dyes, and the interparticle molecular interactions and reactivities, which provide important physical and chemical insights into the design of dye-nanoparticle structured functional nanomaterials.

Adsorption↗

Highly charging of nanoparticles through electrospray of nanoparticle suspension.

Patterned deposition of nanoparticles is a prerequisite for the application of unique properties of nanoparticles in future nanodevices. Recent development of nanoxerography requires highly charged aerosol nanoparticles to avoid noise deposition due to random Brownian motion. However, it has been known that it is difficult to charge aerosol nanoparticles with more than two elementary charges. The goal of this work is to develop a simple technique for obtaining highly charged monodisperse aerosol nanoparticles by means of electrospray of colloidal suspension. Highly charged aerosol nanoparticles were produced by electrospraying (ES) and drying colloidal suspensions of monodisperse gold nanoparticles. Size and charge distributions of the resultant particles were measured. We demonstrate that this method successfully charges monodisperse nanoparticles very highly, e.g., 122 elementary charges for 25.0 nm, 23.5 for 10.5 nm, and 4.6 for 4.2 nm. The method described here constitutes a convenient, reliable, and continuous tool for preparing highly charged aerosol nanoparticles from suspensions of nanoparticles produced by either wet chemistry or gas-phase methods.

Journal Article↗

Size-dependency of nanoparticle-mediated gene transfection: studies with fractionated nanoparticles.

Nanoparticles formulated from biodegradable polymers such as poly (lactic acid) and poly (D,L-lactide-co-glycolide) (PLGA) are being extensively investigated as non-viral gene delivery systems due to their sustained release characteristics and biocompatibility. PLGA nanoparticles for DNA delivery are mainly formulated using an emulsion-solvent evaporation technique. However, this formulation procedure results in the formation of particles with heterogeneous size distribution. The objective of the present study was to determine the relative transfectivity of the smaller- and the larger-sized fractions of nanoparticles in cell culture. PLGA nanoparticles containing a plasmid DNA encoding luciferase protein as a marker were formulated by a multiple emulsion-solvent evaporation method (mean particle diameter = 97 +/- 3 nm) and were fractionated using a membrane (pore size: 100 nm) filtration technique. The particles that passed through the membrane were designated as the smaller-sized nanoparticles (mean diameter = 70 +/- 2 nm) and the fraction that was retained on the membrane as the larger-sized nanoparticles (mean diameter = 202 +/- 9 nm). The smaller-sized nanoparticles showed a 27-fold higher transfection than the larger-sized nanoparticles in COS-7 cell line and a 4-fold higher transfection in HEK-293 cell line. The surface charge (zeta potential), cellular uptake, and the DNA release were almost similar for the two fractions of nanoparticles, suggesting that some other yet unknown factor(s) is responsible for the observed differences in the transfection levels. The results suggest that the particle size is an important factor, and that the smaller-sized fraction of the nanoparticle formulation predominantly contributes towards their transfection.

Biocompatible Materials↗

Label-free biosensing by surface plasmon resonance of nanoparticles on glass: optimization of nanoparticle size.

The unique optical properties of noble metal nanoparticles have been used to design a label-free biosensor in a chip format. In this paper, we demonstrate that the size of gold nanoparticles significantly affects the sensitivity of the biosensor. Gold nanoparticles with diameters in the range of 12-48 nm were synthesized in solution and sensor chips were fabricated by chemisorption of these nanoparticles on amine-functionalized glass. Sensors fabricated from 39-nm-diameter gold nanoparticles exhibited maximum sensitivity to the change of the bulk refractive index and the largest "analytical volume", defined as the region around the nanoparticle within which a change in refractive index causes a change in the optical properties of the immobilized nanoparticles. The detection limit for streptavidin-biotin binding of a sensor fabricated from 39-nm-diameter nanoparticles was 20-fold better than a previously reported sensor fabricated from 13-nm-diameter gold nanoparticles. We also discuss several other factors that could improve the performance of the next generation of these immobilized metal nanoparticle sensors.

Glass↗

Nanoparticles in plant extracts: influence of drugs on the formation of nanoparticles and precipitates in black tea infusions.

The influence of the neuroleptics fluphenazine and promethazine on the formation of nanoparticles in aqueous tea infusions was investigated using photon correlation spectroscopy. Formation of nanoparticles and of precipitates was observed in decaffeinated tea and caffeine-containing tea. The amount of drug in the nanoparticle fraction was determined at different starting concentrations using high-performance liquid chromatography. In the case of fluphenazine, between 8 and 30% are assigned to the nanoparticles fraction, in the case of promethazine between 30 and 56%. The concentration of free active principle is reduced by about 99% for fluphenazine or by about 90% for promethazine. A loss of pharmacological activity of the neuroleptics is probable. The addition of promethazine to infusions of caffeine containing tea resulted in the formation of nanoparticles with a small size distribution; their mean size was comparable to the diameter of nanoparticles in pure tea infusions. In the case of fluphenazine the mean particle size grew with increasing concentration. Adding promethazine to infusions of decaffeinated tea resulted in the formation of nanoparticles with a broad size distribution. Two different size classes were formed after addition of fluphenazine. Caffeine and neuroleptics both take part in the formation of nanoparticles in caffeine containing tea. The particles were visualized using scanning electron microscopy. Molecular modelling calculations were performed to investigate probable geometries between neuroleptics and thearubigins.

Caffeine↗

Nanoparticle based systemic gene therapy for lung cancer: molecular mechanisms and strategies to suppress nanoparticle-mediated inflammatory response.

Cancer gene therapy for the treatment of lung cancer has shown promise in the laboratory and in Phase I/II clinical trials. However, it is currently limited to treating localized tumors due to host-immunity against the gene delivery vector and the transgene. Therefore, there is a tremendous effort to develop and test alternate gene delivery vectors that are efficient, non-immunogenic, and applicable for systemic therapy. One such gene delivery vehicle is the non-viral vector, DOTAP:cholesterol (DOTAP:Chol) nanoparticle. Preclinical studies from our laboratory has shown that DOTAP:Chol. nanoparticles are effective systemic gene delivery vectors that efficiently deliver tumor-suppressor genes to disseminated lung tumors. Based on our findings we have recently initiated a Phase-I trial for systemic treatment of lung cancer using a novel tumor suppressor gene, FUS1. Although DOTAP:Chol. nanoparticles complexed to DNA (DNA-nanoparticles) are efficient vectors for systemic therapy, induction of an inflammatory response in a dose-dependent fashion has also been observed thereby limiting its use. A better understanding of the underlying mechanism for DNA-nanoparticles-mediated inflammatory response will allow us to develop strategies to suppress inflammation and expand the therapeutic window in treating human cancer. In the present study we conducted experiments examining the mechanism of nanoparticle-mediated inflammatory response in vitro and in vivo. We demonstrate that systemic administration of DNA-nanoparticles induced multiple signaling molecules both in vitro and in vivo that are associated with inflammation. Use of small molecule inhibitors against the signaling molecules resulted in their suppression and thereby reduced inflammation without affecting transgene expression. Our results provide a rationale to use small molecule inhibitors to suppress nanoparticle-mediated inflammation when administered systemically. Further development and testing will allow us to incorporate this strategy into future clinical trials that is based on systemic non-viral vector gene therapy.

Animals↗

Magnetic properties of monodisperse NiHx nanoparticles and comparison to those of monodisperse Ni nanoparticles.

We produced, for the first time, monodisperse NiH(x) nanoparticles with particle diameters of 7.0 nm and investigated their magnetic properties. We also produced monodisperse Ni nanoparticles with nearly the same particle diameters as those of NiH(x) nanoparticles as a comparison. The magnetic properties of NiH(x) nanoparticles were quite different from those of Ni nanoparticles. We observed two compositional phases in NiH(x) nanoparticles, similar to bulk material: one is the nearly pure Ni phase with the blocking temperature (T(B)) of 11 K and the other is the hydride phase. We observed T(B) of 40 K in Ni nanoparticles.

Hydrogen↗

Water-soluble nanoparticles from random copolymer and oppositely charged surfactant, 3a. Nanoparticles of poly(ethylene glycol)-based cationic random copolymer and fatty acid salts.

In this report, we investigate the nanoparticle formation between random copolymers (RCPs) of methoxy-poly(ethylene glycol) monomethacrylate (MePEGMA) and (3-(methacryloylamino)propyl)trimethylammonium chloride (MAPTAC) and oppositely charged natural surfactants, sodium oleate and sodium laurate, using turbidimetric titration, steady-state fluorescence, dynamic light scattering, and electron microscopy. Though sodium oleate and sodium laurate are sparingly soluble in water, the nanoparticle complexes formed between the RCPs and these surfactants are soluble in the entire range of compositions studied here, including the stoichiometric electronetural complexes. The spherical nature of these nanoparticle complexes is revealed by electron microscopic (EM) analysis. Dynamic light scattering (DLS) showed that the average diameters of the nanoparticles are in the range 50 to 150 nm, which is supported by EM analysis. Pyrene fluorescence experiments suggested that these soluble nanoparticles have hydrophobic cores, which may solubilize hydrophobic drug molecules. The polarity index (I(1)/I(3)) obtained from the pyrene fluorescence spectra and the conductometric measurements showed that the critical concentration of fatty acid salts needed to obtain nanoparticles are in the order of 10(-4) M. Further, the complexation of such poorly water-soluble amphiphilic surfactants with polymers offers a useful method for the immobilization of hydrophobic compounds towards water-soluble drug carrier formulations. The formation of water-soluble nanoparticles by the self-assembly of fatty acid salts upon interacting with oppositely charged poly(ethylene glycol)-based polyions.

Bile Acids and Salts↗

Thin films of Ag nanoparticles prepared from the reduction of AgI nanoparticles in self-assembled films.

A novel method for the preparation of thin films of Ag nanoparticles is reported. Using mercaptoacetic acid as the stabilizing agent, AgI nanoparticles were prepared in aqueous solution. And based on electrostatic interactions, the thiol-passivated AgI nanoparticles were assembled in a self-assembled film by alternative deposition with a cationic polyelectrolyte. Then the AgI nanoparticles in the composite film were reduced by NaBH(4), which resulted in the formation of a thin film of Ag nanoparticles. UV-visible spectra and X-ray photoelectron spectroscopy data confirmed the transformation from AgI to Ag. Atomic force microscopy (AFM) showed that the formed Ag nanoparticles distributed on the film homogeneously. Surface-enhanced Raman spectroscopy (SERS) measurement indicated that the prepared thin films could be used as effective SERS substrates. The reduction process was also carried out by UV light at selective surface regions, which resulted in the formation of patterned nanoparticle arrays.

Journal Article↗

Synthesis of dendrimer-protected TiO2 nanoparticles and photodegradation of organic molecules in an aqueous nanoparticle suspension.

Dendrimer-protected TiO2 nanoparticles were synthesized by hydrolysis of TiCl4 in solutions of poly(amido amine) dendrimers (64 terminals) under cooling. The morphology of dendrimers surrounding TiO2 nanoparticles depended on the terminal groups (amine, carboxyl, hydroxy) of dendrimers. The size (4.4-6.7 nm) of dendrimer-protected TiO2 nanoparticles was slightly smaller than that (7.5 nm) of bare TiO2 nanoparticles. The photodegradation of 2,4-dichlorophenoxyacetic acid revealed that dendrimer-protected TiO2 nanoparticles are more active as a photocatalyst than TiO2 nanoparticles without protectors. This suggests that the dendrimer acts as a reservoir of photoreacting reagents besides acting as a protector of nanoparticles.

Journal Article↗

Facile fabrication of Ag-Pd bimetallic nanoparticles in ultrathin TiO(2)-gel films: nanoparticle morphology and catalytic activity.

Ag-Pd bimetallic nanoparticles were prepared directly in ultrathin TiO(2)-gel films by a stepwise ion-exchange/reduction approach. Ion-exchange sites were created in ultrathin films using Mg(2+) ions as template. Ag(+) ion was then incorporated by ion exchange, and converted into metallic nanoparticles by low-temperature H(2) plasma, regenerating ion-exchange sites. The same procedure was then carried out for Pd(2+) ion, producing Pd-on-Ag bimetallic nanoparticles, as TEM observation and plasmon resonance absorption indicate. By contrast, reversed metal incorporation procedure appeared to give a mixture of individual Ag and Pd nanoparticles, as confirmed by TEM, absorption spectroscopy and X-ray photoelectron spectroscopy. For hydrogenation of methyl acrylate, the catalytic activity of the Pd-on-Ag nanoparticle is 367 times as large as that of commercial Pd black and 1.6 times as large as that of Pd monometallic nanoparticle. The outstanding catalytic activity was explicable by the large fraction of the surface-exposed Pd atoms. The formation process of the bimetallic nanoparticle and their general morphological feature are discussed.

Journal Article↗