Linear assembly of gold nanoparticle clusters via centrifugation.

Centrifugation is widely used in the synthesis and handling of solution-phase nanoparticles to improve their purity and to change the composition of the solvent. Herein, we couple the optical properties of citrate-stabilized gold nanoparticles and silica encapsulation to investigate how centrifugation impacts the formation of stabilized nanoparticle clusters in solution without the use of linker molecules or asymmetric functionalization. Gold nanoparticles preconcentrated using a high (9,400) g force result in linear assemblies of gold cores that are spaced by approximately 1-4 nm within Au(n)@SiO(2) structures (n = number of gold nanoparticle cores per silica shell) with approximately 30% monomers, 30% dimers, 20% trimers, and 10% 4-7mers. In comparison, nanoparticles preconcentrated using (stirred) ultrafiltration and low (23) g force centrifugation have statistically identical cluster distributions (90% monomers, 9% dimers, and 1% trimers) whereas nanoparticles that are not preconcentrated always exhibit 100% monomers using the same silica coating procedure. We hypothesize that under high g force, the electrical double layer surrounding the gold nanoparticles is slightly polarized thereby increasing the attraction between nanoparticles and the formation of stable clusters. The conductivity of the solution plays an important role in this stabilization. This novel demonstration of linear cluster formation of gold nanoparticles using centrifugation suggests that this commonly used preparative tool can both positively or negatively impact the fundamental properties of these materials and their use in various applications.

Ligand-stabilized metal nanoparticles in organic solvent.

This critical review reports the fundamental behavior of metal nanoparticles in different organic solvents, i.e., metal organosol. An overview on metal organosol and then their smart synthetic approaches, characterization, and potential applications in the fields of catalysis and spectroscopy with special emphasis on SERS are embodied. Aspects of organosol fabrication, stabilization, morphology control, growth mechanisms, and physical properties as mono- and bimetallic nanoparticles are discussed. The article inspires the repetitive usage of metal nanoparticles as stable deliverable organic and molecular compounds.

Oxidase-like activity of polymer-coated cerium oxide nanoparticles.

Inorganic enzyme? Ceria nanoparticles exhibit unique oxidase-like activity at acidic pH values. These redox catalysts can be used in immunoassays (ELISA) when modified with targeting ligands (see picture; light blue and yellow structures are nanoparticles with attached ligands). This modification allows both for binding and for detection by the catalytic oxidation of sensitive colorimetric dyes (e.g. TMB).

Synthesis, magnetic characterization and sensing applications of novel dextran-coated iron oxide nanorods.

Monodisperse, water-soluble dextran-coated iron oxide (Fe(3)O(4)) nanorods were synthesized using a facile and scalable approach. Our room temperature method involves the mixing of an acidic solution of iron salts with a basic solution of ammonium hydroxide to facilitate initial formation of iron oxide crystals. The stability, crystalinity and shape of these nanorods depends on the time of addition of the dextran, as well as the degree of purity of the polymer. The as-synthesized nanorods exhibit unique magnetic properties, including superparamagnetic behavior and high spin-spin water relaxivity (R2). Additionally, they possess enhanced peroxidase activity when compared to those reported in the literature for spherical iron oxide nanoparticles. Thus, this high yield synthetic method for polymer-coated iron oxide nanorods will expedite their use in applications from magnetic sensors, devices and nanocomposites with magnetic and catalytic properties.

Rapid nanoparticle-mediated monitoring of bacterial metabolic activity and assessment of antimicrobial susceptibility in blood with magnetic relaxation.

Considering the increased incidence of bacterial infections and the emergence of multidrug resistant bacteria at the global level, we designed superparamagnetic iron oxide nanoparticles as nanosensors for the assessment of antimicrobial susceptibility through magnetic relaxation. In this report, we demonstrate that iron oxide nanosensors, either dextran-coated supplemented with Con A or silica-coated conjugated directly to Con A, can be used for the fast (1) quantification of polysaccharides, (2) assessment of metabolic activity and (3) determination of antimicrobial susceptibility in blood. The use of these polysaccharide nanosensors in the determination of antimicrobial susceptibility in the clinic or the field, and the utilization of these nanoprobes in pharmaceutical R&D are anticipated.

Dextran-coated gold nanoparticles for the assessment of antimicrobial susceptibility.

Bacteria rapidly evolve mechanisms to become resistant to antibiotics. Therefore, identifying an effective antibiotic or antibacterial agent and administering it at concentrations that will successfully prevent bacterial growth (antimicrobial susceptibility) is critical for health care decision making and vital for the battle against multi-drug-resistant bacteria. Currently, the determination of antimicrobial susceptibility requires at least 24 h. Herein, we describe a nanoparticle-based antimicrobial susceptibility assay based on the concanavalin A-induced clustering of dextran-coated gold nanoparticles, which sense the presence of available complex carbohydrates in bacterial suspension. Under conditions of bacterial growth inhibition, addition of concanavalin A results in the formation of extensive dextran gold nanoassemblies, which are facilitated by the presence of free carbohydrates in solution and result in large shifts in the surface plasmon band of the nanoparticles. Meanwhile, at conditions of increased bacterial growth, a decrease in the amount of free carbohydrates in solution will occur due to an increased carbohydrate uptake by the proliferating bacteria. This will result in a decrease in the size of the gold nanoparticle clusters and an increase in the number of nanoparticles that bind to bacterial surface carbohydrates, causing lower shifts in the plasmonic band. The gold nanoparticle-based assessment of antimicrobial susceptibility yields results within 3 h and can be used for the high-throughput screening of samples during epidemics and identification of potential antimicrobial agents to expedite clinical decision-making in point-of-care diagnostics.

Synthesis of plant-mediated gold nanoparticles and catalytic role of biomatrix-embedded nanomaterials.

Growth of Sesbania seedlings in chloroaurate solution resulted in the accumulation of gold with the formation of stable gold nanoparticles in plant tissues. Transmission electron microscopy revealed the intracellular distribution of monodisperse nanospheres, possibly due to reduction of the metal ions by secondary metabolites present in cells. X-ray absorption near-edge structure and extended X-ray absorption fine structure demonstrated a high degree of efficiency for the biotransformation of Au(III) into Au(0) by planttissues. The catalytic function of the nanoparticle-rich biomass was substantiated by the reduction of aqueous 4-nitrophenol (4-NP). This is the first report of gold nanoparticle-bearing biomatrix directly reducing a toxic pollutant, 4-NP.

Room temperature synthesis of coinage metal (Ag, Cu) chalcogenides.

Coinage metal chalcogenides in their nanoregime have been synthesized in aqueous medium at room temperature by mixing the nanoparticles of silver or copper with selenium nanoparticles which are authenticated by UV-vis, XRD and TEM analyses.

Reduction of methylene blue by thiocyanate: kinetic and thermodynamic aspects.

This article reports the reduction of methylene blue (MB) by thiocyanate ions (SCN(-)) in aqueous and micellar solutions. Thiocyanate ions are found to be an effective reducing agent for the decolorization of methylene blue under ambient condition. Effects of salting-in and salting-out agents have been investigated for real-time application in the reduction process. The salting-in agent urea has been found to uniquely enhance the rate of the reduction of MB by thiocyanate ion in the presence of micelles. Again, the catalytic activity of nanoparticles in the reduction of MB has also been studied. Detailed kinetic and thermodynamic aspects have been considered to realize the interaction between methylene blue and thiocyanate. Kinetic studies revealed that the reaction is reversible and follows first-order reaction kinetics.

Layer-by-layer deposition of bimetallic nanoshells on functionalized polystyrene beads.

Bimetallic nanoshells on functionalized polystyrene beads have been fabricated through a layer-by-layer deposition technique exploiting electrostatic interaction. The synthesis has been achieved through the immobilization and successive reduction of the corresponding precursor ions. It has been shown that the thickness of the shell can be controlled by a number of cyclic depositions of respective metals onto the surface of the polystyrene beads.

Synthesis and characterization of N,N-dimethyldodecylamine-capped Aucore-Pdshell nanoparticles in toluene.

In this paper a convenient route for synthesizing Au(core)-Pd(shell) bimetallic nanoparticles in toluene has been reported as a result of co-reduction of gold(III) and palladium(II) precursors in toluene. N,N-Dimethyldodecylamine was used as a capping agent for the core-shell particles, which not only imparts stability to the organosol but also controls morphology of the evolved particles. The particles were characterized using UV-visible, transmission electron microscopy, and X-ray diffraction measurements. All results substantiate the formation of core-shell structure of the synthesized particles.

Photo-induced decolorization of dimethylmethylene blue with selenious acid: a novel method to examine selective monomer-dimer distribution of the dye in micelle.

In this report, selenious acid (H2SeO3) has been exploited to study the decolorization of a cationic dye, dimethylmethylene blue (DMMB) with UV-light. Micelles have effectively been employed as organized media to promote the rate of decolorization of the dye molecules. Micellar catalysis has been explained as a consequence of electrostatic, hydrophobic and charge transfer interactions. It has also been shown that strong charge transfer and electrostatic interaction lead to an appreciable enhancement of the reaction rate in micelle, whereas, weak hydrophobic interaction is of marginal importance. Existence of monomer-dimer equilibrium for the dye molecules under certain selective environments has been identified spectrophotometrically. Then the shift of dimer-monomer equilibrium of the dye has been successfully studied in aqueous and micellar environments exploiting photodecolorization process for the dye in solution. 'Salting-in' and 'salting-out' agents were introduced into the reaction mixture to examine the viability of the dye decolorization process for dye contaminated water samples.

Size-selective synthesis and stabilization of gold organosol in C(n)TAC: enhanced molecular fluorescence from gold-bound fluorophores.

Gold nanoparticles of variable sizes have been synthesized in toluene employing two-phase (water-toluene) extraction of AuCl4- followed by its reduction with sodium borohydride in the presence of a series of cationic surfactants of a homologous series having the general formula C(n)TAC. The solubility features of the gold particles in the organic solvent have been accounted qualitatively by calculating the van der Waals interaction potential between the particles. The effect of thermal energy and medium dielectric constant on the stability of metal particles has been studied by measuring the surface plasmon resonance. The stabilization of surfactant-mediated gold particles as hydrosol or organosol has been elucidated by considering the double-layer interaction as a function of the dielectric constant of the solvent medium. The influence of the counterion of the phase transfer reagent and stabilizing ligand on the photochemical stability of the gold colloids has been investigated. The fluorescence probe 1-methylaminopyrene (MAP) was considered for the surface functionalization of the gold particles, and it has been found that there is an enhancement of molecular fluorescence from the gold-probe assembly.

Synthesis, characterization, and optical properties of AuSe nanoalloys.

A solution phase approach to synthesize a new metal-semiconductor nanocomposite, AuSe nanoalloy has been reported. The synthesis has been achieved through UV-photoactivation of preformed Au and Se nanoparticles in micelle. Non-ionic surfactant Triton X-100 was exploited as a micellar medium for effective fusion of gold and selenium particles under UV. Both physical and chemical studies have been performed to characterize the composition and morphology of the particles. UV-visible, TEM, SEM, XPS and AFM analyses were done for characterization purpose. The optical properties of nanocomposites have been substantiated through their interaction with a fluorescent probe, eosin in aqueous solution. The spectroscopic investigation of dye-metal-semiconductor assembly has been examined critically. It has been found that the dye experiences J and H types of aggregation on the surfaces of gold and selenium nanoparticles respectively. Again, the composition dependent change of the emission profile of the probe on different nanocomposite surfaces has been rationalized in accordance with the molecular dimerization of the dye.

Immobilization and recovery of au nanoparticles from anion exchange resin: resin-bound nanoparticle matrix as a catalyst for the reduction of 4-nitrophenol.

The immobilization of gold nanoparticles in anion exchange resin and their quantitative retrieval by means of a cationic surfactant, cetylpyridinium chloride, is studied. The resin-bound gold nanoparticles (R-Au) have been used successfully as a solid-phase catalyst for the reduction of 4-nitrophenol by sodium borohydride. At the end of the reaction, the solid matrix remains activated and separated from the product. The recycling of catalyst particles after the quantitative reduction of 4-nitrophenol and the recovery of gold nanoparticles with unaffected particle morphology from the resin-bound gold nanoparticle entity have been reported.

A new route to obtain shape-controlled gold nanoparticles from Au(III)-beta-diketonates.

Ligands with a beta-diketone skeleton have been employed for the first time as reductant to produce ligand stabilized gold nanoparticles of different shapes from aqueous HAuCl(4) solution. Evolution of stable gold nanoparticles follows first order (k approximately equal to 10(-2) min(-1)) kinetics with respect to Au(0) concentration. Growth of particles of different shapes (spherical or triangular or hexagonal) goes hand in hand under the influence of different beta-diketones, which have excellent capping and reducing properties. Chlorine insertion was observed to take place in the beta-diketone skeleton.

Solution phase evolution of AuSe nanoalloys in Triton X-100 under UV-photoactivation.

A solution phase UV-irradiation technique has been exploited to produce an AuSe nanoalloy through fusion of preformed Au (photoproduced) and Se (chemically prepared) in a micellar (TX-100) medium.

Emission behavior of 1-methylaminopyrene in aqueous solution of anionic surfactants.

A new fluorescent probe, methylamino derivative of pyrene, has been considered to characterize the concentration dependent emission behavior of an aqueous solution of anionic surfactants, viz., SDS, DSS, and SDBS. It was found that the emission of the probe is uniquely sensitive to the changes in surfactant (anionic) concentration due to the functional group effect of the probe over the parent moiety, pyrene. Here, 1-methylaminopyrene (MAP) showed significant quenching of emission well below the critical micellar concentration (cmc) of the surfactant. Excimer emission of the probe due to the formation of premicellar aggregates of the surfactant solutions at a concentration close to but below the cmc and again an enhanced emission of the probe above the cmc were observed as a consequence of definite MAP-surfactant interactions. These observations assisted the possible quantification ofsurfactant concentrations and their chain length dependent premicellar aggregate formations. Significant monomer emission in relation to probe distribution in micelle was analytically authenticated. Dynamic light scattering (DLS) studies revealed the incorporation of the probe molecules in the micellar core. The fluorophore emission showed nonlinear behavior when the surfactant concentration was far above the cmc. Abrupt changes in the emission characteristics in relation to the micellar concentration led to the determination of the cmc of the surfactants.