Preparation of sterically stabilized gold nanoparticles for plasmonic applications

Plasmonic nanoparticles such as those of gold or silver have been recently investigated as a possible way to improve light absorption in thin film solar cells. Here, a simple method for the preparation of spherical plasmonic gold nanoparticles in the form of a colloidal solution is presented. The nanoparticle diameter is controlled in the range from several nm to tens of nm depending on the synthesis parameters with the size dispersion down to 14 %. The synthesis is based on thermal decomposition and reduction of the chloroauric acid in the presence of a stabilizing capping agent (surfactant) that is very slowly injected into the hot solvent. The surfactant prevents uncontrolled nanoparticle aggregation during the growth process. The nanoparticle size and shape depend on the type of the stabilizing agent. Surfactants with different lengths of the hydrocarbon chains such as Z-octa-9-decenylamine (oleylamine) with AgNO₃ and polyvinylpyrrolidone with AgNO₃ were used for the steric stabilization. Hydrodynamic diameter of the gold nanoparticles in the colloidal solution was determined by dynamic light scattering while the size of the nanoparticle metallic core was found by small-angle X-ray scattering. The UV-VIS-NIR spectrophotometer measurements revealed a plasmon resonance absorption in the 500–600 nm range. Self-assembled nanoparticle arrays on a silicon substrate were prepared by drop casting followed by spontaneous evaporation of the solvent and by a modified Langmuir-Blodgett deposition. The degree of perfection of the self-assembled arrays was analyzed by scanning electron microscopy and grazing-incidence small-angle X-ray scattering. Homogeneous close-packed hexagonal ordering of the nanoparticles stretching over large areas was evidenced. These results document the viability of the proposed nanoparticle synthesis for the preparation of high-quality plasmonic templates for thin film solar cells with enhanced power conversion efficiency, surface enhanced Raman scattering, and other applications.     

Extinction coefficient of gold nanoparticles with different sizes and different capping ligands

Extinction coefficients of gold nanoparticles with core size ranging from approximately 4 to 40 nm were determined by high resolution transmission electron microscopy analysis and UV-vis absorption spectroscopic measurement. Three different types of gold nanoparticles were prepared and studied: citrate-stabilized nanoparticles in five different sizes; oleylamide-protected gold nanoparticles with a core diameter of 8 nm, and a decanethiol-protected nanoparticle with a diameter of around 4 nm. A linear relationship between the logarithms of extinction coefficients and core diameters of gold particles was found independent of the capping ligands on the particle surface and the solvents used to dissolve the nanoparticles. This linear relation may be used as a calibration curve to determine the concentration or average size of an unknown nanoparticle or nanoparticle-biomolecule conjugate sample.     

Controlled interparticle spacing for surface-modified gold nanoparticle aggregates

Aggregation of gold nanoparticles of increasing size has been studied as a consequence of adsorption of 2-aminothiophenol (ATP) on gold nanoparticle surfaces. The capping property of ATP in the acidic pH range has been accounted from UV-vis absorption spectroscopy and surface-enhanced Raman scattering (SERS) studies. The effect of nanoparticle size (8-55 nm) on the nature of aggregation as well as the variation in the optical response due to variable degree of interparticle coupling effects among the gold particles have been critically examined. Various techniques such as transmission electron microscopy, X-ray diffraction, zeta-potential, and average particle size measurement were undertaken to characterize the nanoparticle aggregates. The aggregate size, interparticle distances, and absorption band wavelengths were found to be highly dependent on the pH of the medium and the concentration of the capping agent, ATP. The acquired SERS spectra of ATP relate the interparticle spacing. It has been observed that the SERS signal intensities are different for different sized gold nanoparticles.     

Green synthesis of well-dispersed gold nanoparticles using Macrotyloma uniflorum

The synthesis of metal nanoparticles of different sizes, shapes, chemical composition and controlled monodispersity is an important area of research in nanotechnology because of their interesting physical properties and technological applications. Present work describes an eco-friendly method for the synthesis of spherical gold nanoparticles using aqueous extract of Macrotyloma uniflorum. The effects of quantity of extract, temperature and pH on the formation of nanoparticles are studied. The nanoparticles are characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and FTIR analysis. The high crystallinity of nanoparticles with fcc phase is evident from HRTEM images, SAED and XRD patterns. Synthesized nanoparticles have size in the range 14-17nm. FTIR spectrum indicates the presence of different functional groups present in the bio-molecule capping the nanoparticles. The possible mechanism leading to the formation of gold nanoparticles is suggested.     

稳定分散的纳米银溶胶的制备及其表征

Stable aqueous dispersive colloidal Ag nanoparticles were prepared by reducing silver nitrate with sodium borohydride in the presence of 3-mercaptopropionic acid. The formation process of the Ag nanoparticles was investigated by UV-Visible spectroscopy and transmission electron microscopy. The results show that the spherical and rodlike particles and aggregates are formed in the initial stage of the reaction， then the rodlike particles and aggregates are gradually decomposed into small spherical particles， and the final obtained Ag nanoparticles with an average size of 8 nm are in uniform shapes and narrow size distribution， and the colloid remains stable for more than one month， which makes it convenient for use in practice. The presence of capping agent plays an extra role over nanoparticles stabilization and morphology. The presence of capping agent on the surface of Ag nanoparticle is confirmed by the X-ray photoelectron spectroscopy. It is found that Ag nanoparticles are negatively charged in alkaline condition， whereas they are positively charged in acid condition. Electrosteric effect is responsible for their long-term stability.     

Synthesis of highly faceted pentagonal- and hexagonal-shaped gold nanoparticles with controlled sizes by sodium dodecyl sulfate

We report the synthesis of pentagonal- and hexagonal-shaped gold nanoparticles with controlled diameters ranging from 5 to 50 nm. These nanoparticles were prepared by a seeding growth approach. Sodium dodecyl sulfate (SDS) molecules served as the capping agent to restrict the particle size. In addition, the formation of highly faceted gold nanoparticles may be facilitated by the possibly ineffective capping interactions between the lamellar micellar structures formed by the SDS molecules and the gold nanoparticles. The crystal structure of the highly faceted particles was found to consist of mostly [111] surfaces as particle size increases, as revealed by both TEM and XRD results.     

Single-step biofriendly synthesis of surface modifiable, near-spherical gold nanoparticles for applications in biological detection and catalysis

There is an increased interest in understanding the toxicity and rational design of gold nanoparticles (GNPs) for biomedical applications in recent years. Such efforts warrant reliable, viable, and biofriendly synthetic methodology for GNPs with homogeneous sizes and shapes, particularly sizes above 30 nm, which is currently challenging. In the present study, an environmentally benign, biofriendly, single-step/single-phase synthetic method using dextrose as a reducing and capping agent in a buffered aqueous solution at moderate temperature is introduced. The resulting GNPs are near-spherical, stable, catalytically active, place exchangeable, and water-soluble within the size range of 10-120 nm. The added advantage of the biologically friendly reaction medium employed in this new synthetic approach provides a method for the direct embedment/integration of GNPs into biological systems such as the E. coli bacterium without additional capping ligand or surface modification processes.     

Synthesis of uniform gold nanoparticles using non-pathogenic bio-control agent: evolution of morphology from nano-spheres to triangular nanoprisms

Green synthesis of gold nanospheres with uniform diameter and triangular nanoprisms with optically flat surface was carried out using a non-pathogenic bio-control agent Trichoderma asperellum for reduction of HAuCl(4). Kinetics of the reaction was monitored by UV-Vis absorption spectroscopy. No additional capping/complexing agent was used for stabilizing the gold nanoparticles. Evolution of morphology from pseudospherical nanoparticles to triangular nanoprisms was studied by transmission electron microscopy (TEM). It revealed that three or more pseudospheres fused to form nanoprisms of different shapes and sizes. Slow rate of reduction of HAuCl(4) by constituents of cell-free fungal extract was instrumental in producing such exotic morphologies. Isolation of gold nanotriangles from the reacting masses was achieved by differential centrifugation.     

Biosynthesis of Au nanoparticles using olive leaf extract: 1st Nano Updates

The biological synthesis of gold nanoparticles (AuNPs) of various shapes (triangle, hexagonal, and spherical) using hot water olive leaf extracts as reducing agent is reported. The size and the shape of Au nanoparticles are modulated by varying the ratio of metal salt and extract in the reaction medium. Only 20 min were required for the conversion into gold nanoparticles at room temperature, suggesting a reaction rate higher or comparable to those of nanoparticles synthesis by chemical methods. The variation of the pH of the reaction medium gives AuNPs nanoparticles of different shapes. The nanoparticles obtained are characterized by UV–Vis spectroscopy, photoluminescence, transmission electron microscopy (TEM), X-ray diffraction (XRD), FTIR spectroscopy and thermogravimetric analysis. The TEM images showed that a mixture of shapes (triangular, hexagonal and spherical) structures was formed at lower leaf broth concentration and high pH, while smaller spherical shapes were obtained at higher leaf broth concentration and low pH.     

Environmentally sensitive silver nanoparticles of controlled size synthesized with PNIPAM as a nucleating and capping agent

Metal nanoparticles combined with environmentally sensitive polymers can lead to enhanced nanometer-sized switches. We present a silver nanoparticle synthesis method that uses poly(N-isopropylacrylamide) (PNIPAM) as the nucleating, capping, and stabilizing agent. The synthesis is performed at room temperature by sodium borohydride-mediated reduction of silver nitrate in the presence of a fully hydrated polymer. The resulting metal nanoparticles have a narrow size distribution comparable to or better than those achieved with other synthesis methods. The silver particles can be thermally precipitated by the collapse of the PNIPAM shell and resolubilized with fast response times, as shown by surface plasmon spectroscopy. The silver-PNIPAM composite allows for combined surface plasmon and thermal switching applications.     

Aqueous-organic phase-transfer of highly stable gold, silver, and platinum nanoparticles and new route for fabrication of gold nanofilms at the oil/water interface and on solid supports

A simple but effective aqueous-organic phase-transfer method for gold, silver, and platinum nanoparticles was developed on the basis of the decrease of the PVP's solubility in water with the temperature increase. The present method is superior in the transfer efficiency of highly stable nanoparticles to the common phase-transfer methods. The gold, silver, and platinum nanoparticles transferred to the 1-butanol phase dispersed well, especially silver and platinum particles almost kept the previous particle size. Electrochemical synthesis of gold nanoparticles in an oil-water system was achieved by controlling the reaction temperature at 80 degrees C, which provides great conveniences for collecting metal particles at the oil/water interface and especially for fabricating dense metal nanoparticle films. A technique to fabricate gold nanofilms on solid supports was also established. The shapes and sizes of gold nanoparticles as the building blocks may be controllable through changing reaction conditions.     

Stability and Morphology of Gold Nanoisland Arrays Generated from Layer-by-Layer Assembled Nanoparticle Multilayer Films: Effects of Heating Temperature and Particle Size

This article reports the effects of heating temperature and composition of nanoparticle multilayer films on the morphology, stability, and optical property of gold nanoisland films prepared by nanoparticle self-assembly/heating method. First, nanoparticle-polymer multilayer films are prepared by the layer-by-layer assembly. Nanoparticle multilayer films are then heated at temperature ranging from 500 °C to 625 °C in air to induce an evaporation of organic matters from the films. During the heating process, the nanoparticles on the solid surface undergo coalescence, resulting in the formation of nanostructured gold island arrays. Characterization of nanoisland films using atomic force microscopy and UV-vis spectroscopy suggests that the morphology and stability of gold island films change when different heating temperatures are applied. Stable gold nanoisland thin film arrays can only be obtained after heat treatments at or above 575 °C. In addition, the results show that the use of nanoparticles with different sizes produces nanoisland films with different morphologies. Multilayer films containing smaller gold nanoparticles tend to produce more monodisperse and smaller island nanostructures. Other variables such as capping ligands around nanoparticles and molecular weight of polymer linkers are found to have only minimal effects on the structure of island films. The adsorption of streptavidin on the biotin-functionalized nanoisland films is studied for examining the biosensing capability of nanoisland arrays.     

Influence of Capping Ligands on the Self—organization of Gold Nanoparticles into Superlattices from CTAB Reverse Micelles

Gold nanoparticles with size 3-10nm (diameter) were prepared by the reduction of HAuCl4 in a CTAB/octane 1-butanol/H2O reverse micelle system using NaBH4 as the reducing agent.The as-formed gold nanoparticle colloid was characterized by UV/vis absorption spectrum and transmission electron microscopy(TEM).Various capping ligands,such as alkylthiols with different chain length and shape,trioctylphosphine(TOP),and pyridine are used to passivate the gold nanoparticles for the purpose of self-organization into superstructures.It is shown that the ligands have a great influence on the selforganization of gold nanoparticles into superlattices,and dodecanethiol C12H25SH is confirmed to be the best ligand for the self-organization.Self-organization of C12H25SH-capped gold nanoparticles into 1D,2D and 3D supperlattices has been observed on the carbon-coated copper grid by TEM without using any selective precipitation process.     

A Green Approach for Synthesis of Gold and Silver Nanoparticles by Leishmania sp.

The application of microorganisms for the synthesis of metal nanoparticles as an eco-friendly and promising approach is ongoing. In this paper, an attempt has been made to investigate the capability of Leishmania sp. for synthesis of metal nanoparticles from aqueous silver and gold ions. The samples were analyzed by a UV?CVis spectroscopy and the results showed the absorbance peak values at 420 and 540?nm, respectively, for the surface plasmon resonance of silver and gold nanoparticles. The surface morphology of the nanoparticles in solution was visualized by atomic force microscope and scanning electron microscope images, which showed the production of metallic nanoparticles by this protozoan. Fourier transform infrared spectroscopy analyses confirmed the presence of different bands of protein as capping and stabilizing agent on the nanoparticles surfaces. The synthesized silver and gold nanoparticles were with dimensions ranging between 10 and 100?nm for silver and 50?C100?nm for gold. These results of the present study have demonstrated the efficiency of this protozoan for synthesis of nanoparticles, by offering the merits of environmentally friendly, amenability, and time saving for large-scale production.     

First synthesis by liquid-liquid phase transfer of magnetic CoxPt100-x nanoalloys

Controlled synthesis of magnetic nanoparticles with a well-known size and composition is always a challenge. A soft chemical synthesis was developed to obtain magnetic alloy nanocrystals with a high ability to control composition, size, and polydispersity. Cobalt-platinum alloy nanocrystals were synthesized using a colloidal approach by the liquid-liquid phase transfer method. Structural characterization using HRTEM and XRD was carried out on nanocrystals in the range of 25-75% cobalt composition, which indicated the formation of nanoalloy bimetallic CoxPt100-x. Adjusting the alkylamine capping agent and the kinetics of the reduction process allowed tuning of the size in the range of 1.8-4 nm while keeping an equiatomic composition. The narrow size distribution led to the possibility of inducing nanoparticle self-organization over a long range. The magnetic properties of the Co50Pt50 nanoalloy in the disordered face-centered cubic phase A1 were studied for different nanoparticle sizes.     

Formyloxyl radical-gold nanoparticle binding: a theoretical study

The citrate reduction method is one of the simplest and most common methods used in the synthesis of gold nanoparticles. It has been thought that citrate acts as both a reducing agent for the gold salt and as the capping agent. However, it has recently been reported using density functional theory (DFT) that electron density builds up on uncomplexed apex gold atoms and the binding of formate (the simplest carboxylate and a model for citrate) becomes unfavorable after two additions, limiting citrate's utility as a capping agent. In this study, Au(20)-formyloxyl radical interactions are investigated using DFT at the BP86/DZ level of theory to model neutral carboxylate-gold nanoparticle binding (corresponding to carboxylates interacting with a partially oxidized gold nanoparticle). Binding energies are refined using a TZP basis set. It is found that the incremental binding energies of formyloxyl radicals remain highly favorable through eight additions (the highest number tested). The addition of one formyloxyl radical is 56 kJ/mol less than the addition of one formate but becomes 210 kJ/mol more favorable for the second addition. The range of binding energies through the eight additions is 154-331 kJ/mol. Furthermore, after the third addition, the most favorable geometries feature distortion of the gold tetrahedron. These results suggest that oxidized species formed in the citrate reduction method are likely capping agents and that binding of these ligands may affect the properties of the nanoparticles through distortion of the gold structure.     

Generalized route to metal nanoparticles with liquid behavior

We report the generalized synthesis of metal nanoparticles with liquid-like behavior. We introduce a thiol-containing ionic liquid, N,N-dioctyl-N-(3-mercaptopropyl)-N-methylammonium bromide, which serves as a ligand for platinum, gold, palladium, and rhodium nanoparticles. A rapid reduction using THF-soluble metal salts in the presence of the thiol generates nanoparticles with tunable sizes and size distributions. The as-synthesized nanoparticles are a solid and decompose before melting. Upon exchange of the halide anion for an amphiphilic sulfonate anion, however, the nanoparticles exhibit liquid-like properties at room temperature. The liquids have high metal loadings; for example, the 2.7 nm platinum nanoparticle liquid is 36% platinum by mass.     

Defining rules for the shape evolution of gold nanoparticles

The roles of silver ions and halides (chloride, bromide, and iodide) in the seed-mediated synthesis of gold nanostructures have been investigated, and their influence on the growth of 10 classes of nanoparticles that differ in shape has been determined. We systematically studied the effects that each chemical component has on the particle shape, on the rate of particle formation, and on the chemical composition of the particle surface. We demonstrate that halides can be used to (1) adjust the reduction potential of the gold ion species in solution and (2) passivate the gold nanoparticle surface, both of which control the reaction kinetics and thus enable the selective synthesis of a series of different particle shapes. We also show that silver ions can be used as an underpotential deposition agent to access a different set of particle shapes by controlling growth of the resulting gold nanoparticles through surface passivation (more so than kinetic effects). Importantly, we show that the density of silver coverage can be controlled by the amount and type of halide present in solution. This behavior arises from the decreasing stability of the underpotentially deposited silver layer in the presence of larger halides due to the relative strengths of the Ag(+)/Ag(0)-halide and Au(+)/Au(0)-halide interactions, as well as the passivation effects of the halides on the gold particle surface. We summarize this work by proposing a set of design considerations for controlling the growth and final shape of gold nanoparticles prepared by seed-mediated syntheses through the judicious use of halides and silver ions.     

One‐pot dual size‐ and shape selective synthesis of tetrahedral Pt nanoparticles

One‐pot dual size‐ and shape‐selective synthesis of tetrahedral Pt nanoparticles is achieved using the pre‐prepared Pt nanoparticles as the ‘external seeds’, and controlling the slow diffusional growth under hydrogen reduction in the presence of PVP as the capping agent. Copyright © 2006 John Wiley & Sons, Ltd.     

热敏性聚(N-乙烯基异丁酰胺)接枝高分子微球的合成

用自由基聚合和端基反应法合成了大分子单体聚 (N 乙烯基异丁酰胺 ) (PNVIBA) ,将其与苯乙烯在乙醇 水的混合溶剂中进行分散共聚 ,得到了PNVIBA接枝聚苯乙烯 (PNVIBA g PSt)高分子微球 .用GPC、激光光散射和电子显微镜等对聚合物的分子量和微球直径及形态进行了表征 .研究结果表明 ,大分子单体PNVIBA和PNVIBA g PSt高分子微球具有明显的热敏性 ,并且发现PNVIBA g PSt微球直径和形态可通过改变反应条件加以控制 ,得到了一种新形态的亚微米级高分子微球