Stable and efficient silver substrates for SERS spectroscopy

Silver substrates have been obtained, by depositing silver colloidal nanoparticles on a roughened silver plate treated with 1,10-phenanthroline, and checked by means of AFM microscopy and Raman spectroscopy. The ligand molecules are located between two silver substrates and undergo the SERS (Surface Enhanced Raman Scattering) enhancement of both the roughened silver plate and the silver colloidal layer deposited on it. These SERS-active substrates, which show the advantages of being stable with respect to the metal colloidal suspensions, along with an easy and reproducible preparation, can be very useful for catalytic and analytical applications of the SERS spectroscopy.     

Shape‐Dependent Catalytic Activity of Silver Nanoparticles for the Oxidation of Styrene

Metal nanoparticles with different shapes have different crystallographic faces. It is therefore of interest to study the effect of the shape of metal nanoparticles on their catalytic activity in various organic and inorganic reactions. Truncated triangular silver nanoplates with well‐defined planes were synthesized by a simple solvothermal approach. The activity of these truncated triangular silver nanoparticles was compared with that of cubic and near‐spherical silver nanoparticles in the oxidation of styrene in colloidal solution. It was found that the crystal faces of silver nanoparticles play an essential role in determining the catalytic oxidation properties. The silver nanocubes had the {100} crystal faces as the basal plane, whereas truncated triangular nanoplates and near‐spherical nanoparticles predominantly exposed the most‐stable {111} crystal faces. As a result, the rate of the reaction over the nanocubes was more than 14 times higher than that on nanoplates and four times higher than that on near‐spherical nanoparticles.     

Remarks on the reactions of a tetracarboxylic porphyrin with gold and silver ions: A spectrophotometric,TEM and SEM study

The coproporphyrin-I (CPI) behaves as a reducing agent for silver and gold metal ions and as stabilizing agent for the formed colloidal metallic nanoparticles. The peculiarity of silver and gold nanoparticles obtained in the reactions of monomeric form of CPI with their metal ions has been studied. The optical properties of the colloidal forms of these metals have been investigated by UV–Vis spectrophotometry, and their morphology by TEM and SEM measurements. The structures and the size distributions of Ag and Au particles have been characterized and determined by computerized TEM images.     

Synthesis of silver nanoparticles with different shapes

Today the synthesis of silver nanoparticles is very common due to their numerous applications in various fields. Silver nanoparticles have unique properties such as: optical and catalytic properties, which, depend on the size and shape of the produced nanoparticles. So, today the production of silver nanoparticles with different shapes which have various uses in different fields such as medicine, are noted by many researchers. This article, is an attempt to present an overview of the shape-controlled synthesis of silver nanoparticles using various methods.     

金核银壳纳米粒子薄膜的制备及SERS活性研究

采用柠檬酸化学还原法制备金溶胶, 通过自组装技术在石英片表面制备金纳米粒子薄膜, 在银增强剂混合溶液中反应获得金核银壳纳米粒子薄膜. 用紫外-可见吸收光谱仪和原子力显微镜(AFM)研究了不同条件下制备的金核银壳纳米粒子薄膜的光谱特性和表面形貌, 并以结晶紫为探针分子测量了金核银壳纳米粒子薄膜的表面增强拉曼光谱(SERS). 结果表明, 金纳米粒子薄膜的分布、银增强剂反应时间的长短对金核银壳纳米粒子薄膜的形成均有重要影响. 制备过程中, 可以通过控制反应条件获得一定粒径的、具有良好表面增强拉曼散射活性的金核银壳纳米粒子薄膜.     

Study of Shear Properties of Nanoparticle Suspensions

Low-frequency complex shear modulus of the colloidal suspensions of nanoparticles Nd:YAG in ethylene glycol was measured for the first time by using acoustic a resonance method with piezoquartz vibrator. Dependence of viscoelastic properties of the colloidal suspensions on nanoparticles sizes and their concentrations has been carried out.     

Thermal and optical properties of silver-poly(methylmethacrylate) nanocomposites prepared by in-situ radical polymerization

Surface modified silver nanoparticles dispersed in chloroform were encapsulated in poly(methylmethacrylate) (PMMA) by in-situ radical polymerization of methyl methacrylate initiated by 2,2′-azobisisobutyronitrile. The particle size distribution of colloidal silver nanoparticles was determined using transmission electron microscopy. The obtained transparent nanocomposite films were characterized using UV-vis spectroscopy, ¹H NMR spectroscopy and gel permeation chromatography. Effective medium Maxwell-Garnett theory was used in order to explain optical properties of nanocomposite films taking into account inhomogeneous spatial distribution of silver nanoparticles in PMMA matrix. The influence of the silver nanoparticles on the thermal properties of the PMMA matrix was investigated using thermo-gravimetric analysis and differential scanning calorimetry. Thermo-oxidative stability of the PMMA in the presence of low content of inorganic phase is significantly improved. The glass transition temperatures of nanocomposites are slightly lower compared to the pure polymer.     

Colloidal self-assemblies used as templates to control size,shape and self-organization of nanoparticles

In this paper we show that the use of colloidal assemblies as templates favors the control of the size and shape of nanoparticles. As expected theoretically, the change in size and shape of copper metal nanosized particles induces changes in their optical properties. Cylindrical copper metal particles having the same size and shape can be obtained in various regions of the phase diagram when the template is made of interconnected cylinders. Self-assembly of silver metal nanoparticles is reported. Monolayers of particles organized in a hexagonal network are formed over very large domains. Small or large aggregates can also be produced, and, in these aggregates, the particles are highly organized and form pseudo-crystals with a face-centered cubic structure for various particles sizes. The optical properties of the silver nanoparticles isolated in micellar solution or self-assembled in 2D or 3D supperlattices are reported. Syntheses of magnetic fluids differing in their particle size are presented. The magnetic properties differ with the particle size.     

Structure and properties of biodegradable carboxymethyl cellulose films containing silver nanoparticles

Silver nanoparticles stabilized in a solution of sodium carboxymethyl cellulose with a degree of substitution of 0.85 and a degree of polymerization of 600 have been synthesized. The structuring; physical, chemical, and mechanical properties; and antimicrobial activities of films prepared from sodium carboxymethyl cellulose solutions containing silver nanoparticles have been studied. The shapes, quantities, and sizes of the silver nanoparticles occurring in the sodium carboxymethyl cellulose films were determined with the use of transmission electron microscopy, atomic force microscopy, and UV spectroscopy. It was found that an increase in the concentration of silver nitrate in sodium carboxymethyl cellulose solutions, as well as photoirradiation of the films, leads to the changes in the sizes and shapes of silver nanoparticles. The shapes, sizes, and quantities of silver nanoparticles determine their biological activity. An increase in the quantity of 5- to 25-nm silver nanoparticles was found to enhance the microbicidal activities of the carboxymethyl cellulose films.     

Comparative study of the properties of silver hydrosols prepared by “citrate” and “citrate-sulfate” procedures

Comparative study of the properties of silver hydrosols prepared with the use of two classical procedures (“citrate” and “citrate-sulfate”) is performed. The possibility of using these procedures for the synthesis of stable monodisperse silver hydrosols with particle diameters of 20 nm and more is studied. The effect of the main parameters of synthesis (the ratio of initial components, the rate of their mixing, etc) on the hydrosol characteristics is investigated. It is revealed that, in the case of “citrate” synthesis, it is quite impossible to realize conditions ensuring the reproducible preparation of colloidal solutions with particles having sufficiently uniform size and shape. The procedure for the one-stage preparation of “citrate-sulfate” hydrosol (without multiple precipitation-redispersion of nanoparticles) is elaborated and it is shown that the thus prepared hydrosol is greatly superior in both the optical characteristics and the morphological uniformity of particles to the citrate sol. An increase in synthesis temperature to 100°C leads to a substantial enhancement of the stability of colloidal solution. The possibility of using “citrate-sulfate” hydrosol for the design of two-dimensional ensembles of silver nanoparticles on the quartz and silicon surfaces modified with poly(2-vinylpyridine) is demonstrated. It is shown that such ensembles possess optical properties that allow to use them in designing “two-dimensional” polymer-metal nanocomposites potentially suitable for using as active media in devices working on the principle of surface plasmon resonance.     

Hydrothermal-induced assembly of colloidal silver spheres into various nanoparticles on the basis of HTAB-modified silver mirror reaction

Small colloidal silver spheres (diameter < 10 nm) were found to assemble into various silver nanoparticles including cubes, triangles, wires, and rods in water in the presence of HTAB (n-hexadecyltrimethylammonium bromide) at 120 degrees C, while the colloids were generated in situ on the basis of a HTAB-modified silver mirror reaction during the synthesis process. Adjustment of the synthesis parameters, in particular the concentrations of HTAB and [Ag(NH3)2]+, led to an obvious shape evolution of silver nanoparticles, thus resulting in the shape-selective formation of the silver nanoparticles. The monodisperse nanocubes with a well-defined crystallographical structure (a single crystal bounded by six {200} facets) have a strong tendency to assemble into two-dimensional arrays on substrates. The nanowires with uniform diameter usually existed in the form of two-dimensional alignments. The findings suggested that hydrothermal-induced assembly of small silver colloidal particles should be a convenient and effective approach to the preparation of various silver nanoparticles.     

Antibacterial activity of glutathione-coated silver nanoparticles against Gram positive and Gram negative bacteria

In the present paper, we study the mechanism of antibacterial activity of glutathione (GSH) coated silver nanoparticles (Ag NPs) on model Gram negative and Gram positive bacterial strains. Interference in bacterial cell replication is observed for both cellular strains when exposed to GSH stabilized colloidal silver in solution, and microbicidal activity was studied when GSH coated Ag NPs are (i) dispersed in colloidal suspensions or (ii) grafted on thiol-functionalized glass surfaces. The obtained results confirm that the effect of dispersed GSH capped Ag NPs (GSH Ag NPs) on Escherichia coli is more intense because it can be associated with the penetration of the colloid into the cytoplasm, with the subsequent local interaction of silver with cell components causing damages to the cells. Conversely, for Staphylococcus aureus, since the thick peptidoglycan layer of the cell wall prevents the penetration of the NPs inside the cytoplasm, the antimicrobial effect is limited and seems related to the interaction with the bacterial surfaces. Experiments on GSH Ag NPs grafted on glass allowed us to elucidate more precisely the antibacterial mechanism, showing that the action is reduced because of GSH coating and the limitation of the translational freedom of NPs.     

Multimode resonances in silver nanocuboids

A rich variety of dipolar and higher order plasmon resonances have been predicted for nanoscale cubes and parallopipeds of silver, in contrast to the simple dipolar modes found on silver nanospheres or nanorods. However, in general, these multimode resonances are not readily detected in experimental colloidal ensembles, due primarily to the usual variation of size and shape of the particles obscuring or blending the individual extinction peaks. Recently, methods have been found to prepare silver parallopipeds with unprecedented shape control by nucleating the silver onto a tightly controlled suspension of gold nanorods (Okuno, Y.; Nishioka, K.; Kiya, A.; Nakashima, N.; Ishibashi, A.; Niidome, Y. Uniform and Controllable Preparation of Au-Ag Core-Shell Nanorods Using Anisotropic Silver Shell Formation on Gold Nanorods. Nanoscale 2010, 2, 1489-1493). The optical extinction spectra of suspensions of such monodisperse particles are found to contain multiple extinction peaks, which we show here to be due to the multimode resonances predicted by theoretical studies. Control of the radius of the nanoparticle edges is found to be an effective way to turn some of these modes on or off. These nanoparticles provide a flexible platform for the excitation, manipulation, and exploration of higher order plasmon resonances.     

Surface plasmon resonances, optical properties, and electrical conductivity thermal hystersis of silver nanofibers produced by the electrospinning technique

In the present study, silver metal nanofibers have been successfully prepared by using the electrospinning technique. Silver nanofibers have been produced by electrospinning a sol-gel consisting of poly(vinyl alcohol) and silver nitrate. The dried nanofiber mats have been calcined at 850 degrees C in an argon atmosphere. The produced nanofibers do have distinct plasmon resonance compared with the reported silver nanoparticles. Contrary to the introduced shapes of silver nanoparticles, the nanofibers have a blue-shifted plasmon resonance at 330 nm. Moreover, the optical properties study indicated that the synthesized nanofibers have two band gap energies of 0.75 and 2.34 eV. An investigation of the electrical conductivity behavior of the obtained nanofibers shows thermal hystersis. These privileged physical features greatly widen the applications of the prepared nanofibers in various fields.     

The rheological properties of hydrogenated castor oil crystals

The present study focuses on the rheological performance of a surfactant-rich aqueous suspension containing hydrogenated castor oil (HCO) crystals. HCO can be typically crystallized in five distinct shapes: spherically shaped, irregularly shaped, star-shaped (also called rosettes), short needles, and thick or thin fibers. The effect of the differences in shape on the rheological performance is studied, and the rheological properties are compared to the behavior of other triacylglycerol’s (TAG) suspensions. A suspension of TAG crystals usually behaves as a colloidal gel wherein a colloidal gel is defined as a network of flocs, with each floc being an aggregate of smaller subunits. All of these surfactant-rich aqueous suspensions of HCO crystals behaved according to a colloidal gel in the transient regime, independent of the studied crystal shapes, except the long thin fibers at a concentration above 0.1 wt% HCO transitioning from a heterogeneous fractal rod network to a homogeneous rod network, shifting from a colloidal gel to a glass.     

聚丙烯酰胺存在下微波高压合成银纳米粒子及其光谱特性

以聚丙烯酰胺为还原剂和稳定剂 ,采用微波高压液相合成法制备了黄色银纳米粒子。用吸收光谱和共振散射光谱研究了其制备条件的影响。在 4 2 1.6nm处产生最大吸收峰 ,在 4 70nm处产生一个最强共振散射峰。实验表明 :该法制备的银纳米粒子粒径均匀 ,平均粒径为 6 6nm ,其稳定性和分散性较好 ,合成方法简便、快捷。     

Silver Metallic Nanoparticles with Surface Plasmon Resonance: Synthesis and Characterizations

Silver nanoparticles were synthesized by the reduction of the silver nitrate (AgNO₃) using the latex copolymer in ethanol solution under microwave (MW) heating. The reaction parameters such as silver precursor concentration (from 0.005 to 0.1 g/l) and MW power (200–800 W) significantly affect the formation rate, shape, size and distribution of the silver nanoparticles. A significant reduction of irradiation time was observed when the MW energy is compared to conventional thermal reduction processes. The prepared silver nanoparticles show uniform and stable sizes from 5 to 11 nm, which can be stored at room temperature for approximately 12 months without any visible change. These peculiarities indicate that the latex copolymer is a good stabilizer for the silver nanoparticles. The optical properties, morphology, and crystalline structure of the silver-latex copolymer nanocomposites were characterized by the Ultraviolet–Visible spectroscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The study of the TEM images at high magnifications identified the silver nanoparticles as face-centered cubic (fcc) structure with spherical and hexagonal shapes.     

Synthesis of pure colloidal silver nanoparticles with high electroconductivity for printed electronic circuits: the effect of amines on their formation in aqueous media

This paper describes a practical and convenient method to prepare stable colloidal silver nanoparticles for use in printed electronic circuits. The method uses a dispersant and two kinds of reducing agents including 2-(dimethylamino) ethanol (DMAE), which play important roles in the reduction of silver ions in an aqueous medium. The effect of DMAE and dispersant, as well as the factors affecting particle size and morphology are investigated. In the formation of the silver nanoparticles, reduction occurs rapidly at room temperature and the silver particles can be separated easily from the mixture in a short time. In addition, organic solvents are not used. Pure, small and relatively uniform particles with a diameter less than 10 nm can be obtained that exhibit high electroconductivity. The silver nanoparticles are stable, and can be isolated as a dried powder that can be fully redispersed in deionized water. This method of producing colloidal silver nanoparticles will find practical use in electronics applications.     

Spectroscopic studies of fractal aggregates of silver nanospheres undergoing local restructuring

We present an experimental spectroscopic study of large random colloidal aggregates of silver nanoparticles undergoing local restructuring. We argue that such well-known phenomena as strong fluctuation of local electromagnetic fields, appearance of "hot spots" and enhancement of nonlinear optical responses depend on the local structure on the scales of several nanosphere diameters, rather than the large-scale fractal geometry of the sample.     

Bottom-up assembly of colloidal gold and silver nanostructures for designable plasmonic structures and metamaterials

We report on bottom-up assembly routes for fabricating plasmonic structures and metamaterials composed of colloidal gold and silver nanostructures, such as nanoparticles ("metatoms") and shape-controlled nanocrystals. Owing to their well-controlled sizes/shapes, facile surface functionalization, and excellent plasmonic properties in the visible and near-infrared regions, these nanoparticles and nanocrystals are excellent building blocks of plasmonic structures and metamaterials for optical applications. Recently, we have utilized two kinds of bottom-up techniques (i.e., multiple-probe-based nanomanipulation and layer-by-layer self-assembly) to fabricate strongly coupled plasmonic dimers, one-dimensional (1D) chains, and large-scale two-dimensional/three-dimensional (2D/3D) nanoparticle supercrystals. These coupled nanoparticle/nanocrystal assemblies exhibit unique and tunable plasmonic properties, depending on the material composition, size/shape, intergap distance, the number of composing nanoparticles/nanocrystals (1D chains), and the nanoparticle layer number in the case of 3D nanoparticle supercrystals. By studying these coupled nanoparticle/nanocrystal assemblies, the fundamental plasmonic metamaterial effects could be investigated in detail under well-prepared and previously unexplored experimental settings.