Oleic acid-assisted phase transfer of nanosized silver colloids

In this study, it is demonstrated that silver nanoparticles can be transferred from formamide to chloroform using oleic acid as a phase transfer agent with a transfer efficiency of 90–95%. The silver nanoparticles are initially formed as an organosol by the reduction of silver ions with formamide. On aging the complex, the particles self-assemble to form an ordered close-packed two-dimensional array of silver nanocrystals when dissolved in CHCl₃. The size distribution of the colloidal silver particles after transfer in different solvents remains almost the same. On the basis of IR spectroscopy, we discuss the adsorption of oleic acid over the silver particles.     

Synthesis of nanosized silver colloids by microwave dielectric heating

Silver nanosized crystallites have been synthesized in aqueous and polyols viz., ethylene glycol and glycerol, using a microwave technique. Dispersions of colloidal silver have been prepared by the reduction of silver nitrate both in the presence and absence of stabilizer poly(vinylpyrolidone) (PVP). It was observed that PVP is capable of complexing and stabilizing Ag nanoparticles formed through the reduction of Ag⁺ ions in water and ethylene glycol. In the case of ethylene glycol, it has been shown that the use of PVP leads to particles with a high degree of stability. The colloids are stable in glycerol for months even in the absence of stabilizer.     

银离子在二氧化硅粒子表面上的成核反应

在含有乙醇的SiO₂溶胶中,Ag⁺不管在碱性、中性或在弱碱、弱酸情况下都能在SiO₂粒子表面上还原成核,形成金属Ag颗粒.研究表明,银的等离子体共振吸收峰的移动是尺寸效应和表面效应共同作用的结果.     

Rapid synthesis of Au, Ag, and bimetallic Au core-Ag shell nanoparticles using Neem (Azadirachta indica) leaf broth

We report on the use of Neem (Azadirachta indica) leaf broth in the extracellular synthesis of pure metallic silver and gold nanoparticles and bimetallic Au/Ag nanoparticles. On treatment of aqueous solutions of silver nitrate and chloroauric acid with Neem leaf extract, the rapid formation of stable silver and gold nanoparticles at high concentrations is observed to occur. The silver and gold nanoparticles are polydisperse, with a large percentage of gold particles exhibiting an interesting flat, platelike morphology. Competitive reduction of Au3+ and Ag+ ions present simultaneously in solution during exposure to Neem leaf extract leads to the synthesis of bimetallic Au core-Ag shell nanoparticles in solution. Transmission electron microscopy revealed that the silver nanoparticles are adsorbed onto the gold nanoparticles, forming a core-shell structure. The rates of reduction of the metal ions by Neem leaf extract are much faster than those observed by us in our earlier studies using microorganisms such as fungi, highlighting the possibility that nanoparticle biological synthesis methodologies will achieve rates of synthesis comparable to those of chemical methods.     

Cationic Spherical Polyelectrolyte Brushes as Nanoreactors for the Generation of Gold Particles

Summary: If long polyelectrolyte chains are attached densely to colloidal latex particles, a spherical polyelectrolyte brush results. These spherical polyelectrolytes are dispersed in water and carry a high charge. We demonstrate that these systems can be used to immobilize ions of heavy metals, such as gold, as counter‐ions. Reduction of these ions leads to metallic nanoparticles. In this way the brush layer attached to the surface of the particles becomes a “nanoreactor” that may be used for chemical conversions of the metal ions. We show that the reduction of AuClequation/tex2gif-stack-1.gif ions within these nanoreactors leads to well‐defined and rather monodisperse gold nanoparticles that are attached to the surface of the core. A stable dispersion of polymeric core particles with attached nanoparticles results. All results reported here suggest that chemical reactions of ions immobilized in spherical polyelectrolyte brushes provide a new route to composite particles of inorganic and organic materials.

Transmission electron micrograph of gold particles on a core‐shell system.     

Mechanism of silver ion reduction in concentrated solutions of amphiphilic invertible polyesters in nonpolar solvent at room temperature

Fast formation and efficient stabilization of silver nanoparticles from [Ag(NH3)2]OH are achieved in concentrated nonpolar solutions of amphiphilic invertible polyesters based on poly(ethylene oxide) (PEO) and aliphatic dicarboxylic acids. Surface-modified silver nanoparticles able to be dispersed in both a polar and nonpolar medium are developed in the form of a ready-to-use colloidal solution with an enhanced silver concentration. The PEO fragments of polyesters form cavities (also called pseudo-crown ester structures) that can bind metal ions. The reduction of bound metal ions proceeds via oxidation of polyoxyethylene fragments. No chemical reducing agents are necessary in this approach. The polyesters act simultaneously as an efficient reducing agent and stabilizer. The main focus of the present research is to clarify the chemical mechanism of silver ion reduction in amphiphilic polyester solutions. A one-electron reduction mechanism is proposed to explain the formation of silver nanoparticles. The effect of the poly(ethylene oxide) fragment length and the polyester concentration are explored by examining several amphiphilic polyesters.     

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.     

Transmetalation reaction between hydrophobic silver nanoparticles and aqueous chloroaurate ions at the air-water interface

The transmetalation reaction between a sacrificial nanoparticle and more noble metal ions in solution has emerged as a novel method for creating unique hollow and bimetallic nanostructures. In this report, we investigate the possibility of carrying out the transmetalation reaction between hydrophobic silver nanoparticles assembled and constrained at the air-water interface and subphase gold ions. We observe that facile reduction of the subphase gold ions by the sacrificial silver nanoparticles occurs resulting in the formation of elongated gold nanostructures that appear to cross-link the sacrificial silver particles. This transmetalation reaction may be modulated by the insertion of an electrostatic barrier in the form of an ionizable lipid monolayer between the silver nanoparticles and the aqueous gold ions that impacts the gold nanoparticle assembly. Transmetalation reactions between nanoparticles constrained into a close-packed structure and appropriate metal ions could lead to a new strategy for metallic cross-linking of nanoparticles and generation of coatings with promising optoelectonic behavior.     

Synthesis of silver nanoparticles in NMMO and their in situ doping into cellulose fibers

We present a method for synthesis of silver nanoparticles in N-methylmorpholine N-oxide (NMMO) and the associated mechanism, as well as their use for in situ volume modification of cellulose fibers. The synthesized particles had diameter of about 4 nm, and their colloid solution was stable for 1 year. The nanoparticles were stabilized using polyethylenimine, which apart from preventing nanoparticle agglomeration, also accelerated Ag⁺ ion reduction and prevented NMMO degradation. A mechanism for the nanoparticle synthesis is suggested based on the electrochemical potentials of all ions in solution, with perhydroxyl ions resulting from NMMO reducing the silver ions. We also created nanocomposites from fibers and silver nanoparticles, in which the latter showed very good dispersion in the fiber volume. Such spun fibers showed improved mechanical parameters in comparison with unmodified fibers.     

Antibacterial properties of Ag nanoparticle loaded multilayers and formation of magnetically directed antibacterial microparticles

Antibacterial coatings based on hydrogen-bonded multilayers containing in situ synthesized Ag nanoparticles were created on planar surfaces and on magnetic colloidal particles. We report the antibacterial properties of these coatings, determined using a disk-diffusion (Kirby-Bauer) test, as a function of the film thickness and the concentration of Ag nanoparticles in the hydrogen-bonded multilayers. The zone of inhibition (ZoI) determined by the disk-diffusion test increases as the thickness of the multilayer film is increased. Results obtained for the values of the ZoI as a function of film thickness can be described adequately with a simple diffusion model (i.e., the square of the zone of inhibition (ZoI) depended linearly on the logarithm of the thickness of the silver-loaded films). This observation suggests that, in order to incrementally increase the ZoI, an exponentially increasing amount of Ag is required within the multilayers. In general, there was no statistically significant correlation between the zone of inhibition and the number of Ag loading and reduction cycles. The duration of sustained release of antibacterial Ag ions from these coatings, however, could be prolonged by increasing the total supply of zerovalent silver in the films via multiple loading and reduction cycles. These results indicate that the release of silver is controlled by an oxidation mechanism at the surface of the nanoparticles and that repeated loading and reduction of silver leads preferentially to growth of the existing silver nanoparticles in the film as opposed to nucleation of new Ag nanoparticles. We also show that magnetic microspheres coated with silver nanoparticle loaded hydrogen-bonded multilayer thin films can be used to deliver antibacterial agents to specific locations. The minimum inhibitory concentration (MIC) of nanocomposite coated microspheres was determined by the agar dilution technique: antibacterial magnetic microspheres with higher concentrations of Ag nanoparticles exhibited lower MIC values.     

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.     

Green synthesis of colloidal silver nanoparticles using natural rubber latex extracted from Hevea brasiliensis

Colloidal silver nanoparticles were synthesized by an easy green method using thermal treatment of aqueous solutions of silver nitrate and natural rubber latex (NRL) extracted from Hevea brasiliensis. The UV–Vis spectra detected the characteristic surface plasmonic absorption band around 435 nm. Both NRL and AgNO₃ contents in the reaction medium have influence in the Ag nanoparticles formation. Lower AgNO₃ concentration led to decreased particle size. The silver nanoparticles presented diameters ranging from 2 nm to 100 nm and had spherical shape. The selected area electron diffraction (SAED) patterns indicated that the silver nanoparticles have face centered cubic (fcc) crystalline structure. FTIR spectra suggest that reduction of the silver ions are facilitated by their interaction with the amine groups from ammonia, which is used for conservation of the NRL, whereas the stability of the particles results from cis-isoprene binding onto the surface of nanoparticles. Therefore natural rubber latex extracted from H. brasiliensis can be employed in the preparation of stable aqueous dispersions of silver nanoparticles acting as a dispersing and/or capping agent. Moreover, this work provides a new method for the synthesis of silver nanoparticles that is simple, easy to perform, pollutant free and inexpensive.     

Preparation, characterization, and surface modification of silver nanoparticles in formamide

The reduction of silver ions in formamide is shown to take place spontaneously at room temperature without addition of any reductant. The growth of Ag particles was found to be dependent on Ag+ ion concentration. In the absence of any stabilizer, deposition of silver film on the glass walls of the container takes place. However, in the presence of poly(N-vinyl-2-pyrrolidone) (PVP) or colloidal silica (SiO2), which are capable of stabilizing silver nanoparticles by complexing and providing support, a clear dispersion was obtained. The formation of the silver nanoparticles under different conditions was investigated through UV-visible absorption spectrophotometry, gas chromatography, and also electron and atomic force microscopic techniques. Atomic force microscopy results for silver films prepared in the absence of any stabilizer showed the formation of polygonal particles with sizes around 100 nm. Transmission electron microscopy results showed that the prepared silver particles in the presence of PVP were around 20 nm. The Ag nanoparticles get oxidized in the presence of chloroform and toluene. Surface modification of silver film was done in the presence of the tetrasodium salt of ethylenediaminetetraaceticacid (Na4EDTA). It was shown that the reactivity of the silver film increased in its presence. The Fermi potential of silver particles in the presence of Na4EDTA seems to lie between -0.33 and -0.446 V vs NHE.     

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.     

Role of phenol derivatives in the formation of silver nanoparticles

We demonstrate that dihydroxy benzenes are excellent reducing agents and may be used to reduce silver ions to synthesize stable silver nanoparticles in air-saturated aqueous solutions. The formation of Ag nanoparticles in deaerated aqueous solution at high pH values suggests that the reduction of silver ions occurs due to oxidation of dihydroxy benzenes and probably on the surface of Ag2O. Pulse radiolysis studies show that the semi-quinone radical does not participate in the reduction of silver ions at short time scales. Nevertheless, results show that primary intermediates undergo slower transformation in the presence of dihydroxy benzenes than in their absence. This slow transformation eventually leads to the formation of silver nanoparticles. The Ag nanoparticles were characterized by UV-vis absorption spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM). XRD and TEM techniques showed the presence of Ag nanoparticles with an average size of 30 nm.     

Colloidal copper and peculiarities of its reaction with silver ions in aqueous solution

Interactions between colloidal copper and silver ions lead to the formation of silver nanoparticles. The reaction proceeds through the intermediate stage of the formation of a copper-silver contact pair. The formation of bimetallic Ag_coreCu_shell nanoparticles is observed in the presence of the “seeding” silver nanoparticles and upon the simultaneous radiochemical reduction of Ag⁺ and Cu²⁺ ions.     

Preparation of Silver Nanoparticles through Alcohol Reduction with Organoalkoxysilanes

Silver nanoparticles of narrow size distribution were prepared through the chemical reduction in an alcohol solution with several organoalkoxysilanes. In this system, organoalkoxysilanes served as a stabilizer, protecting silver nanoparticles from aggregation. The changes in size and morphology of colloidal silver nanoparticles were investigated with the addition of organoalkoxysilanes such as 3-aminopropyltriethoxysilane (APS), methyltriethoxysilane (MTS), phenyltrimethoxysilane (PTS), vinyltriethoxysilane (VTS), and 3-glycidoxypropyltrimethoxysilane (GPS) as stabilizers. The organic functional groups of organoalkoxysilanes interact with silver ions and clusters, which stabilize silver nanoparticles in the system. The silver nanoparticles obtained were characterized with transmission electron microscopy (TEM), UV-vis spectroscopy, etc.     

The Effect of the Conditions of Catalytic Synthesis of Nanoparticles of Metallic Silver on Their Plasmon Resonance

The formation of nanoparticles of metallic silver in the reduction of Ag⁺ ions catalyzed by colloidal Ag₂S was investigated. It was established that the position of the surface plasmon resonance bands of the Ag nanoparticles is affected by the concentration of the catalyst, its particle size and the amount of particles with the same size, the stabilization conditions, the concentration of Ag⁺ ions, and the temperature at which the process is conducted. An explanation for the spectral changes that occur is proposed.     

Theoretical consideration on preparing silver particle films by adsorbing nanoparticles from bulk colloids to an air-water interface

In our previous paper, a method for preparing enormous surface-enhanced Raman scattering (SERS) active substrates through the aggregation of silver particles trapped at an air-water interface was reported. Here, further efforts were devoted to investigate the origin of assembling silver particle films by adsorbing nanoparticles from bulk colloids to the air-water interface. It was revealed that it is thermodynamically favorable for a colloidal particle in bulk colloids to adsorb to the air-water interface; however, a finite sorption barrier between it and the nearby particles usually restrains the adsorption process. When an electrolyte such as KCl, which is commonly used as an activating agent for additional SERS enhancement, was added into silver colloids, it largely reduced the sorption barrier. Thus, silver nanoparticles can break through the sorption barrier, pop up, and be trapped at the air-water interface. The trapped silver particles are more inclined to aggregate at the interface than those in bulk colloids due to the increase of van der Waals forces and the reduction of electrostatic forces. The morphology of the as-prepared silver particle films was characterized by scanning electron microscope, and their SERS activity was tested using NaSCN as a probe molecule. The surface enhancement of the silver particle films is about 1-2 orders of magnitude higher compared with that of silver colloids, because most of the silver particles in the films are in the aggregation form that provides enormous SERS enhancement. Furthermore, the stability of such type of films is much better that of colloid solutions.     

An aqueous colloidal silver solution stabilized with carbonate ions

A method has been developed for the preparation of a stable “pure” silver hydrosol containing nanoparticles with an average size of 10 nm and stabilizing carbonate ions. The method consists in the photochemical reduction of silver ions with oxalate ions, which simultaneously generate carbonate ions. Optical spectroscopy, electron microscopy, and dynamic light scattering are used to study the hydrosol