Small-sized silver nanoparticles for studies of biological effects

The influence of the hydration extent, AOT and silver ion concentration on average particle size and size distribution in micellar solution of silver nanoparticles obtained by biochemical synthesis was investigated. Formation and stability of nanoparticles were controlled by measurements of optical absorption spectra. Particle sizes were determined by transmission electron microscopy. Combinations of varied parameters have been found, making it possible to prepare three micellar solutions of spherical silver nanoparticles with a different average size in the range 4.6–10.5 nm and narrow size distribution (the standard deviation does not exceed 2.5 nm). For the water dispersions prepared from such solutions by the specially developed procedure, possible applications for studies of size effects in the biological action of nanoparticles are also discussed.     

维生素E绿色还原法制备银纳米粒子的研究

采用一种绿色还原法制备银纳米粒子,以维生素E为还原剂,淀粉为稳定剂,在液相中还原硫酸银,通过改变溶液的pH值和反应时间,得到不同粒径的黄色银纳米粒子,并分别采用透射电镜、红外光谱、紫外-可见吸收光谱、扫描电镜和电化学方法对银纳米粒子进行表征。结果表明:维生素E在溶液中被氧化生成苯醌,反应得到的银纳米粒子为球形,粒径为8~25 nm;在较强碱性条件下,得到的银纳米粒子尺寸较小,分布较均匀,其平均粒径约为10 nm;不同条件下生成的银溶胶分别在417、411、409、408 nm处出现紫外吸收峰,这些吸收峰均为银纳米粒子的表面共振吸收;生成的银纳米粒子具有很好的电化学性质,并对L-半胱氨酸的电化学反应显示了良好的催化活性。     

Thiosalicylic acid-functionalized silver nanoparticles synthesized in one-phase system

A series of silver colloidal dispersions were prepared by two protocols, i.e., addition of the reductant-NaBH(4) and the stabilizer-thiosalicylic acid (TSA) into Ag(+) solution simultaneously or successively. The products were compared and characterized by TEM, electrochemical measurements, XPS, UV-vis, and FT-IR spectra. The size distributions of the Ag nanoparticles prepared by the former and latter protocols are bimodal and monodisperse, respectively. The analytic results of UV-vis spectra coincide with the TEM observation. A tentative explanation was given to the relationship between particle sizes and different synthetic protocols. The changes of the reduction potential of the reductant invoked a variance in particle diameter and size distribution. Electrochemical measurements corroborated our assumption. The composition information of TSA-derived silver nanoparticles was obtained from XPS and FT-IR spectroscopic measurements.     

琥珀酸二异辛酯磺酸钠微乳体系中纳米银的制备及其连续相的影响

在琥珀酸二异辛酯磺酸钠(AOT)为表面活性剂、环己烷为连续相形成的微乳体系中, 利用水合肼还原AgNO₃制备了分散性良好的纳米银. 利用紫外-可见(UV-Vis)光谱和透射电镜(TEM)对所得产物进行了表征, TEM显微图像表明形成粒子为球形结构, 平均粒径为5.10 nm, 标准偏差为2.84 nm. 分别利用正己烷、正庚烷、正辛烷、环己烷和十二烷等作连续介质, 研究了微乳液中连续相对纳米银形成的影响. 随着正烷烃碳链长度的增加, 微乳液中胶束之间的交换速率增大, 形成粒子的平均粒径逐渐减小. 十二烷形成的微乳体系制备的纳米银溶胶具有最宽的共振吸收峰, 所得的纳米银粒子平均粒径最小. 环己烷形成的微乳液中反胶束具有特殊的界面强度, 导致纳米银晶核的形成速率过低, 纳米银晶粒的生长不完全.     

Silver metal nanosized particles: Control of particle size,self assemblies in 2D and 3D superlattices and optical properties

Water in oil droplets are used to control the size of silver metal nanoparticles. After synthesis, the silver metal particles are extracted from reverse micelles and redispersed in a non polar solvent. By increasing the size of the water droplets the average size of silver nanoparticles increases from 2 nm to 7 nm with a rather high size distribution. To narrow the panicle distribution a size selected precipitation method is used. By deposition of a dilute solution containing the coated particles on a carbon grid, the particles arrange themselves in a monolayer organized in a hexagonal network. At high particle concentration, the particles are organized in multilayers forming microcrystals arranged in a face centered cubic structure. The optical properties of the silver nanoparticles isolated in micellar solution or self-assembled in 2D or 3D supperlattices are reported.     

Stabilization of silver nanoparticles with copolymers of maleic acid

Silver nanoparticles are obtained by reducing AgNO₃ with sodium borohydride in an aqueous solution in the presence of maleic acid copolymers with ethylene, N-vinylpyrrolidone, or styrene, as well as their octadecylamide group-containing hydrophobized derivatives, as dispersants. The influence of the structural features of the dicarboxylic acid copolymers on the silver nanoparticle formation process and the conditions for producing sols containing spherical nanoparticles with sizes of 1.5–3.5 nm (according to the data of transmission electron microscopy) are determined. It is shown that, at the equimolar copolymer/silver cation ratio, the morphology of resulting silver nanoparticles weakly depends on the nature of comonomers of maleic acid and the presence of hydrophobic fragments, which play an auxiliary role in the stabilization of dispersions of nanoparticles by increasing their stability with respect to ionic strength and oxidation. Evolution of the particle sizes in the system is monitored beginning with copolymer solutions to silver sols by the methods of light scattering, transmission electron microscopy, and atomic force microscopy. According to the light scattering data, copolymers and their complexes with silver ions in solutions are partly aggregated at concentrations corresponding to the conditions of nanosilver synthesis. Silver sols are shown to contain stabilized nanoparticles, which represent core-polyelectrolyte corona-type micelles and micellar clusters with polyelectrolyte coronas.     

Green synthesis of silver nanoparticles for ammonia sensing

Silver nanoparticles synthesized by a reagent less method involving only UV radiation have been used in colorimetric assay for the detection of ammonia in solution. The silver nanoparticles were synthesized by the exposure of a silver nitrate solution to a low-power UV source in the presence of poly(methacrylic acid) (PMA), which acted both as reducing and capping agent. The synthesis of the silver nanoparticles was studied by monitoring the changes in position and amplitude of the localized plasmon resonance (LSPR) band using UV-vis spectroscopy. The morphology of the particles was studied using transmission electron microscopy which confirmed the formation of spherical particles with an average particle size around 8 nm. Interestingly, the silver nanoparticles solution was found to display a strong color shift from purple to yellow upon mixing with increasing concentration of ammonia ranging from 5 to 100 ppm. Hence, the nanoparticles prepared with this method could be used as colorimetric assay for sensing applications of ammonia in water.     

Redox-mediated synthesis and encapsulation of inorganic nanoparticles in shell-cross-linked cylindrical polyferrocenylsilane block copolymer micelles

Detailed studies of a new approach to the synthesis and encapsulation of silver and silver halide nanoparticles inside shell-cross-linked cylindrical block copolymer polyisoprene-block-polyferrocenyldimethylsilane (PI-b-PFS) micelles (1) through in situ redox reactions are reported. The cylindrical nanostructures 1 were prepared by the solution self-assembly of the PI-b-PFS diblock copolymer in the PI-selective solvent hexane followed by Pt(0)-catalyzed PI shell-cross-linking hydrosilylation reactions. The partial preoxidation of the swollen PFS core using tris(4-bromophenyl)aminium hexachloroantimonate [p-BrC6H4)3N][SbCl6] (2, Magic Blue) followed by redox reaction between the remaining Fe(II) centers in the PFS core and Ag(+) cations led to the formation of silver nanoparticles. High-resolution scanning transmission electron microscopy images of the resulting peapod structures provided a clear indication that the nanoparticles were encapsulated inside the micelles. The composition of the nanoparticles was analyzed by energy-dispersive X-ray spectroscopy (EDX). By combining the evolution of the UV-vis spectra of the reaction mixture and EDX measurements, we surprisingly found that silver halide seed particles were formed through a precipitation reaction at an early stage of the encapsulation process. The size of the silver nanoparticles varied with different amounts of silver ions added to the micelle solution. When I2 was used as the preoxidant, AgI nanoparticles were formed and encapsulated inside the cylinders through the precipitation reaction between iodide anions and silver ions. The packing density of the resulting AgI nanoparticles was increased by an iterative addition method, which utilizes the reversible redox properties of PFS. The small encapsulated AgI nanoparticles were also shown to serve as seeds for the formation of larger Ag nanoparticles when a silver salt was subsequently added.     

Determining the hydrodynamic radii of AOT micelles with silver nanoparticles by means of photon correlation spectroscopy

The possibility of determining the sizes of micelles of sodium di(2-ethylhexyl)sulfosuccinate (AOT) with silver nanoparticles in decane against the background of a large excess of empty micelles by means of photon correlation spectroscopy with unimodal analysis of the autocorrelation function is demonstrated. Contributions from all components to the light scattering are estimated by measuring the static (Rayleigh) light scattering and allowing for partial absorption of the laser radiation by silver nanoparticles. Areas of the correct determination of the hydrodynamic radius of the micelles with nanoparticles are determined via unimodal analysis of the autocorrelation function in dependence on the nanoparticle size (10–2 nm) and silver concentration (1–30 mM) at a constant AOT concentration (0.25 mol/L) and aqueous pseudophase content (1 vol %).     

Comparative evaluation of antibacterial activity of silver nanoparticles synthesized using Rhizophora apiculata and glucose

The focus of the study is to compare the antibacterial efficacy of silver nanoparticles (AgNPs) fabricated by exploiting biological (a mangrove plant, Rhizophora apiculata) and chemical means (Glucose). The synthesized nanoparticles were characterised using UV-visible absorption spectrophotometry (UV-vis), Fourier transform Infra-red Spectroscopy (FTIR) and Transmission electron microscopy (TEM). Biologically synthesized silver nanoparticles (BAgNPs) were observed at 423 nm with particle sizes of 19-42 nm. The chemically synthesized silver nanoparticles (CAgNPs) showed a maximum peak at 422 nm with particle sizes of 13-19 nm. An obvious superiority of the antibacterial potency of BAgNPs compared to the CAgNPs as denoted by the zone of inhibition (ZoI) was noted when the nanoparticles were treated against seven different Microbial Type Culture Collection (MTCC) strains. The current study therefore elucidates that the synthesized AgNPs were efficient against the bacterial strains tested.     

Extracellular synthesis of silver nanoparticles using culture supernatant of Pseudomonas aeruginosa

Bio-directed synthesis of metal nanoparticles is gaining importance due to their biocompatibility, low toxicity and eco-friendly nature. We used culture supernatant of Pseudomonas aeruginosa strain BS-161R for the simple and cost effective green synthesis of silver nanoparticles. The reduction of silver ions occurred when silver nitrate solution was treated with the Pseudomonas aeruginosa culture supernatant at room temperature. The nanoparticles were characterized by UV-visible, TEM, EDAX, FT-IR and XRD spectroscopy. The nanoparticles exhibited an absorption peak around 430 nm, a characteristic surface plasmon resonance band of silver nanoparticles. They were mono-dispersed and spherical in shape with an average particle size of 13 nm. The EDAX analysis showed the presence of elemental silver signal in the synthesized nanoparticles. The FT-IR analysis revealed that the protein component in the form of enzyme nitrate reductase and the rhamnolipids produced by the isolate in the culture supernatant may be responsible for reduction and as a capping material. The XRD spectrum showed the characteristic Bragg peaks of 111, 200, 220 and 311 facets of the face centered cubic silver nanoparticles and confirms that these nanoparticles are crystalline in nature. The prepared silver nanoparticles exhibited strong antimicrobial activity against gram-positive, gram-negative and different Candida species at concentrations ranging between 4 and 32 μg ml(-1).     

Formation of nanocomposite platinum catalysts on porous silicon

Platinum nanoparticles supported on porous silicon were synthesized by radiation-chemical reduction in solutions of reverse micelles. The Pt nanoparticles obtained are electrondeficient. The degree of porosity, conductivity type, pore geometry of the silicon matrix, and precursor parameters affect the size, shape, and charge state of the platinum catalysts.     

Synthesis and Characterization of Silver Hydrosols in the Presence of Carboxyalkylated Amine Complexones

The specifics of formation of silver nanoparticles in aqueous solution in the presence of carboxyalkylated amine complexones (NTA and DTPA) have been studied for the first time. Sols with these ligands are found to be formed in alkali solutions at рН ≥ 10.0 and 80°С. Their optical spectra and the particle sizes and morphologies are determined by synthesis conditions: рН, the ratio Ag⁺/L, and the order of mixing components. A scheme has been suggested for silver nanoparticle formation in the presence of NTA and DTPA, consistent with the experimental results. The efficacy of the prepared silver sols in SERS measurements is shown.     

Formation dynamics of reverse micelles and nanosized effects that accompany chemical reduction of silver nanoparticles in them

Dynamic light scattering has been employed to study the time evolution of a sodium bis(2-ethylhexyl) sulfosuccinate/isooctane/water/quercetin/AgNO₃ system during the formation of reverse micelles (RMs), as well as water solubilization and formation of Ag nanoparticles (NPs) in them. It has been shown that physicochemical processes occurring in the reverse micellar system lead to the formation of light-scattering elements with average sizes of 0.67?2 nm (individual molecules of the surfactant and reductant), 2.5?4.5 nm (“dry” RMs) and 16?20 nm (RMs containing Ag NPs). The synthesis is accompanied by the formation of silver NPs with other sizes in an amount of less than 5%.     

Solid state morphology and band gap studies of ETS-10 supported CdS nanoparticles

Engelhard titanosilicate (ETS-10) supported cadmium sulphide (CdS) nanoparticles were synthesized and characterized by various solid state techniques including: XRD, DR UV-Vis, TEM and FESEM. The effect of different synthesis routes of CdS nanoparticles on its physicochemical character was studied. It was observed that CdS nanoparticles prepared by both in situ sulphur reduction (CdS-IS) and reverse micelle (CdS-RM) methods showed similar roperties. However, CdS-IS nanoparticles are more feasible and economically practical. The reflectance measurements of the as-synthesized CdS nanoparticles are apparently blue-shifted compared to bulk CdS. This phenomenon of blue-shifted absorption edge has been ascribed to an increase in bandgap energy with a decrease in particle sizes. The bandgap of the as-synthesized CdS samples was calculated from the linear correlation of [F(R) hν]² and hν. The bandgap of CdS in ETS-10 was noticeably slightly reduced when compared with the as-synthesized CdS (8 nm) due to the formation of cluster arrays on the pores of ETS-10.     

Formal kinetics of growth of nanosized silver particles upon silver nitrate reduction with sodium citrate in a reverse micellar solution of AOT

The growth kinetics of silver nanoparticles upon silver(I) reduction with sodium citrate in an aqueous solution solubilized to a reverse micellar solution of sodium bis(2-ethylhexyl) sulfosuccinate in decane is studied spectrophotometrically under constant conditions of irradiation of the reaction mixture with visible light. The formal kinetics of the process corresponds to an autocatalytic mechanism. The effective rate constants of growth of silver nanoparticles, unlike those of gold nanoparticles, are independent of the size of the inner micellar cavity when its radius changes from 2 to 6 nm. This is most likely due to a great effect of the photochemical factor or Ag⁺ localization in the inner surface layer of the micelles on the rate constants.     

Synthesis and optical properties of silver nanoparticles and arrays.

This Minireview systematically examines optical properties of silver nanoparticles as a function of size. Extinction, scattering, and absorption cross-sections and distance dependence of the local electromagnetic field, as well as the quadrupolar coupling of 2D assemblies of such particles are experimentally measured for a wide range of particle sizes. Such measurements were possible because of the development of a novel synthetic method for the size-controlled synthesis of chemically clean, highly crystalline silver nanoparticles of narrow size distribution. The method and its unique advantages are compared to other methods for synthesis of metal nanoparticles. Synthesis and properties of nanocomposite materials using these and other nanoparticles are also described. Important highlights in the history of the field of metal nanoparticles as well as an examination of the basic principles of plasmon resonances are included.     

单分散性银纳米粒子的可控制备

以卤化银或氧化银作为前驱体,室温下以水为溶剂,在较高溶液浓度下,利用化学还原法制备了单分散性银纳米粒子,并通过改变前驱体的种类,实现了粒径可控制备。采取扫描电子显微镜（SEM）、紫外-可见光谱仪（UV-Vis）、X射线-粉末衍射仪（XRD）、X射线-光电子能谱仪（XPS）等对所制备的银纳米粒子的形貌及成分进行了表征。结果显示,所制备的银纳米粒子具有较高的单分散性,粒径在40~150 nm之间,具有面心立方多晶结构。该方法制备的银纳米粒子可用于喷墨打印RFID天线。     

Control of nucleation and growth of gold nanoparticles in AOT/Span80/isooctane mixed reverse micelles

In this study, we demonstrate that mixed reverse micelles are good candidates to be used as nanoreactors for formation of shape-controlled high-quality colloidal nanocrystals and nanowires under mild conditions. Manipulation of the rate of nucleation and subsequent growth of the Au in the mixed reverse micelles induce drastic changes in the particle shape and structure. Here we demonstrate that control of the nucleation and growth kinetics of the Au in the mixed reverse micelles can be used to vary the shapes of the resulting particles from a nearly spherical morphology to cylinders, trigons and cubics. The characterization of the resultant particles, the effects of synthesis conditions (such as concentration of NaCl, addition of glycerol, and reaction temperature) on particle sizes, particle size distribution, and shape of particle formation have been investigated. This study will help us to understand the chemical control synthesis of crystal growth processes at the atomic level.     

Synthesis and size control of silver nanoparticles using reverse micelles of sucrose fatty acid esters

Silver nanoparticles were prepared in reverse micelles of sucrose fatty acid esters. The TEM image showed that the obtained silver nanoparticles displayed a wide variety of shapes. The size of silver nanoparticles was strongly dependent upon a kind of reducing agents and tended to increase with an increase in reaction temperature. Moreover, the size of silver nanoparticles was controlled by using sucrose fatty acids at a different esterification degree or by mixing sucrose fatty acid monoesters with polyoxyethylene sorbitan fatty acid monoesters. The resultant silver colloid could be preserved for at least 1 month without precipitation.