聚合物存在下纳米银复合材料的制备与表征

以聚丙烯腈聚乙二醇嵌段共聚物PAN-b-PEG-b-PAN为稳定剂, 在超声辐照下成功地制备了分散性较好、尺寸均匀的纳米银颗粒. 用X射线衍射(XRD)、红外光谱(FTIR)、透射电镜(TEM)、紫外-可见吸收光谱(UV-Vis)和热分析(TGA)等对制备的纳米银复合材料进行了表征. 红外结果表明超声辐照并没有破坏聚合物的链结构. 聚合物的引入, 对纳米银颗粒起到了很好的分散保护作用. 用低浓度的硝酸银溶液, 得到粒径较小的纳米银颗粒; 随着硝酸银浓度增大, 纳米银颗粒粒径也增大. 而聚合物的浓度增大时, 所得银纳米颗粒粒径减小. 对银纳米颗粒的形成机理进行了讨论.     

Facile synthesis of high-concentration, stable aqueous dispersions of uniform silver nanoparticles using aniline as a reductant

A facile method was developed for preparing uniform silver nanoparticles with small particle sizes of less than 10 nm at high concentrations, in which aniline was used to reduce silver nitrate (AgNO(3)) to silver nanoparticles in the presence of dodecylbenzenesulfonic acid (DBSA) as a stabilizer. Upon the addition of excess NaOH to the DBSA-aniline-AgNO(3) (DAA) system, the formation of silver nanoparticles was almost complete in just 2 min at 90 °C (in 94% yield). The average size of those resultant silver nanoparticles was 8.9 ± 1.1 nm, and the colloids were stable for more than 1 year at ambient temperature. A possible mechanism for the formation of silver nanoparticles was proposed to be related to two factors: one was the mesoscopic structures of the DAA system in which silver ions were restricted in the dispersed phases composed of DBSA and aniline; the other was Ag(2)O nanocrystallites generated in situ that could be readily reduced by aniline to small silver nanoparticles at high concentrations.     

Green Synthesis of Silver Nanoparticles Using an Aqueous Extract of <Emphasis Type="Italic">Monotheca buxifolia</Emphasis> (Flac.) Dcne

This study deals with the synthesis and physicochemical investigation of silver nanoparticles using an aqueous extract of Monotheca buxifolia (Flac.). On the treatment of aqueous solution of silver nitrate with the plant extract, silver nanoparticles were rapidly fabricated. The synthesized particles were characterized by using UV–visible spectrophotometry (UV), Fourier transform infrared spectroscopy (FTIR), Energy dispersive X-ray (EDX) and Scanning electron microscopy (SEM). The formation of AgNPs was confirmed by noting the change in colour through visual observations as well as via UV–Vis spectroscopy. UV–Vis spectrum of the aqueous medium containing silver nanoparticles showed an absorption peak at around 440 nm. FTIR was used to identify the chemical composition of silver nanoparticles and Ag-capped plant extract. The presence of elemental silver was also confirmed through EDX analysis. The SEM analysis of the silver nanoparticles showed that they have a uniform spherical shape with an average size in the range of 40–78 nm. This green system showed better capping and stabilizing agent for the fine particles. Further, in vitro the antioxidant activity of Monotheca buxifolia (Flac.) and Ag-capped with the plant was also evaluated using FeCl₃/K₃Fe (CN)₆ essay.     

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。     

Role of stabilizing agents in the formation of stable silver nanoparticles in aqueous solution: Characterization and stability study

The stability of silver nanoparticles is controlled mainly by two major factors, namely, aggregation and oxidation. In the present study, silver nanoparticles were synthesized by using different series of reducing agents like a strong reducing agent (sodium borohydride), a mild reducing agent (tri-sodium citrate), and a weak reducing agent (glucose) with different capping agents, namely, polyvinyl pyrrolidone (PVP K 30), starch, and sodium carboxyl methyl cellulose (NaCMC). The synthesized silver nanoparticles were characterized by UV-Visible absorption spectroscopy, dynamic light scattering (DLS), atomic force microscopy (AFM), and anti-microbial activity. The particle size of silver nanoparticles varies in the following order: sodium borohydride < tri-sodium citrate < glucose. Combination of sodium borohydride–polyvinyl pyrrolidone and tri-sodium citrate-polyvinyl pyrrolidone yields stable silver nanoparticles compared to other combinations of reducing agents and capping agents. The stability results confirmed that a refrigerated condition (8°C) was more suitable for storage of silver nanoparticles. Anti-microbial activity of silver nanoparticles synthesized in a sodium borohydride–polyvinyl pyrrolidone mixture shows a larger zone of inhibition compared to other silver nanoparticles. Anti-microbial results confirmed that the anti-microbial activity is better with smaller particle size. The size and stability of silver nanoparticles in the presence of different combinations of stabilizing and capping agents are reported.     

Silver colloid nanoparticles: synthesis, characterization, and their antibacterial activity

A one-step simple synthesis of silver colloid nanoparticles with controllable sizes is presented. In this synthesis, reduction of [Ag(NH(3))(2)](+) complex cation by four saccharides was performed. Four saccharides were used: two monosaccharides (glucose and galactose) and two disaccharides (maltose and lactose). The syntheses performed at various ammonia concentrations (0.005-0.20 mol L(-1)) and pH conditions (11.5-13.0) produced a wide range of particle sizes (25-450 nm) with narrow size distributions, especially at the lowest ammonia concentrations. The average size, size distribution, morphology, and structure of particles were determined by dynamic light scattering (DLS), transmission electron microscopy (TEM), and UV/Visible absorption spectrophotometry. The influence of the saccharide structure (monosacharides versus disaccharides) on the size of silver particles is briefly discussed. The reduction of [Ag(NH(3))(2)](+) by maltose produced silver particles with a narrow size distribution with an average size of 25 nm, which showed high antimicrobial and bactericidal activity against Gram-positive and Gram-negative bacteria, including highly multiresistant strains such as methicillin-resistant Staphylococcus aureus. Antibacterial activity of silver nanoparticles was found to be dependent on the size of silver particles. A very low concentration of silver (as low as 1.69 mug/mL Ag) gave antibacterial performance.     

Nanoparticle-mirror sandwich substrates for surface-enhanced Raman scattering

Sandwich surface-enhanced Raman scattering (SERS) substrates (3S) utilizing coupling between continuous metal films and plasmonic particles were fabricated using silver mirrors, electrochemically roughened films, and various sizes of silver nanoparticles. The effect of excitation wavelength and nanoparticle size on SERS spectra of poly(vinylpyridine), selected as a model compound, was studied to determine the optimum conditions for the strongest SERS signal. The Raman enhancement resulted from the plasmon coupling of silver nanoparticles to the underlying continuous film as well as the lateral plasmon coupling between the silver nanoparticles. The formation of the charge transfer complex was also observed. The 3S configuration was used to obtain SERS spectra of dipicolinic acid (DPA), a chemical signature for Bacillus anthracis.     

Preparation and characterization of silver nanoparticles by chemical reduction method

Silver nanoparticles were prepared by the reduction of AgNO(3) with aniline in dilute aqueous solutions containing cetyltrimethlyammonium bromide, CTAB. Nanoparticles growth was assessed by UV-vis spectroscopy and the average particle size and the size distribution were determined from transmission electron microscopy, TEM. As the reaction proceeds, a typical plasmon absorption band at 390-450nm appears for the silver nanoparticles and the intensities increase with the time. Effects of [aniline], [CTAB] and [Ag(+)] on the particle formation rate were analyzed. The apparent rate constants for the formation of silver nanoparticles first increased until it reached a maximum then decreased with [aniline]. TEM photographs indicate that the silver sol consist of well dispersed agglomerates of spherical shape nanoparticles with particle size range from 10 to 30nm. Aniline concentrations have no significant effect on the shape, size and the size distribution of Ag-nanoparticles. Aniline acts as a reducing as well as adsorbing agent in the preparation of roughly spherical, agglomerated and face-centered-cubic silver nanoparticles.     

Murraya Koenigii leaf-assisted rapid green synthesis of silver and gold nanoparticles

A facile bottom-up 'green' and rapid synthetic route using Murraya Koenigii leaf extract as reducing and stabilizing agent produced silver nanoparticles at ambient conditions and gold nanoparticles at 373 K. The nanoparticles were characterized using UV-vis, transmission electron microscopy (TEM), X-ray diffraction (XRD) and FTIR analysis. This method allows the synthesis of well-dispersed silver and gold nanoparticles having size ～10 nm and ～20 nm, respectively. Silver nanoparticles with size ～10 nm having symmetric SPR band centered at 411 nm is obtained within 5 min of addition of the extract to the solution of AgNO3 at room temperature. Nearly spherical gold nanoparticles having size ～20 nm with SPR at 532 nm is obtained on adding the leaf extract to the boiling solution of HAuCl4. Crystallinity of the nanoparticles is confirmed from the high-resolution TEM images, selected area electron diffraction (SAED) and XRD patterns. From the FTIR spectra it is found that the biomolecules responsible for capping are different in gold and silver nanoparticles. A comparison of the present work with the author's earlier reports on biosynthesis is also included.     

Magnetite nanoparticles with tunable gold or silver shell

Fe3O4 nanoparticles with size approximately 13 nm have been prepared successfully in aqueous micellar medium at approximately 80 degrees C. To make Fe3O4 nanoparticles resistant to surface poisoning a new route is developed for coating Fe3O4 nanoparticles with noble metals such as gold or silver as shell. The shell thickness of the core-shell particles becomes tunable through the adjustment of the ratio of the constituents. Thus, the route yields well-defined core-shell structures of size from 18 to 30 nm with varying proportion of Fe3O4 to the noble metal precursor salts. These magnetic nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), FTIR, differential scanning calorimetry (DSC), Raman and temperature-dependent magnetic studies.     

Silver nanoparticle formation in microemulsions acting both as template and reducing agent

A novel method of making silver nanoparticles in water-in-oil microemulsions using the surfactants as both the reducing agent and as the structure-directing agent is presented. Since no external strong reducing agent is used the kinetics of the formation is slow, which makes it possible to study the silver nanoparticle formation in situ. The microemulsions used were based on either the nonionic surfactant Brij30 (C12E4), which reduces the silver ion to metallic silver and is thereby partly oxidized, or mixtures of Brij30 and AOT (sodium bis(2-ethylhexyl) sulfosuccinate, where the latter does not reduce the silver ions. The influences of silver ion and nonionic surfactant concentrations on the formation kinetics of the nanoparticles were followed in situ using UV-vis spectroscopy, and both parameters were found to have a big influence. The microemulsion droplet's size, size distribution, and shape were examined by small-angle X-ray scattering (SAXS), and the formed silver nanoparticles were studied using both transmission electron microscopy and SAXS. The SAXS measurements showed that the presence of silver nitrate does not affect the microemulsion systems noticeably and that the droplet's size and shape are retained during the particle formation. It is shown that the size and morphology of the particles do not directly follow the shape and size of the microemulsion droplets even though there is a relation between the droplet size and the radii of the formed particles.     

Silver nanoparticles capped by oleylamine: formation, growth, and self-organization

Nearly monodisperse silver nanoparticles have been prepared in a simple oleylamine-liquid paraffin system. Intensive study has found that the formation process of silver nanoparticles could be divided into three stages: growth, incubation, and Ostwald ripening stages. Ultraviolet-visible spectroscopy, transmission electron microscopy (TEM), and high-resolution TEM have all demonstrated the occurrence of Ostwald ripening, which could result in better control over the size and size distribution of silver nanoparticles. SAXS (small-angle X-ray scattering) results show that the as-obtained silver nanoparticles can self-assemble into ordered arrays. The possible reduction mechanism of silver ions by oleylamine is related to the Ag+-mediated conversion of primary amines to nitriles.     

Preparation and characterization of silver colloids with different morphologies under ultrasonic field

In the ultrasonic field, stable silver colloids were produced by the reduction of AgNO₃ with the protection of PVP using KBH₄ or N₂H₄·H₂O as reductant. The main factors affecting the morphology of silver nanoparticles, such as distribution of the ultrasonic field, ultrasonic time, ultrasonic power, and the species of reductant, were studied. The silver colloids were identified by TEM and spectrophotometry. The results indicate that the factors such as distribution of the ultrasonic field, ultrasonic time, ultrasonic power, and the species of reductant have a great impact on the morphology of the silver nanoparticles. The size of the silver nanoparticles decreases with the ultrasonic power and ultrasonic time increasing. Ag nanoparticles prepared in standing wave field preferentially grow in a certain direction, which is propitious for forming hexagonal-and spherical-like silver nanoparticles. Monodispersed spherical silver nanoparticles are easily synthesized in the diffusion field. The stability of silver colloid becomes improved by ultrasonic treatment. For example, precipitate is not found after several weeks for the silver colloid prepared with an ultrasonic treatment time of 180 min. The silver nanoparticles prepared without ultrasonic treatment are large spherical-like and hexagonal. Well-dispersed spherical silver particles with a mean size of about 20 nm have been prepared under ultrasonic treatment. Spherical, spherical-like, and hexagonal silver nanoparticles can be obtained by changing the reductants. __________ Translated from Journal of Tianjin University, 2006, 39(1) (in Chinese)     

Size-controlled synthesis of monodispersed silver nanoparticles capped by long-chain alkyl carboxylates from silver carboxylate and tertiary amine

Monodispersed silver nanoparticles capped by long-chain alkyl carboxylates were prepared by the reaction of silver carboxylate with tertiary amine at 80 degrees C for 2 h. This approach is a unique, size-controlled synthetic method for the large-scale preparation of silver nanoparticles. Long-chain alkyl carboxylate derived from a precursor acts as a stabilizer to avoid the aggregation of silver nanoparticles and to control particle size. In addition, amine plays an important role both as a reagent to form a thermally unstable, amine-coordinated intermediate, bis(amine)silver(I) carboxylate, and as a mild reducing agent for the intermediate to produce nanoparticles at a low temperature. The silver core and carboxylate-capping ligand of silver nanoparticles were characterized by various techniques such as transmission electron microscopy, optical absorption spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, gas chromatograph mass spectroscopy, and thermogravimetric and differential thermal analysis. The diameter of the nanoparticles can be strongly influenced by the alkyl chain length and the structure of the carboxylate. The average diameters of the silver nanoparticles were controlled to less than 5 nm in the case of silver carboxylate with a single alkyl chain length of 13 or 17 carbon atoms. On the contrary, the average diameters of silver nanoparticles became large and polydisperse in the case of silver carboxylate with a chain length of 7 carbon atoms or a branched chain. In comparing triethylamine with trioctylamine, there was no obvious effect to regulate the size distribution of the nanoparticles because they could not function as a capping ligand of the nanoparticles due to their weak coordination to silver. In addition, the heat treatment of silver nanoparticles in solution rather than in the solid state was effective for the growth of particles while maintaining narrow size distributions.     

In situ formation of silver nanoparticles within an amphiphilic graft copolymer film

Silver nanoparticles were prepared by UV irradiation from silver salts, such as AgBF₄ or AgNO₃, when dissolved in an amphiphilic film of poly((oxyethylene)₉ methacrylate)‐graft‐poly((dimethyl siloxane)_n methacrylate), POEM‐g‐mPDMS. The in situ formation of silver nanoparticles in the graft copolymer film was confirmed by transmission electron microscopy (TEM), UV‐visible spectroscopy, and wide angle X‐ray scattering (WAXS). The results demonstrated that the use of AgBF₄ yielded silver nanoparticles with a smaller size (～5 nm) and narrower particle distribution when compared with AgNO₃. The formation of silver nanoparticles was explained in terms of the interaction strength of the silver ions with the ether oxygens of POEM, as revealed by differential scanning calorimetry (DSC) and X‐ray photoelectron spectroscopy (XPS). It was thus concluded that a stronger interaction of silver ions with the ether oxygens results in a more stable formation of silver nanoparticles, which produces uniform and small‐sized nanoparticles. DSC and small angle X‐ray scattering (SAXS) data also showed the selective incorporation and in situ reduction of the silver ions within the hydrophilic POEM domains. Excellent mechanical properties of the nanocomposite films (3–5 × 10⁵ dyn/cm²) were observed, mostly because of the confinement of silver nanoparticles in the POEM chains as well as interfaces created by the microphase separation of the graft copolymer film. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1283–1290, 2007     

Synthesis and characterization of silver—poly(methylmethacrylate) nanocomposites

The optical properties of silver nanoparticles embedded in poly(methylmethacrylate) (PMMA) was investigated as well as the influence of silver nanoparticles on the thermal properties of polymer matrix. The average size and particle size distribution of silver nanoparticles was determined using transmission electron microscopy. The obtained transparent nanocomposite films were optically characterized using UV-Vis and FTIR spectroscopy. Thermal stability of polymer matrix was improved upon incorporation of small amount of silver nanoparticles. Also, silver nanoparticles have pronounced effect on thermo-oxidative stability of PMMA matrix. The glass transition temperatures of nanocomposites are lower compared to the pure polymer.     

A novel one step synthesis of silver nanoparticles using room temperature ionic liquid and their biocidal activity

This article reports the synthesis of silver Nan particles (SNPs) using 1-(dodecyl) 2 amino-pyridinium bromide ionic liquid. This is a new one phase method for the synthesis of uniform monodispersed crystalline silver nanoparticles in a water-ionic liquid system. In this work, the functionalized room temperature IL acts as stabilizing agent and solvent. Hydrazine hydrate acts as reducing agent. To the best of our knowledge, there is no report of the synthesis of metal nanoparticles using this ionic liquid. The synthesis of silver nanoparticles is very primarily studied by UV-Visible spectroscopic analysis. The TEM and particle size distribution was used to study morphology and size of the particles. The charge on synthesized SNPs was determined by Zeta potential. The silver nanoparticles have been known to have inhibitory and bactericidal effect. The investigation of antibacterial activities of ionic liquid stabilized silver nanoparticles was performed by measurement of the minimum inhibitory concentration.     

A versatile strategy to fabricate hydrogel-silver nanocomposites and investigation of their antimicrobial activity

In this study, hydrogel-silver nanocomposites have been synthesized by a unique methodology, which involves formation of silver nanoparticles within swollen poly (acrylamide-co-acrylic acid) hydrogels. The formation of silver nanoparticles was confirmed by transmission electron microscopy (TEM) and surface plasmon resonance (SPR) which was obtained at 406 nm. The TEM of hydrogel-silver nanocomposites showed almost uniform distribution of nanoparticles throughout the gel networks. Most of the particles, as revealed from the particle-size distribution curve, were 24-30 nm in size. The X-ray diffraction pattern also confirmed the face centered cubic (fcc) structure of silver nanoparticles. The nanocomposites demonstrated excellent antibacterial effects on Escherichia coli (E. coli). The antibacterial activity depended on size of the nanocomposites, amount of silver nanoparticles, and amount of monomer acid present within the hydrogel-silver nanocomposites. It was also found that immersion of plain hydrogel in 20 mg/30 ml AgNO(3) solution yielded nanocomparticle-hydrogel composites with optimum bactericidal activity.     

Green Synthesis and Characterization of Silver Nanoparticles Using Ferocactus echidne Extract as a Reducing Agent

The green synthesis of silver nanoparticles using an aqueous extract of Ferocactus echidne(a member of the cactus family) as a reducing agent is reported. It is simple, efficient, rapid, and ecologically friendly compared to chemical-mediated methods. Ferocactus echidne is a plant of high medicinal value and rich in polyphenolic antioxidants. The extraction is simple and the product rapidly reduces silver ions without involvement of any external chemical agent. The reduction of silver nanoparticles was characterized by ultraviolet-visible spectrometry as a function of time and concentration. The results show that Ferocactus echidne reduces silver ions within 6 h depending upon the concentration. Further increases in reaction time may result in a blue shift, indicating an increase in particle size, whereas concentration had a minor effect on the particle size. The structure of synthesized nanoparticles was investigated by infrared spectroscopy, scanning electron microscopy, and X-ray diffraction. The infrared spectra indicated the association of organic materials with silver nanoparticles to serve as capping agents. Scanning electron micrographs showed that synthesized silver nanoparticles were nearly uniform and elliptical in shape with diameters of 20 to 60 nm. X-ray diffraction confirmed the formation of silver nanoparticles with an approximate 20 nm particle size calculated using the Debye-Scherer equation. Biological tests revealed that the silver nanoparticles were active against gram positive and negative bacteria( Escherichia coli and Staphylococcus aureus) and fungi (Candida albicans), indicating their broad spectrum antibiotic and antifungal abilities.