Importance of poly(ethylene glycol) conformation for the synthesis of silver nanoparticles in aqueous solution

Silver nanoparticles (NPs) were prepared using silver nitrate (AgNO₃) as a precursor in an aqueous solution of poly(ethylene glycol) (PEG), which acted as both a reducing and stabilizing agent. The UV/Vis spectra showed that PEG 100 (100 kg/mol) has a remarkable capability to produce silver NPs at 80 °C, but the production of silver NPs by both PEG 2 (2 kg/mol) and PEG 35 (35 kg/mol) was negligible. This difference was explained by the conformation of PEG in the reaction solution: the entangled conformation for PEG 100 and the single-coiled conformation for PEG 2 and PEG 35, which were confirmed by pulse-field-gradient ¹H NMR and viscosity measurements. In an aqueous solution, the entangled conformation of PEG 100 facilitated the reduction reaction by caging silver ions and effectively prevented the agglomeration of formed NPs. The reaction in an aqueous PEG 100 solution was observed to be stable under the conditions of a prolonged reaction time or an increased temperature, while no reduction reaction occurred in the PEG 2 solution. The synthesis of silver NPs by PEG 100 was well controlled to produce fine silver NPs with 3.68 ± 1.03 nm in diameter, the size of which remained relatively constant throughout the reaction.     

Fabrication of silver nanoparticles in a continuous flow,low temperature microwave-assisted polyol process

The performed experiments showed that continuous microwave-assisted polyol synthesis at about 70 °C is a viable process to give silver nanoparticles with a narrow size distribution in bulk amounts. The increase of silver precursor concentration in reaction system from 0.0097 to 0.0389 M resulted in the formation of fine nanoparticles 5–10 nm in size, in addition to the larger ones 30–100 nm, and that changed the pattern of particle size distribution from monomodal to bimodal. The effect of specific process variables was found to be the same in the continuous process as in batch operation. An aqueous glycerol solution was found suitable for use as both solvent and reducing agent.     

聚丙烯胺稳定铜纳米粒子的制备及其SERS活性研究

报道了聚丙烯胺稳定的球形和棒状铜纳米粒子的制备方法。在水溶液中空气条件下,通过水合肼还原二价铜离子到铜纳米粒子。聚丙烯胺的作用除稳定粒子防止聚集外,也可使粒子分散在水溶液中。该法的优点是在室温下,无需惰性气体保护,即可制备水溶液中分散的铜纳米粒子。紫外光谱和透射电镜监测了铜纳米粒子的生长过程。发现氢氧化钠的用量,聚丙烯胺浓度,反应时间等因素都影响到铜纳米粒子的组成,尺寸,形貌和聚集程度。氢氧化钠用量决定了制备粒子的组成成分是铜或氧化亚铜。所制备的球形铜纳米粒子表现出优良的表面增强拉曼散射活性。     

Effect of phytochemicals on optical absorption spectra during biogenic synthesis of self-assembled silver nanoparticles and studies relevant to food applications

The facile biogenic synthesis of silver nanoparticles was done using avocado seed aqueous extract and silver salt. Avocado seed aqueous extract was used as an active biomolecule for in situ fabrication of self-assembled silver nanoparticles. This green approach to the mechanism for the formation of uniform sized silver nanoparticles was studied by ultraviolet-visible spectroscopy, field emission scanning electron microscopy and Fourier transform infrared spectroscopy. The effect of incubation time, concentration of silver nitrate, and avocado seed extract concentrations in the synthesis of silver nanoparticle was studied. Spectral splitting in the visible region with the generation of a new plasmon resonance band resulted with concurrent increase in the concentration of phytochemicals and reaction time during the synthesis of particles was observed. This was due to the chemisorption of phytochemicals accompanied by a charge-transfer transition, which may be responsible for the organization and self-assembly of nanoparticles. The phytochemicals present in the extract acted as a reducing agent and simultaneously fabricating the nanoparticles with the phenolics and sugar compounds. The antibrowning and antibacterial activity of silver nanoparticles were tested and could be exploited for their use in food packaging and preservation.     

Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of ?41.98 mV for the gold nanoparticles and ?53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV–visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7–99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.     

Synthesis and characterization of monodisperse copper nanoparticles using gum acacia

A simple method was put forward in this paper for preparing colloidal copper nanoparticles in aqueous solutions using copper sulfate, gum acacia and hydrazine hydrate as copper precursor, capping agents and reducing agents, respectively, without any inert gas. The formation of nanosized copper was confirmed by its characteristic surface plasmon absorption peak at 604 nm in UV–vis spectra. The transmission electron microscopic (TEM) and scanning electron microscope (SEM) images show that the as-synthesized copper fine spherical particles are distributed uniformly with a narrow distribution from 3 nm to 9 nm. The X-ray diffraction (XRD) and high resolution transmission electron microscopic (HRTEM) demonstrated that the obtained metallic nanoparticles are single crystalline copper nanoparticles. Fourier transform infra-red (FT-IR) spectroscopic data suggested that the copper nanoparticles are coated with gum acacia. The effects of the quantity of gum acacia on the particle size were investigated by the UV–vis spectra and TEM images. The growth process of the nanoparticles was monitored by the UV–vis spectra. The mechanism of the formation copper nanoparticles was discussed. The process raised in this study can be served as an excellent candidate for the preparation of copper nanoparticles in a large scale production.     

Continuous synthesis of colloidal silver nanoparticles by electrochemical discharge in aqueous solutions

This article presents an electrochemical discharge (ECD) method that consists of a combination of chemical methods and electric arc discharges. In the method, 140 V is applied to an Ag electrode from a DC power supply. The arc-discharge between the electrodes produces metallic silver nanoparticles and silver ions in the aqueous solution. Compared with the original arc discharge, this ECD method creates smaller nanoparticles, prevents clumping of the nanoparticles, and shortens the production time. The citrate ions also reduce the silver ions to silver nanoparticles. In addition, the citrate ions cap the surface of the produced silver nanoparticles and the zeta potential increases. In this article, the weight loss of the electrodes and the reduction of silver ions to silver nanoparticles as a function of citrate concentration and electric conductivity of the medium are discussed. Furthermore, the properties of the colloidal silver prepared with ECD are analyzed by UV–Vis spectroscopy, dynamic light scattering, electrophoresis light scattering, and scanning electron microscopy. Finally, a continuous production apparatus is presented for the continuous production of colloidal silver.     

Influence of several factors on the growth of selenium nanowires induced by silver nanoparticles

This paper presents a study on the crystallization and growth mechanism of selenium nanowires induced by silver nanoparticles at ambient conditions with special reference to the effects of factors such as the shapes and size of silver nanoparticles, the induced reaction time, and the molar ratio of Ag⁰ to SeO₃²⁻ ions. The synthesis approach is conducted with no need of any stabilizers, and with no sonochemical process and/or templates. It is found that whether silver spherical particles or colloids can lead to the formation of nanowires with average diameter of 25 nm and lengths up to a few micrometers, and silver nanoplates lead to the formation of flat Se nanostructures. In particular, Au, Cu, Pt, and Pd particles cannot induce the growth of selenium nanowires in aqueous solution at room temperature. The results indicate that silver particles play a critical role in determining the growth of selenium nanowires. The lattice match between hexagonal-Se and orthorhombic- or trigonal-Ag₂Se particles is the major driving force in the growth of such nanostructures. The findings would be useful for design and construction of heterogeneous nanostructures with similar lattice parameter(s).     

Electrochemical method for the synthesis of silver nanoparticles

The article deals with a novel electrochemical method of preparing long-lived silver nanoparticles suspended in aqueous solution as well as silver powders. The method does not involve the use of any chemical stabilising agents. The morphology of the silver nanoparticles obtained was studied using transmission electron microscopy, scanning electron microscopy, atomic force microscopy and dynamic light scattering measurements. Silver nanoparticles suspended in water solution that were produced by the present technique are nearly spherical and their size distribution lies in the range of 2 to 20 nm, the average size being about 7 nm. Silver nanoparticles synthesised by the proposed method were sufficiently stable for more than 7 years even under ambient conditions. Silver crystal growth on the surface of the cathode in the electrochemical process used was shown to result in micron-sized structures consisting of agglomerated silver nanoparticles with the sizes below 40 nm.     

Simple and environmentally friendly preparation and size control of silver nanoparticles using an inhomogeneous system with silver-containing glass powder

A simple, environmentally friendly method for preparing highly size-controlled spherical silver nanoparticles was developed that involved heating a mixture of silver-containing glass powder and an aqueous solution of glucose. The stabilizing agent for silver nanoparticles was found to be caramel, which was generated from glucose when preparing the nanoparticles. The particle size was independent of the reaction time, but it increased proportionally with the square root of the glucose concentration in the range 0.25–8.0 wt% (corresponding to particle sizes of 3.48 ± 1.83 to 20.0 ± 2.76 nm). Difference of the generation mechanism of silver nanoparticles between this inhomogeneous system and a system in which Ag⁺ was homogeneously dispersed was discussed.     

Preparation of triethylamine stabilized silver nanoparticles for low-temperature sintering

In this article, silver nanoparticles were synthesized by chemical reduction from silver nitrate using triethylamine as the protecting and reducing agents simultaneously. The average size of the silver nanoparticles was about 2.10–4.65 nm, which allowed low-temperature sintering of the metal. X-ray diffraction (XRD), thermogravimetric analysis (TGA), and energy dispersive spectrometric (EDS) analysis results indicate that silver nitrate has been converted to silver nanoparticles completely. Using a 20 wt% silver nanoparticles suspension with thermal treatment at 150 °C, silver films with a resistivity of 8.09 × 10⁻⁵ Ω cm have been produced, which is close to the resistivity of bulk silver.     

Synthesis and antibacterial activity of silver nanoparticles with different sizes

Silver nanoparticles with different sizes (7, 29, and 89 nm mean values) were synthesized using gallic acid in an aqueous chemical reduction method. The nanoparticles were characterized using transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray diffraction (XRD), and ultraviolet–visible (UV–Vis) absorption spectroscopy; the antibacterial activity was assessed using the standard microdilution method, determining the minimum inhibitory concentration (MIC) according to the National Committee for Clinical Laboratory Standards. From the microscopies studies (TEM) we observed that silver nanoparticles have spherical (7 and 29 nm) and pseudospherical shape (89 nm) with a narrow size distribution. The sizes of the silver nanoparticles were controlled by varying some experimental conditions. It was found that the antibacterial activity of the nanoparticles varies when their size diminishes.     

Preparation of CuO nanoparticles by metal salt-base reaction in aqueous solution and their metallic bonding property

This article describes a method for preparing CuO nanoparticles in aqueous solution, and a demonstration of feasibility of metallic bonding with the use of the CuO particles. Colloid solution of CuO nanoparticles was prepared from Cu(NO₃)₂ aqueous solution (0.01 M) and NaOH aqueous solution (0.019 M) at 5–80 °C. Leaf-like aggregates with an average size of 567 nm composed of CuO nanoparticles were produced at 20 °C. The size of leaf-like aggregates decreased with increasing reaction temperature. Metallic copper discs could be bonded using the CuO nanoparticles under annealing at 400 °C and pressurizing at 1.2 MPa for 5 min in H₂ gas. A shear strength required for separating the bonded discs was 25.4 MPa for the CuO nanoparticles prepared at 20 °C, whose aggregates were the largest among the CuO particles examined. These results indicated that the formation of leaf-like aggregates of CuO nanoparticles led to efficient metallic bonding.     

Green synthesis of finely-dispersed highly bactericidal silver nanoparticles via modified Tollens technique

In this article, we represent a versatile and effective technique which using non-toxic chemicals to prepare stable aqueous dispersions of silver nanoparticles (NPs) via modified Tollens process. It was shown that as-prepared silver colloids consisted of finely-dispersed NPs with average diameter about 10 nm and a relatively narrow size distribution. Moreover, they could be stored very stable after several months without observation of aggregates or sedimentation. In comparison with previous works where Tollens process was being used, we for the first time applied UV-irradiation simultaneously with glucose reduction of silver salt through NPs preparation. The colloidal solutions of silver NPs were found to exhibit a high antibacterial activity against gram-negative Escherichia coli. The concentration of silver leading to a complete inhibition of bacteria growth was revealed as low as at 1.0 μg ml⁻¹ and found much lower compared to earlier reports. These advantages of aqueous dispersions of silver NPs make them ideal for green industrial, medicinal, microbiological and other applications.     

Methoxycarbonyl-terminated hyperbranched poly(amine-ester) as templates for synthesis of silver nanoparticles

Highly stable and spherical silver nanoparticles, stabilized by methoxycarbonyl-terminated hyperbranched poly(amine-ester) (HPAE-COOCH₃), were synthesized in water with reducing AgNO₃/HPAE-COOCH₃ using two methods, viz. NaBH₄ and ultraviolet irradiation. HPAE-COOCH₃ was found to play a key role in the formation of nanoparticles. UV–visible absorption, Transmission electron microscopic (TEM), and Fourier transform infrared spectroscopy (FT-IR) had been used to study the structure and characterization of the silver nanoparticles. The absorption peaks of the silver nanoparticles appear at ~420 nm in UV–visible absorption spectra; average particle size reduced by NaBH₄ is ~30 nm, which is ~10 and ~15 nm, respectively, when ultraviolet irradiation time is 12 and 24 h. FT-IR spectra confirm that there is strong interaction between silver nanoparticles and HPAE-COOCH₃. And silver nanoparticles/HPAE-COOCH₃ aqueous solution can keep stable for more than 3 months.     

UV-induced synthesis,characterization and formation mechanism of silver nanoparticles in alkalic carboxymethylated chitosan solution

The silver nanoparticles (AgNPs) were synthesized in an alkalic aqueous solution of silver nitrate (AgNO₃)/carboxymethylated chitosan (CMCTS) with ultraviolet (UV) light irradiation. CMCTS, a water-soluble and biocompatible chitosan derivative, served simultaneously as a reducing agent for silver cation and a stabilizing agent for AgNPs in this method. UV–vis spectra and transmission electron microscopy (TEM) images analyses showed that the pH of AgNO₃/CMCTS aqueous solutions, the concentrations of AgNO₃ and CMCTS can affect on the size, amount of synthesized AgNPs. Further by polarized optical microscopy it was found that the CMCTS with a high molecular weight leads to a branch-like AgNPs/CMCTS composite morphology. The diameter range of the AgNPs was 2–8 nm and they can be dispersed stably in the alkalic CMCTS solution for more than 6 months. XRD pattern indicated that the AgNPs has cubic crystal structure. The spectra of laser photolysis of AgNO₃/CMCTS aqueous solutions identified the early reduction processes of silver cations (Ag⁺) by hydrated electron formed by photoionization of CMCTS. The rate constant of corresponding reduction reaction was 5.0 × 10⁹ M⁻¹ s⁻¹.     

A simple method for selective immobilization of silver nanoparticles

Size-adjustable silver nanoparticles were selectively in situ produced and immobilized on glass surface by simply UV exposing poly(vinylpyrrolidone) (PVP) film containing silver nitrate and 4,4′-diazostilbene-2,2′-disulfonic acid disodium salt (DAS) with the presence of a photomask, during which the crosslink between PVP and DAS completed and the silver nitrate was reduced to silver nanoparticles under the assistance of UV. Because the reduction speed of silver nitrate is much slower than the crosslink reaction of PVP, and a mount of unreduced silver nitrate still existed in the formed PVP micro-scale patterns after removing unexposed PVP by water, we can easily adjust the size of silver nanoparticles through further controlling the reduction of unreduced silver nitrate in the formed PVP micro-scale patterns. Optical microscope, UV–vis-spectroscopy, AFM and SEM-EDX were used to characterize the morphology and distribution of those silver nanoparticles immobilized on glass surface. The results indicate that it is an effective way to immobilize silver nanoparticles with high selectivity.     

Zinc sulfide nanoparticles: Spectral properties and photocatalytic activity in metals reduction reactions

Formation of zinc sulfide nanocrystals in aqueous solutions of various polymers has been studied. Spectral properties of ZnS nanoparticles have been investigated, the structure of the long-wave edge of the fundamental absorption band of ZnS nanocrystals has been analyzed. It has been shown that the variation of the synthesis conditions (stabilizer nature and concentration, solution viscosity, ZnS concentration, etc.) allows tailoring of the ZnS nanocrystals size in the range of 3–10 nm. Photochemical processes in colloidal ZnS solutions, containing zinc chloride and sodium sulfite, have been investigated. It has been found that the irradiation of such solutions results in the reduction of Zn(II), the rate of this reaction growing at a decrease in the size of ZnS nanoparticles. Kinetics of photocatalytic Zn(II) reduction has been studied. It has been concluded that two-electron reduction of adsorbed Zn(II) species is the rate-determining stage of this reaction. Photocatalytic activity of ZnS nanoparticles in KAu(CN)₂ reduction in aqueous solutions has been discovered. Spectral characteristics and kinetics of ZnS/Au⁰ nanocomposite formation have been studied. It has been shown that the photoreduction of gold(I) complex is the equilibrium reaction due to the reverse oxidation of gold nanoparticles by ZnS valence band holes.     

Fluorescent silver nanoparticles via exploding wire technique

Aqueous solution containing spherical silver nanoparticles of 20–80 nm size have been generated using a newly developed novel electro-exploding wire (EEW) technique where thin silver wires have been exploded in double distilled water. Structural properties of the resulted nanoparticles have been studied by means of X-ray diffractometer (XRD) and transmission electron microscopy (TEM). The absorption spectrum of the aqueous solution of silver nanoparticles showed the appearance of a broad surface plasmon resonance (SPR) peak centered at a wavelength of 390 nm. The theoretically generated SPR peak seems to be in good agreement with the experimental one. Strong green fluorescence emission was observed from the water-suspended silver nanoparticles excited with light of wavelengths 340, 360 and 390 nm. The fluorescence of silver nanoparticles could be due to the excitation of the surface plasmon coherent electronic motion with the small size effect and the surface effect considerations     

Phyllanthin-assisted biosynthesis of silver and gold nanoparticles: a novel biological approach

Abstract  The anisotropic gold and spherical–quasi-spherical silver nanoparticles (NPs) were synthesized by reducing aqueous chloroauric acid (HAuCl₄) and silver nitrate (AgNO₃) solution with the extract of phyllanthin at room temperature. The rate of reduction of HAuCl₄ is greater than the AgNO₃ at constant amount of phyllanthin extract. The size and shape of the NPs can be controlled by varying the concentration of phyllanthin extract and thereby to tune their optical properties in the near-infrared region of the electromagnetic spectrum. The case of low concentration of extract with HAuCl₄ offers slow reduction rate along with the aid of electron-donating group containing extract leads to formation of hexagonal- or triangular-shaped gold NPs. Transmission electron microscopy (TEM) analysis revealed that the shape changes on the gold NPs from hexagonal to spherical particles with increasing initial concentration of phyllanthin extract. The Fourier transform infrared spectroscopy and thermogravimetric analyses reveal that the interaction between NPs and phyllanthin extract. The cyclic voltammograms of silver and gold NPs confirms the conversion of higher oxidation state to zero oxidation state. Graphical abstract  Anisotropic gold and silver nanoparticles were synthesized by a simple procedure using phyllanthin extract as reducing agent. The rate of bioreduction of AgNO₃ is lower than the HAuCl₄ at constant concentration of phyllanthin extract. The required size of the nanoparticles can be prepared by varying the concentration of phyllanthin with AgNO₃ and HAuCl₄.