室温条件下纳米银的温和制备和形貌调控

目的 探究室温条件下不同还原剂以及其他实验助剂在化学还原纳米银过程中对其颗粒粒径、尺寸分布和形貌的影响。方法 以抗坏血酸为还原剂,聚乙烯吡咯烷酮（PVP）为分散剂,柠檬酸钠为保护剂和第2还原剂,选择葡萄糖和硼氢化钠作对照,在室温下通过化学还原的方法来制备纳米银颗粒。通过马尔文激光粒度仪、紫外–可见光谱（UV–vis）、透射电镜（TEM）等对所制备纳米银进行表征。结果 采用抗坏血酸作为还原剂时,通过调控抗坏血酸体积（0.2 mL）,固定柠檬酸钠和PVP体积分别为0.5、0.6 mL,制备出粒径较小（平均粒径为56 nm）且尺寸分布较均一的球形纳米银;采用葡萄糖和硼氢化钠作还原剂时纳米银颗粒尺寸过大（平均粒径分别为216nm和189nm）。结论 采用抗坏血酸作为还原剂,调控柠檬酸钠、PVP等实验参数在最佳范围,更容易制备出球形度好、粒径小的均匀纳米银溶液。     

A novel thermal electrochemical synthesis method for production of stable colloids of “naked” metal (Ag) nanocrystals

This paper describes a novel thermal electrochemical synthesis (TECS) method for producing aqueous solutions (or sols) that contain metal silver nanocrystals as small as a few nanometers. The TECS method requires mild conditions (25 to 100 °C), low voltage (1 to 50 V DC) on silver electrodes, and water or simple aqueous solutions as the reaction medium. Furthermore, a tubular dialysis membrane that surrounds the electrodes provides favorable conditions for producing nanosized (less than 10 nm) silver nanocrystals. Unlike nanocrystals reported in the literature, our nanocrystals have several unique features: (1) small nanometer-scale size, (2) “nakedness” (i.e., surfaces of metal nanocrystals are free of organic ligands or capping molecules and need no dispersant in synthesis solutions), and (3) colloidal stability in water solutions. It was discovered that silver nanoparticles with initially large size distribution can be homogenized into near-monodispersed colloidal sol by a low-power (less than 15 mW) He–Ne laser exposure treatment. The combination of the TECS technique and the laser treatment could lead to a new technology that produces metal nanoparticles that are naked, colloidally stable, and uniformly sized. In the presence of a stabilizing agent (also a supporting electrolyte) such as polyvinyl alcohol, high yields of silver nanoparticles (less than 100 nm) in the form of thick milky sols are produced.     

Influence of processing method on the properties of hydroxyapatite nanoparticles in the presence of different citrate ion concentrations

The objective of this study was to investigate the effect of processing methods on the formation of ultra fine hydroxyapatite (HAp) nanoparticles in the presence of citrate ions and analyze their various physical properties. The addition of the citrate ions was found to reduce the size and prevent the agglomeration of HAp particles dramatically in the high gravity (HG) method compared to precipitation method. In precipitation method, the particle size reduced from 300 ± 70 nm to 90 ± 20 nm with the addition of citrate ions. In high gravity method, the particle size decreased more significantly from 80 ± 10 nm to 13 ± 5 nm with the addition of citrate ions. Furthermore, more uniform size distribution of nanoparticles was achieved in high gravity method. X-ray diffraction of nanoparticles prepared in both method exhibited slight shift of peaks to the higher angle with the addition of citric acid, indicating the incorporation of carbonate (CO₃) content in the HAp nanoparticles irrespective of the particle size. The mechanical properties of HWMPE matrix composite reinforced with nanoparticles was examined and this nanocomposite with nanoparticles prepared in high gravity method with the addition of citrate ions showed increased mechanical strength due to the considerable reduction in the particle size and higher uniformity of the particles. In vitro cellular analyses of the nanoparticle prepared in high gravity with the addition of citrate ions also displayed the most pronounced spreading of cell growth.     

Effects of supersaturation on CdS film growth from dilute solutions on glass substrate in chemical bath deposition process

CdS films were prepared on a glass substrate and their growth was analyzed as a function of the supersaturation ratio in dilute solutions. Nanocrystalline CdS with a hexagonal (wurtzite) structure is present in the CdS films and aggregated into colloidal particles. The particle size increases from 117 nm to 357 nm when the relative supersaturation ratio (S_r) increases from 0.4 to 1.0, but particle size decreases to 149 nm and the absorption edge blue shifts from 488 nm to 456 nm when S_r increases further to 4.0. The evolution of the CdS film is explained on the basis of the proposed growth kinetic model.     

Biological synthesis of silver nanoparticles using the fungus Aspergillus flavus

The fungus, Aspergillus flavus when challenged with silver nitrate solution accumulated silver nanoparticles on the surface of its cell wall in 72 h. These nanoparticles dislodged by ultrasonication showed an absorption peak at 420 nm in UV-visible spectrum corresponding to the plasmon resonance of silver nanoparticles. The transmission electron micrographs of dislodged nanoparticles in aqueous solution showed the production of reasonably monodisperse silver nanoparticles (average particle size: 8.92 ± 1.61 nm) by the fungus. X-ray diffraction spectrum of the nanoparticles confirmed the formation of metallic silver. The Fourier transform infrared spectroscopy confirmed the presence of protein as the stabilizing agent surrounding the silver nanoparticles. These protein-stabilized silver nanoparticles produced a characteristic emission peak at 553 nm when excited at 420 nm in photoluminescence spectrum. The use of fungus for silver nanoparticles synthesis offers the benefits of eco-friendliness and amenability for large-scale production.     

Dendrigraft polymer-based synthesis of silver nanoparticles showing bright blue fluorescence

A novel method is reported here for the synthesis of optically clear and stable colloidal solutions of silver nanoparticles. According to size they show different colours depending upon their plasmonic absorption frequencies. The materials have been synthesized at room temperature by chemical reduction of silver ions (silver nitrate) coordinated with dendrigraft polymer, polyethyleneimine (PEI) using formaldehyde in aqueous medium. UV-vis absorption and transmission electron microscopy (TEM) studies show single-band absorption with peak maximum at 354 nm for ∼3 nm sized particles, whereas a side band at ∼400 nm was observed when the particle size increased to ∼20 nm. Highly narrow particle size distribution was observed in case of samples having ∼3 nm size silver particles and also the process of reduction could be completed within minutes. More interestingly, the 3-nm sized particles showed strong blue (474 nm) fluorescence under UV excitation. Thin films of all synthesized samples were prepared on silica substrate by fine spray coating technique.     

Silver nanoparticles: Ultrasonic wave assisted synthesis, optical characterization and surface area studies

Silver nanoparticles have been successfully synthesized by the sonochemical route using sodium borohydride and sodium citrate as the reducing agents. The effect of the reducing agents on the particle size and morphology has been studied by carrying out the two reactions at the same ultrasound frequency (20 KHz). The strong reducing agent (NaBH₄) produced spherical silver nanoparticles of sizes 10 nm whereas sodium citrate led to much smaller silver nanoparticles of ~ 3 nm diameter. Powder X-ray diffraction studies reveal a high degree of crystallinity and monophasic silver particles. UV-Visible studies show the presence of a surface plasmon band at 405 nm. However the reflectance spectra give a broad band between 340 and 360 nm which is characteristic for the quasi-spherical silver nanoparticles. The specific surface area was found to be 2.6 and 13.1 m²/g and the pore radius was found to be 15.2 and 12.3 Å for silver nanoparticles obtained by the sodium borohydride and sodium citrate reduction respectively.     

Directed growth of nanoarchitected hybrid phosphor particles synthesized at low temperature

Sub-micronic particles are of considerable interest for a wide variety of applications, such as catalyst or optical ceramics, due to their unique properties determined by size, composition and structure. In this work, we have reported a simple, rapid, single-step aerosol processing for the continuous synthesis of nanostructured particles having homogeneous composition and narrow size distributions, good crystallinity and fluorescence response. This paper presents the synthesis, optimization and characterization of hybrid Ag@Y₂O₃:Eu (9 at.% Eu³⁺) phosphor particles by means of spray pyrolysis method from water solutions of common nitrates precursors. The effect of silver concentration on particle structure, morphology and functional properties was specially evaluated. The as-prepared samples were additionally heated from 800 to 1200 °C/12 h under constant argon flow to avoid the silver oxidation. It was evident the cubic phase with Ia-3 symmetry as the principal one in all as-prepared and thermally treated samples. For the case high silver nitrate concentrations in precursor solutions a minority crystalline phase having Fm3m symmetry was identified. The luminescence emission spectra have been taken after excitation at 235 nm wavelength. It is evident the increase in the emission caused by the presence of metallic silver nanoparticles onto Y₂O₃:Eu³⁺ particle surface. It was also determined the silver concentration influence on the fluorescence response.     

A new and effective chemical reduction method for preparation of nanosized silver powder and colloid dispersion

Nanosized uniform silver powders and colloidal dispersions of silver were prepared from AgNO₃ by a chemical reduction method involving the intermediate preparation of Ag₂O colloidal dispersion in the presence of sodium dodecyle sulfate CH₃(CH₂)₁₁OSO₃Na as a surfactant. Several reducing agents such as hydrazine hydrate (N₂H₄·H₂O), formaldehyde (HCOH) and glucose (C₆H₁₀O₅) have been found to be preferable in this study from a practical point of view. The silver powder with the 60-120 nm particle size and colloidal dispersion with the particles size 10-20 nm and 0.5-2.0 wt.% concentration were successfully synthesized.     

Synthesis and characterization of silver nanoparticles impregnated into bacterial cellulose

This article presents a study about the synthesis of colloidal silver (Ag)/biopolymer where Ag submicron particles were prepared in situ on bacterial cellulose (BC) produced by Gluconacetobacter xylinus. Different reducing agents were compared (hydrazine, hydroxylamine or ascorbic acid) together with the influence of gelatin or polyvinylpyrrolidone (PVP) employed as colloid protectors. Particle size distribution and morphology were investigated by scanning electron microscope (SEM). SEM images show silver nanoparticles (40–100 nm) size range attached on (BC) microfibrils. XRD analyses confirmed the Ag cubic phase deposited on to BC fibrils. The ash contents determined by thermogravimetric analyses have indicated high level of silver loading on the obtained composites.     

Synthesis of silver/poly (diallyldimethylammonium chloride) hybride nanocomposite

This paper presents a method for the preparation of silver nano-particles in poly (diallyldimethylammonium chloride) (PDDA) using N,N-dimethylformamide (DMF) as a medium has been performed successfully. A golden solution in its UV–vis absorption spectrum showed surface plasmon resonance absorption bands between 410 and 425 nm in solutions and at about 461 nm in a transparent film. The Ag/PDDA nano-composite was characterized by X-ray diffraction (XRD) measurement, transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier-transform-infrared spectroscopy (FT-IR) and thermo-gravimetric analysis (TGA). XRD showed the fcc crystal structure of the bulk Ag with particles of <22 nm in size similar to that is observed by TEM and PDDA is crucial to the formation of such silver nano-composite. SEM indicated uniform distribution of particles in the film. TGA confirmed enhanced thermal stability of the polymer.     

A comparative study of eco-friendly silver nanoparticles synthesis using Prunus domestica plum extract and sodium citrate as reducing agents

Through the current comparative study, colloidal silver nanoparticles (AgNPs) were synthesized with various morphologies and sizes using Prunus domestica (P-dom) extract and sodium citrate as green and chemical reducing agents, respectively. AgNPs were synthesized employing different concentrations of the reducing agents in an aqueous solution at various pH values (3–10) and temperatures (25–85 °C). The UV–visible absorption spectrum indicated characteristic SPR peaks of AgNPs at 380–450 nm. Fourier transform infrared spectroscopy revealed aqueous-soluble polyols (such as glycosides, phenols, and flavanols) participation in Ag ions reduction to the corresponding AgNPs at various pH values. The crystallinity of AgNPs was detected by an X-ray diffractometer. Different morphologies (polygonal, oval, and spherical) of the AgNPs with varying pH values were confirmed conducting transmission electron microscopy (TEM). Average particle sizes of 16–50 nm were determined using scanning electron microscopy, TEM, and dynamic light scattering assessments for AgNPs synthesized at various reaction conditions. This study is a demonstration for a facile, cheap, and eco-friendly stimuli-sensitive preparation of the AgNPs.     

Association of radionuclides with the colloidal matter of underground waters taken from observation wells in the zone of impact of Lake Karachai

Associations of radionuclides with colloidal particles of various sizes, isolated from underground waters of the Lake Karachai contamination area, were studied. Analysis by photon correlation spectroscopy showed that the total content of colloidal matter in deeper horizons is higher by an order of magnitude than in near-surface horizons. The mean particle radius also increases with the depth. The major fraction of Pu, Am, and Cm is associated with colloids (40–90%). U and Np are associated with colloidal particles to a lesser extent (2–20%), which determines their higher migration mobility in underground waters. The amount of actinides associated with coarse colloidal particles of size from 450 to 200 nm is insignificant. A considerable fraction of actinides is in the deep-lying water (depth ≥40 m) is associated with colloidal particles of size from 200 to 50 nm. No more than 30% of Pu and Am in water of these horizons is associated with finer colloids (from 10 kDa to 50 nm). With approaching the surface, the amount of actinides in the fraction of nanometer-sized particles (50 nm-10 kDa) increases (to 50%).     

Fabrication of antibacterial monodispersed Ag-SiO2 core-shell nanoparticles with high concentration

Monodispersed Ag-SiO₂ core-shell nanoparticles with a high concentration of 400 mg/L were successfully fabricated by using tetraethoxysilane as silica precursor and reducing silver nitrate with ascorbic acid in the presence of cetyltrimethylammonium bromide as stabilizing agent. The nanoparticles had a spherical silver core in a size range from 14-26 nm in diameter and an amorphous silica shell of 15-28 nm thickness, respectively. The antibacterial effects of Ag-SiO₂ core-shell particles against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were tested by the usual twofold serial dilution method for minimal inhibitory concentration (MIC) and minimal bactericidal concentration (MBC). The results indicated that the core-shell nanoparticles owned excellent antibacterial effects.     

Green synthesis of silver nanoparticles using flower extract of Malva sylvestris and investigation of their antibacterial activity

High‐quality colloidal silver nanoparticles (AgNP) were synthesised via a green approach by using hydroalcoholic extracts of Malva sylvestris. Silver nitrate was used as a substrate ion while the plant extract successfully played the role of reducing and stabilising agents. The synthesised nanoparticles were carefully characterised by using transmission electron microscopy, atomic‐force microscopy, energy dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy and UV–vis spectroscopy. The maximum absorption wavelengths of the colloidal solutions synthesised using 70 and 96% ethanol and 100% methanol, as extraction solvents, were 430, 485 and 504 nm, respectively. Interestingly, the size distribution of nanoparticles depended on the used solvent. The best particle size distribution belonged to the nanoparticles synthesised by 70% ethanol extract, which was 20–40 nm. The antibacterial activity of the synthesised nanoparticles was studied on Escherichia coli, Staphylococcus aureus and Streptococcus pyogenes using disk diffusion, minimum inhibitory concentrations and minimum bactericidal concentrations assays. The best antibacterial activity obtained for the AgNPs produced by using 96% ethanolic extract.Inspec keywords: silver, nanoparticles, nanofabrication, antibacterial activity, colloids, particle size, transmission electron microscopy, atomic force microscopy, X‐ray chemical analysis, Fourier transform spectra, infrared spectra, ultraviolet spectra, visible spectra, microorganisms, nanomedicine, biomedical materialsOther keywords: Green synthesis, flower extract, Malva sylvestris, antibacterial activity, high‐quality colloidal silver nanoparticles, hydroalcoholic extracts, plant extract, reducing agents, stabilising agents, transmission electron microscopy, atomic‐force microscopy, energy dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy, UV– vis spectroscopy, colloidal solutions, particle size distribution, Escherichia coli, Staphylococcus aureus, Streptococcus pyogenes, disk diffusion, minimum inhibitory concentrations, minimum bactericidal concentrations assays, ethanolic extract, size 430 nm, size 485 nm, size 504 nm, size 20 nm to 40 nm, Ag     

Synthesis of Starch-Stabilized Silver Nanoparticles and Their Antimicrobial Activity

In this study, silver nanoparticles were prepared using silver nitrate as the metal precursor, starch as protecting agent, and sodium borohydride (NaBH₄) as a reducing agent by the chemical reduction method. The formation of the silver nanoparticles was monitored using ultraviolet-visible absorption spectroscopy, cyclic voltammetry, and particle size analyzer and characterized by transmission electron microscopy (TEM) and x-ray diffraction (XRD). Synthesis of nanoparticles were carried out by varying different parameters, such as reaction temperature, concentration of reducing agent, concentration of silver ion in feed solution, type and concentration of the stabilizing agent, and stirrer speed expressed in terms of particle size and size distribution. Dispersion destabilization of colloidal nanoparticles was detected by Turbiscan. It was observed that size of the starch stabilized silver nanoparticles were lower than 10 nm. The microbial activity of synthesized silver nanoparticles was examined by modified Kirby-Bauer disk diffusion method. Silver nanoparticles were tested for their antibacterial activity against Gram negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, and Gram positive bacteria such as Staphylococcus aureus and Staphylococcus epidermidis. High bacterial activity was observed at very low concentrations of silver (below 1.39 μg/ml). The antifungal activity of silver nanoparticles has been assayed against Candida albicans.     

Sintering behavior of spherical aggregated nanoparticles prepared by spraying colloidal precursor in a heated flow

The sintering behavior of spherical aggregated nanoparticles prepared by spraying colloidal precursor into a heated flow was investigated both experimentally and theoretically. Spherical micrometer-sized particles consisting of compactly aggregated nanoparticles were formed, due to solvent evaporation and the drying process of the colloidal precursor. The degree of sintering of aggregated nanoparticles depended on the furnace temperature profile, residence time and primary particle size of the aggregated nanoparticles. Spherical monodispersed colloidal silica, in sizes ranging from 22 to 100 nm was selected as the primary particles. The sintering rate increased with temperature and residence time, and decreased with increasing primary particle size. The aggregated nanoparticles sintered completely, resulting in particles with smooth surfaces that were synthesized at 1400 °C, residence time 31.7 s that was obtained by using a carrier gas flow rate of 1.5 L/min and 0.1 M colloidal silica nanoparticles 100 nm in size. An appropriate model of sintering in the system was proposed to explain the shrinkage and the neck growth of the aggregated nanoparticles. The sintering analysis suggested that solid-state volume diffusion suitably described the sintering mechanism of spherical aggregated silica nanoparticles in a heated flow.     

聚苯乙烯-银胶体晶体的制备及自组装行为

利用冠醚可与银离子复合的特性,制备了聚苯乙烯-冠醚乳胶粒,采用原位还原的方法在乳胶粒表面引入银纳米颗粒,通过垂直沉降,乳胶粒子可自组装成紧密堆积具有面心立方的聚苯乙烯-银胶体晶体。结果表明:引入聚苯乙烯-银乳胶粒表面的银为胶粒总质量的6.7%,乳胶粒具有以银纳米颗粒为壳,聚苯乙烯为核的核壳结构,乳胶粒大小为260 nm,并具有很好的单分散性。由于Bragg散射,该胶体晶带隙位于580 nm,在可见光区域产生明显的光子带隙而呈现出亮丽的绿色。     

pH effect on the aggregation of silver nanoparticles synthesized by chemical reduction

Silver colloidal nanoparticles were prepared according to the chemical reduction method in which the ascorbic acid was used as a reducing agent and sodium citrate as a stabilizing agent. The absorption spectra of all prepared samples obtained using the UV-Vis spectrophotometer showed a surface plasmon peak at a wavelength of about 420 nm. The size of the silver nanoparticles was controlled by changing the pH values of the reaction system. At high pH, smaller size silver nanoparticles were obtained compared to low pH values. This difference can be attributed to the difference in the reduction rate of the precursor. In addition to the inverse proportionality between the size and the pH value it is clear that increasing the pH value enables us to obtain spherical nanoparticles while at low pH, rods and triangular particle shapes were formed. Poor balance between nucleation and growth processes could be the cause of this result.     

Preparation and thermomechanical properties of Ag-PVA nanocomposite films

Metal–polymer hybrid nanocomposites have been prepared from an aqueous solution of polyvinyl alcohol (PVA) and silver nitrate (AgNO₃). The silver nanoparticles were generated in PVA matrix by the reduction of silver ions with PVA molecule at 60–70 °C over magnetic stirrer. UV–vis analysis, X-ray diffraction studies, transmission electron microscopy, scanning electron microscopy and current–voltage analysis were used to characterize the nanocomposite films prepared. The X-ray diffraction analysis reveals that silver metal is present in face centered cubic (fcc) crystal structure. Average crystallite size of silver nanocrystal is 19 nm, which increases to 22 nm on annealing the film at 150 °C in air. This result is in good agreement with the result obtained from TEM. The UV–vis spectrum shows a single peak at 433 nm, arising from the surface plasmon absorption of silver nanocolloids. This result clearly indicates that silver nanoparticles are embedded in PVA. An improvement of mechanical properties (storage modulus) was also noticed due to a modification of PVA up to 0.5 wt% of silver content. The current–voltage (I–V) characteristic of nanocomposite films shows increase in current drawn with increasing Ag-content in the films.