壳聚糖修饰银纳米颗粒的制备及抗菌性能研究

采用液相化学还原法,以壳聚糖为修饰剂,硼氢化钠为还原剂,制备了壳聚糖修饰银纳米颗粒(chitosan-Ag NPs)。通过X射线粉末衍射仪、透射电子显微镜、傅立叶变换红外光谱仪等对所制备样品的结构和形貌进行了表征。结果表明,所制备纳米颗粒具有面心立方Ag的晶型结构,壳聚糖通过氨基和羟基中的N、O原子与Ag+的化学键合作用修饰在纳米颗粒表面,起到了限制颗粒粒径长大和防止其团聚的作用。采用肉汤连续稀释法检测了样品对大肠杆菌和金黄色葡萄球菌的抑菌杀菌性能,结果表明chitosan-Ag NPs具有优异的抗菌性,抗菌性能受到粒径大小的影响。     

X射线吸收精细结构谱在材料科学中的应用

简单介绍了X射线吸收精细结构谱的物理基础,数据处理方法,讨论了X射线吸收精细结构谱在元素组成,价态和结构环境方面的分析结果。结果显示,在钠钙硅酸盐平板玻璃中,二价铁离子和三价铁离子同时存在。在Ag-Na离子交换后,二价铁离子被银离子氧化成三价铁离子。当Ti2O3和锐钛矿被分别掺入硼硅酸盐玻璃后,钛离子主要以四价存在,Ti^4＋离子占据五重配位点。在玻璃中同时掺入锐钛矿和还原剂C,诱导三价钛离子生成,三价钛离子占据八面体配位点,使得Ti K边预边峰高度降低。包裹在钠钙硅酸盐玻璃中的银纳米颗粒界面存在张应力,使得银晶格膨胀,银原子存在两种结构环境：Ag-O配位和Ag-Ag配位。孤立银原子的存在,使得最近邻Ag-Ag配位数显著降低。     

常温下赋予不锈钢抗菌性能的实验研究

以AgNO3为主要原料制备了含有Ag^ 的冷敷液，在常温条件下，采用将冷敷液涂抹在不锈钢表面上或将不锈钢浸入冷敷液中的方法，制备了出表面含有抗菌Ag^ 离子的新型抗菌不锈钢。用扫描电镜(SEM)、X射线衍射(XRD)和原子吸收光谱(AAS)进行表征，表征结果表明，不锈钢表面形成一层含有柠檬酸银和过氧化银的薄膜，Ag^ 还渗透到不锈钢的内部。还对此材料的的抗菌性能进行了奎因实验，实验结果显示，抗菌不锈钢在接种金黄色葡萄球菌和大肠杆菌后培养24h后，不锈钢表面的菌落数均为0。     

Catalytic properties of silica/silver nanocomposites

The catalytic properties of silver nanoparticles supported on silica and the relation between catalytic activity of silver particles and the support (silica) size are investigated in the present article. The silver nanoparticles with 4 nm diameters were synthesized and were attached to silica spheres with sizes of 40, 78, 105 nm, respectively. The reduction of Rhodamine 6G (R6G) by NaBH4 was designed by using the SiO2/Ag core-shell nanocomposites as catalysts. The experimental results demonstrated that the catalytic activity of silica/silver nanoparticles depends on not only the concentration of catalysts (silver) but also the support silica size. Silver particles supported on small SiO2 spheres (approximately 40 nm) show high catalytic activity. Moreover, by making a comparison between the UV-vis spectra of the catalyst before and after the catalytic reaction, we found that the position of surface plasma resonance (SPR) peak of Ag nanoparticles changes little. The above results suggested that the size and morphology of silver particles were probably kept unchanged after the reduction of R6G and also implied that the catalytic activity of silver particles was hardly lost during the catalytic reaction.     

Directly ultraviolet photochemical deposition of silver nanoparticles on silica spheres: Preparation and characterization

A simple method was developed to directly deposit silver nanoparticles on the surface of silica spheres. The photochemical reduction was carried out by ultraviolet irradiation in air atmosphere at room temperature. The [Ag(NH₃)₂]⁺was reduced to silver atoms upon ultraviolet irradiation. Silver atoms subsequently deposited on the surface of silica spheres and agglomerated into silver nanoparticles. Silica spheres with silver nanoparticles of different size and density can be simply controlled by adjusting the UV-light irradiation time. The silver nanoparticles deposited on silica spheres were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy, and field emission scanning electron microscopy.     

Cerium doped soda-lime-silicate glasses: effects of silver ion-exchange on optical properties

Effects of silver ion-exchange on optical absorption (OA) and photoluminescence (PL) spectra of a cerium doped soda-lime-silicate glass at room temperature are investigated. The optical spectra are described in terms of the characteristic transitions 4f↔5d originated in Ce³⁺ ions placed mainly in two different sites of the glass network. As Ag⁺ ions are introduced into the cerium doped glass, they are reduced to elementary silver (Ag⁰) which are favoured by the reaction Ce³⁺+Ag⁺→Ce⁴⁺+Ag⁰. Then, the number of Ce³⁺ ions decrease inversely with depth from the surface contrarily to Ce⁴⁺ ions does, and elementary silver diffuses and aggregates to form nanoparticles. As a consequence of these changes, the OA spectra of exchanged samples increase substantially in the UV range and the luminescence decreases significantly. The high sensitivity of PL together with deconvolution analysis of spectra, however, allows us to detect changes in the excitation and emission spectra from the earlier stages of ion-exchange. This indicates that during the ion-exchange we deal with fast processes (much shorter than 1 min). In fact, transmission electron microscopy observations of samples from the glass exchanged for a short time as 1 min at 325°C show the presence of a scanty number of silver nanoparticles, which confirms this point. Furthermore, with increasing the length of time of ion-exchange, PL spectra exhibit a progressive red shift indicative in part of a covalence increment in the oxygen–cerium coordinated bonding. We observe no luminescence from Ag⁺ ions and other silver molecular species in contrast with other preliminary PL studies on silver ion-exchange in soda-lime-silicate glasses free of cerium. The effect is discussed on the basis of a supplementary increase in the number of Ce⁴⁺ ions mainly due to the reaction Ce³⁺+Ag⁺→Ce⁴⁺+Ag⁰, which prevents efficiently the luminescence of the silver centers.     

Preparation of silver nanoparticles having low melting temperature through a new synthetic process without solvent

This study presents a new synthetic method of silver nanoparticles using a novel polyoxyethylene maleate-based surfactant (PEOM). Unlike conventional process using large amount of a solvent to dissolve silver salts, large amount of silver salts (AgNO3) can be dissolved and stabilized by our surfactant without solvent. Silver salts can be dissociated within PEOM by the formation of charge complex between hydrophilic-COOH segments and Ag+NO3-, resulting in formation of self-assembled microstructures which acting as a nano-reactor and stabilizer. After reduction using NaBH4, uniform sized silver nanoparticles were formed in the hydrophilic domain of PEOM. Silver contents in the colloids were changed by 0.5 approximately 3 wt%. Distribution of silver nanoparticle sizes was investigated by using TEM and XRD. Melting temperature of silver nanoparticles was measured by differential scanning calorimetry, which depends upon the particle size of silver nanoparticles. The lowest melting temperature of 112 degrees was measured from 3.5 nm average-sized silver particles.     

Characterization of silver nanoparticles synthesized on titanium dioxide fine particles

Silver nanoparticles with a narrow size distribution were synthesized over the surface of two different commercial TiO(2) particles using a simple aqueous reduction method. The reducing agent used was NaBH(4); different molar ratios TiO(2):Ag were also used. The nanocomposites thus prepared were characterized using transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), dynamic light scattering (DLS) and UV-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 microscopy studies (TEM and STEM) we observed that the silver nanoparticles are homogeneously distributed over the surface of TiO(2) particles and that the TiO(2):Ag molar ratio plays an important role. We used three different TiO(2)Ag molar ratios and the size of the silver nanoparticles is 10, 20 and 80?nm, respectively. It was found that the antibacterial activity of the nanocomposites increases considerably comparing with separated silver nanoparticles and TiO(2) particles.     

Synthesis of nanostructured silver/silver halides on titanate surfaces and their visible-light photocatalytic performance

Dense and uniform silver halides AgX (X = Cl, Br, I) nanoparticles were successfully fabricated on layered titanate nanowired honeycomb (TNHC) thin films. The growth of AgX nanocrystals was carried out through two steps. Firstly, ion-exchange was employed to incorporate Ag(+) ions into the interlayer of the titanate nanowires. Secondly, hydrogen halide (HX) solution was rapidly injected onto the ion-exchanged silver TNHC surface to generate nanosized AgX particles on TNHC films. The effect of the reaction time, solution pH, and concentration of halide anions on the morphology of the AgX photocatalysts has been studied. Followed by light-irradiation, the optimized Ag/AgX thin films exhibited excellent degradation performance under visible light because of localized surface plasmon resonance effect.     

超支化聚(胺-酯)为模板Ag纳米粒子的制备

以超支化聚(胺-酯)为模板,采用NaBH4直接还原和紫外灯光照射合成了Ag纳米粒子。超支化聚(胺-酯)对Ag纳米粒子形成起着重要的作用。TEM分析表明,Ag纳米粒子形貌为球形结构,分布均匀,粒径约为45 nm(NaBH4还原)和20 nm(紫外灯光照射)。发现在UV-Vis谱图中420 nm左右有Ag纳米粒子特征表面等离子共振吸收峰。FT-IR分析发现Ag纳米粒子和超支化聚(胺-酯)之间有较强的相互作用,超支化聚(胺-酯)对Ag纳米粒子的稳定性起保护作用。     

The effect of substrate material on silver nanoparticle antimicrobial efficacy

With the advent of nanotechnology, silver nanoparticles increasingly are being used in coatings, especially in medical device applications, to capitalize on their antimicrobial properties. The attractiveness of nanoparticulate silver systems is the expected increased antimicrobial efficacy relative to their bulk counterparts, which may be attributed to an increased silver ion (Ag+) solubility, and hence availability, that arises from capillarity effects in small, nanometer-sized particles. However, a change of the material upon which the antimicrobial nanoparticulate silver is deposited (herein called "substrate") may affect the availability of Ag+ ions and the intended efficacy of the device. We utilize both theory and experiment to determine the effect of substrate on ion release from silver particles in electrochemical environments and find that substrate surface charge, chemical reactivity or affinity of the surface for Ag+ ions, and wettability of the surface all affect availability of Ag+ ions, and hence antimicrobial efficacy. It is also observed that with time of exposure to deionized water, Ag+ ion release increases to a maximum value at 5 min before decreasing to undetectable levels, which is attributed to coarsening of the nanoparticles, and which subsequently reduces the solubility and availability of Ag+ ions. This coarsening phenomenon is also predicted by the theoretical considerations and has been confirmed experimentally by transmission electron microscopy.     

Polyurethane–silver fibers prepared by infiltration and reduction of silver nitrate

Silver-incorporating polyurethane fibers were prepared by infiltration of silver nitrate on electrospun polyurethane fibers and reduction with sodium borohydride. They were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray system. The Ag nanoparticles prepared by reduction of silver nitrate showed nano-sized crystals of 4–10 nm in diameter. However, larger aggregated Ag particles of 50–200 nm were also found to be dispersed in the polyurethane matrix when Ag particles were formed in electrospun fibers by the infiltration–reduction process of silver nitrate. As a result, infiltration method of silver nitrate into the electrospun fibers was significantly effective to produce silver-incorporating fibers due to a high specific surface area of fibers.     

Biosynthesis of gold and silver nanoparticles using Emblica Officinalis fruit extract, their phase transfer and transmetallation in an organic solution

The design, synthesis and characterization of biologically synthesized nanomaterials have become an area of significant interest. In this paper, we report the extracellular synthesis of gold and silver nanoparticles using Emblica Officinalis (amla, Indian Gooseberry) fruit extract as the reducing agent to synthesize Ag and Au nanoparticles, their subsequent phase transfer to an organic solution and the transmetallation reaction of hydrophobized silver nanoparticles with hydrophobized chloroaurate ions. On treating aqueous silver sulfate and chloroauric acid solutions with Emblica Officinalis fruit extract, rapid reduction of the silver and chloroaurate ions is observed leading to the formation of highly stable silver and gold nanoparticles in solution. Transmission Electron Microscopy analysis of the silver and gold nanoparticles indicated that they ranged in size from 10 to 20 nm and 15 to 25 nm respectively. Ag and Au nanoparticles thus synthesized were then phase transferred into an organic solution using a cationic surfactant octadecylamine. Transmetallation reaction between hydrophobized silver nanoparticles and hydrophobized chloroaurate ions in chloroform resulted in the formation of gold nanoparticles.     

Structural analysis of graphene oxide/silver nanocomposites: optical properties,electrochemical sensing and photocatalytic activity

In the present study, graphene oxide/silver (GO/Ag) nanocomposites were synthesized via a facile simple one pot chemical reduction method using ethylene glycol/sodium borohydrate (EG/NaBH₄) as solvent and reducing agent. GO was selected as a substrate and stabilizer to prepare GO/Ag nanocomposites. The synthesized GO/Ag nanocomposites were characterized by a series of techniques. Highly monodispersed stable crystalline silver nanoparticles having a face-centered cubic (fcc) phase were confirmed by X-ray powder diffraction (XRD) on GO signature. Scanning electron microscopy images showed that Ag nanoparticles are deposited on the GO sheet with a narrow size distribution. Transmission electron microscopy observations revealed that large numbers of Ag nanoparticles were uniformly distributed on GO sheet and well separated with an average size of 18 nm. Ultraviolet–visible (UV–Vis) spectroscopic results showed the peak of GO and surface plasmon resonance (SPR) of Ag nanoparticles. The SPR property of GO/Ag nanocomposites showed that there was an interaction between Ag nanoparticles and GO sheet. The intensities of the Raman signal of GO/Ag nanocomposites are gradually increased with attachment of Ag nanoparticles i.e. there is surface-enhanced Raman scattering activity. Electrochemical investigations indicated that the nanocomposites possessed an excellent performance for detecting towards 4-nitrophenol. An application of the obtained GO/Ag nanocomposites as a catalyst in the reduction of 4-nitrophenol to 4-aminophenol by NaBH₄ was demonstrated. The GO/Ag nanocomposites exhibited high activity and stability for the catalytic reduction of 4-nitrophenol. The prepared GO/Ag nanocomposites act as photo-catalysts.     

Ag-catalyzed synthesis of ultrafine nickel nanoparticles: A facile way to size control

We report here a facile strategy, Ag-catalyzed reduction of Ni²⁺ ions, for the synthesis of metallic nickel nanoparticles. The phase structure and morphology of particles were analyzed by means of X-ray diffraction and scanning electron microscopy. It was found that the resultant Ni nanoparticles had narrow size distribution, and the control of particle size could be easily achieved through manipulation of the molar ratio between nickel salts and silver seeds. XRD analysis of the final particles showed the crystalline nickel structure and the presence of metallic Ag, which was influenced by the Ni/Ag molar ratio. The effects of reduction temperature on the final particle size were also investigated.     

Synthesis and characterization of dextran-capped silver nanoparticles with enhanced antibacterial activity

Dextran-capped silver nanoparticles were synthesized by reducing silver nitrate with NaBH4 in the presence of dextran as capping agent. The characters of silver nanoparticles were investigated using UV-Vis spectrophotometer, nano-grainsize analyzer, X-ray diffraction, and transmission electron microscopy. Results showed that the silver nanoparticles capped with dextran were in uniform shape and narrow size distribution. Moreover, compared with polyvinylpyrrolidone (PVP)-capped silver nanoparticles, the dextran-capped ones possessed better stability. Antibacterial tests of these silver nanoparticles were carried out for Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa, and Klebsiella pneumoniae. Results suggested that the dextran-capped silver nanoparticles had high antibacterial activity against both Gram-positive and Gram-negative bacteria. In addition, the cytotoxicity in vitro of the dextran-capped silver nanoparticles was investigated using mouse fibrosarcoma cells (L929). The toxicity was evaluated by the changes of cell morphology and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide assay. Results indicated that these silver nanoparticles had slight effect on the survival and proliferation of L-929 cells at their minimal inhibitory concentration (MIC). After modified by dextran, the physiochemical properties of the silver nanoparticles had been improved. We anticipated that these dextran-capped silver nanoparticles could be integrated into systems for biological and pharmaceutical applications.     

Colored and functional silver nanoparticle-wool fiber composites

Silver nanoparticles utilizing the surface plasmon resonance effect of silver have been used to color merino wool fibers as well as imparting antimicrobial and antistatic properties to them to produce a novel silver nanoparticle-wool composite material. This is accomplished by the reduction of silver ions in solution by trisodium citrate (TSC) in the presence of merino wool fibers or fabrics. The silver metal nanoparticles simultaneously bind to the amino acids of the keratin protein in the wool fibers using TSC as the linker. The colors of the resulting merino wool-silver nanoparticle composites range from yellow/brown to red/brown and then to brown/black, because of the surface plasmon resonance effect of silver, and are tuned by controlling the reduction of silver ions to silver nanoparticles to give the required particle size on the fiber surface. In addition to the surface plasmon resonance optical effects, the silver nanoparticle-wool composites exhibit effective antimicrobial activity, thus inhibiting the growth of microbes and also an increase in the electrical conductivity, imparting antistatic properties to the fibers. Therefore, silver nanoparticles function as a simultaneous colorant and antimicrobial and antistatic agent for wool. Chemical and physical characterizations of the silver nanoparticle-merino wool composite materials have been carried out using scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, synchrotron radiation X-ray diffraction, atomic absorption spectroscopy, X-ray photoelectron spectroscopy, direct-current electrical conductivity measurements, wash-fast and rub-fast tests, and antimicrobial tests.     

Fabrication of electrospun polycaprolactone coated withchitosan-silver nanoparticles membranes for wound dressing applications

In this study, electrospun polycaprolactone membrane coated with chitosan-silver nanoparticles (CsAg), electrospun polycaprolactone/chitosan/Ag nanoparticles, was fabricated by immersing the plasma-treated electrospun polycaprolactone membrane in the CsAg gel. The plasma modification of electrospun polycaprolactone membrane prior to CsAg coating was tested by methylene blue stain and scanning electron microscope. The presence of silver and chitosan on the plasma-treated electrospun polycaprolactone membrane was confirmed by energy-dispersive X-ray spectroscopy and FT-IR spectrum. Scanning electron microscope observation was employed to observe the morphology of the membranes. The release of Ag ions from electrospun polycaprolactone/chitosan/Ag nanoparticles membrane was tested using atomic absorption spectrometry. Electrospun polycaprolactone/chitosan/Ag nanoparticles membrane inherited advantages from both CsAg gel and electrospun polycaprolactone membrane such as: increasing biocompatibility, mechanical strength, and antibacterial activity against both Gram-negative and Gram-positive bacteria. Thus, this investigation introduces a highly potential membrane that can increase the efficacy of the wound dressing process.     

Biological synthesis of gold and silver nanoparticles mediated by the bacteria Bacillus subtilis

Biological synthesis of gold and silver nanoparticles was carried out using the bacteria Bacillus subtilis. The reduction processes of chloroaurate and silver ions by B. subtilis were found to be different. Gold nanoparticles were synthesized both intra- and extracellularly, while silver nanoparticles were exclusively formed extracellularly. The gold nanoparticles were formed after 1 day of addition of chloroaurate ions, while the silver nanoparticles were formed after 7 days. The nanoparticles were characterized by X-ray diffraction, UV-vis spectra and transmission electron spectroscopy. X-ray diffraction revealed the formation of face-centered cubic (fcc) crystalline gold nanoparticles in the supernatant, broth solution and bacterial pellet. Silver nanoparticles also exhibited diffraction peaks corresponding to fcc metallic silver. UV-vis spectra showed surface plasmon vibrations for gold and silver nanoparticles centered at 530 and 456 nm, respectively. TEM micrographs depicted the formation of gold nanoparticles intra- and extracellularly, which had an average size of 7.6 +/- 1.8 and 7.3 +/- 2.3 nm, respectively, while silver nanoparticles were exclusively formed extracellularly, with an average size of 6.1 +/- 1.6 nm. The bacterial proteins were analyzed by sodium dodecyl sulfonate-polyacrylamide electrophoresis (SDS-PAGE) before and after the addition of metal ion solutions. We believe that proteins of a molecular weight between 25 and 66 kDa could be responsible for chloroaurate ions reduction, while the formation of silver nanoparticles can be attributed to proteins of a molecular weight between 66 and 116 kDa. We also believe that the nanoparticles were stabilized by the surface-active molecules i.e., surfactin or other biomolecules released into the solution by B. subtilis.     

载银沸石应用的研究进展

沸石微孔晶体材料的比表面积较大、水热稳定性较高、微孔丰富均一以及表面性质可调,可用于吸附、催化、抗菌、药物输运和水处理。沸石的阳离子交换能力很强。在用离子交换法制备的载银沸石中,Ag主要以Ag⁺、银团簇和银纳米颗粒三种状态存在。Ag⁺良好的生物相容性以及银团簇高效和可调的发光性能,受到了极大的关注和深入研究。本文综述了通过离子交换法制备的载银沸石在白光LED以及可调多色发光荧光粉、传感器、抗菌材料、吸附和催化等方面的应用。