Spontaneous Agglomeration of Silver Nanoparticles Deposited on Carbon Film Surface

The spontaneous aggregation of silver nanoparticles on a two-dimensional surface at room temperature is investigated. The nanoparticles were deposited on a carbon film and have been observed by a transmission electron microscope (TEM) for over one year. These particles were about 10nm, spherical and well dispersed initially, and an obviously spontaneous agglomeration was observed at the 12th day, the values, coverage rate of the silver particles on carbon film, were increased with time (before 40th day), but reduced with time (after 40th day). These show that the aggregates of the particles tend to have the smallest surface to reduce their surface free energy and are compact three-dimensional cluster in which the most size is above 100nm. Agglomerating is a successively slow diffusion-limited aggregation (DLA) growth. Another phenomenon, a big aggregate gathering some particles and a small aggregate to form a still bigger one, is observed. This indicates that the aggregating processes are controlled by migration of the particles on carbon film surface and surface energy of the particles.     

纳米银对表面吸附核黄素分子光谱性质的影响

采用氧化还原法制备了纳米尺寸的银溶胶,研究了纳米银粒子对核黄素(Riboflavin,Ri)水溶液吸收光谱和荧光光谱的影响.Ri溶液中加入纳米银粒子,随着纳米银浓度的增大,吸收强度不断增强,372 nm处吸收峰红移,而444 nm处吸收峰蓝移,同时发生荧光猝灭现象.从无辐射通道增强、纳米银表面局域场减弱及Ri分子第一激...     

The Cytotoxicity of Metal Nanoparticles Depends on Their Synergistic Interactions

With a steady growth in use of engineered nanoparticles (NPs) in consumer products the unintended exposure to humans has increased. The risks associated with introduction of NPs in the environment have been widely investigated, but mostly for single type of NPs. Herein, a single NP and NP co-exposure study is reported: the cellular effects of silver and platinum NPs on the main components of the blood–brain barrier, human cerebral microvascular endothelial cells, and human primary astrocytes. The synergy is quantitatively evaluated as per the Chou–Talalay method. NP co-exposure synergistically inhibits proliferation of both cell types, to a greater extent for endothelial cells. In addition, astrocytes are more tolerant to NPs. The mechanism of synergy with short-duration incubation time points (up to 30 min) is further explored. Although intracellular trafficking studies and quantitative assessments of NP uptake does not explain the mechanisms of synergistic cytotoxicity, a proteomics analysis suggests that it arises from activation of an immune modulating response and deregulation of the extracellular matrix organization. The substantial synergetic effects in the co-exposure studies highlight the importance of this work in relation to assessment of the health risks associated with nanomaterials.     

Phytosynthesis of Silver Nanoparticles Using Andrographis paniculata Leaf Extract and Evaluation of Their Antibacterial Activities

Use of nanotechnology in biological systems by the synthesis of metallic nanoparticles is a burning area of research in recent times. In the present investigation, aqueous extract of Andrographis paniculata was used to produce silver nanoparticles by reduction of silver nitrate. It was noted that the synthesizing process was quite rapid and silver nanoparticles form within minutes of silver ions coming in contact with plant extract. UV-Vis spectrum of the aqueous medium containing silver ions indicated a peak at 432 nm corresponding to the plasmon absorbance of the silver nanoparticles. Fourier transform infrared spectroscopic analysis of the silver nanoparticles showed the presence of proteins that might be acting as capping agents around the nanoparticles. From scanning electron microscopy analysis, the size of the silver nanoparticles was measured and it was found that the average size was between 40 and 60 nm. Furthermore, the antibacterial activity of synthesized silver nanoparticles exhibited effective inhibition zones against seven bacterial strains tested. Among the bacteria tested Pseudomonas aeruginosa was found to be most susceptible to the silver nanoparticles. Phytochemical screening of the plant extract indicated the presence of alkaloids, flavonoids, amino acids, saponins, tannins, and terpenoids.     

The Effect of Boundary Conditions on Gas-phase Synthesised Silver Nanoparticles

We have prepared spherical non-agglomerated silver nanoparticles by an evaporation–condensation–dilution/cooling technique. Silver was evaporated from a crucible in a tubular flow reactor. A porous tube diluter was used to quench the carrier gas at the outlet of the reactor to enhance the formation of small particles and to suppress agglomeration and other particle growth mechanisms. The number size distribution of the prepared particles was measured with a differential mobility analyser–condensation nucleus counter combination and the size and the shape of the particles were analysed with transmission electron microscope. The system was modelled using a sectional aerosol dynamics computer code to estimate the importance of different aerosol processes. In all conditions the particles obtained were non-agglomerated and spherical. The mean particle diameter varied from 4 to 10-nm depending on boundary conditions. From the modelling studies it can be concluded that the nucleation rate is the most important parameter controlling the final particle size.     

光谱法研究pH值对纳米银及其与赖氨酸相互作用的影响

利用化学方法合成纳米银,调节pH值,加入赖氨酸溶液,通过紫外光谱和动态光散射法研究pH对纳米银及纳米银-赖氨酸体系稳定性的影响,利用表面增强拉曼光谱考察赖氨酸与纳米银的相互作用方式。紫外光谱显示纳米银和纳米银-赖氨酸体系在pH值为5~10时,均具有较强的吸收峰;应用动态光散射测定了不同pH的纳米银及其赖氨酸体系的粒径及强度自相关函数,在pH值为5~10时,粒径分布均匀,DLS自相关曲线平滑,说明纳米银和纳米银-赖氨酸体系稳定性良好;SERS研究了pH为4、7、10时,赖氨酸在银粒子表面的吸附作用,体系出现比较明显的赖氨酸特征峰,当pH为4时,为δ(NH3+)的1444cm~(-1)谱峰和δ(COO-)的1576cm~(-1),此时赖氨酸通过氨根和羧酸根共同与银纳米粒子发生相互作用,当pH为10时,NH_3~+发生去质子化,此时赖氨酸只出现COO-的伸缩振动在1576cm~(-1)处,说明此条件下赖氨酸以羧酸根吸附在银粒子表面。     

Optical Detection of Some Hydrazine Compounds Based on the Surface Plasmon Resonance Band of Silver Nanoparticles

An indirect colorimetric method is presented for spectrophotometric determination of hydrazine, phenylhydrazine, and isoniazid. Reduction of silver ions to silver nanoparticles (AgNPs) by these analytes as active reducing agents in the presence of polyvinylpyrrolidone (PVP) and also cetyltrimethylammonium chloride (CTAC) as a stabilizer is the basis of the proposed method. The changes in plasmon absorbance of the AgNPs at λ = 415 nm in the presence of PVP were proportional to concentration of hydrazine, phenylhydrazine, and isoniazid in the ranges of 4.0–150.0 µM, 1.0–55.0 µM, and 2.0–30.0 µM, respectively, and the detection limit obtained was 0.79 µM. In the presence of CTAC, the linear ranges were 0.5–10.0 and 10.0–300.0 µM for hydrazine, 1.0–40.0 µM for phenylhydrazine, and 0.2–10.0 and 10.0–90.0 µM for isoniazid, and the detection limit was 0.12 µM. The method has been applied for determination of these analytes in different real samples such as boiler feed water and tablet.     

纳米银溶胶的制备及利用其SERS效应检测BPA的研究

制备了银溶胶作为表面增强活性基底,以此为基础详细研究了BPA的表面增强拉曼光谱(SERS)。研究了促凝剂氯化钠的加入对增强效果的影响。实验结果表明,当BPA乙醇溶液的浓度低至10-7g/mL时,依然可以得到明显的SERS信号。此方法操作简便快捷,无需对样品进行预处理,在BPA的快速检测方面具有很大应用潜力。     

银和去合金银-金纳米粒子的SERS活性研究

用乙二醇还原硝酸银,聚乙烯吡咯烷酮作表面活性剂合成了大量的银纳米颗粒。银纳米颗粒和HAuCl4发生置换反应后形成去合金银-金纳米粒子。以吡啶和SCN-作为探针分子研究了它们的SERS活性。结果表明,当探针分子吸附于银纳米颗粒和去合金银-金纳米粒子上时,探针分子的特征振动峰强度增强、频率发生位移。SERS可表征纳米粒子物理和化学性质的变化。     

Protein Corona Modulates Distribution and Toxicological Effects of Silver Nanoparticles In Vivo

Exploitation of silver nanoparticles (AgNPs) in biomedicine represents more than one third of their overall applications. Despite their wide use, detailed toxicokinetic data and information on their action mechanisms in vivo are still scarce. One important obstacle is their fate and transformation patterns in biological environments where AgNPs get a “new face” after interaction with biomolecules, particularly proteins. The impact of protein corona on AgNP effects in vivo is eludicated. The in vivo effects of AgNPs prepared with two different protein coronas, albumin, and metallothionein, with polymer‐coated AgNPs are compared in male and female Wistar rats after intravenous administration. The results demonstrate that the character of the protein coronas on the AgNP surface affects not only distribution, but also oxidative stress response and genotoxicity in tissues of rat exposed to AgNPs. Additionally, sex‐related effects are observed. By emphasizing the importance of protein corona formation and sex‐related response, the obtained data support a reliable evidence base needed for assessing the health risks of the steadily increasing human exposure to AgNPs.     

Study on Synthesis of Silver Nanoparticles Using dsDNA as Template and Detection of GSH

In this work, silver nanoparticles are synthesized using a simple and sensitive method by using double-stranded DNA (dsDNA-Ag NPs) as a template. The prepared dsDNA-Ag NPs are characterized by fluorescence spectroscopy analysis, X-ray photoelectron spectroscopy analysis, and transmission electron microscopy analysis. The excitation wavelength of the prepared silver nanoparticles is 295 nm, the emission wavelength is 377 nm, the average particle size is 11.2 nm, and the dispersion is uniform with pleasurable stability. The nanomaterials are used as fluorescent probes to detect glutathione (GSH). After adding glutathione to the dsDNA-Ag NPs fluorescent probes, the fluorescence of dsDNA-Ag NPs is burst due to electron transfer and S Ag bond generation, and the linear range of detection concentration is 0–90 mm with a detection limit of 0.37 mm .     

胶体金纳米颗粒的表面等离子体发射特性

利用电化学方法制备出粒径为20-80 nm的胶体金纳米颗粒。研究其荧光发射光谱特性,在485nm处观察到表面自由电子集体激发导致的表面等离子体共振发射峰,其位置不随激励光波长的变化而移动。当激励光波长为485 nm时,观察到最强的发射峰。在240和640 nm处,还观察到倍频发射峰和3/4分频发射峰。增加金纳米颗粒粒径,观察到发射谱的峰值增大而发射峰的位置只有很小的红移。     

金银纳米粒子的电化学性质及联苯胺的SERS研究

采用柠檬酸钠还原氯金酸,硼氢化钠还原硝酸银分别制备了较小粒径的金、银纳米粒子。运用紫外可见吸收光谱(UV-Vis)、扫描电子显微镜(SEM)、循环伏安法(CV)对金、银纳米粒子进行了表征。结果表明：所得金、银纳米粒子粒径分别约为16和10 nm,并能以亚单层形式组装于导电玻璃(ITO)表面;CV图显示金、银纳米粒子分别有一对不对称的氧化还原峰,而且纳米粒子的浓度对其氧化还原电位存在一定的影响。采用自组装方法,以联苯胺为偶联分子, 在粗糙金基底表面构筑了金/银纳米粒子的双层有序结构。表面增强拉曼光谱研究表明, 在有序金银纳米粒子组装体中偶联分子的拉曼散射得到了增强。     

Polymer-Nanoparticle Composites Composed of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Coated Silver Nanoparticles

The effects of addition of synthesized organic-suspension silver nanoparticles on the crystallization and thermal stability of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) were studied by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (XRD), UV-Vis absorption spectroscopy, polarized optical microscopy (POM), and thermal gravimetric analysis (TGA). The TEM images showed the average primary size of the as-synthesized silver nanoparticles, coated with a monolayer of the surfactants consisting of oleic acid and an alkylamine, was about 5 nm with narrow distribution, and that they were uniformly dispersed in n-heptane. PHBV/silver nanocomposites were prepared by melt mixing in an internal mixer and then injection molded into rectangle-shaped specimens by a labscale injection molding device. The coated silver nanoparticles showed a homogenuous dispersion in the PHBV matrix when the content of coated silver nanoparticles was about 1%. Both the DSC and POM data showed the efficient heterogeneous nucleation by the coated silver nanoparticles for facilitating PHBV crystallization. The thermal stability of the PHBV/silver nanocomposites improved with the increase in the content of the coated silver nanoparticles.     

Variable Frequency Microwave Synthesis of Silver Nanoparticles

Synthesis of silver nanoparticles based on a polyol process and variable frequency microwave (VFM) was investigated. Comparing to a thermal method, the reaction by VFM radiation was much faster. The effects of silver nitrate concentration, poly(N-vinylpyrrolidone) (PVP) concentration, reaction time and reaction temperature were studied. It was found that the higher concentration of silver nitrate, longer reaction time and higher temperature increased the particle size while the higher concentration of PVP decreased the particle size.     

绿色合成银纳米粒子及其在SERS中的应用

采用无毒、绿色的酪氨酸作为还原剂和稳定剂,在碱性条件下还原硝酸银,经60 ℃恒温水浴处理20 min,成功地合成了银纳米粒子。混合溶液颜色由淡黄色变为棕黄色直观地呈现了银纳米粒子的生成。利用紫外可见吸收光谱(UV-Vis)和透射电子显微镜(TEM)对制备样品进行分析和表征。粒子的UV-Vis吸收在412 nm附近。TEM图像显示,银纳米粒子的形状近似球形,粒子直径在15～25 nm。分别以结晶紫(CV)和叶酸(FA)为探测分子,进一步研究了该银纳米粒子的表面增强拉曼散射(SERS)效应。实验结果表明,该合成方法不仅方便、快速、绿色环保,而且合成的银纳米粒子对CV和FA分子有很好的SERS效应。     

银纳米颗粒对掺铒铋酸盐玻璃光谱性质的影响

采用传统熔融淬火技术制备了一系列Er3+离子掺杂复合银纳米颗粒的铋酸盐玻璃样品.研究了纳米银含量的改变对Er3+离子荧光发射特性的影响.研究发现,铒在1.53 μm处的荧光强度在银纳米颗粒质量分数为0.2%处取得最大值,为未掺杂银纳米颗粒时的4.6倍.其荧光增强的原因归结于银纳米颗粒表面等离子体共振导致局域场增强和Ag...     

Long‐Term Colloidal and Chemical Stability in Aqueous Media of NaYF4‐Type Upconversion Nanoparticles Modified by Ligand‐Exchange

Surface capping is an essential component of nanoparticles as it provides access to their outstanding properties in the real world. Upconversion nanoparticles are predominantly interesting for use in biological environments, due to their excellent optical properties such as the conversion of near‐infrared excitation light into emissions in the visible or UV range of the spectrum, high photostability, and the absence of any intermittence. One of the most efficient upconversion nanoparticles, consisting of lanthanide doped NaYF₄, suffers from limited stability in aqueous media. This study investigates a set of five types of surface coatings, ranging from small ligands to polymers of different charge and different coordinating groups, on monodisperse 28 ± 0.9 nm sized NaYF₄(Yb,Er) nanoparticles modified by a two‐step ligand exchange mediated by NOBF₄. Information on the long‐term chemical and colloidal stability for highly diluted aqueous dispersions of these particles is acquired by transmission electron microscopy, dynamic light scattering, and luminescence spectroscopy. The findings are of importance for the development of probes and labels based on upconversion nanoparticles for biological applications.     

Metabolic Profiling of Murine Macrophages Exposed to Silver Nanoparticles at Dose and Time Dependencies

The macrophage time-dependent metabolic profile changing basal metabolism triggered by nanoparticles can be obtained and used to improve wound healing treatments. Herein this study demonstrates that metabolic status responds systematically to cytotoxicity manipulation, providing an interesting way of cellular control. Nuclear magnetic resonance (NMR) based metabolomics and cytotoxic assays are used to study RAW 264.7 cells exposed to AgNPs at different concentrations and incubation times. Cytotoxicity data show a slight decrease in cellular expansion rates accompanied by morphological changes in cells. Metabolomics show that despite the glycolytic activity of treated and non-treated cells remains unchanged; however, only the treated cells present a rich Citrate environment signaling up-regulation of Tricarboxylic-Acid-Cycle (TCA). Cells choose aerobic routes instead of anaerobic ones to produce energy and self-regulate their amino acid metabolism to balance TCA. Choline metabolism is down-regulated once its sub-products, Betaine and Glycine, are reduced, thus compromising Creatine synthesis. Phospholipid metabolism is down-regulated due to the decreasing of Phosphocholine and Sn-Glycerol-3-PC, in agreement with the cytotoxicity results. Pyroglutamate decreases in treated cells, signaling different levels of oxidative stress. These analytical tools can characterize AgNPs-treatments, even distinguishing dose and time dependencies. Therefore, the fine-tuning of exposition parameters can modulate cellular activity to achieve better wound healing.