金种子生长法制备小尺寸金纳米星

本研究采用金种子生长法,通过优化氯金酸溶液用量、生长液pH值以及反应温度等条件,制备出一种全新的小尺寸金纳米星(Au-NSs)颗粒,方法具有可控、稳定、简单、Au-NSs粒径均一等优点。紫外-可见-近红外(UV-Vis-NIR)光谱和透射电子显微镜(TEM)检测表明,该方法制备出的Au-NSs的粒径在40nm左右,远小于常规方法制得的Au-NSs(~80nm)。最终制备条件确定为:生长液、金种溶液和抗坏血酸(AA)的体积比为600∶9∶7;生长液的pH≈3.05;制备Au-NSs的温度条件为先冰浴加入金种,回升至室温后加入AA还原。     

紫外辐照法合成单分散钨酸纳米颗粒

通过紫外光照射柠檬酸钨氧配合物水溶液,制备了平均粒径约为20 nm的单分散钨酸纳米颗粒。红外光谱研究表明,柠檬酸钨氧配合物在紫外光照射下发生分解,形成柠檬酸和钨酸,而柠檬酸在钨酸的催化作用下发生光降解。XRD结果表明,单分散钨酸纳米颗粒是由WO₃·2H₂O和WO₃·H₂O组成的。此外,还考察了光照时间以及柠檬酸与钨酸钠的物质的量之比(n_cit/n_st)对产物结构和形貌的影响。随着光照时间延长,产物中WO₃·2H₂O的含量降低而WO₃·H₂O含量升高,产物粒径增大且分布加宽;随着n_cit/n_st增加,产物中WO₃·2H₂O含量增高,而WO₃·H₂O含量降低,且产物粒径变小而粒径分布变窄。     

单分散纳米金尺寸的分步晶种生长控制

以聚乙烯吡咯烷酮(poly(vinylpyrrolidone), PVP)为保护剂, 硼氢化钠为还原剂, 合成了尺寸为(1.9±0.4) nm的单分散金胶体, 再以其作为一级晶种, 并分别用抗坏血酸和PVP为还原剂和保护剂, 通过改变各步晶种尺寸和氯金酸与晶种的摩尔比分步逐级合成了尺寸为3.2、4.7、6.3、8.0、10.3、14.0 nm的系列金纳米颗粒. 以LaMer模型为基础, 对分步晶种生长过程中影响金胶体产物尺寸分布(单分散性)的主要因素进行了讨论. 缓慢加入抗坏血酸并降低氯金酸对晶种的相对量对于单分散金纳米颗粒的控制合成有决定性作用. 快速加入抗坏血酸会因二次成核而导致金颗粒尺寸分布范围变宽.     

紫外线辐照制备单分散ZnS纳米颗粒

以硫代硫酸钠和乙酸锌为反应物、柠檬酸为调控剂,在紫外光辐照下制备出单分散的ZnS纳米颗粒。采用XRD、TEM、低温氮吸附-脱附、HRTEM和EDS等方法研究了反应物浓度、辐照时间和柠檬酸用量等因素对产物颗粒尺寸和分布的影响。结果表明,随着反应时间延长,产物收率增高,平均晶粒度增大,比表面积变小。反应物浓度对产物组成和比表面积有较大影响,但对产物的平均晶粒度影响不大。适量添加柠檬酸,有利于制备单分散的ZnS纳米颗粒。     

大粒径单分散金纳米粒子的水相合成

近年来,随着纳米科技的兴起,纳米尺度的金颗粒以其独特的光学、电学性质［１-３］在许多领域表现出潜在的应用价值,引起了人们浓厚的研究兴趣［４-７］．迄今为止,已有多种制备金纳米粒子的方法见诸报导．制备简便、单分散性好、粒径可控,一直是各种方法追求的目标．...     

单分散、小粒径金纳米颗粒的形貌控制增长

利用种子生长法合成了形状规则、尺寸单一的形状不同金纳米颗粒. 其中立方体纳米颗粒的边长为33±2 nm, 它是在十六烷基三甲基溴化胺(CTAB)存在的条件下, 在种子的表面上用弱还原剂——抗坏血酸还原而成的. 在这个体系中, 表面活性剂CTAB既作为保护剂又作为颗粒成长的导向剂. 用UV-vis, TEM, XRD对纳米颗粒的光学性质、几何形状、纳米颗粒的单层膜概貌以及纳米颗粒的晶体结构作了表征. 考察了种子生长的时间、种子的量、抗坏血酸的量对生成纳米颗粒形状的影响.     

单分散水溶性金纳米团簇的制备及表征

采用改进的Brust方法,用硼氢化钠还原氯金酸,并以巯基丁二酸(MSA)、氮乙酰基半光胺酸(NAC)作为包裹剂,成功制备了单分散的水溶性金纳米团簇。高分辨透射电镜(HRTEM)结果表明,增大硫醇与氯金酸的比例并增加氯金酸的初始浓度,有利于得到尺寸更小的金纳米粒子。当氯金酸的浓度(C_Au)为9.3 mmol·L^-1,C_Au:C_S为1:30时,得到了直径约为1 nm、标准偏差为0.2 nm的Au@MSA纳米团簇。结合紫外(UV)、热重(TG)和X射线光电子能谱(XPS)分析结果,可以推测出单分散金纳米簇的化学式为[Au₃₈(MSANa)₂₆]或[Au₃₉(MSANa)₂₇]。     

单分散酸性纳米二氧化硅的合成新方法

非极性有机溶剂中,乙酸和醇在没有酸性催化剂的情况下发生酯化反应,酯化生成的水水解TEOS(硅酸乙酯)合成单分散酸性纳米二氧化硅,粒径从数十纳米到数百纳米。TEM研究表明,溶剂的极性影响二氧化硅的形态,只有在非极性溶剂中才可以得到球形粒子,醇的种类和TEOS的浓度影响粒子的大小和粒径分布,利用FTIR和GC对TEOS的水解和二氧化硅形成过程进行研究。同时,文中提出了有机相在TEOS的酯化水水解、晶核的形成和生长的过程模型。     

云母表面金纳米颗粒单层膜的制备

近年来 ,随着纳米科技的兴起 ,纳米尺度的金颗粒以其独特的光学和电学性质在许多领域表现出潜在的应用价值 ,引起人们浓厚的研究兴趣 .金纳米颗粒单层膜在表面增强拉曼基底及纳米刻蚀等方面有着广泛的应用 [1,2 ] .以往人们多用双官能团硅烷化试剂对硅氧化物基底 ,如玻璃和石英等进行表面修饰 ,获得氨基、巯基或氰基等修饰的表面 ,再利用金纳米颗粒与上述功能团之间的化学相互作用 ,来制备金纳米颗粒单层膜 [3,4 ] .Fig.1　 Crystal structure of muscovite mica云母为层状结构的硅铝酸钾 (晶体结构示于图 1 ) ,表层为 0 0 0 1晶面 ,K+ 离…     

单分散磁性纳米颗粒的制备及生物高分子在其上的组装

磁性纳米颗粒因其潜在的生物医学应用价值而成为纳米生物材料领域研究的前沿。本文综述了单分散磁性纳米颗粒的制备方法以及生物高分子在磁性纳米颗粒上的组装的研究进展。     

Heat-Induced Formation of Monodisperse Gold Nanoparticles in Different Conditions

We investigate the preparation of nearly monodisperse gold nanoparticles by heat treatment in different conditions. The effects of various solvents, heating temperature, and heating time length on the monodispersity of gold nanoparticles were studied systematically and a general route to generate gold nanoparticles with uniform size was determined. The first step was to prepare gold nanoparticles with less than 3 nm and the following operation was to heat the gold nanoparticles in the present of thiolated solvents where monodispersed gold nanoparticles could be obtained easily. Our approach has enriched synthesis of monodisperse gold nanoparticles, and may provide some valuable experimental data about how the heating process affects the size evolution of gold nanoparticles.     

Gram-Scale Synthesis of Isolated Monodisperse Gold Nanorods

Although gold nanorods (AuNRs) have strong potential applications in nanotechnology, plasmonics, and sensing, the scale-up synthesis of isolated AuNRs in gram quantities remains a challenge. Nearly all previously reported methods produce aqueous solutions of cetyltrimethylammonium bromide (CTAB)-coated AuNRs in milligram quantities with yields of approximately 20–30 % in terms of Au^I to Au⁰ conversion. In addition, it is difficult to remove the CTAB bilayer from the surface of AuNRs and yet make them soluble and functionalized for further processing and chemical modification. This report describes the synthesis of monodisperse functionalized AuNRs (standard deviation, σ≈5 %) in gram quantities. Our approach involved increasing the concentration of HAuCl₄ ⋅ 3 H₂O in the growth solution to produce larger quantities of starting AuNRs and further reducing the remaining Au^I ions onto the surface of AuNRs. The slow and controlled addition of ascorbic acid as a reducing agent continued the conversion of Au^I into Au⁰ (through a disproportionation reaction) onto the surface of the nanorods, which maintained their uniform morphology without creating any unwanted impurities of various shapes. In addition, this approach significantly narrowed the size distribution owing to continuous growth of the partially grown AuNRs during the initial stage of the synthesis. To isolate a 1 g quantity of the AuNRs and to make them functionalized for further chemical reactions, a ligand-exchange approach was utilized, in which the CTAB surfactant was replaced with 4-mercaptophenol. The thiol group from 4-mercaptophenol formed a covalent bond with the surface of the AuNRs, leaving free functional OH groups available for further chemical coupling reactions. For the ligand-exchange process, a concentrated solution of 4-mercaptophenol in tetrahydrofuran solution was introduced into the AuNRs solution. Pure AuNRs functionalized with 4-mercaptophenol were isolated by dispersion and rinsing with an excess amount of THF, followed by centrifugation.     

单分散介孔氧化硅纳米颗粒的制备及其在生物材料方面的应用

单分散介孔氧化硅纳米颗粒由于其自身的优点,在当前许多领域有着广泛的应用前景。本文综述了近十几年来单分散介孔氧化硅纳米颗粒的制备方法以及在生物材料方面的应用。在制备方法方面,根据其制备机理分为稀溶液法、微乳法、模板剂法以及向反应体系中加入不同的添加剂等方法,制备出分散性好、不同形态、孔径尺寸可调的介孔氧化硅纳米颗粒。在生物材料的应用方面,主要介绍了其在药物与生物活性分子的负载与控制释放、生物大分子的固载与分离、生物标记与临床诊断等方面的应用。     

甲烷氧化菌素催化纳米金合成

甲烷氧化菌素(methanobactin,mb)是具有过氧化氢还原酶活性的荧光肽.从甲基弯菌Methylosinus trichospo-rium IMV3011限铜培养介质中分离mb,采用紫外可见全波长扫描法观察mb催化对苯二酚还原氯金酸合成纳米金的作用和影响,当mb/氯金酸/对苯二酚反应液中mb的浓度分别是2.5×10-5mol/L、5.0×10-5mol/L和1.0×10-4mol/L时,形成的纳米金溶液的特征峰分别是561.5 nm(OD561=0.158)、548.0 nm(OD5 48=0.426)、536.5 nm(OD5 36=0.541),特征峰波长减小,对应的吸光值增大,表明mb能够催化对苯二酚还原氯金酸合成纳米金,并且可以通过调控mb的浓度控制纳米金的合成量及粒径大小.     

Synthesis and Characterization of Monodisperse Spherical Zirconia Particles

Monodisperse zirconia spherical particles are prepared by hydrolysis of zirconium propoxide in 2-methoxyethanol in presence of decanoic acid as a shape stabilizer. The powder is analyzed by computer image analysis on TEM micrographs, TG-DSC, FTIR, X-ray diffraction and nitrogen adsorption isotherms. A competition phenomenon between aggregation and individual growth of the particles during precipitation is deduced from the observations.     

Dendronized Gelatin-Mediated Synthesis of Gold Nanoparticles

Thermoresponsive dendronized gelatins (GelG1) or gelatin methacrylates (GelG1MA) were used as precursors to modulate the efficient reduction of Au(III) to form stable gold nanoparticles (AuNPs) through UV irradiation. These dendronized gelatins were obtained through the amidation of gelatin or gelatin methacrylates with dendritic oligoethylene glycols (OEGs). Crowded OEG dendrons along the gelatin backbones create a hydrophobic microenvironment, which promotes the reduction of Au(III). Gelatin backbones act as ligands through the electron-rich groups to facilitate the reduction, while the dendritic OEGs provide shielding effects through crowding to form a hydrophobic microenvironment, which not only enhances the reduction but also stabilize the formed AuNPs through encapsulation. The effects of dendron coverage on the dendronized biomacromolecules and their thermoresponsiveness on the reduction kinetics were examined. Dendronized gelatin/AuNPs hydrogels were further prepared through the in situ photo-crosslinking of GelG1MA. The modification of natural macromolecules through dendronization presented in this report facilitates a novel platform for the environmentally friendly synthesis of noble metal nanoparticles, which may form a new strategy for developing smart nano-biosensors and nano-devices.     

纳米尺度的消化熟化及其在单分散纳米材料制备中的应用

近年来，消化熟化方法已经被广泛采用来制备单分散纳米粒子，特别是在制备亚10 nm的小尺寸纳米粒子方面具有显著优势.但是，目前国内尚未发现关于此方法的中文文献报道，影响了部分国内学者对消化熟化方法的认识和应用.因此，从纳米尺度的消化熟化现象的发现过程和机理的提出开始，分析了沉淀反应前驱物、消化熟化剂种类、热处理温度和时间、溶剂类型以及其他因素对消化熟化现象的影响，介绍了基于颗粒表面带电与曲率效应、颗粒表面与配体分子层的相互作用以及消化熟化过程中的竞争反应平衡等因素的理论模型和研究结果，阐述了消化熟化法在制备金属纳米粒子、合金纳米粒子、金属氧化物和硫族化合物量子点以及其他纳米粒子等单分散纳米材料中的应用，最后展望了消化熟化法制备的单分散纳米粒子在纳米组装和多相催化等领域的应用.     

Parametric Study of Gold Nanoparticles Synthesis under Micro-Continuous Flow Conditions

The synthesis of gold nanoparticles (GNPs) using chemical reduction in batch and microreactor methods has been reported. A parametric study of the effect of several parameters on the size of gold nanoparticles was performed in batch synthesis mode using the modified Martin method. The best-obtained conditions were used to synthesize gold nanoparticles using a glass chip microreactor, and the size of the resulting GNPs from both methods was compared. The presence of polyvinyl alcohol (SC) was used as a capping agent, and sodium borohydride (SB) was used as a reducing agent. Several parameters were studied, including HAuCl₄, SC, SB concentrations, the volumetric ratio of SB to gold precursor, pH, temperature, and mixing speed. Various techniques were used to characterize the resulting nanoparticles, including Atomic Absorbance spectroscopy (AAS), Ultraviolet-visible spectroscopy (UV-Vis), and dynamic light scratching (DLS). Optimum conditions were obtained for the synthesis of gold nanoparticles. Under similar reaction conditions, the microreactor consistently produced smaller nanoparticles in the range of 10.42–11.31 nm with a reaction time of less than 1 min.