发光铜纳米粒子的制备及其在生化传感、环境监测中的应用综述

发光铜纳米簇具有与金、银贵金属纳米簇相媲美的荧光性质,还具有原料储量丰富、制备经济、合成过程简便等优点,具有广阔的应用前景。系统地介绍了铜纳米簇的主要性质、制备方法及应用现状,重点总结了近年来荧光铜纳米簇在生化传感器、生物探针、细胞成像、环境标志物检测等领域的应用进展。     

精确尺寸巯基保护贵金属纳米团簇的合成进展

金属纳米团簇作为凝聚态物质的初始形态之一,在金属原子/分子化合物向金属纳米颗粒形成的过程中起着桥梁作用.因其具有量子局限效应,团簇往往表现出特异的光学、催化等性质.近几十年来的研究发现,单个原子的改变会对团簇的几何结构以及电子结构产生显著的影响.同时,精确的结构可以有效地建立结构与性质之间的关系.因此,合成具有精确结构的纳米团簇在近年来受到广泛关注.笔者对巯基保护精确结构金属纳米团簇合成方法的建立以及发展进行了综述.     

金属纳米团簇在生物医学领域的研究进展

金属纳米团簇具有独特的超小尺寸和光、磁、催化等性能,以及优异的生物相容性等特征,在生物医学研究中备受关注.但其存在发光效率偏低、活体代谢速度较快等问题.为此介绍近几年通过合成优化和发光调控等方法提高金属纳米团簇的检测与成像灵敏度和肿瘤诊疗能力的研究进展.探究金属纳米团簇的肾代谢和生物酶催化性能;开发具有精确原子数、高效生物相容性和肿瘤靶向性的金属纳米团簇;突破其近红外发光量子产率限制,提高光声-磁共振造影等性能,将是未来该领域研究的重要方向.     

制备体系酸度对AlMSU介孔材料结构性能的影响

利用β沸石纳米簇和曲拉通TX-100分别作为骨架构筑前驱物和孔道导向剂,在酸性介质中通过(N^oH⁺)Cl^-S⁺组装机制合成了蠕虫状孔道排列的AlMSU介孔材料,并借助测试手段对其进行了系统表征。结果表明：制备体系盐酸浓度对AlMSU的结构性能、骨架组成及收率有着显著影响。介质酸浓度较低（<0.5mol/L）时所得AlMSU的物化性质较差,而且产物收率低（基于样品粉末质量）;而体系酸浓度大于2.5mol/L时将造成部分铝原子从骨架中析出,导致最终产物中铝元素含量显著降低。基于结构性能、骨架组成和样品收率等综合因素,体系酸浓度介于1.5~2.0mol/L时是合成AlMSU介孔材料的合适区间     

DNA调控的银纳米簇的合成及应用进展

荧光银纳米簇具有独特的光电学及化学性质,凭借合成简便、荧光强度大、量子产率高、抗光漂白能力强、荧光发射波长可调及生物相容性好等优势,近年来在生物检测、成像分析等领域受到了越来越广泛的关注。前期研究人员进行了大量的DNA调控荧光银纳米簇的合成方法研究,本工作以此为基础,总结目前已取得的关于DNA序列、长度、二级结构等对银纳米簇荧光性质的影响规律,并详细介绍荧光银纳米簇在分析检测和生物成像应用方面的最新进展。相信随着荧光纳米簇材料的应用优势逐步凸显,该领域的研究将吸引更广泛的关注,并推动相关交叉学科的进展。     

One-step facile synthesis of Pd nanoclusters supported on carbon and their electrochemical property

Well-crystallized Pd nanoclusters supported on Ketjen Black(KB) were successfully fabricated when Pd wires were served as an electrode pair by a solution plasma technique at atmospheric pressure. The synthesis of Pd nanoclusters was almost simultaneous with their dispersion on KB.Pd nanoclusters with the average diameter of about 2 nm were equably distributed on KB, and showed good electrochemical property corresponding to their obvious characteristic peaks. Multi-scan cyclic voltammetry and chronoamperometry clarified that as-prepared Pd nanoclusters have better electrochemical stability in alkaline solution than that of in acidic solution. Thus as-obtained Pd nanoclusters would become a promising electrocatalyst for fuel cells or Li-air batteries.     

介孔TiO2材料的改性及其应用的研究进展

介孔TiO2材料由于具有特殊的性能展示了广阔的潜在应用前景,近年来备受关注。对纯介孔TiO2的合成现状和介孔TiO2的改性方法进行了综述,着重介绍了通过引入金属杂质的改性方法及其应用。     

新杂环偶氮类试剂合成及其与金属离子显色反应的研究

合成了三种新试剂２－（５－硝基－２－吡啶偶氮）－５－二甲氨基苯胺（５－ＮＯ２－ＰＡＤＭＡ），５－（５－硝基－２－吡啶偶氮）－２，４－二氨基甲苯（５－ＮＯ２－ＰＡＤＡＴ）和２－（６－硝基－２－苯并噻唑偶氮）－５－二甲氨基苯甲酸（６－ＮＯ２－ＢＴＡＭＢ）．用分光光度法测定了试剂的三级质子化常数．在弱酸性或磁性介质中，试剂可与铁、镍、铜、钯、铑和钌等金属离子反应，生成稳定的有色配合物．     

Structural effects on the magnetic hyperthermia properties of iron oxide nanoparticles

Magnetic iron oxide nanoparticles(IONPs) are heavily explored as diagnostic and therapeutic agents due to their low cost, tunable properties, and biocompatibility. In particular, upon excitation with an alternating current(AC) magnetic field, the NPs generate localized heat that can be exploited for therapeutic hyperthermia treatment of diseased cells or pathogenic microbes. In this review, we focus on how structural changes and inter-particle interactions affect the heating efficiency of iron oxide-based magnetic NPs. Moreover, we present an overview of the different approaches to evaluate the heating performance of IONPs and introduce a new theranostic modality based on magnetic imaging guided–hyperthermia.     

Chiral ligand-protected gold nanoclusters: Considering the optical activity from a viewpoint of ligand dissymmetric field

Chirality is a geometric property of a physical, chemical, or biological object, which is not superimposable on its mirror image. Its significant presence has led to a strong demand in the development of chiral drugs, sensors, catalysts, and photofunctional materials. In recent years, chirality of nanoscale organic/inorganic hybrids has received tremendous attention owing to potential applications in chiral nanotechnology. In particular, with the recent progress in the syntheses and characterizations of atomically precise gold nanoclusters protected by achiral thiolates, atomic level origins of their chirality have been unveiled. On the other hand, chirality or optical activity in metal nanoclusters can also be introduced via the surface chiral ligands, which should be universal for the nanosystems. This tutorial review presents some optically-active metal (gold) nanoclusters protected by chiral thiolates or phosphines, and their chiroptical (or circular dichroism; CD) properties are discussed mostly from a viewpoint of the ligand dissymmetric field scheme. The examples are the gold nanoclusters protected by (R)-/(S)-2-phenylpropane-1-thiol, (R)-/(S)-mercaptosuccinic acid, phenylboronate-D/L-fructose complexes, phosphine sulfonate-ephedrinium ion pairs, or glutathione. Some methodologies for versatile asymmetric transformation and chiroptical controls of the nanocluster compounds are also described. In the dissymmetric field model as the origin of optical activity, the chiroptical responses of the gold nanoclusters are strongly associated with coupled oscillator and/or CD stealing mechanisms based on the concept of induced CD (ICD) derived from a perturbation theory, so on this basis, some characteristic features of the observed CD responses of chiral ligand-protected gold nanoclusters are presented in detail. We believe that various kinds of origins of chirality found in ligand-protected gold nanoclusters may provide models for understanding those of many related nanomaterials.     

铈和铬对纯铜性能的影响

研究了不同铈和铬的加入量对纯铜的导电率、强度、硬度、耐磨性及显微组织的影响。研究发现,在纯铜中加入适量和铬可以在不影响纯铜的良好导电性的同时,提高其强度、硬度,并可有效的细化组织,净化基体。试验结果表明当铜中铈铈的加入量为0．08％,铬的加入量为0．4％时,具有良好的综合性能。     

关于几类不变线性函数的概念、判定和应用

拟线性函数、伪线性函数作为一种广义凸函数已经被广泛研究，本文将该类函数进行推广，提出预不变线性函数、预拟不变线性函数、伪不变线性函数的概念，并讨论了这几类新函数的性质，最后给出伪不变函数最优解集的特征。     

一种新型Schiff碱双核Cu(II)配合物的合成与表征

合成了一种新型Schiff碱配体并采用常规法和模板法合成了其双核Cu(II)配合物.运用红外、紫外可见、荧光光谱、元素分析、电子喷雾质谱和电导率等测试方法对所合成的配合物进行了表征,推测了其组成和结构,讨论了结构与性质关系,并提出了提高反应产率的方法     

焙烧条件对Cu/ZnO/Al2O3甲醇催化剂的影响

介绍了用草酸盐胶态共沉淀法制备纳米Cu/ZnO/Al2O3催化剂过程中焙烧条件对催化剂结构性质及其二氧化碳加氢制甲醇催化活性的影响。结合多种现代表征手段，研究了焙烧气氛、焙烧温度和焙烧过程不同升温速率对催化剂晶粒大小、结构及各组分间相互作用的影响。在此基础上，将该催化剂用于二氧化碳加氢制甲醇反应。催化反应结果表明，纳米金属铜催化剂显示出优良的二氧化碳加氢反应性能，焙烧条件对催化剂性质影响显著。     

混合钼钒多金属氧酸盐的水热合成、结构表征及磁性研究

通过水热方法合成了一种混合钼钒多金属氧酸盐[Cu(phen)_2]_4{HPMo_8~Ⅵ V_6~ⅣO_(42)[Cu(phen)]_2}·2H_2O.采用X射线单晶衍射、元素分析、红外光谱对其进行了表征,同时对其磁学性质进行了研究.结果表明:标题化合物包含高度还原的二帽假Keggin结构的多氧阴离子支撑2个过渡金属配合物,即铜配合物阳离子[Cu(phen)_2]~+和结晶水;该化合物呈铁磁性相互作用.     

不同形貌铜纳米颗粒的制备与催化性能研究

目的制备一系列不同形貌的铜纳米颗粒,探讨影响金属纳米晶体形貌和尺寸的因素,并研究其催化性能。方法采用化学还原法和水热法进行合成。结果合成出立方体,小球体,片状和枝状形貌的铜纳米颗粒,并选用立方体和小球体这两种具有代表性的铜纳米颗粒应用于苯羟基化反应中,发现立方体形状的铜纳米颗粒具有更高的催化活性。结论就大多数反应而言,较低的反应前驱物浓度、较低的反应体系温度、较长的反应时间以及适当的助剂,有利于生成形貌规整,尺寸均匀,分散性较好的纳米晶体;且铜纳米颗粒催化活性与其暴露晶面有关,高能晶面的催化活性较高。     

光纤表面等离子体共振传感器敏感膜的仿真研究

为了研究光纤表面等离子体共振传感器的传感特性,利用TFCalc软件仿真研究光纤表面等离子体共振(SPR)传感器的反射光谱特性,分别考查敏感膜为Au膜、Ag膜、Al膜和Cu膜对反射光谱特性的影响。仿真结果表明,Au膜和Ag膜有较高的灵敏度,Al膜和Cu膜厚度分别在10 nm和30 nm有较明显的共振现象。     

Fabrication of copper nanorods by low-temperature metal organic chemical vapor deposition

Copper nanorods have been synthe-sized in mesoporous SBA-15 by a low-temperature metal organic chemical vapor deposition (MOCVD) employing copper (II) acetylacetonate, Cu(acac)2, and hydrogen as a precursor and reactant gas, re- spectively. The hydrogen plays an important role in chemical reduction of oganometallic precursor which enhances mass transfer in the interior of the SBA-15 porous substrate. Such copper nanostructures are of great potentials in the semiconductor due to their unusual optical, magnetic and electronic properties. In addition, it has been found that chemically modi- fying the substrate surface by carbon deposition is crucial to such synthesis of copper nanostructures in the interior of the SBA-15, which is able to change the surface properties of SBA-15 from hydrophilic to hydrophobic to promote the adsorption of organic cupric precursor. It has also been found that the copper nanoparticles deposited on the external sur- face are almost eliminated and the copper nanorods are more distinct while the product was treated with ammonia. This approach could be achieved under a mild condition: a low temperature (400℃) and vac-uum (2 kPa) which is extremely milder than the con- ventional method. It actually sounds as a foundation which is the first time to synthesize a copper nanorod at a mild condition of a low reaction temperature and pressure.     

1，3，2－苯并二氧磷杂环戊烷衍生物的晶体结构研究

近年来人们对含磷杂环化合物的结构特点、物理化学性质及反应机制，特别是对它们的生物活性及用途进行了广泛的研究［１，２］。标题化合物的合成已经进行了报道［３］，本文将报道标题化合物的晶体结构。     

离心奥氏体──贝氏体球墨铸铁管

比较系统地研究了合金元素Ｃｕ、Ｍｏ和等淬时间及温度对离心奥氏体／贝氏体球墨铸铁管组织与性能的影响，找出了合金元素Ｃｕ、Ｍｏ对离心奥氏体／贝氏体球墨铸铁管的影响规律，确定了适宜的热处理工艺参数，并在实验室生产出性能良好的离心奥氏体／贝氏体球墨铸铁管。