多酸的光化学和光催化（上）

综述了多酸光化学研究的发展历程,阐明了多酸光化学的原理及相应的理论模型,总结了各种化合物作为光催化剂在有机反应、环境化学及分解水方面的应用,最后指明了目前正在进行的与多酸光化学相关的前沿研究。     

十八钼硫酸四丁基铵的光化学研究及其一、四电子还原物的合成

多酸化学历史悠久。作为多核化合物中的一类，由于它们在水中良好的溶解性，多酸被视为可溶解的氧化物半导体的模型，而一直为人们所重视。近十多年来，多酸化合物已由单一的合成、性质研究逐步转向功能化合物的开发阶段，一系列的化合物在抗病毒、均相催化、探针分析等领域得到广泛的应用。值得关注的是自七十年代中期起，多酸光化学的研究已悄然兴起，并在太阳能的转换和利用上取得了一定的成果。很早就有人发现杂多酸的荷移谱带（受激吸收带）随中心杂原子电荷的升高而红移，所以可以预计合成以S6＋、Cl7＋为中心的杂多酸应当在光化学上…     

环境光化学的研究进展

介绍了大气、水体、土壤中光化学的研究，并结合国内外在光化学领域的研究指出了光化学的发展方向及存在的问题。     

Fe（Ⅲ）-5-Br-PADAP络合物光化学还原反应的研究

研究了溶液酸度、光强度、有机酸及其浓度对Fe(Ⅲ)-5-Br-PADAP络合物光化学还原反应的影响,并对该光化学还原反应的机理作了初步探讨.结果表明,在pH为5.5的HAc-NaAc缓冲溶液中,Fe(Ⅲ)-5-Br-PADAP络合物的光化学还原反应速度较快;光强度增加,该光化学还原反应速度加快;甲酸等有机酸能加速该光化学还原反应;乙二酸、丙二酸能明显抑制该光化学还原反应;能促进反应的有机酸浓度增加,该光化学还原反应的速度加快.     

二氧化碳还原技术的研究进展

本文简要地介绍了近十多年来二氧化碳的电化学及光化学还原技术的研究进展，并指出了光化学还原技术今后的研究方向。     

p—（N,N—二甲氨基）肉桂酸乙酯在分子聚集体中的光化学行为

本文报道了ｐ－（Ｎ－，Ｎ－二甲氨基）肉桂酸乙酯（ＤＭＡＣ）在十二酸（ＬＡ）聚集体中的光谱和光化学性质。这种肉桂酸衍生物的吸收和发射光谱表现出典型的分子内电荷转移的特征，在十二酸存在下，观察到ＤＭＡＣ激基缔合物荧光，荧光强度随ＤＭＡＣ浓度增加而增加，与普通溶液中的反应相比，十二酸聚集体中的ＤＭＡＣ具有较大的光二聚反应速度。用荧光光谱跟踪反应的结果表明，ＤＭＡＣ激基缔合物具有较ＤＭＡＣ单体更高的光化学     

丁烯酸内酯的合成

根据Gratz及Grove等报道的方法删繁就简、避难就易地合成了丁烯酸内酯(镰刀菌毒素)。这种毒素是利用糠醛经过光化学氧化形成的4-乙氧基-4-羟基-2-丁烯酸-γ-内酯制备的。假酯水解后再与乙酰胺反应即得丁烯酸内酯。产率27.2％。     

超分子光化学的前景

超分子光化学的前景吴世康（中国科学院感光化学研究所，北京１００１０１）关键词超分子，光化学，分子探针，分子器件近二十年来光化学研究取得了巨大进展。其基本状况可归纳为下列几个方面：一是大量的有机分子、配位化合物、金属有机化合物的光化学和光物理行为已被了...     

浅谈光化学的研究与进展

本文着重讨论光化学研究内容及实验技术方面的一些进展。前言光化学是近代化学的重要研究领域。近年来,不论在气相、液相和固休材料,还是在生物体系的光化学研究中都取得了丰硕戍果.一自古人们就知道,植物只有靠     

脱羧反应研究进展

本文综述了关于脱羧反应研究的最新方法，包括光化学，电化学方法及用含氮杂环化合物，过渡金属催化脱羧法。     

Strategies for oxidation catalyzed by polyoxometalates at the interface of homogeneous and heterogeneous catalysis

A basic premise behind the use of polyoxometalates in oxidation chemistry is the fact that polyoxometalates are oxidatively stable. This, a priori, leads to the conclusion that for practical purposes polyoxometalates would have distinct advantages over widely investigated organometallic compounds that are vulnerable to decomposition due to oxidation of the ligand bound to the metal center. Since polyoxometalate synthesis is normally carried out in water by mixing the stoichiometrically required amounts of monomeric metal salts and adjusting the pH to a specific acidic value many structure types are accessible by variation of the reaction stoichiometry, replacement of one or more addenda atoms with other transition or main group metals, and pH control. The structural variety available has enabled the use of polyoxometalates as catalysts for oxidation of hydrocarbons and functionalized organic substrates (alcohols, amines, sulfides, etc.) with a wide range of oxygen donors ranging from molecular oxygen, hydrogen peroxide, nitrous oxide, ozone, alkyl hydroperoxides, periodate, sulfoxide and others. The wide purview of oxidation reactions is enabled because the structural variety leads to oxidation through a number of different mechanistic motifs.From a synthetic organic point of view, the most applicable uses of polyoxometalates as catalysts involve the green oxygen donors – hydrogen peroxide and molecular oxygen. Since practical applications are in hand in this area, practical considerations concerned with catalyst recycle and/or recovery and the elimination of environmentally problematic solvents are also coming to the forefront. In this paper, we will present some of our activities in the area of catalyst engineering for catalytic synthetic applications by polyoxometalates including: (a) catalytic mesoporous solids from organic-polyoxometalate hybrid materials, (b) fluorous phase polyoxometalates with and without fluorous solvents and (c) the use of aqueous biphasic media for oxidation with hydrogen peroxide.     

Synthesis and characterization of novel polyoxometalates with an inverted-Keggin structure as a new class of building unit

Novel polyoxometalates with an inverted-Keggin structure were prepared and isolated as the tetra-alkylammonium salts from an aqueous organic solution. They were characterized using elemental analysis, X-ray analysis, UV–vis, IR and Raman spectroscopy. This study demonstrates that these novel polyoxometalates with an inverted-Keggin structure could be used as a new building block material because they have both a carboxy group and an alkene part, which could react with other organic substrates.     

Electronic Properties and Molecular Simulations of Polyoxometalates

Taking classical polyoxometalates such as Lindqvist, Keggin, Dawson, and Preyssler anions as the starting point, a walk is taken through the electronic and structural properties of polyoxoanions in solution. We will discuss nucleation mechanisms, redox properties, and isomerism of polyoxometalates. The effects of confinement on water molecules and cation distributions inside nanocapsules are other topics discussed in the present review.     

多金属氧酸盐催化的醇类分子氧氧化研究进展

多金属氧酸盐作为一类廉价易得的绿色催化剂,在研究开发醇类分子氧氧化新型催化剂体系过程中起着重要的作用。概述了近十几年来多金属氧酸盐对醇类分子氧氧化的催化作用,催化剂体系主要有磷钒钼基类、磷钨酸类等,并介绍了多金属氧酸盐结合超临界二氧化碳体系的研究现状。指出利用多金属氧酸盐结合超临界二氧化碳有可能开发出完全清洁的醇类氧化技术。     

Keggin-type lacunary and transition metal substituted polyoxometalates as heterogeneous catalysts: A recent progress

In this article we discussed synthesis and catalytic applications of heterogeneous catalysts based on lacunary polyoxometalates (LPOMs) and transition metal substituted polyoxometalates (TMSPOMs), however exclusively the focus has been given to the mono LPOMs and mono-TMSPOMs. As the field of supported LPOMs/TMSPOMs is upcoming important field, some aspects about choice of support as well as methods of supporting have also been described. We also include a few of our new research results in order to understand the effect of support and active species as well as choice of organic transformation.     

光化学研究进展综述

主要对生物光化学、海洋光化学、环境光化学等进展进行综述,并对光化学应用和发展前景进行展望,提出了今后的重点研究方向.     

Polyoxometalate/polymer hybrid materials: fabrication and properties

In this article we provide an overview of the fabrication and properties of polyoxometalate/polymer hybrid materials. Physical blending, electrostatic adsorption, covalent bonding and supramolecular modification are the main strategies to incorporate polyoxometalates into organic or inorganic (taking silica as an example) polymer matrices. The polyoxometalate/polymer hybrid materials obtained concurrently possess the unique optical, electrical or catalytic properties of polyoxometalates and the favorable processability and stability of polymer matrices. Polyoxometalate/polymer hybrid materials may have potential applications in optics, electronics, biology, medicine and catalysis. Copyright © 2009 Society of Chemical Industry     

Surface segregation of branched polyethyleneimines in a thermoplastic polyurethane

Hyperbranched polyethyleneimines were modified with methacrylated fluorosurfactants and aliphatic epoxides to provide a library of macromolecules with controlled chain ends and residual amine functionality. These materials were co-dissolved with a thermoplastic polyurethane-ether and the blends were subsequently deposited as films cast from solution. The surface chemistry of the cast films was determined using angle resolved X-ray photoelectron spectroscopy (AR-XPS) and Rutherford backscattering spectroscopy (RBS). Experimental results indicate that the modified hyperbranched polymers (HBPs) concentrate at the air-polymer interface. Furthermore, HBPs that were complexed to polyoxometalates (POMs) using electrostatic interactions also exhibited surface segregation in cast polymer films, resulting in ca. 10-fold increase of metal at the film surface relative to the known bulk concentration. Results from XPS and RBS examination of the films are consistent with surface segregation of the HBP-POM hybrids, exhibiting increased metal, fluorine, and nitrogen content near the surface of the film, as well as significant changes in wetting behavior. This study indicates that modified HBPs may be used to selectively transport inorganic species such as polyoxometalates to polymer film surfaces.     

杂多化合物催化过氧化氢氧化烯烃环氧化反应研究进展

烯烃的环氧化反应是化学工业中重要的化学反应之一,其环氧化物是用途极为广泛的有机原料和化学中间体。文章综述了以杂多酸为催化剂,过氧化氢为氧化剂的烯烃环氧化反应研究进展,指出了今后此类环氧化反应催化剂发展方向。