基于有机硼酸的共价键有机框架研究进展

共价键有机框架(Covalent Organic Frameworks,COFs)是具有明确孔径分布的多孔晶体材料,在气体贮藏、催化、分离、光学器件和化学传感等方面均有应用前景。有机硼酸中硼原子最外层空的p轨道能与π键产生特殊的轨道作用,也可与路易斯碱发生配位作用。上述特点使其能够作为结构和功能导向的基元而用于构筑共价键有机框架。本文从合成、结构以及性质等方面对有机硼酸构筑的共价键有机框架进行了介绍。     

有机电化学的发展史

本文回顾了有机电化学和有机电化学工业的发展历程，阐述了有机电化学的研究领域，从而展望了有机电化学的发展方向。     

有机小分子电致发光研究进展

有机电致发光具有发光亮度和发光效率高,材料易加工等传统的无机和液晶显示材料无可比拟的优点,并且可以通过改变分子结构或掺杂调谐发光的颜色.本文评述了近年来有机小分子电致发光材料的研究进展,简要介绍了有机电致发光的原理及其广阔的应用前景.     

有机光纤研究进展

综述了近年来有机光纤(塑料光纤) 研究状况, 对有机光纤的分类及适用范围也给予了简单的说明。讨论了影响信号传输的因素和有机光纤光传输损耗的极限, 并对当前受到广泛重视的渐变型有机光纤的研究进展给予了特别的关注。     

新型功能材料有机钌络合物和有机钌聚合物

有机钌络合物和有机钌聚合物具有特殊的光、电性能,是一种新型功能材料,正在形成一个新的研究领域。本文介绍有机钌络合物和有机钌聚合物的光致电子转移、光致发光和电致发光等现象以及它们在发光二极管、发光电池、氧化传感器等方面的应用。     

非金属有机催化剂及其在有机化学反应中的应用

非金属有机催化剂在有机化学反应中有着独特的催化性能和优良的催化效果,尤其是在不对称合成中应用广泛.综述了近年来几类常用的非金属有机催化剂和它们所催化的各类有机化学反应包括不对称合成反应,同时对其催化机理做了总结.     

负载有机膦的合成及其在有机催化领域的应用

有机膦是一类重要的有机催化剂,作为一种亲核催化剂已得到广泛的应用。小分子叔膦作为一种均相催化剂影响产物的分离和催化剂的回收,将膦负载可以弥补上述缺陷。负载叔膦作为一类有机催化剂在近几年才受到关注。本文简要介绍了不同载体负载叔膦的合成方法及应用,综述了其催化Baylis-Hillman、加成、炔酮异构化和羟基保护反应的研究进展,并对研究前景进行了展望。     

有机和金属有机非线性光学晶体材料

非线性光学材料是激光技术的重要物质基础之一,是高技术研究的一个组成部分。二十多年来,非线性光学材料的研究经历了无机晶体、有机材料的阶段,现在又开始了金属有机非线性光学材料的探索。本文拟综述有机和金属有机二阶非线性光学晶体材料的研究进展,而不讨论高分子材料以及三阶非线性光学效应。鉴于刊物读者的特     

有机光伏材料与器件研究的新进展

近几年有机光伏电池应用研究发展迅猛。本文综述了有机光伏薄膜电池在材料(包括有机小分子材料与聚合物材料)、器件构造方面的最新进展，分析了有机聚合物光伏电池目前效率低的主要原因，并探讨了该领域进一步研究的方向和前景。     

有机电路及其基本元器件

半导体电路及其元器件是实现现代信息传递的重要组成部分,随着无机电路特别是硅基电路的研究发展进入瓶颈,有机电路及其基本元器件的研究对于电路及系统的未来发展意义更加重大。近十年来,有机电路及其基本元器件取得了飞速的发展,多种基本元件器性能已经达到可应用程度,特别是在显示领域,基于有机半导体制备的OLED显示电路已经成为新一代显示器的选择。同时,有机电路也因其所具有的低成本、可弯折、高透光等特性而具有了更多的发展空间。本综述从构成有机电路的各基本部件出发,以各部分器件在电路系统中的应用为线索,从系统信息采集、信息处理、信息存储和信息输出4个方面简述了各部分基础元件的发展情况,并以基于有机场效应晶体管的器件为基础,对器件的结构、电性能的优化以及所面临的问题进行了讨论。     

Synthesis and Properties of Novel Polyanions of Potential Antitumor Activity

A large number of naturally occurring polyanionic materials are known each of which possesses its own set of physiological properties. Within recent years, a wide variety of synthetic polyanions have become available, and investigators have compared their physiological properties with the naturally occurring polyanions. Perhaps, the most widely investigated synthetic polyanion is the 1:2 regularly alternating cycloco-polymer (DVE-MA) of divinyl ether (DVE) and maleic anhydride (MA), first discovered in these laboratories in 1951. This material has been investigated extensively, both from the standpoint of its chemical structure and its biological activity. Although certain aspects of its structure remain to be determined, it has been shown to possess a wide spectrum of biological activity. It possesses antitumor as well as other activities and is an interferon inducer. Many structural modifications of DVE-MA have been synthesized which also possess antitumor activity and interferon-inducing capability. A recent structural modification incorporated 5-fluorouracil (5-FU) into DVE-MA. This polymer is hydrolyzed readily to release 5-FU, and the material exhibited considerable activity against P388 lymphocytic leukemia. A novel series of polyanions have been synthesized via reactions of N-substituted triazolinediones with a variety of olefins and diene polymers. The synthesis and physiological properties of certain of these polyanions are discussed in this paper.     

多金属氧酸盐抗病毒药物研究

多金属氧酸盐在抗病毒、抗肿瘤、抗细菌方面的研究取得了重要进展，本文综述了近30年来多金属氧酸盐在抗艾滋病毒(HIV)、疱疹病毒(HSV-1、HSV-2)、流感病毒等方面的研究情况，详细总结了各种类型多金属氧酸盐的抗病毒效果。结合本课题组的研究结果比较分析了多金属氧酸盐的结构及其抗病毒效果的差异。     

Redox properties of hybrid Dawson type polyoxometalates disubstituted with organo-silyl or organo-phosphoryl moieties

This paper reports on the electrochemical study of Dawson-type polyoxometalates (POMs) disubstituted with phenyl-phosphonate, phenyl silyl or tertbutylsilyl moieties. The polyanions were studied by cyclic voltammetry and on rotating disk electrode in acetonitrile with tetraphenylphosphonium chloride as supporting electrolyte. We found that these hybrid polyoxometalates can accept up to five electrons and that the organic substituents modify the first and second reduction potential of the POM compared to the unsubstituted POM [P₂W₁₈O₆₂]⁶⁻. Phenyl-phosphonate lowers the reduction potential, whereas the phenyl silyl or tertbutylsilyl moieties shift them cathodically. We also recorded by spectroelectrochemistry the spectrum of the monoreduced and the bisreduced species of the polyoxometalate disubstituted with phenyl-phosphonate.     

Lanthanoid Single-Ion Magnets Based on Polyoxometalates with a 5-fold Symmetry: The Series [LnP(5)W(30)O(110)](12-) (Ln(3+) = Tb, Dy, Ho, Er, Tm, and Yb)

A robust, stable and processable family of mononuclear lanthanoid complexes based on polyoxometalates (POMs) that exhibit single-molecule magnetic behavior is described here. Preyssler polyanions of general formula [LnP(5)W(30)O(110)](12-) (Ln(3+) = Tb, Dy, Ho, Er, Tm, and Yb) have been characterized with static and dynamic magnetic measurements and heat capacity experiments. For the Dy and Ho derivatives, slow relaxation of the magnetization has been found. A simple interpretation of these properties is achieved by using crystal field theory.     

Synthesis and Crystal Structures of Novel Keggin and Dawson Polyoxometalates Containing Amantadine

Heteropolyoxometalates are a large family of potent medicines due to their excellent antiviral and antitumor activity 1-4, while their application in clinic meets great difficulties for their toxicity 5. How to synthesize heteropolyoxometalate medicines possessing high activity and low toxicity has become the focus in heteropolyoxometalate medicine research. Previously reported polyoxometalates showing medical activities are all salts simple Na+, K+ or NH4+ etc. inorganic cations, in which o…     

<Emphasis Type="Italic">In vitro</Emphasis> inhibitory effect of polyoxometalates on human tumor cells

H₇[NiV₁₃O₃₈] was synthesized from K₇[NiV₁₃O₃₈] using an ion exchange method. Then Pr₂H[NiV₁₃O₃₈] was obtained by double decomposition of H₇[NiV₁₃O₃₈] with Pr₂(CO₃)₃. The actual amount of praseodymium measured by elemental analysis coincides with the designed amount of praseodymium in Pr₂H[NiV₁₃O₃₈]. The i.r. spectra suggested that the [NiV₁₃O₃₈]^7– anion did not collapse after the ion exchange and double decomposition. The ⁵¹V n.m.r. spectrum of Pr₂H[NiV₁₃O₃₈] showed four peaks and their ratio of the relative intensity was 4:4:4:1. This result agrees with the chemical environment of V atoms in the [NiV₁₃O₃₈]^7– anion. In vitro antitumor activities of polyoxometalates on several human tumor cells have been investigated using the MTT method. Pr₂H[NiV₁₃O₃₈] is the most effective polyoxometalate tested in this study for inhibiting KB cell. Pr₂H[NiV₁₃O₃₈] also showed remarkable inhibitory effect on some other tumor cells: HCT, Bel, B₁₆, BCAP and ESCL cells. These results indicate that Pr₂H[NiV₁₃O₃₈] is a potent broad spectrum antitumor agent. The structure type of polyoxometalates greatly influences their antitumor activity: the order of structure type for inhibiting KB cell is: [NiV₁₃O₃₈]^7–>[Mo₇O₂₄]^6–>Anderson structure Keggin structure Dawson structure. Moreover, the nature of the polyatom in the polyoxometalates also greatly influences their antitumor activity: the polyatom order for inhibiting KB cell is: V>Mo W. On the other hand, the nature of the counter cation and the heteroatom in the polyoxometalates exerted a relatively small influence on the inhibitory effect against the KB cell, although the praseodymium salt of [NiV₁₃O₃₈]^7– showed a higher antitumor activity than its potassium salt.     

合成高分子量无规聚丙烯的研究 Ⅰ.单茂基钛化合物/MAO催化丙烯聚合

用合成得到的五甲基环戊二烯基三苄氧基钛［ＣｐＴｉ（ＯＢｚ）３］与甲基铝氧烷（ＭＡＯ）组成新型催化体系进行丙烯的均聚合,研究了影响聚合活性及产物分子量的各种因素．结果表明,用甲基取代钛化合物茂环上的氢可使聚合产物分子量增大一个数量级,所制得的聚丙烯为无规聚丙烯,具有高分子量（Ｍｗ＝２０～１００×１０４）．     

Preparation,antitumor activity in mice,pharmacokinetics and tissue distribution in rats of di‐n‐butyl‐di‐(4‐chlorobenzohydroxamato)tin(IV) liposome

Di‐n‐butyl‐di‐(4‐chlorobenzohydroxamato)tin(IV) (DBDCT) is an antitumor compound with high activity and relatively low bioavailability. In order to improve the pharmacokinetic characteristics and raise its therapeutic index, a liposome of DBDCT (DBDCT‐L) was prepared for the first time. A study of the pharmacokinetics and tissue distribution after intravenous administration of DBDCT‐L compared with free DBDCT to rats was investigated. DBDCT‐L showed a slower clearance, increased half‐time and a larger AUC value than those of free DBDCT, which demonstrated that DBDCT‐L could significantly alter the tissue distribution pattern of DBDCT in rats. The highest concentration distribution for DBDCT‐L was detected in liver, which may be associated with the enhanced antitumor activity in vivo against hepatocellular carcinoma H₂₂ and possible target release of the compound. Acute toxicity assay showed that the LD₅₀ value of DBDCT‐L was higher than that of free DBDCT. Further in vivo antitumor test showed that DBDCT‐L displayed higher antitumor activity against the hepatocellular carcinoma H₂₂ than free DBDCT, indicating that the liposome could prolong the action time of DBDCT in the system circulation, change its distribution in rats, reduce acute toxicity and finally increase antitumor activity. Copyright © 2014 John Wiley & Sons, Ltd.     

Interaction of polyanions with basic proteins, 2(a) : influence of complexing polyanions on the thermo-aggregation of oligomeric enzymes

The ability of synthetic polyanions to suppress thermo-aggregation of the oligomeric enzymes (glyceraldehyde-3-phosphate dehydrogenase, lactate dehydrogenase, and aspartate aminotransferase) has been established. The ability of the polyanions to reduce the thermo-aggregation increased in the order poly(methacrylic acid) < poly(acrylic acid) < sodium poly(styrene sulphonate), which agreed well with the increase, in the same order, of the charge density of the chains. The lengthening of the chains, as well as the rise in their relative content, resulted in an increase of the ability to reduce thermo-aggregation, mentioned above. Complete prevention of the enzyme aggregation was achieved when highly charged polyanions of a relatively high degree of polymerization were used in a concentration sufficient to solubilize the protein. Complexing with the polyanions prevented thermo-aggregation of the enzymes, but not their thermo-denaturation. The adverse effect of the complexing polyanions on the catalytic activity was reduced by the addition of a synthetic polycation, which resulted in a significant reactivation (up to 40%) of the enzyme. The possibility of preventing the thermo-aggregation of enzyme molecules and then partly restoring the enzyme activity, appears to be of particular interest when studying the aggregation mechanism of proteins that are prone to form the amyloid structures responsible for the development of neurodegenerative diseases like Alzheimer's disease, bovine spongiform encephalopathy and Huntington disease. This finding can also be considered as an important step in the creation of artificial chaperones.     

苯乙烯间规聚合催化剂进展

综述了苯乙烯间规聚合主催化剂的研究和开发状况。主要介绍茂、茚、多元稠合环，氟和非茂钛等较高活性催化剂的催化特性，从取代基的电子效应和空间效应以及活性种稳定性等方面阐述了不同催化剂的聚合活性差异。