铜三氟柳配合物的合成,结构和仿生催化溴化

合成了一系列2-羟基-4-三氟甲基苯甲酸（h₂tba）-铜配合物：[Cu（htba）₂（pz）₂]（1）,[Cu（htba）（2,2''-bipy）]（htba）（2）和[Cu（htba）₂（4,4''-bipy）]（3）（h₂tba=2-羟基-4-三氟甲基苯甲酸,pz=吡唑,2,2''-bipy=2,2''-联吡啶,4,4''-bipy=4,4''-联吡啶）,并且通过元素分析、红外光谱、紫外光谱、粉末X射线衍射、单晶X射线衍射和热重分析方法对配合物结构进行了表征。这些配合物能够在过氧化氢和溴化物存在的条件下催化苯酚红溴化,并且展示出了较高的催化溴化活性。     

二丙胺的结构微调对磷酸铝分子筛晶化过程影响的凝胶组成依赖性

以二丙胺异构体（二正丙胺DPA和二异丙胺D-iPA）为结构导向剂,在200℃加热2组反应原料物质的量之比不同的初始凝胶,合成出了高结晶度的磷酸铝分子筛AlPO₄-11。利用X射线粉末衍射分析、元素分析等表征手段,研究了凝胶的晶化过程和液相的pH值以及Al和P的浓度演化。初始凝胶各组分物质的量之比为n_Al2O3：n_P2O5：n_DPA/D-iPA：n_H2O2=1.0：1.0：1.2：75时,以DPA为结构导向剂,晶化过程中无中间相生成,而以D-iPA为结构导向剂时,晶化过程中生成了具有12元环孔道结构的磷酸铝分子筛AlPO₄-5中间相;初始凝胶各组分物质的量之比为n_Al2O3：n_P2O5：n_DPA/D-iPA：n_H2O2=1.0：1.0：1.0：75时,以DPA为结构导向剂,晶化过程中生成了具有18元环孔道结构的磷酸铝分子筛VPI-5中间相,而以D-iPA为结构导向剂时,晶化过程中同时出现了VPI-5及AlPO₄-5两种中间相。表明对于同一种有机胺,凝胶物质的量之比的改变影响了其结构导向效应。理论计算结果显示质子化的DPA及D-iPA中N原子上的电荷有差异,表明有机胺的结构微调影响其结构导向效应,但该影响依赖于凝胶组成。     

钯纳米粒子的形貌可控合成与催化性能

借助于一种全新的表面活性剂N,N-dimethyloctadecylammonium bromide acetate sodium（OTAB-Na）,成功实现了对小尺寸钯纳米粒子微结构的控制。通过对合成条件的微扰,高度均匀且分散性良好的枝化结构和凹面体结构的钯纳米粒子被成功地制备。催化测试（利用氨硼烷作为氢化试剂来还原4-硝基苯酚为4-胺基苯酚）发现,钯纳米粒子的催化活性与其微观纳米结构相关,其中枝化结构的钯纳米粒子表现出了更为突出的催化性能。     

Asymmetric Synthesis, Antifungal Activity and Molecular Modeling of Iodiconazole Isomers

Iodiconazole is a novel antifungal agent that was developed in its racemic form. In order to investigate the ef- fects of the chiral center on the antifungal activity, R- and S-isomers of iodiconazole were prepared on the basis of the asymmetric Sharpless epoxidation. （S）-Iodiconazole was proved to have better antifungal activity than the （R）- isomer. The binding modes of the two isomers with lanosterol 14~z-demethylase were clarified by molecular dock- ing.     

Design and Synthesis of Tri-substituted Chiral Pyrrolidin-2-one Derivatives as CCR4 Antagonists

A series of tri-substituted chiral pyrrolidin-2-one derivatives have been designed and synthesized as CC chemokine receptor 4 （CCR4） antagonists. The structure of CCR4 was built by homology modeling. Asymmetric synthesis was applied to synthesize the R,R configuration chiral pyrrolidin-2-one scaffold. The stereoisomeric con- figurations of the compounds were identified by 2D I H-~H COSY spectroscopy and 1D NOESY spectroscopy. This method was more economical and convenient than traditional X-ray single crystal diffraction. In addition, the inter- actions between these compounds and the N-terminal extracellular tail of CCR4 were studied using capillary zone electrophoresis. The CCR4 chemotaxis inhibition effect was tested in CCR4-transfected HEK293 cells. Several compounds showed potent activities as CCR4 antagonists. Among these compounds, lc is the most active one. Its apparent binding constant of CZE experiment result is （1.569±0.11）× 10s L·mol ^-1, and its percentage inhibition of the HEK293/CCR4 cells migration with the concentration of I gmol·L ^-1 in DMSO is 59%. And compound If has slightly higher affinity to N-terminal of CCR4 according to its apparent binding constant than lb because of the in- troduced ester linkage. Further studies on the mechanism of these compounds are in progress.     

Formal synthesis of（＋）-tashiromine and study toward the total synthesis of（＋）-stemoamide

An effcient formal synthesis of（＋）-tashiromine was achieved by employing an intermolecular asymmetric Mannich-type reaction as the key step.Concurrently,a novel approach toward the total synthesis of（＋）-stemoamide through dyotropic rearrangement of 3,4-cis-b-lactone was also explored.     

长链超支化聚合物的合成研究进展

长链超支化聚合物(HyperMacs)凭借其含有大量的功能端基和可调控的链结构等优点已经引起国内外科研人员越来越广泛的关注。HyperMcs除了拥有超支化聚合物固有的低粘度、溶解性好、含有大量的功能性端基的特点外,同时拥有高剪切敏感性、熔体弹性、冲击强度和零剪切粘度,因而在药物载体、能量存储及传递和纳米催化剂等方面可能拥有更为广泛的应用。本文根据HyperMacs合成方法的不同,分别从迭代法和ABx线型大分子单体法两个主要方面对其研究进展进行了总结和评述,并在此基础上展望了该类聚合物的研究方向和发展趋势。     

H_6P_2W_（18）O_（62）á18H_2O： A green and reusable catalyst for one-pot synthesis of pyrano[4,3-b]pyrans in water

A convenient,effcient and environmentally benign procedure has been developed for the synthesis of pyrano[4,3-b]pyran derivatives via a one-pot,three-component reaction of 4-hydroxy-6-methylpyran-2-one,aldehydes and malononitrile in water using H6P2W18O62á18H2O as catalyst.Reusability of the catalyst and reaction media,short reaction times and easy isolation of products are some added advantages of the present methodology.     

Distereoselective one-pot synthesis of pyrimidopyrimidines using sulfated tin oxide as a reusable catalyst： An extension of Biginelli-type reaction

The Biginelli-type compounds 4,5,8a-triarylhexahydropyrimido[4,5-d]pyrimidine-2,7（1H,3H）-diones were synthesized by a one-pot three-component reaction using sulfated tin oxide as a reusable catalyst. This method has the advantages of high yields, short reaction time, simple starting materials and reusability of catalyst for several times.     

十三氟辛基修饰的疏水有机-无机杂化二氧化硅膜孔结构、氢气分离及水热稳定性

采用1,2-双（三乙氧基硅基）乙烷（BTESE）和十三氟辛基三乙氧基硅烷（PFOTES）为前驱体,在酸性条件下通过溶胶-凝胶法制备了十三氟辛基修饰的有机-无机杂化SiO₂膜材料。利用接触角测量、红外光谱、动态光散射和N₂吸附等测试技术分别对膜材料的疏水性、溶胶粒径和孔结构进行表征,并深入研究有支撑膜材料的氢气渗透、分离性能以及长期水热稳定性。结果表明,十三氟辛基修饰后的膜材料由亲水性变成了疏水性,当n_PFOTES/n_BTESE=0.6时膜材料对水的接触角达到（110.4±0.4）°,膜材料还保持微孔结构,孔径分布在0.5~0.8nm。氢气在修饰后的膜材料中的输运遵循微孔扩散机理,在300℃时,氢气的渗透率达到8.5×10^-7mol·m^-2·s^-1·Pa^-1,H₂/CO₂,H₂/CO和H₂/SF₆的理想分离系数分别为5.49,5.90和18.36,均高于相应的Knudsen扩散分离因子。在250℃且水蒸气物质的量分数为5%水热环境下陈化250h,氢气渗透率和H₂/CO₂的理想分离系数基本保持不变,膜材料具有良好的水热稳定性。