Keggin结构杂多酸热性质研究

本文利用DSC, TG-DTA, X射线衍射, 变温红外光谱和溶解性试验方法, 系统地研究了Keggin结构杂多酸HnXM12O40(X=Si, P, Ge; M=Mo, W)的热稳定性, 提出杂多化合物热分解的新判据, 给出了Keggin结构杂多酸的热分解过程, 推导出预测热分解温度的半经验公式。     

A Mild and Efficient Deprotection of Geminal Diacetates Catalyzed by FeCl3 ·6H2O in Ionic Liquid

The selective deprotection of geminal diacetates promoted by FeCl3·6H2O in the ionic liquid [bmim] [BF4] canbe efficiently achieved in good yields. The ionic liquid and the catalyst can be recycled easily and the process is car ried out under mild conditions.     

Electrochemical and Spectroscopic Studies on Interaction between Complex of Copper(Ⅱ) with Schiff Base Ligand and DNA

The crystal structure of ( [CuL (H2O) 2 ] (ClO4) 2 · 2H2O, CuL) (L ＝ N- (5-sulfosalicylidene)-4' -bromoaniline) was determined by means of X-ray crystallography. The interaction between CuL and salmon sperm DNA in a 0. 1 mol/L HOAc-NaOAc buffer solution (pH 5.10) was investigated by cyclic voltammetry and UV-Vis spectroscopy. A couple of redox peaks of CuL in the cyclic voltammograms(CV) can be seen at the glassy carbon electrode. It was found that the peak current of CuL decreased significantly with a negative shift of the peak potential in the presence of DNA compared with that in the absence of DNA. In addition,the decreased absorbance of CuL was observed with increasing the concentration of DNA; the absorption spectrum of an ethidium bromide(EB)-DNA system inthe presence of CuL confirms that the binding mode of CuL to DNA is different from the intercalation of EB with DNA. All the experimental results indicate that CuL can bind to DNA by electrostatic binding and form a 1:1 association complex with a binding constant of 2.72×104 L/mol.     

温控聚乙二醇两相体系中纳米钯催化肉桂醛选择性加氢反应

将具有“高温混溶、室温分相”功能的聚乙二醇4000(PEG₄₀₀₀)与甲苯-正庚烷组成的两相体系用于纳米钯催化的肉桂醛选择性加氢反应中.在优化的反应条件下,肉桂醛转化率和氢化肉桂醛选择性分别为99%和98%.钯纳米催化剂经简单分相即可与产物分离,且循环使用8次,其活性和选择性基本保持不变.     

A Novel Organic—Inorganic Complex：Synthesis and Crystal Structure of [Ca（DMSO）5（H2O）]2 SiMo12O40

It is becoming a focus to synthesize and assemble organic-inorganic materials, especially, to synthesize charge-transfer complexes formed by polyoxometalate and organic donors. They have attracted much attention because such complexes are active in their electric, magnetic and optic properties1-4, many investigations about them have been done and some crystal structures of them were reported5-6. But, the disadvantage of these crystals is instability at room temperature. According to the view…     

On the Criteria of Instability for Electrochemical Systems

Both cyclic-voltammetry-based and impedance-based experimental criteria that have been developed recently for the oscillatory electrochemical systems are critically appraised with two typical categories of oscillators.Consistent conclusions can be drawn by the two criteria for the category of oscillators that involve the coupling of charge transfer mainly with surface steps(e.g.ad-and desorption)such as in the electrooxidation of C1 organic molecules.Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the coupling of charge transfer mainly with mass transfer(e.g.diffusion and convection) such as in the Fe(CN)6^3- reduction accompanying periodic hydrogen evolution.The reason is that the negative impedance cannot include the feedback information of convection mass transfer induced by the hydrogen evolution.However,both positive and negative nonlinear feedbacks,i.e., the diffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)6^3- surface concentration,that coexist between the bistability,i.e.,Fe(CN)6^3- reduction with and without hydrogen evolution at lower and higher potential sides respectively,are all reflected in the crossed cyclic voltammogram(CCV).It can be concluded that the voltammetry-based criterion(in time domain)is more intuitive,less time-consuming and has a wider range of applications than the impedancebased one (in frequency domain).     

三缺位杂多阴离子PW_9(O_(34))~(9-) 的二苯基硅衍生物的合成和表征

以Na8 H[PW9O3 4 ]·nH2 O与Ph2 SiCl2 为原料于乙腈中合成了三缺位杂多阴离子的二苯基硅衍生物(TBA)3[α-A -PW9O3 4 (Ph2 Si)3 ](TBA为四丁基铵盐的缩写)(记为I),并由元素分析、红外光谱、紫外光谱对化合物进行了表征,结果表明,二苯基硅通过六个Si-O -W桥键填充到三缺位杂多阴离子的骨架上,形成了开环的饱和笼形结构.热分析结果表明,该化合物的热分解温度在 4 95.2℃左右     

配合物[Cu_2(TS)(H_2O)]·H_2O的自组装制备、晶体结构和电化学性质

利用单核配合物Na2 CuTS·H2 O在溶剂中的不稳定性质 ,自分解并重新组装得到了双核配合物 [Cu2 (TS)(H2 O) ]·H2 O .配合物为单斜晶系 ,空间群P2 1/C ,晶胞参数为a =0 .80 830 (16 )nm ,b =1.70 79(3)nm ,c =1.4 0 73(3)nm ,β =10 5 .0 8(3)° ,V =1.86 5 4 (6 )nm3 ,Z =4 ,最终一致性因子R =0 .0 6 4 4 .该分子结构为双核单元 ,金属原子通过两个酚氧原子桥联在一起 .结合晶体结构对配合物作了电化学研究     

酰胺型手性固定相直接拆分克仑特罗对映体

 将酰胺型手性固定相用于正相高效液相直接拆分 β2 受体兴奋剂克仑特罗。讨论了三元流动相中正己烷、1,2 二氯乙烷和甲醇含量的变化以及柱温和流速对分离的影响 ;优化了实验条件 :流动相为V(正己烷 )∶V(二氯乙烷 )∶V(甲醇 ) =5 4∶38∶8,柱温为 17℃ ,流速为 1 0mL/min ;并对拆分的机理加以探讨。方法简单、快速。     

双核配合物[Cu2(TS)(H2O)]·CH3OH的自组装制备和晶体结构

The binuclear complex [Cu₂(TS)(H₂O)]·CH₃OH, where TS denotes the binucleating ligand derived from the schiff base N,N′-bis(3-carboxylsalidene)trimethylenediamine, was obtained from the self-decomposition of mononuclear complex Na₂CuTS·H₂O. It crystallizes in the monoclinic system, space group P2₁/c. The lattice parameters are a=11.935(2)?,b=15.667(3)?,c=11.621(2)?,β=111.60(3)°,V=2020.2(7)?³, Z=4 with R=0.0467. The structure is made of binuclear units, in which two copper atoms are bridged by two phenolic oxygen atoms. The “inside”copper atom is coordinated by two nitrogens, two phenolic oxygens in a planar coordi-nation site, the copper atom deviates from the mean plane by 0.47?. The “outside” copper atom is five coordinated by two phenolic oxygen atoms、two equatorial carboxyl oxygen atoms and one axial water oxygen atom in a distorted tetragonal cone site, the copper atom is pulled out of the equatorial plane by 0.46?.