一个类立方烷型的四核钼原子簇化合物{Mo4(μ3-S)3(μ3-O)[S2P(OEt)2]6}.3CH3CN的合成和晶体结构

将MoCl3.3H2O溶于无水乙醇中,加入适量的P2S5,产物用乙腈重结晶,获得四核钼原子簇化合物{Mo4(μ3-S)3(μ3-O)[S2P(OEt)2]6}.3CH3CN.晶体属三方晶系,空间群为R3;晶胞系数;a=b=c=12.852(3)A;α=β=γ=108.37(2);V=1697.3A[3];Z=1;Dc=1.693g.cm[-3].用PATTERSON法解出结构,并经全矩阵最小二乘法修正,偏离因子为0.072.结构分析表明,由四个钼原子组成的四面体及三个μ3-O原子一个μ3-O原子形成类立方烷型的簇骼,结构中存在六个表观的键序平均为5/6的Mo-Mo键,键长分别为2.700(1)和2.831(1)A。     

无机阴离子对镍—4—[（5—氯—2—吡啶）偶氮]—1,3—二氨基苯显色反应…

被试的六种无机钠盐对Ｎｉ＾２＋－５－Ｃｌ－ＰＡＤＡＢ显色体系有不同程度的增敏作用，并能提高显色应的选择性。初步探讨了无机阴离子对显色反应的机理。已成功地将Ｎｉ＾２＋－５－Ｃｌ－ＰＡＤＡＢ－ＮａＢｒ体系用于废水中镍的测定。     

Synthesis of Two Novel Rhenium（I） Bipyridyl Photosensitive Dyes

Two novel rhenium(I) 2, 2′-bipyridyl complexes, [(4,4′-di-COOEt-bipy) Re(CO)3 (NCCH3)PF6] and [(4,4′-di-COOEt-bipy) Re (CO)3 (NCS)], a model complex [(4,4′-di-COOEt-bipy) Re (CO)3 (pyridine)PF6], were synthesized. Their ground state electronic spectra and emission spectra were measured in acetonitrile. The MLCT absorption maximum of the complex exhibited a considerable red shift as the ligand changed from pyridine to CNCH3, or SCN.     

共聚物配体交替结构与其催化活性关系的理论研究

本文采用以ASED-MO(含原子对排斥的EHMO法)为基础的结构自动优化的EHTOPT法及Monte-Carlo法, 对甲醇羰基化制乙酸催化剂的共聚物配体交替结构进行了理论研究。计算了AA, AB, BB, BA二聚反应的反应途径, 找出了过渡态, 并确定了反应活化势垒。在假设两反应频率因子相同的前提下, 求出竞聚率, 采用Monte-Carlo法模拟共聚物结构, 计算出共聚物配体中起催化活性的AB交替结构所占比率。比较不同共聚物配体的活性, 并研究了温度及单体配比对共聚物配体交替结构的影响。     

One—Pot Synthese of 3,4—Dihydropyrimidine—2（1H）—thiones Catalyzed by La（OTf）3

A general and practical procedure for the syntheses of 3,4-di-hydropyrimidine-2(1H)-thiones by a one-pot condensation of aldehyde,β-ketoester or β-diketone and thiourea using La(OTf)3 as the catalyst is described.Mild reaction conditions,excellent yields as well as the environmentally friendly character of La(OTf)3 make it an important alternative to the classic acid-catalyzed Biginelli‘s reaction.     

树枝形聚合物修饰的双8-羟基喹啉光物理研究

研究了树枝形聚合物修饰的双8-羟基喹啉衍生物(Gn-QMQ, n=1~3)在二氯甲烷和乙腈中的荧光猝灭过程和荧光衰减过程. 随着代数n的增加, 猝灭速率常数减小, 核心双8-羟基喹啉基团荧光寿命增长, 非辐射失活速率常数减小. 研究结果表明, 随着代数的增加, 树枝形骨架对核心基团的位点分离作用增大, 在乙腈中树枝形骨架趋于紧密构象, 具有更强的位点分离作用.     

新显色剂噻二唑偶氮二甲氨基苯甲酸与铜(Ⅱ)显色反应的研究和应用

本文研究了噻二唑偶氮二甲氨基苯甲酸与Cu(Ⅱ)显色反应条件,确定在pH3.0～4.5范围形成蓝紫色络合物,组成比为1:1,摩尔吸光系数ε=4.55×10~4L·mol~(-1)·cm~(-1),1gβ=7.32。应用拟定的方法测定天然水中微量铜,获得满意的结果。     

聚合物异核交叉弛豫及二维NOE谱

The heteronuclear cross-relaxation rates in polymers were determined by selective and conventional ~(13)C spin-lattice relaxation experiments, the proton-carbon distances were calculated by the theoretical formula, and two-dimensional NOE spectra of the polymers were also measured. The results showed that (1) the measured proton-carbon distances coincide with the distances from molecular models, (2) there is the observable dipolar cross-relaxation effect between the quaternary carbons and their neighboring protons, and (3) the optimum mixing times depend on the relaxation properties of the proton and carbon.     

高分子药物研究Ⅰ．5－氨基水杨酸与二元羧酸缩聚物的合成

通过５－氨基水杨酸与二元羧酸进行缩聚反应，合成了六种主链含有５－氨基水杨酸的高分子化合物，用红外光谱和元素分析确定了聚合物的结构。聚合物水解实验表明，它们在酸性、中性和碱性介质中均能水解，水解速率（ｒ）的大小依次为ｒｐＨ＝１３．０＞ｒｐＨ＝７．０＞ｒｐＨ＝２．０。