钴膦簇合物的催化环丙烷化反应

本文首次利用碳基钴簇合物ＰｈＰＣｏ_３（ＣＯ）_９催化剂，在常压和－２０℃－０℃，用苯乙烯和重氮乙酸乙酯进行环丙烷化反应，合成了菊酸酯，重氮乙酸乙酯可全部转化，酯的选择性可达８５％。产物经减压分馏后，由ＩＲ和￣１ＨＮＭＲ分析，确证了产物为菊酸酯，表明了羰基钴簇合物对苯乙烯的环丙烷化反应有良好的催化性能，为四面体异核簇合物用于不对称催化反应打下了基础。     

聚醚聚氨酯双离子型离聚物的介电性能研究

以4,4＇-二苯基甲烷二异氰酸酯(MDI)、N-甲基二乙醇胺(MDEA)和聚四氢呋喃(PTMD)以2:1:1(mol比)合成聚醚型聚氨酯,MDEA的叔胺基与γ-丙磺内酯反应,制备了不同磺化程度的双离子型离聚物.在不同温度与频率(-150-30℃,20Hz—100KHz)下,测定了其介电性能.结果表明,随离子化程度的提高,ε＇增大,α弛豫介电损耗峰移向低温,说明相分离越趋完善;β弛豫单元的活化能(△Hβ)基本不变;α弛豫单元的活化能(△Hα)依次变小.介电测量结果与动态力学方法研究结果相吻合.     

混合配体配合物钯(Ⅱ)-联喹啉-苯乙基丙二酸根与DNA作用研究

The mixed ligand complex [Pd(biqu)(pmal)]·H₂O (where biqu is 2,2′-biquinoline, pmal is phenethylmalonate) has been synthesized and its interaction with sperm DNA was determined by fluorescent spectra、 UV-Vis spectra and CD-spectra. The binding constant (K_b) of the complex and sperm DNA is 1.26×10⁴ and its interaction with pBR322 plasmid DNA was also determined by gel electrophoresis. The results show that the complex interact with DNA mainly by intercalative mode.     

一维链状冠醚配合物:[{Na(18-C-6)}2(H2O)]n[M(SCN)4]n(M=Pd、Pt)的合成与结构

The reactions of 18-crown-6 with Na₂[M(SCN)₄] (M= Pd,Pt) were studied and the complex 1 [{Na(18-C-6)}₂(H₂O)]_n[Pd(SCN)₄]_n and complex 2 [{Na(18-C-6)}₂(H₂O)]_n[Pt(SCN)₄]_n were characterized by ele-mental analysis, IR and X-ray diffraction analysis. The complexes belong to monoclinic, space group P2₁/n with cell dimensions, 1:a=1.05734(7),b=1.42250(10),c=1.47762(10) nm,β=107.5330(10)°,V=2.1192(2)nm³,Z=2,D_calcd=1.460g·cm^-3,F(000)=964,R₁=0.0406,wR₂=0.1264 and 2:a=1.05985(19),b=1.4237(3),c=1.4744(3) nm,β=107. 096(3)°, V=2.1264(7)nm³,Z=2,D_calcd=1.690g·cm^-3,F(000)=1028,R₁=0.0292,wR₂=0.0859. In the solid state, the complexes 1 and 2 show an one-dimensional chain of [{Na(18-C-6)}₂(H₂O)]²⁺ complex cations and [M(SCN)₄]^2- (M=Pd,Pt) complex anions bridged by Na-N in-teractions.     

Synthesis and Structure of Dimolybdenum Carbonyl Thiolate Compound [Et4N]2[Mo2（CO）8（SC6H4—CH3—m）2]

1 INTRODUCTION In 1984, thiolate ligand was successfully introduced into molybdenum carbonyl compound by the reaction of Mo(CO)6 with [Et4N]SR( R = C6H5, But) in a moderate condition[1]. From then on, a series of dinuclear molybdenum(0) carbonyl thiolate compounds have been synthesized and characterized by using a variety of thiolate ligands in our research group. It was found that a planar Mo2S2 unit is in the compound [Et4N]2[Mo2(CO)8(SC6H4-CH_3-p)2][2] (2) and a "butterfly" t…     

β—环糊精交联聚合物与有机显色剂客体包结反应研究

β－环糊精与环氧氯丙烷交联共聚物是一种具有三维网状结构的聚合树脂，它保留了β－环糊精所原有的与有机疏水基团形成包结物的特性，与一系列含有芳得环的有机显色剂配体（如吡啶偶氮染料，变色酸双偶氮试剂，三苯甲烷类碱性与酸性染料以及杂氧蒽酮类试剂等）均可形成相应的包结配合物，着重研究了有关包结配合物的稳定性及影响稳定性的各种因素，为进一步研究包结物分离富集痕量金属提供必要的理论依据。     

配合物[Mn(phendione)(PDC)(H2O)2]·2H2O的合成与晶体结构

The title compound [Mn(phendione)(PDC)(H₂O)₂]·2H₂O (H₂PDC=pyridine-2，6-dicarboxylic acid) has been prepared in aqueous solution and characterized by single X-ray diffraction structure determination， elemental analysis， IR spectroscopy， and thermal analyses. The compound crystallizes in Monoclinic system， space group C2/c， a=1.017 51(11) nm， b=1.483 25(11) nm， c=1.461 21(13) nm， β=109.86(10)°， V=2.074 1(3) nm³， Z=4， F(000)=1 028， μ=0.701 mm^-1， D_c=1.609 g·cm^-3， R₁=0.028 9， wR₂=0.078 8 [I>2σ(I)]. Crystal structure reveals that complex consists of one-dimensional chain framework bridged by hydrogen bonds that formed by uncoordinated water and oxygen atom of carboxyl group in PDC^2-. Furthermore， the complexes form a three-dimensional super-molecular structure through hydrogen bonds. CCDC: 648570.     

纳米CoHCF修饰电极的制备及其对血红蛋白的电化学测定研究

A cobalt hexacyanoferrate （CoHCF） nanoparticle （size ca. 60 nm） chemically modified electrode （CME） was fabricated and the electrochemical behavior of hemoglobin （Hb） at this nanosized CoHCF CME was studied. In comparison with a bare glassy carbon electrode （GCE） and a general CoHCF CME electrodeposited in a traditional manner, the present nanosized CoHCF CME performed efficiently electrocatalytic reduction for Hb with relatively high sensitivity, stability, and longlife, Combined with liquid chromatography （LC）, the nanosized CoHCF CME was used as the electrochemical detector of Hb in the established flow injection analysis-electrochemical determination （FIA-ECD） system. The peak current was a linear function of concentrations in the range from 2.5×10^-8 to 5.0×10^-6mol/L for Hb, with detection limit of 1.4×10^-8 mol/L. The FIA-ECD system has been successfully applied to assess the Hb content of clinic blood samples with advantages of sensitiveness, speediness, easy control and small sample-consumption.     

2,2′-对苯二甲硫基二乙酸配合物的合成及表征

本文报道了配体 2 ,2′-对苯二甲硫基二乙酸和过渡金属铜 ( )、钴 ( )、镍 ( )配合物的合成。经元素分析、X射线衍射分析、红外光谱、差热 -热重分析等推算了它们的组成并指认了谱带的归属。对铜 ( )配合物进行了电子顺磁共振谱研究。     

（H2O）^＋n（n=1,2）的几何结构优化和振动光谱分析

采用Ｈａｒｔｒｅｅ－Ｆｏｃｋ和ＭＰ２方法在多种水平下优化了（Ｈ２Ｏ）＾＋ｎ（ｎ ＝１，２）的几何结构，并进行了振动光谱分析。结果表明：对（Ｈ２Ｏ）＾＋采用ＭＰ２／６－３１１＋＋Ｇ（ｄ，ｐ）可得出最满意的结论。