卟啉化合物与核酸的相互作用研究

本文综述了卟啉化合物与核酸相互作用时的结合模式、光谱方法和重要的应用研究, 并对该领域的研究前景作了展望。     

在碘酸钾存在下铝与茜素S的络合吸附波研究

在pH7.6的三乙醇胺缓冲溶液中,铝-茜素S络合物于-0.90V可产生一个灵敏的极谱波,加入碘酸钾后,极谱波负移至-0.94V,波高迅速增大,灵敏度增大约30倍。导数波高与Al^3 浓度在0.06-～10μg/L范围内呈线性关系,检测限达0.02μg/L。研究了极谱波性质及电极反应机理,证明极谱波为络合吸附催化波,在电极上还原的是络合剂茜素S,电还原的中是产物又被氧化回原状态而形成催化循环,使波高增大。利用本法直接测定了天然水中痕量铝。     

手性膦酸二酯类化合物的合成与结构

手性呋喃酮1a1b与亚磷酸三酯2a2b通过串联的不对称Michael加成/分子内Michalis-Arbazov重排反应,得到含磷官能团的新手性化合物5-(S)-(1S)-冰片氧基-4-膦酸二酯基-3-卤素-2(5H)-呋喃酮(3a～3d).该反应具有条件温和,产率高(69%～93%),光学纯度单一(d.e.≥98%)等特点.通过元素分析,IR,UV¹HNMR¹³CNMR,MS,[α]_D²⁰等分析数据以及X射线四圆衍射确定了它们的化学结构和绝对构型.     

固载杂多酸催化性能的研究

在气相体系中考察了固载于活性炭 (C)上的磷钨 (PW12 )、硅钨 (SiW12 )及磷钼 (PMo12 )杂多酸对异丙醇脱水反应的催化性能 .不加水时主要生成丙烯 ;加入适量的水有助于降低丙烯而提高异丙醚的选择性 ;催化活性除与酸性有关外 ,与杂多酸的特殊结构“假液相”模型密切相关     

ZnCl2-氨基酸 (Leu/Try/Val/Thr)-H2O体系的等温溶度

The solubility properties of the zinc chloride amino acids(Leu/Try/ Val/Thr) water systems at 25 ℃ in the whole concentration range have been investigated by equilibrium method, the corresponding phase diagrams and refractive index curves were constructed. The results indicate the formation of the congruently soluble compound of Zn(Leu)Cl2（A） in Leu system and the incongruently soluble compounds of Zn(Try)Cl2•1/2H2O(B)、 Zn(Val)Cl2 •H2O(C)、 Zn(Val)2Cl2(D)、 Zn(Thr)Cl2•H2O(E) and Zn(Thr)2Cl2(F) in Try/Val/Thr systems, which have not been reported in literature. According to the phase equilibrium result, six solid complexes have been prepared in water, and their compositions have been determined by chemical analysis which are consistent with the results of phase diagrams.     

The role of radicals in enzymatic processes

Research on the mechanism of action of coenzyme B12, adenosylcobalamin, as a graduate student introduced the author to the field of organic free radicals in enzymology. Twenty years later, related work on S-adenosylmethionine (SAM) as a "poor man's coenzyme B12" was initiated in a detailed analysis of the mechanism of action of lysine 2,3-aminomutase (LAM). The interconversion of L-lysine and L-beta-lysine is catalyzed by LAM, which requires SAM, pyridoxal-5'-phosphate (PLP), and a [4Fe-4S] cluster as coenzymes. The mechanism of this reaction has been delineated as a radical isomerization, in which radical formation is initiated by the [4Fe-4S]-dependent cleavage of the SAM into methionine and the 5'-deoxyadenosyl radical. The mechanism of this process is discussed, together with the role of this radical in hydrogen abstraction from lysine to initiate the substrate radical isomerization. The chemistry underlying the functions of SAM, PLP, and [4Fe-4S] in the action of LAM is novel in all respects, except for the formation of a lysine-PLP aldimine at the active site. Of the four free radicals in the mechanism, three have been characterized by EPR spectroscopy. In the suicide inactivation of adenosylcobalamin-dependent dioldehydrase (DDH) by glycolaldehyde, the formation of cob(II)alamin and 5'-deoxyadenosine is accompanied by the conversion of glycolaldehyde to cis-ethanesemidione radical at the active site. The cis-ethanesemidione radical has been characterized by EPR spectroscopy. Its exceptional stability at the active site is the basis for the inactivation of DDH by glycolaldehyde.     

Synthesis and Spectroscopy of Novel‐α‐Pyrazolylglycine Derivatives

The synthesis of α‐pyrazolylglycine derivatives(7a‐d) with different substituents, starting from glycine have been pre pared. The spectroscopy of intermediate compounds and the final amino acids have been discussed.     

Differentiation of α‐COOH from β‐COOH in aspartic acids by N‐phosphorylation

The biomimic reactions of N‐phosphoryl amino acids, which involved intramolecular penta‐coordinate phosphoric‐carboxylic mixed anhydrides, are very important in the study of many biochemical processes. The reactivity difference between the α‐COOH group and β‐COOH in phosphoryl amino acids was studied by experiments and theoretical calculations. It was found that the α‐COOH group, and not β‐COOH, was involved in the ester exchange on phosphorus in experiment. From MNDO calculations, the energy of the penta‐coordinate phosphoric intermediate containing five‐member ring from α‐COOH was 35 kJ/mol lower than that of the six‐member one from β‐COOH. This result was in agreement with that predicted by HF/6‐31G** and B3LYP/6‐31G** calculations. Theoretical three‐dimensional potential energy surface for the intermediates predicted that the transition states 4 and 5 involving α‐COOH or β‐COOH group had energy barriers of ΔE=175.8 kJ?mol^?1 and 210.4 kJ?mol^?1, respectively. So the α‐COOH could be differentiated from β‐COOH intramolecularly in aspartic acids by N‐phosphorylation. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 83: 41–51, 2001     

Synthesis and Crystal Structure of 2 Benzoyl Pyridine Thiosemicarbazato Palladium(II) Chloride

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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…