Synthesis, characterization and ascorbic acid oxidase mimetic catalytic activity of copper(II) picolyl hydrazone complexes

Synthesis, characterization and ascorbic acid oxidase mimetic catalytic activity of copper(II) picolyl hydrazone complexes
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铜(II)吡啶甲基腙配合物的合成、表征及抗坏血酸氧化酶模拟催化活性

DOI:
10.1007/s11243-005-0414-x
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发表时间:
2005
影响因子:
1.7
通讯作者:
R. Issa
R. Issa
中科院分区:
化学4区
文献类型:
--
作者:
A. El;M. Ramadan;R. Issa

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以α-甲酰基-(L1)、α-乙酰基-(L2)、α-苯甲酰基-(L3)吡啶和α-甲酰基-(L4)噻吩席夫碱缩合,合成了四个新的吡咯酰肼类化合物。合成了这些肼类化合物的铜(II)络合物和一系列含(L2)和各种阴离子(Cl、Br、NO3、SCN、SO4、ClO4、ACO、PF6和BF4)的铜(II)络合物。元素分析、热分析、摩尔电导率、磁矩测量和光谱(I.R.、电子学和E.S.R.)研究已经用来对所制备的化合物进行表征。已报道的铜(II)络合物的总体结构和反应活性关键取决于配体结构和络合物分子中反阴离子的性质。提出了八面体[配合物(7)]、四方锥体[配合物(8)]和正方形平面单体物种[配合物(1-6)、(9)和(10)]以及正方形平面构型的氧桥二聚体结构[配合物(11)和(12)]。已报道的铜(II)络合物对维生素C的有氧氧化具有良好的催化活性。酶催化活性与母体配体的供体性质所产生的中心铜(II)离子的Lewis-酸性以及配位环境的不规则性之间存在线性关系。讨论了催化氧化反应的可能机理。
Four new picolyl hydrazones were prepared via Schiff-base condensation of picolonic acid hydrazide with α-formyl-(L1), α-acetyl-(L2), α-benzoyl-(L3) pyridine and α-formyl-(L4) thiophene. Copper(II) complexes of these hydrazones and a series of copper(II) complexes containing (L2) and various anions (Cl, Br, NO3, SCN, SO4, ClO4, AcO, PF6 and BF4) have been synthesized. Elemental, thermal analysis, molar conductivity, magnetic moment measurements and spectral (i.r., electronic and e.s.r.) studies have been used to characterize the prepared compounds. The overall structure and reactivity of the reported copper(II) chelates critically depend on the ligand structure and the nature of counter anion incorporated in the complex molecule. Octahedral [complex (7)], square-pyramidal [complex (8)] and square-planar monomeric species [complexes (1–6), (9) and (10)] and a dimeric structure with oxygen bridge in square-planar geometry [complexes (11) and (12)] were suggested. The reported copper(II) complexes exhibit promising oxidase catalytic activity towards the aerobic oxidation of vitamin C. A linear correlation exists between the oxidase catalytic activity and the Lewis-acidity of the central copper(II) ion created by the donating properties of the parent ligand, as well the irregularity of the coordination environment. The probable mechanistic implications of the catalytic oxidation reactions are discussed.
生物化学中的定制生物化学:催化抗体
DOI: --
发表时间: 2004
期刊: Chemistry and Chemical Industry 57
影响因子: --
作者:
Naoko Takahashi-Ando;Hiroyuki Kakinuma;Ikuo Fujii;Yoshisuke Nishi;Ikuo Fujii
通讯作者: Ikuo Fujii