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含有生物源共配体的新型氧桥联过氧钨配合物作为碱性磷酸酶活性的有效抑制剂。

New oxo-bridged peroxotungsten complexes containing biogenic co-ligand as potent inhibitors of alkaline phosphatase activity.

作者信息

Hazarika Pankaj, Kalita Diganta, Sarmah Swapnalee, Islam Nashreen S

机构信息

Department of Chemistry, Darrang College, Tezpur, 784001, India.

出版信息

Mol Cell Biochem. 2006 Mar;284(1-2):39-47. doi: 10.1007/s11010-005-9011-8. Epub 2006 Feb 14.

DOI:10.1007/s11010-005-9011-8
PMID:16477386
Abstract

Novel dinuclear peroxo complexes of tungsten with coordinated cystine of the type A(2)[W(2)O(3)(O(2))(4)(cystine)].4H(2)O, A = Na (1) or K (2) have been synthesized from the reaction of A(2)WO(4,)cysteine and 30% H(2)O(2)at pH 2.5. The synthesized compounds were characterized by elemental analysis, spectral and physico-chemical methods. The two W(VI) centres with side-on bound peroxo groups of the dinuclear complex species are bridged by an oxo group and a cystine ligand, formed from the oxidation of cysteine. Cystine occurring as zwitterion binds the metal centers of the complex ion through O(carboxylate) atoms leading to hepta co-ordination around each W(VI). The compounds exhibit high stability toward decomposition in solution of acidic as well as physiological pH and serve as weak substrates to catalase, undergoing degradation in presence of the enzyme at a rate much slower relative to H(2)O(2). The compounds efficiently oxidized GSH to GSSG, a reaction in which only two of the peroxide groups of the complex species were found to participate. The compounds induce strong inhibitory effect on alkaline phosphatase activity with a potency higher than that of the free cystine, tungstate, or peroxotungstate.

摘要

新型双核钨过氧配合物A(2)[W(2)O(3)(O(2))(4)(胱氨酸)].4H(2)O(A = Na (1) 或 K (2))由A(2)WO(4)、半胱氨酸与30% H(2)O(2)在pH 2.5条件下反应合成。通过元素分析、光谱和物理化学方法对合成的化合物进行了表征。双核配合物物种中两个带有侧基结合过氧基团的W(VI)中心由一个氧原子和一个由半胱氨酸氧化形成的胱氨酸配体桥连。以两性离子形式存在的胱氨酸通过O(羧酸盐)原子与络合离子的金属中心结合,导致每个W(VI)周围形成七配位。这些化合物在酸性和生理pH溶液中对分解表现出高稳定性,并且作为过氧化氢酶的弱底物,在酶存在下相对于H(2)O(2)以慢得多的速率降解。这些化合物有效地将谷胱甘肽氧化为氧化型谷胱甘肽,在该反应中发现只有配合物物种的两个过氧基团参与。这些化合物对碱性磷酸酶活性具有强烈的抑制作用,其效力高于游离胱氨酸、钨酸盐或过氧钨酸盐。

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