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通过将活性中心引入金刚烷基分子构建具有溶剂依赖性催化行为的新型客体仿生谷胱甘肽过氧化物酶。

Construction of a novel guest biomimetic glutathione peroxidase with solvent-dependent catalytic behavior by incorporating the active center into adamantyl molecule.

作者信息

Yin Yanzhen, Lang Chao, Hua Xiaoxi, Shia Zhongfeng, Wang Yun, Jiao Shufei, Cai Chengxiang, Liu Junqiu

出版信息

Bioorg Khim. 2014 Mar-Apr;40(2):178-85.

PMID:25895337
Abstract

A novel guest biomimetic glutathione peroxidase (3,3'-tellurobis(propane-3,1-diyl) diadamantanecarboxylate, denoted as ADA-Te-ADA) was synthesized. ADA-Te-ADA functioned to overcome the disadvantages in the construction of building block for giant supramolecular biomimetic enzyme. To reveal the catalytic property of hydrophobic ADA-Te-ADA, the catalytic mechanism was investigated using PBS (phosphate buffer (pH 7.0. 50 mM))/methanol solvent mixture as assay solution. Itindicated that ADA-Te-ADA exhibited typical enzyme catalytic behavior by saturation kinetics measurement. Importantly, ADA-Te-ADA exhibited the typical solvent-dependent catalytic behavior. And the highest catalytic rate 4.29 µM x min-1 was obtained when the volume ratio of PBs: methanol was 5 : 5. Especially, the catalytic rates obtained based on various substrates proved that ADA-Te-ADA slightly displayed special substrate selectivity, which was the ideal catalytic characterization of building block for giant supramolecular biomimetic enzyme. The successfully synthesis of ADA-Te-ADA might highlight for the understanding of the catalytic mechanism of hydrophobic guest biomimetic glutathione peroxidase. And it also might provide the basement for the construction of giant supramolecular biomimetic enzyme.

摘要

合成了一种新型客体仿生谷胱甘肽过氧化物酶(3,3'-碲双(丙烷-3,1-二基)二金刚烷羧酸盐,记为ADA-Te-ADA)。ADA-Te-ADA的作用是克服构建巨型超分子仿生酶构建模块时的缺点。为了揭示疏水性ADA-Te-ADA的催化特性,以PBS(磷酸盐缓冲液(pH 7.0,50 mM))/甲醇溶剂混合物作为测定溶液研究了其催化机制。通过饱和动力学测量表明ADA-Te-ADA表现出典型的酶催化行为。重要的是,ADA-Te-ADA表现出典型的溶剂依赖性催化行为。当PBS与甲醇的体积比为5:5时,获得最高催化速率4.29 μM·min-1。特别是,基于各种底物获得的催化速率证明ADA-Te-ADA略微表现出特殊的底物选择性,这是巨型超分子仿生酶构建模块的理想催化特性。ADA-Te-ADA的成功合成可能有助于理解疏水性客体仿生谷胱甘肽过氧化物酶的催化机制。它也可能为构建巨型超分子仿生酶提供基础。

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