基于分子机器的复合与解离构建pH响应性人工硒酶

doi:10.3969/j.issn.2095-2198.2023.05.006

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含硒天然酶是生命体中一类重要的抗氧化酶，对于保持体内活性氧分子的代谢平衡并保护机体免受氧化损伤起到了重要的作用.对体内硒酶进行人工模拟，尤其是构建具有环境响应性的人工硒酶，能够揭示天然酶的催化机制，并拓展其在抗氧化药物开发中的潜在应用.设计并合成了同时含有硒酶催化中心和两个仲胺基团的N-乙基乙胺双硒醚分子.pH=6时，两个仲胺基团均处于质子化状态，N-乙基乙胺双硒醚分子能够与葫芦［6］脲分子（CB［6］）复合从而组装形成分子机器，此时活性中心被包埋于CB［6］的疏水空腔之中，几乎不能展现出催化活性［（2.1±0.06）×10^-5μmol·min^-1·μmol^-1］；pH=8时，仲胺基团的质子化程度降低，分子机器部分解离，活性中心被释放到溶液之中，从而能够展现出（0.31±0.01）×10^-³ μmol·min^-1·μmol^-1的催化活性.结果表明:通过改变体系pH，使其在6和8之间变化，以控制分子机器发生复合及部分解离，成功调控了人工酶活性的关闭与开启，从而构建了具有pH响应性的人工硒酶.

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人工硒酶分子机器 pH响应性葫芦［6］脲

Abstract:

As a very important antioxidant enzyme in vivo,selenoenzyme plays a very important role in maintaining the metabolic balance of reactive oxygen species(ROS)and protecting body from oxidative stress.The artificial simulation of selenoenzyme especially the construction of environmental-responsive smart artificial enzymes can reveal the catalytic mechanism of nature enzyme and expand the potential applications in the development of antioxidant drugs.In this research,compound V was designed and synthesized.The new organic selenium compound contained both selenoenzyme catalytic center and two secondary amine groups.Two secondary amine groups were both protonated at pH=6.The compound V can assemble with cucurbit［6］uril(CB［6］)to form molecular machine.The active center was encapsulated in the hydrophobic cavity of CB［6］so that almost no catalytic activity can be shown［(2.1±0.06)×10^-5μmol·min-1·μmol^-1］.The protonation degree of two secondary amine groups had a significantly decrease at pH=8 which lead to the partly dissociation of molecular machine.The active center was exposed to solution at this time and the catalytic activity was (0.31±0.01)×10^-³μmol·min^-1·μmol^-1.Therefore,pH-responsive artificial selenoenzyme can be successfully constructed by the association and dissociation of molecular machine through the changing the pH between 6 and 8 in order to control the recombination and partial dissociation of molecular machines.

Key words: artificial selenoenzyme')" href="#">

artificial selenoenzyme molecular machine pH-responsive cucurbit［6］uril

出版日期: 2023-10-27 发布日期: 2024-06-06 整期出版日期: 2023-10-27

ZTFLH:

Q 554+.6

基金资助:

辽宁省教育厅基本科研青年项目(LJKQZ20222453)

通讯作者: 李佳锡

作者简介: 许洪峰（1997—），男，河南新乡人，硕士研究生在读，主要从事有机合成化学方面的研究.

引用本文:

许洪峰, 李思, 许远航, 李佳锡.

基于分子机器的复合与解离构建pH响应性人工硒酶 [J]. 沈阳化工大学学报, 2023, 37(5): 425-434.
XU Hongfeng, LI Si, XU Yuanhang, LI Jiaxi.

Construction of pH-Responsive Artificial Selenoenzyme Based on the Association and Dissociation of Molecular Machine . Journal of Shenyang University of Chemical Technology, 2023, 37(5): 425-434.

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https://xuebao.syuct.edu.cn/CN/10.3969/j.issn.2095-2198.2023.05.006 或 https://xuebao.syuct.edu.cn/CN/Y2023/V37/I5/425

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