...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Environmental Science & Technology >Comprehensive Understanding of Fluoroacetate Dehalogenase-Catalyzed Degradation of Fluorocarboxylic Acids: A QM/MM Approach
【24h】

Comprehensive Understanding of Fluoroacetate Dehalogenase-Catalyzed Degradation of Fluorocarboxylic Acids: A QM/MM Approach

机译：综合了解氟乙酸酯脱氢酶催化氟羧酸的降解：QM / mm方法

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Fluorochemicals are persistent, bioaccumulative, and toxic compounds that are widely tributed in the environment. Developing efficient biodegradation strategies to decompose the fluorochemicals via breaking the inert C-F bonds presents a holistic challenge. As a promising biodegradation enzyme candidate, fluoroacetate dehalogenase (FAcD) has been reported as the only non-metallic enzyme to catalyze the cleavage of the strong C-F bond. Here, we systematically investigated the catalytic actions of FAcD toward its natural substrate fluoroacetate using molecular dynamics simulations and quantum mechanism/molecular mechanism calculations. We propose that the enzymatic transformation involves four elementary steps, (Ⅰ) C-F bond activation, (Ⅱ) nucleophilic attack, (Ⅲ) C-O bond cleavage, and (Ⅳ) proton transfer. Our results show that nucleophilic attack is the rate-determining step. However, for difluoroacetate and trifluoroacetate, C-F bond activation, instead of nucleophilic attack, becomes the rate-determining step. We show that FAcD, originally recognized as a-fluorocarboxylic acid degradation enzyme, can catalyze the defluorination of difluoroacetate to glyoxylate, which is captured by our high-resolution mass spectrometry experiments. In addition, we employed amino acid electrostatic analysis method to screen potential mutation hotspots for tuning FAcD's electrostatic environment to favor substrate conversion. The comprehensive understanding of catalytic mechanism will inform a rational enzyme engineering strategy to degrade fluorochemicals for benefits of environmental sustainability.
机译：含氟化合物是持续的，生物累积性和有毒化合物，这些化合物在环境中广泛致敬。通过破坏惰性C-F键来显影有效的生物降解策略，以分解氟化物化学物质呈现整体挑战。作为有前途的生物降解酶候选，氟乙酸酯脱氢酶（FACD）据报道，唯一的非金属酶以催化强C-F键的切割。在这里，我们通过分子动力学模拟和量子机制/分子机制计算系统地研究了FACD对其天然底物氟乙酸酯的催化作用。我们提出酶促转化涉及四个基本步骤，（Ⅰ）C-F键活化，（Ⅱ）亲核攻击，（Ⅲ）C-O键切割，（Ⅳ）质子转移。我们的结果表明，亲核攻击是速率确定步骤。然而，对于二氟乙酸酯和三氟乙酸酯，C-F键活化而不是亲核攻击，成为速率确定步骤。我们表明，最初被认为是氟羧酸降解酶的FACD可以催化二氟乙酸酯的偏氟化甲磺酸盐，其通过我们的高分辨率质谱实验捕获。此外，我们使用氨基酸静电分析方法来筛选电位突变热点，用于调整FACD的静电环境，以支持基板转换。综合了解催化机制将推送Rational酶工程策略，降低含氟化合物以获得环境可持续性的益处。

著录项

  • 来源
    《Environmental Science & Technology》 |2021年第14期|9817-9825|共9页
  • 作者

    Yue Yue; Jiaqian Fan; Guoqing Xin; Qun Huang; Jian-bo Wang; Yanwei Li; Qjngzhu Zhang; Wenxing Wang;

  • 作者单位

    Environment Research Institute Shandong University Qingdao 266237 P. R. China;

    Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education) College of Chemistry and Chemical Engineering Hunan Normal University Changsha 410081 P. R. China;

    Wuhan National High Magnetic Field Center (WHMFC) Huazhong University of Science and Technology Wuhan 430074 P. R. China;

    Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education) College of Chemistry and Chemical Engineering Hunan Normal University Changsha 410081 P. R. China;

    Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education) College of Chemistry and Chemical Engineering Hunan Normal University Changsha 410081 P. R. China;

    Environment Research Institute Shandong University Qingdao 266237 P. R. China;

    Environment Research Institute Shandong University Qingdao 266237 P. R. China;

    Environment Research Institute Shandong University Qingdao 266237 P. R China;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    quantum mechanics/molecular mechanics; fluoroacetate dehalogenase; polyfluorinated compounds; perfluorinated compounds; rate-determining step; C-F bond activation;

    机译：量子力学/分子力学;氟乙酸酯去卤代酶;多氟化合物;全氟化合物;速率确定步骤;C-F债券激活;

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号