Insight into the Mechanism Underlying Dehalococcoides mccortyi Strain CBDB1-Mediated B_(12)-Dependent Aromatic Reductive Dehalogenation

Shangwei Zhang; Wu Wen; Xinghui Xia

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Insight into the Mechanism Underlying Dehalococcoides mccortyi Strain CBDB1-Mediated B_(12)-Dependent Aromatic Reductive Dehalogenation

机译：Insight into the Mechanism Underlying Dehalococcoides mccortyi Strain CBDB1-Mediated B_(12)-Dependent Aromatic Reductive Dehalogenation

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Anaerobic bacteria transform aromatic halides through reductive dehalogenation.This dehalorespiration is catalyzed by the supernucleophilic coenzyme vitamin B_(12),cob(I)-alamin,in reductive dehalogenases.So far,the underlying inner-sphere electron transfer(ET)mechanism has been discussed controversially.In the present study,all 36 chloro-,bromo-,and fluorobenzenes and full-size cobalamin are analyzed at the quantum chemical density functional theory level with respect to a wide range of theoretically possible inner-sphere ET mechanisms.The calculated reaction free energies within the framework of Co-X(X = F,Cl,and Br)attack rule out most of the inner-sphere pathways.The only route with feasible energetics is a proton-coupled two-ET mechanism that involves a B_(12)side-chain tyrosine(modeled by phenol)as a proton donor.For 12 chlorobenzenes and 9 bromobenzenes with experimental data from Dehalococcoides mccartyi strain CBDB1,the newly proposed PC-TET mechanism successfully discriminates 16 of 17 active from 4 inactive substrates and correctly predicts the observed regiospecificity to 100%.Moreover,fluorobenzenes are predicted to be recalcitrant in agreement with experimental findings.Conceptually,based on the Bell-Evans-Polanyi principle,the computational approach provides novel mechanistic insights and may serve as a tool for predicting the energetic feasibility of reductive aromatic dehalogenation.

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《Environmental Science & Technology: ES&T》 |2023年第29期|10773-10781|共9页
作者
Shangwei Zhang; Wu Wen; Xinghui Xia;
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作者单位

Advanced Interdisciplinary Institute of Environment and Ecology,Beijing Normal University,Zhuhai 519087,China;

Instrumentation and Service Center for Science and Technology,Beijing Normal University,Zhuhai 519087,China;

State Key Laboratory of Water Environment Simulation,School of Environment,Beijing Normal University,Beijing 100875,China;

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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
正文语种英语
中图分类环境科学、安全科学;
关键词
Dehalococcoides; reductive dehalogenation; aromatic halide; thermodynamics; reaction mechanism;

Insight into the Mechanism Underlying Dehalococcoides mccortyi Strain CBDB1-Mediated B_(12)-Dependent Aromatic Reductive Dehalogenation

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