Knowledge Management System Of Guangzhou Institute of Geochemistry,CAS
Zhang, Shangwei1,2,3; Wen, Wu4; Xia, Xinghui3; Ouyang, Wei1,3; Mai, Bi-xian2; Adrian, Lorenz5,6; Schuurmann, Gerrit7,8 | |
Insight into the Mechanism Underlying Dehalococcoides mccartyi Strain CBDB1-Mediated B-12-Dependent Aromatic Reductive Dehalogenation | |
Source Publication | ENVIRONMENTAL SCIENCE & TECHNOLOGY |
ISSN | 0013-936X |
2023-07-10 | |
Volume | 57Issue:29Pages:10773-10781 |
DOI | 10.1021/acs.est.3c00364 |
Language | 英语 |
WOS Research Area | Engineering ; Environmental Sciences & Ecology |
Abstract | Thermodynamics reveal a proton-coupledtwo-electron transfermechanism underlying microbial B-12-dependent reductivedehalogenation of aromatics, furthering our mechanistic understandingof the dehalogenation process. Anaerobic bacteria transform aromatic halides throughreductivedehalogenation. This dehalorespiration is catalyzed by the supernucleophiliccoenzyme vitamin B-12, cob(I)alamin, in reductive dehalogenases.So far, the underlying inner-sphere electron transfer (ET) mechanismhas been discussed controversially. In the present study, all 36 chloro-,bromo-, and fluorobenzenes and full-size cobalamin are analyzed atthe quantum chemical density functional theory level with respectto a wide range of theoretically possible inner-sphere ET mechanisms.The calculated reaction free energies within the framework of Co-I & BULL;& BULL;& BULL;X (X = F, Cl, and Br) attack rule out mostof the inner-sphere pathways. The only route with feasible energeticsis a proton-coupled two-ET mechanism that involves a B-12 side-chain tyrosine (modeled by phenol) as a proton donor. For 12chlorobenzenes and 9 bromobenzenes with experimental data from Dehalococcoides mccartyi strain CBDB1, the newlyproposed PC-TET mechanism successfully discriminates 16 of 17 activefrom 4 inactive substrates and correctly predicts the observed regiospecificityto 100%. Moreover, fluorobenzenes are predicted to be recalcitrantin agreement with experimental findings. Conceptually, based on theBell-Evans-Polanyi principle, the computational approachprovides novel mechanistic insights and may serve as a tool for predictingthe energetic feasibility of reductive aromatic dehalogenation. |
Keyword | Dehalococcoides reductive dehalogenation aromatic halide thermodynamics reaction mechanism |
WOS ID | WOS:001025893900001 |
Indexed By | SCI |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.gig.ac.cn/handle/344008/74448 |
Collection | 有机地球化学国家重点实验室 |
Corresponding Author | Xia, Xinghui; Schuurmann, Gerrit |
Affiliation | 1.Beijing Normal Univ, Adv Interdisciplinary Inst Environm & Ecol, Zhuhai 519087, Peoples R China 2.Chinese Acad Sci, Guangzhou Inst Geochem, State Key Lab Organ Geochem, Guangzhou 510640, Peoples R China 3.Beijing Normal Univ, Sch Environm, State Key Lab Water Environm Simulat, Beijing 100875, Peoples R China 4.Beijing Normal Univ, Instrumentat & Serv Ctr Sci & Technol, Zhuhai 519087, Peoples R China 5.Helmholtz Ctr Environm Res, UFZ Dept Environm Biotechnol, D-04318 Leipzig, Germany 6.Tech Univ Berlin, Chair Geobiotechnol, D-13355 Berlin, Germany 7.Helmholtz Ctr Environm Res, UFZ Dept Ecol Chem, D-04318 Leipzig, Germany 8.Tech Univ Bergakademie Freiberg, Inst Organ Chem, D-09596 Freiberg, Germany |
Recommended Citation GB/T 7714 | Zhang, Shangwei,Wen, Wu,Xia, Xinghui,et al. Insight into the Mechanism Underlying Dehalococcoides mccartyi Strain CBDB1-Mediated B-12-Dependent Aromatic Reductive Dehalogenation[J]. ENVIRONMENTAL SCIENCE & TECHNOLOGY,2023,57(29):10773-10781. |
APA | Zhang, Shangwei.,Wen, Wu.,Xia, Xinghui.,Ouyang, Wei.,Mai, Bi-xian.,...&Schuurmann, Gerrit.(2023).Insight into the Mechanism Underlying Dehalococcoides mccartyi Strain CBDB1-Mediated B-12-Dependent Aromatic Reductive Dehalogenation.ENVIRONMENTAL SCIENCE & TECHNOLOGY,57(29),10773-10781. |
MLA | Zhang, Shangwei,et al."Insight into the Mechanism Underlying Dehalococcoides mccartyi Strain CBDB1-Mediated B-12-Dependent Aromatic Reductive Dehalogenation".ENVIRONMENTAL SCIENCE & TECHNOLOGY 57.29(2023):10773-10781. |
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