Insight into the Mechanism Underlying Dehalococcoides mccartyi Strain CBDB1-Mediated B-12-Dependent Aromatic Reductive Dehalogenation

doi:10.1021/acs.est.3c00364

	Zhang, Shangwei 1,2,3; Wen, Wu 4; Xia, Xinghui 3; Ouyang, Wei 1,3; Mai, Bi-xian 2; Adrian, Lorenz 5,6; Schuurmann, Gerrit 7,8
	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	57 Issue:29 Pages: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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