Insight into the Mechanism Underlying Dehalococcoides mccartyi Strain CBDB1-Mediated B-12-Dependent Aromatic Reductive Dehalogenation
文献类型：期刊论文
| 作者 | Zhang, Shangwei6,7,8; Wen, Wu5; Xia, Xinghui6; Ouyang, Wei6,8; Mai, Bi-xian7; Adrian, Lorenz1,4; Schuurmann, Gerrit2,3 |
| 刊名 | ENVIRONMENTAL SCIENCE & TECHNOLOGY
 |
| 出版日期 | 2023-07-10 |
| 卷号 | 57期号:29页码:10773-10781 |
| 关键词 | Dehalococcoides reductive dehalogenation aromatic halide thermodynamics reaction mechanism |
| ISSN号 | 0013-936X |
| DOI | 10.1021/acs.est.3c00364 |
| 英文摘要 | 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. |
| WOS研究方向 | Engineering ; Environmental Sciences & Ecology |
| 语种 | 英语 |
| WOS记录号 | WOS:001025893900001 |
| 源URL | [http://ir.gig.ac.cn/handle/344008/74447]  |
| 专题 | 有机地球化学国家重点实验室 |
| 通讯作者 | Xia, Xinghui; Schuurmann, Gerrit |
| 作者单位 | 1.Helmholtz Ctr Environm Res, UFZ Dept Environm Biotechnol, D-04318 Leipzig, Germany 2.Tech Univ Bergakademie Freiberg, Inst Organ Chem, D-09596 Freiberg, Germany 3.Helmholtz Ctr Environm Res, UFZ Dept Ecol Chem, D-04318 Leipzig, Germany 4.Tech Univ Berlin, Chair Geobiotechnol, D-13355 Berlin, Germany 5.Beijing Normal Univ, Instrumentat & Serv Ctr Sci & Technol, Zhuhai 519087, Peoples R China 6.Beijing Normal Univ, Sch Environm, State Key Lab Water Environm Simulat, Beijing 100875, Peoples R China 7.Chinese Acad Sci, Guangzhou Inst Geochem, State Key Lab Organ Geochem, Guangzhou 510640, Peoples R China 8.Beijing Normal Univ, Adv Interdisciplinary Inst Environm & Ecol, Zhuhai 519087, Peoples R China |
| 推荐引用方式 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. |
入库方式： OAI收割
来源：广州地球化学研究所
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