Outer-sphere electron transfer does not underpin B12-dependent olefinic reductive dehalogenation in anaerobes

Literature Information

Publication Date 2021-12-01
DOI 10.1039/D1CP04632B
Impact Factor 3.676
Authors


View Original

Abstract

Anaerobic microbial B12-dependent reductive dehalogenation may pave a way to remediate soil, sediment, and underground water contaminated with halogenated olefins. The chemical reaction is initiated by electron transfer (ET) from supernucleophilic cob(I)alamin (B12s). However, the inherent mechanism as outer-sphere or inner-sphere route is still under debate. To clarify the possibility of an outer-sphere pathway, we calculated free energy barriers of the initial steps of all outer-sphere ET routes by Marcus theory employing density functional theory (DFT). For 18 fluorinated, chlorinated, and brominated ethenes as representative olefins, 164 of 165 reactions with free energy barriers larger than 20 kcal mol−1 are not feasible under physiological dehalogenase conditions. Moreover, electronic structure analysis of perbromoethene with an outer-sphere free energy barrier of 18.2 kcal mol−1 reveals no ET initiation down to Co⋯Br and Co⋯C distances of 3.15 Å. The results demonstrate that the B12-catalyzed reductive dechlorination of olefins in microbes should proceed through an inner-sphere ET pathway.

Related Literature

Effects of Pt dispersion on electronic and oxide ionic conductivity in Pr1.90Ni0.71Cu0.24Ga0.05O4

J. Hyodo, H. Schraknepper, K. Tominaga

2016-03-22 Paper

DOI: 10.1039/C5CP07192E

Proton coupled electron transfer from the excited state of a ruthenium(ii) pyridylimidazole complex

Andrea Pannwitz, Oliver S. Wenger

2016-04-08 Paper

DOI: 10.1039/C6CP00437G

Inside back cover

Cover

DOI: 10.1039/C6CP90112C

Numerical simulations of the role of a ferroelectric polymer interfacial layer in organic solar cells

Bo Liu, Feng Xu, Xinghua Zhang, Dadong Yan, Dan Lu

2016-01-07 Paper

DOI: 10.1039/C5CP04872A

Indented Cu2MoS4 nanosheets with enhanced electrocatalytic and photocatalytic activities realized through edge engineering

Bang-Bao Chen, De-Kun Ma, Qing-Ping Ke, Wei Chen, Shao-Ming Huang

2016-02-08 Paper

DOI: 10.1039/C5CP07900D

Charge carrier dynamics of methylammonium lead iodide: from PbI2-rich to low-dimensional broadly emitting perovskites

Johannes R. Klein, Oliver Flender, Mirko Scholz, Kawon Oum, Thomas Lenzer

2016-03-14 Paper

DOI: 10.1039/C5CP07167D

Electronic transport properties of ultra-thin Ni and Ni–C nanowires

Leining Zhang, Weikang Wu, Yi Zhou, Hongru Ren, Jichen Dong, Hui Li

2016-01-21 Paper

DOI: 10.1039/C5CP07641B

Cyanophenyl vs. pyridine substituent: impact on the adlayer structure and formation on HOPG and Au(111)

B. Eggers, M. Metzler, D. Künzel, A. Groß, T. Jacob, U. Ziener

2016-02-01 Paper

DOI: 10.1039/C5CP07853A

You might also like

155412-88-71-(3-Aminophenyl)-3-...
Compound Q&A

How should waste containing 1-(D-Ribofuranosyl)-1,4-dihydro-3-pyridinecarboxamide (CAS: 19132-12-8) be handled?

Waste containing 1-(D-Ribofuranosyl)-1,4-dihydro-3-pyridinecarboxamide (CAS: 191...

19132-12-81-(D-Ribofuranosyl)-...
Compound Q&A

What regulatory guidelines apply to 2-Methyl-2-propanyl 3-bromo-3-(hydroxymethyl)-1-azetidinecarboxylate (CAS: 2007919-81-3)?

2-Methyl-2-propanyl 3-bromo-3-(hydroxymethyl)-1-azetidinecarboxylate (CAS: 20079...

2007919-81-32-Methyl-2-propanyl ...
Compound Q&A

What is N-(4-Chloro-2-pyridinyl)acetamide (CAS: 245056-66-0)?

N-(4-Chloro-2-pyridinyl)acetamide (CAS: 245056-66-0) is a chemical compound with...

245056-66-0N-(4-Chloro-2-pyridi...
Compound Q&A

What is 5-Chloro-2-hydroxybenzoic acid (CAS: 321-14-2)?

5-Chloro-2-hydroxybenzoic acid, also known as 5-chlorosalicylic acid, is an arom...

321-14-25-Chloro-2-hydroxybe...
Compound Q&A

What precautions should be taken when handling 1,1-Dichloro-1-fluoroethane (CAS: 1717-00-6)?

When handling 1,1-Dichloro-1-fluoroethane (CAS: 1717-00-6), it is important to u...

1717-00-61,1-Dichloro-1-fluor...
Compound Q&A

What are the physical and chemical properties of Fmoc-(2S,3R)-3-phenylpyrrolidine-2-carboxylic acid (CAS: 281655-32-1)?

Fmoc-(2S,3R)-3-phenylpyrrolidine-2-carboxylic acid is a white crystalline solid ...

281655-32-1Fmoc-(2S,3R)-3-pheny...
Compound Q&A

What are the main uses of 4-Amino-5-bromo-2-pyridinecarboxylic acid (CAS: 1363381-01-4)?

4-Amino-5-bromo-2-pyridinecarboxylic acid is primarily used as a precursor in th...

1363381-01-44-Amino-5-bromo-2-py...
1007881-98-2(S)-tert-butyl 2-((2...
Compound Q&A

What precautions should be taken when handling 8-bromo-2,2-dimethyl-3,4-dihydro-2H-1,4-benzoxazin-3-one (CAS: 688363-73-7)?

When handling 8-bromo-2,2-dimethyl-3,4-dihydro-2H-1,4-benzoxazin-3-one, use prop...

688363-73-78-bromo-2,2-dimethyl...

Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Recommended Compounds

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.