Outer-sphere electron transfer does not underpin B12-dependent olefinic reductive dehalogenation in anaerobes
Literature Information
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
DOI: 10.1039/C5CP07192E
Proton coupled electron transfer from the excited state of a ruthenium(ii) pyridylimidazole complex
Andrea Pannwitz, Oliver S. Wenger
DOI: 10.1039/C6CP00437G
Exploring the mechanism of water-splitting reaction in NiOx/β-Ga2O3 photocatalysts by first-principles calculations
Xin Zhou, Hao Dong, Ai-Min Ren
DOI: 10.1039/C5CP07260C
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
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
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
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
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
DOI: 10.1039/C5CP07853A
Elucidation of adsorption processes at the surface of Pt(331) model electrocatalysts in acidic aqueous media
Marcus D. Pohl, Viktor Colic
DOI: 10.1039/C5CP08000B
You might also like
What are the main uses of 1-(3-Aminophenyl)-3-[(3R)-1-(3,3-dimethyl-2-oxobutyl)-2-oxo-5-(2-pyridinyl)-2,3-dihydro-1H-1,4-benzodiazepin-3-yl]urea (CAS: 155412-88-7)?
This compound is mainly used as an intermediate in the synthesis of antipsychoti...
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...
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...
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...
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...
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...
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 ...
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...
What precautions should be taken when handling (S)-tert-butyl 2-((2-(4-bromophenyl)-2-oxoethyl)carbamoyl)pyrrolidine-1-carboxylate (CAS: 1007881-98-2)?
Handling this compound should be done with personal protective equipment (PPE) i...
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...
Source Journal
Physical Chemistry Chemical Physics

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.










![1-[3-(4-Morpholinylsulfonyl)phenyl]methanamine structure 1-[3-(4-Morpholinylsulfonyl)phenyl]methanamine structure](https://static.chemtradehub.com/structs/933/933989-32-3-51af.webp)



