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Cobalamins uncovered by modern electronic structure calculations

Jensen, Kasper LU and Ryde, Ulf LU (2009) In Coordination Chemistry Reviews 253(5-6). p.769-778
Abstract
This review describes how computational methods have contributed to the held of cobalamin chemistry since the start of the new millennium. Cobalamins are cobalt-dependent cofactors that are used for alkyl transfer and radical initiation by several classes of enzymes. Since the entry of modern electronic-structure calculations, in particular density functional methods, the understanding of the molecular mechanism of cobalamins has changed dramatically, going from a dominating view of trans-steric strain effects to a much more complex view involving an arsenal of catalytic strategies. Among these are cis-steric distortions, electrostatic stabilization of radical products, the realization that nucleotide units can serve as polar handles, and... (More)
This review describes how computational methods have contributed to the held of cobalamin chemistry since the start of the new millennium. Cobalamins are cobalt-dependent cofactors that are used for alkyl transfer and radical initiation by several classes of enzymes. Since the entry of modern electronic-structure calculations, in particular density functional methods, the understanding of the molecular mechanism of cobalamins has changed dramatically, going from a dominating view of trans-steric strain effects to a much more complex view involving an arsenal of catalytic strategies. Among these are cis-steric distortions, electrostatic stabilization of radical products, the realization that nucleotide units can serve as polar handles, and the careful design of the active sites, with polar residues in the radical enzymes and non-polar residues in the transferases. Together, these strategies explain the enigmatic Co-C bond cleavage necessary for catalysis by these enzymes. (C) 2008 Elsevier B.V. All rights reserved. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Enzymes, Organometallics, Vitamin B-12, Cobalamin, DFT
in
Coordination Chemistry Reviews
volume
253
issue
5-6
pages
769 - 778
publisher
Elsevier
external identifiers
  • wos:000264701900016
  • scopus:60649108976
ISSN
0010-8545
DOI
10.1016/j.ccr.2008.04.015
language
English
LU publication?
yes
id
3593180b-ce0e-40ea-9c5a-9567ee1c90ee (old id 1401123)
date added to LUP
2009-06-15 11:30:31
date last changed
2017-11-26 03:27:35
@article{3593180b-ce0e-40ea-9c5a-9567ee1c90ee,
  abstract     = {This review describes how computational methods have contributed to the held of cobalamin chemistry since the start of the new millennium. Cobalamins are cobalt-dependent cofactors that are used for alkyl transfer and radical initiation by several classes of enzymes. Since the entry of modern electronic-structure calculations, in particular density functional methods, the understanding of the molecular mechanism of cobalamins has changed dramatically, going from a dominating view of trans-steric strain effects to a much more complex view involving an arsenal of catalytic strategies. Among these are cis-steric distortions, electrostatic stabilization of radical products, the realization that nucleotide units can serve as polar handles, and the careful design of the active sites, with polar residues in the radical enzymes and non-polar residues in the transferases. Together, these strategies explain the enigmatic Co-C bond cleavage necessary for catalysis by these enzymes. (C) 2008 Elsevier B.V. All rights reserved.},
  author       = {Jensen, Kasper and Ryde, Ulf},
  issn         = {0010-8545},
  keyword      = {Enzymes,Organometallics,Vitamin B-12,Cobalamin,DFT},
  language     = {eng},
  number       = {5-6},
  pages        = {769--778},
  publisher    = {Elsevier},
  series       = {Coordination Chemistry Reviews},
  title        = {Cobalamins uncovered by modern electronic structure calculations},
  url          = {http://dx.doi.org/10.1016/j.ccr.2008.04.015},
  volume       = {253},
  year         = {2009},
}