DFT analysis of Co-alkyl and Co-adenosyl vibrational modes in B12-cofactors

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DOIResolve DOI: http://doi.org/10.1021/ic052069j
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TypeArticle
Journal titleInorganic Chemistry
ISSN0020-1669
Volume45
Issue14
Pages55855590; # of pages: 6
AbstractDensity functional theory (DFT)-based normal mode calculations have been carried out on models for B12-cofactors to assign reported isotope-edited resonance Raman spectra, which isolate vibrations of the organo-Co group. Interpretation is straightforward for alkyl-Co derivatives, which display prominent Co-C stretching vibrational bands. DFT correctly reproduces Co-C distances and frequencies for the methyl and ethyl derivatives. However, spectra are complex for adenosyl derivatives, due to mixing of Co-C stretching with a ribose deformation coordinate and to activation of modes involving Co-C-C bending and Co-adenosyl torsion. Despite this complexity, the computed spectra provide a satisfactory re-assignment of the experimental data. Reported trends in adenosyl-cobalamin spectra upon binding to the methylmalonyl CoA mutase enzyme, as well as on subsequent binding of substrates and inhibitors, provide support for an activation mechanism involving substrate-induced deformation of the adenosyl ligand.
Publication date
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedNo
Identifier10007817
NPARC number12328605
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Record identifier3db70a89-127c-4d78-99e9-3cfe23da23f9
Record created2009-09-10
Record modified2016-05-09
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