title: Corrin ring-induced redox tuning.
abstract: The density functional calculations suggest that the expansion of the corrin macrocycle's N(4) core by 0.06-0.10 Å leads to an appreciable lowering of 100-150 mV vs. saturated calomel electrode in the reduction potentials of two biologically important B(12) cofactors namely methylcobalamin and adenosylcobalamin respectively. This redox tuning of B(12) cofactors may encourage the electron transfer-based activation mechanism for B(12)-dependent enzymes.
authors.affiliation: Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA.
authors.forename: Manoj
authors.initials: M
authors.lastname: Kumar
authors.forename: Pawel M
authors.initials: PM
authors.lastname: Kozlowski
mesh_terms: D003038:Cobamides / Q000737:chemistry; D045728:Corrinoids / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D014805:Vitamin B 12 / Q000031:analogs & derivatives / Q000737:chemistry
chemical_list: D003038:Cobamides; D045728:Corrinoids; C473700:corrin; C019476:mecobalamin; C000913:cobamamide; D014805:Vitamin B 12