title: Time-resolved spectroscopic studies of B(12) coenzymes: a comparison of the primary photolysis mechanism in methyl-, ethyl-, n-propyl-, and 5'-deoxyadenosylcobalamin.
abstract: An ultrafast transient absorption study of the primary photolysis of ethyl- and n-propylcobalamin in water is presented. Data have been obtained for two distinct excitation wavelengths, 400 nm at the edge of the UV gamma-band absorption, and 520 nm in the strong visible alphabeta-band absorption. These data are compared with results reported earlier for the B(12) coenzymes, methyl- and adenosylcobalamin. The data obtained for ethylcobalamin and n-propylcobalamin following excitation at 400 nm demonstrate the formation of one major photoproduct on a picosecond time scale. This photoproduct is spectroscopically identifiable as a cob(II)alamin species. Excitation of methyl-, ethyl-, and n-propylcobalamin at 520 nm in the low-lying alphabeta absorption band results in bond homolysis proceeding via a bound cob(III)alamin MLCT state. For all of the cobalamins studied here competition between geminate recombination of caged radical pairs and cage escape occurs on a time scale of 500 to 700 ps. The rate constants for geminate recombination in aqueous solution fall within a factor of 2 between 0.76 and 1.4 ns(-1). Intrinsic cage escape occurs on time scales ranging from <or=0.5 ns for methyl radical to 2.3 ns for adenosyl, the largest radical studied. The solvent caging correlates well with the size of the radical following anticipated trends: 0 <or= F(C) <or= 0.3 for methyl radical, 0.4 for ethyl radical, 0.57 for n-propyl radical, and 0.72 for adenosyl radical.
authors.affiliation: Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055, USA.
authors.forename: Allwyn G
authors.initials: AG
authors.lastname: Cole
authors.forename: Laurie M
authors.initials: LM
authors.lastname: Yoder
authors.forename: Joseph J
authors.initials: JJ
authors.lastname: Shiang
authors.forename: Neil A
authors.initials: NA
authors.lastname: Anderson
authors.forename: Larry A
authors.initials: LA
authors.lastname: Walker
authors.forename: Mark M
authors.initials: MM
authors.lastname: Banaszak Holl
authors.forename: Roseanne J
authors.initials: RJ
authors.lastname: Sension
mesh_terms: D003038:Cobamides / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D010782:Photolysis; D013056:Spectrophotometry, Ultraviolet; D014805:Vitamin B 12 / Q000031:analogs & derivatives / Q000737:chemistry
chemical_list: D003038:Cobamides; D005609:Free Radicals; C450701:ethylcobalamin; C450702:n-propylcobalamin; C000913:cobamamide; D014805:Vitamin B 12