As a model for riboflavin, lumiflavin was investigated using density functional theory methods (B3LYP/6-31G* and B3LYP/6-31+G**) with regard to the proposed cascade of intermediates formed after ...excitation to the triplet state, followed by electron-transfer, proton-transfer, and radicalbondradical coupling reactions. The excited triplet state of the flavin is predicted to be 42 kcal/mol higher in energy than the singlet ground state, and the pi radical anion lies 45.1 kcal/mol lower in energy than the ground-state flavin and a free electron in the gas phase. The former value compares to a solution-phase triplet energy of 49.8 kcal/mol of riboflavin. For the radical anion, the thermodynamically favored position to accept a proton on the flavin ring system is at N(5). A natural population analysis also provided spin density information for the radicals and insight into the origin of the relative stabilities of the six different calculated hydroflavin radicals. The resulting 5H-LF* radical can then undergo radicalbondradical coupling reactions, with the most thermodynamically stable adduct being formed at C(4'). Vibrational spectra were also calculated for the transient species. Experimental time-resolved infrared spectroscopic data obtained using riboflavin tetraacetate are in excellent agreement with the calculated spectra for the triplet flavin, the radical anion, and the most stable hydroflavin radical.
We have recently reported phospholipid bicelles (bilayered micelles) that have positive anisotropy of the magnetic susceptibility and align with their normals parallel to an external magnetic field ...J. Am. Chem. Soc. 2001, 123, 1537. Improvements have been made via the synthesis of a new phospholipid, 1-dodecanoyl-2-(4-(4-biphenyl)butanoyl)-sn-glycero-3-phosphocholine (DBBPC). Bicelles can be formed by mixing DBBPC with a short-chain phospholipid, 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) in a ratio between 5.1:1 and 6.5:1 in an aqueous medium. The (31)P NMR spectra clearly show that these bicelles align with their principal axes parallel to the magnetic field within a wide temperature range. The (31)P chemical shifts indicate that the conformation of the polar headgroup in these bicelles may be different from that in common bicelles. The phase behavior of a mixture of DBBPC/DHPC with 6:1 mole ratio was investigated in the temperature range of 10-75 degrees C using (31)P, (2)H, and (23)Na NMR. At lower temperatures (10-54 degrees C), the system is dominated by the bicellar phase. At higher temperatures (54-75 degrees C), isotropic micelles are formed and coexist with the bicelles. The partial alignment of maltotriose in the DBBPC/DHPC system was studied at three temperatures, and the (1)H-(13)C dipolar coupling constants are compared with those obtained for two other bicelle solutions.
Cobalt(III) carboxypeptidase A Kang, E P; Storm, C B; Carson, F W
Journal of the American Chemical Society,
11/1975, Letnik:
97, Številka:
23
Journal Article