Kinetics of photoinduced electron transfer reactions of ruthenium(II) complexes and phenols, tyrosine, N-acetyl-tyrosine and tryptophan in aqueous solutions measured with modulated fluorescence spectroscopy.

Photooxidation kinetics of phenol, 1-naphthol, 2-naphthol, tyrosine (TyrOH) and N-acetyl-tyrosine (AcTyrOH), tryptophan (TrpH) by ruthenium(II) polypyridyl complexes: [Ru(bpy)3]Cl2 (1), [Ru(phen)3]Cl2 (2), [Ru(bpy)(phen)(bpg)]Cl2 (3), and [Ru(dpq)2(bxbg)]Cl2 (4) where bpy is 2,2'-bipyridine, phen - 1,10-phenanthroline, bpg - bipyridine-glycoluril, dpq - dipyrido[3,2-d:2',3'-f]quinoxaline, and bxbg - bis(o-xylene)bipyridine-glycoluril are investigated. Rate constants have been measured by steady-state luminescence and phase-modulation fluorometry in aqueous solutions at different pH's. The rates for the oxidation of the phenols and phenolic aromatic amino acids spreads over a wide range from 4.2×10(6) to 6.8×10(9)M(-1)s(-1), depending on pH and the nature of solutes. At pH>pKa of the quenchers, the presence of reactive species (PhO(-)) in the alkaline solutions is accounted for the rapid ET rates. In the pH range between 4 and 10 (pH