Kinetics and mechanism of the photochemical reaction of 2,2 '-dipyridyl with tryptophan in water: Time-resolved CIDNP and laser flash photolysis study

The mechanism of the reactions between photoexcited 2,2′-dipyridyl and N-acetyl tryptophan has been studied by laser flash photolysis and time-resolved CIDNP (Chemically Induced Dynamic Nuclear Polarization). The transient absorption spectra obtained at different delays after the laser pulse are attributed to the triplet state of dipyridyl and to dipyridyl and tryptophan radicals. Depending on the pH of the solution, all three intermediates can be present in either protonated or deprotonated forms. It is shown that irrespective of pH the primary photochemical step is electron transfer from the tryptophan to triplet dipyridyl followed by protonation/deprotonation of the radicals so formed. The rate constant of the reaction of triplet dipyridyl with tryptophan is close to the diffusion-controlled limit and decreases slightly with increasing pH. The kinetics and the stationary value of the CIDNP are determined by the rates of radical termination, nuclear paramagnetic relaxation, and degenerate electron exchange. The last reaction is important for the protonated tryptophan radical and determines the CIDNP kinetics of tryptophan in acidic conditions. The nuclear relaxation times estimated from the CIDNP kinetics are 44 ± 9 μs for all protons in the dipyridyl radical, 91 ± 20 μs for the β-CH2, 44 ± 9 μs for H2,6, and 63 ± 12 μs for H4 aromatic protons in the tryptophan radical