LIFETIME AND REACTIVITY OF THE VERATRYL ALCOHOL RADICAL-CATION - IMPLICATIONS FOR LIGNIN PEROXIDASE CATALYSIS

The formation and decay of veratryl alcohol radical cation upon oxidation of veratryl alcohol by thallium (II) ions was studied by pulse radiolysis with spectrophotometric and conductometric detection. In aqueous solution at pH 3 the radical cation decays by a first order process, assigned to the deprotonation from the ru-carbon. On the basis of its Lifetime (59 +/- 8 ms) and of its ability to oxidize a polymeric dye (Poly R-478) we estimate that the radical cation can diffuse about 7 mu m in an aqueous environment to act as a mediator of oxidations over long distances. However, 4-methoxymandelic acid is not oxidized by the veratryl alcohol radical cation in homogeneous solution, and the comparison with previous studies on lignin peroxidase catalysis suggests a second role for veratryl alcohol radical cation in the enzyme action: it may exist as an enzyme-bound species that has either a longer lifetime or a higher reduction potential than the free radical cation in bulk solution.