Studies of reactions between flavins and quinones, mercaptans, and enolates.

Abstract

A. Equilibrium and second-order rate constants have been measured for the redox reaction between phthaloquinone and dihydroriboflavin (and its reverse) at a number of pH values. The equilibria and kinetic determinations are in agreement. No intermediates could be found in the reaction, and it is proposed that with this and other quinones electron transfer occurs within a complex of the flavin and hydroquinone (or dihydroflavin and quinone). B. A survey of the reaction between mercaptans and flavins is reported, as well as data showing that with mercaptoethanol the reaction is reversible, the disulfide and reduced flavin giving mercaptan and flavin. C. The reaction of alkylphenone enolates with isoalloxazine is described. This reaction leads t 50% isoalloxazine radical anion and an adduct of the enolate with the ketone. A possible route for this process is discussed.