The conversion of NADH to NAD+ and of the reverse reaction, in the coenzyme as well as in its synthetic analogues, 1,4-dihydropyridines and 9,10-dihydroanthracenes is discussed. Two mechanisms of the NADHŰNAD+ conversion are compared: one-step hydride transfer and stepwise electron-proton-electron transfer. Direct characterization of transient species in the stepwise process, namely radical cations and radicals, is presented based on the pulse radiolysis and laser flash photolysis studies both in solution and low-temperature matrices. On ionization of NADH and 1,4-dihydropyridines the stability order of the keto and enol tautomers is inversed as compared to their neutral precursors. Both types of radical cations are characterized and their role in the stepwise process is discussed.
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