Coenzyme models. Part 35. Charge separation on the micelle surface as a strategy to prove the multi-step reaction mechanism in NADH model reductions

Abstract

We have found that (i) the reaction of NADH model compounds with potassium persulphate (PPS) in anionic and non-ionic micelles initiates radical polymerisation of acrylamide and (ii) that reductive desulphonation of 2,4,6-trinitrobenzenesulphonate and 4-carboxy-2,6-dinitrobenzenesulphonate by NADH model compounds in deuterium oxide in the presence of the micelles gives 1,3,5-trinitrobenzene and 3,5-dinitrobenzoic acid, respectively, which contain 3–16% deuterium. The results indicate that the reactions proceed through multi-step hydrogen transfer via radical ion-pair intermediates and the micelle is capable of dissociating the radical ion-pairs.