Photochemistry and Photobiology 1993-07-01

The photooxidation of diethylhydroxylamine by rose bengal in micellar and nonmicellar aqueous solutions.

P Bilski, A G Motten, M Bilska, C F Chignell

Index: Photochem. Photobiol. 58(1) , 11-8, (1993)

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Abstract

The photooxidation of N,N-diethylhydroxylamine (DEHA) by Rose Bengal (RB) has been investigated in micellar and nonmicellar aqueous solutions. We measured the quantum yield of oxygen consumption forming H2O2 and monitored two intermediates, the superoxide and diethylnitroxide radicals. When the pH was varied, the quantum yield of oxidation remained constant for 6 < pH < 10.5, decreased in acidic pH, and increased considerably in NaOH solution; these changes could be attributed to the protonation and dissociation processes of the > N-OH moiety of DEHA. The formation of diethylnitroxide radical was enhanced by superoxide dismutase or strong alkaline solution. Around neutral pH, the oxidation proceeded mainly via electron transfer from DEHA to the RB triplet (kq = 10(7) M-1 s-1) with little 1O2 participation (kq < 10(5) M-1 s-1). However, when RB was incorporated into micelles in alkaline solution, the contribution of the singlet oxygen pathway increased at the expense of electron transfer, which was inhibited by the less polar micellar environment. Dark autoxidation of DEHA was accelerated by heavy metal impurities and increased very strongly in NaOH solution.