PHOTOOXIDATION AND SINGLET OXYGEN SENSITIZATION BY PROTOPORPHYRIN IX AND ITS PHOTOOXIDATION PRODUCTS

Protoporphyrin IX and its various ester derivatives have been previously shown to undergo self-sensitized photooxygenation to yield hydroxyaldehydes (photoprotoporphyrin) and mono- and diformyl deuteroporphyrin derivatives. In the present study the photoreactions of these products in the presence of oxygen have been investigated. All of the photooxidation products are themselves good sensitizers of singlet oxygen. In addition spin trapping experiments indicate these products can produce superoxide in low-to-moderate efficiency by an excited state electron transfer process. The photo-products themselves are somewhat more stable to photooxidation than protoporphyrin IX itself. The two monoformyl-monovinyl deuteroporphyrins have been found to undergo further photooxidation at the vinyl groups to yield primarily monoformyl hydroxyaldehydes in a reaction mainly involving singlet oxygen analogous to the initial reaction of protoporphyrin IX.