Studies on the mechanism of the hematoporphyrin-sensitized photooxidation of 1,3-diphenylisobenzofuran in ethanol and unilamellar liposomes.
The 5 microM hematoporphyrin-sensitized photooxidation of 1,3-diphenylisobenzofuran (DPBF) was studied in homogeneous ethanolic solutions and in aqueous dispersions of unilamellar liposomes of dipalmitoylphosphatidylcholine; both the porphyrin and DPBF are embedded in the phospholipid bilayer. The rate and quantum yield of DPBF photooxidation were found to increase upon increasing the substrate concentration and were higher in the liposome system, while they were unaffected by the fluidity of the phospholipid bilayer. Time-resolved spectroscopic measurements showed that the photooxidation of DPBF in ethanol solution proceeds by a type II O2(1 delta g)-involving mechanism. In the liposomal vesicles the high local concentration of hematoporphyrin (Hp) and DPBF in the phospholipid bilayer (ca 2000-fold higher than the stoichiometric concentration) enhances the probability of energy transfer from triplet Hp to DPBF with generation of triplet DPBF; hence O2 (1 delta g) formation can be promoted by both triplet Hp and triplet DPBF. A minor fraction of triplet DPBF quenchings appears to generate radical species which propagate DPBF damage by chain reaction.
Reddi
E
E
Department of Biology, University of Padova, Italy.
Valduga
G
G
Rodgers
M A
MA
Jori
G
G
D015060:1,2-Dipalmitoylphosphatidylcholine; D001572:Benzofurans / Q000528:radiation effects*; D000431:Ethanol; D006415:Hematoporphyrins; D008081:Liposomes; D010084:Oxidation-Reduction; D010777:Photochemistry
D001572:Benzofurans; D006415:Hematoporphyrins; D008081:Liposomes; D015060:1,2-Dipalmitoylphosphatidylcholine; D000431:Ethanol; C011238:1,3-diphenylisobenzofuran