Effects of the micro-environment on the photophysical properties of hematoporphyrin

The photochemical degradation of histidine, cysteine and tyrosine with hematoporphyrin as sensitizer was potentiated by the presence of Sephadex, BioGel or Percoll particles. This effect could only partly be explained by binding of the sensitizer to the gel particles, leading a.o. to monomerization of aggregated sensitizer molecules in the aqueous environment. The hematoporphyrin triplet state life time increased from 250 microseconds in phosphate buffer to 1992 microseconds in the presence of 50% Percoll. Most likely the effect of the gel particles on the sensitizer triplet state is, at least partly, mediated by the solvent. A plausible explanation seems to be that the vicinal water structure at the particle interface stabilizes the sensitizer triplet.