Spectroscopic studies of photobleaching and photoproduct formation of porphyrins used in tumour therapy.

The illumination of haematoporphyrin, meso-tetraphenylporphyrin tetrasulphonate and haematoporphyrin derivative in aqueous solution causes two simultaneously occurring processes: photodegradation and the formation of stable photoproducts absorbing in the red spectral region. In the case of haematoporphyrin and its derivatives, these photoproducts have an absorption maximum around 640 nm (photoproduct 640). The former process, which is detected as the bleaching of the porphyrin absorption spectrum as well as a decrease in the fluorescence intensity, is slightly dependent on the solution pH and becomes dominant when the formation of the photoproduct reaches saturation. For the most part, the photodegradation can be explained as the opening of the porphyrin ring, leading to an increase in light absorbance in the UV region. The formation of photoproduct 640 is closely related to the aggregation state of the porphyrins, and shows a distinct dependence on the medium pH. The effectiveness of photoproduct 640 formation strongly increases in neutral and alkaline solutions, whereas the porphyrins are photostable below pH 5. The spectroscopic features of the photoproducts of haematoporphyrin and haematoporphyrin derivative, with absorption bands in the visible region, are similar to those of chlorin and/or porphyrin-chlorin linked systems. On the basis of these spectroscopic studies, it is suggested that photoproduct 640 is a chlorin-type molecule formed predominantly from the aggregates of porphyrins when photo-oxidation and photoreduction are in competition.