Studies on the chelation of hypocrellin A with aluminium ion and the photodynamic action of the resulting complex.
Hypocrellin A (HA), a perylenoquinone derivative, is an efficient phototherapeutic agent. The chelation of HA with aluminium ion (Al3+) results in the formation of a 1:1 complex (Al(3+)-HA). The probable structure for this complex has been proposed. Compared with HA, this complex has a much higher solubility in water. In addition, Al(3+)-HA preserves the 1O2-generating function of HA as demonstrated by diphenylanthracene photo-bleaching experiments. In irradiated oxygen-saturated solutions of Al(3+)-HA superoxide radical anion and hydroxyl radical are formed as verified using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as the electron spin resonance (ESR) spin trapping agent. The production of superoxide radical anion is enhanced significantly in the presence of electron donors such as 1-benzyl-1,4-dihydronicotinamide (BNAH). These results suggest that the photodynamic action of Al(3+)-HA proceeds via both type 1 and type 2 reactions.