Photoreactivity (3655 Å) of various skin-photosensitizing furocoumarins with nucleic acids

The photoreaction at 3655 A between skin-photosensitizing furocoumarins and DNA leads to a photo-C4-cyclo-addition reaction in which the 5 - 6 double bond of the pyrimidine bases and the 3 -4 or the 4' -5′ double bond of the furocoumarins are involved. In continuing the research in this field, the authors have investigated the photoreactions (3655 A) of psoralen, xanthotoxin (8-methoxy-psoralen), bergapten (5-methoxy-psoralen) and 8-methyl-psoralen with native calf thymus DNA. with heat-denatured DNA and with ribosomal yeast-RNA, using labelled furocoumarins and examining also the influence of the temperature at which the irradiation was made. At room temperature (22° -30°C) psoralen photoreacts in almost equally extent with each of the three nucleic acid samples, while xanthotoxin, bergapten and 8-methyl-psoralen photoreact to a greater extent with native DNA than with denatured DNA and RNA. The temperature during the irradiation (in the range examined: 2° - 30°C) does not affect the rate of the photoreactions between the four furocoumarins and native DNA, whereas it has an evident influence on the photoreactions with denatured DNA and with RNA. In the photoreaction of psoralen this influence concerns the double bond (3 - 4 or 4' -5′) of the furocoumarin which is engaged in the C4-cycloaddition to pyrimidine bases. In the case of the other furocoumarins, the rate of the photoreactions is affected: at 2° - 8°C it is greater than at 30 °C. The preliminary formation (in the dark) of a complex between the furocoumarins and the macromolecules is involved in this temperature influence.