The reduction of thymine residues in DNA by the combined action of UV light and hypophosphite.
UV irradiation (lambda = 254 nm) of thymine and uracil in aqueous solution containing salts of phosphinic acid (hypophosphites) results in the formation of the corresponding dihydropyrimidine derivatives. The peculiarities of this new photochemical reaction consist of a specificity towards 2,4-dioxophyrimidines, a high quantum yield and a neutral pH optimum. The quantum yield of photoconversion of thymine at pH 7.0 is equal to 1.9 x 10(-2) in 1 M NaH2PO2; it is diminished to 8.5 x 10(-3) in 0.1 M NaH2PO2. The same decrease in quantum yield with concentration is also found for uracil and uridine; quantum yields of their transformations in 0.1 M NaH2PO2 at pH 7.0 are 6.6 x 10(-2) and 1.5 x 10(-1) respectively. The mild conditions and high quantum yields characteristic of the photoinduced reaction above open up the possibility of obtaining DNA molecules which contain among pyrimidine photoproducts mainly dihydropyrimidine residues. A correlation between various types of thymine modifications in UV-irradiated double-stranded DNA (dimers and dihydrothymidine residues) and the amplitude of the intense negative band in the circular dichroism (CD) spectra specific for DNA liquid crystalline dispersions has been established. A possible application of this base-specific modification to the investigation of nucleic acids is considered.
D002942:Circular Dichroism; D004247:DNA / Q000737:chemistry / Q000187:drug effects* / Q000528:radiation effects*; D004249:DNA Damage; D007700:Kinetics; D010084:Oxidation-Reduction; D010721:Phosphinic Acids / Q000494:pharmacology*; D011071:Poly T / Q000528:radiation effects; D011743:Pyrimidines / Q000528:radiation effects; D011789:Quantum Theory; D011838:Radiation-Sensitizing Agents; D013329:Structure-Activity Relationship; D013941:Thymine / Q000528:radiation effects*; D014466:Ultraviolet Rays; D014498:Uracil / Q000528:radiation effects*
D010721:Phosphinic Acids; D011743:Pyrimidines; D011838:Radiation-Sensitizing Agents; D011071:Poly T; D014498:Uracil; D004247:DNA; D013941:Thymine