Radiation-induced structural modifications in dsDNA analysed by FT-Raman spectroscopy.

Structural changes of double stranded DNA in aqueous solution induced by ionizing radiation were studied by Fourier-Transform-Raman spectroscopy. In addition to base damage, strand breaks, structural changes, i.e. unstacking of the bases, premelting effects and disordering of the B-form backbone could be observed. The amount of these different kinds of damage depended on the concentration of the DNA solution. Specifically, the following modifications were found depending on the gamma-ray dose and DNA concentration. (1) Intensity increase of the lines of dT (1240 cm-1) and dA (729, cm-1) indicating unstacking of these bases. (2) Intensity and frequency changes of the marker bands of all four bases indicating structural modifications. (3) Intensity decrease of the sugar marker lines showing change of the bonds in the deoxyribose and of bonds between the sugar moiety and the phosphodiester. (4) Intensity decrease of the lines of the phosphodiester groups (1094 and 790 cm-1) with simultaneous appearance of a difference peak at 1080 cm-1 and a new peak at 980 cm-1 suggesting the presence of strand breaks. (5) Intensity decrease of the B-form marker band (approximately 835 cm-1) and new lines at 876 cm-1), at approximately 660 cm-1 (C3'-endo/anti of dG) and at 1312 cm-1 (C3'endo/syn of dA) indicating decrease of the B-form conformation and the developing of partly new secondary forms of the DNA representing a helix-to-coil transition.