Radical Formation and Chemical Track Structure in Ion-Beam Irradiated DNA

Abstract

Ion‐beam irradiation of hydrated DNA at 77 K results in formation of at least three base radicals and a variety of radicals on the sugar phosphate backbone that can be observed using Electron Spin Resonance (ESR) spectroscopy. From dose‐response curves for these radicals, we have formulated a radiation‐chemical model of the track structure for ion‐beam irradiated DNA. The model for chemical behavior posits that the base radicals trapped at 77 K are formed almost entirely in the track penumbra. The lower yields observed in ion‐beam irradiated samples results from the fact that only a portion of the energy deposited by the ion beam ends up in this γ‐like region. The remainder of the energy is deposited in the core in which the proximity of ion‐radical formation results in the fast recombination of oppositely charged radicals, so few survive in the core at 77 K. However, a second group of radicals, neutral sugar radicals, are not as susceptible to recombination as are ion radicals, and can survive after formation in the core; these are presumed to form predominantly in the core. They include the sugar radicals, C1′⋅C3′⋅C5′⋅, formed from oxidative processes, and C3′⋅dephos and phosphorous radicals which are formed after immediate strand breaks. The later species are thought to result from reductive cleavage by low energy electrons (LEE.) The high energy density in the core results in excited state processes that produce additional sugar radicals. The spatial characteristics of the radicals, deduced from PELDOR experiments, indicates that multiply damaged cluster sites (MDS) are formed in the core; these would be biologically significant, if formed in cells.