Nascent stages of DNA radiolysis: secondary electron and reactive ion induced damage

Full text: It is by now well understood that most of the energy deposited in solids by ionizing radiation is converted within less than attoseconds into the production of ions, radicals, and ballistic low-energy secondary electrons. The latter are known to decompose small molecules even at electron energies well below molecular ionization thresholds regardless of molecular aggregation state, and have recently been shown to induce substantial yields of single and double strand breaks in supercoiled DNA. In that study, we found that the electron-energy dependent strand break yields have a strong maximum near 10 eV, which was attributed to the decomposition of transient molecular anion (TMA) states, i.e. resonances. The localization of these resonances on the different components of DNA leads to dissociations into anion and radical fragments within femtoseconds, where subsequent fragment reactions on similar timescales are thought to lead to the final observed DNA damage. In order to unravel this sequence of secondary electron and reactive ion induced events, and to better understand their fundamental reaction pathways, we have performed, and will present: (a) measurements of the basic mechanisms by which low-energy (0-30 eV) electrons induce damage to different components of DNA, e.g. H20, deoxyribose analogs, bases, as well as other organic model systems, and (b) measurements of the basic reaction pathways by which some of the energetic ion fragments observed in (a) induce further damage in simple hydrocarbon films, as well as solids of DNA components, or their structural analogs. Our experiments show that: (i) for electron energies below 15 eV dissociative electron attachment (i.e. resonances) results in exocyclic and complex endocyclic bond cleavages in any of the molecular systems studied, leading to the formation of a vast variety of reactive radical and anion fragments, whereas above 15 eV electronic excitations and ionizations (nonresonant mechanisms) may also lead to formation of cation fragments. (ii) Even ionic fragments that are formed with only 1 - 6 eV kinetic energy may easily react with DNA components, such as deoxyribose analogs, or other organic molecules (e.g. linear and cyclic hydrocarbons). Observed ion-molecule reactions include atom abstraction, atom or functional group exchange, dissociative charge (and energy) transfer, as well as numerous complex reactive scattering channels, all of which occur on similar dimensional scales (∼ 2 - 3 nm) as the DNA's diameter, and proceed via the formation and decay of transient charged collision complexes on sub-picosecond time scales