title: Absolute electron total ionization cross-sections: molecular analogues of DNA and RNA nucleobase and sugar constituents.
abstract: Accurate ionization cross-sections for DNA and RNA constituents in the condensed or aqueous phase are important parameters for models simulating radiation damage to genetic material in living cells. In this work, absolute gas-phase electron total ionization cross-sections (TICSs) have been measured for a series of six aromatic and eight non-aromatic cyclic species that can be considered as prototype functional group analogues for the nucleobases and sugar backbone constituents of DNA and RNA. TICSs for water, hexane, and ethylacetamide (a peptide bond analogue) are also reported. The experimental apparatus utilizes a cylindrical ion collector that surrounds the ionization region, providing essentially unit detection efficiency. Two theoretical models, the polarizability-correlation method and binary-encounter Bethe theory, are able to reproduce the measured maximum TICS well for all species studied. An empirical energy-dependent correction is found to yield improvement in the agreement between experimental energy-dependent cross sections and the predictions of the BEB model. Having characterised and optimised the performance of both models, they are then used to predict TICSs for gas-phase DNA and RNA nucleobases and sugars. Direct experimental determinations of TICSs for these species are difficult because of their low volatility, which makes it difficult to prepare suitable gas-phase samples for measurement.
authors.affiliation: Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, UK. claire.vallance@chem.ox.ac.uk.
authors.forename: James N
authors.initials: JN
authors.lastname: Bull
authors.forename: Jason W L
authors.initials: JW
authors.lastname: Lee
authors.forename: Claire
authors.initials: C
authors.lastname: Vallance
mesh_terms: D000081:Acetamides / Q000737:chemistry; D002241:Carbohydrates / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D004583:Electrons; D006586:Hexanes / Q000737:chemistry; D011789:Quantum Theory; D012313:RNA / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D000081:Acetamides; D002241:Carbohydrates; D006586:Hexanes; D014867:Water; D012313:RNA; D004247:DNA