10–100 eV Ar+ ion induced damage to d-ribose and 2-deoxy-d-ribose molecules in condensed phase

Abstract

We report that 10–100 eV Ar⁺ ion irradiation induces severe damage to the biologically relevant sugar molecules D-ribose and 2-deoxy-D-ribose in the condensed phase on a polycrystalline Pt substrate. Ar⁺ ions with kinetic energies down to 15 eV induce effective decomposition of both sugar molecules, leading to the desorption of abundant cation and anion fragments, including CH₃⁺, C₂H₃⁺, C₃H₃⁺, H₃O⁺, CHO⁺, CH₃O⁺, C₂H₃O⁺, H⁻, O⁻, and OH⁻, etc. Use of isotopically labelled molecules (5-¹³C D-ribose and 1-D D-ribose) reveals the site specificity for some of the fragment origins, and thus the nature of the chemical bond breaking. It is found that all of the chemical bonds in both molecules are vulnerable to ion impact at energies down to 15 eV, particularly both the endo- and exocyclic C–O bonds. In addition to molecular fragmentation, several chemical reactions are also observed. A small amount of O⁻/O fragments abstract hydrogen to form OH⁻. It is found that the formation of the H₃O⁺ ion is related to the hydroxyl groups of the sugar molecules, and is associated with additional hydrogen loss from the parent or adjacent molecules via hydrogen abstraction or proton transfer. The formation of several other cation fragments also requires hydrogen abstraction from its parent or an adjacent molecule. These fragmentations and reactions are likely to occur in a real biomedium during ionizing radiation treatment of tumors and thus bear significant radiobiological relevance.