H2O˙+ and OH+ reactivity versus furan: experimental low energy absolute cross sections for modeling radiation damage

Abstract

Radiotherapy is one of the most widespread and efficient strategies to fight malignant tumors. Despite its broad application, the mechanisms of radiation-DNA interaction are still under investigation. Theoretical models to predict the effects of a particular delivered dose are still in their infancy due to the difficulty of simulating a real cell environment, as well as the inclusion of a large variety of secondary processes. This work reports the first experimental study of the ion–molecule reactions of the H₂O˙⁺ and OH⁺ ions, produced by photoionization with synchrotron radiation, with a furan (c-C₄H₄O) molecule, a template for deoxyribose sugar in DNA. The present experiments, performed as a function of the collision energy of the ions and the tunable photoionization energy, provide key parameters for the theoretical modelling of the effect of radiation dose, like the absolute cross sections for producing protonated furan (furanH⁺) and a radical cation (furan˙⁺), the most abundant products, which can amount up to 200 Ų at very low collision energies (<1.0 eV). The experimental results show that furanH⁺ is more fragile, indicating how the protonation of the sugar component of the DNA may favor its dissociation with possible major radiosensitizing effects. Moreover, the ring opening of furanH⁺ isomers and the potential energy surface of the most important fragmentation channels have been explored by molecular dynamics simulations and quantum chemistry calculations. The results show that, in the most stable isomer of furanH⁺, the ring opening occurs via a low energy pathway with carbon–oxygen bond cleavage, followed by the loss of neutral carbon monoxide and the formation of the allyl cation CH₂CHCH₂⁺, which instead is not observed in the fragmentation of furan˙⁺. At higher energies the ring opening through the carbon–carbon bond is accompanied by the loss of formaldehyde, producing HCCCH₂⁺, the most intense fragment ion detected in the experiments. This work highlights the importance of the secondary processes, like the ion–molecule reactions at low energies in the radiation damage due to their very large cross sections, and it aims to provide benchmark data for the development of suitable models to approach this low collision energy range.