Damage to DNA via dissociative electron attachment has been well-studied in both the gas and condensed phases; however, understanding this process in bulk solution at a fundamental level is still a challenge. Here, we use a picosecond pulse of a high energy electron beam to generate electrons in liquid diethylene glycol and observe the electron attachment dynamics to ribothymidine at different stages of electron relaxation. Our transient spectroscopic results reveal that the quasi-free electron with energy near the conduction band effectively attaches to ribothymidine leading to a new absorbing species that is characterized in the UV-visible region. This species exhibits a nearly concentration-independent decay with a time constant of ~350 ps. From time-resolved studies under different conditions, combined with data analysis and theoretical calculations, we assign this intermediate to an excited anion radical that undergoes N1-C1′ glycosidic bond dissociation rather than relaxation to its ground state.
In the present work, methyl viologen (1,1′-dimethyl-4,4′-bipyridinium dichloride) is used as a scavenger to estimate the radiolytic yields of water decomposition products from room temperature to 400 °C by pulse radiolysis method. {G(e aq -) + G(OH) + G(H)} has been studied using a 0.5 mM MV 2+ solution in the presence of 10 mM NaCOOH up to 200 °C and in the presence of 0.2 M ethanol up to 400 °C. The results show that the {G(e aq -) + G(OH) + G(H)} increases with temperature up to 350 °C at 25 MPa, while it depends also on pressure in supercritical conditions. The G(e aq -) was estimated using MV 2+ solutions in the presence of 0.2 M tert-butyl alcohol. The results agree well with the reported data up to around 300 °C at 25 MPa; however, in supercritical conditions a very significant density effect was observed. At a given temperature, G(e aq -) and {G(e aq -) + G(OH) + G(H)} decrease with increasing density while at a fixed density they decrease with increasing temperature.
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