Proton Transfer Behavior in Irradiated Adenine Derivatives: ESR and ENDOR Study of X-ray Irradiated Arabinofuranosyl Adenine Single Crystals

 Jun Seog Kang

 

Department of Physics and Astronomy, GSU

Abstract

ESR and ENDOR were used to study free radicals produced in single crystals of 9-b-D arabinofuranosyl adenine (ara-A) by X-irradiation and observation at 10K. The ara-A is an isomer of adenosine differing only in the sugar group. Previously, adenosine [Close et al., Radiat. Res. 117, 367-378 (1989)] and deoxyadenosine [Nelson et al. Radiat. Res. 149,75-86 (1998)], which have similar hydrogen-bonding environment to ara-A, were studied, and radical R2 (the adenine anion protonated at N3) and radical R1 (the adenine cation deprotonated at the amino) were reported. Based on these observations, the previous work proposed a model for radical stabilization based on the possibility of proton transfers within the hydrogen bonding networks in the crystals.
In this work, Radical R2 was identified and its magnetic properties were characterized. However, the experiment found no evidence for the amino-deprotonated structure R1. Based on this evidence, that the R1 structure was not stabilized in ara-A, a refinement to the previous proton transfer model is proposed.