Hydrogen-Atom Addition to Nucleobases in the Solid State: Characterization of the Corresponding Muoniated Radicals Using μSR.

The radicals formed by muonium (Mu) addition to four nucleobases (adenine, guanine, cytosine, and thymine) have been characterized by avoided level-crossing muon spin resonance (ALC-μSR). Mu is considered to be a light isotope of the hydrogen atom, and the muoniated radicals observed by ALC-μSR are isotopomers of the radicals initially produced by H addition to the nucleobases. The observed radicals have been assigned by considering the relative energies of the possible radicals reported in the literature and comparing the experimental muon and proton hyperfine coupling constants with values from previously reported electron paramagnetic resonance and ab initio calculations that have been scaled to account for the larger magnetic moment of the muon and its lighter mass compared with the proton. Mu addition is observed to occur only at secondary carbons of the purine rings in adenine and guanine. Mu adds to C8 and C2 of adenine with the relative amount being ∼70:30%, and Mu adds exclusively to C8 of guanine. Mu addition is predominantly to the secondary carbons of the pyrimidine ring in cytosine (C5 and C6 with relative yields ∼80:20%) with a small amount of addition at N3. Mu adds to both the secondary C6 and tertiary C5 in thymine with approximately equal yields as well as the O4 adduct being a minor product.