title: Computational studies of electronic circular dichroism spectra predict absolute configuration assignments for the guanine oxidation product 5-carboxamido-5-formamido-2-iminohydantoin.
abstract: Oxidation of the guanine heterocycle by two electrons can yield the chiral product 5-carboxamido-5-formamido-2-iminohydantoin (2Ih). The2Ihfree base enantiomers were synthesized from 2'-deoxyguanosine oxidized with a Cu(II)/H2O2oxidant system followed by hydrolysis of theN-glycosidic bond. These isomers were each studied by electronic circular dichroism spectroscopy for determination of their absolute configurations. Time-dependent density functional theory calculations of the expected spectra were completed in both the gas phase and with solvent modeling in order to interpret the experimental spectra and provide the absolute configuration assignments.
authors.affiliation: Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112-0850, USA.
authors.forename: Aaron M
authors.initials: AM
authors.lastname: Fleming
authors.affiliation: Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112-0850, USA.
authors.forename: Omar
authors.initials: O
authors.lastname: Alshykhly
authors.affiliation: Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112-0850, USA ; Center for High Performance Computing, University of Utah, Salt Lake City, Utah 84112-0190, USA.
authors.forename: Anita M
authors.initials: AM
authors.lastname: Orendt
authors.affiliation: Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112-0850, USA.
authors.forename: Cynthia J
authors.initials: CJ
authors.lastname: Burrows
keywords: 2-Iminohydantoin; Electronic Circular Dichroism; Guanine Oxidation; Time-dependent Density Functional Theory