Ultraviolet photoelectron studies of biological purines: the valence electronic structure of adenine.

AUTOR(ES)

Peng, S

RESUMO

The UV photoelectron spectra of adenine, 9-methyladenine, and 6-methylaminopurine contain highly resolved bands arising from the six highest occupied molecular orbitals. The spectra have been analyzed using UV absorption data, photoelectron data from previous studies of heterocyclic compounds, and results from both semi-empirical and ab initio molecular orbital calculations. The analysis indicates that the first, third, and fifth photoelectron bands in adenine and the two methyl substituted derivatives arise from pi orbitals. The second, fourth, and sixth bands arise from nitrogen atom lone-pair orbitals. Compared to adenine, the six uppermost orbitals of 9-methyladenine and 6-methylaminopurine have lower ionization potentials. This destabilization of the valence electrons is expected to play an important role in causing the increase in base stacking forces observed in methyl substituted adenines.

Documentos Relacionados

• Mechanism of stimulation of respiration by purines: I. Inhibitor studies 1
• Three recognition events at the branch-site adenine.
• The Pairwise Correlated Generalized Valence Bond Model of Electronic Structure I; The Estimation of Pair Energies from Orbital Overlaps
• Misincorporation of dAMP opposite 2-hydroxyadenine, an oxidative form of adenine.
• 23S ribosomal ribonucleic acid of macrolide-producing streptomycetes contains methylated adenine.