An ab initio SCF study on the tautomerisation of fapy-guanine

• Published in: Journal of molecular structure. Theochem 1996-09, Vol.369 (1), p.93-104
• Main Authors: Cysewski, Piotr, Jeziorek, Danuta, Oliński, Ryszard
• Format: Article
• Language: English
• Subjects: 2,6-Diamino-4-hydroxy-5-formamidopyrimidine; Ab initio calculation; Fapy-guanine; Tautomerism
• ISSN: 0166-1280; 1872-7999
• DOI: 10.1016/S0166-1280(96)04596-4

The quantum chemistry calculations were performed on the fapy-guanine tautomers. The semiempirical PM3 as well as ab initio (STO-3G, 6-31G, 6-31G ∗) methods were used for geometry optimisations. The gradient minimisation (6-31G ∗) was followed by single point correlation energy estimation in the MP2 (6-31G ∗) terms. The fapy-guanine may have a complicated structure. Among a variety of potential tautomers two seem to be dominant. The most stable in the isolated state is the di-keto-di-amino isomer. The next stable structure corresponding to 4-enol-8-keto-2,6-diamino tautomer is about 2 kcal mol −1 (6-31G ∗ MP2) above the most stable one. The third tautomer (6,8-diketo-2-imino-9-amino) is destabilised by more than 10 kcal mol −1. The rest of tautomers are even less stable. Thus the fapy-guanine exists in the isolated state mainly as a mixture of two tautomers with predominantly the first structure. As a result in the significant differences in the electrostatic potential properties these tautomers are supposed to have different miscoding potential.