No abstract

We studied for the first time 16 tautomers/rotamers of diphosphocytosine by four computational methods. Some of these tautomers/rotamers are isoenergetic although they have different structures. High-level electron correlation MP2 and MP4(SDQ) ab initio methods and density functional methods employing a B3LYP and the new M06-2X functional were used to study the structure and relative stability of 16 tautomers/rotamers of diphosphocytosine. The dienol tautomers of diphosphocytosine are shown to be much more stable than the keto-enol and diketo forms. The tautomers/rotamers stability could be ranked as PC3 = PC12 < PC2 = PC11 < PC1 < PC10 < PC8 < PC9 < PC15 < PC16 < PC6 ∼ PC7 < PC13 < PC4 ∼ PC14 < PC5. This stability order was discussed in the light of stereo and electronic factors. Solvation effect has been modeled in a high dielectric solvent, water using the polarized continuum model (PCM). Consideration of the solvent causes some reordering of the relative stability of diphosphocytosine tautomers: PC3 ∼ PC12 ∼ PC2 ∼ PC11 < PC1 < PC10 < PC8 < PC9 < PC15 ∼ PC16 < PC13 < PC6 ∼ PC7 ∼ PC14 < PC4 ∼ PC5.