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Energetic, Topological and Electric Field Analyses of Cation‐Cation Nucleic Acid Interactions in Watson‐Crick Disposition
Author(s) -
Alkorta Ibon,
Mata Ignasi,
Molins Elies,
Espinosa Enrique
Publication year - 2019
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201800878
Subject(s) - chemistry , electrophile , nucleophile , molecular structure of nucleic acids: a structure for deoxyribose nucleic acid , lone pair , hydrogen bond , heteroatom , acceptor , cationic polymerization , crystallography , electric field , computational chemistry , stereochemistry , molecule , base pair , organic chemistry , ring (chemistry) , dna , biochemistry , physics , quantum mechanics , condensed matter physics , catalysis
A theoretical study of the effect of the diprotonation on the nucleic acid bases (A : U, A : T and G : C) in Watson‐Crick conformation has been carried out by means of DFT computational methods in vacuum. In addition, the corresponding neutral and monoprotonated binary complexes have been considered. Most of the diprotonated species studied are stable, even though the binding energy is positive due to the overall repulsive electrostatic term. Local electrostatic attractive forces in the regions of hydrogen bonds (HBs) are responsible for equilibrium geometries, as shown by the electric field lines connecting the electrophilic and nucleophilic sites involved in the HB interactions. Secondary electrostatic effects also affect the assembling of the nucleic acid complexes in either neutral or cationic form. In particular, the electric field lines flowing from electrophilic sites in one base to nucleophilic sites in the other reinforce the linking between them. Hence, when the nucleophilic site concerns the free lone pair of the heteroatom involved in the HB interaction as acceptor, the HB distance shortens. However, if the free lone pair of the HB acceptor interacts with an electrophilic site in the same molecule, the HB distance elongates, weakening the HB interaction. The topological analysis of the electron density distribution in HB regions indicates that neutral, monoprotonated and diprotonated complexes show no differences in the nature of their HB's.