Evaluating the Effects of the Nonplanarity of Nucleic Acid Bases on NMR, IR, and Vibrational Circular Dichroism Spectra: A Density Functional Theory Computational Study

0347407 - ÚOCHB 2011 RIV US eng J - Článek v odborném periodiku
Vokáčová, Zuzana - Trantírek, Lukáš - Sychrovský, Vladimír
Evaluating the Effects of the Nonplanarity of Nucleic Acid Bases on NMR, IR, and Vibrational Circular Dichroism Spectra: A Density Functional Theory Computational Study.
Journal of Physical Chemistry A. Roč. 114, č. 37 (2010), s. 10202-10208. ISSN 1089-5639. E-ISSN 1520-5215
Grant CEP: GA ČR GPP208/10/P398; GA ČR GAP205/10/0228
Výzkumný záměr: CEZ:AV0Z40550506; CEZ:AV0Z60220518
Klíčová slova: 3J(C8/6-H1' * 3JC4/2-H1' * VCDS
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 2.732, rok: 2010

The pyramidalizations of N9/1 glycosidic nitrogens in DNA and RNA nucleosides were found to have significant effects on the structural interpretation of the 3J(C4/2-H1′) and 3J(C8/6-H1′) NMR scalar couplings in purine/pyrimidine nucleosides. The calculated structural deforomations in nucleosides are depended on sugar-to-base orientation. The sign alternation of this correction in syn and anti nucleosides arises from the stereoinversion of the N9/1 glycosidic nitrogen occurring upon reorientation of the glycosidic torsion. Utilization of the calculated phase-shift corrections in the design of Karplus equations for the 3J couplings was suggested, and the effects on structural interpretation of the experimental couplings were evaluated. The calculated effects on IR and vibrational circular dichroism (VCD) spectra were only minor.
Trvalý link: http://hdl.handle.net/11104/0006022