Three-Bond Sugar-Base Couplings in Purine versus Pyrimidine Nucleosides: A DFT Study of Karplus Relationships for 3JC2/4-H1' and 3JC6/8-H1' in DNA

MUNZAROVÁ, Markéta and Vladimír SKLENÁŘ. Three-Bond Sugar-Base Couplings in Purine versus Pyrimidine Nucleosides: A DFT Study of Karplus Relationships for 3JC2/4-H1' and 3JC6/8-H1' in DNA. Journal of the American Chemical Society. Washington, D.C.: American Chemical Society, 2002, vol. 124, No 36, p. 10666-10667. ISSN 0002-7863.

Basic information

• Original name: Three-Bond Sugar-Base Couplings in Purine versus Pyrimidine Nucleosides: A DFT Study of Karplus Relationships for 3JC2/4-H1' and 3JC6/8-H1' in DNA
• Authors: MUNZAROVÁ, Markéta (203 Czech Republic) and Vladimír SKLENÁŘ (203 Czech Republic, guarantor).
• Edition: Journal of the American Chemical Society, Washington, D.C. American Chemical Society, 2002, 0002-7863.

Other information

• Original language: English
• Type of outcome: Article in a journal
• Field of Study: 10403 Physical chemistry
• Country of publisher: Czech Republic
• Confidentiality degree: is not subject to a state or trade secret
• Impact factor: Impact factor: 6.201
• RIV identification code: RIV/00216224:14310/02:00006453
• Organization unit: Faculty of Science
• Keywords in English: NUCLEIC-ACIDS; CONSTANTS; OLIGONUCLEOTIDES
• Tags: CONSTANTS, NUCLEIC-ACIDS, Oligonucleotides

Abstract

3JC2/4-H1' and 3JC6/8-H1' scalar spin-spin coupling constants have been calculated for deoxyadenosine, deoxyguanosine, deoxycytidine, and deoxythymidine as functions of the glycosidic torsion angle c by means of density functional theory. Except for deoxythymidine, 3JC2/4-H1' depends little on the base type. On the contrary, 3JC6/8-H1' follow the usual trans to cis ratio (3JC-H(cis) < 3JC-H(trans)) for purine nucleosides but reveal the opposite relation (3JC-H(cis) > 3JC-H(trans)) for pyrimidine nucleosides. Our results compare well with the experiment for deoxyguanosine and predict a novel trend in the case of pyrimidine bases for which no NMR results are available in the syn region. A breakdown of the key Fermi contact part of 3JC6/8-H1' into MO contributions rationalizes this trend in terms of an unusual coupling mechanism in the syn orientation that is very effective for pyrimidine nucleosides and considerably weaker for purine nucleosides.

Links

• LN00A016, research and development project: Name: BIOMOLEKULÁRNÍ CENTRUM

Investor: Ministry of Education, Youth and Sports of the CR, Biomolecular Center