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

J 2002

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

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

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10403 Physical chemistry

Country of publisher

Czech Republic

Confidentiality degree

není předmětem státního či obchodního tajemství

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

Abstract

V originále

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

Citovat

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.

@article{405486,
   author = {Munzarová, Markéta and Sklenář, Vladimír},
   article_location = {Washington, D.C.},
   article_number = {36},
   keywords = {NUCLEIC-ACIDS; CONSTANTS; OLIGONUCLEOTIDES},
   language = {eng},
   issn = {0002-7863},
   journal = {Journal of the American Chemical Society},
   title = {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},
   volume = {124},
   year = {2002}
}

TY  - JOUR
ID  - 405486
AU  - Munzarová, Markéta - Sklenář, Vladimír
PY  - 2002
TI  - 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
JF  - Journal of the American Chemical Society
VL  - 124
IS  - 36
SP  - 10666
EP  - 10666
PB  - American Chemical Society
SN  - 00027863
KW  - NUCLEIC-ACIDS
KW  - CONSTANTS
KW  - OLIGONUCLEOTIDES
N2  - 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.
ER  -

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. \textit{Journal of the American Chemical Society}. Washington, D.C.: American Chemical Society, 2002, vol.~124, No~36, p.~10666-10667. ISSN~0002-7863.

Detailed Information on Publication Record