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. |
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@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.
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