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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F02%3A00006453" target="_blank" >RIV/00216224:14310/02:00006453 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216224:14310/06:00016826

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/LN00A016" target="_blank" >LN00A016: BIOMOLEKULÁRNÍ CENTRUM</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2006

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

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Svazek periodika

124

Číslo periodika v rámci svazku

36

Stát vydavatele periodika

CZ - Česká republika

Počet stran výsledku

2

Strana od-do

10666

Kód UT WoS článku

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EID výsledku v databázi Scopus

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