2003
The effect of water on NMR spin-spin couplings in DNA: Improvement of calculated values by application of two solvent models
SYCHROVSKÝ, Vladimír, Bohdan SCHNEIDER, Pavel HOBZA, Lukáš ŽÍDEK, Vladimír SKLENÁŘ et. al.Základní údaje
Originální název
The effect of water on NMR spin-spin couplings in DNA: Improvement of calculated values by application of two solvent models
Autoři
SYCHROVSKÝ, Vladimír (203 Česká republika), Bohdan SCHNEIDER (203 Česká republika), Pavel HOBZA (203 Česká republika), Lukáš ŽÍDEK (203 Česká republika) a Vladimír SKLENÁŘ (203 Česká republika, garant)
Vydání
Physical Chemistry Chemical Physics, Great Britain, ROYAL SOC CHEMISTRY, 2003, 1463-9076
Další údaje
Jazyk
angličtina
Typ výsledku
Článek v odborném periodiku
Obor
10403 Physical chemistry
Stát vydavatele
Velká Británie a Severní Irsko
Utajení
není předmětem státního či obchodního tajemství
Impakt faktor
Impact factor: 1.959
Kód RIV
RIV/00216224:14310/03:00007956
Organizační jednotka
Přírodovědecká fakulta
UT WoS
000181278300011
Klíčová slova anglicky
NMR; coupling constants; DNA hairpin DFT
Štítky
Změněno: 20. 6. 2008 12:55, prof. RNDr. Vladimír Sklenář, DrSc.
Anotace
V originále
A water solvent effects on isotropic one-bond 1J(X,H), 1J(C,X) and two-bond 2J(X,H), (X=C,N) indirect NMR spin-spin coupling constants measured previously in 13C, 15N-labeled DNA hairpin molecule d(GCGAAGC) were investigated theoretically at ab initio level by application of explicit and PCM models of solvent. Sensitivity of the Fermi contact contribution to the total J coupling towards the solvent inclusion calculated using coupled perturbed density functional theory with B3LYP hybrid functional is dominating, while the solvent shifts of the other three J contributions are negligible. Consideration of the solvent leads to the noticeable shift of especially 1J(C,H) couplings. The largest shift of 6.1 Hz was found for 1J(C8,H8) coupling in guanine. Further inclusion of solvent decreases mean absolute deviation between calculated and experimental J constants from 1.7 to 1.1 Hz for guanine, from 2.4 to 0.6 Hz for cytosine, and from 2.3 to 1.6 Hz for adenine. In the case of explicit solvent, the 1J(C8,H8) solvent shift seems to be sensitive to the magnitude of charge transfer from water sigma bonding O-H and Oxygen lone pair orbitals to the sigma* antibonding C8-H8, C8-N7, and C8-N9 orbitals of guanine. Both explicit and PCM solvent models provide similar improvement of calculated couplings.
Návaznosti
GA203/96/1513, projekt VaV |
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MSM 143100005, záměr |
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