10.1021/ja0367041.s001
Elke Duchardt
Elke
Duchardt
Christian Richter
Christian
Richter
Oliver Ohlenschläger
Oliver
Ohlenschläger
Matthias Görlach
Matthias
Görlach
Jens Wöhnert
Jens
Wöhnert
Harald Schwalbe
Harald
Schwalbe
Determination of the Glycosidic Bond Angle χ in RNA from
Cross-Correlated Relaxation of CH Dipolar Coupling and N
Chemical Shift Anisotropy
American Chemical Society
2004
angle χ
heteronuclear NMR pulse sequence
RNA structure calculations
CH Dipolar
glycosidic torsion angle χ
13 C
3 J
NMR experiments
10 degrees
mer
HCN
Glycosidic Bond Angle χ
torsion angle information
determination
N Chemical Shift Anisotropy
15 N chemical shift tensors
2004-02-25 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Determination_of_the_Glycosidic_Bond_Angle_in_RNA_from_Cross_Correlated_Relaxation_of_CH_Dipolar_Coupling_and_N_Chemical_Shift_Anisotropy/3348613
A new heteronuclear NMR pulse sequence, the quantitative Γ(HCN) experiment, for the
determination of the glycosidic torsion angle χ in <sup>13</sup>C,<sup>15</sup>N-labeled oligonucleotides is described. The Γ(HCN)
experiment allows measurement of CH dipole−dipole, N chemical shift anisotropy cross-correlated relaxation
rates (
and
for pyrimidines and
and
for purines). A nucleotide-specific
parametrization for the dependence of these Γ-rates on χ based on <sup>15</sup>N chemical shift tensors determined
by solid-state NMR experiments on mononucleosides (Stueber, D.; Grant, D. M. <i>J. Am. Chem. Soc</i>. <b>2002</b>,
<i>124</i>, 10539−10551) is presented. For a 14-mer and a 30-mer RNA of known structures, it is found that the
Γ(HCN) experiment offers a very sensitive parameter for changes in the angle χ and allows restraining of
χ with an accuracy of around 10 degrees for residues which do not undergo conformational averaging.
Therefore, the Γ(HCN) experiment can be used for the determination of χ in addition to data derived from
<sup>3</sup><i>J</i>(C,H)-coupling constants. As shown for the 30-mer RNA, the derived torsion angle information can be
incorporated as additional restraint, improving RNA structure calculations.