By Derek Horton
When you consider that its inception in 1945, this serial has supplied serious and integrating articles written via examine experts that combine commercial, analytical, and technological elements of biochemistry, natural chemistry, and instrumentation technique within the research of carbohydrates. The articles offer a definitive interpretation of the present prestige and destiny traits in carbohydrate chemistry and biochemistry.
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Extra info for Advances in Carbohydrate Chemistry and Biochemistry, Vol. 62
29) of Fraser et al. The results from inclusion of all four contributions showed that the spin–dipolar term is negligible, whereas the paramagnetic spin–orbital and diamagnetic spin–orbital terms have comparable magnitudes, but opposite signs, thus leading to a slightly modified equation: 3 JHCOH ¼ 5:76 À 2:05 cos ’ þ 6:78 cos 2’ ð31Þ The situation is more complicated for 3JHCOH involving the C-1–O-1 bond, because in one of the rotamers about this bond, HO-1 is anti to O-5, which (by Booth’s effect) reduces the value of 3JHCOH in this rotamer, causing the magnitudes of the two gauche DEVELOPMENTS IN THE KARPLUS EQUATION 35 A 20 Computed 3JH1, O1H (Hz) couplings to be non-equivalent, and the derived Karplus curve to be phase-shifted relative to that predicted from Eq.
The third rotamer was gauche and was associated exclusively with the S-type sugar ring, with the value e(-, S) ¼ 266 . Within experimental error, the magnitudes of these three angles were found to be independent of base sequence, with one exception: d(CG), which had e(t, S) ¼ 197 . 109 measured JHH in the deoxyribose ring by 2D and 3D HCCH-E. COSY, JCH couplings across the glycosidic torsion angle w (see Fig. 8) by refocused HMBC, and 2JCP and 3JHP about the backbone torsion angle e by a P-FIDS-CT-HSQC experiment.
36 Hz. 03 for NH2, NHR, NR2, OH, OR, and R ¼ alkyl. 58,59 MCSCF ab initio calculations of 3JHCCH in ethane have given the 32 B. 60 In a different approach,61 3JHCCH values (and also 1JCH and 2JHCH) have been computed by DFT methods for exocyclic hydroxymethyl groups on aldopyranosyl rings, and the values compared with experiment and correlated with the O-5–C-5–C6–O-6 torsion angle o, according to the equations: 3 JHÀ5;HÀ6R ¼ 5:08 þ 0:47 cos o þ 0:90 sin o À 0:12 cos 2o þ 4:86 sin 2o ð22Þ 3 JHÀ5;HÀ6S ¼ 4:92 À 1:29 cos o þ 0:05 sin o þ 4:58 cos 2o þ 0:07 sin 2o ð23Þ These relationships have been confirmed by DFT calculations on hydroxymethyltetrahydropyran analogues of aldohexopyranosides,62 using a set of staggered and eclipsed geometries, which on least-squares fitting of the theoretical coupling constants yielded: 3 JHÀ5;HÀ6R ¼ 5:06 þ 0:45 cos o þ 0:80 sin o À 0:90 cos 2o þ 4:65 sin 2o ð24Þ 3 JHÀ5;HÀ6S ¼ 4:86 À 1:22 cos o þ 0:04 sin o þ 4:32 cos 2o þ 0:07 sin 2o ð25Þ This study62 also led to the equation: 2 JHÀ6R;HÀ6S ¼ À10:97 þ 0:11 cos o þ 0:59 cos 2o À 0:79 cos y þ 2:00 cos 2y ð26Þ reflecting the dependence of this geminal coupling on both of the torsion angles o and y, about C-5–C-6 and C-6–O-6, respectively, and the more significant dependence on y.