By Derek Horton
Seeing that its inception in 1945, this serial has supplied serious and integrating articles written by way of learn experts that combine commercial, analytical, and technological facets of biochemistry, natural chemistry, and instrumentation technique within the learn of carbohydrates. The articles supply a definitive interpretation of the present prestige and destiny traits in carbohydrate chemistry and biochemistry.
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Additional info for Advances in Carbohydrate Chemistry and Biochemistry, Vol. 62
The applicability of Eqs. (53) and (54) to similar coupling pathways was investigated for 3JC-2,HO-1, 3JC-3,HO-2, 3JC-5,HO-4, and 3 JC-1,HO-2 in additional model structures, using only staggered H–O–C–C torsion angles. Consideration of the presence or absence of terminal in-plane electronegative substituent effects led to a further equation for pathways without these effects: 44 B. COXON B θ (d eg) 180 120 60 0 –60 –120 –180 eg) 0 eg) θ (d eg) eg) 3J 180 120 60 0 –60 –120 –180 ω (d ω (d eg) 180 120 60 0 –60 –120 –180 8 6 4 2 0 60 12 0 18 0 θ (d 60 12 0 18 0 CCOH 0 –1 8 –1 0 20 –6 0 0 5 3J 10 CCOH (HZ) D –1 8 –1 0 20 –6 0 0 C 5 ω (d ω (d eg) 180 120 60 0 –60 –120 –180 60 12 0 18 0 (HZ) eg) 60 12 0 18 0 –1 8 –1 0 20 –6 0 0 3J 0 θ (d (HZ) 10 CCOH 5 3J CCOH 10 –1 8 –1 0 20 –6 0 0 (HZ) A Fig.
0 Hz) for 3JCCOP, but since these equations were constructed in tandem, there is a small influence on 3JHCOP. On the basis of this reparametrization,110 seven equations were presented that related the populations of the b and g conformers to the values of 3JH,P and 3JC,P. It was recognized that the parametrization is a little weak in the 0 –60 region, as only one indirectly estimated value of 3JC,P was available, for ’ ¼ 60 . The A, B, and C parameters were modified again by Plavec and Chattopadhyaya111 based on 17 values of 3JC,P and the corresponding X-ray derived torsion angles for 30 ,50 -cyclonucleotides, giving: 3 JCCOP ¼ 9:1 cos2 ’ À 1:9 cos ’ þ 0:8 ð71Þ Inclusion of the coupling constants of ‘‘strained’’ cyclonucleotides had been criticized earlier.
For non-anomeric protons, inclusion of only the Fermi contact term resulted in a generalized Karplus equation: 3 JHCOH ¼ 6:06 À 3:26 cos ’ þ 6:54 cos 2’ ð30Þ which is similar to Eq. (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.
Advances in Carbohydrate Chemistry and Biochemistry, Vol. 62 by Derek Horton