By Derek Horton
Due to the fact its inception in 1945, this serial has supplied severe and integrating articles written via study experts that combine commercial, analytical, and technological points of biochemistry, natural chemistry, and instrumentation technique within the research of carbohydrates. The articles supply a definitive interpretation of the present prestige and destiny tendencies in carbohydrate chemistry and biochemistry.
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Additional info for Advances in Carbohydrate Chemistry and Biochemistry, Vol. 62
Calculations using the GAUSSIAN03 program indicated that non-FC contributions to 3JC-1,HO-2 were negligible. 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.
Dihedral angles were derived from MM2 force field calculations, and when substituent effects from branching and methyl substitution in the norbornanes were taken into account, the following equation was obtained: 3 JHCCC ¼ 4:50 À 0:87 cos ’ þ 4:03 cos 2’ ð46Þ 42 B. 92 In sugars, the 13C resonance of a deuterium-substituted carbon may disappear,93 due either to quadrupolar relaxation by deuterium, and/or to saturation caused by lengthening of the 13C T1 on replacement of dipolar relaxation by a proton with the weaker effect of a deuteron.
A threestep procedure was used to construct a Haasnoot–Altona equation. 833. Secondly, by using the A, B, and C values from Eq. (41), the effect of anomeric configuration was accounted for by fitting the data for the a-furanosides to the full Haasnoot–Altona equation: 3 JCÀ1;HÀ4 ¼ A cos2 ’ þ B cos ’ þ C È Â ÃÉ þ G D À E cos2 ð’ðxÞ þ F Â GÞ È Â ÃÉ þ H D À E cos2 ðÀ’ðxÞ þ F Â HÞ ð42Þ where G and H are the electronegativities of the substituents at C-1, thereby giving: 3 JCÀ1;HÀ4 ðaÞ ¼ 8:14 cos2 ’ À 0:61 cos ’ À 0:15 È Â ÃÉ þ G 0:71 À 1:46 cos2 ð’ðxÞ þ 44:3GÞ È Â ÃÉ þ H 0:71 À 1:46 cos2 ðÀ’ðxÞ þ 44:3HÞ ð43Þ DEVELOPMENTS IN THE KARPLUS EQUATION 41 In the same manner, an equation was constructed for the b-glycosides: 3 JCÀ1;HÀ4 ðbÞ ¼ 8:14 cos2 ’ À 0:61 cos ’ À 0:15 È Â ÃÉ þ G 0:72 À 1:47 cos2 ð’ðxÞ þ 40:1GÞ È Â ÃÉ þ H 0:72 À 1:47 cos2 ðÀ’ðxÞ þ 40:1H Þ ð44Þ Thirdly, the D–F values from the 3JC-1,H-4 (a) and (b) equations were averaged to give: 3 JCÀ1;HÀ4 ¼ 8:14 cos2 ’ À 0:61 cos ’ À 0:15 È Â ÃÉ þ G 0:71 À 1:46 cos2 ð’ðxÞ þ 42GÞ È Â ÃÉ þ H 0:71 À 1:46 cos2 ðÀ’ðxÞ þ 42HÞ ð45Þ The curve from this equation was similar to that from Eq.