By Derek Horton

Considering that its inception in 1945, this serial has supplied severe and integrating articles written by way of examine experts that combine commercial, analytical, and technological points of biochemistry, natural chemistry, and instrumentation method within the examine of carbohydrates. The articles supply a definitive interpretation of the present prestige and destiny tendencies in carbohydrate chemistry and biochemistry.

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018 Hz, and a maximum 28 B. 06 Hz, but the parent ethane and monohalo- and 1,1-dihalo-ethanes were exceptions that had to be parametrized differently. 49 The theoretical coupling constants generated in this study were fitted by expanding Pachler’s equation [Eq. 50 suggested that it could be approximated by the function: DJ ¼ T cos2 ðP À Pb Þ ð16Þ where ÁJ is a decrease in the size of the coupling due to the transmission effect, P is the phase angle of pseudorotation in the five-membered ring, Pb is the phase angle of the envelope form for which a maximum effect is reached, and T depends strongly on the nature of the atom through whose orbitals the effect is transmitted.

2 Hz between experimental and back-calculated 3JCCOP values. This deviation was slightly smaller than that achieved with the three-parameter Eq. 111 5. Carbon–Carbon Couplings Due to NMR sensitivity constraints, these coupling constants have most often been measured by use of selectively or uniformly 13C-substituted compounds. 112 Complete sets of 1JCC, 2JCC, and 3JCC couplings constants were measured for sucrose and the methyl D-fructofuranosides by 1D 13C NMR, with assistance from 1D 13C INADEQUATE, for which various mixing times were used to observe selectively, carbon nuclei coupled to the 13C-substituted site.

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  GÞ È Â ÃÉ þ H D À E cos2 ðÀ’ðxÞ þ F  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.

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Advances in Carbohydrate Chemistry and Biochemistry, Vol. 62 by Derek Horton
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