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

By Derek Horton

ISBN-10: 0123747430

ISBN-13: 9780123747433

Seeing that its inception in 1945, this serial has supplied serious and integrating articles written by way of examine experts that combine business, analytical, and technological facets of biochemistry, natural chemistry, and instrumentation method within the learn of carbohydrates. The articles offer a definitive interpretation of the present prestige and destiny developments in carbohydrate chemistry and biochemistry.

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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.

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.

5–6 Hz expected122 for ’CCOC ¼ 0 and 2–4 Hz for ’CCOC ¼ 180 . In most Karplus equations of the three-parameter type, the B coefficient (of the cos’ term) for positive coupling constants is negative, which leads to an increased value of the coupling for ’ ¼ 180 over that for ’ ¼ 0 . 122 excluded the cos ’ term from Eq. (75) and refitted their data to give a simplified equation: 3 JCCOC ¼ 3:49 cos2 ’ þ 0:16 ð76Þ which they stated was better supported by the available data, and which corresponds to identical maxima for ’ ¼ 0 and 180 .

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


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