By Derek Horton
Because its inception in 1945, this serial has supplied serious and integrating articles written by way of learn experts that combine commercial, analytical, and technological features of biochemistry, natural chemistry, and instrumentation technique within the examine of carbohydrates. The articles offer 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
48 studied the electronegativity dependence of the torsion angle-independent term A in equations such as (7). 02 Hz. 48 A least-squares fit was applied to the J values of 55 mono- and 38 1,1-di-substituted ethanes, including 22 isopropyl derivatives. Altona et al. also proposed that any nonadditivity or interaction effect on the coupling constants could be described well by the introduction of cross terms, including the product of either the electronegativity differences, ÁwiÁwj, or of the substituent constants, lilj.
In fitting data to the modified equation, the experimental coupling constants were weighted by the reciprocals of the assigned precisions. 56 Plotting of Mullay’s group electronegativities, wsub against 26 3JHCCH values for substituted ethanes revealed a good linear relationship: 3 JHCCH ¼ A þ Bðwsub À wH Þ ¼ A þ BDwi ð17Þ 30 B. 2088. 56 The cos3’ and cos2 2’ terms represent testing of logical extensions of the series of terms in the original Karplus equation [Eq. (2)], and in Eq. (18), the angle yi subtended by the electronegative substituent with respect to a coupled proton has been parametrized separately from the HCCH dihedral angle ’, or the cos (’ þ 120 ) and cos (’ À 120 ) terms used in other studies.
56 However, Eq. 56 Some 14 years after publication of the original Haasnoot equation, it was reparametrized to include a li group electronegativity scale and specific parameters for substituted ethane derivatives,57 regardless of degree of substitution: 3 JHCCH ¼ 14:63 cos2 ’ À 0:78 cos ’ þ 0:60 X Â Ã þ li 0:34 À 2:31 cos2 ðsi ’ þ 18:4jli jÞ ð20Þ i where the sign parameter is now si ¼ Æ 1. 57 Molecular geometries were recalculated using the MM2-85 force field. 36 Hz. 03 for NH2, NHR, NR2, OH, OR, and R ¼ alkyl.
Advances in Carbohydrate Chemistry and Biochemistry, Vol. 62 by Derek Horton