By Derek Horton
Due to the fact its inception in 1945, this serial has supplied severe and integrating articles written by means of examine experts that combine commercial, analytical, and technological facets of biochemistry, natural chemistry, and instrumentation technique within the research of carbohydrates. The articles offer a definitive interpretation of the present prestige and destiny tendencies in carbohydrate chemistry and biochemistry.
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Extra resources for Advances in Carbohydrate Chemistry and Biochemistry, Vol. 62
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.
5144. 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.
Wi is the difference in electronegativity between the a-substituent and hydrogen on the Huggins scale and, as before, x is the ‘‘sign’’ parameter that takes values of þ1 or À1, depending on the orientation of the substituent (see Fig. 2). 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.