The conformational analysis of oligosaccharides by H-NMR and HSEA calculation.

Abstract:

:The application of 1H-nuclear Overhauser enhancement, 1H-spin-lattice-relaxation-time and 1H-chemical shift measurements for the assessment of the conformational preferences of oligosaccharides are briefly reviewed. It is demonstrated that additivity rules, for the correlation of the chemical shifts of similar hydrogen atoms in different oligosaccharides, can be useful in the conformational analysis of oligosaccharides when the differential chemical shifts are greater than 0.1 ppm. These often can be attributed to specific interunit deshielding of a hydrogen atom by an oxygen atom with which it is in strong nonbonded interaction. HSEA calculations are used to demonstrate that differential chemical shifts of less than 0.1 ppm can have origins that are not significant to the overall conformational preferences of the oligosaccharides which are being compared. Both shielding and deshielding effects can arise from a change in the orientation of a substituent group as the result of the introduction of a sugar on a neighboring unit. It is demonstrated that substituent groups, such as hydroxymethyl and acetamido groups, on occasions, should be treated in HSEA calculations as freely rotating about their linkage to a pyranose ring.

journal_name

Arch Biochem Biophys

authors

Lemieux RU,Bock K

doi

10.1016/0003-9861(83)90128-5

subject

Has Abstract

pub_date

1983-02-15 00:00:00

pages

125-34

issue

1

eissn

0003-9861

issn

1096-0384

pii

0003-9861(83)90128-5

journal_volume

221

pub_type

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