A NUCLEAR-MAGNETIC-RESONANCE SPECTROSCOPIC INVESTIGATION OF KDO-CONTAINING OLIGOSACCHARIDES RELATED TO THE GENUS-SPECIFIC EPITOPE OF CHLAMYDIA LIPOPOLYSACCHARIDES

The H-1- and C-13-NMR parameters, chemical shifts and coupling constants, for the pentasaccharide of the genus-specific epitope of Chlamydia lipopolysaccharide and related di-, tri-. and tetra-saccharides have been measured and assigned completely using 1D and 2D techniques, and their structures have been confirmed. NOE experiments indicated the preferred conformation of the pentasaccharide and the component oligosaccharides. The 3J(H,H) demonstrate a change in conformation by rotation of the C-6-C-7 bond of the side chain of the (2 --> 8)-linked Kdo (unit b) in alpha-Kdo-(2 --> 8)-alpha-Kdo-(2 --> 4)-alpha-Kdo-(2 --> 6)-beta-GlcN-(1 --> 6)-GlcNol, alpha-Kdo-(2 --> 8)-alpha-Kdo-(2 --> 4)-alpha-Kdo-(2 --> 6)-beta-GlcNAc-(1 --> O)-allyl, and alpha-Kdo-(2 --> 8)-alpha-Kdo-(2 --> 4)-alpha-Kdo-(2 --> O)-allyl relative to that preferred in alpha-Kdo-(2 --> 4)-alpha-Kdo-(2 --> 6)-beta-GlcNAc-(1 --> O)-allyl, alpha-Kdo-(2 --> 8)-alpha-Kdo-(2 --> O)-allyl, alpha-Kdo-(2 --> 4)-alpha-Kdo-(2 --> O)-allyl, and alpha-Kdo-(2 --> 6)-beta-GlcNAc-(1 --> O)-allyl. irrespective of the size of the aglycon, e.g., allyl or beta-D-GlcN residues. The conformational results have been substantiated by computer calculations using the HSEA approach.