Table I.
Unita |
3JH1,H2 (Hz) |
3JH2,H3 (Hz) |
|||||
---|---|---|---|---|---|---|---|
NMRb | QM calculatedc | Karplus derivedd | NMR | QM calculated | Karplus derived | ||
α-l-Fucp | 4.4 ± 0.9 | 4.9 ± 0.8 | 2.9 ± 0.5 | 11.6 ± 2.3 | 10.0 ± 0.5 | 7.1 ± 0.3 | |
Cr | 2-Sulfated α-l-Fucp | 4.5 ± 0.9 | 4.5 ± 1.2 | 3.1 ± 0.5 | 10.2 ± 2.0 | 9.8 ± 0.9 | 7.0 ± 0.4 |
Br | 2,4-Disulfated α-l-Fucp | 4.9 ± 1.0 | 3.9 ± 0.6 | 3.0 ± 0.5 | 12.1 ± 2.4 | 9.1 ± 0.3 | 7.1 ± 0.4 |
Dr | 4-Sulfated α-l-Fucp | 4.0 ± 0.8 | 4.4 ± 0.5 | 3.1 ± 0.5 | 11.7 ± 2.3 | 9.6 ± 0.7 | 7.1 ± 0.4 |
Anr | 2-Sulfated α-l-Fucp | 4.7 ± 0.9 | 3.6 ± 0.6 | 2.8 ± 0.5 | 10.3 ± 2.0 | 10.0 ± 0.4 | 7.1 ± 0.3 |
Cnr | 2-Sulfated α-l-Fucp | 4.5 ± 0.9 | 4.1 ± 0.9 | 3.0 ± 0.5 | 10.2 ± 2.0 | 10.0 ± 0.6 | 7.0 ± 0.4 |
Bnr | 2,4-Disulfated α-l-Fucp | 4.9 ± 1.0 | 3.7 ± 0.4 | 3.0 ± 0.5 | 12.1 ± 2.4 | 9.5 ± 0.6 | 7.1 ± 0.4 |
4-Sulfated α-l-Fucp | 4.0 ± 0.8 | 5.1 ± 0.3 | 3.1 ± 0.5 | 11.7 ± 2.3 | 9.6 ± 0.4 | 7.0 ± 0.4 |
aUnits labeled with subscript “nr” belong to the tetrasaccharide repeating units placed at the non-reducing end side, while those units labeled with subscript “r” belong to the tetrasaccharide repeating unit of the reducing end side.
bValues obtained from DQF-COSY spectrum (Supplementary data, Figure S3). Five DQF-COSY spectra were collected under the same conditions for generating average and error values.
cAll quantum calculations were performed at B3LYP/HIII-SU3//HF/6-31++G(2d,2p) level of theory, with all of the fucose ring torsions constrained at the average solution conformation.
dParameterization of the Karplus equation followed (Haasnoot et al. 1980).