VOLUME 289 (2017) PAGES 2745–2754
There was an error in the structure of Shigella sonnei phase II ECALPS. The anomeric configuration of residue J should be assigned as a β anomer [→4)-β-d-GlcpNAc-(1→] based on its chemical shifts (Tables 1 and 2) and JH1,C1 (162 Hz). The correction results in an inverted anomeric configuration of the d-GlcNAc residue in the first ECA unit linked to the core oligosaccharide, whereas an α-configuration is characteristic for polymeric chain (Fig. 3). Chemical shifts of the residue J were in agreement with predictions carried out by the CASPER program (http://www.casper.organ.su.se/casper/), where professor Göran Widmalm is kindly acknowledged for the error identification (
1.
, 2.
). This correction does not affect the general results and conclusions of this work.Table 11H and 13C NMR chemical shifts of fraction IV containing core OS substituted by ECA trisaccharide ([ECA]-dLOS) isolated from S. sonnei phase II LOS
| Residue | Description | Chemical shift (ppm) | |||||||
|---|---|---|---|---|---|---|---|---|---|
| H-1/C-1 | H-2/C-2 | H-3(H3ax,eq)/C-3 | H-4/C-4 | H-5/C-5 | H-6a, H-6b/C-6 | H-7a, H-7b/C-7 (NHAc) | H-8a, H-8b/C-8 [C(O)] | ||
| A | →5)-α-Kdop | ND | −/96.3 | (1.90, 2.25)/34.1 | 4.11/66.3 | 4.17/73.3 | 3.69/69.7 | 3.80/72.6 | 3.47, 3.93/64.7 |
| B | →3)-l-α-d-Hepp4PPEtn-(1→ | 5.20/100.1 | 4.01/71.6 | 4.08/78.5 | 4.61/72.3 | 4.22/72.0 | 4.10/69.3 | 3.72, 3.72/63.8 | |
| C | →3,7)-l-α-d-Hepp4P-(1→ | 5.10/103.5 | 4.38/70.6 | 4.12/79.8 | 4.40/69.4 | 3.80/73.2 | 4.23/68.5 | 3.58, 3.75/68.4 | |
| D | l-α-d-Hepp-(1→ | 4.98/100.2 | 3.93/70.7 | 3.87/71.4 | 3.84/66.9 | 3.61/71.9 | 4.04/69.5 | 3.65, 3.72/63.7 | |
| E | →3)-α-d-Glcp-(1→ | 5.20/102.0 | 3.66/71.0 | 4.07/76.7 | 3.77/71.2 | 3.91/73.1 | 3.79,3.92/60.5 | ||
| F | →2,3)-α-d-Glcp-(1→ | 5.80/95.3 | 3.87/73.3 | 4.17/78.7 | 3.56/68.7 | 4.10/71.9 | 3.78,3.95/61.0 | ||
| F′ | →2,3)-α-d-Glcp-(1→ | 5.81/95.1 | 3.88/73.3 | 4.19/78.8 | 3.57/68.7 | 4.11/72.0 | 3.79,3.96/61.0 | ||
| G | →2)-α-d-Galp-(1→ | 5.61/92.1 | 3.98/73.2 | 4.19/68.9 | 3.98/70.7 | 4.13/72.0 | 3.74,3.74/61.9 | ||
| H | α-d-Galp-(1→ | 5.31/96.6 | 3.85/69.0 | 3.95/70.1 | 3.99/70.1 | 4.13/72.0 | 3.75,3.75/61.9 | ||
| I | →3)-β-d-Glcp-(1→ | 4.73/103.1 | 3.39/73.6 | 3.68/85.4 | 3.49/68.9 | 3.44/76.3 | 3.72,3.89/61.4 | ||
| I′ | β-d-Glcp-(1→ | 4.75/103.1 | 3.33/73.9 | 3.51/76.6 | 3.40/70.4 | 3.45/76.6 | 3.73,3.91/61.4 | ||
| J | →4)-β-d-GlcpNAc-(1→ | 4.78/102.3 | 3.75/56.3 | 3.74/72.7 | 3.68/79.5 | 3.54/75.2 | 3.86,3.70/60.9 | (2.03/23.0) | [175.5] |
| K | →4)-β-d-ManpNAcA-(1→ | 4.93/99.7 | 4.49/54.2 | 4.07/73.2 | 3.82/74.8 | 3.86/77.2 | −/175.1 | (2.07/22.6) | [176.2] |
| L | α-d-Fucp4NAc-(1→ | 5.35/99.5 | 3.64/69.3 | 4.00/69.1 | 4.20/54.6 | 4.18/66.5 | 1.06/16.2 | (2.07/22.6) | [176.3] |
| PPEtn | 4.20/63.1 | 3.29/40.7 | |||||||
a ND, not determined.
b Residue F′ is a variant of residue F present in the core OS that is devoid of ECA trisaccharide.
c Residue I′ is a terminal residue I present in the core OS that is devoid of ECA trisaccharide.
Table 2Selected inter-residue NOE and 3JH,C connectivities from the anomeric atoms of ([ECA]-dLOS) dodecasaccharide isolated from S. sonnei phase II LOS
| Residue | Description | Atom δH/δC (ppm) | Connectivity to | Inter-residue atom/residue | |
|---|---|---|---|---|---|
| δC | δH | ||||
| B | →3)-l-α-d-Hepp4PPEtn-(1→ | 5.20/100.1 | − | 4.17 | H-5 of A |
| C | →3,7)-l-α-d-Hepp4P-(1→ | 5.10/103.5 | 78.5 | 4.08 | C-3, H-3 of B |
| D | l-α-d-Hepp-(1→ | 4.98/100.2 | 68.5 | 3.59/3.74 | C-7, H-7a, H-7b of C |
| E | →3)-α-d-Glcp-(1→ | 5.20/102.0 | − | 4.12 | H-3 of C |
| F | →2,3)-α-d-Glcp-(1→ | 5.80/95.3 | − | 4.07 | H-3 of E |
| F′ | →2,3)-α-d-Glcp-(1→ | 5.81/95.1 | − | 4.07 | H-3 of E |
| G | →2)-α-d-Galp-(1→ | 5.61/92.1 | − | 3.87 | H-2 of F |
| H | α-d-Galp-(1→ | 5.31/96.6 | − | 3.97 | H-2 of G |
| I | →3)-β-d-Glcp-(1→ | 4.73/103.1 | 78.7 | 4.17 | H-3 of F |
| I′ | β-d-Glcp-(1→ | 4.75/103.1 | 78.8 | 4.19 | H-3 of F′ |
| J | →4)-β-d-GlcpNAc-(1→ | 4.78/102.3 | 85.3 | 3.68 | H-3 of I |
| K | →4)-β-d-ManpNAcA-(1→ | 4.93/99.7 | 79.4 | 3.69 | H-4 of J |
| L | α-d-Fucp4NAc-(1→ | 5.35/99.5 | 74.7 | 3.81 | H-4 of K |
a Value represents NOE connectivities only.
b Residue F′ is a variant of residue F present in the core OS that is devoid of ECA trisaccharide.
c Residue I′ is a terminal residue I present in the core OS that is devoid of ECA trisaccharide.
References
- Structure analysis of glycans by NMR chemical shift prediction.Anal. Chem. 2011; 83 (21280662): 1514-1517
- Sequence determination of oligosaccharides and regular polysaccharides using NMR spectroscopy and a novel Web-based version of the computer program CASPER.Carbohydr. Res. 2006; 341 (16564037): 1003-1010
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Published online: July 20, 2018
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