TY - JOUR

T1 - Characterization of oligosaccharides from the chondroitin/dermatan sulfates. 1H-NMR and 13C-NMR studies of reduced trisaccharides and hexasaccharides.

AU - Huckerby, Thomas N.

AU - Nieduszynski, Ian A.

AU - Giannopoulos, Marcos

AU - Weeks, Stephen D.

AU - Sadler, Ian H.

AU - Lauder, Robert M.

PY - 2005/12

Y1 - 2005/12

N2 - Chondroitin and dermatan sulfate (CS and DS) chains were isolated from bovine tracheal cartilage and pig intestinal mucosal preparations and fragmented by enzymatic methods. The oligosaccharides studied include a disaccharide and hexasaccharides from chondroitin ABC lyase digestion as well as trisaccharides already present in some commercial preparations. In addition, other trisaccharides were generated from tetrasaccharides by chemical removal of nonreducing terminal residues. Their structures were examined by high-field 1H and 13C NMR spectroscopy, after reduction using sodium borohydride. The main hexasaccharide isolated from pig intestinal mucosal DS was found to be fully 4-O-sulfated and have the structure: ΔUA(β1–3)GalNAc4S(β1–4)l-IdoA(α1–3)GalNAc4S(β1–4)l-IdoA(α1–3)GalNAc4S-ol, whereas one from bovine tracheal cartilage CS comprised only 6-O-sulfated residues and had the structure: ΔUA(β1–3)GalNAc6S(β1–4)GlcA(β1–3)GalNAc6S(β1–4)GlcA(β1–3)GalNAc6S-ol. No oligosaccharide showed any uronic acid 2-sulfation. One novel disaccharide was examined and found to have the structure: GalNAc6S(β1–4)GlcA-ol. The trisaccharides isolated from the CS/DS chains were found to have the structures: ΔUA(β1–3)GalNAc4S(β1–4)GlcA-ol and ΔUA(β1–3)GalNAc6S(β1–4)GlcA-ol. Such oligosaccharides were found in commercial CS/DS preparations and may derive from endogenous glucuronidase and other enzymatic activity. Chemically generated trisaccharides were confirmed as models of the CS/DS chain caps and included: GalNAc6S(β1–4)GlcA(β1–3)GalNAc4S-ol and GalNAc6S(β1–4)GlcA(β1–3)GalNAc6S-ol. The full assignment of all signals in the NMR spectra are given, and these data permit the further characterization of CS/DS chains and their nonreducing capping structures.

AB - Chondroitin and dermatan sulfate (CS and DS) chains were isolated from bovine tracheal cartilage and pig intestinal mucosal preparations and fragmented by enzymatic methods. The oligosaccharides studied include a disaccharide and hexasaccharides from chondroitin ABC lyase digestion as well as trisaccharides already present in some commercial preparations. In addition, other trisaccharides were generated from tetrasaccharides by chemical removal of nonreducing terminal residues. Their structures were examined by high-field 1H and 13C NMR spectroscopy, after reduction using sodium borohydride. The main hexasaccharide isolated from pig intestinal mucosal DS was found to be fully 4-O-sulfated and have the structure: ΔUA(β1–3)GalNAc4S(β1–4)l-IdoA(α1–3)GalNAc4S(β1–4)l-IdoA(α1–3)GalNAc4S-ol, whereas one from bovine tracheal cartilage CS comprised only 6-O-sulfated residues and had the structure: ΔUA(β1–3)GalNAc6S(β1–4)GlcA(β1–3)GalNAc6S(β1–4)GlcA(β1–3)GalNAc6S-ol. No oligosaccharide showed any uronic acid 2-sulfation. One novel disaccharide was examined and found to have the structure: GalNAc6S(β1–4)GlcA-ol. The trisaccharides isolated from the CS/DS chains were found to have the structures: ΔUA(β1–3)GalNAc4S(β1–4)GlcA-ol and ΔUA(β1–3)GalNAc6S(β1–4)GlcA-ol. Such oligosaccharides were found in commercial CS/DS preparations and may derive from endogenous glucuronidase and other enzymatic activity. Chemically generated trisaccharides were confirmed as models of the CS/DS chain caps and included: GalNAc6S(β1–4)GlcA(β1–3)GalNAc4S-ol and GalNAc6S(β1–4)GlcA(β1–3)GalNAc6S-ol. The full assignment of all signals in the NMR spectra are given, and these data permit the further characterization of CS/DS chains and their nonreducing capping structures.

U2 - 10.1111/j.1742-4658.2005.05009.x

DO - 10.1111/j.1742-4658.2005.05009.x

M3 - Journal article

VL - 272

SP - 6276

EP - 6286

JO - FEBS Journal

JF - FEBS Journal

SN - 1742-464X

IS - 24

ER -