Structural determination of novel tetra- and hexasaccharide sequences isolated from chondroitin sulfate H (oversulfated dermatan sulfate) of hagfish notochord
Structural determination of novel tetra- and hexasaccharide sequences isolated from chondroitin sulfate H (oversulfated dermatan sulfate) of hagfish notochord
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从盲鳗脊索硫酸软骨素 H（过硫酸皮肤素硫酸盐）中分离的新型四糖和六糖序列的结构测定
DOI：
10.1023/a:1007022229813
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发表时间：
1999
影响因子：
3
通讯作者：
K. Sugahara
中科院分区：
文献类型：
--
作者：
C. Ueoka;S. Nadanaka;N. Seno;K. Khoo;K. Sugahara
从盲鳗棘索中分离出的过硫酸软骨素H （CS-H）是一种独特的皮肤硫酸盐，主要由IdoAα1- 3galnac （4S,6S）组成，其中IdoA、GalNAc、4S和6S分别代表l-伊杜醛酸、n -乙酰- d -半乳糖胺、4- o -硫酸盐和6- o -硫酸盐。通过细菌软骨素酶B的部分消化，从CS-H中分离出多个四糖和六糖组分，研究了多糖中IdoAα1-3GalNAc（4S,6S）单元的顺序排列。通过酶解、质谱和1H NMR对分离的低聚糖进行结构分析表明，主要的四糖具有共同的二磺酸核心结构Δ4,5HexAα1- 3galnac (4S)β1-4IdoAα1-3GalNAc(4S)，具有0 ~ 3个额外的o-硫酸盐基团，其中Δ4,5HexA代表4-脱氧-α- l -三己基-4-烯基氨基醛酸。主要的六糖具有共同的三磺化核心结构Δ4,5HexAα1-3GalNAc(4S)β1-4IdoAα1-3GalNAc(4S)β1-4IdoAα1-3GalNAc（4S）具有1 ~ 4个额外的o -硫酸盐基团。在四糖和六糖中，一些额外的硫酸盐基团位于Δ4、5HexA或IdoA内部残基的C-2位置，或4- o -硫酸化的GalNAc残基的C-6位置，形成独特的二硫酸化或三硫酸化的双糖单元，IdoA (2S)-GalNAc（4S）、IdoA-GalNAc（4S,6S）和IdoA (2S)-GalNAc(4S,6S)，其中2S代表2- o -硫酸盐。在已证实的序列中，含有这些单位的5个四糖和4个六糖序列是新的。
Oversulfated chondroitin sulfate H (CS-H) isolated from hagfish notochord is a unique dermatan sulfate consisting mainly of IdoAα1-3GalNAc(4S,6S), where IdoA, GalNAc, 4S and 6S represent L-iduronic acid, N-acetyl-D-galactosamine, 4-O-sulfate and 6-O-sulfate, respectively. Several tetra- and hexasaccharide fractions were isolated from CS-H after partial digestion with bacterial chondroitinase B to investigate the sequential arrangement of the IdoAα1-3GalNAc(4S,6S) unit in the CS-H polysaccharide. A structural analysis of the isolated oligosaccharides by enzymatic digestions, mass spectrometry and 1H NMR spectroscopy demostrated that the major tetrasaccharides shared the common disulfated core structure Δ4,5HexAα1-3GalNAc(4S)β1-4IdoAα1-3GalNAc(4S) with 0 ∼ 3 additional O-sulfate groups, where Δ4,5HexA represents 4-deoxy-α-L-threo-hex-4-enepyranosyluronic acid. The major hexasaccharides shared the common trisulfated core structure Δ4,5HexAα1-3GalNAc(4S)β1-4IdoAα1-3GalNAc(4S)β1-4IdoAα1-3GalNAc(4S) with 1 ∼ 4 additional O-sulfate groups. Some extra sulfate groups in both tetra- and hexasaccharides were located at the C-2 position of a Δ4,5HexA or an internal IdoA residue, or C-6 position of 4-O-sulfated GalNAc residues, forming the unique disulfated or trisulfated disaccharide units, IdoA (2S)-GalNAc(4S), IdoA-GalNAc(4S,6S) and IdoA (2S)-GalNAc(4S,6S), where 2S represents 2-O-sulfate. Of the demonstrated sequences, five tetra- and four hexasaccharide sequences containing these units were novel.