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糖胺聚糖中L-艾杜糖醛酸残基糖苷键的酸不稳定性。

The acid lability of the glycosidic bonds of L-iduronic acid residues in glycosaminoglycans.

作者信息

Conrad H E

出版信息

Biochem J. 1980 Nov 1;191(2):355-63. doi: 10.1042/bj1910355.

DOI:10.1042/bj1910355
PMID:6453583
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC1162225/
Abstract

Heparan sulphate, heparin and dermatan sulphate were hydrolysed in 0.5M-H2SO4 at 100 degrees C. At intervals portions of the hydrolysate were removed and treated with HNO2 at pH 4.0 to cleave the glycosidic bonds of the N-unsubstituted hexosamine residues and to convert both free and combined hexosamines into anhydrohexoses. These hydrolysis/deamination mixtures were reduced with NaB3H4 and analysed by radiochromatography for alpha-L-iduronosylanhydrohexose, beta-D-glucuronosylanhydrohexose, and the free uronic acids and anhydrohexose. These data gave a kinetic profile of the cleavage of the alpha-L-iduronosyl and the beta-D-glucuronosyl bonds in these glycosaminoglycans. The beta-D-glucuronosyl bonds showed the expected resistance to acid hydrolysis, but the alpha-L-iduronosyl bonds were found to be as labile to acid as some neutral sugar glycosides. This unusual lability of alpha-D-iduronosyl-anhydromannitol and beta-D-glucuronosylanhydromannitol. The procedures used to follow the kinetics of glycosaminoglycan hydrolysis can also be sued to obtain quantitative analyses of L-iduronic acid, D-glucuronic acid and hexosamine in these polymers.

摘要

硫酸乙酰肝素、肝素和硫酸皮肤素在0.5M - H₂SO₄中于100℃水解。每隔一段时间取出部分水解产物,在pH 4.0条件下用HNO₂处理,以裂解N - 未取代己糖胺残基的糖苷键,并将游离和结合的己糖胺都转化为脱水己糖。这些水解/脱氨混合物用NaB₃H₄还原,并通过放射色谱法分析α - L - 艾杜糖醛酸基脱水己糖、β - D - 葡萄糖醛酸基脱水己糖以及游离糖醛酸和脱水己糖。这些数据给出了这些糖胺聚糖中α - L - 艾杜糖醛酸基和β - D - 葡萄糖醛酸基键裂解的动力学曲线。β - D - 葡萄糖醛酸基键表现出预期的对酸水解的抗性,但发现α - L - 艾杜糖醛酸基键对酸的稳定性与一些中性糖苷一样不稳定。α - D - 艾杜糖醛酸基 - 脱水甘露糖醇和β - D - 葡萄糖醛酸基脱水甘露糖醇具有这种不寻常的不稳定性。用于跟踪糖胺聚糖水解动力学的方法也可用于对这些聚合物中的L - 艾杜糖醛酸、D - 葡萄糖醛酸和己糖胺进行定量分析。

相似文献

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The acid lability of the glycosidic bonds of L-iduronic acid residues in glycosaminoglycans.糖胺聚糖中L-艾杜糖醛酸残基糖苷键的酸不稳定性。
Biochem J. 1980 Nov 1;191(2):355-63. doi: 10.1042/bj1910355.
2
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Distribution of sulphate and iduronic acid residues in heparin and heparan sulphate.硫酸根和艾杜糖醛酸残基在肝素和硫酸乙酰肝素中的分布。
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The distribution of sulfated uronic acid and hexosamine residues in heparin and heparan sulfate.硫酸化糖醛酸和己糖胺残基在肝素和硫酸乙酰肝素中的分布。
Connect Tissue Res. 1975;3(1):97-104. doi: 10.3109/03008207509152346.
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Hydrazinolysis of heparin and other glycosaminoglycans.肝素及其他糖胺聚糖的肼解作用。
Biochem J. 1984 Jan 1;217(1):187-97. doi: 10.1042/bj2170187.
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The co-polymeric structure of pig skin dermatan sulphate. Distribution of L-iduronic acid sulphate residues in co-polymeric chains.猪皮肤硫酸皮肤素的共聚结构。共聚链中硫酸L-艾杜糖醛酸残基的分布。
Biochem J. 1975 Feb;145(2):379-89. doi: 10.1042/bj1450379.
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Changes in disaccharide composition of heparan sulphate fractions with increasing degrees of sulphation.随着硫酸化程度增加,硫酸乙酰肝素组分中二糖组成的变化。
Biochem J. 1983 Feb 1;209(2):315-22. doi: 10.1042/bj2090315.
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Biosynthesis of dermatan sulphate. Loss of C-5 hydrogen during conversion of D-glucuronate to L-iduronate.硫酸皮肤素的生物合成。D-葡萄糖醛酸转化为L-艾杜糖醛酸过程中C-5氢的丢失。
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The disaccharides formed by deaminative cleavage of N-deacetylated glycosaminoglycans.由N-脱乙酰化糖胺聚糖的脱氨基裂解形成的二糖。
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引用本文的文献

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A novel bacterial enzyme with D-glucuronyl C5-epimerase activity.一种具有 D-葡糖醛酸基 C5-差向异构酶活性的新型细菌酶。
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2
Hydrazinolysis of heparin and other glycosaminoglycans.肝素及其他糖胺聚糖的肼解作用。
Biochem J. 1984 Jan 1;217(1):187-97. doi: 10.1042/bj2170187.
3
Changes in disaccharide composition of heparan sulphate fractions with increasing degrees of sulphation.随着硫酸化程度增加,硫酸乙酰肝素组分中二糖组成的变化。
Biochem J. 1983 Feb 1;209(2):315-22. doi: 10.1042/bj2090315.
4
Glycosyl transferases in chondroitin sulphate biosynthesis. Effect of acceptor structure on activity.硫酸软骨素生物合成中的糖基转移酶。受体结构对活性的影响。
Biochem J. 1985 Mar 15;226(3):705-14. doi: 10.1042/bj2260705.
5
The disaccharides formed by deaminative cleavage of N-deacetylated glycosaminoglycans.由N-脱乙酰化糖胺聚糖的脱氨基裂解形成的二糖。
Biochem J. 1986 Apr 1;235(1):225-36. doi: 10.1042/bj2350225.

本文引用的文献

1
Uronic Acid of Chondroitin Sulfate B.硫酸软骨素B的糖醛酸
Science. 1956 Dec 21;124(3234):1252. doi: 10.1126/science.124.3234.1252.
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INVESTIGATIONS ON THE CHEMISTRY OF HEPARIN. IV. THE GLYCOSIDIC LINKAGES.肝素化学研究。IV. 糖苷键
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Chemistry of beta-heparin (chondroitinsulfuric acid-B).β-肝素(硫酸软骨素-B)的化学性质
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The structure of the Aerobacter aerogenes A3(S1) polysaccharide. II. Sequence analysis and hydrolysis studies.产气气杆菌A3(S1)多糖的结构。II. 序列分析和水解研究。
Biochemistry. 1966 Sep;5(9):2808-17. doi: 10.1021/bi00873a005.
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Acid-catalyzed hydrolysis of glycosides.糖苷的酸催化水解
Adv Carbohydr Chem Biochem. 1967;22:25-108. doi: 10.1016/s0096-5332(08)60151-4.
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Uronic acid composition of heparins and heparan sulfates.肝素和硫酸乙酰肝素的糖醛酸组成
Biochemistry. 1973 Sep 11;12(19):3633-7. doi: 10.1021/bi00743a010.
7
Qualitative and quantitative analysis of reducing carbohydrates by radiochromatography on ion-exchange papers.离子交换纸上放射色谱法对还原糖的定性和定量分析
Anal Biochem. 1973 Feb;51(2):486-500. doi: 10.1016/0003-2697(73)90505-8.
8
The structure of the serotype 2 capsular polysaccharide of Aerobacter aerogenes.产气气杆菌2型荚膜多糖的结构
Biochemistry. 1967 Sep;6(9):2755-67. doi: 10.1021/bi00861a016.
9
Biosynthesis of heparin. 3. Formation of iduronic acid residues.肝素的生物合成。3. 艾杜糖醛酸残基的形成。
J Biol Chem. 1974 Jun 25;249(12):3908-15.
10
Stoichiometric depolymerization of polyuronides and glycosaminoglycuronans to monosaccharides following reduction of their carbodiimide-activated carboxyl groups.在碳二亚胺活化的羧基还原后,聚糖醛酸和糖胺聚糖醛酸聚糖化学计量解聚为单糖。
Biochemistry. 1972 Apr 11;11(8):1383-8. doi: 10.1021/bi00758a009.