Regioselective sulfation of alginate at 2-O-position of mannuronic acid unit with Py∙SO3 in DMSO

IF 2.4 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY
Karl Martin Ingerma , Indrek Reile , Rando Tuvikene
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Abstract

Alginates are brown algal polysaccharides consisting of β-D-mannuronic (M) and α-l-guluronic acid (G) residues linked with 1→4 glycosidic bonds. To functionalize these natural resources for biomedical use, alginates can be chemically modified, including by sulfation. Here regioselective sulfation of alginates at M-2 in DMSO with Py∙SO3 is described, by either sulfating alginates directly or through using alginates with added protecting groups (PG-s), including TBDMS-ether, Piv-, Bz-esters and intramolecular 3,6-lactone. Highest regioselectivity was found by sulfating TBDMS- and Piv-protected alginates, with over 65 % of M-residues being 2-O-sulfated. However significant reduction in molecular weight was found when alginates were sulfated in DMSO. Results from this work will allow a degree of control over substitution patterns in sulfated alginates. This will allow to more accurately determine structure-property relationships in biomedical research.

Abstract Image

在二甲基亚砜中用 Py∙SO3 在甘露糖酸单元的 2-O 位对海藻酸进行区域选择性硫酸化反应
藻酸盐是褐藻多糖,由 1→4 个糖苷键连接的 β-D-mannuronic (M) 和 α-l-guluronic acid (G) 残基组成。为了使这些天然资源具有生物医学用途,可以对海藻酸盐进行化学改性,包括硫酸化。本文介绍了在 DMSO 中用 Py∙SO3 对 M-2 级海藻酸盐进行区域选择性硫酸化的方法,硫酸化海藻酸盐的方法可以是直接硫酸化海藻酸盐,也可以是使用添加了保护基团(PG-s)的海藻酸盐,包括 TBDMS-ether、Piv-、Bz-酯和分子内 3,6-内酯。硫酸化 TBDMS 和 Piv 保护的藻酸盐具有最高的区域选择性,65% 以上的 M-残基被 2-O 硫酸化。不过,在二甲基亚砜中硫酸化藻酸盐时,分子量会明显降低。这项工作的结果将在一定程度上控制硫酸化海藻酸盐的取代模式。这将有助于更准确地确定生物医学研究中的结构-性质关系。
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来源期刊
Carbohydrate Research
Carbohydrate Research 化学-生化与分子生物学
CiteScore
5.00
自引率
3.20%
发文量
183
审稿时长
3.6 weeks
期刊介绍: Carbohydrate Research publishes reports of original research in the following areas of carbohydrate science: action of enzymes, analytical chemistry, biochemistry (biosynthesis, degradation, structural and functional biochemistry, conformation, molecular recognition, enzyme mechanisms, carbohydrate-processing enzymes, including glycosidases and glycosyltransferases), chemical synthesis, isolation of natural products, physicochemical studies, reactions and their mechanisms, the study of structures and stereochemistry, and technological aspects. Papers on polysaccharides should have a "molecular" component; that is a paper on new or modified polysaccharides should include structural information and characterization in addition to the usual studies of rheological properties and the like. A paper on a new, naturally occurring polysaccharide should include structural information, defining monosaccharide components and linkage sequence. Papers devoted wholly or partly to X-ray crystallographic studies, or to computational aspects (molecular mechanics or molecular orbital calculations, simulations via molecular dynamics), will be considered if they meet certain criteria. For computational papers the requirements are that the methods used be specified in sufficient detail to permit replication of the results, and that the conclusions be shown to have relevance to experimental observations - the authors'' own data or data from the literature. Specific directions for the presentation of X-ray data are given below under Results and "discussion".
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