Homogeneous sulfation of polyguluronic acids (poly-G-s) with Py·SO3 in DMSO and their characterization with NMR-spectroscopy

IF 2.4 3区化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY

Carbohydrate Research Pub Date : 2025-05-21 DOI:10.1016/j.carres.2025.109543

Karl M. Ingerma , Indrek Reile , Angelica Närep , Rando Tuvikene

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Abstract

Sulfated polyguluronates (poly-G) have shown promising bioactivities, including immunomodulatory, anticoagulative, antiviral and anti-inflammatory activity. However they have seen only a limited amount of structural characterization, making it difficult to determine structure-activity relationships and thus complicating their application into practice. Therefore poly-G-s were sulfated with Py·SO₃ in DMSO and the resulting derivatives were systematically characterized with NMR-spectroscopy to assign the signals of sulfated residues and to identify how different sulfation patterns manifest in NMR spectra. With lower concentration of the sulfating reagent, a slight preference for G-3 was found, while with higher concentration, G-2 preference increased alongside G-2,3-disulfation. Protecting groups (PG) were additionally used to direct selectivity and thus aid structural characterization. A degree of G-2 sulfation preference was achieved with TBDMS-ether as PG, while with Bz-ester PG, G-3 preference was achieved. Degradation by β-elimination of poly-G was found to be minimal under the developed experimental conditions.

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聚谷醛酸（聚g -s）与Py·SO3在DMSO中的均匀磺化及其核磁共振表征

硫酸聚guluronates （poly-G）具有良好的生物活性，包括免疫调节、抗凝血、抗病毒和抗炎活性。然而，他们只看到了有限数量的结构表征，使得难以确定结构-活性关系，从而使其在实践中的应用复杂化。因此，在DMSO中用Py·SO3对聚g -s进行了磺化处理，并用核磁共振光谱系统地表征了所得到的衍生物，以确定磺化残留物的信号，并确定不同磺化模式在核磁共振光谱中的表现。硫酸化剂浓度较低时，对G-3有轻微的偏好，而浓度较高时，对G-2的偏好随g -2,3-二磺酸的增加而增加。另外，保护基团（PG）用于指导选择性，从而有助于结构表征。以tbdms -醚作PG可获得一定程度的G-2磺化偏好，而以bz -酯作PG可获得一定程度的G-3磺化偏好。在开发的实验条件下，发现β-消除聚g的降解最小。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

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".