A simplified NMR-based method to assign the absolute configuration of aldose monosaccharides

IF 2.5 3区化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY

Carbohydrate Research Pub Date : 2025-10-06 DOI:10.1016/j.carres.2025.109696

Neil P.J. Price , Karl E. Vermillion , Michael A. Jackson

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Abstract

A straightforward, aqueous-based procedure is described to determine the absolute configuration of aldose monosaccharides, a critical task in carbohydrate analysis. This approach leverages the reaction of aldose monosaccharide enantiomers with L-cysteine, a readily-available chiral amino acid, to form cyclic thiazolidine diastereomers. These derivatives can be analyzed using Heteronuclear Single Quantum Coherence (HSQC) NMR spectroscopy, specifically looking at the H-1 – C-1 proton-carbon single bond correlations. This NMR technique provides the necessary data to determine the absolute configuration of the parent monosaccharide. Several monosaccharide D-/L-enantiomeric pairs are analyzed as examples, and the technique is utilized to determine the compositional stereochemistry of complex polysaccharides (gellan and xanthan gums). We have also established the previously unknown stereochemistry of the arabinosyl residues found in frost grape polysaccharide (FGP) isolated from vines of the grape species, Vitis riparia Michx. The generalized method described is anticipated to be valuable to analytical carbohydrate chemists for the facile assignment of carbohydrate stereochemistry.

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一种简化的基于核磁共振的醛糖单糖绝对构型分配方法。

一个简单的，基于水的程序描述了确定醛糖单糖的绝对构型，在碳水化合物分析的关键任务。这种方法利用醛糖单糖对映体与l -半胱氨酸（一种容易获得的手性氨基酸）的反应，形成环噻唑烷非对映体。这些衍生物可以使用异核单量子相干（HSQC）核磁共振波谱分析，特别是观察H-1 - C-1质子-碳单键的相关性。这种核磁共振技术提供了必要的数据来确定母体单糖的绝对构型。以几种单糖D-/ l -对映体对为例进行了分析，并利用该技术确定了复合多糖（结冷胶和黄原胶）的组成立体化学。我们还建立了以前未知的立体化学，在从葡萄品种Vitis riparia micx的葡萄中分离的霜葡萄多糖（FGP）中发现阿拉伯糖基残基。所描述的广义方法预计对分析碳水化合物化学家来说是有价值的，可以方便地分配碳水化合物的立体化学。

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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".