Monosaccharide composition analysis of polysaccharides based on derivatization and non-derivatization strategies: A review.

Complete hydrolysis of polysaccharides and stable recovery of monosaccharides are the core prerequisite for precise analysis of monosaccharide composition, a task further impeded by the structural diversity, high polarity, and lack of native chromophores of monosaccharides. To address these coupled challenges, this review constructs a complete analytical framework for monosaccharide analysis of polysaccharides, covering the workflow from hydrolysis optimization and detection method selection to precise qualitative and quantitative analysis. Derivatization and non-derivatization represent two complementary analytical strategies for monosaccharide analysis. Derivatization strategies, via targeted chemical modification of monosaccharides, enable simultaneous profiling of a broad spectrum of monosaccharides (aldoses, ketoses, uronic acids, and amino sugars), with significantly improved separation selectivity, detection sensitivity, and compatibility with gas chromatography (GC), high-performance liquid chromatography (HPLC) and mass spectrometry (MS). However, they are inherently limited by tedious pretreatment, risks of incomplete derivatization, side reactions and potential analyte loss. Non-derivatization approaches, represented by hydrophilic interaction liquid chromatography (HILIC), high-performance anion-exchange chromatography (HPAEC) and nuclear magnetic resonance spectroscopy (NMR), avoid laborious derivatization and related side reactions, serving as indispensable complementary tools. Nevertheless, some techniques face inherent bottlenecks, including poor trace-level sensitivity, limited selectivity in complex matrices, and insufficient chromatographic retention. By systematically comparing these two mainstream strategies, this review defines their applicable boundaries in detection sensitivity, qualitative and quantitative capabilities, and matrix compatibility, thus offering reliable guidance for monosaccharide composition analysis.