Neutral monosaccharide composition analysis of plant-derived oligo- and polysaccharides by high performance liquid chromatography

•A simple and fast HILIC-CAD method was developed for monosaccharides profiling.•Effects of column type, additives, temperature and pH were studied for optimal conditions.•Validation of the method showed good linearity, accuracy, precision and sensitivity.•Successfully applied to monosaccharide analysis of stachyose and EAPW.•First report on the simultaneous and direct determination of the eight sugars by HPLC. A novel analytical method for neutral monosaccharide composition analysis of plant-derived oligo- and polysaccharides was developed using hydrophilic interaction liquid chromatography coupled to a charged aerosol detector. The effects of column type, additives, pH and column temperature on retention and separation were evaluated. Additionally, the method could distinguish potential impurities in samples, including chloride, sulfate and sodium, from sugars. The results of validation demonstrated that this method had good linearity (R2≥0.9981), high precision (relative standard deviation≤4.43%), and adequate accuracy (94.02–103.37% recovery) and sensitivity (detection limit: 15–40ng). Finally, the monosaccharide compositions of the polysaccharide from Eclipta prostrasta L. and stachyose were successfully profiled through this method. This report represents the first time that all of these common monosaccharides could be well-separated and determined simultaneously by high performance liquid chromatography without additional derivatization. This newly developed method is convenient, efficient and reliable for monosaccharide analysis.