Novel Method for Comprehensive Annotation of Plant Glycosides Based on Untargeted LC-HRMS/MS Metabolomics

Glycosides are a large family of secondary metabolites in plants, which play a critical role in plant growth and development. Due to the complexity and diversity in structures and the limited availability of authentic standards, comprehensive annotation of the glycosides remains a great challenge. I...

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Bibliographic Details
Published in:Analytical chemistry (Washington) 2022-12, Vol.94 (48), p.16604-16613
Main Authors: Zhang, Xiuqiong, Zheng, Fujian, Zhao, Chunxia, Li, Zaifang, Li, Chao, Xia, Yueyi, Zheng, Sijia, Wang, Xinxin, Sun, Xiaoshan, Zhao, Xinjie, Lin, Xiaohui, Lu, Xin, Xu, Guowang
Format: Article
Language:English
Subjects:
Aglycones
Analytical chemistry
Annotations
Chemistry
Chromatography, High Pressure Liquid - methods
Chromatography, Liquid - methods
Corn
Flavonoids
Glycosides
Glycosides - analysis
Glycosylation
High resolution
Ions
Liquid chromatography
Mass spectrometry
Mass spectroscopy
Metabolites
Metabolomics
Negative ions
Plant Extracts - chemistry
Plant growth
Positive ions
Secondary metabolites
Spectrometry, Mass, Electrospray Ionization - methods
Tandem Mass Spectrometry - methods
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Summary:Glycosides are a large family of secondary metabolites in plants, which play a critical role in plant growth and development. Due to the complexity and diversity in structures and the limited availability of authentic standards, comprehensive annotation of the glycosides remains a great challenge. In this study, using maize as an example, a deep annotation method of glycosides was proposed based on untargeted liquid chromatography–high-resolution tandem mass spectrometry metabolomics analysis. First, knowledge-based in silico aglycone and glycosyl/acyl-glycosyl libraries were built. A total of 1240 known and potential aglycones from databases and literature were recorded. Next, the MS parameters beneficial to aglycone ion-rich MS/MS were explored using 1782 high-resolution MS/MS spectra of glycosides from the MassBank of North America (MoNA) and confirmed by 52 authentic glycoside standards. Then, screening rules for aglycon ions in MS/MS were recommended. Glycoside candidates were further filtered by MS/MS-based chemical classification and MS/MS similarity of aglycon–glycoside pairs. Finally, the glycosylation sites of flavonoid mono-O-glycosides were recommended by characteristic fragmentation patterns. The developed method was validated using glycosides and nonglycosides from the MoNA library. The annotation accuracy rates were 96.8, 94.9, and 98.0% in negative ion mode (ESI–), positive ion mode (ESI+), and the combined ESI– & ESI+, respectively. The annotation specificity was 99.6% (ESI–), 99.6% (ESI+), and 99.2% (ESI– & ESI+). A total of 274 glycosides (including 34 acyl-glycosides) were tentatively annotated in maize by the developed method. The method enables effective and reliable annotation for plant glycosides.
ISSN:0003-2700
1520-6882
DOI:10.1021/acs.analchem.2c02362