Rania Benazza, Mathieu Fanuel, Hélène Rogniaux, David Ropartz
{"title":"Deciphering Branched Galactomannan Structures via Multistage Ion Mobility MS and MS<sup>n</sup> Fragmentation (Multistage IMS<sup>n</sup>).","authors":"Rania Benazza, Mathieu Fanuel, Hélène Rogniaux, David Ropartz","doi":"10.1002/rcm.10100","DOIUrl":null,"url":null,"abstract":"<p><strong>Rationale: </strong>Hemicelluloses are abundant carbohydrate components in plant cell walls. They play a crucial structural role in binding cellulose microfibrils, in addition to other biological functions. Their high structural variability directly influences their biological properties, making it important to establish a structure-function relationship. In the case of galactomannans, this complexity lies in branching, large size, in addition to isomerism, which makes their characterization challenging. In this context, we have demonstrated that cyclic ion mobility spectrometry (IMS), combined with porous graphitic carbon (PGC) chromatography, mass spectrometry (MS), and multistage MS/MS fragmentation (IMS<sup>n</sup>), is a powerful tool for the detailed elucidation of galactomannan structures.</p><p><strong>Methods: </strong>In this study, we show that our multistage IMS<sup>n</sup> sequencing approach, previously validated for homo-linear oligosaccharides (OS), can be successfully applied to hetero-branched hemicelluloses with careful adjustments. Our approach consists of building a database (DB) library of high-resolution IMS (HR-IMS) profiles of disaccharidic and trisaccharidic fragments. Then, the sequence of the oligosaccharide of interest is retrieved by comparing the HR-IMS profile of its disaccharidic and trisaccharide fragments with the profiles from the DB library.</p><p><strong>Results: </strong>In fact, our IMS<sup>n</sup> experiments on galactomannan reveal arrival time distribution (ATD) profiles matching with known reference structures, confirming the co-existence of multiple isomers. In addition, we proved that this approach could be improved by incorporating trisaccharidic fragments to our DB library, serving in the characterization of higher degree of polymerization (DP) structures (DP4 in this case).</p><p><strong>Conclusions: </strong>Overall, this work paves the way for the characterization of even more complex oligosaccharides, which can be potentially used for bio-based material conception.</p>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":" ","pages":"e10100"},"PeriodicalIF":1.8000,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Rapid Communications in Mass Spectrometry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/rcm.10100","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"BIOCHEMICAL RESEARCH METHODS","Score":null,"Total":0}
引用次数: 0
Abstract
Rationale: Hemicelluloses are abundant carbohydrate components in plant cell walls. They play a crucial structural role in binding cellulose microfibrils, in addition to other biological functions. Their high structural variability directly influences their biological properties, making it important to establish a structure-function relationship. In the case of galactomannans, this complexity lies in branching, large size, in addition to isomerism, which makes their characterization challenging. In this context, we have demonstrated that cyclic ion mobility spectrometry (IMS), combined with porous graphitic carbon (PGC) chromatography, mass spectrometry (MS), and multistage MS/MS fragmentation (IMSn), is a powerful tool for the detailed elucidation of galactomannan structures.
Methods: In this study, we show that our multistage IMSn sequencing approach, previously validated for homo-linear oligosaccharides (OS), can be successfully applied to hetero-branched hemicelluloses with careful adjustments. Our approach consists of building a database (DB) library of high-resolution IMS (HR-IMS) profiles of disaccharidic and trisaccharidic fragments. Then, the sequence of the oligosaccharide of interest is retrieved by comparing the HR-IMS profile of its disaccharidic and trisaccharide fragments with the profiles from the DB library.
Results: In fact, our IMSn experiments on galactomannan reveal arrival time distribution (ATD) profiles matching with known reference structures, confirming the co-existence of multiple isomers. In addition, we proved that this approach could be improved by incorporating trisaccharidic fragments to our DB library, serving in the characterization of higher degree of polymerization (DP) structures (DP4 in this case).
Conclusions: Overall, this work paves the way for the characterization of even more complex oligosaccharides, which can be potentially used for bio-based material conception.
期刊介绍：
Rapid Communications in Mass Spectrometry is a journal whose aim is the rapid publication of original research results and ideas on all aspects of the science of gas-phase ions; it covers all the associated scientific disciplines. There is no formal limit on paper length ("rapid" is not synonymous with "brief"), but papers should be of a length that is commensurate with the importance and complexity of the results being reported. Contributions may be theoretical or practical in nature; they may deal with methods, techniques and applications, or with the interpretation of results; they may cover any area in science that depends directly on measurements made upon gaseous ions or that is associated with such measurements.
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