PMID- 33497195 OWN - NLM STAT- MEDLINE DCOM- 20210621 LR - 20210621 IS - 1520-6882 (Electronic) IS - 0003-2700 (Linking) VI - 93 IP - 5 DP - 2021 Feb 9 TI - Structural Characterization of Isomeric Oligogalacturonan Mixtures Using Ultrahigh-Performance Liquid Chromatography-Charge Transfer Dissociation Mass Spectrometry. PG - 2838-2847 LID - 10.1021/acs.analchem.0c04142 [doi] AB - Pectins are natural polysaccharides made from galacturonic acid residues, and they are widely used as an excipient in food and pharmaceutical industries. The degree of methyl-esterification, the monomeric composition, and the linkage pattern are all important factors that influence the physical and chemical properties of pectins, such as the solubility. This work focuses on the successful online coupling of charge transfer dissociation-mass spectrometry (CTD-MS) with ultrahigh-performance liquid chromatography (UHPLC) to differentiate isomers of oligogalacturonans derived from citrus pectins. This work employed CTD fragmentation of the pectin mixtures in data-dependent acquisition mode. Compared to the UHPLC with collision-induced dissociation mass spectrometry (UHPLC-CID-MS), UHPLC-CTD-MS yielded fewer ambiguous ions and more structurally informative results. The developed UHPLC-CTD-MS method resulted in abundant cross-ring cleavages-and especially (1,4)X(n), (1,5)X(n), and (2,4)X(n) ions-which helped to identify most of the isomers. The Gal A isomers differed only in the methyl group position along the galacturonic acid backbone. The combination of CTD in real time with UHPLC provides a new tool for the structural characterization of complex mixtures of oligogalacturonans and potentially other classes of oligosaccharides. FAU - Mendis, Praneeth M AU - Mendis PM AD - C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506-6121, United States. FAU - Sasiene, Zachary J AU - Sasiene ZJ AD - C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506-6121, United States. FAU - Ropartz, David AU - Ropartz D AUID- ORCID: 0000-0003-4767-6940 AD - INRAE, UR BIA, Nantes F-44316, France. AD - INRAE, BIBS Facility, Nantes F-44316, France. FAU - Rogniaux, Helene AU - Rogniaux H AUID- ORCID: 0000-0001-6083-2034 AD - INRAE, UR BIA, Nantes F-44316, France. AD - INRAE, BIBS Facility, Nantes F-44316, France. FAU - Jackson, Glen P AU - Jackson GP AUID- ORCID: 0000-0003-0803-6254 AD - C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506-6121, United States. AD - Department of Forensic and Investigative Science, West Virginia University, Morgantown, West Virginia 26506-6121, United States. LA - eng GR - R01 GM114494/GM/NIGMS NIH HHS/United States PT - Journal Article PT - Research Support, N.I.H., Extramural PT - Research Support, U.S. Gov't, Non-P.H.S. DEP - 20210126 PL - United States TA - Anal Chem JT - Analytical chemistry JID - 0370536 RN - 0 (Oligosaccharides) RN - 0 (Polysaccharides) SB - IM MH - Chromatography, High Pressure Liquid MH - Chromatography, Liquid MH - Isomerism MH - Mass Spectrometry MH - *Oligosaccharides MH - *Polysaccharides EDAT- 2021/01/27 06:00 MHDA- 2021/06/22 06:00 CRDT- 2021/01/26 17:09 PHST- 2021/01/27 06:00 [pubmed] PHST- 2021/06/22 06:00 [medline] PHST- 2021/01/26 17:09 [entrez] AID - 10.1021/acs.analchem.0c04142 [doi] PST - ppublish SO - Anal Chem. 2021 Feb 9;93(5):2838-2847. doi: 10.1021/acs.analchem.0c04142. Epub 2021 Jan 26.