Distinguishing Galactoside Isomers with Mass Spectrometry and Gas-Phase Infrared SpectroscopyClick to copy article linkArticle link copied!
- Jordan S. HoJordan S. HoDepartment of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue Cambridge, Massachusetts 02139, United StatesMore by Jordan S. Ho
- Amira GharbiAmira GharbiUniv. Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière, F-69622 Villeurbanne, FranceMore by Amira Gharbi
- Baptiste SchindlerBaptiste SchindlerUniv. Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière, F-69622 Villeurbanne, FranceMore by Baptiste Schindler
- Oznur YeniOznur YeniUniv. Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière, F-69622 Villeurbanne, FranceMore by Oznur Yeni
- Richard BrédyRichard BrédyUniv. Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière, F-69622 Villeurbanne, FranceMore by Richard Brédy
- Laurent LegentilLaurent LegentilUniv. Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226 − ISCR, F-35000 Rennes, FranceMore by Laurent Legentil
- Vincent FerrièresVincent FerrièresUniv. Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226 − ISCR, F-35000 Rennes, FranceMore by Vincent Ferrières
- Laura L. Kiessling*Laura L. Kiessling*[email protected]Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue Cambridge, Massachusetts 02139, United StatesMore by Laura L. Kiessling
- Isabelle Compagnon*Isabelle Compagnon*[email protected]Univ. Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière, F-69622 Villeurbanne, FranceMore by Isabelle Compagnon
Abstract

Sequencing glycans is demanding due to their structural diversity. Compared to mammalian glycans, bacterial glycans pose a steeper challenge because they are constructed from a larger pool of monosaccharide building blocks, including pyranose and furanose isomers. Though mammalian glycans incorporate only the pyranose form of galactose (Galp), many pathogens, including Mycobacterium tuberculosis and Klebsiella pneumoniae, contain galactofuranose (Galf) residues in their cell envelope. Thus, glycan sequencing would benefit from methods to distinguish between pyranose and furanose isomers of different anomeric configurations. We used infrared multiple photon dissociation (IRMPD) spectroscopy with mass spectrometry (MS-IR) to differentiate between pyranose- and furanose-linked galactose residues. These targets pose a challenge for MS-IR because the saccharides lack basic groups, and galactofuranose residues are highly flexible. We postulated cationic groups that could complex through hydrogen bonding would offer a solution. Here, we present the first MS-IR analysis of hexose ammonium adducts. We compared their IR fingerprints with those of lithium adducts. We determined the diagnostic MS-IR signatures of the α- and β-anomers of galactose in furanose and pyranose forms. We also showed these signatures could be applied to disaccharides to assign galactose ring size. Our findings highlight the utility of MS-IR for analyzing the unique substructures that occur in bacterial glycans.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 15 publications.
- Ali H. Abikhodr, Stephan Warnke, Ahmed Ben Faleh, Thomas R. Rizzo. Combining Liquid Chromatography and Cryogenic IR Spectroscopy in Real Time for the Analysis of Oligosaccharides. Analytical Chemistry 2024, 96
(4)
, 1462-1467. https://doi.org/10.1021/acs.analchem.3c03578
- Oznur Yeni, Simon Ollivier, Baptiste Moge, David Ropartz, Hélène Rogniaux, Laurent Legentil, Vincent Ferrières, Isabelle Compagnon. Ring-Size Memory of Galactose-Containing MS/MS Fragments: Application to the Detection of Galactofuranose in Oligosaccharides and Their Sequencing. Journal of the American Chemical Society 2023, 145
(28)
, 15180-15187. https://doi.org/10.1021/jacs.3c01925
- Rianne E. van Outersterp, Pieter C. Kooijman, Jona Merx, Udo F.H. Engelke, Nematollah Omidikia, Mei-Lan H. Tonneijck, Kas J. Houthuijs, Giel Berden, Tessa M.A. Peters, Dirk J. Lefeber, Michel A. A. P. Willemsen, Jasmin Mecinovic, Jeroen J. Jansen, Karlien L.M. Coene, Ron A. Wevers, Thomas J. Boltje, Jos Oomens, Jonathan Martens. Distinguishing Oligosaccharide Isomers Using Far-Infrared Ion Spectroscopy: Identification of Biomarkers for Inborn Errors of Metabolism. Analytical Chemistry 2023, 95
(26)
, 9787-9796. https://doi.org/10.1021/acs.analchem.3c00363
- Simon Ollivier, Laurent Legentil, Oznur Yeni, Louis-Philippe David, Vincent Ferrières, Isabelle Compagnon, Hélène Rogniaux, David Ropartz. Gas-Phase Behavior of Galactofuranosides upon Collisional Fragmentation: A Multistage High-Resolution Ion Mobility Study. Journal of the American Society for Mass Spectrometry 2023, 34
(4)
, 627-639. https://doi.org/10.1021/jasms.2c00333
- Zhixin Xiong, Meixian Yang, Xiuting Chen, Yu Gong. Influence of Metal Coordination on the Gas-Phase Chemistry of the Positional Isomers of Fluorobenzoate Complexes. Journal of the American Society for Mass Spectrometry 2022, 33
(11)
, 2181-2190. https://doi.org/10.1021/jasms.2c00236
- Robert P. Pellegrinelli, Lei Yue, Eduardo Carrascosa, Ahmed Ben Faleh, Stephan Warnke, Priyanka Bansal, Thomas R. Rizzo. A New Strategy Coupling Ion-Mobility-Selective CID and Cryogenic IR Spectroscopy to Identify Glycan Anomers. Journal of the American Society for Mass Spectrometry 2022, 33
(5)
, 859-864. https://doi.org/10.1021/jasms.2c00043
- Dávid Szamosvári, Munhyung Bae, Sunghee Bang, Betsabeh Khoramian Tusi, Chelsi D. Cassilly, Sung-Moo Park, Daniel B. Graham, Ramnik J. Xavier, Jon Clardy. Lyme Disease, Borrelia burgdorferi, and Lipid Immunogens. Journal of the American Chemical Society 2022, 144
(6)
, 2474-2478. https://doi.org/10.1021/jacs.1c12202
- Stephan Warnke, Ahmed Ben Faleh, Thomas R. Rizzo. Toward High-Throughput Cryogenic IR Fingerprinting of Mobility-Separated Glycan Isomers. ACS Measurement Science Au 2021, 1
(3)
, 157-164. https://doi.org/10.1021/acsmeasuresciau.1c00018
- Marc Safferthal, Łukasz Polewski, Chun-Wei Chang, Kim Greis, Kevin Pagel. Cold-ion Spectroscopy of Carbohydrates. 2024, 76-94. https://doi.org/10.1039/9781839166433-00076
- Darren T. Gass, Ana V. Quintero, Jacob B. Hatvany, Elyssia S. Gallagher. Metal adduction in mass spectrometric analyses of carbohydrates and glycoconjugates. Mass Spectrometry Reviews 2024, 43
(4)
, 615-659. https://doi.org/10.1002/mas.21801
- M. P. Dvores, P. Çarçabal, R. B. Gerber. Selective reactivity of glycosyl cation stereoisomers: the role of intramolecular hydrogen bonding. Physical Chemistry Chemical Physics 2023, 25
(39)
, 26737-26747. https://doi.org/10.1039/D3CP03326K
- Min Kou, Young-Ho Oh, Sungyul Lee, Xianglei Kong. Distinguishing gas phase lactose and lactulose complexed with sodiated
l
-arginine by IRMPD spectroscopy and DFT calculations. Physical Chemistry Chemical Physics 2023, 25
(37)
, 25116-25121. https://doi.org/10.1039/D3CP03406B
- Baptiste Moge, Oznur Yeni, Alicia Infantino, Isabelle Compagnon. CO2 laser enhanced rapid IRMPD spectroscopy for glycan analysis. International Journal of Mass Spectrometry 2023, 490 , 117071. https://doi.org/10.1016/j.ijms.2023.117071
- Kim Greis, Carla Kirschbaum, Gert von Helden, Kevin Pagel. Gas-phase infrared spectroscopy of glycans and glycoconjugates. Current Opinion in Structural Biology 2022, 72 , 194-202. https://doi.org/10.1016/j.sbi.2021.11.006
- Oznur Yeni, Baptiste Schindler, Baptiste Moge, Isabelle Compagnon. Rapid IRMPD (InfraRed multiple photon dissociation) analysis for glycomics. The Analyst 2022, 147
(2)
, 312-317. https://doi.org/10.1039/D1AN01870A
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.