Synthesis of an Exhaustive Library of Naturally Occurring Galf-Manp and Galp-Manp Disaccharides. Toward Fingerprinting According to Ring Size by Advanced Mass Spectrometry-Based IM-MS and IRMPD

Abstract

HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

Gas-Phase Behavior of Galactofuranosides upon Collisional Fragmentation: A Multistage High-Resolution Ion Mobility Study

“…This peculiar behavior will be studied in more details in later sections of this article. In addition, we observed a doublet of peaks at 22.8 and 21.5 ms, which are specific of Gal f -(β1,4)-Man according to our disaccharide database, that contains all regioisomers of Gal f -Man p and Gal p -Man p disaccharides (see Table S1). This indicates that in the case of trisaccharide ③ there has been a migration of the Gal f residue to C-4 of the reducing Man, with an internal residue loss of a Man subunit.…”

“…The Gal-Man disaccharides used as references in this study were previously used to build a library of IMS-MS and IRMPD profiles. Their synthesis and NMR validation are reported in this earlier publication by Favreau et al…”

“…Gas-phase methods that are sensitive to isomerismsuch as Ion Mobility-Mass Spectrometry (IMS-MS) − and InfraRed Multiple Photon Dissociation (IRMPD) spectroscopy ,− have been reported recently as promising complements to MS. In Favreau et al, both methods achieved a specific signature for Gal p or Gal f from a library of eight synthetic Gal-Man disaccharides, composed of all Gal f /Gal p pairs for the four linkage regioisomers of the Gal-Man linkage. This proof-of-concept work proposed that both IMS-MS and IRMPD could be considered to specifically detect Gal f -containing motifs in larger naturally occurring polysaccharides by using a bottom-up strategy involving fragmentation approaches such as CID (collision-induced dissociation).…”

Carboxyl-Based CPMP Tag for Ultrasensitive Analysis of Disaccharides by Negative Tandem Mass Spectrometry

“…The chemical derivatization approach can, on the one hand, enhance the mass spectrometric response signal of sugars by increasing their hydrophobicity. − On the other hand, the derivatized sugars can be sequenced and isomerized by characteristic fragments generated via multiple-stage mass spectrometry (MS n ). , PMP (1-phenyl-3-methyl-5-pyrazolone) is a distinct reagent for labeling saccharides under moderate conditions. , Although PMP-labeled disaccharides have been successfully used for the identification of isomeric disaccharides by positive IM-MS, the quantification was restricted to the low resolution to obtain the baseline separation of isomers . In addition, multiple positive ion adducts such as [M + H] + , [M + Na] + , [M + NH 4 ] + , and [M + K] + complicate the MS interpretation and decrease their detection sensitivity. , For the relative quantitative analysis of glycan by derivatization methods, the design and synthesis of stable isotope labeling reagents were traditionally emphasized. , However, the application of the derivatization method for isomeric disaccharides’ quantification has not been reported so far.…”

“…43,44 PMP (1-phenyl-3-methyl-5-pyrazolone) is a distinct reagent for labeling saccharides under moderate conditions. 45,46 Although PMP-labeled disaccharides have been successfully used for the identification of isomeric disaccharides by positive IM-MS, the quantification was restricted to the low resolution to obtain the baseline separation of isomers. 47 In addition, multiple positive ion adducts such as [M + H] + , [M + Na] + , [M + NH 4 ] + , and [M + K] + complicate the MS interpretation and decrease their detection sensitivity.…”