title: Selective detection of carbohydrates and their peptide conjugates by ESI-MS using synthetic quaternary ammonium salt derivatives of phenylboronic acids.
abstract: We present new tags based on the derivatives of phenylboronic acid and apply them for the selective detection of sugars and peptide-sugar conjugates in mass spectrometry. We investigated the binding of phenylboronic acid and its quaternary ammonium salt (QAS) derivatives to carbohydrates and peptide-derived Amadori products by HR-MS and MS/MS experiments. The formation of complexes between sugar or sugar-peptide conjugates and synthetic tags was confirmed on the basis of the unique isotopic distribution resulting from the presence of boron atom. Moreover, incorporation of a quaternary ammonium salt dramatically improved the efficiency of ionization in mass spectrometry. It was found that the formation of a complex with phenylboronic acid stabilizes the sugar moiety in glycated peptides, resulting in simplification of the fragmentation pattern of peptide-derived Amadori products. The obtained results suggest that derivatization of phenylboronic acid as QAS is a promising method for sensitive ESI-MS detection of carbohydrates and their conjugates formed by non-enzymatic glycation or glycosylation.
authors.affiliation: Faculty of Chemistry, University of Wroclaw, Wroclaw, Poland, monika.kijewska@chem.uni.wroc.pl.
authors.forename: Monika
authors.initials: M
authors.lastname: Kijewska
authors.forename: Adam
authors.initials: A
authors.lastname: Kuc
authors.forename: Alicja
authors.initials: A
authors.lastname: Kluczyk
authors.forename: Mateusz
authors.initials: M
authors.lastname: Waliczek
authors.forename: Aleksandra
authors.initials: A
authors.lastname: Man-Kupisinska
authors.forename: Jolanta
authors.initials: J
authors.lastname: Lukasiewicz
authors.forename: Piotr
authors.initials: P
authors.lastname: Stefanowicz
authors.forename: Zbigniew
authors.initials: Z
authors.lastname: Szewczuk
mesh_terms: D001897:Boronic Acids / Q000737:chemistry*; D002241:Carbohydrates / Q000032:analysis* / Q000737:chemistry; D010455:Peptides / Q000032:analysis* / Q000737:chemistry; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
chemical_list: D001897:Boronic Acids; D002241:Carbohydrates; D010455:Peptides; D000644:Quaternary Ammonium Compounds; C010686:benzeneboronic acid