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Effects of calcium complexation on heparin‐like disaccharides. A combined theoretical, tandem mass spectrometry and ultraviolet experiment
Author(s) -
Ortiz Daniel,
Enjalbert Quentin,
MacAleese Luke,
Dugourd Philippe,
Salpin JeanYves
Publication year - 2015
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.7204
Subject(s) - chemistry , dissociation (chemistry) , photodissociation , fragmentation (computing) , ultraviolet , metal , mass spectrometry , calcium , tandem mass spectrometry , tandem , deprotonation , analytical chemistry (journal) , ion , photochemistry , chromatography , organic chemistry , physics , quantum mechanics , computer science , operating system , materials science , composite material
Rationale In order to shed light on the influence of the Ca 2+ metal cation on the structure of heparin‐like (Hp) disaccharides, we have explored the gas‐phase structures of both [Hp, −2H] 2− and [Ca(Hp), −3H] − ions by coupling experimental and theoretical methods. Methods The goal of this work was to (i) provide new evidence of the metal influence on the Hp structure, which can have important biological consequences, and (ii) to study the usefulness of metal complexation for the analytical distinction of Hp isomers. Collision‐induced dissociation (CID) and ultraviolet photodissociation (UVPD) fragments, as well as optical spectra recorded in the gas phase for both [Hp, −2H] 2− and [Ca(Hp), −3H] − complexes were compared for I‐H, II‐S and III‐S isomers of Hp. Results In the case of CID fragmentation, a change in the fragmentation pattern was observed upon calcium complexation, with respect to deprotonated Hp. Conclusions Remarkably, when optical spectra are compared in the UV range, the metal effect on the carboxylic group absorption can be detected by an unambiguous blue‐shift (~20 nm). Copyright © 2015 John Wiley & Sons, Ltd.