title: Fragmentation of mycosporine-like amino acids by hydrogen/deuterium exchange and electrospray ionisation tandem mass spectrometry.
abstract: The determination and identification of mycosporine-like amino acids (MAAs) from algae remain a major challenge due to the low concentration. Mass spectrometry (MS) can make an invaluable contribution in the search and identification of MAAs because of its high sensitivity, possibility of coupling with liquid chromatography, and the availability of powerful tandem mass spectrometric techniques. However, the unequivocal determination of the presence and location of important functional groups present on the basic skeleton of the MAAs is often elusive due to their inherent instability under MS conditions. In this study, the use of hydrogen/deuterium (H/D) exchange and electrospray ionisation tandem mass spectrometry (ESI-MS/MS) for characterisation of four MAAs (palythine, asterina, palythinol and shinorine) isolated from the macroalgae Gracilaria tenuistipitata Chang et Xia was investigated. The accurate-mass confirmation of the protonated molecules was performed on a Q-TOF instrument. We demonstrate that employing deuterium labelling in ESI-MS/MS analysis provides a convenient tool for the determination of new MAAs. Although the fragmentation patterns of MAAs were discussed earlier, to our knowledge, this is the first time that mechanisms are proposed.
authors.affiliation: Universidade de São Paulo, Instituto de Química, Departamento de Bioquímica, Av Professor Lineu Prestes, 748 CP 20780, CEP 05508900, São Paulo-SP, Brazil.
authors.forename: Karina H M
authors.initials: KH
authors.lastname: Cardozo
authors.forename: Valdemir M
authors.initials: VM
authors.lastname: Carvalho
authors.forename: Ernani
authors.initials: E
authors.lastname: Pinto
authors.forename: Pio
authors.initials: P
authors.lastname: Colepicolo
mesh_terms: D020418:Algal Proteins / Q000032:analysis*; D000596:Amino Acids / Q000032:analysis* / Q000737:chemistry; D041961:Deuterium Exchange Measurement / Q000379:methods*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D044724:Gracilaria / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
chemical_list: D020418:Algal Proteins; D000596:Amino Acids