title: Vibrational signatures of protonated, phosphorylated amino acids in the gas phase.
abstract: Structural characterization of protonated phosphorylated serine, threonine, and tyrosine was performed using mid-infrared multiple photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations. The ions were generated and analyzed by an external electrospray source coupled to a Paul ion-trap type mass spectrometer. Their fragmentation was induced by the resonant absorption of multiple photons from a tunable free electron laser (FEL) beam. IRMPD spectra were recorded in the 900-1850 cm(-1) energy range and compared to the corresponding computed IR spectra. On the basis of the frequency and intensity of two independent bands in the 900-1400 cm(-1) energy range, it is possible to identify the phosphorylated residue. IRMPD spectra for a 12-residue fragment of stathmin in its phosphorylated and nonphosphorylated forms were also recorded in the 800-1400 cm(-1) energy range. The lack of spectral congestion in the 900-1300 cm(-1) region makes their distinction facile. Our results show that IRMPD spectroscopy may became a valuable tool for structural characterization of small phosphorylated peptides.
authors.affiliation: Laboratoire des Mécanismes Réactionnels, Département de Chimie, Ecole Polytechnique, CNRS, 91128 Palaiseau Cedex, France.
authors.forename: Catarina F
authors.initials: CF
authors.lastname: Correia
authors.forename: Petru O
authors.initials: PO
authors.lastname: Balaj
authors.forename: Debora
authors.initials: D
authors.lastname: Scuderi
authors.forename: Philippe
authors.initials: P
authors.lastname: Maitre
authors.forename: Gilles
authors.initials: G
authors.lastname: Ohanessian
mesh_terms: D005740:Gases / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D010766:Phosphorylation; D011522:Protons; D012694:Serine / Q000737:chemistry*; D013055:Spectrophotometry, Infrared / Q000379:methods; D013912:Threonine / Q000737:chemistry*; D014443:Tyrosine / Q000737:chemistry*; D014732:Vibration
chemical_list: D005740:Gases; D011522:Protons; D013912:Threonine; D014443:Tyrosine; D012694:Serine