title: Infrared multiphoton dissociation spectroscopy of cationized serine: effects of alkali-metal cation size on gas-phase conformation.
abstract: The gas-phase structures of alkali-metal cation complexes of serine (Ser) are examined using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser, in conjunction with ab initio calculations. Spectra of Li+(Ser) and Na+(Ser) are similar and relatively simple, whereas Cs+(Ser) includes distinctive new IR bands, and K+(Ser) and Rb+(Ser) exhibit intermediate behavior. Measured IRMPD spectra are compared to spectra calculated at a B3LYP/6-311+G(d,p) level to identify the structures present in the experimental studies. On the basis of these experiments and calculations, the only conformations accessed for the complexes to the smaller alkali-metal cations, Li+ and Na+, are charge-solvated structures involving tridentate coordination to the amine and carbonyl groups of the amino acid backbone and to the hydroxyl group of the side chain, M1[N,CO,OH]. For the cesiated complex, a band corresponding to a zwitterionic structure, ZW[CO2-], is clearly visible. K+(Ser) and Rb+(Ser) exhibit evidence of the charge-solvated analogue of the zwitterions, M3[COOH], in which the metal cation binds to the carboxylic acid group. Calculations indicate that the relative stability of the M3[COOH] structure is very strongly dependent on the size of the metal cation, consistent with the range of conformations observed experimentally.
authors.affiliation: Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA.
authors.forename: P B
authors.initials: PB
authors.lastname: Armentrout
authors.forename: M T
authors.initials: MT
authors.lastname: Rodgers
authors.forename: J
authors.initials: J
authors.lastname: Oomens
authors.forename: J D
authors.initials: JD
authors.lastname: Steill