title: Electrospray ionization ion mobility spectrometry of carboxylate anions: ion mobilities and a mass-mobility correlation.
abstract: A number of carboxylate anions spanning a mass range of 87-253 amu (pyruvate, oxalate, malonate, maleate, succinate, malate, tartarate, glutarate, adipate, phthalate, citrate, gluconate, 1,2,4-benzenetricarboxylate, and 1,2,4,5-benzenetetracarboxylate) were investigated using electrospray ionization ion mobility spectrometry. Measured ion mobilities demonstrated a high correlation between mass and mobility in both N2 and CO2 drift gases. Such a strong mass-mobility correlation among structurally dissimilar ions suggests that the carboxylate functional group that these ions have in common is the source of the correlation. Computational analysis was performed to determine the most stable conformation of the studied carboxylate anions in the gas phase under the current experimental conditions. This analysis indicated that the most stable conformations for multicarboxylate anions included intramolecular hydrogen-bonded ring structures formed between the carboxylate group and the neutral carboxyl group. The carboxylate anions that form ring confirmations generally show higher ion mobility values than those that form extended conformations. This is the first observation of intramolecular hydrogen-bonded ring conformation of carboxylate anions in the gas phase at atmospheric pressure.
authors.affiliation: Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Hugh I
authors.initials: HI
authors.lastname: Kim
authors.forename: Paul V
authors.initials: PV
authors.lastname: Johnson
authors.forename: Luther W
authors.initials: LW
authors.lastname: Beegle
authors.forename: J L
authors.initials: JL
authors.lastname: Beauchamp
authors.forename: Isik
authors.initials: I
authors.lastname: Kanik
mesh_terms: D000838:Anions; D002264:Carboxylic Acids / Q000737:chemistry*; D008962:Models, Theoretical; D015394:Molecular Structure; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
chemical_list: D000838:Anions; D002264:Carboxylic Acids