title: Production of doubly-charged highly reactive species from the long-chain amino acid GABA initiated by Ar9+ionization.
abstract: We present a combined experimental and theoretical study of the fragmentation of multiply-charged γ-aminobutyric acid molecules (GABAz+, z = 2, 3) in the gas phase. The combination of ab initio molecular dynamics simulations with multiple-coincidence mass spectrometry techniques allows us to observe and identify doubly-charged fragments in coincidence with another charged moiety. The present results indicate that double and triple electron capture lead to the formation of doubly-charged reactive nitrogen and oxygen species (RNS and ROS) with different probabilities due to the different charge localisation and fragmentation behaviour of GABA2+and GABA3+. The MD simulations unravel the fast (femtosecond) formation of large doubly charged species, observed on the experimental microsecond timescale. The excess of positive charge is stabilised by the presence of cyclic X-member (X = 3-5) ring structures. 5-Member cyclic molecules can sequentially evaporate neutral moieties, such as H2, H2O and CO2, leading to smaller doubly charged fragments as those observed in the experiments.
authors.affiliation: Departamento de Química, Módulo 13, Universidad Autónoma de Madrid, 28049 Madrid, Spain. dariusz.piekarski@uam.es sergio.diaztendero@uam.es.
authors.forename: Dariusz Grzegorz
authors.initials: DG
authors.lastname: Piekarski
authors.forename: Rudy
authors.initials: R
authors.lastname: Delaunay
authors.forename: Arkadiusz
authors.initials: A
authors.lastname: Mika
authors.forename: Sylvain
authors.initials: S
authors.lastname: Maclot
authors.forename: Lamri
authors.initials: L
authors.lastname: Adoui
authors.forename: Fernando
authors.initials: F
authors.lastname: Martín
authors.forename: Manuel
authors.initials: M
authors.lastname: Alcamí
authors.forename: Bernd A
authors.initials: BA
authors.lastname: Huber
authors.forename: Patrick
authors.initials: P
authors.lastname: Rousseau
authors.forename: Sergio
authors.initials: S
authors.lastname: Díaz-Tendero
authors.forename: Alicja
authors.initials: A
authors.lastname: Domaracka
mesh_terms: D001128:Argon / Q000737:chemistry*; D004583:Electrons; D005740:Gases / Q000737:chemistry; D007477:Ions / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D026361:Reactive Nitrogen Species / Q000737:chemistry; D017382:Reactive Oxygen Species / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D005680:gamma-Aminobutyric Acid / Q000737:chemistry*
chemical_list: D005740:Gases; D007477:Ions; D026361:Reactive Nitrogen Species; D017382:Reactive Oxygen Species; D005680:gamma-Aminobutyric Acid; D001128:Argon