title: Mechanistic study of the collision-induced dissociation of sodium-cationized polylactide oligomers: a joint experimental and theoretical investigation.
abstract: The low-kinetic energy collision-induced dissociation (CID) behavior of different sodium-cationized polylactide (PLA) oligomers was thoroughly investigated to shed some light on the analytical potentialities of CID experiments in the context of polymer characterization. Indeed, investigation of several end-groups modified PLA reveals that, in addition to the expected end-group specific dissociations, collisionally-excited PLA.Na(+) suffer from a backbone cleavage. The so-obtained sodium-bound dimer cations consecutively undergo the loss of a monomeric residue that corresponds to neutral acrylic acid. The experimental observations, performed on a hybrid Q-ToF instrument, were totally corroborated by a theoretical study involving DFT calculations, molecular mechanics, and molecular dynamics calculations.
authors.affiliation: Mass Spectrometry Research Group, Centre Interdisciplinaire de Spectrométrie de Masse (CISMa), University of Mons, Mons, Belgium.
authors.forename: Julien
authors.initials: J
authors.lastname: De Winter
authors.forename: Vincent
authors.initials: V
authors.lastname: Lemaur
authors.forename: Philippe
authors.initials: P
authors.lastname: Marsal
authors.forename: Olivier
authors.initials: O
authors.lastname: Coulembier
authors.forename: Jérôme
authors.initials: J
authors.lastname: Cornil
authors.forename: Philippe
authors.initials: P
authors.lastname: Dubois
authors.forename: Pascal
authors.initials: P
authors.lastname: Gerbaux
mesh_terms: D002412:Cations / Q000737:chemistry; D008958:Models, Molecular; D011091:Polyesters / Q000737:chemistry*; D012964:Sodium / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods*; D013696:Temperature; D013816:Thermodynamics
chemical_list: D002412:Cations; D011091:Polyesters; C033616:poly(lactide); D012964:Sodium