Mechanistic study of the collision-induced dissociation of sodium-cationized polylactide oligomers: a joint experimental and theoretical investigation.
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.
De Winter
Julien
J
Mass Spectrometry Research Group, Centre Interdisciplinaire de Spectrométrie de Masse (CISMa), University of Mons, Mons, Belgium.
Lemaur
Vincent
V
Marsal
Philippe
P
Coulembier
Olivier
O
Cornil
Jérôme
J
Dubois
Philippe
P
Gerbaux
Pascal
P
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
D002412:Cations; D011091:Polyesters; C033616:poly(lactide); D012964:Sodium