title: Matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectra of poly(butylene adipate).
abstract: Matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectrometry (MALDI-TOF/TOF-MS/MS) was employed to analyze four poly(butylene adipate) (PBAd) oligomers and to investigate their fragmentation pathways as a continuation of our work on the MALDI-TOF/TOF-MS/MS study of synthetic polymers. MALDI-TOF/TOF-MS/MS analysis was performed on oligomers terminated by carboxyl and hydroxyl groups, methyl adipate and hydroxyl groups, dihydroxyl groups, and dicarboxyl groups. The sodium adducts of these oligomers were selected as precursor ions. Different end groups do not influence the fragmentation of sodiated polyester oligomers and similar series of product ions were observed in all the MALDI-TOF/TOF-MS/MS spectra. According to the structures of the most abundant product ions identified in the present work, three fragmentation pathways have been proposed to occur most frequently in PBAd: beta-hydrogen-transfer rearrangement, leading to the selective cleavage of the --O--CH(2)-- bonds; --CH(2)--CH(2)-- (beta--beta) bond cleavage in the adipate moiety; and ester bond scission.
authors.affiliation: Istituto di Chimica e Tecnologia dei Polimeri, Consiglio Nazionale delle Ricerche, V. le A. Doria 6, 95125 Catania, Italy. prizzarelli@dipchi.unict.it
authors.forename: Paola
authors.initials: P
authors.lastname: Rizzarelli
authors.forename: Concetto
authors.initials: C
authors.lastname: Puglisi
authors.forename: Giorgio
authors.initials: G
authors.lastname: Montaudo
mesh_terms: D002072:Butylene Glycols / Q000032:analysis*; D007202:Indicators and Reagents; D011108:Polymers / Q000032:analysis*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D053719:Tandem Mass Spectrometry
chemical_list: D002072:Butylene Glycols; D007202:Indicators and Reagents; D011108:Polymers; C009204:butylene glycol adipic acid polyester