Elucidating the Fragmentation Pathways of Cyclic and Linear Poly(dimethylpropanoate) via Tandem Mass Spectrometry and Ion Mobility Mass Spectrometry
Year: 2026
Type: article
Abstract: More than one-half of the world's plastic waste comes from poorly recyclable polymers, such as polyethylene and polypropylene. The increased accumulation of plastic waste is a growing environmental challenge. This led to the employment of polyesters with controlled degradation behavior for a variety of materials applications. Understanding the relationship between polymer structure and fragmentation pathways is essential for designing materials that balance durability and sustainability. Polyesters and polyamides with an Cα adjacent to the carbonyl, fragment via 1,5- and 1,3-hydrogen rearrangements; however, the fragmentation of a polyester where an is not present adjacent to the carbonyl has not been researched thoroughly. This work reports the first detailed characterization of the fragmentation behavior of both linear and cyclic poly(dimethylpropanoate) (poly(DMP)). Poly(DMP) possesses a neopentyl carbon which slows degradation and inhibits the typical 1,5-hydrogen rearrangements common in other polyesters. Cyclic poly(DMP) undergoes ring opening at various points before fragment generation, resulting in a mixture of ring-opened linear species, while the linear polymer predominantly fragments through single-bond cleavages. Additionally, the fragmentation patterns are influenced by poly(DMP) end groups, with distinct patterns observed for hydroxyl-terminated, halogen-terminated, and pyridinium-initiated polymers. Moreover, ion mobility mass spectrometry (IM-MS) effectively distinguishes isomeric fragments in cyclic poly(DMP) based on the differences in the collision cross-section of cyclic precursor and the resulting linear fragment ions.
Institutions: Tulane University, University of Akron
Language: English
Subfield: Spectroscopy
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: Collaborative Research: Comprehending the Unique Polyhydroxylated Dendritic Compounds and their Utility for Advanced Dielectric Applications, MRI: Track 1: Acquisition of a MALDI-TOF-TOF Mass Spectrometer with TOF/TOF Capabilities, G6807129519, MRI: Acquisition of a MALDI‐ToF Mass Spectrometer to Advance Research and Education in Polymer Science and Engineering, G8507380447
OpenAlex ID: W7223410845