Molecular level structure of novel synthetic analogues of aliphatic biopolyesters as revealed by multistage mass spectrometry

•We examine the molecular structure of novel PHA analogues by ESI-MSn.•Sequence distribution of low molecular mass copolyesters has been determined.•ESI-MSn approach for structural studies of random copolyesters is described.

The present study focuses on electrospray ionisation (ESI) tandem mass spectrometry of novel copolyesters obtained by anionic ring-opening copolymerisation of β-substituted β-lactones. Detailed analysis of these copolyesters, including molecular chain architecture as well as the structures of the end groups, was performed using ESI-MS/MS collision-induced dissociation spectra. The random arrangement of comonomeric units along the copolyester chains was demonstrated by comparison of ESI-MSn fragmentation spectra and fragmentation pathways. Sequence distribution analysis of comonomeric units confirmed the copolymer's random structure. ESI-MSn proved to be a promising technique for structural analysis of copolyesters obtained via anionic ROP.

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