Analysis of monodisperse,sequence-defined,and POSS-functionalized polyester copolymers by MALDI tandem mass spectrometry

Abstract

Monodisperse, sequence-defined polymers can be potentially used for digital data storage. This study reports the sequence analysis and differentiation of monodisperse polyester copolymers carrying side chains functionalized in a specific order by polyhedral oligomeric silsesquioxane (POSS) nanoparticles. Steglich esterification and succinic anhydride ring-opening chemistries were utilized iteratively to synthesize the intended sequences, which were characterized by matrix-assisted laser desorption ionization tandem mass spectrometry (MALDI-MS²). Isomeric oligomers were readily distinguished based on their different fragmentation patterns. The sequences embedded in the oligomers were decrypted by their specific backbone dissociation pathways. The robustness of using MALDI-MS² as a sequencing method for monodisperse synthetic macromolecules was assessed and validated by the characterization of longer oligomers.

Keywords

Polyester copolymers isomeric sequences isomer differentiation MALDI tandem mass spectrometry sequence decoding

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