Assessing Transesterification Reagents for Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry of Biodegradable Polymers

초록

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is a powerful technique for polymer identification because it can ionize intact macromolecules with large molecular weights (>100 kDa) and detect them over a theoretically unlimited mass range. However, limited mass resolution, accuracy, and sensitivity in the high-mass region restrict detailed structural characterization of polymers. Depolymerization into smaller fragments using established chemistry, such as transesterification, provides a versatile alternative approach. The resulting characteristic fragments (<3 kDa) are polymer-specific and enable both polymer identification and detailed structural analysis, benefiting from the higher mass accuracy and sensitivity in the low-mass range and allowing MS/MS-based identification. To establish general sample-preparation conditions, this study systematically investigated the effects of transesterification of biodegradable polyesters using MeO-/MeOH, EtO-/EtOH, and t-BuO-/t-BuOH on subsequent MALDI-TOF MS analysis. Among the reagents examined, EtO-/EtOH combined with THAP/THF matrix treatment was found to be the most efficient, enabling rapid polyester analysis by MALDI-TOF MS within 10 min when the reaction time and reagent concentration were carefully controlled within an optimal window.

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