Modern mass spectrometry in the characterization and degradation of biodegradable polymers

• Recent trends in the structural characterization of biodegradable polymers by MALDI and ESI MS are discussed.
• MALDI MS as a noteworthy tool to follow the synthetic polymerization route of biodegradable materials is evidenced.
• Elucidation of degradation mechanisms by modern MS techniques is examined.
• ESI MS and HPLC–ESI MS are highlighted as highly suitable methods for structural and quantitative analysis of water-soluble biodegradation products.
• Novel MS methods developed ad hoc and new MALDI matrices for biodegradable polymers are reviewed.

In the last decades, the solid-waste management related to the extensively growing production of plastic materials, in concert with their durability, have stimulated increasing interest in biodegradable polymers. At present, a variety of biodegradable polymers has already been introduced onto the market and can now be competitive with non biodegradable thermoplastics in different fields (packaging, biomedical, textile, etc.). However, a significant economical effort is still directed in tailoring structural properties in order to further broaden the range of applications without impairing biodegradation. Improving the performance of biodegradable materials requires a good characterization of both physico-chemical and mechanical parameters. Polymer analysis can involve many different features including detailed characterization of chemical structures and compositions as well as average molecular mass determination. It is of outstanding importance in troubleshooting of a polymer manufacturing process and for quality control, especially in biomedical applications. This review describes recent trends in the structural characterization of biodegradable materials by modern mass spectrometry (MS). It provides an overview of the analytical tools used to evaluate their degradation. Several successful applications of MALDI-TOF MS (matrix assisted laser desorption ionization time of flight) and ESI MS (electrospray mass spectrometry) for the determination of the structural architecture of biodegradable macromolecules, including their topology, composition, chemical structure of the end groups have been reported. However, MS methodologies have been recently applied to evaluate the biodegradation of polymeric materials. ESI MS represents the most useful technique for characterizing water-soluble polymers possessing different end group structures, with the advantage of being easily interfaced with solution-based separation techniques such as high-performance liquid chromatography (HPLC).

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