Click-chemistry-driven sorbent design: A thiol-ene-yne functionalized silica for the extraction of acrylamide as a...

Click chemistry represents a powerful and modular approach for the rational design of functional materials; however, its application in the development of analytical extraction phases remains largely underexplored. The efficient extraction of small and highly polar analytes still poses significant challenges, particularly in complex food matrices, where conventional sorbents often show limited retention and selectivity.

In this study, a novel multifunctional silica-based sorbent was synthesized through a combined thiol-ene and thiol-yne click functionalization strategy. Vinyl-modified silica was sequentially reacted with dithiothreitol and propargylamine under radical conditions, generating a highly polar surface enriched in Thioether, -OH, and -NH groups. The resulting material (Silica@ene@yne@SH) was designed to provide a hydrogen-bonding-rich and chemically versatile interface for the retention of polar analytes. The sorbent was implemented as an in-tip solid-phase microextraction (SPME) phase and evaluated using acrylamide as a model compound. Coupling the in-tip SPME platform with UHPLC-MS/MS enabled rapid extraction, efficient matrix cleanup, and sensitive determination of acrylamide in potato chips, with reduced solvent consumption and minimal sample handling.

This study demonstrates the potential of thiol-based click chemistry for engineering advanced microextraction sorbents with tailored surface functionality. The proposed approach provides a sustainable and efficient analytical platform, demonstrated here for acrylamide, for the determination of highly polar contaminants, expanding the role of click-functionalized materials in modern sample preparation. This work serves as a proof-of-concept for the extraction of small polar analytes in complex food matrices.