Analysis of acrylamide in food additives via Michael addition derivatization and liquid chromatography-tandem mass spectrometry.

Acrylamide (AA) is a highly polar compound that exhibits poor retention and low selectivity in conventional reversed-phase LC-MS analyses. To establish a derivatization-based LC-MS/MS method for AA, we evaluated the potential of 5-(dimethylamino)-N-(2-sulfanylethyl)naphthalene-1-sulfonamide (DNS-SH) as an effective derivatization reagent and compared its performance with that of other representative thiol reagents. The ionization efficiency, the formation of product ions during collision-induced dissociation, and the progress of the reaction-as analyzed by LC-MS (MS/MS)-were accurately evaluated based on the molar ratios determined by 1H-qNMR. The DNS derivative of AA (AA-DNS) exhibited a superior MS response than its other thiol derivatives, providing a 4-17-fold higher MS/MS signal intensity. In addition, computational studies indicate that DNS-SH has the potential to be a more effective derivatization reagent with higher reactivity. These results indicate that analytical performance is strongly influenced by the structural characteristics of thiol reagents, particularly their ionization efficiency and product-ion formation. The newly developed analytical method was applied to quantify AA in food additives subjected to heating during manufacturing, revealing that its concentration was negligible in these samples. This finding suggests that food additives contribute minimally to overall dietary exposure to AA. Thus, the proposed method provides a highly sensitive approach for determining AA.