Characterization of chemical interferences in the determination of unsaturated aldehydes using aromatic hydrazine reagents and liquid chromatography

Abstract

A systematic investigation on interferences in the determination of unsaturated aldehydes and ketones using the 2,4-dinitrophenylhydrazine (DNPH) method is described. Acrolein, crotonaldehyde, methacrolein and 1-buten-3-one are derivatized with DNPH in the presence of an acidic catalyst to form the respective hydrazones. The unstable hydrazones react with excess reagent to form adducts. These are identified by high-performance liquid chromatography (HPLC)-mass spectrometry and spectroscopic techniques after cryogenic fraction collection of the adducts. The quantification of the unsaturated carbonyls with the DNPH method remains difficult. N-Methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) was used as an alternative reagent for this purpose. As with DNPH, the formation of a side product is observed. In contrast to DNPH, the alteration of the pH immediately after sampling leads to only one reaction product, which is stable and storable in solution at 4 °C for 2 days.