Protein carbonylation: 2,4-dinitrophenylhydrazine reacts with both aldehydes/ketones and sulfenic acids.

Free Radic Biol Med, 2009/5/15;46(10):1411-9.

Dalle-Donne I[1], Carini M, Orioli M, Vistoli G, Regazzoni L, Colombo G, Rossi R, Milzani A, Aldini G

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PMID: 19268703DOI: 10.1016/j.freeradbiomed.2009.02.024

Impact factor: 8.101

Abstract
Most of the assays for detection of carbonylated proteins, the most general and widely used marker of severe protein oxidation, involve derivatization of the carbonyl group with 2,4-dinitrophenylhydrazine (DNPH), which leads to formation of a stable dinitrophenyl hydrazone product. Here, by using a Cys-containing model peptide and high-resolution mass spectrometry, we demonstrate that DNPH is not exclusively selective for carbonyl groups, because it also reacts with sulfenic acids, forming a DNPH adduct, through the acid-catalyzed formation of a thioaldehyde intermediate that is further converted to an aldehyde. beta-Mercaptoethanol prevents the formation of the DNPH derivative because it reacts with the oxidized Cys residue, forming the corresponding disulfide.
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