title: Determination of aldehydes and ketones using derivatization with 2,4-dinitrophenylhydrazine and liquid chromatography-atmospheric pressure photoionization-mass spectrometry.
abstract: Atmospheric pressure photoionization-mass spectrometry (APPI-MS) is used for the analysis of aldehydes and ketones after derivatization with 2,4-dinitrophenylhydrazine (DNPH) and liquid chromatographic separation. In the negative ion mode, the [M - H]- pseudomolecular ions are most abundant for the carbonyls. Compared with the established atmospheric pressure chemical ionization (APCI)-MS, limits of detection are typically lower using similar conditions. Automobile exhaust and cigarette exhaust samples were analyzed with APPI-MS and APCI-MS in combination with an ion trap mass analyzer. Due to improved limits of detection, more of the less abundant long-chain carbonyls are detected with APPI-MS in real samples. While 2,4-dinitrophenylazide, a known reaction product of DNPH with nitrogen dioxide, is detected in APCI-MS due to dissociative electron capture, it is not observed at all in APPI-MS.
authors.affiliation: Department of Chemical Analysis and MESA+ Institute for Nanotechnology, University of Twente, 7500 AE Enschede, The Netherlands.
authors.forename: Suze M
authors.initials: SM
authors.lastname: van Leeuwen
authors.forename: Laurens
authors.initials: L
authors.lastname: Hendriksen
authors.forename: Uwe
authors.initials: U
authors.lastname: Karst
mesh_terms: D000447:Aldehydes / Q000032:analysis*; D001274:Atmospheric Pressure; D002853:Chromatography, Liquid / Q000379:methods*; D007659:Ketones / Q000032:analysis*; D013058:Mass Spectrometry / Q000379:methods*; D010659:Phenylhydrazines / Q000032:analysis*; D010777:Photochemistry
chemical_list: D000447:Aldehydes; D007659:Ketones; D010659:Phenylhydrazines; C004787:2,4-dinitrophenylhydrazine