Structure Elucidation of 2,4-Dinitrophenylhydrazone Derivatives of Carbonyl Compounds in Ambient Air by HPLC/MS and Multiple MS/MS Using Atmospheric Chemical Ionization in the Negative Ion Mode
Ion trap multiple fragmentation mass spectrometry(MSn)combined with high-performance liquid chromatography(HPLC) has been used for the structure elucidation andidentification of 2,4-dinitrophenylhydrazone derivativesofcarbonyl compounds in ambient air samples. Atmospheric pressure chemical ionization in the negative ionmode was the most suitable detection method.Differentmeasures are described to decrease the MS backgroundoriginating from the HPLC system. Low-picogramquantities were detectable in extracted mass chromatogramsgenerated from full-scan records. Fragment ions produced by MS/MS allowed identification of substructuresof the carbonyls. Detailed fragmentation paths werestudied by MS3 to MS4 using referencecompounds. Afragmentation scheme was established which enabled astructure confirmation and identification with 1-10 ngby HPLC/MS/MS. The identification of a compoundcoeluting with n-pentanal-DNPH and of adimerizationbyproduct are given as examples.