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Derivatization of β‐dicarbonyl compound with 2,4‐dinitrophenylhydrazine to enhance mass spectrometric detection: application in quantitative analysis of houttuynin in human plasma
Author(s) -
Duan Xiaotao,
Zhong Dafang,
Chen Xiaoyan
Publication year - 2008
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1382
Subject(s) - chemistry , derivatization , chromatography , mass spectrometry , detection limit , tandem mass spectrometry , selected reaction monitoring , benzophenone , chemical ionization , ionization , organic chemistry , ion
Houttuynin (decanoyl acetaldehyde), a β‐dicarbonyl compound, is the major antibacterial constituent in the volatile oil of Houttuynina cordata Thunb. In the present work, detection of houttuynin in human plasma based on the chemical derivatization with 2,4‐dinitrophenylhydrazine (DNPH) coupled with liquid chromatography/tandem mass spectrometry was described. The primary reaction products between the β‐dicarbonyl compound and DNPH in aqueous phase were identified as heterocyclic structures, of which the mass spectrometric ionization and fragmentation behavior were characterized with the aid of high‐resolution multistage mass spectral analysis. For quantification, houttuynin and internal standard (IS, benzophenone) in plasma were firstly converted to their DNPH derivatives without sample purification, then extracted from human plasma with n ‐hexane and detected by liquid chromatography tandem mass spectrometry performed in selected reaction monitoring (SRM) mode. This method allowed for a lower limit of quantification (LLOQ) of 1.0 ng/ml using 100‐µl plasma. The validation results showed high accuracy (%bias < 2.1) and precision (%CV < 7.2) at broad linear dynamic range (1.0–5000 ng/ml). The simple and quantitative derivatization coupled with tandem mass spectrometric analysis facilitates a sensitive and robust method for the determination of plasma houttuynin in pharmacokinetic studies. Copyright © 2008 John Wiley & Sons, Ltd.