Atmospheric pressure chemical ionization mass spectrometry of aldehydes in biological matrices

Abstract

Application of high-performance liquid chromatography (HPLC) and tandem mass spectrometry (MS/MS) for detection of aldehydes in biological samples such as blood, yoghurt, and milk, is reported. Sample preparation is easy, and the presented method is both sensitive and selective. It is based on the widely used dinitrophenylhydrazine derivatization, followed by extraction with n-hexane and a simple reversed-phase HPLC separation. Detection is performed by atmospheric pressure chemical ionization (APCI) in negative ion mode, with detection limits in the low picogram range. Using MS/MS, acetone and propionaldehyde can clearly be distinguished, facilitating propionaldehyde quantitation even in the presence of high acetone levels. Quantitation by direct MS/MS is also feasible, well suited for high-throughput applications, although not as accurate as using HPLC/MS/MS.

Development of an on-line weak-cation exchange liquid chromatography–tandem mass spectrometric method for screening aldehyde products in biological matrices

“…In order to analyze aldehydes by GC-MS or LC-MS, derivatization is required. The most widely used derivatization agent for aldehydes is 2,4-dinitrophenylhydrazine (DNPH) [14][15][16][17]. Alternatively, pentafluorophenyl-, 2-chloro-, 2,4-dichlorophenylhydrazine and cyclohexanedione are applied as derivatization reagents [13,18].…”

“…This is useful to clean-up plasma or urine samples and especially important to analyze the low abundant aldehydes and to reduce matrix effects. Most used derivatization agents like DNPH need labour-intensive sample pre-treatment to extract the derivatives [15,17], with off-line liquid-liquid extraction or solid phase extraction (SPE) on C18 cartridges. The automation of this process by on-line coupling of the SPE to HPLC results in methods that are generally faster, less expensive and less prone to errors, thus resulting in better reproducibility [21][22][23][24][25][26][27][28].…”

Detection limits of electron and electron capture negative ionization-mass spectrometry for aldehydes derivatized with o-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine hydrochloride

“…A ldehydes, as products of the lipid peroxidation reactions and various atmospheric processes, are often detected in biological and environmental matrices [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. Derivatization of aldehydes is typically employed before the analysis to improve chromatographic separation and detection limits [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15].…”

“…Derivatization of aldehydes is typically employed before the analysis to improve chromatographic separation and detection limits [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15].…”

Liquid chromatography–tandem mass spectrometry for the determination of low-molecular mass aldehydes in human urine

“…Liquid chromatography (LC) with UV detection has also been used for the determination of LMMAs in urine samples, although these methods have some drawbacks with regard to specificity and sensitivity due to the nature of UV measurements [15][16][17]. However, recent LC-MS methods seem to be valuable choices with respect to the GC-MS analysis of carbonyl compounds in biological matrices including urine [18][19][20][21][22]. As in GC determinations, the high polarity and reactivity of aldehydes impose the need for their derivatization prior to their detection, 2,4-dinitrophenylhydrazine (DNPH) being the most widely used derivatization agent [18][19][20][21].…”