Determination of malondialdehyde in human blood by headspace-solid phase micro-extraction gas chromatography–mass spectrometry after derivatization with 2,2,2-trifluoroethylhydrazine

Malondialdehyde (MDA) has been proposed as a useful biomarker of lipoperoxidation in biological samples, and more developed analytical methods are necessary. A simple and sensitive gas chromatography–mass spectrometry (HS-SPME-GC–MS) was described for the determination of malondialdehyde (MDA) in blood. Acetone-d6 was used as internal standard. MDA and acetone d6 in blood reacted for 40 min at 50 °C with 2,2,2-trifluoroethylhydrazine in headspace vial and simultaneously the formed TFEH derivatives were vaporized and adsorbed on polydimethylsiloxane-divinylbenzene (PDMS-DVB). The compounds were desorbed for 1 min at 240 °C and injected in GC–MS. The reaction solution showed good recoveries at pH 4.0. In the established condition, the method detection limit (MDL) was 0.4 μg/L in 0.1 mL blood sample and the relative standard deviation was less than 8% at the concentration of 25.0 and 50.0 μg/L. The mean concentrations of MDA in normal human blood (n = 20) were measured to be 187.9 μg/L (2.61 μmol/L).