Rapid and simultaneous determination of hair polyamines as N-heptafluorobutyryl derivatives by gas chromatography–mass spectrometry

We have developed a simple and sensitive method for the simultaneous determination of putrescine, spermidine and spermine in hair as their N-heptafluorobutyryl derivatives by gas chromatography–mass spectrometry (GC–MS) in selected ion-monitoring (SIM) mode. After base hydrolysis, hair samples were extracted with solid-phase extraction (SPE) with diatomaceous earth columns, followed by derivatization with heptafluorobutyryl chloride (HFB-Cl) and elution with n-hexane simultaneously. This method was linear (r ≥ 0.9989), reproducible (intra-day R.S.D. = 3.4–15.5%, inter-day R.S.D. = 2.6–14.6%), accurate (recoveries = 67.8–94.6%) and sensitive (LOD = 0.05–1.0 ng). The method was successfully applied to the analysis of 36 hair samples from 14 healthy men and 22 healthy women. Results showed that the levels of hair polyamines were 4.39–12.15 μg/g for putrescine, 3.89–27.91 μg/g for spermidine, and 0.81–15.15 μg/g for spermine. Either in the male or female group, the most abundant hair polyamine was spermidine, followed by putrescine and spermine, while the mean levels of the three polyamines in hair samples were all found to be higher in men than in women.