Determination of polyamines in urine via electrospun nanofibers-based solid-phase extraction coupled with GC-MS and application to gastric cancer patients

The simultaneous determination of polyamines and their metabolites in urine samples was achieved by gas chromatography-mass spectrometry in the selected ion monitoring mode. After conjugating with the ion-pair reagent bis-2-ethylhexylphosphate in the aqueous phase, the polyamines in the samples were extracted with polystyrene nanofiber-based packed-fiber solid-phase extraction followed by a derivatization step using pentafluoropropionyl anhydride. With optimal conditions, all analytes were separated well. For analytes of putrescine, cadaverine, N-acetylputrescine, and N-acetylcadaverine, the linearity was good in the range of 0.05-500 mu mol/L (R-2 >= 0.993). While for spermidine, spermine, acetylspermidine, N-8-acetylspermidine, and N-acetylspermine, the linearity was good in the range of 0.5-500 mu mol/L (R-2 >= 0.990). The recoveries of three spiked concentrations (0.5, 5, 300 mu mol/L) were 85.6%-108.4%, and relative standard deviations for intra- and interday were in the range of 2.9%-13.4% and 4.5%-15.1%, respectively. The method was successfully applied to the analysis of urine samples of gastric cancer patients. The results showed that the levels of most polyamines and N-acetylated polyamines from the patient group were significantly higher than those from the control group. The altered concentrations of the above-mentioned metabolites suggest their role in the pathogenesis of gastric cancer, and they should be further evaluated as potential markers of gastric cancer.