The Determination of Eight Biogenic Amines Using MSPE-UHPLC-MS/MS and Their Application in Regard to Changes in These Biogenic Amines in Traditional Chinese Dish-Pickled Swimming Crabs

In this study, a method for the determination of eight biogenic amines (BAs), including tyramine (Tyr), 2-phenylethylamine (2-Phe), histamine (His), tryptamine (Trp), spermidine (Spd), spermine (Spm), cadaverine (Cad), and putrescine (Put), in crab was established using ultra-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS), using a magnetic solid-phase extraction (MSPE) pretreatment, without derivatization, and the content changes in regard to these eight biogenic amines in the traditional Chinese dish, pickled swimming crabs, were investigated. The samples were purified via MSPE, using C nanofiber-coated magnetic nanoparticles (Fe₃O₄@C-NFs) as sorbents. The experimental variables involved in the MSPE, including the solution pH, adsorption and desorption time, adsorbent usage, and type and volume of the eluent, were investigated and optimized. Method validation indicated that the developed method showed good linearity (R² > 0.995); the average recovery rates were 84.7% to 115%, with the intra-day and inter-day relative standard deviations (RSD, <i>n</i> = 6) ranging from 3.7% to 7.5% and 4.2% to 7.7%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) for the eight BAs were 0.1 mg/kg~1.0 mg/kg and 0.3 mg/kg~3.0 mg/kg, respectively. Finally, this method was applied to determine the changes in the eight biogenic amines in pickled swimming crabs (<i>Portunus trituberculatus</i>) during storage at 20 °C and 400 BAC. Among the BAs evaluated, Cad, Put, and Tyr were the predominant amines formed during storage. The final content of Cad, Put, and Tyr reached 22.9, 20.1, and 29.0 mg/100 g at 4 °C for 16 d, and 47.1, 52.3, and 72.0 mg/100 g at 20 °C for 96 h, respectively. The results from this study can be used to expand the application range of magnetic materials in biogenic amine pretreatment and to strengthen the quality control of the traditional Chinese dish, pickled swimming crabs.