Hydrophobic Mesoporous Silica-Coated Solid-Phase Microextraction Arrow System for the Determination of Six Biogenic Amines in Pork and Fish

In this study, a functionalized mesoporous silica-coated solid-phase microextraction (SPME) Arrow system was developed for the enrichment of six biogenic amines (BAs) from pork and fish samples before gas chromatographic separation with a mass spectrometer as a detector. MCM-41 was utilized as the substrate material and thereby functionalized by titanate and sodium dodecyl sulfate to adjust its surface acidity and hydrophobicity, respectively. The functionalized MCM-41 (named as MCM-T-H) was coated on a bare SPME Arrow using the dipping method and polyacrylonitrile was used as the adhesive. The extraction capacity and selectivity of the MCM-T-H-SPME Arrow for six kinds of derivatized BAs were studied and compared with commercial SPME Arrows. Experimental parameters, e.g., sample volume, derivatization reagent amount, extraction time, and desorption time, which have a dramatic effect on SPME Arrow pretreatment, were optimized. Acidity enhanced MCM-T-H coating showed a much higher affinity to derivatized BAs compared to a commercial SPME Arrow in terms of extraction capacity. In addition, hydrophobicity modification significantly reduced the interference of water molecules on the interaction between MCM-T-H and the derivatized BAs. The MCM-T-H-SPME Arrow showed efficient separation and enrichment capacity for derivatized BAs from complex matrices and therefore, the sample pretreatment time was saved. According to the experimental results, the optimal condition was to add 10 μL derivatization reagent to a 10 mL sample and maintain an agitation speed of 1250 r min(−1). The MCM-T-H-SPME showed excellent reproducibility (RSD < 9.8%) and fast adsorption kinetics (30 min) and desorption kinetics (5 min) for derivatized BAs under optimal conditions. In summary, the MCM-T-H-SPME Arrow based method was employed for accurate monitoring of the variations of BAs in pork and fish, and good results were achieved.