Application of novel β-cyclodextrin/metal-organic frameworks nanofibers/cellulose (β-CD-MOF/CE) biosorbent and solid phase Microextraction method followed by GC-MS and HPLC to determine biogenic amines as hygienic quality indicators of fish
摘要
The problems caused by biogenic amines (BAs) produced by amino acid decomposition, are very harmful to public health due to affecting the quality and safety of food. Therefore, finding sensitive and reliable diagnostic methods for biogenic amines is of great importance to ensure food safety and public health. Biosorbents offer a powerful and simple approach for the detection of amines with high selectivity and sensitivity, fast response, low cost, and easy operation. In this research, solid phase microextraction (SPME) based β-cyclodextrin/metal-organic frameworks nanofibers/Cellulose (β-CD-MOF/CE) biosorbent) and powerful analytical instrument gas chromatography mass-spectrometry (GC-MS) was optimized and validated for the simultaneous determination of biogenic amines (histamine, cadaverine, tyramine and putrescine) in canned fish samples. Novel MOF biosorbent were prepared via an Electrospinning technique and employed as the SPE sorbents for extraction of biogenic amines from canned fish and meat samples. In the preparation of MOF nanofibers, CD-MOF biosorbent was first prepared via hydrothermal technique and β-cyclodextrin (β-CD) as ligand, to overcome real-world application drawbacks of MOFs such as toxicity of preparation reagents and components. To achieve good mechanical properties, modify structure and adsorption property of biosorbent, Cellulose (CE) nanofibers containing β-CD-MOF biosorbent were successfully fabricated via simple electrospinning. Fourier transform infrared spectroscopies, X-ray diffraction, scanning electron microscopy and BET analyze are the techniques that were used to characterize the nanofibers. β-CD -MOFs biosorbent incorporate the porous features, controllable functions and extraordinarily high surface area of MOFs and the encapsulation capability and highly flexible structure of β-CD to absorb analyte molecules, leading to outstanding properties compared to traditional adsorbents. The affecting parameters in micro extraction of biogenic amines from sample tissue were identified and optimized. Following extraction, the biogenic amines were quantified by GC-MS. According to the optimization results, dynamic linear range for all biogenic amines is between 0.1 and 40 µgL−1. The limits of detection were between 0.09 and 0.15 ppb. The β-CD-MOFs biosorbent showed excellent reusability even after 5 recycles. The β-CD -MOFs biosorbent was successfully applied for extraction of biogenic amines in spiked and unspiked canned fish and meat samples. Also, the amount of biogenic amines in fish as an indicator of fish quality was extracted using biosorbent under optimal conditions and analyzed by High Performance Liquid Chromatography (HPLC). According to the results, the use of a biosorbent to analyze the contents of histamine, as well as cadaverine and putrescine is suggested as a qualitative index to evaluate the quality of fresh fish, which showed a good correlation with storage time. This work introduced a new path toward obtaining advanced β-CD-MOF based nanocomposites with functional properties. This research presents a new path with challenges and future prospects regarding biosensors based on β-CD-MOFs, which will shed new light on the application of metal-organic frameworks in various fields. This method holds great potential for improving the monitoring of biogenic amines in food products, thus contributing to enhanced food safety and public health.