基于金属有机骨架萃取剂的一步式快速固相萃取检测饮料中胭脂红

胭脂红是一种广泛应用的偶氮类色素,我国对其在食品中的添加量有严格规定。由于食品基质的复杂性,针对这类痕量色素很难建立一种灵敏度高、富集性强且高效便捷的检测方法。研究利用卟啉环中的羧基与金属锆离子的配位作用制备了一种高比表面积的金属有机骨架材料(PCN-222),并将纳米材料填入注射式固相萃取装置中,以简化前处理过程,用于快速萃取饮料中胭脂红色素。采用多种表征手段研究了PCN-222纳米材料的形貌、结构及性能。较高的比表面积和静电作用共同决定了新型萃取剂对胭脂红色素具有极强的富集性能。通过优化萃取剂用量、样品溶液pH值、洗脱条件和洗脱剂体积等萃取条件,使目标物实现瞬时吸附,样品前处理时间缩短至5 min。在最佳条件下,该方法可使样品在高、中、低3个水平的加标回收试验中的回收率达到99.5%~109.4%,相对标准偏差小于3%,方法的检出限为0.1 μg/L(S/N=3),定量限为0.3 μg/L(S/N=10)。此外,针对所合成的材料进行萃取-解吸后发现,PCN-222在重复使用4次后仍保持90%以上的萃取能力,表明材料具备可循环性。该方法通过制备的新型金属骨架材料建立了一种高效、便捷、绿色环保的前处理技术,极低的检出限、较高的准确度和较好的重复性表明方法适用于饮料中痕量色素胭脂红的富集和检测。新型固相萃取技术的开发为食品安全检测提供了新思路。

Determination of new carmine in beverages by one step rapid solid phase extraction based on metal organic framework extractant

New coccine is an azo pigment that is widely used in food. To mitigate potential health issues arising from excessive consumption, China has issued provisions on the allowed addition limit of new coccine in food. Currently, there are certain difficulties with establishing detection methods for such trace pigments in foods; for example, preprocessing is complex and time-intensive. In addition, the low content of the target substance in the sample could be disturbed by food matrix, resulting in poor detection sensitivity. Metal organic frameworks (MOFs), as a novel class of highly efficient adsorbents, have attracted increasing attention because of their stability and large specific surface area. MOFs are porous coordination crystal structures that connect metal clusters with organic ligands via coordination. Owing to their molecule-sized pores, MOFs can be used in various fields such as adsorption, catalysis, and drug dispersion. However, at the same time, their ultra-high specific surface area also leads to ultra-low weight of the material itself; this makes it difficult to collect the material even under high-speed centrifugation. In this study, a MOF material (PCN-222) with a high specific surface area was prepared by the coordination of the carboxyl group in the porphyrin ring and metal zirconium ions. To simplify pretreatment, the nanomaterials were filled into an injection solid phase extraction device for the rapid extraction of new coccine pigments from beverages. The morphology, structure, and properties of the PCN-222 nanomaterials were studied by transmission electron microscopy, particle size analysis, X-ray single-crystal diffraction, infrared spectroscopy, and ultraviolet spectroscopy. The specific surface area of the synthesized material was 979 m²/g. A high specific surface area was conducive to the adsorption of trace target compounds. The surface charge of the material could be controlled by adjusting the pH value of the solution, which was beneficial to the selective adsorption and desorption of ionic pigments. The π-π interaction between the benzene ring of the porphyrin ring and the benzene ring of the azo pigment also promoted extraction. Thus, the extractant exhibited strong enrichment performance for the new coccine anionic pigment. The solid phase extraction conditions were optimized, and it was found that saturated adsorption capacity was achieved by filling 3 mg of extractant. The effect of pH on adsorption was also explored; the adsorption effect was the best at pH 3. In the desorption experiment, N,N-dimethylformamide at pH 11 was conducive to better elution of the target. Further elution volume studies showed that maximum recovery could be achieved by adding 3 mL of eluent. Subsequently, the sample pretreatment time was reduced to 5 min. The enriched sample was separated using a Zorbax eclipse XDB-C18 column (250 mm×4.6 mm, 5 μm), eluted with an ammonium acetate-methanol solvent system, and detected at 254 nm. Under the optimum conditions, the recoveries of the samples at high, medium, and low levels reached 99.5%-109.4%, and the relative standard deviation was less than 3%. The limit of detection (LOD, S/N=3) of this method was 0.1 μg/L and the limit of quantification (LOQ, S/N=10) was 0.3 μg/L. In the actual sample detection experiment, the detection signal of new coccine in the sample was amplified by solid phase extraction to achieve enrichment. In addition, the extraction capacity of PCN-222 remained higher than 90% after four uses, and the synthesized material could be recycled. The high precision and low detection limit indicate that the method is suitable for the enrichment and detection of trace carmine in beverages. The findings of this study will aid in the development of a new solid phase extraction technology for food safety evaluation.