石墨烯/碳纳米管复合纳米材料改良QuEChERS联合UPLC-MS/MS技术检测养殖水产品中抗生素残留的研究

[目的]为提高养殖水产品中抗生素的检测效率,[方法]本文以新型石墨烯/碳纳米管复合材料为吸附剂,采用QuEChERS前处理,通过UPLC-MS/MS建立了一种可同时实现不同养殖水产品中28种抗生素残留检测的技术方法。[结果]通过加标回收率研究了不同提取溶剂,不同吸附剂添加量,不同种类吸附剂对养殖水产品中抗生素检测效率的影响,并确定了最佳的QuEChERS操作参数。最后,根据食品法典指南(CAC/GL-71)进行方法学验证,性能指标包括线性、检测限、定量限、基质效应、回收率、日内精密度和日间精密度。[结论]结果表明,当以乙腈:甲醇(75:25,V/V)为提取剂,吸附剂的添加量为10 mg时,石墨烯/碳纳米管复合纳米材料的吸附效果达到最佳。此时,所建立技术方法的线性良好(R2^>0.99),检出限为0.06 μg/kg ~1.42 μg/kg,定量限为0.20 μg/kg~4.72 μg/kg,多数抗生素(SIA、SQX、DAN、LOM除外)基质效应较低(<10%)。在5 μg/kg~100 μg/kg的添加水平下,平均回收率为80.1%~100.4%。日内精密度< 10.3%,日间精密度< 13.4%。将该方法应用于草鱼,大口黑鲈,南美白对虾,中华绒螯蟹,厚壳贻贝中28种抗生素的检测,结果表明,所建立的方法重复性好,灵敏度高,适用于常规检测。[意义]本研究的结论表明石墨烯/碳纳米管复合纳米材料可以较好吸附养殖水产样品中的脂肪、色素等杂质,提高养殖鱼肉中抗生素的检测效率,在水产品质量安全控制方面具有较好的应用前景。

Study on graphene/carbon nanotube composite nanomaterials modified QuEChERS combined with UPLC-MS/MS technology for the detection of antibiotic residues in aquaculture products

Aquatic products play an important role in human diet. Compared with other livestock and poultry products, aquatic products are featured with low fat content, high protein content, and easy digestion. Therefore, aquatic products are deeply loved by consumers. Generally speaking, aquatic products can be divided into two categories: naturally caught aquatic products and aquaculture aquatic products. In recent years, with the decline of marine resources and the increase of marine pollution, aquaculture is booming. In order to improve the efficiency of aquaculture, antibiotics are usually used, which brings risk to human health. Therefore, the monitoring of antibiotic residues in aquaculture products has been an important part in the field of food safety. To supervise antibiotic residues in aquaculture products, a modified QuEChERS combined with UPLC-MS/MS for the simultaneous determination of 28 antibiotic residues in aquaculture products was established, featuring with nano grapheme oxide/multi walled carbon nanotubes (n-G@MWCNTs) composite as the adsorbent. Moreover, the parameters, such as the ratio of acetonitrile and methanol in extractant, the amount of the n-G@MWCNTs, were optimized. Besides, the adsorbent action of n-G@MWCNTs was also compared with PSA, C18, MWCNTs, and graphene. Finally, the method validation was accomplished according to Codex guideline (CAC/GL-71) with the following performance characteristics: the linearity, limit of detection and quantification, matrix effects, recovery, intra-day and inter-day precision. The results showed that the absorption effect of n-G@MWCNTs was the best with acetonitrile: methanol (75:25, V/V) and 10 mg of n-G@MWCNTs. Good linearity (R2>0.99) was observed for all tested drugs with the limit of detection and quantification were 0.06 μg/kg ~1.42 μg/kg and 0.20 μg/kg~4.72 μg/kg. Low matrix effects (<10%) was observed for most tested drugs (except for SIA, SQX, DAN and LOM). The average recovery of this protocol was 80.1%~100.4% in the spiked levels of 5 μg/kg~100 μg/kg. The intra-day precision was lower than 10.3%, while the inter-day precision below 13.4%. Method applications authenticated that the established method had favorable repeatability and high sensitivity, which could be applied to the regulatory routine analysis.