新型改良QuEChERS前处理技术联合UPLC-MS/MS监测几种常见养殖水产品中抗生素的残留  

Novel modified QuEChERS combined with UPLC-MS/MS technology for the detection of antibiotic residues in several common kinds of aquaculture products

作　　者：徐雪姣 黄程 杨加成 戴志远 郑振霄 XU Xuejiao;HUANG Cheng;YANG Jiacheng;DAI Zhiyuan;ZHENG Zhenxiao(College of Biology and Environmental Engineering,Zhejiang Shuren University,Hangzhou 310015,China;Greentown Agricultural Testing Technology Co.,Ltd.,Hangzhou 310052,China;Collaborative Innovation Center of Seafood Deep Processing,Zhejiang Province Joint Key Laboratory of Aquatic Products Processing,Institute of Seafood,Zhejiang Gongshang University,Hangzhou 310012,China)

机构地区：[1]浙江树人学院生物与环境工程学院,浙江杭州310015 [2]绿城农科检测技术有限公司,浙江杭州310052 [3]浙江工商大学海洋食品研究院,浙江省水产品加工技术研究联合重点实验室,海洋食品精深加工关键技术省部共建协同创新中心,浙江杭州310012

出　　处：《水产学报》2024年第7期105-115,共11页Journal of Fisheries of China

基　　金：浙江省自然科学基金(LQ22C200008,LQ22C200010);浙江树人学院省属高校基本科研业务费专项(2022XZ008)。

摘　　要：为提高养殖水产品中抗生素的检测效率,本研究以新型石墨烯/碳纳米管复合材料为吸附剂,采用QuEChERS前处理,联合UPLC-MS/MS技术实现了不同养殖水产品中28种抗生素残留的同时检测。通过加标回收率研究了不同提取溶剂、不同种类吸附剂及添加量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。然后,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等。结果显示,当以乙腈∶甲醇(75∶25,体积比)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0.06~1.42μg/kg,定量限为0.20~4.72μg/kg,多数抗生素[磺胺二甲异恶唑(SIA)、磺胺喹恶啉(SQX)、丹诺沙星(DAN)、洛美沙星(LOM)除外]基质效应较低(<10%)。在5~100μg/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、凡纳滨对虾、中华绒螯蟹和厚壳贻贝中28种抗生素的检测,结果显示所建立的方法重复性好,灵敏度高,适用于常规检测。研究表明,石墨烯/碳纳米管复合纳米材料可以较好地吸附养殖水产样品中的共提取杂质,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。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 quick,easy,cheap,effective,rugged,and safe(QuEChERS)combined with UPLC-MS/MS for the simultaneous determination of 28 antibiotic residues in aquaculture products was established,with nano grapheme oxide/multi walled carbon nanotubes(n-GO/MWCNTs)composite as the adsorbent.Moreover,parameters such as the ratio of acetonitrile and methanol in extractant,the amount of the n-GO/MWCNTs,were optimized through the recovery of 28 antibiotics.Besides,the adsorbent action of n-GO/MWCNTs was also compared with PSA,C18,MWCNTs,and graphene.Finally,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-GO/MWCNTs was the best with acetonitrile:methanol(75∶25,V/V)and 10 mg of n-GO/MWCNTs.Good linearity(R2>0.99)was observed for all tested antibiotics with the limit of detection and quantification were 0.06-1.42μg/kg and 0.20-4.72μg/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 5-100μ

关 键 词：养殖水产品 石墨烯 多壁碳纳米管 QUECHERS UPLC-MS/MS 抗生素 

分 类 号：S98[农业科学—捕捞与储运] TS254.7[农业科学—水产科学]