新型手性杀虫剂唑虫酯异构体拆分及其在蔬菜中的分析方法建立  

Chiral separation of new chiral insecticide pyraquinil isomers and establishment of analytical methods in vegetables

作　　者：陈炎 黄聪灵 江薰垣 陈志廷 王刚 万凯 唐雪妹 CHEN Yan;HUANG Congling;JIANG Xunyuan;CHEN Zhiting;WANG Gang;WAN Kai;TANG Xuemei(Institute of Quality Standard and Monitoring Technology for Agro-products of Guangdong Academy of Agricultural Sciences,Key Laboratory of Testing and Evaluation for Agro-product Safety and Quality,Ministry of Agriculture and Rural Affairs,Guangdong Provincial Key Laboratory of Quality&Safety Risk Assessment for Agro-products,National Benchmark Laboratory for Agricultural Testing(Pesticide Residues),Guangzhou 510000,China)

机构地区：[1]广东省农业科学院农业质量标准与监测技术研究所,农业农村部农产品质量安全检测与评价重点实验室,广东省农产品质量安全风险评估重点实验室,国家农业检测基准实验室(农药残留),广东广州510000

出　　处：《色谱》2022年第7期634-643,共10页Chinese Journal of Chromatography

基　　金：国家重点研发计划(2019YFC1605600);广东省自然科学基金(2020A1515010620);广东省农业科学院科技创新战略专项资金(高水平农科院建设);广东省农产品质量安全风险评估重点实验室项目(2019B121203009).

摘　　要：以全新手性杀虫剂唑虫酯为研究对象,通过筛选手性色谱柱和优化流动相比例,建立了唑虫酯及其氧化代谢物异构体的拆分方法,在此基础上开发利用高效液相色谱-串联质谱(HPLC-MS/MS)同时测定小白菜和蕹菜中唑虫酯及其氧化产物手性异构体的分析方法。以纤维素-三(3,5-二氯苯基氨基甲酸酯)共价键合手性柱(Chiral INC)(250 mm×4.6 mm,5μm)为分析柱,乙腈和2 mmol/L甲酸铵水溶液作为流动相进行梯度洗脱分离,在多反应监测负离子模式下进行检测,唑虫酯4个异构体分离度分别为1.63、2.83和1.74,唑虫酯氧化产物异构体分离度为5.82。通过衍生化的方法进一步确定出峰顺序为RS-唑虫酯、SS-唑虫酯、RR-唑虫酯、SR-唑虫酯、S-唑虫酯氧化产物和R-唑虫酯氧化产物。唑虫酯和其氧化产物的手性异构体分别在1.25~1250μg/L和2.5~2500μg/L范围内具有良好的线性关系,相关系数(R^(2))大于0.99。在蕹菜和小白菜样品中同时添加唑虫酯和唑虫酯氧化产物消旋体进行添加回收试验,添加水平为1、20、400μg/kg(即唑虫酯异构体为0.25、5、100μg/kg;唑虫酯氧化代谢产物异构体为0.5、10、200μg/kg),回收率为72.6%~110.6%,相对标准偏差(RSD)均在9.4%以下,其中日内重复性的RSD在0.5%~9.4%之间;日间重复性的RSD在1.0%~8.6%之间,表明该方法具有良好的回收率和精密度。该研究可为唑虫酯这一新型手性农药的环境行为研究及后续质量控制、药效评价等提供相应的分析技术,为新农药开发应用提供有力的技术支撑。Pyraquinil(Pyr),with a new skeleton of pyrazolo[1,5-a]quinazoline fused heterocycle,is a new chiral insecticide independently developed by South China Agricultural University in 2017.In previous studies,we found that pyraquinil can effectively control the lepidopteran pest population on cruciferous crops.Remarkably,the insecticidal activity of pyraquinil was 64-fold better than that of fipronil against the fipronil-resistant Plutella xylostella field population.Pesticides with new active mechanisms should be developed in the future to cope with the development of resistance to Plutella xylostella.Therefore,pyraquinil with new active sites has the potential to be the main rotation variety for the control of Plutella xylostella.Thus,pyraquinil has a broad prospect for application in the future.However,a chiral separation and analysis method for pyraquinil and oxidation products using high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS)has not been established yet.Based on the physical and chemical properties of the new chiral pesticide pyraquinil,we screened chiral chromatographic columns and optimized the mobile phase ratio in this study.The separation and analysis methods for pyraquinil were developed based on the QuEChERS(quick,easy,cheap,effective,rugged,safe)system.Simultaneously,we also established oxidation metabolites.These methods were used for the simultaneous determination of the chiral isomers of pyraquinil and oxidation products in pakchoi(Brassica rapa ssp.chinensis L.)and water spinach(Ipomoea aquatica Forsk)via HPLC-MS/MS.The Chiral INC column(250 mm×4.6 mm,5μm)was used for separation.Ammonium formate aqueous solution(2 mmol/L)and acetonitrile were used as the mobile phases.The column temperature was 28℃.The injection volume was 1μL,and the flow rate was 0.5 mL/min.MS analysis was performed using an electrospray ionization source in the negative and multiple reaction monitoring modes.We found that under the optimized conditions,the resolution of the four isomers of pyraqu

关 键 词：高效液相色谱-串联质谱 唑虫酯 小白菜 蕹菜 手性分离 

分 类 号：O658[理学—分析化学]