固相萃取/超高效液相色谱-串联质谱法测定白术中井冈霉素和丙环唑残留量

doi:10.3969/j.issn.1004-1524.2022.12.18

浙江农业学报 ›› 2022, Vol. 34 ›› Issue (12): 2750-2758.DOI: 10.3969/j.issn.1004-1524.2022.12.18

固相萃取/超高效液相色谱-串联质谱法测定白术中井冈霉素和丙环唑残留量

张春荣(), 郭钤, 孔丽萍, 吴园园, 林琴, 许振岚, 汤涛()

浙江省农业科学院农产品质量安全与营养研究所/农产品质量安全危害因子与风险防控国家重点实验室/农业农村部农药残留检测重点实验室,浙江杭州 310021

收稿日期:2021-09-28 出版日期:2022-12-25 发布日期:2022-12-26
通讯作者: 汤涛
作者简介:*汤涛,E-mail:tangtao80@126.com
张春荣(1970—),女,河南温县人,硕士,副研究员,主要从事农药环境归趋与农药残留研究工作。E-mail:crzhang001@126.com
基金资助:
国家自然科学基金(31501668)

Determination of jingangmycin and propiconazole in Atractylodes macrocephala by solid phase extraction/ultrahigh performance liquid chromatography-tandem mass spectrometry

ZHANG Chunrong(), GUO Qian, KONG Liping, WU Yuanyuan, LIN Qin, XU Zhenlan, TANG Tao()

State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-Products/Key Laboratory for Pesticide Residue Detection of Ministry of Agriculture and Rural Affairs/Institute of Agro-Product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, China

Received:2021-09-28 Online:2022-12-25 Published:2022-12-26
Contact: TANG Tao

摘要/Abstract

摘要：

建立固相萃取/超高效液相色谱-串联质谱(SPE/UPLC-MS/MS)检测白术鲜样及干样中井冈霉素和丙环唑残留的分析方法。样品经甲醇/水(9∶1,V/V)提取,Oasis HLB和 Cleanert AQ C18固相萃取小柱净化,HSS T3 超高效液相色谱柱进行分离,电喷雾正离子多重反应监测(MRM)模式进行测定。结果表明:浓度在0.000 1~0.1 mg·L^-1 范围内,井冈霉素和丙环唑在溶剂及基质中的峰面积与其对应的质量浓度间线性关系良好,R²≥0.999 6。在添加 0.01、0.5、5.0 mg·kg^-1 标准品浓度下,井冈霉素在白术中的添加回收率为72.4%~85.8%,相对标准偏差(RSD)为0.89%~6.20%;在添加0.005、0.1、1.0 mg·kg^-1标准品浓度下,丙环唑在白术中的添加回收率为88.1%~98.9%,RSD为1.4%~4.8%。井冈霉素和丙环唑在白术中的定量限(LOQ)分别为0.01 mg·kg^-1和0.005 mg·kg^-1。通过对实际样品的检测,表明该方法操作简单,重复性好,准确度、精密度及检出限均可满足农药残留分析要求。

关键词: 井冈霉素, 丙环唑, 白术, 超高效液相色谱-串联质谱, 残留

Abstract:

A simple and sensitive method was developed for the determination of jingangmycin A and propiconazole in fresh and dry samples of Atractylodes macrocephala by solid phase extraction/ultrahigh performance liquid chromatography-tandem mass spectrometry (SPE/UPLC-MS/MS). The samples were extracted with methanol/water(9∶1, V/V),purified with an Oasis HLB column (for jingangmycin A) and Cleanert AQ C18 column (for propiconazole),and separated on a HSS T3 column,finally analyzed in multiple reaction monitoring (MRM) mode via positive electrospray ionization (ESI⁺). Under the optimum condition,the calibration curves for the analyte were linear in the range of 0.000 1-0.1 mg·L^-1,with correlation coefficients(R²) not less than 0.999 6. At spiked levels of 0.01,0.5 and 5.0 mg·kg^-1,the recoveries for jingangmycin A in two matrices were in the range of 72.4%-85.8% with relative standard deviations(RSD) of 0.89%-6.20%; At spiked levels of 0.005,0.1 and 1.0 mg·kg^-1,the recoveries for propiconazole in two matrices were in the range of 88.1%-98.9% with relative standard deviations(RSD) of 1.4%-4.8%. The method was simple, reproducible, accurate, precise and the detection limit could meet the requirements of pesticide residue analysis.

Key words: jingangmycin A, propiconazole, Atractylodes macrocephala, ultrahigh performance liquid chromatography-tandem mass spectrometry, residues

中图分类号:

S567.233

张春荣, 郭钤, 孔丽萍, 吴园园, 林琴, 许振岚, 汤涛. 固相萃取/超高效液相色谱-串联质谱法测定白术中井冈霉素和丙环唑残留量[J]. 浙江农业学报, 2022, 34(12): 2750-2758.

ZHANG Chunrong, GUO Qian, KONG Liping, WU Yuanyuan, LIN Qin, XU Zhenlan, TANG Tao. Determination of jingangmycin and propiconazole in Atractylodes macrocephala by solid phase extraction/ultrahigh performance liquid chromatography-tandem mass spectrometry[J]. Acta Agriculturae Zhejiangensis, 2022, 34(12): 2750-2758.

图/表 8

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化合物 Compound	母离子 Precursor ion(m/z)	子离子 Product ion(m/z)	驻留时间 Retention time/ms	Q1偏转电压 Q1 bias voltage/V	碰撞能量 Collision energy/eV	Q3偏转电压 Q3 bias voltage/V
井冈霉素Jiangangmycin A	498.10	178.2^*,124.3	100	-24,-25	-26,-40	-21,-27
丙环唑Propiconazole	341.90	159.0^*,69.1	100	-24,-25	-35,-21	-18,-28

化合物 Compound	母离子 Precursor ion(m/z)	子离子 Product ion(m/z)	驻留时间 Retention time/ms	Q1偏转电压 Q1 bias voltage/V	碰撞能量 Collision energy/eV	Q3偏转电压 Q3 bias voltage/V
井冈霉素Jiangangmycin A	498.10	178.2^*,124.3	100	-24,-25	-26,-40	-21,-27
丙环唑Propiconazole	341.90	159.0^*,69.1	100	-24,-25	-35,-21	-18,-28

农药 Pesticide	基质 Matrix	添加浓度 Spiked concentration/(mg·kg^-1)	平均回收率 Average recovery/%	RSD/%
井冈霉素Jiangangmycin A	鲜样Fresh samples	0.01、0.5、5.0	72.4、83.5、85.8	3.0、2.8、2.9
	干样Dry samples	0.01、0.5、5.0	85.5、78.1、79.6	6.2、2.1、0.89
丙环唑Propiconazole	鲜样Fresh samples	0.005、0.1、1.0	90.8、96.9、92.4	3.7、2.9、2.3
	干样Dry samples	0.005、0.1、1.0	98.9、93.3、88.1	4.8、1.4、3.0

农药 Pesticide	基质 Matrix	添加浓度 Spiked concentration/(mg·kg^-1)	平均回收率 Average recovery/%	RSD/%
井冈霉素Jiangangmycin A	鲜样Fresh samples	0.01、0.5、5.0	72.4、83.5、85.8	3.0、2.8、2.9
	干样Dry samples	0.01、0.5、5.0	85.5、78.1、79.6	6.2、2.1、0.89
丙环唑Propiconazole	鲜样Fresh samples	0.005、0.1、1.0	90.8、96.9、92.4	3.7、2.9、2.3
	干样Dry samples	0.005、0.1、1.0	98.9、93.3、88.1	4.8、1.4、3.0

化合物 Compound	时间 Time/d	浙江省Zhejiang Province		湖南省Hunan Province		安徽省Anhui Province		湖北省Hebei Province
化合物 Compound	时间 Time/d	鲜样 Fresh samples	干样 Dry samples	鲜样 Fresh samples	干样 Dry samples	鲜样 Fresh samples	干样 Dry samples	鲜样 Fresh samples	干样 Dry samples
井冈霉素	28	<0.010	<0.010	<0.010	<0.010	<0.010	<0.010	<0.010	<0.010
Jiangangmycin A	35	<0.010	<0.010	<0.010	<0.010	<0.010	<0.010	<0.010	<0.010
丙环唑	28	0.020	0.040	0.012	0.042	0.009 6	0.024	0.046	0.12
Propiconazole	35	0.010	0.036	0.008 3	0.028	<0.005	0.010	0.036	0.098

固相萃取/超高效液相色谱-串联质谱法测定白术中井冈霉素和丙环唑残留量

Determination of jingangmycin and propiconazole in Atractylodes macrocephala by solid phase extraction/ultrahigh performance liquid chromatography-tandem mass spectrometry

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