基于磁性共轭微孔聚合物的超高效液相色谱-串联质谱法测定果蔬中7种有机磷杀虫剂

doi:10.3724/SP.J.1123.2019.06033

摘要/Abstract

摘要：

建立了基于磁性共轭微孔聚合物的磁固相萃取-超高效液相色谱-串联质谱（UPLC-MS/MS）测定果蔬中7种有机磷杀虫剂的方法。将亚苯基亚乙炔基修饰的Fe₃O₄与1，3，5-三溴苯、1，3，5-三乙炔苯反应，制备磁性共轭微孔聚合物，材料能有效吸附共轭结构的有机磷杀虫剂，并在外磁场中实现便捷磁分离。方法的检出限（LOD）为0.12~5.0 ng/kg，加标回收率为80.8%~125%，相对标准偏差（RSD）小于6%（n=5）。方法应用于分析市场上果蔬样品中7种有机磷杀虫剂，检出含量为1.1~500.0 ng/kg。该方法灵敏度高，准确可靠，对果蔬中有机磷杀虫剂的检测具有良好的应用潜力。

关键词: 超高效液相色谱-串联质谱, 磁固相萃取, 共轭微孔聚合物, 有机磷杀虫剂, 果蔬

Abstract:

A method was developed for the determination of seven organophosphorus insecticides in fruits and vegetables by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) based on magnetic conjugated microporous polymers (CMPs). Fe₃O₄ nanoparticles modified by phenylene and ethynylene were cross-linked with 1, 3, 5-tribromobenzene and 1, 3, 5-trialkynylbenzene to obtain magnetic CMPs. This material with a three-dimensional network structure and covalently built-in Fe₃O₄ nanoparticles could effectively enrich organophosphorus insecticides with a conjugated structure, thus allowing for convenient magnetic separation in an external magnetic field. Under the optimized conditions, the seven organophosphorus pesticides were extracted by using the magnetic CMPs as magnetic solid phase extraction adsorbents. The limits of detection (LODs) of the seven target analytes were in the range of 0.12-5.0 ng/kg. The recoveries were between 80.8% and 125%, and the relative standard deviations (RSDs, n=5) were less than 6%. The organophosphorus insecticides were detected in fruits and vegetables at concentrations in the range of 1.1-500.0 ng/kg. The method is sensitive, accurate and reliable, and it shows good application potential for the determination of the organophosphorus pesticides in fruits and vegetables.

Key words: ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), magnetic solid-phase extraction, conjugated microporous polymers (CMPs), organophosphorus insecticides, fruits and vegetables

蔡伟秋, 雷皓宇, 胡玉玲, 李攻科. 基于磁性共轭微孔聚合物的超高效液相色谱-串联质谱法测定果蔬中7种有机磷杀虫剂[J]. 色谱, 2020, 38(1): 113-119.

CAI Weiqiu, LEI Haoyu, HU Yuling, LI Gongke. Determination of seven organophosphorus insecticides in fruits and vegetables by ultra-high performance liquid chromatography-tandem mass spectrometry based on magnetic conjugated microporous polymers[J]. Chinese Journal of Chromatography, 2020, 38(1): 113-119.

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Compound	Retention time/min	Precursor ion (m/z)	Production ions (m/z)	Collision energy/eV
* Quantitative ion.
Azinphos-methyl (APM)	3.8	317.9	132.2, 125.0^*	15
Phosmet (PSM)	3.9	318.1	132.9, 77.3^*	44
Fenamiphos (FMP)	4.0	304.2	217.0, 202.0^*	20
Triazophos (TZP)	4.2	314.2	162.1, 119.1^*	20
Fenthion (FT)	4.4	279.1	247.0, 169.0^*	13
Phosalone (PSL)	4.5	368.1	182.1, 111.1^*	14
Phoxim (POX)	4.6	299.2	129.1, 77.1^*	12

Compound	Retention time/min	Precursor ion (m/z)	Production ions (m/z)	Collision energy/eV
* Quantitative ion.
Azinphos-methyl (APM)	3.8	317.9	132.2, 125.0^*	15
Phosmet (PSM)	3.9	318.1	132.9, 77.3^*	44
Fenamiphos (FMP)	4.0	304.2	217.0, 202.0^*	20
Triazophos (TZP)	4.2	314.2	162.1, 119.1^*	20
Fenthion (FT)	4.4	279.1	247.0, 169.0^*	13
Phosalone (PSL)	4.5	368.1	182.1, 111.1^*	14
Phoxim (POX)	4.6	299.2	129.1, 77.1^*	12

Compound	Linear equation	Linear range/(ng/L)	r²	LOD/(ng/kg)	LOQ/(ng/kg)
y: peak area; x: mass concentration, ng/L.
APM	y=2.57×10³x+1.13×10⁴	2.5-1000	0.9995	1.6	5.3
PSM	y=8.65×10²x+8.33×10³	2.5-1000	0.9990	1.7	5.7
FMP	y=3.90×10⁴x-3.36×10⁴	0.5-200	0.9997	0.26	0.87
TZP	y=5.04×10⁴x-6.23×10⁴	0.5-200	0.9998	0.12	0.40
FT	y=4.58×10³x-5.47×10³	2.5-1000	0.9995	1.6	5.3
PSL	y=9.01×10²x+7.36×10³	7.5-3000	0.9990	5.0	17
POX	y=1.58×10³x-5.21×10⁴	7.5-3000	0.9993	4.9	16

Compound	Linear equation	Linear range/(ng/L)	r²	LOD/(ng/kg)	LOQ/(ng/kg)
y: peak area; x: mass concentration, ng/L.
APM	y=2.57×10³x+1.13×10⁴	2.5-1000	0.9995	1.6	5.3
PSM	y=8.65×10²x+8.33×10³	2.5-1000	0.9990	1.7	5.7
FMP	y=3.90×10⁴x-3.36×10⁴	0.5-200	0.9997	0.26	0.87
TZP	y=5.04×10⁴x-6.23×10⁴	0.5-200	0.9998	0.12	0.40
FT	y=4.58×10³x-5.47×10³	2.5-1000	0.9995	1.6	5.3
PSL	y=9.01×10²x+7.36×10³	7.5-3000	0.9990	5.0	17
POX	y=1.58×10³x-5.21×10⁴	7.5-3000	0.9993	4.9	16

Method	Compound	Matrix	Linear range/(ng/L)	LOD/(ng/kg)	LOQ/(ng/kg)
HPLC-MS/MS^[22]	PSM	lentinus edodes	20000-200000	-	8900
	TZP			-	8200
LC-MS/MS^[9]	PSM	tomato	2000-20000	-	2000
	TZP			-	300
	FT			-	1300
	PSL			-	400
	POX			-	200
Present Method	TZP	fruit, vegetable	0.5-200	0.12	0.4
	PSM		2.5-1000	1.7	5.7
	FT			1.6	5.3
	PSL		7.5-3000	5	17
	POX			4.9	16