Determination of seven organophosphorus insecticides in fruits and vegetables by ultra-high performance liquid chromatography-tandem mass spectrometry based on magnetic conjugated microporous polymers

doi:10.3724/SP.J.1123.2019.06033

Abstract

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

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.

Figures/Tables 7

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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