In-situ solvothermal polymerization of metal-organic framework/carbon-nitrogen nanosheet-coated solid-phase microextraction fiber for highly sensitive detection of pesticide residues in black tea

doi:10.3724/SP.J.1123.2019.10036

Abstract

Abstract:

Pyrethroids (PYs) and organochlorine pesticides (OCPs) are widely used to control pests and diseases in plants; however, they threaten human health. In this study, a metal-organic framework/carbon-nitrogen nanosheet composite nanomaterial (UiO-66/HOCN)-coated solid-phase microextraction (SPME) fiber was prepared by in-situ thermal polymerization. The prepared UiO-66/HOCN composite material was characterized by transmission electron microscopy, X-ray diffraction, nitrogen adsorption porosimetry, thermogravimetric analysis, and zeta potentiometry. The prepared UiO-66/HOCN composite-coated MSPE fiber was used for the enrichment and separation of OCPs and PYs, which showed good thermal and chemical stability as well as high extraction efficiency. Combined with gas chromatography-mass spectrometry (GC-MS), an efficient and sensitive method for the detection of trace levels of OCPs and PYs was developed. Under the optimal experimental conditions, wide linear ranges (0.1-800.0 ng/L), good linearity (≥ 0.9978), low limits of detection (0.03-0.30 ng/L), and acceptable repeatability (RSD ≤ 8.9%, n=3) were obtained. Typical black tea samples were analyzed by the developed method, and trace levels of aldrin (6.6 ng/g), α -endosulfan (54.7 ng/g), and bifenthrin (185.8 ng/g) were detected. The results demonstrate that the developed method has immense potential for the detection of pesticides in a complicated matrix.

Key words: porous carbon-nitrogen nanosheet, metal-organic framework (MOF), solid-phase microextraction (SPME), gas chromatography-mass spectrometry (GC-MS), pesticides, black tea

ZHANG Wenmin, FENG Zunmei, HUANG Chuanhui, GAO Jia, ZHANG Lan. In-situ solvothermal polymerization of metal-organic framework/carbon-nitrogen nanosheet-coated solid-phase microextraction fiber for highly sensitive detection of pesticide residues in black tea[J]. Chinese Journal of Chromatography, 2020, 38(3): 332-340.

Figures/Tables 10

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Compound	Retention time/min	Quantitative ion (m/z)	Qualitative ions (m/z)
Heptachlor (七氯)	13.92	272	273, 272, 237
Aldrin (艾试剂)	14.82	263	263, 255, 220
Heptachlor epoxide	15.98	263	353, 263, 193
(环氧七氯)
α-Chlordane (α-氯丹)	17.01	373	375, 373, 272
p, p′-DDE (p, p′-滴滴伊)	17.63	318	318, 246, 176
α-Endosulfan (α-硫丹)	18.64	241	241, 206, 195
p, p′-DDD (p, p′-滴滴滴)	18.92	235	235, 200, 165
p, p′-DDT (p, p′-滴滴涕)	20.10	235	235, 200, 165
Bifenthrin (联苯菊酯)	21.91	181	386, 241, 181

Compound	Retention time/min	Quantitative ion (m/z)	Qualitative ions (m/z)
Heptachlor (七氯)	13.92	272	273, 272, 237
Aldrin (艾试剂)	14.82	263	263, 255, 220
Heptachlor epoxide	15.98	263	353, 263, 193
(环氧七氯)
α-Chlordane (α-氯丹)	17.01	373	375, 373, 272
p, p′-DDE (p, p′-滴滴伊)	17.63	318	318, 246, 176
α-Endosulfan (α-硫丹)	18.64	241	241, 206, 195
p, p′-DDD (p, p′-滴滴滴)	18.92	235	235, 200, 165
p, p′-DDT (p, p′-滴滴涕)	20.10	235	235, 200, 165
Bifenthrin (联苯菊酯)	21.91	181	386, 241, 181

Compound	Linear range/(ng/L)	R	LOD/(ng/L)	RSDs/% (n=3)
				Single fiber		Fibers of batch-to-batch
				Intra-day	Inter-day	Fibers of batch-to-batch
Heptachlor	0.3-300.0	0.9996	0.1	4.9	6.8	7.2
Aldrin	0.3-500.0	0.9997	0.1	4.5	4.5	6.2
Heptachlor epoxide	0.3-300.0	0.9989	0.1	7.5	8.9	9.0
α-Chlordane	0.5-300.0	0.9986	0.3	5.1	7.9	9.2
p, p′-DDE	0.3-500.0	0.9978	0.1	4.5	8.2	8.3
α-Endosulfan	0.3-800.0	0.9999	0.1	4.2	4.7	5.2
p, p′-DDD	0.1-300.0	0.9999	0.03	4.3	6.4	7.8
p, p′-DDT	0.1-300.0	0.9999	0.03	5.4	6.5	8.4
Bifenthrin	0.8-500.0	0.9990	0.3	3.3	7.4	9.7

Compound	Linear range/(ng/L)	R	LOD/(ng/L)	RSDs/% (n=3)
				Single fiber		Fibers of batch-to-batch
				Intra-day	Inter-day	Fibers of batch-to-batch
Heptachlor	0.3-300.0	0.9996	0.1	4.9	6.8	7.2
Aldrin	0.3-500.0	0.9997	0.1	4.5	4.5	6.2
Heptachlor epoxide	0.3-300.0	0.9989	0.1	7.5	8.9	9.0
α-Chlordane	0.5-300.0	0.9986	0.3	5.1	7.9	9.2
p, p′-DDE	0.3-500.0	0.9978	0.1	4.5	8.2	8.3
α-Endosulfan	0.3-800.0	0.9999	0.1	4.2	4.7	5.2
p, p′-DDD	0.1-300.0	0.9999	0.03	4.3	6.4	7.8
p, p′-DDT	0.1-300.0	0.9999	0.03	5.4	6.5	8.4
Bifenthrin	0.8-500.0	0.9990	0.3	3.3	7.4	9.7

Coating material	Linear range/(μg/L)	R	LODs/(ng/L)	RSDs/%	Ref.
PDMS: polydimethylsiloxane; DVB: divinylbenzene; CAR: carboxen; PEG: polyethylene glycol.
UiO-66/HOCN	0.1×10^-3-0.8	0.9978-0.9999	0.03-0.30	3.3-9.7	this study
ZnO/g-C₃N₄	0.3×10^-2-5.0	0.9981-0.9993	1.0-2.5	2.3-11.3	[9]
PDMS	0.1-500	0.9906-0.9988	40-410	3.2-11.3	[10]
PDMS/DVB	0.5-100	0.9901-0.9999	3-560	＜15	[11]
DVB/CAR/PDMS	1-100	0.9755-0.9997	200-400	7.2-24.6	[12]
PEG	-	0.9930-0.9990	3-145	4.2-10.0	[13]