十八烷基离子液体杂化固相微萃取整体柱用于检测咖啡中的多环芳烃

doi:10.7503/cjcu20170068

摘要/Abstract

摘要：

以自制的1-十八烷基-3-(γ-三乙氧基硅基丙基)咪唑溴盐离子液体(C₁₈IL)、二苯基二甲氧基硅烷(DDS)和四乙氧基硅烷(TEOS)为功能单体, 采用溶胶-凝胶法制备了烷基咪唑基离子液体管内固相微萃取整体柱(C₁₈IL in-tube SPME). 以多环芳烃为分析对象, 考察了C₁₈IL含量对C₁₈IL in-tube SPME萃取性能的影响, 并对萃取条件进行了优化. 建立了基于C₁₈IL in-tube SPME-气相色谱(GC-FID)的分析方法, 用于检测萘、芴、菲、荧蒽和芘5种多环芳烃. 该方法的检出限(S/N=3)为0.007~0.072 μg/L, 定量限(S/N=10)为0.023~0.24 μg/L, 日内和日间精密度(RSD)除菲类多环芳烃外均小于10%. 将该方法用于检测咖啡中5种多环芳烃, 3个不同浓度下的加标回收率为85.79%~103.42%.

关键词: 离子液体, 整体柱, 管内固相微萃取, 多环芳烃

Abstract:

Ionic liquid of 1-octadecyl-3-(γ-triethoxysiliconpropyl)imidazole bromide(C₁₈IL) was synthesized and then used as a functional monomer to produce the in-tube solid microextraction monolithic column(C₁₈IL in-tube SPME) via sol-gel reaction. After that, five polycyclic aromatic hydrocarbons(PAHs), naphthalene, fluorine, phenanthrene, fluoranthene and pyrene, were employed as probe analytes to evaluate the preparation method of the column and optimize the extraction conditions. Finally, a method of C₁₈IL in-tube SPME hyphen gas chromatography was established for the determination of PAHs in water. The limits of detection(LODs, S/N=3) were between 0.007 and 0.072 μg/L, and the limits of quantification(LOQs, S/N=10) varied from 0.023 to 0.24 μg/L. The intra- and inter-day relative standard deviations(RSDs) of the PAHs were below 10% except for that of phenanthrene. The proposed method was also applied to the determination of the PAHs in a coffee sample, and the recoveries for the five PHAs(spiked in the coffee sample at three levels) ranged from 85.79% to 103.42%.

Key words: Ionic liquid, Monolithic column, In-tube solid phase microextraction, Polycyclic aromatic hydrocarbons

中图分类号:

O657

TrendMD:

张娜, 万昕, 宋旭燕, 黄龙, 郑京京, 邢钧. 十八烷基离子液体杂化固相微萃取整体柱用于检测咖啡中的多环芳烃. 高等学校化学学报, 2017, 38(6): 1033.

ZHANG Na, WAN Xin, SONG Xuyan, HUANG Long, ZHENG Jingjing, XING Jun. Application of Octadecyl Ionic Liquid Hybrid Solid-phase Microextraction Monolithic Column in the Detection of Polycyclic Aromatic Hydrocarbons in Coffee^†. Chem. J. Chinese Universities, 2017, 38(6): 1033.

图/表 10

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PAHs	RSD(%)
PAHs	Repeatability(n=3)	Column-to-column repeatability(n=3)
Nap	10.1	12.2
Flu	7.4	7.9
Phe	6.9	7.2
FL	4.8	11.7
Pyr	4.9	9.4

PAHs	RSD(%)
PAHs	Repeatability(n=3)	Column-to-column repeatability(n=3)
Nap	10.1	12.2
Flu	7.4	7.9
Phe	6.9	7.2
FL	4.8	11.7
Pyr	4.9	9.4

PAHs	Linear range/ (μg·L^-1)	Linear regression			LOD/ (μg·L^-1)	LOQ/ (μg·L^-1)	RSD(%, n=5)
PAHs	Linear range/ (μg·L^-1)	Slope			Intercept	R²	Intra-day	Inter-day
Nap	0.4—200	605.28	1192.7	0.9998	0.072	0.240	7.9	9.6
Flu	0.1—200	1192.00	-152.13	0.9994	0.016	0.053	6.3	9.7
Phe	0.1—200	1081.40	480.43	0.9997	0.008	0.027	5.3	12.6
FL	0.1—200	845.05	-424.32	0.9992	0.007	0.023	2.0	8.4
Pyr	0.1—200	770.26	120.27	0.9995	0.013	0.043	2.2	4.9

PAHs	Linear range/ (μg·L^-1)	Linear regression			LOD/ (μg·L^-1)	LOQ/ (μg·L^-1)	RSD(%, n=5)
PAHs	Linear range/ (μg·L^-1)	Slope			Intercept	R²	Intra-day	Inter-day
Nap	0.4—200	605.28	1192.7	0.9998	0.072	0.240	7.9	9.6
Flu	0.1—200	1192.00	-152.13	0.9994	0.016	0.053	6.3	9.7
Phe	0.1—200	1081.40	480.43	0.9997	0.008	0.027	5.3	12.6
FL	0.1—200	845.05	-424.32	0.9992	0.007	0.023	2.0	8.4
Pyr	0.1—200	770.26	120.27	0.9995	0.013	0.043	2.2	4.9

Method	Sample	LOD/(μg·L^-1)						Ref.
Method	Sample	Nap		Flu	Phe	FL	Pyr	Nap
C₁₈IL in-tube SPME(10 cm)-GC-FID	Coffee	0.072	0.016	0.008	0.007	0.013	0.072	This work
LDS-DLLME^a-GC-MS	Water	0.058	0.023	0.028	0.038	0.037	0.058	[27]
Polyester fibers-in-tube(30 cm) SPME-HPLC-DAD	Water	0.01	0.01	0.01	0.03	0.01	0.01	[28]
Poly(SAM-DVB) monolithic(50 cm)-CEC-APCI-MS	Seafood		26.7		2.7	1.1		[29]
MSPE^b-HPLC-FLD	Coffee and tea			0.005				[30]
Si-MWCNTs monolithic(3 cm)-SPME-GC-MS	Water	0.1		0.1	0.1	0.1	0.1	[31]