磁性金属有机框架表面分子印迹的制备及富集蔬菜样品中2, 4-二氯苯氧乙酸的应用

麻敏瑞; 祝新月; 刘晓燕; 张海霞

doi:10.16495/j.1006-3757.2021.04.005

磁性金属有机框架表面分子印迹的制备及富集蔬菜样品中2, 4-二氯苯氧乙酸的应用

doi: 10.16495/j.1006-3757.2021.04.005

兰州大学化学化工学院, 甘肃兰州 730000

详细信息

作者简介:
麻敏瑞(1996-), 女, 硕士, 主要从事样品前处理研究工作, E-mail: mamr18@lzu.edu.cn

通讯作者:
张海霞(1970-)，女，博士生导师，《分析测试技术与仪器》编委，主要从事分离科学与光谱分析工作，E-mail: zhanghx@lzu.edu.cn

中图分类号: O641.4;O635
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- 被引次数: 0
出版历程
- 收稿日期: 2021-08-26
- 修回日期: 2021-09-13
- 网络出版日期: 2021-12-21
- 刊出日期: 2021-12-30

Preparation of Molecular Imprinting on Surface of Magnetic Metal-Organic Framework and Application of Enrichment of 2, 4-Dichlorophenoxyacetic Acid in Vegetables Samples

College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China

摘要

摘要: 以固相研磨法制备的磁性金属有机框架为基质，2, 4-二氯苯酚为傀儡模板分子，3-氨基丙基三乙氧基硅烷为功能单体，在室温下通过溶胶-凝胶法制备了磁性分子印迹材料Fe₃O₄@ZIF-MIP. 使用X射线衍射、红外光谱、扫描电镜、透射电镜和氮气吸附对分子印迹材料进行了表征. 当2, 4-苯氧乙酸的质量浓度为500 μg/mL时，Fe₃O₄@ZIF-MIP的吸附容量为120.31 mg/g，印迹因子为3.64，材料重复使用6次后性能保持在95%以上，所建立的方法适用于蔬菜中低含量2, 4-二氯苯氧乙酸含量的富集.
- 2, 4-二氯苯氧乙酸 /
- 分子印迹 /
- 磁固相萃取
Abstract: The magnetic molecular-imprinted material Fe₃O₄@ZIF-MIP was prepared by a sol-gel method at room temperature with magnetic metal-organic frameworks as the matrixes, 2, 4-dichlophenol as the pseudotemplate molecule and 3-aminopropyltriethoxysilane as the functional monomer. The molecular-imprinted materials were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption. The adsorption capacity of Fe₃O₄@ZIF-MIP was 120.31 mg/g at a concentration of 500 μg/mL of 2, 4-phenoxyacetic acid, and the blotting factor was 3.64, the properties of the material remained above 95% after repeated use for 6 times, and the established method is suitable for the enrichment of low content 2, 4-dichlorophenoxyacetic acid in vegetables.
- 2, 4-dichlorophenoxyacetic acid /
- molecular imprinting /
- magnetic solid phase extraction

HTML全文

图 1 Fe₃O₄@ZIF-MIP的合成示意图

Figure 1. Schematic diagram of synthesis of Fe₃O₄@ZIF-MIP

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图 2 模拟ZIF-8、Fe₃O₄@ZIF、Fe₃O₄@ZIF-NIP和Fe₃O₄@ZIF-MIP的XRD谱图(A)，Fe₃O₄@ZIF、Fe₃O₄@ZIF-NIP和Fe₃O₄@ZIF-MIP的IR谱图(B)

Figure 2. XRD spectra of simulated ZIF-8, Fe₃O₄@ZIF, Fe₃O₄@ZIF-NIP and Fe₃O₄@ZIF-MIP (A), FT-IR spectra of Fe₃O₄@ZIF, Fe₃O₄@ZIF-NIP and Fe₃O₄@ZIF-MIP (B)

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图 3 Fe₃O₄@ZIF(A)、Fe₃O₄@ZIF-MIP(B)和Fe₃O₄@ZIF-NIP(C)的SEM图，Fe₃O₄(D)、Fe₃O₄@ZIF(E)和Fe₃O₄@ZIF-MIP(F)的TEM图

Figure 3. SEM images of Fe₃O₄@ZIF(A), Fe₃O₄@ZIF-MIP(B) and Fe₃O₄@ZIF-NIP(C), TEM images of Fe₃O₄(D), Fe₃O₄@ZIF(E) and Fe₃O₄@ZIF-MIP(F)

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图 4 Fe₃O₄@ZIF和Fe₃O₄@ZIF-MIP的氮气吸附-解吸等温线

Figure 4. Nitrogen adsorption-desorption isotherms of Fe₃O₄@ZIF and Fe₃O₄@ZIF-MIP

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图 5 Fe₃O₄@ZIF和Fe₃O₄@ZIF-MIP的热重图

Figure 5. Thermogravimetric drawings of Fe₃O₄@ZIF and Fe₃O₄@ZIF-MIP

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图 6 Fe₃O₄@ZIF(A)和Fe₃O₄@ZIF-MIP(B)的表面水接触角光学照片

Figure 6. Surface water contact angle optical photos of Fe₃O₄@ZIF (A) and Fe₃O₄@ZIF-MIP (B)

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图 7 Fe₃O₄@ZIF、Fe₃O₄@ZIF-MIP和Fe₃O₄@ZIF-NIP的磁滞回线

(插图为使用外加磁场之后的照片)

Figure 7. Hysteresis loops of Fe₃O₄@ZIF, Fe₃O₄@ZIF-MIP and Fe₃O₄@ZIF-NIP

(illustration: photo after applying an external magnetic field)

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图 8 解吸溶剂、解吸时间和解吸体积的优化

Figure 8. Optimization of desorption solvent, desorption time and desorption volume

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图 9 萃取时间和pH优化

Figure 9. Optimization of extraction time and solution pH

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图 10 Fe₃O₄@ZIF-MIP和Fe₃O₄@ZIF-NIP吸附动力学曲线(A)和吸附等温线(B)

Figure 10. Adsorption kinetic curves (A) and adsorption isotherms (B) of Fe₃O₄@ZIF-MIP and Fe₃O₄@ZIF-NIP

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图 11 Fe₃O₄@ZIF-MIP、Fe₃O₄@ZIF-NIP和Fe₃O₄@ZIF对不同化合物的吸附情况(A), Fe₃O₄@ZIF-MIP的重复使用次数(B)

Figure 11. Adsorption of Fe₃O₄@ZIF-MIP, Fe₃O₄@ZIF-NIP and Fe₃O₄@ZIF on different compounds (A), number of reuse of Fe₃O₄@ZIF-MIP (B)

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图 12 黄瓜(A)、青椒(B)、西红柿(C)和豆芽(D)样品经材料富集后(a)和加标3.0 μg/g(b)时的色谱图

Figure 12. Chromatograms of cucumber (A), green pepper (B), small tomato (C) and bean sprout (D) samples after material enrichment (a) and at spiked 3.0 μg/g (b)

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表 1 Fe₃O₄@ZIF和Fe₃O₄@ZIF-MIP的比表面积和孔结构参数

Table 1. Specific surface area and pore structure parameters of Fe₃O₄@ZIF and Fe₃O₄@ZIF-MIP

材料	S_BET/(m²/g)^a	V_BJH/(cm³/g)^b		D_BJH/nm^c
材料	S_BET/(m²/g)^a	吸附	解吸	吸附	解吸
Fe₃O₄@ZIF	419.13	0.11	0.11	10.67	10.26
Fe₃O₄@ZIF-MIP	16.74	0.03	0.03	11.88	12.10
a: BET surface area b: BJH adsorption and desorption cumulative volume of pores c: BJH adsorption and desorption average pore width (4 V/A)

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表 2 Fe₃O₄@ZIF-MIP和Fe₃O₄@ZIF-NIP对分析物的吸附动力学模型参数

Table 2. Model parameters for adsorption kinetics of Fe₃O₄@ZIF-MIP and Fe₃O₄@ZIF-NIP for 2, 4-D

材料	准一级动力学模型ln(Q_e-Q_t)=lnQ_e-kt			准二级动力学模型t/Q_t=1/kQ_e²+t/Q_e
材料	Q_e/(mg/g)	k/(g/mg/min)	r	Q_e/(mg/g)	k/(g/mg/min)	r
Fe₃O₄@ZIF-MIP	0.32	0.020 1	0.269 6	12.33	1.934 5	0.999 0
Fe₃O₄@ZIF-NIP	0.45	0.007 6	0.712 7	3.86	0.056 5	0.978 2

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表 3 Fe₃O₄@ZIF-MIP和Fe₃O₄@ZIF-NIP对分析物的等温吸附模型

Table 3. Isothermal adsorption model parameters of Fe₃O₄@ZIF-MIP and Fe₃O₄@ZIF-NIP on analytes

材料	Langmuir模型			Freundlich模型
材料	Q_m/(mg/g)	K_L/(L/mg)	r	K_F(L/mg)	n	r
Fe₃O₄@ZIF-MIP	/	/	0.806 0	0.129 1	0.917 3	0.994 6
Fe₃O₄@ZIF-NIP	15.90	0.004 2	0.690 2	0.013 0	0.827 1	0.763 5

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表 4 本文方法与文献报道方法的测定结果的比较

Table 4. Comparison of analytical method used in experiment with other determination methods reported in literature

材料	样品	样品体积/mL	吸附时间/min	检测方法	吸附量/(mg/g)	LOD/(ng/mL)	参考文献
CNTs@SiO₂@MIPs	Water	10	150	HPLC-SPD	2.3	100.0	[18]
MIPs@ZIF-8	Water	10	60	UV	108.1	-	[19]
Fe₃O₄@MIP	Tap water, Chinese cabbage	1.0	60	HPLC-DAD	9.9	4.0	[20]
mag-MWCNTs-DMIPs	Crop	10	30	UPLC-MS/MS	17.8	1.3~1.5	[21]
C-C₆Cl₆	Water	10	30	HPLC-DAD	89.5	-	[22]
Fe₃O₄@SiO₂-NH₂	Water	200	60	HPLC-UV	158.0	-	[23]
GO/Fe₃O₄/TBA	Water, Vegetables	10	30	HPLC-UV	-	7.0	[24]
Fe₃O₄@graphene	Water	200	360	HPLC-UV	31.6	-	[25]
Fe₃O₄@ZIF-MIP	Vegetables	5	30	HPLC-UV	120.3	5.0	本文方法

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表 5 蔬菜样品中的检测和加标回收试验

Table 5. Detection and spiked recovery experiments in vegetable samples

蔬菜样品	加标量/(μg/g)	测定值/(μg/g)	加标回收率/%	RSD (n=3)/%
黄瓜	0.0	0.75	-	3.8
	1.2	1.89	95.3	3.4
	3.0	3.65	96.7	0.7
	12.0	10.68	82.8	5.6
青椒	0.0	-	-	-
	1.2	1.18	98.8	0.3
	3.0	2.53	84.5	2.0
	12.0	9.70	80.8	1.9
西红柿	0.0	-	-	-
	1.2	1.02	85.2	1.4
	3.0	2.44	81.5	0.7
	12.0	8.62	71.8	1.9
豆芽	0.0	-	-	-
	1.2	1.26	104.8	0.8
	3.0	2.98	99.4	6.5
	12.0	9.97	83.1	6.4

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表 6 标准方法处理蔬菜样品的加标回收试验

Table 6. Spiked recovery experiments of vegetable samples treated by standard method

蔬菜样品	加标量/(μg/g)	测定值/(μg/g)	加标回收率/%	RSD (n=3)/%
黄瓜	0.00	-	-	-
	0.32	0.34	105.8	0.5
	0.80	0.83	103.8	1.4
	3.20	2.76	86.4	4.5
青椒	0.00	-	-	-
	0.32	0.29	89.5	0.1
	0.80	0.73	91.2	0.6
	3.20	2.51	78.4	0.3
西红柿	0.00	-	-	-
	0.32	0.26	82.0	1.8
	0.80	0.84	104.8	0.5
	3.20	2.82	88.0	1.2
豆芽	0.00	-	-	-
	0.32	0.32	100.6	0.1
	0.80	0.69	86.6	0.6
	3.20	2.70	84.5	2.7

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