磁性氧化石墨烯的制备及其在环境水样中7种内分泌干扰物检测中的应用

doi:10.3724/SP.J.1123.2019.10007

摘要/Abstract

摘要：

制备了十二胺修饰的磁性氧化石墨烯纳米材料并将其用于磁固相萃取。在对磁固相萃取材料合成与萃取条件以及液相色谱分离等条件进行优化的基础上，建立了磁固相萃取与高效液相色谱-紫外检测对环境水样中7种内分泌干扰物的分析方法。该方法对雌酮、雌二醇、雌三醇、双酚A、17α-乙炔基雌二醇、己烷雌酚和雄烯二酮7种内分泌干扰物的检出限在0.10~0.23 nmol/L之间。将该方法分别应用于废水样品和湖水样品的加标回收试验，回收率在73.9%~112.9%和74.9%~114.7%之间。该方法操作简便，分析成本较低，可为环境水体中内分泌干扰物的分析提供技术支持。

关键词: 磁性石墨烯, 磁固相萃取, 内分泌干扰物, 环境水样

Abstract:

Magnetic graphene oxide (MGO) modified with dodecylamine (DDA) was synthesized in this work. The as-prepared MGO-DDA was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and vibrating sample magnetometer measurements. The material was used as the absorbent in magnetic solid-phase extraction (MSPE) for seven environmental endocrine-disrupting chemicals (EDCs):estrone (E1), β-estradiol (E2), estriol (E3), 17α-ethynylestradiol (EE2), hexoestrol (HEX), androstendione (AND), and bisphenol A (BPA). MSPE combined with HPLC-UV was developed for the determination of EDCs in environmental water samples. The effects of the amount of adsorbent, adsorbing time, and the type and volume of eluents on the recoveries of the EDCs were investigated. Under the optimal conditions, good linear relationships between the UV signals and the EDC concentrations were obtained, with R² greater than 0.999. The limits of detection for all the EDCs were between 0.10 and 0.23 nmol/L. The MSPE-HPLC-UV method was successfully applied to the analysis of the seven EDCs in environmental water samples such as lake water and sewage water samples. The recoveries of all the EDCs in spiked lake water and sewage water samples were between 73.9% and 114.7%, and the RSDs ranged from 0.7% to 11.8%. Thus, the proposed MSPE-HPLC-UV method is simple, reliable, sensitive, and low-cost.

Key words: magnetic graphene oxide, magnetic solid-phase extraction, endocrine-disrupting chemicals, environmental water samples

郭菁豪, 童裳伦. 磁性氧化石墨烯的制备及其在环境水样中7种内分泌干扰物检测中的应用[J]. 色谱, 2020, 38(5): 522-528.

GUO Jinghao, TONG Changlun. Synthesis of magnetic graphene oxide modified with dodecylamine and its application for the determination of seven endocrine-disrupting chemicals in environmental water samples[J]. Chinese Journal of Chromatography, 2020, 38(5): 522-528.

图/表 8

图1 MGO-DDA材料的X射线衍射图及与Fe3O4准卡片的对比

Fig. 1 XRD spectrum of the synthesized MGO-DDA and the comparison with standard JCPDS card of Fe3O4 MGO: magnetic graphene oxide; DDA: dodecylamine; JCPDS: Joint Committee on Powder Diffraction Standards.

图2 (a) MGO和MGO-DDA的傅里叶红外光谱图和(b)MGO-DDA的磁滞回线

Fig. 2 (a) FTIR spectrum of MGO and MGO-DDA and (b) the magnetic hysteresis loop of MGO-DDA

图3 MGO-DDA中MGO和DDA质量比对EDCs萃取效率的影响(n=3)

Fig. 3 Effect of MGO/DDA mass ratios in MGO-DDA on the extraction efficiencies of EDCs (n=3) EDCs: endocrine-disrupting chemicals; E1: estrone; E2: β-estradiol; E3: estriol; EE2: 17 α-ethynylestradiol; HEX: hexoestrol; AND: androstendione; BPA: bisphenol A.

图4 MGO-DDA材料用量对EDCs萃取效率的影响(n=3)

Fig. 4 Effect of the dosage of MGO-DDA on the extraction efficiencies of EDCs (n=3)

图5 磁固相萃取条件对EDCs萃取效率的影响(n=3)

Fig. 5 Effect of the MSPE conditions on the extraction efficiencies of EDCs (n=3) a. pH of water sample; b. adsorption time; c. eluent types; d. eluent volume.

表1 方法的线性范围与检出限

Table 1 Linear ranges and the limits of detection (LODs) of the proposed method

Analyte	Linear range/ (nmol/L)	Regression equation	Correlation coefficient (R²)	LOD/ (nmol/L)
y: peak area; x: concentration, nmol/L.
E3	1.0-100	y=1.5355x+0.3909	0.9998	0.23
BPA	1.0-100	y=6.7025x+0.6213	0.9999	0.10
E2	1.0-100	y=1.7549x+2.6002	0.9993	0.18
EE2	1.0-100	y=2.1008x+1.3735	0.9999	0.18
E1	1.0-100	y=1.6963x+1.6818	0.9997	0.22
HEX	1.0-100	y=8.5825x-1.3276	0.9999	0.19
AND	1.0-100	y=4.7044x+3.2523	0.9997	0.14

图6 (a) 标准溶液(0.2 μmol/L)与加标50.0 nmol/L的(b)废水和(c)湖水样品的色谱图

Fig. 6 Chromatograms of (a) standard solution (0.2 μmol/L) and spiked samples of (b) sewage water and (c) lake water at 50.0 nmol/L

表2 水样中EDCs的加标回收率

Table 2 Recoveries of EDCs in the spiked water samples

Analyte	Sewage water				Lake water
Analyte	Added/ (nmol/L)	Found/ (nmol/L)	Recovery/ %	RSD/% (n=5)	Added/ (nmol/L)	Found/ (nmol/L)	Recovery/ %	RSD/% (n=5)
ND: not detected.
E3	0	ND			0	ND
	5	5.2±0.4	103.0	8.5	5	4.2±0.2	84.5	4.2
	50	45.2±4.2	90.4	9.3	50	37.5±1.4	74.9	3.7
BPA	0	ND			0	ND
	5	4.5±0.1	90.7	2.4	5	4.7±0.1	93.1	2.4
	50	37.0±0.5	73.9	1.3	50	38.9±0.3	77.8	0.7
E2	0	ND			0	ND
	5	4.6±0.5	92.6	11.8	5	4.6±0.2	91.1	4.7
	50	39.4±1.6	78.7	4.1	50	37.9±1.4	75.7	3.7
EE2	0	ND			0	ND
	5	5.1±0.5	101.4	9.9	5	4.8±0.2	96.3	3.3
	50	45.1±1.4	90.3	3.1	50	45.2±0.6	90.4	1.3
E1	0	ND			0	ND
	5	5.6±0.5	112.9	9.6	5	5.7±0.3	114.7	5.6
	50	40.7±1.7	81.4	4.2	50	40.3±1.9	80.6	4.6
HEX	0	ND			0	ND
	5	5.1±0.2	102.3	3.1	5	4.5±0.2	90.5	3.4
	50	47.9±1.2	95.7	2.4	50	45.7±0.6	91.4	1.3
AND	0	ND			0	ND
	5	5.3±0.4	105.7	7.3	5	5.3±0.1	105.6	1.6
	50	44.8±1.0	89.6	2.3	50	44.7±0.7	89.4	1.6

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