磁性金属有机骨架-聚多巴胺的制备并用于水产养殖水样中阳离子染料的萃取检测

doi:10.3724/SP.J.1123.2019.05045

摘要/Abstract

摘要：

利用多巴胺（DA）中的儿茶酚基团能与金属有机骨架晶体（MOFs）中金属离子螯合的原理，以ZIF-67为模板，经DA蚀刻-自聚合形成具有孔洞结构的聚多巴胺（PDA）壳层，制备了磁性-MOFs-PDA（Fe₃O₄@Z67D）新型材料。多种表征手段验证了材料的形貌、结构和性能。新型材料具有亲水性的表面、纳米级的孔径，以及良好的磁响应，被用作磁固相萃取吸附剂。结合高效液相色谱分析手段，建立了萃取检测亚甲蓝（MB）和结晶紫（CV）两种阳离子染料的新方法。在最优的萃取和色谱分析条件下，MB和CV的线性范围分别为0.5~200 μg/L和0.01~50 μg/L，检出限分别为0.04 μg/L和0.008 μg/L，对两种染料的富集因子分别为777和688。新型材料重复使用10次，其萃取性能未见发生变化。该方法成功应用于检测淡水鱼养殖用水中痕量的MB和CV，加标回收率为82.0%~109.0%，RSD低于2.9%。

关键词: 金属有机骨架, 聚多巴胺, 磁固相萃取, 高效液相色谱, 阳离子染料

Abstract:

The catechol group of dopamine (DA) can chelate with the metal ion in the crystal of molecular organic frameworks (MOFs). Based on this principle, a magnetic metal polydopamine (PDA) framework (Fe₃O₄@Z67D) was prepared using ZIF-67 as the template, which was etched by DA, followed by polymerization of the DA monomers to form a PDA coating with a porous structure. The morphology, structure, and properties of the material were determined by various characterization methods. Fe₃O₄@Z67D was used as an adsorbent, and a magnetic solid-phase extraction/high-performance liquid chromatography method for the determination of two cationic dyes, methylene blue (MB) and crystal violet (CV), was established. Under the optimized extraction and detection conditions, the linear ranges for MB and CV were 0.5-200 μg/L and 0.01-50 μg/L, respectively, and the corresponding detection limits were 0.04 μg/L and 0.008 μg/L. The experimental results showed that the enrichment factors of Fe₃O₄@Z67D for the two dyes were 777 and 688, respectively. The extraction performance was largely unaffected even after the new material was reused 10 times. The method was applied successfully for the adsorption and detection of the above mentioned two dyes in fishpond water. The spiking recoveries of the two cationic dyes ranged from 82.0% to 109.0%, and the RSD was lower than 2.9%.

Key words: metal-organic frameworks (MOFs), polydopamine, magnetic solid-phase extraction (MSPE), high-performance liquid chromatography (HPLC), cationic dyes

杨晓涵, 吴雯倩, 王彬, 林风, 吴小海, 卢昕. 磁性金属有机骨架-聚多巴胺的制备并用于水产养殖水样中阳离子染料的萃取检测[J]. 色谱, 2020, 38(2): 195-205.

YANG Xiaohan, WU Wenqian, WANG Bin, LIN Feng, WU Xiaohai, LU Xin. Preparation of magnetic metal-organic frameworks-polydopamine for extraction and detection of cationic dyes from water samples in a fishery[J]. Chinese Journal of Chromatography, 2020, 38(2): 195-205.

图/表 13

图1 Fe3O4@Z67D的(a)合成示意图及(b)磁固相萃取流程图

Fig. 1 Schemes of (a) synthesis of Fe3O4@Z67D and (b) MSPE process PEG: polyethylene glycol; EG: ethylene glycol; PDA: polydopamine; MSPE: magnetic solid-phase extraction.

图2 Fe3O4、ZIF-67、Fe3O4@ZIF-67和Fe3O4@Z67D的(a)X射线衍射谱图和(b)红外光谱图

Fig. 2 (a) X-ray diffraction spectra and (b) infrared spectra of Fe3O4, ZIF-67, Fe3O4@ZIF-67 and Fe3O4@Z67D

图3 (a) Fe3O4、(b)Fe3O4@ZIF-67和(c)Fe3O4@Z67D的扫描电镜图, 以及(d)Fe3O4@Z67D和(e, f)Fe3O4@Z67D的透射电镜图

Fig. 3 Scanning electron microscope images of (a) Fe3O4, (b) Fe3O4@ZIF-67, (c) Fe3O4@Z67D and transmission electron microscopy images of (d) Fe3O4@ZIF-67 and (e, f) Fe3O4@Z67D

图4 (a) Fe3O4@ZIF-67和(b)Fe3O4@Z67D的能量色散X射线光谱图

Fig. 4 Energy dispersive X-ray spectra of (a) Fe3O4@ZIF-67 and (b) Fe3O4@Z67D

图5 Fe3O4@Z67D的(a)X射线光电子能谱全扫描分析及(b)Fe 2p、(c)Co 2p、(d)O 1s、(e)C 1s和(f)N 1s的高分辨X射线光电子能谱分析

Fig. 5 X-ray photoelectron spectroscopy full-scan analysis of (a) Fe3O4@Z67D and high resolution X-ray photoelectron spectroscopy analysis of (b) Fe 2p, (c) Co 2p, (d) O 1s, (e)C 1s and (f) N 1s

图6 Fe3O4@ZIF-67和Fe3O4@Z67D的(a)N2吸附-解吸等温线及(b)孔径分布

Fig. 6 (a)N2 adsorption-desorption isotherm and (b) pore size distribution of Fe3O4@ZIF-67 and Fe3O4@Z67D

图7 Fe3O4, Fe3O4@ZIF-67 and Fe3O4@Z67D的磁滞回线

Fig. 7 Hysteresis loops of Fe3O4, Fe3O4@ZIF-67 and Fe3O4@Z67D

图8 (a) Fe3O4@Z67D吸附剂的用量、(b)萃取时间, 以及样品溶液的(c)体积、(d)pH和洗脱剂(e)类型、(f)体积对两种染料回收率的影响(n=3)

Fig. 8 Effects of (a) the amount of Fe3O4@Z67D, (b) the extraction time, (c) the volume and (d) pH of sample solution, and (e) the type and (e) volume of the eluent solvents on the recoveries of the two dyes (n=3) MeOH: methanol; ACN: acetonitrile; HAc: acetic acid.

图9 Fe3O4@Z67D重复使用后的回收率(n=3)

Fig. 9 Recoveries obtained on Fe3O4@Z67D after reuse(n=3)

表1 MSPE-HPLC测定两种染料的方法学参数

Table 1 Analytical performance data of the MSPE-HPLC method for the determination of the two dyes

Analyte	Regression equation	Linear range/(μg/L)	R²	LOD/(μg/L)	RSD/%(n=5)	Enrichment factor
Y: peak area; X: mass concentrition, μg/L.
MB	Y=6.0×10⁴X-2.8×10⁴	0.5-200	0.9999	0.04	1.2	777
CV	Y=1.0×10⁵X+6.2×10³	0.01-50	0.9998	0.008	3.6	688

表2 养殖鱼塘水样中MB和CV的测定结果及加标回收率

Table 2 Analytical results of MB and CV in fishpond water samples and the spiked recoveries (n=5)

Analyte	Added/(μg/L)	Found/(μg/L)	Recovery/%	RSD/%
-: not applicable.
MB	0	0.7	--
	1	0.9	88.6	2.3
	10	9.0	90.3	2.9
CV	0	0.2	--
	5	5.5	109.0	2.2
	50	41.0	82.0	1.4

图10 MSPE处理后的鱼塘水样的色谱图

Fig. 10 Chromatograms obtained from fishpond water samples treated after MSPE a. blank sample; b. sample spiked with 10 μg/L MB and 5 μg/L CV.Conditions: SpursilTM C18 column(250 mm×4.6 mm, 5 μm); mobile phase, methanol-0.0125 mol/L ammonium acetate buffer solution (85:15, v/v)(pH adjusted to 4.5 by acetic acid); flow rate, 1.0 mL/min; detection wavelength, 580 nm; injection volume, 20 μL; column temperature, 35 ℃.

表3 本方法与相关文献中的方法比较

Table 3 Comparison of this method with reported methods

Method	Matrix	Linear range/(μg/L)		LOD/(μg/L)		Recovery/%	RSD/%	Reference
Method	Matrix	MB	CV	MB	CV	Recovery/%	RSD/%	Reference
PLS-1: partial least squares method; NACE: non-aqueous capillary electrophoresis; ED: electrochemical detection; -: not available; *: μg/kg.
SPE-UPLC-MS-MS	silver carp	5.0-200	2.5-100	0.30^*	0.15^*	75.4-87.8	4.33-10.4	[53]
SPE-UV/PLS-1	stream water	150-8000	120-8000	48	28	79.8-83.6	2.3-4.2	[54]
SPE-NACE-ED	river and lake water	100-700	100-700	0.13	0.11	43-98	-	[55]
MSPE-HPLC-UV	fishpond water	0.5-200	0.01-50	0.04	0.008	82.0-109.0	1.4-2.9	this work

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