聚苯胺/二氧化钛纳米管固相微萃取纤维的组装及应用

doi:10.3724/SP.J.1123.2019.10012

摘要/Abstract

摘要：

以钛丝表面原位阳极氧化生成的二氧化钛纳米管为基体，通过电聚合苯胺组装得到新型聚苯胺包覆二氧化钛复合纳米管阵列固相微萃取纤维。实验讨论了无机酸介质、苯胺浓度和氧化电压对电聚合苯胺的影响，经过对纤维表面形貌和元素成分的分析，得到最佳的纤维涂层条件：电解液组成为1 mol/L的H₂SO₄-0.5 mol/L的苯胺，聚合电压10 V，氧化时间60 min。采用所制备的纤维与高效液相色谱联用萃取水样中的紫外线吸收剂并优化萃取条件，固相微萃取条件如下：萃取时间40 min，解吸时间4 min，萃取温度40℃，搅拌速率600 r/min，样品溶液中不加NaCl。同时对环境水样中的目标物分析测定，并做加标试验，目标分析物的平均回收率为78.2%~118%，相对标准偏差为4.4%~8.9%。该方法简便、灵敏、准确，适用于环境水样中紫外线吸收剂的快速测定。

关键词: 固相微萃取, 高效液相色谱, 紫外线吸收剂, 二氧化钛, 聚苯胺

Abstract:

A novel solid phase microextraction fiber of polyaniline coated titania composite nanotube (PANI@TiO₂NTs/Ti) array was fabricated on a titanium wire by in situ oxidation. The effects of the inorganic acid medium, aniline concentration, and oxidation voltage on the electropolymerization of aniline were discussed. The best forming conditions for the composite fiber obtained by analyzing the surface morphology and composition of the fibers were as follows:electrolyte composing, 0.5 mol/L aniline-1 mol/L H₂SO₄; electropolymerization, 10 V for 60 min. The developed fibers were used in conjunction with high performance liquid chromatography for the extraction and determination of ultraviolet filters in samples, and the extraction conditions optimized were as follows:extraction time 40 min, desorption time 4 min, extraction temperature 40℃, stirring rate 600 r/min. The average recoveries of the target analytes spiked in real samples ranged from 78.2% to 118%, and the relative standard deviations ranged from 4.4% to 8.9%. The developed method is simple, rapid, and accurate, and it is suitable for the sensitive determination of UV filters in environmental water samples.

Key words: solid phase microextraction (SPME), high performance liquid chromatography (HPLC), ultraviolet filters, titanium dioxide, polyaniline

马明广, 魏云霞, 刘海霞, 刘芳, 尚琼. 聚苯胺/二氧化钛纳米管固相微萃取纤维的组装及应用[J]. 色谱, 2020, 38(6): 639-646.

MA Mingguang, WEI Yunxia, LIU Haixia, LIU Fang, SHANG Qiong. Fabrication and application of polyaniline/titanium dioxide nanotube solid phase microextraction fiber[J]. Chinese Journal of Chromatography, 2020, 38(6): 639-646.

图/表 9

图1 钛纤维基体表面的SEM图

Fig. 1 Scanning electron microscope (SEM) images of Ti fiber substrate surface a. untreated Ti wire; b. untreated Ti wire; c. TiO2 NTs/Ti fiber; d. PANI@TiO2NTs/Ti fiber (perchloric acid medium); e. PANI@TiO2NTs/Ti fiber (nitric acid medium); f. PANI@TiO2NTs/Ti fiber (sulfuric acid medium).

图2 不同苯胺浓度下PANI@TiO2NTs涂层的SEM图

Fig. 2 SEM images of PANI@TiO2NTs coatings at various aniline concentrations a. 0.1 mol/L; b. 0.2 mol/L; c. 0.4 mol/L; d. 0.5 mol/L.

图3 不同聚合电压下PANI@TiO2NTs涂层的SEM图

Fig. 3 SEM images of PANI@TiO2NTs coating at different electropolymerization voltages a. 6 V; b. 8 V; c. 10 V; d. 12 V.

图4 不同有机物采用PANI@TiO2NTs/Ti纤维萃取后的色谱图

Fig. 4 Chromatograms of different organics extracted with the PANI@TiO2NTs/Ti fiber a. PAEs; b. PCBs; c. CPs; d. UV filters.PCB-28: 2, 4, 4′-trichlorobiphenyl; PCB-31: 2, 4′, 5-trichlorobiphenyl; PCB-118: 2, 3′, 4, 4′, 5-pentachlorobiphenyl; PCB-153: 2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl; 2-CP: 2-chlorophenol; 2, 4-DCP: 2, 4-dichlorophenol; TCS: 2-(2, 4-dichlorophenoxy)-5-chlorophenol; BP-3: 2-hydroxy-4-methoxy-benzophenone; OD-PABA: 2-ethylhexyl 4-(N, N-dimethylamino) benzoate; EHMC: 2-ethylhexyl-4-methoxycinnamate; EHS: 2-ethylhexyl salicylate.

图5 采用不同纤维萃取紫外线吸收剂的色谱图

Fig. 5 Chromatograms of the UV filters extracted with different fibers

表1 4种紫外线吸收剂的线性范围、相关系数、检出限、定量限和相对标准偏差

Table 1 Linear ranges, correlation coefficients (R2), limits of detection (LODs), limits of quantification (LOQs) and relative standard deviations (RSDs)

UV filter	Linear range/ (μg/L)	R²	LOD/(μg/L)	LOQ/(μg/L)	RSDs/%^*
UV filter	Linear range/ (μg/L)	R²	LOD/(μg/L)	LOQ/(μg/L)	Single fiber (n=5)	Fiber-to-fiber (n=3)
* Calculated at the mass concentration of 25 μg/L.
BP-3	0.25-500	0.9998	0.05	0.19	4.7	7.6
OD-PABA	0.25-500	0.9987	0.05	0.18	5.7	8.8
EHMC	0.25-500	0.9992	0.04	0.14	4.3	6.9
EHS	0.25-500	0.9953	0.06	0.22	5.3	9.3

图6 实际污水样品中4种紫外线吸收剂的色谱图

Fig. 6 Chromatograms of the four UV filters in a real wastewater sample a. sample spiked with 5 μg/L UV filters, pretreatment with SPME; b. sample without addition, pretreatment with SPME; c. sample without addition, without SPME.

表2 不同环境水样中4种紫外线吸收剂的含量、加标回收率和相对标准偏差(n=3)

Table 2 Contents, spiked recoveries and RSDs of four UV filters in different environmental water samples (n=3)

Sample	Analyte	Background/ (μg/L)	Spiked with 5 μg/L			Spiked with 10 μg/L
Sample	Analyte	Background/ (μg/L)	Detected/ (μg/L)	Recovery/ %	RSD/ %	Detected/ (μg/L)	Recovery/ %	RSD/ %
^a ND: not detected or lower than LOD.
River water under Bapanxia Bridge	BP-3	0.62	5.96	106	4.4	9.34	88.0	6.7
	OD-PABA	0.84	6.82	117	5.6	12.8	118	7.2
	EHMC	0.96	6.45	108	4.4	9.98	91.1	5.8
	EHS	ND^a	4.86	97.2	7.0	9.63	96.3	7.9
River water under Yintan Bridge	BP-3	3.08	7.52	93.1	5.5	12.6	96.3	6.7
	OD-PABA	2.89	8.73	111	6.0	13.5	105	7.3
	EHMC	1.28	6.64	106	5.1	13.0	115	6.8
	EHS	ND	5.40	108	7.9	7.82	78.2	8.5
River water under Zhongshan Bridge	BP-3	1.82	6.27	91.9	5.5	10.4	88.0	6.5
	OD-PABA	2.01	6.36	90.7	5.9	11.6	96.6	7.1
	EHMC	2.52	6.49	86.3	4.7	14.0	112	5.7
	EHS	ND	4.51	90.2	8.3	10.8	108	7.9
River water under Donggang Bridge	BP-3	2.28	6.96	95.6	5.0	13.4	109	5.3
	OD-PABA	2.16	8.44	118	5.2	12.0	98.7	6.3
	EHMC	2.10	6.82	96.1	4.6	13.5	112	5.9
	EHS	ND	5.18	104	7.6	11.0	102	8.5
River water under Shichuan Bridge	BP-3	2.02	6.54	93.2	5.0	13.3	111	6.1
	OD-PABA	2.54	6.78	89.9	5.6	14.1	112	6.8
	EHMC	1.02	6.64	110	5.0	10.6	96.2	5.9
	EHS	ND	4.87	97.4	8.2	10.6	106	8.4
Wastewater	BP-3	2.83	6.87	87.74	5.7	13.6	106	6.6
	OD-PABA	3.52	7.23	84.86	6.1	15.2	112	7.1
	EHMC	2.17	6.52	90.93	5.0	13.5	111	6.9
	EHS	ND	4.62	92.40	7.3	9.07	90.7	8.9

表3 本方法与文献报道检测紫外线吸收剂方法的分析比对

Table 3 Comparison of the developed method with other methods for extraction and determination of UV filters

Method	Extraction time/min	Linear range/(μg/L)	LOD/(μg/L)	RSD/%	Recovery/%	Ref.
CPE: cloud point extraction; SDME: single drop microextraction; HF-LPME: hollow fiber liquid phase microextraction; DLLME: dispersive liquid-liquid microextraction; MSA-DLLME magnetic stirring assisted dispersive liquid-liquid microextraction.
CPE	30	0.5-30	0.14-1.27	3.9-5.2	98.5-102	[28]
SDME	37	1-300	0.06-3.0	2.8-7.9	92-115	[29]
HF-LPME	50	5-1000	0.2-0.5	1.1-8.4	95.2-105	[30]
DLLME	10	0.5-500	0.06-0.16	2.8-7.6	92.8-114	[31]
MSA-DLLME	25	5-20000	0.2-0.8	1.4-4.8	91.3-97.1	[32]
SPME	40	0.25-500	0.04-0.06	4.3-8.9	90.6-110	this method

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