Preparation of porous boron nitride-doped polypyrrole-2,3,3-trimethylindole solid-phase microextraction coating for polycyclic aromatic hydrocarbon detection

doi:10.3724/SP.J.1123.2023.03015

Abstract

Abstract:

Most polycyclic aromatic hydrocarbons (PAHs), which are persistent organic pollutants, have strong carcinogenicity, teratogenicity, and mutagenicity, and pose serious threats to the ecological environment and human health. Owing to the complexity of the matrix and low PAH content of environmental samples, separating and enriching PAHs in environmental samples is necessary prior to their detection. Solid-phase microextraction (SPME) technology is commonly used to detect PAHs owing to its advantages of simple operation, online connection with other instruments, low solvent usage, and integrability of sampling separation, enrichment, and desorption. The extraction coating is the core of this technology, and the type and thickness of the coating are important factors affecting the sensitivity and accuracy of the analysis. Common commercial extraction coatings include polydimethylsiloxane and quartz fiber; however, these materials have a number of disadvantages, such as poor thermal stability and high cost. Several methods, including electrochemical, sol-gel, molecular imprinting, and other coating methods, have been developed to prepare SPME coatings. Electrochemical methods have attracted considerable attention because of their simplicity, short duration, and high coating stability. In the development of an electrochemical method, the selection of the conductive polymer is of particular importance. Polypyrroles (Ppy) are easily synthesized and have numerous advantages, such as good conductivity and stable chemical properties. Thus, their use as a substrate material for SPME coatings is beneficial for improving the overall stability of the coating. Copolymerization with other polymers can enhance the adsorption performance of such coatings via synergistic effects. When doped with inorganic materials with high thermal stability, the composite coating can exhibit high temperature resistance.

In this study, a porous boron nitride-doped Ppy-2,3,3-trimethylindole (Ppy/P2,3,3-TMe@In/BN) composite was prepared as a new SPME copolymer coating to detect three PAHs: naphthalene (NAP), acenaphthene (ANY), and fluorene (FLU). Scanning electron microscopy, thermal stability analysis, Fourier transform infrared spectroscopy, and other techniques were used to characterize the Ppy/P2,3,3-TMe@In/BN composite coating. The results showed that the coating featured a large number of porous and wrinkled dendritic structures, which increased the specific surface area of the composite coating and enabled the extensive enrichment of the three PAHs. When the sample inlet temperature of the chromatograph is 320 ℃, the chromatographic baseline of the coating is basically stable. Compared with commercial coatings, the prepared coating had better thermal stability. The coating formed stable intermolecular forces with the three PAHs owing to its numerous carbon-carbon double bonds (C=C), hydrogen bonds, and other structures, thereby achieving excellent enrichment of the target analytes. Compared with Ppy, Ppy/PIn, Ppy/P2,3,3-TMe@In, Ppy/BN, and polydimethylsiloxane (PDMS) coatings, the prepared Ppy/P2,3,3-TMe@In/BN composite coating exhibited better extraction effects for the three PAHs. The Ppy/P2,3,3-TMe@In/BN composite coating was polymerized on the surface of a stainless-steel wire by cyclic voltammetry and combined with gas chromatography-hydrogen flame ionization detection (GC-FID) to optimize the conditions influencing the extraction and separation of the three PAHs, thereby establishing a highly sensitive analytical method for detecting NAP, ANY, and FLU. This method had low limits of detection (LODs) of 10.6-14.5 ng/L (S/N=3) and high stability. The SPME-GC-FID method was used to detect the three PAHs in two environmental water samples, and a small amount of ANY (1.39 μg/L) was detected in one water sample. Satisfactory recoveries (82.5%-113.9%) were obtained when both water samples were spiked with the three PAHs at three levels. The experimental results indicate that the established analytical method can detect the three PAHs in environmental water samples.

Key words: solid-phase microextraction (SPME), gas chromatography (GC), cyclic voltammetry (CV), polycyclic aromatic hydrocarbons (PAHs), environmental water samples

CLC Number:

O658

DU Jie, SUN Pengchao, ZHANG Menglu, LIAN Zete, YUAN Fenggang, WANG Gang. Preparation of porous boron nitride-doped polypyrrole-2,3,3-trimethylindole solid-phase microextraction coating for polycyclic aromatic hydrocarbon detection[J]. Chinese Journal of Chromatography, 2023, 41(9): 789-798.

Figures/Tables 12

Fig. 1 Influence of (a) volume ratio of py and 2,3,3-TMe@In and (b) BN mass concentration on the extraction efficiency of Ppy/P2,3,3-TMe@In/BN fiber for the PAHs (n=3) Common experimental conditions: mass concentration of PAHs, 15 μg/L; extraction temperature, 45 ℃; NaCl mass concentration, 300 g/L; stirring rate, 600 r/min; extraction time, 35 min; desorption time, 5 min; desorption temperature, 280 ℃. py: pyrrole; 2,3,3-TMe@In: 2,3,3-trimethylindole; Ppy/P2,3,3-TMe@In/BN: porous boron nitride-doped Ppy-2,3,3-trimethylindole composite. PAHs: polycyclic aromatic hydrocarbons; NAP: naphthalene; ANY: acenaphthene; FLU: fluorene.

Fig. 2 FTIR spectra of (a) Ppy, (b) Ppy/P2,3,3-TMe@In and (c) Ppy/P2,3,3-TMe@In/BN

Fig. 3 Thermostability of Ppy/P2,3,3- TMe@In/BN coating

Fig. 4 SEM images of (a) BN, (b) Ppy, (c) Ppy/P2,3,3-TMe@In and (d) the coating of Ppy/P2,3,3-TMe@In/BN

Fig. 5 Influence of (a) extraction temperature, (b) extraction time, (c) mass concentration of NaCl and (d) stirring rate on the extraction efficiency of Ppy/P2,3,3-TMe@In/BN coating (n=3) Other conditions are the same as that in Fig. 1.

Fig. 6 Influence of (a) desorption temperature and (b) desorption time on desorption efficiency of target analytes (n=3) Other conditions are the same as that in Fig. 1.

Fig. 7 Comparison of the extraction efficiency of the Ppy, Ppy/Pin, Ppy/P2,3,3-TMe@In, Ppy/BN, Ppy/P2,3,3-TMe@In/BN and PDMS for the PAHs (n=3) Other conditions are the same as that in Fig. 1.

Table 1 Analytical parameters for PAHs measured with Ppy/P2,3,3-TMe@In/BN fiber based SPME-GC-FID method

Analyte	LOD/ (ng/L)	Linear range/ (μg/L)	Regression equation	Correlation coefficient	RSDs/%
Analyte	LOD/ (ng/L)	Linear range/ (μg/L)	Regression equation	Correlation coefficient	One fiber (n=5)	Fiber to fiber (n=5)
NAP	10.6	0.05-80	Y=3.43×10⁴X+8.0×10⁵	0.9974	5.41	9.13
ANY	14.5	0.05-80	Y=9.20×10⁴X+1.4×10⁶	0.9968	7.73	12.1
FLU	12.8	0.05-80	Y=7.53×10⁴X+8.1×10⁵	0.9983	6.37	9.94

Fig. 8 Variation of extraction efficiency with the times used Other conditions are the same as that in Fig. 1.

Table 2 Spiked recoveries and precisions of the three PAHs at three levels in environmental water samples (n=3)

Sample No.	Analyte	Background/ (μg/L)	1 μg/L		10 μg/L		50 μg/L
Sample No.	Analyte	Background/ (μg/L)	Rec./%	RSD/%	Rec./%	RSD/%	Rec./%	RSD/%
1	NAP	ND	85.7	8.2	84.5	7.9	94.0	3.7
	ANY	1.39	88.4	7.5	113.9	6.4	110.0	5.1
	FLU	ND	83.5	7.1	93.6	8.2	101.0	5.3
2	NAP	ND	87.4	6.7	86.1	5.0	96.3	4.9
	ANY	ND	92.8	8.8	100.6	6.9	105.0	2.8
	FLU	ND	82.5	6.9	108.7	8.3	102.0	3.6

Fig. 9 Chromatograms of water sample 1 and water sample 2

Table 3 Comparison of PAHs detection methods in water samples between this method and literature reports

Coating	Method	Analytes	LODs/(ng/L)	Rec./%	RSDs/%	Ref.
ZIF-8	SPME-GC-FID	ANY, FLU	40-230	88.3-105.3	3.1-7.3	[26]
TiO₂NTs/Ti	SPME-HPLC	NAP, FLU	30-50	97.8-111	3.7-8.9	[27]
Ppy/P2,3,3-TMe@In/BN	SPME-GC-FID	NAP, ANY, FLU	10.6-14.5	82.5-113.9	2.8-8.8	this work

References

[1]	Majdafshar M, Piryaei M, Abolghasemi M M, et al. Sep Sci Technol, 2019, 54(10): 1553
[2]	Ghaemmaghami M, Yamini Y, Amanzadeh H, et al. Chem Commun (Camb), 2018, 54(5): 507
[3]	Zhang W M, Li Q Q, Fang M, et al. Chinese Journal of Chromatography, 2022, 40(11): 1022
[3]	张文敏, 李青青, 方敏, 等. 色谱, 2022, 40(11): 1022
[4]	Liu Y, Liu H L, Wang X F, et al. Analytical Instrumentation, 2023(2): 1
[4]	刘媛, 刘海灵, 王香凤, 等. 分析仪器, 2023(2): 1
[5]	Gutierrez-Serpa A, Napolitano-Tabares P I, Pino V, et al. Microchim Acta, 2018, 185(7): 1
[6]	Xu S-N, Zhao Q, He H-B, et al. Anal Methods-UK, 2014, 6(17): 7046
[7]	Liu Y, Chen G, Tian C, et al. Environ Technol, 2019, 40(27): 3602
[8]	Ghiasvand A R, Abdolhosseini S, Heidari N, et al. J Iran Chem Soc, 2018, 15(11): 2585
[9]	Rahimi Z, Shahbazi Y, Ahmadi F. Food Anal Methods-UK, 2016, 10(4): 955
[10]	Gong S X, Wang X, Li L, et al. Anal Bioanal Chem, 2015, 407(29): 8673
[11]	Li H, Hou B, Wang L, et al. J Sep Sci, 2021, 44(7): 1521
[12]	Lambropoulou D A, Sakkas V A, Albanis T A. Anal Bioanal Chem, 2002, 374(5): 932
[13]	Augusto F, Carasek E, Silva R G, et al. J Chromatogr A, 2010, 1217(16): 2533
[14]	Yue J F, Song A Y, Zhao Y B, et al. Guangzhou Chemical Industry, 2023, 51(3): 49
[14]	岳敬芳, 宋爱英, 赵翌博, 等. 广州化工, 2023, 51(3): 49
[15]	Qi M, Tu C, Li Z, et al. Food Anal Method, 2018, 11(10): 2885
[16]	Wang X Y, Chen Y L, Li G K. Chinese Journal of Chromatography, 2021, 39(9): 1012
[16]	王兴益, 陈彦龙, 李攻科. 色谱, 2021, 39(9): 1012
[17]	Kuang Y X, Zhou S X, Hu Y L, et al. Chinese Journal of Chromatography, 2022, 40(10): 882
[17]	况逸馨, 周素馨, 胡亚兰, 等. 色谱, 2022, 40(10): 882
[18]	Chen J J, Zhang Z R, Yu J F, et al. Chinese Journal of Chromatography, 2022, 40(11): 1031
[18]	陈静静, 张卓然, 于剑峰, 等. 色谱, 2022, 40(11): 1031
[19]	Li Z, Zhou J B, Wang X, et al. Journal of Instrumental Analysis, 2018, 37(8): 871
[19]	李振, 周家斌, 王霞, 等. 分析测试学报, 2018, 37(8): 871
[20]	Fontana A R, Silva M F, Mart Nez L D, et al. J Chromatogr A, 2009, 1216(20): 4339
[21]	Sun S T, Yan Q, Li N, et al. Rock and Mineral Testing, 2020, 39(3): 408
[21]	孙书堂, 严倩, 黎宁, 等. 岩矿测试, 2020, 39(3): 408
[22]	Zhou J B, She X K, Xing H Z, et al. J Sep Sci, 2016, 39(10): 1955
[23]	Devasurendra A M, Zhang C, Young J A, et al. ACS Appl Mater Interfaces, 2017, 9(29): 24955
[24]	Pang Y, Zang X, Wang M, et al. Microchim Acta, 2018, 185(12): 1
[25]	Marchesini S, Mcgilvery C M, Bailey J, et al. ACS Nano, 2017, 11(10): 10003
[26]	Shen X T, Yang X D, Yang M Q, et al. Modern Chemical Research, 2023, 133(8): 62
[26]	申雪通, 杨晓丹, 杨梦奇, 等. 当代化工研究, 2023, 133(8): 62
[27]	Ma M G, Wei Y X, et al. Chinese Journal of Applied Chemistry, 2020, 37(2): 218
[27]	马明广, 魏云霞. 应用化学, 2020, 37(2): 218