Preparation and application of chlortetracycline electrochemical sensor based on molecularly imprinting technique

doi:10.11949/0438-1157.20220199

Abstract

Abstract:

The abuse of chlortetracycline (CTC) has brought serious adverse effects on the natural environment and human health. In this paper, a simple, economical and efficient molecularly imprinted electrochemical sensor for CTC was developed. The sensor was constructed by the electropolymerization of o-phenylenediamine on a reduced graphene oxide-polyethyleneimine complex (RGO-PEI) modified glassy carbon electrode. The RGO-PEI composite was characterized by scanning electron microscopy, infrared spectrum and ultraviolet visible spectrum. The high specific surface area and richness of amino groups of the RGO-PEI composite make it an excellent candidate for the detection of CTC due to the improved detection sensitivity and the stability of the molecularly imprinted film. Under optimized conditions, the sensor exhibited a wide linear range of (5.0×10^-7)—(1.0×10^-4) mol/L with a detection limit of 1.67×10^-7 mol/L (S/N=3). Additionally, there was little response to interfering substances such as kanamycin, oxytetracycline and doxycycline hydrochloride. The proposed method was successfully used for the detection of CTC in real sample with the recoveries of 102.7％—104.7％, showing a simple and efficient electrochemical method in practical application.

Key words: chlortetracycline, molecularly imprinting, graphene, electrochemical, o-phenylenediamine

摘要：

金霉素（CTC）的滥用给自然环境和人类健康带来了严重的不良影响。建立了一种简便、经济、高效的CTC分子印迹电化学传感器。该传感器的分子印迹膜由邻苯二胺在还原型氧化石墨烯-聚乙烯亚胺复合物（RGO-PEI）修饰的玻碳电极上电聚合而成。采用扫描电子显微镜、红外吸收光谱和紫外可见吸收光谱对RGO-PEI复合材料进行了表征。RGO-PEI复合材料的高比表面积和丰富的氨基基团提高了该传感器检测的灵敏度和稳定性。在优化条件下，该传感器对CTC浓度响应的线性范围为（5.0 × 10^-7）~（1.0 × 10^-4）mol/L，检测限为 1.67 × 10^-7 mol/L （信噪比，S/N=3）。此外，该传感器对卡那霉素、土霉素和盐酸多西环素等干扰物质的响应很小，可用于实际样品中CTC的检测，回收率为102.7% ~ 104.7%，是一种简单、高效的电化学方法。

关键词: 金霉素, 分子印迹, 石墨烯, 电化学, 邻苯二胺

CLC Number:

O 657.14

Shuang HAN, Nan ZHANG, Hui WANG, Xuan ZHANG, Jinluan YANG, Manlin ZHANG, Zhichao ZHANG. Preparation and application of chlortetracycline electrochemical sensor based on molecularly imprinting technique[J]. CIESC Journal, 2022, 73(8): 3758-3767.

韩双, 张楠, 王慧, 张璇, 杨金栾, 张蔓琳, 张志超. 金霉素分子印迹电化学传感器的制备与应用[J]. 化工学报, 2022, 73(8): 3758-3767.

Figures/Tables 16

Fig.1 Schematic representation of the fabrication procedures of the CTC MIP sensor

Fig.2 SEM images of GO and RGO-PEI and EDX image of RGO-PEI

Fig.3 FTIR spectra of GO and RGO-PEI

Fig.4 UV-Vis spectra of GO and RGO-PEI

Fig.5 Cyclic voltammograms for the electropolymerization of 5.0 mmol/L o-PD on GCE/RGO-PEI in the presence (a) and in the absence (b) of CTC in pH4.8 acetate buffer (scan rate: 0.050 V/s)

Fig.6 Cyclic voltammograms of 5.0 mmol/L K3[Fe(CN)6]/0.1 mol/L KCl on the bare GCE (a), GCE/RGO-PEI (b), GCE/RGO-PEI after electropolymerization (c), MIP GCE/RGO-PEI/PPD after the removal of CTC (d), MIP GCE/RGO-PEI/PPD after incubation of CTC (e)

Fig.7 Cyclic voltammograms of 5.0 mmol/L K3[Fe(CN)6]/0.1 mol/L KCl on the MIP GCE/RGO-PEI/PPD at different scan rates

Fig.8 Relationship between the scan rate and peak currents

Fig.9 Effect of the electropolymerization cycles on the peak current of the CV response in the presence of 5.0 mmol/L K3[Fe(CN)6]/ 0.1 mol/L KCl (I0 is the current of the MIP GCE/RGO-PEI/PPD after elution; I is the current of the MIP GCE/RGO-PEI/PPD after incubation of CTC)

Fig.10 Effect of pH on the peak current of CV response in the presence of 5.0 mmol/L K3[Fe(CN)6]/ 0.1 mol/L KCl(ΔI = I0 - I)

Fig.11 Effect of elution time on the peak current of CV response in the presence of 5.0 mmol/L K3[Fe(CN)6]/ 0.1 mol/L KCl (I′ is the current of the GCE/RGO-PEI/PPD after electropolymerization)

Fig.12 Effect of incubation time on the peak current of CV response in the presence of 5.0 mmol/L K3[Fe(CN)6]/ 0.1 mol/L KCl

Fig.13 Linear sweep voltammograms of 5.0 mmol/L K3[Fe(CN)6]/0.1 mol/L KCl at 0.050 V/s for CTC-free MIP films after rebinding CTC at different concentrations

Fig.14 Linear calibration curve of ΔI with CTC concentrations

Fig.15 The the current change of MIP GCE/RGO-PEI/PPD in the presence of 5.0 mmol/L K3[Fe(CN)6]/ 0.1 mol/L KCl after incubation in 25.0 μmol/L CTC, 25.0 μmol/L CTC +100.0 μmol/L kanamycin, 25.0 μmol/L CTC + 100.0 μmol/L DOC, 25.0 μmol/L CTC + 100.0 μmol/L OTC(ΔI0 = I0 -ICTC; ΔI = I0 -ICTC+others)

Table 1 Recoveries for CTC detection in lake samples

样品	加入量/(μmol/L)	测得量/(μmol/L)	回收率/%	平均回收率/%	RSD(n=3)/%
1	10.0	10.51, 10.71, 10.47	105.1, 107.1, 104.7	104.7	1.22
2	50.0	52.61, 51.41, 50.05	105.2, 102.8, 100.1	102.7	2.49

References 55

1	Qiao M, Ying G G, Singer A C, et al. Review of antibiotic resistance in China and its environment[J]. Environment International, 2018, 110: 160-172.
2	Pan L X, Feng X X, Cao M, et al. Determination and distribution of pesticides and antibiotics in agricultural soils from northern China[J]. RSC Advances, 2019, 9(28): 15686-15693.
3	Cai C Y, Li J Y, Wu D, et al. Spatial distribution, emission source and health risk of parent PAHs and derivatives in surface soils from the Yangtze River Delta, eastern China[J]. Chemosphere, 2017, 178: 301-308.
4	Lv J, Zhang L, Chen Y Y, et al. Occurrence and distribution of pharmaceuticals in raw, finished, and drinking water from seven large river basins in China[J]. Journal of Water and Health, 2019, 17(3): 477-489.
5	Han S, Li B Q, Song Z, et al. A kanamycin sensor based on an electrosynthesized molecularly imprinted poly-o-phenylenediamine film on a single-walled carbon nanohorn modified glassy carbon electrode[J]. Analyst, 2016, 142(1): 218-223.
6	Han S, Zhang X, Sun H D, et al. Electrochemical behavior and voltammetric determination of chloramphenicol and doxycycline using a glassy carbon electrode modified with single-walled carbon nanohorns[J]. Electroanalysis, 2022, 34(4): 735-742.
7	Pulicharla R, Brar S K, Rouissi T, et al. Degradation of chlortetracycline in wastewater sludge by ultrasonication, Fenton oxidation, and Ferro-sonication[J]. Ultrasonics Sonochemistry, 2017, 34: 332-342.
8	Meng L, Lan C W, Liu Z H, et al. A novel ratiometric fluorescence probe for highly sensitive and specific detection of chlorotetracycline among tetracycline antibiotics[J]. Analytica Chimica Acta, 2019, 1089: 144-151.
9	Zhou Y T, Niu L L, Zhu S Y, et al. Occurrence, abundance, and distribution of sulfonamide and tetracycline resistance genes in agricultural soils across China[J]. Science of the Total Environment, 2017, 599/600: 1977-1983.
10	Pulicharla R, Das R K, Brar S K, et al. Toxicity of chlortetracycline and its metal complexes to model microorganisms in wastewater sludge[J]. Science of the Total Environment, 2015, 532: 669-675.
11	Han J, Jiang D, Chen T S, et al. Simultaneous determination of olaquindox, oxytetracycline and chlorotetracycline in feeds by high performance liquid chromatography with ultraviolet and fluorescence detection adopting online synchronous derivation and separation[J]. Journal of Chromatography B, 2020, 1152: 122253.
12	Weng R, Sun L S, Jiang L P, et al. Electrospun graphene oxide-doped nanofiber-based solid phase extraction followed by high-performance liquid chromatography for the determination of tetracycline antibiotic residues in food samples[J]. Food Analytical Methods, 2019, 12(7): 1594-1603.
13	Du F Y, Zheng X, Sun L, et al. Development and validation of polymerized high internal phase emulsion monoliths coupled with HPLC and fluorescence detection for the determination of trace tetracycline antibiotics in environmental water samples[J]. Journal of Separation Science, 2015, 38(21): 3774-3780.
14	Valverde R S, Pérez I S, Franceschelli F, et al. Determination of photoirradiated tetracyclines in water by high-performance liquid chromatography with chemiluminescence detection based reaction of Rhodamine B with cerium (Ⅳ)[J]. Journal of Chromatography A, 2007, 1167(1): 85-94.
15	Gajda A, Antczak M, Mitrowska K, et al. Development, validation and application to real samples of a liquid chromatography with tandem mass spectrometry method for the determination of tetracyclines in beeswax[J]. Journal of Separation Science, 2018, 41(20): 3821-3829.
16	Tong L, Liu H, Xie C, et al. Quantitative analysis of antibiotics in aquifer sediments by liquid chromatography coupled to high resolution mass spectrometry[J]. Journal of Chromatography A, 2016, 1452: 58-66.
17	Jiao Z, Zhang S L, Chen H W. Determination of tetracycline antibiotics in fatty food samples by selective pressurized liquid extraction coupled with high-performance liquid chromatography and tandem mass spectrometry[J]. Journal of Separation Science, 2015, 38(1): 115-120.
18	Pamreddy A, Hidalgo M, Havel J, et al. Determination of antibiotics (tetracyclines and sulfonamides) in biosolids by pressurized liquid extraction and liquid chromatography-tandem mass spectrometry[J]. Journal of Chromatography A, 2013, 1298: 68-75.
19	Chang X S, Meyer M T, Liu X Y, et al. Determination of antibiotics in sewage from hospitals, nursery and slaughter house, wastewater treatment plant and source water in Chongqing region of Three Gorge Reservoir in China[J]. Environmental Pollution, 2010, 158(5): 1444-1450.
20	Patyra E, Kowalczyk E, Grelik A, et al. Screening method for the determination of tetracyclines and fluoroquinolones in animal drinking water by liquid chromatography with diode array detector[J]. Polish Journal of Veterinary Sciences, 2015, 18(2): 283-289.
21	Patyra E, Kowalczyk E, Kwiatek K. Screening method for the determination of selected tetracyclines in water by liquid chromatography with diode array detector[J]. Bulletin of the Veterinary Institute in Pulawy, 2014, 58(1): 65-70.
22	Karageorgou E, Armeni M, Moschou I, et al. Ultrasound-assisted dispersive extraction for the high pressure liquid chromatographic determination of tetracyclines residues in milk with diode array detection[J]. Food Chemistry, 2014, 150: 328-334.
23	Patyra E, Kowalczyk E, Kwiatek K. Development and validation method for the determination of selected tetracyclines in animal medicated feedingstuffs with the use of micellar liquid chromatography[J]. Analytical and Bioanalytical Chemistry, 2013, 405(21): 6799-6806.
24	Loetanantawong B, Suracheep C, Somasundrum M, et al. Electrocatalytic tetracycline oxidation at a mixed-valent ruthenium oxide: ruthenium cyanide-modified glassy carbon electrode and determination of tetracyclines by liquid chromatography with electrochemical detection[J]. Analytical Chemistry, 2004, 76(8): 2266-2272.
25	Wu X Y, Xu Z Q, Huang Z, et al. Large volume sample stacking of cationic tetracycline antibiotics toward 10 ppb level analysis by capillary electrophoresis with UV detection[J]. Electrophoresis, 2016, 37(22): 2963-2969.
26	Guo Y X, Meng L, Zhang Y H, et al. Sensitive determination of four tetracycline antibiotics in pig plasma by field-amplified sample stacking open-tubular capillary electrochromatography with dimethylethanolamine aminated polychloromethyl styrene nano-latex coated capillary column[J]. Journal of Chromatography B, 2013, 942/943: 151-157.
27	Wangfuengkanagul N, Siangproh W, Chailapakul O. A flow injection method for the analysis of tetracycline antibiotics in pharmaceutical formulations using electrochemical detection at anodized boron-doped diamond thin film electrode[J]. Talanta, 2004, 64(5): 1183-1188.
28	Si X J, Wang H L, Wu T H, et al. Novel methods for the rapid detection of trace tetracyclines based on the fluorescence behaviours of Maillard reaction fluorescent nanoparticles[J]. RSC Advances, 2020, 10(71): 43256-43261.
29	Gan T, Lv Z, Liu N, et al. Electrochemical detection method for chlorotetracycline based on enhancement of yolk–shell structured carbon sphere@MnO₂ [J]. Journal of the Electrochemical Society, 2015, 162(4): H200-H205.
30	Ni Y N, Li S Z, Kokot S. Simultaneous voltammetric analysis of tetracycline antibiotics in foods[J]. Food Chemistry, 2011, 124(3): 1157-1163.
31	Arabi M, Ostovan A, Li J H, et al. Molecular imprinting: green perspectives and strategies[J]. Advanced Materials, 2021, 33(30): 2100543.
32	Tarannum N, Khatoon S, Dzantiev B B. Perspective and application of molecular imprinting approach for antibiotic detection in food and environmental samples: a critical review[J]. Food Control, 2020, 118: 107381.
33	Li S P, Guan H M, Xu G B, et al. Progress in molecular imprinting electrochemiluminescence analysis[J]. Chinese Journal of Analytical Chemistry, 2015, 43(2): 294-299.
34	Li W, Zheng Y P, Zhang T W, et al. A surface plasmon resonance-based optical fiber probe fabricated with electropolymerized molecular imprinting film for melamine detection[J]. Sensors, 2018, 18(3): 828.
35	Tlili A, Attia G, Khaoulani S, et al. Contribution to the understanding of the interaction between a polydopamine molecular imprint and a protein model: ionic strength and pH effect investigation[J]. Sensors, 2021, 21(2): 619.
36	Tang X S, Zhang D, Zhou T S, et al. Fe₃O₄@Au sphere molecular imprinting with self-assembled monolayer for the recognition of parathion-methyl[J]. Analytical Methods, 2011, 3(10): 2313.
37	Yu Y J, Zhang Q, Buscaglia J, et al. Quantitative real-time detection of carcinoembryonic antigen (CEA) from pancreatic cyst fluid using 3-D surface molecular imprinting[J]. The Analyst, 2016, 141(14): 4424-4431.
38	Yin D X, Ulbricht M. Protein-selective adsorbers by molecular imprinting via a novel two-step surface grafting method[J]. Journal of Materials Chemistry B, 2013, 1(25): 3209.
39	Zhao M, Chen X J, Zhang H T, et al. Well-defined hydrophilic molecularly imprinted polymer microspheres for efficient molecular recognition in real biological samples by facile RAFT coupling chemistry[J]. Biomacromolecules, 2014, 15(5): 1663-1675.
40	Blanco-López M C, Lobo-Castañón M J, Miranda-Ordieres A J, et al. Voltammetric sensor for vanillylmandelic acid based on molecularly imprinted polymer-modified electrodes[J]. Biosensors and Bioelectronics, 2003, 18(4): 353-362.
41	Li H D, Guan H M, Dai H, et al. An amperometric sensor for the determination of benzophenone in food packaging materials based on the electropolymerized molecularly imprinted poly-o-phenylenediamine film[J]. Talanta, 2012, 99: 811-815.
42	Wu S X, He Q Y, Tan C L, et al. Graphene-based electrochemical sensors[J]. Small, 2013, 9(8): 1160-1172.
43	Chen D, Feng H B, Li J H. Graphene oxide: preparation, functionalization, and electrochemical applications[J]. Chemical Reviews, 2012, 112(11): 6027-6053.
44	Geim A K, Novoselov K S. The rise of graphene[J]. Nature Materials, 2007, 6(3): 183-191.
45	Lawal A T. Graphene-based nano composites and their applications. A review[J]. Biosensors and Bioelectronics, 2019, 141: 111384.
46	Huang X, Qi X Y, Boey F, et al. Graphene-based composites[J]. Chemical Society Reviews, 2012, 41(2): 666-686.
47	Atar N, Yola M L, Eren T. Sensitive determination of citrinin based on molecular imprinted electrochemical sensor[J]. Applied Surface Science, 2016, 362(1): 315-322.
48	Yola M L, Eren T, Atar N. A sensitive molecular imprinted electrochemical sensor based on gold nanoparticles decorated graphene oxide: application to selective determination of tyrosine in milk[J]. Sensors and Actuators B, 2015, 210: 149-157.
49	Zhou X H, Chen Z X, Yan D H, et al. Deposition of Fe-Ni nanoparticles on polyethyleneimine-decorated graphene oxide and application in catalytic dehydrogenation of ammonia borane[J]. Journal of Materials Chemistry, 2012, 22(27): 13506.
50	Gan S Y, Zhong L J, Han D X, et al. Probing bio-nano interactions between blood proteins and monolayer-stabilized graphene sheets[J]. Small, 2015, 11(43): 5814-5825.
51	Kim H, Namgung R, Singha K, et al. Graphene oxide-polyethylenimine nanoconstruct as a gene delivery vector and bioimaging tool[J]. Bioconjugate Chemistry, 2011, 22(12): 2558-2567.
52	Guo H L, Wang X F, Qian Q Y, et al. A green approach to the synthesis of graphene nanosheets[J]. ACS Nano, 2009, 3(9): 2653-2659.
53	Zhang Y, Chen B, Zhang L M, et al. Controlled assembly of Fe₃O₄ magnetic nanoparticles on graphene oxide[J]. Nanoscale, 2011, 3(4): 1446-1450.
54	Yang S, Yue W B, Huang D Z, et al. A facile green strategy for rapid reduction of graphene oxide by metallic zinc[J]. RSC Advances, 2012, 2(23): 8827-8832.
55	Gao Y, Li Y, Zhang L, et al. Adsorption and removal of tetracycline antibiotics from aqueous solution by graphene oxide[J]. Journal of Colloid and Interface Science, 2012, 368(1): 540-546.

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