Abstract
Herein, a simple, rapid, cost-effective and sensitive poly(thionine)-based electrochemical sensor is described to determine trace amounts of tetracycline. In the present work, electropolymerization of thionine was performed to create a stable film on the surface of carbon nanotube paste electrode. The modified electrode surface was investigated by scanning electron microscopy (SEM) and its complete formation was confirmed. Moreover, the unmodified and modified electrodes were then studied by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) technique. The linear sweep voltammetry (LSV) technique was used for the quantification of tetracycline 0.1 M phosphate buffer solution (PBS) at pH 6.0 by the modified electrode as a poly(thionine)/carbon nanotube/carbon paste electrode (PTH/CNT/CPE). Also, the effects of different experimental parameters including type of the supporting electrolyte, pH value, and scan rate were evaluated. The proposed sensor indicated a linear range of 0.50–20.0 µM, a limit of quantification and detection of 0.05 µM and 0.13 µM, respectively, under the optimized conditions. Low relative standard deviation values confirmed that the repeatability and reproducibility of the modified electrodes are acceptable in preparation and determination fully procedures. Finally, the proposed method was successfully applied for tetracycline determination in urine and 250 mg TC tablet with satisfactory results.
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Jing X-R, Wang Y-Y, Liu W-J, Wang Y-K, Jiang H (2014) Enhanced adsorption performance of tetracycline in aqueous solutions by methanol-modified biochar. Chem Eng J 248:168–174
Levkovitz Y, Fenchel D, Kaplan Z, Zohar J, Cohen H (2015) Early post-stressor intervention with minocycline, a second-generation tetracycline, attenuates post-traumatic stress response in an animal model of PTSD. Eur Neuropsychopharm 25:124–132
Li W-Q, Cho E, Khalili H, Wu S, Chan AT, Qureshi AA (2016) Rosacea, use of tetracycline, and risk of incident inflammatory bowel disease in women. Clin Gastroenterol Hepatol 14:220–225
Pan Z, Xin L, Huang Y, Lu R, Jiang D (2019) Determination of 4 kinds of tetracycline antibiotics in meat powder samples from food analysis performance assessment scheme by high performance liquid chromatography-tandem mass spectrometry. J Food Safety Quality 10:3120–3125
Luo Y, Xu J, Li Y, Gao H, Guo J, Shen F, Sun C (2015) A novel colorimetric aptasensor using cysteamine-stabilized gold nanoparticles as probe for rapid and specific detection of tetracycline in raw milk. Food Control 54:7–15
Rodríguez MP, Pezza HR, Pezza L (2016) Ultrasound-assisted dispersive liquid–liquid microextraction of tetracycline drugs from egg supplements before flow injection analysis coupled to a liquid waveguide capillary cell. Anal Bioanal Chem 408:6201–6211
Vilela FP, Gomes CN, Passaglia J, Rodrigues DP, Costa RG, Tiba Casas MR, Fernandes SA, Falcao JP, Campioni F (2019) Genotypic resistance to quinolone and tetracycline in Salmonella Dublin strains isolated from humans and animals in Brazil. Microb Drug Resist 25:143–151
Bookstaver PB, Bland CM, Griffin B, Stover KR, Eiland LS, McLaughlin M (2015) A review of antibiotic use in pregnancy, Pharmacotherapy. J Hum Pharmacol Drug Ther 35:1052–1062
Dg Guo, Ni L, Wang L, Shao L (2019) Separation and determination of tetracycline hydrochloride in real water samples using binary small molecule alcohol-salt aqueous two-phase system coupled with high-performance liquid chromatography. Chirality 31:658–668
Meisen I, Wisholzer S, Soltwisch J, Dreisewerd K, Mormann M, Müthing J, Karch H, Friedrich AW (2010) Normal silica gel and reversed phase thin-layer chromatography coupled with UV spectroscopy and IR-MALDI-o-TOF-MS for the detection of tetracycline antibiotics. Anal Bioanal Chem 398:2821–2831
Hou J, Li H, Wang L, Zhang P, Zhou T, Ding H, Ding L (2016) Rapid microwave-assisted synthesis of molecularly imprinted polymers on carbon quantum dots for fluorescent sensing of tetracycline in milk. Talanta 146:34–40
Faria LV, Lima AP, Araújo FM, Lisboa TP, Matos MA, Munoz RA, Matos RC (2019) High-throughput amperometric determination of tetracycline residues in milk and quality control of pharmaceutical formulations: flow-injection versus batch-injection analysis. Anal Method 11:5328–5336
Chen T-W, Rajaji U, Chen S-M, Ramalingam RJ (2019) A relative study on sonochemically synthesized mesoporous WS2 nanorods and hydrothermally synthesized WS2 nanoballs towards electrochemical sensing of psychoactive drug (Clonazepam). Ultrason Sonochem 54:79–89
Afzali M, Mostafavi A, Shamspur T (2019) Designing an Au/reduced graphene oxide modified carbon paste electrode for the electrochemical quantification of agnuside. Sensor Actuat B Chem 290:188–194
Afzali M, Mostafavi A, Nekooie R, Jahromi Z (2019) A novel voltammetric sensor based on palladium nanoparticles/carbon nanofibers/ionic liquid modified carbon paste electrode for sensitive determination of anti-cancer drug pemetrexed. J Mol Liq 282:456–465
Alam AU, Qin Y, Howlader MM, Hu N-X, Deen MJ (2018) Electrochemical sensing of acetaminophen using multi-walled carbon nanotube and β-cyclodextrin. Sensor Actuat B: Chem 254:896–909
Kong L, Yin X, Yuan X, Zhang Y, Liu X, Cheng L, Zhang L (2014) Electromagnetic wave absorption properties of graphene modified with carbon nanotube/poly(dimethyl siloxane) composites. Carbon 73:185–193
Jiang Q, Wang X, Zhu Y, Hui D, Qiu Y (2014) Mechanical, electrical and thermal properties of aligned carbon nanotube/polyimide composites. Compos Part B Eng 56:408–412
Deng Y, Lu H, Cao Y, Xu B, Hong Q, Cai W, Yang W (2019) Multi-walled carbon nanotube interlayers with controllable thicknesses for high-capacity and long-life lithium metal anodes. J Power Source 412:170–179
Pöhls J-H, Schütt F, O’Neill C, Shree S, Johnson MB, Mishra YK, Adelung R, White MA (2019) Thermal and electrical transport properties in multi-walled carbon nanotube-coated ZnO tetrapods and self-entangled multi-walled carbon nanotube tubes. Carbon 144:423–432
Wang L, Qiu H, Liang C, Song P, Han Y, Han Y, Gu J, Kong J, Pan D, Guo Z (2019) Electromagnetic interference shielding MWCNT-Fe3O4@Ag/epoxy nanocomposites with satisfactory thermal conductivity and high thermal stability. Carbon 141:506–514
Munir A, Bozal-Palabiyik B, Khan A, Shah A, Uslu B (2019) A novel electrochemical method for the detection of oxymetazoline drug based on MWCNTs and TiO2 nanoparticles. J Electroanal Chem 844:58–65
Bagotia N, Choudhary V, Sharma D (2019) Synergistic effect of graphene/multiwalled carbon nanotube hybrid fillers on mechanical, electrical and EMI shielding properties of polycarbonate/ethylene methyl acrylate nanocomposites. ComposPart B Eng 159:378–388
Xiong W, Zeng G, Yang Z, Zhou Y, Zhang C, Cheng M, Liu Y, Hu L, Wan J, Zhou C (2018) Adsorption of tetracycline antibiotics from aqueous solutions on nanocomposite multi-walled carbon nanotube functionalized MIL-53 (Fe) as new adsorbent. Sci Total Environ 627:235–244
Sultana A, Sazawa K, Islam MS, Sugawara K, Kuramitz H (2019) Determination of tetracycline by microdroplet hydrodynamic adsorptive voltammetry using a multiwalled carbon nanotube paste rotating disk electrode. Anal Lett 52:1153–1164
Panahi Y, Motaharian A, Hosseini MRM, Mehrpour O (2018) High sensitive and selective nano-molecularly imprinted polymer based electrochemical sensor for midazolam drug detection in pharmaceutical formulation and human urine samples. Sensor Actuat B Chem 273:1579–1586
Lai Y, Deng Y, Yang G, Li S, Zhang C, Liu X (2018) Molecular imprinting polymers electrochemical sensor based on AuNPs/PTh modified GCE for highly sensitive detection of carcinoma embryonic antigen. J Biomed Nanotechnol 14:1688–1694
Cho SJ, Noh H-B, Won M-S, Cho C-H, Kim KB, Shim Y-B (2018) A selective glucose sensor based on direct oxidation on a bimetal catalyst with a molecular imprinted polymer. Biosens Bioelectron 99:471–478
Yuan CJ, Hsu CL, Wang SC, Chang KS (2005) Eliminating the interference of ascorbic acid and uric acid to the amperometric glucose biosensor by cation exchangers membrane and size exclusion membrane. Electroanal Int J Devoted Fund Pract Aspect Electroanal 17:2239–2245
Blanco-Lopez M, Gutierrez-Fernandez S, Lobo-Castanon M, Miranda-Ordieres A, Tunon-Blanco P (2004) Electrochemical sensing with electrodes modified with molecularly imprinted polymer films. Anal Bioanal Chem 378:1922–1928
Ren Y-N, Xu W, Si Z-X, Zhou L-X, Zheng Y-Q (2018) Photocatalytic degradation of tetracycline antibiotics under visible light using uranyl isophthalate coordination polymers. Polyhedron 152:195–201
Ahoulou S, Vilà N, Pillet S, Schaniel D, Walcarius A (2019) Coordination polymers as template for mesoporous silica films: a novel composite material Fe(Htrz)3@SiO2 with remarkable electrochemical properties. Chem Mater 31:5796–5807
Gan T, Shi Z, Sun J, Liu Y (2014) Simple and novel electrochemical sensor for the determination of tetracycline based on iron/zinc cations–exchanged montmorillonite catalyst. Talanta 121:187–193
Yasin MN, Brooke RK, Rudd S, Chan A, Chen W-T, Waterhouse GI, Evans D, Rupenthal ID, Svirskis D (2018) 3-Dimensionally ordered macroporous PEDOT ion-exchange resins prepared by vapor phase polymerization for triggered drug delivery: fabrication and characterization. Electrochim Acta 269:560–570
Zhang N, Zhang K, Zhang L, Wang H, Shi H, Wang C (2015) A label-free electrochemical DNA sensor based on ZrO2/poly(thionine)/CNT modified electrode and its application for detecting CaMV35S transgene gene sequence. Anal Method 7:3164–3168
Warren S, Munteanu G, Rathod D, McCormac T, Dempsey E (2019) Scanning electrochemical microscopy imaging of poly(3,4-ethylenedioxythiophene)/thionine electrodes for lactate detection via NADH electrocatalysis. Biosens Bioelectron 137:15–24
Yu ME, Cheong BS, Cho HG (2017) SERS Spectroscopy and DFT studies of thionine and its derivatives adsorbed on silver colloids: which N atom is used for coordination of a phenothiazine-based natural dye to electron-deficient metal surface? Bull Korean Chem Soc 38:928–934
Tuite EM, Nordén B (2018) Linear and circular dichroism characterization of thionine binding mode with DNA polynucleotides. Spectrochim Acta Part A Mol Biomol Spect 189:86–92
Ruiyi L, Jiajia W, Ling L, Zaijun L (2016) Ultrasensitive direct detection of dsDNA using a glassy carbon electrode modified with thionin-functionalized multiple graphene aerogel and gold nanostars. Microchim Acta 183:1641–1649
Wang T, Zhu R, Zhuo J, Zhu Z, Shao Y, Li M (2014) Direct detection of DNA below ppb level based on thionin-functionalized layered MoS2 electrochemical sensors. Anal Chem 86:12064–12069
Shamspur T, Biniaz Z, Mostafavi A, Torkzadeh-Mahani M, Mohamadi M (2018) An electrochemical immunosensor based on poly(thionine)-modified carbon paste electrode for the determination of prostate specific antigen. IEEE Sensor J 18:4861–4868
Pankratova G, Szypulska E, Pankratov D, Leech D, Gorton L (2019) Electron transfer between the gram-positive Enterococcus faecalis bacterium and electrode surface through osmium redox polymers. Chem Electro Chem 6:110–113
Kong D, Zhuang Q, Han Y, Xu L, Wang Z, Jiang L, Su J, Lu C-H, Chi Y (2018) Simultaneous voltammetry detection of dopamine and uric acid in human serum and urine with a poly(procaterol hydrochloride) modified glassy carbon electrode. Talanta 185:203–212
Sierra T, Dortez S, González MC, Palomares FJ, Crevillen AG, Escarpa A (2019) Disposable carbon nanotube scaffold films for fast and reliable assessment of total α1-acid glycoprotein in human serum using adsorptive transfer stripping square wave voltammetry. Anal Bioanalyt Chem 411:1887–1894
Chowdhury NR, Kant R (2018) Theory of generalized Gerischer impedance for quasi-reversible charge transfer at rough and finite fractal electrodes. Electrochim Acta 281:445–458
Yang P, You X, Yi J, Fang D, Bao R, Shen T, Liu Y, Tao J, Li C, Tan S (2018) Simultaneous achievement of high strength, excellent ductility, and good electrical conductivity in carbon nanotube/copper composites. J Alloy Compound 752:431–439
Yang M, Guo M, Feng Y, Lei Y, Cao Y, Zhu D, Yu Y, Ding L (2018) Sensitive voltammetric detection of metronidazole based on three-dimensional graphene-like carbon architecture/polythionine modified glassy carbon electrode. J Electrochem Soc 165:B530–B535
Li K, Li Y, Yang L, Wang W, Ye B (2014) Sensitive determination of urapidil at an electrochemically pretreated glassy carbon electrode by linear sweep voltammetry. Anal Method 6:6548–6554
Nady H, El-Rabiei M, El-Hafez GA (2017) Electrochemical oxidation behavior of some hazardous phenolic compounds in acidic solution. Egypt J Petrol 26:669–678
Owino J, Arotiba O, Hendricks N, Songa E, Jahed N, Waryo T, Ngece R, Baker P, Iwuoha E (2008) Electrochemical immunosensor based on polythionine/gold nanoparticles for the determination of aflatoxin B1. Sensors 8:8262–8274
Yang R, Ruan C, Dai W, Deng J, Kong J (1999) Electropolymerization of thionine in neutral aqueous media and H2O2 biosensor based on poly(thionine). Electrochim Acta 44:1585–1596
Devkota L, Nguyen LT, Vu TT, Piro B (2018) Electrochemical determination of tetracycline using AuNP-coated molecularly imprinted overoxidized polypyrrole sensing interface. Electrochim Acta 270:535–542
Kushikawa RT, Silva MR, Angelo AC, Teixeira MF (2016) Construction of an electrochemical sensing platform based on platinum nanoparticles supported on carbon for tetracycline determination. Sensor Actuat B Chem 228:207–213
Sun X-M, Ji Z, Xiong M-X, Chen W (2017) The electrochemical sensor for the determination of tetracycline based on graphene/l-cysteine composite film. J Electrochem Soc 164:B107–B112
Cherkashina K, Vakh C, Lebedinets S, Pochivalov A, Moskvin L, Lezov A, Bulatov A (2018) An automated salting-out assisted liquid-liquid microextraction approach using 1-octylamine: online separation of tetracycline in urine samples followed by HPLC-UV determination. Talanta 184:122–127
Qi H, Teng M, Liu M, Liu S, Li J, Yu H, Teng C, Huang Z, Liu H, Shao Q (2019) Biomass-derived nitrogen-doped carbon quantum dots: highly selective fluorescent probe for detecting Fe3+ ions and tetracyclines. J Colloid Interf Sci 539:332–341
Acknowledgements
The authors would like to express their sincere appreciation to the founders of Shahid Bahonar University of Kerman, Mr. A. R. Afzalipour and Mrs. F. Saba, for their foresight and generosity in training future generations of doctors, engineers and scientists. Also, the authors would like to acknowledge their thanks to Dr. P. Dabiri for his generous support for the research activities of the chemistry and nano laboratories in Shahid Bahonar University of Kerman.
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Jahromi, Z., Afzali, M., Mostafavi, A. et al. Electropolymerization of thionine as a stable film along with carbon nanotube for sensitive detection of tetracycline antibiotic drug. Iran Polym J 29, 241–251 (2020). https://doi.org/10.1007/s13726-020-00788-7
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DOI: https://doi.org/10.1007/s13726-020-00788-7