Abstract
The electropolymerization of p-anisidine on graphite electrodes (GE) was investigated in acidic and basic media using cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), electrochemical impedance spectroscopy (EIS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and scanning electron microscopy (SEM). The results showed significant differences in the polymer formation between the two media. In acidic media, a more electroactive but less stable material is deposited on the electrode surface, whereas the polymer formed in basic media exhibits high resistivity. The CV of the ferricyanide solutions highlighted these differences compared to the unmodified electrode, with an increased current for the acidic polymer and an almost non-existent redox response for the basic polymer. The EIS data corroborated the voltammetry results, revealing significant differences between the resistance values of the two polymers. The charge-transfer resistance increased with increasing pH, indicating slow electron-transfer kinetics. The SEM images show important differences between the graphite electrode and modified electrodes, suggesting the formation of distinct polymer films. ATR-FTIR spectra indicated polymer formation involving nitrogen atoms, with the methoxy group remaining unchanged. Based on electrochemical and spectroscopic evidence, a polymerization mechanism was proposed, involving the formation of tertiary amines in the polymer backbone. The irregular structure of the polymer formed in basic media can explain its resistive behavior. These findings contribute to the understanding of p-anisidine electropolymerization and development of polymer-modified electrodes for potential biosensor applications.
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References
Arshad N, Ikramullah AM, Sher M (2017) Electrochemical investigations of some newly synthesized arylazapyrazole derivatives. Monatshefte Für Chemie - Chem Monthly 148:245–255. https://doi.org/10.1007/s00706-016-1768-9
Bacon J, Adams RN (1968) Anodic oxidations of aromatic amines. III. substituted anilines in aqueous media. J Am Chem Soc 90:6596–6599. https://doi.org/10.1021/ja01026a005
Chaudhari S, Gaikwad AB, Patil PP (2009) Poly(o-anisidine) coatings on brass: synthesis, characterization and corrosion protection. Current Appl Phys 9:206–218. https://doi.org/10.1016/j.cap.2008.01.012
Chemicalize (2022) Chemicalize - Instant Cheminformatics Solutions. https://chemicalize.com/app/calculation. Accessed 6 Apr 2022
Cordeiro TAR, Martins HR, Franco DL et al (2020) Impedimetric immunosensor for rapid and simultaneous detection of chagas and visceral leishmaniasis for point of care diagnosis. Biosens Bioelectron 169:112573. https://doi.org/10.1016/j.bios.2020.112573
da SantosPimentaThomasini CCTCRL et al (2019) Electropolymerization of phenol and aniline derivatives: Synthesis, characterization and application as electrochemical transducers. J Electroanal Chem 846:113163. https://doi.org/10.1016/j.jelechem.2019.05.045
de Oliveira AA, Coelho RM, Machado ÂR et al (2024) Low-cost immunosensing approach for Chagas disease: exploiting modified pencil graphite electrodes with polymer films. J Solid State Electrochem. https://doi.org/10.1007/s10008-024-06069-0
Fischer AE, McEvoy TM, Long JW (2009) Characterization of ultrathin electroactive films synthesized via the self-limiting electropolymerization of o-methoxyaniline. Electrochim Acta 54:2962–2970. https://doi.org/10.1016/j.electacta.2008.12.023
Franco DL, Afonso AS, Vieira SN et al (2008) Electropolymerization of 3-aminophenol on carbon graphite surface: Electric and morphologic properties. Mater Chem Phys. https://doi.org/10.1016/j.matchemphys.2007.08.006
Ghoreishi SM, Shabani-Nooshabadi M, Behpour M, Jafari Y (2012) Electrochemical synthesis of poly(o-anisidine) and its corrosion studies as a coating on aluminum alloy 3105. Prog Org Coat 74:502–510. https://doi.org/10.1016/j.porgcoat.2012.01.016
Goto M, Otsuka K, Chen X et al (2004) Kinetic analysis of reactions of p-anisidine and N-methyl-p-anisidine cation radicals in acetonitrile using an electron-transfer stopped-flow method. J Phys Chem A 108:3980–3986. https://doi.org/10.1021/jp035579c
Guenbour A, Kacemi A, Benbachir A, Aries L (2000) Electropolymerization of 2-aminophenol: electrochemical and spectroscopic studies. Prog Org Coat 38:121–126. https://doi.org/10.1016/S0300-9440(00)00085-0
Guo B, Ma PX (2018) Conducting polymers for tissue engineering. Biomacromol 19:1764–1782. https://doi.org/10.1021/acs.biomac.8b00276
Helaly FM, Darwich WM, Abd El-Ghaffar MA (1999) Effect of some polyaromatic amines on the properties of NR and SBR vulcanizates. Polym Degrad Stab 64:251–257. https://doi.org/10.1016/S0141-3910(98)00197-9
Koval’chuk EP, Stratan NV, Reshetnyak OV et al (2001) Synthesis and properties of the polyanisidines. Solid State Ion 141:217–224. https://doi.org/10.1016/S0167-2738(01)00748-2
Kumar R, Singh RBT-RM (2020) Processing of Conducting Polymers for Sensors Applications: A State of Art Review and Future Applications. Elsevier
Lacroix JC, Garcia P, Audière JP et al (1991) Electropolymerization of methoxyaniline: experimental results and frontier orbital interpretation. Synth Met 44:117–132. https://doi.org/10.1016/0379-6779(91)91827-W
Lima TM, Soares PI, Do Nascimento LA et al (2021) A novel electrochemical sensor for simultaneous determination of cadmium and lead using graphite electrodes modified with poly(p-coumaric acid). Microchem 168:106406. https://doi.org/10.1016/j.microc.2021.106406
Macinnes D, Funt BL (1988) Poly-o-methoxyaniline: a new soluble conducting polymer. Synth Met 25:235–242. https://doi.org/10.1016/0379-6779(88)90248-2
Matos MFF, Soares PI, Lima TM et al (2022) Comparison of the modification of graphite electrodes with poly(4-aminobenzoic acid) and poly(4-hydroxyphenylacetic acid) for determination of Pb(II). Chem Pap 76:5691–5704. https://doi.org/10.1007/s11696-022-02282-1
Mattoso LHC, Bulhões LOS (1992) Synthesis and characterization of poly(o-anisidine) films. Synth Met 52:171–181. https://doi.org/10.1016/0379-6779(92)90305-3
NamsheerRout KCS (2021) Conducting polymers: a comprehensive review on recent advances in synthesis, properties and applications. RSC Adv 11:5659–5697. https://doi.org/10.1039/D0RA07800J
Naveen MH, Gurudatt NG, Shim Y-B (2017) Applications of conducting polymer composites to electrochemical sensors: a review. Appl Mater Today 9:419–433. https://doi.org/10.1016/j.apmt.2017.09.001
Omel’chenko OD, Gribkova OL, Nekrasov AA et al (2011) Nonadditive phenomena during polyaniline synthesis in the presence of mixtures of rigid-chain and flexible-chain polymer sulfoacids and their effect on properties of obtained interpolymer complexes. Protect Metals and Phys Chem Surfaces 47:503–511. https://doi.org/10.1134/S2070205111040149
Oyama M, Kirihara K (2004) Spectroscopic investigation of oxidation products of ortho- or meta-substituted aniline derivatives in acetonitrile using an electron-transfer stopped-flow method. Electrochim Acta 49:3801–3806. https://doi.org/10.1016/j.electacta.2003.12.056
Ozyilmaz AT, Ozyilmaz G, Yigitoglu O (2010) Synthesis and characterization of poly(aniline) and poly(o-anisidine) films in sulphamic acid solution and their anticorrosion properties. Prog Org Coat 67:28–37. https://doi.org/10.1016/j.porgcoat.2009.09.010
Patil S, Mahajan JR, More MA, Patil PP (1998) Influence of electrolyte pH on the electrochemical synthesis of poly(O-anisidine) thin films. Mater Lett 35:108–115. https://doi.org/10.1016/S0167-577X(97)00230-9
Patil S, Mahajan JR, More MA, Patil PP (1999) Influence of supporting electrolyte on the electrochemical synthesis of poly(o-methoxyaniline) thin films. Mater Lett 39:298–304. https://doi.org/10.1016/S0167-577X(99)00024-5
Patil D, Gaikwad AB, Patil P (2007) Poly(o-anisidine) films on mild steel: electrochemical synthesis and biosensor application. J Phys D Appl Phys 40:2555–2562. https://doi.org/10.1088/0022-3727/40/8/021
Pavia DL, Lampman GM, Kriz GS (2001) Introduction to Spectroscopy, Third Edit. Thomson Learning, United States of America (USA)
Santos PCM, Lima TM, Soares PI et al (2022) Electropolymerization in multilayers of aromatic monomers over graphite electrodes for the development of a biosensor for Chagas disease. Mater Chem Phys 288:126364. https://doi.org/10.1016/j.matchemphys.2022.126364
Sauerbrey G (1959) Verwendung von Schwingquarzen zur Wägung dünner Schichten und zur Mikrowägung. Z Phys 155:206–222. https://doi.org/10.1007/BF01337937
Shan J, Han L, Bai F, Cao S (2003) Enzymatic polymerization of aniline and phenol derivatives catalyzed by horseradish peroxidase in dioxane(II). Polym Adv Technol 14:330–336. https://doi.org/10.1002/pat.316
Sharma LR, Kalia RK (1976) Anodic oxidation of p-anisidines at the tubular graphite electrode. Electrochim Acta 21:1085–1087. https://doi.org/10.1016/0013-4686(76)85090-6
Silva TS, Freitas GRO, Ferreira LF, Franco DL (2024) Development of a label-free impedimetric immunosensor for the detection of respiratory syncytial virus. J Solid State Electrochem. https://doi.org/10.1007/s10008-024-05999-z
Silverstein RM, Webster FX, Kiemle DJ (2005) Spectrometric Identification of Organic Compounds, 7th edn. Wiley, USA
Simon P, Farsang G, Amatore C (1997) Mechanistic investigation of the oxidation of p-anisidine in unbuffered DMF using fast scan rates at ultramicroelectrodes. J Electroanal Chem 435:165–171. https://doi.org/10.1016/S0022-0728(97)00284-2
Soares PI, Lima TM, Do Nascimento Luiza A et al (2023) Co-detection of copper and lead in artisanal sugarcane spirit using caffeic acid-modified graphite electrodes. Electroanalysis. https://doi.org/10.1002/elan.202200302
Stéfanne e Silva T, Soares IP, Gonçalves Lacerda LR et al (2020) Electrochemical modification of electrodes with polymers derived from of hydroxybenzoic acid isomers: optimized platforms for an alkaline phosphatase biosensor for pesticide detection. Mater Chem Phys 252:123221. https://doi.org/10.1016/j.matchemphys.2020.123221
Tammam RH, Saleh MM (2014) Electrocatalytic oxidation of formic acid on nano/micro fibers of poly(p-anisdine) modified platinum electrode. J Power Sources 246:178–183. https://doi.org/10.1016/j.jpowsour.2013.07.068
Valentini L, Bavastrello V, Stura E et al (2004) Sensors for inorganic vapor detection based on carbon nanotubes and poly(o-anisidine) nanocomposite material. Chem Phys Lett 383:617–622. https://doi.org/10.1016/j.cplett.2003.11.091
Wang Y (2018) Preparation and application of polyaniline nanofibers: an overview. Polym Int 67:650–669. https://doi.org/10.1002/pi.5562
Wang Y, Liu A, Han Y, Li T (2020) Sensors based on conductive polymers and their composites: a review. Polym Int 69:7–17. https://doi.org/10.1002/pi.5907
Yuqing M, Jianrong C, Xiaohua W (2004) Using electropolymerized non-conducting polymers to develop enzyme amperometric biosensors. Trends Biotechnol 22:227–231. https://doi.org/10.1016/j.tibtech.2004.03.004
Acknowledgements
The authors are grateful for the financial support from the Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) under grant numbers APQ-02902-17, APQ-00207-21, RED-00032-22 and RED-00196-23 and the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) under grant number 404210/2021-0. This study was partially funded by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Brazil (Finance Code 001).
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Ana Consuelo Felipe: Methodology, Investigation. Luiza Aguiar do Nascimento: Methodology, Investigation, Writing—Original Draft. Thaís Machado Lima: Methodology, Investigation, Writing—Original Draft. Priscila Izabela Soares: Methodology, Investigation, Writing—Original Draft. Ângelo Rafael Machado: Methodology, Investigation, Writing—Original Draft. Diego Leoni Franco: Conceptualization, Writing—Review & Editing. Lucas Franco Ferreira: Supervision, Project administration, Funding acquisition, Writing—Review & Editing. Ana Graci Brito-Madurro: Supervision, Project administration, Funding acquisition, Writing—Review & Editing. João Marcos Madurro: Supervision, Project administration, Funding acquisition, Writing—Review & Editing.
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Felipe, A.C., do Nascimento, L.A., Lima, T.M. et al. Electropolymerization of p-anisidine: influence of pH on electrosynthesis. Chem. Pap. 79, 2091–2104 (2025). https://doi.org/10.1007/s11696-025-03908-w
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DOI: https://doi.org/10.1007/s11696-025-03908-w