Permselective modifier films are very important in preparing highly sensitive electrochemical sensors. In this work, for the first time, the behavior of gold and glassy carbon electrodes coated with biocompatible zein film as a permselective membrane for the electrochemical detection of various compounds has been investigated. For this purpose, several electroactive cationic (methylene blue, brilliant green, and thionine) and anionic (potassium ferricyanide, alizarin red S, and riboflavin-5’-phosphate) compounds have been used as model. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) showed that zein membranes prepared from casting solution containing 1% zein in ethanol/water have porous structures with high nanometric roughness. The capacitance values of electrical double layers of electrodes modified with zein film were very high for hydrophilic ions in comparison with hydrophobic ions. Point of zero charge pH (pHpzc) of zein membrane was 4.8. The results of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) as well as pHpzc study indicated that zein permselective membrane acts as ion exchanger film for selected cationic compounds with fast electrochemical kinetics responses in aqueous solution (pH=7). This behavior was confirmed by circulating solutions containing model compounds from homemade continuous cell equipped with polyamide membranes modified with zein film.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
Tax calculation will be finalised during checkout.
Brunetti B, Desimoni E (2014) Permselectivity and preconcentration properties of taurine/graphite oxide electrode coatings: Analytical perspectives. Electrochem Commun 43:51–54
Perumal P, Christopher Selvin P (2020) Red algae-derived k-carrageenan-based proton-conducting electrolytes for the wearable electrical devices. J Solid State Electrochem 24(10):2249–2260
Kiruthika S, Malathi M, Selvasekarapandian S, Tamilarasan K, Moniha V, Manjuladevi R (2019) Eco-friendly biopolymer electrolyte, pectin with magnesium nitrate salt, for application in electrochemical devices. J Solid State Electrochem 23(7):2181–2193
Szentirmay MN, Martin C-R (1984) Ion-exchange selectivity of nafion films on electrode surfaces. Anal Chem 56(11):1898–1902
Singh K, Shahi V-K (1998) Electrochemical studies on Nafion membrane. J Membr Sci 140(1):51–56
Ciriello R, Cataldi T-R-I, Centonze D, Guerrieri A (2000) Permselective behavior of an electrosynthesized, nonconducting thin film of poly(2-naphthol) and its application to enzyme immobilization. Electroanal 12(11):825–830
Ghita M, Arrigan D-W-M (2004) Electrochemical overoxidation of polyindole and its cation-permselective behavior. Electroanal 16(12):979–987
Ozden M, Ekinci E, Karagozler A-E (1998) Synthesis and optimization of permselective polymer (polyindoline) film. J Solid State Electrochem 2:427–431
Zhou L, Shang F, Pravda M, Glennon J-D, Luong J-H-T (2009) Selective detection of dopamine using glassy carbon electrode modified by a combined electropolymerized permselective film of polytyramine and polypyrrole-1-propionic acid. Electroanal 21:797–803
Michalska A, Gałuszkiewicz A, Ogonowska M, Ocypa M, Maksymiuk K (2004) PEDOT films: multifunctional membranes for electrochemical ion sensing. J Solid State Eletrochem 8(6):381–389
Yano J, Shimoyama A, Ogura K (1992) Poly(o-phenylenediamine)-film-coated electrode having a permselective response to halogenide ions. J Electrochem Soc 139(5):L52–L53
Guerrieri A, Ciriello R, Centonze D (2009) Permselective and enzyme-entrapping behaviours of an electropolymerized, non-conducting, poly(o-aminophenol) thin film-modified electrode: a critical study. Biosens Bioelectron 24(6):1550–1556
Fattakhova-Rohlfing D, Wark M, Rathousky J (2007) Ion-permselective pH-switchable mesoporous silica thin layers. Chem Mater 19(7):1640–1647
Elbert J, Krohm F, Rüttiger C, Kienle S, Didzoleit H, Balzer B-N, Hugel T, Stühn B, Gallei M, Brunsen A (2014) Polymer-modified mesoporous silica thin films for redox-mediated selective membrane gating. Adv Funct Mater 24(11):1591–1601
Brunsen A, Micoureau S, Tagliazucchi M, Szleifer I, Azzaroni O, Soler-Illia G-J-A-A (2015) Mesoporous hybrid thin film membranes with PMETAC@silica architectures: controlling ionic gating through the tuning of polyelectrolyte density. Chem Mater 27(3):808–821
Li S, Luo Q, Zhang Z, Shen G, Wu H, Chen A, Liu X, Li M, Zhang A (2018) Electrochemistry study of permselectivity and interfacial electron transfers of a branch-tailed fluorosurfactant self-assembled monolayer on gold. Molecules 23(11):2998–3012
Özden M, Ekinci E, Karagözler E (1999) Electrochemical preparation of poly(o-toluidine) film and its application as a permselective membrane. J Appl Polym Sci 71(13):2141–2146
Dong F, Padua G-W, Wang Y (2013) Controlled formation of hydrophobic surfaces by self-assembly of an amphiphilic natural protein from aqueous solutions. Soft Matter 9(25):5933–5941
Pereira T-S, Oliveira G-C-M, Santos F-A, Raymundo-Pereirab P-A, Oliveira O-N, Janegitz B-C (2019) Use of zein microspheres to anchor carbon black and hemoglobin in electrochemical biosensors to detect hydrogen peroxide in cosmetic products, food and biological fluids. Talanta 194:737–744
Chen X, Li D, Li G, Luo L, Ullah N, Wei Q, Huang F (2015) Facile fabrication of gold nanoparticle on zein ultrafine fibers and their application for catechol biosensor. Appl Surf Sci 328:444–452
Hajilari F, Farhadi K, Eskandari H (2019) Extraction and trace analysis of trihalomethanes in water samples using zein@Fe3O4 nanocomposite. Bull Environ Contam Toxicol 102(4):581–588
Azizi B, Farhadi K, Samadi N (2019) Functionalized carbon dots from zein biopolymer as a sensitive and selective fluorescent probe for determination of sumatriptan. Microchem J 146:965–973
Jangju A, Farhadi K, Mehdi Hatami M, Amani S, Esma-ali F, Moshkabadi A, Hajilari F (2017) Application of zein-modified magnetite nanoparticles in dispersive magnetic micro-solid-phase extraction of synthetic food dyes in foodstuffs. J Sep Sci 40(6):1343–1352
Cheng Q, Brajter-Toth A (1995) Permselectivity and high sensitivity at ultrathin monolayers. Effect of film hydrophobicity. Anal Chem 67(17):2767–2775
Sun T, Feng L, Gao X, Jiang L (2005) Bioinspired surfaces with special wettability. Acc Chem Res 38(8):644–652
Huddleston J-G, Visser A-E, Reichert W-M, Willauer H-D, Broker G-A, Rogers R-D (2001) Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation. Green Chem 3(4):156–164
Valente N-I, Muteto P-V, Farinha A-S, Tomé A-C, Oliveira J-A, Gomes M-T-S (2011) An acoustic wave sensor for the hydrophilic fluoride. Sensors Actuators B Chem 157(2):594–599
Azzaroni O, Moya S, Farhan T, Brown A-A, Huck W-T-S (2005) Switching the properties of polyelectrolyte brushes via “Hydrophobic Collapse”. Macromolecules 38(24):10192–10199
Hu K, Xub B, Shao H-B (2015) Determination of hydrophobicity scale of tetraphenylborate and its derivatives by ferrocene based three-phase electrodes. Electrochem Commun 50:36–38
Wang Q, Wang J-F, Geil P-H, Padua G-W (2004) Zein adsorption to hydrophilic and hydrophobic surfaces investigated by surface plasmon resonance. Biomacromolecules 5(4):1356–1361
Wang Y, Padua G-W (2004) Water sorption properties of extruded zein films. J Agric Food Chem 52(10):3100–3105
Porter M-D, Bright T-B, Allara D-L, Chidsey C-E-D (1987) Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared Spectroscopy, and electrochemistry. J Am Chem Soc 109(12):3559–3568
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Hasanzadeh, M., Farhadi, K. & Tajik, H. Zein film as a novel natural biopolymer membrane in electrochemical detections. J Solid State Electrochem (2021). https://doi.org/10.1007/s10008-021-04910-4
- Biopolymer membrane
- Solid electrodes
- Permselective modifier films
- Anion blocker
- Cation permeability