Advances in nanomaterial application in enzyme-based electrochemical biosensors: a review

Abstract

Electrochemical enzyme-based biosensors are one of the largest and commercially successful groups of biosensors. Integration of nanomaterials in the biosensors results in significant improvement of biosensor sensitivity, limit of detection, stability, response rate and other analytical characteristics. Thus, new functional nanomaterials are key components of numerous biosensors. However, due to the great variety of available nanomaterials, they should be carefully selected according to the desired effects. The present review covers the recent applications of various types of nanomaterials in electrochemical enzyme-based biosensors for the detection of small biomolecules, environmental pollutants, food contaminants, and clinical biomarkers. Benefits and limitations of using nanomaterials for analytical purposes are discussed. Furthermore, we highlight specific properties of different nanomaterials, which are relevant to electrochemical biosensors. The review is structured according to the types of nanomaterials. We describe the application of inorganic nanomaterials, such as gold nanoparticles (AuNPs), platinum nanoparticles (PtNPs), silver nanoparticles (AgNPs), and palladium nanoparticles (PdNPs), zeolites, inorganic quantum dots, and organic nanomaterials, such as single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), carbon and graphene quantum dots, graphene, fullerenes, and calixarenes. Usage of composite nanomaterials is also presented.

Fig. 1. Ways of embedding NMs in the enzyme-based biosensors. (a) Enzyme immobilization on the NM-modified electrode. (b) Schematic of the biosensor based on phosphotriesterase (PTE) immobilized via glutaraldehyde on the graphene surface with platinum nanoparticles. Reprinted with permission from J. A. Hondred, J. C. Breger, N. J. Alves, S. A. Trammell, S. A. Walper, I. L. Medintz and J. C. Claussen, Printed Graphene Electrochemical Biosensors Fabricated by Inkjet Maskless Lithography for Rapid and Sensitive Detection of Organophosphates, ACS Applied Materials & Interfaces, 2018, 10, 11125–11134. Copyright 2018 American Chemical Society. (c) Enzyme/NM co-immobilization on the electrode. (d) Schematic of the biosensor based on glucose oxidase encapsulated in a chitosan-kappa-carrageenan bionanocomposite. Reprinted from Material Science and Engineering: C, 95, I. Rassas, M. Braiek, A. Bonhomme, F. Bessueille, G. Rafin, H. Majdoub, and N. Jaffrezic-Renault, Voltammetric glucose biosensor based on glucose oxidase encapsulation in a chitosan-kappa-carrageenan polyelectrolyte complex, 152–159, Copyright (2018), with permission from Elsevier.

Fig. 2. Preparation of the potentiometric sulfite biosensor: modification of the working electrode surface with PtNPs followed by the immobilization of sulfite oxidase (SOx) in the polypyrrole film. Reprinted by permission from: Springer-Verlag Wien, Microchimica Acta, (Potentiometric sulfite biosensor based on entrapment of sulfite oxidase in a polypyrrole film on a platinum electrode modified with platinum nanoparticles, S. B. Adeloju and S. Hussain), © (2016).

Fig. 3. Operation of the amperometric sensor for hydrogen peroxide detection. (a) Cyclic voltammograms obtained with rGO electrode and PdNP/TNM/rGO in 0.1 M PBS, with 5 mM H₂O₂. (b) Amperometric responses of rGO, TNM/rGO, and Pd/TNM/rGO sensor to 1–12 mM H₂O₂ in 0.1 M PBS at pH 7.4 at applied potential of −0.1 V. Inset: corresponding calibration plot of Pd/TNM/rGO sensor. Reprinted from Analytica Chimica Acta, 989, S. Bozkurt, B. Tosun, B. Sen, S. Akocak, A. Savk, M. F. Ebeoğlugil and F. Sen, A hydrogen peroxide sensor based on TNM functionalized reduced graphene oxide grafted with highly monodisperse Pd nanoparticles, 88–94, Copyright (2017), with permission from Elsevier.

Fig. 4. Morphology of nanosized aluminosilicates: nanozeolite beta (A), nanozeolite L (B), 80 nm silicalite-1 (C), 160 nm silicalite-1 (D), 450 nm silicalite-1 (E), mesoporous silica spheres (F), zeolite L (G). Reproduced from ref. 77 Copyright 2015 Springer.

Fig. 5. Schematics of the hydrogen peroxide biosensor based on oligoaniline-cross-linked HRP/CNT composite and cyclic voltammograms of the biosensor obtained in the absence of H₂O₂ (a) and in the presence of 5 μM H₂O₂ (b). Reprinted from Enzyme and Microbial Technology, 113, K. M. Kafi, M. Naqshabandi, M. M. Yusoff and M. J. Crossley, Improved peroxide biosensor based on Horseradish Peroxidase/Carbon Nanotube on a thiol-modified gold electrode, 67–74, Copyright (2017), with permission from Elsevier.

Fig. 6. (a) Chemical reactions that are the basis for the glycerol biosensor operation. Glycerol dehydrogenase (GDH), toluidine blue and electrochemically reduced graphene oxide (ERGO) are deposited on indium-tin oxide (ITO) electrode. Second enzyme (lipase) is not shown. (b) Response studies of the biosensor to varying concentrations of triglyceride (tributyrin). Inset: corresponding calibration curve. Reproduced from ref. 147 with permission from The Royal Society of Chemistry.

Fig. 7. Working principle of the glucose biosensor based on glucose dehydrogenase, fullerene C₇₀, and AuNPs. Electrons from glucose are transferred to NAD⁺, fullerene, AuNPs, and finally to the working electrode. Reproduced from ref. 154 – published by The Royal Society of Chemistry.

Fig. 8. Preparation of the glucose biosensor based on conductive polymer poly(2-(2-octyldodecyl)-4,7-di(selenoph-2-yl)-2H-benzo[d][1,2,3]triazole) (poly[SBTz]), calixarene, AuNPs and GOx. Graphite electrode is modified with conductive polymer, calixarene, and AuNPs followed by GOx immobilization. Reproduced from ref. 112 with permission from The Royal Society of Chemistry.

Fig. 9. Schematic diagram of the fabrication of FET glucose biosensor (top) and structure of the biosensor sensitive element (bottom). For the biosensor fabrication, Pd nanoflowers were electrodeposited and patterned with gold, then Nafion®/rGO membrane was deposited by spin coating, and finally GOx/GO dispersion was drop-casted. Reprinted from Sensors and Actuators B: Chemical, 264, D. H. Shin, W. Kim, J. Jun, J. S. Lee, J. H. Kim and J. Jang, Highly selective FET-type glucose sensor based on shape-controlled palladium nanoflower-decorated graphene, 216–223, Copyright (2018), with permission from Elsevier.

From left to right: O. O. Soldatkin, S. V. Dzyadevych, D. Yu Kucherenko, I. S. Kucherenko, and O. V. Soldatkina