Conducting polymers in the design of glucose biosensors Arunas Ramanavicius1,2*, Natalija German3, Asta Kausaite-Minkstimiene1,3, Deivis Plausinaitis1, Povilas Genys1, Linas Sinkevicius1, Almira Ramanaviciene1,3 1 Department of Physical Chemistry, Faculty of Chemistry, Vilnius University, Lithuania; 2. Laboratory of BioNanotechnology, Division of Materials Science and Electronics, Institute of Semiconductor Physics, State Scientific Research Institute Center for Physical Sciences and Technology, Lithuania; 3. Division of Immunology, State Research Institute Center for Innovative Medicine, Lithuania. [email protected] In this presentation some recent achievement’s in the applications of conducting polymers in the design of glucose biosensors will be overviewed. Glucose biosensors based on glucose oxidase (GOx) immobilised on several different types electrodes modified by some conducting polymers and redox mediators and/or gold nanoparticles were designed and electro-analytical characteristics of these sensors were evaluated. Conducting polymer layers on GOx-modified electrodes were deposited in two different ways: (i) electrochemically; (ii) chemically. The most interesting results were achieved when conducting polymers (polypyrrole (Ppy) and polyaniline (PANI)) were deposited on the GOx-modified electrodes by chemical method, which was based on the generation of hydrogen peroxide by GOx catalysed reaction and initiation of pyrrole or aniline polymerization into Ppy or PANI by hydrogen peroxide. The influence of the formed polypyrrole layer on sensitivity and Michaelis–Menten model based kinetics of designed electrochemical biosensors was investigated. Here proposed method of conducting polymer deposition allowed to change analytical characteristics biosensors based on GOx-modified electrodes. Particularly the increase of Michaelis constant (KM) and some decrease of both maximal current and sensitivity was observed by the increase of polymerization reaction duration [1]. Hence, here applied ‘enzymatic polymerisation’ of pyrrole and aniline has increased linear detection range of glucose biosensors based on immobilized GOx, and the linear glucose detection interval for GOx/CR and GOx/Au-NPs/CR electrodes was dependent on the duration of polymerisation. In addition to electrochemical investigations, the enzymatic formation of Ppy [2], PANI, polythiophene [3] and some other conjugated polymers was performed by immobilized and by dissolved GOx and evaluated by atomic force microscopy and dynamic light scattering and isotope method [4]. Hydrogen peroxide induced Ppy layer formation was evaluated by electrochemical quartz crystal microbalances [5]. Electrochemically polymerized 1,10-phenanthroline-5,6-dione was applied as a redox mediating layer for some GOx-based sensors [6], which will be discussed in this presentation. Acknowledgement: This research was funded by a grant (No. SEN-15095) from the Research Council of Lithuania. 1. A. Ramanavicius, A. Kausaite, A. Ramanaviciene Self-encapsulation of oxidases as a basic approach to tune upper detection limit of amperometric bosensors. Analyst 2008, 133, 1083–1089. 2. N. German, A. Kausaite-Minkstimiene, A. Ramanavicius, T. Semashko, R. Mikhailova, A. Ramanaviciene. The use of different glucose oxidases for the development of an amperometric reagentless glucose biosensor based on gold nanoparticles covered by polypyrrole. Electrochimica Acta 2015, 169, 326–333. 3. V. Krikstolaityte, J. Kuliesius, A. Ramanaviciene, L. Mikoliunaite, A. Kausaite-Minkstimiene, Y. Oztekin, A. Ramanavicius, Enzymatic polymerization of polythiophene by immobilized glucose oxidase. Polymer 2014, 55, 1613-1620. 4. A. Garbaras, L. Mikoliunaite, A. Popov, A. Ramanaviciene, V. Remeikis, A. Ramanavicius. Isotope method for the determination of stoichiometry between compounds forming polypyrrole and glucose oxidase composite. Physical Chemistry Chemical Physics 2015, 17, 2252–2258. 5. D. Plausinaitis, V. Ratautaite, L. Mikoliunaite, L. Sinkevicius, A. Ramanaviciene, A. Ramanavicius Quartz crystal microbalance based evaluation of electrochemical formation of aggregated polypyrrole particle based layer. Langmuir 2015, 31, 3186-3193. 6. A. Ramanavicius, P. Genys, A. Ramanaviciene Electrochemical Impedance Spectroscopy Based Evaluation of 1,10-Phenanthroline-5,6-dione and Glucose Oxidase Modified Graphite Electrode Electrochimica Acta 2014, 146, 659-665.
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