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Reagentless Biosensor Based on Glucose Oxidase Wired by the Mediator Freely Diffusing in Enzyme Containing Membrane
Chemistry and Material Science Faculties of M.V. Lomonosov Moscow State University, Moscow, Russia.
Chemistry and Material Science Faculties of M.V. Lomonosov Moscow State University, Moscow, Russia.
Chemistry and Material Science Faculties of M.V. Lomonosov Moscow State University, Moscow, Russia.
Chemistry and Material Science Faculties of M.V. Lomonosov Moscow State University, Moscow, Russia.
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2012 (English)In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 84, no 3, 1220-1223 p.Article in journal (Refereed) Published
Abstract [en]

Wiring glucose oxidase in the membrane with an immobilized mediator is possible due to the diffusion ability of the latter, if the enzyme containing membrane is formed according to the proposed protocol, including exposing proteins to water–organic mixtures with the high content of organic solvent. In the course of the study, the new glucose oxidase mediator, unsubstituted phenothiazine, was discovered. The diffusion coefficient of the mediator in the resulting membrane is independent of the presence of enzyme. The cyclic voltammograms of the enzyme electrode after appearance of the only glucose in solution obtain a well-defined catalytic shape, which is normally observed for both the enzyme and the mediator in solution. Analytical performances of the resulting biosensor are comparable to the advanced second generation ones, which, however, require covalent linking of the mediator either to the membrane forming polymer or to the enzyme. Even without such covalent linking, the reported biosensor is characterized by an appropriate long-term operational stability allowing reagentless sensing.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2012. Vol. 84, no 3, 1220-1223 p.
National Category
Analytical Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-112343DOI: 10.1021/ac203056mPubMedID: 22206508OAI: oai:DiVA.org:liu-112343DiVA: diva2:765544
Available from: 2014-11-24 Created: 2014-11-24 Last updated: 2017-12-05Bibliographically approved
In thesis
1. Novel reagentless electrodes for biosensing
Open this publication in new window or tab >>Novel reagentless electrodes for biosensing
2014 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

Analytical chemical information is needed in all areas of human activity including health care, pharmacology, food control and environmental chemistry. Today one of the main challenges in analytical chemistry is the development of methods to perform accurate and sensitive rapid analysis and monitoring of analytes in ‘real’ samples. Electrochemical biosensors are ideally suited for these applications.

Despite the wide application of electrochemical biosensors, they have some limitations. Thus, there is a demand on improvement of biosensor performance together with a necessity of simplification required for their mass production. In this thesis the work is focused on the development of electrochemical sensors with improved performance applicable for mass production, e.g. by screen printing.

Biosensors using immobilized oxidases as the bio-recognition element are among the most widely used electrochemical devices. Electrical communication between redox enzymes and electrodes can be established by using natural or synthetic electron carriers as mediators. However, sensors based on soluble electronshuttling redox couples have low operational stability due to the leakage of water-soluble mediators to the solution. We have found a new hydrophobic mediator for oxidases – unsubstituted phenothiazine. Phenothiazine and glucose oxidase, lactate oxidase or cholesterol oxidase were successfully co-immobilized in a sol-gel membrane on a screen-printed electrode to construct glucose, lactate and cholesterol biosensors, respectively. All elaborated biosensors with phenothiazine as a mediator exhibited long-term operational stability. A kinetic study of the mediator has shown that phenothiazine is able to function as an efficient mediator in oxidase-based biosensors.

To improve sensitivity of the biosensors and simplify their production we have developed a simple approach for production of graphite microelectrode arrays. Arrays of microband electrodes were produced by screen printing followed by scissor cutting, which enabled the realization of microband arrays at the cut edge. The analytical performance of the system is illustrated by the detection of ascorbic acid through direct oxidation and by detection of glucose using a phenothiazine mediated glucose biosensor. Both systems showed enhanced sensitivity due to improved mass transport. Moreover, the developed approach can be adapted to automated electrode recovery.

Finally, two enzyme-based electrocatalytic systems with oxidation and reduction responses, respectively, have been combined into a fuel cell generating a current as an analytical output (a so-called self-powered biosensor). This was possible as a result of the development of the phenothiazine mediated enzyme electrodes, which enabled the  construction of a cholesterol biosensor with self-powered configuration. The biosensor generates a current when analyte (cholesterol) is added to the cell. The biosensor has been applied for whole plasma analysis.

All developed concepts in the thesis are compatible with a wide range of applications and some of them may even be possible to realize in a fully integrated biosensor unit based on printed electronics.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2014. 53 p.
Series
Linköping Studies in Science and Technology. Thesis, ISSN 0280-7971 ; 1689
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:liu:diva-112345 (URN)10.3384/lic.diva-112345 (DOI)978-91-7519-187-4 (ISBN)
Presentation
2014-11-28, Shrödinger, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 13:15 (English)
Opponent
Supervisors
Available from: 2014-11-24 Created: 2014-11-24 Last updated: 2017-11-03Bibliographically approved
2. Facilitating electron transfer in bioelectrocatalytic systems
Open this publication in new window or tab >>Facilitating electron transfer in bioelectrocatalytic systems
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Bioelectrocatalytic systems are based on biological entities, such as enzymes, whole cells, parts of cells or tissues, which catalyse electrochemical processes that involve the interaction between chemical change and electrical energy. In all cases, biocatalysis is implemented by enzymes, isolated or residing inside cells or part of cells. Electron transfer (ET) phenomena, within the protein molecules and between biological redox systems and electronics, enable the development of various bioelectrocatalytic systems, which can be used both for fundamental investigations of enzymatic biological processes by electrochemical methods and for applied purposes, such as power generation, bioremediation, chemical synthesis and biosensing.

Electrical communication between the biocatalyst’s redox centre and an electrode is essential for the functioning of the system. This can be established using two main mechanisms: indirect ET and direct ET. The efficiency of the ET influences important parameters such as the turnover rate of the biocatalyst, the generated current density and partially the stability of the system, which in their turn determine response time, sensitivity, detection limit and operational stability of biosensing devices or the power densities and current output of biofuel cells, and hence should be carefully considered when designing bioelectrocatalytic systems.

This thesis focuses on approaches that facilitate ET in bioelectrocatalytic systems based on indirect and direct ET mechanisms. Both fundamental aspects of ET in bioelectrocatalytic systems and applications of such systems for biosensing and power generation are considered. First, a new hydrophobic mediator for oxidases – unsubstituted phenothiazine and its improved ET properties in comparison with commonly used mediators are discussed. Application of the mediator in electrochemical biosensors is demonstrated by glucose, lactate and cholesterol sensing. Utilisation of mediated biocatalytic cholesterol oxidation, as the anodic reaction for the construction of a biofuel cell acting as a power supply and an analytical device at the same time, is investigated to deliver a selfpowered biosensor. Also the enhancement of mediated bioelectrocatalysis by employment of microelectrodes as a transducer is examined. The effect of surface roughness on the current response of the microelectrodes under conditions of convergent diffusion is considered. The applicability of the laccase-based system for total phenol analysis of weakly supported water is demonstrated. Finally, a new electrochemical approach derived from collision-based electrochemistry applicable for examination of the ET process of a single enzyme molecule is described.

All together, the results presented in this thesis contribute to the solution of the ‘electronic coupling problem’, arising when interfacing biomolecules with electronics and limiting the performance of bioelectrocatalytic systems in specific applications. The developed methods to facilitate ET will hopefully promote future biosensing devices and biofuel cells. I believe the new approach for investigation of ET processes at a single enzyme molecule will complement existing single molecule techniques, giving further insights into enzymatic ET mechanisms at the molecular level and filling the gap between fundamental understanding of biocatalytic processes and their potential for bioenergy production.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2016. 74 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1738
National Category
Chemical Sciences Chemical Engineering Chemical Process Engineering
Identifiers
urn:nbn:se:liu:diva-125242 (URN)10.3384/diss.diva-125242 (DOI)978-91-7685-841-7 (ISBN)
Public defence
2016-03-18, Planck, Fysikhuset, Campus Valla, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2016-02-17 Created: 2016-02-17 Last updated: 2017-11-03Bibliographically approved

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Sekretaryova, Alina N.

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