Enzymatic bioelectrodes applied in biofuel cells: experimental and simulation

• Grant number: 13/04663-4
• Support Opportunities: Regular Research Grants
• Start date: September 01, 2013
• End date: August 31, 2015
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Frank Nelson Crespilho
• Grantee: Frank Nelson Crespilho
• Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil

Abstract

Biofuel Cells (BCs) are bioelectrochemical devices that convert chemical energy directly into electrical energy through biocatalytic reactions of oxidation and reduction. For enzyme BFCs, enzymes are used in cathodic and /or anodic surfaces, which are responsible for accelerating the conversion of substrates into products from the redox process. The electrochemical kinetics applied in bioeletrodos can be divided into two processes. The first, called biocatalytic is resulting from the derivation of Michaelis-Menten kinetics or non- Non Michaelis-Menten, providing information on the rate of substrate (fuel or oxidant) consumed. The second process, called non-catalytic, or post- biocatalysis, the heterogeneous electron transfer occurs from enzyme cofactor to the electrode surface, whose mechanism can be derived from the theory of Marcus-Hush or the Butler-Volmer formalism, providing information about the speed which the charge is transferred to the electrode surface . Today it is known that the molecular structure of the enzyme, as well as its orientation in space and the nature of the materials composing the electrode surface influences both the heterogeneous constant charge transfer (kET) and the catalytic constant (Kcat) enzyme. Several methods of enzyme immobilization and configurations of materials in solid electrodes have been proposed in the literature for maximizing these two constants. However, most work in the area overlooking the modeling of these two processes, and few of them allude to the accurate calculation of the two constants. Thus, this research project aims to obtain kET and Kcat for bioelectrodes in different configurations, using the enzyme cytochrome c, glucose oxidase and glucose dehydrogenase operating in half-cells for application in BFCs. Gold nanoparticles, graphene and organic electron mediators (eg. methylene green) will be used in different configurations with the above enzymes, and also by using different kinds of electrodes, such as flexible carbon fiber, glassy carbon and gold. It is intended to model the enzyme kinetics, as well as apply the theory of Marcus-Hush compared with the Butler-Volmer approach to heterogeneous charge transfer for enzyme electrode. The results of numerical simulation are compared with experimental results. It is expected that with different materials supported on different types of electrodes, the bioelectrocatalytic responses can be influenced and thus valuable information on the performance of bioelectrode applied BCs can be obtained. (AU)

Scientific publications

(15)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

LUZ, ROBERTO A. S.; PEREIRA, ANDRESSA R.; DE SOUZA, JOAO C. P.; SALES, FERNANDA C. P. F.; CRESPILHO, FRANK N.. Enzyme Biofuel Cells: Thermodynamics, Kinetics and Challenges in Applicability. CHEMELECTROCHEM, v. 1, n. 11, SI, p. 1751-1777, NOV 11 2014. (13/04663-4, 11/01541-0)

DE SOUZA, JOAO C. P.; IOST, RODRIGO M.; CRESPILHO, FRANK N.. Nitrated carbon nanoblisters for high-performance glucose dehydrogenase bioanodes. BIOSENSORS & BIOELECTRONICS, v. 77, p. 860-865, MAR 15 2016. (13/04663-4, 13/14262-7)

LUZ, ROBERTO A. S.; CRESPILHO, FRANK N.. Gold nanoparticle-mediated electron transfer of cytochrome c on a self-assembled surface. RSC ADVANCES, v. 6, n. 67, p. 62585-62593, 2016. (13/04663-4, 13/14262-7, 15/16672-3, 09/17898-4)

SANTOS, GERMANO P.; MELO, ANTONIO F. A. A.; CRESPILHO, FRANK N.. Magnetically controlled single-nanoparticle detection via particle-electrode collisions. Physical Chemistry Chemical Physics, v. 16, n. 17, p. 8012-8018, 2014. (13/04663-4, 11/01541-0)

RODRIGO M. IOST; MARCCUS V.A. MARTINS; FRANK N. CRESPILHO. Dendritic Gold Nanoparticles Towards Transparent and Electroactive Electrodes. Anais da Academia Brasileira de Ciências, v. 91, n. 4, 2019-11-28. (13/04663-4, 15/16672-3, 09/12000-0, 13/14262-7)

GONCALVES, WAGNER D.; IOST, RODRIGO M.; CRESPILHO, FRANK N.. Diffusion Mechanisms in Nanoelectrodes: Evaluating the Edge Effect. Electrochimica Acta, v. 123, p. 66-71, MAR 20 2014. (11/01541-0, 13/04663-4)

IOST, RODRIGO M.; CRESPILHO, FRANK N.; ZUCCARO, LAURA; YU, HAK KI; WODTKE, ALEC M.; KERN, KLAUS; BALASUBRAMANIAN, KANNAN. Enhancing the Electrochemical and Electronic Performance of CVD-Grown Graphene by Minimizing Trace Metal Impurities. CHEMELECTROCHEM, v. 1, n. 12, p. 2070-2074, DEC 11 2014. (13/04663-4, 13/14262-7)

MARTINS, MARCCUS V. A.; PEREIRA, ANDRESSA R.; LUZ, ROBERTO A. S.; LOST, RODRIGO M.; CRESPITHO, FRANK N.. Evidence of short-range electron transfer of a redox enzyme on graphene oxide electrodes. Physical Chemistry Chemical Physics, v. 16, n. 33, p. 17426-17436, SEP 7 2014. (13/04663-4, 11/01541-0)

CABRERA, FLAVIO C.; DE SOUZA, JOAO C. P.; JOB, ALDO E.; CRESPILHO, FRANK N.. Natural-rubber-based flexible microfluidic device. RSC ADVANCES, v. 4, n. 67, p. 35467-35475, 2014. (11/23362-0, 13/04663-4, 13/14262-7)

CABRERA, FLAVIO C.; DOGNANI, GUILHERME; FAITA, FABRICIO L.; DOS SANTOS, RENIVALDO J.; AGOSTINI, DEUBER L. S.; BECHTOLD, IVAN H.; CRESPILHO, FRANK N.; JOB, ALDO E.. Vulcanization, centrifugation, water-washing, and polymeric covering processes to optimize natural rubber membranes applied to microfluidic devices. Journal of Materials Science, v. 51, n. 6, p. 3003-3012, MAR 2016. (11/23362-0, 13/04663-4, 13/14262-7)

CABRERA, FLAVIO C.; MELO, ANTONIO F. A. A.; DE SOUZA, JOAO C. P.; JOB, ALDO E.; CRESPILHO, FRANK N.. A flexible lab-on-a-chip for the synthesis and magnetic separation of magnetite decorated with gold nanoparticles. LAB ON A CHIP, v. 15, n. 8, p. 1835-1841, 2015. (11/23362-0, 13/04663-4, 13/14262-7)

IOST, RODRIGO M.; SALES, FERNANDA C. P. F.; MARTINS, MARCCUS V. A.; ALMEIDA, MARIA C.; CRESPILHO, FRANK N.. Glucose Biochip Based on Flexible Carbon Fiber Electrodes: In Vivo Diabetes Evaluation in Rats. CHEMELECTROCHEM, v. 2, n. 4, p. 518-521, APR 15 2015. (13/04663-4, 13/14262-7)

MELO, ANTONIO F. A. A.; SEDENHO, GRAZIELA C.; OSICA, IZABELA; ARIGA, KATSUHIKO; CRESPILHO, FRANK N.. Electrochemical Behavior of Cytochrome C Immobilized in a Magnetically Induced Mesoporous Framework. CHEMELECTROCHEM, v. 6, n. 23, p. 5802-5809, DEC 2 2019. (16/25806-6, 15/22973-6, 13/14262-7, 11/01541-0, 13/04663-4)

LUZ, ROBERTO A. S.; PEREIRA, ANDRESSA R.; DE SOUZA, JOAO C. P.; SALES, FERNANDA C. P. F.; CRESPILHO, FRANK N.. Enzyme Biofuel Cells: Thermodynamics, Kinetics and Challenges in Applicability. CHEMELECTROCHEM, v. 1, n. 11, p. 27-pg., 2014-11-11. (11/01541-0, 13/04663-4)

MELO, ANTONIO F. A. A.; HASSAN, AYAZ; MACEDO, LUCYANO J. A.; OSICA, IZABELA; SHRESTHA, LOK KUMAR; JI, QINGMIN; OLIVEIRA, JR., OSVALDO N.; HENZIE, JOEL; ARIGA, KATSUHIKO; CRESPILHO, FRANK N.. Microwires of Au-Ag Nanocages Patterned via Magnetic Nanoadhesives for Investigating Proteins using Surface Enhanced Infrared Absorption Spectroscopy. ACS APPLIED MATERIALS & INTERFACES, v. 11, n. 20, p. 18053-18061, MAY 22 2019. (17/20493-2, 13/14262-7, 16/25806-6, 13/04663-4, 11/01541-0)