Understanding the charge transfer mechanisms in biological and biomimetic systems using in-situ and operando techniques: from fundamental science to energy application

• Grant number: 22/09164-5
• Support Opportunities: Regular Research Grants
• Start date: February 01, 2023
• End date: January 31, 2025
• 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
• City of the host institution: São Carlos
• Associated research grant(s): 23/01529-7 - Bioengineering of bifunctional metalloproteins applied in the production of added value products, AP.R

Abstract

Redox processes play a critical role in maintaining life on Earth, and they are facilitated by biomolecules. In 2020, we described in Nature Communications how and why the copper-containing bilirubin oxidase (BOD) is an exceptional biocatalyst for the O2 reduction reaction (ORR). A longstanding goal of our research group is the establishment of new frontiers in in-situ techniques for the characterization of bioelectrocatalyst and the elucidation of the mechanism underlying the complex electrochemical reactions in which they are employed. Success in this endeavor would be ground-breaking in electrochemistry, as it would allow the further development of fuel cells sustainable batteries and thus contribute to the current efforts towards realizing clean energy. However, the synthesis of catalysts with three-dimensional organization remains challenging, and it opposes the prevailing trend which focuses on single atoms and two-dimensional materials. Here we propose an advance in the use of in-situ techniques and also in the preparation of mimetic batteries through the knowledge acquired in bioelectrocatalysis studies. For this, we propose 3 specific aims; the first two being for the realization of in-situ techniques to study biological and mimetic redox systems, and the last one for the development of bioinspired organic batteries, that can be applied in ingestible and wearable devices. (AU)

Scientific publications

(20)

(The scientific publications listed on this page originate from the Web of Science or SciELO databases. Their authors have cited FAPESP grant or fellowship project numbers awarded to Principal Investigators or Fellowship Recipients, whether or not they are among the authors. This information is collected automatically and retrieved directly from those bibliometric databases.)

DE SOUZA, JOAO C. P.; SILVA, WANDERSON O.; FREITAS, LUIS P. M.; COLOMBO, RAFAEL N. P.; IOST, RODRIGO M.; FELICIANO, GUSTAVO T.; LIMA, FABIO H. B.; CRESPILHO, FRANK N.. Dynamics of the activated state of NAD-dependent dehydrogenase investigated by a weighted histogram analysis semi-empirical method. CATALYSIS SCIENCE & TECHNOLOGY, v. 14, n. 13, p. 9-pg., 2024-05-22. (22/09164-5, 21/05665-7, 19/15333-1, 19/12053-8, 18/22214-6)

CRESPILHO, FRANK N.; BRITO-PEREIRA, RICARDO; POLICIA, RITA; PEREIRA, NELSON; SEDENHO, GRAZIELA C.; COSTA, CARLOS M.; LANCEROS-MENDEZ, SENENTXU. Yeast bio-batteries. SUSTAINABLE ENERGY & FUELS, v. 8, n. 22, p. 5-pg., 2024-10-01. (22/09164-5, 23/13288-4)

CLARINDO, JOSE EDUARDO DOS SANTOS; COLOMBO, RAFAEL NERI PRYSTAJ; SEDENHO, GRAZIELA CRISTINA; FARIA, LUANA CRISTINA ITALIANO; BERTAGLIA, THIAGO; LIMA, FILIPE CAMARGO DALMATTI ALVES; GOMES, ROBERTO DA SILVA; AZIZ, MICHAEL J.; CRESPILHO, FRANK NELSON. Molecular Mechanism and Electrostatic Effect Enabling Symmetric All-Quinone Aqueous Redox Flow Batteries. ACS SUSTAINABLE CHEMISTRY & ENGINEERING, v. 12, n. 31, p. 10-pg., 2024-07-23. (22/09164-5, 19/21089-6, 21/05665-7, 19/15333-1, 17/15714-0, 20/04796-8, 15/22973-6, 21/14537-2, 20/03681-2, 18/22214-6, 19/12053-8, 23/17506-6)

FARIA, LUANA C. I.; SEDENHO, GRAZIELA C.; BERTAGLIA, THIAGO; MACEDO, LUCYANO J. A.; CRESPILHO, FRANK N.. A comparative study of chemically oxidized carbon cloth and thermally treated carbon paper electrodes applied on aqueous organic redox flow batteries. Electrochimica Acta, v. 485, p. 8-pg., 2024-03-16. (22/09164-5, 20/12404-2, 19/21089-6, 20/04796-8, 17/20493-2, 20/03681-2, 18/22214-6)

DE ALBUQUERQUE, FHYSMELIA FIRMINO; IOST, RODRIGO MICHELIN; CRESPILHO, FRANK NELSON. Comparative Roles of Hydrogels, Deep Eutectic Solvents, and Ionic Liquids in Enzyme-Based Biosensors, Bioelectronics and Biomimetics Devices. ACS MEASUREMENT SCIENCE AU, v. 5, n. 4, p. 19-pg., 2025-07-15. (23/13288-4, 23/17020-6, 23/10667-4, 18/22214-6, 19/15333-1, 19/12053-8, 23/01529-7, 18/22214-6, 22/09164-5, 20/03681-2)

SEDENHO, GRAZIELA C.; GHIRALDELLI, GUILHERME H. S.; IOST, RODRIGO M.; BRITO-PEREIRA, RICARDO; POLICIA, RITA; LANCEROS-MENDEZ, SENENTXU; CRESPILHO, FRANK N.. Bioelectrochemical systems and engineered living materials: a tutorial on carbon capture and sustainable energy. SUSTAINABLE ENERGY & FUELS, v. 9, n. 21, p. 22-pg., 2025-09-01. (22/06563-6, 20/04796-8, 20/12404-2, 23/13288-4, 22/09164-5, 23/10667-4, 24/22202-9, 18/22214-6)

MENDES, GIOVANA ROSSI; MODENEZ, IAGO DE ASSIS; CAGNANI, GIOVANA ROSSO; COLOMBO, RAFAEL N. P.; CRESPILHO, FRANK NELSON. Exploring Enzymatic Conformational Dynamics at Surfaces through μ-FTIR Spectromicroscopy. Analytical Chemistry, v. 95, n. 30, p. 9-pg., 2023-07-17. (20/10724-0, 21/05665-7, 19/15333-1, 19/12053-8, 18/22214-6, 22/09164-5)

CASTRO, KARLA P. R.; COLOMBO, RAFAEL N. P.; IOST, RODRIGO M. M.; DA SILVA, BEATRIZ G. R.; CRESPILHO, FRANK N. N.. Low-dimensionality carbon-based biosensors: the new era of emerging technologies in bioanalytical chemistry. ANALYTICAL AND BIOANALYTICAL CHEMISTRY, v. N/A, p. 17-pg., 2023-02-09. (22/09164-5, 21/05665-7, 18/22214-6)

SEDENHO, GRAZIELA C.; COLOMBO, RAFAEL N. P.; CRESPILHO, FRANK N.. Insights from Enzymatic Catalysis: A Path towards Bioinspired High-Performance Electrocatalysts. CHEMCATCHEM, v. N/A, p. 18-pg., 2023-07-06. (21/05665-7, 22/09164-5, 18/22214-6, 20/04796-8)

MELO, ANTONIO F. A. A.; SINGH, SALAM J.; CHINNAMUTHU, PAULSAMY; CRESPILHO, FRANK N.; RYDZEK, GAULTHIER. Magnetically Stimulated Bio- and Electrochemical Systems: State-of-the-Art, Applications, and Future Directions. HEMNANOMA, v. N/A, p. 22-pg., 2023-07-19. (20/12404-2, 18/22214-6, 22/09164-5)

COLOMBO, RAFAEL N. P.; SEDENHO, GRAZIELA C.; NECKEL, ITAMAR T.; CRESPILHO, FRANK N.. Enzymatic X-ray absorption spectroelectrochemistry. Nature Protocols, v. N/A, p. 46-pg., 2025-10-02. (23/01529-7, 18/22214-6, 21/05665-7, 20/04796-8, 22/09164-5)

ALBUQUERQUE, FHYSMELIA F.; IOST, RODRIGO M.; FONSECA, GABRIEL C.; VENKATKARTHICK, RADHAKRISHNAN; PACHECO, JESSICA C.; COLOMBO, RAFAEL N. P.; LIMA, FABIO H. B.; CRESPILHO, FRANK N.. Biomimetic Cobalt Complex Stabilized by Hydrogel on High-Edge-Density Graphite for ORR and HER in Quiescent Solutions. Langmuir, v. 41, n. 34, p. 11-pg., 2025-08-19. (23/10667-4, 20/03681-2, 20/04796-8, 19/21089-6, 23/17020-6, 18/22214-6, 19/03033-3, 22/09164-5, 19/22183-6, 23/08260-3, 20/12404-2, 16/08711-1, 20/15098-0, 22/06563-6, 25/05509-6, 23/01529-7)

IOST, RODRIGO M.; LANCEROS-MENDEZ, SENENTXU; CRESPILHO, FRANK N.. Bioelectrocatalysis for solar fuels and sustainable energy. CATALYSIS SCIENCE & TECHNOLOGY, v. 15, n. 13, p. 13-pg., 2025-05-29. (22/09164-5, 23/13288-4, 23/10667-4)

BERTAGLIA, THIAGO; NEUBERT, TILMANN J.; IOST, RODRIGO M.; BALASUBRAMANIAN, KANNAN; CRESPILHO, FRANK N.. Consequences of edge and substrate modifications on graphene electrochemistry. CURRENT OPINION IN ELECTROCHEMISTRY, v. 50, p. 9-pg., 2025-01-25. (20/12404-2, 22/09164-5, 23/08260-3, 22/06563-6, 18/22214-6, 23/10667-4, 20/03681-2, 23/01529-7, 23/13288-4)

BERTAGLIA, THIAGO; COSTA, CARLOS M.; LANCEROS-MENDEZ, SENENTXU; CRESPILHO, FRANK N.. Eco-friendly, sustainable, and safe energy storage: a nature-inspired materials paradigm shift. MATERIALS ADVANCES, v. 5, n. 19, p. 15-pg., 2024-08-06. (22/09164-5, 23/08260-3, 20/12404-2, 23/13288-4, 20/03681-2, 18/22214-6, 23/01529-7)

CRESPILHO, FRANK N.; COSTA, CARLOS M.; LANCEROS-MENDEZ, SENENTXU. Sustainable Battery Biomaterials. CHEMELECTROCHEM, v. 12, n. 3, p. 11-pg., 2024-12-20. (22/09164-5, 23/13288-4)

BERTAGLIA, THIAGO; KERR, EMILY F.; SEDENHO, GRAZIELA C.; WONG, ANDREW A.; COLOMBO, RAFAEL N. P.; MACEDO, LUCYANO J. A.; IOST, RODRIGO M.; FARIA, LUANA C. I.; LIMA, FILIPE C. D. A.; TEOBALDO, GABRIEL B. M.; et al. Self-Gelling Quinone-Based Wearable Microbattery. ADVANCED MATERIALS TECHNOLOGIES, v. 9, n. 17, p. 11-pg., 2024-06-09. (22/09164-5, 20/12404-2, 16/24531-3, 19/21089-6, 21/05665-7, 19/15333-1, 20/04796-8, 17/20493-2, 20/03681-2, 18/22214-6, 23/01529-7, 23/17506-6)

CARVALHO, CAIO LENON CHAVES; NASCIMENTO, STEFFANE Q.; BERTAGLIA, THIAGO; FARIA, LUANA C. I.; MANULI, ERIKA R.; PEREIRA, GEOVANA M.; DA SILVA, WELTER CANTANHEDE; COSTA, CARLOS M.; MAESTU, JOSU FERNANDEZ; LANCEROS-MENDEZ, SENENTXU; et al. Sustainable Electrochemical-Magnetic Biosensor Fabricated from Recycled Materials for Label-Free Detection of SARS-CoV-2 in Human Saliva. ACS SENSORS, v. 10, n. 3, p. 16-pg., 2025-03-14. (22/09164-5, 18/22214-6, 20/03681-2, 23/13288-4, 19/15333-1, 19/12053-8, 18/22214-6)

IOST, RODRIGO M.; VENKATKARTHICK, RADHAKRISHNAN; NASCIMENTO, STEFFANE Q.; LIMA, FABIO H. B.; CRESPILHO, FRANK N.. Hydrogen bioelectrogeneration with pH-resilient and oxygen-tolerant cobalt apoenzyme-saccharide. CHEMICAL COMMUNICATIONS, v. 60, n. 18, p. 3-pg., 2024-02-01. (22/09164-5, 23/10667-4, 21/05665-7, 18/22214-6, 23/01529-7, 20/15098-0)

SEDENHO, GRAZIELA C.; COLOMBO, RAFAEL N. P.; IOST, RODRIGO M.; LIMA, FILIPE C. D. A.; CRESPILHO, FRANK N.. Exploring electron transfer: Bioinspired, biomimetics, and bioelectrochemical systems for sustainable energy and Value-Added compound synthesis. APPLIED PHYSICS REVIEWS, v. 11, n. 2, p. 25-pg., 2024-06-01. (22/09164-5, 21/05665-7, 18/22214-6, 23/01529-7, 14/50869-6, 23/17506-6)