Study of metalloenzymes through electrochemistry coupled to vibrational spectroscopy

• Grant number: 17/20493-2
• Support type: Scholarships in Brazil - Doctorate
• Effective date (Start): February 01, 2018
• Effective date (End): January 31, 2022
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal researcher: Frank Nelson Crespilho
• Grantee: Lucyano Jefferson Alves de Macêdo
• Home Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
• Associated research grant: 13/14262-7 - Nanostructured films from biologically-relevant materials, AP.TEM

Abstract

Among the different types of proteins, enzymes are those whose main function is the catalysis in biological medium. The class known as metalloenzymes is represented by the enzymes whose structure has a prosthetic group containing one or more metallic atoms, which often are coordinated to organometallic unities. For many years, it was presumed that those prosthetic groups performed a role only in terms of structure, that is, they kept the three-dimensional structure of the enzyme and, consequently, their functionality and catalytic efficiency. However, recent studies point out that, for metalloenzymes, prosthetic groups perform roles far beyond the structural, interfering, for example, on the electron transfer, communication between the active site and the substrate and signalizing of molecular events. Therefore, this PhD project proposes the study of metallic centers of two enzymes of huge relevance in technology and biology: alcohol dehydrogenase (ADH) and endonuclease III (EndoIII). It is intended to gather electrochemical and spectroscopic information, by vibrational spectroscopy (FTIR) under electrochemical control of the redox processes of the metalloprotein. Besides, it is glimpsed the understanding of the organometallic bonds role on the catalytic performance of these enzymes. In particular for EndoIII, it is intended to study the metallic cluster [Fe4S4], given the charge transfer once the enzyme is bonded to DNA, aiming to clarify the explanation of charge transport mechanisms through the DNA double-helix.

Scientific publications

(14)

(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)

MACEDO, LUCYANO J. A.; RODRIGUES, FERNANDO P.; HASSAN, AYAZ; MAXIMO, LEANDRO N. C.; ZOBI, FABIO; DA SILVA, ROBERTO S.; CRESPILHO, FRANK N. Non-destructive molecular FTIR spectromicroscopy for real time assessment of redox metallodrugs. ANALYTICAL METHODS, DEC 2021. Web of Science Citations: 0.

MODENEZ, IAGO A.; MACEDO, LUCYANO J. A.; MELO, ANTONIO F. A. A.; PEREIRA, ANDRESSA R.; OLIVEIRA JR, OSVALDO N.; CRESPILHO, FRANK N. Nanosized non-proteinaceous complexes III and IV mimicking electron transfer of mitochondrial respiratory chain. Journal of Colloid and Interface Science, v. 599, p. 198-206, OCT 2021. Web of Science Citations: 0.

MACEDO, LUCYANO J. A.; SANTO, ANDERSON A. E.; SEDENHO, GRAZIELA C.; HASSAN, AYAZ; IOST, RODRIGO M.; FELICIANO, GUSTAVO T.; CRESPILHO, FRANK N. Three-dimensional catalysis and the efficient bioelectrocatalysis beyond surface chemistry. JOURNAL OF CATALYSIS, v. 401, p. 200-205, SEP 2021. Web of Science Citations: 0.

SANCHES, NATALIA M.; HASSAN, AYAZ; MATTIOLI, ISABELA A.; MACEDO, LUCYANO J. A.; SEDENHO, GRAZIELA C.; CRESPILHO, FRANK N. Tuning Vertical Electron Transfer on Graphene Bilayer Electrochemical Devices. ADVANCED MATERIALS INTERFACES, v. 8, n. 20 SEP 2021. Web of Science Citations: 0.

HASSAN, AYAZ; MACEDO, LUCYANO J. A.; MATTIOLI, ISABELA A.; RUBIRA, RAFAEL J. G.; CONSTANTINO, CARLOS J. L.; AMORIM, RODRIGO G.; LIMA, FILIPE C. D. A.; CRESPILHO, FRANK N. A three component-based van der Waals surface vertically designed for biomolecular recognition enhancement. Electrochimica Acta, v. 376, APR 20 2021. Web of Science Citations: 0.

MATTIOLI, ISABELA A.; HASSAN, AYAZ; SANCHES, NATALIA M.; VIEIRA, NIRTON C. S.; CRESPILHO, FRANK N. Highly sensitive interfaces of graphene electrical-electrochemical vertical devices for on drop atto-molar DNA detection. BIOSENSORS & BIOELECTRONICS, v. 175, MAR 1 2021. Web of Science Citations: 0.

SEDENHO, GRAZIELA C.; HASSAN, AYAZ; MACEDO, LUCYANO J. A.; CRESPILHO, FRANK N. Stabilization of bilirubin oxidase in a biogel matrix for high-performance gas diffusion electrodes. Journal of Power Sources, v. 482, JAN 15 2021. Web of Science Citations: 1.

DE SOUZA, JOAO C. P.; MACEDO, LUCYANO J. A.; HASSAN, AYAZ; SEDENHO, GRAZIELA C.; MODENEZ, IAGO A.; CRESPILHO, FRANK N. In Situ and Operando Techniques for Investigating Electron Transfer in Biological Systems. CHEMELECTROCHEM, v. 8, n. 3 DEC 2020. Web of Science Citations: 0.

HASSAN, AYAZ; MACEDO, LUCYANO J. A.; CRESPILHO, FRANK N. Recognizing conductive islands in polymeric redox surfaces using electrochemical-coupled vibrational spectromicroscopy. CHEMICAL COMMUNICATIONS, v. 56, n. 71, p. 10309-10312, SEP 14 2020. Web of Science Citations: 0.

RODRIGUES, FERNANDO POSTALLI; MACEDO, LUCYANO J. A.; MAXIMO, LEANDRO N. C.; SALES, FERNANDA C. P. F.; DA SILVA, ROBERTO S.; CRESPILHO, FRANK N. Real-time redox monitoring of a nitrosyl ruthenium complex acting as NO-donor agent in a single A549 cancer cell with multiplex Fourier-transform infrared microscopy. NITRIC OXIDE-BIOLOGY AND CHEMISTRY, v. 96, p. 29-34, MAR 1 2020. Web of Science Citations: 0.

HASSAN, AYAZ; MACEDO, LUCYANO J. A.; DE SOUZA, JOAO C. P.; LIMA, FILIPE C. D. A.; CRESPILHO, FRANK N. A combined Far-FTIR, FTIR Spectromicroscopy, and DFT Study of the Effect of DNA Binding on the [4Fe4S] Cluster Site in EndoIII. SCIENTIFIC REPORTS, v. 10, n. 1 FEB 6 2020. Web of Science Citations: 0.

MACEDO, LUCYANO J. A.; HASSAN, AYAZ; SEDENHO, GRAZIELA C.; CRESPILHO, FRANK N. Assessing electron transfer reactions and catalysis in multicopper oxidases with operando X-ray absorption spectroscopy. NATURE COMMUNICATIONS, v. 11, n. 1 JAN 16 2020. Web of Science Citations: 0.

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. Web of Science Citations: 3.

MACEDO, LUCYANO J. A.; IOST, RODRIGO M.; HASSAN, AYAZ; BALASUBRAMANIAN, KANNAN; CRESPILHO, FRANK N. Bioelectronics and Interfaces Using Monolayer Graphene. CHEMELECTROCHEM, v. 6, n. 1, SI, p. 31-59, JAN 2 2019. Web of Science Citations: 3.

Academic Publications

(References retrieved automatically from State of São Paulo Research Institutions)

MACÊDO, Lucyano Jefferson Alves de. In situ and operando spectroelectrochemistry for solving catalytic mechanisms involving redox centers of metalloenzymes and biomimetics. 2022. Doctoral Thesis - Universidade de São Paulo (USP). Instituto de Química de São Carlos (IQSC/BT) São Carlos.