Nanoelectronics and nanoscale electrochemistry: fundaments and applications

• Grant number: 17/24839-0
• Support Opportunities: Research Projects - Thematic Grants
• Duration: August 01, 2018 - January 31, 2025
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Analytical Chemistry
• Principal Investigator: Paulo Roberto Bueno
• Grantee: Paulo Roberto Bueno
• Host Institution: Instituto de Química (IQ). Universidade Estadual Paulista (UNESP). Campus de Araraquara. Araraquara , SP, Brazil
• Pesquisadores principais: Eduardo Maffud Cilli ; Marcelo Ornaghi Orlandi ; Ronaldo Censi Faria
• Associated researchers: Carlos Frederico de Oliveira Graeff ; Gustavo Troiano Feliciano ; Marcelo Mulato ; Marcelo Ornaghi Orlandi ; Maria Manuela Marques Raposo
• Associated grant(s): 20/05761-3 - Study of the action of synthetic peptides as antivirals against SARS-CoV-2 (COVID-19) and combined evaluation with commercial anti-inflammatories, AP.R; 20/05497-4 - A reagentless viral detection platform, AP.R; 20/04635-4 - Development of a simple and affordable disposable device for rapid diagnosis of coronavirus (SARS-CoV-2), AP.R; 18/23820-7 - À-conjugated heterocyclic compounds: synthesis, reactivity and applications in optoelectronics and medicine, AV.EXT
• Associated scholarship(s): 22/05681-5 - Nanoelectronics and nanoscale electrochemistry: fundaments and applications, BP.DD; 22/07433-9 - Nanoelectronics and nanoscale electrochemistry: fundaments and applications, BP.PD; 21/00726-8 - The Nanoscale Designing of Electrodes Aiming at the Development of High-Performance Supercapacitors, BP.PD; + associated scholarships 21/11915-6 - Nanoelectronics and nanoscale electrochemistry: fundaments and applications, BP.DD; 21/07936-8 - Nanoelectronics and nanoscale electrochemistry: fundaments and applications, BP.PD; 20/12905-1 - Development of aptasensors using organic electrochemical transistors, BP.PD; 19/27510-5 - Molecular electronics of organic compounds, BP.DD; 19/18856-5 - Photo(electro)chemical applications for the production of renewable fuels using nanocomposites based on tin oxide (SnO and Sn3O4) and carbon compounds (reduced graphene oxide and graphitic carbon nitride), BP.PD; 19/24188-5 - Electrochemical capacitive platform for the field-based, label-free detection of DENV, BP.IC; 18/24395-8 - Fabrication of Biosensors Based on Organic FET and Architected via Organic Electronics and Electrochemistry, BP.PD; 19/06568-5 - In-operando Study of Nanoscale Proprieties of Molecular Switching Devices, BP.PD; 18/18787-0 - Study of the (photo)catalytic properties of tin oxides modified with graphene and/or noble metals for the elucidation of the degradation mechanisms of organic contaminants, BP.PD; 18/22223-5 - Modular biosensors based on electrolyte gated organic field effect transistors with polyaniline thin films, BP.IC; 18/24525-9 - Nanoelectronics and nanoscale electrochemistry: fundaments and applications, BP.DD; 18/26273-7 - Label-free electrochemical capacitive biosensors for disease diagnosis, BP.DR; 18/23577-5 - Nanoelectronics and Nanoscale Electrochemistry: Fundaments and Applications., BP.PD; 18/21911-5 - Effect of ordered gold surfaces on the insulating/conductive properties of tiolated molecular junctions, BP.IC - associated scholarships

Abstract

Chemical covalent attachment of molecules over conductive electrodes and the control of the properties of the nanoscale junction is the state-of-art for molecular electronics and molecular electrochemistry. In the present proposal we suggest to measure the time-dependent electronic features as accessed by impedance methods for fundamental studies and applications of different types of nanoscale junctions in an electrochemical environment. Impedance methods shall be supported by other complementary techniques such as kelvin probe, scanning electrochemical microscopic, Fourier transform infrared spectroscopy and computational simulations. The essence of the problematic is that it has been recently demonstrated that both capacitive and resistive phenomenon involved with electron dynamics throughout molecular-scale junctions embedded in an electrolyte environment are governed by mesoscopic principles. Although this is demonstrated, the mesoscopic physics of nanoelectronics and electrochemistry are marginally exploited up to now. Particularly it has been demonstrated (by our research group) that the electrochemistry of a two-dimensional molecular ensemble made of individual molecular point contacts is a particular case of a quantum resistance-capacitance circuit. The intrinsic electrical current exchange (resonant) between electrochemical accessible sites and the electrode is enlightened by considering quantum resistive-capacitive ensembles (a collection of parallel individual quantum point contacts) in such a way that the electron transfer rate, which govern the rate of electrochemical reactions, is given by k=G/C¼, wherein C¼ is the electrochemical capacitance and G is the conductance accompanying the Landauer formula. Astonishingly this simple equation reconciles molecular electronics and electrochemistry and its usefulness is demonstrated in accessing the energy for charging molecular redox switches (in the Fermi energy of the interface) and thus use these switches as energy transducers in molecular diagnostics. Additionally the concepts were also applied in obtaining the conductance of DNA nanowires (in different chemically designed double strands) and finally in explaining the supercapacitance phenomenon of reduced graphene molecular layers. Even so, the use of specifically designed molecular switches and semiconductive (organic or inorganic) layers under different electric or optical estimulative conditions yet remains to be exploited in both fundamental and experimental features so this constitutes the main goal of the present proposal allied to continuing the investigation of designed switches for molecular diagnostics. For this we are gathering different expertises. (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)

FELICIANO, GUSTAVO T.; BUENO, PAULO R.. Two-Dimensional Nature and the Meaning of the Density of States in Redox Monolayers. Journal of Physical Chemistry C, v. 124, n. 27, p. 14918-14927, JUL 9 2020. (17/13401-4, 17/24839-0)

PICCOLI, JULIA P.; SOARES, ANDREY C.; OLIVEIRA, JR., OSVALDO N.; CILLI, EDUARDO M.. Nanostructured functional peptide films and their application in C-reactive protein immunosensors. BIOELECTROCHEMISTRY, v. 138, APR 2021. (18/22214-6, 13/07600-3, 18/18953-8, 17/24839-0, 18/18231-2)

GARCIA NICHOLSON, MELANY ISABEL; BUENO, PAULO ROBERTO; FELICIANO, GUSTAVO TROIANO. Ab Initio QM/MM Simulation of Ferrocene Homogeneous Electron-Transfer Reaction. Journal of Physical Chemistry A, v. 125, n. 1, p. 25-33, JAN 14 2021. (17/24839-0, 17/13401-4)

BUENO, PAULO ROBERTO; CRUZEIRO, VINICIUS WILIAN D.; ROITBERG, ADRIAN E.; FELICIANO, GUSTAVO T.. The density-of-States and equilibrium charge dynamics of redox-active switches. Electrochimica Acta, v. 387, AUG 10 2021. (17/24839-0, 17/13401-4)

GARROTE, BEATRIZ L.; SANTOS, ADRIANO; BUENO, PAULO R.. Label-free capacitive assaying of biomarkers for molecular diagnostics. Nature Protocols, v. 15, n. 12, OCT 2020. (17/02974-3, 18/26273-7, 16/17185-1, 17/24839-0)

DE OLIVEIRA, TASSIA R.; ERBERELI, CAMILA R.; MANZINE, PATRICIA R.; MAGALHAES, THAMIRES N. C.; BALTHAZAR, MARCIO L. F.; COMINETTI, MARCIA R.; FARIA, RONALDO C.. Early Diagnosis of Alzheimer's Disease in Blood Using a Disposable Electrochemical Microfluidic Platform. ACS SENSORS, v. 5, n. 4, p. 1010-1019, APR 24 2020. (14/22401-0, 15/26084-1, 18/15571-7, 17/24839-0, 17/24053-7, 15/19890-1)

SANTOS, ADRIANO; TEFASHE, USHULA M.; MCCREERY, RICHARD L.; BUENO, PAULO R.. Introducing mesoscopic charge transfer rates into molecular electronics. Physical Chemistry Chemical Physics, v. 22, n. 19, p. 10828-10832, MAY 21 2020. (17/24839-0)

BATISTUTI, MARINA R.; BUENO, PAULO R.; MULATO, MARCELO. The importance of the assembling of DNA strands on the performance of electrochemical genosensors. Microchemical Journal, v. 159, DEC 2020. (17/24839-0, 15/14403-5, 14/09562-4)

BUENO, PAULO ROBERTO. Electron transfer and conductance quantum. Physical Chemistry Chemical Physics, v. 22, n. 45, p. 26109-26112, DEC 7 2020. (17/24839-0)

FELIX, A. A.; BARBOSA, M. S.; BUENO, P. R.; ORLANDI, M. O.. Real-Time Monitoring of Electrochromic Memory Loss of Layered alpha-MoO3 Nanoplates. Journal of the Electrochemical Society, v. 167, n. 16, DEC 1 2020. (19/06568-5, 17/26219-0, 17/24839-0)

SANTOS, ADRIANO; GARCIA NICHOLSON, MELANY ISABEL; FELICIANO, GUSTAVO TROIANO; BUENO, PAULO ROBERTO. Low-fouling properties in serum of carboxylic-oligo(ethylene glycol)-based interfaces. COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS, v. 618, JUN 5 2021. (17/24839-0)

SANTO, ANDERSON A. E.; FELICIANO, GUSTAVO T.. Genetic Algorithms Applied to Thermodynamic Rational Design of Mimetic Antibodies Based on the GB1 Domain of Streptococcal Protein G: An Atomistic Simulation Study. Journal of Physical Chemistry B, v. 125, n. 29, p. 7985-7996, JUL 29 2021. (17/13401-4, 17/24839-0)

PINZON, EDGAR F.; DOS SANTOS, ADRIANO; BUENO, PAULO R.. Density of States of a Nanoscale Semiconductor Interface as a Transduction Signal for Sensing Molecules. ACS APPLIED ELECTRONIC MATERIALS, v. 3, n. 8, p. 3411-3417, AUG 24 2021. (17/24839-0)

SANTO, ANDERSON APARECIDO DO ESPIRITO; FELICIANO, GUSTAVO TROIANO. Thermodynamic and structural aspects of molecular recognition in mannose-binding protein complexes: a theoretical study over HRP-ArtinM association. Journal of Molecular Modeling, v. 27, n. 4, MAR 15 2021. (17/24839-0)

DUTTA, GORACHAND; FERNANDES, FLAVIO C. B.; ESTRELA, PEDRO; MOSCHOU, DESPINA; BUENO, PAULO R.. Impact of surface roughness on the self-assembling of molecular films onto gold electrodes for label-free biosensing applications. Electrochimica Acta, v. 378, MAY 10 2021. (17/24839-0)