Spectroscopy signal enhancement: nanomaterials, theory, and computer simulation

• Grant number: 22/11983-4
• Support Opportunities: Research Projects - Thematic Grants
• Start date: October 01, 2023
• End date: September 30, 2028
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Mauro Carlos Costa Ribeiro
• Grantee: Mauro Carlos Costa Ribeiro
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Pesquisadores principais: Leonardo José Amaral de Siqueira ; Lucas Carvalho Veloso Rodrigues ; Paola Corio ; Rômulo Augusto Ando
• Associated researchers: Danilo Manzani ; Diego Pereira dos Santos ; Leonardo José Amaral de Siqueira ; Lucas Carvalho Veloso Rodrigues
• Associated research grant(s): 23/13861-6 - Multi-user equipment approved in grant 2022/11983-4: darkfield microscope, AP.EMU
• Associated scholarship(s): 24/21790-4 - New methodologies for the synthesis of glass-ceramics combining plasmon-enhanced upconversion and persistent luminescence, BP.DD; 24/20725-4 - Mechanochemical synthesis of Luminescent rare earth tetrafluoride nanomaterials for infrared and X-ray excitation, BP.IC; 24/17764-8 - Detection of emerging pollutants adsorben on microplastics by SERS spectroscopy, BP.IC; + associated scholarships 24/17972-0 - Theoretical Investigation of the Chemical Effect on SERS Enhancement by Multiconfigurational Calculations, BP.IC; 24/15731-5 - Development of Self-Assembled Monolayers of Lead-Free Double Halide Perovskites on Commercial Glass Substrates for Photocatalysis Applications, BP.IC; 24/09973-6 - Study of the specific interactions between neurotransmitters (serotonin, dopamine and adrenaline) and their specific receptors in the presence and absence of drugs with selective serotonin reuptake inhibitory action (SSRI), BP.PD; 24/03365-4 - Advanced oxidative processes and electrochemical methodologies for the synthesis of Graphene Quantum Dots, BP.IC; 23/16685-4 - Raman spectroscopy and in situ measurements of physico-chemical properties of ionic liquids and deep eutectic solvents., BP.DD; 23/14995-6 - Technical support in electronics and computers for scientific calculations and operation of spectrometers., BP.TT; 23/04980-1 - Ab initio molecular dynamics simulation of plastic crystal of protic ionic liquids, BP.PD; 22/15586-0 - Monitoring and characterization of microplastics photoaging combining vibrational spectroscopy approaches and toxic potential evolution, BP.PD; 22/12709-3 - Photophysical properties of lanthanide charge transfer complexes with organic semiconductors for applications in OLEDs, BP.PD; 21/07031-5 - Multiconfigurational Calculations in the Description of Excited States Dynamics and its Correlation with Resonance Raman Spectroscopy, BP.PD - associated scholarships

Abstract

The excitation of plasmon-polariton modes on the surface of metallic nanoparticles (NPs) enables a variety of applications for these materials, such as photocatalysts and photovoltaic and sensing devices. Plasmon excitation in NPs implies an increase in the intensity of spectroscopic signals from adsorbed molecules, in particular, the enhancement of Raman spectra (surface-enhanced Raman scattering, SERS). In a resonance condition between the excitation radiation and an electronic transition of the molecule, the signal intensification also results from the resonant Raman effect (RR). The combination of NO and rare earth ions makes it possible to enhance luminescence by unconventional processes such as upconversion and persistent luminescence. Recent advances in the preparation of NPs include the use of new solvents such as ionic liquids (ILs) and deep eutectic solvents (DES) due to their performance in colloidal stabilization. These neoteric liquids, in turn, also have various applications as media for chemical reactions, catalysis, gas absorption etc.. The detailed understanding of the relationship between molecular structure, liquid structure and its physicochemical properties is still a challenge. In this sense, this Thematic Project brings together expertise in nanoparticle synthesis, spectroscopy, theory and computer simulation of researchers from different universities: USP-São Paulo, USP-São Carlos, UNIFESP and UNICAMP. It is intended to relate the morphology of NPs and plasmonic catalysis, in particular the nanostructures, with the dual function of promoting the photocatalytic reaction and giving rise to the intensification of the Raman spectrum. The ILs and DES will be solvents for the preparation of NPs, but also as liquids for the absorption of polluting gases (CO2 and SO2), whether physical or chemical sorption. In SERS theory, classical electrodynamics calculations will be performed to obtain the spatial distribution of the electric field around the NPs, and in RR theory, quantum chemistry calculations of the dynamics of excited electronic states will be performed using multiconfiguration perturbative methods. Vibrational spectroscopy in a wide range of temperature and pressure will be used in the study of phase transitions of ILs or DES, and molecular dynamics (MD) simulation in the study of the structure and dynamics of liquids. MD simulations of these liquids will be performed for nanoparticle dispersion in order to understand the structure of the liquid-nanoparticle interface, and dispersion of porous carbon materials in order to assess the absorption of gases. (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)

EDISON HUERTAS-MONTOYA; ANERISE DE BARROS; LUCAS M. F. OLIVEIRA; PAOLA A. CARO APONTE; ALEXANDRE L. R. OLIVEIRA; FLAVIO M. SHIMIZU; ALESSANDRA SUSSULINI; FERNANDO A. SIGOLI; ITALO O. MAZALI. Detection of Psychoactive N,N-Dimethyltryptaniine Alkaloid Based on Surface-Enhanced Raman Scattering Using Gold Nanostars in Flexible Inkjet-Printing Paper Substrates. Journal of the Brazilian Chemical Society, v. 35, n. 12, 2024-07-22. (22/02893-1, 21/02754-9, 14/50906-9, 22/11983-4)

ASSUNCAO, ISRAEL P.; COSTA, ISRAEL F.; BLOIS, LUCCA; FELINTO, MARIA CLAUDIA F. C.; DEFLON, VICTOR M.; ANDO, ROMULO A.; MALTA, OSCAR L.; BRITO, HERMI F.. High red luminescence intensity under sunlight exposure of a PMMA polymer doped with a tetrakis Eu³⁺ β-diketonate complex containing a benzimidazolium counterion. RSC ADVANCES, v. 15, n. 1, p. 11-pg., 2025-01-02. (22/12709-3, 21/08111-2, 22/11983-4, 20/16795-6)

PASCHOAL, VITOR H.; RIBEIRO, MAURO C. C.. Phase transitions of choline dihydrogen phosphate: A vibrational spectroscopy and periodic DFT study. Journal of Chemical Physics, v. 160, n. 9, p. 12-pg., 2024-03-07. (22/11983-4, 19/00207-0)

PEREIRA, RAFAEL GUIMARAES; SAMPAIO, ABNER MASSARI; SILVA, ISABEL AMARAL; SIQUEIRA, LEONARDO JOSE AMARAL. Enhancing power and energy densities of supercapacitors with slit porous carbon electrodes by playing with pore width and ion shapes. Electrochimica Acta, v. 492, p. 8-pg., 2024-05-09. (17/11631-2, 19/18125-0, 22/11983-4)

RUBIO, THIAGO I.; FRANCISCO, DANIEL DOS SANTOS; ANDO, ROMULO A.; FILHO, UBIRAJARA PEREIRA RODRIGUES; FERREIRA-NETO, ELIAS P.; MANZANI, DANILO. Bifunctional titanium boron-phosphate glass containing Ag nanoparticles for the detection and photocatalysis of organic compounds. Materials Chemistry and Physics, v. 320, p. 9-pg., 2024-05-09. (22/01626-0, 19/16230-1, 22/11983-4)

DE MORAES, BEATRIZ R.; PASCHOAL, VITOR H.; KEPPELER, NICOLAS; EL SEOUD, OMAR A.; ANDO, ROMULO A.. The Coiling Effect in Ether Ionic Liquids: Exploiting Acetate as a Probe for Transport Properties and Microenvironment Analysis. Journal of Physical Chemistry B, v. 128, n. 19, p. 11-pg., 2024-04-12. (22/11983-4, 20/09250-3, 16/21070-5)

SAMPAIO, ABNER M.; BI, SHENG; SALANNE, MATHIEU; SIQUEIRA, LEONARDO J. A.. Molecular dynamics simulations of ionic liquids confined into MXenes. ENERGY STORAGE MATERIALS, v. 70, p. 11-pg., 2024-06-07. (19/18125-0, 22/11983-4)

PAGANOTO, GIORDANO TOSCANO; TEMPERINI, MARCIA LAUDELINA ARRUDA; DOS SANTOS, DIEGO PEREIRA. Nanoparticle Shape Effects on the SERS Properties of Small Conductive Bridges. Journal of Physical Chemistry C, v. 128, n. 38, p. 11-pg., 2024-09-16. (22/11983-4, 16/21070-5)

DA SILVA, ARUA CLAYTON; HU, XIAOFENG; PASCHOAL, VITOR HUGO; HAGIS, NICHOLAS; ZAJAC, AGNIESZKA JOANNA; RIBEIRO, MAURO CARLOS COSTA; MINEV, IVAN RUSEV. Bipolar electrochemistry-driven wireless drug loading and energy harvesting in conductive hybrid hydrogels. COMMUNICATIONS MATERIALS, v. 6, n. 1, p. 11-pg., 2025-02-11. (22/11983-4, 19/00207-0)

SILVA, VINICIUS D.; MELO, EDUARDO C.; MARTINS, VITOR L.; DE OLIVEIRA, PAULO F. M.; ANDO, ROMULO A.; CATALANI, LUIZ H.; TORRESI, ROBERTO M.. Additive- and binder-free hard carbon nanofibers for sodium-ion batteries. NANO ENERGY, v. 136, p. 14-pg., 2025-04-01. (22/11983-4, 22/12609-9, 21/00675-4, 20/14955-6, 19/26309-4)

PASCHOAL, VITOR HUGO; RIBEIRO, MAURO C. C.. Short-time collective dynamics of an ionic liquid: A computer simulation study with non-polarizable and polarizable models, and ab initio molecular dynamics. Journal of Chemical Physics, v. 161, n. 24, p. 10-pg., 2024-12-28. (22/11983-4, 19/00207-0)

SEBASTIAO, GLAUCIA I. A.; RANI-BORGES, BARBARA; DIPOLD, JESSICA; FREITAS, ANDERSON Z.; WETTER, NIKLAUS U.; ANDO, ROMULO A.; WALDMAN, WALTER R.. Forensic determination of adhesive vinyl microplastics in urban soils. Journal of Environmental Management, v. 373, p. 10-pg., 2024-12-06. (22/11983-4, 22/15586-0, 22/12104-4, 17/50332-0, 18/19240-5)

ALVES, RAISA SIQUEIRA; MAZALI, ITALO ODONE; DOS SANTOS, DIEGO PEREIRA. Enhanced Surface Fields Driven by Fano Resonances in Silver Nanocube Dimers for Efficient Hot Electron Generation. Journal of Physical Chemistry C, v. 128, n. 22, p. 11-pg., 2024-05-27. (22/11983-4, 16/21070-5)

SILVA, ISABEL AMARAL; FILETI, EUDES ETERNO; SIQUEIRA, LEONARDO JOSE AMARAL. Atomistic insights into the superior performance of C60-decorated graphene supercapacitors. JOURNAL OF MOLECULAR LIQUIDS, v. 404, p. 8-pg., 2024-05-08. (22/11983-4, 18/21401-7, 19/18125-0, 17/11631-2)

CORREA, LEONARDO M.; FAIRCLOUGH, SIMON M.; SCHER, KALEIGH M. R.; ATTA, SUPRIYA; DOS SANTOS, DIEGO PEREIRA; DUCATI, CATERINA; FABRIS, LAURA; UGARTE, DANIEL. Atomic Structure and 3D Shape of a Multibranched Plasmonic Nanostar from a Single Spatially Resolved Electron Diffraction Map. ACS NANO, v. 18, n. 39, p. 11-pg., 2024-09-21. (14/01045-0, 22/11983-4, 16/21070-5)