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Doctoral Thesis
DOI
https://doi.org/10.11606/T.46.2023.tde-11122023-141249
Document
Author
Full name
Jorge da Silva Shinohara
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2023
Supervisor
Committee
Toma, Henrique Eisi (President)
Toledo, Kalil Cristhian Figueiredo
Santos, Antonio Domingues dos
Zamarion, Vitor de Moraes
Title in English
Hyperspectral Dark Field and Confocal Raman Microscopy Studies in Chemistry and Nanotechnology
Keywords in English
Confocal Raman
Darkfield Microscopy
Pentacyanidoferrates
Plasmonic Nanoparticles
Raman spectroscopy
SERS
Spot Tests
Abstract in English
Hyperspectral imaging can provide accurate information on the distribution of the chemical species in materials and biological samples, based on the analysis of their electronic and vibrational profiles. In special, confocal Raman microscopy is one of the best ways to access the chemical distribution of molecules, especially under resonance Raman or SERS conditions. On the other hand, enhanced dark field optical microscopy can be employed for hyperspectral imaging in the visible and near-IR region, while extending the optical resolution up to the nanoscale dimension. It allows the detection of gold or silver single nanoparticles, as well as spectral monitoring from the characteristic surface plasmon bands. The two hyperspectral microscopies can be conveniently combined to provide nanoscale electronic and vibrational information of the species present in a wide variety of chemical and biological systems. Case studies, including the classical spot-test analysis of nickel(II) ions with dithizone are here reported. A great enhancement of sensitivity in the detection of nickel(II) ions, by at least 4 orders of magnitude, has been observed in this work. Hyperspectral measurements allowed the mapping of the gold nanoparticles (AuNP) distribution on cellulose fibers and on glass, and the evaluation of their extinction and SERS spectra for analytical purposes. Spot tests analysis metal ions with pentacyanidoferrate(II) complexes have also been examined from the point of view of electronic and Raman spectral images. Differentiation of the chemical and electromagnetic mechanisms in the SERS spectra of substituted terpyridine iron(II) complexes with gold nanoparticles has been reported. Characterization of Turkevich nanodisks, and ranelate induced gold nanoparticles formation have also been conducted in this thesis. Finally, hyperspectral techniques have been successfully employed to probe the interaction of gold nanoparticles with microtubules associated with molecular machines.
Title in Portuguese
Estudos de hipermicroscopia de campo escuro e Raman confocal em Química e Nanotecnologia
Keywords in Portuguese
Espectroscopia Raman
Microscopia Hyperspectral
Nanopartículas Plasmônicas
Pentacianidoferratos
Raman Confocal
SERS
Spot Tests
Abstract in Portuguese
A imagem hiperespectral pode fornecer informações precisas sobre a distribuição das espécies químicas em materiais e amostras biológicas, mediante a análise de seus perfis eletrônicos e vibracionais. Em particular, a microscopia confocal Raman é uma das melhores formas de acessar a distribuição químicos das moléculas, especialmente sob condições de ressonância Raman ou SERS. Por outro lado, a microscopia óptica de campo escuro pode ser empregada para obter imagens hiperespectrais na região do visível e infravermelho próximo, estendendo a resolução óptica até a nanoescala. Ele tem permitido a detecção de nanopartículas unitárias de ouro ou prata, bem como o monitoramento espectral das bandas dos plásmon de superfície. As duas microscopias hiperespectrais podem ser convenientemente combinadas para fornecer informações eletrônicas e vibracionais em nanoescala das espécies presentes em uma ampla variedade de sistemas químicos e biológicos. Estudos de casos, incluindo a clássica análise via spottest de íons de níquel (II) com ditizona são relatados nesta tese. Um grande aumento da sensibilidade na detecção de íons níquel(II), em pelo menos 4 ordens de grandeza, foi observado. Medidas hiperespectrais permitiram o mapeamento da distribuição de nanopartículas de ouro (AuNP) em fibras de celulose e em vidro, e a avaliação de seus espectros de extinção e SERS para fins analíticos. Testes pontuais de análise de íons metálicos com complexos de pentacianidoferrato(II) também foram examinados do ponto de vista de imagens eletrônicas e espectrais Raman. Foi relatada a diferenciação dos mecanismos químicos e eletromagnéticos, nos espectros SERS de complexos de terpiridina ferro(II) substituídos com nanopartículas de ouro. A caracterização de nanodiscos de Turkevich e a formação de nanopartículas de ouro, induzidas por ranelato, também foram conduzidas nesta tese. Finalmente, técnicas hiperespectrais foram empregadas com sucesso para sondar a interação de nanopartículas de ouro com microtúbulos associados a máquinas moleculares.
 
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Publishing Date
2024-01-23
 
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