Optically active helical microparticles are studied in the forms of thin films, suspensions and powders. From fabricated helical porous thin films, microparticle suspensions are obtained by removing the microparticles (film columns) from their substrates and dispersing them into water. For removing microparticles, four methods are explored and compared: sacrificial NaCl layer, gold (Au) layer, buffered oxide etching, and direct ultrasonic agitation. The primary film material studied in this work is amorphous silicon (Si). Physical morphology of the microparticles is examined with scanning electron microscopy (SEM). Methods employed to characterize optical activity of the microparticles include: polarimetry, spectrophotometry, and spectroscopic ellipsometry (SE). The produced chiral microparticles exhibit optical activity: optical rotation (OR) and circular dichroism (CD - in the form of differential circular transmission (DCT)). Significant findings include: (a) we observe the largest optical rotatory power ever reported in scientific literature, 11◦/μm at 610 nm wavelength for a Si film; (b) for the helical thin films, there is one dominant DCT band in the measured wavelength range; however for microparticle suspensions and powders, there exist two DCT bands: one broad band at long wavelengths, and one narrow band in the short wavelength range; compared to their thin film forms, microparticle suspensions and powders have inverted sign for the broad DCT band. A discrete dipole approximation (DDA) model is employed to calculate optical response (e.g. extinction, scattering, and absorption cross-sections) of the microparticles, so as to enable us to understand the effects of different structural parameters of the microparticles on their optical response. Calculation confirms that optical activity of chiral microparticles is due to coherent light scatterings with the chiral structures of the particles. The inversion in sign of the broad DCT bands of microparticle suspensions and powders is likely due to the averaging effect from random orientation of the helical microparticles, as is indicated both from experimental results and from calculation. / Thesis (Ph.D, Physics, Engineering Physics and Astronomy) -- Queen's University, 2012-07-06 09:59:20.751

Orientador: Celio Pasquini / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-06T07:12:46Z (GMT). No. of bitstreams: 1 Pereira_ClaudeteFernandes_D.pdf: 2102754 bytes, checksum: 94aabfeb5b023dd70dc648a8f2343f52 (MD5) Previous issue date: 2006 / Resumo: A espectroscopia de correlação bidimensional (2D) foi utilizada neste trabalho como ferramenta de seleção de variáveis espectrais na região do infravermelho próximo (NIR) para a determinação dos seguintes parâmetros de qualidade de gasolinas: teor de etanol, MON e RON. Para tanto, foi sugerido um sistema de perturbação de concentração em fluxo. Tal sistema apresenta algumas vantagens em relação aos sistemas de perturbação em batelada: os experimentos são realizados em sistema fechado; uma maior velocidade na aplicação da perturbação é obtida, além de se trabalhar em micro-escala. Em outra etapa do trabalho, sugeriu-se a construção de um espectropolarímetro baseado em Filtro Óptico Acústico Sintonizável (AOTF) que opera na região do Infravermelho próximo (800 ¿ 1600 nm). A medida de rotação óptica no instrumento proposto é feita utilizando-se a razão entre os dois feixes difratados pelo AOTF (espectro de rotação óptica), a qual é proporcional ao ângulo de rotação da luz polarizada imposto pela amostra. O instrumento foi empregado na obtenção de espectros de rotação óptica na região NIR de sacarose, glicose, frutose e cânfora. Esses espectros são proporcionais às concentrações das espécies estudadas e curvas analíticas com bons coeficientes de correlação foram obtidas / Abstract: The two-dimensional correlation spectroscopy was used in this work as a tool for spectral variable selection in the near-infrared (NIR) region aiming the determination of the following quality parameters of gasoline: ethanol content, MON (Motor Octane Number) and RON (Research Octane Number). To achieve this objective, it was developed a flow system to automated the perturbation by concentration. This system presents some advantages in relation to batch systems employed to the same purpose: the experiments are accomplished in a closed system; a greater velocity in the application perturbation can be obtained and the experiments are made in micro-scale. In another part, this work presents the construction of a spectropolarimeter based on the acousto-optic tunable filter (AOTF), which works on the near-infrared region (800 ¿ 1600 nm). The measure of optical rotation on the instrument is made using the ratio between two diffracted beams by the AOTF (optical rotation spectrum), which is proportional to the rotation angle of the polarized light imposed by the sample. The instrument was applied in the investigation of NIR optical rotation spectra of sucrose, glucose, fructose and camphor. These spectra are proportional to the concentration of species studied and analytical curves with good correlation coefficients were obtained. / Doutorado / Quimica Analitica / Doutor em Ciências

Abstract In this thesis, the magnetic resonance and magneto-optical rotation parameters are studied in single-layer carbon systems of two different dimensionalities. Based on electronic structure calculations, the spectral parameters are predicted for both extended (2D) and finite, molecular (0D) systems consisting of pure sp²-hybridised pristine graphene (G), as well as hydrogenated and fluorinated, sp³-hybridised graphene derivatives, graphane (HG) and fluorographene (FG), respectively. Nuclear magnetic resonance (NMR) parameters are calculated for G, HG and FG systems at their large-system limit. For their 0D counterparts, graphene flakes, qualitative spectral trends are predicted as functions of their size and perimeter type. The last group of studied carbon systems consists of 2D graphenes containing spin-1/2 paramagnetic defects. Electron spin resonance (ESR) parameters and paramagnetic NMR shieldings are predicted for four different paramagnetic systems, including the vacancy-defected graphane and fluorographene, as well as graphene with hydrogen and fluorine adatoms. The magneto-optic properties of G and HG flakes are studied in terms of Faraday optical rotation and nuclear spin optical rotation parameters, to investigate the effects of their finite size and also the different level of hydrogenation. All the different investigated parameters displayed characteristic sensitivity to the electronic and atomic structure of the studied graphenes. The parameters obtained provide an insight into the physics of these 0D and 2D carbon materials, and encourage experimental verification.