published_or_final_version / Chemistry / Master / Master of Philosophy

Medidas eletroquímicas, incluindo cronoamperometria, voltametria cíclica, procedimentos eletroquímicos de envelhecimento de filmes superficiais, espectroscopia de absorção no infravermelho, espectroscopia Raman in situ e ex situ, incluindo o efeito SERS, foram empregados no estudo da redução eletroquímica de íons perclorato a cloreto sobre eletrodo de estanho. Solução de perclorato de sódio 0,5 mol L-1 foi utilizada como eletrólito. Observou-se que a concentração máxima de cloreto produzida em decorrência da redução de íons perclorato (5,0 x 10-5 mol L-1) ocorre na região de potenciais localizada no final da contribuição de corrente da dupla camada elétrica e início da região de desprendimento de hidrogênio. A concentração limite de cloreto é decorrente do estabelecimento de um equilíbrio entre os íons cloreto na solução e cloreto adsorvido que inativa os sítios na superfície, impedindo a continuidade do processo. Programas de perturbação de potencial visando a eletromodificação da superfície do estanho foram aplicados, com o objetivo de verificar a ocorrência de mudanças das propriedades eletrocatalíticas dessas superfícies. A influência das variáveis, velocidade da perturbação, tempo de duração e limites de potencial na cinética de redução de perclorato e na concentração máxima de cloreto foi estudada. Em todos os casos a concentração máxima de cloreto detectada na solução foi de 2,0 x 10-5 mol L-1, exceto no tratamento de ativação eletroquímica quando essa concentração atinge 5,0 x 10-5 mol L-1. A influência da presença de óxidos superficiais, temperatura e agitação da solução, pH, e tempo de polarização no processo de redução de perclorato também foi avaliada. Concluiu-se que (i) a presença de óxidos catalisa o processo de redução; (ii) a influência da temperatura é significativa a 70 °C; (iii) a agitação e o pH da solução não exercem influência na concentração máxima de cloreto produzida e (iv) a concentração máxima de cloreto estabiliza-se após cerca de 150 minutos de polarização. / Electrochemical measurements including chronoamperometry, cyclic voltammetry, film surface electrochemical ageing procedures, FTIR and Raman spectroscopy including the SERS effect were carried out in order to study the electrochemical reduction of perchlorate ions at tin electrodes. Sodium perchlorate solution 0.5 mol L-1 was employed as electrolyte. It was observed that maximum chloride concentration produced by the perchlorate reduction (5.0 x 10-5 mol L-1), takes place within a potential range comprising the negative side of de double layer region and the positive side of the hydrogen evolution region. The upper limit of chloride concentration occurs due to the establishment of an equilibrium between the chloride ions in solution and the adsorbed chloride ions that blocks the surface sites where the reduction process takes place. In order to electromodify the tin surface, the electrode was subjected to perturbing potential programs, aiming to evaluate changes in the electrocatalytic properties of the modified sufaces. The influence of the experimental variables perturbation sweep rate as well as perturbation time and potential limits on the perchrolate reduction kinetic and on the maximum chloride concentration was studied. Except to the activation treatment, the maximum chloride concentration was 2.0 x 10-5 mol L-1 for all the applied perturbation programs. The influence of the oxides on the electrode surface, stirring, temperature, pH and polarization time on the reduction process was evaluated too. It was shown that (i) the presence of oxides on the electrode surface favors the reduction reaction; (ii) there is significant influence of temperature at 70 °C; (iii) pH and stirring the solution exerts no influence on the maximum chloride concentration produced and (iv) the maximum chloride concentration produced by electroreduction is reached after 150 minutes.

Este trabalho tem por objetivo o desenvolvimento e otimização de uma cavidade laser self-Raman de aplicações oftalmológicas. A cavidade laser é do tipo estado sólido bombeada longitudinalmente por um diodo laser infravermelho. A cavidade é dita self-Raman pois um cristal Raman intracavidade faz o papel de meio ativo e deslocador Raman. Esse tipo de configuração é extremamente vantajoso uma vez que promove uma redução dimensional, de custos e de perdas intracavidade. Outro elemento não linear intracavidade é responsável pela geração do segundo harmônico da primeira linha Stokes gerada pelo cristal Raman. Dessa maneira obtém-se radiação em 586.5 nm da cavidade laser, o que corresponde a porção amarela do espectro eletromagnético. Essa região amarelo-alaranjada do espectro é de muita importância e aplicabilidade na indústria, ciências e na medicina. Na oftalmologia, em particular, é de enorme interesse que se construa um laser amarelo para fotocoagulação da retina uma vez que há muito tempo sabe-se que essa porção do espectro possui uma absorção desprezível pela Xantofila, cromóforo abundantemente presente na mácula. A mácula é a porção da retina responsável pela visão central e não deve absorver radiação laser pois isso seria desastroso para o paciente. / The objective of this work is the development and optimization of a self-Raman laser cavity with ophthalmological applications. The laser cavity is a longitudinally diode pumped solid state laser. The laser cavity is so-called self-Raman because an intracavity Raman crystal plays a role as an active media and Raman shifter. This type of configuration is extremely advantageous because it promotes a reduction in costs, dimensions and intracavity losses. Another non linear intracavity element is responsible for the second harmonic generation of the first Stokes line generated by the Raman crystal. Thereby one obtains 586.5 nm radiation coming out of the laser cavity, a wavelength in the yellow portion of the electromagnetic spectra. This yellow-orange range of the spectra is of great importance because and has many and increasingly applications in science, industry and medicine. Particularly in ophthalmology, a yellow laser for retina photocoagulation is of great interest once it is well known that this portion of the spectra is negligibly absorbed by the Xanthophylls, pigment strongly present at the macula. The macula is the portion of the retina responsible for the central vision and because of this laser absorption would be disastrous for the patients eye.

Liang Tak-keung. / "June 2004." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

Thesis (Ph. D.)--University of Hong Kong, 2007. / Title proper from title frame. Also available in printed format.

Two colour pumping was used to investigate the short-pulse technique of Multifrequency Raman Generation (MRG) in the transient regime of Raman scattering. In the course of this study we have demonstrated the ability to generate over thirty Raman orders spanning from the infrared to the ultraviolet, investigated the dependence of this generation on the pump intensities and the dispersion characteristics of the hollow-fibre system in which the experiment was conducted, and developed a simple computer model to help understand the exhibited behaviours. These dependence studies have revealed some characteristics that have been previously mentioned in the literature, such as the competition between MRG and self-phase modulation, but have also demonstrated behaviours that are dramatically different than anything reported on the subject. Furthermore, through a simple modification of the experimental apparatus we have demonstrated the ability to scatter a probe pulse into many Raman orders, generating bandwidth comparable to the best pump-probe experiments of MRG. By using a numeric fast Fourier transform, we predict that our spectra can generate pulses as short as 3. 3fs, with energies an order of magnitude larger than pulses of comparable duration that are made using current techniques.

Two colour pumping was used to investigate the short-pulse technique of Multifrequency Raman Generation (MRG) in the transient regime of Raman scattering. In the course of this study we have demonstrated the ability to generate over thirty Raman orders spanning from the infrared to the ultraviolet, investigated the dependence of this generation on the pump intensities and the dispersion characteristics of the hollow-fibre system in which the experiment was conducted, and developed a simple computer model to help understand the exhibited behaviours. These dependence studies have revealed some characteristics that have been previously mentioned in the literature, such as the competition between MRG and self-phase modulation, but have also demonstrated behaviours that are dramatically different than anything reported on the subject. Furthermore, through a simple modification of the experimental apparatus we have demonstrated the ability to scatter a probe pulse into many Raman orders, generating bandwidth comparable to the best pump-probe experiments of MRG. By using a numeric fast Fourier transform, we predict that our spectra can generate pulses as short as 3. 3fs, with energies an order of magnitude larger than pulses of comparable duration that are made using current techniques.

The strong electromagnetic field that is induced at the surface of a plasmonic nanoparticle can be utilized for many important applications, including spectroscopic enhancement and electromagnetic waveguides. The focus of this thesis is to study some of the properties of induced plasmonic fields around metal nanoparticles. Current methodologies for fabricating nanoparticles are discussed, including lithography and colloidal synthesis. This dissertation includes studies on plasmonic driven nanoparticle motion of surface supported gold nanoprisms from a substrate into solution via a femtosecond pulse. The mechanism of particle motion is discussed and the stability of the unprotected nanoprisms in solution is studied. Fundamental plasmonic near-field coupling between two plasmonic nanoparticles is also examined. Experimental results using electron beam lithography fabricated samples are used to explicitly describe the plasmonic coupling between dimers as a function of the nanoparticle size, shape, and orientation. These variables are systematically studied and the dependence is compared to mathematically derived functional dependencies in order to model and predict the effects of plasmonic coupling. As an extension, the coupling between plasmonic nanoparticles is shown in a common application, surface enhanced Raman scattering. The final chapter is devoted to an investigation of the nature of nanocatalysis, homogeneous and heterogeneous, for several reactions using metal nanoparticles.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references (leaves 123-128). Also available on the Internet.

Thesis (M. Phil.)--University of Hong Kong, 2001. / Includes bibliographical references (leaves 80-85).