Dissertations / Theses on the topic 'Nitroanilina'

Orientador: Sergio de Toledo
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba
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Resumo:A doença periodontal tem como fator etiológico primário o acúmulo de biofilme dental que pode ser favorecido por uma grande variedade de fatores retentivos locais, como por exemplo, próteses parciais removíveis, que podem alterar a progressão e o risco da doença. O objetivo deste trabalho foi avaliar o efeito do uso de próteses parciais removíveis (PPRs) sobre as condições clínicas periodontais e alterações qualitativas do biofilme dos dentes suportes por um período de dois anos. Foram selecionados 13 pacientes com média de idade de 55,8 (±14,8) anos, de acordo com os seguintes critérios: parcialmente dentados e que não utilizaram PPRs nos últimos 18 meses previamente ao início do estudo, sem envolvimento sistêmico e não fumantes. Os seguintes parâmetros clínicos periodontais foram avaliados: Índice de Placa de Silness & Löe (1964) ¿ IPL, o Índice Gengival de Löe (1967) ¿ IG, profundidade de sondagem ¿ PS, recessão gengival - RG e Nível de inserção clínico ¿ NIC; medidos através de uma sonda periodontal eletrônica de pressão controlada (Florida Probeâ, Gainesville, FL, USA). A atividade de enzimas tipo tripsina no biofilme dental dos dentes suportes foi analisada por um teste enzimático (teste BAPNA). Os dados foram coletados em quatro períodos experimentais: T0 = antes da reabilitação protética, T6 = após 6 meses de uso, T18 ¿ 18 meses e T24 após 24 meses de uso continuado das próteses. Os resultados obtidos em todos os períodos (T0, T6, T18 e T24) foram respectivamente: valores medianos para IPL (1, 1, 1 e1) e IG (0, 0, 1 e 1), valores médios e desvio padrão para PS (2,3mm ±0,3; 2,28mm ±0,4; 2,17mm ±0,2 e 2,26mm ±0,3), RG (0,78mm ±0,7; 0,87mm ±0,7; 0,87mm ±0,7 e 0,95mm ±0,8), NIC (3,08mm ±0,8; 3,15mm ±0,9; 3,04mm ±0,9 e 3,21mm ±0,9) e teste BAPNA (5,479 nmol/mg de biofilme X min ±2,2; 6,22nmol/mg de biofilme X min ±2,9; 8,199 nmol/mg de biofilme X min ±2,7 e 13,852 nmol/mg de biofilme X min ±11,7). A análise estatística demonstrou diferença para o índice gengival entre os períodos T24 e T18 em relação ao T0 e do T24 para T6 (p<0,05) e também para o teste BAPNA entre os períodos T24 e T18 em relação ao T0 e do T24 para T6 (p<0,05) indicando aumento na atividade enzimática. Concluiu-se que a simples presença das próteses parciais removíveis, mesmo em pacientes com adequado controle de placa, foi capaz de alterar um parâmetro indicativo de inflamação gengival e a composição qualitativa do biofilme destes pacientes durante um período de dois anos de uso das próteses
Abstract: The dental biofilm is the primary etiological factor of the periodontal disease and its accumulation can be influenced by a great variety of local factors, such as removable partial dentures. The aim of this study was to evaluate the possible influence of the presence of removable partial dentures (RPDs) on the periodontal clinical parameters and in the dental biofilm of the connectors¿ teeth. Thirteen partially edentulous volunteers with a mean age of 55.8 (±14.8), without RPDs, no systemic diseases, no smokers were selected. The following clinical parameters were evaluated: Plaque Index (Silness & Löe, 1964) PI, Gingival Index (Löe, 1967) GI, Probing Depth - PD, Gingival Recession ¿ GR and Clinical Attachment Level ¿ CAL; PD, GR and CAL were obtained with an electronic computerized probe (Florida Probeâ, Gainesville, Fla, USA). The tripsin-like activity on the biofilm of the connectors¿ teeth was evaluated by an enzymatic test (BAPNA). The data were collected in four experimental periods: T0 = before the rehabilitation, T6 = six months after rehabilitation, T18 = eighteen months and T24 = 24 months of continuous use of RPDs. The clinical measurements in T0, T6, T18 and T24 were respectively: median value for PI (1, 1, 1, 1) and GI (0, 0, 1, 1); mean value and standard deviation for PD (2.3mm ±0.3; 2.28mm ±0.4; 2.17mm ±0.2 e 2.26mm ±0.3), GR (0.78mm ±0.7; 0.87mm ±0.7; 0.87mm ±0.7 e 0.95mm ±0.8), CAL (3.08mm ±0.8; 3.15mm ±0.9; 3.04mm ±0.9 e 3.21mm ±0.9). For the trypsin-like activity in T0, T6, T18 and T24 the mean value and standard deviation were T0 ¿ 5.479nmol/mg of biofilm X min ±2.2, T6 ¿ 6.22nmol/mg of biofilm X min ±2.9, T18 ¿ 8.199 nmol/mg of biofilm X min ±2.7 and T24 ¿ 13.852 nmol/mg of biofilm X min ±11.7. Statistical analysis showed differences for GI for T18 and T24 compared to T0 and T24 compared to T6 (p<0.05) and the same was observed for BAPNA harboring differences for T24 and T18 compared to T0 and between T24 and T6. It was concluded that, even in patients with good plaque control, the presence of Removable Partial Dentures does altered the health status of periodontal tissues and the trypsin-like activity of dental biofilm over a period of two years of continuous use of RPDs
Doutorado
Periodontia
Doutor em Clínica Odontológica

The aim of this project was to investigate the cyclisation reactions of some o-nitroaryl derivatives of amino acids, with a view to the synthesis of potentially biologically active heterocyclic compounds. Chapter one is concerned with an overview of the synthesis of heterocyclic N-oxides, mainly via the cyclisations of ortho-substituted nitroaromatics. Firstly, the properties of heterocyclic N-oxides are considered, then both reductive and non-reductive methods of their synthesis by cyclisation reactions are explored. After a discussion of intramolecular condensations leading to cyclisation, the possibilities for alternative mechanisms for these reactions are deliberated. Chapter Two begins with an introduction to the specific cyclisation reactions of o-nitroaryl- and 2, 4-dinitrophenyl-amino acids. The preparation and cyclisation reactions of o-nitrophenyl derivatives of amino acid esters are then described with emphasis on the implications for the mechanism of these cyclisation reactions. Chapter Three discusses the related cyclisations of N-alkyl-o-nitroanilines which have no activating group (for example, an ester) on the N-alkyl chain. The mechanistic implications of this are explored, in the context of the cyclisations discussed in Chapter Two. In Chapter Four, the synthesis of benzimidazole and quinoxaline acyclic nucleoside analogues is briefly described. These have the potential to be biologically active compounds.

Die Elektrochemie und die Spektroelektrochemie von Nitroanilinen (ortho-, meta- und para- Isomere) und deren entsprechenden Diaminoverbindungen (ortho-, meta- und para-Phenylendiamin) wurden an zwei verschiedenen Elektroden (Platin und Gold) und in zwei Elektrolytlösungen (saure und neutrale Perchloratlösung) untersucht. Die erhaltenen Messergebnisse wurden als Referenz für die spektroelektrochemische Untersuchung von Polyvinylaminen mit o- oder p- Nitroanilinsubstituenten verwendet. Es wurden außerdem spektroelektrochemische Untersuchungen mit anderen Polyvinylaminen, die das Wurster Kationradikal oder Stilbene als Substituenten enthalten, durchgeführt. Die oxidative und reduktive Elektrochemie von drei Nitroanilinisomeren wurde in neutraler (0.1 M KClO4) und saurer (0.1 M HClO4) wässriger Elektrolytlösung mit zyklischer Voltammetrie und oberflächenverstärkter Ramanspektroskopie (Surface Enhanced Raman Spectroscopy SERS) untersucht. Die zyklischen Voltammogramme, die mit einer Goldelektrode in saurer Elektrolytlösung für o- und p-Nitroanilin aufgezeichnet wurden, zeigten die Bildung von o- und p-Phenylendiamin beim Potenzialdurchlauf in kathodischer Richtung. In neutraler Elektrolytlösung ist die Situation anders und die Endprodukte der elektrochemischen Reduktion dieser Isomere sind o- und p- Amino-N-phenylhydroxylamin. Aus den zyklischen Voltammogrammen, die mit Gold- und Platinelektroden bei anodischem Potenzialdurchlauf für diese Isomere in saurer und neutraler Elektrolytlösung aufgezeichnet wurden, erhält man folgende Reihenfolge für die Lage der Oxidationspotentiale m-Nitroanilin > p-Nitroanilin > o-Nitroanilin. Eine Sauerstoff-Gold-Adsorbat- Streckschwingung wurde zwischen 400 und 430 cm-1 in den SER-Spektren der drei isomeren Nitroaniline in beiden Elektrolytlösungen bei positiven Elektrodenpotenzialen beobachtet. Das SERS-Experiment zeigte auch eine senkrechte Orientierung der adsorbierten Nitroaniline zur Oberfläche der Goldelektrode. Für die isomeren Phenylendiamine wurde in beiden Elektrolytlösungen und mit beiden Elektroden im anodischen Durchlauf das gleiche Verhalten beobachtet. Das beim Ein- Elektronenübergang erhaltene Oxidationsprodukt (Radikalkation) reagiert im Fall von o- und m- Phenylendiamin über eine C-N-Kopplung mit einem weiteren Radikal zum Dimer (1.Schritt der Elektropolymerisation). p-Phenylendiamin wird nach dem ECE-Mechanismus (E = Elektronentransfer, C = chemische Reaktion) oxidiert, wobei die Ladungsübertragung in zwei Schritten erfolgt, gekoppelt mit Säure-Base-Reaktionen, was zur Bildung des Diimin führt. Aus den SERS-Messungen kann man schlussfolgern, dass m- und p-Phenylendiamin waagerecht zur Metalloberfläche über den Benzenring und die Stickstoffatome adsorbiert sind. Die Adsorption von o-Phenylendiamin erfolgt über die Stickstoffatome und mit schräger Orientierung zur Metalloberfläche. Die zyklischen Voltammogramme, die mit einer Goldelektrode in saurer und neutraler Elektrolytlösung von den Polyvinylaminen mit Nitroanilinsubstituenten aufgenommen wurden, zeigen dasselbe Verhalten wie Nitroanilinmonomere beim Potenzialdurchlauf in kathodischer Richtung. Die für diese Polymere im anodischen Durchlauf erhaltenen Zyklovoltammogramme unterscheiden sich von denen für die Monomere. Die Zahl der Adsorptionsplätze und die Adsorptionsstärke der Polyvinylamine verändern sich in Abhängigkeit vom Elektrodenpotential, vom Prozentsatz und der Art des aromatischen Substituenten am Polymerrückgrat und vom pH-Wert der Lösung
The electrochemistry and spectroelectrochemistry of nitroanilines (ortho, meta, and para isomers) and their respective amino compounds (ortho-, meta- and paraphenylenediamines) have been investigated at two different electrodes (platinum and gold) and in two different electrolyte solutions (acidic and neutral perchlorate). The results of these investigations were used as a reference for the spectroelectrochemistry of polyvinylamines containing o- or p-nitroaniline substituents. Spectroelectrochemical investigations of polyvinylamine containing Wurster radical cation or stilbene as a substituent were also carried out. The oxidative and reductive electrochemistry of the three isomeric nitroanilines has been studied in neutral (0.1 M KClO4) and acidic (0.1 M HClO4) aqueous electrolyte solutions with cyclic voltammetry and Surface Enhanced Raman Spectroscopy (SERS). The cyclic voltammograms recorded with a gold electrode in acidic electrolyte solution showed formation of o- and p-phenylenediamine in the negative going potential scan for o- and pnitroaniline respectively. In neutral electrolyte solution the situation is different and the final products of electrochemical reduction of these isomers are o- and p-amino-Nphenylhydroxylamine. The order of increasing electrochemical oxidation potential is mnitroaniline > p-nitroaniline > o-nitroaniline as observed from cyclic voltammograms recorded with a gold and platinum electrodes and in the positive going potentials scan for these isomers in acidic and neutral electrolyte solutions. An oxygen-gold adsorbate stretching mode was detected between 400 to 430 cm-1 in SER-spectra of the three isomeric nitroanilines in both electrolyte solutions at positive electrode potentials. The SERS experiments showed also a perpendicular orientation of adsorbed nitroanilines on a gold electrode with respect to the metal surface. General trends are observed in the anodic scans of isomeric phenylenediamines at both electrodes and in both electrolyte solutions. The one-electron electrochemical oxidation product (radical cation) in case of o- and m-phenylenediamine go into fast C-N coupling between radicals to form dimers (the first step of electropolymerization). The pphenylenediamine is oxidized according to an ECE mechanism (E = electron transfer reaction, C = chemical reaction), which involved two charge transfer steps coupled with acidbase reactions to form diimine. As we deduced from SERS measurements, m- and p-phenylenediamine adsorbed in flat orientation with respect to the metal surface via benzene ring and nitrogen atoms, respectively. o-Phenylenediamine adsorption is taking place via nitrogen atoms and with tilted orientation with respect to the metal surface. The cyclic voltammograms recorded with a gold electrode in acidic and neutral electrolyte solutions of polyvinylamines containing o- or p-nitroaniline substituents exhibit the same features like nitroaniline monomers in the negative going potentials scan. The result observed in the anodic scan for these polymers are different from those observed for monomers. Adsorption site and strength of the polyvinylamine polymer varies according to the applied electrode potential, percentage and type of the aromatic substituent at the polymer backbone, and the pH of the medium

This paper describes the development of simple and efficient electrochemical sensors, based on multi-walled carbon nanotubes (MWNCT) chemically modified with nitroanilines (NA), and electroreduced products. These sensors were developed for the simultaneous determination of uric acid (UA), ascorbic acid (AA) and dopamine (DO). NAs, on the MWCNT-modified glassy carbon, suffer reduction, where the nitro group is reduced irreversibly generating the redox couple hydroxylamine/nitroso, originating the chemically modified electrode (CME). The techniques employed for this work were cyclic voltammetry and chronoamperometry, which were used to study the electrochemical behavior of the modified electrode, for detection of analytes in biological samples, obtaining the kinetic parameters and analytical characterization of the platform. In order to assess the effect of the nitro group position in the series of nitroanilines, the isomers ortho-nitroaniline (oNA) and meta-nitroaniline (mNA) were evaluated for sensitivity and response toward AA and UA detection, following the same procedure applied for para-nitroaniline (pNA), which showed the highest current variation, indicating greater effectiveness. The chronoamperometric studies were used, in order to obtain more information about the redox process between AA and the functionalized platforms, since this proved to be a catalytic process. Thus, by means of graphs and Cottrell equation, it was possible to obtain values for the apparent diffusion coefficient (DAA) and the catalytic constant (kcat) for the reaction with AA. The values of kcat and DAA determined for AA were 3.83 x 10-6 cm-2 s-1 and 1.879 x 106 M-1 s-1, respectively. The amperometric sensor allowed the determination of AA, DO and UA. The following figures of merit were obtained: for AA: linear range 5 to 80 M and detection limit of 9.84 M; for DO, linear range of 5 to 80 M and detection limit of 2.13 M and, for UA, linear range of 5 to 80 M and detection limit of 2.30 M. From the obtained performance, the use of nanostructured platform composed of MWNCT and activated pNA is justified, mainly for the simultaneous determination of AA, DO and UA. The comparative study of the isomers showed that the pNA and mNA chemically modified sensors showed increased sensitivity toward the analytes AA and UA, compared to oNA. The study with diazonium salts showed that para-nitroaniline adheres to the surface of the electrode by grafting.
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Neste trabalho é descrito o desenvolvimento de um sensor eletroquímico simples e eficiente à base de nanotubos de carbono de paredes múltiplas (do inglês MWNCT) e quimicamente modificado com nitroanilinas polimerizadas e seus produtos de redução, no intuito de desenvolver um sensor para determinar simultaneamente ácido úrico (AU), ácido ascórbico (AA) e dopamina (DO). As nitroanilinas sobre o MWNCT depositado em carbono vítreo, são reduzidas, gerando o par redox hidroxilamina/nitroso, originando o eletrodo quimicamente modificado (EQM). As técnicas empregadas para a realização deste trabalho foram voltametria cíclica e cronoamperometria, as quais foram utilizadas para estudar o comportamento eletroquímico dos eletrodos modificados, detecção dos analitos em amostras biológicas, obtenção dos parâmetros cinéticos e caracterização analítica da plataforma. Com o intuito de verificar a influência da posição do grupo nitro na série das nitroanilinas, os isômeros orto-nitroanilina (oNA) e meta-nitroanilina (mNA) foram avaliados em relação à sensibilidade e resposta para a detecção de AA e AU, seguindo a mesma metodologia de modificação e ativação do sensor modificado com para-nitroanilina (pNA), que apresentou maior variação de corrente, indicativa de maior sensibilidade. Os estudos cronoamperométricos foram realizados com o objetivo de obter maiores informações acerca dos processos redox entre AA e a plataforma funcionalizada, uma vez que este demonstrou ser um processo catalítico. Assim, por meio de gráficos e equações de Cottrell, foi possível obter os valores aparentes para o coeficiente de difusão (DAA) e a constante catalítica (kcat) da reação para o AA. Os valores do DAA e de kcat, determinados para AA, foram de 3,83 x 10-6 cm-2 s-1 e 1,88 x 106 M-1 s-1, respectivamente. O sensor amperométrico apresentou como figuras de mérito relativas à determinação de AA, DO e AU, os seguintes valores: em relação ao AA apresentou faixa linear de 5 a 80 M e limite de detecção 9,84 M; para DO, faixa linear de 5 a 80 M e limite de detecção de 2,13 M e, em relação a AU, faixa linear de 5 a 80 M, e limite de detecção de 2,30 M. A partir do desempenho obtido, justifica-se a utilização da plataforma nanoestruturada fundamentada em MWNCT e pNA ativado como sensor principalmente para a determinação simultânea de AA, DO e AU. O estudo comparativo entre os isômeros evidenciou que os sensores formados por pNA e mNA mostraram maior sensibilidade frente aos analitos AA e AU quando comparados com a plataforma formada por oNA. O estudo com os sais de diazônio, utilizando os mesmos parâmetros da oxidação e ativação, mostrou que a para-nitroanilina adere a superfície do eletrodo por grafitagem.

Dissertação (mestrado)—Universidade de Brasília, Instituto de Física, Programa de Pós-Graduação em Física, 2015.
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O estudo apresentado neste trabalho de dissertação é importante para conhecer as propriedades eletrônicas de algumas moléculas orgânicas que são de interesse em Física, Química e Química Industrial; tais como o benzeno (Bz), a anilina (An) e as nitroanilinas (NAn). Esses sistemas quando ionizados podem levar a espécies metaestáveis resultando em compostos intermediários de grande reatividade. Fizemos cálculos de estrutura eletrônica utilizando o programa Gaussian 09, partindo das espécies neutras para duplamente ionizadas. Esses cálculos mostraram que há desestabilização de algumas ligações interatômicas dos sistemas dicatiônicos em relação aos sistemas neutros, dando origem ao processo de fragmentação molecular. Nossos estudos revelaram modificações nos comprimentos da ligação, ordens de ligação (BO) e distribuição de carga em compostos aromáticos quando comparamos os sistemas duplamente ionizados com os neutros. Também investigamos a possibilidade de formação de dímeros motivados por resultados experimentais de fotofragmentação das NAns, obtidos recentemente em nosso grupo de pesquisa, na linha PGM (Plane Grating Monochromator) do Laboratório de Luz Síncrotron do Canadá (Canadian Light Source-CA). Os experimentos de espectroscopia de massa por tempo de voo mostraram assinaturas de metaestabilidade em seus espectros de coincidência elétron-íon-íon (PEPIPICO), as quais não podem ser explicadas pela fragmentação direta de moléculas isoladas. Sabendo disso, realizamos cálculos de estrutura eletrônica com otimização de geometria nos monômeros neutros e dicatiônicos e nos dímeros dicatiônicos, com o objetivo principal de propor um modelo teórico de fotofragmentação via cálculo de estrutura eletrônica. Empregamos o método DFT para a determinação de índices de ligação de Wiberg e cargas (CHELPG), utilizamos o funcional e o sistema de base UB3LYP/aug-cc-pVDZ para os cálculos dos monômeros. Já para os dímeros, usamos o funcional corrigido de longo alcance UwB97X-D/aug-cc-pVDZ de Head-Gordon. A partir da função de onda calculada anteriormente no Gaussian 09, determinamos as densidades eletrônicas e analisamos os mapas de contorno das densidades eletrônicas dos monômeros utilizando o programa Chemissian. As informações topológicas das ligações químicas entre pares de átomos, assim como, seus pontos críticos de ligação (BCP) foram investigadas utilizando a Teoria Quântica de Átomos em Moléculas (QTAIM). Essas grandezas foram esquematizadas utilizando o programa AIMAll. Concluímos que os monômeros dicatiônicos, apresentam maiores estiramentos das ligações nos pares de átomos do Benzeno r(C1-C2) e r(C4-C5); da Anilina r(C2-C3) e r(C7-C2); da Ortonitroanilina r(C2-C3), r(C3-C4), r(C3-N9) e r(C7-C2); da metanitroanilina r(C4-C5), r(C4-N9) e r(C7-C2) e por último da paranitroanilina r(C2-C3), r(C4-C5), r(C5-C6), r(C5-N9) e r(C7-C2). Sendo que o processo de transferência de carga e distribuição eletrônica nas nitroanilinas acontece na região do grupo doador de elétrons –NO2. Nos sistemas diméricos encontramos que os pontos críticos de ligação nos grupos –NH2 e –NO2 estabilizam suas densidades de cargas aproximadamente em 0.3 e/03 e 0.5 e/03 dando origem a ligações intermoleculares, o que estabiliza os sistemas An2+, oNAn2+, mNAn2+ e pNAn2+.
The study presented in this dissertation is important to know the electronic properties of some organic molecules that are of interest in Physics, Chemistry and Industrial Chemistry; such as benzene (Bz), aniline (An) and the nitroanilines (NAn). These systems when ionized can lead to metastable species resulting in intermediate compounds of great reactivity. We made electronic structure calculations using the Gaussian 09 program, starting from the neutral species to doubly ionized. These calculations showed that there is destabilization of some of the interatomic bonds in dicationics in relation to neutral systems, giving rise to molecular fragmentation process. Our studies revealed changes in the bond length, the bond order (BO) and the charge distribution in aromatic compounds when comparing the doubly ionized systems with neutral. We also investigated the possibility of dimer formation motivated by photofragmentation experimental results of nitroaniline, recently obtained in our research group, in beamline PGM (Plane Grating Monochromator) of Canadian Light Source Laboratory - CA. Time of Flight Mass spectroscopy experiments showed metastability signatures in the coincidence spectra electron-ion-ion (PEPIPICO), which cannot be explained by direct fragmentation of single molecules. Knowing this, we performed electronic structure calculations with geometry optimization in neutral and dicationic monomers and dicationic dimers, with the main objective to propose a theoretical model of photofragmentation via electronic structure calculation. We employ DFT method for determining the bonding index of Wiberg and charges (CHELPG), we use the functional and the base system UB3LYP / aug-cc-pVDZ for calculation of the monomers. As for the dimers, we use the corrected functional long-range UwB97X-D / aug-cc-pVDZ of Head-Gordon. From the wave function calculated earlier in Gaussian 09, we determine the electronic densities and analyze the contour maps of the electronic densities of the monomers using Chemissian program. The topological information of the chemical bonds between pairs of atoms, as well as its bond critical point (BCP) were investigated using the Quantum Theory of Atoms in Molecules (QTAIM). These quantities were outlined using the AIMAll program. We conclude that dicationic monomers have larger stretches of the bonds in the atoms pairs of benzene r(C1-C2) and r(C4-C5); of aniline r(C2-C3) and r(C2-C7); of ortho-nitroaniline r(C2-C3) r(C3 -C4) r(C3-N9) r(C2-C7); of meta-nitroaniline r(C4-C5), r(C4-N9) and r(C2-C7) and finally the para-nitroaniline r(C2-C3) r(C4-C5), r(C5-C6) r(C5 -N9) and r(C2-C7). Since the charge transfer process and the electronic distribution in nitroanilines happens in the electrons donor group region -NO2. In dimeric systems we found that the critical points in bond groups -NH2 and -NO2 stabilize their charge densities approximately in 0.3 e/03 and 0.5 e/03 resulting in intermolecular bonds, which stabilizes An2+, oNAn2+, mNAn2+ and pNAn2+.

Most microbial activity in nature takes place at interfaces where redox discontinuities are present. Organic pollutants in groundwater encounter oxic/anoxic interfaces when they emerge to surface water bodies or volatilize above the plume. Such oxic/anoxic interfaces are key habitats for aerobic bacteria and are in turn created by the bacteria that degrade organic electron donors. In the absence of biodegradation, synthetic pollutants can migrate from the plume and impact a variety of receptors. The aims of our study were to determine whether microbes at oxic/anoxic interfaces can use synthetic chemicals as electron donors and protect the overlying vadose zone or surface water from groundwater pollutants. The approach was to design columns representing the interfaces and measure activities of the microbial communities responsible for the biodegradation of synthetic compounds.Taken together the above studies established clearly that contaminants recalcitrant under anaerobic conditions but degradable under aerobic conditions can be biodegraded at the narrow oxic/anoxic interface resulting in the protection of the overlying soil or water. The findings provide the basis for new approaches to natural attenuation that can serve to dramatically reduce the cost of bioremediation actions. Synthetic chemicals are widespread in the environment because of their extensive use in industry. These chemicals were recalcitrant until their microbial degradation pathways evolved. Currently the biodegradation pathways of many synthetic chemicals are known and serve as the basis for bioremediation strategies. The second part of the research described here involved discovery of the aerobic degradation pathway of a dye additive: 4-nitroaniline (4NA). Annotation of the whole genome sequence coupled with assays and supported with cloned enzymes revealed that the 4NA biodegradation pathway contains two monooxygenase steps prior to ring cleavage. Because nitroaniline degradation was not previously understood our work advanced the understanding of metabolic diversity in degradation of amino and nitro compounds by providing enzymes with unique activities.

Pantothenate-p-nitroanilide has been synthesized for use as a substrate in a continuous spectrophotometric assay of pantetheinase activity monitoring absorbance at 41 0 nm. Pantothenate-p-nitroanilide is a crystalline compound with a molecular weight of 338.0 and a melting point of 146-149°C. Use of this substrate in the described assay is suitable for enzyme activity determination in high protein content media such as blood serum. Serum pantetheinase activity was determined for rats of varying pantothenate nutriture. Rats with mildly (but significantly, p

In this study, the effect of compatibilizers on the gas separation performance of polycarbonate (PC) membranes was investigated. Membranes were prepared by solvent evaporation method. They were characterized by single gas permeability measurements of O2, N2, H2 and CO2 as well as scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and Fourier transform infrared spectrometry (FTIR). Membranes containing 0.5 to 10 w% p-nitroaniline (pNA) were prepared to study the effect of compatibilizer concentration on the membrane performance. Permeabilities of all gases decreased but selectivities increased with pNA concentration. The membranes with 5 w% pNA showed a selectivity of 114.5 for H2 over N2, 53.9 for CO2 over N2 and 13.4 for O2 over N2 at room temperature, whereas, the H2/N2, CO2/N2 and O2/N2 selectivities for pure PC membranes were 43.5, 20.6 and 5.6, respectively. The N2 permeabilities through pure PC membrane and 5 w% pNA/PC membrane were 0.265 and 0.064 barrer, respectively. The glass transition temperature of the membranes decreased with increasing pNA concentration. FTIR spectra showed that the peaks assigned to nitro and amine groups of pNA shifted and/or broadened. The DSC and FTIR results suggested an interaction between PC and pNA. The effect of type of compatibilizer was also studied. The compatibilizers were 4-amino 3-nitro phenol (ANP), Catechol and 2-hydroxy 5-methyl aniline (HMA). Similar to membranes prepared with pNA, membranes prepared with these compatibilizers had a lower permeability and glass transition temperature but higher selectivity than pure PC membranes. Their FTIR spectra were also indicated a possible interaction between PC and compatibilizer. In conclusion, PC/compatibilizer blend membranes for successful gas separation were prepared. Low molecular weight compounds with multifunctional groups were found to effect membrane properties at low concentration range, 0.5-5 w%.

In der vorliegenden Arbeit wird die Synthese und Charakterisierung von chiralen prolylfunktionalisierten Farbstoffen vorgestellt. Als chromophore Schlüsselverbindungen wurden Nitroaniline aber auch größere push-pull pi-Systeme wie Schiffsche Basen, Azofarbstoffe und Merocyanine gewählt. Im Fokus dieser Arbeit stehen dabei deren solvatochrome Eigenschaften, pH-Sensitivität sowie mögliche Wechselwirkung mit Biomolekülen und verschiedenen An- und Kationen. Zusätzlich erfolgten Umsetzungen ausgewählter prolylfunktionalisierter chromophorer Bausteine zu Estern und Amiden. Der Einfluss des Prolylbausteins auf das im Festkörper ausgebildete Wasserstoffbrückenbindungsmusters wurde über Einkristallröntgenstrukturanalysen untersucht und nach der Graph Set Methode von Etter klassifiziert. Neben der Einkristallröntgenstrukturanalyse erfolgte die weitere Untersuchung der Festkörpereigenschaften mit Hilfe von UV/Vis- sowie NMR-spektroskopischen Methoden. Das solvatochrome Verhalten der prolylfunktionalisierten Verbindungen wurde mittels multipler linearer Regressionsanalyse gemäß der LSER- (linear solvation energy relationship) Beziehung nach den Ansätzen von Kamlet-Taft und Catalán beschrieben und vergleichend interpretiert.

Cette étude avait pour objectif de développer un nouveau support photocatalytique pour des applications potentielles dans le domaine du traitement des eaux. Le choix s'est porté sur les nanotubes d'oxyde de titane (TiO2) et l'étude a plus particulièrement porté sur l'optimisation de leurs propriétés photocatalytiques vis-à-vis de la l'oxydation de solution aqueuse de composés azotés. Les nanotubes de TiO2 ont été préparés par anodisation électrochimique en faisant varier le potentiel appliqué, la durée d'anodisation, le pH et la viscosité du milieu électrolytique (milieu aqueux ou milieu glycérol), ainsi que la nature du substrat sur lequel étaient déposés ces nanotubes. Une fois anodisés, ces nanotubes amorphes et se présentant sous forme sous-stœchiométrique (O/Ti <2) ont été recuits à différentes températures afin d'obtenir des phases de TiO2 variées (anatase, anatase/rutile). Au cours de ces différentes étapes, les différents nanotubes obtenus ont été caractérisés morphologiquement et structurellement par analyses par diffraction des rayons X (DRX) et par microscopie électronique à balayage (MEB).L'activité photocatalytique de ces différents matériaux a été déterminée à partir des rendements de photodégradation d'un composé modèle, la 4-nitroaniline. Là aussi, différents facteurs ont été étudiés, à savoir le pH du milieu réactionnel, le type de lampe UV et les durées d'irradiation.Les résultats montrent que les performances photocatalytiques des nanotubes de TiO2 les meilleures sont obtenues lorsqu'ils sont déposés sur substrat de Ti massif, anodisés en solution aqueuse à 20 V et pendant 20 minutes, et recuits à 450 °C (structure anatase)
This study aimed to design a new photocatalytic support for potential uses in the field of water treatment. Titanium dioxide (TiO2) nanotubes were chosen and studied as a function of their photocatalytic properties towards nitrogenous compounds.TiO2 nanotubes were prepared by electrochemical anodization by varying the applied potential, anodization duration, pH and viscosity of the electrolytic medium (aqueous or glycerol medium), and by the nature of substrates where these nanotubes were deposited (titanium foil (Ti) or deposited on silicon (Ti / Si)). Once anodized, these amorphous and under-stoechiometric (O/Ti <2) were calcined at various temperatures in order to obtain different TiO2 phases (anatase or anatase/rutile). During these different steps, the whole nanotubes obtained were morphologically and structurally characterized par X-ray diffraction (XRD) and scanning electron microscopy (SEM). The photocatalytic activity of the different materials was determined from the photodegradation yields of a model compound, namely 4-nitroaniline. Here again, different factors were studied, such as pH of reaction medium, kind of UV lamps and irradiation durations. The results show that the best photocatalytic performances of TiO2 nanotubes were obtained when deposited on Ti foils, anodized in aqueous medium at 20 V and for 20 minutes, and calcined at 450 °C (anatase phase)

In der vorliegenden Arbeit wird die Synthese und Charakterisierung von chiralen 1,2- und 1,3-diolfunktionalisierten solvatochromen Chromophoren vorgestellt. Als chromophore Systeme wurden Nitroaniline, SCHIFFsche Basen, Azofarbstoffe und Merocyanine gewählt. Das solvatochrome Verhalten der diolfunktionalisierten Verbindungen wurde mittels LSER (linear solvation energy realtionship) unter Verwendung der Lösungsmittelparameter nach KAMLET-TAFT und CATALÁN quantifiziert. Der Einfluss der Diolfunktion auf die Kristallstruktur der Nitroanilinderivate wurde über Einkristallröntgenstrukturanalyse untersucht und nach der Graph Set Methode von ETTER beschrieben. Es erfolgte eine Kondensation ausgewählter diolfunktionalisierter Bausteine mit verschieden substituierten Arylboronsäuren. Ein besonderes Augenmerk wurde auf den Einfluss des Boratoms und der Ringgröße des resultierenden Boronsäureesters, auf das solvatochrome Verhalten sowie das Reaktionsverhalten gegenüber Fluorid, Cyanid und Acetat gelegt. Weiterhin erfolgte die Verknüpfung von diolfunktionalisierten Chromophoren mit chromophoren Arylboronsäuren zu Bis-Chromophoren, deren Eigenschaften ebenfalls studiert wurden.

Developing new membrane morphologies and modifying the existing membrane materials are required to obtain membranes with improved gas separation performances. The incorporation of zeolites and low molecular-weight additives (LMWA) into polymers are investigated as alternatives to modify the permselective properties of polymer membranes. In this study, these two alternatives were applied together to improve the separation performance of a polymeric membrane. The polycarbonate (PC) chain characteristics was altered by incorporating p-nitroaniline (pNA) as a LMWA and the PC membrane morphology was modified by introducing zeolite 4A particles as fillers. For this purpose, pure PC and PC/pNA dense homogenous membranes, and PC/zeolite 4A and PC/pNA/zeolite 4A mixed matrix membranes (MMM) were prepared by solvent-evaporation method using dichloromethane as the solvent. The pNA and zeolite 4A concentrations in the casting solutions were changed between 1-5% (w/w) and 5-30% (w/w), respectively. Membranes were characterized by SEM, DSC, and single gas permeability measurements of N2, H2, O2, CH4 and CO2. They were also tested for their binary gas separation performances with CO2/CH4, CO2/N2 and H2/CH4 mixtures at different feed gas compositions. DSC analysis of the membranes showed that, incorporation of zeolite 4A particles into PC/pNA increased the glass transition temperatures, Tg, but incorporation of them to pure PC had no effect on the Tg, suggesting that pNA was a necessary agent for interaction between zeolite 4A and PC matrix. The ideal selectivities increased in the order of pure PC, PC/zeolite 4A MMMs and PC/pNA/zeolite 4A MMMs despite a loss in the permeabilities with respect to pure PC. A significant improvement was achieved in selectivities when the PC/pNA/zeolite 4A MMMs were prepared with pNA concentrations of 1 % and 2 % (w/w) and with a zeolite loading of 20 % (w/w). The H2/CH4 and CO2/CH4 selectivities of PC/pNA (1%)/zeolite 4A (20%) membrane were 121.3 and 51.8, respectively, which were three times higher than those of pure PC membrane. Binary gas separation performance of the membranes showed that separation selectivities of pure PC and PC/pNA homogenous membranes were nearly the same as the ideal selectivities regardless of the feed gas composition. On the other hand, for PC/zeolite 4A and PC/pNA/zeolite 4A MMMs, the separation selectivities were always lower than the respective ideal selectivities for all binary gas mixtures, and demonstrated a strong feed composition dependency indicating the importance of gas-membrane matrix interactions in MMMs. For CO2/CH4 binary gas mixture, when the CO2 concentration in the feed increased to 50 %, the selectivities decreased from 31.9 to 23.2 and 48.5 to 22.2 for PC/zeolite 4A (20%) and PC/pNA (2%)/zeolite 4A (20%) MMMs, respectively. In conclusion, high performance PC based MMMs were prepared by blending PC with small amounts of pNA and introducing zeolite 4A particles. The prepared membranes showed promising results to separate industrially important gas mixtures depending on the feed gas compositions.

The venom of cone snails (predatory marine molluscs of the genus Conus) has yielded a rich source of novel neuroactive peptides or “conotoxins”. Conotoxins are bioactive peptides found in the venom duct of Conus spp. Like other neuropeptides, conotoxins are expressed as propeptides that undergo posttranslational proteolytic processing. Peptides derived from propeptides are typically cleaved at a pair of dibasic residues (Lys-Arg, Arg-Arg, Lys-Lys or Arg-Lys) by proteases found in secretory vesicles. However, many precursor peptides contain multiple sets of basic residues, suggesting that highly substrate specific or differentially expressed proteases can determine processing outcomes. As many of the substrate-specific proteases remain unidentified, predicting new bioactive peptides from cDNA sequences is presently difficult, if not impossible. In order to understand more about the substrate specificity of conotoxin substrate-specific proteases a characterisation study of one such endoprotease isolated from the venom duct of Conus textile was undertaken. The C. textile mollusc was chosen as a good source from which to isolate the endoprotease for two reasons; firstly, these cone shells are found in great abundance on the Great Barrier Reef (Queensland, Australia) and are readily obtainable and secondly, a number of conotoxin precursors and their cleavage products have been previously identified in the venom duct. In order to purify the endoprotease an activity-guided fractionation protocol that included a para-nitroanilide (p-NA) substrate assay was developed. The p-NA substrate mimicked the cleavage site of the conotoxin TxVIA, a member of the C. textile O-superfamily of toxins. The protocol included a number of chromatographic techniques including ion exchange, size-exclusion and reverse-phased HPLC and resulted in isolation of an active protease, termed Tex31, to >95% purity. The purification of microgram quantities of Tex31 made it possible to characterise the proteolytic nature of Tex31 and to further characterise the O-superfamily conopeptide propeptide cleavage site specificity. Specificity experiments showed Tex31 requires a minimum of four residues including a leucine in the P4 position (LNKR↓) for efficient substrate processing. The complete sequence of Tex31 was determined from cDNA. A BLAST search revealed Tex31 to have high amino acid sequence similarity to the CAP (abbreviated from CRISP (Cysteine-rich secretory protein), Antigen 5 and PR-1 (pathogenesis-related protein)) superfamily and most closely related to the CRISP family of mammalian and venom proteins that, like Tex31, have a cysteine-rich C-terminal domain. The CAP superfamily is widely distributed in the animal, plant and fungal kingdoms, and is implicated in processes as diverse as human brain tumour growth and plant pathogenesis. This is the first report of a biological role for the N-terminal domain of CAP proteins. A homology model of Tex31 constructed from two PR-1 proteins, Antigen 5 and P14a, revealed the highly conserved and likely catalytic residues, His78, Ser99 and Glu115. These three amino acids fall within a structurally conserved N-terminal domain found in all CAP proteins. It is possible that other CAP proteins are also substrate-specific proteases. With no homology to any known proteases, Tex31 may belong to a new class of protease. The sequence alignment of five Tex31-like proteins cloned from C. marmoreus, C. litteratus, C. arentus, C. planboris, and C. omaria show very high sequence similarity to Tex31 (~80%), but only one weakly conserved serine residue was identified when the conserved residues of the new Tex31-like protein sequences were aligned with members of the CAP superfamily. Future work to identify members of catalytic diad or triad, e.g. by site-directed mutagenesis, will rely on the expression of active recombinant Tex31. In this study neither Escherichia coli nor Pichia pastoris expression systems yielded active recombinant Tex31 protein, possibly due to the number of cysteine residues hindering the expression of correctly folded active Tex31. This study has shown Tex31 to be highly sequence specific in its cleavage site and it is likely that this high substrate specificity has confounded previous attempts to identify the proteolytic nature of other CAP proteins. With the proteolytic nature of one member of the CAP protein family confirmed, it is hoped this important discovery may lead the way to discovering the role of other CAP family members.

Le present travail porte sur l'etude a l'aide du rayonnement synchrotron, des petites perturbations structurales dans les cristaux moleculaires, induites soit par une transition de phase, soit par une contrainte exterieure. En particulier, nous avons mesure avec une grande precision, les satellites du conducteur organique ttf-tcnq a partir desquels une analyse detaillee de la structure modulee accompagnant la transition de peierls a pu etre obtenue. Nous avons aussi etudie la reponse d'un cristal moleculaire a un champ electrique basse frequence. A cette fin, nous avons monte un dispositif experimental a la national synchrotron light source de brookhaven, etats-unis. Afin de mesurer des variations relatives d'intensites i/i aussi petites que 10##4 et des deplacements de raies de l'ordre de 10##3#o, nous avons perfectionne et mis au point la methode tres precise de modulation. Nous avons applique cette technique avec succes au cristal organique 2-methyle 4-nitroaniline (mna), connu pour ses proprietes optiques non lineaires exceptionnelles. Nous apportons ainsi des informations experimentales nouvelles sur la reponse dielectrique. En particulier, un premier modele de la reponse electronique de mna a un champ electrique a pu etre elabore a partir de la mesure des variations d'intensite i/i. De la mesure du decalage d'un grand nombre de raies, nous avons deduit le tenseur piezo-electrique complet de mna, domine par le coefficient d#1#114 pc/n, le plus grand jamais observe dans un cristal organique. Cette premiere etude fait l'objet a l'heure actuelle d'un developpement important, tant sur le plan experimental (mesures complementaires au synchrotron, sur mna et d'autres cristaux), que sur le plan theorique, ou un travail approfondi de modelisation de la reponse (lineaire et non lineaire) d'un cristal moleculaire a un champ electrique est en cours

碩士
明志科技大學
化學工程研究所
101
The adsorption for P-Nitroaniline(PNA) by modified multiwalled carbon nanotubes (MWCNTs) were investigated in this study. MWCNTs were modified by H2SO4/HNO3,CO2 and KOH. The influences of the functional groups of MWCNTs were observed by modified MWCNTs. After modification, the MWCNTs broke into smaller sizes with defects on their surface. From Raman spectral analysis , the degree of graphitization is the order of ACID-MWCNT > COM-MWCNT > KOH-MWCNT > CO2-MWCNT. From thermogravimetry analysis, the residual mass of samples is the order of KOH-MWCNT > COM-MWCNT >ACID-MWCNT >CO2-MWCNT. From BET analysis, the surface area of samples is the order of KOH-MWCNT > CO2-MWCNT > COM-MWCNT > ACID-MWCNT. The adsorption capacity of KOH-MWCNT, CO2-MWCNT, ACID-MWCNT and COM-MWCNT were 171.3, 123.4, 26.8 and 49.6 mg/g for PNA, respectively. The adsorption processes follow a pseudo second-order kinetic rate equation. The adsorption rate is not only controlled by intra-particle diffusion but also by extra-particle diffusion. However, for MWCNT, intra-particle diffusion is not the rate-controlling step. The equilibrium adsorbing capacity of PNA increases with the increase of initial concentration. The adsorption for PNA by KOH-MWCNT or CO2-MWCNT , the adsorption process follows Freundlish adsorption isotherm. The adsorption for PNA by ACID-MWCNT or COM-MWCNT, the adsorption process follows Freundlish adsorption isotherm. At different pH values, ACID-MWCNT is not conducive to adsorption at pH 11. Increase the amount of adsorbent of different carbon nanotubes，the equilibrium adsorbing capacity changes are different. Stirring speed increased will help to improve the adsorption efficiency. In the desorption recycling, recycling rate is the order of ACID-MWCNT > COM-MWCNT > CO2-MWCNT > KOH-MWCNT.

碩士
高雄醫學大學
醫藥暨應用化學研究所
102
Nanonized noble metal composites have been known for their excellent catalysis properties. However, the mechanisms and the intermediates formed on the surfaces of the catalysts during the catalysis process are mostly speculated with insufficient evidence. To get the further understandings about the roles of noble metal nano-catalysts played during the catalytic reactions, surface-enhanced Raman scattering (SERS) technique is introduced to monitor the surfaces of the silver nano-catalysts. Meanwhile, UV/Vis spectrometry is used to trace the concentration variations of reactants and products in the bulk solution. 　　Silver nano-catalysts were prepared by reducing naked silver nanoparticles on the porous glass filter plates and were used as the catalysts of the reduction of nitroanalines. The results indicate that the morphologies of silver nanoparticle reduced on the glass filter plates are varied as the conditions of the catalysts preparation change, which affect the efficiency of the catalysts significantly. Meanwhile, the catalysis process was also influenced by the reaction temperature, pH, the porosity of the substrates, and the concentration of the reducing agents. By analyzing the SERS spectra and UV/Vis spectra collected, a new insight into the silver nanoparticle catalysis can be provided and the roles of silver nano-catalysts can be further comprehended.

碩士
國立交通大學
應用化學研究所
99
N,N-Dimethyl-p-nitroaniline (DMPNA) in mixed solvents of acetonitrile (ACN) and tetrachloroethylene (C2Cl4) was studied with FT-IR spectroscopy and IR electroabsorption spectroscopy. Previous studies using Raman and IR electroabsorption spectroscopy show that p-nitroaniline (PNA), an analogue of DMPNA, forms specific solvation structures with ACN in ACN/CCl4. To examine the effect of N,N-dimethyl substitution on the formation of those solvation structures, we measured the ACN mole fraction dependence of FT-IR spectra and the angle χ dependence of IR electroabsorption (∆A) spectra of DMPNA in ACN/C2Cl4. Here χ is the angle between an applied electric field and the electric field vector of IR probe light. In the FT-IR spectra, the NO2 symmetric stretch band of DMPNA shows continuous redshift with increasing ACN mole fraction, indicating that, unlike PNA, DMPNA does not exhibit specific solvated forms in the mixed solvents. Singular value decomposition analysis of the χ-dependent ∆A spectra also supports this conclusion. More interestingly, through efforts to improve the data, we observed a ∆A signal (CH3 symmetric deformation of ACN) in the vicinity of the DMPNA band. We used the ∆A signal of DMPNA, which has been shown to form no specific solvation structures, as an internal intensity standard to evaluate the dipole moment of ACN. Using the value of the dipole moment μP, of DMPNA in the literature, we obtained μP of ACN as 5.7 D, which is about 1.7 times as large as that of individual ACN molecules (~3.4 D). Thus a head-to-tail linear dimer in which two ACN molecules align linearly pointing to the same direction is most plausible as the association structure in the mixed solvents.

碩士
國立臺灣師範大學
化學系
104
A surface display system was used for green synthesis of gold and platinum nanoparticles via an autotranspoter protein, immunoglobulin A protease (IgA protease) from Neisseria gonorrheae as carrier proteins. Metal binding peptides were expressed on the outer membranes of Escherichia coli and Ralstonia eutropha to recover metal ions. The results of this study showed that cells expressing metal binding peptides could synthesize and display the nanoparticles on the cell surfaces, simultaneously. Next, the metal nanoparticle-coated microorganisms were used as whole-cell biocatalysts for the reduction of 4-nitroaniline. Besides, we designed a protein-based fluorescence resonance energy transfer (FRET) reporter for detection of copper (I), silver (I), and gold (III) ions. The A-66 reporter (CFP-GGSGGS-CueR-GGSGGS-YFP) was selected for in vitro and in vivo metal ions detection.

by Lui Bong Chun, Richard.
Thesis (M.Phil.)--Chinese University of Hong Kong, 1995.
Includes bibliographical references.
Abstract
Acknowledgment
Chapter Chapter 1 --- Introduction --- p.1
Chapter 1.1 --- Background for the Project --- p.1
Chapter 1.1.1 --- Interests in Blue-Green Laser --- p.1
Chapter 1.1.2 --- Progress of Blue-Green Laser --- p.2
Chapter 1.2 --- The Aim of the Project --- p.3
Chapter 1.3 --- Overview the Remaining Parts of this Thesis --- p.4
Chapter 1.4 --- References --- p.6
Chapter Chapter 2 --- Sum Frequency Generation --- p.8
Chapter 2.1 --- Introduction --- p.8
Chapter 2.2 --- Sum Frequency Generation --- p.8
Chapter 2.2.1 --- Theoretical Background for Sum Frequency Generation --- p.9
Chapter 2.2.2 --- The Coupled Wave Equations for SFG --- p.13
Chapter 2.2.3 --- Phase Matching Considerations --- p.16
Chapter 2.3 --- References --- p.18
Chapter Chapter 3 --- Cerenkov Radiation --- p.19
Chapter 3.1 --- Introduction --- p.19
Chapter 3.2 --- The Properties of Cerenkov Radiation by Using TM Mode --- p.21
Chapter 3.2.1 --- Refractive Index Notation --- p.23
Chapter 3.2.2 --- Fundamental Wave TM Guides Mode --- p.23
Chapter 3.2.3 --- Second Harmonic TM Radiation Mode --- p.24
Chapter 3.2.4 --- Efficiency of SHG --- p.25
Chapter 3.3 --- Simplified Model Analysis of Cerenkov Radiation in TE Mode --- p.29
Chapter 3.4 --- Simulation --- p.33
Chapter 3.4.1 --- Modeling the LiNb03 --- p.33
Chapter 3.4.2 --- Modeling an Asymmetric Slab Waveguide ´ؤPMMA doped with MNA on Fused Quartz --- p.37
Chapter 3.4.3 --- Modeling a Symmetric Slab Waveguide ´ؤPMMA doped with MNA on Fused Quartz --- p.42
Chapter 3.5 --- References --- p.47
Chapter Chapter 4 --- Ellipsometry --- p.49
Chapter 4.1 --- Introduction --- p.49
Chapter 4.2 --- General Principles --- p.49
Chapter 4.3 --- Basic Operation --- p.50
Chapter 4.4 --- The Optical Constants of the Bulk Materials --- p.51
Chapter 4.5 --- Calculation the Refractive Index of the Substrates --- p.53
Chapter 4.6 --- Ellipsometric Theory for the Thin Film --- p.57
Chapter 4.7 --- Measurement the Refractive Index and the Thickness of the Thin Film --- p.59
Chapter 4.7.1 --- Data --- p.62
Chapter 4.7.2 --- Discussions --- p.73
Chapter 4.8 --- Calculation the Refractive Index of the thin Film by Considering as a Bulk Material --- p.78
Chapter 4.9 --- References --- p.80
Chapter Chapter 5 --- Prism Coupling --- p.81
Chapter 5.1 --- Introduction --- p.81
Chapter 5.2 --- Coupling of a Plane Wave --- p.82
Chapter 5.3 --- Numerical Approach for the Calculation of the Coupling Efficiency --- p.85
Chapter 5.4 --- Experiment --- p.88
Chapter 5.4.1 --- Experimental Setup --- p.88
Chapter 5.4.2 --- Experimental Result and Discussions --- p.90
Chapter 5.5 --- References --- p.92
Chapter Chapter 6 --- Conclusion --- p.93
Chapter Chapter 7 --- Future Plans --- p.96
Chapter 7.1 --- Simplified Model of Corona Poling --- p.96
Chapter 7.2 --- Advanced Models of Poling --- p.98
Chapter 7.2.1 --- Slab Waveguide --- p.98
Chapter 7.2.2 --- Channel Waveguide --- p.99
Chapter 7.3 --- References --- p.100
Chapter Appendix 1 --- Materials' Descriptions --- p.A-l
Chapter A.1.1 --- 2-Methyl-4-Nitoaniline --- p.A-1
Chapter A.1.2 --- Poly ( Methyl Methacrylate ) --- p.A-3
Chapter A.1.3 --- References --- p.A-4
Chapter Appendix 2 --- Fabrication Procedures --- p.A-5
Chapter A.2.1 --- Cleaning the Apparatus --- p.A-5
Chapter A.2.2 --- Cleaning the Substrate --- p.A-5
Chapter A.2.3 --- Thin film Fabrication --- p.A-5
Chapter A.2.4 --- Thin Film Removal --- p.A-6
Chapter A.2.5 --- References --- p.A-6
Chapter Appendix 3 --- Alpha Step --- p.A-7
Chapter A.3.1 --- Introduction --- p.A-7
Chapter A.3.2 --- Experimental Setup --- p.A-8
Chapter A.3.3 --- Experimental Results --- p.A-9
Chapter A.3.3.1 --- Thin Film of PMMA without Dopant --- p.A-9
Chapter A.3.3.2 --- Thin Film of PMMA doped with MNA --- p.A-19
Chapter A.3.4 --- Discussions --- p.A-27
Chapter A.3.5 --- References --- p.A-28
Chapter Appendix 4 --- Scanning Electron Microscope --- p.A-29
Chapter A.4.1 --- Scanning Electron Microscope --- p.A-29
Chapter A.4.2 --- Reference --- p.A-30
Chapter Appendix 5 --- Gaussian Beam & Coordinate System Transformation --- p.A-31
Chapter A.5.1 --- Gaussian Beam in a Homogeneous Medium --- p.A-31
Chapter A.5.2 --- Transformation of the Coordinate Systems --- p.A-32
Chapter A.5.3 --- Reference --- p.A-32
Chapter Appendix 6 --- Waist Size Measurement of Gaussian Beam --- p.A-33
Chapter A.6.1 --- Waist Size Measurement of Gaussian Beam --- p.A-33
Chapter A.6.2 --- References --- p.A-34
Chapter Appendix 7 --- Quasi Phase Matching --- p.A-35
Chapter A. 7.1 --- Introduction --- p.A-35
Chapter A.7.2 --- Basic Concept of QPM --- p.A-36
Chapter A.7.3 --- References --- p.A-38
Chapter Appendix 8 --- Program Listing --- p.A-41
Chapter A.8.1 --- Program Listing ( Chapter 3 ) --- p.A-41
Chapter A.8.1.1 --- Program 3.1 (transcendental.m ) --- p.A-41
Chapter A.8.1.2 --- Program 3.2 (linbo3.m) --- p.A-42
Chapter A.8.2 --- Program Listing ( Chapter 4 ) --- p.A-45
Chapter A.8.2.1 --- Program 4.1 ( ellipsometry.m ) --- p.A-45
Chapter A.8.3 --- Program Listing ( Chapter 5 ) --- p.A-47
Chapter A.8.3.1 --- Program 5.1 ( parameter.m ) --- p.A-47
Chapter A.8.3.2 --- Program 5.2 ( coupling.m ) --- p.A-49
Chapter A.8.3.3 --- Program 5.3 ( v_3_amp.m ) --- p.A-50
Chapter A.8.3.4 --- Program 5.4 ( input_profile.m ) --- p.A-51

In der vorliegenden Arbeit wird die Synthese und Charakterisierung von chiralen 1,2- und 1,3-diolfunktionalisierten solvatochromen Chromophoren vorgestellt. Als chromophore Systeme wurden Nitroaniline, SCHIFFsche Basen, Azofarbstoffe und Merocyanine gewählt. Das solvatochrome Verhalten der diolfunktionalisierten Verbindungen wurde mittels LSER (linear solvation energy realtionship) unter Verwendung der Lösungsmittelparameter nach KAMLET-TAFT und CATALÁN quantifiziert. Der Einfluss der Diolfunktion auf die Kristallstruktur der Nitroanilinderivate wurde über Einkristallröntgenstrukturanalyse untersucht und nach der Graph Set Methode von ETTER beschrieben. Es erfolgte eine Kondensation ausgewählter diolfunktionalisierter Bausteine mit verschieden substituierten Arylboronsäuren. Ein besonderes Augenmerk wurde auf den Einfluss des Boratoms und der Ringgröße des resultierenden Boronsäureesters, auf das solvatochrome Verhalten sowie das Reaktionsverhalten gegenüber Fluorid, Cyanid und Acetat gelegt. Weiterhin erfolgte die Verknüpfung von diolfunktionalisierten Chromophoren mit chromophoren Arylboronsäuren zu Bis-Chromophoren, deren Eigenschaften ebenfalls studiert wurden.