We may summarize the purposes of this investigation as follows: A report on this investigation was made to Dr. John H. Yoe of the University of Virginia in order to see what reactions he considered to be of analytical significance and should be further investigated. He considers only three to be of any practical importance. They are as follows: 1. 7A-Oleic Acid. Solubility of the alkaline earth salts of some higher fatty acids. 2. 69A- 2-Acetamino 6-Aminobenzo Thiazole. A colorimetric reagent for iridium. 3. 71A 2-Hydroxy 3-Nitro 5-Sulfobenzoic Acid. A colorimetric reagent for ferric iron. A further investigation of compound 71A, as a colorimetric reagent for ferric iron, reveals that the sensitivity of this reaction is not great enough for it to be of any practical importance, since we have reagents (2) for this ion that are several times more sensitive. Prospective reagent No. 69A for iridium is being further investigated by Mr. J. R. Noell (1). A report on 7A will be taken up in Part II of this thesis. 1. It has been shown that there is very little difference in the solubility of the same alkaline earth salt of stearic, oleic, linoleic, and linolenic acids in the solvents, water, benzene, absolute ethyl alcohol and ether. 2. It has been shown that there is very little difference in the solubility of the different alkaline earth salt of stearic, oleic, linoleic, and linolenic acids in the solvents, water, benzene, absolute ethyl alcohol and ether, and benzene. 3. The solubility of the alkaline earth salt of these acids increases slightly with unsaturation, but does not increase as the degree of unsaturation increases. / M.S.

The purpose of this investigation may be summarized as follows: (1) Search for new colorimetric organic reagents. (2) Discovery of any organic compound that shows properties of an indicator. (3) Discovery of any organic compound that shows properties of an oxidizing or reducing agent. (4) Discovery of any other information that may be of analytical importance. / M.S.

This dissertation examined the relationships between color contrast and legibility for digital raster video imagery. CIE colorimetric components were combined into three-dimensional color coordinate systems whose coordinates map one-to-one with the physical energy parameters of all colors. The distance between any two colors' coordinates in these 3-spaces is termed Color-Difference (ΔE). ΔE was hypothesized as a metric of the speed (RS) with which observers possessing normal vision could accurately read random numeral strings of one color displayed against backgrounds of another color. Two studies totaling 32064 practice and experimental trials were conducted. The first study determined that the CIE Uniform Color Spaces are inappropriate for the modeling of RS. Subsequently, a different 3-space geometry and colorimetric component scaling were empirically derived from the Study 1 data to produce a one-dimensional ΔE scale which ” approximates an interval scale of RS. This ΔE scale and others were then applied to the different stimulus conditions in Study 2 to determine the generalizability of such ΔE metrics. The pair of studies is conclusive: several ΔE scales exist which serve equally well to describe or prescribe RS with multicolor CRT raster imagery for a range of character luminances in both positive and negative presentation polarities. These are the Y,u',v', logY,u',v', L*,u',v', and L*,u*,v* rescaled color spaces. Because of its predictive accuracy and simplicity, a luminance—generalized, ΔE—standardized Y,u',v' metric, accounting for 71% and 75% of the RS variability in Studies 1 and 2, respectively, is recommended as the most appropriate metric of emissive display legibility to be tested in these studies. / Ph. D.

Yes / The association constants for formation of 1 : 1 complexes between a H-bond donor, 1-naphthol, and a diverse range of charged and neutral H-bond acceptors have been measured using UV/vis absorption and fluorescence emission titrations. The performance of 1-naphthol as a dual colorimetric and fluorescent molecular recognition probe for determining the H-bond acceptor (HBA) parameters of charged and neutral solutes has been investigated in three solvents. The data were employed to establish self-consistent H-bond acceptor parameters (β) for benzoate, azide, chloride, thiocyanate anions, a series of phosphine oxides, phosphate ester, sulfoxide and a tertiary amide. The results demonstrate both the transferability of H-bond parameters between different solvents and the utility of the naphthol-based dual molecular recognition probe to exploit orthogonal spectroscopic techniques to determine the HBA properties of neutral and charged solutes. The benzoate anion is the strongest HBA studied with a β parameter of 15.4, and the neutral tertiary amide is the weakest H-bond acceptor investigated with a β parameter of 8.5. The H-bond acceptor strength of the azide anion is higher than that of chloride (12.8 and 12.2 respectively), and the thiocyanate anion has a β value of 10.8 and thus is a significantly weaker H-bond acceptor than both the azide and chloride anions. / Supported by the ESPRC.

A controlled assembly of natural beta-cyclodextrin modified Au NPs mediated by dopamine is demonstrated. Furthermore, a simple and sensitive colorimetric detection for dopamine is established by the concentration-dependent assembly.

This thesis describes the design, synthesis, analysis, mechanistic evaluation and optimisation of small molecule probes for the specific detection of proteins, focusing on the target protein human arylamine <i>N</i>-acetyltransferase type 1 (HUMAN(NAT1)) and its murine homologue, mouse arylamine <i>N</i>-acetyltransferase type 2 (MOUSE(NAT2)). The HUMAN(NAT1) gene is reported to be one of the most highly overexpressed genes in estrogen-receptor-positive (ER+) breast tumours, leading to its potential use as both a novel diagnostic biomarker and a novel therapeutic target for this disease. <strong>Chapter 1</strong> reviews the literature on optical methods for the specific detection of a protein target, exploring strategies both based on biosensors and on chemical probes, before introducing the arylamine <i>N</i>-acetyltransferases as a family of enzymes. In <strong>Chapter 2</strong>, a family of naphthoquinone inhibitors of HUMAN(NAT1) are introduced, which undergo a colour change from red to blue upon binding specifically to the enzyme. The mechanism of this colour change, a proton transfer-mediated process, is discussed via the synthesis, pharmacological and colorimetric evaluation of close analogues of the hit compound lacking a key acidic sulfonamide-N<i>H</i> proton. During these studies, it was found that direct <i>O</i>-methylation of a sulfonamide is possible under certain conditions; such a reaction has not previously been reported. Furthermore, upon heating in polar solvents the <i>O</i>-methylated sulfonamide was observed to undergo rearrangement, and the mechanism of this process is investigated via NMR and kinetic studies. In <strong>Chapter 3</strong>, the design, synthesis and evaluation of HUMAN(NAT1) inhibitors with improved pharmacological and colorimetric profiles over the initial hit are described. From this optimisation, structure-activity relationships and an in silico model of interactions between the inhibitors and enzyme are evaluated. Testing of these compounds in cellular environments, however, exposes some limitations of this approach, notably the lack of sensitivity of the probes when dosed at low concentrations in cellular samples. In order to overcome this limitation, in <strong>Chapter 4</strong> fluorescent analogues of the hit compound are designed and synthesised. Initial compounds developed in this series possess promising properties, but each compound generated suffers from either a low fluorescent intensity, lack of a <i>p</i>H-dependent switch in fluorescence or a low fluorescence excitation wavelength, which overlaps with those of tryptophan or tyrosine residues in proteins. Insights into the mechanism of molecular fluorescence and application of some simple quantum mechanical principles, however, lead to the design of a species which possesses all the required properties. The fluorescent emission intensity of this probe correlates linearly with [MOUSE(NAT2)] in E. coli cell extracts, and can quantify as little as 0.64% MOUSE(NAT2) in the samples; furthermore, the probe is capable of unambiguously detecting HUMAN(NAT1) within a cell extract from the ER+ breast cancer cell line ZR-75-1; future work on this probe may therefore enable its clinical use in improved early diagnosis of breast tumours. This study also represents, to the best of our knowledge, the first ever example of a small molecule, non-covalent probe capable of quantifying the concentration of a target protein in cellular extracts. In <strong>Chapter 5</strong>, the series of naphthoquinone probes is further optimised in order to study the roles of HUMAN(NAT1) in a cellular environment. Firstly, structure-activity relationships are utilised to design inhibitors with improved physical properties such as aqueous solubility and cell membrane permeability, in order to test the effect of HUMAN(NAT1) inhibitors in tumour cell models, which could have implications for the future use of a HUMAN(NAT1) inhibitor as a therapeutic agent in oncology. Secondly, the effect of the cofactor folic acid on the function and activity of HUMAN(NAT1) is explored. Finally, in <strong>Chapter 6</strong>, the conclusions of this study are outlined and a hypothesis as to how the concepts developed in this thesis might be applied to alternative, more ubiquitous biological targets is discussed, paving the way for future investigations.

Flotação é uma operação unitária à base de química de superfície que envolve a captura de partículas hidrofóbicas por bolhas de ar na suspensão aquosa, na qual são transportadas para a superfície, com posterior remoção desta camada de espuma. Por outro lado, porque as partículas hidrofílicas não aderem a bolhas de ar, elas tendem a afundar e ir para o fluxo inferior do tanque de flotação. A separação de apatita-ganga através de flotação de espuma é o controle eficaz dos fenômenos de molhabilidade, que, por sua vez, determina a seletividade do processo. A regulação da interação de minerais (apatita e ganga) com moléculas de água (natureza hidrofílica) e também com as bolhas de ar (natureza hidrofóbica) é conseguida com a adição de reagentes químicos (coletores, modificadores e espumantes) na polpa de flotação. Adsorção de reagentes químicos na interface mineral/solução é o método mais eficaz para promover a hidrofobicidade das partículas de apatita (favorecendo sua flotação) e também reforçar a hidrofilicidade dos minerais de ganga, inibindo sua flotação. Este trabalho tem o objetivo de construir uma curva de calibração para o coletor Berol®867 através do método colorimétrico de Bradford, método na presença do corante Coomassie Brilliant Blue. Medidas simulando condições típicas de flotação foram também realizadas em laboratório. Medições em soluções de flotação foram realizadas pelo tensiômetro IP6000 que baseia-se no método da pressão máxima de bolha (MPMB) na qual é muito mais adequado para líquidos puros, mas não para soluções aquosas contendo surfactantes. Por conseguinte, os valores de L/G obtidos por MPMB são deterministicamente superiores aos gerados pelo Método com Wilhelmy (MPW), que é considerada como sendo adequada para soluções contendo tensioativos, mas não suficientemente robusta para aplicações industriais in-situ. / Froth flotation is a chemistry-based surface unit operation that involves the capture of hydrophobic particles by air bubbles in aqueous slurry, followed by levitation and collection in a froth layer. Conversely, because hydrophilic particles do not adhere to air bubbles, they are likely to sink and go to the underflow of the flotation cell. The selectivity of apatite-gangue separation via froth flotation is determined by the efficient control of the wetting phenomena. Adding chemical reagents to the flotation pulp, like collectors or frothers, it is possible to regulate the interfacial affinity of each mineral, apatite or gangue, turning them hydrophilic or hydrophobic. Adsorption of chemical reagents onto interfaces is the most effective approach to promote the hydrophobicity of the mineral, which is desired to float, and also the reinforcement of the wettability by water of the minerals which are desired to sink. This work had as objective to construct a calibration curve for the Berol®867 collector through the Bradford colorimetric method in the presence of Coomassie Brilliant Blue dye. Measurements simulating typical flotation conditions were also run at the laboratory. Measurements of flotation solution performed by tensiometer IP6000 are based on the Maximum Bubble Pressure Method (MBPM) which is very suitable for pure liquids, but not for aqueous solutions containing surfactants. Therefore, the values of ?LG yielded by MBPM are deterministically higher than those yielded by the Wilhelmy Plate Method (WPM), which is regarded as suitable for surfactant solutions but not sufficiently robust for in-situ industrial applications.

O monitoramento ambiental de forma contínua e em tempo real são desafios da realidade atual dos grandes centros urbanos, com a finalidade de prevenir desastres ambientais que possam pôr em perigo a saúde dos seres humanos e a existência de sistemas biológicos. Na presente tese foram propostos e desenvolvidos sistemas optoeletrônicos portáteis aplicados na detecção de O2, OD e íons de metais pesados, visando seu emprego no monitoramento de sistemas hidrológicos como mares, rios, lagos e lençóis freáticos. A definição final da estrutura do sistema portátil foi atingida após o desenvolvimento sistemático de diferentes ensaios experimentais. Primeiramente, foram estudadas e analisadas matrizes hospedeiras em estado sólido que fossem capazes de hospedar sistemas moleculares corantes sensíveis a certas substâncias específicas. A seguir, foi proposta e executada a integração direta dos filmes hospedeiros, dopados com moléculas corantes ativas, diretamente na superfície ativa de dispositivos fotodetectores para detecção de O2 e OD. Os resultados obtidos com estes sistemas que integram o detector e o filme ativo mostraram o mesmo nível de desempenho aos espectrômetros de bancada. Finalmente, de posse destes resultados, foi projetado e desenvolvido um sistema colorimétrico e fluorimétrico portátil e embarcado em uma placa de aquisição (myRIO-1900) da National Instruments, aplicado na detecção e classificação de íons metálicos. Destaque principal é outorgado à aplicação do colorímetro que, juntamente com o processamento de sinais e análises de padrões, utilizando o método de discriminante de Fisher, permitiu obter resultados excelentes na detecção e classificação dos íons de Pb2+, Cd2+, Zn2+, Cu2+, Fe3+ e Ni2+, com os mesmos níveis de desempenho que os obtidos a partir de espectrômetros de bancada de elevada resolução espectral. O sistema portátil desenvolvido sugere sua aplicação no controle ambiental in situ e em tempo real, podendo ser integrado em uma rede de sensores que possam fornecer dados de maneira contínua e receber comandos de centros de controle de monitoramento ambiental. No entanto, seria necessária a formulação de algoritmos eficientes no processo de mineração de dados da rede de sensores. / The continuous and in real time environmental monitoring are challenges of the current days of large urban centers, with the aim of preventing environmental disasters that could endanger human health and the existence of biological systems. In this thesis we have proposed and developed portable optoelectronic systems applied to the detection of O2, OD and heavy metal ions, aiming its use in monitoring hydrological systems such as oceans, rivers, lakes and groundwater. The final definition of the portable system structure was achieved after the systematic development of different experimental assays. First, host matrices were studied and analyzed in solid state which were able to host dye molecular systems sensitive to certain substances. Then, we proposed and executed the direct integration of the host film, doped with active dye molecules directly on the active surface of photodetector devices to the detection of O2 and OD. The results obtained with these systems that integrate the detector and the active film showed the same level of performance than those of benchtop spectrometers. Finally, with these results, we designed and developed a colorimetric and fluorimetric portable system with an embedded acquisition board (myRIO-1900) from National Instruments, applied to the detection and classification of metal ions. Main focus is given to the application of the colorimeter which, along with the signal processing and pattern analysis using the Fisher discriminant method, allowed to obtain excellent results in the detection and classification of Pb2+, Cd2+, Zn2+, Cu2+, Fe3+ and Ni2+ ions, with the same level of performance related to those obtained from high spectral resolution benchtop spectrometers. The portable system developed in the present thesis suggests its application in environmental control in situ and in real time, so that it can be integrated in a network of sensors that may provide continuous data and receive commands from environmental monitoring control center; nevertheless, requiring for that the development of efficient algorithms in data mining process of the sensor network.

O monitoramento ambiental de forma contínua e em tempo real são desafios da realidade atual dos grandes centros urbanos, com a finalidade de prevenir desastres ambientais que possam pôr em perigo a saúde dos seres humanos e a existência de sistemas biológicos. Na presente tese foram propostos e desenvolvidos sistemas optoeletrônicos portáteis aplicados na detecção de O2, OD e íons de metais pesados, visando seu emprego no monitoramento de sistemas hidrológicos como mares, rios, lagos e lençóis freáticos. A definição final da estrutura do sistema portátil foi atingida após o desenvolvimento sistemático de diferentes ensaios experimentais. Primeiramente, foram estudadas e analisadas matrizes hospedeiras em estado sólido que fossem capazes de hospedar sistemas moleculares corantes sensíveis a certas substâncias específicas. A seguir, foi proposta e executada a integração direta dos filmes hospedeiros, dopados com moléculas corantes ativas, diretamente na superfície ativa de dispositivos fotodetectores para detecção de O2 e OD. Os resultados obtidos com estes sistemas que integram o detector e o filme ativo mostraram o mesmo nível de desempenho aos espectrômetros de bancada. Finalmente, de posse destes resultados, foi projetado e desenvolvido um sistema colorimétrico e fluorimétrico portátil e embarcado em uma placa de aquisição (myRIO-1900) da National Instruments, aplicado na detecção e classificação de íons metálicos. Destaque principal é outorgado à aplicação do colorímetro que, juntamente com o processamento de sinais e análises de padrões, utilizando o método de discriminante de Fisher, permitiu obter resultados excelentes na detecção e classificação dos íons de Pb2+, Cd2+, Zn2+, Cu2+, Fe3+ e Ni2+, com os mesmos níveis de desempenho que os obtidos a partir de espectrômetros de bancada de elevada resolução espectral. O sistema portátil desenvolvido sugere sua aplicação no controle ambiental in situ e em tempo real, podendo ser integrado em uma rede de sensores que possam fornecer dados de maneira contínua e receber comandos de centros de controle de monitoramento ambiental. No entanto, seria necessária a formulação de algoritmos eficientes no processo de mineração de dados da rede de sensores. / The continuous and in real time environmental monitoring are challenges of the current days of large urban centers, with the aim of preventing environmental disasters that could endanger human health and the existence of biological systems. In this thesis we have proposed and developed portable optoelectronic systems applied to the detection of O2, OD and heavy metal ions, aiming its use in monitoring hydrological systems such as oceans, rivers, lakes and groundwater. The final definition of the portable system structure was achieved after the systematic development of different experimental assays. First, host matrices were studied and analyzed in solid state which were able to host dye molecular systems sensitive to certain substances. Then, we proposed and executed the direct integration of the host film, doped with active dye molecules directly on the active surface of photodetector devices to the detection of O2 and OD. The results obtained with these systems that integrate the detector and the active film showed the same level of performance than those of benchtop spectrometers. Finally, with these results, we designed and developed a colorimetric and fluorimetric portable system with an embedded acquisition board (myRIO-1900) from National Instruments, applied to the detection and classification of metal ions. Main focus is given to the application of the colorimeter which, along with the signal processing and pattern analysis using the Fisher discriminant method, allowed to obtain excellent results in the detection and classification of Pb2+, Cd2+, Zn2+, Cu2+, Fe3+ and Ni2+ ions, with the same level of performance related to those obtained from high spectral resolution benchtop spectrometers. The portable system developed in the present thesis suggests its application in environmental control in situ and in real time, so that it can be integrated in a network of sensors that may provide continuous data and receive commands from environmental monitoring control center; nevertheless, requiring for that the development of efficient algorithms in data mining process of the sensor network.

Made available in DSpace on 2017-07-21T18:53:03Z (GMT). No. of bitstreams: 1 Priscila Judacewski.pdf: 1953850 bytes, checksum: 9d42323aa08ff06768c755a6db587472 (MD5) Previous issue date: 2015-02-12 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The Camembert is considered one of the finest cheeses. Presents as main characteristic the surface covered with a white mycelium of the fungus Penicillium candidum, which provides peculiar sensory characteristics greatly appreciated. In Brazil, little has been studied about this cheese, in this way, in order to generate scientific technical knowledge about factors that may influence the standard of quality cheeses such as Camembert, this work was divided into two parts. In the first (Chapter II), the objective was to evaluate the application of different primary cultures, and different concentrations of salt in the curing process. In the second (Chapter III), the objective was to develop and evaluate a protocol for obtaining fresh biomass of Penicillium candidum for use as a catch crop. Were used as primary cultures mesophilic homofermentative, heterofermentative mesophilic and thermophilic. The concentration of the brine used was 15, 20, 25 and 29º Brix. The biomass of P. candidum obtained in synthetic medium was recovered, and micro fragmented sprayed onto cheeses, with score of 2.106 spores / cheese. Of physical and chemical composition analyzes were performed, maturation index, colorimetric analysis and texture profile in the samples during maturation. The mycelia growth was established by the whiteness index (WI), which proved effective for this purpose, it is fast and inexpensive. Although the texture profile parameters were similar during maturation with different primary cultures, resilience showed lower value for processed cheeses with thermophilic culture, and was the only parameter that showed significant differences between cultures. Another positive factor for cheeses with this culture was superficial development of white mold mycelium with one-day gain, compared to mesophilic. Samples with different salt concentrations, showed significant differences (p <0.05) between the moisture, protein, dry matter, ash, sodium and sodium chloride, and did not affect the growth of the fungus P. candidum. The physical and chemical composition of cheeses matured with biomass was similar to cheeses matured with spores, but proteolysis of cheeses matured with biomass was more intense, with the end of 15 days of aging, free amino acid content of 14% more, compared with samples containing only spores. Among the samples with the application of the inoculums, the tyrosine levels and fat, as well as the cohesiveness of the texture profile parameter showed significant difference. The mycelium overlaid cheese with a day in advance when compared only with the inoculums of spores and showed greater height. This work demonstrates ways to monitor and speed up the mycelium closing within two days, using colorimetric analysis, thermophilic culture and micro fragmented biomass. These results can be readily used by companies to establish quality standards for cheese like Camembert. / O Camembert é considerado um dos principais queijos finos. Apresenta como principal característica a superfície recoberta por um micélio branco do fungo Penicillium candidum, que proporciona características sensoriais peculiares muito apreciadas. No Brasil pouco foi estudado sobre este queijo, desta forma com o propósito de gerar conhecimento técnico científico sobre fatores que podem influenciar o padrão de qualidade de queijos tipo Camembert, esta dissertação foi dividida em duas partes. Na primeira (Capítulo II) o objetivo foi avaliar a aplicação de diferentes culturas primárias, e diferentes concentrações de sal no processo de salga. Na segunda (Capítulo III) o objetivo foi desenvolver e avaliar um protocolo de obtenção de biomassa fresca de Penicillium candidum para utilização como cultura secundária. As culturas primárias utilizadas foram mesofílica homofermentativa, mesofílica heterofermentativa e termofílica. As concentrações das salmouras foram de 15, 20, 25 e 29º Brix. A biomassa de P. candidum obtida em meio sintético foi recuperada, microfragmentada e aspergida sobre os queijos, com contagem de 2.106 de esporos/queijo. Foram realizadas análises de composição físico-química, índice de maturação, análise colorimétrica e perfil de textura nas amostras durante a maturação. O crescimento do micélio foi estabelecido pelo índice de brancura (WI) o qual se mostrou eficiente para este propósito, sendo rápido e de baixo custo. Embora os parâmetros do perfil de textura tenham sido semelhantes durante a maturação com diferentes culturas primárias, a resiliência apresentou menor valor para os queijos processados com cultura termofílica, e foi o único parâmetro que apresentou diferença significativa entre as culturas. Outro fator positivo para os queijos com esta cultura, foi o desenvolvimento superficial do micélio do mofo branco com ganho de um dia, em comparação às mesofílicas. As amostras com diferentes concentrações de sal, apresentaram diferença significativa (p< 0,05) entre os teores de umidade, proteína, extrato seco, cinzas, cloreto de sódio e sódio, e não interferiram no crescimento do fungo P. candidum. A composição físico-química dos queijos maturados com biomassa foi semelhante aos queijos maturados com esporos, porém a proteólise dos queijos maturados com biomassa foi mais intensa, apresentando ao final de 15 dias de maturação, teor de aminoácidos livres de 14% a mais, comparado com amostras contendo apenas esporos. Entre as amostras com as aplicações dos inóculos, os teores de tirosina e gordura, assim como o parâmetro coesividade do perfil de textura, apresentaram diferença significativa. O micélio recobriu o queijo com um dia de antecedência quando comparado apenas com o inóculo de esporos e apresentou maior altura. Este trabalho demonstra formas de monitorar e acelerar o fechamento do micélio em até dois dias, utilizando análise colorimétrica, cultura termofílica e biomassa microfragmentada. Estes resultados podem ser prontamente utilizados por empresas a fim de estabelecer padrões de qualidade para queijos tipo Camembert.