The use of fluorescent imaging probes for the real time detection of cellular malfunctions, such as enzyme over expression has shown promise. Fluorescent dyes with absorption and emission values below 600 nm are limited in their in vivo applications due to high background auto-fluorescence and low resolution images. Employing near infrared (NIR) fluorophores such as cyanine dyes can overcome this disadvantage. Cyanine dyes can be synthesised using solution or solid-phase techniques with the use of solution phase chemistry allowing for larger scale and higher yielding reactions. Utilising a selection of functional groups and varying polymethine chain lengths a cyanine dye library with tuneable absorption and emission wavelengths was synthesised. This thesis gives the first detailed examples of how modifications on heptamethine cyanine dyes alter their cellular uptake and cellular toxicity. Furthermore, a NIR fluorescent microsphere is reported as well as NIR functionalised microspheres with the ability to be tracked within cells. Additional lines of work involved the synthesis of a fluorescent sensor for the visualisation of bacteria. Aminopeptidases are present within the peptidoglycan cell wall of Gram negative bacteria and therefore can be targeted for real time detection of bacteria to aid in the detection of infectious diseases. A coumarin based probe is reported which detects aminopeptidase in gram negative bacteria in vitro.

No description available.

Routes to novel heterocyclic azo compounds and components of use as potential inkjet dyes were investigated. A new route to fluorenones from biphenyl acid chlorides using FVP (Flash Vacuum Pyrolysis) has been discovered. Fluorenone and 4-methylfluoren-9-one were prepared by FVP of 2-phenylbenzoyl chloride and 2-methylbiphenyl-2-carbonyl chloride respectively. Xanthen-9-one and thioxanthen-9-one were also prepared by FVP from the corresponding acid chlorides. 9-Phenanthrol could also be prepared via the FVP of biphenylacetyl choride and the application of this method to a heterocylic thiophene system afforded naphtho[1,2-b]thiophen-4-ol. Naphtho[2,1-b]thiophen-4-ol and naphtho[1,2-b]furan- 4-ol could be obtained in low yields by the FVP of (2-thiophen-3-ylphenyl)acetic acid methyl ester and (2-furan-2-ylphenyl) acetic acid methyl ester over a tungsten trioxide catalyst. Coupling of these systems with the diazonium salt of Acid Yellow 9 afforded the corresponding azo compounds. New heterocyclic dyes were also prepared from the condensation of heterocyclic hydrazines with 4,9-disulfophenanthrenequinone. Pyridine, pyridazine, phthalazine, isoquinoline and 2-quinoline disulfophenanthrene quinone metallised 2:1 nickel complexed magenta dyes were prepared. Industrial tests by standard methods revealed the pyridazine dye has a particularly impressive balance of light and ozone fastness over similar magenta dyes. The reaction of an arylnitro compound with 2-aminopyridine appeared to be an attractive and high yielding route to 2-(phenylazo)pyridine. However, application of this reaction to substituted and naphthalene systems failed. This afforded byproducts due to nucleophilic substitution of groups such as methoxy and the relatively uncommon nucleophilic substitution of hydrogen with none of the required azo products obtained. Therefore it appeared that the reaction of a nitro and amine was not a robust and versatile route to heterocyclic azo compounds. An alternate route to heterocyclic azo compounds involved the use of the Mills reaction by the condensation o-anisidine, p-chloroaniline, 2-aminophenol, 3- aminophenol, naphthylamine, 8-amnioquinoline and 2-acetylamino-5-aminobenzenesulfonic acid with 2-nitrosopyridine afforded the heterocyclic azo products in moderate to high yields. The Mills reaction does appear to be the favored route to heterocyclic azo compounds. Several factors were identified which affect the process of bisazo coupling of chromotropic acid and products obtained. Reaction at the ipso position of monoPACAs (2-phenylazochromotropic acid) leading to increased yields of the ipso substitution monoPACA by-product as opposed to the expected bisazo coupling position was a major problem. Studies indicated reactivity at the ipso position was greatly reduced by the presence of electron withdrawing groups around the phenyl ring of the monoPACA. Further study indicated reaction at the bisazo coupling position increased with the strength of the diazonium salt used in bisazo coupling. Therefore the electronic nature of the monoPACA starting material and the diazonium salt used in bisazo coupling greatly affected the products obtained. Reaction pH studies also revealed attack at the bisazo coupling position increases with pH and at lower pH (5.0 – 8.0) attack at the ipso position dominated. Reactivity of the monoPACA starting material also increased with pH. The influence of steric effects upon bisazo coupling revealed, in the cases where ortho sulfonic acid groups were present in the monoPACA, a reduction in attack at the ipso position. Hence the reaction appeared to be directed towards the required bisazo coupling position.

This dissertation deals with the characterization of the nonlinear absorption and refraction of two representative metallophthalocyanine dyes: chloro aluminum phthalocyanine dissolved in methanol, referred to as CAP, and a silicon naphthalocyanine derivative dissolved in toluene, referred to as SiNc. Using the Z-scan technique, the experiments are performed on both the picosecond and nanosecond timescales at a wavelength of 0.532 μm.

PhD. (Chemistry) / Please refer to full text to view abstract

Neste trabalho, são utilizados diversos métodos de química teórica para estudar as propriedades eletrônicas e o espectro de absorção de seis corantes catiônicos: laranja de acridina (LA), proflavina (PF), safranina (SF), vermelho neutro (VN), azul de metileno (AM) e tionina (TN). Inicialmente é realizado um estudo para verificar a influência do solvente na geometria e no espectro desses corantes utilizando diversos métodos de química quântica, o método de solvatação contínuo IEFPCM e a simulação de Monte Carlo (MC). A seguir são estudados a diprotonação, a dimerização e alguns modelos para a argila do tipo montmorilonita e para a interação desta com os corantes, fenômenos esses que explicam a metacromasia observada experimentalmente. / This work presents a theoretical study on the electronic properties and the absorption spectra of six cationic dyes: acridine orange, proflavine, safranine, neutral red, methylene blue and thionine. First of all, we have carried out calculations to verify the solvent effects on geometries and spectra employing methods of Quantum Chemistry and including solvent effects with the polarizable continnum model and Monte Carlo (MC) simulation. Also, we have studied diprotonation, dimerization and some models of the montmorillonite clay and its interaction with the cationic dyes under study here, phenomena that explain the experimental methacromatic behavior of these dyes.

A polimerização de monômeros vinílicos fotoiniciada por corantes foi estudada em diferentes meios (meio orgânico, ausência de solvente e meio hidrotrópico). A polimerização fotoiniciada do MMA pelo corante Vermelho Neutro na presença de trietilamina foi estudada com o objetivo de se determinar o mecanismo que leva à formação dos radicais iniciadores. Uma expressão para o rendimento de radicais livres foi deduzida a partir do mecanismo proposto, os valores experimentais para o equilíbrio e as constantes de reação para os estados fundamental, singlete e triplete do corante na presença de outras espécies e de trietilamina (co-iniciador) foram utilizadas para simular o comportamento do sistema de polimerização. A amina aromática 4-anisidina também foi utilizada como coiniciador. As cinéticas de fotopolimerização de monômeros multifuncionais foram acompanhadas com as técnicas de Fotocalorimetria Diferencial de Varredura (Foto-DSC) e Espectroscopia de Infravermelho por Transformada de Fourier em Tempo Real (RT-FTIR). Os iniciadores utilizados foram os corantes safranina e tioxantona. Os co-iniciadores usados foram as aminas TEA, TEOHA e EDB. Todos os sistemas foram estudados na ausência de solvente. Filmes poliméricos foram preparados para verificar a absorção de clorofórmio mediante a técnica de gravimetria. Tal estudo avaliou a relação entre a densidade de entrecruzamento dos polímeros e o fotoiniciador utilizado. Copolímeros de ESS e MMA ou HEMA foram preparados em meio hidrotrópico por polimerização fotoiniciada utilizando o corante catiônico safranina. A concentração de ESS utilizada foi de 0,5 M, pois nessa concentração há a formação de agregados de ESS, caracterizando o meio como hidrotrópico. As polimerizações dos monômeros MMA (hidrofóbico) e HEMA (hidrofílico) apresentaram comportamentos distintos frente ao meio hidrotrópico. / The photoinitiation of the polymerization of methyl methacrylate by the dye neutral red in the presence of thiethylamine was studied in order to determine the mechanism that leads to the formation of the initiating radicals. An expression for the yield of free radicals was deduced from the mechanism, and the experimental values for the equilibrium and reaction constants of the ground, singlet and triplet states of the dye in the presence of the other components of the formulation, were used to calculat the behaviour of the system when varying the concentration of the co-initiator triethylamine. The observed dependence fits closely the global polymerization rates obtained directly from polymerization kinetics studied by dilatometry. The amine 4-anisidine has also been used as co-initiator. The photoinitiated polymerization of multifunctional monomers was followed by real time infrared spectroscopy (RTIR) and by photo differential scanning calorimeter (Photo- DSC). Several parameters influence this kinetic such as temperature, photoinitiator concentration, light intensity, polymerizable function concentration, and material thickness. The initiators used in this study were the dyes safranine and thioxanthone. The co-initiators used were the amines TEA, TEOHA and EDB. The swelling of films of these copolymers were determined by chloroform absorption. A good inverse relationship was found between the swelling and the polymerization rates. Copolymers of styrenesulfonate and methyl methacrylate, or hydroxyethyl methacrylate, were prepared by photoinitiation polymerization using the cationic dye Safranine in hydrotropic medium. The reactions were be carried out at Stys concentrations higher than the MHC (minimum hydrotrope concentration) where the monomer forms aggregates.

Orientador: Maria Valnice Boldrin / Banca: Marilda das Dores Assis / Banca: Marcio Fernando Bergamini / Resumo: A tintura de cabelo é um processo adotado por milhões de pessoas, independente da raça, sexo, nacionalidade, religião ou idade. No entanto, os métodos analíticos disponíveis para avaliação destes produtos em formulação comercial, efluentes de salão de beleza, esgotos e águas superficiais são escassos. O presente trabalho investiga o desenvolvimento de um método analítico baseado em cromatografia líquida de alta eficiência com detector de arranjo de diodos para determinação dos corantes: Azul básico 99, Violeta ácido 43, Marrom básico 16, Vermelho básico 76 e Amarelo básico 57, usados em tinturas semipermanentes de cabelo. As melhores condições experimentais para separação dos corantes de cabelo de interesse foram: acetonitrila/água 35:65 (v/v) com adição de 4,0 x 10-2 mol L-1 de líquido iônico tetrafluoroborato de 1-butil-3-metilimidazólio (BMIm-BF4), à fase móvel, vazão: 0,4 mL min-1. Nestas condições experimentais observa-se melhor resolução e definição dos picos presentes nos cromatogramas nos respectivos tempos de retenção: AB 99 (tr =8,80 min), VA 43 (tr =14,78 min), MB 16 (tr =19,10 min), VB 76 (tr =25,08 min) e AB 57 (tr =34,17 min), confirmados pelos respectivos espectros hidrodinâmicos UV-Vis obtidos e comparados com o padrão de cada corante. O uso de liquido iônico como aditivo da fase móvel mostrou-se relevante para a detecção de corantes de cabelo melhorando significativamente a separação e encaudamento dos picos. Curvas analíticas foram construídas para cada corante de cabelo no intervalo de concentração de 1,0x10-7 a 8,0x10-5 mol L-1. O índice de recuperação dos corantes em água fortificadas por cada corante indicou valores entre 84 - 117 %. Amostras da tintura de cabelo comercial (HF 65, Arianor) foram submetidas à análise usando o método proposto e a concentração obtida... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The hair dye is a process used by millions of people regardless of race, sex, nationality, religion or age. However, the analytical methods available for evaluating these products in pharmaceutical formulation effluent salon, sewers and surface waters are scarce. This paper investigates the development of an analytical method based on high performance liquid chromatography with diode array detector for determination of dyes: Basic blue 99, Acid violet 43, Basic brown 16, Basic red 76 and Basic yellow 57 dyes used in semipermanent hair. Optimum conditions for separation of hair dyes of interest were acetonitrile / water 35:65 (v / v) with addition of 40 x 10-3 mol L-1 ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMIm-BF4), to the mobile phase flow rate: 0,4 ml min-1. Under these experimental conditions is observed better resolution and definition of these peaks in the chromatograms in the respective retention times: 99 AB (tr = 8.80 min) and VA 43 (tr = 14.78 min), 16 MB (tr = 19, 10 min), VB 76 (tr = 25.08 min) and 57 AB (tr = 34.17 min), confirmed by the respective UV-Vis spectra hydrodynamic obtained and compared with the pattern of each dye. The addition of ionic liquid additive as the mobile phase was found to be relevant for the detection of hair dyes significantly improved separation and peak tailing. Curves were constructed for each hair dye in the range of 1x10-7 to 8x10-5 mol L-1. The recovery rate of dyes in fortifield water indicated values between 84-117%. Samples of commercial hair dye (HF 65, Arianor) were analyzed using the proposed method and the concentration obtained for the dyes in the dye indicated the occurrence of AB 99, VA 43, MB 16, VB 76 and AB 57 in a concentration of 4,33 x 10-5, 8,81 x 10-6, 5,86 x 10-6, 1,31 x 10-4 and 1,99 x 10-5 mol L-1, respectively. The analytical method... (Complete abstract click electronic access below) / Mestre

Orientador: Maria Valnice Boldrin Zanoni / Co-orientador: Lucio César de Almeida / Banca: Maria del Pilar Taboada Sotomayor / Banca: Magno Aparecido Gonçalves Trindade / Resumo:Em virtude do alto consumo de corantes de cabelo e sua alta diluição em efluentes e estações de tratamento de água após tratamento incompleto, a demanda por métodos analíticos cada vez mais sensíveis e robustos para sua quantificação é altamente pertinente. Diante disso, o presente trabalho descreve a construção de dois sensores eletroquímicos para quantificação de corantes de cabelo. O primeiro consiste no desenvolvimento de um eletrodo de carbono vítreo modificado com compósito de MWCNTs-CHT para determinação simultânea de PPD e RSN em amostras comerciais de tintura permanente de cabelo e em amostras de água de torneira. A Ipa obtida para PPD e RSN são 60% e 100% maiores, respectivamente, quando são comparadas ao eletrodo sem modificação. A reação entre ambos foi monitorada pelas técnicas de espectrofotometria na região UV-Vis, espectrometria de massas e oxidação eletroquímica, onde foi possível diagnosticar a formação da Base de Bandrowski e outros produtos correspondentes à coloração do cabelo. Uma curva analítica foi construída para PPD e RSN com relação linear entre 0,55 a 21,20 mg L-1 e limites de detecção de 0,79 e 0,58 mg L-1, respectivamente. O método foi aplicado em amostras de água de torneira com recuperações em torno de 100% e em amostra da tintura de cabelo comercial (EMBELLEZE MAXTON (2.0 preto natural)), encontrando-se 24,10 e 10,34 mg g-1 de tintura para PPD e RSN, respectivamente. O método foi validado por espectrofotometria. Outro método eletroanalítico foi desenvolvido usando eletrodo de carbono impresso modificado com grafeno para determinação do corante temporário BA-41 em 0,10 mol L-1 de tampão B-R pH 6,90. A corrente de pico é 1.300% maior quando comparada aos eletrodos de carbono impresso e carbono vítreo, ambos sem modificação. Utilizando-se a técnica de onda quadrada, os parâmetros foram otimizados através de... / Abstract: Due to the use of dyes hair and the your high dilution in wastewater and water treatment plants after incomplete treatment, the demand for increasingly sensitive and robust analytical methods for its quantification is highly relevant. Thus, the present work describes the construction of two sensors for quantification of hair dyes. The first was the development of a glassy carbon electrode modified with composite MWCNTs-CHT for simultaneous determination of PPD and RSN in samples of commercial hair dye and in samples of tap water. The Ipa of RSN and PPD presented 60% and 100% increase, respectively, in modified electrode compared to the electrode without modification. The reaction between both was monitored by spectrophotometry in the region UV-Vis, mass spectrometry and electrochemical oxidation where it was possible to diagnose the formation of the Bandrowski base and other related products the hair coloring. An analytical curve for PPD and RSN was constructed and finding a linear range in the interval of 0.55 to 21.2 mg L-1 with detection limit of 0.79 and 0.58 mg L-1, respectively. The method was applied to samples of tap water with recovery around 100% and in sample of commercial hair dye (EMBELLEZE MAXTON (2.0 preto natural)), finding 24.10 and 10.34 mg g-1 of dye for PPD and RSN, respectively. The method was valeted by spectrophotometry. Other electroanalytical method was developed using screen printed electrode modified with grapheme for determining of the temporary dye BA-41 in 0,1 mol L-1 of B-R buffer pH 6,90. The peak current is 1,300% greater when compared with screen printed and glassy carbon electrodes, both unmodified. Through the technique of square wave voltammetry, the method was optimized of multivariate form using factorial design 24 and Doehlert matrix. Under optimized conditions of f (67 Hz), pH (6,90), ΔE (128 mV) and Esw (6 mV), we constructed a calibration curve with a... / Mestre

Diante do caos, principalmente ambiental e social, que o planeta terra tem vivenciado, muito tem se falado em sustentabilidade e suas correspondentes estratégias para tentar deter essa situação. Indo ao encontro desta iniciativa foi desenvolvido o presente trabalho, intitulado de Uso dos corantes de origem natural no tingimento de artigos têxteis de Moda cujo objetivo principal foi o de trazer pigmentações naturais sem formulações tão agressivas para a aplicação em artigos do vestuário de moda e, assim, tentar conter, ao menos, em parte, o estrago que a indústria têxtil, uma das maiores poluidoras do meio ambiente, tem causado no mundo. Para isto, foi estabelecida uma metodologia que consistiu em quatro etapas, ou seja, pesquisa de dados bibliográficos para servir de referência sobre a temática em questão e a obtenção de pigmentos naturais oriundos de plantas amazônicas, escolha dos substratos têxteis, selecionados de acordo com a afinidade com os extratos corantes, análise da potencialidade de aplicação dos corantes nos substratos estudados (verificação do índice de solidez dos corantes à lavagem e à luz) e produção de uma cartela de cores, uma coleção e artigos de vestuário com os tecidos tingidos com alguns dos corantes estudados. Como principais resultados deste trabalho obtiveram-se corantes que, na interação com as fibras, provocaram tingimentos uniformes, pouca quantidade usada destes materiais, composição química inserida nos padrões sustentáveis, poucos resíduos expelidos nas sobras dos banhos de tingimento, uma cartela de cores variadas, boa solidez às lavagens e à luz, uma coleção de roupas e quatro peças confeccionadas da mesma, com o uso dos corantes naturais, o que conferiu aos extratos corantes a qualidade de sustentáveis. / Faced with the chaos, especially environmental and social, that the planet earth has experienced, much has been said in sustainability and their corresponding strategies to try to stop this situation. Going to meet this initiative is the present work, entitled \"Use of natural dyes in textile dyeing Fashion\" whose main objective is to bring natural pigmentations without such aggressive formulations for use in articles of clothing industry, thus try to contain, at least in part, the damage to the textile industry, a major environmental pollutant, has caused in the world. For this, a methodology was established which consisted of four steps, i.e., search of bibliographic data for reference on the subject in question and obtaining natural pigments from Amazonian plants, choice of textile substrates selected according to the affinity with dye extracts, analysis of potential application of dyes on the substrates studied (check the index of dye fastness to washing and light) and production of a color palette, a collection and garments with dyed fabrics with some of the dyes studied. The main results of this work were obtained dyes that, in interaction with the fibers, caused uniforms dyes, little amount of these materials used, chemical composition inserted in sustainable patterns, little waste expelled the remains of dye baths, a varied color palette, good fastness to washing and light, clothing collection and four pieces made, with the use of natural dyes, which gave the dye extracts sustainable quality.