Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 132-142).

Thesis (Ph.D. in Neuroscience) -- University of Colorado Denver, 2007. / Typescript. Includes bibliographical references (leaves 84-93). Free to UCD affiliates. Online version available via ProQuest Digital Dissertations;

Thesis (Ph. D.)--Auburn University. / Abstract. Vita. Includes bibliographical references (p. 153-178).

Orientador: Carlos Renato Corso / Banca: Cassiana Maria Reganhan Coneglian / Banca: Sandra Mara Martins Franchetti / Resumo: Entre as questões ambientais mais discutidas pela sociedade, está a poluição pelos diversos ramos da indústria. As indústrias têxteis estão entre os responsáveis pela contaminação, pois, muitas vezes, eliminam seus efluentes sem tratamento adequado nos mananciais, portanto, sem a completa remoção dos corantes. Os corantes azóicos são os mais utilizados pela indústria têxtil e são caracterizados pela presença de grupos azo (N=N). Dos vários métodos de tratamento de efluentes existentes, o tratamento biológico tem sido amplamente estudado. Buscando uma maneira de melhorar o tratamento biológico, o presente trabalho teve como objetivo comparar a capacidade de biossorção e biodegradação do corante azóico Direct Blue 71 em solução pelos fungos Phanerochaete chrysosporium e Aspergillus oryzae, na forma paramorfogênica. Para isso utilizou-se uma solução de corante DB71 a 100 μg/mL. Foram realizados testes de biossorção, por um período de 2 horas, com cinco diferentes concentrações de biomassa e três valores de pH, 2.5, 4.5 e 6.5, sendo que o pH 2.5 proporcionou a melhor condição para a biossorção. A adsorção do corante pela parede celular de ambos os fungos foi avaliado com o auxílio das isotermas de Freundlich, modelo seguido por P. chrysosporium, e Langmuir, seguido por A. oryzae. Para os testes de biodegradação, por 240 horas, utilizou-se apenas uma concentração de biomassa. Com espectrofotometria UV-VIS foi possível determinar porcentagem de descoloração e absorbância relativa do corante após realização dos testes de biossorção e biodegradação, respectivamente. Análises de FTIR permitiram a identificação de moléculas presentes na solução antes e após a biodegradação. Com A. oryzae obteve-se os melhores resultados de biossorção e biodegradação. Contudo, P. chrysosporium também se mostrou eficiente para os tratamentos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Among many environmental issues discussed in society, all sorts of pollution from industrial branches arise as an important matter. Textile industries are responsible by such contamination, since they often eliminate their effluents in the environment without proper treatment, therefore, without complete dye removal. Azo dyes are frequently used in textile industry and characterized by the presence of azo groups (N = N). Of the various methods of wastewater treatment available, biological treatment has been extensively studied. Thus, to improve biological treatment in textile industries, this study aimed to compare the ability of biosorption and biodegradation of Azo dye Direct Blue 71 solution by Phanerochaete chrysosporium and Aspergillus oryzae fungi in paramorfogenic form. In order to achieve this, a 100 μg/mL DB7 dye solution was used. Biosorption tests were performed within two hours with five different biomass concentrations and three pH values, 2.5, 4.5 and 6.5. It was observed that pH 2.5 solutions presented best biosorption conditions. The dye adsorption through studied fungi cell wall was evaluated with the Freundlich isotherm model for P. chrysosporium, and Langmuir for A. oryzae. For the biodegradation tests in 240 hours, it was used only one biomass concentration. Through an UV-VIS spectrophotometry the percentage of relative absorbance and dye discoloration was determined after biosorption and biodegradation tests respectively. FTIR analysis allowed molecular compounds identification in solution before and after biodegradation. The best results were obtained with A. oryzae in both biosorption and biodegradation. Yet even then P. chrysosporium was also efficient in all treatments. Hence, both A. oryzae and P. chrysosporium have great potential of dye removal in wastewaters. These results may contribute to improve effluent treatment systems in textile industries. / Mestre

Orientador: Maria Valnice Boldrin Zanoni / Banca: Cintia Duarte de Freitas Milagre / Banca: Hideko Yamanaka / Banca: Silvia Helena Pires Serrano / Banca: Patricia Alves Carneiro / Resumo: Corantes sintéticos do tipo azo têm sido um assunto de grande preocupação ambiental devido ao potencial genotóxico e mutagênico dos produtos de biotransformação. Deste modo, nos últimos anos a consequência da ingestão destes corantes presentes na agua potável servida à população é discutida por diversos autores. Este estudo avalia a ação de microssomas de fígado de rato, enzimas redutoras produzidas pela bactéria Escherichia coli (E. coli) e nitroredutase imobilizada na biotransformação de três corantes dispersos que possuem grupos azo, Disperse Red 73 (DR 73), Disperse Red 78 (DR 78) e Disperse Red 167 (DR 167). A técnica de Espectrofotometria de absorção molecular na região do Uv- visível, Cromatografia Líquida de Alta Eficiência com detector de arranjo de diodos (CLAE-DAD) e Cromatografia líquida acoplada à espectrometria de massas (LC-MS/MS) foram técnicas usadas para identificar os principais produtos gerados após os processos de degradação dos corantes. Polímeros de impressão molecular magnéticos (MMIPs) foram investigados usando reações de polimerização por precipitação para pré-concentração do corante DR 73, juntamente com a degradação por fotoeletrocatálise e subsequente análise dos produtos por LC-MS/MS. Os estudos in vitro do metabolismo de biotransformação dos corantes têxteis com microssoma de fígado de rato mostraram que as reações ocorreram preferencialmente no grupo azo e nitro dos corantes, indicando a redução destes grupos pelas enzimas do citocromo P-450. F... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Synthetic azo dyes have been a matter of great concern due to the genotoxic and mutagenic potential of the products originating from azo dye biotransformation. Thus, in recent years the result of the intake of these dyes present in drinking water supplied to a population is discussed by several authors. This work evaluates the action of rat liver microsomes, reducing enzymes produced by the Escherichia coli ( E. coli ) and nitroreductase immobilized on biotransformation of three disperse dyes bearing azo groups, namely Disperse Red 73 (DR 73), Disperse Red 78 (DR 78), and Disp erse Red 167 (DR 167) . UV - Vis spectrophotometry, high - performance liquid chromatography with diode array detector (HPLC - DAD), and liquid chromatography coupled to mass spectrometry (LC - MS/MS) were techniques used to identify the main products generated aft er the process degradation of dyes. Magnetic molecularly imprinted polymers (MMIPs) were investigated using precipitation polymerization reactions for preconcentration of the dye DR 73, together with the photoelectrocatalysis degradation and subsequent ana lysis of the products by LC - MS/MS. In vitro studies of biotransformation metabolism of textile dyes with rat liver microsome showed that the reactions occur preferentially in the group of azo and nitro dyes, indicating the reduction of these groups by enzy mes of the cytochrome P - 450. There were obtained two degradation products for each dye after reaction with E. coli ; the dye DR 73 gave the product 3 - ((4 - aminophenyl) (ethyl) amino) propanitrila and 4 - nitroaniline, the product 3 - ((4 - aminophenyl) (ethyl) amino) propanitrila and 2 - chloro - 4 - nitroaniline were obtained after reaction with the dye DR78 and DR 167 gave 3,3' - dimethyl - ((3 - acetamido - 4 - aminophenyl) azanediyl) dipropanoato and 2 - chloro - 4 - nitroaniline; indicating cleavage of the azo group, possibly b y azoredutase enzyme... / Doutor

abstract: Most of the sunlight powering natural photosynthesis is absorbed by antenna arrays that transfer, and regulate the delivery of excitation energy to reaction centers in the chloroplast where photosynthesis takes place. Under intense sunlight the plants and certain organisms cannot fully utilize all of the sunlight received by antennas and excess redox species are formed which could potentially harm them. To prevent this, excess energy is dissipated by antennas before it reaches to the reaction centers to initiate electron transfer needed in the next steps of photosynthesis. This phenomenon is called non-photochemical quenching (NPQ). The mechanism of NPQ is not fully understood, but the process is believed to be initiated by a drop in the pH in thylakoid lumen in cells. This causes changes in otherwise nonresponsive energy acceptors which accept the excess energy, preventing oversensitization of the reaction center. To mimic this phenomenon and get insight into the mechanism of NPQ, a novel pH sensitive dye 3'6'-indolinorhodamine was designed and synthesized which in a neutral solution stays in a closed (colorless) form and does not absorb light while at low pH it opens (colored) and absorbs light. The absorption of the dye overlaps porphyrin emission, thus making energy transfer from the porphyrin to the dye thermodynamically possible. Several self-regulating molecular model systems were designed and synthesized consisting of this dye and zinc porphyrins organized on a hexaphenylbenzene framework to functionally mimic the role of the antenna in NPQ. When a dye-zinc porphyrin dyad is dissolved in an organic solvent, the zinc porphyrin antenna absorbs and emits light by normal photophysical processes. Time resolved fluorescence experiments using the single-photon-timing method with excitation at 425 nm and emission at 600 nm yielded a lifetime of 2.09 ns for the porphyrin first excited singlet state. When acetic acid is added to the solution of the dyad, the pH sensitive dye opens and quenches the zinc porphyrin emission decreasing the lifetime of the porphyrin first excited singlet state to 23 ps, and converting the excitation energy to heat. Under similar experimental conditions in a neutral solution, a model hexad containing the dye and five zinc porphyrins organized on a hexaphenylbenzene core decays exponentially with a time constant of 2.1 ns, which is essentially the same lifetime as observed for related monomeric zinc porphyrins. When a solution of the hexad is acidified, the dye opens and quenches all porphyrin first excited singlet states to <40 ps. This converts the excitation energy to heat and renders the porphyrins kinetically incompetent to readily donate electrons by photoinduced electron transfer, thereby mimicking the role of the antenna in photosynthetic photoprotection. / Dissertation/Thesis / Ph.D. Chemistry 2012

Orientador: Odair Aparecido Fernandes / Banca: Enrico de Beni Arrigoni / Banca: Celso Omoto / Banca: Sérgio de Freitas / Banca: Arlindo Leal Boiça Junior / Resumo: Com a adoção de plantas geneticamente modificadas que expressam toxinas de Bacillus thuringiensis há a necessidade de estabelecimento de estratégias para retardar o desenvolvimento da resistência de insetos, tais como áreas de refúgio. Para tanto, informações sobre a dispersão dos insetos alvo desta tecnologia são essenciais para aprimoramento de técnicas de manejo de insetos-praga. Nos estudos de dispersão normalmente são usadas técnicas de marcação-liberação-recaptura. Assim, objetivou-se com este trabalho marcar Diatraea saccharalis e avaliar a capacidade de dispersão de Spodoptera frugiperda. Para a marcação, dois corantes lipossolúveis em diferentes concentrações (100 a 400 ppm), Sudan Red 7B e Solvente Blue, foram adicionados à dieta artificial de D. saccharalis e avaliados sobre parâmetros biológicos do desenvolvimento de lagartas, pupas e adultos (fecundidade e longevidade). A adição dos corantes em dieta artificial fornecida para alimentação de lagartas de D. saccharalis proporcionou a marcação de adultos e ovos em todas as concentrações testadas. No caso da avaliação da capacidade de dispersão de S. frugiperda foram realizados experimentos durante as safras 2005/2006 e 2006/2007. A dispersão se dá por difusão e foi possível registrar distâncias máximas de recaptura de 806 m para machos e 608 m para fêmeas de S. frugiperda. / Abstract: With the adoption of genetically modified plants expressing Bacillus thuringiensis toxins there is a need of establishing strategies to delay the development of insect resistance (e.g. refugee areas). Thus, information on target insects dispersal are essential to improve pest management techniques. In dispersal studies, markingrelease- recapture techniques are usually used. The objective of this work was to mark Diatraea saccharalis and evaluate the dispersal capacity of Spodoptera frugiperda. For marking D. saccharalis, different concentrations (100 to 400 ppm) of two oil soluble dyes (Sudan Red 7B and Solvent Blue) were added to larval artificial diet. Larval and pupal development as well as adult fecundity and longevity were evaluated. The addition of dyes into the diet marked both adults and eggs, regardless the concentration used. For evaluating the dispersal capacity of S. frugiperda, experiments were carried out during 2005/2006 and 2006/2007 growing seasons. Dispersal is diffused and the maximum recapture distances were 806 m for males and 608 m for females of S. frugiperda. / Doutor

The need to reduce the cost of adsorption technology has led scientists to explore the use of many low cost adsorbents especially those from renewable resources. Lignocellulose and montmorillonite clay have been identified as potentially low cost and efficient adsorbent materials for the removal of toxic heavy metals and organic substances from contaminated water. Montmorillonite clay has good adsorption properties and the potential for ion exchange. Lignocellulose possesses many hydroxyl, carbonyl and phenyl groups and therefore, both montmorillonite and lignocellulose are good candidates for the development of effective and low cost adsorbents in water treatment and purification. The aim of this study was to prepare composite materials based on lignocellulose and montmorillonite clay and subsequently evaluate their efficacy as adsorbents for heavy metal species and organic pollutants in aqueous solution. It was also important to assess the adsorption properties of the modified individual (uncombined) lignocellulose and montmorillonite. Lignocellulose and sodium-exchanged montmorillonite (NaMMT) clay were each separately modified with methyl methacrylate (MMA), methacrylic acid (MAA) and methacryloxypropyl trimethoxysilane (MPS) and used as adsorbents for the removal of heavy metals and dyes from aqueous solution. The lignocellulose and NaMMT were modified with MMA, MAA and MPS through free radical graft polymerisation and/or condensation reactions. NaMMT was also modified through Al-pillaring to give AlpMMT. The materials were characterised by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and small angle X-ray scattering (SAXS) and characterisation results showed that the modification of the montmorillonite with MAA, MMA and MPS was successful. The modified lignocellulose and montmorillonite materials were evaluated for the adsorption of heavy metal ions (Cd2+ and Pb2+) from aqueous solution by the batch method. The adsorption isotherms and kinetics of both Cd2+ and Pb2+ onto the NaMMT clay, AlpMMT and lignocellulose materials are presented. The Langmuir isotherm was found to be the best fit for the adsorption of both heavy metals onto all the adsorbents. AlpMMT showed very poor uptake for heavy metals (both Cd2+ and Pb2+). PMMAgMMT, PMAAgMMT, PMAAgLig and PMPSgLig showed improved adsorption for both heavy metals. The mechanism of heavy metal adsorption onto the adsorbents was best represented by the pseudo second-order kinetic model. PMPSgLig, NaMMT and AlpMMT showed relatively high adsorption capacities for methyl orange, while the adsorption of neutral red was comparable for almost all the adsorbents. Neither the Langmuir model nor the Freundlich model was found to v adequately describe the adsorption process of dyes onto all the adsorbents. The pseudo second-order model was found to be the best fit to describe the adsorption mechanism of both dyes onto all the adsorbents. The modification of lignocellulose and montmorillonite with suitable organic groups can potentially produce highly effective and efficient adsorbents for the removal of both heavy metals and dyes from contaminated water. Novel adsorbent composite materials based on lignocellulose and montmorillonite clay (NaMMT) were also prepared and evaluated for the removal of pollutants (dyes and heavy metals) from aqueous solution. The lignocellulose-montmorillonite composites were prepared by in situ intercalative polymerisation, using methyl methacrylate, methacrylic acid and methacryloxypropyl trimethoxysilane (MPS) as coupling agents. The composite materials were characterised by FTIR, TGA, TEM and SAXS. SAXS diffractograms showed intercalated nanocomposites of PMMAgLig-NaMMT and PMAAgLig-NaMMT, whereas PMPSgLig-NaMMT showed a phase-separated composite and the same results were confirmed by TEM. The lignocellulose-montmorillonite composites were assessed for their adsorption properties for heavy metal ions (Cd2+ and Pb2+) and dyes (methyl orange and neutral red) from aqueous solution. Among these composite materials, only PMAAgLig-NaMMT showed a marked increase in the uptake of both Cd2+ and Pb2+ relative to lignocellulose and montmorillonite when used independently. The adsorption data were fitted to the Langmuir and Freundlich isotherms, as well as to the pseudo first-order and pseudo second-order kinetic models. The data were best described by the Langmuir isotherm and the pseudo second-order kinetic model. On the adsorption of dyes, only PMPSgLig-NaMMT showed enhanced adsorption of methyl orange (MetO) compared with lignocellulose and montmorillonite separately. The enhanced adsorption was attributed to the synergistic adsorption due to the presence of MPS, lignocellulose and NaMMT. Competitive adsorption studies were carried out from binary mixtures of MetO and Cd2+ or Pb2+ in aqueous solution. The adsorption process of MetO onto the composite material was found to follow the Freundlich adsorption model, while the mechanism of adsorption followed both the pseudo first-order and pseudo second-order models. This particular composite can be used for the simultaneous adsorption of both heavy metals and organic dyes from contaminated water. The adsorption of neutral red to the composite materials was comparable and the pseudo second-order kinetic model best described the adsorption mechanism.

The thesis explored the use of different sorbent materials in solid phase extraction method development. The methods included the use of the polymeric Agilent Bond Elut Plexa solid phase extraction and electrospun polymer-silica composite sorbents for clean-up and preconcentration. Sample clean-up for alkaloids (hydrastine and berberine) in goldenseal, Hydrastis canadensis and flavonoids (quercetin, kaempferol and isorhamnetin) in Ginkgo biloba was achieved using Bond Elut Plexa SPE sorbent. Clean-up of flavonoids in Ginkgo biloba was also achieved using electrospun polymer-silica composite (polystyrene-silica, polyacrylonitrile-silica and nylon 6-silica) sorbents. All analysis of flavonoids and alkaloids was carried out using an Agilent 1200 Series HPLC coupled with a diode array detector. Good peak separation was achieved in less than 6 min employing an Agilent ZORBAX Eclipse Plus C18 column (4.6 x 75 mm, 3.5 μm) at 35⁰C. The mobile phases employed were 0.1% phosphoric acid/methanol gradient and 0.5% phosphoric acid/methanol (40:60) for alkaloids and flavonoids respectively. The calibration curves exhibited linearity up to 120 μg mL⁻¹ with correlation coefficients of more than 0.9980. The recoveries ranged from 73-109% with relative standard deviation of less than 5% for all analytes. Agilent Chem Elut supported liquid extraction was employed for the development of a sample preparation method for the determination of 24 banned aromatic amines from azo dyes in textile following the EU standard method EN 14362-1:2003 (E) and the Chinese standard method GB/T 17592-2006. The supported liquid extraction was effective in the extraction of the aromatic amines from textile (cotton, wool and polyester/cotton [80%:20%]). Most of the recoveries obtained were conforming to the minimum requirements set in the EN 14362-1:2003 (E) standard method and the relative standard deviations were less than 15%. Good peak separation was obtained within 70 min run time using the Agilent Zorbax SB-Phenyl column (4.6 mm x 250 mm, 5-micron) or the Agilent DB-35 MS (J & W) (30 m x 0.25 mm, 0.25 μm film thickness. It was demonstrated that the polymeric Agilent Bond Elut Plexa, electrospun nanofibers and diatomaceous earth were effective in extraction of alkaloids, flavonoids and aromatic amines in different matrices. The developed methods were simple, rapid and reproducible.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-09-05T17:55:13Z No. of bitstreams: 1 Dissertação (Fredson Santos Guimarães).pdf: 3047547 bytes, checksum: ab4e997db06f03d33d60e156a51abba1 (MD5) / Approved for entry into archive by Vanessa Reis (vanessa.jamile@ufba.br) on 2016-09-06T10:42:39Z (GMT) No. of bitstreams: 1 Dissertação (Fredson Santos Guimarães).pdf: 3047547 bytes, checksum: ab4e997db06f03d33d60e156a51abba1 (MD5) / Made available in DSpace on 2016-09-06T10:42:39Z (GMT). No. of bitstreams: 1 Dissertação (Fredson Santos Guimarães).pdf: 3047547 bytes, checksum: ab4e997db06f03d33d60e156a51abba1 (MD5) / CAPES / A hidrotalcita é um hidroxicarbonato de magnésio e alumínio que consiste em camadas do tipo brucita e ocorre na natureza como lâminas contorcidas e folheadas e/ou massa fibrosa. Quando Mg2+ e Al3+ são trocados completamente ou parcialmente com M2+ (M = Co, Ni, Cu, Zn, Fe) e M3+ (Cr e Fe) respectivamente, materiais cristalinos com estrutura hidrotalcita podem ser obtidos. A fórmula geral do LDH é [M2+1-xM3+x(OH)2]+(An-x/n)yH2O, onde M2+ e M3+ são respectivamente cátions metálicos di e trivalentes. Neste trabalho, pigmentos híbridos derivados de hidróxidos duplos lamelares (LDHs) com o corante vermelho congo (diazo) e o corante negro de eriocromo T (azo) foram preparados por dois métodos diferentes: i) adsorção de uma solução de corante sobre MgAl-LDH, previamente preparado por coprecipitação em pH = 11 empregando Na2CO3; ii) automontagem por coprecipitação em pH = 11 dos íons Mg2+ e Al3+ com NaOH em uma solução contendo o corante (self assembly). Análises de DRX mostraram que o espaçamento basal (d003) da matriz MgAl-LDH dos pigmentos preparados por adsorção não sofreu variação, sugerindo que as moléculas dos corantes estão adsorvidas na superfície externa dos cristais de LDH enquanto que os preparados pelo método self assembly revelaram que parte dos corantes azo encontra-se intercalada. Análises TG/DTG mostraram que as temperaturas de decomposição oxidativa dos corantes foram deslocadas para valores superiores, sugerindo que as moléculas do corante são termicamente mais estáveis na estrutura do LDH. As análises de microscopia eletrônica de varredura corroboraram os resultados de DRX, mostrando que os pigmentos preparados pelos métodos da adsorção e self assembly tem morfologia lamelar, típica de compostos tipo hidrotalcita ratificando os resultados das análises de DRX. Quando submetidos a testes de estabilidade em solventes de diferentes polaridades (água, etanol e acetonitrila), os pigmentos híbridos mostraram-se mais estáveis quando o solvente foi a água. Pode-se atribuir essa estabilidade a diferenças estruturais mais significativas na estrutura dos corantes com a molécula da água quando comparado com outros solventes. / Hydrotalcite is a hydroxycarbonate of magnesium and aluminium and occurs in nature in foliated and contorced plates and/or fibrous masses. When Mg2+. and Al3+. are replaced wholly or partially with M2+. (M.Co, Ni, Cu, Zn, Fe) and M3+. (M.Cr, Fe), respectively, crystalline materials with the hydrotalcite can be obtained. The general formula of LDH is [M2+1-xM3+x(OH)2]+(An-x/n)yH2O, where M2+ and M3+ are respectively metallic cations divalents and trivalents. In this work, hybrid pigments, derived from layered double hydroxides (LDHs) with the diazo dye congo red and azo dye eriochrome black t , were prepared using two different methods: i) adsorption of aqueous solution of congo red onto MgAl-LDH, previously prepared by coprecipitation at pH = 11, using Na2CO3; and ii) coprecipitation of Mg2+and Al3+ in a congo red containing solution, at pH = 11, using NaOH as precipitating agent (self assembly); iii) adsorption of aqueous solution of eriochrome black t onto MgAl-LDH, previously prepared by coprecipitation at pH = 11, using Na2CO3; and ii) coprecipitation of Mg2+and Al3+ in a eriochrome black t containing solution, at pH = 11, using NaOH as precipitating agent (self assembly). X-ray diffraction show in the samples prepared by adsorption no change in the basal space (d003) was observed, suggesting that intercalation of the anionic dye did not occur significantly. In the sample prepared by self-assembly, it was observed the formation of a LDH containing at least part of the dye in the interlayer region. In the thermogravimetric analysis TGA show the temperature of oxidation decomposition of the dyes occurs at a temperature higher, indicating that the thermal stability of pigment is enhanced by intercalation in the layered host. Scanning electron micrographs analysis shows the morphology of the hybrid pigments prepared by adsorption and self assembly show morphology characteristic of hydrotalcite materials which was observed for all samples. When to subdue the stability tests in solvents of polarity different (water, ethanol , acetonitrile), the hybrids pigments show higher stabily when the solvents is water.