It is the responsibility of humans, as environmental stewards, to monitor our impact on the environment so that efforts can be made to remediate the effects of our actions and change behaviors. To better understand our environmental footprint, sensitive and simple analytical methods are needed to quantify the contaminants that we discharge into our natural surroundings. Emerging environmental contaminants are of particular concern because there is limited or no information available on their occurrence, fate, and toxicity. As a result, the implications of using these chemicals are not well understood. Therefore, accurate environmental data are needed to help scientists and government policy-makers make informed decisions on research directions and chemical regulation. However, challenges exist for the analysis of emerging contaminants, including a lack of suitable analytical standards and internal standards, their broad range of chemical properties, and that they are frequently present at trace levels and in complex environmental matrices. The work presented within this dissertation focuses on the development, validation, and comparison of analytical methodologies based on large-volume injection high-performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS) for the analysis of emerging environmental contaminants in aqueous environmental matrices. Large-volume injection (e.g. 900 μL to 4,500 μL) is an analytical technique that eliminates sample preparation associated with pre-concentration by injecting larger-than-traditional volumes of sample directly onto a HPLC column. In Chapter 2, a direct aqueous large-volume injection method was developed and validated for the quantification of natural and synthetic androgenic steroids in wastewater influent, wastewater effluent, and river water. This method was then applied to hourly composite samples of wastewater influent that were taken over the course of a single day. This work expands on the research of the endocrine-disrupting chemicals that occur in wastewater and provides an estimate of the community use/abuse of synthetic androgenic steroids. Environmental analytical methods should be as environmentally friendly as possible and efforts should be made to reduce the waste generated during analysis while maintaining analytical performance. In Chapter 3, a method based on large-volume injection was compared to two methods based on solid-phase extraction. The purpose of this comparison was to demonstrate that the same method performance could be achieved by large-volume injection as that by solid-phase extraction while reducing waste, labor, and costs. Estrogens and perfluorinated chemicals were used as model analytes and wastewater influent was used as a model matrix. The results of this study provide convincing reasons for analysts to adopt large-volume injection as an alternative to solid-phase extraction. In Chapter 4, a novel analytical method was developed and validated to quantify newly-identified and legacy fluorinated chemicals in groundwater. The final method combined micro liquid-liquid extraction, non-aqueous large-volume injection, and orthogonal chromatographic separations. Ground water samples collected from six different U.S. military bases was used to demonstrate the method. This is the first report on the occurrence of these newly-identified fluorinated chemicals in any environmental media and serves as a rational for conducting future research on their environmental fate and toxicity. The breadth of the research presented in this dissertation advances the field of environmental analytical chemistry in several areas. First, classes of environmental contaminants for which there is limited (synthetic androgenic steroids) or no (newly-identified fluorochemicals) environmental data were studied. Second, novel methods based on direct-aqueous and non-aqueous large-volume injection were developed and validated to identify and quantify those contaminants. Third, it was demonstrated that solid-phase extraction is not a "necessary evil" needed to develop methods for emerging environmental contaminants in aqueous matrices. Finally, this work is a platform on which other environmental chemists can use to develop large-volume injection methods in the future. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Aug. 2, 2012 - Feb. 2, 2013

Thesis (Ph. D.)--University of Washington, 2001. / Vita. Includes bibliographical references (leaves 169-182).

Thesis (Ph.D.)--McMaster University, 2004. / Advisor: G. J. Schrobilgen. Includes bibliographical references (leaves 333-352). Also available online.

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Made available in DSpace on 2014-10-09T12:34:55Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:11Z (GMT). No. of bitstreams: 0 / Apesar dos constantes avanços no tratamento de câncer, essa doença continua sendo umas das principais causas de mortalidade no mundo todo, portanto, é imperativo que novas modalidades de tratamento sejam desenvolvidas. Venenos de serpentes causam uma variedade de efeitos biológicos, pois constituem uma mistura complexa de substâncias como disintegrinas, proteases (serino e metalo), fosfolipases A2, L-aminoácido oxidases entre outras. No presente trabalho pesquisou-se em alguns venenos de serpentes frações com atividade antitumoral, pois há relatos de compostos ofídicos que apresentam esta atividade. Após fracionamento de venenos de serpentes das famílias Viperidae e Elapidae foram feitas incubações das frações obtidas com células normais de fibroblasto L929 e de melanoma B16-F10. Os resultados mostraram que as frações do veneno da serpente Notechis ater niger apresentaram a maior especificidade e potencial antitumoral em células de melanoma murino B16-F10 que os demais venenos utilizados. Este achado, aliado ao fato de ser um veneno pouco explorado foram determinantes para que este veneno fosse selecionado para dar continuidade aos estudos. As frações citotóxicas deste veneno foram submetidas a análises para identificar e caracterizar os componentes que apresentaram esta atividade atitumoral. Ensaios de western-blot e zimografia sugerem que estas proteínas não pertencem à classe das metalo e serinoproteinases. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

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Orientadores: Fernanda Miori Pascon, Regina Maria Puppin Rontani / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-25T06:58:59Z (GMT). No. of bitstreams: 1 Varanda_Thais_M.pdf: 1172292 bytes, checksum: 71c27c4d27c0cb61adf62bbf82fa7e88 (MD5) Previous issue date: 2014 / Resumo: Lesões de mancha branca são comumente observadas em dentes decíduos (DD) e quando diagnosticadas e tratadas precocemente com diversos materiais que liberam fluoretos, apresentam prognóstico favorável. Os objetivos desta dissertação foram: (1) avaliar quanti-qualitativamente dois tempos de formação de lesões de cárie sub-superficiais (LCSS) em DD; (2) avaliar quanti-qualitativamente o efeito de três vernizes fluoretados: Duraphat®, MI Varnish¿, e Vanish¿ em LCSS de DD. Para o objetivo 1, utilizou-se 20 DD distribuídos em 2 grupos (n=10): 8 e 16h. Foram produzidas LCSS em blocos de esmalte utilizando-se solução desmineralizadora. Profundidade (análise quantitativa) e homogeneidade (análise qualitativa) das lesões foram avaliadas em microscopia de luz polarizada (MLP). Para a profundidade foram realizadas 3 medidas em cada lesão (em µm) e calculou-se a média. Para a homogeneidade as imagens foram classificadas em escores (0=ausência de homogeneidade; 1=homogeneidade). Os dados quantitativos foram submetidos ao teste de normalidade, Shapiro-Wilk e uma vez que não obedeceram à distribuição normal dos dados, estes foram submetidos ao teste de Mann-Whitney. Quanto à profundidade não se observou diferença significativa entre 8 (75,61±41,46) e 16h (104,53±90,00) (p=0,6272). Para a homogeneidade, 8h promoveu formação de 50% de LCSS homogêneas comparada a 100% em 16h (p=0,0149). Para o objetivo 2, utilizou-se 36 DD (n=9). LCSS foram produzidas em blocos de esmalte por 16h. Os materiais foram aplicados e após 7 dias os espécimes foram seccionados e analisados quanto à profundidade das LCSS (em MLP), perda mineral (dureza Knoop) e quantidade de cálcio (Ca) e fósforo (P) (espectroscopia por energia dispersiva - EDS). A profundidade foi calculada conforme descrito anteriormente. Para a dureza Knoop realizou-se três fileiras de 12 impressões (10, 20, 30, 40, 50, 60, 80, 100, 120, 140, 160 e 180 µm) (25g/5s). Valores de dureza Knoop (KHN) foram obtidos e calculou-se a variação do KHN (?S). Para EDS os espécimes foram observados em microscópio eletrônico de varredura e a quantidade de cálcio (Ca) e fósforo (P) foi calculada nas regiões superficiais e sub-superficiais. As imagens obtidas em MLP foram submetidas à análise descritiva. Os dados quantitativos foram submetidos aos testes Shapiro-Wilk, ANOVA e Tukey como teste post-hoc (?=5%). Não foram observadas diferenças significativas entre os grupos em relação à média das profundidades das LCSS analisadas em MLP. Os grupos tratados apresentaram valores médios semelhantes (39,73±14,20 µm; 32,77±11,86 µm; 38,13±9,17 µm, para Duraphat®, MI VarnishTM e VanishTM, respectivamente), diferente numericamente do grupo controle (54,10±34,56 µm). Para a dureza, observou-se que Duraphat® (2022±1071) apresentou a menor perda mineral comparado aos grupos controle (5239±2299), MI VarnishTM (4505±1098) e VanishTM (4431±1512) (p<0,001, p=0,0022 e p=0,0036, respectivamente). Para EDS tanto para Ca, quanto para P, observou-se ausência de interação entre os materiais e regiões estudadas, porém observou-se diferença significativa para a quantidade de Ca entre as regiões (p<0,05). A região superficial apresentou menor quantidade de Ca que a região sub-superficial. Pode-se concluir que: dezesseis horas foi o tempo mais adequado para formação das LCSS em dentes decíduos; os vernizes fluoretados modificados não se mostraram efetivos em reduzir a perda mineral de LCSS em dentes decíduos; Duraphat® foi o material que apresentou maior efetividade em diminuir a perda mineral de LCSS em dentes decíduos / Abstract: White spot lesions are commonly observed in primary teeth (PT) and when early diagnosed and treated using with various materials that release fluoride, they have a favorable prognosis. The aims of this study were: (1) to evaluate quantitatively and qualitatively 2 formation times of subsurface carious lesions (SCL) in PT; (2) to evaluate quantitatively and qualitatively the effect of three fluoride varnishes: Duraphat®, MI Varnish¿, Vanish¿ in SCL of PT. For the first aim, 20 PT were selected and divided into 2 groups (n = 10): 8 and 16h. SCL was produced in enamel blocks using demineralizing solution. Depth (quantitative analysis) and homogeneity (qualitative analysis) of the lesions were evaluated in polarized light microscopy (PLM). For depth lesion determination 3 measurements were performed in each lesion (µm) and the average was calculated. For homogeneity the images were classified into scores (0 = no homogeneity, 1 = homogeneity). Quantitative data were subjected to normality test, Shapiro-Wilk and once did not show normal data distribution; they were subjected to the Mann-Whitney test. Regarding lesion depth no significant difference was observed between 8h (75.61±41.46) and 16h (104.53±90.00) (p=0.6831). For homogeneity, 8h promoted formation of homogeneous SCL in 50% compared to 100% in 16h (p<0.01). For the second aim, 36 PT (n = 9) were selected. SCL were produced in enamel blocks for 16h. The materials were applied and after 7 days the specimens were sectioned and analyzed for the depth of the SCL (PLM), mineral loss (Knoop hardness) and calcium (Ca) and phosphorus (P) (energy dispersive spectroscopy - EDS). For PLM the lesion depth was calculated as described above. For microhardness, three rows with 12 impressions each were performed (10, 20, 30, 40, 50, 60, 80, 100, 120, 140, 160 and 180?m) (25g/5s). Knoop microhardness (KHN) was obtained and calculated the KHN variation (?S). For EDS specimens were observed in a scanning electron microscope and the amount of calcium (Ca) and phosphorus (P) was calculated in surface and sub-surface regions. The images obtained in PLM were subjected to descriptive analysis. Quantitative data were subjected to the Shapiro-Wilk test, ANOVA and Tukey's test as post-hoc (? = 5%). No significant differences were observed between groups in relation to the average depths of the SCL analyzed in PLM. The treated groups had similar mean values (39.73±14.20µm; 32.77±11.86µm; 38.13±9.17µm to Duraphat®, MI VarnishTM and VanishTM, respectively), numerically different from the control group (54.10±34.56µm). For the hardness, it was observed that Duraphat® (2022±1071) had the lowest mineral loss compared to the control (5239±2299), MI VarnishTM (4505±1098) and VanishTM (4431±1512) (p<0.001, p=0.0022 and p=0.0036, respectively). For EDS, both for Ca and P, there was no interaction between materials and regions studied, but there was a significant difference to the amount of Ca between regions (p<0.05). The surface region showed a lower content of Ca that the sub-surface region. It can be concluded that 16 hours was the most appropriate time for the formation of SCL in primary teeth; modified fluoride varnishes they were not effective in reducing SCL mineral loss of in primary teeth; Duraphat® was the material that showed effectiveness to reduce SCL mineral loss of in primary teeth / Mestrado / Odontopediatria / Mestra em Odontologia