Choosing the right solvent is critical for many industrial applications. A useful property for selection of solvents is their solubility parameters. This concept of solubility parameters is central to this thesis and has been used in two different case studies of material treatment applications. Silicone rubber (crosslinked poly(dimethyl siloxane), PDMS) has many favorable material properties making it useful in biomedical devices. However, a limiting aspect of its material properties is a hydrophobic surface. The aim of this work was to prepare a hydrophilic PDMS material while retaining the transparency of the material. To do this, PDMS was combined with a hydrophilic polymer, polyvinylpyrrolidone (PVP) in an interpenetrating polymer network (IPN). A two-step IPN synthesis method was developed and it was found that the solvent used for polymerization of PVP had a significant influence on the water-wettability and the transparency of the PVP/PDMS IPN. Several different analytical techniques were used for determining the degree of phase separation in the PVP/PDMS IPN. It was found, by using microscopy techniques, that the PVP phase domains varied between 200 nm up to a few micrometers, and the size of the phase domains was correlated to the solvent used for polymerization of the IPN. The second topic for which solvent effects were explored was for the use of mesoporous silica particles as potential drug delivery devices. In the present work a drug molecule, ibuprofen, was loaded into mesoporous silica particles using different solvents, and in addition adsorption isotherms were established in each solvent. The maximum loading of ibuprofen in the mesoporous material was achieved when using a nonpolar solvent, in particular liquid carbon dioxide was successfully used. One of the advantages of using liquid carbon dioxide is that no solvent residues are left in the final material, which is important for pharmaceutical applications. Furthermore, it was concluded that ibuprofen was stored in an X-ray amorphous form in the mesoporous particles. Release studies in water showed a rapid release of ibuprofen from the mesoporous silica particles, while the dissolution of samples with crystalline ibuprofen was slower. This was verified to be an effect of a larger exposed ibuprofen area in the ibuprofen-loaded mesoporous silica particles, and it was concluded that the intrinsic dissolution rate for the samples were identical.

This work had as aim the evaluation of the central and peripheral hearing system of the subjects exposed to fuels. It was a prospective study, where attendants of three gas stations from Santa Maria were evaluated. After the adaptation to the inclusion criteria, the sample was composed of 24 subjects. A control group, of 24 was used in order to compare the results. The applied examinations were: Pure Tone Audiometry (PTA), Impedance Audiometry, research on acoustic reflexes, audiometry of high frequencies and the Auditory Brain Response (ABR). The average threshold of the study group was superior to the control group. The same occurred to the average thershold of the audiometry of high frequencies, in the range 9 to 14 kHz. In the frequencies from 16 to 20 kHz, the occurence of absent responses was higher in the study group in both ears. When compare in relation to the time of exposition, the average thresholds in high frequencies (9-14kHz) had significant statistical difference (p <0.05) in all the frequencies (9-14 kHz), when compared the control group to the study group. It was observed a greater absence of ipsilateral and contralateral acoustic reflexes in the right ear. In the left ear, there was no difference between the groups, concerning the occurrence of the ipsilateral reflex. The absence of contralateral reflex was bigger in the study group in all the teste frequencies. In the ABR, there was a change in the absolute latencies of Waves I and III and in all the interpeak latencies, in the right ear. In the left ear there was a change in the absolute latency of all the waves, and in all the interpeaks. The absolute latency of Wave III had greater occurrence of change, in both ears. The interaural difference of Wave V had a change in 19% of the subjects. The group exposed to fuels for at least three years demonstrated a change in the III-V interpeak of the right ear and in the absolute latency of Wave V in the left ear. In the group exposed for more than five years, the number of subjects with a change was statistical significant in: I-V interpeak of the right ear; absolute latency of Wave I and interpeak III-V of the left ear. It was verified that the subjects exposed to fuels had a statistically significant change in the average hearing thresholds in the frequencies 0.5 kHz (p=0.004), 2 kHz (p=0.001), 3 kHz (p=0.025), 9 kHz (p=0.007) and 10 kHz (p=0.026). In the ABR, it was observed a significant statistical difference in the interpeak III-V of the right ear (p=0.027) and the absolute latency of Wave V in the left ear (p=0.0257), in the group exposed for at least three years. In the group exposed for more than five years it was statistically significant the number of subjects with change in the I-V interpeak of the right ear (p=0.0173), in the absolute latency of Wave I and in the III-V interpeak of the left ear ( p=0.0173). / O presente trabalho teve como objetivo avaliar o sistema auditivo periférico e central de frentistas. Trata-se de um estudo prospectivo, onde foram avaliados frentistas de três postos de gasolina da cidade de Santa Maria. Após a adequação dos critérios de inclusão, a amostra totalizou 24 sujeitos. Um grupo controle, composto por 24 sujeitos, foi utilizado para comparação dos resultados. Os exames aplicados foram: audiometria tonal liminar (ATL), imitanciometria, audiometria de altas frequências e potenciais evocados auditivos de tronco encefálico (PEATE). A média de limiar na audiometria tonal liminar do grupo estudo foi superior a do grupo controle. O mesmo ocorreu com a média de limiar da audiometria de altas frequências, na faixa de 9 a 14kHz. Nas frequências de 16 a 20kHz, a ocorrência de respostas ausentes foi maior no grupo estudo em ambas as orelhas. Quando comparadas em relação ao tempo de exposição, as médias de limiares em altas frequências (9-14kHz) mostraram diferença estatisticamente (p<0,05) significante em todas as frequências (9-14kHz), quando comparados o grupo controle e o grupo estudo. Observou-se maior ausência de reflexos acústicos ipsi e contralateral no grupo estudo, na orelha direita. Na orelha esquerda, não houve diferença entre os grupos, quanto à ocorrência do reflexo ipsilateral. A ausência de reflexo contralateral foi maior no grupo estudo em todas as frequências testadas. No PEATE, houve alteração nas latências absolutas das ondas I e III e em todas as latências interpicos, na orelha direita. Na orelha esquerda houve alteração na latência absoluta de todas as ondas, e em todos os intervalos interpicos. A latência absoluta da onda III foi a que teve maior ocorrência de alteração, em ambas as orelhas. A diferença interaural da onda V mostrou alteração em 19% dos sujeitos. O grupo exposto a combustíveis há pelo menos três anos, apresentou alteração no intervalo interpico III-V da orelha direita e latência absoluta da onda V na orelha esquerda. No grupo exposto há mais de cinco anos, foram estatisticamente significantes o número de sujeitos com alteração: no intervalo interpico I-V da orelha direita; na latência absoluta da onda I e no intervalo interpico III-V da orelha esquerda. Verificou-se que frentistas apresentaram alteração estatisticamente significante nas médias de limiares auditivos nas frequências de 0,5 (p=0,004), 2 (p=0,001), 3 kHz (p=0,025),9kHz (p=0,007) e 10 kHz (p=0,026). No PEATE, observou-se diferença estatisticamente significante no intervalo interpico III-V da orelha direita (p=0,027) e na latência absoluta da onda V na orelha esquerda (p=0,0257), no grupo exposto por pelo menos três anos. No grupo exposto há mais de cinco anos foram estatisticamente significantes o número de sujeitos com alteração no intervalo interpico I-V da orelha direita (p=0,0173), na latência absoluta da onda I e no intervalo interpico III-V da orelha esquerda (p=0,0173).

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Submitted by Maria Suzana Diniz (msuzanad@hotmail.com) on 2015-10-14T14:54:42Z No. of bitstreams: 1 arquivototal.pdf: 2900404 bytes, checksum: 1ee5854e28bd882478910deb4dcb5943 (MD5) / Made available in DSpace on 2015-10-14T14:54:42Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2900404 bytes, checksum: 1ee5854e28bd882478910deb4dcb5943 (MD5) Previous issue date: 2015-02-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Workers chronically exposed to a variety of organic solvents may suffer from changes in color vision and contrast sensitivity (CS). However, few studies have investigated whether there are sex-related differences in these changes, one of the factors that can change the toxicokinetics of solvents. Hence, the aim of this study was to determine whether there would be differences between women and men exposed in terms of their chromatic and achromatic visual psychophysical responses. A total of 44 individuals, Control Group total (CGt; n = 22) and Study Group total (SGt; n = 22) participated in the experiment, subdivided into the following groups: Study Group men (SGm): 11 men exposed to solvents (Age, M = 30.18, SD = 6.48; Education level, M = 9.73, SD = 2.10; Work duration, M = 6.53, SD = 4.38); Study Group women (SGw): 11 women exposed to solvents (Age, M = 26.91, SD = 5.86; Education level, M = 10, 36, SD = 0.92; Work duration, M = 4.70, SD = 3.53); Control Group men (CGm): 11 unexposed men (Age, M = 26.73, SD = 6.5; Education level, M = 9.73; SD = 1.8); Control Group women (CGm): 11 unexposed women (Age, M = 26.55, SD = 6.5; Education level, M = 10.45; SD = 1.51). The project was approved by the Ethics Committee of the Health Sciences Center (SCC) at the Federal University of Paraíba (UFPB), with CAAE registry number 21350113.9.0000.5188. Initially the participants underwent a screening step, with the following inclusion criteria, among others: a 20/20 or corrected visual acuity (evaluated via optotypes and Rasquin testing) and no dyschromatopsia (evaluated using Ishirara Test). Assessment of color perception was performed using the D15 desaturated Lanthony test (D15d) and the Cambridge Colour Test (CCT). The evaluation was performed by CS stimulation using sinusoidal gratings with a vertical spatial frequency of 0.2, 0.5, 1.0, 2.0, 5.0, 10, and 16 cycles per degree (cpd) of visual angle. Furthermore, an assessment of body composition from an examination of bioimpedance. The data were analyzed using the SPSS software package, version 21. First, the overall results between the SGt group (n = 22) and CGt group (n = 22) were compared, and were subsequently compared by sex (n = 11). The results showed that the study group (SGt) (Mdn = 1.18; M = 1.31, SD = 0.32) had a significantly higher ICC (U = 128, p = 0.01) than the CGt (Mdn = 1.09; M = 1.10, SD = 0.26), while there were no significant differences between solvent-exposed men and women (U = 51.0, p = 0.53). In CCT testing (Trivector Protocol), the SGt had a length corresponding to the vector protan axis (Mdn = 50.00; M = 54.00, SD = 16.42), and was significantly higher (U = 133.50, p = 0, 01) than the combined CGt group (Mdn = 40.00; M = 42.59, SD = 16.42), while according to the ellipse protocol, the SGt (Mdn = 981.15; M = 8086.81 ; SD = 22787.81) had a significantly higher ellipse area in A3 (U = 158.00, p = 0.04) compared to the CGt (Mdn = 657.30; M = 781.75, SD = 528.68), but men and women showed no significant differences in both CCT protocols (p > 0,05). The results of the CS showed that the SGt had lower CS in the following frequencies: 0.2 (U = 116,500, p = 0.003); 0.5 (U = 117.00, p = 0.003); 5.0 (U = 149.50, p = 0.03) and 10 cpd (U = 150.00, p = 0.03) compared to the CGt. The SGm (U = 25.0, p = 0.02) had significantly higher CS than SGm at the 0.5 cpd frequency value. The correlational analyses showed that among SGw, the diameter values of circles equivalent to the A1 and A2 ellipse areas retained a significant correlation with MCM: ρ = -0.68; p = 0.02 and ρ = -0.83; p = 0.01, respectively. Among SGw, the diameter value of the circle equivalent to the A2 area was negatively correlated with fat mass: ρ = -0.67; p = 0.02, in other words a greater amount of fatty tissue was correlated with a lower error trend in the red-green opponency axis, in addition, the diameter value of the circle equivalent to the A3 area had a positive correlation with MCM: ρ = 0.61; p = 0.04, i.e. a greater amount of MCM was correlated with a greater tendency to error in the color opponency axis. In short, the data on color vision and the SC obtained by solvent-exposed women and men found no strong evidence of possible differences between the sexes. However, the associations of psychophysiological measurements with the body measurements seem to indicate that fat can act as a protective factor of the organism against the effects of solvents, since fatty tissues may retain a proportion of solvents. In this regard, women could be less affected by solvents by having, on average, a larger proportion of adipose tissue than men. / Trabalhadores expostos de forma crônica à mistura de solventes orgânicos podem sofrer alterações na visão de cores e na sensibilidade ao contraste (SC). Entretanto, poucos estudos investigaram se há diferenças entre os sexos, um dos fatores que podem alterar a toxicocinética dos solventes. Diante disto, o objetivo do presente estudo foi verificar se haveria diferença entre mulheres e homens expostos quanto as respostas psicofísicas visuais cromáticas e acromáticas. Participaram 44 pessoas, Grupo de Estudo total (GEt; n = 22) e Grupo Controle total (GCt; n = 22) que formaram os seguintes grupos: Grupo de Estudo Homens (GEh): 11 homens expostos (Idade M = 30,18; DP = 6,48; Escolaridade M = 9,73; DP = 2,10; Tempo de serviço M = 6,53; DP = 4,38); Grupo de Estudo Mulheres (GEh): 11 mulheres expostas (Idade M = 26,91; DP = 5,86; Escolaridade M = 10, 36; DP = 0,92; Tempo de serviço M = 4,70; DP = 3,53); Grupo Controle Homens (GCh): 11 homens não expostos (Idade M = 26,73; DP = 6,5; Escolaridade M = 9,73; DP = 1,8); Grupo Controle Mulheres (GCm): 11 mulheres não expostas (Idade M = 26,55; DP = 6,5; Escolaridade M = 10,45; DP = 1,51). O projeto foi aprovado pelo Comitê de Ética do Centro de Ciências da Saúde (CCS) da Universidade Federal da Paraíba (UFPB), com número de CAAE: 21350113.9.0000.5188. Inicialmente os participantes realizaram uma de triagem, permanecendo aqueles que, entre outros critérios, apresentaram acuidade visual 20/20 ou corrigida (Optotipos E de Rasquin) e ausência de discromatopsias congênitas (Teste de Ishirara). A avaliação da percepção cromática foi realizada por meio dos testes D15 Dessaturado de Lanthony (D15d) e Cambridge Colour Test (CCT). A avaliação da SC foi realizada com estímulos de grades senoidais verticais de frequências espaciais de 0,2; 0,5; 1,0; 2,0; 5,0; 10 e 16 cpg de ângulo visual. Ainda foi realizada uma avaliação da composição corporal a partir de um exame de biompedância. Os dados foram analisados por meio do software SPSS, versão 21. Primeiramente, foram comparados os resultados entre o GEt (n = 22) e o GCt (n = 22), em seguida os resultados foram comparados por sexo (n = 11). Os resultados mostraram que o GEt apresentou ICC (Mdn = 1,18; M = 1,31; DP = 0,32) significativamente maior (U = 128; p = 0,01) ao GC (Mdn = 1,09; M = 1,10; DP = 0,26), ao passo que entre mulheres e homens expostos não houve diferenças (U = 51,0; p = 0,53). Com relação ao CCT, Protocolo Trivector, o GEt apresentou comprimento correspondente ao vetor do eixo protan (Mdn = 50,00; M = 54,00; DP = 16,42) significativamente maior (U = 133,50; p = 0,01) que o GC (Mdn = 40,00; M = 42,59; DP = 16,42), já no Protocolo Elipse, o GEt obteve área da elipse A3 (Mdn = 981,15; M = 8086,81; DP = 22787,81) significativamente maior (U = 158,00; p = 0,04) em relação ao GCt (Mdn = 657,30; M = 781,75; DP = 528,68), mas homens e mulheres não apresentaram diferenças em ambos os protocolos do CCT (p > 0,05).. Os resultados da SC mostraram que o GEt apresentou SC menor nas frequências: 0,2 (U = 116,50; p = 0,003); 0,5 (U = 117,00; p = 0,003); 5,0 (U = 149,50; p = 0,03) e 10 cpg (U = 150,00; p = 0,03) comparado ao GCt. O GEm obtive SC significativamente maior (U = 26,0; p 0,02) que o GEh na frequência 0,5 cpg. As análises correlacionais evidenciaram que entre o GEh, os valores dos diâmetros dos círculos equivalentes as áreas das elipses A1 e A2 mantiveram correlação com a MCM: = -0,68; p = 0,02 e = -0,83; p = 0,01, respectivamente. Já entre o GEm o valor do diâmetro do círculo equivalente a área A2 apresentou correlação negativa com a massa de gordura: = -0,67; p = 0,02, ou seja quanto mais gordura, menor tendência de erro no eixo de oponência de cor vermelho-verde, e ainda o valor do diâmetro do círculo equivalente a área A3 obteve correlação positiva com a MCM: = 0,61; p = 0,04, isto é quanto maior a quantidade de MCM, maior tendência de erro no eixo de oponência de cor. Em suma, os dados relativos à visão de cores e a SC obtidos por mulheres e homens expostos não encontraram fortes evidências de possíveis diferenças entre os sexos. Entretanto, as associações das medidas psicofísicas com as medidas corporais parecem indicar que a gordura pode atuar como um fator de proteção do organismo contra os efeitos dos solventes, já que tecidos gordurosos podem reter produto. Nesta perspectiva, as mulheres poderiam ser menos afetadas por apresentarem quantidade maior de tecido adiposo.

Submitted by RODOLFO JOSÉ TÓFOLI null (rodolfo_tofoli@hotmail.com) on 2017-04-27T16:00:45Z No. of bitstreams: 1 DISSERTAÇÃO VERSAO FINAL.pdf: 1411835 bytes, checksum: 522077674c28c7cf92bf9e1eaf83b999 (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-05-03T14:38:01Z (GMT) No. of bitstreams: 1 tofoli_rj_me_assis.pdf: 1411835 bytes, checksum: 522077674c28c7cf92bf9e1eaf83b999 (MD5) / Made available in DSpace on 2017-05-03T14:38:01Z (GMT). No. of bitstreams: 1 tofoli_rj_me_assis.pdf: 1411835 bytes, checksum: 522077674c28c7cf92bf9e1eaf83b999 (MD5) Previous issue date: 2017-03-09 / No Brasil, há uma grande biodiversidade de espécies de algas lóticas, Dentre as mais conhecida, encontradas em rios e riachos da região sudeste do estado de São Paulo destaca-se a Oedogonium sp. e a Nitella microcarpa var. wrightii., dois gêneros de algas verdes. Entretanto, estudos de caracterização química de extratos destas algas ainda são inexistentes. Por esse motivo destaca-se a importância deste trabalho, o qual encontra-se subdivido em dois estudos. O primeiro teve por objetivo avaliar e quantificar compostos fenólicos e capacidade antioxidade de extratos de diferentes solventes da alga Oedogonium sp. Utilizou-se um delineamento experimental de mistura para determinar a influência dos solventes e verificou-se qual desses apresentou melhor rendimento na extração desses compostos da alga em pó. O segundo estudo teve por objetivo realizar a caracterização de duas macroalgas verdes: Nitella microcarpa var. wrightii, e Oedogonium sp., através da obtenção de um extrato, com o melhor sistema de solventes obtidos no primeiro estudo. Desta forma, foi possível quantificar quanto a presença de minerais, flavonoides, umidade, carotenoides, compostos fenólicos e capacidade antioxidante. No primeiro estudo, os resultados sugeriram que a mistura acetona-etanol apresentou melhor rendimento de extração tanto para compostos fenólicos como à capacidade antioxidante. No segundo estudo, a alga Oedogonium sp. destacou-se por apresentar uma grande quantidade de carotenoides totais. Já a espécie Nitella microcarpa var. wrightii, obteve altos valores de minerais. / In Brazil, there is a great biodiversity of lotic algae species. Among the most well known species found in rivers and streams in the southeast region of the state of São Paulo is Oedogonium sp. and Nitella microcarpa var. Wrightii., Two genus of green algae. However, studies of chemical characterization of extracts of these algae are still non existent. For this reason the importance of this work is highlighted, which is subdivided in two studies. The first one had the objective to evaluate and quantify phenolic compounds and antioxidant capacity of extracts of different solvents of the algae Oedogonium sp. An experimental design of the mixture was used to determine the influence of the solvents and it was verified which of them presented better yield in the extraction of these compounds from the powdered seaweed. The second study aimed to characterize two green macroalgae: Nitella microcarpa var. Wrightii, and Oedogonium sp., by obtaining an extract, with the best solvent system obtained in the first study. In this way, it was possible to quantify the presence of minerals, flavonoids, moisture, carotenoids, phenolic compounds and antioxidant capacity. In the first study, the results suggested that the acetone-ethanol-water mixture had a better extraction yield for both phenolic compounds and antioxidant capacity. In the second study, the alga Oedogonium sp. was characterized by a large amount of total carotenoids. The other alga, of the species Nitella microcarpa var. Wrightii, has achieved high mineral values.

La présence de Composés Organiques Halogénés Volatils (COHV) dans les eaux souterraines est particulièrement problématique car celle-ci peut les contaminer pendant des dizaines d’années. Le traitement de ces sites, dont les pollutions sont souvent mixtes et complexes, nécessite de développer des techniques fiables. Particulièrement dans le contexte d’un aquifère hétérogène, les techniques classiques souffrent du faible potentiel de balayage de la pollution par les agents remédiant. La génération de mousse in situ est une technique de dépollution innovante permettant de contrôler la mobilité de ces agents. La démarche générale du travail de thèse porte sur le développement de l’injection de mousse et son applicabilité dans le contexte d’un site industriel en activité contaminé par des solvants chlorés. L’originalité de ce travail porte sur l’utilisation de la mousse comme agent confinant (hydrauliquement) d’une zone source au sein même de l’usine. Le premier objectif de cette thèse consiste en la définition de l’origine de la pollution et des processus responsables du transport des composés dissous dans un système aquifère multicouche et hétérogène. Dans ce cadre, un modèle de transport en 3 dimensions a été développé et contraint à partir de données géologiques (structure 3D), hydrogéologiques (piézométrie, mesure de vitesse), et chimiques (solvant chlorés et ions majeurs). Cette combinaison d’approches a eu un impact réel sur la compréhension de la dynamique hydrogéologique du système souterrain présent au droit du site d’étude, et a permis de définir la zone d’injection de mousse. En parallèle des travaux de caractérisation du site, un travail expérimental en laboratoire a permis de définir les mécanismes à l’origine de la réduction de la perméabilité relative à l’eau par l’injection de mousse. Au travers d’une approche multi échelle, ces travaux ont notamment permis de (i) définir une formulation (concentrations en tensio-actifs et composition) et les paramètres d’injection (qualité de mousse, débit d’injection, mode d’injection) pour générer une mousse favorable à la réduction de la saturation en eau (colonne 1D). Cette baisse de saturation ayant conduit à une réduction de la perméabilité à l’eau d’un facteur supérieur à 100. (ii) D’estimer le comportement de la mousse le long d’un profil d’injection et son impact sur la réduction de la saturation en eau à quelques centimètres d’un point d’injection (pilote 2D décimétrique). (iii) De vérifier l’applicabilité en 3D du système d’injection développé et de suivre les évolutions de l’impact de la mousse dans un aquifère (essai sur un piézomètre réel). Enfin, un test d’injection de mousse en continu pendant 96h au droit de la zone source du site industriel contaminé a été réalisé. La réalisation d’un essai de pompage (post injection) au centre de la zone confinée, couplé à des mesures de flux de polluant (pré et post injection) et implémenté dans un modèle 2D, ont permis de mettre en évidence l’impact réel de la mousse sur un rayon supérieur à 2m avec une réduction du flux de polluant en aval hydraulique d’un facteur 4,5. Les différents travaux de laboratoire et de modélisation mettent en évidence les avancées et limites de la technique développée et permettent de proposer des voies d’amélioration. / The presence of Volatile Organic Compounds (VOCs) in groundwater is particularly problematic because it can contaminate them for decades. The treatment of these sites, whose pollution is often mixed and complex, requires the development of reliable techniques. Particularly in the context of a heterogeneous aquifer, conventional techniques suffer from the low potential for pollution sweeping by remedying agents. In situ foam generation is an innovative technique to control the mobility of these agents. The general approach of the thesis concerns the development of foam injection and its applicability. in the context of an industrial site in activity contaminated by chlorinated solvents. The originality of this work concerns the use of foam as a confining agent (hydraulically) of a source zone within the plant itself. The first objective of this thesis is to define the origin of pollution and the processes responsible for the transport of dissolved compounds in a multilayered and heterogeneous aquifer system. In this context, a 3-dimensional transport model has been developed and constrained based on geological data (3D structure), hydrogeological data (piezometry, groundwater velocity measurement), and chemical data (chlorinated solvent and major ions). The combination of these approaches had a real impact on the understanding of the hydrogeological dynamics of the underground system present at the study site, and allowed us to define the foam injection zone. In parallel with site characterization, experimental work in laboratory allows to define the mechanisms responsible for reducing the water-relative permeability by injecting foam. Through a multi-scale approach, we (i) define a formulation (surfactant concentrations and composition) and injection parameters (foam quality, injection rate, injection mode ) to generate a foam favorable to the reduction of water saturation (column 1D). This saturation decrease led to a reduction of the water relative permeability by a factor greater than 100. (ii) Estimate the behavior of the foam along an injection profile and its impact on the reduction saturation in water a few centimeters from an injection point (2D decimetric pilot). (iii) Verify the 3D applicability of the developed injection system and to follow the evolutions of the impact of the foam in an aquifer (test on a real piezometer). Finally, a continuous foam injection test during 96 hours at the source zone of the contaminated industrial site was carried out. Conducting a pumping test (post injection) in the center of the confined zone, coupled with contaminant fluxes measurements (pre and post injection) and implemented in a 2D model, highlighted the real impact of the injected foam over a radius greater than 2m with a reduction of the flow of pollutant downstream by a factor 4.5. The various laboratory and modeling work highlight the advances and limitations of the developed technique and make it possible to propose ways of improvement.

Made available in DSpace on 2014-12-17T15:01:17Z (GMT). No. of bitstreams: 1 ErikaaAS.pdf: 744693 bytes, checksum: 969bbaf028a15425563a34bdced20b1e (MD5) Previous issue date: 2005-07-21 / The formation of paraffin deposits is common in the petroleum industry during production, transport and treatment stages. It happens due to modifications in the thermodynamic variables that alter the solubility of alkanes fractions present in petroleum. The deposition of paraffin can provoke significant and growing petroleum losses, arriving to block the flow, hindering to the production. This process is associated with the phases equilibrium L-S and the stages and nucleation, growth and agglomeration the crystals. That process is function of petroleum intrinsic characteristics and temperature and pressure variations, during production. Several preventive and corrective methods are used to control the paraffin crystallization, such as: use of chemical inhibitors, hot solvents injection, use of termochemistry reactions, and mechanical removal. But for offshore exploration this expensive problem needs more investigation. Many studies have been carried through Wax Appearance Temperature (WAT) of paraffin; therefore the formed crystals are responsible for the modification of the reologics properties of the oil, causing a lot off operational problems. From the determination of the WAT of a system it is possible to affirm if oil presents or not trend to the formation of organic deposits, making possible to foresee and to prevent problems of wax crystallization. The solvent n-paraffin has been widely used as fluid of perforation, raising the production costs when it is used in the removal paraffin deposits, needing an operational substitute. This study aims to determine the WAT of paraffin and the interference off additives in its reduction, being developed system paraffin/solvent/surfactant that propitiates the wax solubilization. Crystallization temperatures in varied paraffin concentrations and different solvents were established in the first stage of the experiments. In the second stage, using the methodology of variation of the photoelectric signal had been determined the temperature of crystallization of the systems and evaluated the interferences of additives to reduction of the WAT. The experimental results are expressed in function of the variations of the photoelectric signals during controlled cooling, innovating and validating this new methodology to determine WAT, relatively simple with relation the other applied that involve specific equipments and of high cost. Through the curves you differentiate of the results had been also identified to the critical stages of growth and agglomeration of the crystals that represent to the saturation of the system, indicating difficulties of flow due to the increase of the density / A forma??o de dep?sito paraf?nico ? comum na ind?stria do petr?leo durante as etapas de produ??o, movimenta??o e tratamento e ocorre em decorr?ncia de modifica??es nas vari?veis termodin?micas que alteram a solubilidade das fra??es de alcanos presentes no petr?leo. A cristaliza??o de parafinas pode provocar significativas e crescentes perdas de petr?leo, chegando a bloquear o fluxo, impedindo ? produ??o. Esse processo est? associado ao equil?brio de fases L-S e as etapas de nuclea??o, crescimento e aglomera??o dos cristais. Existem v?rios m?todos preventivos e corretivos para controlar a cristaliza??o de parafinas, dentre os quais se destacam: o uso de inibidores qu?micos, a inje??o de solventes aquecidos, o emprego de rea??es termoqu?micas e a remo??o mec?nica, por?m quanto ? explora??o offshore pouco se conhece, tornando-se indispens?vel investigar este custoso problema. Muitos estudos t?m sido realizados quanto ? temperatura de in?cio do aparecimento dos cristais (TIAC) da parafina, pois os cristais formados s?o respons?veis pela modifica??o das propriedades reol?gicas do petr?leo, causando diversos problemas operacionais. A partir da determina??o da TIAC de um sistema ? poss?vel afirmar se um petr?leo apresenta ou n?o tend?ncia ? forma??o de dep?sitos org?nicos, possibilitando prever e evitar problemas de cristaliza??o paraf?nica. O solvente n-parafina tem sido amplamente utilizado como fluido de perfura??o, elevando os custos de produ??o quando ? empregado na remo??o de dep?sitos paraf?nicos, necessitando de um substituto operacional. Este estudo visa determinar a TIAC da parafina e ? interfer?ncia de aditivos na sua redu??o, desenvolvendo um sistema parafina/solvente/tensoativo que propicie a solubiliza??o paraf?nica. Na primeira etapa dos experimentos, foram determinadas as temperaturas de cristaliza??o em concentra??es de parafina variadas e diferentes solventes. Na segunda etapa, utilizando a metodologia de varia??o do sinal fotoel?trico foi determinada a temperatura de cristaliza??o dos sistemas e avaliadas as interfer?ncias dos aditivos quanto ? redu??o da TIAC. Os resultados s?o expressos em fun??o das varia??es do sinal fotoel?trico, durante resfriamento controlado, inovando e validando esta metodologia de determina??o da TIAC, relativamente simples com rela??o ?s outras aplicadas que envolvem equipamentos espec?ficos e de alto custo. Atrav?s das curvas diferencias dos resultados tamb?m foram identificadas ?s etapas cr?ticas de crescimento e aglomera??o dos cristais que representam ? satura??o do sistema, indicando dificuldades de fluxo devido ao aumento da densidade

O objetivo deste estudo foi avaliar as propriedades químicas, biológicas e antimicrobianas dos solventes endodônticos, Citrol, Eucaliptol, d-Limoneno, Xilol e Endosolv E. Dentre os testes químicos, foram avaliados a microdureza dentinária, onde utilizamos blocos de dentina bovina que foram expostos aos solventes por 2 períodos, 5 e 15 min e submetidos ao teste de microdureza. Outro teste químico foi a capacidade de dissolução dos materiais obturadores pelo teste de imersão nos solventes em 3 períodos, 2, 5 e 15 min. Para essa avaliação foram, confeccionados corpos de prova dos cimentos, AH Plus, Acroseal, Sealer 26, Endofill, MTA Fillapex e RealSeal SE e dos cones de guta-percha estandardizado Dentsply (DP), ProTaper e Resilon. Um terceiro teste, foi realizado para avaliar a capacidade de desobturação dos canais radiculares e o efeito da agitação ultrassônica dos solventes endodônticos após a desobturação. Sessenta incisivos centrais superiores foram divididos em 6 grupos sendo um para cada solvente (n=10) mais um grupo controle (solução fisiológica). Todos dentes foram instrumentados e obturados pela mesma técnica e escaneados no Micro-CT. Os dentes foram então desobturados utilizando ProTaper Retratamento/ProTaper Universal como técnica para todos grupos, associada a um dos solventes e foram escaneados novamente para a avaliação do volume de material remanescente após a desobturação. Cada um dos dentes foi desobturado e preenchido com o mesmo solvente utilizado na desobturação. Cada solvente foi agitado pelo ultrassom por 1 min e novamente foram escaneados e avaliados os volumes restantes dos materiais nos canais radiculares. Na avaliação biológica, utilizamos o teste de citotoxicidade com células de camundongo NIH-3T3 pelo ensaio MTT. As culturas celulares foram plaqueadas e submetidas aos solventes diluídos nas concentrações de 0.5 a 2.5%, e avaliados quanto à viabilidade celular. Por fim o último teste foi o antimicrobiano, avaliado pelo teste de contato direto em biofilme misto, formado in situ sobre blocos de dentina bovina. Os biofilmes foram expostos por 5 min a um dos solventes, corados com Live/Dead e avaliados em microscopia confocal de varredura a laser. Como resultados encontramos que todos solventes causaram alterações físicas na dentina e foram capazes de comprometer a microdureza dentinária, sendo que esta ação foi aumentada quando o tempo de contato foi maior. O Xilol e o Endosolv E foram mais efetivos na dissolução dos cimentos AH Plus e Endofill no período de 15 minutos em relação aos demais solventes. O Endosolv E apresentou capacidade de dissolução mais efetiva sobre os cones de guta-percha DP no período de 15 minutos em relação aos outros solventes estudados. Nos demais cimentos, materiais sólidos e nos outros períodos, os solventes apresentaram capacidade de dissolução semelhantes. Na avaliação do Micro-CT, todos solventes foram capaz de remover as obturações dos canais radiculares inclusive o grupo controle, porém nenhum foi capaz de remover os materiais obturadores completamente. A agitação ultrassônica dos solventes favoreceu um aumento na remoção do material obturador, porém não proporcionou a remoção completa do material. A agitação ultrassônica dos solventes removeu mais material obturador remanescente do que a agitação sem solvente (controle). No teste biológico todos solventes foram citotóxicos, no entanto somente o Xilol foi capaz de manter mais de 50% de células viáveis. E por fim, o Xilol e o Eucaliptol foram os solventes que apresentam a melhor ação antimicrobiana enquanto que o Citrol mostrou a pior. / The aim of this study was to evaluate the chemical, biological and antimicrobial properties of the Endodontic solvents, Citrol, Eucalyptol, d-Limonene, Xylene and Endosolv E. First chemical properties analysis were evaluated by dentin microhardness, where we used bovine dentin blocks that were exposed to the solvents in 2 periods, 5 and 15 min and subjected to the microhardness test. Second test was to evaluate the ability of endodontic solvents to dissolve root-filling materials by immersion test in, 2, 5 and 15 minutes. Specimens of sealers, AH Plus, Acroseal, Sealer 26, Endofill, MTA Fillapex an RealSeal SE and guttapercha Dentsply (DP), ProTaper and Resilon points were prepared and evaluated in the three periods. Next test was conducted to evaluate the ability of solvents to desobturate root canals filled and analyse the effect of the ultrasonic passive agitation of solvents after canal unfill procedure. Sixty maxillary central incisors were prepared and obturated by same technique and randomly divided into 6 groups, one for each solvent (n=10) and a control group (saline solution). Teeth were scanned in Microcomputed Tomography (Micro-CT), unfilled with ProTaper Retratament/Protaper Universal with one of the solvents and scanned again. The residual root-fillings volumes were analysed and all teeth root canal were filled with the same solvent used in unfilling process and were passive-ultrasonically agitated (PUl) for 1 min. All teeth were scanned again in Micro-CT and data were analysed. Biological properties assessments were evaluated by cytotoxicity test with NIH-3T3 mouse cells by MTT assay. Cell cultures were subjected to diluted solvents at concentrations of 0.5 to 2.5%, and cell viability were analysed. Last evaluation in our study was the antimicrobial test. A total of 60 bovine dentin specimens infected intraorally were exposed for 5 min in direct contact to one of the solvents evaluated. After that, the dentin blocks with biofilms were stained with Live/Dead and the proportions of dead and live bacteria assessed by Confocal Laser Scanning Microscopy were analysed. The results revealed that that all solvents caused physical changes in dentin and were able to compromise the dentin microhardness, and this action was increased when the contact time was higher. In the dissolving test, Xylene and Endosolv E were more effective to dissolve AH Plus sealers and Endofill in the 15 min period, compared to other solvents. The highest dissolution capacity of Endosolv E was observed on guttapercha cones DP also in the period of 15 minutes an this dissolving capacity was more effectively then other solvents. In all other root-fillings and gutta-percha and Resilon points and in other periods (2 and 5 min), the solvents showed similar dissolution capacity. In Micro-CT evaluation all solvents were able to remove the root canal filling materials, including saline solution, but none could remove it completely. Solvents PUl, showed an increase in root-filling material left from unfilling procedure, but also provided incomplete removal. When solvents were PUl, they removed the remaining materials significantly compared to control group (saline solution). In biological test all solvents showed high cytotoxicity, however only the Xylene was able to maintain more than 50% of viable cells. According to the antimicrobial evaluation, Xylene and Eucalyptol showed best antimicrobial action while the Citrol showed the worst.

Orientador: Mário Fernando de Góes / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-18T00:31:21Z (GMT). No. of bitstreams: 1 Antunes_AlbertoNogueiradaGama_D.pdf: 9481155 bytes, checksum: a267a90e105bb7a35b7e5367aa915a36 (MD5) Previous issue date: 2011 / Resumo: O objetivo do estudo foi avaliar a resistência à tração e nanoinfiltração de adesivos autocondicionantes unidos à dentina em função do período de armazenamento em água. Cinquenta molares humanos foram aleatoriamente distribuídos em cinco grupos com 10 dentes cada, de acordo com o adesivo: Single Bond 2, Easy One, Silorane (3M ESPE), Bond Force (Tokuyama) e Adhese One (Ivoclair Vivadent). O esmalte oclusal foi seccionado para obter uma superfície plana em dentina. Os adesivos foram aplicados sobre a superfície da dentina de acordo com as orientações de cada fabricante. Um bloco de resina composta foi construído sobre cada dente, armazenados por 24 horas em água a 37ºC, seguidos pelo seccionamento e obtenção de corpos-de-prova com o formato de palitos com área de secção transversal de 0,8±0,1mm2. Foram usados 5 palitos de cada dente (n=5) em cada período de armazenamento, 24h, 3 e 6 meses, para o teste de resistência à tração (Instron, 0,5mm/minuto). O padrão de fratura foi analisado em microscópio eletrônico de varredura. Três palitos de cada grupo (n=5), em cada período de armazenamento, foram imersos em prata amoniacal para a análise da região da união. Os valores médios obtidos no ensaio de tração (MPa) e nanoinfiltração (%) foram submetidos à Análise de Variância e teste de Fischer (p<0,05). Os valores da resistência à tração (MPa) e nanoinfiltração (%) nos períodos de 24h, 3 e 6 meses foram, respectivamente: Single Bond 2 (48,78, 37,24 e 30,32), (4,78, 4,79 e 6.14); Easy One (48,55, 39,71 e 29,96), (3,22, 2,51 e 4,87); Silorane (41,77, 36,5 e 26,27), (0,77, 0,79 e 2,18); BondForce (39,10, 34,44 e 22,54), (4,28, 4,67 e 13,10); Adhese One (24,65, 24,48 e 16,69), (3,14, 2,93 e 6,74). A resistência à tração do Adhese One foi estatisticamente diferente e inferior aos demais adesivos nos 3 períodos de armazenamento. Single Bond 2, Silorane e BondForce apresentaram resistência à tração estatisticamente diferentes nos períodos de 24h e 6 meses, enquanto que o Easy One e o Adhese One não foram diferentes estatisticamente nos mesmos períodos. O valor médio da nanoinfiltração do Silorane foi inferior e diferente estatisticamente em relação aos demais adesivos, que não apresentaram diferenças entre si no período de 24h. O adesivo BondForce apresentou o maior valor de infiltração de prata em relação aos demais adesivos com a exceção do Adhese One. Os adesivos Single Bond 2, Easy One e Silorane não apresentaram diferenças estatisticamente significantes entre si. O Silorane, BondForce e Adhese One apresentaram valores estatisticamente diferentes em relação ao período de 24h e 6 meses de armazenamento, enquanto que o Single Bond 2 e o Easy One não apresentaram diferenças no mesmo período de tempo. A fratura coesiva na camada de adesivo foi o padrão predominante para os adesivos autocondicionantes nos diferentes tempos de armazenamento. O Single Bond 2 mostrou um padrão de fratura misto, distribuído nas regiões da base da camada híbrida, coesiva no adesivo, dentina, camada híbrida e resina composta nos 3 períodos de armazenamento / Abstract: The aim of this study was to evaluate the tensile strength and nanoleakage of adhesives to dentin surface according to water storage period. Fifty human molars were randomly assigned to five groups of 10 teeth each, according to the adhesive Single Bond 2, Easy One, Silorane (3M ESPE), Bond Force (Tokuyama) and Adhese One (Ivoclair Vivadent). The occlusal enamel was sectioned to obtain a flat dentin surface. The adhesives were applied on the dentin surface according to manufacturer' s instruction. A composite block was built-up on each flat dentin, stored for 24h in water at 37°C, followed by sectioning to obtain beams with crosssectional area of 0.8 ± 0.1mm2. It was used 5 beams from each tooth (n=5) at each storage period - 24h, 3 and 6 months - to evaluate the tensile strength (Instron, 0.5mm/minute). The fracture pattern was analyzed in scanning electron microscope. Three beams of each group (n=5) in each storage period were immersed in ammoniacal silver nitrate to evaluate the nanoleakage. The average values obtained in tensile test (MPa) and nanoleakage (%) were submitted to ANOVA and Fischer's test (p<0.05). The tensile strength (MPa) and nanoleakage (%) values for 24h, 3 and 6 months were: Single Bond 2 (48.78, 37.24 and 30.32), (4.78, 4.79 and 6.14); Easy One (48.55, 39.71 and 29.96), (3.22, 2.51 and 4.87); Silorane (41.77, 36.5 and 26, 27), (0.77, 0.79 and 2.18); BondForce (39.10, 34.44 and 22.54), (4.28, 4.67 and 13.10); Adhese One (24.65, 24.48 and 16.69), (3.14, 2.93 and 6.74). The tensile strength of Adhese One was inferior and statistically different from the other groups on the three periods of storage. Single Bond 2, Silorane Bond Force 24h tensile strength values showed statistically difference to the 6 months groups, while the Easy One and One Adhese were not statistically different in the same periods. The nanoleakage of Silorane was lower and statistically different compared to the other adhesives, which do not differ from each other within 24 hours. The adhesive Bond Force showed the highest infiltration of silver compared to Easy One and Silorane while it was not statistically different from Single Bond 2 and Adhese One other adhesives with the exception of Adhese One and Single Bond 2. The Silorane, BondForce Adhese One showed 6 months nanoleakage values statistically different from 24h, but Single Bond 2 and Easy One presented no differences in the same period. A cohesive failure in adhesive layer was the predominant pattern of self-etching adhesives in three storage periods. The Single Bond 2 showed a mixed fracture pattern, distributed in hybrid layer base, cohesive in adhesive, dentin, hybrid layer and composite resin in three storage periods / Doutorado / Materiais Dentarios / Doutor em Materiais Dentários

Orientador: Douglas Soares Galvão / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-09T02:37:49Z (GMT). No. of bitstreams: 1 Autreto_PedroAlvesdaSilva_M.pdf: 14908796 bytes, checksum: 389f8f28e3d38fbfe32aeab511893f6e (MD5) Previous issue date: 2007 / Resumo: As melaninas constituem uma classe de pigmentos biológicos de destaque devido, sobretudo, a sua predominante presença nos tecidos dos mamíferos. Há fortes evidências que sugerem que a pigmentação por melanina tem por objetivo proteger a pele contra efeitos prejudiciais da radiação ultravioleta. Além deste papel de fotoproteção, outras funções biológicas são especuladas em razão da presença do pigmento em regiões não iluminadas do corpo como por exemplo no cérebro em que há uma aparente destruição preferencial das células que contém melanina quando ocorrem doenças como o mal de Parkinson. Apesar de décadas de investigações, nenhuma amostra de melanina foi estruturalmente bem caracterizada. Dentre os diversos obstáculos que são responsáveis pelo lento progresso que marca a pesquisa deste pigmento, o maior deles é que as melaninas naturais são altamente insolúveis e de presumido alto peso molecular. Pesquisas recentes desenvolvem sínteses alternativas para as melaninas utilizando outros solventes e demonstram que até 20 % da estrutura desta pode ser composta por água. Assim, neste trabalho investigamos, por métodos quânticos, a geometria e estrutura eletrônica das moléculas 5,6 indolquinona, suas formas reduzidas (semiquinona e hidroquinona) e 27 dímeros obtidos a partir destas, em seus estados neutros e iônicos ( ± 1 e ± 2), no vácuo e nos solventes DMF(dimetilformamida), DMSO (dimetilsulfóxido) e água. Verificamos como o solvente altera as propriedades eletrônicas e espectroscópicas destas estruturas e como este pode ser fundamental para a determinação de suas geometrias. Utilizamos dois modelos para simular o solvente: um modelo contínuo, COSMO (Conductor-like Screening Model) e um discreto, que considera explicitamente cada molécula do solvente e é baseado em simulações Monte Carlo. Notamos que o solvente altera a propriedade de aceitador de dois elétrons de diversas estruturas, fato até então não observado e de importante consequência biológica, visto as eumelaninas poderem ser base de um mecanismo de defesa celular contra radicais livres. Os picos dos espectros de absorção, de um modo geral, são deslocados para o vermelho e, em alguns casos, tem um alargamento. Isto poderia contribuir para a constrção da larga banda característica das eumelaninas. Diversos outros aspectos importantes, em excelente acordo com dados experimentais, são também apresentados ao se considerar o solvente. Um dos mais relevantes mostra que o solvente tem forte influência na geometria da molécula com o menor custo de dimerização, o que nos leva a concluir que esta pode ser de fato a semente de "nucleação" para a formação do polímero de melanina. / Abstract: Melanins belong to an important class of biological pigments due to its abundant presence in mamal tissues. There are strong evidences that suggest that the pigmentation due to melanin would protect the skin against the biochemical devastation induced by solar exposure. Besides the photo-protection feature, other biological functions have been speculated to melanin due to its presence in non-illuminated areas of the body and the apparent preferential destruction of melanin-containing cells in the substancia nigra of the brain in Parkinsonism. Unfortunately, in what concerns structural and chemical composition, no melanin sample has been fully and unambiguously characterized yet, despite the enormous amount of experimental work done so far. The main difficulty for that is that melanin is insoluble in most organic solvents and has high molecular weight. A new synthetic route for melanins, using organic solvents, has been recently achieved and it was demonstrated that about 20 % of the structure of the pigment is composed by water. In this work we have investigated using quantum methods the geometries and electronic structure of 5,6 indolquinone, their redox forms (semiquinone and hidroquinone) and 27 dimers associated, in their neutral and ionic states ( ± 1 e ± 2). The calculation were carried in vacuum and in the solvents dimethyl sulfoxide (DMSO), N,N-dimethyl formamide (DMF) and water. We study the effect of the solvent on the electronic and spectroscopic properties and its importance to determine eumelanin structure. Two models for solvents were used. The first was a continuum model, COSMO (Conductor-like Screening Model), and the second one (based on Monte Carlo simulations) explicitly considers each molecule of the solvent. The results showed that the solvents affected the electron accepton properties allowing the acceptance of two electrons. These aspects have been not been observed before from vacuum calculations and it is of important biological consequence because the melanins can be the base of mechanism of cellular defense against free radicals. The peaks of absorption spectra of the solvated structure are dislocated from red and broadened. This could contribute to the characteristic broad band of eumelanins. Many others important aspects are in better agreement with experimental data when solvent aspects are explicitly taken into account. One of most important results was the observation that solvent effects can alter the order of the lowest energy dimer configuration in relation to the structures in vacuum. This dimer was suggested to be the nucleation seed for the polymer formation. / Mestrado / Física Atômica e Molecular / Mestre em Física