Orientador: Ângela Maria Moraes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Agrícola / Made available in DSpace on 2018-08-25T01:12:46Z (GMT). No. of bitstreams: 1 Souza_FernandaCarlaBombaldide_M.pdf: 2498035 bytes, checksum: f26cf0a46c0249d60c3316fd94c93e91 (MD5) Previous issue date: 2014 / Resumo: A quitosana, a goma guar e a policaprolactona são exemplos de polímeros muito usados na obtenção de curativos para a terapia de lesões de pele devido ao fato de serem biocompatíveis e biodegradáveis. A fim de aumentar a atividade biológica destes curativos, a incorporação de compostos bioativos que estimulam o processo de cura das lesões pode ser feita. Neste contexto, este trabalho teve como objetivo a obtenção de curativos biologicamente ativos, por meio da incorporação do alfa-bisabolol, um composto antioxidante e anti-inflamatório de origem natural, a membranas constituídas de quitosana combinada com goma guar (Q-G) e de policaprolactona (PCL). Dois métodos de incorporação foram utilizados: adição direta do composto ativo à mistura polimérica (AD) e impregnação do composto nas membranas por imersão em solução etanólica (IE). As membranas produzidas foram caracterizadas quanto ao seu aspecto visual, cor e opacidade, morfologia, ângulo de contato com água, propriedades mecânicas e espessura em diferentes umidades, capacidade de absorção e perda de massa em etanol e em soluções aquosas, taxa de transmissão de vapor d¿água e espectro FTIR. A eficiência de incorporação do alfa-bisabolol às membranas e a atividade antioxidante deste composto foram determinadas, e sua cinética de liberação estudada. Os resultados mostraram que tanto os filmes de Q-G como de PCL apresentaram comportamento mais adequado para a aplicação no tratamento de lesões pouco exsudativas. As propriedades mecânicas dos filmes sofreram variação significativa apenas quando estes foram expostos a condições de umidade elevada. O alfa-bisabolol utilizado nos ensaios apresentou elevado grau de pureza, porém atividade antioxidante relativamente baixa. A inserção do composto na matriz ocasionou mudanças significativas em sua aparência e alterações em sua microestrutura. Para Q-G, baixas eficiências de incorporação foram obtidas, sendo o valor máximo atingido pelo método AD igual a 1,65%, o equivalente a 4,96 mg/g, enquanto que para o método IE atingiu-se cerca de 18%, com uma retenção de aproximadamente 1080 mg/g. Já no caso da PCL, alta eficiência de incorporação foi observada (100%). A liberação mostrou-se relativamente lenta em ambos os casos e a percentagem máxima de alfa-bisabolol liberado ficou em torno de 6% e 30%, o equivalente a 12 e 300 mg/g para filmes de PCL e de Q-G, respectivamente. O tempo prolongado de liberação permitiria a troca do curativo com intervalos de tempo maiores, tornando o tratamento menos incômodo para o paciente / Abstract: Chitosan, guar gum and polycaprolactone are polymers widely used to obtain wound dressings due to their biocompatibility and biodegradability. To increase the biological activity of these dressings, bioactive compounds which accelerate wound healing can be incorporated. In this context, this work aimed the development of biologically active dressings, through the incorporation of alpha-bisabolol, a natural antioxidant and anti-inflammatory compound, to membranes made of chitosan associated with guar gum (C-G) and of polycaprolactone (PCL). The incorporation of alpha-bisabolol was performed by two distinct methods: addition directly to the polymeric mixture (AD) and absorption of the active compound from an ethanolic solution (AS). The membranes were characterized regarding to visual appearance, color and opacity, morphology, water contact angle, water vapor transmission rate, swelling capacity in ethanol and in aqueous solutions as well as mass loss in the same media, strain at break, tensile strength and thickness in different humidities conditions and FTIR spectrum. Alpha-bisabolol incorporation efficiency and its antioxidant activity were determined and the release kinetics was studied. Results showed that both films are more suitable for the use in the treatment of lesions with low exudate levels. Mechanical properties suffered significant change only after exposure of the films to high humidity conditions. The alpha-bisabolol used in this study exhibits high purity, but relatively low antioxidant activity. The addition of the compound to the matrix led to significant changes in the appearance and to modifications in the microstructure of the films. The C-G membranes presented low incorporation efficiencies, with the maximum value of 1.65%, equivalent to 4.96 mg/g, for the AD method, and 18%, approximately 1080 mg/g, for the AS method. In the case of PCL, high incorporation efficiency (100%) was observed. The release of alpha-bisabolol from the matrices was relatively slow and the maximum percentage of compound released reached about 6% and 30%, equivalent to 12 and 300 mg/g for PCL and C-G films, respectively. A prolonged release would allow less frequent dressing changes, turning the treatment more comfortable for the patient / Mestrado / Engenharia Química / Mestra em Engenharia Química

Orientador: Pedro Luiz Onófrio Volpe / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-25T19:42:54Z (GMT). No. of bitstreams: 1 Fozia_D.pdf: 5148812 bytes, checksum: 468649b9d5c06383a0fcd0b39c0fc098 (MD5) Previous issue date: 2014 / Resumo: Híbridos polisilsesquioxanos arranjados em pontos, foram sintetizados e caracterizados por análise elementar, espectroscopia de absorção na região do infravermelho, ressonância magnética nuclear no estado sólido, difração de raios X, microscopia eletrônica de varredura e transmissão eletrônica. Os dados de sorção/dessorção de nitrogênio para sílica pura, SBA-15 e os híbridos funcionalizados resultaram na isoterma do tipo IV com histerese do tipo H1. A estrutura da sílica mesoporosa ficou preservada após a pós-funcionalização com cadeias orgânicas. Pos-funcionalização da superfície com amina e outros grupos orgânicos contendo estrutura hidrofóbica, resultou numa diminuição da área da superfície 802,4-63,0 m2g-1 e volume de poros de 0,09 nm e aumento capacidade de carga de ibuprofeno a partir de 18,0 até 29% e um muito lento taxa de liberação ao longo do período de 72,5 h. Para investigar a taxa de liberação e o mecanismo a partir desses materiais híbridos sintetizados, zero-ordem, primeira ordem, Higuchi, Hixson-Crowell, Peppas e Korsmeyer-Peppas modelos cinéticos foram aplicados. Os materiais foram utilizados para a liberação controlada do fármaco ibuprofeno. Estes também foram avaliados quanto à capacidade de remover o corante aniônico azul reativo-15 e o corante catiônico verde brilhante de soluções aquosas. As sílicas modificadas apresentaram alta capacidade de carregamento do fármaco ibuprofeno e de sorção seletiva para o corante azul reativo 15. A sílica não modificada, SBA-15, apresentou alta capacidade de remover o corante verde brilhante. As isotermas de equilíbrio obtidas foram ajustadas aos modelos de Langmuir, Freundlich e Sips e os dados cinéticos foram ajustados aos modelos de pseudo-primeira-ordem e pseudo-segunda-ordem. Os resultados sugerem que os compostos organofuncionalizados de sílica podem ser um método simples, eficiente, barato e conveniente para a liberação controlada de fármacos e também para a remoção eficaz e seletiva de poluentes orgânicos tais como, corantes em soluções aquosas / Abstract: Bridged polysilsesquioxane silica hybrids, synthesized by the combination of SBA-15 type silica with new synthesized silylating agents containing bridged chains, were characterized by elemental analysis, absorption spectroscopy in the infrared region, nuclear magnetic resonance in the solid state, X-ray diffraction, scanning/transmission electron microscopy and thermogravimetry. The sorption/desorption of nitrogen to pure silica, SBA-15 and functionalized hybrids resulted in the isotherms of type IV with type H1 hysteresis. The structure of the precursor mesoporous silica was preserved after post-functionalization with bridged organic bridged chains. The precursor and its derivative silicas were ibuprofen-loaded for controlled delivery in simulated biological fluids. Surface functionalization with amine and other organic groups containing bridged hydrophobic structure resulted in significantly decreased surface area from 802.4 to 63.0 m2g-1 and pore volume to 0.09 nm, which ultimately increased the drug-loading capacity from 18.0 up to 29 % and a very slow release rate of ibuprofen over the period of 72.5 h. To investigate the release rate and mechanism from these synthesized hybrid materials, Zero-order, first-order, Higuchi, Hixson-Crowell and Peppas and Korsmeyer-Peppas kinetic models were applied. The synthesized materials were also evaluated for their ability to remove the anionic dye reactive blue-15 and cationic dye brilliant green from aqueous solutions. The hybrid silica showed selective sorption capacity for the anionic dye, reactive blue 15. The unmodified silica, SBA -15 showed high ability to remove the cationic dye, brilliant green from the aqueous medium. The obtained equilibrium isotherms were fitted to Langmuir, Freundlich and Sips models and the kinetic data were used to fit pseudo-first-order and pseudo-second-order. The results suggest that the organo-functionalized hybrid silicates could be a simple, efficient, inexpensive and convenient for the controlled release of drugs and for effective and selective removal of organic pollutants such as dyes from the aqueous solutions / Doutorado / Quimica Inorganica / Doutora em Ciências

Orientadoresr: Daniele Ribeiro de Araujo, Eneida de Paula / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-21T08:56:23Z (GMT). No. of bitstreams: 1 Guilherme_VivianeAparecida_M.pdf: 3020599 bytes, checksum: ce06e2f6da5344128ba90d18a9b569f2 (MD5) Previous issue date: 2012 / Resumo: Compostos anti-inflamatórios não esteroídais (AINEs) são amplamente utilizados para o combate da inflamação, mas frequentemente acarretam efeitos adversos que impedem a continuação do tratamento. Atualmente, a terapia a base de plantas tem sido bastante empregada a fim de desenvolver novos fármacos que apresentem eficácia analgésica e anti-inflamatória. Nesse contexto, a utilização de sistemas carreadores, como as nanopartículas de hidróxidos duplos lamelares (HDL), visa melhorar propriedades biofarmacêuticas e farmacológicas dos compostos nelas intercalados. Dessa forma, este estudo teve como objetivo caracterizar a interação entre o ácido coumárico (AC), um composto fenólico extraído de plantas, e hidróxido duplo lamelares (HDL), nanopartículas inorgânicas, considerando parâmetros como a cinética de liberação in vitro, a citotoxicidade e as atividades analgésica-antiinflamatória em relação ao fármaco não intercalado. Os ensaios de liberação in vitro foram realizados utilizando uma célula de difusão vertical (com membrana de acetato de celulose, MWCO 1000 Da) e a viabilidade celular avaliada em células 3T3 pelo teste de incorporação do vermelho neutro (VN). Os testes farmacológicos realizados em camundongos swiss foram: a determinação do número de contorções abdominais, teste tail-flick, ensaios de peritonite e teste de formalina para o composto livre e intercalado nas concentrações de 10, 20 ou 30 mg/kg. Os ensaios de liberação in vitro mostraram que a intercalação reduziu significativamente a constante de liberação (Klib) do AC, em relação ao fármaco livre, sendo os valores de Klib de 41,6 ± 1,5 %.h-1 e 32,4 ± 1,5 %.h-1 , para o AC e AC-HDL, respectivamente. A viabilidade celular foi reduzida apenas em concentrações mais elevadas de AC e AC-HDL (10 e 12,5 mM). Porém, mesmo nestas concentrações foi observada porcentagem de viabilidade celular maior que 50%. Por fim, a avaliação farmacológica apontou o AC-HDL como um sistema de liberação com atividades analgésica e anti-inflamatória mais pronunciadas do que as observadas para anti-inflamatórios não esteroidais como a indometacina (p< 0,001). Esses efeitos foram obtidos para teste de tail-flick, quando o AC foi intercalado em HDL aumentou a duração da analgesia (~ 1,7 vezes) quando comparado com o grupo de controle indometacina. Assim, os resultados indicam que o AC intercalado em nanopartículas inorgânicas de HDL apresentou uma taxa de liberação lenta e também induziu uma atividade analgésica - anti-inflamatória, possivelmente, por um mecanismo semelhante ao observado para um anti-inflamatório não esteroidais como a indometacina / Abstract: Non-steroidal anti-inflammatory drugs (NSAIDs) are widely used to avoid inflammation, but these compounds can evoke some side effects, considering these as an important limitation to the treatment. Currently, the plant-based therapy has been widely employed to develop new drugs which have analgesic and anti-inflammatory pharmacological activities. In this context, the use of inorganic nanoparticles is important to improve biopharmaceutical and pharmacological properties of the intercalated molecules. Thus, this study aimed to characterize the interaction between coumaric acid (CA), a phenolic compound extracted from plants, and layered double hydroxide (LDH), inorganic nanoparticles, considering parameters such as the in vitro release kinetics cytotoxicity and analgesic-antiinflammatory activities compared to the non-intercalated-CA. In vitro release tests were performed using a vertical diffusion cell (with cellulose acetate membrane, MWCO 1000 Da) and cell viability assessed in 3T3 cells by the neutral red (NR) uptake test. Pharmacological assays were carried in Swiss mice out in order to determine the number of writhings, tail-flick test, peritonitis test and formalin test for the free compound at three different concentrations (10, 20 or 30 mg/kg). In vitro release tests showed that the release constant (Krel) value was significantly reduced when compared to the non-intercalated CA (Krel values of 41.6 ± 1.5 %.h-1 and 32.4 ± 1.5 %.h-1 for the free CA and CA-HDL, respectively). Cell viability was reduced only at higher concentrations (10 and 12.5 mM) of CA and CA-HDL. However, even at these concentrations the percentage of cell viability was more than 50%. Finally, the pharmacological evaluation reveal the CA-HDL as a drug-release system with more pronounced analgesic-antiinflammatory effects than those observed for classic NSAIDs, such as indomethacin (p <0.001). Those effects were obtained, specially, for tail-flick test, when the treatment with CA-LDH increased the duration of analgesia (~ 1.7 times), when compared with the control group (indomethacin). Thus, the results pointed out that the system CA-LDH showed a slow release rate and also induced in vivo analgesic-anti-inflammatory activities, possibly using similar mechanisms to that observed for classic non-steroidal anti-inflammatory drugs, such as indomethacin / Mestrado / Bioquimica / Mestre em Biologia Funcional e Molecular

Submitted by Gabriela Lopes (gmachadolopesufpel@gmail.com) on 2017-03-09T15:58:23Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertação _Thaís Antolini Veçozzi (para impressão).pdf: 2198036 bytes, checksum: 0b6a9f3bfafdc322a425a6d9fd27a705 (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2017-03-10T19:34:35Z (GMT) No. of bitstreams: 2 Dissertação _Thaís Antolini Veçozzi (para impressão).pdf: 2198036 bytes, checksum: 0b6a9f3bfafdc322a425a6d9fd27a705 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-03-10T19:34:35Z (GMT). No. of bitstreams: 2 Dissertação _Thaís Antolini Veçozzi (para impressão).pdf: 2198036 bytes, checksum: 0b6a9f3bfafdc322a425a6d9fd27a705 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2015-05-13 / Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul - FAPERGS / A eficiência dos fertilizantes nitrogenados utilizados no cultivo de arroz é baixa, reflexo da susceptibilidade do N a perdas no sistema solo-planta, destacando aquelas originadas da produção de óxido nitroso (N2O). O N2O, juntamente com o metano (CH4) e o dióxido de carbono (CO2), são os principais gases de efeito estufa e suas emissões para a atmosfera são apontadas como a principal causa das mudanças climáticas globais. No Brasil, grande parte da emissão desses gases advém da agricultura e do desmatamento, caracterizando estas atividades como potenciais para reduzir suas emissões. Os fertilizantes nitrogenados de liberação controlada (FLC) são utilizados visando aumentar o aproveitamento de N, em função de sua propriedade de liberar gradativamente o nutriente ao solo. Este trabalho buscou avaliar a eficiência agronômica de fertilizante de liberação controlada e seus efeitos nas emissões de CH4 e N2O no arroz irrigado. O Estudo 1 foi realizado através de um experimento delineado em blocos casualizados, com quatro repetições, em casa de vegetação e composto pelos tratamentos: T1: testemunha sem aplicação de N; T2: ureia aplicada de acordo com a recomendação para a cultura; T3: ureia incorporada; T4: FLC 1; T5: FLC 2. Foram analisadas as concentrações de NH4+e NO3- na solução do solo ao longo do alagamento do solo e o N mineral das plantas. O Estudo 2 foi realizado em condições de campo, com três repetições e os tratamentos: T0: testemunha sem a aplicação de N; T1: ureia aplicada de acordo com a recomendação; T2: FLC em cobertura na semeadura; T3: FLC no sulco de plantio. Foram avaliadas as emissões de CH4 e N2O, o Potencial de Aquecimento Global parcial (PAGp), as concentrações de compostos minerais na solução do solo ao longo do período de alagamento, a eficiência dos fertilizantes e o rendimento de grãos. De acordo com os resultados, a solubilização dos fertilizantes de liberação controlada ocorreu mais rapidamente do que o esperado, não ultrapassando 23 dias de alagamento. A eficiência agronômica no uso de N foi de 17,20 kg kg-1 para o tratamento com uréia, 13,55 kg kg-1 no tratamento com FLC em superfície e 11,51 kg kg-1 para o FLC aplicado incorporado ao solo, resultados que não mostraram diferença estatística. A emissão de CH4 não foi influenciada pelas fontes e formas de aplicação de N. A emissão total de N2O foi de 0,44 kg/ha no tratamento sem N, de 1,09 kg/ha no tratamento com ureia, 2,09 kg/ha no tratamento com FLC em superfície e de 2,94 kg/ha no tratamento com FLC incorporado ao solo. O potencial de aquecimento global parcial não foi afetado pelo manejo da adubação nitrogenada. A aplicação de FLC não tem potencial para reduzir as emissões de CH4 e N2O do solo cultivado com arroz irrigado. O uso de FLC no arroz irrigado não eleva o rendimento de grãos. As contradições e variações observadas nos estudos com fertilizantes de liberação controlada demostram a necessidade de pesquisas amplas que avaliem seu comportamento no solo e a rentabilidade econômica. / Nitrogen use efficiency of the fertilizers used is low, as a result of its loss susceptibility in plant-soil system, highlighting among these those originated of the production of N2O. N2O, along with methane (CH4) and carbon dioxide (CO2) are the main greenhouse gases and these gases emissions to the atmosphere are seen as the main cause of possible climate change. In Brazil, much of the greenhouse gas emissions comes from agriculture and deforestation, featuring such activities as potential to reduce air pollution. Controlled-release nitrogen fertilizers (CRF) are used to increase the use of N by plants, due to its property to gradually release nutrients to the soil. This study aimed to evaluate the controlled release fertilizer agronomic efficiency and its effects on CH4 and N2O emissions in irrigated rice cultivation. Study 1 was conducted through an experiment in randomized block design with four replications, conducted in a greenhouse and composed for the treatments: T1: control without N fertilization; T2: application of urea according to Southern Brazil recommendation; T3: all dose of urea incorporated; T4: CRF 1; T5: CRF 2. NH4 + and NO3 - concentration were analyzed in the soil solution along the soil flooding and mineral N in plant aerial part. Study 2 was conducted by experiment under field conditions, with three replications and the treatments: T0: control without N application; T1: urea applied in according with the recommendation; T2: CRF in coverage at sowing; T3: CRF in the furrow. Were evaluated CH4 and N2O emissions along the cultivation, Global Warming Potential partial (GWPp), concentrations of mineral compounds in the soil solution along the soil flooding, efficiency of fertilizers and grain yield. According to the results, the solubilization of the controlled release fertilizer is occurs more faster than expected, not exceeding 23 days flooding. The agronomic N use efficiency was 17,20 kg kg -1 for treatment with urea, 13,55 kg kg-1 in the treatment with CRF in coverage at sowing and 11,51 kg kg-1 for CRF in the furrow, results statistically not difference. The CH4 emission was not influenced by sources and N forms of application. The N2O emission total was 0,44 kg/ha treatment without N, 1,09 kg/ha of treatment with urea, 2,09 kg/ha of treatment with CRF in coverage at sowing and 2,94 kg/ha on treatment with CRF in the furrow. Global Warming Potential partial was not affected by nitrogen fertilization management. The application of CRF has no potential to reduce CH4 and N2O emissions in soil cultivated with rice. The use of CRF in the rice does not increase the yield. Contraventions and variations observed in studies with controlled-release fertilizers demonstrate the need for extensive research to assess the behavior in soil and the economic profitability of these products.

Mosquitoes spread diseases that shorten and worsen the lives of many people, chiefly children in poor countries, around the world. Since Ronald Ross' discovery at the end of the nineteenth century that mosquitoes transmit malaria, field entomologists have collected a great deal of information about mosquito ecology. Despite this tremendous effort, there still remain significant gaps in our knowledge of mosquito ecology, in part, reflecting the significant variation in mosquito ecology across species and geographies. The main aim of this thesis is an attempt to synthesise the substantial information that field entomologists have collected on mosquito lifespan. In Chapters 2 and 3, I conduct meta-analyses of the two predominant approaches used to estimate mosquito lifespan: mark-release-recapture experiments and female mosquito dissection-based studies, respectively. These analyses produce estimates of mosquito lifespan by species and genus, and more broadly, allow for an appraisal of these two experimental approaches. In Chapter 4, I describe a recently developed approach, known as near-infrared spectroscopy, which enables estimation of the age of individual mosquitoes, and then perform an in silico analysis to explore the use of this technology for estimating the average lifespan of wild populations of mosquitoes. The emergence of mosquito resistance to the main insecticides used in vector control, along with the concerning recent discovery that the malaria parasites in Asia are becoming resistant to arteminisin - an important drug used to treat malaria - highlight the need for novel approaches to control disease transmission. Some recently-proposed approaches involve genetic modification of the mosquito vectors, for example, to render them incapable of acting as hosts for disease or to reduce their fecundity. In Chapter 5, I model the impact of a release of mosquitoes carrying a genetic construct known as a homing endonuclease, which has been constructed to bias the sex of mosquito offspring towards males, in computational environments that capture some facets of the real life landscapes where mosquito borne disease is rife. About a century ago, the famous Italian Malariologist Giovanni Grassi declared that malaria was a "giant with clay feet"; reflecting the optimism, in some academic circles at the time, that eradication of this terrible disease would soon occur. Unfortunately, a century of often unsuccessful attempts to control and eradicate malaria, and other mosquito borne diseases, would follow Grassi's statement, meaning that this fight is likely to continue throughout the twenty-first century. We now know much more about mosquitoes and mosquito borne disease than we did a generation ago, but there is still crucial information that we do not. In this thesis, I argue that in order to make significant inroads to disease eradication, further research on mosquito ecology is crucial. Only when we better understand our unwitting mosquito foe, can we design and implement effective disease control measures that are so desperately needed in those most desperate parts of the world.

The use of pop-up satellite archival tags (PSATs) eliminates many of the limitations associated with acoustic and conventional tags by using fishery-independent data collection and retrieval. Previous research techniques have provided information on longer-term movements, migrations, and behavior patterns, but there is still a need for additional tagging studies using tags with depth and light data and increased memory that will further define the short-duration activity patterns and habitat utilization of juvenile swordfish in the western North Atlantic. PSATs have been successfully used on other large pelagic fishes, but have yet to be used on juvenile swordfish. This study investigated two main topics: a) the post-release survival rates of juvenile swordfish after being released from the recreational rod-and-reel fishery and commercial swordfish buoy gear fishery in the Florida Straits, and b) the habitat utilization of juvenile swordfish following release. High-resolution PSAT technology was used to estimate the post-release survival of 16 individual juvenile swordfish captured with standard recreational or buoy fishing gear and techniques in the southeast Florida swordfish fishery. Analysis of release mortality estimates was done using the “Release Mortality” Program. Five of the fourteen reporting tags showed a mortality within 48 hours, for a release mortality rate of 35.7%. However, no common thread could be found among the five mortalities. Results of the Release Mortality program indicated that if the true mortality rate was 35.7%, approximately 1800 tags would have to be deployed to increase the precision of the mortality estimates to +/- 5% of the true value. The nine surviving fish varied in straight-line distance traveled and in direction, and could withstand a wide range of temperatures. A deterministic, periodic model was developed to fit to the data and describe the fishes’ habitat utilization. This model identified both diurnal and lunar signals in the data, confirming that juveniles do move vertically based on the daily cycle of the sun and the lunar cycle of the moon and that their diurnal movements are much greater than their lunar movements. The results of this study can be valuable to management practices in future stock assessments and decisions regarding mandatory release of undersized fish.

During the winters in recent years Laholmsbuktens VA's treatment plant in Halmstad has recorded unexcepted levels of phosphorus from the polishing pond. Only between 8 and 20 January 2016 samples indicates a realese of net 75 kg. In winter the pond temperature never goes below about 8oC, which attracts wintering waterfowl. In February 19, 2016 the largest number of birds in the inventory for this thesis was noted, 325 individuals, of which 208 were tufted ducks.  Even if the number of waterfowl at peak levels was to be about 1000 individuals, their combined contribution of phosphorus through droppings into the pond could not be more than 500 g per day. This study proposes that a significant factor is the foraging activity of tufted ducks, which are diving ducks. In search of food at daytime they disturb the sediment at the bottom of the pond, i.e bioturbation.  The higher proportion of particle-bound phosphorus in samples with high phosphorus content also fits well with this hypothesis. A scientific investigation in which the bottom of this part of the pond was stirred up mechanically gave similar proportions between phosphorus and water-soluble phosphorus.

Ce travail de thèse a pour objectif de formuler un emballage comestible à base d’un mélange de chitosan et de gélatine (bœuf ou poisson), de mieux comprendre l’influence d’irradiations par faisceaux d’électrons et de l’incorporation d’antioxydants naturels sur les propriétés physico-chimiques et fonctionnelles des films. Une étude de l’effet de l’irradiation sur la cinétique de libération des antioxydants dans un milieu liquide simple a été étudiée pour validation. Une étude préliminaire a montré d’abord que la densification de la solution filmogène puis du gel pendant le séchage ne dépend ni de l’épaisseur, ni de la concentration, ni du temps et laisse supposer une diffusion Fickienne de l’eau dans la matrice. La perméabilité à la vapeur d’eau augmente linéairement avec l’épaisseur de films et d’autant plus lorsque l’étendue du différentiel d’humidités relatives est élevé. Ce phénomène est attribué à un mécanisme de gonflement et de plastification du réseau de gélatine-chitosan par l’eau. L’effet du taux de mélange de deux biopolymères a montré une amélioration des propriétés mécaniques et barrières à l’eau et à l’oxygène des films de chitosan. Ces gains de performances sont dus à la bonne miscibilité des deux macromolécules et aux interactions moléculaires établies suite à la formation d’un complexe polyélectrolytique, confirmé par analyse FTIR. L’irradiation des films après séchage accroit la polarité de surface et l’hydrophilie des films et ainsi induit une augmentation des propriétés barrières à la vapeur d’eau et à l’oxygène, mais aussi des mécaniques et thermiques des films. Toutefois, l’irradiation ne modifie pas la cristallinité des films. L’incorporation des antioxydants (acide férulique, coumarine, quercétine et tyrosol) avec ou sans irradiation agit différemment, selon leur nature, sur l’organisation du réseau macromoléculaire et donc sur les propriétés des films. Ainsi, l’acide férulique et le tyrosol réduise la perméabilité à la vapeur d’eau mesurée à un gradient de 0-30% d’humidité relative, alors qu’ils l’augmentent jusqu’à 90 fois avec un gradient 30-84% et un traitement d’irradiation. La perméabilité à l’oxygène diminue d’une façon significative après ajout de quercétine ou de tyrosol et après irradiation. L’acide férulique et la coumarine augmente la force à la rupture des films alors que ce sont la quercétine et l’acide férulique qui permettent d’accroitre la résistance thermique des films. Ces résultats mettent ainsi en évidence la complexité des interactions mises en jeu entre les antioxydants et les chaînes de chitosan et/ou de gélatine, leur dépendance au niveau d’hydratation du système et à l’impact du traitement de réticulation par irradiation. Il faut noter que l’irradiation a permis de protéger les molécules actives contre l’oxydation durant une longue période de stockage des films. La libération en milieu aqueux de l’acide férulique est la plus ralentie avec une rétention dans les films la plus élevée à l’équilibre (27%). Les coefficients de diffusion des antioxydants, déterminés à partir des cinétiques de libération ont pu être modulés (50%) grâce à l’irradiation. / This thesis aims to develop an edible packaging made of a mixture of chitosan and gelatin (beef or fish), to better understand the influence of the electron beam irradiation and of the incorporation of natural antioxidants on the physico-chemical and functional properties of the films. A study of the effect of irradiation on antioxidants release kinetics in a simple liquid medium was studied for validation. A preliminary study first showed that the densification of the film-forming solution and the gel during drying does not depend on the thickness or concentration or time and suggests a Fickian diffusion of water in the matrix. The permeability to water vapor increases linearly with film thickness and especially when the extent of the relative humidity differential is high. This phenomenon is attributed to a swelling mechanism and plasticization of the gelatin-chitosan network by the water. The effect of the chitosan-gelatin ratio showed an improvement of the mechanical properties and barrier to water and oxygen of the films compared to chitosan films. These performance gains are due to the good miscibility of the two macromolecules and to the molecular interactions established after the formation of a polyelectrolyte complex, as confirmed by FTIR analysis. Irradiation of films after drying increases the polarity of the surface and the film hydrophilicity, and thus induces an increase in barrier properties to water vapor and oxygen, and also of the mechanical and thermal films. However, irradiation does not change the crystallinity of the films. The incorporation of antioxidants (ferulic acid, coumarin, quercetin and tyrosol) with or without irradiation acts differently on the organization of the macromolecular network and thus on the film properties. Thus, ferulic acid and tyrosol reduce the permeability of water vapor measured in a gradient of 0-30% relative humidity, while it increases up to 90 times with a gradient 30-84 % and an irradiation treatment. The oxygen permeability decreases significantly after addition of quercetin or tyrosol and after irradiation. Ferulic acid and coumarin increases the tensile strength of the films while they are quercetin and ferulic acid which allow to increase the thermal resistance of the films. These results thus demonstrate the complexity of the interactions involved between antioxidants and the chains of chitosan and/or gelatin, their dependence on the moisture level of the system and on the impact of cross-linking treatment by irradiation. It is noticed that the irradiation has protected the active molecules against oxidation for a long period of storage of the films. Release in aqueous medium of ferulic acid is the more delayed with the highest retention in the film at equilibrium (27%). The antioxidants diffusion coefficients, determined from the release kinetics, could be modulated (about 50%) by the irradiation treatments.

Therapeutics based on siRNA represent a promising hope for the treatment of many congenital and acquired disorders. This method is based on posttranscriptional silencing of pathological gene or set of genes (RNAi process), which are responsible for the actual cause of the disease. Access is therefore based on the assumption of treatment options for the disease at the point of origin of the defect intervention at the molecular level, which is different from the conventional, so-called symptomatic therapy, which focuses only on the treatment or suppression of symptoms. Despite rapidly increasing understanding of gene function and cause a number of genetic diseases, the expansion of siRNA therapeutics limited the development of efficient and safe transport systems (vectors). In order to ensure efficient transport of siRNA in vivo conditions, the vectors must sufficiently reduce the size of the siRNA, protect it against degradation during transport, and release in the cytoplasm of the target cell. For this purpose they were developed sophisticated transport systems based on viral and non-viral origin. This diploma thesis is focused on the preparation of new transport systems, siRNA-based synthetic hydrophilic polymers, such as non-viral vectors. For in vitro testing the effectiveness during transport of siRNA...

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16387号 / 工博第3468号 / 新制||工||1524(附属図書館) / 29018 / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 田中 宏明, 教授 清水 芳久, 教授 伊藤 禎彦 / 学位規則第4条第1項該当