<p>Validerat; 20130918 (global_studentproject_submitter)</p>

Ce mémoire porte sur l'élaboration et la caractérisation d'un matériau composite chitosane/phosphate de calcium destiné à une utilisation dans le domaine de la substitution osseuse. Le procédé d'atomisation-séchage a été choisi pour élaborer ce composite sous forme d'une poudre susceptible d'être transformée en revêtement ou objet 3D. Une étude préliminaire a permis d'appréhender les mécanismes de synthèse du phosphate de calcium, la phase minérale, par atomisation-séchage. Une suspension de particules d'hydroxyapatite stœchiométrique ou d'apatite biomimétique dispersées dans une solution acide mène systématiquement à l'apparition d'une phase amorphe. La proportion de cette phase amorphe dans la poudre atomisée-séchée est dépendante de la taille et de la cristallinité du matériau d'origine. L'atomisation séchage d'une solution acide contenant les ions précurseurs de calcium et phosphate mène à la formation d'une phase principalement amorphe. Cette poudre a pu être décrite à différentes échelles : à une échelle de l'ordre du nanomètre apparaissent des clusters, à une échelle de l'ordre de la centaine de nanomètres des agrégats sphériques de clusters organisés en chapelet tortueux et imbriqués sont identifiés et enfin à une échelle micrométrique des agglomérats de nanoparticules ont été mises en évidence. Le phosphate de calcium ainsi synthétisé possède un rapport molaire Ca/P proche de 1.3. Au-delà de ce rapport dans la solution à atomiser, de l'acétate de calcium (utilisé ici comme précurseur) recristallise dans la poudre. Pour élaborer la poudre composite, le polymère a été solubilisé et ajouté d'abord dans une suspension acide d'hydroxyapatite avant atomisation. Cette première stratégie mène à la formation d'un composite qui présente de fortes inhomogénéités de répartition des phases organiques et minérales. Pour limiter ce problème lié à la distribution de tailles de grains de la phase minérale, une seconde stratégie a été développée. Une solution de polymère contenant des précurseurs de phosphate de calcium a été préparée pour favoriser l'association à l'échelle nanométrique des deux phases. Après atomisation-séchage, un matériau composite présentant une très bonne dispersion de la phase minérale dans la matrice organique est synthétisé. La structuration de la phase minérale est modifiée par la présence du polymère. Cette modification se traduit par une diminution de la fraction volumique des clusters et, à l'échelle supérieure, la phase minérale n'est plus présente sous forme de chapelet mais en particules sphériques isolées. Par ailleurs, une interaction chimique est envisagée en raison des liaisons de type hydrogène, ioniques ou de coordinations possibles entre les deux phases. La présence du polymère inhibe également la formation de l'acétate de calcium cristallin en favorisant la formation d'un sel d'acétate de chitosane. Deux techniques de mises en forme ont été étudiées (MAPLE, pour l'élaboration de revêtements minces et l'impression 3D de pâte pour l'obtention d'objet massif) et ont permis de mettre en avant le potentiel de transformation de la poudre préparée par atomisation séchage. Les études biologiques faites sur le revêtement ont de plus permis de démontrer les propriétés antibactériennes du matériau utilisé. / This thesis deals with the development and characterization of a chitosan/calcium phosphate composite material for use in the field of bone substitution. The spray-drying method was chosen to develop this composite in the form of a powder that could be transformed into a coating or 3D object. A preliminary study made it possible to understand the mechanisms of synthesis of calcium phosphate, the mineral phase, by spray-drying. A suspension of stoichiometric hydroxyapatite particles or biomimetic apatite dispersed in an acidic solution systematically leads to the appearance of an amorphous phase. The proportion of this amorphous phase in the spray-dried powder is dependent on the size and crystallinity of the original material. The spray drying of an acidic solution containing the precursor ions of calcium and phosphate leads to the formation of a mainly amorphous phase. This powder could be described at different scales: on a scale of about one nanometer appear clusters, on a scale of about one hundred nanometers spherical aggregates of clusters organized into tortuous and nested chaplets are identified and finally on a micrometric scale, agglomerates of nanoparticles were highlighted. The calcium phosphate thus synthesized has a molar ratio Ca/P close to 1.3. Beyond this ratio in the solution to be atomized, calcium acetate (used here as a precursor) recrystallizes in the powder. To develop the composite powder, the polymer was solubilized and added first into an acid suspension of hydroxyapatite before atomization. This first strategy leads to the formation of a composite that has strong in homogeneities in the distribution of organic and inorganic phases. To limit this problem related to the grain size distribution of the mineral phase, a second strategy has been developed. A polymer solution containing calcium phosphate precursors has been prepared to promote nanoscale association of the two phases. After spray-drying, a composite material having a very good dispersion of the mineral phase in the organic matrix is synthesized. The structuring of the mineral phase is modified by the presence of the polymer. This modification results in a reduction of the volume fraction of the clusters and, on the larger scale, the mineral phase is no longer present in the form of a string but in isolated spherical particles. Moreover, a chemical interaction is envisaged because of the hydrogen, ionic or possible coordination bonds between the two phases. The presence of the polymer also inhibits the formation of crystalline calcium acetate by promoting the formation of a salt of chitosan acetate. Two shaping techniques were studied (MAPLE, for the elaboration of thin coatings and the 3D printing of dough for obtaining massive objects) and made it possible to highlight the transformation potential of the prepared powder by spray drying. The biological studies made on the coating have also demonstrated the antibacterial properties of the material used.

Ng, Yiu Ming. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references (leaves 99-114). / Abstracts in English and Chinese. / Acknowledgements --- p.2 / Abstract --- p.3 / 摘要 --- p.5 / Content --- p.6 / List of abbreviations and symbols --- p.10 / Chapter Chapter 1 - --- Introduction --- p.13 / Chapter 1.1 --- Introduction to nanoparticles (NPs) --- p.13 / Chapter 1.2 --- How to treat solid cancers using nanoparticle drugs --- p.17 / Chapter 1.3 --- What is Chitosan (CS)? --- p.22 / Chapter 1.4 --- Possible peptide candidates to be trapped --- p.26 / Chapter 1.4.1 --- Luffin PI - Ribosome inactivating peptide --- p.26 / Chapter 1.4.2 --- Buforin lib (Bllb) - Antimicrobial peptide --- p.27 / Chapter 1.5 --- Aims of study --- p.30 / Chapter Chapter 2 - --- Materials and Methods --- p.31 / Chapter 2.1 --- Materials --- p.31 / Chapter 2.2 --- Methods --- p.31 / Chapter 2.2.1 --- Construction and expression of Luffin P1 --- p.31 / Chapter 2.2.2 --- Circular dichroism spectroscopy --- p.32 / Chapter 2.2.3 --- Static light scattering --- p.33 / Chapter 2.2.4 --- In vitro N-glycosidase assay --- p.34 / Chapter 2.2.5 --- Preparation of CS particles --- p.34 / Chapter 2.2.5.1 --- Preparation of positive CS NPs --- p.34 / Chapter 2.2.5.2 --- Preparation of negative CS NPs --- p.35 / Chapter 2.2.5.3 --- Preparation of buforin lib incorporated NPs --- p.35 / Chapter 2.2.5.4 --- Preparation of Cy5 incorporated NPs --- p.36 / Chapter 2.2.6 --- Characterization of CS NPs --- p.36 / Chapter 2.2.7 --- Buforin lib (Bllb) encapsulation efficiency and loading capacity --- p.36 / Chapter 2.2.8 --- In vitro release study --- p.37 / Chapter 2.2.9 --- Confocal Microscopy --- p.37 / Chapter 2.2.10 --- Cytotoxicity assay --- p.38 / Chapter 2.2.11 --- Statistical analysis --- p.38 / Chapter Chapter 3 - --- "Cloning, expression, purification and structural characterization of Luffin PI" --- p.39 / Chapter 3.1 --- Introduction --- p.39 / Chapter 3.2 --- Results --- p.41 / Chapter 3.2.1 --- Construction of Luffin PI plasmid --- p.41 / Chapter 3.2.2 --- Expression and purification of Luffin PI --- p.41 / Chapter 3.3.3 --- Molecular weight and secondary structure determination of Luffin PI --- p.43 / Chapter 3.3.4 --- 3D solution structure of Luffin PI --- p.45 / Chapter 3.3.5 --- In vitro N-glycosidase activity of Luffin PI --- p.49 / Chapter 3.3 --- Discussion --- p.51 / Chapter Chapter 4 - --- Generation of positively charged CS particles and Bllb incorporation --- p.60 / Chapter 4.1 --- Introduction --- p.60 / Chapter 4.2 --- Results --- p.62 / Chapter 4.2.1 --- Positively charged CS NPs generation --- p.62 / Chapter 4.2.2 --- Bllb incorporated +ve CS NPs generation --- p.68 / Chapter 4.2.3 --- In vitro release study --- p.70 / Chapter 4.2.4 --- In vitro cytotoxicity test --- p.72 / Chapter 4.3 --- Discussion --- p.74 / Chapter Chapter 5 - --- Generation of negatively charged CS particles and Bllb incorporation --- p.83 / Chapter 5.1 --- Introduction --- p.83 / Chapter 5.2 --- Results --- p.85 / Chapter 5.2.1 --- -ve CS NPs generation --- p.85 / Chapter 5.2.2 --- -ve CS-Bllb NPs generation --- p.88 / Chapter 5.2.3 --- In vitro release study --- p.91 / Chapter 5.2.4 --- Localization study of -ve CS-Bllb NPs --- p.93 / Chapter 5.2.5 --- In vitro cytotoxicity test --- p.96 / Chapter 5.3 --- Discussion --- p.98 / Chapter Chapter 6 - --- Conclusion and future work --- p.108 / Copyright --- p.110 / References --- p.111

Made available in DSpace on 2014-12-17T15:41:54Z (GMT). No. of bitstreams: 1 ElisamaVS_DISSERT.pdf: 3256609 bytes, checksum: 7bb56ee7f0f5f70ae8afd8e24e21825f (MD5) Previous issue date: 2011-07-05 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In this work, chitosan was used as a coating of pure perlite in order to increase the accessibility of the groups OH- e NH2+the adsorptionof ions Mn2+ e Zn2+.The characterization results of the expanded perlite classified as microporous and whose surface area 3,176 m2 g-1after the change resulted in 4,664 m2g-1.From the thermogravimetry(TG) it was found that the percentage of coating was34,3%.The infrared analysis can prove the presence of groups Si-OH, Si-O e Al-O-Siresulting from the perlite and C=O, NH2and OH characterization of chitosan. The experiments on experiments on the adsorption of Mn and Zn were performed in the concentration range of10 a 50 mgL-1and the adsorption capacity inpH 5,8 e 5,2 was 19,49 and 23,09 mgg-1to 25 oC,respectively.The adsorption data were best fitted to Langmuir adsorption model to Langmuir adsorption model for both metalionsisindicative of monolayer adsorption. The kinetics of adsorption were calculated from the equation of Lagergren fitting the model pseudo-second-order for all initial concentrations, suggesting that adsorption of ions Mn2+ and Zn2+ follows the kinetics of pseudo-second-order and whose constant Speedk2(g/mg.min) are 0,105 e 3,98 and capacity and maximum removal qe 4,326 e 3,348,respectively.In this study we used a square wave voltammetry cathodic stripping voltammetry to quantify the adsorbed ions, and the working electrode glassy carbon, reference electrode silver / silver chloride and a platinum auxiliary electrode. The attainment of the peaks corresponding to ions Mn2+ and Zn2+ was evaluated in and electrochemical cell with a capacity of 30 mL using a buffer system (Na2HPO4/NaH2PO4)at pH 4 and was adjusted with solutionsH3PO4 0,1molL-1and NaOH 0,1 molL-1and addition of the analyte has been a cathodic peak in- 0,873 Vand detection limit of2,55x10-6molL-1para Zn.The dough used for obtaining the adsorption isotherm was 150 mg and reached in 120 min time of equilibrium for both metal ions.The maximum adsorption for 120 min with Mn concentration 20 mgL-1 and Zn 10 mgL-1,was91, 09 e 94, 34%, respectively / Nesse trabalho a quitosana foi utilizada como revestimento da perlita expandida pura com o objetivo de aumentar a acessibilidade dos grupos OH- e NH2+ na adsor??o dos ?ons Mn2+ e Zn2+. A perlita expandida foi classificada como microporoso com uma ?rea superficial de 3,176m2 g-1 e ap?s modifica??o resultou em 4,664m2 g-1. A partir da Termogravimetria (TG) verificou-se que o percentual de revestimento foi de 37,5%. A an?lise de infravermelho comprovou a presen?a dos grupos Si-OH, Si-O e Al-O-Si decorrentes da perlita e C=O, NH2 e OH caracter?sticos da quitosana. Os experimentos na adsor??o de Mn2+ e Zn2+ foram realizados no intervalo de concentra??o de 10 a 50 mg L-1 e acapacidade de adsor??o em pH 5,2 e 5,8 foi de 23,09 e 19,49 mg g-1 a 25 oC, respectivamente. Os dados de adsor??o se ajustaram melhor ao modelo de adsor??o de Langmuir para ambos os c?tions met?licos sendo indicativo de adsor??o f?sica em monocamada.As constantes de velocidade de adsor??o foram calculadas a partir da equa??o Lagergren se ajustando ao modelo de pseudo-segunda-ordem para todas as concentra??es iniciais, sugerindo que a adsor??o dos ?ons Mn2+ e Zn2+ segue a cin?tica de pseudo-segunda-ordem e cujas constantes de velocidade k2(g/mg.min) s?o 0,105 e 3,98 e capacidade m?xima de remo??o qe 4,326 e 3,348 mg g-1, respectivamente. Utilizou-se a voltametria de onda quadrada de redissolu??o cat?dica para a quantifica??o dos ?ons adsorvidos, com o eletrodo de trabalho de carbono v?treo, eletrodo de refer?ncia prata/cloreto de prata e um eletrodo auxiliar de platina. A obten??o dos picos correspondente aos ?ons Mn2+ e Zn2+ foi avaliado em uma c?lula eletroqu?mica com capacidade para 30 mL utilizando um sistema tamp?o (Na2HPO4/NaH2PO4) cuja concentra??o 0,1 mol L-1em pH 4, sendo ajustado com solu??es H3PO4 0,1 mol L-1e NaOH 0,1 mol L-1e adi??o do analito, tendo verificado um pico cat?dico em 0,873 V com limite de detec??o de Mn 7,76x10-7 mol L-1 e um pico an?dico de -1,1 V e limite de detec??o de 2,55x10-6mol L-1 para Zn2+.A massa utilizada para a obten??o das isotermas de adsor??o foi de 150 mg, tendo atingido o tempo de equil?brio de 120 min para ambos ?ons met?licos. A m?xima adsor??o em 120 min para Mn2+ com concentra??o de 20 mg L-1 e Zn 10 mg L-1, foi de 91,09 e 94,34% ,respectivamente

Made available in DSpace on 2014-12-17T15:41:58Z (GMT). No. of bitstreams: 1 VictorAVO_DISSERT.pdf: 1098770 bytes, checksum: b51c2db6f7a42c08650cb24f90bc77c8 (MD5) Previous issue date: 2012-03-30 / Dynamic light scattering was used to monitor relaxation processes in chitosan solutions at concentrations within the semi-dilute and concentrated regimes, Kowhlrausch-Williams-Watts (KWW) equation being successfully fitted to intensity correlation function data. The dependence of KWW equation parameters on chitosan concentration indicated that an increase in concentration from semi-dilute to concentrated regimes resulted in narrowing the distribution of relaxation rates; temperature dependence indicated the relaxation process as described as an energy activated process, whose parameters were function of the interaction between chitosan chains (enthalpy of activation) and rigidity of chitosan conformations (pre-exponential factor) / O espalhamento din?mico de luz foi utilizado para monitorar processos de relaxa??es em solu??es de quitosana em concentra??es dentro dos regimes semidilu?das e concentradas, a equa??o Kowhlrausch-Williams-Watts (KWW) foi ajustada com ?xito para os dados de intensidade de fun??o de correla??o. A depend?ncia dos par?metros da equa??o KWW sobre a concentra??o de quitosana indicam que um aumento na concentra??o de semidilu?da ? concentrada resultou no estreitamento da distribui??o das taxas de relaxa??o; a depend?ncia da temperatura indicada no processo de relaxa??o, foi descrito como energia de ativa??o do processo, cujos par?metros foram fun??es da intera??o entre as cadeias de quitosana (entalpia de ativa??o) e rigidez das conforma??es de quitosana (fator pr?-exponencial)

Resumo: Perdas significativas ocorrem durante o armazenamento e a comercialização de uvas de mesa devido, principalmente, à ocorrência do mofo cinzento (Botrytis cinerea Pers.:Fr.) e, visando o controle de patógenos emprega-se, geralmente, o dióxido de enxofre (SO2). Diante da restrição crescente ao uso de produtos químicos em pós-colheita, tem ocorrido considerável interesse em métodos alternativos de controle. Este trabalho teve como principal objetivo avaliar os efeitos dos agentes bióticos (Lentinula edodes (Berk.) Pegler e Agaricus blazei (Murril) ss. Heinem) e abióticos (quitosana, ácido acético e irradiação UV-C), possíveis indutores de resistência, na proteção de uva Itália pós-colheita contra B. cinerea. In vivo, avaliou-se o efeito direto e indireto dos agentes de controle através do tratamento dos cachos de uva, antes e após a inoculação com o patógeno. Utilizaram-se extratos aquosos dos cogumelos A. blazei (linhagem ABL 29) e L. edodes (linhagem LED 17) nas concentrações de 0,0; 2,5; 5,0; 10,0; 20,0 ou 40,0 % (v/v); quitosana nas concentrações de 0,00; 0,25; 0,50; 1,00; 1,50 e 2,00 % (v/v); vapor de ácido acético a 0,0; 2,6; 5,2; 10,5 ou 21,0 mg.L-1 e; irradiação UV-C (254 nm) nas doses de 0,00; 0,84; 1,30; 2,40; 3,60; 4,80 e 7,50 kJ.m-2. Para inoculação, em cada cacho foram feridas 10 bagas, fazendo-se um furo por baga de 2 mm de profundidade, procedendo-se em seguida, a aspersão da suspensão de conídios ( 105 conídios.mL-1) de B. cinerea. Após os tratamentos, os cachos foram mantidos a 25 1 C / 80-90 % UR; quando avaliações de incidência e severidade foram realizadas diariamente, além de análises físicas e físico-químicas da uva. Avaliações in vitro do efeito dos agentes de controle sobre o patógeno também foram realizadas analisando-se o crescimento micelial e a germinação dos conídios de B. cinerea... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Significant losses of table grapes occur during storage and commercialization due mainly to the occurrence of gray mold (Botrytis cinerea Pers.:Fr.), and sulfur dioxide (SO2) is frequently used to control such pathogens. Due to increasing restrictions on the postharvest use of chemical products, considerable interest in alternative control measures has arisen. The main objective of this study was to evaluate the effects of biotic (Lentinula edodes (Berk.) Pegler and Agaricus blazei (Murril) ss. Heinem) and abiotic (chitosan, acetic acid and UV-C irradiation) agents as possible resistance inducers in 'Itália' grapes, aimed at post-harvest protection against B. cinerea. The direct and indirect effects of these control agents were evaluated in vivo by treating bunches of grapes before and after inoculation with the pathogen. Aqueous extracts of the mushrooms A. blazei (strain ABL 29) and L. edodes (strain LED 17) were used in the concentrations of 0.0; 2.5; 5.0; 10.0; 20.0 and 40.0 % (v/v); chitosan at 0.00; 0.25; 0.50; 1.00; 1.50 and 2.00 % (v/v); acetic acid vapor at 0.0; 2.6; 5.2; 10.5 and 21.0 mg.L-1 and UV-C (254 nm) irradiation at doses of 0.00; 0.84; 1.30; 2.40; 3.60; 4.80 and 7.50 kJ.m-2. For inoculation, 10 grapes in each bunch were injured by piercing the grape to a depth of 2 mm, followed by spraying with the inoculum of B. cinerea conidia ( 105 conidia.mL-1). After the treatments, the bunches were kept at 25 1 C / 80-90 % RH, carrying out daily evaluations of disease incidence and severity, as well as physical and physical-chemical analyses of the grapes. In vitro evaluations of the effect of the control agents were also carried out based upon mycelial growth and germination of B. cinerea conidia. The results showed that the extracts of A. blazei and L. edodes failed to control deterioration by B. cinerea in 'Itália' grapes when applied after inoculation. However, the A. blazei... (Complete abstract, click electronic access below) / Orientador: Eliane Aparecida Rodrigues da Silva / Coorientador: Sérgio Florentino Pascholati / Banca: Nilton Luiz de Souza / Banca: José Maria Monteiro Sigrist / Mestre

A indústria cerâmica tem destinado produtos para as mais diversas áreas e, com a crescente exigência de alta qualidade, tornou-se necessário desenvolver novas técnicas para o processamento cerâmico. O objetivo consiste em produzir corpos a verde (antes da queima) mais homogêneos, com menor incidência de micro-defeitos. Tais materiais podem ser produzidos preparando-se suspensões aquosas de pós cerâmicos como o óxido de alumínio (Al2O3), conhecido como alumina. Estas suspensões possuem um alto teor de sólidos no meio. A adição de outras espécies ao meio auxilia a dispersão das partículas, aumentando a estabilidade da suspensão. Estas espécies podem ser polieletrólitos (polímeros com cargas) que interagem com a superfície das partículas de alumina, através de vários mecanismos, promovendo um impedimento à aproximação de outras partículas. Neste trabalho, foram utilizados três tipos de taninos, que são macromoléculas de origem vegetal, de nome comercial Weibull e Macrospec; e Dispersan, sendo que a diferença entre eles está na quantidade de grupos hidroxila, maior em Macrospec com relação a Weibull, e na mistura com polímero sintético, o poliacrilato de sódio, caso do Dispersan. Um derivado quaternizado de quitosana, (nitrogênio trimetilado), um polissacarídeo natural, também foi utilizado como agente de estabilização. A meta pretendida correspondia à obtenção de suspensões com partículas menores e portanto menor viscosidade e maior fluidez, ou seja a suspensões mais homogêneas que levem a produtos de melhor qualidade. A avaliação da estabilidade das suspensões, devido à adição das macromoléculas, foi feita através de medidas de viscosidade, potencial zeta, diâmetro médio de partícula, além de testes de sedimentação. Dentre os agentes de estabilização utilizados, os taninos Weibull, Macrospec e Dispersan, no geral, apresentaram desempenho similar, contribuindo para uma diminuição da viscosidade e do tamanho das partículas da suspensão e no teste de sedimentação, um melhor empacotamento. A quitosana quaternizada também levou à estabilização da suspensão em determinadas condições mas, comparativamente aos taninos, apresentou desempenho inferior. Os resultados foram promissores, todavia, devendo o estudo ser aprofundado considerando-se condições diversificadas. / The ceramic industry provides products for several areas, and new processing techniques became necessary to meet the quality requirements. The objective is to produce more homogeneous green microstructures (bodies before burning), with lower number of micro-defects. Such materials can be produced from aqueous suspensions of aluminum oxide (Al2O3), known as alumina. These suspensions have a large number of solid particles, and dispersion of particles may be assisted by the addition of other species, increasing stability. These species can be polyelectrolytes (polymers with charges) that interact with the surface of alumina particles, hindering the approach of other particles. In this work, vegetal macromolecules such as tannins and chitosan, polysaccharides found in exoskeleton of crustaceans, are used as stabilizing (stabilization) agents of the suspension. Evaluation of the suspension stability, due to addition of these macromolecules, is performed through measurements of viscosity, zeta potential, particle diameter, pore size and sedimentation tests. The overall aim is the attainment of less viscous suspensions with smaller particles and greater fluidity, i.e. more homogeneous suspensions that lead to better-quality products. Amongst the stabilizing agents used, the tannins presented the better performance, contributing for a reduction in viscosity and particle size, in addition to a better wrapping up in the sedimentation tests. Although the quaternized chitosan has also contributed for a decrease in viscosity and particle size, it presented inferior performance, in comparison to that of tannins. These results were nevertheless promising, and a further study with chitosan is recommended, in which other conditions are employed.

Este trabalho tem como foco dois aspectos principais: i) O processamento e caracterização de elementos porosos vítreos, a partir de vidro reciclado e ii) A deposição de filmes de quitosana (CHI) e carboximetilcelulose (CMC). O objetivo é a avaliação da interação superficial desses filmes com o herbicida atrazina (ATZ) em meio aquoso. O processamento seguiu o princípio do preenchimento (filler principle), fazendo uso dos sais NaCl e o MgCO3 como fases formadoras de poros. A caracterização mostra que o NaCl, age como um elemento solúvel, inerte, exceto na interface NaCl-matriz vítrea, cuja estrutura cristalina final é a cristobalita. Contrariamente, o MgCO3 reage com a matriz introduzindo novas fases como o CaMg(SiO3)2. A estrutura final, de poros e da matriz, é distinta para cada um dos sais utilizados, principalmente quanto ao aspecto morfológico dos poros e as análises semiquantitativas mostraram que o cátion Na+ na interface vidro-NaCl e o íon Mg++ atuam como modificadores de cadeia. Medidas de porosimetria indicam que nos materiais processados com NaCl apresentam estruturas dos poros abertos com uniformidade na distribuição dos tamanhos e com certa regularidade de formatos quando comparados com os materiais processados com MgCO3. Com respeito à interação herbicida - materiais vítreos, esta foi avaliada por técnicas espectroscópicas, podendo-se inferir que há interação entre as superfícies ativadas quimicamente e a ATZ. A remoção do herbicida por filtragem simples através dos filmes de CHI e filmes de CHI+CMC depositados sobre as membranas foram inferiores numericamente aos valores obtidos pela ação da superfície vítrea ausente de filmes. Entretanto, os resultados indicam que ocorre uma melhor interação entre a CHI e o ATZ, quando ambos estão em solução a pH = 3,0. Por espectroscopia de fotoelétrons excitada por raios-X (XPS) houve o aumento das espécies O (1s), C (1s), N (1s) e Cl (2s) confirmando as interações com o herbicida, porém não sendo possível inferir se esta se dá por algum grupo proveniente da CHI ou por sítios livres disponíveis na superfície vítrea. Análises numéricas indicam remoções de ATZ na ordem de 10-12% com respeito às medidas realizadas em sistemas contendo uma única membrana. Avaliação complementar da remoção do metal (Cd) confirmam a vantagem das superfícies depositadas com CHI, para este tipo de interação, indicando que sistemas compostos podem ser vantajosos na remoção de diversos contaminantes. / This work is focused in two main aspects: i) The processing and characterization of porous vitreous pieces, produced from waste glass and ii) The deposition of chitosan (CHI) and carboximethilcelullose (CMC) on the vitreous surface. The evaluation of the active aspects aiming at interactions with the herbicide atrazine (ATZ) was realized in aqueous medium. The processing follows the filler principle making use of NaCl and MgCO3 as porous phases formation. Characterization showed that NaCl acts as a soluble, inert phase, with interaction over NaCl-Matrix interface, resulting in cristobalite phase as final structure. Conversely, the MgCO3 reacts along the matrix generating new phases such as CaMg(SiO3)2. The final porous and matrix structure also differs to each used salt, mainly concerning morphological aspects of the porous where semiquantitive analysis point to the Na+ in glass-NaCl interface and to Mg++ as the main chain modifiers. Measurements by porosimetry has showed that in the materials processed with NaCl the porous structure are typically open with uniform size distribution and present a certain regularity of forms when compared with the membranes processed with MgCO3. Concerning an herbicide interaction, which was evaluated by spectroscopic techniques inferring interaction between chemically active surfaces and ATZ. The herbicide removal through CHI and CHI+CMC deposited films resulted numerically lower than those values attained to glass surface absent of films. Nevertheless, the results point that to a better interaction between CHI and ATZ when both are dissolved at pH 3,0. By XPS scanning it was possible to follow the variation of the surface concentration with increasing of the elements O (1s), C (1s), N (1s) e Cl (2s) confirming surface interaction, despite not being feasible to define what functional groups take place in the interaction. Numerical analysis presents herbicide removal in the order of 10-12% concerning measure performed over a single membrane. Complementary tests of metal removal (Cd) confirmed the advantage of CHI surface in this type of interaction, making evident that composed filtration system could be ideal in the removal of distinct contaminants.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / The application of edible coatings on minimally processed products aims to maintain the quality and freshness of the fruit. This study aimed to clarify the influence of a coating based on chitosan incorporated with trans-cinnamaldehyde on the antioxidant metabolism and the structural integrity of melons minimally. Cantaloupensis ripe melons were processed into cubes and immersed in the coating solution and then stored at 4 ÂC, and were evaluated every five days for a total of 20 days. The evaluations were related to: activity of antioxidant enzymes, cell wall hydrolytic enzymes and browning, composition of the cell wall material, electrolyte leakage and hydrogen peroxide content, degree of peroxidation of membrane lipids and histology of pulp the fruit. The firmness of fresh-cut melons was statistically higher in fruits coated with chitosan, decreasing from 16.0 to 14.8 N. The degree of lipid peroxidation, electrolyte leakage and H2O2 levels were significantly reduced by coating with chitosan added transcinamaldeÃdo. The activity of pectin methylesterase enzyme and poligalacturoanse were significantly inhibited by treatment with chitosan, therefore, the coating was efficient in maintaining the firmness of the processed 20 days storage melons probably due to its action as a physical barrier to gas exchange and decreasing breathing subsequent events dependent on O2. The action of the coating as a barrier to the breathing gases can be evidenced in the results of oxidative metabolsimo when a lower content of hydrogen peroxide resulted in lower activity of enzymes that use it as a substrate, catalase and peroxidase. / A aplicaÃÃo de coberturas comestÃveis em produtos minimamente processados visa manter a qualidade e o frescor dos frutos. Este trabalho teve como objetivo esclarecer a influÃncia de um revestimento à base de quitosana incorporada com trans-cinamaldeÃdo sobre o metabolismo antioxidante e a integridade estrutural de melÃes minimamente. MelÃes Cantaloupensis maduros foram processados em cubos e imergidos na soluÃÃo de revestimento e depois, armazenados a 4 ÂC, sendo avaliados a cada cinco dias por um total de 20 dias. As avaliaÃÃes realizadas foram quanto Ã: atividade de enzimas antioxidantes, de enzimas hidrolÃticas de parede celular e de escurecimento, composiÃÃo do material de parede celular, extravasamento de eletrÃlitos e conteÃdo de perÃxido de hidrogÃnio, grau de peroxidaÃÃo de lipÃdios de membrana e histologia da polpa do fruto. A firmeza dos melÃes minimamente processados foi estatisticamente mais alta nos frutos revestidos com quitosana, decaindo de 16,0 para 14,8 N. O grau de peroxidaÃÃo lipÃdica, o extravasamento de eletrÃlitos e os nÃveis de H2O2 foram significativamente reduzidos pelo revestimento com quitosana adicionado de transcinamaldeÃdo. A atividade da enzima pectinametilesterase e da poligalacturoanse foram inibidas significativamente pelo tratamento com quitosana, Portanto, o revestimento foi eficiente em manter a firmeza dos melÃes processados pelos 20 dias de armazenamento devido provavelmente a sua aÃÃo como barreira fÃsica à trocas gasosas diminuÃndo a respiraÃÃo e os consequentes eventos dependentes de O2. A aÃÃo do revestimento como barreira aos gases da respiraÃÃo pode ser evidenciada nos resultados do metabolsimo oxidativo, quando um menor conteÃdo de perÃxido de hidrogÃnio resultou em menor atividade das enzimas que o utilizam como substrato, catalase e peroxidases.

Neste trabalho foi estudada a influência da adição de quitosana e sílica a monômeros dimetacrílicos, BisEMA e TEGDMA, por meio das técnicas de fotocalorimetria, termogravimetria e análise dinâmico mecânica. Os resultados dos experimentos de fotocalorimetria demonstraram que a quitosana pode aumentar a velocidade de polimerização e o máximo de conversão para alguns sistemas em determinadas concentrações da mesma, já a sílica tem pouco efeito nas reações de fotopolimerização das amostras. Para os experimentos de termogravimetria, a quitosana tem pouca influência na degradação das amostras não alterando significativamente as curvas TGA/DTG, por outro lado a sílica acelerou a degradação térmica das amostras. A avaliação das propriedades mecânicas demonstrou que a quitosana diminui a temperatura de transição vítrea e a resposta elástica dos sistemas não afetando os valores dos módulos de armazenamento e módulos de perda. A sílica apresentou a tendência de aumento de temperatura de transição vítrea e não alteração da resposta elástica das amostras. / In this work we studied the influence of the addition of chitosan and silica in dimethacrylic monomers, BisEMA and TEGDMA, by photocalorimetry, thermogravimetric analysis and dynamic mechanical analysis. The results of photocalorimetry experiments demonstrated that chitosan can increase the polymerization rate and the degree of conversion for some concentrations. Silica has little effect on photopolymerization reactions of samples. For thermogravimetric experiments, chitosan has little influence on the degradation of samples and does a slightly change the TGA / DTG curves, on the other hand silica accelerated thermal degradation of the samples. The evaluation of mechanical properties showed that chitosan reduces the glass transition temperature and elastic response of the samples but does not affect the values of the storage modulus and loss modulus. Silica showed an effect of increasing glass transition temperature and almost no change in the elastic response of the samples.