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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
381

Hyaluronic acid hydrogel materials

Zawko, Scott Andrew 02 February 2011 (has links)
Hyaluronic acid (HA) is one of the primary chemical building blocks of the extracellular matrix and thus is an attractive material for biomedical applications. FDA approved HA-based materials are available as dermal fillers, joint viscosupplements, vitreous substitutes, and abdominal adhesion barriers. The engineering of new HA-based materials and applications is an active area of research. Here we develop several new types of HA-based hydrogels with unique and useful properties. To address the challenge of delivering hydrophobic drugs from hydrophilic hydrogel matrices we have grafted HA hydrogels with [Beta]-cyclodextrin to create hydrogels capable of binding poorly water soluble drugs. To create HA hydrogels with unique anisotropic swelling behavior we have developed a dual-crosslinking technique in which a super-swelling chemically crosslinked hydrogel is patterned with low-swelling photocrosslinked domains. When this dual-crosslinked hydrogel is swelled it contorts into a new shape because of differential swelling among photopatterned regions. To address the challenge of creating hydrogel scaffolds with biomimetic branched porosity we have invented a "crystal templating" technique. This technique grows dendritic crystals throughout a biopolymer solution, crosslinks the biopolymer around the crystals, and washes the crystals away to yield a hydrogel with a dendritic macroporous network. Lastly, we invented a method for patterning a substrate with a microarray of hydrogel compartments. A microarray of living cells is obtained when cells are seeded on the hydrogel patterned substrate. This method addresses the need for an inexpensive, simple method for obtaining living cell microarrays that does not require clean room labs and lithographic expertise. Each of these new materials were based on hyaluronic acid hydrogels but the methods are generalizable to hydrogels of other polymers too. In conclusion, the novel methods in this dissertation are a significant contribution to the engineering of HA-based materials. / text
382

Étude de la diffusion dans les hydrogels polymères par spectroscopie et imagerie RMN

Thérien-Aubin, Héloïse January 2007 (has links)
Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal
383

Optimalios gelio su kaštonų sėklų ekstraktu sudėties paieška, technologija ir vertinimas / The search of optimal composition of gel with chestnut seeds extract, its technology and evaluation

Zubrickaitė, Rasa 28 June 2011 (has links)
Lėtinis venų nepakankamumas (LVN) apibūdinamas kaip būklė, apimanti galūnių venas, sukeldama veninę hipertenziją, kuri savo ruožtu sąlygoja kitų patologijų – skausmo, tinimo, edemos, odos pokyčių ir opų, atsiradimą. Paprastojo kaštono sėklų ekstrakto saponinai yra viena iš keturių venas veikiančių grupių, kuri buvo įvertinta LVN gydyme, nes lengvina simptomus ir apsaugo venas nuo antrinių komplikacijų vystymosi bei ligos progreso. Šis tyrimas apima: 1) polifenolinių junginių skvarbos in vitro pro pusiau laidžią membraną iš dvidešimties skirtingų gelių su kaštonų sėklų ekstraktu, 1 proc. polimerinio pagrindo (Carbopol Ultrez 10, Carbopol Ultrez 20, Carbopol 980 ir Carbopol 940), propilenglikoliu, izopropilo alkoholiu, trietanolaminu analizę; 2) visų gelių klampos ir jos įtakos polifenolinių junginių skvarbai in vitro vertinimą. Rezultatai: Geliai be eterinio aliejaus buvo naudojami kaip standartiniai pavyzdžiai, vertinant skirtingų karbomerinių pagrindų įtaką skvarbai in vitro. Carbopol Ultrez 20 polimero geliai pasižymėjo mažiausia, o Carbopol 980 – didžiausia dinamine klampa. Didinant eterinio aliejaus koncentraciją, gelių klampa mažėja, o skirtumai tarp 0 proc. ir 1,5 proc. eterinio aliejaus buvo statistiškai patikimi (p<0,05). Polifenolinių junginių kiekis, prasiskverbęs iš gelių, tam tikrais laiko tarpais buvo nustatomas spektrofotometriniu metodu. Nustatyta, kad gelio su Carbopol Ultrez 20 polimeru (0 proc. eterinio aliejaus) srautas per pirmąjį pusvalandį (1,655 mg/cm... [toliau žr. visą tekstą] / Chronic venous insufficiency (CVI) describes a condition that affects the venous system of the lower extremities with venous hypertension causing various pathologies including pain, swelling, edema, skin changes, and ulcerations. Saponosides from horse chestnut extract are one of four groups of venoactive drugs, that have been evaluated in the treatment of CVI to reduce symptoms and help prevent the development of secondary complications and the progression of disease. This study assessed the following: (1) the permeability in vitro through cellulose membranes of polyphenolic compounds in twenty different horse chestnut seed extract (0,5% w/w) gel formulations (Ultrez 10, Ultrez 20, Carbopol 980 and Carbopol 940 gels (1%) with different peppermint oil concentrations (0; 0,1; 0,5; 1; 1,5%), propylenglycol, isopropyl alcohol, TEA, water); (2) the viscosity of all gels and its influence for in vitro permeation. Results: As the base-gels to investigate the effect of the in vitro penetration from different carbomers was formultions without peppermint oil. Gels with Ultrez 20 had the lowest and with Carbopol 980 the highest viscosity. By increasing concentration of peppermint oil, viscosity decreased and the difference between 0% and 1,5% in all carbomers was statistically significant (p<0,05). The quantity of the released polyphenols in time function was determined by spectrophotometric method. Ultrez 20 gel (0% peppermint oil) showed the highest flux during the first half hour (... [to full text]
384

Autologuous cell-ladened hydrogel sheet for prevention of post-surgical abdominal adhesion / Plaque d’hydrogel chargée de cellules autologues pour la prévention des adhérences postopératoires abdominales

Bresson, Lucie 10 November 2017 (has links)
Introduction :Les adhérences abdominales post-opératoires représentent les complications les plus fréquentes de la chirurgie abdominale et sont un enjeu de santé publique– douleurs abdominales chroniques, occlusions intestinales et infertilité féminine- et coût de prise en charge. Elles se développent après une mauvaise cicatrisation du péritoine –séreuse composée d’une monocouche de cellules mesothéliales. Leur prévention pourrait passer par des techniques de thérapie cellulaire ou tissulaire, visant à fabriquer un « néo »peritoine alliant des cellules du patient à une « scaffold » ou « échaffaudage ». Les cellules mesothéliales, différenciées, fonctionnelles sont indispensables, mais en nombre limité, potentiellement malades et leur prélèvement invasif. Elles pourraient être remplacées par des cellules souches adipocytaires qui ont un potentiel de différenciation. D’autre part, les polymères d’hydrogels comme biomatériau pour notre substitut sont attractifs par leur tolérance et leurs propriétés de ressemblance à la matrice extra cellulaire native.Les étapes majeures de notre projet de médecine régénérative sont de comparer la thérapie cellulaire à la thérapie tissulaire utilisant une « scaffold », de comparer les deux cellules sources potentielles, d’étudier les qualités de l’hydrogel BD-Purastat® et enfin de transplanter notre substitut cellularisé dans un modèle préétabli d'adhérences chez le rat.Matériel et méthode :La première étape validait le modèle animal d’adhérences post opératoires comparant plusieurs dommages péritonéaux. Puis les cellules étaient comparées en terme d'isolement, de culture, de caractérisation et de différenciation. Une étude de preuve de concept était réalisée afin de comparer les techniques de thérapie cellulaire aux techniques de thérapie tissulaire avec la greffe de péritoine lui-même. Ensuite, BD-Purastat® était testé grâce à une collaboration avec le laboratoire 3D Matrix. Enfin l’implantation in vivo d’une plaque d’hydrogel chargée de cellules autologues était évaluée sur le modèle de rat mis au point.Résultats :Deux modèles d'adhérences post-opératoires étaient validés chez le rat. Les deux techniques étaient efficaces et pertinentes pour l'application clinique. Les cellules mésothéliales présentaient un aspect typique polygonal avec des bords brillants et exprimaient les marqueurs intra-cellulaires de la vimentine et des cytokeratines. Elles présentaient une sénescence précoce comme attendu pour des cellules adultes bien différenciées. Les cellules souches adipocytaires étaient allongées et fines, stellaires, avec une bonne capacité d'expansion, se différenciaient en ostéocytes et en adipocyte et formaient des colonies comme attendu pour des cellules souches. L'étude de preuve de concept a permis de montrer que les cellules mésothéliales contribuaient à la repéritonéalisation seulement si elles étaient bien orientées et transplantées au sein d’un tissu. Ainsi, l’ajout d'une « scaffold » était crucial. Concernant le choix des biomatériaux, BD-Purastat® présentait de bonnes propriétés mécaniques, de biocompatibilité et implanté seul permettait déjà une réduction des adhérences postopératoires. L'implantation du substitut cellularisé n'avait pas permis d’améliorer les résultats obtenus avec le gel seul.Conclusion et perspectives :Notre étude permettait de montrer que des cellules mésothéliales au sein d'une « scaffold » étaient la clé du succès de la repéritonéalisation pour la prévention des adhérences postopératoires en charge abdominale. La différenciation des cellules souches adipocytaires vers le phénotype mésothélial avait encore besoin d'être prouvée. BD-Purastat® diminuait l’étendue des adhérence postopératoires. Le comportement des cellules dans cette « scaffold » nécessitait d'être étudié pour pouvoir obtenir l'efficacité clinique du substitut péritonéal de cellules autologues et d'hydrogel. / Introduction: Postoperative abdominal adhesions are a major complication leading to medical and economical problems. Replace injured peritoneum, which is composed of a monolayer of mesothelial cells (MC), using cell-therapy or cell-laden scaffold are two promising strategies to prevent adhesions. MC as functional and differentiated cells are crucial. However, adipose stem cells (ASCs) could replace MCs thanks to their potential of differentiation. Furthermore, hydrogel polymers are attractive scaffolds mimicking the properties of the native ECM. So, milestones of our project of regenerative medicine are comparison of cell-laden scaffolds and cell-therapy, choice of cell source and biomaterial, and finally transplantation of the cell-laden hydrogel scaffold, in a pre-established rat model of adhesion.Materiel and Method: Firstly, models of adhesion were compared usingdifferent peritoneal injuries. Then, MCs and ASCs were compared for isolation, culture, characterization, and differentiation. Nextly, cell-therapy using MC intra peritoneal injection (IP) or cell-sheet technology was compared with tissue-therapy using peritoneal grafts through a proof of concept study. BD-Purastat® hydrogel was tested in collaboration with 3D Matrix firm. Cell-laden hydrogel gels were implanted and assessed on adhesion prevention.Results: Two animal models of adhesion were validated and both techniques were effective and clinically relevant. MCs and ASCs were isolated from respectively tunica vaginalis and subcutaneous inguinal fat pad. MCs, with typical cobble-stone morphology and bright edges, were positively stained for vimentin and cytokeratin. Senescence arrived after only three passages for these adult well-differentiated cells. Spindle-shaped ASCs had a good capacity of expansion, were able to differentiate in osteocytes and adipocytes, and to form colonies as expected for stem cells. Autologuous peritoneal grafts prevented postoperative abdominal adhesions in the rat model. As the mechanism of this prevention, the MC survived and contributed to reperitonealization, only when they were transplanted as a part of the autologous peritoneal grafts and were located on the surface exposed to the abdomen. Cell sheet technology and MCs IP injection failed in the adhesion prevention. BD-Purastat® presented good mechanical properties and biocompatibility. Alone, it reduced significantly adhesion extent. But, cell encapsulation into BD-Purastat® did not improve this prevention.Conclusion and perspectives: Our study supported that MCs and scaffold are both needed to succeed in peritoneum’s engineering to prevent adhesion. ASCs differentiation into MCs phenotype has still to be shown. BD- Purastat® decreases adhesion extent and behavior of the cell into this scaffold needs to be studied to improve the effectiveness of the cell-laden hydrogel application.
385

Avaliação da potencialidade do uso de hidrogéis poliméricos na terapeutica de leishmaniose cutânea / Evaluation of polymeric hydrogels drug delivery systems in cutaneous leishmaniasis therapeutics

Silva, Vanessa Bezerra da 10 November 2015 (has links)
Submitted by Daniele Amaral (daniee_ni@hotmail.com) on 2016-09-21T20:58:24Z No. of bitstreams: 1 DissVBS.pdf: 1740289 bytes, checksum: f0f9dfa6182cf0c0dfe8b39ff3cda89c (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-04T18:07:59Z (GMT) No. of bitstreams: 1 DissVBS.pdf: 1740289 bytes, checksum: f0f9dfa6182cf0c0dfe8b39ff3cda89c (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-04T18:08:06Z (GMT) No. of bitstreams: 1 DissVBS.pdf: 1740289 bytes, checksum: f0f9dfa6182cf0c0dfe8b39ff3cda89c (MD5) / Made available in DSpace on 2016-10-04T18:08:13Z (GMT). No. of bitstreams: 1 DissVBS.pdf: 1740289 bytes, checksum: f0f9dfa6182cf0c0dfe8b39ff3cda89c (MD5) Previous issue date: 2015-11-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Poly(vinyl alcohol) - PVA is a high hydrophilic semicrystalline polymer which has excellent properties such as good chemical resistance and high biodegradability and biocompatibility. Due to its semi-crystalline nature, crystalline domains, under controlled conditions, may act as physical crosslinking points, while maintaining the integrity of the structure under swelling. This feature makes PVA hydrogels promising for the development of drug, or other bioactive substances, delivery systems. Another interesting feature of this kind of hydrogels is the ability to form high stable network from crystalline domains formed through freezing and thawing cycles. This method shows the formation of crystallites which act as physical crosslinks while maintaining the insolubility of the material in water. Recently many studies show the use of nanostructures to improve mechanics properties and diffusional behavior of small molecules. Paromomycin is an aminoglycoside antibiotic widely used for cutaneous leishmaniasis therapeutics in Brazil. In the last years some studies have revealed that the patience adhesion to the treatments of cutaneous leishmaniasis with ointments form is low. Therefore hydrogels are an interesting alternative to the ointment forms. As the main objective of this work was the preparation and characterization of poly(vinyl alcohol) hydrogels containing sepiolite nanoparticles for the preliminary feasibility of using as controlled release system for paromomycin, hydrogels were prepared by cryogelation process. This ensures the formation of the hydrogel, as long as the crystalline domains formed during the PVA cycles act as crosslinking points, allowing the membranes water transport measurements of the drug in the presence of sepiolite. In this investigation membranes were characterized by differential calorimetry, thermogravimetry and X-ray diffraction. Furthermore polymer retention, swelling in simulated body fluid, hemocompatibility and drug delivery were studied to establish structure-properties correlations. The results show that cryogelation cycles significantly alter the swelling of the membranes; interactions polymer-nanoparticle increases the rigidity of the amorphous phase. Comparing to pure PVA hydrogels, in nanocomposites hydrogels the hemolysis decreased. Increasing the percentage of nanoparticles the membrane crystallinity decreases. The samples degradation profile, the thermal stability and drug delivery profile are not modified by the amount of nanoparticles incorporated. / Poli(álcool vinílico) - PVA é um polímero semicristalino altamente hidrofílico que possui excelentes propriedades, como boa resistência química e elevada biodegradabilidade e biocompatibilidade. Devido à sua natureza semicristalina, os domínios cristalinos, sob condições controladas de crescimento, podem atuar como pontos de reticulação físicos, mantendo a integridade da estrutura sob inchamento. Esta característica torna hidrogéis de PVA bastante promissores em relação ao desenvolvimento de sistemas de carreamento de fármacos e outras substâncias bioativas. Soluções aquosas de PVA podem formar hidrogéis com boas propriedades mecânicas através de ciclos de resfriamento e aquecimento. Este método resulta na formação de cristalitos que atuam como reticulações físicas, mantendo a insolubilidade do material em água. Recentemente muitos estudos mostram o uso de nanoestruturas para melhorar as propriedades mecânicas e o comportamento difusional de pequenas moléculas. Paromomicina é um antibiótico aminoglicosídeo muito utilizado para o tratamento de Leishmaniose cutânea (LC) no Brasil. Nos últimos anos, estudos mostraram que a adesão de pacientes ao tratamento de LC com pomadas é baixa. Portanto hidrogéis são uma interessante alternativa para este tratamento. Como o principal objetivo deste trabalho foi o preparo e a caracterização de hidrogéis poliméricos nanocompósitos de PVA contendo nanopartículas de SEP para a viabilidade preliminar do uso como sistema de liberação controlada para paromomicina, os hidrogéis foram preparados através de um processo de criogelificação. Este procedimento garante a formação do hidrogel, pois os domínios cristalinos do PVA formados durante os ciclos atuam como pontos de reticulação da membrana, permitindo a avaliação das medidas de transporte de água e do fármaco das membranas na presença de SEP. Neste estudo as membranas foram caracterizadas através de calorimetria diferencial, termogravimetria e difração de raios-X. Ainda foram feitos estudos de retenção polimérica, inchamento em plasma simulado, hemocompatibilidade, carreamento e liberação de fármaco. Os resultados mostram que os ciclos de criogelificação alteram significativamente o inchamento das membranas; as interações polímero-nanopartícula aumentam a rigidez da fase amorfa. O grau de hemólise diminui nos hidrogéis nanocompósitos quando comparados com os hidrogéis puros. O aumento da porcentagem de nanopartícula diminui a cristalinidade da membrana. O perfil de degradação, a estabilidade térmica das amostras e a liberação do fármaco não são modificados pela quantidade de nanopartícula incorporada.
386

Obtenção de membranas de hidrógeis para tratamento alternativo da Leishmaniose tegumentar / Obtaining membranes for alternative treatment hydrogeis of cutaneous Leishmaniasis

OLIVEIRA, MARIA J.A. de 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:41:20Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:03Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP:09/50926-1
387

Hidrógeis poliméricos com nanopartículas de prata para aplicações médicas / Polymeric hydrogels with silver nanoparticles for medical applications

ALCANTARA, MARA T.S. 03 March 2015 (has links)
Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-03-03T10:48:26Z No. of bitstreams: 0 / Made available in DSpace on 2015-03-03T10:48:26Z (GMT). No. of bitstreams: 0 / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
388

Desenvolvimento de matrizes poliméricas biodegradáveis à base de quitosana e possíveis blendas como sistemas de liberação controlada de fármacos / Development of biodegradable polymeric matrices based on chitosan and possible blend as controlled release systems for drugs.

BATISTA, JORGE G. dos S. 08 April 2016 (has links)
Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-04-08T12:18:22Z No. of bitstreams: 0 / Made available in DSpace on 2016-04-08T12:18:23Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
389

Novas metodologias de ressonância magnética nuclear para o estudo da dinâmica lenta em materiais orgânicos no estado sólido: aplicações em polímeros e proteínas / New nuclear magnetic resonance methods for studying slow dynamics in organic solids: applications to polymers and proteins

Eduardo Ribeiro de Azevêdo 30 November 2001 (has links)
RMN de Exchange em estado sólido é uma importante técnica utilizada na caracterização de processos dinâmicos em ciência dos materiais. Entretanto, a utilização desta técnica no estudo de materiais complexos tem sido limitada. Neste trabalho, serão propostas novas metodologias de RMN de Exchange em estado sólido, que permitem analisar eficientemente movimentos moleculares na escala de tempo de milisegundos. A técnica denominada Pure Exchange Solid-State NMR (PUREX), provê a supressão dos segmentos rígidos dos espectros de exchange, tomando possível observar os segmentos com mobilidade na escala de ms seletivamente. A técnica Centerband-Only Detection of Exchange (CODEX), permite a observação e caracterização de reorientações moleculares lentas com a maior sensibilidade e resolução disponíveis em RMN de estado sólido, através de espectros obtidos sob rotação da amostra em tomo do ângulo mágico (MAS). Utilizando essas técnicas as funções e tempos de correlação e a geometria de movimentos moleculares lentos podem ser determinadas diretamente, sem a necessidade da utilização de modelos que relacionem as grandezas medidas e as características do movimento molecular. A utilização dos métodos apresentados, permite a identificação e caracterização da dinâmica lenta em materiais complexos, tais como polímeros amorfos, semicristalinos e proteínas. Com objetivo inicial de demonstrar as técnicas, elas foram aplicadas para confirmar detalhes da dinâmica molecular em amostras modelo. Através destas técnicas foi possível confirmar a escala de tempo e os ângulos de reorientação envolvidos na dinâmica molecular de cristais orgânicos, Dimetil Sulfona (DMS), e também para revisitar processos de relaxação local em alguns polímeros, polimetacritato de metila (PMMA) e isotatico polipropileno (iPP). As metodologias foram também aplicadas no estudo da transição vítrea em polímeros semicristalinos, isotatico poli(1-buteno) (iPB 1) e sindiotático polipropileno, os quais não tinham sido ainda estudados por técnicas de RMN de Exchange, já que neste caso a maioria dos segmentos moleculares (porção cristalina do polímero) é rígida durante a transição vítrea. Utilizando os métodos CODEX e PUREX os movimentos lentos que ocorrem na região amorfa destes polímeros em temperaturas próximas as suas temperaturas de transição vítrea foram caracterizados. Um estudo dos movimentos lentos que ocorrem em tomo das temperaturas de transição vítrea nas cadeias poliméricas de dois tipos de nanocompostos híbridos siloxano/(polietileno glicol) (ormolitas) também é apresentado. Heterogeneidades nos movimentos das cadeias poliméricas associados com a interação PEG/siloxano foram diretamente observadas através de experimentos PUREX 1D de Exchange 2D. Evidenciais da presença de movimentos de grande e pequena amplitude foram observados para os dois tipos de híbridos. Os resultados revelam que a restrição do movimento das cadeias poliméricas pelas estruturas de siloxano depende tanto do comprimento da cadeia como da natureza das interações entre as fases orgânica e inorgânica do nanocomposto. Finalmente os resultados referentes a caracterização da dinâmica molecular rápida e lenta e sua relação com as propriedades estruturais de um hidrogel protéico são apresentados. Utilizando uma versão modificada da técnica CODEX, juntamente com experimentos de polarização direta, polarização cruzada e RMN de correlação 2D, foi possível não somente confirmar a estrutura e o modelo de formação propostos para o gel, mas também determinar a geometria e a escala de tempo dos movimentos lentos que ocorrem na região de hélice do hidrogel protéico em grandes detalhes. A demonstração teórica e experimental das técnicas e suas aplicações no estudo dessas importantes classes de materiais serão apresentadas. / Solid-State Exchange NMR is an important method to characterize details of dynamic process in materials science. However, the application of these techniques to study complex materials has been limited. In this work new solid-state Exchange NMR techniques, which allows efficient analysis of molecular motions in the millisecond time scale, are presented. The Pure Exchange Solid-State NMR (PUREX) method provides the suppression of the rigid segments in standard exchange spectrum, making possible to observe the slow moving moieties selectively. The Centerband-Only Detection of Exchange (CODEX) technique allows observing and characterizing slow segmental reorientations with the highest available NMR sensitivity and site resolution, in a magic angle spinning (MAS) NMR spectrum. Correlation functions, correlation times and information about the motional amplitude and geometry can be direct1y obtained using the techniques, without any model assumption. These methods allowed identifying and characterizing slow dynamics in complex materials such as, semicrystalline and amorphous polymers and proteins. To demonstrated the proposed techniques they have been applied to confirm some kwon aspect of the slow dynamics of model samples. Using the methods it was possible o confirm the time scale and the reorientation angles involved in the molecular dynamics of organic crystals, Dimethyl Sulfone (DMS), and also to revisit some relaxation process in standard polymers, such as the beta relaxation of poly(methyl metacrylate) (PMMA) and the alfa relaxation in isotactic polypropylene (iPP). The time scale and the geometry of the molecular motions responsible by these relaxation process obtained using the PUREX and CODEX techniques are in excellent agreement with the data taken from the literature, confirming the reliability of the proposed methods. Moreover, the techniques were also applied to study the slow molecular motions involved in the glass transition of semicrystalline polymers, such as isotactic poly (l-butene) form I (iPB1) and syndiotactic Polypropylene (sPP). The glass transition of these polymers had not been studied using Exchange NMR methods because most of the molecular segments (crystalline portion of the polymers) are rigid during the glass transition. Using the PUREX and CODEX methods the slow molecular reorientations within the amorphous region of the polymers were characterized for temperatures near its glass transition. A study of the slow motions occurring around the glass transition temperature in the polymer chains of two types of siloxane/(polyethylene glycol) nanocomposites (ormolites) is also presented. Motional heterogeneities associated with PEG/ siloxane interactions were directly observed in the 13C 1D PUREX and 2D exchange data. Evidences of both small and large angle amplitude motions were direct1y observed for both types of hybrids. The results revealed that the hindrance to the slow molecular motions of the polymer chains due to the siloxane structures depends on the chain length and the nature of the interaction between the organic and inorganic phases. Finally the results concerning the characterization of the fast and slow dynamics and its relationship with the structural properties of a protein hidrogel are presented. Using a modified version of the CODEX technique, together with standard direct polarization, cross polarization and 2D NMR correlation experiments, it was possible not only to confirm the proposed structure and the gel formation model, but also to characterize the geometry and the time scale of the slow motions in the helical domains of the protein hidrogel in great detail. The theoretical and experimental demonstration of all proposed methods and also its applications in these important classes of material will be present.
390

Estudo de nanocompósitos poli(metacrilato de hidroxietila) / laponita para revestimento de sementes / Study of nanocomposites poly (hydroxyethyl methacrylate) / laponite for seed coating

Lima, Kelly Santana 28 February 2018 (has links)
Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / The search for more productive seeds and with better transport and storage conditions has developed the interest of companies and researchers. In this section, nanotechnology, in particular, polymer / clay nanocomposites has proved to be an excellent alternative. By means of these nanomaterials it is possible to transport assets that allow the plant to better growth, productivity and germination rates, through the transport of fertilizers, agrochemicals or even essential micronutrients. The aim of this work was to synthesize and study nanocomposites polymer / clay; poly (hydroxyethyl methacrylate), pure laponite (pHEMA / Lap) and enriched with manganese micronutrients (pHEMA / LapMn). These materials aim to provide water and concomitantly provide nutrients to the seeds. The best formulation for the samples, amounts of polymer and clay was studied, and from this the micronutrient was incorporated into the formulation. The materials were characterized by absorption spectroscopy in the infrared region (FTIR), X-ray diffractometry (XRD) and thermogravimetry (TG). In addition, the water uptake capacity of the samples was evaluated. TG results showed an increase in thermal stability due to the interaction of the polymer chain with the clay. The XRD study showed that pure Lap and Lap Mn presented similar basal spacing to that found in the literature and that the nanocomposite had an exfoliated structure of the materials. The observation of the degree of swelling of the samples showed that the nanocomposites showed a capacity of water absorption 10% higher than the pure hydrogel. The seed coating affected the germination rate of the seeds, showing an optimization of this process. / A busca por sementes mais produtivas e com melhores condições de transporte e armazenamento tem desenvolvido o interesse de empresas e pesquisadores. Nesta vertente, a nanotecnologia, em especial, os nanocompósitos polímero/argila tem se mostrado uma excelente alternativa. Por meio destes nanomateriais é possível transportar ativos que possibilitem a planta melhor crescimento, produtividade e taxas de germinação, por meio do transporte de fertilizantes, agroquímicos ou até micronutrientes essenciais. Neste trabalho buscou-se sintetizar e estudar nanocompósitos polímero/argila; poli(metacrilato de hidroxietila) (pHEMA), laponita pura (pHEMA/Lap) e enriquecida com micronutrientes manganês (pHEMA/LapMn). Estes materiais tem por objetivo fornecer água e concomitantemente fornecer nutrientes para as sementes. Estudou-se qual a melhor formulação para as amostras, quantidades de polímero e de argila e a partir desta incorporou-se o micronutriente a formulação. Os materiais foram caracterizados por espectroscopia de absorção na região do infravermelho (FTIR), difratometria de raios X (DRX) e termogravimetria (TG). Além disso, a capacidade de absorção de água das amostras foi avaliada. Houve aumento da estabilidade térmica decorrente da interação da cadeia polimérica com a argila. O estudo por DRX mostrou que a Lap pura e a Lap Mn apresentaram espaçamento basal similar ao encontrado na literatura e que o nanocompósito apresentou estrutura esfoliada dos materiais. A observação do grau de intumescimento das amostras mostrou que os nanocompósitos apresentaram uma capacidade de absorção de água 10% superior à do hidrogel puro. O revestimento das sementes prejudicou a taxa de germinação das mesmas mostrando-se necessário uma otimização deste processo. / São Cristóvão, SE

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