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Thesis (Ph. D.)--University of Wisconsin--Madison, 1959. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 144-157).

Thesis (Ph.D.) - University of Queensland, 2004. / Includes bibliographical references.

Thesis (M.S.)--West Virginia University, 2005. / Title from document title page. Document formatted into pages; contains vii, 73 p. : ill. (some col.). Includes abstract. Includes bibliographical references.

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Made available in DSpace on 2015-04-09T12:28:18Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-12-01Bitstream added on 2015-04-09T12:47:44Z : No. of bitstreams: 1 000815629.pdf: 3612183 bytes, checksum: a0dcded8d5c5e1ee59f6fc9150c62163 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / O amido resistente é um polissacarídeo que apresenta elevada estabilidade térmica e baixa solubilidade. A gelana é um polissacarídeo natural com importantes propriedades bioadesivas. Ambos os polímeros podem formar hidrogéis capazes de controlar a liberação de fármacos. A associação desses polissacarídeos naturais pode permitir o aperfeiçoamento das características físico-químicas desses materiais que muitas vezes são inexistentes nos polímeros isolados. A mistura de gelana/amido retrogradado, bem como a reticulação desses polímeros bioadesivos permite a modificação de importantes propriedades como resistência mecânica, intumescimento e mucoadesividade e desta forma, representam uma estratégia importante para aperfeiçoar o desempenho de sistemas de liberação sítio-específica de fármacos. No presente trabalho, hidrogéis de gelana/amido retrogradado foram utilizadas para obtenção de micropartículas pelo método de geleificação ionotrópica ou reticulação iônica (interações entre íons de cargas opostas) e dupla reticulação (introdução de ligações covalentes). A caracterização físico-química dos hidrogéis foi realizada através das análises de textura (dureza, adesividade e coesividade), propriedades reológicas, morfologia e difração de raiosx. Na análise do comportamento de textura foi verificado que as maiores concentrações de polímeros melhoraram as propriedades mecânicas dos hidrogéis e que a reticulação iônica contribuiu para o aumento da dureza e coesividade, enquanto a dupla reticulação aumentou a adesividade. A análise reológica demonstrou que as técnicas de reticulação contribuíram para obtenção de sistemas de caráter predominantemente elástico, sendo que a dupla reticulação originou estruturas com maior grau de elasticidade. As análises da estrutura interna dos hidrogéis evidenciaram a formação de estruturas mais densas e compactas na presença do ... / Resistant starch exhibits high thermal stability and low solubility. Gellan gum is a natural polysaccharide with important bioadhesive properties. Both polymers can build hydrogels able to control drug release rates. The blending of these natural polysaccharides can improve the physicochemical characteristics of these materials that are often absent in the isolated polymers. Gellan gum/retrograded starch association and crosslinking reaction should promote important modification of properties of these materials such as mechanical strength, swelling and mucoadhesiveness and thus, these strategies can improve the performance of site-specific drug delivery systems. In this study, hydrogels of gellan gum/retrograded starch were used to obtain microparticles by ionotropic gelation or ionic crosslinking (interactions between oppositely charged ions) and dual crosslinking (introducing covalent bonds) methods. The physicochemical characterization of the hydrogels was performed by analysis of profile (hardness, adhesiveness and cohesiveness), rheological properties, morphology and X-ray diffraction. Texture analysis of the behavior was found that higher concentrations of polymer improved the mechanical properties of hydrogels and that the ionic crosslinking improved the hardness and cohesiveness of hydrogels, while the dual crosslinking increased adhesiveness. The set of rheological properties showed that the crosslinking techniques contributed to the elastic character of the systems, and the dual crosslinking originated structures with the most elasticity degree. SEM analysis showed that denser and more packed structures were built in the presence of the ketoprofen. According to the XRD data, the microparticles showed semicrystalline structures and the DR increased the crystallinity. Physicochemical characterization of microparticles was performed by analyzes as moisture content, yield, encapsulation efficiency, size and shape. Ionotropic ...

Orientador: Beatriz Stringhetti Ferreira Cury / Banca: Ana Dóris de Castro / Banca: Ruth Meri Lucinda Silva / Resumo: O amido resistente é um polissacarídeo que apresenta elevada estabilidade térmica e baixa solubilidade. A gelana é um polissacarídeo natural com importantes propriedades bioadesivas. Ambos os polímeros podem formar hidrogéis capazes de controlar a liberação de fármacos. A associação desses polissacarídeos naturais pode permitir o aperfeiçoamento das características físico-químicas desses materiais que muitas vezes são inexistentes nos polímeros isolados. A mistura de gelana/amido retrogradado, bem como a reticulação desses polímeros bioadesivos permite a modificação de importantes propriedades como resistência mecânica, intumescimento e mucoadesividade e desta forma, representam uma estratégia importante para aperfeiçoar o desempenho de sistemas de liberação sítio-específica de fármacos. No presente trabalho, hidrogéis de gelana/amido retrogradado foram utilizadas para obtenção de micropartículas pelo método de geleificação ionotrópica ou reticulação iônica (interações entre íons de cargas opostas) e dupla reticulação (introdução de ligações covalentes). A caracterização físico-química dos hidrogéis foi realizada através das análises de textura (dureza, adesividade e coesividade), propriedades reológicas, morfologia e difração de raiosx. Na análise do comportamento de textura foi verificado que as maiores concentrações de polímeros melhoraram as propriedades mecânicas dos hidrogéis e que a reticulação iônica contribuiu para o aumento da dureza e coesividade, enquanto a dupla reticulação aumentou a adesividade. A análise reológica demonstrou que as técnicas de reticulação contribuíram para obtenção de sistemas de caráter predominantemente elástico, sendo que a dupla reticulação originou estruturas com maior grau de elasticidade. As análises da estrutura interna dos hidrogéis evidenciaram a formação de estruturas mais densas e compactas na presença do ... / Abstract: Resistant starch exhibits high thermal stability and low solubility. Gellan gum is a natural polysaccharide with important bioadhesive properties. Both polymers can build hydrogels able to control drug release rates. The blending of these natural polysaccharides can improve the physicochemical characteristics of these materials that are often absent in the isolated polymers. Gellan gum/retrograded starch association and crosslinking reaction should promote important modification of properties of these materials such as mechanical strength, swelling and mucoadhesiveness and thus, these strategies can improve the performance of site-specific drug delivery systems. In this study, hydrogels of gellan gum/retrograded starch were used to obtain microparticles by ionotropic gelation or ionic crosslinking (interactions between oppositely charged ions) and dual crosslinking (introducing covalent bonds) methods. The physicochemical characterization of the hydrogels was performed by analysis of profile (hardness, adhesiveness and cohesiveness), rheological properties, morphology and X-ray diffraction. Texture analysis of the behavior was found that higher concentrations of polymer improved the mechanical properties of hydrogels and that the ionic crosslinking improved the hardness and cohesiveness of hydrogels, while the dual crosslinking increased adhesiveness. The set of rheological properties showed that the crosslinking techniques contributed to the elastic character of the systems, and the dual crosslinking originated structures with the most elasticity degree. SEM analysis showed that denser and more packed structures were built in the presence of the ketoprofen. According to the XRD data, the microparticles showed semicrystalline structures and the DR increased the crystallinity. Physicochemical characterization of microparticles was performed by analyzes as moisture content, yield, encapsulation efficiency, size and shape. Ionotropic ... / Mestre

A study was made of two glucomannans, one isolated by alkaline borate extraction of Sitka spruce wood and the second from black spruce. These were methylated by the Hakomori procedure employing sodium hydride in dimethyl sulfoxide. Considerable experimentation was done to determine the best conditions for methylation and to demonstrate the utility and practicability of analysis by these methods. Some inferences regarding the structure of the glucomannans are drawn from the methylation data. / Science, Faculty of / Chemistry, Department of / Graduate

The structural elucidation of bacterial capsular polysaccharides is traditionally performed by using "wet chemical procedures" but instrumental methods such as nuclear magnetic resonance spectroscopy and novel mass spectrometric techniques are coming into prominence. In this thesis three different mass spectrometric techniques were investigated to establish their applicability for the sequencing of bacterial capsular polysaccharides. These techniques included fast atom bombardment (FAB), desorption chemical ionisation (DCI) and laser desorption ionisation Fourier transform ion cyclotron resonance spectroscopy (LDI-FTICR). The soft ionisation produced by these methods allows sequential loss of individual sugar residues without excess thermal decomposition of the ring. Thus sequencing of oligosaccharides could be achieved. The most common of all these three techniques is FAB which is already considered to be a well established form of soft ionisation, although the exact mechanism of ionisation is unknown. The utilisation of DCI has not been thoroughly exploited in carbohydrate research, due to the non-volatility of oligosaccharides and the possible thermal decomposition of the sample in the source. LDI-FTICR due to the general unavailability of the instrument has only been used for model studies of "shelf carbohydrates". In the course of this work it was found that FAB MS and DCIMS complement each other. The sequence of linear oligosaccharides of up to five sugar units can be deduced from either the native or permethylated sample. If the oligosaccharides investigated were generated by phage-borne enzyme, the total sequence of the native polysaccharide can be established. This was illustrated by the use of FABMS on Klebsiella K44 de-O-acetylated oligosaccharide and the reduced oligosaccharide. The sequence of the polysaccharide was shown to be: [Formula Omitted] The structural elucidation of bacterial capsular polysaccharides is traditionally performed by using "wet chemical procedures" but instrumental methods such as nuclear magnetic resonance spectroscopy and novel mass spectrometric techniques are coming into prominence. In this thesis three different mass spectrometric techniques were investigated to establish their applicability for the sequencing of bacterial capsular polysaccharides. These techniques included fast atom bombardment (FAB), desorption chemical ionisation (DCI) and laser desorption ionisation Fourier transform ion cyclotron resonance spectroscopy (LDI-FTICR). The soft ionisation produced by these methods allows sequential loss of individual sugar residues without excess thermal decomposition of the ring. Thus sequencing of oligosaccharides could be achieved. The most common of all these three techniques is FAB which is already considered to be a well established form of soft ionisation, although the exact mechanism of ionisation is unknown. The utilisation of DCI has not been thoroughly exploited in carbohydrate research, due to the non-volatility of oligosaccharides and the possible thermal decomposition of the sample in the source. LDI-FTICR due to the general unavailability of the instrument has only been used for model studies of "shelf carbohydrates". In the course of this work it was found that FAB MS and DCIMS complement each other. The sequence of linear oligosaccharides of up to five sugar units can be deduced from either the native or permethylated sample. If the oligosaccharides investigated were generated by phage-borne enzyme, the total sequence of the native polysaccharide can be established. This was illustrated by the use of FABMS on Klebsiella K44 de-O-acetylated oligosaccharide and the reduced oligosaccharide. The sequence of the polysaccharide was shown to be: [Formula Omitted] The location of acid-labile pyruvic acid acetal group, like base-labile acetate group, is also difficult to establish chemically. The fragment ions arising from permethylated oligosaccharides were mostly non-reducing end residues. This is due to the stability of oxonium ion formation. However, when an amino sugar was investigated, oxonium ions were not observed. Instead the cleavage took place between the glycosidic oxygen and the reducing end residue. This fragmentation route is in sharp contrast to previously reported spectral data. This may be due to the fact that amino sugars strengthen the glycosidic bond between the oxygen and the carbon-1. LDI-FTICR was investigated for its applicability to a "real" sample. The sequence of the linear Klebsiella K44 de-O-acetylated, phage degraded oligosaccharide was determined from the spectrum. Furthermore, a few positions of linkage were also deduced from ring cleavage fragments. Although linkage positions can be obtained from methylation analysis data, some sugar residues such as deoxyhexoses are more labile than others, thus positions of linkage obtained from LDI-FTICR can be used for confirmation. / Science, Faculty of / Chemistry, Department of / Graduate