published_or_final_version / abstract / Anatomy / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Physiology / Master / Master of Philosophy

published_or_final_version / Physiology / Master / Master of Philosophy

Ma Ka Ming. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references (leaves 99-118). / Abstracts in English and Chinese. / Chapter Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- What are prebiotics? --- p.1 / Chapter 1.2 --- Current prebiotics and their development --- p.2-3 / Chapter 1.3 --- The intestinal microflora --- p.3-4 / Chapter 1.3.1 --- Bacteroides --- p.5 / Chapter 1.3.2 --- Bifidobacteria --- p.5 / Chapter 1.3.3 --- Clostridia --- p.5-6 / Chapter 1.3.4 --- Lactobacilli --- p.6 / Chapter 1.4 --- Bacterial colonic fermentation --- p.7-8 / Chapter 1.4.1 --- Carbohydrates metabolism in colonic bacteria --- p.8-10 / Chapter 1.4.1.1 --- Carbohydrates metabolism in Bacteroides --- p.11 / Chapter 1.4.1.2 --- Carbohydrates metabolism in Bifidobacteria --- p.11 / Chapter 1.4.1.3 --- Carbohydrates metabolism in Clostridia --- p.11 / Chapter 1.4.1.4 --- Carbohydrates metabolism in Lactobacilli --- p.12 / Chapter 1.5 --- Health benefits of prebiotics --- p.12-13 / Chapter 1.6 --- Metabolites of fermentation: Short-chain fatty acids (SCFAs) --- p.14-15 / Chapter 1.7 --- Applications of prebiotics as functional food ingredients --- p.16 / Chapter 1.8 --- Methodology for evaluating prebiotics --- p.17 / Chapter 1.8.1 --- In vivo fermentation study --- p.17 / Chapter 1.8.2 --- Human clinical study --- p.17-18 / Chapter 1.8.3 --- In vitro fermentation study --- p.18-19 / Chapter 1.9 --- Methods of bacterial enumeration --- p.19-20 / Chapter 1.9.1 --- Fluorescent in situ hybridisation --- p.20-22 / Chapter 1.9.2 --- Bacterial enumeration by automatic image analysis --- p.22-23 / Chapter 1.10 --- Sugar alcohols --- p.23 / Chapter 1.10.1 --- Sugar alcohols and their functions --- p.23-25 / Chapter 1.10.2 --- Digestion and absorption of sugar alcohols --- p.25-26 / Chapter 1.10.3 --- Metabolism of sugar alcohols in humans --- p.26 / Chapter 1.10.4 --- Adverse effect of sugar alcohols --- p.26-27 / Chapter 1.11 --- Fermentation of sugar alcohols in colonic bacteria --- p.27 / Chapter 1.12 --- Project objectives --- p.28 / Chapter Chapter 2. --- Materials and Methods --- p.29 / Chapter 2.1 --- Materials --- p.29 / Chapter 2.2 --- Static batch culture fermentation --- p.29 / Chapter 2.2.1 --- Substrate preparation --- p.29-30 / Chapter 2.2.2 --- Human fecal inoculum preparation --- p.30-31 / Chapter 2.3 --- Dry matter and organic matter disappearance in batch fermentation --- p.31 / Chapter 2.4 --- Determination of flow rate in the continuous fermentation system. --- p.32-33 / Chapter 2.5 --- Three-stage continuous fermentation culture system --- p.34 / Chapter 2.5.1 --- Initial set-up --- p.34-35 / Chapter 2.5.2 --- Continuous fermentation --- p.35-36 / Chapter 2.6 --- Validation of fluorescent in situ hybridisation (FISH) method --- p.36 / Chapter 2.6.1 --- Oligonucleotide probes for FISH --- p.36-37 / Chapter 2.6.2 --- Cultivation of pure human intestinal bacterial culture --- p.37-38 / Chapter 2.6.3 --- Validation of oligonucleotide probes for FISH --- p.38-40 / Chapter 2.7 --- Bacterial enumeration of fermentation broth by FISH --- p.41 / Chapter 2.7.1 --- Automated image analysis --- p.41-42 / Chapter 2.7.2 --- Quantification of bacteria --- p.43 / Chapter 2.8 --- Gas chromatographic determination of short-chain fatty acids (SCFAs) --- p.44-46 / Chapter 2.9 --- Statistical analysis --- p.46 / Chapter Chapter 3: --- Results and Discussion --- p.47 / Chapter 3.1 --- Dry matter and organic matter disappearance in batch fermentations --- p.47-48 / Chapter 3.2 --- Validation of genus-specific oligonucleotide probes for FISH by pure bacterial culture --- p.48-50 / Chapter 3.3 --- FISH and multi-color FISH of human fecal bacteria --- p.50-53 / Chapter 3.4 --- Enumeration of fecal bacteria with the CellC software --- p.53-54 / Chapter 3.5 --- Colonic bacterial profile in batch culture in vitro fermentation --- p.55 / Chapter 3.5.1 --- Total colonic bacteria --- p.55-56 / Chapter 3.5.2 --- Bacteroides --- p.57-59 / Chapter 3.5.3 --- Bifidobacteria --- p.60-62 / Chapter 3.5.4 --- Clostridia --- p.63-64 / Chapter 3.5.5 --- Lactobacilli --- p.65-66 / Chapter 3.6 --- Short-chain fatty acids (SCFAs) in batch in vitro fermentation --- p.67 / Chapter 3.6.1 --- Total SCFAconcentration --- p.67-68 / Chapter 3.6.2 --- Acetate --- p.68 / Chapter 3.6.3 --- Propionate --- p.69 / Chapter 3.6.4 --- Butyrate --- p.69-70 / Chapter 3.7 --- Determination of flow rate in three-stage continuous fermentation system --- p.71-73 / Chapter 3.8 --- Colonic bacterial profile in three-stage continuous fermentation system --- p.74 / Chapter 3.8.1 --- Total colonic bacteria --- p.74-75 / Chapter 3.8.2 --- Bacteroides --- p.76 / Chapter 3.8.3 --- Bifidobacteria --- p.77-78 / Chapter 3.8.4 --- Clostridia --- p.79-80 / Chapter 3.8.5 --- Lactobacilli --- p.81 / Chapter 3.9 --- SCFAs in three-stage continuous fermentation system --- p.82 / Chapter 3.9.1 --- Total SCFA concentration --- p.82-87 / Chapter 3.9.2 --- SCFA molar ratio --- p.88-89 / Chapter 3.9.3 --- Acetate --- p.90-91 / Chapter 3.9.4 --- Propionate --- p.92-93 / Chapter 3.9.5 --- Butyrate --- p.94-95 / Chapter Chapter. 4 --- Conclusions and Future Works --- p.96-98 / List of References --- p.99-117 / Related Publications --- p.118

Nos curtumes, as operações de ribeira geram quantidades elevadas de resíduos sólidos. Durante o tratamento das peles na ribeira, especificamente na etapa de pré-descarne é removido material adiposo que constitui a camada subcutânea da pele, esse resíduo é composto de gorduras e proteínas. Através dos processos de digestão/extração e winterização, é possível produzir oleína dos resíduos sólidos do pré-descarne. A oleína é um composto de triacilgliceróis formado por ácidos graxos insaturados com potencial para ser convertido a polióis e utilizado na manufatura de poliuretanos (PU), gerando uma alternativa para substituir os derivados de petróleo comumente utilizados nesse processo. Este trabalho tem como objetivo produzir polióis de oleína por glicerólise alcalina e, a partir dos polióis produzidos, preparar espumas flexíveis de poliuretano (EFPUs) Empregou-se um planejamento experimental fatorial completo 24 com 4 repetições no ponto central para otimizar a produção de polióis de oleína. As espumas EFPUs foram preparadas com razões molares NCO/OH de 1,1 e 1,2, usando-se poliisocianatos alifáticos lineares e cíclicos, água como agente de expansão e surfactante de silicone. O poliol à base de oleína (PO2 - produzido na melhor condição de glicerólise alcalina estudada) apresentou índice de hidroxila elevado (acima de 300 mg KOH.g-1) e funcionalidade próxima a 3. A estabilidade térmica da espuma de poliuretano produzida foi maior que a estabilidade térmica do poliol de oleína. A densidade, o alongamento na ruptura e a resiliência das espumas de PU foram dependentes da razão molar de NCO/OH. As microscopias de MEV das espumas de PU mostraram estruturas das células como polígono totalmente fechados, outros com aberturas e muitas paredes enrugadas. Os materiais extrativos das espumas de PU foram inferiores a 3%, indicando a formação de estrutura reticulada. / In the tanneries, the beamhouse generate high amounts of solid waste. During the treatment of skins in beamhouse, specifically in pre-fleshing stage is removed adipose material that constitutes the subcutaneous layer of the skin, this residue is composed of fats and proteins. Through the processes of digestion/extraction and winterization, it is possible to produce olein from the solid waste from the pre-fleshing. Olein is a triacylglycerol compound formed by unsaturated fatty acids that can be converted to polyols and used to manufacture polyurethane, an alternative to replace the petroleum derivatives, commonly employed in the process. This work aims to obtain polyol from olein through alkaline glycerolysis and, from the polyols produced, to produce flexible polyurethane foams (FPUFs). A 24 full factorial design with 4 repetitions at the central point was used to optimize the production of olein polyols. EFPUs were prepared with NCO/OH molar ratios of 1.1 and 1.2, linear and cyclic aliphatic polyisocyanates, water as blowing agent and silicone surfactant. The olein-based polyol (PO2 - produced in the best alkaline glycerolysis condition studied) showed high hydroxyl number (above 300 mg KOH.g-1) and functionality near to 3. Thermal stability of produced polyurethane foams was greater than thermal stability of olein polyol. Density, elongation at break and resilience of PU foams have been dependents of NCO/OH ratio. SEM microscopy of FPUFs show cells structures with polygon totally closed, others with openings and many wrinkled walls. Extractable materials of polyurethane foams was lower than 3% indicating that a crosslinked structure is formed.

Under the conditions of transfer hydrogenation employing ortho-cyclometallated iridium C,O-benzoate catalysts, two protocols of iterative chain elongation of 1,3-diols to furnish 1,3-polyols were developed. First, one-directional chain elongation employing mono-protected 1,3-diols as starting materials was achieved. In all cases, high levels of catalyst-directed enantioselectivity and diastereoselectivity were observed. Then, double asymmetric allylation of 1,n-glycols to deliver C₂-symmetric adducts with exceptional level of enantioselectivity was devised. Iterative two-directional elongation of 1,3-diols to furnish 1,3-polyols with high level of catalyst-directed diastereoselectivity was then achieved. Implementation of this methodology and other hydrogenative C-C bond formations proved to be effective means for the preparation of a known bryostatin A-ring fragment and the total synthesis of bryostatin 7. / text

The thesis describes the synthesis and application of various alkynones derived from the bis-Weinreb amide of tartaric acid in the total synthesis of macrolactone natural products. The thesis is divided into three sections. First section of the thesis describes the optimization and generalization of the procedure for the addition of alkynyl Grignard / lithium reagents to the bis-Weinreb amide derived from tartaric acid to yield the mono alkynyl ketones was developed. Application of the formed γ-oxo amides was demonstrated in the synthesis of polyols with varied substitutions particularly the synthesis of 1,2,4-triols was accomplished using Ley’s dithianylation as the key step. Scheme 1: Synthesis of polyols from the bis-weinreb amide of tartaric acid. Application of the strategy to the total synthesis of decanolactone natural products achaetolide and (Z)-isomer of (6S,7R,9R)-6,7-dihydroxy-9-propylnon-4-eno-9-lactone was featured. Section B of the thesis deals with the enantiospecific total synthesis of 14-membered macrolactone Sch 725674. Key reactions in the synthesis include the synthesis of the 1,2,4-triol unit from tartaric acid, olefin cross metathesis and ring closing metathesis. Scheme 4: Enantiospecific total synthesis of Sch 725674. Section C of the thesis describes the enantiospecific synthesis of the C9-C22 fragment of the 28-membered polyene polyol macrolide pentamycin. Although isolated in 1958, total synthesis of this antifungal compound was not reported. In application of the methodology developed, the alkynone prepared from the bis-Weinreb amide was elaborated to the required fragment.

L'alumine, utilisée comme support de catalyseurs pour la réaction de Fischer-Tropsch ou pour la conversion de la biomasse, se transforme partiellement en présence d'eau en phases (oxy)hydroxydes à l'origine de fines qui posent problème dans la mise en ¿uvre de procédés en réacteurs de type slurry. Afin de concevoir des catalyseurs plus stables et plus résistants, ce travail de thèse visait à identifier le mécanisme d'hydratation et de dégradation des alumines de transition en phase aqueuse, et à étudier la façon dont des additifs organiques (alcools, polyols) ou inorganiques (Mg, Zr, Ni et Si) permettent de limiter cette dégradation. La conduite d'une étude systématique sur l'hydratation des alumines à 70°C à pression atmosphérique, ou à 150°C en conditions hydrothermales, a permis de définir un mécanisme général en deux étapes: une dissolution de la surface de l'alumine, suivie d'une précipitation, respectivement, d'hydroxydes d'aluminium Al(OH)3 ou de boehmite AlOOH sur les grains d'alumine. Par ailleurs, la dégradation chimique tend à favoriser la dégradation sous contraintes mécaniques. La présence de polyols en phase aqueuse, principalement des molécules à 5 ou 6 atomes de carbone, ralentit la dissolution de l'alumine et inhibe la précipitation de la boehmite. Les ions métalliques utilisés comme dopants de l'alumine ont tous un effet similaire sur la diminution de l'hydratation. Une inhibition totale de l'hydratation est obtenue par greffage de silicium à partir de TEOS. Une étude DRIFT dans la région des vibrations OH suggère que les additifs inorganiques inhibent la dissolution de l'alumine en bloquant des sites Al-OH localisés sur les faces latérales des particules. / Alumina, used as a catalyst support for the Fischer-Tropsch reaction or for the conversion of biomass, partially transforms in presence of water into (oxy)hydroxides phases. The formation of the latter leads to the production of fine particles that may cause plugging problems in the implementation of processes based on slurry bubble column reactors. In order to design more stable and more resistant catalysts, this PhD work aimed at identifying the mechanism of hydration and degradation of transition aluminas in aqueous phase, and to study how organic (alcohols, polyols) or inorganic (Mg, Zr, Ni and Si) additives can limit this degradation. The conduct of a systematic study on the hydration of alumina at 70°C under atmospheric pressure, or at 150°C in hydrothermal conditions, allowed defining a general two-step mechanism: a dissolution of the surface of alumina, followed by a precipitation of, respectively, aluminum hydroxides (Al(OH)3) or boehmite (AlOOH) on alumina grains. Furthermore, the chemical degradation tends to promote the degradation under mechanical stress. The presence of polyols in aqueous phase, mainly molecules with 5 or 6 carbon atoms, slows down the dissolution of alumina and inhibit the precipitation of boehmite. Metal ions used as dopants of alumina all have a similar effect on the decrease of hydration. A total inhibition of hydration is obtained by grafting silicon using TEOS. A DRIFTS study in the OH vibration region suggests that inorganic additives inhibit the dissolution of alumina by blocking Al-OH sites located on the lateral facets of the particles.

Nos curtumes, as operações de ribeira geram quantidades elevadas de resíduos sólidos. Durante o tratamento das peles na ribeira, especificamente na etapa de pré-descarne é removido material adiposo que constitui a camada subcutânea da pele, esse resíduo é composto de gorduras e proteínas. Através dos processos de digestão/extração e winterização, é possível produzir oleína dos resíduos sólidos do pré-descarne. A oleína é um composto de triacilgliceróis formado por ácidos graxos insaturados com potencial para ser convertido a polióis e utilizado na manufatura de poliuretanos (PU), gerando uma alternativa para substituir os derivados de petróleo comumente utilizados nesse processo. Este trabalho tem como objetivo produzir polióis de oleína por glicerólise alcalina e, a partir dos polióis produzidos, preparar espumas flexíveis de poliuretano (EFPUs) Empregou-se um planejamento experimental fatorial completo 24 com 4 repetições no ponto central para otimizar a produção de polióis de oleína. As espumas EFPUs foram preparadas com razões molares NCO/OH de 1,1 e 1,2, usando-se poliisocianatos alifáticos lineares e cíclicos, água como agente de expansão e surfactante de silicone. O poliol à base de oleína (PO2 - produzido na melhor condição de glicerólise alcalina estudada) apresentou índice de hidroxila elevado (acima de 300 mg KOH.g-1) e funcionalidade próxima a 3. A estabilidade térmica da espuma de poliuretano produzida foi maior que a estabilidade térmica do poliol de oleína. A densidade, o alongamento na ruptura e a resiliência das espumas de PU foram dependentes da razão molar de NCO/OH. As microscopias de MEV das espumas de PU mostraram estruturas das células como polígono totalmente fechados, outros com aberturas e muitas paredes enrugadas. Os materiais extrativos das espumas de PU foram inferiores a 3%, indicando a formação de estrutura reticulada. / In the tanneries, the beamhouse generate high amounts of solid waste. During the treatment of skins in beamhouse, specifically in pre-fleshing stage is removed adipose material that constitutes the subcutaneous layer of the skin, this residue is composed of fats and proteins. Through the processes of digestion/extraction and winterization, it is possible to produce olein from the solid waste from the pre-fleshing. Olein is a triacylglycerol compound formed by unsaturated fatty acids that can be converted to polyols and used to manufacture polyurethane, an alternative to replace the petroleum derivatives, commonly employed in the process. This work aims to obtain polyol from olein through alkaline glycerolysis and, from the polyols produced, to produce flexible polyurethane foams (FPUFs). A 24 full factorial design with 4 repetitions at the central point was used to optimize the production of olein polyols. EFPUs were prepared with NCO/OH molar ratios of 1.1 and 1.2, linear and cyclic aliphatic polyisocyanates, water as blowing agent and silicone surfactant. The olein-based polyol (PO2 - produced in the best alkaline glycerolysis condition studied) showed high hydroxyl number (above 300 mg KOH.g-1) and functionality near to 3. Thermal stability of produced polyurethane foams was greater than thermal stability of olein polyol. Density, elongation at break and resilience of PU foams have been dependents of NCO/OH ratio. SEM microscopy of FPUFs show cells structures with polygon totally closed, others with openings and many wrinkled walls. Extractable materials of polyurethane foams was lower than 3% indicating that a crosslinked structure is formed.

Made available in DSpace on 2014-06-11T19:24:45Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-02-24Bitstream added on 2014-06-13T19:47:05Z : No. of bitstreams: 1 moser_p_me_sjrp.pdf: 1240757 bytes, checksum: 3044993e185eb69154b3203e4e23361b (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Atualmente, os substitutos de açúcares têm ganhado destaque devido à crescente demanda do mercado mundial por alimentos que possuem baixo teor calórico e que atendam dietas específicas. Considerando que os componentes presentes nas formulações podem modificar as propriedades funcionais dos hidrocolóides, o objetivo deste trabalho foi estudar o comportamento reológico das gomas guar e xantana na presença de polióis. Soluções de goma guar (0,1, 0,5 e 1 %) e xantana (0,5 %) na presença de maltitol, sorbitol e xilitol nas concentrações de 10 à 40 % foram investigadas. O comportamento dessas misturas foi avaliado através de cisalhamento estacionário e oscilatório sob duas condições: em temperatura de 25 ºC e após o ciclo de congelamento e descongelamento. Em geral a adição dos polióis e o aumento de sua concentração elevaram a viscosidade aparente dos sistemas; somente para as soluções de guar 1 % com 40 % de poliol e xantana com 10 % de poliol a viscosidade foi reduzida. Os modelos Ostwald De Waelle e Herschel-Bulkley representaram satisfatoriamente o comportamento dos sistemas. Todas as soluções se mostraram pseudoplásticas e as soluções de guar 1 % com os polióis apresentaram tixotropia. As soluções de xantana com os polióis apresentaram tensão inicial para o escoamento. Os polióis também aumentaram os módulos dinâmicos (G’ e G’’) das soluções hidrocolóide/poliol, tornando os sistemas mais elásticos. Somente a solução de 10 % de sorbitol reduziu o valor de G’ da goma xantana, tornando o sistema menos consistente. Nas misturas de guar com 40 % de poliol, observou-se que o ângulo de fase apresentou valor ligeiramente inferior à 1 rad, com dependência da frequência, o que é característico de solução concentrada. A xantana pura possui características de solução... / Sugar substitutes have gained prominence because of the growing global market demand for foods that are low in calories and meet specific diets. Since the components present in the formulations may modify the functional properties of hydrocolloids, the aim of the present work was to study the rheological behavior of guar gum and xanthan in the presence of polyols. Solutions of guar gum (0,1, 0,5 and 1%) and xanthan (0,5%) in the presence of maltitol, sorbitol and xylitol at concentrations of 10 to 40% were investigated. The behavior of these mixtures was evaluated by steady and oscillatory shear under two conditions: at the temperature of 25 °C and after freezing and thawing cycle. In general, the addition of polyols and increasing their concentration increased the apparent viscosity of the systems; only for solutions of guar 1% with 40% polyol and xanthan with 10% polyol the viscosity was reduced. The Ostwald Waelle and Herschel-Bulkley models satisfactorily represented the behavior of systems. All solutions showed pseudoplastic behavior and guar solutions 1% with polyols showed thixotropy. Xanthan solutions with polyols showed yield stress to flow. Polyols also increased the dynamic modulus (G 'and G'') of hydrocolloid/polyol solutions, making systems more elastic. Only solution of sorbitol 10% reduced the value of G'of xanthan gum, making the system less consistent. For mixtures of guar with 40 % polyol, it was observed that the phase angle showed a value slightly lower than 1, with frequency dependence, which is characteristic of a concentrated solution. The pure xanthan has characterized concentrated solution in the presence of polyols and the value of δ was next to 0,5 rad, with little dependence on frequency, which characterizes weak gel. In solutions of guar and xanthan 0,5% polyols helped to preserve the... (Complete abstract click electronic access below)