Dissertations / Theses on the topic 'Compound numbers'

Observation du passage d'un regime kondo mixte a un regime kondo pur ou a un regime de valence intermediaire sous l'effet de la pression chimique. Etude du diagramme de phases magnetiques. Determination du coefficient de couplage entre electrons 4 f et la bande de conduction jn(e::(f)). Coefficient de la chaleur specifique, temperature de kondo et coefficient de grueneisen electronique de ceincu::(2)

Etude des proprietes electriques et structurales de deux series de composes a coordinat dmit : composes a etat d'oxydation fractionnaire (m(dmit)::(2))c::(x) et composes donneur-accepteur d(m(dmit)::(2))::(y) (avec m = zn,ni,pt,pd; c = nbu**(+)::(4) et asph**(+)::(4); d = ttf, tmttf, ttmttf, bedt-ttf et tmtsf; n dans (m(dmit)::(2))**(n-) etant egal a 2,1,x,0). Mise en evidence de la nature 2d des composes de la premiere serie et quasi 3d de ceux de la deuxieme; relations structure-conductivite. Mise en evicence de la supraconduction dans le cas du complexe ttf(ni(dmit)::(2))::(2), avec une temperature de transition de 1,62 k sous 7 kbar

Doutoramento em Bioquímica
Os polissacarídeos são os componentes maioritários dos grãos de café verde e torrado e da bebida de café. Os mais abundantes são as galactomananas, seguindo-se as arabinogalactanas. Durante o processo de torra, as galactomananas e arabinogalactanas sofrem modificações estruturais, as quais estão longe de estar completamente elucidadas devido à sua diversidade e à complexidade estrutural dos compostos formados. Durante o processo de torra, as galactomananas e arabinogalactanas reagem com proteínas, ácidos clorogénicos e sacarose, originando compostos castanhos de alto peso molecular contendo nitrogénio, designados de melanoidinas. As melanoidinas do café apresentam diversas atividades biológicas e efeitos benéficos para a saúde. No entanto, a sua estrutura exata e os mecanismos envolvidos na sua formação permanecem desconhecidos, bem como a relação estrutura-atividade biológica. A utilização de sistemas modelo e a análise por espectrometria de massa permitem obter uma visão global e, simultaneamente, detalhada das modificações estruturais nos polissacarídeos do café promovidas pela torra, contribuindo para a elucidação das estruturas e mecanismos de formação das melanoidinas. Com base nesta tese, oligossacarídeos estruturalmente relacionados com a cadeia principal das galactomananas, (β1→4)-Dmanotriose (Man3), e as cadeias laterais das arabinogalactanas, (α1→5)-Larabinotriose (Ara3), isoladamente ou em misturas com ácido 5-Ocafeoilquínico (5-CQA), o ácido clorogénico mais abundante nos grãos de café verde, e péptidos compostos por tirosina e leucina, usados como modelos das proteínas, foram sujeitos a tratamento térmico a seco, mimetizando o processo de torra. A oxidação induzida por radicais hidroxilo (HO•) foi também estudada, uma vez que estes radicais parecem estar envolvidos na modificação dos polissacarídeos durante a torra. A identificação das modificações estruturais induzidas por tratamento térmico e oxidativo dos compostos modelo foi feita por estratégias analíticas baseadas principalmente em espectrometria de massa, mas também em cromatografia líquida. A cromatografia de gás foi usada na análise de açúcares neutros e ligações glicosídicas. Para validar as conclusões obtidas com os compostos modelo, foram também analisadas amostras de polissacarídeos do café obtidas a partir de resíduo de café e café instantâneo. Os resultados obtidos a partir dos oligossacarídeos modelo quando submetidos a tratamento térmico (seco), assim como à oxidação induzida por HO• (em solução), indicam a ocorrência de despolimerização, o que está de acordo com estudos anteriores que reportam a despolimerização das galactomananas e arabinogalactanas do café durante a torra. Foram ainda identificados outros compostos resultantes da quebra do anel de açúcares formados durante o tratamento térmico e oxidativo da Ara3. Por outro lado, o tratamento térmico a seco dos oligossacarídeos modelo (individualmente ou quando misturados) promoveu a formação de oligossacarídeos com um maior grau de polimerização, e também polissacarídeos com novos tipos de ligações glicosídicas, evidenciando a ocorrência de polimerização através reações de transglicosilação não enzimática induzidas por tratamento térmico a seco. As reações de transglicosilação induzidas por tratamento térmico a seco podem ocorrer entre resíduos de açúcares provenientes da mesma origem, mas também de origens diferentes com formação de estruturas híbridas, contendo arabinose e manose como observado nos casos dos compostos modelo usados. Os resultados obtidos a partir de amostras do resíduo de café e de café instantâneo sugerem a presença de polissacarídeos híbridos nestas amostras de café processado, corroborando a ocorrência de transglicosilação durante o processo de torra. Além disso, o estudo de misturas contendo diferentes proporções de cada oligossacarídeo modelo, mimetizando regiões do grão de café com composição distinta em polissacarídeos, sujeitos a diferentes períodos de tratamento térmico, permitiu inferir que diferentes estruturas híbridas e não híbridas podem ser formadas a partir das arabinogalactanas e galactomananas, dependendo da sua distribuição nas paredes celulares do grão e das condições de torra. Estes resultados podem explicar a heterogeneidade de estruturas de melanoidinas formadas durante a torra do café. Os resultados obtidos a partir de misturas modelo contendo um oligossacarídeo (Ara3 ou Man3) e 5-CQA sujeitas a tratamento térmico a seco, assim como de amostras provenientes do resíduo de café, mostraram a formação de compostos híbridos compostos por moléculas de CQA ligadas covalentemente a um número variável de resíduos de açúcar. Além disso, os resultados obtidos a partir da mistura contendo Man3 e 5-CQA mostraram que o CQA atua como catalisador das reações de transglicosilação. Por outro lado, nas misturas modelo contendo um péptido, mesmo contendo também 5-CQA e sujeitas ao mesmo tratamento, observou-se uma diminuição na extensão das reações transglicosilação. Este resultado pode explicar a baixa extensão das reações de transglicosilação não enzimáticas durante a torra nas regiões do grão de café mais ricas em proteínas, apesar dos polissacarídeos serem os componentes maioritários dos grãos de café. A diminuição das reações de transglicosilação na presença de péptidos/proteínas pode dever-se ao facto de os resíduos de açúcares redutores reagirem preferencialmente com os grupos amina de péptidos/proteínas por reação de Maillard, diminuindo o número de resíduos de açúcares redutores disponíveis para as reações de transglicosilação. Além dos compostos já descritos, uma diversidade de outros compostos foram formados a partir dos sistemas modelo, nomeadamente derivados de desidratação formados durante o tratamento térmico a seco. Em conclusão, a tipificação das modificações estruturais promovidas pela torra nos polissacarídeos do café abre o caminho para a compreensão dos mecanismos de formação das melanoidinas e da relação estrutura-atividade destes compostos.
Polysaccharides are the major components of green and roasted coffee beans, and coffee brew. The most abundant ones are galactomannans, followed by arabinogalactans. During the roasting process, galactomannans and arabinogalactans undergo structural modifications that are far to be completely elucidated due to their diversity and complexity of the compounds formed. During the roasting process, galactomannans and arabinogalactans react with proteins, chlorogenic acids, and sucrose, originating high molecular weight brown compounds containing nitrogen, known as melanoidins. Several biological activities and beneficial health effects have been attributed to coffee melanoidins. However, their exact structures and the mechanisms involved in their formation remain unknown, as well as the structure-biological activity relationship. The use of model systems and mass spectrometry analysis allow to obtain an overall view and, simultaneously, detailed, of the structural modifications in coffee polysaccharides promoted by roasting, contributing to the elucidation of the structures and formation mechanisms of melanoidins. Based on this thesis, oligosaccharides structurally related to the backbone of galactomannans, (β1→4)-D-mannotriose, and the side chains of arabinogalactans, (α1→5)-Larabinotriose, alone or in mixtures with 5-O-caffeoylquinic acid, the most abundant chlorogenic acid in green coffee beans, and dipeptides composed by tyrosine and leucine, used as models of proteins, were submitted to dry thermal treatments, mimicking the coffee roasting process. The oxidation induced by hydroxyl radicals (HO•) was also studied, since these radicals seem to be involved in the modification of the polysaccharides during roasting. The identification of the structural modifications induced by thermal and oxidative treatment of the model compounds was performed mostly by mass spectrometry-based analytical strategies, but also using liquid chromatography. Gas chromatography was used in the analysis of neutral sugars and glycosidic linkages. To validate the conclusions achieved with the model compounds, coffee polysaccharide samples obtained from spent coffee grounds and instant coffee were also analysed. The results obtained from the model oligosaccharides when submitted to thermal treatment (dry) or oxidation induced by HO• (in solution) indicate the occurrence of depolymerization, which is in line with previous studies reporting the depolymerization of coffee galactomannans and arabinogalactans during roasting. Compounds resulting from sugar ring cleavage were also formed during thermal treatment and oxidative treatment of Ara3. On the other hand, the dry thermal treatment of the model oligosaccharides (alone or when mixed) promoted the formation of oligosaccharides with a higher degree of polymerization, and also polysaccharides with new type of glycosidic linkages, evidencing the occurrence of polymerization via non-enzymatic transglycosylation reactions induced by dry thermal treatment. The transglycosylation reactions induced by dry thermal treatment can occur between sugar residues from the same origin, but also of different origins, with formation of hybrid structures, containing arabinose and mannose in the case of the model compounds used. The results obtained from spent coffee grounds and instant coffee samples suggest the presence of hybrid polysaccharides in these processed coffee samples, corroborating the occurrence of transglycosylation during the roasting process. Furthermore, the study of mixtures containing different proportions of each model oligosaccharide, mimicking coffee bean regions with distinct polysaccharide composition, subjected to different periods of thermal treatment, allowed to infer that different hybrid and non-hybrid structures may be formed from arabinogalactans and galactomannans, depending on their distribution in the bean cell walls and on roasting conditions. These results may explain the heterogeneity of melanoidins structures formed during coffee roasting. The results obtained from model mixtures containing an oligosaccharide (Ara3 or Man3) and 5-CQA and subjected to dry thermal treatment, as well as samples derived from spent coffee grounds, showed the formation of hybrid compounds composed by CQA molecules covalently linked to a variable number of sugar residues. Moreover, the results obtained from the mixture containing Man3 and 5-CQA showed that CQA acts as catalyst of transglycosylation reactions. On the other hand, in the model mixtures containing a peptide, even if containing 5-CQA and subjected to the same treatment, it was observed a decrease in the extent of transglycosylation reactions. This outcome can explain the low extent of non-enzymatic transglycosylation reactions during roasting in coffee bean regions enriched in proteins, although polysaccharides are the major components of the coffee beans. The decrease of transglycosylation reactions in the presence of peptides/proteins can be related with the preferential reactivity of reducing residues with the amino groups of peptides/proteins by Maillard reaction, decreasing the number of reducing residues available to be directly involved in the transglycosylation reactions. In addition to the compounds already described, a diversity of other compounds were formed from model systems, namely dehydrated derivatives formed during dry thermal treatment. In conclusion, the identification of the structural modifications in coffee polysaccharides promoted by roasting pave the way to the understanding of the mechanisms of formation of melanoidins and structure-activity relationship of these compounds.

Copies of author's previously published articles inserted.
Bibliography: leaves 176-187.
xiii, 187 leaves ; 30 cm.
Title page, contents and abstract only. The complete thesis in print form is available from the University Library.
Describes the syntheses of three 1,4,7-triazayclonane macrocyclic ligands functionalised with increasing numbers of 2-hydroxyethyl pendant arms.
Thesis (Ph.D.)--University of Adelaide, Dept. of Chemistry, 1999

Multiphase flows abound in nature and enterprises. Our daily interactions with fluids - washing, drinking, and cooking, for example - occur at a free surface and within the realm of multiphase flows. The applications of multiphase flows within the context of emulsions, which are caused by mixing two immiscible fluids, have been of interest since the nineteenth century: compartmentalizing one fluid in another is particularly of interest in applications in pharmaceutical, materials, microfluidics, chemical, and biological engineering. Even more control in compartmentalization and delivery can be obtained through the usage of double emulsions, which are emulsions of smaller drops (i.e., inner drop) within larger drops (i.e., outer drop). The goal of this work is to understand the dynamic behavior of compound drops in confined flow at low Reynolds numbers. These behaviors include the migration patterns, limit cycles, and equilibrium locations in confined flows such as channel flows.

Firstly, we look at non-concentric compound drops that are subject to simple shear flows. The eccentricity in the inner drop is either within the place of shear, normal to the plane of shear, or mixed. We show unreported motions that persist throughout time regardless of the initial eccentricity, given that the deformations of the inner and outer drops are small. Understanding the temporal dynamics of compound drops within the simple shear flow, one of the simplest background flows that may be imposed, allows us to probe at the dynamics of more complicated background flows.

Secondly, we look at the lateral migration of compound drops in a Poiseuille flow. Depending on the initial condition, we show that there are multiple equilibria. We also show that the majority of initial configurations results in the compound drop with symmetry about the short wall direction. We then show the time it takes for the interfaces to merge if a given initial configuration does not reach the aforementioned symmetry.

Thirdly, while the different equilibria of compound drops offer some positional differences at different radii ratio, we show that the lift force profiles at non-equilibrium locations offer distinctly different results for compound drops with different radii ratio. We then look at how this effect is greater than changes that arise due to viscosity ratio changes, and offer insights on what may create such a change in the lift force profile.

A declining population of ring-necked pheasants (Phasianus colchicus) was studied at Tule Lake National Wildlife Refuge (TLNWR) from the summer of 1990 through the spring of 1993. Pheasant densities/50 ha at TLNWR in 1989, 1991, and 1992 were considerably lower (16.86, 8.49, and 6.81) than the >62 density seen in the mid-1950s. Mean body weight of hen pheasants at TLNWR was significantly lower than hens at nearby Lower Klamath National Wildlife Refuge (LKNWR) which was not intensively farmed. Mean tarsal lengths of hens at TLNWR were also significantly shorter than hens at LKNWR, suggesting reduced skeletal growth and potential nutritional problems. The lack of adequate cover was responsible for poor early nest success at TLNWR. Later in the season, spring planted crops provided adequate cover to conceal nesting hens; however, only 0.21 young in 1991 and 0.02 young in 1992 were produced per radio-equipped hen. These rates are extremely low compared to rates required to maintain a stable population. Most adult mortality occurred during the spring and early summer months at TLNWR before crops provided adequate cover, and long before pesticide applications. The main predator of the pheasants was the golden eagle (Aquila chrvsaetos). Of special concern at TLNWR was pheasant and other wildlife exposure to anticholinesterase (antiChE) insecticides used on agricultural croplands at the refuge. Direct toxicity of antiChE compounds (in this case methamidophos) killed 2 young pheasants, but no adult radio-equipped hens died as a direct result of insecticide intoxication. This finding was of particular interest because 15% of the adult pheasants collected in and around potato fields had 55% brain ChE inhibition. The extent of the effects of insecticide exposure on the survivorship of pheasant young was uncertain as they were not radio-equipped. The overriding factor impacting the pheasant population at TLNWR and to a lesser extent LKNWR was poor habitat, especially in the spring when most mortality occurred. The poor habitat also resulted in extremely low recruitment (up to 1 September). Nearly all adult mortality and most of the low recruitment occurred before the insecticide spray season. The population was nearly extirpated during the severe winter of 1992-93.
Graduation date: 1995