Made available in DSpace on 2014-12-17T15:42:01Z (GMT). No. of bitstreams: 1 MarcosPSG_DISSERT.pdf: 1772497 bytes, checksum: df93ce17acaae55571d307fc84ed5f3e (MD5) Previous issue date: 2011-12-20 / Universidade Federal do Rio Grande do Norte / A partially hydrolyzed polyacrylamide (HPAM) is a copolymer composed of acrylamide and sodium acrylate. Due to its wide range of applications there are different methods for its quantification and characterization in solution systems. Evaluation of C* is important to describe the transition from dilute to semi-dilute, behavior, when the solution will have its characteristic viscosity at concentrations above C*. This dissertation describes the determination of the critical concentration of overlap C* by potentiometry of partially hydrolyzed polyacrylamide - HPAM under acidic conditions. Based on the law of mass action and the proper treatment of the constant of aggregate formation, polymer molecular weight, degree of polymerization and hydrolysis were calculated. The inflection point was determined by the intersection of the resulting equation and mathematical development, statistically satisfy the experimental points relating the number of moles of monomers (n), equilibrium constant of formation of the entanglements (K*), pH, C* and acidity constant of the polymer (Ka). The viscometric parameters of C* showed a percentage difference compared to potentiometers. The results for the determination of C*, and degree of copolymerization molar mass proved to be a simple alternative for the characterization of polymers with protonated monomers and water soluble / A poliacrilamida parcialmente hidrolisada (HPAM) ? um copol?mero formado por acrilamida e acrilato de s?dio. Em fun??o de sua ampla faixa de aplica??o existem diferentes m?todos para a sua quantifica??o e caracteriza??o em solu??o. A avalia??o de C* ? importante para descrever a transi??o do regime dilu?do para o semi dilu?do, isto ?, quando a solu??o ter? sua viscosidade caracter?stica, em concentra??es acima de C*. Este trabalho descreve a determina??o da concentra??o cr?tica de overlap C* por potenciometria da poliacrilamida parcialmente hidrolisada HPAM em meio ?cido. Baseando-se na lei de a??o das massas e no tratamento adequado da constante de forma??o do agregado polim?rico foram calculados a massa molar, grau de hidr?lise e de polimeriza??o da HPAM empregada. O ponto de inflex?o foi determinado pelo m?todo da interse??o e a equa??o resultante do desenvolvimento matem?tico, satisfez estatisticamente os pontos experimentais, relacionando o n?mero de mols de mon?meros (n), constante de equil?brio de forma??o do novelo (K*), pH do meio, C* e constante de acidez do pol?mero (Ka). Os par?metros viscosim?tricos de C* apresentaram uma diferen?a percentual em rela??o aos potenciom?tricos. Os resultados para determina??o da C*, grau de copolimeriza??o e massa molar se mostraram uma alternativa simples para caracteriza??o de pol?meros com mon?meros proton?veis e sol?veis em ?gua

Neste trabalho estudou-se a influência das substâncias húmicas (SH) extraídas de turfa, com diferentes massas molares, utilizadas para a preparação de águas com cor de 100 uH ± 5 uH, nos ensaios de coagulação, floculação e sedimentação no tratamento de água. Foram realizadas caracterizações das SH por meio das técnicas de ultrafiltração (UF), análise elementar (AE), ultravioleta/visível (UV/Vis), infravermelho (IF), ressonância magnética nuclear de C13 (RMN de C13), ressonância paramagnética eletrônica (EPR). Essas caracterizações demonstraram que as frações de menor massa molar (30 - 100 kDa e <30 kDa), obtidas por UF, apresentaram uma maior concentração de grupos contendo oxigênio, enquanto que a fração de maior massa molar (>100 kDa) e a contendo todas as massas molares juntas (filtrada apenas em membrana com tamanho de poro de 0,45 &#956m) apresentaram maior concentração de grupamentos aromáticos. Verificou-se também que nas frações de menor massa molar (30 - 100 kDa e <30 kDa) a porcentagem de ácidos fúlvicos é maior do que a de ácidos húmicos. Nas frações de maior massa molar (> 100kDa e filtrada em membrana com tamanho de poro de 0,45 &#956m) ocorreu o contrário. Os ensaios de coagulação, floculação e sedimentação realizados com águas preparadas com as diferentes frações de diferentes massas molares, mostraram que quanto maior a massa molar, maior é a facilidade de coagulação, floculação e sedimentação, o que proporciona maior eficiência na remoção da cor aparente. Os diagramas de coagulação obtidos para o coagulante sulfato de alumínio (Al2(SO4)3 . 14,3 H2O) mostraram que independente da massa molar, a região de pH ótimo de coagulação esteve entre 6 e 7, sendo que a remoção da cor aparente foi crescente com a diminuição da velocidade de sedimentação (Vs= 3,0, 1,5 e 0,5 cm/min). Com a diminuição da massa molar houve um aumento na dosagem de Al2(SO4)3 . 14,3 H2O necessária para se obter curvas de remoção da cor aparente iguais às obtidas com a água preparada com a fração de maior massa molar (> 100 kDa). Os ensaios de coagulação, floculação, sedimentação e filtração demonstraram boa reprodutibilidade em relação aos resultados de remoção de cor aparente obtidos para a confecção dos diagramas de coagulação. Após a filtração foi verificado que os valores da cor aparente não foram detectados pela técnica de medição da cor utilizada, para todas as águas de estudo, com exceção da água preparada com a fração de menor massa molar (<30 kDa). Conclui-se que, quanto menor a massa molar, maior a porcentagem de ácidos fúlvicos presentes e maior a concentração de grupamentos com oxigênio ligado. Assim, será necessária uma maior dosagem de coagulante Al2(SO4)3 . 14,3 H2O para que ocorra uma remoção eficiente da cor. / The present thesis deals with the influence of humic substances (HS) on coagulation, flocculation and sedimentation tests for water treatment. These substances were extracted from peat, had different molecular weight and were used for the preparation of water with 100 ± 5 uH color. Characterizations of HS were performed by the following techniques ultra filtration (UF), elemental analysis (EA), ultraviolet/ visible (UV/Vis), infrared (IF), C13 nuclear magnetic resonance (NMR of C13) and electron paramagnetic resonance (EPR). Such characterizations showed that fractions of smaller molecular weight (30 - 100 kDa and < 30 kDa) obtained by UF presented a higher concentration of groups containing oxygen, while the fraction with the largest molecular weight (>100 kDa) and the one containing all the molecular weight together (filtered only in membrane with pore size of 0,45 &#956m) presented a higher concentration of aromatic groupings. It was also possible to verify that in the fractions with smaller molecular weight (30 - 100 kDa e <30 kDa) the percentage of fulvic acids was higher than the one of humic acids . However the opposite occurred of larger molecular weight (>100 kDa and filtered in membrane with pore size of 0,45 &#956m). The tests of coagulation, flocculation and sedimentation conducted with waters prepared with different fractions of different molecular weight showed that the larger the molecular weight, the easier the coagulation, flocculation and sedimentation, resulting in higher efficiency in the removal of the apparent color. The coagulation diagrams obtained for aluminum sulphate (Al2(SO4)3 .14,3 H2O) showed that independently of the molecular weight, the region with optimum pH for coagulation was between 6 and 7 and the removal of the apparent color increased with the decrease in the sedimentation velocity (Vs= 3,0, 1,5 e 0,5 cm/min). Due to the decrease in the molecular weight there was as increase in the dosage of Al2(SO4)3 .14,3 H2O necessary to obtain curves of the removal of the apparent color similar to the ones obtained with the water prepared with the fraction of the largest molecular weight (> 100 kDa). Tests of coagulation, flocculation, sedimentation and filtration showed good reproducibility in relation to the results of removal of apparent color, obtained for the construction of coagulation diagrams. After filtration it was possible to verify that the values of apparent color were not detected by the technique of color measurement utilized for all the waters studied, except for the water prepared with the fraction of the smallest molecular weight (< 30 kDa). It was possible concluded that the smaller the molecular weight, the higher the percentage of present fulvic acids and the higher the concentration of groupings with bond oxygen. Thus a higher dosage of coagulant Al2(SO4)3 .14,3 H2O will be necessary for an efficient removal of color.

A distribuição de pesos moleculares (DPM) de um polímero afeta as propriedades mecânicas, térmicas e reológicas do material. Além disso, a análise em tempo real de uma reação de polimerização é uma tarefa complicada e, consequentemente, os procedimentos de controle devem ser baseados em valores gerados pelos modelos. Por isso, é extremamente importante ter dados confiáveis sobre distribuições de pesos moleculares, melhorar a eficiência dos métodos existentes e desenvolver novos métodos capazes de prever as heterogeneidades das reações de polimerização. Experimentalmente, a DPM pode ser obtida usando técnicas como a cromatografia de permeação em gel. Para predizer a DPM, vários métodos foram desenvolvidos nas ultimas décadas. Um dos principais é o dos momentos estatísticos, baseado em conceitos puramente estatísticos, que não conseguem descrever completamente a DPM. Além disso, as aproximações com método de Galerkin usam polinômios ortogonais - no caso especifico polinômios de Laguerre - cujos coeficientes são calculados empregando os momentos estatísticos e a distribuição é gerada resolvendo um número de equações definido pelo usuário, relacionado à precisão desejada. Enfim, o método das funções geradoras de probabilidades foi utilizado para prever as DPMs, porém necessitando uma inversão da transformada de Laplace, que introduz problemas numéricos nem sempre possíveis de serem resolvidos. No presente trabalho, o sistema rigoroso de equações diferenciais ordinárias foi resolvido, com objetivo de reduzir as imprecisões e as limitações introduzidas pelas aproximações. Obter diretamente a DPM completa requer a resolução de um sistema contendo cerca de 2Nmax até 3Nmax equações diferenciais ordinárias rígidas, tarefa que há alguns anos era inviável devido a limitações relacionadas à capacidade de cálculo. Foi modelada a DPM para uma reação de polimerização radicalar livre de estireno e de metacrilato de metila. Um interesse especial foi dado à taxa de terminação que é, no momento, um dos temas mais investigados em polimerização por radicais livres. Os resultados das simulações foram comparados com dados experimentais tirados de reatores convencionais e, subsequentemente, com dados experimentais provenientes de um millireactor não convencional. / It is well known that the molecular weight distribution (MWD) of a synthetic polymer affects its mechanical, thermal and rheological properties. Furthermore, the on-line analysis for polymerization reaction is a difficult task and, consequently, the control procedures must rely on values given by models. As such, it is extremely important to have reliable data on the MWD, improve the efficiency of existing methods and develop new ones to predict the heterogeneities of polymerization reactions. Experimentally, the MWD can be obtained using techniques such as Gel Permeation Chromatography (GPC). To predict the MWD, many methods have been developed over the last decades. One of the main methods is the statistical moment treatment, which is based on a pure statistical concept and do not describe the whole MWD. Moreover, Galerkin approximation uses orthogonal polynomials -in general Laguerre polynomials- whose coefficients are calculated exploiting the statistical moment definition and the distribution is generated by solving a user-defined number of equations based on the desired precision. Finally, probability-generating functions that have been used to predict MWDs require Laplace transforms inversions, introducing numerical issues that must be bypassed and are not always solvable. It has been decided to base the approach without adopting any of these methods but directly solving the rigorous ordinary differential equation (ODE) system in order to reduce the inaccuracies and the limitations introduced by approximations. The direct obtention of the MWD requires the resolution of a system containing approximately 2Nmax up to 3Nmax stiff ODE equations that, a few years ago, was unfeasible due computational time limitations. The MWDs for a free radical styrene polymerization system and a methyl methacrylate system have been modeled. A special focus was given to the termination rate constant, which is, at the present, one of the most investigated topics in free radical polymerization. The results of the simulations were compared to experimental data taken from conventional reactors and, subsequently, to experimental data coming from an unconventional millireactor.

Um modelo matemático da reação de copolimerização em emulsão de acrilato de butila e estireno em reator batelada e semi-batelada isotérmico foi desenvolvido e apresentou bons resultados quando comparado a experimentos disponíveis em literatura científica. O modelo contemplou a solução do balanço populacional, tanto para a distribuição de tamanho de partículas quando para a distribuição média de radicais por partícula. Contemplou-se também a solução do balanço de momentos, para obtenção da massa molar média numérica e mássica. O problema descrito foi resolvido através da solução numérica de um conjunto de equações algébricodiferenciais e o balanço populacional foi resolvido pelo método dos pivots fixos. Foi possível validar com boa aderência a conversão dos monômeros, o diâmetro médio de partículas, número de partículas por litro de emulsão, número médio de radicais por partícula, a distribuição de tamanho de partículas e a massa molar média numérica e mássica ao longo do tempo para um conjunto de experimentos. / A mathematical model of emulsion copolymerization reaction of styrene and butyl acrylate for batch and semi-batch isothermal reactor was developed and presented good results when compared to experiments available in the scientific literature. The model included the solution of the population balance for both particle size distribution and average number of radicals per particle. The balances of moments of the molecular weight distribution are solved to obtain the weight- and numberaveraged molecular weight of the polymer. The problem described was solved by numerical solution of a set of algebraic-differential equations and the population balance was solved by the method of fixed pivots. The model prediction were validated with a set of experiments with respect to the changes of monomer conversion, average particle diameter, number of particles per liter of emulsion, average number of radicals per particle, particle size distribution, number- and weight-average molecular weight during process time.

O impacto da oxidação com ozônio na transformação de compostos orgânicos de elevada massa molar (HMW) para o aumento da biodegradabilidade dos efluentes da indústria de celulose e papel foi investigado sob diferentes doses de ozônio. Os experimentos foram realizados utilizando-se os efluentes primário e de extração alcalina de duas indústrias de celulose sob dois valores iniciais de pH (12 e 7). Utilizou-se um reator em escala de laboratório equipado com um difusor de bolhas finas para a aplicação do ozônio. Os resultados revelaram o potencial da aplicação de ozônio como uma etapa de tratamento anterior ao processo biológico convencional. Para o efluente primário, a aplicação de 0,70 mg\'O IND.3\'/mL efluente elevou a razão DBO5/DQO de 0,18 para 0,35 e foi alcançada uma remoção de cor na ordem de 87%. Para o efluente de extração alcalina da indústria Howe Sound, a razão DBO5/DQO foi elevada de 0,07 para 0,15 (pH inicial 12) e para 0,20 (pH inicial 7) e obteve-se uma remoção de cor por volta de 44% com a aplicação de 0,80 mg\'O IND.3\'/mL efluente. Para o efluente de extração alcalina da indústria Catalyst Paper, obteve-se uma remoção de cor por volta de 78% e a razão DBO5/DQO foi elevada de 0,07 para 0,16 após a aplicação de uma dose de ozônio de 0,80 mg\'O IND.3\'/mL efluente. Essas modificações foram alcançadas por uma redução nas frações de elevada massa molar durante a aplicação de ozônio. Para o efluente primário, observou-se uma elevada redução da faixa de maior massa molecular ( > 2kDa) após a aplicação de 0,72 mg\'O IND.3\'/mL efluente. Alcançaram-se 85% e 61% de remoção da faixa superior a 5 kDa para os efluentes de extração alcalina da indústria Howe Sound sob pH inicial 7 e 12, respectivamente, com a aplicação de cerca de 0,72 mg\'O IND.3\'/mL efluente. A faixa de maior massa molar ( > 10 kDa) dos efluentes de extração alcalina da indústria Catalyst Paper foi removida com a aplicação de aproximadamente 0,80 mg \'O IND.3\'/mL efluente. O papel do ozônio molecular disponível sob pH neutro parece ser de fundamental importância quando o objetivo é a redução dos compostos de elevada massa molecular. / The impact of ozone oxidation in transforming high molecular weight (HMW) organic compounds in order to improve the biodegradability of pulp and paper effluents was investigated under different ozone doses. The experiments were conducted uppon a primary treated effluent and an alkaline bleach plant effluent taken from two pulp mills. The effluents were investigated under different initial pH (7 and 12). Ozone was applied using a semi-batch reactor equipped with fine bubble diffuser. The results showed the potential for using ozone as a pre-treatment to the conventional biological process. Applying 0.70 mg\'O IND.3\'/mLww to the primary treated effluent enhanced the ratio of BOD5/COD was from 0.18 to 0.35 and decreased the colour by 87%. The ratio of BOD5/COD was increased from 0.07 to 0.15 (initial pH 12) and to 0.20 (initial pH 7) and colour was reduced by 44% after applying 0.80 mg\'O IND.3\'/mLww to the alkaline bleach effluent from Howe Sound\'s mill. A similar behavior was observed after 0.80 mg\'O IND.3\'/mLww was applied to the alkaline bleach effluent from Catalyst\'s mill. The ratio of BOD5/COD was increased from 0.07 to 0.16 and the effluent colour decreased by 78%. These changes were primarily driven by reductions of the HMW fractions of the effluent during ozonation. Organics with molecular range higher than 2 kDa were completely removed from the primary treated effluent. Aproximately 85% and 61% of the organics higher than 5 kDa were removed from the Howe Sound\'s alkaline bleach effluent under initial pH 7 and 12, respectively, after applying 0.72 mg\'O IND.3\'/mLww. Organic compounds with molecular weight higher than 10 kDa were completely removed from the Catalyst\'s alkaline bleach effluent after applying 0.80 mg\'O IND.3\'/mLww. Molecular ozone available under neutral conditions seems to play an important role when the removal of the high molecular weight organic compounds is the main objective.

Le polyéthylène à ultra haute masse molaire (UHMWPE) présente une viscosité si forte à l’état fondu que seuls des procédés de mise en forme de type frittage peuvent être employé. Ce procédé rarement utilisé pour les polymères reste peu étudié. En particulier les deux principaux mécanismes généralement mentionnés que sont le réenchevêtrement et la cocristallisation aux interfaces sont difficilement observables séparément. Le UHMWPE, grâce à sa très haute viscosité à l’état fondu et grâce à son plateau caoutchoutique extrêmement étendue en température, peut faire l’objet d’essais mécaniques à la fois à l’état semi-cristallin et à l’état fondu. Des poudres natives de UHMWPE de masses molaires comprises entre 0,6 et 10,5 Mg.mol-1 sont utilisées comme matériau de départ pour leur mise en oeuvre par frittage. La consolidation des interfaces par soudage des particules a été effectuée sous pression à différentes températures supérieures au point de fusion et pour différentes durées. Des expériences de traction effectuées soit à température ambiante soit au-dessus du point de fusion ont permis de distinguer le rôle de l'interdiffusion des chaînes au travers des interfaces de celle de la cocristallisation dans les mécanismes de soudage de particules. Il s'est avéré qu’un soudage efficace se produit dans une échelle de temps très courte. La très faible influence de la durée de frittage par rapport à celle de la température de frittage a prouvé que l'interdiffusion des chaînes n'est pas régie par un mécanisme de reptation. L'explosion à la fusion des cristaux « hors-équilibre » de la poudre native est suggérée être le mécanisme principal permettant un réenchevêtrement dans un laps de temps beaucoup plus court que celui de la reptation. La cocristallisation est un phénomène si efficace dans la consolidation de l'interface à l'état solide qu'elle masque significativement la cinétique de réenchevêtrement gouverné par la température, visible dans les tests mécaniques à l’état fondu. / One of the main issues of ultra-high-molecular-weight polyethylene (UHMWPE) is to overcome its very high viscosity. Powder sintering is then often required instead of injection or extrusion. However, sintering mechanisms remain partially understood. Indeed, the two main mechanisms generally mentioned for interparticle welding, i.e. re-entanglement and cocrystallization, can hardly be observed separately. Fortunately, due to its very high molecular weight, UHMWPE exhibits an exceptionally broad rubbery plateau so that mechanical tensile tests can be easily performed both below and above the melting point. Four UHMWPE of molecular weight in the range of 0.6.106 g.mol-1 to 10.5.106 g.mol-1 have been processed by means of sintering of nascent powders. The interface consolidation or particle welding was carried out under pressure at various temperatures above the melting point and for various durations. Tensile drawing experiments performed either at room temperature or above the melting point enabled to discriminate the role of chain interdiffusion through the particle interface from that of cocrystallization in the mechanism of particle welding. It turned out that an efficient welding occurred within a very short time scale. The very weak influence of sintering time compared to that of sintering temperature gave evidence that chain interdiffusion was not governed by a reptation mechanism. The entropy-driven melting explosion of the “non-equilibrium” crystals in the nascent powder is suggested to be the main mechanism of the fast chain reentanglement and subsequent particle welding within a time scale much shorter than the reptation time. Cocrystallization is so much efficient in the interface consolidation in the solid state that it significantly hides the temperature-governed kinetics.

Immune heparin-induced thrombocytopenia (HIT) is a potentially serious complication of heparin therapy and is associated with antibodies directed against a complex of platelet factor 4 (PF4) and heparin. Early diagnosis of HIT is important to reduce morbidity and mortality. I developed an enzyme immunoassay that detects the binding of HIT IgG to PF4-heparin in the fluid phase. This required techniques to purify and biotinylate PF4. The fluid phase assay produces consistently low background and can detect low levels of anti-PF4-heparin. It is suited to testing alternative anticoagulants because, unlike in an ELISA, a clearly defined amount of antigen is available for antibody binding. I was able to detect anti-PF4-heparin IgG in 93% of HIT patients. I also investigated cross-reactivity of anti-PF4-heparin antibodies with PF4 complexed to alternative heparin-like anticoagulants. Low molecular weight heparins cross-reacted with 88% of the sera from HIT patients while half of the HIT sera weakly cross-reacted with PF4-danaparoid (Orgaran). The thrombocytopenia and thrombosis of most of these patients resolved during danaparoid therapy, indicating that detection of low affinity antibodies to PF4-danaparoid by immunoassay may not be an absolute contraindication for danaparoid administration. While HIT patients possess antibodies to PF4-heparin, I observed that HIT antibodies will also bind to PF4 alone adsorbed on polystyrene ELISA wells but not to soluble PF4 in the absence of heparin. Having developed a technique to affinity-purify anti-PF4-heparin HIT IgG, I provide the first estimates of the avidity of HIT IgG. HIT IgG displayed relatively high functional affinity for both PF4-heparin (Kd=7-30nM) and polystyrene adsorbed PF4 alone (Kd=20-70nM). Furthermore, agarose beads coated with PF4 alone were almost as effective as beads coated with PF4 plus heparin in depleting HIT plasmas of anti-PF4-heparin antibodies. I conclude that the HIT antibodies which bind to polystyrene adsorbed PF4 without heparin are largely the same IgG molecules that bind PF4-heparin and thus most HIT antibodies bind epitope(s) on PF4 and not epitope(s) formed by part of a PF4 molecule and part of a heparin molecule. Binding of PF4 to heparin (optimal) or polystyrene/agarose (sub-optimal) promotes recognition of this epitope. Under conditions that are more physiological and sensitive than previous studies, I observed that affinity-purified HIT IgG will cause platelet aggregation upon the addition of heparin. Platelets activated with HIT IgG increased their release and surface expression of PF4. I quantitated the binding of affinity-purified HIT 125I-IgG to platelets as they activate in a plasma milieu. Binding of the HIT IgG was dependent upon heparin and some degree of platelet activation. Blocking the platelet Fc??? receptor-II with the monoclonal antibody IV.3 did not prevent HIT IgG binding to activated platelets. I conclude that anti-PF4-heparin IgG is the only component specific to HIT plasma that is required to induce platelet aggregation. The Fab region of HIT IgG binds to PF4-heparin that is on the surface of activated platelets. I propose that only then does the Fc portion of the bound IgG activate other platelets via the Fc receptor. My data support a dynamic model of platelet activation where released PF4 enhances further antibody binding and more release.

Adiponectin is an adipose-derived protein (adipocytokine) that is secreted by adipose tissue. It has insulin-sensitizing, anti-inflammatory and cardio-protective properties, and is thought to be protective against obesity-related diseases such as type 2 diabetes. Humans and cats are two species that commonly develop type 2 diabetes associated with insulin resistance, impaired beta cell function and spontaneous islet amyloid deposition. The domestic cat (Felis catus) has recently been proposed as an animal model for human type 2 diabetes. However, little is known about the physiology of adiponectin in cats. Therefore, we set out to investigate the association of adiponectin profiles with dietary carbohydrate intake, feeding, body weight, fat mass, and insulin sensitivity in healthy young adult cats (n=32; 2-4 years old; gender ratio 1:1; body condition 4-5/9). Cats were fed a moderate carbohydrate diet (37% ME) at maintenance energy requirements for four weeks. Cats were then assigned to either receive a low (19% ME) or high (52% ME) carbohydrate diet and fed at maintenance energy requirements for another four weeks, followed by ad-libitum feeding for eight weeks to facilitate weight gain. Adiponectin profiles including total circulating adiponectin and its distribution [low molecular weight (LMW) and high molecular weight (HMW) adiponectin], and proportion of adiponectin that is HMW (SA) were measured by ELISA and velocity sedimentation using sucrose gradients, followed by Western blotting, respectively. We demonstrated inter-animal variation in total adiponectin concentration at baseline (0.6 to 15.0 g/mL), with the adiponectin present in both LMW and HMW forms. Feeding with a high carbohydrate diet for four weeks at maintenance energy requirements resulted in increased total adiponectin concentration, which was associated with an increased concentration of LMW adiponectin. In contrast, feeding with a low carbohydrate diet for four weeks at maintenance energy requirements resulted in increased concentration of HMW adiponectin, decreased LMW adiponectin concentration, and increased SA, without a change in total adiponectin concentration. In cats fed the high carbohydrate diet, total adiponectin and HMW adiponectin concentrations become lower at six hours after feeding, as compared to the fasting concentrations. This phenomenon was not observed in cats fed a low carbohydrate diet, indicating a diet-dependent postprandial effect. There was no effect of gender on any of the adiponectin profiles in cats. Unlike other studies in humans and mice in which adiponectin concentrations decreased as fat mass increased, our data indicate that a moderate weight gain achieved by ad libitum feeding of a low carbohydrate diet for eight weeks correlated with increased adiponectin concentrations. Total adiponectin concentration (mirrored by HMW adiponectin) was positively correlated with body weight gain and fat mass gain (but not absolute fat mass) in our overweight cats. Furthermore, the fat mass-related increases in plasma adiponectin over eight weeks correlated with insulin sensitivity (higher adiponectin concentration corresponded to greater insulin sensitivity in overweight cats). These data hint at the possibility that in overweight animals, adiponectin is similar to other adipokines that rise concomitantly with increased of moderate fat mass gain and thus increases insulin sensitivity. Overall, the knowledge in this study therefore provides useful information to veterinarians and cat food manufacturers, and forms a foundation for future studies to extend our knowledge of adiponectin in cats. Data gathered in cats may also be applicable to humans and could therefore inform research using cats as an animal model of human obesity and type 2 diabetes.

No description available.

Externally initiated o-tolyl initiated poly(3-hexylthiophene) (P3HT) was synthesized according to Grignard metathesis polymerization at varying chain length to compare number average molecular weights (Mn) obtained by gel permeation chromatography (GPC) and 1H NMR end group analysis. The extent of overestimation by GPC (1.3) was determined to be lower than previously reported for low Mn polymers. However, an apparent GPC quantification limit was observed as NMR Mn correlated well to predicted results. Static light scattering studies on high Mn polymers provided evidence that the true molecular weight was more similar to GPC-derived Mn. Despite nearly 100% external initiation efficiency, at a certain Mn limit new uninitiated chains may be synthesized. It is suggested that the synthesis of externally initiated P3HT should be limited to Mn below 40 kDa to ensure fully externally initiated chains. A proposal for the synthesis of externally initiated macrocyclic P3HT will also be discussed.