In this study, the unsteady velocity function of the ions and electrons in the collisional presheath and collisionless sheath of a plasma near a completely absorbing wall are determined from a kinetic analysis. The collisions in the presheath are modeled by a relaxtion time approximation (namely BGK model¡ABhatnagar-Gross-Krook ). The model and analysis from Emmert et al. are used to find the variation in electrostatic potential with position. Distribution functions of the ions and electrons in a collisionless presheath and sheath can be exactly obtained. Velocities of the ions in the presheath and sheath are highly non-Maxwell-Boltzmann distributions. The electrons in the presheath are close to Maxwell-Boltzmann distributions, but those in the sheath are non-Maxwell-Boltzmann distributions. The computed distribution functions for a completely absorbing surface agree with theoretical results provided in the literature.

The underlying idea of this thesis is that the surface chemical and morphological nature of bacterial strains uniquely differentiates one from another and hence can be used as the basis for their identification and control. It follows that their interactions with an artificial substratum uniquely characterize them. In principle, potentially it is easier and faster to evaluate the interfacial energy between a bacterium and a substratum than to characterize its genome or determine molecular biomarkers characteristic of the strain, hence validation of this thesis opens the way to rapid screening and diagnosis. Auxiliary to this main idea, an advanced metrology for evaluating the interfacial energies has been developed, exploiting the power of kinetic analysis.

The research described in this thesis focuses on the catalytic acylative kinetic resolution (KR) of aromatic secondary alcohols, using a planar-chiral 4-(dimethylamino)pyridine (DMAP) organocatalyst. In the first part of this thesis, the substrate scope of the above mentioned process was expanded to aromatic secondary alcohols that contain an extra functional group in the alkyl moiety, such as 1,2-azido alcohols, 2-hydroxy-2-aryl-ethylphosphonates and 2-hydroxy-2-aryl esters. Thus, the preparation of highly functionalized compounds in their enantiomerically pure form with excellent enantiomeric excess (up to 99% ee) was achieved. Furthermore, the synthetic applicability of this methodology was illustrated through the synthesis of two high value compounds, (R)-Pronethalol and (S)-3-hydroxy-N-methyl-3-phenylpropanamide, which is an immediate precursor of bioactive molecules such as (S)-Fluoxetine. The second part of this thesis deals with the mechanistic study of the acylative KR catalyzed by the planar-chiral DMAP derivative. Reaction Progress Kinetic Analysis methodology was used in the investigation of the reaction mechanism, probing that no notable product inhibition or decomposition of the catalyst occurs in the studied system. The reaction rate showed fractional order dependence on the concentration of both reactants. Furthermore, NMR spectroscopy was utilized to study the equilibrium between the different catalyst states, which explains the measured kinetics of the reaction.

A displasia coxofemoral (DCF) é uma doença poligênica, hereditária que acomete várias espécies e é influenciada por diversos fatores durante o desenvolvimento causando incongruência articular. É uma das afecções ortopédicas mais comuns em cães e possui alta incidência em animais da raça Pastor Alemão. O objetivo desse estudo foi correlacionar o grau de severidade da DCF com a locomoção dos cães através da análise cinética pelo sistema de baropodometria (Tekscan®) que propicia de modo quantitativo os valores das forças verticais de reação ao solo verificando assim alterações no apoio de cães displásicos durante a locomoção. Foram formados 5 grupos de acordo com a classificação de DCF segundo as categorias A, B, C, D e E com 8 pastores alemães em cada. Os animais foram examinados para controle e descrição dos sinais apresentados, bem como realizaram o teste de análise cinética do qual foi retirado 5 passagens válidas sobre a plataforma múltipla para comparação entre as forças de reação ao solo (FRS). Na análise cinética foram avaliados: - pico de força vertical (PFV), impulso vertical (IV) e tempo de apoio (TA) com a velocidade constante entre 1,3 a 1,6 m/s. Além da metodologia convencional foi realizada a análise de cada região de apoio, a fim de verificar a distribuição das FRS nos coxins e dígitos. Dos resultados obtidos nota-se uma tendência a diminuição progressiva do PFV nos membros pélvicos (MPs) a partir do grupo de cães com displasia leve (C) e o impulso se apresentou diminuído nos cães displásicos sem qualquer correlação com a severidade da doença. Nenhuma compensação relevante foi encontrada nos membros torácicos (MTs) e não houve diferença entre o TA em cães displásicos. A simetria entre o lado direito e esquerdo foi constatada em todos os grupos pela análise convencional. A nova metodologia permitiu a descrição detalhada do padrão da curva de força em formato de M realizada pelo coxim no inicio do apoio e pelos dígitos em um segundo momento. Entretanto dada a variabilidade e assimetria do apoio nessas regiões pode-se inferir que o coxim dos MTs têm maior porcentagem de apoio em relação aos dos MPs e essa distribuição não é afetada de modo regular na DCF. Os sinais clínicos apresentados ao exame físico como a dor, claudicação, atrofia muscular e diminuição de amplitude articular, corroboram com a diminuição do apoio em cães displásicos. Conclui-se que de acordo com o grau de severidade da DCF os animais têm uma tendência a apoiarem menos nos MPs, entretanto deve-se levar em conta a condição individual de cada animal, pois há cães displásicos que possuem o mesmo padrão de apoio de cães livres de DCF. / Hip dysplasia (HD) is a polygenic disease, inherited that affects many species and is influenced by several factors during development causing joint incongruity. It is one of the most common orthopedic disorders in dogs and has a high incidence in German shepherd dogs. The objective of this study was to correlate the degree of severity of the HD with the locomotion of dogs by kinetic analysis trough the pressure walkway system (Tekscan®) that provides quantitative values of vertical ground reaction forces (GRF) to the changes in the support of dysplastic dogs during locomotion. Five groups were performed according to HD´s classification in the categories A, B, C, D and E in German shepherd dogs total of 8 animals in each group. Dogs were examined and kinetic analysis was performed with 5 valid passages on the multiple platforms were used for comparison each groups. In kinetic analysis was assessed the peak vertical force (PVF), vertical impulse (VI), and stance phase (SF) with a constant speed between 1.3 to 1.6m/s. Besides conventional methodology the analysis of support checking the distribution of GRF in the pad and digits in each region were innovative. Results had a tendency to decrease progressively the PVF in the hindlimbs (HL) from group C (mild dysplasia) and VI is decreased in dysplastic dogs without any correlation with the severity of disease. Relevant compensation was not found in the forelimbs (FL) and even in dysplastic dogs there were no difference between the SF. Symmetry between the right and left side was found in all groups by conventional analyze. The new methodology has allowed a detailed description of the standard curve of force in M-shaped held by the support pad at the beginning and the digits in a second time. However given the variability and asymmetry of support in these areas we can only assert that the FL pads have a higher percentage of support from HL and this distribution is not affected on a regular basis in the HD. The clinical signs presented by physical examination like pain, lameness, muscle atrophy and articulate amplitude decreased, corroborated with the support decrease in dysplastic dogs. We conclude that according to the severity HD degree animals have tendencies to support less at the HL. However it should be consider the individual response because there are dysplastic dogs that have the same pattern of support that dogs free of HD.

A esclerose múltipla é a principal doença desmielinizante do sistema nervoso central (SNC). É considerada a principal causa de incapacidade neurológica em adultos jovens. O comprometimento cognitivo é muito comum nessa doença, envolvendo o aprendizado, a memória e a organização cortical do movimento, funções vitais que são reguladas pelo sistema colinérgico. O modelo de desmielinização tóxica induzida pelo brometo de etídio (BE) foi utilizado neste estudo, para avaliar a atividade da enzima acetilcolinesterase (AChE) no estriado (ST), hipocampo (HP), córtex cerebral (CC), hipotálamo (HY) e ponte (PN) associado ao tratamento com interferon beta (IFN-b), ciclosporina A (CsA), vitamina E (vit E) e ebselen (Ebs). Além disso, também foi investigado o efeito in vitro do BE na atividade da AChE, juntamente com os parâmetros cinéticos dessa enzima no ST, HP, CC e CB de ratos adultos. Os resultados demonstraram que o BE inibiu significativamente a atividade da AChE no ST, HP, CC e CB nas concentrações de 0,00625, 0,0125, 0,025, 0,05 e 0,1mM e a análise dos dados cinéticos mostraram uma inibição do tipo incompetitiva no ST, HP e CC, enquanto no CB a inibição foi do tipo mista. No estudo in vivo, foi observado uma inibição na atividade da AChE no CC, ST, HP, HY, PN e CB nos diferentes períodos avaliados pós-injeção do BE (3, 7, 15, 21 e 30 dias). Quando ratos desmielinizados com BE foram tratados com IFN-b e CsA, não houve alteração na atividade dessa enzima. Por outro lado, o tratamento com Vit E e Ebs foram capazes de aumentar a atividade da AChE no ST, CC e HP. Estudos imuno-histoquímicos demonstraram que nos ratos tratados com Vit E e Ebs as lesões induzidas pelo BE foram menores, sugerindo que estes compostos interferem no desenvolvimento de lesões desmielinizantes. Foi também avaliado o efeito per se do IFN-b, da CsA, da Vit E e do Ebs na atividade da AChE, os quais demonstraram um efeito inibitório sobre a atividade dessa enzima. Em plaquetas de ratos desmielinizados, foi observado uma diminuição na atividade da NTPDase e o tratamento com a Vit E e o Ebs modularam a hidrólise dos nucleotídeos de adenina. O presente trabalho demonstrou que o BE é um potente inibidor da atividade da AChE in vitro e os resultados in vivo demonstraram que a atividade dessa enzima está alterada após um evento de desmielinização tóxica no SNC. Os resultados deste estudo ajudaram a confirmar que drogas utilizadas no tratamento de pacientes com esclerose múltipla tais como o IFN-b e a CsA causam efeitos na atividade da AChE. A Vit E e o Ebs, além de demonstrarem uma interação com a neurotransmissão colinérgica, também modularam a hidrólise dos nucleotídeos de adenina em plaquetas de ratos, contribuindo no controle da coagulação plaquetária em processos desmielinizantes. Neste contexto, sugere-se que o IFN-b, a CsA, a vitamina E e o ebselen podem ser investigados em estudos futuros com a intenção de encontrar uma melhor terapia para beneficiar pacientes com patologias desmielinizantes. / Multiple sclerosis is the main demyelinating disease of the central nervous system (CNS). It is the most common cause of neurological disability among young adults. The cognitive impairment is very commum in this illness, involving learning, memory and cortical organization of the movement, vital functions regulated by the cholinergic system. The model of toxic demyelination induced by ethidium bromide (EB) was used to evaluate brain acetylcholinesterase (AChE) activity in the striatum (ST), hippocampus (HP), cerebral cortex (CC), cerebellum (CB), hypothalamus (HY) and pons (PN), associated with treatment with interferon beta (IFN-b), ciclosporine A (CsA), vitamin E (Vit E) and ebselen (Ebs). In addition, the per se effect of EB on AChE activity was studied in vitro together with the kinetic parameters of this enzyme in the ST, HP, CC and CB of adult rats. The results showed that EB in vitro significantly inhibited AChE activity in the ST, HP, CC and CB at concentrations of 0.00625, 0.0125, 0.025, 0.05 and 0.1mM. The kinetic analysis demonstrated an uncompetitive inhibition in the ST, HP and CC, whereas in the CB the inhibition type was mixed. In relation to the in vivo results, AChE activity was inhibited after demyelination by EB in the CC, ST, HP, HY, PN and CB at the post-injection points of time evaluated (3-7-15-21 and 30 days). When demyelinated rats were submitted to the treatment with IFN-b and CsA, the results demonstrated that these compounds did not alter AChE activity. However, Vit E and Ebs were able to increase AChE activity in the ST, CC and HP. In addition, immunohistochemistry studies demonstrated that in Vit E and Ebs treated rats, the lesions induced by EB were smaller suggesting that these compounds somehow interfered in the development of the lesions. The per se effect of IFN-b, CsA, Vit E and Ebs were also evaluated, demonstrating that these compounds have an inhibitory effect on AChE activity. Platelets of the demyelinated rats demonstrated a reduction in NTPDase activity and the treatments with Ebs and Vit E modulated adenine nucleotide hydrolysis. The present investigation demonstrated that EB is a strong inhibitor of AChE activity in vitro and the results in vivo showed that the activity of this enzyme is altered after an event of toxic demyelination in the CNS. The results this study help the confirm that drugs used in the treatment of the patients with multiple sclerosis such as IFN-b and CsA cause effects in the AChE activity. The Vit E and Ebs besides of interaction with the cholinergic neurotransmission also modulated adenine nucleotide hydrolysis in platelets of the rats, contributing to the control of the platelet coagulant status in the demyelinating process. In this context, we can suggest that IFN-b, CsA, Vit E and Ebs may be investigated in future studies with the intention of finding a better therapy for to improve patients with demyelinating pathologies.

A hérnia perineal é uma das afecções cirúrgicas frequentemente observadas na rotina da clínica cirúrgica de pequenos animais e acometem na sua maioria, cães machos, não castrados e acima de cinco anos. Apresenta elevado índice de recidivas e complicações pós-cirúrgicas, e devido a este fato, muitas técnicas foram preconizadas e utilizadas para a sua correção. Os objetivos do presente estudo foram avaliar a locomoção cinética dos cães com hérnia perineal bilateral, submetidos à técnica de transposição do músculo semitendinoso antes e após a sua transposição; verificar a capacidade de adaptação do membro pélvico operado, após a transposição do semitendinoso, até 90 dias de pós-operatório e analisar a viabilidade dessa técnica de reparação em casos de hérnia perineal bilateral. Foram operados onze cães com diagnostico de hérnia perineal bilateral, no Serviço de Cirurgia de Pequenos Animais junto ao Hospital Veterinário da Faculdade de Medicina Veterinária da Universidade de São Paulo (HOVET-FMVZ / USP). Todos foram submetidos à técnica de transposição do músculo e avaliados com exames baropodométricos antes e após a cirurgia, nos períodos de 30, 60 e 90 dias pós-operatório. As variáveis pico de força vertical (PFV) e impulso vertical (IV) foram utilizadas como parâmetros para a análise de mudanças na locomoção. A PFV e IV não mostraram diferença estatística (p> 0,05) entre os membros operados e não operados, respectivamente (18,62 0 &plusmn 4,93 e 18,51 &plusmn 3,75), indicando que não houve alteração na locomoção dos cães após a transposição do músculo semitendinoso. A diferença no comportamento dessas variáveis no período pré-operatório nos permitiu aferir que o desconforto provocado pela hérnia perineal possa interferir na locomoção do animal gerando assimetria, considerando que após o procedimento operatório a simetria da locomoção apresentou valores mais compatíveis dentro do normal. As diferenças em PFV e IV, embora não significativas, nos dá uma idéia da recuperação desses cães e sugere que a transposição não afeta a função locomotora do membro operado. / A perineal hernia is a surgical lesion frequently observed in surgical clinic for small animals, affecting mainly dogs neutered over five years. Has a high recurrence rate and postoperative complications, and due to this fact, many techniques have been proposed and used for its correction. The objectives of this study were to evaluate the kinetic movement of dogs with bilateral perineal hernia, submitted to the technique of transposition of the semitendinosus muscle before and after its implementation and verify the adaptability of the pelvic limb surgery, after transposition of the semitendinosus 90 days of postoperatively and analyze the feasibility of this technique of repair in cases of bilateral perineal hernia. Eleven dogs were operated with diagnosis of bilateral perineal hernia, on the Surgery Service of the animal small of the Veterinary Hospital of the Faculty of Veterinary Medicine, University of São Paulo (HOVET-FMVZ / USP). All patients underwent the technique of muscle transposition and evaluated baropodometric examinations before and after surgery, in periods of 30, 60 and 90 days postoperatively. The variables peak vertical force (PFV) and vertical impulse (VI) were used as parameters for the analysis of changes in locomotion. The PFV and IV showed no statistical difference (p> 0.05) between the operated and non operated limbs, respectively (18.62 &plusmn 4.93 and 18.51 &plusmn 3.75), indicating that there was no change in locomotion dogs after the transposition of the semitendinosus muscle. The difference in behavior of these variables in the preoperative period allowed us to infer that the discomfort caused by perineal hernia can interfere with the locomotion of the asymmetry animal generating, whereas after the operative procedure, the symmetry of locomotion showed more next values of the normal. The difference in PFV and IV, although not significant, gives us an idea of the recovery of these dogs and suggests that the transposition does not affect the motor function of the limb.

Cellular adhesion research has recently focused on the small scale at the level of individual receptor-ligand bonds. This trend in research is primarily due to experimental advances which allow such individual bond force measurements. Here, one of these techniques, micromanipulation, has been extended to not only determine the bond force of individual receptor-ligand pairs, but also the intrinsic kinetic rates of the interaction. Using transmembrane (TM ) Fc gamma receptor III (CD16a-TM) and human IgG (hIgG), the dependence of adhesion probability on receptor-ligand expression densities, contract duration and contact area was quantitated. A probabilistic based theoretical formulation was developed and validated that relates the intrinsic molecular kinetic rates of the receptorVligand interaction to the experimentally determined adhesion probability. This theoretical formulation describing individual receptor-ligand kinetics has also allowed direct evaluation of existing biophysical bond strength/kinetics paradigms at the extreme condition of single bonds. A force-displacement model was also developed to quantitate the force exerted on the RBC membrane transducer during the micropipette retraction process and found to be in agreement with previous work. In addition to CD16a-TM, the kinetic rates of CD16a anchored via a glycosyl phosphatidylinositol (GPI) moiety (CD16a-GPI) and the two alleles of CD16b (NA1 and NA2) were determined for human, rabbit, and mouse IgG species. The binding affinity of these CD16 interactions to soluble IgG was also measured by traditional bulk chemistry approaches and compared to those measured via the micromanipulation protocol in which the IgG ligand is membrane bound in the solid phase. These data suggest that the membrane anchor itself can alter CD16 binding properties. This represents the first reported effect of the anchor on an intrinsic receptor property, its kinetic rates and binding affinity. This thesis presents two specific aims or goals. These goals were achieved and reported in this thesis. During the course of this research, I also explored other directions and gathered initial data. These directions were further explored by other researchers but the initial data is also presented here.

In recent years, the application of thermal analysis to study the combustion and pyrolysis behavior of fossil fuels has gained a wide acceptance because of its significance for industry and economy. In this thesis, the thermal and kinetic analysis of different origin crude oil samples are performed by two well-known thermal analysis techniques: Differential Scanning Calorimetry (DSC) and Thermogravimetry (TG/DTG). The investigation of combustion and pyrolysis behaviors, kinetic analysis of oil samples and the determination of heating rate effect are the main objectives of this study. Six different crude oils from the Southeastern region of Turkey are analyzed throughout the study. All experiments are performed at different heating rates (5, 10 and 15&ordm / C/min) and air is used for combustion and nitrogen for pyrolysis experiments. In combustion experiments, TGA and DSC techniques indicate that the combustion process of crude oils studied is composed of two main reaction regions. These are low-temperature (LTO) and high-temperature oxidation (HTO) regions. In LTO, huge mass loss occurs (from 69 to 87 %) due to high amount of free moisture and volatile hydrocarbons contained in oil samples. Combustion reactions continue up to 900 K. On DSC curves, two exothermic regions of oxidation regimes are detected. Comparing TG/DTG and DSC curves, it can be understood that the mass loss under combustion is accompanied by exothermic peaks because of the oxidative degradation of crude oil components. As in combustion, two distinct reaction regions are revealed under pyrolysis for all samples. The first region indicates distillation and the second one is due to thermal cracking reactions occur at high temperatures and completed up to 840 K. As expected, lighter crude oils have relatively higher amounts of mass loss in distillation region as compared to heavier ones. Besides, residue amount and burn-out temperatures are higher for heavier oils with higher asphaltene content in cracking region. DSC curves for both reactions show endothermic effects. In combustion and pyrolysis experiments, it is noticed that higher heating rates are resulted in higher reaction regions. Distinguishing peaks of samples shift to higher temperatures with an increase in heating rate. Heat of reaction amount under DSC curves is related to asphaltene content and &amp / #730 / API gravity of crude oils. It is deduced that, when &amp / #730 / API gravity of crude oils decreases, the heat value of this reaction increases. The kinetic parameters are evaluated by different kinetic models and mean activation energies (Em) of samples are obtained. At the end, a correlation is established between Em and &amp / #730 / API gravity of oil samples. It is concluded that heavier oils have higher activation energy and Arrhenius constant values for each reaction region. Besides, it is proved that the activation energy is mostly insensitive to the heating rate.

In this thesis, four different crude oil samples and their saturate, aromatic and resin fractions were analyzed by two different thermoanalytical methods, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The experiments were performed at three different heating rates (5, 10 and 15 &deg / C/min) under air atmosphere. Same gas flow rate and same pressure were applied to all samples. The aim is to determine the kinetic analysis and combustion behavior of crude oils and their fractions and also determining the effect of heating rate on all samples. For all samples two main reaction regions were observed in thermogravimetry (TG), differential thermogravimetry (DTG) and DSC curves due to the oxidative degradation of crude oil components. It was deduced that the free moisture, volatile hydrocarbons were evaporated from the crude oils, light hydrocarbons were burned and fuel was formed in the first reaction region. The second reaction region was the main combustion region where the fuel was burned. From the TGA curves, it was detected that the heavier fraction, resins, lost considerable amounts of their initial mass, approximately 35%, while saturates lost only approximately 3% of their initial mass in the second reaction region. DSC curves of the samples were also examined and observed that as the sample got heavier, the heat of the reaction increased. Saturates, lightest part of the crude oil fractions, gave minimum heat of reaction. As the heating rate increased, shift of peak temperatures to high values and higher reaction regions were observed. The kinetic analysis of crude oils and their fractions were also performed using different kinetic methods. Activation energies (E), mean activation energies (Emean) and Arrhenius constants were found for crude oils and fractions. It was deduced that the resins gave the highest activation energy and Arrhenius constant for both reaction regions. Moreover, it was encountered that heating rate has no effect on activation energies.

In this thesis, a new software, THERA-Kinetics was developed for the evaluation of kinetic parameters using non-isothermal data. Different computational methods, available in the software, were applied to a set of experimental and simulated data distributed in the ICTAC (International Confederation for Thermal Analysis and Calorimetry) Kinetics Project. The reliability of the software was verified by comparing the kinetic results, which were in good agreement, with those obtained by the participants of the ICTAC Kinetics Project. It was also within the scope of this study to examine the combustion characteristics and kinetics of three same origin coal samples. A series of thermogravimetry (TG) and differential scanning calorimetry (DSC) measurements were carried out in non-isothermal conditions at heating rates of 5, 10 and 15 K/min. Reaction regions, peak and burn-out temperatures, weight loss percentages and heat of reactions of the samples were determined for each heating rate from TG and DSC curves. A variety of computational methods, available in the software developed, were applied to experimental data for the evaluation of the kinetic parameters of the coal samples. It was observed that there was no general trend in the activation energy values from the point of heating rate.