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Hyder, A. H. M. Golam. "Sorption Characteristics of Hexavalent Chromium [Cr(VI)] onto Bone Char and Bio-char." Thesis, KTH, Mark- och vattenteknik (flyttat 20130630), 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-171833.
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The sorption characteristics of hexavalent chromium [Cr(VI)] onto bone char and bio-char were evaluated as a function of pH, initial Cr(VI) concentration, and dosages of bone char and bio-char. Batch tests were conducted by using synthetic wastewater in this study. The effects of various initial Cr(VI) concentrations between 5 mg/L and 1000 mg/L were evaluated using bone char as a sorbent. A Cr(VI) removal efficiency of 100 % was achieved at pH 1 with 2 g of bone char in 50 mL of solution at 3 hours of reaction time using initial Cr(VI) concentration of 10 mg/L. About 100 % of Cr(VI) was removed at pH 2 with initial Cr(VI) concentrations of 10 mg/L using 4 g of bio-char in 200 mL of solution at 5 hours of reaction time. The initial Cr(VI) concentrations were varied between 10 mg/L and 500 mg/L when bio-char was used as the sorbent. The maximum sorption capacities of bone char and bio-char were determined to 6.46 mg Cr(VI)/g, and 1.717 mg Cr(VI)/g, respectively. Equilibrium, kinetics, and isotherms of the sorption process were also investigated. The sorption kinetics of Cr(VI) onto bone char and bio-char followed the second order kinetic model suggesting that the sorption reaction rate depends on two parameters, which might be the sorbate concentration and sorbent dosage. The Langmuir isotherm model was the best one for the description of sorption of Cr(VI) onto bone char and bio-char.
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Conradi, Carsten. "Multistationarity in (bio)chemical reaction networks with mass action kinetics model discrimination, robustness and beyond." Aachen Shaker, 2008. http://d-nb.info/989018172/04.
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Gu, Xiangyu. "Molten-salt Catalytic Pyrolysis (MSCP): A Single-pot Process for Fuels from Biomass." Digital WPI, 2015. https://digitalcommons.wpi.edu/etd-theses/504.
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A novel process for single-pot conversion of biomass to biofuels was developed called the molten salt catalytic pyrolysis (MSCP) method. The proposed single-pot MSCP process proved to be an inherently more efficient and cost-effective methodology for converting lignocellulosic biomass. In this study, several parameters that affect yield of bio-oil were investigated including carrier gas flow rate; pyrolysis temperature; feed particle size; varying types of molten salt and catalysts. Use of molten salt as the reaction medium offered higher liquid yield and experiments containing ZnCl2 showed higher yield than other chloride salts. The highest yield of bio-oil was up to 66% obtained in a ZnCl2-KCl-LiCl ternary molten salt system compared with 32.2% at the same condition without molten salts. In addition, the effect of molten salt on the composition of bio-oil was also studied. It was observed that molten salt narrowed the product distribution of bio-oil with furfural and acetic acid as the only two main components in the liquid with the exception of water. Finally, a thermogravimetric kinetic study on the pyrolysis of biomass in MSCP was conducted.
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Conradi, Carsten [Verfasser]. "Multistationarity in (bio)chemical reaction networks with mass action kinetics: model discrimination, robustness and beyond / Carsten Conradi." Aachen : Shaker, 2008. http://d-nb.info/1162791837/34.
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Williams, Alexander W. "An investigation of the kinetics for the fast pyrolysis of loblolly pine woody biomass." Diss., Georgia Institute of Technology, 2011. http://hdl.handle.net/1853/41093.
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In the search for fossil fuel alternatives the production of bio-oil through the pyrolysis of biomass is one method which has shown evidence of scalability, meaning that the technology could be scaled up for the processing of biomass on the order of tons per day. Pyrolysis is the thermal degradation of compounds in the absence of oxygen. Of particular interest is the pyrolysis of sustainable energy crops such as Loblolly pine (Pinus taeda). The goal of this study is to develop a new method of characterizing the fast pyrolysis of biomass for the advancement of reactor design. The objectives are to determine bulk kinetic coefficients for the isothermal fast pyrolysis of biomass, evaluate the interchangeability of fast and slow pyrolysis kinetic parameters and compare generally accepted pyrolysis mechanisms derived from a common data set. A technical objective is to apply the most suitable derived kinetic parameters to model pyrolysis within a moving bed reactor.
A novel fast pyrolysis micro-reactor is presented along with its design and development process. The micro-reactor allows for the control over both temperature and residence time of the reacting biomass. This system provides the experimental data for the characterization of biomass pyrolysis kinetic parameters. Thermal validation tests are presented and experimental yield results are given for raw Loblolly Pine, Avicel cellulose and Beechwood xylan for the derivation of kinetic descriptors. Cellulose and xylan results show good agreement with literature when the proper experimental conditions are met and whole wood pyrolysis results clearly demonstrate the dissimilarity between fast and slow pyrolysis apparent kinetic rates.
The experimental results are then used to evaluate five different pyrolysis kinetic model configurations: single component global pyrolysis, two component global pyrolysis, product based pyrolysis, pseudo-component based pyrolysis and pseudo-component pyrolysis with an intermediate solid compound. Pseudo-component models are of particular interest because they may provide a generalized model, parameterized by the fractional composition of cellulose, hemicellulose and lignin in biomass species. Lignin pyrolysis yields are calculated to evaluate the suitability of a pseudo-component parallel non-competing superposition pyrolysis model. Lignin yields are estimated by taking the difference between whole wood pyrolysis and predicted cellulose and hemicellulose pyrolysis behaviors. The five models are then evaluated by comparison of predicted yields to the results for the pyrolysis of Scots pine (Pinus sylvestris) and Norway spruce (Picea abies). Model evaluations show that pseudo-component superposition is not suitable as a generic pyrolysis model for the fast pyrolysis of biomass observed using the micro-reactor. Further analytical evaluations indicate that the assumption of parallel non-competing reactions between pseudo-components is not valid. Among the other models investigated the intermediate solid compound model showed the best fit to the verification experimentation results followed closely by the two component global model.
Finally, the derived kinetic parameters are applied to the design of moving bed vacuum pyrolysis reactors which provide for the separation of heat and mass transfer pathways, resulting in the reduction of char entrainment and secondary reactions within collected bio-oils. Reaction kinetics and porous bed heat and mass transfer are accounted for within the bed model. Model development and predictive results are presented and sensitivity to activation energy variations investigated.
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Chen, Wei. "The force regulation on binding kinetics and conformations of integrin and selectins using a bio-membrane force probe." Diss., Georgia Institute of Technology, 2009. http://hdl.handle.net/1853/33814.
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Cell adhesion plays an important role in inflammation and immunological responses. Adhesion molecules (e.g., selectins and integrins) are key modulators in mediating these cellular responses, such as leukocyte trafficking under shear stress. In this thesis, we use a bio-membrane force probe (BFP) to study force regulation on kinetics and conformations of selectin and LFA-1 integrin. A new BFP was built up, and a new assay, using thermal fluctuation of the BFP, was developed and used to monitoring selectins and their ligands association and dissociations. The new BFP was also used to investigate the force and force history dependence of selectin-ligand interactions. We found tri-phasic transition of force-dependent off-rates and force-history dependence of selectin/ligaind interactions. The BFP was also used to characterize force-dependent lifetimes of the LFA-1-ICAM-1 interaction. We found that LFA-1/ICAM-1 bonds behaved as catch bond and that LFA-1-ICAM-1's catch bonds were abolished blocking the downward movement of αA domain α7 helix. Finally, the BFP was applied to dynamically probe the global conformational changes of LFA-1 and to characterize force-regulated transitions among different conformational states on a living cell. We observed dynamic transitions of LFA-1 between extended and bent conformations on living cells. The observed average distance change of LFA-1's extensions was about 18nm, while that of the bending was only about 14nm. We also found that forces could facilitate extension but they slow down the bending of LFA-1. The observed transition time of extension was less than 0.1s, while that of contraction was longer than 0.2s. Our observations here are the first in-situ evidence to demonstrate how integrins dynamically transit different conformations and how force regulates these transitions.
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Bakharieva, Ganna, Serhii Petrov, and Tetiana Falalieieva. "Development of the mathematical model of the kinetics of the stationary process of bio-cleaning with substratic inhibition." Thesis, Scientific Route OU, 2018. http://repository.kpi.kharkov.ua/handle/KhPI-Press/46262.
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A scientifically sound method for calculating the parameters of bio-cleaning should contain as a basic a reliable mathematical description of the stationary process. The results of stationary laboratory experiments are presented in the coordinates “specific rate of destruction V – concentration ρ”. Statistical processing proves the presence of substrate inhibition for both gaseous and soluble and dissolved harmful substances in water. For an analytical description of the dependence of the biooxidation rate on the concentration of contaminants, a phenomenological approach is applied, taking into account in a simple form two obvious phenomena: the contact of a microorganism with a substrate molecule and the inhibitory effect of the medium on it. The numerical values of empirical dependency coefficients for the studied processes are calculated. A differential equation is proposed at the macro level that describes the kinetics of biochemical destruction. The concept
of a macrokinetic mathematical model of bioremediation is defined as a system of two functions that quantitatively reflect the dependence of the specific oxidation rate of pollution on its concentration and concentration on time, as well as satisfying the relationship between the relationships of the same parameters in differential form. The dependence of concentration on time is defined both in the form of a numerical integration algorithm and in the form of an approximate formula. The adequacy and universality of the proposed model for the studied processes is proved. The advantage of the proposed model of substrate inhibition kinetics is the simplicity of the structure of the basic formula and the ease of determining empirical coefficients based on this. In addition to numerical integration for determining the time of destruction, an approximate analytical solution is found, which can be adequately used in the concentration range of the experimental study. Further research is aimed at developing methods for calculating non-stationary processes in biochemical purification plants of certain specific types.
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Bashir, Abdala A. "Bio-based Resins and Fillers for Use in Thermosetting Composites." University of Akron / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=akron1574463236644168.
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Pedrosa, Marcelo Mendes. "Bio-?leo e biog?s da degrada??o termoqu?mica de lodo de esgoto dom?stico em cilindro rotativo." Universidade Federal do Rio Grande do Norte, 2011. http://repositorio.ufrn.br:8080/jspui/handle/123456789/15915.
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Previous issue date: 2011-12-22The objective of this study was to produce biofuels (bio-oil and gas) from the thermal treatment of sewage sludge in rotating cylinder, aiming industrial applications. The biomass was characterized by immediate and instrumental analysis (elemental analysis, scanning electron microscopy - SEM, X-ray diffraction, infrared spectroscopy and ICP-OES). A kinetic study on non-stationary regime was done to calculate the activation energy by Thermal Gravimetric Analysis evaluating thermochemical and thermocatalytic process of sludge, the latter being in the presence of USY zeolite. As expected, the activation energy evaluated by the mathematical model "Model-free kinetics" applying techniques isoconversionais was lowest for the catalytic tests (57.9 to 108.9 kJ/mol in the range of biomass conversion of 40 to 80%). The pyrolytic plant at a laboratory scale reactor consists of a rotating cylinder whose length is 100 cm with capable of processing up to 1 kg biomass/h. In the process of pyrolysis thermochemical were studied following parameters: temperature of reaction (500 to 600 ? C), flow rate of carrier gas (50 to 200 mL/min), frequency of rotation of centrifugation for condensation of bio-oil (20 to 30 Hz) and flow of biomass (4 and 22 g/min). Products obtained during the process (pyrolytic liquid, coal and gas) were characterized by classical and instrumental analytical techniques. The maximum yield of liquid pyrolytic was approximately 10.5% obtained in the conditions of temperature of 500 ?C, centrifugation speed of 20 Hz, an inert gas flow of 200 mL/min and feeding of biomass 22 g/min. The highest yield obtained for the gas phase was 23.3% for the temperature of 600 ?C, flow rate of 200 mL/min inert, frequency of rotation of the column of vapor condensation 30 Hz and flow of biomass of 22 g/min. The non-oxygenated aliphatic hydrocarbons were found in greater proportion in the bio-oil (55%) followed by aliphatic oxygenated (27%). The bio-oil had the following characteristics: pH 6.81, density between 1.05 and 1.09 g/mL, viscosity between 2.5 and 3.1 cSt and highest heating value between 16.91 and 17.85 MJ/ kg. The main components in the gas phase were: H2, CO, CO2 and CH4. Hydrogen was the main constituent of the gas mixture, with a yield of about 46.2% for a temperature of 600 ? C. Among the hydrocarbons formed, methane was found in higher yield (16.6%) for the temperature 520 oC. The solid phase obtained showed a high ash content (70%) due to the abundant presence of metals in coal, in particular iron, which was also present in bio-oil with a rate of 0.068% in the test performed at a temperature of 500 oC.
O objetivo deste trabalho foi produzir biocombust?veis (bio-?leo e g?s), a partir do tratamento t?rmico do lodo de esgoto dom?stico em cilindro rotativo, visando aplica??o industrial. A biomassa foi caracterizada por an?lise imediata e instrumental (An?lise Elementar, Microsc?pica Eletr?nica de Varredura - MEV, Difra??o de Raios-X, Espectroscopia no Infravermelho, ICP-OES). Um estudo cin?tico, em regime n?o estacion?rio foi realizado para o c?lculo da energia de ativa??o por An?lise T?rmica Gravim?trica avaliando os processos termoqu?micos e termocatal?ticos do lodo, sendo este ?ltimo na presen?a da ze?lita USY. Como esperado, a energia de ativa??o avaliada pelo modelo matem?tico "Model-free kinetics" aplicando t?cnicas isoconversionais foi menor para os ensaios catal?ticos (57,9 108,9 kJ/mol, no intervalo de convers?es da biomassa de 40 ? 80%). A planta pirol?tica, em escala de laborat?rio ? constitu?da de um reator de cilindro rotativo cujo comprimento ? 100 cm, com capacidade de processar at? 1 Kg biomassa/h. No processo da pir?lise termoqu?mica foram estudados os seguintes par?metros: temperatura da rea??o (500 ? 600 ?C), vaz?o do g?s de arraste (50 ? 200 mL/min), freq??ncia de rota??o de centrifuga??o (20 ? 30 Hz) para condensa??o do bio-?leo e vaz?o m?ssica de biomassa (4 e 22 g/min). Os produtos obtidos durante o processo (l?quido pirol?tico, carv?o e g?s) foram caracterizados atrav?s de t?cnicas anal?ticas cl?ssicas e instrumentais. O rendimento m?ximo de l?quido pirol?tico foi da ordem de 10,5% obtido nas condi??es de temperatura de 500 ?C, rota??o da centrifuga??o de 20 Hz, vaz?o de g?s inerte de 200 mL/min e vaz?o m?ssica de biomassa 22 g/min. O maior rendimento obtido para a fase gasosa foi de 23,3 %, para a temperatura da rea??o de 600 oC, vaz?o de inerte 200 mL/min, freq??ncia de rota??o da coluna de condensa??o de vapores 30 Hz e vaz?o m?ssica de biomassa de 22 g/min. Os hidrocarbonetos alif?ticos n?o oxigenados foram encontrados em maior propor??o no bio-?leo (55%) seguido pelos compostos alif?ticos oxigenados (27%). O bio-?leo apresentou as seguintes caracter?sticas: pH 6,81, densidade entre 1,05 e 1,09 g/mL, viscosidade entre 2,5 e 3,1 cSt e poder calor?fico superior entre 16,91 e 17,85 MJ/kg. Os principais componentes obtidos na fase gasosa foram: H2, CO, CO2, CH4. O hidrog?nio foi o principal constituinte da mistura gasosa, com rendimento da ordem de 46,2 %, para a temperatura de 600 oC e, dentre os hidrocarbonetos formados, o metano foi encontrado em maior rendimento (16,6 %) para a temperatura 520 oC. A fase s?lida obtida apresentou elevado teor de cinzas (70%), devido ? presen?a abundante de metais no carv?o, em particular, o ferro, o qual esteve tamb?m presente no bio-?leo com um percentual de 0,068 % no ensaio realizado na temperatura de 500 oC
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DANTAS, FILHO Francisco Ferreira. "Estudo do bio-óleo e carvão obtido a partir do lodo de tratamento de esgoto sanitário por conversão à baixa temperatura." Universidade Federal de Campina Grande, 2013. http://dspace.sti.ufcg.edu.br:8080/jspui/handle/riufcg/1782.
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O presente trabalho discorre sobre uma alternativa para mitigar o problema do Lodo de Esgoto Sanitário – LES. Esse resíduo influencia negativamente de várias formas o meio ambiente, destacando-se a poluição das águas superficiais e subterrâneas. Teve como objetivo utilizar a biomassa presente no LES para a produção de combustíveis (Bio-óleo e Carvão). Tratou-se de um estudo experimental com a biomassa obtida na Estação Experimental de Tratamento Biológico de Esgotos Sanitários – EXTRABES, localizada na cidade de Campina Grande – PB. O experimento foi realizado em duas etapas: a primeira correspondente ao estudo termogravimétrico e cinético do LES; a segunda, a obtenção do bio-óleo e carvão oriundo da pirólise do LES, realizado no LABCON, instalado na Universidade Federal Fluminense – UFF. Os resultados obtidos do estudo termogravimétrico nas três razões de aquecimento 5,10 e 15ºC.min-1, constatam uma estabilidade térmica a 30ºC sobre atmosferas de ar sintético e N2. No estudo cinético determinaram-se os seguintes parâmetros: Energia de Ativação (Ea), Fator de frequência (A-1), Desvio padrão (sd) e o Coeficiente linear (r), que foram calculados por termogravimetria pelos métodos Coats-Redfern (CR); Madhusudanan (MD); Van Krevelen (VK) e Horowitz-Metzger (HM). Os espectros de FTIR da amostra do LES apresentaram bandas referentes à água, matéria orgânica e óxidos de silício. O bio-óleo foi obtido através do processo da conversão à baixa temperatura, em atmosfera de nitrogênio, atingindo 380°C com tempo de detenção de 2h. O proc esso de pirólise do LES resultou em 9% de bio-óleo, 57% de carvão e 34% de água de pirólise. Observou-se que o bio-óleo obtido é uma mistura complexa de hidrocarbonetos alifáticos, aromáticos, esteróides, compostos oxigenados e nitrogenados, que foi identificada pelas técnicas FTIR, RMN 1H, CG-EM. O carvão apresentou baixa área superficial, não sendo considerado potencialmente bom suporte catalítico, tanto pela metodologia de Langmuir, SLANG 0,748 m2.g-1 quanto por BET, SBET = 0,695m2.g-1. Os resultados confirmam que à Conversão à Baixa Temperatura é uma técnica promissora, tanto para o destino do LES, quanto para obtenção de biocombustíveis.
The present study discusses an alternative to mitigate Sewage Sludge – SS problem. This residue adversely affects the environment in various ways, highlighting pollution of surface and groundwater. It aimed to use the biomass present in the SS for fuel production (Biooil and coal). It was an experimental study with biomass obtained from the Estação Experimental de Tratamento Biológico de Esgotos Sanitários – EXTRABES, located in the city of Campina Grande – PB. The experiment was conducted in two stages: first corresponding to thermogravimetric and kinetic study of the SS; second, obtainment of biooil and coal originated from the pyrolysis of SS, conducted at LABCOM, installed at the Fluminense Federal University – FFU. The results obtained from the thermogravimetric study in the three heating rates 5, 10 and 15oC min-1, found a thermal stability at 30°C on atmospheres of synthetic air and N2. In the kinetic study the following parameters were determined: Activation Energy (Ea), frequency factor (A-1), standard deviation (sd) and linear coefficient (r), that were calculated by thermogravimetry by the Coats-Redern (CR); Madhusudanan (MD); Van Krevelen (VK) and Horowitz-Metzger (HM) methods. The FTIR spectrums from the SS sample presented bands related to water, organic matter and silicon oxides. The biooil was obtained through the conversion at low temperature process, in nitrogen atmosphere, reaching 380oC with holding time of 2h. The pyrolysis process of the SS resulted in 9% of biooil, 57% of coal and 34% of pyrolysis water. It was observed that the biooil obtained is a complex mixture of aliphatic hydrocarbons, aromatics, steroids, nitrogenous and oxygenated compounds, which was identified by the FTIR, RMN 1H, CG-EM techniques. The coal presented low superficial area, not being considered a potentially good catalytic support, by the Langmuir methodology, SLANG 0,748 m2.g-1 as well as the BET, SBET = 0,695m2.g-1. The results confirm that the Conversion at Low Temperature is a promising technique, for both the destination of the SS as well as for the obtainment of biofuels.
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Namysl, Sylvain. "Experimental study of the formation of pollutants during the combustion of bio-oil surrogate molecules." Electronic Thesis or Diss., Université de Lorraine, 2019. http://www.theses.fr/2019LORR0279.
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En 2016, les combustibles fossiles représentaient environ 80% de l'approvisionnement mondial total en énergie primaire. Cependant, cette ressource est limitée et a un impact énorme sur la pollution de l'environnement en raison de la production de gaz à effet de serre. C’est pourquoi le monde industriel et des transports s’intéressent aux biocarburants, en particulier aux bio-huiles, afin de réduire considérablement les émissions de gaz à effet de serre. Le projet IMPROOF est un projet financé par l'Union européenne dans le cadre du programme SPIRE. Son objectif est d'améliorer de 20% l'efficacité énergétique des fours de vapocraquage et, parallèlement, de réduire de 25% par tonne d'éthylène les émissions de polluants tels que les NOx ou les gaz à effet de serre. Cette thèse porte sur l'utilisation de combustibles de substitution, notamment de bio-huiles, pour le chauffage des fours de vapocraquage. Afin de mieux évaluer l'oxydation ou la pyrolyse de la bio-huile, une revue bibliographique des publications traitant de la composition des bio-huiles a été réalisée. Il ressort de cette revue que les bio-huiles peuvent être décrites comme un mélange composé de six principaux types de composés chimiques : les alcools, les aldéhydes, les acides carboxyliques, les furannes et leurs dérivés, les composés aromatiques oxygénés et les composés azotés organiques. Afin de compléter certaines lacunes relevées dans la littérature, le but de cette thèse était de produire un nouvel ensemble de données expérimentales pour certaines molécules appartenant aux cinq premières familles chimiques précédemment présentées. Un réacteur agité par jets a été choisi pour réaliser les expériences en raison de son homogénéité de concentration et de composition. Ce type de réacteur «idéal» convient en effet pour le développement de données fiables pour le développement et la validation de modèles cinétiques. Au cours de ce travail, huit combustibles ont été sélectionnés et étudiés : le n-butanol, le n-pentanol, le n-butanal, le n-pentanal, l’acide butanoïque, l’acide pentanoïque, le furane ainsi que le benzaldéhyde. Pour chacun de ces carburants, les résultats expérimentaux ont été utilisés pour développer et valider un modèle cinétique. Ces modèles ont ensuite été utilisés pour étudier les voies de décomposition des espèces étudiéesIn 2016, fossil fuels represented about 80% of the world total primary energy supply. However, this resource is limited and has a huge impact on the environment pollution because of the production of greenhouse gases. In order to drastically reduce greenhouse gases emissions, a focus on biofuels, and especially bio-oils, is made in the industrial world and for transportation. The IMPROOF project is funded by the European Union under the SPIRE framework. Its objective is to improve the energy efficiency in the case of steam cracking furnaces by 20% and in parallel to decrease by 25% per ton of ethylene the emission of pollutants like NOx or greenhouse gases. This PhD is focused on the part concerning the use of alternative fuels and especially bio-oils for the heating of the steam cracking furnaces. To better assess bio-oil oxidation or pyrolysis, a bibliographical review about the publications dealing with the composition of bio-oils have been performed. From this review, it comes out that bio-oils could be described as a mixture composed of six main types of chemical compounds: alcohols, aldehydes, carboxylic acids, furans and derivatives, oxygenated aromatic compounds and nitrogen organic compounds. In order to complete some detected lack in the literature, the aim of this thesis was to produce a new experimental dataset for molecules owning to the five first chemical families previously presented. A jet-stirred reactor was chosen to perform the experiments, due to its homogeneity in concentration and composition. This kind of “ideal” reactor is indeed convenient for the development of reliable data for the development and validation of kinetic models. During this work, eight fuels were selected and studied: n-butanol, n-pentanol, n-butanal, n-pentanal, butanoic acid, pentanoic acid, furan and benzaldehyde. For each fuel, the experimental results were used to develop and validate a kinetic model. Those models were afterward used to study the decomposition pathways of the studied species
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Ramirez, Lancheros Helena. "Etude expérimentale et modélisation cinétique de l'oxydation, l'auto-inflammation et la combustion de carburants Diesel et bio-Diesel." Phd thesis, Université d'Orléans, 2012. http://tel.archives-ouvertes.fr/tel-00717701.
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L'oxydation d'un gazole commercial et d'un gazole modèle (70% n-décane/30% 1-méthylnaphtalène en mol), ainsi que l'oxydation d'un carburant B30 " réel " (30% EMHV en vol.) et d'un B30 modèle (49% de n-décane, 21% de 1-méthylnaphtalène et 30% d'octanoate de méthyle en mole), a été étudiée dans un réacteur auto-agité par jets gazeux, un tube à choc et une bombe sphérique. Les études ont été effectuées dans un réacteur auto-agité en silice fondue, dans les mêmes conditions expérimentales initiales (560-1030 K, à 6 et 10 bar, à des richesses allant de 0,25 à 1,5). Les résultats de cette série d'expériences sont constitués de profils de concentration des espèces intermédiaires stables et des produits de combustion mesurés en fonction de la température, après prélèvement à basse pression par une sonde sonique, par infrarouge et par chromatographie en phase gazeuse. Les résultats obtenus avec les " carburants réels " ainsi qu'avec les carburants modèles (gazole et B30) ont été comparés, montrant que les carburants modèles sont d'excellents substituts simplifiés pour les " carburants réels " gazole et B30. Nous avons mesuré des délais d'auto-inflammation du carburant modèle B30 dans un tube à choc à haute pression dans une large gamme de conditions expérimentales (20 et 40 bar, intervalle de richesse de 0.5 à 1.5, et températures allant de 700 à 1200 K). Les vitesses fondamentales de flammes de 1-méthylnaphtalène, de l'octanoate de méthyle, et des carburants modèles gazole et B30 ont été mesurées dans une bombe sphérique, sous différentes conditions expérimentales (une pression initiale de 1 et 4 bar, une température initiale de 423K et une large gamme de richesses). Un mécanisme détaillé a été développé, validé, puis été réduit. Il prédit raisonnablement les données expérimentales obtenues en bombe sphérique dans cette étude.
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Nait, Saidi Chourouk. "Modélisation de la conversion thermique de carburants verts de type bio-huiles." Thesis, Institut polytechnique de Paris, 2020. http://www.theses.fr/2020IPPAE010.
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La production de bio-huiles par conversion thermochimique de la biomasse estun procédé prometteur pour le bio-raffinage. Alors que la cinétique en phase gazeuse de la conversion de la bio-huile est bien avancée, sa réactivité en phase liquide reste mal connue.L’objectif de cette thèse est de comprendre le mécanisme cinétique détaillé de la décomposition thermochimique de la biomasse à basse température en phase liquide. Comme indiqué par Basu et al. (June 2010) et Nakamura et al. (2007a,b)et Kawamoto (2017), une phase liquide est observée pendant la première étape de la pyrolyse de la biomasse. Dans cette étude, nous tenterons de modéliser le premier stade de la pyrolyse de la biomasse. A notre connaissance, aucune étude de modélisation de la réactivité en phase liquide n’a été proposée pour la pyrolyse de la biomasse. L’étude des réactions en phase liquide de ces systèmes complexes nécessite une bonne connaissance de l’influence du solvant sur la cinétique. Nous avons en premier temps comparé la prédiction des modèles COSMO-SAC avec celles du modèle de solvatation Abraham, en considérant la base de données COMPSOL de Moine et al. (2017) comme données de référence. Nous avons ensuite proposé une re-paramétrisation de ces modèles COSMO-SAC qui conduit à de bien meilleures prédictions et nous permets d’étendre ces modèles à l’utilisation des cavités CPCM (Nait Saidi et al. (2020)). Les méthodes prédictives basées sur des calculs ab initio peuvent être très précises pour prédire les propriétés thermochimiques en phase gazeuse et sont généralement plus polyvalentes que les méthodes de contribution de groupe. Une extension de la méthode ab initio de prédiction des enthalpies de formation de Paulechka et Kazakov (2017) a été proposée dans ce travail (Mielczarek et al. (2019)) et utilisée pour les composés de la biomasse. En troisième partie de cette étude, nous avons prédit les différents chemins réactionnels possibles de la décomposition des composés représentatifs de la partie lignine de la biomasse à l’aide du générateur de mécanismes réactionnels (RMG). Les composés choisis sont le créosol, le gaïacol et le méthoxy vinylphénol. Ce travail peut être considéré comme une extension du mécanisme en phase gazeuse de la pyrolyse proposé par Ranzi et al.(2017a,b) en considérant la recombinaison radicalaire et la polymérisation qui se produit à basse température entre100°C et 300°C. Pour modéliser la cinétique des réactions clés, nous les avons étudiés par l’approche des états de transition à l’aide de Gaussian09 et d’ORCA. L’estimation des paramètres cinétiques est ensuite déterminé par la théorie des états de transition à l'aide du Kisthelp tool (Canneaux et al. (2014)) pour la cinétique en phase gazeuse et cinétique en phase liquide à partir de l’approche Green (Jalan et al. July 2013)Production of bio-oils through thermochemical biomass conversion is a promising process for biorefining. While gas phase kinetics of bio-oil conversion has been improving, its liquid phase reactivity is currently poorly understood. The aim work of my thesis is about the understanding of detailed kinetics mechanism of biomass thermochemical decomposition at low temperature range in the liquid phase. As mentionned by Basu (June 2010); Nakamura et al. (2007a,b); Kawamoto (2017) a liquid phase is observed during the initial stage of biomass pyrolysis. In this study, we will try to model the initial stage of biomass pyrolysis. To our knowledge, no modelling study of the rate of reactions in the liquid phase has been proposed for biomass pyrolysis. The investigation of liquid phase reactions of such complex systems requires a good knowledge of solvent effects. We compared the prediction capabilities of COSMO-SAC with those of the Abraham solvation model, by considering the COMPSOL database of Moine (2017) as the reference data. We then proposed a re-parametrization of these COSMO-SAC models that leads to much better predictions, and extended these models to CPCM cavities(Nait Saidi et al. (2020)). Predictive methods based on ab initio calculations can be very accurate for predicting gas phase thermochemical properties and are usually more versatile than group contribution methods. An extension of Paulechka and Kazakov (2017) ab initio prediction method of enthalpies of formation was proposed in this study (Mielczarek et al. (2019)) and used for biomass compounds. We then used Reaction Mechanism Generator (RMG) to investigate the possible reaction mechanism of different Tar surrogate compounds of biomass decomposition. The surrogate compounds that we chose are Creosol, guaiacol and methoxy vinylphenol to model the lignin. This work can be considered as an extension of the gas phase reaction mechanism of pyrolysis proposed by Ranzi(2017a,b) taking in consideration the primary tar recombination/polymerisation reaction that occur in the temperature range 100°C to 300°C.To model the kinetics of the key reaction, we investigated the transitional state using Gaussian 09 and ORCA. We then estimated the kinetics parameters using Transitional State Theory with Kisthelp tool (Canneauxet al. (2014)) and liquid phase kinetics approach based on the gas phase kinetics and solvation free energies correction (Jalan et al. July 2013)
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Xavier, Francisco José Seixas. "Bio-resolução de adutos de Morita-Baylis-Hillman mediada pela enzima Lipase CALB:bioatividade de seus enantiômeros puros." Universidade Federal da Paraíba, 2013. http://tede.biblioteca.ufpb.br:8080/handle/tede/7090.
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Previous issue date: 2013-08-21Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
This work aimed to perform the kinetic bioresolution of Morita Baylis Hillman adducts (MBHA) using CALB lipase derived from Candida Antarctica fungus. Initially three MBHA we synthesized using acrylonitrile and m e p nitro benzaldehyde. Subsequently the respective acetates from MBHA were prepared in high yields using acetyl chloride and TEA. Methodologies for bioresolution of AMBH (obtained from nitro aldehydes m e p) were successfully developed producing the R enantiomers with 99.9% of enantiomeric excess determined by gas chromatography (using the beta cyclodextrin chiral column). However, using the same methodology it was not possible performed the bioresolution of AMBH derived from the o-benzaldehyde. To obtain the S enantiomers, the hydrolysis reactions of esters obtained from biocatalysis were made and separated by liquid chromatography. These hydrolysis reactions were carried out using K2CO3 and methanol, yielding the S enantiomers with 100% and 10% of chemical yields and 86.8% and 97.48% of enantiomeric excesses respectively. Using the method of Mosher through double derivatization chemical shift values obtained from 1H NMR spectra generated a NORS> and NORS 0 <0, which indicates that the absolute configuration of the asymmetric carbon of AMBH hydrolyzed by enzyme is R. The values of [S] D derived from m and p nitro aldehydes (S configuration) are +37 and +30 degrees. The values of [S] D of S corresponding acetates are -7 and -9 degrees respectively. The AMBH obtained from the m nitro aldehyde were bioavaliados in vitro in a R/S, R and S forms. The racemate was the most effective on L. braziliensis promastigotes and the S enantiomer was the lowest active. In the cell cytotoxicity analysis which were evaluated in the safe murine macrophages, the racemate was the most cytotoxic and the S enantiomer the less cytotoxic (some cytotoxicity were only observed at concentrations over 40 mg/mL) concluding that all evaluated compounds were more cytotoxic for L. braziliensis parasite that the safe macrophage.
Nesse trabalho visou-se a bio-resolução cinética dos Adutos de Morita Baylis Hillman (AMBH) utilizando a Lipase CALB derivada do fungo Candida Antarctica. Inicialmente foram sintetizados três AMBH usando acrilonitrila e os respectivos o, m e p nitrobenzaldeídos. Subsequentemente os seus respectivos acetatos foram preparados em altos rendimentos, usando cloreto de acetila e TEA. Foram desenvolvidas com êxito, metodologias para a bio-resolução dos AMBH oriundos dos nitroaldeídos m e p, obtendo os enantiômeros R com excessos enantioméricos de 99,9%, determinados pela técnica de cromatografia gasosa, usando à coluna quiral beta ciclodextrina e fase móvel (N2). Porém usando as metodologias acima não foi possível a bio-resolução do AMBH derivado do o-benzaldeído. Para obter os enantiômeros S, foram feitas as reações de hidrólise dos respectivos ésteres devidamente separados por cromatografia líquida das reações de biocatálise. As reações de hidrólise foram feitas usando K2CO3 e metanol, obtendo-se os enantiômeros S com rendimentos químicos de 100% e 10% e excessos enantioméricos de 86,8% e 97,48% respectivamente. Usando o método de Mosher através da dupla derivatização os valores de deslocamentos químicos obtidos dos espectros de RMN1H geraram um NORS>0 e NORS<0, o que demonstra que a configuração absoluta do carbono assimétrico dos AMBH os quais a enzima hidrolisou é R. Os valores de [S]D oriundos dos AMBH nitroaldeídos m e p (configuração R) são +37 e +30. Os valores de [S]D dos correspondentes acetatos S são -7 e -9 respectivamente. O AMBH oriundo do m-nitroaldeído nas formas R/S, R e S foram bioavaliados in vitro. A mistura racêmica foi a que se apresentou mais efetiva sobre promastigotas de L. braziliensis, e a substância S foi a que apresentou a menor atividade. Na análise de citotoxicidade celular no macrófago sadio de murinos observou-se que a mistura racêmica foi a mais citotóxica e o S o menos citotóxico (citotoxidade apenas a partir da concentração de 40 Xg/mL) constatando que todas as substâncias avaliadas foram mais citotóxicas para o parasita do que para macrófagos.
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Nguyen, Tien Cuong. "In-situ and ex-situ multi-scale physical metrologies to investigate the destructuration mechanisms of lignocellulosic matrices and release kinetics of fermentescible cellulosic carbon." Thesis, Toulouse, INSA, 2014. http://www.theses.fr/2014ISAT0036/document.
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La bioconversion des biomasses lignocellulosiques est actuellement un grand défi pour le développement de technologies de bio-raffinage. Le manque de connaissances des mécanismes de liquéfaction et de saccharification est l’un des principaux facteurs qui pénalisent le développement des procédés de bio-raffinage. Ce travail est centré sur le développement d’analyses physiques et biochimiques in-situ (viscosimétrie, focus beam reflectance measurement) et ex-situ (rhéometrie, granulométrie laser, morphogranulométrie, sédimentation…) pour améliorer la compréhension des mécanismes de déstructuration desfibres lignocellulosiques et caractériser les cinétiques de libération de carbone fermentescible. Des substrats modèles (cellulose microcristalline, papier Whatman) et industriels (pâte à papier, bagasse de canne à sucre) ont été utilisés avec différentes conditions d'hydrolyse (1% à 30%w/v, 0.1 à 0.5mL enzyme/ g cellulose). Les résultats obtenus ont permis:- de proposer et de valider les mesures in-situ de la viscosité de la suspension et de la distribution des longueurs de corde des particules, ainsi que sa conversion en distribution de diamètre.- de montrer l'impact de la nature et de la concentration de substrat et des ratios enzyme/substrat sur les évolutions des paramètres physico-biochimiques lors de l'hydrolyse. Ces effets ont été quantifiés sur les limitations de transfert.- d'établir un modèle phénoménologique de comportement rhéologique des suspensions initiales- de montrer que les cinétiques physico et bio-chimiques sont des cinétiques du second ordre- de montrer que, pour des hydrolyses à haute teneur en matière sèche, on peut réduire considérablement la limitation des transferts liée aux hautes concentrations et contrôler la cinétique de production de glucose par une stratégie d’ajouts cumulés desubstratIn the context of biofuels and chemicals production of petroleum substitutes from renewable carbon, bioconversion of lignocellulose biomasses is currently a major challenge. The limited knowledge of liquefaction and saccharification mechanisms stands as the main factor which penalizes bio-refinery progress. The present work is centred on the development of in-situ(viscosimetry, focus beam reflectance measurement) and ex-situ (rheometry, diffraction light scattered, morphometry, decantation…) physical and biochemical analysis to expand our understanding of the destructuration mechanisms of lignocellulose fibres and to characterise the release kinetics of fermentable cellulosic carbon. Model (microcrystalline cellulose,Whatman paper) and industrial (paper-pulp, sugarcane bagasse) lignocellulose matrices under a large range of hydrolysis conditions (1% up to 30%w/v and 0.1 up to 0.5mL enzyme/g cellulose) were studied during 24h hydrolysis experiments (pertinent period to appreciate transfer limitations). Our scientific results allow:- to propose and validate the in-situ measurements of the suspension viscosity and chord length distribution together with its conversion into particle size distribution.- to demonstrate the impact of the substrate nature and concentration and of the enzymatic ratios on the evolution of physical- and biochemical parameters during hydrolysis. Their impacts on transfer phenomena were quantified.- to establish phenomenological models for rheological behaviour of initial suspensions.- to describe all physical (viscosity, particle size) and biochemical (substrate and product) kinetics by second order reaction models.- to demonstrate that, for high dry matter concentration hydrolysis, a cumulative feeding substrate strategy allows considerably reducing the transfer limitations linked to high concentrations and to control the glucose production kinetics
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Fowler, Terry-Ann. "Kinetics of the ferric sulphate leaching of sphalerite and sphalerite/pyrite mixtures : a study of the chemical leaching of base metal minerals under conditions similar to that of bio-leaching by thiobacilli." Master's thesis, University of Cape Town, 1996. http://hdl.handle.net/11427/21699.
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Bibliography: pages 98-105.The work presented in this dissertation is an investigation of-the ferric leaching of zinc from sphalerite. A further aspect of this study was an investigation of the influence of pyrite on the dissolution rate of sphalerite due to possible galvanic interactions. This study is one component of a larger study of the sub-processes involved in the bioleaching of sulphide minerals in which the ferric leaching of the sulphide mineral is assumed to be a chemical step with the bacteria oxidising ferrous iron to ferric iron and elemental sulphur, if formed, to sulphate. The literature showed that two types of model have been used to describe the ferric leaching of the sphalerite. The first type was a shrinking-particle model in which there action was described by first order kinetics or an electrochemical mechanism. The second type included a mass transfer resistance in terms of a shrinking-core model described by half-order kinetics or a decaying diffusion coefficient. All four of these models were tested for their ability to predict published data for the ferric leaching of sphalerite. It was found that the models fitted the data for the initial period of a leach up to conversions of about 50%. However, no one of the models was found to be successful in predicting the data for prolonged leaching to high conversions.
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Leung, Suet-ying, and 梁雪瑩. "A study of step kinetics by kinetic Monte Carlo simulation." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2002. http://hub.hku.hk/bib/B31226322.
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Oliveira, Samuel Alves de. "Avalia??o cin?tica e potencial do Nb2O5 obtido a partir de um complexo de ni?bio para forma??o do oleato de metila atrav?s da rea??o de esterifica??o do ?cido oleico." Universidade Federal do Rio Grande do Norte, 2014. http://repositorio.ufrn.br:8080/jspui/handle/123456789/15854.
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Previous issue date: 2014-01-30Among the heterogeneous catalysts materials made from niobium show up as an alternative to meet the demand of catalysts for biodiesel production. This study aims to evaluate the potential of a heterogeneous catalyst derived from a complex of niobium in the reaction of methyl esterification of oleic acid. The catalyst was synthesized after calcination at different temperatures of a niobium complex ((NH4)3[NbO(C2O4)3].H2O) generating a niobium oxide nanostructure with a different commercial niobium oxide used to synthesize the complex. The commercial niobium oxide, the complex niobium and niobium catalyst were characterized by thermogravimetry (TG and DTA), surface area analysis (BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD), showing the catalyst has researched morphological and crystallographic indicating a catalytic potential higher than that of commercial niobium oxide characteristics. Factorial with central composite design point, with three factors (calcination temperature, molar ratio of alcohol/oleic acid and mass percentage of catalyst) was performed. Noting that the optimal experimental point was given by the complex calcination temperature of 600?C, a molar ratio alcohol/oleic acid of 3.007/1 and the catalyst mass percentage of 7.998%, with a conversion of 22.44% oleic acid in methyl oleate to 60 min of reaction. We performed a composite linear and quadratic regression to determine an optimal statistical point of the reaction, the temperature of calcination of the complex at 450?C, the molar ratio of alcohol/oleic acid 3.3408/1 and mass percentage of catalyst of 7.6833% . Kinetic modeling to estimate parameters for heterogeneous catalysis it set well the experimental results with a final conversion of 85.01% with 42.38% of catalyst and without catalyst at 240 min reaction was performed. Allowing to evaluate the catalyst catalytic studied has the potential to be used in biodiesel production
Dentre os catalisadores heterog?neos os materiais a base de ni?bio mostram-se como uma alternativa para suprir a demanda de catalisadores para a produ??o de biodiesel. O presente trabalho visa avaliar o potencial de um catalisador heterog?neo derivado de um complexo de ni?bio na rea??o de esterifica??o met?lica do ?cido oleico. O catalisador foi sintetizado ap?s a calcina??o em diferentes temperaturas de um complexo de ni?bio ((NH4)3[NbO(C2O4)3].H2O) gerando um ?xido de ni?bio com uma nanoestrutura diferente do ?xido de ni?bio comercial, usado para sintetizar o complexo. O ?xido de ni?bio comercial, o complexo de ni?bio e o catalisador de ni?bio foram caracterizados por termogravimetria (TG e DTA), an?lise de ?rea superficial (BET), microscopia eletr?nica de varredura (MEV) e difra??o de raios-X (DRX), demostrando que o catalisador pesquisado possui caracter?sticas morfol?gicas e cristalogr?ficas que indicam um potencial catal?tico superior ao ?xido de ni?bio comercial. Foi realizado um planejamento fatorial composto com ponto central, com tr?s fatores (temperatura de calcina??o, raz?o molar de ?lcool/?cido oleico e percentual m?ssico de catalisador). Verificando que o ponto ?timo experimental se deu mediante a temperatura de calcina??o do complexo em 600?C, uma raz?o molar de ?lcool/?cido oleico de 3,007/1 e percentual m?ssico de catalisador de 7,998%, apresentando uma convers?o de 22,44% do ?cido oleico em oleato de metila em 60 min de rea??o. Realizou-se uma regress?o linear e quadr?tica composta para se determinar de um ponto ?timo estat?stico da rea??o, sendo a temperatura de calcina??o do complexo em 450?C, raz?o molar de ?lcool/?cido oleico de 3,3408/1 e percentual m?ssico de catalisador de 7,6833%. Foi realizada uma modelagem cin?tica para estima??o de par?metros para a cat?lise heterog?nea que se ajustou satisfatoriamente aos resultados experimentais com uma convers?o final de 85,01% com catalisador e de 42,38% sem o catalisador em 240 min de rea??o. Permitindo avaliar que o catalisador estudado possui potencial catal?tico para ser utilizado na produ??o de biodiesel
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Monton, Silva Alejandro <1988>. "Structural and kinetic characterization of DNA polymerases I and III from Escherichia coli." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2015. http://amsdottorato.unibo.it/6794/.
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DNA elongation is performed by Pol III α subunit in E. coli, stimulated by the association with ε and θ subunits. These three subunits define the DNA Pol III catalytic core. There is controversy about the DNA Pol III assembly for the simultaneous control of lagging and leading strands replication, since some Authors propose a dimeric model with two cores, whereas others have assembled in vitro a trimeric DNA Pol III with a third catalytic core, which increases the efficiency of DNA replication. Moreover, the function of the PHP domain, located at the N-terminus of α subunit, is still unknown. Previous studies hypothesized a possible pyrophosphatase activity, not confirmed yet.
The present Thesis highlights by the first time the production in vivo of a trimeric E. coli DNA Pol III by co-expressing α, τ, ε and θ subunits. This trimeric complex has been enzymatically characterized and a molecular model has been proposed, with 2 α subunits sustaining the lagging-strand replication whereas the third core replicates the leading strand. In addition, the pyrophosphatase activity of the PHP domain has been confirmed. This activity involves, at least, the H12 and the D19 residues, whereas the D201 regulates phosphate release.
On the other hand, an artificial polymerase (HoLaMa), designed by deleting the exonuclease domain of Klenow Fragment, has been expressed, purified and characterized for a better understanding of bacterial polymerases mechanism. The absence of exonuclease domain impaired enzyme processivity, since this domain is involved in DNA binding. Finally, Klenow enzyme, HoLaMa, α subunit and DNA Pol III αεθ have been characterized at the single-molecule level by FRET analysis, combining ALEX and TIRF microscopy. Fluorescently-labeled DNA molecules were immobilized, and changes in FRET efficiency enabled us to study polymerase binding and DNA polymerization.
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Costa, da Cruz Ana Rita. "Compositional and kinetic modeling of bio-oil from fast pyrolysis from lignocellulosic biomass." Thesis, Lyon, 2019. http://www.theses.fr/2019LYSE1006/document.
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La pyrolyse rapide est une des voies de conversion thermochimique qui permet la transformation de biomasse lignocellulosique en bio-huiles. Ces bio-huiles, différentes des coupes lourdes du pétrole ne peuvent pas être directement mélangés dans les procédés de valorisation. En effet, en raison de leur forte teneur en oxygène, les bio-huiles nécessitent une étape de pré-raffinage, telle que l’hydrotraitement, pour éliminer ces composants.L’objectif de ce travail est de comprendre la structure, la composition et la réactivité de la bio-huile grâce à la modélisation de données expérimentales. Pour comprendre leur structure et leur composition, des techniques de reconstruction moléculaire basées sur des données analytiques, ont été appliquées, générant un mélange synthétique, dont les propriétés correspondent à celles du mélange. Pour comprendre leur réactivité, l'hydrotraitement de molécules modèles a été étudié: gaïacol et furfural. Pour cela, un modèle déterministe et stochastique a été créé pour chacun d’eux. L’approche déterministe visait à récupérer une gamme de paramètres cinétiques, qui ont ensuite été affinés par l’approche stochastique créant un nouveau modèle. Cette approche a permis de générer un réseau de réactions en définissant et en utilisant un nombre limité de familles et règles des réactions. Finalement, le mélange synthétique a été utilisé dans la simulation stochastique de l’hydrotraitement de la bio-huile, étayée par la cinétique des molécules modèles.En conclusion, ce travail a permis de recréer la fraction légère de la bio-huile et de simuler leur l'hydrotraitement, via les paramètres cinétiques des composés modèles, qui prédisent de manière raisonnable les effluents de l'hydrotraitement de celles-ci, mais sont inadéquat pour le bio-huileFast pyrolysis is one of the thermochemical conversion routes that enable the transformation of solid lignocellulosic biomass into liquid bio-oils. These complex mixtures are different from oil fractions and cannot be directly integrated into existing petroleum upgrading facilities. Indeed, because of their high levels of oxygen compounds, bio-oils require a dedicated pre-refining step, such as hydrotreating, to remove these components.The aim of the present work is to understand the structure, composition and reactivity of bio-oil compounds through modeling of experimental data. To understand the structure and composition, molecular reconstruction techniques, based on analytical data, were applied generating a synthetic mixture, whose properties are consistent with the mixture properties. To understand the reactivity, the hydrotreating of two model molecules was studied: Guaiacol and Furfural. A deterministic and stochastic model were created for each compounds. The deterministic approach intended to retrieve a range of kinetic parameters, later on refined by the stochastic simulation approach into a new model. This approach generates an reaction network by defining and using a limited number of reaction classes and reaction rules. To consolidate the work, the synthetic mixture was used in the stochastic simulation of the hydrotreating of bio-oils, supported by the kinetics of the model compounds.In sum, the present work was able to recreate the light fraction of bio-oil and simulate the hydrotreating of bio-oils, via the kinetic parameters of model compounds, which can reasonably predict the effluents of the hydrotreating of these, but are unsuitable for bio-oil.Fast pyrolysis is one of the thermochemical conversion routes that enable the transformation of solid lignocellulosic biomass into liquid bio-oils. These complex mixtures are different from oil fractions and cannot be directly integrated into existing petroleum upgrading facilities. Indeed, because of their high levels of oxygen compounds, bio-oils require a dedicated pre-refining step, such as hydrotreating, to remove these components.The aim of the present work is to understand the structure, composition and reactivity of bio-oil compounds through modeling of experimental data. To understand the structure and composition, molecular reconstruction techniques, based on analytical data, were applied generating a synthetic mixture, whose properties are consistent with the mixture properties. To understand the reactivity, the hydrotreating of two model molecules was studied: Guaiacol and Furfural. A deterministic and stochastic model were created for each compounds. The deterministic approach intended to retrieve a range of kinetic parameters, later on refined by the stochastic simulation approach into a new model. This approach generates an reaction network by defining and using a limited number of reaction classes and reaction rules. To consolidate the work, the synthetic mixture was used in the stochastic simulation of the hydrotreating of bio-oils, supported by the kinetics of the model compounds.In sum, the present work was able to recreate the light fraction of bio-oil and simulate the hydrotreating of bio-oils, via the kinetic parameters of model compounds, which can reasonably predict the effluents of the hydrotreating of these, but are unsuitable for bio-oil
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Jalab, Chadi. "Contribution à l'étude de la sollicitation du métabolisme aérobie au cours d'un 100 m nage libre." Thesis, Poitiers, 2012. http://www.theses.fr/2012POIT2265/document.
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Le modèle bioénergétique de P.E. di PRAMPERO permet d'expliquer la performance dans les disciplines de locomotion (course à pied, cyclisme, natation, ...) à partir d'une puissance métabolique et d'un indice de la dépense d'énergie par unité de distance parcourue. Néanmoins, pour les épreuves de natation de haute intensité telles que le 100m crawl, le contexte environnemental rend l'estimation de la puissance métabolique d'origine aérobie techniquement difficile. L'objectif de cette thèse est alors de proposer une nouvelle approche des réponses aérobies d'un 100-m nage libre, réalisé dans des conditions les plus proches possible d'une compétition. Le travail expérimental a porté sur des nageurs entraînés. Dans un bassin de 25-m, la procédure propose que les nageurs réalisent une performance sur 100-m nage libre à allure de compétition et trois épreuves (25m, 50m, 75m) réitérant les mêmes allures intermédiaires que celles du 100-m. VO2 est mesuré avant et juste après chaque épreuve, pendant 1min, par rétro-extrapolation. Les valeurs de VO2 mesurées à la fin des épreuves de 25m, 50m, 75m et 100m permettent de reconstruire la cinétique de VO2 d'une épreuve de 100-m. Les résultats contrastent avec les estimations des cinétiques de VO2 publiées précédemment : VO2 augmente plus vite dans la première moitié de l'épreuve (à 50m, VO2 ≈ 94%VO2max), atteint 100 %VO2max au 75ème mètre de l'épreuve puis chute de 7% sur le dernier 25-m. Une estimation de la contribution relative du métabolisme aérobie montre également des valeurs plus importantes que celles publiées jusqu'à ce jour, du fait de l'atteinte précoce de VO2max en cours d'épreuveThe bioenergetic model proposed by P.E. di PRAMPERO explains performance in most human locomotions (running, cycling, swimming, ...) using indexes of metabolic power and energy cost of locomotion. Nevertheless, for 100-m front crawl events, environmental conditions make the aerobic power measurement difficult. The main purpose of this thesis is therefore to propose a new procedure to estimate aerobic responses during a 100-m front crawl event, performed in competition conditions. Trained swimmers participated to this study. In a 25-m swimming pool, the procedure includes a 100-m front crawl performance in competition conditions, and then, three tests (25-m, 50-m, 75-m) following the pacing strategy of the 100-m event. VO2 is not measured during the tests, but before and just at the end of each test with a breath-by-breath method. Each post-test VO2 (after 25m, 50m, 75m and 100m) allows to reconstruct the VO2 kinetics of the 100-m performance. The results differ from previous studies in that VO2 increases faster in the first half of the race (at 50m, VO2 ± 94%VO2max), reaches VO2max at the 75th meter; then a decrease in VO2 corresponding to 7% of VO2max appears during the last 25m. The estimation of aerobic contribution shows higher values than those previously published, because VO2max is reached very early during the race
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Pastor, Poquet Vicente. "Experimental and modeling assessment of the main bio-physical-chemical mechanisms and kinetics in high-solids anaerobic digestion of organic waste High-Solids Anaerobic Digestion requires a tradeoff between Total Solids, Inoculum-to-Substrate Ratio and Ammonia Inhibition Semi-continuous Mono-digestion of OFMSW and Co-digestion of OFMSW with Beech Sawdust: Assessment of the Maximum Operational Total Solid Content High-solids anaerobic digestion model for homogenized reactors Non-Ideal Bio-Physical-Chemical Effects on High-Solids Anaerobic Digestion of the Organic Fraction of Municipal Solid Waste." Thesis, Paris Est, 2018. http://www.theses.fr/2018PESC2206.
Full textAbstract:
La fraction fermentescible des ordures ménagères (FFOM) comprend des déchets facilement biodégradables (alimentaires), et des lentement biodégradables (lignocellulosiques). La digestion anaérobie (DA) est une biotechnologie dans laquelle la FFOM est décomposé dans biogaz (CH4 + CO2). En raison de la teneur élevée en CH4 (50-70%), le biogaz pouvant être utilisé comme source d'énergie. En outre, DA produit un digestat partiellement stabilisé, riche d'éléments nutritifs. La DA à haute teneur en solides est une stratégie pour l'amélioration de l'efficacité. Elle correspond à une opération avec une teneur en matières sèches (MS) ≥ 10%, qui permet de réduire la taille du réacteur et les coûts de fonctionnement. Toutefois, l'augmentation de la MS peut entraîner une instabilité biochimique, et même une défaillance par acidification, à cause de la forte charge organique et l'accumulation d'inhibiteurs. L'inhibiteur le plus notable est NH3. Par conséquent, un équilibre entre l'amélioration de l'économie et l'instabilité est requis pour le traitement de la FFOM par DA à haute teneur en solides. Cette thèse de doctorat porte sur les principaux mécanismes cinétiques bio-physiques-chimiques mis en jeu lors de la DA à haute teneur en solides, dans le but d’optimiser son application. Des expériences de laboratoire ont mis en œuvre pour élucider les principales forces et faiblesses de ce procédé. Simultanément, le développement d'un modèle spécifique à la DA à haute teneur en solides a permis de condenser les connaissances expérimentales sur les effets qui se produisent lors de l'augmentation de la teneur de la MS. Les expériences en réacteur batch ont nécessité un compromis entre la teneur initiale en MS, le rapport entre l'inoculum et le substrat (X/S), l'alcalinité et la teneur en azote, afin d'évaluer les effets de l'augmentation de la teneur initiale en MS sur le rendement en CH4, l’élimination de la MS et la conversion de la demande chimique en oxygène. En particulier, des ratios X/S bas ont conduit à l'acidification, tandis que l'accumulation de NH3 a conduit à une accumulation d’acides gras volatils (AGV). Dans des expériences en semi-continue, la DA à haute teneur en solides nécessitait de diminuer le débit de l’effluent pour contrer l'élimination de la masse. Cependant, la mono-digestion de la FFOM facilement biodégradable ne peut pas supporter MS ≥ 10% sans augmenter le risque de surcharge. La surcharge était associée à la forte biodégradabilité et à l'accumulation de NH3. Par conséquent, l'ajout de sciure de bois à FFOM a permis à des réacteurs semi-continus de fonctionner jusqu'à 30% de MS, en raison de la biodégradabilité et de la teneur d'azote plus faibles ce substrat. La principale nouveauté de cette thèse est le développement d'un modèle pour la DA à haute teneur en solides. Ce modèle permet de simuler la dynamique masse et de MS dans des digesteurs, contrairement aux modèles sur des simulations de MS < 10%. Ce modèle prend également en compte l’effet de la concentration en MS sur les espèces solubles. Un module bio-physico-chimique « non idéal », modifiant les constantes d’équilibre acide-base, a été couplé ensuite au modèle. Il est à noter que la DA à haute teneur en solides est souvent caractérisée par une force ionique élevée (I ≥ 0,2 M), affectant le pH, la concentration en NH3 et le transfert de CO2 liquide-gaz. L'étalonnage du modèle a montré que la DA à haute teneur en solides requis plusieurs jeux de données expérimentaux pour contourner la « non-identifiabilité » des paramètres. La DA à haute teneur en solides pouvait fonctionner à une I allant jusqu'à 0,9 M et NH3 allant jusqu'à 2,3 g N/L, à des teneurs en MS élevées (25-30%). En outre, l'étalonnage a suggéré que l'utilisation d'une inhibition non-compétitive de NH3 devrait être testée plus avant. Il a également été recommandé de mettre au point d'autres développements du modèle. Ces résultats pourraient aider à l'optimisation de la DA à haute teneur en solidesThe organic fraction of municipal solid waste (OFMSW) includes readily biodegradable wastes such as food waste, and slowly biodegradable wastes such as lignocellulosic materials. Anaerobic digestion (AD) is a mature treatment biotechnology in which OFMSW is decomposed to a mixture of methane (CH4) and carbon dioxide (CO2), known as biogas. Due to the elevated CH4 content (50-70%), biogas can be used as a source of renewable energy. Moreover, AD yields a partially stabilized digestate, allowing the recycle of nutrients to agriculture. High-solids anaerobic digestion (HS-AD) is a well-suited strategy to enhance the overall AD efficiency for OFMSW treatment. HS-AD is operated at a total solid (TS) content ≥ 10%, permitting to reduce the reactor size and overall operational costs. Nonetheless, the TS increase can result into biochemical instability, and even reactor failure by acidification. Both the high organic load and the buildup of inhibitors can be responsible for the HS-AD instability. The most notable inhibitor in HS-AD of OFMSW is NH3. Therefore, a balance is often required between enhancing the HS-AD economy and the ‘undesired’ instability for OFMSW treatment. This PhD research investigated the main bio-physical-chemical mechanisms and kinetics in HS-AD of OFMSW, with the aim to optimize the industrial application and maximize the kinetic rates. Laboratory-scale batch and semi-continuous experiments highlighted the main strengths and weaknesses of HS-AD. Simultaneously, the development of a HS-AD model permitted to condense the experimental knowledge about the bio-physical-chemical effects occurring when increasing the TS content in HS-AD.HS-AD batch experiments required a tradeoff between the initial TS, the inoculum-to-substrate ratio (ISR), the alkalinity and the nitrogen content, to assess the effects of increasing the initial TS content upon the methane yield, TS removal and chemical oxygen demand conversion. Particularly, a low ISR led to acidification, whereas the NH3 buildup led to volatile fatty acid (VFA) accumulation, reducing the methane yield, whether or not co-digestion of OFMSW with beech sawdust was used.In semi-continuous experiments, HS-AD of OFMSW required a reduced effluent compared to the influent to counterbalance the organic mass removal associated to the biogas production. Nonetheless, mono-digestion of readily-biodegradable OFMSW could not sustain a TS ≥ 10% without exacerbating the risk of substrate overload. Overloading was associated to the high biodegradability and the NH3 buildup. Thus, adding sawdust to OFMSW permitted to operate the reactors up to 30% TS, due to the lower biodegradability and nitrogen content of lignocellulosic substrates. As the main novelty of this PhD research, a HS-AD model based on the Anaerobic Digestion Model No.1 (ADM1) was developed. This model simulates the reactor mass and TS in HS-AD, in contrast of models focusing on ‘wet’ AD simulations (TS < 10%). Moreover, the HS-AD model considers also the TS concentration effect on soluble species. A ‘non-ideal’ bio-physical-chemical module, modifying predominantly the acid-base equilibriums, was subsequently coupled to the HS-AD model. Noteworthy, HS-AD is often characterized by a high ionic strength (I ≥ 0.2 M), affecting the pH, NH3 concentration and CO2 liquid-gas transfer, as the most important triggers for HS-AD inhibition. The HS-AD model calibration required multiple experimental datasets to circumvent parameter non-identifiability. The model calibration showed that HS-AD of OFMSW might be operated at I up to 0.9 M and NH3 up to 2.3 g N/L, particularly at higher TS (25-30%). Moreover, the model calibration suggested that the non-competitive NH3 inhibition should be further tested. Further HS-AD model developments (e.g. precipitation) were also recommended. All these results might aid in the optimization of HS-AD for organic waste treatment, renewable energy and nutrient recovery
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Durfee, Lucille J. "BIO-MATHEMATICS: INTRODUCTION TO THE MATHEMATICAL MODEL OF THE HEPATITIS C VIRUS." CSUSB ScholarWorks, 2016. https://scholarworks.lib.csusb.edu/etd/428.
Full textAbstract:
In this thesis, we will study bio-mathematics. We will introduce differential equations, biological applications, and simulations with emphasis in molecular events. One of the first courses of action is to introduce and construct a mathematical model of our biological element. The biological element of study is the Hepatitis C virus. The idea in creating a mathematical model is to approach the biological element in small steps. We will first introduce a block (schematic) diagram of the element, create differential equations that define the diagram, convert the dimensional equations to non-dimensional equations, reduce the number of parameters, identify the important parameters, and analyze the results. These results will tell us which variables must be adjusted to prevent the Hepatitis C virus from becoming chronic.
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Kempen, Antoine. "Solid state phase transformation kinetics." [S.l.] : [s.n.], 2002. http://deposit.ddb.de/cgi-bin/dokserv?idn=964251191.
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Kempen, Antonius Theodorus Wilhelmus. "Solid state phase transformation kinetics." Stuttgart : Max-Planck-Institut für Metallforschung, 2001. http://www.bsz-bw.de/cgi-bin/xvms.cgi?SWB9795832.
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Milovanović, Nebojša. "A study of controlled auto ignition (CAI) combustion in internal combustion engines." Thesis, Loughborough University, 2003. https://dspace.lboro.ac.uk/2134/19906.
Full textAbstract:
Controlled Auto Ignition (CAI) combustion is a new combustion principle in internal combustion engines which has in recent years attracted increased attention. In CAI combustion, which combines features of spark ignition (SI) and compression ignition (CI) principles, air/fuel mixture is premixed, as in SI combustion and auto-ignited by piston compression as in CI combustion. Ignition is provided in multiple points, and thus the charge gives a simultaneous energy release. This results in uniform and simultaneous auto-ignition and chemical reaction throughout the whole charge without flame propagation. CAI combustion is controlled by the chemical kinetics of air/fuel mixture with no influence of turbulence. The CAI engine offers benefits in comparison to spark ignited and compression ignited engines in higher efficiency due to elimination of throttling losses at part and idle loads. There is a possibility to use high compression ratios since it is not knock limited, and in significant lower NOx emission (≈90%) and particle matter emission (≈50%), due to much lower combustion temperature and elimination of fuel rich zones. However, there are several disadvantages of the CAI engine that limits its practical application, such as high level of hydrocarbon and carbon monoxide emissions, high peak pressures, high rates of heat release, reduced power per displacement and difficulties in starting and controlling the engine. Controlling the operation over a wide range of loads and speeds is probably the major difficulty facing CAI engines. Controlling is actually two-components as it consists of auto-ignition phasing and controlling the rates of heat release. As CAI combustion is controlled by chemical kinetics of air/fuel mixture, the auto-ignition timing and heat release rate are determined by the charge properties such as temperature, composition and pressure. Therefore, changes in engine operational parameters or in types of fuel, results in changing of the charge properties. Hence, the auto-ignition timing and the rate of heat release. The Thesis investigates a controlled auto-ignition (CAI) combustion in internal combustion engines suitable for transport applications. The CAI engine environment is simulated by using a single-zone, homogeneous reactor model with a time variable volume according to the slider-crank relationship. The model uses detailed chemical kinetics and distributed heat transfer losses according to Woschini's correlation [1]. The fundamentals of chemical kinetics, and their relationship with combustion related problems are presented. The phenomenology and principles of auto-ignition process itself and its characteristics in CAI combustion are explained. The simulation model for representing CAI engine environment is established and calibrated with respect to the experimental data. The influences of fuel composition on the auto-ignition timing and the rate of heat release in a CAI engine are investigated. The effects of engine parameters on CAI combustion in different engine concepts fuelled with various fuels are analysed. The effects of internal gas recirculation (IEGR) in controlling the auto-ignition timing and the heat release rate in a CAI engine fuelled with different fuels are investigated. The effects of variable valve timings strategy on gas exchange process in CAI engine fuelled with commercial gasoline (95RON) are analysed.
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Vidaković, Tanja. "Kinetics of methanol electrooxidation on PtRu catalysts in a membrane electrode assembly Kinetik der Elektrooxidation von Methanol an PtRu Katalysatoren auf einer Membranelektrode /." [S.l. : s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=976036134.
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Shaheen, Zeiwar Hussein [Verfasser], Bernd [Akademischer Betreuer] Rogg, and Viktor [Akademischer Betreuer] Scherer. "Development of detailed and reduced bio-diesel kinetic chemical mechanisms / Zeiwar Hussein Shaheen. Gutachter: Bernd Rogg ; Viktor Scherer." Bochum : Ruhr-Universität Bochum, 2016. http://d-nb.info/1082425818/34.
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Ercan, Bayram. "Substitution Kinetics Of The Pentacarbonylbis(trimethylsilyl)ethynetungsten(0) With Triphenylbismuthine." Master's thesis, METU, 2003. http://etd.lib.metu.edu.tr/upload/12604980/index.pdf.
Full textAbstract:
The reaction between pentacarbonylbis(trimethylsilyl)ethynetungsten(0), W(CO)5(η
2-btmse), and triphenylbismuthine, BiØ
3, yields pentacarbonyltriphenylbismuthinetungsten(0), W(CO)5(BiØ
3), as the sole product. The kinetics of the substitution of btmse by BiØ
3 was studied by means of quantitative FT-IR Spectroscopy. The starting complex was prepared photochemically from hexacarbonyltungsten, W(CO)6, in the presence of excess btmse in n-hexane and identified by FT-IR and NMR Spectroscopies. The substitution reactions were performed in cyclohexane solutions at different concentrations of both leaving and entering ligand to observe the dependence of observed rate constant, kobs, on the concentration of entering and leaving ligands and also, at different temperatures to evaluate the activation enthalpy (&
#8710
H&
#8800
) and the activation entropy (&
#8710
S&
#8800
). The IR extinction coefficients for CO stretching were determined for both the starting complex W(CO)5(&
#951
2-btmse), and the product W(CO)5(BiØ
3). Quantitative IR Spectroscopy does not show any significant reduction in the total amount of substance (material balance). Formation of W(CO)6 (in small amount) was attributed to the decomposition of the product, W(CO)5BiØ
3. From the evaluation of kinetic data, a mechanism was proposed in which the rate determining step is the cleavage of btmse ligand from the starting complex, W(CO)5(&
#951
2-btmse) and the formation of solvated complex, W(CO)5(solvent). Thus, the reaction is essentially dissociative. The large positive value of activation entropy (&
#8710
S&
#8800
) and large value of activation enthalpy (&
#8710
H&
#8800
) are indicative of a dissociative mechanism.
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Rouch, Matthias. "Contribution à la compréhension des mécanismes de vieillissement hydrothermique de matériaux composites unidirectionnels polyester insaturé/fibre de lin." Thesis, Normandie, 2018. http://www.theses.fr/2018NORMC210/document.
Full textAbstract:
De nombreux exemples de matériaux composites obtenus par l’association de fibres végétales et de polymères ont permis des allègements conséquents de structures dans divers domaines d’application. Cependant, la question demeure quant de la durabilité de ces pièces en service, essentiellement par manque de connaissances sur le vieillissement des fibres végétales, sur leurs interactions avec la matrice polymère et sur le comportement hydrothermique des composites biosourcés au cours du temps. Dans cette étude, nous avons étudié les cinétiques et mécanismes de sorption du matériau composite afin d’appréhender son comportement hydrique lors des vieillissements hydrothermiques par immersion dans l’eau à 23°C et 70°C. Cette étude a mis en évidence l’influence des fibres végétales sur les grandeurs caractéristiques de l’absorption en eau du matériau composite : forte prise en eau, gonflement anisotrope. Elle a également permis l’identification des mécanismes de dégradation des fibres de lin ; le rôle très nocif des résidus d’écorce rappelle l’importance du rouissage et du défibrage sur les performances de ces fibres. L’étude du comportement des constituants et du composite confrontés à des vieillissements hydrothermiques a ensuite été entreprise afin d’identifier et quantifier l’influence de chacun des matériaux constitutifs, ainsi que leur synergie. Il en ressort que la détérioration des fibres de lin est la principale cause de l’abattement des propriétés mécaniques du matériau composite. Si une immersion à 23°C pendant 70 jours n’a que peu d’effet sur les propriétés mécaniques, l’élévation de la température à 70°C induit des endommagements importants dès 14 jours d’immersion. La destruction des parois cellulaires et la dégradation des interfaces fibre/matrice sous l’effet de la présence d’eau détériorent le transfert de charge matrice/fibre. La corrélation entre les vieillissements accélérés et naturel a fait ressortir une similitude entre le maintien pendant 70 jours dans l’eau à 23°C et l’exposition aux conditions naturelles pendant 24 mois ; l’immersion à 70°C s’avère trop sévère. Une solution d’amélioration serait d’accentuer le rouissage des fibres afin de supprimer davantage les composés pectiques de la lamelle mitoyenne et de la paroi primaire. L’élimination de ces composés facilement hydrolysables par l’eau permettrait de prétendre à une meilleure qualité de l’interface fibres/matrice tout au long du vieillissementA great number of plant fiber – reinforced polymer composites allowed substantial lightening of structures in various fields of application. However, the question remains about the durability of these parts in service, mainly for lack of knowledge about the aging of plant fibers, their interactions with the polymer matrix and the hydrothermal behavior of biosourced composites over time. In this work, water absorption mechanisms and kinetics by the composite material are studied in order to understand the hydric behavior during hydrothermal aging by immersion in deionized water at 23°C or 70°C. The results show that water absorption by the composite is characterized by a high water uptake and an anisotropic swelling. It also allowed the identification of the degradation mechanisms of flax fibers; the very harmful role of bark residues recalls the importance of retting and decortication on the performance of these fibers.The investigation of the behaviors of the constituents and the composite under hydrothermal aging was then undertaken with the aim to identify and quantify the influence of each on the constituent materials, as well as their synergy. It shows that the deterioration of the flax fibers is the main cause of the reduction of the mechanical properties of the composite. If immersion at 23 ° C for 70 days has little effect on the mechanical properties, raising the temperature to 70 ° C induces significant damage from 14 days of immersion. The destruction of the cell walls and the degradation of the fiber/matrix interfaces due to water deteriorate the load transfer efficiency by the fiber/matrix interface. The correlation between accelerated and natural aging showed a similarity between holding for 70 days in water at 23 ° C and exposure to natural conditions for 24 months; immersion at 70 ° C is too severe. An improvement solution would be to increase the retting of the fibers in order to further remove the pectic compounds from the middle lamella and the primary wall. The elimination of these compounds easily hydrolysable by water would claim to a better quality of the fiber / matrix interface throughout aging
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鄭聯喜 and Lianxi Zheng. "Growth kinetics of GaN during molecular beam epitaxy." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2001. http://hub.hku.hk/bib/B31242741.
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葉偉德 and Wai-tak Yip. "Laser induced fluorescence - construction of the apparatus and kineticstudies of the O(3P)+I2 reaction." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1994. http://hub.hku.hk/bib/B31212736.
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Schubert, Frank. "Visualization, kinetics, and thermodynamics of DNA-protein interactions." [S.l.] : [s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=976174790.
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Chan, Wing-wai Stephen, and 陳永偉. "The comparison of recovery kinetics of oxygen consumption and heart rate between children and adults: a practicalsuggestion on maximizing the usage of recovery kinetics in clinicalsetting." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2003. http://hub.hku.hk/bib/B31257367.
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洪克賢 and Newman Hung. "Recovery kinetics in Chinese children with simple repaired congenital heart disease." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2001. http://hub.hku.hk/bib/B31257227.
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Woo, Chit-shing Jackson, and 胡哲誠. "Ochratoxin A: endocrine disruption potential,transplacental kinetics and maternal exposure assessment." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2012. http://hub.hku.hk/bib/B4979954X.
Full textAbstract:
Mycotoxin contamination in food commodities is an age-old problem. Due to the detrimental impact of mycotoxins on human health, exposure to mycotoxins and their health implications have been increasingly recognized. Ochratoxin A (OTA), one of the mycotoxins, has been found to cause diverse toxicities in animals, with potential impact on human health. OTA has been reported to be teratogenic and interfere with steroidogenesis in vivo. Chronic exposure of pregnant women to OTA may be hazardous for the human foetus, especially when endocrine and developmental toxicities are taken into consideration.
Accordingly, in the first part of this project, I hypothesized that OTA may interfere with enzymes involved in human placental steroidogenesis. By evaluation of human placental 3β–hydroxysteroid dehydrogenase/isomerase (3β-HSD) at both mRNA and protein (hormonal) levels, my results showed that OTA could up-regulate 3β-HSD1 expression in human placental cells with concentration relevant to human exposure. This study is the first to report the endocrine disruption potential of OTA in human placental cells.
As several mycotoxins have been demonstrated previously to cross human placental barrier and OTA has been associated with developmental toxicity in vivo, I further hypothesized that OTA may be transferred through human placenta and accumulate in foetal compartment. In the second part of this project, human perfused placenta was used to investigate the placental toxicokinetics of OTA using concentrations found in serum of pregnant women. Findings from this study clearly showed that the transfer of OTA through term human placenta was minimal, contradicting the existing epidemiological studies reporting higher foetal OTA levels than maternal. This is the first study where transplacental kinetics of OTA has been studied in human perfused placenta.
To assess the relevance of the study findings, it is very important to provide information on maternal OTA exposure during pregnancy. Currently there is limited information regarding OTA exposure of pregnant women. The third part of this project aimed at evaluating the frequency and level of exposure to OTA in pregnant women from Egypt, where exposure to dietary mycotoxins is common due to the environmental conditions. Biomonitoring of both serum and urinary OTA levels showed that more than 70% of pregnant women were exposed to OTA with a geometric mean of 0.27 ng/ml in serum and 37.21 pg/mg creatinine in urine indicating frequent exposure of this subpopulation.
As an ultimate aim, maternal-foetal risk assessment served as a conclusive part of this project to predict and evaluate both maternal and foetal risk of exposure to OTA during pregnancy. Data from the exposure of pregnant women in Egypt to OTA were further ultilized to conduct maternal-foetal risk assessment in relation to OTA exposure. Based on the refined Klaassen equation for exposure estimation during pregnancy and the benchmark dose approach for risk assessment, this subpopulation of pregnant women generally was not exposed to OTA in a high-risk manner. However, considering the suspected chronic exposure beginning from early pregnancy with high foetal susceptibility and diverse toxic effects, and in particular the potential endocrine disruption of OTA, keeping OTA exposure to a minimum is recommended.published_or_final_version
Biological Sciences
Doctoral
Doctor of Philosophy
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劉新權 and Sing-quan Lew. "Kinetic and mechanistic study of reactions of hydroxy, methoxy, methylthio, methylseleno and amino derivatives of some heterocyclicand homocyclic polyenes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1991. http://hub.hku.hk/bib/B31232322.
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Sukumaran, Murali. "Photophysical kinetics in TICT-forming compounds-derivates of DMABN." [S.l. : s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=975654411.
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Eurich, Frank. "Coarse-Grained Models for the Kinetics of Polymeric Systems." [S.l. : s.n.], 2002. http://www.bsz-bw.de/cgi-bin/xvms.cgi?SWB10162244.
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Nitsche, Heiko. "Kinetics of crystallization in amorphous alloys nucleation and growth /." [S.l. : s.n.], 2005. http://www.bsz-bw.de/cgi-bin/xvms.cgi?SWB11947826.
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Bikas, Georgios. "Kinetic mechanisms for hydrocarbon ignition." [S.l.] : [s.n.], 2001. http://deposit.ddb.de/cgi-bin/dokserv?idn=964932857.
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Schultz, Martin. "Entwicklung eines metabolisch stabilen Ribozyms gegen die mRNA des Parathormon-verwandten Proteins (PTHrP)." Doctoral thesis, [S.l.] : [s.n.], 2001. http://deposit.ddb.de/cgi-bin/dokserv?idn=962880841.
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遲寧 and Ning Chi. "Deposition and kinetics studies of platinum nanoparticles on highly oriented pyrolytic graphite." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2000. http://hub.hku.hk/bib/B31240057.
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Grochol, Michal. "Optical properties of semiconductor nanostructures in magnetic field." Doctoral thesis, [S.l.] : [s.n.], 2007. http://deposit.ddb.de/cgi-bin/dokserv?idn=98433663X.
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Mandreoli, Lorenzo. "Density based Kinetic Monte Carlo Methods." [S.l.] : [s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=975329111.
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Qamar, Shamsul. "Kinetic schemes for the relativistic hydrodynamics." [S.l.] : [s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=975630040.
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