Le présent travail de thèse porte sur l'étude de l'impact de la texturation par DIC (Détente Instantanée Contrôlée) sur les deux opérations d'extraction d'huile et de transestérification in-situ appliquées aux graines de colza et fèves de Jatropha Curcas. Une analyse fondamentale a prouvé l'importance de la diffusion du solvant ou réactif dans la matrice solide, et permis d'identifier les processus d'intensification au travers des trois caractéristiques physiques de diffusivité effective, d'accessibilité initiale et de rendement d'extraction ; ainsi que la cinétique de transestérification in-situ et le rendement d'ester méthylique d'acides gras. Une étude phénoménologique a permis de déterminer les diverses valeurs de ces caractéristiques en fonction des paramètres opératoires DIC (pression de vapeur d'eau saturée P et temps de traitement t).Dans le cas d'extraction, la diffusivité effective (Deff) de produits traités par DIC peut atteindre 8,01 10-12 m2/s contre 0,715 10-12 m2/s pour le colza non traité et 5,90 10-12 m2/s contre 2,42 10-12 m2/s pour le jatropha non traité. Le taux d'accessibilité initiale de produits traités par DIC peut atteindre 80,53% contre 26,71% pour le colza non traité et 92,58% contre 75,91% pour le jatropha non traité. Au plan du rendement, la DIC a pu impliquer un rendement de 153% pour le colza et 112% pour le jatropha.Dans le cas de la transestérification in-situ, les rendements d'esters méthyliques d'acides gras totaux (FAME total) obtenus pour les produits traités par DIC sont systématiquement supérieurs à ceux de la matière première non traitée par DIC pour les deux cas de colza et de jatropha. Le temps de réaction a été réduit à 30 - 45 minutes contre 120 minutes pour le produit non traité par DIC (cas de colza) et à 15 minutes au lieu de 60 minutes pour le produit non traité par DIC (cas de fèves de jatropha).

Several problems must be solved in the construction, design, and operation of a nuclear fusion reactor. One of the chief problems in the manufacture of high-powered copper/polymer composite magnets is the difficulty to precisely control the fiber volume fraction. In this thesis, the effect of variations in fiber volume fraction on thermal stresses in copper/cyanate ester composite cylinders is investigated. The cylinder is a composite that uses copper wires that run longitudinally in a cyanate ester resin specifically developed by Composite Technology Development, Inc. This composite cylinder design is commonly used in magnets for nuclear fusion reactors. The application of this research is for magnets that use cylindrical coil geometry such as the Mega Amp Spherical Tokamak (MAST) in the UK. However, most stellarator magnet designs use complex geometries including the National Compact Stellarator Experiment (NCSX), and the Quasi-Poloidal Stellarator (QPS). Even though the actual stresses calculated for the cylindrical geometry may not be directly applicable to these projects, the relationship between fiber volume fraction and stresses will be useful for any geometry. The effect of fiber volume fraction on stresses produced by mechanical, thermal and magnetic loads on cylindrical magnet coils is studied using micromechanics with laminate plate theory (LPT) and finite element analysis (FEA). Based on the findings of this research, variations in volume fraction do significantly affect the stress experienced by the composite cylinder. Over a range of volume fractions from 0.3 to 0.5, the LPT results demonstrate that thermally induced stresses vary approximately 30% while stresses due to pressure vary negligibly. The FEA shows that magnetic stresses vary much less at around only 5%. FEA results seem to confirm the LPT model. It was also concluded that the stress in the insulation layers due to all types of loadings is significant and must be considered when using this system in fusion applications.

During attempted enzyme-catalysed resolution of sterically hindered secondary alcohols, hemiacetals and their esters were unexpectedly detected. Hemiacetal esters are reactive compounds that decompose to alcohol, aldehyde and acid under ordinary work-up conditions i.e. in contact with water, acid, or silica gel. Thus, the presence of these side products might decrease the enantiomeric excess of the residual alcohol after workup of a lipase-catalysed resolution. The formation of these hemiacetal esters were further studied using both terpenoid and non-terpenoid substrate alcohols, various acyl donors, and lipases. The prerequisite for their formation is the presence of a sterically hindered substrate alcohol, an aldehyde or an aldehyde releasing acyl donor, and a lipase (PCL-L6, PCL-PS and CAL-B). Enantioselective synthesis of (S)- and (R)-cryptone was performed via a ring closing metathesis (RCM) of (S)- and (R)-6-isopropyl-1,7-octadien-3-one. The stereochemistry was induced by using pseudoephedrine as chiral auxiliary in an alkylation reaction which provided a chiral octadienone. Problems with removal of the RCM-catalyst resulted in low yields and low enantiomeric purity. In an alternative approach, racemic cryptone was subjected to conjugate addition with thiophenol followed by reduction to the corresponding alcohol. Lipase-catalysed resolution of this alcohol yielded, after oxidation and elimination, (R)- and (S)- cryptone with 76% and 98% ee, respectively. Marine fouling of immersed objects is a serious problem. Many coatings contain effective antifouling compounds having the drawback of being toxic to the marine environment. The marine natural product 10-isocyano-4-cadinene is a potentially non-toxic antifouling agent against the barnacle Balanus amphitrite and therefore an interesting target for organic synthesis. Cryptone was used as a starting material in attempted syntheses of this compound and other similar model compounds. / QC 20100901

<p>The production of biodiesel (methyl esters) from vegetable oils represents analternative means of producing liquid fuels from biomass, and one which is growing rapidly in commercial importance and relevance due to increase in petroleum prices and the environmental advantages the process offers. Commercially, biodiesel is produced from vegetable oils, as well as from waste cooking oils and animal fats. These oils are typically composed of C14-C20 fatty acid triglycerides. In order to produce a fuel that is suitable for use in diesel engines, these triglycerides are usually converted into the respective mono alkyl esters by base-catalyzed transesterification with short chain alcohol, usually methanol. In the first part of this study, the transesterification reactions of three different vegetable oils / sunflower (SFO), soybean (SBO) and waste cooking oil (WCO) with methanol was studied using potassium hydroxide as catalyst in a conventional batch process. The production of biodiesel from waste cooking oil was also studied via continuous operation systems (employing the use of low frequency ultrasonic technology and the jet loop reactor). The characterisation of the feedstock used and the methyl ester products were determined by different analytical techniques such as gas chromatography (GC), high performance liquid chromatography (HPLC) and thin layer chromatography (TLC). The effects of different reaction parameters (catalyst amount, methanol to oil ratio, reaction temperature, reaction time) on methyl ester/FAME yield were studied and the optimum reaction conditions of the different process systems were determined. The optimum reaction conditions for production of methyl esters via the batch process with the fresh oil samples (SFO and SBO) were established as follows: a reaction time of 60 min at 60 &ordm / C with a methanol: oil ratio of 6:1 and 1.0 KOH % wt/wt of oil / while the optimum reaction conditions for the used oil (WCO) was observed at a reaction time of 90 min at 60 &ordm / C, methanol: oil ratio of 6:1 and 1.5% KOH wt/wt of oil. The optimum reaction conditions for the transesterification of the WCO via ultrasound technology applied in a continuous system in this study were: a reaction time of 30 min, 30 &ordm / C, 6:1 methanol/oil ratio and a 0.75 wt% (KOH) catalyst concentration. The ultrasound assisted transesterification reactions performed at optimum conditions on the different oil samples led to higher yields of methyl esters (96.8, 98.32 and 97.65 % for WCO, SFO and SBO respectively) compared to methyl esters yields (90, 95 and 96 % for WCO, SFO and SBO respectively) obtained when using conventional batch procedures. A considerable increase in yields of the methyl esters in the ultrasound assisted reaction process were obtained at room temperature, in a remarkably short time span (completed in 30 min) and with a lower amount of catalyst (0.75 wt % KOH) while the results from the continuous jet loop process system showed even better results, at an optimum reaction condition of 25 min of reaction, a methanol: oil ratio of 4:1 and a catalyst amount of 0.5 wt%. This new jet loop process allowed an added advantage of intense agitation for an efficient separation and adequate purification of the methyl esters phase at a reduced time of 30 min. The use of homogeneous catalysts in conventional processes poses many disadvantages / heterogeneous catalysts on the other hand are attractive on the basis that their use could enable the biodiesel production to be more readily performed as a continuous process resulting in low production costs. Consequently, a solid base catalyst (KNO3/FA) prepared from fly ash (obtained from Arnot coal power station, South Africa) and a new zeolite, FA/Na-X synthesized from the same fly ash were used as solid base catalysts in the transesterification reactions in the conversion of a variety of oil feedstock with methanol to methyl esters. Since fly ash is a waste product generated from the combustion of coal for power generation, its utilization in this manner would allow for its beneficiation (as a catalytic support material and raw material for zeolite synthesis) in an environmentally friendly way aimed at making the transesterification process reasonably viable. Arnot fly ash (AFA) was loaded with potassium (using potassium nitrate as precursor) via a wet impregnation method while the synthesized zeolite FA/Na-X was ion exchanged with potassium (using potassium acetate as precursor) to obtain the KNO3/FA and FA/K-X catalysts respectively. Several analytical techniques were applied for characterization purposes. The results of the XRD and XRF showed that the AFA predominantly contained some mineral phases such as quartz, mullite, calcite and lime. The high concentration of CaO in AFA was apparent to be beneficial for the use of fresh fly ash as a support material in the heterogeneous catalysed transesterification reactions. XRD characterisation of KNO3/FA results indicated that the structure of KNO3/FA gradually changed with the increase in KNO3 loading. The catalyst function was retained until the loading of KNO3 was over 10 %. IR spectra showed that the KNO3 was decomposed to K2O on the fly ash support during preparation at a calcination temperature of 500 &ordm / C. The CO2-TPD of the KNO3/FA catalysts showed that two basic catalytic sites were generated which were responsible for high catalytic abilities observed in the transesterification reactions of sunflower oil to methyl esters. On the other hand, XRD results for the as- received zeolite synthesized from AFA showed typical diffraction peaks of zeolite NaX. SEM images of the FA /NaX showed nano platelets unique morphology different from well known pyramidal octahedral shaped crystal formation of faujasite zeolites and the morphology of the FA /KX zeolite did not show any significant difference after ion exchange. The fly ash derived zeolite NaX (FA /NaX) exhibited a high surface area of 320 m2/g. The application of the KNO3/FA catalysts in the conversion reactions to produce methyl esters (biodiesel) via transesterification reactions revealed methyl ester yield of 87.5 % with 10 wt% KNO3 at optimum reaction conditions of methanol: oil ratio of 15:1, 5 h reaction time, catalyst amount of 15 g and reaction temperature 160 &deg / C, while with the use of the zeolite FA/K-X catalyst, a FAME yield of 83.53 % was obtained for 8 h using the ion exchanged Arnot fly ash zeolite NaX catalyst (FA/KX) at reaction conditions of methanol: oil ratio of 6:1, catalyst amount of 3 % wt/wt of oil and reaction temperature of 65 &ordm / C. Several studies have been carried out on the production of biodiesel using different heterogeneous catalysts but this study has been able to uniquely demonstrate the utilization of South African Class F AFA both as a catalyst support and as a raw material for zeolite synthesis / these catalyst materials subsequently applied sucessfully as solid base catalysts in the production of biodiesel.</p>

This thesis aims to investigate the formation of deposits from thermally degraded biodiesel on a hot metal surface under the influence of sodium or copper contaminations. Biodiesel or Fatty Acid Methyl Esters (FAMEs) is a widely utilized biofuel with the potential to replace fossil fuels, however, issues regarding the thermal and oxidative stability prevent the progress of biodiesel for utilization as vehicle fuel. The thermal degradation of biodiesel causes formation of deposits often occurring in the fuel injectors, which could result in reduced engine efficiency, increased emissions and engine wear. However, still have no standard method for evaluation of a fuels’ tendency to form deposits been developed. In this study biodiesel deposits have been formed on aluminum test tubes utilizing a Hot Liquid Process Simulator (HLPS), an instrument based on the principle of the Jet Fuel Thermal Oxidation Tester (JFTOT). Quantitative and qualitative analyses have been made utilizing an array of techniques including Scanning Electron Microscopy (SEM), Gas Chromatography Mass Spectrometry (GCMS) and Attenuated Total Reflectance Fourier Transform Infrared Spectrometry (ATR-FTIR). A multi-factorial trial investigating the effects of sodium hydroxide and copper contaminations at trace levels and the impact of a paraffin inhibitor copolymer additive on three different FAME products, two derived from rapeseed oil and one from waste cooking oil as well as a biodiesel blend with mineral diesel, was conducted.The results exhibited that FAMEs are the major precursor to deposit formation in diesel fuel. The SEM analyses exploited the nature of FAME deposits forming porous structures on hot metal surfaces. Sodium hydroxide proved to participate in the deposit formation by forming carboxylic salts. However, the copper contamination exhibited no enhancing effect on the deposits, possibly due to interference of the blank oil in which copper was received. The paraffin inhibitor functioning as a crystal modifier had significant reducing effect on the deposit formation for all biodiesel samples except for the FAME product derived from waste cooking oil. Further studies are needed in order to investigate the influence of glycerin and water residues to the biodiesel deposit formation. Mechanisms involving oxidative or thermal peroxide formation, polymerization and disintegration have been suggested as degradation pathways for biodiesel. The involvement of oxidation intermediates, peroxides, was confirmed by the experiments performed in this thesis. However, the mechanisms of biodiesel deposit formation are complex and hard to study as the deposits are seemingly insoluble. Nevertheless, ATR-FTIR in combination with JFTOT-processing has potential as standard method for evaluation of deposit forming tendencies of biodiesel.

No description available.

Denna uppsats dokumenterar uppkomst, frontpersoner och verksamhet för Dalarnes sjuksköterskeförening (DSF) mellan åren 1920-1933, vilket är en lokal sjuksköterskeförening som senare blev underavdelning till riksföreningen Svensk sjuksköterskeförening (SSF). DSF var den första lokala sjuksköterskeföreningen och startades 1920 av sjuksköterskor kring området Falun/Borlänge. Det var inte en elitförening likt SSF som i sin professionalisering enbart ville avskärma sig från de underordnade som biträden och kämpa för status och kalltanken. DSF var en förening som ville stärka kårandan men även arbeta för löne- och arbetsförhållandefrågor, vilket på den tiden egentligen hörde samman med socialistiska föreningar. I sin verksamhet ville de även få till stånd en platsbyrå för föreningens medlemmar. Det var en politiskt oberoende förening som arbetade fackligt. År 1933 blev Dalarnes sjuksköterskeförening en underavdelning till SSF som från och med det året började arbeta fackligt på lokalföreningars begäran.

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Several problems must be solved in the construction, design, and operation of a nuclear fusion reactor. One of the chief problems in the manufacture of high-powered copper/polymer composite magnets is the difficulty to precisely control the fiber volume fraction. In this thesis, the effect of variations in fiber volume fraction on thermal stresses in copper/cyanate ester composite cylinders is investigated. The cylinder is a composite that uses copper wires that run longitudinally in a cyanate ester resin specifically developed by Composite Technology Development, Inc. This composite cylinder design is commonly used in magnets for nuclear fusion reactors. The application of this research is for magnets that use cylindrical coil geometry such as the Mega Amp Spherical Tokamak (MAST) in the UK. However, most stellarator magnet designs use complex geometries including the National Compact Stellarator Experiment (NCSX), and the Quasi-Poloidal Stellarator (QPS). Even though the actual stresses calculated for the cylindrical geometry may not be directly applicable to these projects, the relationship between fiber volume fraction and stresses will be useful for any geometry. The effect of fiber volume fraction on stresses produced by mechanical, thermal and magnetic loads on cylindrical magnet coils is studied using micromechanics with laminate plate theory (LPT) and finite element analysis (FEA).Based on the findings of this research, variations in volume fraction do significantly affect the stress experienced by the composite cylinder. Over a range of volume fractions from 0.3 to 0.5, the LPT results demonstrate that thermally induced stresses vary approximately 30% while stresses due to pressure vary negligibly. The FEA shows that magnetic stresses vary much less at around only 5%. FEA results seem to confirm the LPT model. It was also concluded that the stress in the insulation layers due to all types of loadings is significant and must be considered when using this system in fusion applications.

Ischemic injury occurs when the flow of blood is reduced or blocked to an area of the body and can cause significant tissue damage by generation of reactive oxygen species (ROS), activation of apoptotic pathways and through induction of the inflammatory response. Restoration of blood flow and reperfusion of the blocked site, while essential, can generate a second injury that itself needs to be controlled. Together the two injuries are termed ischemia/reperfusion (I/R) injury. This type of injury is frequently encountered in medicine and is a major medical problem. Therapeutic strategies to combat I/R injury include the introduction of compounds that can scavenge ROS or can induce metabolic pathways with the effect of inhibiting apoptosis. Caffeic Acid Phenethyl Ester (CAPE), a polyphenolic compound found in propolis, has been shown to protect a variety of cells types against ROS in vitro and has also been shown to induce a variety of genes including hemeoxygenase 1 (HMOX-1) , an enzyme that has been implicated in a cytoprotective pathway. Despite showing significant cytoprotection of cells against oxidant stress in vitro, CAPE is readily hydrolyzed in plasma and is also quickly removed from circulation. This result may explain the limited cytoprotective effects of CAPE in vivo. We have synthesized a series of CAPE amide derivatives, including Caffeic Acid Phenethyl Amide (CAPA), with the aim of improving CAPE’s stability properties while maintaining the cytoprotective effects of the parent compound. We found that CAPA, in addition to 2 other amide derivatives, were able to protect human umbilical vein endothelial cells (HUVEC) against ROS to a similar degree as CAPE. In addition, we have observed significant improvement in plasma stability of CAPA over CAPE at multiple temperatures. The elimination half-life of CAPA from the systemic circulation was also seen to be significantly improved over CAPE following intravenous administration to male Sprague-Dawley rats. The longer residence time of CAPA over CAPE in circulation may potentially result in greater cytoprotection in vivo. / text