Les procédés de stockage de chaleur haute température par voie thermochimique solide/gaz présentent un grand intérêt pour des applications à des centrales solaires thermodynamiques. Le couple réactif CaO/Ca(OH)2 est adapté à cette application pour des déstockages entre 350 et 550°C sous des pressions de vapeur entre 0,2 et 2bar. Les paramètres de transferts de chaleur et de masse de lits de Ca(OH)2+GNE ont été évalués au travers de corrélations et d'expérimentations. Des expérimentations ont permis d'atteindre des puissances en réaction de déstockage supérieures à 200kW.m-3 pour des durées compatibles avec les centrales solaires (1 à 15h). Un modèle 2D a été développé, validé et exploité afin d'étudier les influences couplées des différents paramètres sur les performances du TCS. Enfin, l'intérêt de différentes configurations d'intégration du TCS dans la centrale solaire ont été mis en évidence en termes de performances et de puissances thermiques échangées avec les sources et puits. / High-temperature heat storage processes using thermochemical solid/gas reaction exhibit great interest for applications in solar thermodynamic power plants. The reactive pair CaO/Ca(OH)2 is suitable for this recovery step application ranging from 350 to 550°C within steam pressures from 0.2 to 2 bar. Heat and mass transfer Ca(OH)2+GNE beds parameters were evaluated through correlations and experimentations. Experiments achieved recovery reaction powers above 200kW.m-3 for compatible durations with solar power plants (1 to 15 hours). A 2D model was developed, validated and exploited to study the coupled influences of different parameters on the performance of TCS. Finally, the benefit of different configurations of TCS integration within the solar power plant have been highlighted in terms of thermal performances and sources and sinks power exchanges.

The first project in this dissertation describes the total synthesis of yaku’amide A analogues. Natural product yaku’amide A possesses potent anticancer activity and exhibits a novel mode of action. However, due to its complex asymmetrical isoleucine dehydroamino acids, the synthesis of this polypeptide poses a unique challenge. Despite the efficient synthesis developed in our lab, the total synthesis of this natural product remains lengthy. In order to simplify the overall synthesis, symmetrical dehydroamino acids were incorporated to replace the dehydroisoleucine residues yielding two analogues of yaku’amide A that closely resembles the conformation of the natural product. Biological testing of the simplified analogues disclosed similar potency to that of yaku’amide A. The second part of this dissertation focuses on the influence that dehydroamino acids have on secondary structures. Peptides have an important role in medicine despite their limitations due to poor bioavailability and stability. Therapeutic use of peptides can be enhanced by designing new strategies to improve the proteolytic stability of these compounds. Attempts to increase peptide stability using trisubstituted and tetrasubstituted dehydroamino acids (ΔAAs) have been reported. Similarly, modified ΔAAs should also help tune the electronic and steric properties of peptides, while improving proteolytic stability. However, studies of peptides containing modified ΔAAs and are scarce. This project describes the synthesis and studies of incipient 310 helical tetrapeptides containing dehydroamino acids. Bulky and cyclic ΔAAs were demonstrated to alter the conformation of these tetrapeptides and impart greater stability against proteolysis and thiol additions. We believe these results can be a powerful tool to design peptide drug candidates with high proteolytic resistance and stability. tetrasubstituted dehydroamino acids (ΔAAs) have been reported. Similarly, modified ΔAAs should also help tune the electronic and steric properties of peptides, while improving proteolytic stability. However, studies of peptides containing modified ΔAAs and are scarce. This project describes the synthesis and studies of incipient 310 helical tetrapeptides containing dehydroamino acids. Bulky and cyclic ΔAAs were demonstrated to alter the conformation of these tetrapeptides and impart greater stability against proteolysis and thiol additions. We believe these results can be a powerful tool to design peptide drug candidates with high proteolytic resistance and stability.

Denna uppsats handlar om den samtida konstnären Oh de Laval och utforskar med en semiotiskt förankrad analysmetod appropriering i två olika konstverk och samhörigheten mellan dem. Verken som analyseras i studien är Oh de Lavals, Luncheon on the grass, 2019 och Édouard Manet, Le Déjeuner sur l'herbe, 1863 och stöds av Pablo Picasso, Le Déjeuner sur l'herbe, 1959-1962. Studiens övergripande syfte undersöker hur appropriering av konst förekommer i de olika verken som analyseras samt en juridisk synvinkel kring ämnet. Studien stöds av teoretiska ramverk som inkluderar postkoloniala och feministiska perspektiv som öppnar upp frågor om ras, jämställdhet, kulturell appropriering och kvinnors representation i konsten.

On the morning of the first day of pregnancy, Wistar rats were administered a single IP injection of either zinc sulfate (10.0 mg/kg) or saline. For the remainder of pregnancy, half the rats in each group then consumed filtered tap water while the other half consumed filtered tap water with 50 ppm of cadmium (CdCl2). At eight weeks after birth, the behavioral profile of male offspring was assessed in the following way: Apomorphine (non-selective dopamine receptor agonist), (+)-7-hydroxy-2-(di-n-propylamino) tetralin (7-OH-DPAT) (D3 agonist) and (+/-)-1-phenyl-2,3,4,5-tetrahydro-(1H)-3-benzazepine-7,8-diol (SKF 38393) (D1 agonist) were used to evaluate stereotyped behavior, yawning activity and oral movements - indices for these respective agonists. In addition, two dopamine receptor antagonists, haloperidol (D2 antagonist) and 7-chloro-8-hydroxy-3-methyl-1-phenyl-2,3,4,5-tetrahydro-(1H)-3-benzapine (SCH 23390) (D1 antagonist) were used to evaluate cataleptogenic activity. Additional behavioral parameters studied were locomotor activity, irritability and reaction to a painful stimulus. Dopamine and its metabolites 3,4-dihydroxyphenylacetic acid (DOPAC), homovanillic acid (HVA) and 3-methoxytyramine (3-MT) were quantified in the striatum, hippocampus and in the frontal cortex of the brain by means of HPLC/ED technique. In addition, cadmium levels were analyzed in the brain, liver, kidney and bone of newborn rats. Our results indicate that prenatal exposure of pregnant rats to cadmium produced alterations in the reactivity of central dopamine receptors and modulated the level of dopamine and its metabolites in the offsprings' brains. A single injection of zinc, preceding cadmium consumption, attenuated some of the effects of cadmium on the offsprings' dopaminergic system. Zinc also reduced cadmium deposition in the brain, kidney and bone, but enhanced its accumulation in liver. In summary, zinc may exert some neuroprotective effects against cadmium neurotoxicity.

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京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24253号 / エネ博第451号 / 新制||エネ||84(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー変換科学専攻 / (主査)教授 川那辺 洋, 教授 林 潤, 教授 澄川 貴志 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

The first project in this dissertation endeavors to outline the total synthesis of yaku'amide A and its analogs. Yaku'amide A is a natural product comprised of dehydroamino acids, including E-dehydro isoleucine, and unprecedented Z-dehydro isoleucine. These amino acids present a significant challenge to their synthesis owing to their unsymmetrical nature. To simplify the synthesis process, we synthesized analogs by substituting the E and Z dehydroamino acids with symmetrical subunits. This substitution facilitated the synthesis process and enabled us to obtain a similar three-dimensional structure to that of the natural product. Furthermore, biological testing of the simplified analogs revealed potency similar to yaku'amide A. The second part of this project describes the synthesis of the bicycle core of virosinine A, commencing with an enantioselective Evans glycolate aldol reaction. Following a series of transformations, an oxime phenyl ether is generated, which, upon microwave irradiation, triggers an iminyl radical cascade reaction. The iminium formed in the microwave reactor is reduced with red-Al, obtaining the desired diastereomer.

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