Cette thèse présente les mesures et l'analyse thermodynamique d'équilibres de phases de systèmes d'hydrates contenant du dioxyde de carbone (CO2), dans le contexte de procédés alternatifs de captage du CO2. Le développement de nouveaux procédés de séparation par voie de cristallisation par hydrates est un point crucial de cette thématique. Les conditions de température et de pression requises et l'utilisation de promoteurs thermodynamiques sont au-delà des opérations habituelles et des bases de données existantes. La connaissance précise des conditions de formation et dissociation d'hydrates de gaz en présence d'additifs chimiques constitue une contrainte importante d'un point de vue thermodynamique et est nécessaire pour la modélisation et l'établissement de la faisabilité de nouveaux procédés industriels impliquant des hydrates de gaz. Dans cette thèse, nous présentons un nouveau dispositif expérimental qui combine techniques statiques et techniques analytiques, ce dernier a été spécialement développé pour mesurer des données d'équilibres des phases hydrate-liquide-gaz à des températures variant entre 233 et 373 K et à des pressions jusqu' à 60 MPa. De nouvelles données d'équilibre de phases des systèmes (CO2 + méthane), (CO2 + azote) et (CO2 + hydrogène) ont été mesurées dans des conditions de formation d'hydrates en suivant la méthode isochorique avec variation de la pression en fonction de la température, et en analysant la composition en phase gazeuse. Les données d'équilibre et les conditions de dissociation d'hydrates générées dans ce travail sont comparées avec les données de la littérature. La fiabilité des modèles thermodynamiques les plus couramment utilisés est aussi étudiée. Les comparaisons entre les données expérimentales et prédites de dissociation d'hydrates suggèrent la nécessité de réajuster les paramètres des modèles thermodynamiques pour les systèmes contenant des hydrates de CO2. En outre, l'effet promoteur du bromure de tetrabutylammonium (TBAB) sur les équilibres des phases des gaz purs et de mélanges contenant du CO2 a été étudié. L'effet le plus important de promotion (réduction de la pression de formation des hydrates > 90%) est observé pour le système (TBAB + azote). Les résultats expérimentaux suggèrent que le CO2 peut être séparé de mélanges de gaz industriels ou de combustion à des températures douces et à de basses pressions à l'aide de TBAB en tant que promoteur thermodynamique. La pression requise pour la formation d'hydrates à partir de mélanges de (CO2 + azote) est réduite de 60 % en présence de TBAB. / This thesis addresses the measurement and thermodynamic analysis of the phase equilibrium behavior of carbon dioxide (CO2) hydrate-forming systems in the context of alternative capture engineering approaches. The development of new technologies based on gas hydrates requires specific temperature and pressure conditions and the utilization of thermodynamic promoters that are beyond usual operations and existing databases. Accurate knowledge of gas hydrates formation and dissociation from thermodynamics point of view in the presence of chemical additives is necessary for modeling purposes and to establish the feasibility of emerging industrial processes involving gas hydrates. In this thesis, a new experimental set-up and method for measuring pressure, temperature and compositional phase equilibrium data of high accuracy are presented. The equipment is based on the ‘static-analytic' technique with gas phase capillary sampling and it is suitable for measurements in a wide temperature range (i.e. 233 to 373 K) and pressures up to 60 MPa. New phase equilibrium data in the (CO2 + methane), (CO2 + nitrogen) and (CO2 + hydrogen) systems under hydrate formation conditions were measured following an isochoric pressure-search method in combination with gas phase compositional analysis. The equilibrium data generated in this work are compared with literature data and also with the predictions of two thermodynamic literature models. Comparisons between experimental and predicted hydrate dissociation data suggest a need of readjusting model parameters for CO2 hydrate-forming systems. In addition, the thermodynamic stability of Tetra-n-Butyl Ammonium Bromide (TBAB) semi-clathrates (sc) with pure and mixed gases was investigated. The largest promotion effect (> 90% reduction in hydrate formation pressure) is observed for (TBAB + nitrogen) sc. The experimental results suggest that CO2 can be separated from highly to low concentrated industrial/flue gas mixtures at mild temperatures and low pressures by using TBAB as thermodynamic promoter. The pressure required for hydrate formation from (CO2 + nitrogen) gas mixtures is reduced by 60% in the presence of TBAB.

The deprotonation characteristics of fluorescent probes -naphthol and 8-hydroxypyrene-1,3,6-trisulphonic acid (HPTS) were studied in this diploma thesis, using steady-state and time-resolved fluorescence spectroscopy. Two cationic surfactants, Septonex and cetyltrimethylammonium bromide (CTAB), were studied. These surfactants were measured in the complex with hyaluronan (1.75 MDa, 1 MDa and 300 kDa). Steady-state fluorescence was used for determination of critical aggregation concentration of each surfactant and pKa*. Time-resolved fluorescence decays were used to calculate the average lifetimes and the deprotonation constants of naphthol and HPTS. The measurement with hyaluronan were compared with the polystyrenesulfonate (PSS) – surfactant system. The effect of hydration shell of hyaluronan on hyaluronan – surfactant complex formation results from the comparison of above mentioned systems. Large differences were found in the deprotonation characteristic between surfactants and even between individual molecular weights of hyaluronan. The measurement shows that the hydration shell is located near to the dissociated carboxyl groups of hyaluronan chain, where the interaction with the positively charged surfactants occurs. Furthermore, the aggregation number of Septonex was determined by quenching of pyrene using cetylpyridinium chloride (CPC) as a quencher. The aggregation number for 20 mM Septonex solution was determined as a value of 104 molecules. CPC was used for confirmation of the localization of -naphthol in the micelles of CTAB and polymer – CTAB, respectively.

In this diploma thesis was studied time-resolved fluorescence in polymer-surfactant system. At first aggregation numbers of cationic (cetyltrimethylammonium bromide), anionic (sodium dodecylsulfate) and nonionic (Triton X-100) surfactants were studied by steady-state and time-resolved fluorescence spectroscopy. These two methods were compared. Aggregation numbers by steady-state method were always lower than aggregation numbers measured by time-resolved method. Steady-state method of determination aggregation numbers is useless for surfactants with high aggregation number and for aerated samples. Addition of hyaluronan to surfactant system was studied. There was observed change in aggregation number after addition of hyaluronan and change in percentage of dynamic quenching after addition of hyaluronan. Hyaluronan affected aggregation number of cetyltrimethylammonium bromide and Triton X-100. Hyaluronan increased percentage of dynamic quenching in cetyltrimethylammonium bromide and in Triton X-100. Pyren in sodium dodecylsulfate was quenched by sphere of action with negligible percentage of dynamic quenching and addition of hyaluronan had no effect on quenching. As next goal of this thesis, the determination of the position of fluorescence probe pyrene in cetyltrimethylammonium bromide, sodium dodecylsulfate and Triton X-100 micelles was chosen. Position of pyrene changed with charge and structure of micelles. Next was studied how percentage of dynamic quenching by iodide compounds changes with different charge of micelle. In all cases majority of dynamic quenching was calculated.

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’Netto-noll utsläpp’ i EU vid 2050 är ett av målen för att påskynda övergången från fossila bränslen till mer förnyelsebara och hållbara alternativ. Detta har däremot introducerat mer turbulens på elnäten. Ett av verktygen för att reglera och förbättra eldistributionen är stor-skaliga batterier, där litium-jon är den mest förekommande kemin. Men på grund av oro kring resursutbud och hopp om teknologidiversifiering har det påbörjat en sökning efter alternativ som kan användas i stället eller tillsammans med litium-jon batterier. Från en lång lista så har tre alternativ med hög potential identifierats. Dessa är nickel-vätgasbatteri, zink-brom flödesbatteri och järn-luftbatteri. Deras lämplighet undersöktes och diskuterades för flertalet användningsområden och för ett speciellt användarfall av Vattenfall. Slutsatsen var att utav de tre, så är det endast nickel-vätgas som kan förväntas vara ett bra alternativ för specifika fall, att zink-brom har få möjligheter att konkurrera och att järn-luft har väldigt hög potential men också många oklarheter som gör det svårt att förutspå dess utveckling. / With net-zero emissions set to be achieved in the EU by 2050, the transition from fossil-based energy sources to more renewable and green options are ever expanding. This puts a strain on the electricity grids because of the intermittent nature from these energy sources. To mitigate this battery systems are used, of which the lithium-ion battery is the most prevalent, and expected to only increase in use. However, material resource concerns and possible danger of over-reliance on one technology has opened for a search to find other alternatives that could be used instead or in conjunction with the battery. Out of a long list of batteries, the nickel-hydrogen battery, zinc-bromide flow battery and iron-air battery are three alternatives that have been identified to have potential. Their suitability was researched and discussed for various grid-applications. The result show that out of the three, it is only believed that the nickel-hydrogen battery have a definitive competitiveness, that the zinc bromide flow battery has few things going for it, and that the iron-air battery has large potential but just as large uncertainty surrounding its future. Lastly, a specific off-shore wind park case was investigated to see the practicality and competitiveness of the nickel-hydrogen battery compared to a specific lithium-ion chemistry.

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Methyl bromide (MBr) was widely used as a soil fumigant to manage soilborne pests in plasticulture vegetable production; however, it has been banned by the United Nations Environment Programme. Alternatives to MBr must be implemented to sustain fresh market tomato productivity. Possible MBr alternatives include new fumigant compounds, improved plastic mulch, and grafting. Methyl iodide (MeI) and dimethyl disulfide (DMDS) were tested as fumigant alternatives to MBr for the control of yellow nutsedge and soilborne pathogens of tomato. Virtually impermeable film (VIF) and totally impermeable film (TIF) were tested for fumigant retention and yellow nutsedge control in tomato. Grafting onto resistant rootstocks was tested for bacterial wilt and nematode management in tomato. In the absence of a soil fumigant, TIF suppressed yellow nutsedge better than VIF. TIF increased fumigant retention compared to VIF at similar application rates. Reduced fumigant application rates could be used in combination with TIF while maintaining fumigant concentrations, weed control, and crop yields comparable to greater use rates with VIF. Shank applied DMDS rates could be lowered to 281 L/ha under TIF from 468 L/ha under VIF; shank applied MeI application rates could be reduced to 56 L/ha under TIF compared to 93 L/ha under VIF and drip applied DMDS could be reduced from 561 L/ha under VIF film to 374 L/ha under TIF. Grafting susceptible commercial tomato cultivars onto resistant tomato hybrid rootstocks increased yields and plant survival in bacterial wilt infested fields. "Cheong Gang", "BHN 998", and "BHN 1054" were the best performing rootstocks for bacterial wilt resistance and tomato fruit yield in severely infested fields. Grafting increased tomato yield and decreased root galling from root-knot nematodes in an infested field. Hybrid rootstock "RST 106" resulted in the lowest root-knot nematode galling. In conclusion, TIF with reduced rates of DMDS or MeI is a viable MBr alternative for fresh market tomato production to retain effective doses of fumigant, manage yellow nutsedge and maintain yields. Grafting is an effective MBr alternative to manage bacterial wilt and root-knot nematode and maintain tomato yields. / Ph. D.

L'utilisation de peptides en tant qu'agents thérapeutiques est une stratégie très répandue dans le domaine médical, en partie grâce aux propriétés pharmacologiques conférées par leurs structures tridimensionnelles. Des méthodes de fabrication de peptides rentables et respectueuses de l'environnement sont souhaitées pour répondre aux demandes du marché thérapeutique. Les azapeptides sont des analogues peptidiques dans lesquels un ou plusieurs atomes de carbone en α (α-C) d’un acide aminé sont substitués par un azote. Ils offrent des propriétés physicochimiques différentes qui augmentent le potentiel thérapeutique de peptides. La synthèse chimique peptidique traditionnelle se déroule du sens C-terminal vers Nterminal. Cette approche nécessite une utilisation importante de groupes protecteurs et de réactifs de condensation, ce qui crée des charges environnementales dues aux déchets chimiques. En outre, les peptides naturels biologiquement actifs présentent souvent une modification au niveau du C-terminal, ce qui rend ce type de modifications difficiles dans le sens classique de synthèse. Leurs synthèses dans le sens inverse peut surmonter ces limitations. Cependant, peu de travaux ont exploré la synthèse peptidique du côté N-terminal vers le côté Cterminal, en raison des épimérisations observées durant l’élongation peptidique. Dans ce mémoire nous démontrons le développement d’une nouvelle méthode pour la synthèse d’azapeptides du côté N-terminal vers le côté C-terminal sur support solide. Nous avons exploré deux voies de synthèses qui reposent sur l’incorporation d’un espaceur entre le support solide et le peptide. L’approche utilisée pour l’élongation peptidique se fera via l’hydrazinolyse du C-terminal protégé, suivie par une activation du couplage peptidique par un intermédiaire acyle d’azoture. L’hydrazinolyse servira également à l’incorporation du motif hydrazine au sein du squelette peptidique pour générer le motif azapeptide. En utilisant la méthionine comme initiateur de la synthèse peptidique, ces travaux ont démontré qu’il est possible de récupérer l’azapeptide synthétisé en utilisant la méthode de clivage de résine via le bromure de cyanogène. / The use of peptides as therapeutic agents is a widespread strategy in the medicinal field, in part due to pharmacological properties conferred by their three-dimensional structures. Costeffective and environmentally friendly peptide manufacturing methods are desired to address therapeutic market demands. Replacement of one or more of the alpha-carbon centers of the amino acid residues in a peptide by a nitrogen yields an azapeptide analog. This substitution may enhance peptide activity and selectivity. Azapeptides can also exhibit prolonged duration of action and increased metabolic stability. Traditional peptide synthesis uses C-terminal to N-terminal elongation. This approach requires significant use of protecting groups and condensation reagents, creating environmental burdens from chemical waste. In addition, biologically active natural peptides often feature a Cterminal modification, making this type of modification difficult to achieve using the classical sense of synthesis. To overcome these challenges, the concept of inverse chemical synthesis has been considered as an alternative for peptide production. However, its adoption has faced hurdles due in part to epimerization. In this study, we explore azapeptide synthesis in the N- to C-direction. Linker strategies were studied for azapeptide elongation in the inverse direction. Two pathways were explored using a spacer strategy between the solid support and the peptide to be elongated. The approach relies on peptide elongation by hydrazinolysis of C-terminal esters, activation and coupling via acyl azides. Hydrazinolysis is also used to incorporate the aza-motif into the peptide backbone. Using methionine as a precursor for azapeptide synthesis, this work demonstrated peptide cleavage using cyanogen bromide.