Många batteriers användningsområden kräver att batterierna har hög upp- och urladdningshastighet samt låg kostnad. För dessa användningsområden är vattenbaserade laddningsbara batterier (ARB) ett möjligt alternativ i och med att de är svårantändliga, har god jonledningsförmåga, lägre inre resistans, billigare elektrolytlösning och tillverkning och har potentiellt högre upp- och urladdningshastigheter.  Genom att utgå från en cell med LiMn2O4 och V2O5 som katod respektive anod, utvecklades en cell med en spänning på 1 V och prestanda för 2 mol/L LiTSFI i organisk respektive vattenlöslig lösning jämfördes i ett SEI-fritt system. Prestandan kvantifierades med avseende på urladdningskapaciteten vid olika urladdningshastigheter samt fördelningen av de interna överpotentialerna. Vid C/4 behöll den organiska elektrolyten 88,3% av den initiala kapaciteten efter 10 cykler medan den vattenlösliga behöll 98,8%. En gräns på 20 °C påvisades för den organiska elektrolyten och vid försök att gå över denna hastighet svällde pouch cellen upp. Den vattenlösliga elektrolyten, å andra sidan, bevarade 37 mAh/g vid 50 °C.  Skillnaden i potentialfördelning i de två systemen analyserades även genom att använda tunnare elektroder. Den organiska elektrolyten visade då en förbättring av prestandan vid höga hastigheter, med en urladdningskapacitet på 8,8 mAh/g vid 50 °C, jämfört med 30 mAh/g för den vattenlösliga elektrolyten. IR-fallet var 7 gånger högre för den organiska elektrolyten. Eventuell skillnad i laddningsöverföring och por-resistans kunde inte analyseras då flera processer ägde rum på samma gång i systemen, vilket gav ett impedansspektrum med en komplex associerad ekvivalent krets. / For several battery applications, high dis-/charge rate and low cost are imperatives. It is for these applications that aqueous rechargeable batteries (ARB) rise as potential candidates given the non-flammability, potentially higher ionic conductivity and dis-/charge rates, lower internal resistances and lower price of the electrolyte solvents and manufacture. By benchmarking a cell with LiMn2O4 and V2O5 as cathode and anode, respectively, a cell with an operating voltage window of 1 V was developed and the performance of 2 mol/L LiTFSI in organic and aqueous solvent compared in a SEI-free system. This performance was quantified in terms of discharge capacity at different rates of discharge and the distribution of internal overpotentials. At C/4, the organic electrolyte held 88.3% of the initial capacity after 10 cycles while the aqueous, 98.8%. A limit of 20 °C for the organic electrolyte was seen, and at the attempt of cycling above this rate, swelling of the pouch cell took place. The aqueous electrolyte, on the other hand, conserved 37 mAh/g at 50 °C. The difference of overpotentials distribution in both systems was also assessed by employing thinner electrodes. The organic electrolyte showed then an improvement on high-rate performance, reaching 50 °C, but with a discharge capacity of 8.8 mAh/g, against 30 mAh/g for the aqueous electrolyte. The IR-drop was 7 times higher for the organic electrolyte. The differentiation between charge-transfer and pore resistance, however, was not possible, because of the presence of several processes taking place at similar time-scales in both systems, yielding an impedance spectra with a complex associated equivalent circuit.

Yes / Small-angle neutron scattering (SANS) and neutron spin-echo (NSE) have been used to investigate the temperature-dependent solution behaviour of highly-branched poly(N-isopropylacrylamide) (HB-PNIPAM). SANS experiments have shown that water is a good solvent for both HB-PNIPAM and a linear PNIPAM control at low temperatures where the small angle scattering is described by a single correlation length model. Increasing the temperature leads to a gradual collapse of HB-PNIPAM until above the lower critical solution temperature (LCST), at which point aggregation occurs, forming disperse spherical particles of up to 60 nm in diameter, independent of the degree of branching. However, SANS from linear PNIPAM above the LCST is described by a model that combines particulate structure and a contribution from solvated chains. NSE was used to study the internal and translational solution dynamics of HB-PNIPAM chains below the LCST. Internal HB-PNIPAM dynamics is described well by the Rouse model for non-entangled chains.

Die chemische Zusammensetzung und die physikalischen Eigenschaften von troposphärischen Gasen, Partikeln und Wolken hängen aufgrund zahlreicher Prozesse stark voneinander ab. Insbesondere chemische Multiphasenprozesse in Wolken können die physiko-chemischen Eigenschaften der Luft und troposphärischer Partikel klein- und großräumig verändern. Diese chemische Prozessierung des troposphärischen Aerosols innerhalb von Wolken beeinflusst die chemischen Umwandlungen in der Atmosphäre, die Bildung von Wolken, deren Ausdehnung und Lebensdauer, sowie die Transmissivität von einfallender und ausgehender Strahlung durch die Atmosphäre. Damit sind wolken-chemische Prozesse relevant für das Klima auf der Erde und für verschiedene Umweltaspekte. Daher ist ein umfassendes Verständnis dieser Prozesse wichtig. Die explizite Behandlung chemischer Reaktionen in der Flüssigphase stellt allerdings eine Herausforderung für atmosphärische Computermodelle dar. Detaillierte Beschreibungen der Flüssigphasenchemie werden deshalb häufig nur für Boxmodelle verwendet. Regionale Chemie-Transport-Modelle und Klimamodelle berücksichtigen diese Prozesse meist nur mit vereinfachten chemischen Mechanismen oder Parametrisierungen. Die vorliegende Arbeit hat zum Ziel, den Einfluss der chemischer Mehrphasenprozesse innerhalb von Wolken auf den Verbleib relevanter Spurengase und Partikelbestandteile mit Hilfe des state‑of‑the‑art 3D-Chemie-Transport-Modells COSMO-MUSCAT zu untersuchen. Zu diesem Zweck wurde das Model um eine detaillierte Beschreibung chemischer Prozesse in der Flüssigphase erweitert. Zusätzlich wurde das bestehende Depositionsschema verbessert, um auch die Deposition von Nebeltropfen zu berücksichtigen. Die durchgeführten Modellerweiterungen ermöglichen eine bessere Beschreibung des troposphärischen Multiphasensystems. Das erweiterte Modellsystem wurde sowohl für künstliche 2D-Bergüberströmungsszenarien als auch für reale 3D-Simulationen angewendet. Mittels Prozess- und Sensitivitätsstudien wurde der Einfluss (i) des Detailgrades der verwendeten Mechanismen zur Beschreibung der Flüssigphasenchemie, (ii) der Größenauflösung des Tropfenspektrums und (iii) der Tropfenanzahl auf die chemischen Modellergebnisse untersucht. Die Studien belegen, dass die Auswirkungen der Wolkenchemie aufgrund ihres signifikanten Einflusses auf die Oxidationskapazität in der Gas- und Flüssigphase, die Bildung von organischer und anorganischer Partikelmasse sowie die Azidität der Wolkentropfen und Partikel in regionalen Chemie-Transport-Modellen berücksichtigt werden sollten. Im Vergleich zu einer vereinfachten Beschreibung der Wolkenchemie führt die Verwendung des detaillierten chemischen Flüssigphasenmechanismus C3.0RED zu verringerten Konzentrationen wichtiger Oxidantien in der Gasphase, einer höheren Nitratmasse in der Nacht, geringeren nächtlichen pH-Werten und einer veränderten Sulfatbildung. Darüber hinaus ermöglicht eine detaillierte Wolkenchemie erst Untersuchungen zur Bildung sekundärer organischer Partikelmasse in der Flüssigphase. Die größenaufgelöste Behandlung der Flüssigphasenchemie hatte nur geringen Einfluss auf die chemischen Modellergebnisse. Schließlich wurde das erweiterte Modell für Fallstudien zur Feldmesskampagne HCCT‑2010 genutzt. Zum ersten Mal wurde dabei ein chemischer Mechanismus mit der Komplexität von C3.0RED verwendet. Die räumlichen Effekte realer Wolken z. B. auf troposphärische Oxidantien oder die Bildung anorganischer Masse wurden untersucht. Der Vergleich der Modellergebnisse mit verfügbaren Messungen hat viele Übereinstimmungen aber auch interessante Unterschiede aufgezeigt, die weiter untersucht werden müssen. / In the troposphere, a vast number of interactions between gases, particles, and clouds affect their physico-chemical properties, which, therefore, highly depend on each other. Particularly, multiphase chemical processes within clouds can alter the physico-chemical properties of the gas and the particle phase from the local to the global scale. This cloud processing of the tropospheric aerosol may, therefore, affect chemical conversions in the atmosphere, the formation, extent, and lifetime of clouds, as well as the interaction of particles and clouds with incoming and outgoing radiation. Considering the relevance of these processes for Earth\'s climate and many environmental issues, a detailed understanding of the chemical processes within clouds is important. However, the treatment of aqueous phase chemical reactions in numerical models in a comprehensive and explicit manner is challenging. Therefore, detailed descriptions of aqueous chemistry are only available in box models, whereas regional chemistry transport and climate models usually treat cloud chemical processes by means of rather simplified chemical mechanisms or parameterizations. The present work aims at characterizing the influence of chemical cloud processing of the tropospheric aerosol on the fate of relevant gaseous and particulate aerosol constituents using the state-of-the-art 3‑D chemistry transport model (CTM) COSMO‑MUSCAT. For this purpose, the model was enhanced by a detailed description of aqueous phase chemical processes. In addition, the deposition schemes were improved in order to account for the deposition of cloud droplets of ground layer clouds and fogs. The conducted model enhancements provide a better insight in the tropospheric multiphase system. The extended model system was applied for an artificial mountain streaming scenario as well as for real 3‑D case studies. Process and sensitivity studies were conducted investigating the influence of (i) the detail of the used aqueous phase chemical representation, (ii) the size-resolution of the cloud droplets, and (iii) the total droplet number on the chemical model output. The studies indicated the requirement to consider chemical cloud effects in regional CTMs because of their key impacts on e.g., oxidation capacity in the gas and aqueous phase, formation of organic and inorganic particulate mass, and droplet acidity. In comparison to rather simplified aqueous phase chemical mechanisms focusing on sulfate formation, the use of the detailed aqueous phase chemistry mechanism C3.0RED leads to decreased gas phase oxidant concentrations, increased nighttime nitrate mass, decreased nighttime pH, and differences in sulfate mass. Moreover, the treatment of detailed aqueous phase chemistry enables the investigation of the formation of aqueous secondary organic aerosol mass. The consideration of size-resolved aqueous phase chemistry shows only slight effects on the chemical model output. Finally, the enhanced model was applied for case studies connected to the field experiment HCCT-2010. For the first time, an aqueous phase mechanism with the complexity of C3.0RED was applied in 3‑D chemistry transport simulations. Interesting spatial effects of real clouds on e.g., tropospheric oxidants and inorganic mass have been studied. The comparison of the model output with available measurements revealed many agreements and also interesting disagreements, which need further investigations.

I present detailed mechanistic analysis on the chemistry of glyoxylate as it pertains to forming biologically relevant molecules on the Hadean Earth. Chemistry covered includes: 1) the dimerization of glyoxylate to form dihydroxyfumarate(DHF), a heretofore unknown reaction, important to substantiating Eschenmoser's glyoxylate scenario. 2) Formation of sugars from polymerization of glyoxylate. 3) Formation of tartrate and sugar acids from high pH reactions of DHF. 4) Formation of glycine polypeptides from glyoxylate by transamination and coupling promoted by hexamethylenetetramine. 5) Formation of glyoxylate under conditions which could be plausibly found on the early earth.

Résumé : La pollution de l'environnement est devenue un problème mondial majeur. Le développement rapide des industries de procédés conduit à une augmentation constante des quantités d'eaux usées et des liqueurs contaminées rejetées. Les acides carboxyliques représentent une part importante de la charge organique des polluants dans les eaux usées et dans les solutions aqueuses industrielles. Une technologie efficace et respectueuse de l'environnement est donc requise pour réduire les effets négatifs de l'industrialisation sur l'environnement et pour éliminer les polluants des eaux usées et des liqueurs industrielles contaminées. Le plasma thermique submergé à courant continu (CC) est l'une des technologies proposées pour éliminer les contaminants des liquides et des solutions. Le réacteur au plasma thermique submergé à courant continu est un nouveau réacteur dans lequel le contact direct entre le plasma et la solution est établi. Une caractéristique importante du plasma thermique type CC est le gaz de plasma. Selon le type du gaz plasmagène, les plasmas thermiques CC présentent différents taux de décomposition, d’espèces réactives, d’enthalpies, de conductivités thermiques, et de temps de vie des électrodes. Parmi les différentes torches des plasmas thermiques CC, la torche à plasma thermique à mélange gazeux à base de CO[indice inférieur 2], récemment inventée, présente une amélioration très significative de la performance, c'est-à-dire une enthalpie plasmatique et une conductivité thermique élevées par rapport à celles des gaz de plasma concurrents. Une approche principalement expérimentale a permis d’étudier la faisabilité et le mécanisme de décomposition de l'acide carboxylique à haut poids moléculaire dans des solutions via les différents plasmas thermique submergés à CC. L'acide sébacique, un acide carboxylique à haut poids moléculaire a été choisi comme représentant de contaminant de type organique dans la liqueur Bayer. Deux différentes torches de plasma, incluant la torche à plasma oxygène et air ainsi que la torche à plasma CO[indice inférieur 2]/CH[indice inférieur 4] nouvellement conçues ont été utilisées. L'effet des différentes conditions de fonctionnement en incluant le temps de traitement, le pH initial de la solution, et la pression du réacteur, ainsi que le rôle des agents oxydants tels que le H[indice inférieur 2]O[indice inférieur 2], ont été étudiés sur la décomposition de l'acide sébacique. Pour identifier le rôle des différents gaz de plasma et des conditions opérationnelles sur le mécanisme de décomposition et sur les produits intermédiaires, une caractérisation qualitative et quantitative a été réalisée sur les solutions traitées avec la méthode de chromatographie ionique couplée à la spectrométrie de masse (IC/MS). L'effet thermochimique des gaz de plasma sur la décomposition de l’acide sébacique et sur les produits intermédiaires a également été étudié. À travers les différents essais réalisés dans cette étude, il a été montré pour la première fois que la décomposition de l'acide carboxylique de poids moléculaire élevé est réalisable avec le plasma thermique submergé en utilisant des gaz de plasmas différents. Le taux de décomposition d'acide sébacique lors de l’utilisation d’un plasma thermique à oxygène en milieu basique est plus élevé par rapport aux autres plasmas thermiques (air, et CO[indice inférieur 2]/CH[indice inférieur 4]) en mode submergé. Il a été constaté que cela est dû principalement à sa forte concentration en espèces oxydantes telles que l’ozone. Il a été observé que la décomposition de l'acide sébacique en milieu basique par l’utilisation de plasma d’oxygène et de plasma à air se produit par un mécanisme d'oxydation consécutif jusqu'à la production finale d'acides di-carboxyliques de plus faibles poids moléculaires et de CO[indice inférieur 2] (dissous dans la solution sous la forme de carbone inorganique). Il a été trouvé aussi pour la première fois que le plasma thermique submergé CO[indice inférieur 2]/CH[indice inférieur 4], peut décomposer l'acide carboxylique de poids moléculaire élevé sur la base d’un mécanisme séquentiel de photo-oxydation en raison de sa forte intensité de rayonnement ultraviolet. Le plasma de CO[indice inférieur 2]/CH[indice inférieur 4] a montré une vitesse de décomposition supérieure dans le milieu neutre. Par contre, en milieu basique, le plasma d'oxygène et le plasma d'air ont montré une vitesse de décomposition plus élevée. Il a également été montré que l'ajout d'H[indice inférieur 2]O[indice inférieur 2] en milieu basique a augmenté la vitesse de décomposition de l'acide sébacique avec le plasma CO[indice inférieur 2]/CH[indice inférieur 4] jusqu’à la même vitesse de décomposition que le plasma d'oxygène dû à une plus grande intensité de rayonnement UV du plasma de CO[indice inférieur 2] en comparaison avec celle du plasma d'oxygène. Dans une perspective plus générale, à travers différentes expériences, il a été montré que le plasma de CO[indice inférieur 2]/CH[indice inférieur 4] peut offrir une grande vitesse de décomposition des acides carboxyliques de poids moléculaire élevés dans un milieu acide et neutre, et également en milieu basique en présence de peroxyde d'hydrogène. Cela permettra le traitement des contaminants dans une grande variété de conditions de solution à l'aide de plasma du gaz CO[indice inférieur 2]. Les résultats de cette thèse aident à mieux comprendre la décomposition des contaminants organiques à hauts poids moléculaires dans les solutions utilisant les plasmas thermiques submergés. De plus, ces résultats proposent une application potentielle pour la torche à plasma de CO[indice inférieur 2] pour le traitement des eaux usées. // Abstract : Environmental pollution has become a major global problem. Rapid development of process industries leads to a constant increase in amounts of wastewater and contaminated industrial process liquors. Carboxylic acids represent a significant portion of the organic load of pollutant in wastewater and industrial aqueous solutions. An effective and environmentally friendly technology is therefore required to reduce the negative effects of industrialization on the environment and subsequently remove pollutants from wastewater and contaminated industrial liquors. DC (Direct Current) submerged thermal plasma is one of the proposed technologies for removing contaminants from liquids and solutions. DC submerged thermal plasma reactor is a novel reactor in which the direct contact between plasma and solution is established. An important characteristic of typical DC thermal plasma is the plasma gas. Depending on the type of plasma gas, DC thermal plasmas present different decomposition rates, reactive species, enthalpy, thermal conductivity, and electrode life time. Among different DC thermal plasma torches, the recently invented CO[subscript 2]-based gas mixture thermal plasma torch exhibits a very significant performance improvement, i.e. high plasma enthalpy and high thermal conductivity in comparison with competing plasma gases. In this study, by a mainly experimental approach, the feasibility and decomposition mechanism of high molecular weight carboxylic acid in solution via different DC submerged thermal plasmas has been investigated. Sebacic acid, a high molecular weight carboxylic acid, was selected as a representative of a typical organic contaminant in Bayer liquor. Two different DC plasma torches have been used including oxygen DC plasma torch and the newly designed CO[subscript 2]/CH[subscript 4] plasma torch. The effect of different operational conditions including treatment time, initial solution pH, and the reactor pressure as well as the role of oxidizing agents such as H[subscript 2]O[subscript 2], were investigated on the decomposition of sebacic acid. To identify the role of different plasma gases and operational conditions on the decomposition mechanism and its intermediate products, qualitative and quantitative characterization was done on the treated solutions with IC/MS (Ion Chromatography/Mass Spectrometry) method. The thermochemical effect of the plasma gases on the decomposition of sebacic acid and its intermediate products was also investigated. Through different experiments, it was shown for the first time that decomposition of high molecular weight carboxylic acid is feasible with submerged thermal plasma by using different plasma gases. The decomposition rate of sebacic acid by using oxygen thermal plasma in basic medium was higher compared with other thermal plasmas (air, and CO[subscript 2]/CH[subscript 4]) in submerged mode. It was found that the higher decomposition rate with oxygen plasma is mostly due to its high concentration of oxidant species such as ozone. The decomposition of sebacic acid in basic medium with oxygen and air plasma was revealed to occur with a consecutive oxidation mechanism up to the final production of the lowest molecular weight di-carboxylic acids and CO[subscript 2] gas (dissolved in solution in the form of inorganic carbon). It was found for the first time that the CO[subscript 2]/CH[subscript 4] submerged thermal plasma can decompose well high molecular weight carboxylic acid based on a sequential photo-oxidation mechanism due to its high ultraviolet (UV) radiation intensity. The CO[subscript 2]/CH[subscript 4] plasma showed higher decomposition rate in neutral medium, however oxygen and air plasma showed higher increased the sebacic acid decomposition rate with the CO[subscript 2]/CH[subscript 4] plasma up to the same decomposition rate of the oxygen plasma due to higher UV radiation intensity of the CO[subscript 2] plasma than that of the oxygen plasma. In a more general perspective, through different experiments, it was shown that CO[subscript 2]/CH[subscript 4] plasma can offer high decomposition rate for high molecular weight carboxylic acids in acidic and neutral medium and also in basic medium in the presence of hydrogen peroxide. This will allow using plasma for treatment of contaminants in a wide variety of solution conditions by using CO[subscript 2] gas. The findings of this thesis therefore will shed light on the decomposition of large organic contaminants in solutions with submerged thermal plasmas. Also, it provides a potential application for CO[subscript 2] plasma torch in wastewater treatment.

Aqueous-biphasic organometallic catalysis is, as illustrated by the industrial hydroformylation of propene and butene, one of the most promising ways to overcome the intrinsic problem of catalyst separation in organometallic catalysis. However, for poorly water-soluble substrates, mass transfer limitations bring the reaction rate below any that could be economically viable, greatly limiting the scope of this elegant technology. We have studied three different strategies to overcome this limitation. We developed additives that speed up the reaction whilst retaining fast phase separation and good metal retention. Evidence suggests that those additives affect the reaction by forming emulsions with poor stability under the reaction conditions These emulsions increase the interfacial surface area but break after settling for a short time. We also developed ligands that allow the catalyst to be reversibly transported between an aqueous and an organic phase upon addition and removal of carbon dioxide. This allows the reaction to be carried out under homogeneous conditions, only limited by intrinsic kinetics, and the catalyst to be separated by aqueous extraction triggered by carbon dioxide. The catalyst can be returned to a fresh organic phase by flushing out the carbon dioxide. By applying this methodology for the hydroformylation of medium chain length alkenes, very high reaction rates were obtained and the catalyst could be recycle three times with excellent retention of activity and low metal leaching. This methodology could also be reversed with the reaction being carried out in an aqueous phase in the presence of carbon dioxide and extracting the catalyst into an organic solvent using nitrogen flushing. Finally, we briefly investigated the use of an oscillatory baffled reactor as a mean for mass transfer improvement for aqueous-biphasic hydroformylation. This new type reactor did not improve the performance of the system under the investigated conditions, but may require less energy input for equivalent agitation and mixing.

<p>The two techniques aqueoustwo-phase partitioning and expanded bed adsorption that bothare suitable for primary protein recovery were studied. Most ofthe work was focused on partition in aqueous two-phase systemsand in particular on the possibility to effect the partitionbehaviour by fusion of short peptide tags or protein domains tothe target protein.</p><p>The partitioning of fusionproteins between different variants of the domain tag Z and thenaturally occurring protein DNA Klenow polymerase were studiedin Breox/Reppal aqueous two-phase systems. Most studies wereperformed with cell homogenate. The Breox/Reppal system was infocus because if the fusion protein can be partitioned to theBreox-rich top phase the next step can be a thermoseparatingaqueous two-phase system. When the Breox phase is heated to50°C it switches from a one-phase system to a two-phasesystem resulting in an almost pure water rich top phase andhighly concentrated Breox-rich bottom phase. The Breox can thenbe reused and the protein recovered from the water phase. TheZ-domain was genetically modified in different ways to Z_basic1, Z_acid2and Z_trp12and fused to the Klenow protein to try toenhance partitioning to the Breox-rich phase. From theexperiments it was not possible to observe any effects on thepartition behaviour irrespectively of tested properties of thedomain tag. Despite the absence of domain tag effects highK-values, i.e. partition to the Breox-rich top phase, wereobserved in the Breox/Reppal system. However, the proteinK-values seemed to be rather sensitive to the cell homogenateload and showed a tendency to decrease with increased cellhomogenate load. Also increased phosphate concentration reducedthe K-values. The partitioning of cell debris also seemed todependent on the cell homogenate load. At higher homogenateload (<=20g DW/L) clear Breox-rich top phases were observedwith the cell debris collected in Reppal-rich bottomphases.</p><p>Two different tetrapeptides,AlaTrpTrpPro and AlaIleIlePro were inserted near the C-terminusof the protein ZZT0. The Trp-rich peptide unit stronglyincreased both the partitioning of ZZT0 into the poly(ethyleneglycol) (PEG)-rich phase in a PEG/potassium phosphate aqueoustwo-phase system and its retention on PEG and propylhydrophobic interaction chromatographic columns with potassiumphosphate as eluent in isocratic systems. Both the partitioningand the retention increased with increasing number of Trp-richpeptide units inserted into ZZT0. Insertion of Ile-richtetrapeptide units affected the partitioning and retention to amuch lesser extent. Partition and modelling data also indicateda folding of inserted Trp and Ile tetrapeptide units, probablyto minimise their water contact. It was also investigated howto predict the partitioning of proteins in isoelectricPEG/phosphate aqueous two-phase systems.</p><p>The capture ofß-galactosidase from<i>E. coli</i>cell homogentate (50g DW/L) by metal chelatexpanded bed adsorption was studied. These experiments showedthat capture, with a certain degree of selectivity, andclarification of ß-galactosidase could be achieved from acell homogenate. However, a rather low recovery of about 35 %was obtained at a capacity of 0.25mg/mL of gel. Thus, severalparameters remain to be optimised like the load buffercomposition and the cell homogenate load.</p><p><b>Keywords:</b><i>E. coli</i>, aqueous two-phase systems, fusion proteins,hydrophobic interaction chromatography, expanded bedadsorption, ß-galactosidase, Klenow polymerase, Z-domain,peptide tags</p>

Mixed association of calix[4]resorcinarene with ethyl sulfonate groups on the lower rim and dimethylaminomethyl groups on the upper rim (CR) and cationic surfactant 4-aza-1-hexadecyl-azoniabicyclo[2.2.2]octane bromide (DABCO-16) is studied by methods of tensiometry, conductometry, potentiometry and NMR spectroscopy at fixed CR concentration and varied surfactant concentration. Beyond ca. 0.4 mM of DABCO-16, mixed aggregates enriched by CR are proved to be formed due to electrostatic forces, while beyond ca. 5 mM, aggregates enriched by surfactant occur due to the hydrophobic effect. Spectrophotometry monitoring of the solubilization of a hydrophobic dye, Orange OT, demonstrated that only the second type of mixed aggregate enriched by DABCO-16 is capable of binding the organic probe, while the mixed system where the surfactant is a minor component shows no binding capacity towards Orange OT. This finding can be used for the design of nanocontainers with controllable binding/release properties. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Biomass is one of the most promising replacements for fossil fuels as a feedstock for chemical and transportation fuel production. The combination of low vapor pressure and high polarity of most biomass derived molecules makes water the ideal solvent for biomass upgrading reaction schemes. Metal oxide and metal oxide supported catalysts are heavily used in oil refining and petrochemical production, and are capable of upgrading biomass molecules as well. However, the surface chemistries that dictate the behavior of aqueous phase biomass upgrading reactions over metal oxide catalysts are not nearly as well understood as in the case of gas phase hydrocarbon refining systems. This dissertation aims to investigate the surface chemistries of biomass derived oxygenate molecules on metal oxide and metal oxide supported metal catalysts. There are three main objectives in this dissertation: to understand how two and three carbon polyols interact with metal oxide surfaces, to elucidate the role of various surface sites on polyol-metal oxide interactions, and to discover the surface species of kinetic importance in aqueous phase reforming reactions of biomass molecules. Transmission infrared spectroscopy and density functional theory modeling were the major techniques used to demonstrate that polyols with alcohol groups on the first and third carbons, 1,3-propanediol and glycerol, form a multidentate surface species with a bridging alkoxide bond and an acid/base interaction through their two primary alcohol groups with Lewis acid sites of g-Al₂O₃. These interactions occur in the presence of bulk water. Polyols with alcohol groups only on the first and second carbons, ethylene glycol and 1,2-propanediol, only formed alkoxy bonds with the g-Al₂O₃ surface when bulk water was not coadsorbed, and these bonds were removed by re-adsorbing water. Glycerol also forms the same surface species on other metal oxides with strong Lewis acidic character: TiO₂ anatase, ZrO₂, and CeO₂. Glycerol only forms hydrogen bonds with MgO, which lacks strongly Lewis acidic sites. Basic surface hydroxyls and surface oxygen atoms of the metal oxides only played a minor role in interacting with the adsorbed glycerol. In-situ attenuated total reflectance infrared spectroscopy demonstrated that the aqueous phase reforming of glycerol over a 5 wt% Pt on g-Al₂O₃ catalyst is hindered by residual platinum bound hydrogen or oxygen atoms from commonly utilized catalyst reduction or cleaning procedures, respectively. A pretreatment consisting of multiple iterations of dissolved oxygen, dissolved hydrogen, and dissolved helium in water flow periods provides the cleanest Pt surface for monitoring carbon monoxide formation dynamics, and allows for observing the rate limiting step of the aqueous phase reforming reactions water-gas shift removal of Pt bound carbon monoxide. The bridging bound carbon monoxide is preferentially removed over the linearly bound species via water gas shift reactions even at room temperature.

Tyrimų objektas – dirvinis garstukas (Sinapis arvensis L.), dirvinė čiužutė (Thlaspi arvense L.), smalkinis tvertikas (Erysimum cheiranthoides L.), trikertė žvaginė (Capsella bursa-pastoris (L.) Medik.). Tyrimų tikslas ir metodai – nustatyti ir palyginti bastutinių šeimos piktžolių alelopatinę įtaką žemės ūkio augalams. Bendrasis fenolinių junginių kiekis buvo nustatytas pagal (Ragaee et al., 2006) metodiką. Praskiedimo būdu paruoštos vandeninės ištraukos: 1:6250, 1:1250, 1:250 ir 1:50 koncentracijų (Гродзинский, 1965; Lazauskas, 1990). Žieminių ir vasarinių rapsų sėklos bei žieminių kviečių ir vasarinių miežių grūdai buvo daiginami keturias paras ant filtrinio popieriaus, sudrėkinto paruoštų koncentracijų vandeninėmis ištraukomis, Petri lėkštelėse, klimatinėje kameroje RUMED 1301, 22 oC temperatūroje ir esant 65 proc. oro drėgniui. Buvo apskaičiuotas sudygusių žemės ūkio augalų kiekis procentais, išmatuotas jų daigų aukštis ir šaknų ilgis. Tyrimų rezultatai – didžiausias bendrasis fenolinių junginių kiekis nustatytas dirvinio garstuko ir smalkinio tvertiko lapuose (atitinkamai 1,70 ± 0,15 mg g-1 ir 1,81 ± 0,03 mg g-1 žaliosios masės), o trikertės žvaginės ir dirvinės čiužutės – žiedynuose (atitinkamai 1,56 ± 0,02 ir 1,70 ± 0,31 mg g-1). Mažiausiai fenolinių junginių kaupiasi piktžolių šaknyse. Žieminių ir vasarinių rapsų sėklų dygimas ir pradinis augimas labiausiai buvo slopinamas dirvinio garstuko vandeninėse ištraukose, lyginant su kitų piktžolių rūšių vandeninėmis... [toliau žr. visą tekstą] / Research object – charlock mustard (Sinapis arvensis L.), field penny cress (Thlaspi arvense L.), treacle mustard (Erysimum cheiranthoides L.), shepherd’s purse (Capsella bursa-pastoris L.). The aim and methods of investigations – The total phenols content was research in accordance with the methodology (Ragaee et al., 2006 ). Treatments of investigations: Factor A – weed species of Brassicaceae family: 1) charlock mustard (Sinapis arvensis L.), 2) field penny cress (Thlaspi arvense L.), 3) treacle mustard (Erysimum cheiranthoides L.), 4) shepherd’s purse (Capsella bursa-pastoris L.). Factor B – concentrations of aqueous extracts: 1) distilled water, 2) 1: 6250 (ratio of aqueous extracts weed biomass and water), 3) 1: 1250, 4) 1: 250, 5) 1:50, 6) 1:10. The seeds of winter and spring oilseed rape, winter wheat and spring barley was grown for four days on filter paper moistened with the prepared aqueous extracts in Petri dishes, in a climate chamber. Research results – The significant highest content of total phenols was in the leaves of charlock mustard and treacle mustard (respectively 1.70 ± 0.15 mg g-1 and 1.81 ± 0.03 mg g-1 of green mass), in the flowers of shepherd’s purse and field pennycress (respectively 1.56 ± 0.02 and 1.70 ± 0.31 mg g-1). The significant least content of total phenols accumulated in the roots of weeds. The germination and early seedling growth of winter and spring oilseed rape were most inhibited in the aqueous extracts of charlock mustard, compared... [to full text]