no / In recent years there have been major advances in our understanding of the mechanisms of phase separation in polymer and copolymer blends, to the extent that good control of phase-separated morphology is a real possibility. Many groups are studying the computational simulation of polymer phase separation. In the light of this, we are exploring methods which will give insight into the mechanical response of multiphase polymers. We present preliminary results from a process which allows the production of a two-dimensional finite-element mesh from the contouring of simulated composition data. We examine the stretching of two-phase structures obtained from a simulation of linear Cahn-Hilliard spinodal phase separation. In the simulations, we assume one phase to be hard, and the other soft, such that the shear modulus ratio ... is large (... ). We indicate the effect of varying composition on the material modulus and on the distribution of strains through the stretched material. We also examine in some detail the symmetric structures obtained at 50% composition, in which both phases are at a percolation threshold. Inspired by simulation results for the deformation of these structures, we construct a "scaling" theory, which reproduces the main features of the deformation. Of particular interest is the emergence of a lengthscale, below which the deformation is non-affine. This length is proportional to ... , and hence is still quite small for all reasonable values of this ratio. The same theory predicts that the effective composite modulus scales also as ..., which is supported by the simulations.

Zellen sind in der Lage, gleichzeitig ganz unterschiedliche biochemische Prozesse zu bewältigen. Dies gelingt ihnen durch eine Einteilung ihres Inneren in Kompartiemente, sogennante Organellen, die die jeweils geeignete biochemische Umgebung für die unterschiedlichen Aufgaben schaffen. Bei membranumschlossenen Kompartimenten ist leicht vorstellbar, dass sie eine andere biochemische Zusammensetzung als ihre Umgebung haben können. Jedoch existieren auch Organelle ohne Membran die durch eine flüssig-flüssig Phasenseparation entstehen. Manche dieser Kompartiemente haben die Fähigkeit, RNA zu binden und Proteinkomplexe auszubilden, während andere auf die Veränderungen innerhalb der Zelle, wie z.B. die Veränderung des pH-Werts und der damit Verbunden Änderung ihres Protonierungszustands, reagieren können. Um diese Prozesse theoretisch analysieren zu können, entwickeln wir zunächst ein allgemeingültiges, thermodynamisches Gerüst, um Systeme zu untersuchen, die im chemischen Gleichgewicht flüssig-flüssig hasensepariert vorliegen können. Dies erlaubt, basierend auf den Erhaltungsgrößen, im chemischen Gleichgewicht thermodynamisch konjungierten Variablen zu identifizieren, welche aus den erhaltenen Komponenten und den zugehörigen chemischen Potentialen bestehen. Mithilfe des obig erwähnten Gerüsts können wir den Einfluss des pH-Wertes auf die flüssig-flüssig Phasenseparation in einem minimalen Modell untersuchen. Dies beschreibt die makromolekulare Phasenseparation, kontrolliert durch Protonierungs- und Deprotonierungreaktionen, welche wiederum vom pH-Wert abhängig sind. Unsere Untersuchung der pH-Abhängigkeit der Phasenseparation kommt zu folgenden Ergebnissen: Erstens liegt die größte Region von Phasenseparation im Phasendiagramm typischerweise im Bereich des isoelektrischen Punkts. Zweitens zeigt das Modell eine Fähigkeit der erneuten Mischung auf. Drittens ist die Topologie des Phasendiagrams von der dominantesten Interaktion bestimmt. Unser Modell stimmt mit experimentellen Beobachtungen zur Phasenseparation von intrinsisch ungeordneten, Proteinen, deren Struktur sich pH abhängig verändern, überein. Das Modell ist außerdem konsistent mit Beobachtungen von Phasenseparation von Proteinen im Zytosol von Hefezellen, die entsteht, wenn der intrazellulare pH-Wert in die Nähe des isoelektrischen Punkt dieser Proteine gebracht wird. Des Weiteren geht diese Arbeit auf den physikalischen Mechanismus ein, mit dem flüssigkeitsähnliche Organellen, sog. P granules, im Organismus Caenorhabditis elegans positioniert werden. Um dieses Phänomen zu analysieren, stellen wir zunächst experimentelle Beobachtungen vor, die zeigen, dass PGL-3, eine Hauptkomponente der P granules, flüssigkeitsähnliche Tropfen bildet, deren Zusammensetzung von RNA moduliert werden kann. Darüber hinaus zeigen wir Daten, die großen Unterschiede zwischen der RNA-Bindungsaffinität von Proteinen wie Mex-5, die für die Positionierung der P granules relevant sind, und solchen, die P granules bilden, wie PGL-3, zeigen. Dies deutet darauf hin, dass eine Konkurrenz zwischen den Bestandteilen der P Granula und MEX-5 um die zur Bindung zur Verfügung stehende RNA besteht, die die Kondensation und Auflösung von P Granula räumlich kontrollieren könnte. Auf diesen experimentellen Befunden aufbauend führen wir ein minimalles Modell ein, in dem wir die Phasenseparation von PGL-3 an Bindungsreaktionen der MEX-5 Proteine und RNA koppeln. Um die experimentellen Beobachtungen beschreiben zu können, muss die Neigung des PGL-3 Proteins zur Phasenseparation zunehmen, wenn es Komplexe mit RNA bildet. Dies unterstützt die Idee, dass MEX-5 diese Phasenseparation unterdrückt, indem es die Anzahl an möglichen RNA-Bindungspartner für PGL-3 herabsetzt und damit die weitere Entstehung derartiger Protein-RNA-Komplexe erschwert. Dieser einfache Mechanismus scheint die Hauptursache dafür zu sein, dass P granules auf der posterioren Seite des Caenorhabditis elegans Embryos zu finden sind. / One of the main features of cells is their incredible ability to control biochemical processes in space and time. They do so by organizing their interior in sub-compartments called organelles, each of them with a different biochemical environment that allows them to perform specific tasks in the cell. It is sometimes believed that these compartments need a membrane in order to have a stable biochemical environment and regulat their compositions. However, there are some organelles which lack a membrane and seem to form and organize via liquid-liquid phase separation. Some of the components that form these membraneless organelles have the ability to bind to RNA and form complexes, while some others react to changes in the intracellular environment such as pH variations, which in turn affects their protonation state. In order to study these processes from a theoretical perspective, we develop a generic thermodynamic framework to study systems exhibiting liquid-liquid phase separation at chemical equilibrium. This framework, based on the use of conservation laws in chemical reactions, allow us to identify thermodynamic conjugate variables at chemical equilibrium, which are given by a set of conserved quantities and the corresponding conjugate chemical potentials. Within the aforementioned framework, we introduce a minimal model to study the effect of pH on liquid-liquid phase separation. Our model explains macromolecular phase separation controlled by protonation and deprotonation reactions, which are tuned by the pH of the system. We study the phase behavior of the system as a function of pH. Our main findings are: Firstly, the broadest region of phase separation is typically found at the isoelectric point. Secondly, the system exhibits reentrant behavior. Thirdly, that the dominating interaction in the system determines the topology of the phase diagrams. Our model is in agreement with experimental observations of in vitro protein phase separation of pH-responsive intrinsically disordered proteins, as well as with observations of protein phase separation exhibited by many cytosolic proteins when the intracellular pH in yeast cells is brought close to the isoelectric point of such proteins. Moreover, this work analyses the physical mechanism behind the positioning of liquid-like organelles in the {\it{Caenorhabditis elegans}} organism known as P granules. In order to study this phenomenon, we first present firm experimental evidence showing that PGL-3 protein, a key component of P granules, forms liquid-like drops whose assembly can be modulated by RNA. We then present data showing that the RNA-binding affinity differs significantly between proteins relevant for the positioning of P granules, such as MEX-5 and the proteins forming the P granules, like the aforementioned PGL-3. This points to a possible mechanism of RNA-binding competition between P granule constituents and MEX-5 in order to spatially control the condensation and dissolution of P granules. Based on the experimental evidence, we propose a minimal model in which we couple phase separation of PGL-3 to a set of binding reactions involving the MEX-5 protein and RNA. We find that in order to explain the experimental data, the tendency for phase separation of the PGL-3 protein increases with the formation of complexes of PGL-3 bound to RNA. This therefore supports the idea that MEX-5 inhibits this protein phase separation by depleting the RNA available for PGL-3 to form such complexes. This simple mechanism is at the core of how P granules localize to the posterior side of the Caenorhabditis elegans embryo.

Concentrating quaternary (positive) charge at polymer surfaces is important for applications including layer-by-layer polyelectrolyte deposition and antimicrobial coatings. Prior techniques to introduce quaternary charge to the surface involve grafting of quaternary ammonium moieties to a substrate or using polyurethanes with modified hard segments however there are impracticalities involved with these techniques. In the case of the materials discussed, the quaternary charge is introduced via polyurethane based polymer surface modifiers (PSMs) with quaternized soft segments. The particular advantage to this method is that it utilizes the intrinsic phase separation between the hard and soft segments of polyurethanes. This phase separation results in the surface concentration of the soft segments. Another advantage is that unlike grafting, where modification has to take place after device fabrication, these PSMs can be incorporated with the matrix material during device fabrication. The soft segments of these quaternized polyurethanes are produced via ring opening copolymerization of oxetane monomers which possess either a trifluoroethoxy (3FOx) side chains or a quaternary ammonium side chain (C12). These soft segments are subsequently reacted with 4,4’-(methylene bis (p-cyclohexyl isocyanate)), HMDI and butanediol (BD) to form the PSM. It was initially intended to increase the concentration of quaternary ammonium charge by increasing PSM soft segment molecular weight. Unexpectedly, produced blends with surface microscale phase separation. This observation prompted further investigation of the effect of PSM soft segment molecular weight on phase separation in PSM-base polyurethane blends and the subsequent effects of this phase separation on the biocidal activity. Analysis of the surface morphology via tapping mode atomic force microscopy (TMAFM) and scanning electron microscopy (SEM) revealed varying complexities in surface morphology as a function of the PSM soft segment molecular weight and initial annealing temperature. Many of these features include what are described as nanodots (100-300 nm), micropits (0.5-2 um) and micropeaks (1-10 um). It was also observed that surface morphology continued to coarsen with time and that the larger features were typically observed in blends containing PSMs with low molecular weight soft segments. This appearance of surface morphological feature correlates with decreased biocidal activity of the PSM blends, that is, the PSM blends exhibit little to no activity upon development of phase separated features. A model has been developed for phase separation and concomitant reduction of surface quaternary charge. This model points the way to future work that will stabilize surface charge and provide durability of surface modification.

GaInAsSb is a promising material for mid-infrared devices such as lasers and detectors because it is a direct band gap material with large radiative coefficient and a cut-off wavelength that can be varied across the mid-infrared (from 1.7 to 4.9 μm) while remaining lattice matched to GaSb. On the other hand, the potential of the alloy is hampered by predicted ranges of concentration where the constituents of the alloy become immiscible when the crystal is grown near thermodynamic equilibrium at typical growth temperatures. There have been efforts to extend the wavelength of GaInAsSb alloys through such techniques as digital alloy growth and non-equilibrium growth, but most of the compositional range has for a long time been inaccessible due to immiscibility challenges. Theoretical studies also supported the existence of thermodynamic immiscibility gaps for non-equilibrium growth conditions. Lower growth temperatures lead to shorther adatom diffusion length. While a shorter adatom diffusion length suppresses phase separation, too short an adatom length is associated with increased defect formation and eventually loss of crystallinity. On the other hand, hotter growth temperatures move epitaxial growth closer to thermodynamic equilib- rium conditions, and will eventually cause phase separation to occur. In this study thick 2 μm; bulk GaInAsSb layers lattice-matched to GaSb substrates were grown across the entire (lattice-matched) compositional range at low growth temperatures (450°C), including the immiscibility region, when grown under non-equilibrium conditions with MBE. High quality epitaxial layers were grown for all compositions, as evidenced by smooth morphology (atomic force microscopy), high structural quality (X-ray diffraction), low alloy fluctuactions (electron dispersive spectroscopy in cross sectioned samples), and bright room temperature photoluminescence. Because initial theoretical efforts have suggessted that lattice strain can influence layer stability, we have studied effects of strain on alloy stability. Unstable and metastable alloys were grown hot enough for the onset of phase separation, then progressively strained and characterized. We show that strain is effective in suppressing phase separation. Finally, we performed time-resolved carrier lifetime measurements for InAsSb alloy with low concentrations of Ga to investigate the role of Ga in influencing nonradiative carrier recombination. There have been studies on non-Ga containing antimonide structures (InAsSb, InAs/InAsSb) that show long carrier lifetimes, which suggest that Ga plays a role in reducing carrier lifetime, because Ga-containing structures such as InAs/GaSb superlattices have much shorter carrier lifetimes. Ga may reduce carrier lifetime through native defects that increase background carrier concentration, or that create mid-gap electronic states. Here, a series of GaInAsSb alloys were grown with low to zero Ga concentration. No difference in carrier lifetime was observed between Ga and Ga-free structures, and minority carrier lifetimes > 600 ns were observed. Additional work remains to be done to obtain background carrier densities in the samples with Hall measurements.

Mushroom (Agaricus bisporus) polyphenoloxidase (PPO) (EC 1.14.18.1) was isolated and purified using an aqueous two phase system composed of octyl phenol (ethyleneglycol) 7-8 ether (Triton X-114/TX-114). TX-114 is a non-ionic surfactant which thermoseparates in water and forms an aqueous two phase system with a surfactant-depleted top phase and a surfactant-enriched bottom phase. Critical micelle concentration (CMC) and cloud point of the surfactant are 0.17 mM and 22&ordm / C respectively. The partitioning behavior of mushroom PPO in water/TX-114 aqueous two-phase systems was studied and the effects of TX-114 concentration, ionic strength, pH, temperature and crude extract preparation on PPO partitioning were studied. PPO generally partitioned to the surfactant-depleted top phase / whereas many other hydrophobic proteins and molecules partitioned to the surfactantenriched bottom phase. When two-step ultrafiltration was used as a pretreatment, complete enzyme recovery was achieved with all studied TX-114 concentrations. Moreover, about 5 fold purification was achieved by using 8% TX-114. The purification increased to 10 fold by using polyvinylpolypyrolidone (PVPP) at pH 7.0 with a recovery of 72%. However changing pH from 7.0 to 6.0 increased the purification factor and enzyme recovery to 15 fold and 100%, respectively. Addition of potassium or sodium salts caused PPO molecules to partition in the surfactantenriched bottom phase. Finally, crude enzyme can be concentrated besides being purified and recovered by doing aqueous two-phase separation at room temperature.

Magnetic oxides exhibit rich complexity in their fundamental physical properties determined by the intricate interplay between structural, electronic and magnetic degrees of freedom. The common themes that are often present in these systems are the phase coexistence, strong magnetostructural coupling, and possible spin frustration induced by lattice geometry. While a complete understanding of the ground state magnetic properties and cooperative phenomena in this class of compounds is key to manipulating their functionality for applications, it remains among the most challenging problems facing condensed-matter physics today. To address these outstanding issues, it is essential to employ experimental methods that allow for detailed investigations of the temperature and magnetic field response of the different phases. In this PhD dissertation, I will demonstrate the relatively unconventional experimental methods of magnetocaloric effect (MCE) and radio-frequency transverse susceptibility (TS) as powerful probes of multiple magnetic transitions, glassy phenomena, and ground state magnetic properties in a large class of complex magnetic oxides, including La0.7Ca0.3-xSrxMnO3 (x = 0, 0.05, 0.1, 0.2 and 0.25), Pr0.5Sr0.5MnO3, Pr1-xSrxCoO3 (x = 0.3, 0.35, 0.4 and 0.5), La5/8−xPrxCa3/8MnO3 (x = 0.275 and 0.375), and Ca3Co2O6. First, the influences of strain and grain boundaries, via chemical substitution and reduced dimensionality, were studied via MCE in La0.7Ca0.3-xSrxMnO3. Polycrystalline, single crystalline, and thin-film La0.7Ca0.3-xSrxMnO3 samples show a paramagnetic to ferromagnetic transition at a wide variety of temperatures as well as an observed change in the fundamental nature of the transition (i.e. first-order magnetic transition to second order magnetic transition) that is dependent on the chemical concentration and dimensionality. Systematic TS and MCE experiments on Pr0.5Sr0.5MnO3 and Pr0.5Sr0.5CoO3 have uncovered the different nature of low-temperature magnetic phases and demonstrate the importance of coupled structural/magnetocrystalline anisotropy in these half-doped perovskite systems. These findings point to the existence of a distinct class of phenomena in transition-metal oxide materials due to the unique interplay between structure and magnetic anisotropy, and provide evidence for the interplay of spin and orbital order as the origin of intrinsic phase separation in manganites. While Pr0.5Sr0.5MnO3 provides important insights into the influence of first- and second-order transitions on the MCE and refrigerant capacity (RC) in a single material, giving a good guidance on the development of magnetocaloric materials for active magnetic refrigeration, Pr1-xSrxCoO3 provides an excellent system for determining the structural entropy change and its contribution to the MCE in magnetocaloric materials. We have demonstrated that the structural entropy contributes significantly to the total entropy change and the structurally coupled magnetocrystalline anisotropy plays a crucial role in tailoring the magnetocaloric properties for active magnetic refrigeration technology. In the case of La5/8−xPrxCa3/8MnO3, whose bulk form is comprised of micron-sized regions of ferromagnetic (FM), paramagnetic (PM), and charge-ordered (CO) phases, TS and MCE experiments have evidenced the dominance of low-temperature FM and high-temperature CO phases. The "dynamic" strain liquid state is strongly dependent on magnetic field, while the "frozen" strain-glass state is almost magnetic field independent. The sharp changes in the magnetization, electrical resistivity, and magnetic entropy just below the Curie temperature occur via the growth of FM domains already present in the material, even in zero magnetic field. The subtle balance of coexisting phases and kinetic arrest are also probed by MCE and TS experiments, leading to a new and more comprehensive magnetic phase diagram. A geometrically frustrated spin chain compound Ca3Co2O6 provides an interesting case study for understanding the cooperative phenomena of low-dimensional magnetism and topological magnetic frustration in a single material. Our MCE studies have yielded new insights into the nature of switching between multi-states and competing interactions within spin chains and between them, leading to a more comprehensive magnetic phase diagram.

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Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14104号 / 工博第2968号 / 新制||工||1440(附属図書館) / 26392 / UT51-2008-L159 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 金谷 利治, 教授 伊藤 紳三郎, 教授 瀧川 敏算 / 学位規則第4条第1項該当

Nanoporous polymer fibres are currently attracting increasing interest due to their unique characteristics. Increased specific surface area, improved mechanical properties and improved cellular growth are amongst the advantages that set porous fibres as ideal candidates in applications like catalysis, separation and tissue engineering. This work explores the single step production of porous poly(ε-caprolactone) (PCL) fibres through combinative electrospinning and Non-solvent Induced Phase Separation (NIPS) technique. Theoretical models, based on three different contact models (Hertzian, DMT, JKR), correlating the fibrous network specific surface area to material properties (density, surface tension, Young s modulus, Poisson s ratio) and network physical properties (density) and geometrical characteristics (fibre radius, fibre aspect ratio, network thickness) were developed in order to calculate the surface area increase caused by pore induction. Experimental results proved that a specific surface area increase of up to 56% could be achieved, compared to networks composed of smooth surfaced fibres. The good solvent effect on electrospun fibre surface morphology and size was examined through experimental investigation of four different good solvent (chloroform, dichloromethane, tetrahydrofuran and formic acid) based solutions at various good/poor solvent ratios. Chloroform was proven to be the most suitable solvent for good /poor solvent ratios varying from 75-90% v/v, whereas alternative mechanisms leading to different fibre morphologies were identified, interpreted and discussed. Evaporation rate of the good solvent was identified as the key parameter of the process. Second order polynomial equations, derived from the experimental data, correlating the feed solution physical parameters (viscosity, conductivity, surface tension) to the fibre average diameter produced were developed and validated. Response surface methodology was implemented for the design and conduction of electrospinning experiments on a 12.5 % w/v Chloroform/DMSO solution 90/10 % v/v in order to determine the individual process parameters (spinning distance, applied voltage, solution flow rate) effect in fibre surface morphology and size. The increase in any of these parameters results in increase of both the fibre size and the tendency for pore generation, whereas applied voltage was the parameter with the strongest effect. Findings from this thesis expand the knowledge about both phenomena occurring during the production process and end product properties, and can be used for the production of controlled morphology and size porous poly(ε-caprolactone) (PCL) fibres.

No description available.