Spin dynamics of NiCl(2)-4SC(NH(2))(2) in the field-induced ordered phase

NiCl(2)-4SC(NH(2))(2) (known as DTN) is a spin-1 material with a strong single-ion anisotropy that is regarded as a new candidate for Bose-Einstein condensation (BEC) of spin degrees of freedom. We present a systematic study of the low-energy excitation spectrum of DTN in the field-induced magnetically ordered phase by means of high-field electron spin resonance measurements at temperatures down to 0.45 K. We argue that two gapped modes observed in the experiment can be consistently interpreted within a four-sublattice antiferromagnet model with a finite interaction between two tetragonal subsystems and unbroken axial symmetry. The latter is crucial for the interpretation of the field-induced ordering in DTN in terms of BEC.

Precursor system of liquid crystalline phase containing propolis microparticles for the treatment of periodontal disease: Development and characterization

Precursor systems of liquid crystalline phase were prepared using the surfactant PPG-5-Ceteth-20, isopropyl myristate, and water; gelatin microparticles containing propolis were then added into these systems. Homogeneity of dispersion, the in-system microparticle morphology, and sedimentation behavior of each formulation were evaluated. The rheological and mechanical properties (hardness, compressibility, and adhesiveness), the work of syringing, and the propolis release profile were also evaluated. All the formulations exhibited pseudoplastic flow and thixotropy, and they displayed storage modulus, loss modulus, dynamic viscosity, and loss tangent that depended on temperature, frequency, and composition. Mechanical properties varied significantly among the formulations being affected by changes in the composition and temperature. Raising the concentration of surfactant and adding propolis microparticles significantly decreased the work of syringing. The drug release was non-Fickian (anomalous) and there was no significant difference between the tested systems in the times required for 10%, 30%, and 50% release of the initial drug loading.

Conductivity/microstructure study of a pyrochlore-type ordered phase in the compound Zr0.75Ce0.08Nd0.17O1.92

The compound Zr0.75Ce0.08Nd0.17O1.92 was investigated as part of a much larger electrical conductivity/microstructure study of the systems ZrO2-CeO2-M2O3 (where M=Nd, Sm, ..., Yb) [Solid State Ionics (2002)]. Electrical conductivity measurements performed in air at 800 degreesC showed significant conductivity degradation over a period of 200 h. Investigation of the annealed and as-fired specimens by ATEM revealed the presence of an emerging, ordered pyrochlore-type phase within the Zr0.75Ce0.08Nd0.17O1.92 defect-fluorite solid solution at much lower dopant levels than observed previously for zirconia binary systems. (C) 2002 Elsevier Science B.V. All rights reserved.

The nature of the ordered phase of the confined self-assembled rigid Rod model

We investigate the nature of the ordered phase and the orientational correlations between adjacent layers of the confined three-dimensional self-assembled rigid rod model, on the cubic lattice. We find that the ordered phase at finite temperatures becomes uniaxial in the thermodynamic limit, by contrast to the ground state (partial) order where the orientation of the uncorrelated layers is perpendicular to one of the three lattice directions. The increase of the orientational correlation between layers as the number of layers increases suggests that the unconfined model may also exhibit uniaxial ordering at finite temperatures.

Liquid-gas phase transition in nuclear matter from realistic many-body approaches

The existence of a liquid-gas phase transition for hot nuclear systems at subsaturation densities is a well-established prediction of finite-temperature nuclear many-body theory. In this paper, we discuss for the first time the properties of such a phase transition for homogeneous nuclear matter within the self-consistent Green's function approach. We find a substantial decrease of the critical temperature with respect to the Brueckner-Hartree-Fock approximation. Even within the same approximation, the use of two different realistic nucleon-nucleon interactions gives rise to large differences in the properties of the critical point.

Liquid crystal phase formation by biopolymers

This review discusses liquid crystal phase formation by biopolymers in solution. Lyotropic mesophases have been observed for several classes of biopolymer including DNA, peptides, polymer/peptide conjugates, glycopolymers and proteoglycans. Nematic or chiral nematic (cholesteric) phases are the most commonly observed mesophases, in which the rod-like fibrils have only orientational order. Hexagonal columnar phases are observed for several systems (DNA, PBLG, polymer/peptide hybrids) at higher concentration. Lamellar (smectic) phases are reported less often, although there are examples such as the layer arrangement of amylopectin side chains in starch. Possible explanations for the observed structures are discussed. The biological role of liquid crystal phases for several of these systems is outlined. Commonly, they may serve as a template to align fibrils for defined structural roles when the biopolymer is extruded and dried, for instance in the production of silk by spiders or silkworms, or of chitin in arthropod shells. In other cases, liquid crystal phase formation may occur in vivo simply as a consequence of high concentration, for instance the high packing density of DNA within cell nuclei.

PATH-ORDERED PHASE-FACTORS IN SCALAR QUANTUM ELECTRODYNAMICS

Starting from linear equations for the complex scalar field, the two- and three-point Green's functions are obtained in the infrared approximation. We show that the infrared singularity factorizes in the vertex function as in spinor QED, reproducing in a simple and straightforward way the result of lengthy perturbative calculations.

Liquid-gas phase transition in Bose-Einstein condensates with time evolution

We study the effects of a repulsive three-body interaction on a system of trapped ultracold atoms in a Bose-Einstein condensed state. The stationary solutions of the corresponding s-wave nonlinear Schrödinger equation suggest a scenario of first-order liquid-gas phase transition in the condensed state up to a critical strength of the effective three-body force. The time evolution of the condensate with feeding process and three-body recombination losses has a different characteristic pattern. Also, the decay time of the dense (liquid) phase is longer than expected due to strong oscillations of the mean-squared radius.

DEVELOPMENT OF CONFOCAL IMAGING TECHNIQUES FOR PROBING INTERFACIAL DYNAMICS IN MICROSCALE, GAS-LIQUID, TWO-PHASE FLOW

Micro-scale, two-phase flow is found in a variety of devices such as Lab-on-a-chip, bio-chips, micro-heat exchangers, and fuel cells. Knowledge of the fluid behavior near the dynamic gas-liquid interface is required for developing accurate predictive models. Light is distorted near a curved gas-liquid interface preventing accurate measurement of interfacial shape and internal liquid velocities. This research focused on the development of experimental methods designed to isolate and probe dynamic liquid films and measure velocity fields near a moving gas-liquid interface. A high-speed, reflectance, swept-field confocal (RSFC) imaging system was developed for imaging near curved surfaces. Experimental studies of dynamic gas-liquid interface of micro-scale, two-phase flow were conducted in three phases. Dynamic liquid film thicknesses of segmented, two-phase flow were measured using the RSFC and compared to a classic film thickness deposition model. Flow fields near a steadily moving meniscus were measured using RSFC and particle tracking velocimetry. The RSFC provided high speed imaging near the menisci without distortion caused the gas-liquid interface. Finally, interfacial morphology for internal two-phase flow and droplet evaporation were measured using interferograms produced by the RSFC imaging technique. Each technique can be used independently or simultaneously when.

Adaptive liquid-crystal phase-only passive devices

This PhD work is focused on liquid crystal based tunable phase devices with special emphasis on their design and manufacturing. In the course of the work a number of new manufacturing technologies have been implemented in the UPM clean room facilities, leading to an important improvement in the range of devices being manufactured in the laboratory. Furthermore, a number of novel phase devices have been developed, all of them including novel electrodes, and/or alignment layers. The most important manufacturing progress has been the introduction of reactive ion etching as a tool for achieving high resolution photolithography on indium-tin-oxide (ITO) coated glass and quartz substrates. Another important manufacturing result is the successful elaboration of a binding protocol of anisotropic conduction adhesives. These have been employed in high density interconnections between ITO-glass and flexible printed circuits. Regarding material characterization, the comparative study of nonstoichiometric silicon oxide (SiOx) and silica (SiO2) inorganic alignment layers, as well as the relationship between surface layer deposition, layer morphology and liquid crystal electrooptical response must be highlighted, together with the characterization of the degradation of liquid crystal devices in simulated space mission environment. A wide variety of phase devices have been developed, with special emphasis on beam steerers. One of these was developed within the framework of an ESA project, and consisted of a high density reconfigurable 1D blaze grating, with a spatial separation of the controlling microelectronics and the active, radiation exposed, area. The developed devices confirmed the assumption that liquid crystal devices with such a separation of components, are radiation hard, and can be designed to be both vibration and temperature sturdy. In parallel to the above, an evenly variable analog beam steering device was designed, manufactured and characterized, providing a narrow cone diffraction free beam steering. This steering device is characterized by a very limited number of electrodes necessary for the redirection of a light beam. As few as 4 different voltage levels were needed in order to redirect a light beam. Finally at the Wojskowa Akademia Techniczna (Military University of Technology) in Warsaw, Poland, a wedged analog tunable beam steering device was designed, manufactured and characterized. This beam steerer, like the former one, was designed to resist the harsh conditions both in space and in the context of the shuttle launch. Apart from the beam steering devices, reconfigurable vortices and modal lens devices have been manufactured and characterized. In summary, during this work a large number of liquid crystal devices and liquid crystal device manufacturing technologies have been developed. Besides their relevance in scientific publications and technical achievements, most of these new devices have demonstrated their usefulness in the actual work of the research group where this PhD has been completed. El presente trabajo de Tesis se ha centrado en el diseño, fabricación y caracterización de nuevos dispositivos de fase basados en cristal líquido. Actualmente se están desarrollando dispositivos basados en cristal líquido para aplicaciones diferentes a su uso habitual como displays. Poseen la ventaja de que los dispositivos pueden ser controlados por bajas tensiones y no necesitan elementos mecánicos para su funcionamiento. La fabricación de todos los dispositivos del presente trabajo se ha realizado en la cámara limpia del grupo. La cámara limpia ha sido diseñada por el grupo de investigación, es de dimensiones reducidas pero muy versátil. Está dividida en distintas áreas de trabajo dependiendo del tipo de proceso que se lleva a cabo. La cámara limpia está completamente cubierta de un material libre de polvo. Todas las entradas de suministro de gas y agua están selladas. El aire filtrado es constantemente bombeado dentro de la zona limpia, a fin de crear una sobrepresión evitando así la entrada de aire sin filtrar. Las personas que trabajan en esta zona siempre deben de estar protegidas con un traje especial. Se utilizan trajes especiales que constan de: mono, máscara, guantes de látex, gorro, patucos y gafas de protección UV, cuando sea necesario. Para introducir material dentro de la cámara limpia se debe limpiar con alcohol y paños especiales y posteriormente secarlos con nitrógeno a presión. La fabricación debe seguir estrictamente unos pasos determinados, que pueden cambiar dependiendo de los requerimientos de cada dispositivo. Por ello, la fabricación de dispositivos requiere la formulación de varios protocolos de fabricación. Estos protocolos deben ser estrictamente respetados a fin de obtener repetitividad en los experimentos, lo que lleva siempre asociado un proceso de fabricación fiable. Una célula de cristal líquido está compuesta (de forma general) por dos vidrios ensamblados (sándwich) y colocados a una distancia determinada. Los vidrios se han sometido a una serie de procesos para acondicionar las superficies internas. La célula se llena con cristal líquido. De forma resumida, el proceso de fabricación general es el siguiente: inicialmente, se cortan los vidrios (cuya cara interna es conductora) y se limpian. Después se imprimen las pistas sobre el vidrio formando los píxeles. Estas pistas conductoras provienen del vidrio con la capa conductora de ITO (óxido de indio y estaño). Esto se hace a través de un proceso de fotolitografía con una resina fotosensible, y un desarrollo y ataque posterior del ITO sin protección. Más tarde, las caras internas de los vidrios se acondicionan depositando una capa, que puede ser orgánica o inorgánica (un polímero o un óxido). Esta etapa es crucial para el funcionamiento del dispositivo: induce la orientación de las moléculas de cristal líquido. Una vez que las superficies están acondicionadas, se depositan espaciadores en las mismas: son pequeñas esferas o cilindros de tamaño calibrado (pocos micrómetros) para garantizar un espesor homogéneo del dispositivo. Después en uno de los sustratos se deposita un adhesivo (gasket). A continuación, los sustratos se ensamblan teniendo en cuenta que el gasket debe dejar una boca libre para que el cristal líquido se introduzca posteriormente dentro de la célula. El llenado de la célula se realiza en una cámara de vacío y después la boca se sella. Por último, la conexión de los cables a la célula y el montaje de los polarizadores se realizan fuera de la sala limpia (Figura 1). Dependiendo de la aplicación, el cristal líquido empleado y los demás componentes de la célula tendrán unas características particulares. Para el diseño de los dispositivos de este trabajo se ha realizado un estudio de superficies inorgánicas de alineamiento del cristal líquido, que será de gran importancia para la preparación de los dispositivos de fase, dependiendo de las condiciones ambientales en las que vayan a trabajar. Los materiales inorgánicos que se han estudiado han sido en este caso SiOx y SiO2. El estudio ha comprendido tanto los factores de preparación influyentes en el alineamiento, el comportamiento del cristal líquido al variar estos factores y un estudio de la morfología de las superficies obtenidas.

Brij Detergents Reveal New Aspects Of Membrane Microdomain In Erythrocytes.

Membrane microdomains enriched in cholesterol, sphingolipids (rafts), and specific proteins are involved in important physiological functions. However their structure, size and stability are still controversial. Given that detergent-resistant membranes (DRMs) are in the liquid-ordered state and are rich in raft-like components, they might correspond to rafts at least to some extent. Here we monitor the lateral order of biological membranes by characterizing DRMs from erythrocytes obtained with Brij-98, Brij-58, and TX-100 at 4 °C and 37 °C. All DRMs were enriched in cholesterol and contained the raft markers flotillin-2 and stomatin. However, sphingomyelin (SM) was only found to be enriched in TX-100-DRMs - a detergent that preferentially solubilizes the membrane inner leaflet - while Band 3 was present solely in Brij-DRMs. Electron paramagnetic resonance spectra showed that the acyl chain packing of Brij-DRMs was lower than TX-100-DRMs, providing evidence of their diverse lipid composition. Fatty acid analysis revealed that the SM fraction of the DRMs was enriched in lignoceric acid, which should specifically contribute to the resistance of SM to detergents. These results indicate that lipids from the outer leaflet, particularly SM, are essential for the formation of the liquid-ordered phase of DRMs. At last, the differential solubilization process induced by Brij-98 and TX-100 was monitored using giant unilamellar vesicles. This study suggests that Brij and TX-100-DRMs reflect different degrees of lateral order of the membrane microdomains. Additionally, Brij DRMs are composed by both inner and outer leaflet components, making them more physiologically relevant than TX-100-DRMs to the studies of membrane rafts.

Defects in vesicle core induced by Escherichia coli dihydroorotate dehydrogenase

Dihydroorotate dehydrogenase (DHODH) catalyzes the oxidation of dihydroorotate to orotate during the fourth step of the de novo pyrimidine synthesis pathway. In rapidly proliferating mammalian cells, pyrimidine salvage pathway is insufficient to overcome deficiencies in that pathway for nucleotide synthesis. Moreover, as certain parasites lack salvage enzymes, relying solely on the de novo pathway, DHODH inhibition has turned out as an efficient way to block pyrimidine biosynthesis. Escherichia coli DHODH (EcDHODH) is a class 2 DHODH, found associated to cytosolic membranes through an N-terminal extension. We used electronic spin resonance (ESR) to study the interaction of EcDHODH with vesicles of 1,2-dioleoyl-sn-glycero-phosphatidylcholine/detergent. Changes in vesicle dynamic structure induced by the enzyme were monitored via spin labels located at different positions of phospholipid derivatives. Two-component ESR spectra are obtained for labels 5- and 1 0-phosphatidylcholine in presence of EcDHODH, whereas other probes show a single-component spectrum. The appearance of an additional spectral component with features related to fast-motion regime of the probe is attributed to the formation of a defect-like structure in the membrane hydrophobic region. This is probably the mechanism used by the protein to capture quinones used as electron acceptors during catalysis. The use of specific spectral simulation routines allows us to characterize the ESR spectra in terms of changes in polarity and mobility around the spin-labeled phospholipids. We believe this is the first report of direct evidences concerning the binding of class 2 DHODH to membrane systems.

Études des interactions détergents/lipides dans les systèmes membranaires

Les liposomes sont des structures sphériques formés par l'auto-assemblage de molécules amphiphiles sous forme d'une bicouche. Cette bicouche sépare le volume intérieur du liposome du milieu extérieur, de la même manière que les membranes cellulaires. Les liposomes sont donc des modèles de membranes cellulaires et sont formulés pour étudier les processus biologiques qui font intervenir la membrane (transport de molécules à travers la membrane, effets des charges en surface, interactions entre la matrice lipidique et d'autres molécules, etc.). Parce qu'ils peuvent encapsuler une solution aqueuse en leur volume intérieur, ils sont aussi utilisés aujourd'hui comme nanovecteurs de principes actifs. Nous avons formulé des liposomes non-phospholipidiques riches en stérol que nous avons appelés stérosomes. Ces stérosomes sont composés d'environ 30 % d'amphiphiles monoalkylés et d'environ 70 % de stérols (cholestérol, Chol, et/ou sulfate de cholestérol, Schol). Quand certaines conditions sont respectées, ces mélanges sont capables de former une phase liquide ordonnée (Lo) pour donner, par extrusion, des vésicules unilamellaires. Certaines de ces nouvelles formulations ont été fonctionnalisées de manière à libérer leur contenu en réponse à un stimulus externe. En incorporant des acides gras dérivés de l’acide palmitique possédant différents pKa, nous avons pu contrôler le pH auquel la libération débute. Un modèle mathématique a été proposé afin de cerner les paramètres régissant leur comportement de libération. En incorporant un amphiphile sensible à la lumière (un dérivé de l’azobenzène), les liposomes formés semblent répondre à une radiation lumineuse. Pour ce système, il serait probablement nécessaire de tracer le diagramme de phase du mélange afin de contrôler la photo-libération de l’agent encapsulé. Nous avons aussi formulé des liposomes contenant un amphiphile cationique (le chlorure de cétylpyridinium). En tant que nanovecteurs, ces stérosomes montrent un potentiel intéressant pour la libération passive ou contrôlée de principes actifs. Pour ces systèmes, nous avons développé un modèle pour déterminer l’orientation des différentes molécules dans la bicouche. La formation de ces nouveaux systèmes a aussi apporté de nouvelles connaissances dans le domaine des interactions détergents-lipides. Aux nombreux effets du cholestérol (Chol) sur les systèmes biologiques, il faut ajouter maintenant que les stérols sont aussi capables de forcer les amphiphiles monoalkylés à former des bicouches. Cette nouvelle propriété peut avoir des répercussions sur notre compréhension du fonctionnement des systèmes biologiques. Enfin, les amphiphiles monoalkylés peuvent interagir avec la membrane et avoir des répercussions importantes sur son fonctionnement. Par exemple, l'effet antibactérien de détergents est supposé être dû à leur insertion dans la membrane. Cette insertion est régie par l'affinité existant entre le détergent et cette dernière. Dans ce cadre, nous avons voulu développer une nouvelle méthode permettant d'étudier ces affinités. Nous avons choisi la spectroscopie Raman exaltée de surface (SERS) pour sa sensibilité. Les hypothèses permettant de déterminer cette constante d’affinité se basent sur l’incapacité du détergent à exalter le signal SERS lorsque le détergent est inséré dans la membrane. Les résultats ont été comparés à ceux obtenus par titration calorimétrique isotherme (ITC). Les résultats ont montré des différences. Ces différences ont été discutées.