This thesis presents an experimental study of the influence of an external field and alignment upon a colloid of a liquid crystal (octycyanobiphenyl denoted 8CB) and a silica gel of aerosil nano-particles. The first techniques used was an AC-calorimetry (alternating current heating) and the systems under investigation were firstly put under the influence of a magnetic field at John Hopkins University in Baltimore by professor Leheny's group. The experiments revealed changes in transition temperatures, nematic range and critical coefficient that could account for what we called a 'memory' of the above mentioned structures. The second technique, dielectric spectroscopy, was applied to the same very densities of mixture s mentioned in the first paragraph. The samples were applied in one procedure an increasingly higher alternating electric field. An overall increase of the capacitance of the sample was measured. The second experiment was to reproduce the application of the magnetic field from the AC-calorimetry experiment now with an electric field. In dielectric spectroscopy case, an increase in transition temperature after the application of the procedure was revealed.

No description available.

A series of phosphotripeptide ligands for the Grb2 SH2 domain was designed and synthesized, each of which derived from the minimal consensus sequence required for binding: Ac-pYXN. The binding affinity and related thermodynamic parameters were determined by isothermal titration calorimetry. Both the size and connectivity of the side-chain was varied. The consequences of incorporating α,α-disubstitution at the pY+1 residue on binding thermodynamics were evaluated, as were the effects of constraining the side-chains in a ring. The series was evaluated from a number of perspectives: (1) increasing size of the pY+1 residue by utilizing various amino acid types: monoalkyl, dialkyl, or cycloalkyl; (2) comparisons between ligands with the same number of carbons (scission control); and (3) by comparing ligands incorporating cyclic pY+1 residues with those incorporating α,α-dialkyl residues with one fewer methylene group (excision control). Inconsistencies in the thermodynamic consequence of constraining the backbone were observed within this set of ligands, which reveal the limitations of our understanding of protein-ligand interactions. Aspects of both the classical and non-classical hydrophobic effect were observed, but the occurance of one over the other could not be explained. / text

No description available.

Cardiac contraction at the level of the sarcomere is regulated by the thin filament (TF) composed of actin, alpha tropomyosin (TPM), and the troponin (Tn) complex (cTnT: cTnC: cTnI). The "gate-keeper" protein, α-TPM, is a highly conserved α-helical, coiled-coil dimer that spans actin and regulates myosin-actin interactions. The N-terminus of one α-TPM dimer inter-digitates with the C-terminus of the adjacent dimer in a head-to-tail fashion forming the flexible and cooperative TPM-overlap that is necessary for myofilament activation. Two dilated cardiomyopathy (DCM) causing mutations in TPM (D84N and D230N) and one hypertrophic cardiomyopathy (HCM) causing mutation (E62Q), all identified in large, unrelated, multigenerational families, were utilized to study how primary alterations in protein structure cause functional deficits. We hypothesize that structural changes from a single point mutation propagate along the -helical coiled-coil of TPM, thus affecting its regulatory function. Structural effects of the mutations studied via differential scanning calorimetry (DSC) on TPM alone revealed significant changes in the thermal unfolding temperatures of both the C- and N-termini for all mutants compared to WT, indicating that mutational effects propagate to both ends of TPM, thus affecting the overlap region. Although, of note, the proximal termini to the mutation has shown more significant structural changes compared to WT. DSC analysis on fully reconstituted TF’s (Tn:TPM:Actin) revealed effects on the TPM-Actin cooperativity of activation, affecting interaction strength (thermal stability), and the rigidity of TPM moving along actin (FWHM). To characterize the resultant functional effect of these discrete changes in thermal stability and TPM rigidity, ATPase assays were used to measure actomyosin activation in the presence and absence of Ca2+. Together, these data will provide a molecular level understanding of the structural and functional deficits caused by these mutations to help elucidate the mechanisms leading to disease.

There are significant differences in the metabolism of nutritional substrates in polytrauma patients. The actual metabolic needs of the patient may not be achieved despite the guidelines and recommendations for energy supply in the parenteral and enteral form of nutrition are followed. Subsequently this may lead to the occurrence of complications. The aim of the study was to compare the energy intake of each nutrient substrate supplied with nutrition by finding the nutritional substrate utilisation value which is obtained from indirect calorimetry measurements in patients with multiple injuries at the surgical ICU 1 of the Hradec Králové Teaching Hospital. By comparing this data you can obtain the optimum value for the nutritional needs of the patients. In the study we used seven spontaneously breathing polytrauma patients, three women and four men, of an average age of 41±21 years. Utilisations of nutritive substrates of each patient were obtained by indirect calorimetry. Accurate information on the amount and composition of nutrition supplied over 24 hours was also obtained. The patients received an average of 3.80±1.40 g/kg/day of carbohydrates, 1.03±0.56 g/kg/day of lipids and 1.40 ± 0.44 g/kg /day of proteins. The total energy intake was on average 30.94±11.03 kcal/kg/day. In six of seven...

Un des principaux objectifs de l'expérience ATLAS auprès du LHC est l'observations ou l'exclusion de nouvelle physique au-delà du Modèle Standard, en passant par les mesures de sections efficaces de production de processus du Modèle Standard. Sachant que le taux de production d'une particule dépends de sa section efficace de production ainsi que de la luminosité, il est necessaire de mesurer cette luminosité avec une grande précision. L'expérience ATLAS possède plusieurs détecteurs capable de mesurer la luminosité, dont les deux principaux: LUCID (Luminosity measurement Using Cerenkov Integrating Detector), et BCM (Beam Condition Monitor). Ces détecteurs sont calibrés absolument pendant des prises de données dédiées appelés van der Meer scans, qui ont permis d'obtenir une erreur systématique sur la détermination de la luminosité de 3.4% en 2010. Afin d'obtenir un maximum de différentes approches à la luminosité, plusieurs autres détecteurs contribuent aux différentes comparaisons. Ce document présente les calorimètres à argon liquide du détecteur ATLAS, et en particulier la mise en route et l'opération de leur système haute-tension. Il est montré qu'en mesurant les courant de ce système haute-tension pendant les prises de données de collisions de protons, il est possible d'obtenir des signaux proportionnels a la luminosité. En calibrant ces courants par rapport a un autre luminomètre, il est montré que cette calibration est stable au niveau de 0.5%. / The main goals of the ATLAS scientific programme are the observation or exclusion of physics beyond the Standard Model (SM), as well as the measurement of production cross-sections of SM processes. As the rate of events N of a given physics process is linked to the cross-section through the luminosity, it is important to measure the luminosity with great precision. The ATLAS experiment has two major luminosity monitors, LUCID (Luminosity measurement Using Cerenkov Integrating Detector), which consists of Cerenkov tubes located around the beam axis 17m away from the interaction point, and BCM (Beam Condition Monitor) which is a diamond-based detector and has both beam-abort and luminosity capabilities. As these detectors provide a relative luminosity measurement, they were absolutely calibrated in 2010 using the van der Meer procedure, achieving a total systematic uncertainty of 3.4%. The ultimate plan is to provide an absolute calibration using the ALFA detector during a run with special beam optics. In order to provide more cross-checks and a better control on the systematic uncertainties, other luminosity handles are always needed. In particular, an independent measurement using the liquid argon forward calorimeter (FCal), based on the readout current of its high-voltage system, has been developed. This document presents the commissioning and operations of the ATLAS liquid argon calorimeter high-voltage system, as well as its usage to perform a luminosity determination. Analysis of the high-voltage currents during LHC collisions and comparisons with other luminosity detectors have led to a calibration of these currents with a precision better than 0.5%.

La mise en place de nouvelles normes, de plus en plus contraignantes, est un défi pour l’élaboration de nouveaux matériaux résistants à haute température. Le premier objectif de l’étude est de mettre au point un panneau – coupe-feu 2h à base de plâtre. Il devra présenter à la fois de bonnes qualités d’isolant thermique et des propriétés mécaniques suffisantes pour maintenir l’intégrité d’un ouvrage d’art. Le second objectif est de comprendre, d’une part, l’influence de divers paramètres sur le phénomène de prise du plâtre et d’autre part, de déterminer les propriétés thermomécaniques du composite. Ce type de matériau est obtenu par l’association d’eau, d’une matrice céramique composée essentiellement de sulfate de calcium dihydraté et de charges utilisées en tant que renforts thermiques et/ou mécaniques.Dans une première partie, l’étude porte essentiellement sur la matrice pour laquelle une granulométrie permettant d’optimiser les propriétés mécaniques est déterminée. La matrice est ensuite caractérisée chimiquement. Une étude par calorimétrie isotherme de la réaction d’hydratation du sulfate de calcium semihydraté (plâtre) est réalisée afin de comprendre le mécanisme de prise du plâtre et de maîtriser les temps de prise. Pour cela, on étudie l’influence de la taille des grains, de la quantité d’eau, de la composition chimique du plâtre et de la présence ou non d’adjuvants sur la cinétique d’hydratation du plâtre.Dans une seconde partie, les renforts nécessaires à l’élaboration du composite sont sélectionnés. Les relations entre les quantités de charges et les propriétés thermomécaniques (conductivité thermique, module d’Young, dureté Shore C) du système sont étudiées. Ainsi, une modélisation du comportement du composite sous sollicitations thermique et mécanique est proposée. Cette étude a permis de définir une formulation de panneau présentant de très bonnes propriétés thermiques et des propriétés mécaniques suffisantes pour assurer l’intégrité d’un ouvrage d’art en cas d’incendie. La formulation mise au point a fait l’objet d’un dépôt de brevet (n° BIP207506FR00 en décembre 2010). Cette formulation est actuellement commercialisée par la société EXTHA sous forme de plaques. / The increase of prevention and the introduction of more and more restrictive standards are challenges for the development of new materials resistant to high temperatures. The aim of the study is to develop a fire panel with both good properties of thermal insulator (low thermal conductivity, fumes tightness) and mechanical properties sufficient to maintain a structure integrity in case of fire.That kind of material is composed of an inorganic matrix mainly composed of calcium sulfate dihydrate and of additives used as thermal and mechanical reinforcements. The first part of the study is focused on the matrix, especially on the determination of a particle size distribution for which the mechanical properties are optimized. Then, the matrix is chemically characterized. A study by isothermal calorimetry of the hydration reaction of the calcium sulfate hemihydrate (plaster) is conducted to understand the mechanism of hydration and to control setting times. For this, the influence of the grain size, of the quantity of water, of the chemical composition of plaster, of additives on the kinetics of hydration of the plaster is studied. The second part of this work resumes the different steps of the selection of additives. After that, the relation between the microstructure and thermo - mechanicals properties (thermal conductivity, Young modulus, Shore C hardness) of the system is studied.This study has permitted to establish a panel formulation having very good thermal and mechanical properties to ensure building integrity in case of fire. The formulation has been patented in December 2010 (No BIP207506FR00) and it is currently marketed as panels by Extha.

Self-assembly and the induced orientation of microscopic biological systems is of great scientific interest, because it holds the promise of many pharmaceutical applications. This dissertation presents experimental studies done on proteins, short DNA fragments, and cholesterol structures self-assembled in an aqueous environment. The goal is to probe the thermo-physical properties of these systems, their phases and phase transitions, in order to better under-stand the principles behind their unique assemblies and function. It is accepted that in all these systems the solvent water plays an important role on the assembly folding, orientation, and activity of biopolymers. However, the abundance of water in typical samples presents many experimental challenges. It is indeed the case that changes in the properties of hydration in watery environments are responsible for the dynamics of protein and DNA biomolecules. We have explored in more detail the thermodynamics, the structural properties, and the dynamics near structural transitions of biomolecules in their native aqueous environment.

Liquid crystals (LCs) are anisotropic fluids that exhibit numerous thermodynamically stable phases in between an isotropic liquid and a three-dimensionally ordered solid. In their simplest ordered phase, the nematic, LCs show orientational order due to molecular self assembly and at the same time maintaining fluid flow properties. In the smectic phase, they show both orientational and partial translational order characterized by a 1-d density wave. Liquid crystalline substances have been extensively studied due to their applications and as important physical models of self-assembly. The effect of the disorder and impurities on LC systems is an important and challenging problem to the fundamental understanding of phases ordering or self-assembly and continually attracts the attention of researchers. The disordered systems often display complex and rich phenomena, being the generalization of the pure (ideal) systems. Disorder can dramatically alter the physical properties of multi-component, composite systems. In particular, the effect of disorder on phase transitions is important as the disorder typically couples to the order parameter, which can be usefully described as a random local field that is conjugate to the order parameter. This is usually realized in systems with random inclusions in a phase ordering media, e.g., a colloidal dispersion of solids in a complex fluid. Another form of disorder is presented by dilution effects, which imposes instead the random breaking or weakening of intermolecular bonds or interactions responsible for the phase ordering. Exploring a good physical system representing random dilution effects in a controlled manner offers a physical probe to unresolved problems in the understanding of mesophasic order. This Dissertation presents a series of studies of dilution and different form of disorder effect on liquid crystal phase transitions. We have used high-resolution AC-calorimetry, dielectric spectroscopy as well as polarizing microscopy to characterize the effects of solvent such as hexane, acetone, decane, and nanomaterials such as multiwall carbon nanotubes and ferroelectric nanoparticles on the phase transitions of several liquid crystals. The liquid crystals of interest are: pentylcyanobiphenyl (5CB), octylcyanobiphenyl (8CB), and decylcyanobiphenyl (10CB). Studies have been carried out as a function of solvent, nanotube, and nanoparticles concentration and temperature spanning the isotropic to nematic (I-N), nematic to smectic-A (N-SmA), and isotropic to smectic-A (I-SmA) phase transitions.