15 search hits
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Low Density 2D-Electron Sheets on Liquid 3He Surface
(2006)
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Sergiy Putselyk
- In this work, experiments with electron mobility on the surface of 3He were carried out. Mobility measurements were done in the temperature range 0.6-600mK, the operating frequencies 1Hz-100kHz, the excitation voltage 4mV - 1V and pressing electrical fields 0-255V/cm on the top electrode and 0-47.5V/cm for three bottom electrodes. Films with different thicknesses 0.2, 0.5 and 1.0mm were also under investigations. In the temperature region above 300mK, electron scattering on 3He vapor atoms was observed. In our measurements we failed to observe Wigner solid crystallization. Possible explanations could be: Interplay of two conductivities, namely conductivity through the electron layer in the center ("bulk") and conductivity through the boundary layer of electrons ("boundary"). Another explanation could be overheating effect or sliding mode of Surface State Electrons, when electron layer was near decoupled from helium surface. In our opinion, it is most probable explanation. We also did measurements below temperature of the superfluid point transition, though we did not observed any change in the signal. Possible explanation could be overheating of electrons by excitation voltage or sliding mode.
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Crystal Structures of Perovskite-related Can(Nb,Ti)nO3n+2 (n=5 and 6)
(2006)
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Jonathan Guevarra
- In this thesis, the crystal structures at room temperature of perovskite-related materials belonging to the homologous series Can(Nb,Ti)nO3n+2 with n = 5 and 6 have been accurately determined by single-crystal X-ray diffraction. The three compounds Ca5Nb5O17 (n = 5), Ca5Nb4TiO17 (n = 5), and Ca6(Nb,Ti)6O20 (n = 6) have been investigated. Their general structural features are the same, independent of the composition n. The crystal structures are composed of slabs of corner-sharing (Nb,Ti)O6 octahedra stacked along the [110] direction of the cubic perovskite structure. Neighboring slabs are separated by additional layers of oxygen atoms and are shifted with respect to each other by half the body diagonal of an octahedron along a. The number of layers of octahedra in a slab, indicated by the parameter n, determines the structure type, which varies therefore with composition. The crystal structures are all monoclinic (b unique) with a centrosymmetric P21/c symmetry for the n = 5 type compounds and an acentric P21 symmetry for the n = 6 type compound (in the latter, pseudo-inversion symmetries have been observed). The distortion of the (Nb,Ti)O6 octahedra increases from the center to the borders of the slabs. For the Ti-doped compounds, an ordering of Nb and Ti ions is observed with Ti ions preferentially occupying the central region of the slabs where the octahedral is least distorted. Nb and Ti ions have computed valences close to their formal valences of 5+ and 4+, respectively, for all sites in the structure. This indicates that Nb and Ti ions are equally well accommodated by the different oxygen environments in the slabs and that the observed ordering of Nb and Ti ions can only be the result of the different octahedral distortions. For the undoped Ca5Nb5O17 (n = 5), computed valences of Nb ions are close to 5+ at the borders and smaller fractional valences are obtained in the middle of the slabs. This suggests that the electrical conduction in this compound is most likely accommodated by the least distorted octahedra. Owing to the similarity in the structural features, a common model was successfully employed in the structural descriptions of the compounds investigated. Applying the superspace approach to the Ti-doped compounds, the crystal structures were characterized as commensurately modulated structures with a common basic structure and a centrosymmetric superspace group valid for both compounds, while the modulation wave vectors and the modulation functions depend on the composition n. Structure refinements in superspace demonstrate the efficiency of the superspace approach. The different occupation factors of Nb and Ti ions in the slabs as obtained in the three-dimensional structure model have been reproduced in the superspace refinements. The higher quality of the structure model obtained from the superspace refinements is illustrated by the computed valences of Nb and Ti ions which are much closer to their formal values of 5+ and 4+, respectively, for all sites in the structure compared to the three-dimensional or supercell model. In the case of n = 6 compound, the application of a centrosymmetric superspace group leads to an equal Nb/Ti ratio on sites that are related by superspace inversion, but that are independent sites in the supercell. In this way, the superspace approach provides a natural explanation for the pseudo-inversion symmetries as they have been observed in the supercell structure, while removing the interdependencies between parameters. The displacive modulation functions for the two compounds exhibit similarities, but in general are not identical. The modulation functions in n = 6 may not be used to describe exactly the atomic displacements in n = 5. Thus it is concluded that for this homologous series, the idea of a unified superspace model does not extend towards the precise atomic positions of the two compounds which are characterized by the displacive modulation functions.
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Study of relaxation processes in simple glass formers by means of 2H NMR spectroscopy
(2006)
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Sorin A. Lusceac
- In the present work molecular glass formers were investigated by means of multidimensional 2H NMR (solid echo and 2D spectra, stimulated echo decays, spin-lattice and spin-spin relaxation). We focused our attention on glass forming liquids that were composed of simple, rigid molecules in order to study the properties of the secondary relaxation processes (beta-processes) in the glassy state (0.5Tg<T<Tg). For several systems we also acquired NMR data at temperatures corresponding to the supercooled liquid state (T>Tg) providing information on the main relaxation process (alpha-process). In addition, extensive random walk simulations were performed to gain a deeper understanding of the experimental findings. As the molecular motion involved in the beta-process displays a highly restricted angular displacement, its effects on the line shape of the solid echo are subtle. The spectral changes due to molecular motion are quantified by the relative spectral intensity at zero 2H NMR frequency R(tp,T) (tp is the interpulse delay). Random walk simulations employing several simple models for the beta-process were performed in order to estimate the evolution of R(tp,T). They proved that 2H NMR can provide a time constant <ln(taubeta)> at a certain temperature. In addition, it was demonstrated that the R(tp,T) traces contain information about the angular amplitude and the distribution of correlation times G[ln(taubeta)]. The available data of ethanol-d1 and ethanol-d2 were successfully analyzed in the view of the simulation results, and the time constant of ethanol-d1 agrees well with dielectric spectroscopy (DS) data. We studied in detail m-fluoroaniline (m-FAN) by 2H NMR as it is a glass former that displays a relatively peculiar beta-process that is faster and shows a much smaller relative relaxation strength than most of the previously studied materials (e.g. toluene, polybutadiene). The geometry of molecular motion involved in the beta-process in m-FAN was found to be similar with the one in toluene with the difference that in the case of m-FAN a smaller angular amplitude suffices to explain the experimental findings. However, a large discrepancy between the NMR and DS time scale of the beta-process was found. The results support the claim of several authors that m-FAN forms hydrogen-bond-induced-clusters. In the quest of further understanding the secondary relaxation processes, toluene and o-terphenyl (OTP) confined in a nanoporous SBA-15 matrix were investigated. The temperature dependence of spin-lattice relaxation time allows us to differentiate type A (without a secondary dielectric beta-peak) from type B glass formers (with a beta-peak). We find that the alpha-process in both OTP (type A) and toluene (type B) in confinement is governed by a broad heterogeneous distribution of correlation times, not seen in the bulk. Additionally there is evidence that the beta-process in toluene changes under confinement conditions, where it exhibits a distribution of spin-lattice relaxation times that is substantially broadened towards faster times. In contrast, the corresponding low temperature relaxation time for OTP is not altered in confinement (T<Tg). Polybutadiene (PBD) is a widely investigated polymer without side groups. At low temperatures (T<Tg) we identified a further secondary process in addition to the beta-process that was designated as the gamma-process. In addition, a mixture of roughly 10% deuterated benzene in PBD was also measured by 2H NMR. The results proved that the benzene molecules display features very similar to those of neat PBD, thus being sensitive to both beta and gamma-process of its host. In the end we established several constraints for any model to explain the gamma-process ruling out a large angle reorientation of the C- 2H bonds at low temperatures (T<Tg). The supercooled plastically crystalline phase of cyanoadamantane was investigated in order to study the alpha-process (T>Tg). Although the orientationally disordered crystalline phase always coexisted with the orientationally ordered crystalline phase, we were able to single out the signal from the former by selective excitation and it was possible to carry out line shape measurements and 2D experiments. The latter directly reveal 6-fold reorientation of the molecular C3 axis via 90° angles, thus reflecting the symmetry of the lattice. We can reproduce the line shape by random walk simulations properly taking into account the molecular motion. Both line shape and 2D experiments yield time constants which agree with those reported by other techniques. We did not find any indication of a small angle motion as usually found for the alpha-process in structural glasses. Thus, the motional process in the glassy crystal appears to be simple and quite different from that in the structural glasses.
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Magnetooptische Untersuchungen an ferromagnetischen GaMnAs-Epitaxieschichten
(2006)
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Ralf Lang
- Die ferromagnetische Phase von dünnen GaMnAs-Epitaxieschichten, die auf GaAs-Substrat aufgebracht sind und einen Mangan-Gehalt von 1,4-8,5% besitzen werden mit Hilfe des magnetooptischen Kerr-Effektes (MOKE) und des magnetischen Zirkular-Dichroismus (MCD) untersucht. Der Temperaturbereich erstreckt sich dabei von 1,9K bis zu 100K und das senkrecht zur Schichtebene orientierte Magnetfeld liegt zwischen -5 und +5 kOe. Um sowohl den MOKE als auch den MCD zu analysieren, wurde ein Modell einer parabolischen Interband dielektrischen Funktion entwickelt, das Beiträge vom schweren- und leichten-Loch-Valenzband sowie vom „Split-Off“-Valenzband und Leitungsband besitzt und ausserdem die Moss-Burstein-Verschiebung berücksichtigt. Die Besetzung der spin-aufgespaltenen Valenzbänder wurde durch die Betrachtung des Fermi-Niveaus der Löcher explizit mit berücksichtigt. Für die Austausch-Wechselwirkung zwischen Mangan-Spins und Löchern wurde eine Molekularfeld-Näherung verwendet, wie sie bei verdünnt magnetischen Halbleitern üblich ist. Die Anpassungsrechungen an die experimentellen Daten ergaben einen Leitungsband-Austauschparameter von zwischen 0,22 und 0,33 eV und einen Valenzband-Austauschparameter zwischen 0,6 und 2,3 eV, abhängig von der Löcherdichte und der Mangan-Konzentration. Diese Werte sind nahe bei denjenigen der II-Mn-VI Halbleiter, allerdings ist das Vorzeichen des Valenband-Austauschparameters umgekehrt verglichen mit den II-Mn-VI-Proben. Das bedeutet, dass ein ferromagnetischer Austausch zwischen Mangan-Spins und freien Löchern im GaMnAs-System vorliegt. Die quantitative Auswertung der wellenlängenabhängigen MOKE- und MCD-Daten führt zur Einführung eines dispersionslosen Leitungsband-Niveaus. Aus den Messungen der Hyterese konnten die Curie-Temperaturen, Koerzitiv-Felder und die kubischen Anisotropie-Konstanten bestimmt werden.
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The one-dimensional spin-1/2 ANNNI model in non-commuting magnetic fields
(2006)
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Adekunle Moses Adegoke
- In this thesis we have investigated the one-dimensional spin-1/2 Axial Next Nearest Neighbour Ising (ANNNI) model in non-commuting magnetic fields. As a starting point we obtained an estimate of the phase diagram of the model by treating the spins as classical vectors. This was followed by an investigation of the zero temperature ground state of the one-dimensional spin-1/2 ANNNI model in a longitudinal magnetic field. By using the symmetries of the Hamiltonian, we were able to diagonalize the longitudinal ANNNI model exactly. We found that there are four different possible ground state configurations for the longitudinal ANNNI model, in the thermodynamic limit. Rayleigh Schroedinger perturbation series for the ground state energy of the ANNNI model in non-commuting fields were then developed in each of the four ordered regions. Order parameters and the associated susceptibilities as well as specific heats were calculated. By application of the finite-size scaling technique it was possible to obtain the phase boundaries of the model numerically. For certain limits of the full Hamiltonian we compared the obtained results with the existing literature and we got good agreement.
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Holographische Datenspeicherung in nanostrukturierten azobenzolhaltigen Polymeren
(2006)
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Michael Häckel
- In der vorliegenden Arbeit werden verschiedene Diblock-Copolymere mit azobenzolhaltigen Seitenketten auf ihr Potential für Anwendungen als wiederbeschreibbares Medium für die holographische Datenspeicherung untersucht. Die Seitenketten dieser Polymere können durch Bestrahlung mit Licht angeregt und umorientiert werden. Infolge der Anisotropie der Seitenketten führt die Umorientierung in den beleuchteten Bereichen des Materials zu Doppelbrechung und damit zu einer räumlichen Brechungsindexmodulation für polarisiertes Licht. Bei Blockcopolymeren tritt Mikrophasenseparation auf. Diese ermöglicht im räumlichen Mittel eine Verdünnung der Azobenzolfarbstoffe bei gleichbleibend hoher lokaler Konzentration in den eingeschlossenen Minoritätsphasen. Die makroskopische Verdünnung ist zur Reduzierung des Absorptionskoeffizienten notwendig, damit das zum Schreiben verwendete Licht Proben mit einer Dicke im Bereich von 1 mm durchdringen kann. Eine hohe lokale Konzentration ist andererseits für die Stabilisierung der eingeschriebenen Information notwendig. Es ist bekannt, dass in azobenzolhaltigen Homopolymeren und statistischen Copolymeren eine stabile Orientierung bei gleichzeitiger schneller lichtinduzierter Umlagerung durch flüssigkristalline Phasen erreicht werden kann. Um festzustellen, ob die kooperative Umorientierung der Seitenketten und ihre gegenseitige Stabilisierung auch in den Minoritätsphasen von Blockcopolymeren auftreten, wurden solche Blockcopolymere untersucht, die in den Seitenketten des photoadressierbaren Blocks methoxysubstituierte Azobenzolgruppen und nichtabsorbierende Dreikernmesogene in unterschiedlichem Verhältnis enthielten. Mit zunehmendem Anteil der mesogenen Seitenketten stieg trotz des gleichzeitig abnehmenden Anteils der Farbstoffgruppen die erreichbare Brechungsindexmodulation eingeschriebener holographischer Gitter an. Damit konnte gezeigt werden, dass sich auch in Blockcopolymeren die mesogenen Seitenketten gemeinsam mit den Farbstoffgruppen umorientieren lassen. Mit steigendem Mesogenanteil stieg die Stabilität der eingeschriebenen Gitter ebenfalls an. Ab einem Anteil von 35 mol-% mesogenen Seitenketten im photoadressierbaren Block war diese so hoch, dass innerhalb eines Zeitraumes von zwei Jahren keine Relaxation der eingeschriebenen Orientierung beobachtet wurde. Nachdem an Gittern, deren Dicke wesentlich größer als die Gitterperiode ist, nur dann Beugung auftritt, wenn die Bragg-Bedingung erfüllt ist, können mehrere Hologramme an der selben Stelle des Mediums eingeschrieben und unabhängig voneinander wieder gelesen werden. Dadurch erhält man zu den üblichen zwei Dimensionen eines flächigen optischen Datenspeichers den Winkel als dritten Freiheitsgrad. An 1,1 mm dicken Spritzgussproben von Mischungen aus einem Blockcopolymer und Polystyrol wurden Experimente zum Winkelmultiplexing einfacher holographischer Gitter durchgeführt. Es gelang, sowohl überlagerte Intensitätsgitter als auch überlagerte Polarisationsgitter einzuschreiben. In azobenzolhaltigen Polymeren wächst die Brechungsindexmodulation holographischer Gitter extrem nichtlinear mit der Belichtungszeit an. Dennoch konnten in der Praxis Intensitätsgitter mit gleicher Belichtungszeit eingeschrieben werden, die am Ende der Einschreibvorgänge nahezu identische Beugungseffizienzen aufwiesen. Bis zu 200 holographische Intensitätsgitter konnten an der selben Stelle des Materials erzeugt werden. In Mischungen von Polystyrol mit Blockcopolymeren, die nichtabsorbierende mesogene Seitenketten oder mesogene Farbstoffgruppen enthielten, wurde sowohl bei einzelnen Hologrammen als auch im Fall mehrerer überlagerter Gitter eine sehr gute Stabilität beobachtet. Als nächsten Schritt hin zur Speicherung realer Daten wurden ausgedehnte Hologramme von zweidimensionalen Testbildern gespeichert. Mehrere dieser Hologramme konnten ebenfalls erfolgreich an der selben Stelle unter unterschiedlichen Winkeln geschrieben und rekonstruiert werden. Die Umorientierung von Azobenzolseitenketten ist reversibel. Die Materialien sind daher wiederbeschreibbar. Es konnte ein geeignetes Verfahren entwickelt werden, das es ermöglicht, Hologramme auf rein optischem Wege nahezu vollständig zu löschen und das Medium mehrere tausend Male wiederzubeschreiben. Zum Löschen wurde jeweils ein zweites holographisches Gitter verwendet, das zu dem ursprünglich eingeschriebenen um 180° phasenverschoben war. Dadurch wurde die Information bereits nahezu vollständig gelöscht. Anschließend wurde mit einem einzelnen Laserstrahl, dessen Polarisation um 90° gedreht war, nachbelichtet, um die Farbstoffgruppen wieder in die Polarisationsrichtung der Schreibstrahlen zu orientieren. Durch diese beiden Schritte konnte die Beugungseffizienz der Hologramme um mehr als zwei Größenordnungen abgeschwächt werden und es wurde nach mehr als 1000 Schreib-Lösch-Zyklen wurde weder eine Abnahme der Beugungseffizienz eingeschriebener Gitter noch eine Verschlechterung des Löschverhaltens beobachtet.
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Modeling Pattern Formation in Biopolymer Systems induced by Reaction Kinetics and Molecular Motors
(2006)
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Falko Ziebert
- In my thesis I studied pattern formation in nonequilibrium (NE) polymer systems motivated from cell biology. Actin and microtubules (MTs) can be met in a state of continuous de-/polymerization (D/P), which is used by the cell e.g. during locomotion. This is a NE state since the polymerization is actively coupled to ATP or GTP hydrolysis. A second NE state of biological relevance is caused by motor proteins. These are mobile crosslinkers that walk on the filaments whereby creating forces and reorienting or transporting the latter. The cell displays filament-related ordered structures like aster patterns in the mitotic spindle, bundles in actin stress fibers and also oscillating structures e.g. in muscle bundles. The question is to what extent these structures inside the cell are governed by the physics of active polymers. In part I of my work, we proposed a pattern forming mechanism in a filament solution at high density that is subject to a D/P state. Since actin and MTs are rod-like objects, at high filament concentration a transition to lyotropic nematic order occurs. This transition is first order and thus accompanied by a phase separation. In the absence of D/P kinetics, the solution will thus tend to decompose into an isotropic domain with low density and a domain of high density and nematic order, i.e. the filaments preferentially aligned in one direction. To highlight that the D/P process interplays with this transition, we assumed that filaments are generated and decaying with some specific rates, implying a finite lifetime for the filaments. Accordingly the latter can only diffuse a finite length during their lifetime, which competes with the tendency of the system to phase separate and gives rise to a finite wavelength instability towards a pattern with alternating isotropic and nematic regions with a wavelength of the order of 10 microns. The model developed to describe these patterns is also interesting since it allows a feasible linear stability analysis of the homogeneous nematic state. Part II is devoted to the NE interaction of motor proteins with the filaments. As the starting point of our modeling efforts we chose a mesoscopic approach, namely a Smoluchowski equation which can be coarse-grained to obtain equations for the density and the orientation of the filaments. The main difference to a passive solution of rods are active motor-mediated currents caused by a motor density assumed sufficiently high and homogeneously distributed. These active contributions can be determined to leading order, introducing phenomenological motor transport rates containing details like active motor density, duty ratio, etc. After a thorough linear analysis of the model we obtained a rich instability diagram with an orientational finite wavelength instability which is either stationary or oscillatory and a demixing instability similar to spinodal decomposition but also motor-mediated. The finite wavelength instability has been analyzed by perturbative techniques and numerical simulations of the model equations. In the stationary case, we calculated the existence and stability regions of stripes and squares, which could be related to bundle-like structures and regular lattices of asters respectively. In the oscillatory case, there is competition between traveling and standing waves in one dimension and between traveling and alternating waves in two dimensions, the latter being a four mode solution built from two standing waves in perpendicular directions with a phase shift of 90 degrees. The long-wavelength demixing instability has also been investigated, showing coarsening aster-like structures. Experiments on MT-motor solutions display dissipative patterns in the NE state. Recent experiments on actin filaments and myosin oligomers show a rather different behavior, namely cluster patterns do not appear until ATP is nearly depleted. We proposed two mechanisms to explain these patterns: first, motors lacking ATP form rigor bonds with actin inducing small bundles, which through a combination of reduced diffusivity and enhanced interaction cross-section can be transported more efficiently, allowing the system to cross one of the instabilities discussed above. A second important feature is the presence of crosslinking proteins in the experiments. We propose that these can be interpreted as a parametric disorder. Assuming in the model a random contribution to the active current, a Ginzburg-Landau equation with multiplicative stationary noise could be derived leading to a threshold reduction. To conclude, it seems to be fruitful to apply and combine methods from statistical physics and pattern formation to NE problems in cell biology to foster the understanding of actively polymerizing filament and motor proteins in their different NE states.
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Mechanics of living cells: nonlinear viscoelasticity of single fibroblasts and shape instabilities in axons
(2006)
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Pablo Fernandez
- Biomechanics is a field of major biological relevance. In spite of the vast complexity of biological matter, a number of generic features are found to hold in the mechanics of soft tissues throughout all of its length scales. A major goal in biomechanics is to reduce its general features to those of the cytoskeleton, the filamentous scaffold which provides cells with mechanical integrity, architecture and contractility. The first part of this report describes single-cell uniaxial stretching experiments performed on fibroblasts. When placed between fibronectin coated microplates, fibroblasts adopt a regular, symmetrical shape and generate forces. When a constant cell length is imposed, an increase with time of the pulling force can be observed. This active behaviour can be probed in more detail by superimposing small-amplitude oscillations at frequencies in the range 0.1--1 Hz. The response to the superimposed oscillations is then characterised by the viscoelastic moduli. These are seen to be a function of the average force acting on the cell. This master-relation holds for all cells. At low forces, both moduli are constant; beyond a crossover force, power-law stress stiffening is observed, where as a function of the average force both moduli go as a power-law with exponents in the range 1-1.8. The loss factor depends only weakly on the average force. Remarkably, the moduli are a function of the average force but are independent of the cell length. Therefore this mechanical behaviour is not strain stiffening; rather, it is an example of active, intrinsic stress stiffening. The precise way of sweeping force-space is seen to be irrelevant. The stiffening relation shows a striking similarity to rheological measurements performed on purified actin gels, in an unprecedented example of quantitative agreement between living and dead matter. This mechanical response originates in the semiflexible behaviour of biopolymers. The precise mechanism is however at present not fully understood. Here, a simple explanation is proposed. It is shown that stress stiffening in fibroblasts bears a strong resemblance to the nonlinear mechanics of Euler-Bernoulli beams, which also show a linear regime at low forces and a crossover to power-law stiffening. Systematic analysis of the response of fibroblasts to large amplitude deformations reveals a striking similarity to plasticity in metals. Fibroblasts can be described as showing kinematic (or directional) hardening, a hallmark of composite materials. The second part of this report addresses experiments performed on neurites. These comprise axons --the processes extended by neurons-- as well as PC12 neurites, a model system for axons. After a sudden increase in the external osmotic pressure, axons swell and a cylindrical-peristaltic shape transformation sets in. We interprete this transition as a Rayleigh-Plateau-like instability triggered by elastic membrane tension, similar to the pearling instability known in membrane tubes. Microtubuli disruption by nocodazol strongly increases the maximum amplitude of the instability, as well as slightly increases the wavenumber of the fastest mode, showing microtubuli to be the most important cytoskeletal component in stabilising neurites. After a hypoosmotic shock the neurite volume increases, reaches a maximum, and relaxes back close to its initial value. These experiments were performed at different temperatures and initial osmotic pressure differences. The relaxation time as a function of the temperature closely follows an Arrhenius dependence, suggesting the rate-limiting factor of the relaxation to be the movement of ions through channels. Similar experiments were also performed under drug-induced perturbation of actin, myosin and microtubuli. Cytoskeleton perturbation does not have any significant effect on volume relaxation, indicating that it takes place solely by changes in osmolarity, without a significant role for hydrostatic pressures. A clear effect of drugs is seen in the initial swelling phase, especially after microtubuli disruption by nocodazol. The rate and extent of swelling are significantly higher. Taking the effect of drugs on the evolution of neurite volume together with that on the pearling instability, we suggest that hydrostatic pressure is present in the initial swelling phase and determines the swelling rate. In conclusion, reproducible, quantitative experiments at the single-cell level have been developed which address biologically relevant phenomena. Following a time-honoured tradition in physics, both the cell-pulling experiments and the shape transformations in axons address highly symmetric systems, where the geometry does not preclude the understanding. First interpretations of the observed phenomena have been found, in terms of generic behaviours common to all objects under tension.
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The Dynamics of Molecular Glasses Studied by Light Scattering
(2006)
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Sergei Adichtchev
- The present work is devoted to studying the dynamics in molecular glass formers applying the light-scattering (LS) technique, in particular tandem Fabry-Perot interferometry which allows to cover the frequency range from 0.3 GHz to 1000 GHz. Chapters 4 to 7 each present, in a self-contained way, different aspects of the dynamics, as summarized below. In Chapter 4, the results of the study of the molecular glass formers 2-picoline and m-tricresyl phosphate are presented. The LS spectra are analyzed in the frame of the Mode Coupling Theory (MCT). At high temperatures the evolution of the susceptibility minimum is well described by MCT. Below the critical temperature Tc, the asymptotic scaling laws of MCT fail due to the appearance of the excess wing of the alpha-process, which shows a universal evolution as a function of relaxation time, as was demonstrated by dielectric spectroscopy. A phenomenological approach, which allows to separate slow (alpha-process) and fast relaxation processes in the LS spectra is developed. Applying this approach, the temperature dependence of the non-ergodicity parameter f is obtained. The anomaly of f as well as a crossover to "white noise" of the fast dynamics spectra is found. In Chapter 5, the most extensive dielectric data of glycerol compiled by Lunkenheimer et al. [Contemp. Phys. 41, 15 (2000)] are reanalyzed. In contrast to the analysis of Lunkenheimer et al., the normalized susceptibility spectra, i.e, the dielectric loss data normalized by the static susceptibility, including the high temperature data, are analyzed. For this purpose a phenomenological approach, which describes the whole dielectric spectrum including the alpha-peak, its high frequency wing, and fast dynamics, is applied. The crossover temperature extracted from the phenomenological analysis and defined by the emergence of the high frequency wing upon cooling agrees well with the critical temperature extracted from the MCT analysis. The crossover temperature Tc=288 is significantly higher than reported before. Extracting the non-ergodicity parameter f, the characteristic anomaly similar to the one of 2-picoline and m-TCP discussed in Chapter 4, is found. In Chapter 6, the study of the fast relaxation below Tg in the molecular glasses 2-picoline, m-TCP, o-terphenyl (OTP), as well as in ethanol is presented. In addition to the boson peak, the depolarized LS spectra reveal quasi-elastic contributions that we attribute to i) the nearly constant loss (NCL) in the frequency range below 10 GHz and ii) a power law contribution with positive exponent alpha at higher frequencies. In the majority of glasses the latter may be attributed to thermally activated dynamics in asymmetric double well potentials (ADWP), as was previously found for the DLS spectra in silica. Following the Gilroy-Phillips model, the exponent alpha shows a master curve as a function of T /Vo for the various glasses where Vo specifies the width of the exponential distribution of barriers g(V), i.e., g(V) is propotional to the exp(-V/Vo). In Chapter 7, the investigation of the fast relaxation processes in the structural glass (T<Tg) and in the glassy crystal phase of ethanol, as well as in cyano cyclohexane, is presented. Depolarized and polarized LS spectra including the Brillouin lines were measured. It was found that depolarized, polarized LS and internal friction data exhibit fairly similar behavior, and thus reflect the same relaxations. The DLS spectra were described by assuming that the NCL contribution dominates below a few tens GHz, while the fast relaxational dynamics dominates at higher frequencies.
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Low Temperature Single-Crystal X-ray Diffraction on A(1-x)A'xMnO3 (A=La,Eu and A'=Ba,Sr)
(2006)
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Nicola Rotiroti
- The present thesis is devoted to A(1-x)A'xMnO3 (A=La and Eu, A'=Ba and Sr) compounds with distorted perovkite-type structure commonly denoted as manganites. The interest toward these compounds manifested when colossal magnetoresistance (CMR) was discovered in manganites. We have selected three particular compositions in order to study three different aspects of their structures, that are: the analysis of the structural behavior (and its correlation to magnetic and electronic properties) of rhombohedral La0.815Ba0.185MnO3 and orthorhombic La0.89Sr0.11MnO3 in dependence on temperature, the studies of the monoclinic symmetry of La0.815Ba0.185MnO3 at T=160K and the evidences of the splitting of the A-site in Eu0.60Sr0.40MnO3. We investigated these materials by single-crystal X-ray diffraction. For La0.815Ba0.185MnO3 the structure was analyzed in the temperature range of 188.9-295K. The temperature of 188.9K has been selected as minimum since the crystal undergoes a first-order structural phase transition from rhombohedral R-3c to monoclinic I2/c at TS=187.1K. We found a change in the thermal expansion coefficient at the transition temperature of the paramagnetic (PI) to ferromagnetic (FM) phase transition (TC=251K), with a larger expansion of the FM phase. Progressive charge localization due to strong electron-phonon interactions in the PI phase might be responsible for a smaller thermal expansion coefficient in the PI phase. Precursor effects near the phase transition at TS towards the monoclinic phase occur for Mn-O distances, Mn-O-Mn angles and the volume of the MnO6 polyhedron, providing a picture of how the structure reacts approaching the structure phase transition. Furthermore, our results allow to conclude that the apparent driving force for the structural phase transition is the replacement of shear-type distortions by Jahn-Teller-type distortions of the MnO6 octahedra, together with a stabilization of the La environment. The same crystal as for studies of the rhombohedral phase was used for analysing the monoclinic phase, but what was a single-crystal in the rhombohedral phase becomes twinned in the monoclinic phase. With the aid of omega-theta mapping of reflection profiles we found that this material displays monoclinic symmetry I2/c despite many reports in the literature of an orthorhombic symmetry Pbnm for this compound as well as for related materials A(1-x)A'xMnO3 with x about 0.2. Another member of the family of perovkite-type materials is represented by La0.89Sr0.11MnO3, with orthorhombic symmetry with space group Pbnm at ambient conditions. The crystal structure was investigated in dependence on temperature, with the aim of analyzing structural changes correlated with the magnetic transitions. A complex evolution of the magnetization measurements against temperature was found. The crystal structure remains orthorhombic over the investigated temperature range 110-240K but several extremes are seen for the lattice parameters as well as for structural and thermal parameters at temperatures where also changes in the magnetic state are observed. The lattice parameters have extreme values at the Curie Temperature of TC=150K. The present results show small anomalies in the temperature dependencies of bond lengths and bond angles, that occur at T=170K. This temperature coincides with the onset of magnetic ordering rather than with TC. Less pronounced maxima at 170K are found for the temperature parameters of oxygen, while the shortest La-O bond is virtually independent on temperature. On the basis of these observations we propose that the tilts and deformations of the MnO6 octahedra are determined by the shortest La-O distance as a kind of boundary condition. The thermal expansion is then accounted for by structural rearrangements while keeping the shortest La-O distance constant at the value corresponding to optimal chemical bonding. The coincidence of structural anomalies with the onset of magnetic order strongly suggests that magnetic ordering occurs at temperatures where the crystal structure allows favorable magnetic interactions. The final part of this work concerns the structural investigation by single-crystal X-ray diffraction at room temperature of Eu0.60Sr0.40MnO3. This composition was never studied before and we found that the crystal structure is orthorhombic with space group Pbnm. Initially, the same positional and displacement parameters were refined for both Eu and Sr atoms, but the difference Fourier maps showed that they do not occupy the same position. The refinement of separate positions reduced the R value, and features in the difference Fourier map were considerably reduced, leading to the first observation of a splitting of the A-A' crystallographic site of A(1-x)A'xMnO3 compounds.
