Hypersonic phonon propagation in mesoscopic systems by Brillouin spectroscopy

Phononic crystals, capable to block or direct the propagation of elastic/acoustic waves, have attracted increasing interdisciplinary interest across condensed matter physics and materials science. As of today, no generalized full description of elastic wave propagation in phononic structures is available, mainly due to the large number of variables determining the band diagram. Therefore, this thesis aims for a deeper understanding of the fundamental concepts governing wave propagation in mesoscopic structures by investigation of appropriate model systems. The phononic dispersion relation at hypersonic frequencies is directly investigated by the non-destructive technique of high-resolution spontaneous Brillouin light scattering (BLS) combined with computational methods. Due to the vector nature of the elastic wave propagation, we first studied the hypersonic band structure of hybrid superlattices. These 1D phononic crystals composed of alternating layers of hard and soft materials feature large Bragg gaps. BLS spectra are sensitive probes of the moduli, photo-elastic constants and structural parameters of the constituent components. Engineering of the band structure can be realized by introduction of defects. Here, cavity layers are employed to launch additional modes that modify the dispersion of the undisturbed superlattice, with extraordinary implications to the band gap region. Density of states calculations in conjunction with the associated deformation allow for unambiguous identication of surface and cavity modes, as well as their interaction with adjacent defects. Next, the role of local resonances in phononic systems is explored in 3D structures based on colloidal particles. In turbid media BLS records the particle vibration spectrum comprising resonant modes due to the spatial confinement of elastic energy. Here, the frequency and lineshapes of the particle eigenmodes are discussed as function of increased interaction and departure from spherical symmetry. The latter is realized by uniaxial stretching of polystyrene spheres, that can be aligned in an alternating electric field. The resulting spheroidal crystals clearly exhibit anisotropic phononic properties. Establishing reliable predictions of acoustic wave propagation, necessary to advance, e.g., optomechanics and phononic devices is the ultimate aim of this thesis.

Analytische Ableitungen der Energie für den "Equation-of-Motion-Coupled-Cluster"-Ansatz zur Berechnung von Ionisationspotentialen

In der vorliegenden Arbeit wird die Theorie der analytischen zweiten Ableitungen für die EOMIP-CCSD-Methode formuliert sowie die durchgeführte Implementierung im Quantenchemieprogramm CFOUR beschrieben. Diese Ableitungen sind von Bedeutung bei der Bestimmung statischer Polarisierbarkeiten und harmonischer Schwingungsfrequenzen und in dieser Arbeit wird die Genauigkeit des EOMIP-CCSD-Ansatzes bei der Berechnung dieser Eigenschaften für verschiedene radikalische Systeme untersucht. Des Weiteren können mit Hilfe der ersten und zweiten Ableitungen vibronische Kopplungsparameter berechnet werden, welche zur Simulation von Molekülspektren in Kombination mit dem Köppel-Domcke-Cederbaum (KDC)-Modell - in der Arbeit am Beispiel des Formyloxyl (HCO2)-Radikals demonstriert - benötigt werden.rnrnDer konzeptionell einfache EOMIP-CC-Ansatz wurde gewählt, da hier die Wellenfunktion eines Radikalsystems ausgehend von einem stabilen geschlossenschaligen Zustand durch die Entfernung eines Elektrons gebildet wird und somit die Problematik der Symmetriebrechung umgangen werden kann. Im Rahmen der Implementierung wurden neue Programmteile zur Lösung der erforderlichen Gleichungen für die gestörten EOMIP-CC-Amplituden und die gestörten Lagrange-Multiplikatoren zeta zum Quantenchemieprogramm CFOUR hinzugefügt. Die unter Verwendung des Programms bestimmten Eigenschaften werden hinsichtlich ihrer Leistungsfähigkeit im Vergleich zu etablierten Methoden wie z.B. CCSD(T) untersucht. Bei der Berechnung von Polarisierbarkeiten und harmonischen Schwingungsfrequenzen liefert die EOMIP-CCSD-Theorie meist gute Resultate, welche nur wenig von den CCSD(T)-Ergebnissen abweichen. Einzig bei der Betrachtung von Radikalen, für die die entsprechenden Anionen nicht stabil sind (z.B. NH2⁻ und CH3⁻), liefert der EOMIP-CCSD-Ansatz aufgrund methodischer Nachteile keine aussagekräftige Beschreibung. rnrnDie Ableitungen der EOMIP-CCSD-Energie lassen sich auch zur Simulation vibronischer Kopplungen innerhalb des KDC-Modells einsetzen.rnZur Kopplung verschiedener radikalischer Zustände in einem solchen Modellpotential spielen vor allem die Ableitungen von Übergangsmatrixelementen eine wichtige Rolle. Diese sogenannten Kopplungskonstanten können in der EOMIP-CC-Theorie besonders leicht definiert und berechnet werden. Bei der Betrachtung des Photoelektronenspektrums von HCO2⁻ werden zwei Alternativen untersucht: Die vertikale Bestimmung an der Gleichgewichtsgeometrie des HCO2⁻-Anions und die Ermittlung adiabatischer Kraftkonstanten an den Gleichgewichtsgeometrien des Radikals. Lediglich das adiabatische Modell liefert bei Beschränkung auf harmonische Kraftkonstanten eine qualitativ sinnvolle Beschreibung des Spektrums. Erweitert man beide Modelle um kubische und quartische Kraftkonstanten, so nähern sich diese einander an und ermöglichen eine vollständige Zuordnung des gemessenen Spektrums innerhalb der ersten 1500 cm⁻¹. Die adiabatische Darstellung erreicht dabei nahezu quantitative Genauigkeit.

Comparative study of the different models for the calculation of BLEVEs overpressure effects

The BLEVE, acronym for Boiling Liquid Expanding Vapour Explosion, is one of the most dangerous accidents that can occur in pressure vessels. It can be defined as an explosion resulting from the failure of a vessel containing a pressure liquefied gas stored at a temperature significantly above its boiling point at atmospheric pressure. This phenomenon frequently appears when a vessel is engulfed by a fire: the heat causes the internal pressure to raise and the mechanical proprieties of the wall to decrease, with the consequent rupture of the tank and the instantaneous release of its whole content. After the breakage, the vapour outflows and expands and the liquid phase starts boiling due to the pressure drop. The formation and propagation of a distructive schock wave may occur, together with the ejection of fragments, the generation of a fireball if the stored fluid is flammable and immediately ignited or the atmospheric dispersion of a toxic cloud if the fluid contained inside the vessel is toxic. Despite the presence of many studies on the BLEVE mechanism, the exact causes and conditions of its occurrence are still elusive. In order to better understand this phenomenon, in the present study first of all the concept and definition of BLEVE are investigated. A historical analysis of the major events that have occurred over the past 60 years is described. A research of the principal causes of this event, including the analysis of the substances most frequently involved, is presented too. Afterwards a description of the main effects of BLEVEs is reported, focusing especially on the overpressure. Though the major aim of the present thesis is to contribute, with a comparative analysis, to the validation of the main models present in the literature for the calculation and prediction of the overpressure caused by BLEVEs. In line with this purpose, after a short overview of the available approaches, their ability to reproduce the trend of the overpressure is investigated. The overpressure calculated with the different models is compared with values deriving from events happened in the past and ad-hoc experiments, focusing the attention especially on medium and large scale phenomena. The ability of the models to consider different filling levels of the reservoir and different substances is analyzed too. The results of these calculations are extensively discussed. Finally some conclusive remarks are reported.

Dynamics of Bora wind over the Adriatic sea: atmospheric water balance and role of air-sea fluxes and orography

The Bora wind is a mesoscale phenomenon which typically affects the Adriatic Sea basin for several days each year, especially during winter. The Bora wind has been studied for its intense outbreak across the Dinaric Alps. The properties of the Bora wind are widely discussed in the literature and scientific papers usually focus on the eastern Adriatic coast where strong turbulence and severe gust intensity are more pronounced. However, the impact of the Bora wind can be significant also over Italy, not only in terms of wind speed instensity. Depending on the synoptic pressure pattern (cyclonic or anticyclonic Bora) and on the season, heavy snowfall, severe storms, storm surges and floods can occur along the Adriatic coast and on the windward flanks of the Apennines. In the present work five Bora cases that occurred in recent years have been selected and their evolution has been simulated with the BOLAM-MOLOCH model set, developed at ISAC-CNR in Bologna. Each case study has been addressed by a control run and by several sensitivity tests, performed with the purpose of better understanding the role played by air-sea latent and sensible heat fluxes. The tests show that the removal of the fluxes induces modifications in the wind approching the coast and a decrease of the total precipitation amount predicted over Italy. In order to assess the role of heat fluxes, further analysis has been carried out: column integrated water vapour fluxes have been computed along the Italian coastline and an atmospheric water balance has been evaluated inside a box volume over the Adriatic Sea. The balance computation shows that, although latent heat flux produces a significant impact on the precipitation field, its contribution to the balance is relatively minor. The most significant and lasting case study, that of February 2012, has been studied in more detail in order to explain the impressive drop in the total precipitation amount simulated in the sensitivity tests with removed heat fluxes with respect to the CNTRL run. In these experiments relative humidity and potential temperature distribution over different cross-sections have been examined. With respect to the CNTRL run a drier and more stable boundary layer, characterised by a more pronounced wind shear at the lower levels, has been observed to establish above the Adriatic Sea. Finally, in order to demonstrate that also the interaction of the Bora flow with the Apennines plays a crucial role, sensitivity tests varying the orography height have been considered. The results of such sensitivity tests indicate that the propagation of the Bora wind over the Adriatic Sea, and in turn its meteorological impact over Italy, is influenced by both the large air-sea heat fluxes and the interaction with the Apennines that decelerate the upstream flow.

Organ-specific eosinophilic disorders of the skin, lung, and gastrointestinal tract

Eosinophils are multifunctional leukocytes that increase in various tissues in patients with a variety of disorders. Locally, they can be involved in the initiation and propagation of diverse inflammatory responses. In this review the clinical association of eosinophils with diseases of the skin, lung, and gastrointestinal tract is summarized. An approach to determining the causal role of eosinophils in these diseases is presented. Recent findings concerning molecular diagnosis, cause, and treatment are discussed.

Alpha4beta1 integrin mediates the recruitment of immature dendritic cells across the blood-brain barrier during experimental autoimmune encephalomyelitis

Dendritic cells (DCs) within the CNS are recognized to play an important role in the effector phase and propagation of the immune response in experimental autoimmune encephalomyelitis (EAE), a mouse model for multiple sclerosis. However, the mechanisms regulating DC trafficking into the CNS still need to be characterized. In this study, we show by performing intravital fluorescence videomicroscopy of the inflamed spinal cord white-matter microvasculature in SJL mice with EAE that immature, and to a lesser extent, LPS-matured, bone marrow-derived DCs efficiently interact with the CNS endothelium by rolling, capturing, and firm adhesion. Immature but not LPS-matured DCs efficiently migrated across the wall of inflamed parenchymal microvessels into the CNS. Blocking alpha4 integrins interfered with the adhesion but not the rolling or capturing of immature and LPS-matured DCs to the CNS microvascular endothelium, inhibiting their migration across the vascular wall. Functional absence of beta1 integrins but not of beta7 integrins or alpha4beta7 integrin similarly reduced the adhesion of immature DCs to the CNS microvascular endothelium, demonstrating that alpha4beta1 but not alpha4beta7 integrin mediates this step of immature DCs interaction with the inflamed blood-brain barrier during EAE. Our study shows that during EAE, especially immature DCs migrate into the CNS, where they may be crucial for the perpetuation of the CNS-targeted autoimmune response. Thus therapeutic targeting of alpha4 integrins affects DC trafficking into the CNS and may therefore lead to the resolution of the CNS autoimmune inflammation by reducing the number of CNS professional APCs.

High-speed Imaging of a Bulk Metallic Glass During Uniaxial Compression

High-speed imaging directly correlates the propagation of a particular shear band with mechanical measurements during uniaxial compression of a bulk metallic glass. Imaging shows shear occurs simultaneously over the entire shear plane, and load data, synced and time-stamped to the same clock as the camera, reveal that shear sliding is coincident with the load drop of each serration. Digital image correlation agrees with these results. These data demonstrate that shear band sliding occurs with velocities on the order of millimeters per second. Fracture occurs much more rapidly than the shear banding events, thereby readily leading to melting on fracture surfaces.

Structural basis for the regulation of cysteine-protease activity by a new class of protease inhibitors in Plasmodium

Plasmodium cysteine proteases are essential for host-cell invasion and egress, hemoglobin degradation, and intracellular development of the parasite. The temporal, site-specific regulation of cysteine-protease activity is a prerequisite for survival and propagation of Plasmodium. Recently, a new family of inhibitors of cysteine proteases (ICPs) with homologs in at least eight Plasmodium species has been identified. Here, we report the 2.6 A X-ray crystal structure of the C-terminal, inhibitory domain of ICP from P. berghei (PbICP-C) in a 1:1 complex with falcipain-2, an important hemoglobinase of Plasmodium. The structure establishes Plasmodium ICP as a member of the I42 class of chagasin-like protease inhibitors but with large insertions and differences in the binding mode relative to other family members. Furthermore, the PbICP-C structure explains why host-cell cathepsin B-like proteases and, most likely, also the protease-like domain of Plasmodium SERA5 (serine-repeat antigen 5) are no targets for ICP.

Dynamic of ion channel expression at the plasma membrane of cardiomyocytes

Cardiac myocytes are characterized by distinct structural and functional entities involved in the generation and transmission of the action potential and the excitation-contraction coupling process. Key to their function is the specific organization of ion channels and transporters to and within distinct membrane domains, which supports the anisotropic propagation of the depolarization wave. This review addresses the current knowledge on the molecular actors regulating the distinct trafficking and targeting mechanisms of ion channels in the highly polarized cardiac myocyte. In addition to ubiquitous mechanisms shared by other excitable cells, cardiac myocytes show unique specialization, illustrated by the molecular organization of myocyte-myocyte contacts, e.g., the intercalated disc and the gap junction. Many factors contribute to the specialization of the cardiac sarcolemma and the functional expression of cardiac ion channels, including various anchoring proteins, motors, small GTPases, membrane lipids, and cholesterol. The discovery of genetic defects in some of these actors, leading to complex cardiac disorders, emphasizes the importance of trafficking and targeting of ion channels to cardiac function. A major challenge in the field is to understand how these and other actors work together in intact myocytes to fine-tune ion channel expression and control cardiac excitability.

Dynamics of Spatial Game Theory Networks with Novel Modifications

Introduction: Advances in biotechnology have shed light on many biological processes. In biological networks, nodes are used to represent the function of individual entities within a system and have historically been studied in isolation. Network structure adds edges that enable communication between nodes. An emerging fieldis to combine node function and network structure to yield network function. One of the most complex networks known in biology is the neural network within the brain. Modeling neural function will require an understanding of networks, dynamics, andneurophysiology. It is with this work that modeling techniques will be developed to work at this complex intersection. Methods: Spatial game theory was developed by Nowak in the context of modeling evolutionary dynamics, or the way in which species evolve over time. Spatial game theory offers a two dimensional view of analyzingthe state of neighbors and updating based on the surroundings. Our work builds upon this foundation by studying evolutionary game theory networks with respect to neural networks. This novel concept is that neurons may adopt a particular strategy that will allow propagation of information. The strategy may therefore act as the mechanism for gating. Furthermore, the strategy of a neuron, as in a real brain, isimpacted by the strategy of its neighbors. The techniques of spatial game theory already established by Nowak are repeated to explain two basic cases and validate the implementation of code. Two novel modifications are introduced in Chapters 3 and 4 that build on this network and may reflect neural networks. Results: The introduction of two novel modifications, mutation and rewiring, in large parametricstudies resulted in dynamics that had an intermediate amount of nodes firing at any given time. Further, even small mutation rates result in different dynamics more representative of the ideal state hypothesized. Conclusions: In both modificationsto Nowak's model, the results demonstrate the network does not become locked into a particular global state of passing all information or blocking all information. It is hypothesized that normal brain function occurs within this intermediate range and that a number of diseases are the result of moving outside of this range.

Inferences regarding the diet of extinct hominins: structural and functional trends in dental and mandibular morphology within the hominin clade

This contribution investigates the evolution of diet in the Pan – Homo and hominin clades. It does this by focusing on 12 variables (nine dental and three mandibular) for which data are available about extant chimpanzees, modern humans and most extinct hominins. Previous analyses of this type have approached the interpretation of dental and gnathic function by focusing on the identification of the food consumed (i.e. fruits, leaves, etc.) rather than on the physical properties (i.e. hardness, toughness, etc.) of those foods, and they have not specifically addressed the role that the physical properties of foods play in determining dental adaptations. We take the available evidence for the 12 variables, and set out what the expression of each of those variables is in extant chimpanzees, the earliest hominins, archaic hominins, megadont archaic hominins, and an inclusive grouping made up of transitional hominins and pre-modern Homo . We then present hypotheses about what the states of these variables would be in the last common ancestor of the Pan – Homo clade and in the stem hominin. We review the physical properties of food and suggest how these physical properties can be used to investigate the functional morphology of the dentition. We show what aspects of anterior tooth morphology are critical for food preparation (e.g. peeling fruit) prior to its ingestion, which features of the postcanine dentition (e.g. overall and relative size of the crowns) are related to the reduction in the particle size of food, and how information about the macrostructure (e.g. enamel thickness) and microstructure (e.g. extent and location of enamel prism decussation) of the enamel cap might be used to make predictions about the types of foods consumed by extinct hominins. Specifically, we show how thick enamel can protect against the generation and propagation of cracks in the enamel that begin at the enamel– dentine junction and move towards the outer enamel surface.

Plakoglobin-dependent disruption of the desmosomal plaque in pemphigus vulgaris

We recently reported that the pathogenesis of pemphigus vulgaris (PV), an autoimmune blistering skin disorder, is driven by the accumulation of c-Myc secondary to abrogation of plakoglobin (PG)-mediated transcriptional c-Myc suppression. PG knock-out mouse keratinocytes express high levels of c-Myc and resemble PVIgG-treated wild-type keratinocytes in most respects. However, they fail to accumulate nuclear c-Myc and loose intercellular adhesion in response to PVIgG-treatment like wild-type keratinocytes. This suggested that PG is also required for propagation of the PVIgG-induced events between augmented c-Myc expression and acantholysis. Here, we addressed this possibility by comparing PVIgG-induced changes in the desmosomal organization between wild-type and PG knock-out keratinocytes. We found that either bivalent PVIgG or monovalent PV-Fab (known to trigger blister formation in vivo) disrupt the linear organization of all major desmosomal components along cell borders in wild-type keratinocytes, simultaneously with a reduction in intercellular adhesive strength. In contrast, PV-Fab failed to affect PG knock-out keratinocytes while PVIgG cross-linked their desmosomal cadherins without significantly affecting desmoplakin. These results identify PG as a principle effector of the PVIgG-induced signals downstream of c-Myc that disrupt the desmosomal plaque at the plasma membrane.

Use of manual adaptive remeshing in the mechanical modeling of an intraneural ganglion cyst

Intraneural Ganglion Cysts expand within in a nerve, causing neurological deficits in afflicted patients. Modeling the propagation of these cysts, originating in the articular branch and then expanding radially outward, will help prove articular theory, and ultimately allow for more purposeful treatment of this condition. In Finite Element Analysis, traditional Lagrangian meshing methods fail to model the excessive deformation that occurs in the propagation of these cysts. This report explores the method of manual adaptive remeshing as a method to allow for the use of Lagrangian meshing, while circumventing the severe mesh distortions typical of using a Lagrangian mesh with a large deformation. Manual adaptive remeshing is the process of remeshing a deformed meshed part and then reapplying loads in order to achieve a larger deformation than a single mesh can achieve without excessive distortion. The methods of manual adaptive remeshing described in this Master’s Report are sufficient in modeling large deformations.

Advanced mechanics of materials with microstructure

The study of advanced materials aimed at improving human life has been performed since time immemorial. Such studies have created everlasting and greatly revered monuments and have helped revolutionize transportation by ushering the age of lighter–than–air flying machines. Hence a study of the mechanical behavior of advanced materials can pave way for their use for mankind’s benefit. In this school of thought, the aim of this dissertation is to broadly perform two investigations. First, an efficient modeling approach is established to predict the elastic response of cellular materials with distributions of cell geometries. Cellular materials find important applications in structural engineering. The approach does not require complex and time-consuming computational techniques usually associated with modeling such materials. Unlike most current analytical techniques, the modeling approach directly accounts for the cellular material microstructure. The approach combines micropolar elasticity theory and elastic mixture theory to predict the elastic response of cellular materials. The modeling approach is applied to the two dimensional balsa wood material. Predicted properties are in good agreement with experimentally determined properties, which emphasizes the model’s potential to predict the elastic response of other cellular solids, such as open cell and closed cell foams. The second topic concerns intraneural ganglion cysts which are a set of medical conditions that result in denervation of the muscles innervated by the cystic nerve leading to pain and loss of function. Current treatment approaches only temporarily alleviate pain and denervation which, however, does not prevent cyst recurrence. Hence, a mechanistic understanding of the pathogenesis of intraneural ganglion cysts can help clinicians understand them better and therefore devise more effective treatment options. In this study, an analysis methodology using finite element analysis is established to investigate the pathogenesis of intraneural ganglion cysts. Using this methodology, the propagation of these cysts is analyzed in their most common site of occurrence in the human body i.e. the common peroneal nerve. Results obtained using finite element analysis show good correlation with clinical imaging patterns thereby validating the promise of the method to study cyst pathogenesis.

Influence of the background wind on the local soil moisture-precipitation feedback

The importance of soil moisture anomalies on airmass convection over semiarid regions has been recognized in several studies. The underlying mechanisms remain partly unclear. An open question is why wetter soils can result in either an increase or a decrease of precipitation (positive or negative soil moisture–precipitation feedback, respectively). Here an idealized cloud-resolving modeling framework is used to explore the local soil moisture–precipitation feedback. The approach is able to replicate both positive and negative feedback loops, depending on the environmental parameters. The mechanism relies on horizontal soil moisture variations, which may develop and intensify spontaneously. The positive expression of the feedback is associated with the initiation of convection over dry soil patches, but the convective cells then propagate over wet patches where they strengthen and preferentially precipitate. The negative feedback may occur when the wind profile is too weak to support the propagation of convective features from dry to wet areas. Precipitation is then generally weaker and falls preferentially over dry patches. The results highlight the role of the midtropospheric flow in determining the sign of the feedback. A key element of the positive feedback is the exploitation of both low convective inhibition (CIN) over dry patches (for the initiation of convection) and high CAPE over wet patches (for the generation of precipitation).