Structural changes and dynamic behaviour of vanadium oxide-based catalysts for gas-phase selective oxidations

Selective oxidation is one of the simplest functionalization methods and essentially all monomers used in manufacturing artificial fibers and plastics are obtained by catalytic oxidation processes. Formally, oxidation is considered as an increase in the oxidation number of the carbon atoms, then reactions such as dehydrogenation, ammoxidation, cyclization or chlorination are all oxidation reactions. In this field, most of processes for the synthesis of important chemicals used vanadium oxide-based catalysts. These catalytic systems are used either in the form of multicomponent mixed oxides and oxysalts, e.g., in the oxidation of n-butane (V/P/O) and of benzene (supported V/Mo/O) to maleic anhydride, or in the form of supported metal oxide, e.g., in the manufacture of phthalic anhydride by o-xylene oxidation, of sulphuric acid by oxidation of SO2, in the reduction of NOx with ammonia and in the ammoxidation of alkyl aromatics. In addition, supported vanadia catalysts have also been investigated for the oxidative dehydrogenation of alkanes to olefins , oxidation of pentane to maleic anhydride and the selective oxidation of methanol to formaldehyde or methyl formate [1]. During my PhD I focused my work on two gas phase selective oxidation reactions. The work was done at the Department of Industrial Chemistry and Materials (University of Bologna) in collaboration with Polynt SpA. Polynt is a leader company in the development, production and marketing of catalysts for gas-phase oxidation. In particular, I studied the catalytic system for n-butane oxidation to maleic anhydride (fluid bed technology) and for o-xylene oxidation to phthalic anhydride. Both reactions are catalyzed by systems based on vanadium, but catalysts are completely different. Part A is dedicated to the study of V/P/O catalyst for n-butane selective oxidation, while in the Part B the results of an investigation on TiO2-supported V2O5, catalyst for o-xylene oxidation are showed. In Part A, a general introduction about the importance of maleic anhydride, its uses, the industrial processes and the catalytic system are reported. The reaction is the only industrial direct oxidation of paraffins to a chemical intermediate. It is produced by n-butane oxidation either using fixed bed and fluid bed technology; in both cases the catalyst is the vanadyl pyrophosphate (VPP). Notwithstanding the good performances, the yield value didn’t exceed 60% and the system is continuously studied to improve activity and selectivity. The main open problem is the understanding of the real active phase working under reaction conditions. Several articles deal with the role of different crystalline and/or amorphous vanadium/phosphorous (VPO) compounds. In all cases, bulk VPP is assumed to constitute the core of the active phase, while two different hypotheses have been formulated concerning the catalytic surface. In one case the development of surface amorphous layers that play a direct role in the reaction is described, in the second case specific planes of crystalline VPP are assumed to contribute to the reaction pattern, and the redox process occurs reversibly between VPP and VOPO4. Both hypotheses are supported also by in-situ characterization techniques, but the experiments were performed with different catalysts and probably under slightly different working conditions. Due to complexity of the system, these differences could be the cause of the contradictions present in literature. Supposing that a key role could be played by P/V ratio, I prepared, characterized and tested two samples with different P/V ratio. Transformation occurring on catalytic surfaces under different conditions of temperature and gas-phase composition were studied by means of in-situ Raman spectroscopy, trying to investigate the changes that VPP undergoes during reaction. The goal is to understand which kind of compound constituting the catalyst surface is the most active and selective for butane oxidation reaction, and also which features the catalyst should possess to ensure the development of this surface (e.g. catalyst composition). On the basis of results from this study, it could be possible to project a new catalyst more active and selective with respect to the present ones. In fact, the second topic investigated is the possibility to reproduce the surface active layer of VPP onto a support. In general, supportation is a way to improve mechanical features of the catalysts and to overcome problems such as possible development of local hot spot temperatures, which could cause a decrease of selectivity at high conversion, and high costs of catalyst. In literature it is possible to find different works dealing with the development of supported catalysts, but in general intrinsic characteristics of VPP are worsened due to the chemical interaction between active phase and support. Moreover all these works deal with the supportation of VPP; on the contrary, my work is an attempt to build-up a V/P/O active layer on the surface of a zirconia support by thermal treatment of a precursor obtained by impregnation of a V5+ salt and of H3PO4. In-situ Raman analysis during the thermal treatment, as well as reactivity tests are used to investigate the parameters that may influence the generation of the active phase. Part B is devoted to the study of o-xylene oxidation of phthalic anhydride; industrially, the reaction is carried out in gas-phase using as catalysts a supported system formed by V2O5 on TiO2. The V/Ti/O system is quite complex; different vanadium species could be present on the titania surface, as a function of the vanadium content and of the titania surface area: (i) V species which is chemically bound to the support via oxo bridges (isolated V in octahedral or tetrahedral coordination, depending on the hydration degree), (ii) a polymeric species spread over titania, and (iii) bulk vanadium oxide, either amorphous or crystalline. The different species could have different catalytic properties therefore changing the relative amount of V species can be a way to optimize the catalytic performances of the system. For this reason, samples containing increasing amount of vanadium were prepared and tested in the oxidation of o-xylene, with the aim of find a correlations between V/Ti/O catalytic activity and the amount of the different vanadium species. The second part deals with the role of a gas-phase promoter. Catalytic surface can change under working conditions; the high temperatures and a different gas-phase composition could have an effect also on the formation of different V species. Furthermore, in the industrial practice, the vanadium oxide-based catalysts need the addition of gas-phase promoters in the feed stream, that although do not have a direct role in the reaction stoichiometry, when present leads to considerable improvement of catalytic performance. Starting point of my investigation is the possibility that steam, a component always present in oxidation reactions environment, could cause changes in the nature of catalytic surface under reaction conditions. For this reason, the dynamic phenomena occurring at the surface of a 7wt% V2O5 on TiO2 catalyst in the presence of steam is investigated by means of Raman spectroscopy. Moreover a correlation between the amount of the different vanadium species and catalytic performances have been searched. Finally, the role of dopants has been studied. The industrial V/Ti/O system contains several dopants; the nature and the relative amount of promoters may vary depending on catalyst supplier and on the technology employed for the process, either a single-bed or a multi-layer catalytic fixed-bed. Promoters have a quite remarkable effect on both activity and selectivity to phthalic anhydride. Their role is crucial, and the proper control of the relative amount of each component is fundamental for the process performance. Furthermore, it can not be excluded that the same promoter may play different role depending on reaction conditions (T, composition of gas phase..). The reaction network of phthalic anhydride formation is very complex and includes several parallel and consecutive reactions; for this reason a proper understanding of the role of each dopant cannot be separated from the analysis of the reaction scheme. One of the most important promoters at industrial level, which is always present in the catalytic formulations is Cs. It is known that Cs plays an important role on selectivity to phthalic anhydride, but the reasons of this phenomenon are not really clear. Therefore the effect of Cs on the reaction scheme has been investigated at two different temperature with the aim of evidencing in which step of the reaction network this promoter plays its role.

Crack measurements in structural concrete with D.I.C. system and validation of a tensile constitutive law

Compared with other mature engineering disciplines, fracture mechanics of concrete is still a developing field and very important for structures like bridges subject to dynamic loading. An historical point of view of what done in the field is provided and then the project is presented. The project presents an application of the Digital Image Correlation (DIC) technique for the detection of cracks at the surface of concrete prisms (500mmx100mmx100mm) subject to flexural loading conditions (Four Point Bending test). The technique provide displacement measurements of the region of interest and from this displacement field information about crack mouth opening (CMOD) are obtained and related to the applied load. The evolution of the fracture process is shown through graphs and graphical maps of the displacement at some step of the loading process. The study shows that it is possible with the DIC system to detect the appearance and evolution of cracks, even before the cracks become visually detectable.

A numerical program for Railway vehicle-track-structure dynamic interaction using a modal substructuring approach

This work presents a program for simulations of vehicle-track and vehicle-trackstructure dynamic interaction . The method used is computationally efficient in the sense that a reduced number of coordinates is sufficient and doesn’t require high efficiency computers. The method proposes a modal substructuring approach of the system by modelling rails , sleepers and underlying structure with modal coordinates, the vehicle with physical lumped elements coordinates and by introducing interconnection elements between these structures (wheel-rail contact, railpads and ballast) by means of their interaction forces. The Frequency response function (FRF) is also calculated for both cases of track over a structure (a bridge, a viaduct ...) and for the simple vehicle-track program; for each case the vehicle effect on the FRF is then analyzed through the comparison of the FRFs obtained introducing or not a simplified vehicle on the system.

Length scales of dynamic heterogeneities of low and high molecular weight glass formers from multidimensional NMR

Das Ziel der vorliegenden Arbeit ist die Untersuchung der räumlichen und zeitlichen Aspekte der heterogenen Dynamik in Modellglasbildnern. Dabei wird vor allem die langsame alpha-Relaxationsdynamik oberhalb des Glasüberganges Tg untersucht. Die nukleare Magnetresonanz zeigt ihre einmalige Vielseitigkeit bei der Untersuchung molekularer Dynamik, wenn die angewandten Techniken und Experimente durch Simulationen unterstützt werden. Die räumliche Aspekt dynamischer Heterogenitäten wird untersucht durch ein reduziertes vierdimensionales Spindiffusionsexperiment (4D3CP), ein Experiment, das Reorientierungsraten örtlich korreliert. Eine Simulation dieses Experimentes an einem System harter Kugeln liefert wertvolle Informationen über die Auswertemethode des 4D3CP Experiments. Glycerol und o-terphenyl werden durch das 4D3CP Experiment untersucht. Die erhaltenen Resultate werden mit bereits publizierten Daten des polymeren Glasbildners PVAc verglichen. Während PVAc und o-terphenyl eine Längenskale von 3.7 nm bzw. 2.9 nm aufweisen, ist die Längenskale von Glycerol signifikant kleiner bei 1.1 nm. Ein neues Experiment, welches sensitiv auf Translationsbewegung reagiert, wird vorgestellt. Durch Verwendung eines pi-Impulszuges kann eine separate Evolution unter dem Hamiltonian der dipolaren Kopplung und der chemischen Verschiebungsanisotropie erreicht werden.

Dynamic identification of structures: experimental assessment of modal parameteres through methods in frequency domain, in time-frequency domain and model updating

Among the experimental methods commonly used to define the behaviour of a full scale system, dynamic tests are the most complete and efficient procedures. A dynamic test is an experimental process, which would define a set of characteristic parameters of the dynamic behaviour of the system, such as natural frequencies of the structure, mode shapes and the corresponding modal damping values associated. An assessment of these modal characteristics can be used both to verify the theoretical assumptions of the project, to monitor the performance of the structural system during its operational use. The thesis is structured in the following chapters: The first introductive chapter recalls some basic notions of dynamics of structure, focusing the discussion on the problem of systems with multiply degrees of freedom (MDOF), which can represent a generic real system under study, when it is excited with harmonic force or in free vibration. The second chapter is entirely centred on to the problem of dynamic identification process of a structure, if it is subjected to an experimental test in forced vibrations. It first describes the construction of FRF through classical FFT of the recorded signal. A different method, also in the frequency domain, is subsequently introduced; it allows accurately to compute the FRF using the geometric characteristics of the ellipse that represents the direct input-output comparison. The two methods are compared and then the attention is focused on some advantages of the proposed methodology. The third chapter focuses on the study of real structures when they are subjected to experimental test, where the force is not known, like in an ambient or impact test. In this analysis we decided to use the CWT, which allows a simultaneous investigation in the time and frequency domain of a generic signal x(t). The CWT is first introduced to process free oscillations, with excellent results both in terms of frequencies, dampings and vibration modes. The application in the case of ambient vibrations defines accurate modal parameters of the system, although on the damping some important observations should be made. The fourth chapter is still on the problem of post processing data acquired after a vibration test, but this time through the application of discrete wavelet transform (DWT). In the first part the results obtained by the DWT are compared with those obtained by the application of CWT. Particular attention is given to the use of DWT as a tool for filtering the recorded signal, in fact in case of ambient vibrations the signals are often affected by the presence of a significant level of noise. The fifth chapter focuses on another important aspect of the identification process: the model updating. In this chapter, starting from the modal parameters obtained from some environmental vibration tests, performed by the University of Porto in 2008 and the University of Sheffild on the Humber Bridge in England, a FE model of the bridge is defined, in order to define what type of model is able to capture more accurately the real dynamic behaviour of the bridge. The sixth chapter outlines the necessary conclusions of the presented research. They concern the application of a method in the frequency domain in order to evaluate the modal parameters of a structure and its advantages, the advantages in applying a procedure based on the use of wavelet transforms in the process of identification in tests with unknown input and finally the problem of 3D modeling of systems with many degrees of freedom and with different types of uncertainty.

Multi-level models and infrastructures for simulating biological system development

The hierarchical organisation of biological systems plays a crucial role in the pattern formation of gene expression resulting from the morphogenetic processes, where autonomous internal dynamics of cells, as well as cell-to-cell interactions through membranes, are responsible for the emergent peculiar structures of the individual phenotype. Being able to reproduce the systems dynamics at different levels of such a hierarchy might be very useful for studying such a complex phenomenon of self-organisation. The idea is to model the phenomenon in terms of a large and dynamic network of compartments, where the interplay between inter-compartment and intra-compartment events determines the emergent behaviour resulting in the formation of spatial patterns. According to these premises the thesis proposes a review of the different approaches already developed in modelling developmental biology problems, as well as the main models and infrastructures available in literature for modelling biological systems, analysing their capabilities in tackling multi-compartment / multi-level models. The thesis then introduces a practical framework, MS-BioNET, for modelling and simulating these scenarios exploiting the potential of multi-level dynamics. This is based on (i) a computational model featuring networks of compartments and an enhanced model of chemical reaction addressing molecule transfer, (ii) a logic-oriented language to flexibly specify complex simulation scenarios, and (iii) a simulation engine based on the many-species/many-channels optimised version of Gillespie’s direct method. The thesis finally proposes the adoption of the agent-based model as an approach capable of capture multi-level dynamics. To overcome the problem of parameter tuning in the model, the simulators are supplied with a module for parameter optimisation. The task is defined as an optimisation problem over the parameter space in which the objective function to be minimised is the distance between the output of the simulator and a target one. The problem is tackled with a metaheuristic algorithm. As an example of application of the MS-BioNET framework and of the agent-based model, a model of the first stages of Drosophila Melanogaster development is realised. The model goal is to generate the early spatial pattern of gap gene expression. The correctness of the models is shown comparing the simulation results with real data of gene expression with spatial and temporal resolution, acquired in free on-line sources.

Dynamic power management: from portable devices to high performance computing

Electronic applications are nowadays converging under the umbrella of the cloud computing vision. The future ecosystem of information and communication technology is going to integrate clouds of portable clients and embedded devices exchanging information, through the internet layer, with processing clusters of servers, data-centers and high performance computing systems. Even thus the whole society is waiting to embrace this revolution, there is a backside of the story. Portable devices require battery to work far from the power plugs and their storage capacity does not scale as the increasing power requirement does. At the other end processing clusters, such as data-centers and server farms, are build upon the integration of thousands multiprocessors. For each of them during the last decade the technology scaling has produced a dramatic increase in power density with significant spatial and temporal variability. This leads to power and temperature hot-spots, which may cause non-uniform ageing and accelerated chip failure. Nonetheless all the heat removed from the silicon translates in high cooling costs. Moreover trend in ICT carbon footprint shows that run-time power consumption of the all spectrum of devices accounts for a significant slice of entire world carbon emissions. This thesis work embrace the full ICT ecosystem and dynamic power consumption concerns by describing a set of new and promising system levels resource management techniques to reduce the power consumption and related issues for two corner cases: Mobile Devices and High Performance Computing.

Stochastic models and dynamic measures for the characterization of bistable circuits

During the last few years, a great deal of interest has risen concerning the applications of stochastic methods to several biochemical and biological phenomena. Phenomena like gene expression, cellular memory, bet-hedging strategy in bacterial growth and many others, cannot be described by continuous stochastic models due to their intrinsic discreteness and randomness. In this thesis I have used the Chemical Master Equation (CME) technique to modelize some feedback cycles and analyzing their properties, including experimental data. In the first part of this work, the effect of stochastic stability is discussed on a toy model of the genetic switch that triggers the cellular division, which malfunctioning is known to be one of the hallmarks of cancer. The second system I have worked on is the so-called futile cycle, a closed cycle of two enzymatic reactions that adds and removes a chemical compound, called phosphate group, to a specific substrate. I have thus investigated how adding noise to the enzyme (that is usually in the order of few hundred molecules) modifies the probability of observing a specific number of phosphorylated substrate molecules, and confirmed theoretical predictions with numerical simulations. In the third part the results of the study of a chain of multiple phosphorylation-dephosphorylation cycles will be presented. We will discuss an approximation method for the exact solution in the bidimensional case and the relationship that this method has with the thermodynamic properties of the system, which is an open system far from equilibrium.In the last section the agreement between the theoretical prediction of the total protein quantity in a mouse cells population and the observed quantity will be shown, measured via fluorescence microscopy.

Applying partial virtualization on ELF binaries through dynamic loaders

The technology of partial virtualization is a revolutionary approach to the world of virtualization. It lies directly in-between full system virtual machines (like QEMU or XEN) and application-related virtual machines (like the JVM or the CLR). The ViewOS project is the flagship of such technique, developed by the Virtual Square laboratory, created to provide an abstract view of the underlying system resources on a per-process basis and work against the principle of the Global View Assumption. Virtual Square provides several different methods to achieve partial virtualization within the ViewOS system, both at user and kernel levels. Each of these approaches have their own advantages and shortcomings. This paper provides an analysis of the different virtualization methods and problems related to both the generic and partial virtualization worlds. This paper is the result of an in-depth study and research for a new technology to be employed to provide partial virtualization based on ELF dynamic binaries. It starts with a mild analysis of currently available virtualization alternatives and then goes on describing the ViewOS system, highlighting its current shortcomings. The vloader project is then proposed as a possible solution to some of these inconveniences with a working proof of concept and examples to outline the potential of such new virtualization technique. By injecting specific code and libraries in the middle of the binary loading mechanism provided by the ELF standard, the vloader project can promote a streamlined and simplified approach to trace system calls. With the advantages outlined in the following paper, this method presents better performance and portability compared to the currently available ViewOS implementations. Furthermore, some of itsdisadvantages are also discussed, along with their possible solutions.

Assessment of vibratory stimulation on neuromuscular system

The thesis analyze a subject of renewed interest in bioengineering, the research and analysis of exercise parameters that maximize the neuromuscular and cardiovascular involvement in vibration treatment. The research activity was inspired by the increasing use of device able to provide localized or whole body vibration (WBV). In particular, the focus was placed on the vibrating platform and the effect that the vibrations have on the neuromuscular system and cardiovascular system. The aim of the thesis is to evaluate the effectiveness and efficiency of vibration applied to the entire body, in particular, it was investigated the effect of WBV on: 1) Oxygen consumption during static and dynamic squat; 2) Resonant frequency of the muscle groups of the lower limbs; 3) Oxygen consumption and electromyographic signals during static and dynamic squat. In the first three chapters are explained the state of the art concerning vibration treatments, the effects of vibration applied to the entire body, with the explanation of the basic mechanisms (Tonic Vibration Reflex, TVR) and the neuromuscular system, with particular attention to the skeletal muscles and the stretch reflex. In the fourth chapter is illustrated the set-up used for the experiments and the software, implemented in LabWindows in order to control the platform and acquire the electromyographic signal. In the fifth chapter were exposed experiments undertaken during the PhD years. In particular, the analysis of Whole Body Vibration effect on neurological and cardiovascular systems showed interesting results. The results indicate that the static squat with WBV produced higher neuromuscular and cardiorespiratory system activation for exercise duration <60 sec. Otherwise, if the single bout duration was higher than 60 sec, the greater cardiorespiratory system activation was achieved during the dynamic squat with WBV while higher neuromuscular activation was still obtained with the static exercise.

Dynamic analysis of the motorcycle chattering behaviour by means of symbolic multibody modelling

Aim of this research is the development and validation of a comprehensive multibody motorcycle model featuring rigid-ring tires, taking into account both slope and roughness of road surfaces. A novel parametrization for the general kinematics of the motorcycle is proposed, using a mixed reference-point and relative-coordinates approach. The resulting description, developed in terms of dependent coordinates, makes it possible to efficiently include rigid-ring kinematics as well as road elevation and slope. The equations of motion for the multibody system are derived symbolically and the constraint equations arising from the dependent-coordinate formulation are handled using a projection technique. Therefore the resulting system of equations can be integrated in time domain using a standard ODE algorithm. The model is validated with respect to maneuvers experimentally measured on the race track, showing consistent results and excellent computational efficiency. More in detail, it is also capable of reproducing the chatter vibration of racing motorcycles. The chatter phenomenon, appearing during high speed cornering maneuvers, consists of a self-excited vertical oscillation of both the front and rear unsprung masses in the range of frequency between 17 and 22 Hz. A critical maneuver is numerically simulated, and a self-excited vibration appears, consistent with the experimentally measured chatter vibration. Finally, the driving mechanism for the self-excitation is highlighted and a physical interpretation is proposed.

Hundertneunundzwanzig Xe NMR for investigations of complex and dynamic systems

In this work, the remarkable versatility and usefulness of applications of Xe-129 NMR experiments is further extended. The application of Xe-129 NMR spectroscopy to very different system is studied, including dynamic and static, solid and liquid, porous and non-porous systems. Using the large non-equilibrium polarization created by hyperpolarization of Xe-129, time-resolved NMR measurements can be used for the online-monitoring of dynamic systems. In the first part of this work, several improvements for medical applications of hyperpolarized Xe-129 are achieved and their feasibility shown experimentally. A large gain in speed and reproducibility of the accumulation process of Xe-129 as ice and an enhancement of the usable polarization in any experiment requiring prior accumulation are achieved. An enhancement of the longitudinal relaxation time of Xe-129 is realized by admixture of a buffer gas during the storage of hyperpolarized Xe-129. Pursuing the efforts of simplifying the accumulation process and enhancing the storage time of hyperpolarized Xe-129 will allow for a wider use of the hyperpolarized gas in (medical) MRI experiments. Concerning the use of hyperpolarized Xe-129 in MRI, the influence of the diffusion coefficient of the gas on parameters of the image contrast is experimentally demonstrated here by admixture of a buffer gas and thus changing the diffusion coefficient. In the second part of this work, a polymer system with unique features is probed by Xe-129 NMR spectroscopy, proving the method to be a valuable tool for the characterization of the anisotropic properties of semicrystalline, syndiotactic polystyrene films. The polymer films contain hollow cavities or channels with sizes in the sub-nanometer range, allowing for adsorption of Xe-129 and subsequent NMR measurements. Despite the use of a ’real-world’ system, the transfer of the anisotropic properties from the material to adsorbed Xe-129 atoms is shown, which was previously only known for fully crystalline materials. The anisotropic behavior towards atomar guests inside the polymer films is proven here for the first time for one of the phases. For the polymer phase containing nanochannels, the dominance of interactions between Xe-129 atoms in the channels compared to interactions between Xe atoms and the channel walls are proven by measurements of a powder sample of the polymer material and experiments including the rotation of the films in the external magnetic field as well as temperature-dependent measurements. The characterization of ’real-world’ systems showing very high degrees of anisotropy by Xe-129 are deemed to be very valuable in future applications. In the last part of this work, a new method for the online monitoring of chemical reactions has been proposed and its feasibility and validity are experimentally proven. The chemical shift dependence of dissolved Xe-129 on the composition of a reaction mixture is used for the online monitoring of free-radical miniemulsion polymerization reactions. Xe-129 NMR spectroscopy provides an excellent method for the online monitoring of polymerization reactions, due to the simplicity of the Xe-129 NMR spectra and the simple relationship between the Xe-129 chemical shift and the reaction conversion. The results of the time-resolved Xe-129 NMR measurements are compared to those from calorimetric measurements, showing a good qualitative agreement. The applicability of the new method to reactions other than polymerization reactions is investigated by the online monitoring of an enzymatic reaction in a miniemulsion. The successful combination of the large sensitivity of Xe-129, the NMR signal enhancements due to hyperpolarization, and the solubility of Xe-129 gives access to the large new field of investigations of chemical reaction kinetics in dynamic and complex systems like miniemulsions.

Engineering in Transition. Approaches, strategies and technologies for implementing system innovation towards sustainability

With the aim to provide people with sustainable options, engineers are ethically required to hold the safety, health and welfare of the public paramount and to satisfy society's need for sustainable development. The global crisis and related sustainability challenges are calling for a fundamental change in culture, structures and practices. Sustainability Transitions (ST) have been recognized as promising frameworks for radical system innovation towards sustainability. In order to enhance the effectiveness of transformative processes, both the adoption of a transdisciplinary approach and the experimentation of practices are crucial. The evolution of approaches towards ST provides a series of inspiring cases which allow to identify advances in making sustainability transitions happen. In this framework, the thesis has emphasized the role of Transition Engineering (TE). TE adopts a transdisciplinary approach for engineering to face the sustainability challenges and address the risks of un-sustainability. With this purpose, a definition of Transition Technologies is provided as a valid instruments to contribute to ST. In the empirical section, several transition initiatives have been analysed especially at the urban level. As a consequence, the model of living-lab of sustainability has crucially emerged. Living-labs are environments in which innovative technologies and services are co-created with users active participation. In this framework, university can play a key role as learning organization. The core of the thesis has concerned the experimental application of transition approach within the School of Engineering and Architecture of University of Bologna at Terracini Campus. The final vision is to realize a living-lab of sustainability. Particularly, a Transition Team has been established and several transition experiments have been conducted. The final result is not only the improvement of sustainability and resilience of the Terracini Campus, but the demonstration that university can generate solutions and strategies that tackle the complex, dynamic factors fuelling the global crisis.

Fault detection, diagnosis and active fault tolerant control for a satellite attitude control system

Modern control systems are becoming more and more complex and control algorithms more and more sophisticated. Consequently, Fault Detection and Diagnosis (FDD) and Fault Tolerant Control (FTC) have gained central importance over the past decades, due to the increasing requirements of availability, cost efficiency, reliability and operating safety. This thesis deals with the FDD and FTC problems in a spacecraft Attitude Determination and Control System (ADCS). Firstly, the detailed nonlinear models of the spacecraft attitude dynamics and kinematics are described, along with the dynamic models of the actuators and main external disturbance sources. The considered ADCS is composed of an array of four redundant reaction wheels. A set of sensors provides satellite angular velocity, attitude and flywheel spin rate information. Then, general overviews of the Fault Detection and Isolation (FDI), Fault Estimation (FE) and Fault Tolerant Control (FTC) problems are presented, and the design and implementation of a novel diagnosis system is described. The system consists of a FDI module composed of properly organized model-based residual filters, exploiting the available input and output information for the detection and localization of an occurred fault. A proper fault mapping procedure and the nonlinear geometric approach are exploited to design residual filters explicitly decoupled from the external aerodynamic disturbance and sensitive to specific sets of faults. The subsequent use of suitable adaptive FE algorithms, based on the exploitation of radial basis function neural networks, allows to obtain accurate fault estimations. Finally, this estimation is actively exploited in a FTC scheme to achieve a suitable fault accommodation and guarantee the desired control performances. A standard sliding mode controller is implemented for attitude stabilization and control. Several simulation results are given to highlight the performances of the overall designed system in case of different types of faults affecting the ADCS actuators and sensors.

Die Regulation der Ubiquitinligase CHIP durch das Cochaperon BAG2 im zellulären System und im Kontext der replikativen Seneszenz

Eine funktionierende Proteinqualitätskontrolle ist essenziell für die Vitalität einer Zelle. Das dynamische Gleichgewicht zwischen Proteinfaltung und -degradation wird von molekularen Chaperonen aufrechterhalten, deren Aktivität wiederum durch die Interaktion mit zahlreichen Cochaperonen moduliert wird. Das Cochaperon CHIP ist ein zentraler Faktor in Proteintriage-Entscheidungsprozessen, da es als Ubiquitinligase Chaperonsubstrate dem Abbau zuführt und somit die Chaperonmaschinerie direkt mit den Systemen der Proteindegradation verbindet. Um Polypeptide vor einem vorzeitigen Abbau zu schützen, wird die destruktive Aktivität von CHIP durch weitere Cochaperone reguliert. rnIn dieser Arbeit konnte die Hemmung der Ligaseaktivität von CHIP durch das Cochaperon BAG2 mechanistisch erstmals in einem zellulären System nachgewiesen werden. Dazu wurde die humane IMR-90 Fibroblasten Zelllinie verwendet. Die Ubiquitinierungsaktivität von CHIP wurde anhand von HSP72 als Modell-CHIP-Substrat untersucht. Durch die verringerte Ubiquitinierung, und damit dem reduzierten Abbau von HSP72, regulierte BAG2 dessen intrazelluläre Proteinspiegel, ohne dabei selbst eine Hitzeschockantwort zu induzieren. Überexprimiertes BAG2 wirkte sich trotz stabilisierter HSP72-Spiegel bei einem appliziertem Hitzestresses negativ auf die Zellvitalität aus, vermutlich da BAG2 durch die Inhibition von CHIP-vermittelter Ubiquitinierung massiv in das Gleichgewicht zwischen Substratfaltung und -degradation eingreift.rnDa sich die Mechanismen der Proteinqualitätskontrolle in der Alterung stark verändern und sich den wandelnden Bedingungen in der Zelle anpassen, wurde in einem zweiten Teil dieser Arbeit mit Hilfe des IMR-90 Zellsystems als etabliertes Modell zellulärer Seneszenz analysiert, inwieweit sich die Aktivität und die Regulation von CHIP durch BAG2 in der zellulären Alterung ändern. In seneszenten Zellen war HSP72 erheblich weniger ubiquitiniert als in jungen Fibroblasten, was auf eine reduzierte CHIP-Aktivität hinweist. Diese blieb jedoch durch BAG2 weiterhin modulierbar. Die Funktion von BAG2 als Inhibitor der Ubiquitinligase CHIP blieb demnach in seneszenten Zellen bestehen. In gealterten Fibroblasten regulierte BAG2 außerdem die Proteinspiegel des CHIP-Substrates und Seneszenzinitiators p53, was BAG2 eine mögliche Rolle in der Etablierung des Seneszenz-Phänotyps zuspricht. Weiterhin unterlagen die Proteinspiegel der beiden funktionell redundanten CHIP-Modulatoren BAG2 und HSPBP1 in der zellulären Alterung einer reziproken Regulation. In gealterten Mäusen trat die gegenläufige Veränderung der beiden Cochaperone gewebsspezifisch in der Lunge auf. Außerdem waren die BAG2-Proteinspiegel im Hippocampus gealterter Tiere signifikant erhöht.rnZusammenfassend konnte anhand der erzielten Ergebnisse die Funktion von BAG2 als Inhibitor von CHIP im zellulären System bestätigt werden. Außerdem durchlaufen die Aktivität und die Regulation von CHIP einen seneszenzspezifischen Adaptationsprozess, welcher für die Erhaltung der Proteostase in der Alterung relevant sein könnte und in welchem die Funktion von BAG2 als CHIP-Modulator möglicherweise eine wichtige Rolle spielt.rnZukünftige Studien könnten die komplexen Mechanismen weiterführend aufklären, mit denen CHIP-Aktivität reguliert wird. Dies kann helfen, der altersbedingten Abnahme an proteostatischer Kontrolle entgegenzuwirken und aberrante Proteinaggregation in altersassoziierten Erkrankungen vorzubeugen.rn