Nano-fabrication of complex functional structures using non- conventional lithography

In Chapter 1 I will present a brief introduction on the state of art of nanotechnologies, nanofabrication techniques and unconventional lithography as a technique to fabricate the novel electronic device as resistive switch so-called memristor is shown. In Chapter 2 a detailed description of the main fabrication and characterization techniques employed in this work is reported. Chapter 3 parallel local oxidation lithography (pLOx) describes as a main technique to obtain accurate patterning process. All the effective parameters has been studied and the optimized condition observed to highly reproducible with excellent patterned nanostructures. The effect of negative bias, calls local reduction (LR) studied. Moreover, the use of AC bias shows faster patterning process respect to DC bias. In Chapter 4 (metal/ e-SiO2/ Si nanojunction) it is shown how the electrochemical oxide nanostructures by using pLOx can be used in the fabrication of novel devices call memristor. We demonstrate a new concept, based on conventional materials, where the lifetime problem is resolved by introducing a “regeneration” step, which restores the nano-memristor to its pristine condition by applying an appropriate voltage cycle. In Chapter 5 (Graphene/ e-SiO2/ Si), Graphene as a building block material is used as an electrode to selectively oxidize the silicon substrate by pLOx set up for the fabrication of novel resistive switch device. In Chapter 6 (surface architecture) I will show another application of pLOx in biotechnology is shown. So the surface functionalization combine with nano-patterning by pLOx used to design a new surface to accurately bind biomolecules with the possibility of studying those properties and more application in nano-bio device fabrication. So, in order to obtain biochips, electronic and optical/photonics devices Nano patterning of DNA used as scaffolds to fabricate small functional nano-components.

Integrazione di tecnologie non distruttive per la caratterizzazione di rocce ornamentali

ABSTRACT: The dimension stone qualification through the use of non-destructive tests (NDT) is a relevant research topic for the industrial characterisation of finite products, because the competition of low-costs products can be sustained by an offer of highqualification and a top-guarantee products. The synthesis of potentialities offered by the NDT is the qualification and guarantee similar to the well known agro-industrial PDO, Protected Denomination of Origin. In fact it is possible to guarantee both, the origin and the quality of each stone product element, even through a Factory Production Control on line. A specific disciplinary is needed. A research developed at DICMA-Univ. Bologna in the frame of the “OSMATER” INTERREG project, allowed identifying good correlations between destructive and non-destructive tests for some types of materials from Verbano-Cusio-Ossola region. For example non conventional ultrasonic tests, image analysis parameters, water absorption and other measurements showed to be well correlated with the bending resistance, by relationships varying for each product. In conclusion it has been demonstrated that a nondestructive approach allows reaching several goals, among the most important: 1) the identification of materials; 2) the selection of products; 3) the substitution of DT by NDT. Now it is necessary to move from a research phase to the industrial implementation, as well as to develop new ND technologies focused on specific aims.

Il risparmio delle risorse alla scala abitativa e di insediamento. Tecnologie non convenzionali e valutazione ambientale attraverso metodologia LCA.

Nel corso del mio lavoro di ricerca mi sono occupata di identificare strategie che permettano il risparmio delle risorse a livello edilizio e di approfondire un metodo per la valutazione ambientale di tali strategie. La convinzione di fondo è che bisogna uscire da una visione antropocentrica in cui tutto ciò che ci circonda è merce e materiale a disposizione dell’uomo, per entrare in una nuova era di equilibrio tra le risorse della terra e le attività che l’uomo esercita sul pianeta. Ho quindi affrontato il tema dell’edilizia responsabile approfondendo l’ambito delle costruzioni in balle di paglia e terra. Sono convinta che l’edilizia industriale abbia un futuro molto breve davanti a sé e lascerà inevitabilmente spazio a tecniche non convenzionali che coinvolgono materiali di semplice reperimento e posa in opera. Sono altresì convinta che il solo utilizzo di materiali naturali non sia garanzia di danni ridotti sull’ecosistema. Allo stesso tempo ritengo che una mera certificazione energetica non sia sinonimo di sostenibilità. Per questo motivo ho valutato le tecnologie non convenzionali con approccio LCA (Life Cycle Assessment), approfondendo gli impatti legati alla produzione, ai trasporti degli stessi, alla tipologia di messa in opera, e ai loro possibili scenari di fine vita. Inoltre ho approfondito il metodo di calcolo dei danni IMPACT, identificando una carenza nel sistema, che non prevede una categoria di danno legata alle modifiche delle condizioni idrogeologiche del terreno. La ricerca si è svolta attraverso attività pratiche e sperimentali in cantieri di edilizia non convenzionale e attività di ricerca e studio sull’LCA presso l’Enea di Bologna (Ing. Paolo Neri).

Modulation Techniques for Multi-Phase Converters and Control Strategies for Multi-Phase Electric Drives

The ever-increasing spread of automation in industry puts the electrical engineer in a central role as a promoter of technological development in a sector such as the use of electricity, which is the basis of all the machinery and productive processes. Moreover the spread of drives for motor control and static converters with structures ever more complex, places the electrical engineer to face new challenges whose solution has as critical elements in the implementation of digital control techniques with the requirements of inexpensiveness and efficiency of the final product. The successfully application of solutions using non-conventional static converters awake an increasing interest in science and industry due to the promising opportunities. However, in the same time, new problems emerge whose solution is still under study and debate in the scientific community During the Ph.D. course several themes have been developed that, while obtaining the recent and growing interest of scientific community, have much space for the development of research activity and for industrial applications. The first area of research is related to the control of three phase induction motors with high dynamic performance and the sensorless control in the high speed range. The management of the operation of induction machine without position or speed sensors awakes interest in the industrial world due to the increased reliability and robustness of this solution combined with a lower cost of production and purchase of this technology compared to the others available in the market. During this dissertation control techniques will be proposed which are able to exploit the total dc link voltage and at the same time capable to exploit the maximum torque capability in whole speed range with good dynamic performance. The proposed solution preserves the simplicity of tuning of the regulators. Furthermore, in order to validate the effectiveness of presented solution, it is assessed in terms of performance and complexity and compared to two other algorithm presented in literature. The feasibility of the proposed algorithm is also tested on induction motor drive fed by a matrix converter. Another important research area is connected to the development of technology for vehicular applications. In this field the dynamic performances and the low power consumption is one of most important goals for an effective algorithm. Towards this direction, a control scheme for induction motor that integrates within a coherent solution some of the features that are commonly required to an electric vehicle drive is presented. The main features of the proposed control scheme are the capability to exploit the maximum torque in the whole speed range, a weak dependence on the motor parameters, a good robustness against the variations of the dc-link voltage and, whenever possible, the maximum efficiency. The second part of this dissertation is dedicated to the multi-phase systems. This technology, in fact, is characterized by a number of issues worthy of investigation that make it competitive with other technologies already on the market. Multiphase systems, allow to redistribute power at a higher number of phases, thus making possible the construction of electronic converters which otherwise would be very difficult to achieve due to the limits of present power electronics. Multiphase drives have an intrinsic reliability given by the possibility that a fault of a phase, caused by the possible failure of a component of the converter, can be solved without inefficiency of the machine or application of a pulsating torque. The control of the magnetic field spatial harmonics in the air-gap with order higher than one allows to reduce torque noise and to obtain high torque density motor and multi-motor applications. In one of the next chapters a control scheme able to increase the motor torque by adding a third harmonic component to the air-gap magnetic field will be presented. Above the base speed the control system reduces the motor flux in such a way to ensure the maximum torque capability. The presented analysis considers the drive constrains and shows how these limits modify the motor performance. The multi-motor applications are described by a well-defined number of multiphase machines, having series connected stator windings, with an opportune permutation of the phases these machines can be independently controlled with a single multi-phase inverter. In this dissertation this solution will be presented and an electric drive consisting of two five-phase PM tubular actuators fed by a single five-phase inverter will be presented. Finally the modulation strategies for a multi-phase inverter will be illustrated. The problem of the space vector modulation of multiphase inverters with an odd number of phases is solved in different way. An algorithmic approach and a look-up table solution will be proposed. The inverter output voltage capability will be investigated, showing that the proposed modulation strategy is able to fully exploit the dc input voltage either in sinusoidal or non-sinusoidal operating conditions. All this aspects are considered in the next chapters. In particular, Chapter 1 summarizes the mathematical model of induction motor. The Chapter 2 is a brief state of art on three-phase inverter. Chapter 3 proposes a stator flux vector control for a three- phase induction machine and compares this solution with two other algorithms presented in literature. Furthermore, in the same chapter, a complete electric drive based on matrix converter is presented. In Chapter 4 a control strategy suitable for electric vehicles is illustrated. Chapter 5 describes the mathematical model of multi-phase induction machines whereas chapter 6 analyzes the multi-phase inverter and its modulation strategies. Chapter 7 discusses the minimization of the power losses in IGBT multi-phase inverters with carrier-based pulse width modulation. In Chapter 8 an extended stator flux vector control for a seven-phase induction motor is presented. Chapter 9 concerns the high torque density applications and in Chapter 10 different fault tolerant control strategies are analyzed. Finally, the last chapter presents a positioning multi-motor drive consisting of two PM tubular five-phase actuators fed by a single five-phase inverter.

Design and development of new green catalytic methodologies for the synthesis of enantiomerically enriched molecules

The following Ph.D work was mainly focused on catalysis, as a key technology, to achieve the objectives of sustainable (green) chemistry. After introducing the concepts of sustainable (green) chemistry and an assessment of new sustainable chemical technologies, the relationship between catalysis and sustainable (green) chemistry was briefly discussed and illustrated via an analysis of some selected and relevant examples. Afterwards, as a continuation of the ongoing interest in Dr. Marco Bandini’s group on organometallic and organocatalytic processes, I addressed my efforts to the design and development of novel catalytic green methodologies for the synthesis of enantiomerically enriched molecules. In the first two projects the attention was focused on the employment of solid supports to carry out reactions that still remain a prerogative of omogeneous catalysis. Firstly, particular emphasis was addressed to the discovery of catalytic enantioselective variants of nitroaldol condensation (commonly termed Henry reaction), using a complex consisting in a polyethylene supported diamino thiopene (DATx) ligands and copper as active species. In the second project, a new class of electrochemically modified surfaces with DATx palladium complexes was presented. The DATx-graphite system proved to be efficient in promoting the Suzuki reaction. Moreover, in collaboration with Prof. Wolf at the University of British Columbia (Vancouver), cyclic voltammetry studies were reported. This study disclosed new opportunities for carbon–carbon forming processes by using heterogeneous, electrodeposited catalyst films. A straightforward metal-free catalysis allowed the exploration around the world of organocatalysis. In fact, three different and novel methodologies, using Cinchona, Guanidine and Phosphine derivatives, were envisioned in the three following projects. An interesting variant of nitroaldol condensation with simple trifluoromethyl ketones and also their application in a non-conventional activation of indolyl cores by Friedel-Crafts-functionalization, led to two novel synthetic protocols. These approaches allowed the preparation of synthetically useful trifluoromethyl derivatives bearing quaternary stereocenters. Lastly, in the sixth project the first γ-alkylation of allenoates with conjugated carbonyl compounds was envisioned. In the last part of this Ph.D thesis bases on an extra-ordinary collaboration with Prof. Balzani and Prof. Gigli, I was involved in the synthesis and characterization of a new type of heteroleptic cyclometaled-Ir(III) complexes, bearing bis-oxazolines (BOXs) as ancillary ligands. The new heteroleptic complexes were fully characterized and in order to examine the electroluminescent properties of FIrBOX(CH2), an Organic Light Emitting Device was realized.

Metodi avanzati di indagine di ammassi rocciosi a blocchi in matrice (bimrock).

The research focuses on the implementation and validation of advanced direct and indirect methods of investigation for the structural and mechanical characterisation of bimrocks. In particular, a non conventional in situ shear test has been develop in order to evaluate the strength parameters of bimrocks by properly taking into account the influence of blocks. Also, a geostatistical approach has been introduced for the investigation of block morphological and spatial properties from digital images, by means of a variographic analysis of the block Indicator Variable.

Use of solvents and environmental friendly materials for applications in Green Chemistry

The present Thesis studies three alternative solvent groups as sustainable replacement of traditional organic solvents. Some aspects of fluorinated solvents, supercritical fluids and ionic liquids, have been analysed with a critical approach and their effective “greenness” has been evaluated from the points of view of the synthesis, the properties and the applications. In particular, the attention has been put on the environmental and human health issues, evaluating the eco-toxicity, the toxicity and the persistence, to underline that applicability and sustainability are subjects with equal importance. The “green” features of fluorous solvents and supercritical fluids are almost well-established; in particular supercritical carbon dioxide (scCO2) is probably the “greenest” solvent among the alternative solvent systems developed in the last years, enabling to combine numerous advantages both from the point of view of industrial/technological applications and eco-compatibility. In the Thesis the analysis of these two classes of alternative solvents has been mainly focused on their applicability, rather than the evaluation of their environmental impact. Specifically they have been evaluated as alternative media for non-aqueous biocatalysis. For this purpose, the hydrophobic ion pairing (HIP), which allows solubilising enzymes in apolar solvents by an ion pairing between the protein and a surfactant, has been investigated as effective enzymatic derivatisation technique to improve the catalytic activity under homogeneous conditions in non conventional media. The results showed that the complex enzyme-surfactant was much more active both in fluorous solvents and in supercritical carbon dioxide than the native form of the enzyme. Ionic liquids, especially imidazolium salts, have been proposed some years ago as “fully green” alternative solvents; however this epithet does not take into account several “brown” aspects such as their synthesis from petro-chemical starting materials, their considerable eco-toxicity, toxicity and resistance to biodegradation, and the difficulty of clearly outline applications in which ionic liquids are really more advantageous than traditional solvents. For all of these reasons in this Thesis a critical analysis of ionic liquids has been focused on three main topics: i) alternative synthesis by introducing structural moieties which could reduce the toxicity of the most known liquid salts, and by using starting materials from renewable resources; ii) on the evaluation of their environmental impact through eco-toxicological tests (Daphnia magna and Vibrio fischeri acute toxicity tests, and algal growth inhibition), toxicity tests (MTT test, AChE inhibition and LDH release tests) and fate and rate of aerobic biodegradation in soil and water; iii) and on the demonstration of their effectiveness as reaction media in organo-catalysis and as extractive solvents in the recovery of vegetable oil from terrestrial and aquatic biomass. The results about eco-toxicity tests with Daphnia magna, Vibrio fischeri and algae, and toxicity assay using cultured cell lines, clearly indicate that the difference in toxicity between alkyl and oxygenated cations relies in differences of polarity, according to the general trend of decreasing toxicity by decreasing the lipophilicity. Independently by the biological approach in fact, all the results are in agreement, showing a lower toxicity for compounds with oxygenated lateral chains than for those having purely alkyl lateral chains. These findings indicate that an appropriate choice of cation and anion structures is important not only to design the IL with improved and suitable chemico-physical properties but also to obtain safer and eco-friendly ILs. Moreover there is a clear indication that the composition of the abiotic environment has to be taken into account when the toxicity of ILs in various biological test systems is analysed, because, for example, the data reported in the Thesis indicate a significant influence of salinity variations on algal toxicity. Aerobic biodegradation of four imidazolium ionic liquids, two alkylated and two oxygenated, in soil was evaluated for the first time. Alkyl ionic liquids were shown to be biodegradable over the 6 months test period, and in contrast no significant mineralisation was observed with oxygenated derivatives. A different result was observed in the aerobic biodegradation of alkylated and oxygenated pyridinium ionic liquids in water because all the ionic liquids were almost completely degraded after 10 days, independently by the number of oxygen in the lateral chain of the cation. The synthesis of new ionic liquids by using renewable feedstock as starting materials, has been developed through the synthesis of furan-based ion pairs from furfural. The new ammonium salts were synthesised in very good yields, good purity of the products and wide versatility, combining low melting points with high decomposition temperatures and reduced viscosities. Regarding the possible applications as surfactants and biocides, furan-based salts could be a valuable alternative to benzyltributylammonium salts and benzalkonium chloride that are produced from non-renewable resources. A new procedure for the allylation of ketones and aldehydes with tetraallyltin in ionic liquids was developed. The reaction afforded high yields both in sulfonate-containing ILs and in ILs without sulfonate upon addition of a small amount of sulfonic acid. The checked reaction resulted in peculiar chemoselectivity favouring aliphatic substrates towards aromatic ketones and good stereoselectivity in the allylation of levoglucosenone. Finally ILs-based systems could be easily and successfully recycled, making the described procedure environmentally benign. The potential role of switchable polarity solvents as a green technology for the extraction of vegetable oil from terrestrial and aquatic biomass has been investigated. The extraction efficiency of terrestrial biomass rich in triacylglycerols, as soy bean flakes and sunflower seeds, was comparable to those of traditional organic solvents, being the yield of vegetable oils recovery very similar. Switchable polarity solvents as been also exploited for the first time in the extraction of hydrocarbons from the microalga Botryococcus braunii, demonstrating the efficiency of the process for the extraction of both dried microalgal biomass and directly of the aqueous growth medium. The switchable polarity solvents exhibited better extraction efficiency than conventional solvents, both with dried and liquid samples. This is an important issue considering that the harvest and the dewatering of algal biomass have a large impact on overall costs and energy balance.

Advanced lithium and lithium-ion rechargeable batteries for automotive applications

The worldwide demand for a clean and low-fuel-consuming transport promotes the development of safe, high energy and power electrochemical storage and conversion systems. Lithium-ion batteries (LIBs) are considered today the best technology for this application as demonstrated by the recent interest of automotive industry in hybrid (HEV) and electric vehicles (EV) based on LIBs. This thesis work, starting from the synthesis and characterization of electrode materials and the use of non-conventional electrolytes, demonstrates that LIBs with novel and safe electrolytes and electrode materials meet the targets of specific energy and power established by U.S.A. Department of Energy (DOE) for automotive application in HEV and EV. In chapter 2 is reported the origin of all chemicals used, the description of the instruments used for synthesis and chemical-physical characterizations, the electrodes preparation, the batteries configuration and the electrochemical characterization procedure of electrodes and batteries. Since the electrolyte is the main critical point of a battery, in particular in large- format modules, in chapter 3 we focused on the characterization of innovative and safe electrolytes based on ionic liquids (characterized by high boiling/decomposition points, thermal and electrochemical stability and appreciable conductivity) and mixtures of ionic liquid with conventional electrolyte. In chapter 4 is discussed the microwave accelerated sol–gel synthesis of the carbon- coated lithium iron phosphate (LiFePO 4 -C), an excellent cathode material for LIBs thanks to its intrinsic safety and tolerance to abusive conditions, which showed excellent electrochemical performance in terms of specific capacity and stability. In chapter 5 are presented the chemical-physical and electrochemical characterizations of graphite and titanium-based anode materials in different electrolytes. We also characterized a new anodic material, amorphous SnCo alloy, synthetized with a nanowire morphology that showed to strongly enhance the electrochemical stability of the material during galvanostatic full charge/discharge cycling. Finally, in chapter 6, are reported different types of batteries, assembled using the LiFePO 4 -C cathode material, different anode materials and electrolytes, characterized by deep galvanostatic charge/discharge cycles at different C-rates and by test procedures of the DOE protocol for evaluating pulse power capability and available energy. First, we tested a battery with the innovative cathode material LiFePO 4 -C and conventional graphite anode and carbonate-based electrolyte (EC DMC LiPF 6 1M) that demonstrated to surpass easily the target for power-assist HEV application. Given that the big concern of conventional lithium-ion batteries is the flammability of highly volatile organic carbonate- based electrolytes, we made safe batteries with electrolytes based on ionic liquid (IL). In order to use graphite anode in IL electrolyte we added to the IL 10% w/w of vinylene carbonate (VC) that produces a stable SEI (solid electrolyte interphase) and prevents the graphite exfoliation phenomenon. Then we assembled batteries with LiFePO 4 -C cathode, graphite anode and PYR 14 TFSI 0.4m LiTFSI with 10% w/w of VC that overcame the DOE targets for HEV application and were stable for over 275 cycles. We also assembled and characterized ―high safety‖ batteries with electrolytes based on pure IL, PYR 14 TFSI with 0.4m LiTFSI as lithium salt, and on mixture of this IL and standard electrolyte (PYR 14 TFSI 50% w/w and EC DMC LiPF 6 50% w/w), using titanium-based anodes (TiO 2 and Li 4 Ti 5 O 12 ) that are commonly considered safer than graphite in abusive conditions. The batteries bearing the pure ionic liquid did not satisfy the targets for HEV application, but the batteries with Li 4 Ti 5 O 12 anode and 50-50 mixture electrolyte were able to surpass the targets. We also assembled and characterized a lithium battery (with lithium metal anode) with a polymeric electrolyte based on poly-ethilenoxide (PEO 20 – LiCF 3 SO 3 +10%ZrO 2 ), which satisfied the targets for EV application and showed a very impressive cycling stability. In conclusion, we developed three lithium-ion batteries of different chemistries that demonstrated to be suitable for application in power-assist hybrid vehicles: graphite/EC DMC LiPF 6 /LiFePO 4 -C, graphite/PYR 14 TFSI 0.4m LiTFSI with 10% VC/LiFePO 4 -C and Li 4 T i5 O 12 /PYR 14 TFSI 50%-EC DMC LiPF 6 50%/LiFePO 4 -C. We also demonstrated that an all solid-state polymer lithium battery as Li/PEO 20 –LiCF 3 SO 3 +10%ZrO 2 /LiFePO 4 -C is suitable for application on electric vehicles. Furthermore we developed a promising anodic material alternative to the graphite, based on SnCo amorphous alloy.

Comparative Analysis of Alternative Hybrid Systems for Automotive Applications

The main objective of this work was to investigate the impact of different hybridization concepts and levels of hybridization on fuel economy of a standard road vehicle where both conventional and non-conventional hybrid architectures are treated exactly in the same way from the point of view of overall energy flow optimization. Hybrid component models were developed and presented in detail as well as the simulations results mainly for NEDC cycle. The analysis was performed on four different parallel hybrid powertrain concepts: Hybrid Electric Vehicle (HEV), High Speed Flywheel Hybrid Vehicle (HSF-HV), Hydraulic Hybrid Vehicle (HHV) and Pneumatic Hybrid Vehicle (PHV). In order to perform equitable analysis of different hybrid systems, comparison was performed also on the basis of the same usable system energy storage capacity (i.e. 625kJ for HEV, HSF and the HHV) but in the case of pneumatic hybrid systems maximal storage capacity was limited by the size of the systems in order to comply with the packaging requirements of the vehicle. The simulations were performed within the IAV Gmbh - VeLoDyn software simulator based on Matlab / Simulink software package. Advanced cycle independent control strategy (ECMS) was implemented into the hybrid supervisory control unit in order to solve power management problem for all hybrid powertrain solutions. In order to maintain State of Charge within desired boundaries during different cycles and to facilitate easy implementation and recalibration of the control strategy for very different hybrid systems, Charge Sustaining Algorithm was added into the ECMS framework. Also, a Variable Shift Pattern VSP-ECMS algorithm was proposed as an extension of ECMS capabilities so as to include gear selection into the determination of minimal (energy) cost function of the hybrid system. Further, cycle-based energetic analysis was performed in all the simulated cases, and the results have been reported in the corresponding chapters.

Virus oncogeni a dna in tumori umani: studio delle infezioni da papillomavirus e poliomavirus in neoplasie di diversa origine.

I virus tumorali inducono oncogenesi nel loro ospite naturale o in sistemi animali sperimentali, manipolando diverse vie cellulari. Ad oggi, sono stati identificati sette virus capaci di causare specifici tumori umani. Inoltre HPV, JCV ed SV40, sono stati associati con un grande numero di tumori umani in sedi corporee non convenzionali, ma, nonostante molti anni di ricerca, nessuna eziologia virale è stata ancora confermata. Lo scopo di questo studio è stato di valutare la presenza ed il significato sia di JCV ed SV40 in tumori ossei umani, e di HPV nel carcinoma della mammella (BC), galattoforectomie (GF), secrezioni mammarie patologiche (ND) e glioblastoma multiforme (GBM). Tecniche di biologia molecolare sono state impiegate per esaminare campioni di tessuto tumorale di 70 tumori ossei (20 osteosarcomi [OS], 20 tumori a cellule giganti [TCG], 30 condrosarcomi [CS]), 168 BCs , 30 GFs, 59 GBM e 30 campioni di ND. Il genoma di SV40 e JCV è stato trovato nel 70% dei CS + 20% degli OS, e nel 13% dei CS +10% dei TCG, rispettivamente. Il DNA di HPV è stato rilevato nel 30% dei pazienti con BC, nel 27% dei campioni GF e nel 13% dei NDs. HPV16 è stato il genotipo maggiormente osservato in tutti questi campioni, seguito da HPV18 e HPV35. Inoltre, il DNA di HPV è stato trovato nel 22% dei pazienti con GBM, in questo tumore HPV6 era il tipo più frequentemente rilevato, seguito da HPV16. L’ ISH ha mostrato che il DNA di HPV è situato all’interno di cellule tumorali mammarie e di GBM. I nostri risultati suggeriscono un possibile ruolo di JCV, SV40 e HPV in questi tumori, se non come induttori come promotori del processo neoplastico, tuttavia diversi criteri devono ancora essere soddisfatti prima di chiarirne il ruolo.

Giunzione mediante laser di materiali difficili, ibridi ed a struttura cellulare

Lo studio presentato in questa sede concerne applicazioni di saldatura LASER caratterizzate da aspetti di non-convenzionalità ed è costituito da tre filoni principali. Nel primo ambito di intervento è stata valutata la possibilità di effettuare saldature per fusione, con LASER ad emissione continua, su pannelli Aluminum Foam Sandwich e su tubi riempiti in schiuma di alluminio. Lo studio ha messo in evidenza numerose linee operative riguardanti le problematiche relative alla saldatura delle pelli esterne dei componenti ed ha dimostrato la fattibilità relativa ad un approccio di giunzione LASER integrato (saldatura seguita da un post trattamento termico) per la realizzazione della giunzione completa di particolari tubolari riempiti in schiuma con ripristino della struttura cellulare all’interfaccia di giunzione. Il secondo ambito di intervento è caratterizzato dall’applicazione di una sorgente LASER di bassissima potenza, operante in regime ad impulsi corti, nella saldatura di acciaio ad elevato contenuto di carbonio. Lo studio ha messo in evidenza come questo tipo di sorgente, solitamente applicata per lavorazioni di ablazione e marcatura, possa essere applicata anche alla saldatura di spessori sub-millimetrici. In questa fase è stato messo in evidenza il ruolo dei parametri di lavoro sulla conformazione del giunto ed è stata definita l’area di fattibilità del processo. Lo studio è stato completato investigando la possibilità di applicare un trattamento LASER dopo saldatura per addolcire le eventuali zone indurite. In merito all’ultimo ambito di intervento l’attività di studio si è focalizzata sull’utilizzo di sorgenti ad elevata densità di potenza (60 MW/cm^2) nella saldatura a profonda penetrazione di acciai da costruzione. L’attività sperimentale e di analisi dei risultati è stata condotta mediante tecniche di Design of Experiment per la valutazione del ruolo preciso di tutti i parametri di processo e numerose considerazioni relative alla formazione di cricche a caldo sono state suggerite.

Crystal Engineering of bright luminescent copper iodide clusters with phosphorus and nitrogen-based ligands

Copper(I) halide clusters are recently considered as good candidate for optoelectronic devices such as OLEDs . Although the copper halide clusters, in particular copper iodide, are very well known since the beginning of the 20th century, only in the late ‘70s the interest on these compounds grew dramatically due their particular photophysical behaviour. These complexes are characterized by a dual triplet emission bands, named Cluster Centred (3CC) and Halogen-to-Ligand charge transfer (3XLCT), the intensities of which are strictly related with the temperature. The CC transition, due to the presence of a metallophylic interactions, is prevalent at ambient temperature while the XLCT transition, located preferentially on the ligand part, became more prominent at low temperature. Since these pioneering works, it was easy to understand the photophysical properties of this compounds became more interesting in solid-state respect to solution with an improvement in emission efficiency. In this work we aim to characterize in SS organocopper(I)iodide compounds to valuate the correlation between the molecular crystal structure and the photophysical properties. It is also considered to hike new strategies to synthesize CuI complexes from the wet reactions to the more green solvent free methods. The advantages in using these strategies are evident but, obtain a single crystal suitable for SCXRD analysis from these batches is quite impossible. The structure solution still remains the key point in this research so we tackle this problem solving the structure by X-ray powder diffraction data. When the sample was fully characterized we moved to design and development of the associated OLED-device. Since copper iodide complexes are often insoluble in organic solvents, the high vacuum deposition technique is preferred. A new non-conventional deposition process have also been proposed to avoid the low complex stability in this practice with an in-situ complex formation in a layer-by layer deposition route.

Sustainable processes using heterogeneous acid catalysts. Some examples of industrial interest.

In recent years the need for the design of more sustainable processes and the development of alternative reaction routes to reduce the environmental impact of the chemical industry has gained vital importance. Main objectives especially regard the use of renewable raw materials, the exploitation of alternative energy sources, the design of inherently safe processes and of integrated reaction/separation technologies (e.g. microreactors and membranes), the process intensification, the reduction of waste and the development of new catalytic pathways. The present PhD thesis reports results derived during a three years research period at the School of Chemical Sciences of Alma Mater Studiorum-University of Bologna, Dept. of Industrial Chemistry and Materials (now Dept. of Industrial Chemistry “Toso Montanari”), under the supervision of Prof. Fabrizio Cavani (Catalytic Processes Development Group). Three research projects in the field of heterogeneous acid catalysis focused on potential industrial applications were carried out. The main project, regarding the conversion of lignocellulosic materials to produce monosaccharides (important intermediates for production of biofuels and bioplatform molecules) was financed and carried out in collaboration with the Italian oil company eni S.p.A. (Istituto eni Donegani-Research Center for non-Conventional Energies, Novara, Italy) The second and third academic projects dealt with the development of green chemical processes for fine chemicals manufacturing. In particular, (a) the condensation reaction between acetone and ammonia to give triacetoneamine (TAA), and (b) the Friedel-Crafts acylation of phenol with benzoic acid were investigated.

Emerging adulthoods. Percorsi giovanili di partecipazione e cittadinanza in prospettiva intergenerazionale

La tesi tematizza come proprio oggetto di indagine i percorsi di partecipazione politica e civica dei giovani nei contesti di transizione alla vita adulta, concentrandosi sull’influenza delle relazioni tra generazioni su tali espressioni di coinvolgimento. L’approfondimento empirico consiste in una ricerca qualitativa condotta presso il quartiere Navile di Bologna nel 2012. Basandosi sull’approccio metodologico della grounded theory, essa ha coinvolto un campione di giovani e un campione di adulti per loro significativi attraverso interviste semistrutturate. Dall’analisi emerge una rilevante disaffezione giovanile nei confronti della politica che, tuttavia, non traduce in un rifiuto del coinvolgimento, ma in una “partecipazione con riserva” espressa attraverso atteggiamenti tutt’altro che passivi nei confronti della politica formale - basati sulla logica della riforma, della resistenza o della ribellione - e mediante un forte investimento in attività partecipative non convenzionali (associazionismo e coinvolgimento). A fare da sfondo all’interesse partecipativo dei giovani si colloca una lettura negativa della propria condizione presente ed un conseguente conflitto intergenerazionale piuttosto manifesto, che si riflette sulle stesse modalità di attivazione. La politica, nelle sue espressioni più strettamente formali, viene interpretata come un ‘territorio adulto’, gestito secondo logiche che lasciano poco spazio ai giovani i quali, per tale ragione, scelgono di attivarsi secondo modalità alternative in cui il confronto con l’altro, quando presente, avviene prevalentemente tra pari o su basi avvertite come più paritarie. Il distanziamento dei giovani dalla politica formale riflette quindi una parallela presa di distanza dagli adulti, i quali risultano smarriti nello svolgimento delle loro funzioni di modello e di riconoscimento. La loro ambivalenza rispetto ai giovani - ossia il continuo oscillare tra il profondo pessimismo e il cieco ottimismo, tra la guida direttiva e la deresponsabilizzazione - si traduce in un riconoscimento parziale delle reali potenzialità ed esigenze dei giovani come cittadini ed adulti emergenti.

Urine proteome in animals of veterinary interest: species comparison and new biomarkers of nephropathy

Urine is considered an ideal source of biomarkers, however in veterinary medicine a complete study on the urine proteome is still lacking. The present work aimed to apply proteomic techniques to the separation of the urine proteome in dogs, cats, horses, cows and some non-conventional species. High resolution electrophoresis (HRE) was also validated for the quantification of albuminuria in dogs and cats. In healthy cats, applying SDS-PAGE and 2DE coupled to mass spectrometry (MS), was produced a reference map of the urine proteome. Moreover, 13 differentially represented urine proteins were linked with CKD, suggesting uromodulin, cauxin, CFAD, Apo-H, RBP and CYSM as candidate biomarkers to be investigated further. In dogs, applying SDS-PAGE coupled to MS, was highlighted a specific pattern in healthy animals showing important differences in patients affected by leishmaniasis. In particular, uromodulin could be a putative biomarker of tubular damage while arginine esterase and low MW proteins needs to be investigated further. In cows, applying SDS-PAGE, were highlighted different patterns between heifers and cows showing some interesting changes during pregnancy. In particular, putative alpha-fetoprotein and b-PAP needs to be further investigated. In horses, applying SDS-PAGE, was produced a reference profile characterized by 13±4 protein bands and the most represented one was the putative uromodulin. Proteinuric horses showed the decrease of the putative uromodulin band and the appearance of 2 to 4 protein bands at higher MW and a greater variability in the range of MW between 49 and 17 kDa. In felids and giraffes was quantified proteinuria reporting the first data for UTP and UPC. Moreover, by means of SDS-PAGE, were highlighted species-specific electrophoretic patterns in big felids and giraffes.