Conservare la cultura, creare una storia. Tradizione e genere nella musica di villaggio dei Banyoro e dei Batooro dell’Uganda.

La dissertazione si articola attorno all’idea di tradizione e alla concettualizzazione di genere nella musica di villaggio dei Banyoro e dei Batooro dell’Uganda occidentale. Il lavoro si sviluppa nel complesso in tre parti principali. Nella prima si presentano le trasformazioni storiche intervenute nelle relazioni di genere dal periodo precoloniale al presente e si introduce la musica di villaggio delle popolazioni considerate, ponendola a confronto con la musica di corte e con quella religiosa. La seconda sezione è dedicata allo studio dei repertori vocali e di danza di villaggio, a partire dalla documentazione realizzata con informatori anziani: di queste musiche sono considerate le caratteristiche stilistiche ed è condotta un’analisi che mira a mettere in luce le idee di genere trasmesse attraverso questi repertori. L’ultima parte del lavoro prende in considerazione le trasformazioni intervenute nel panorama musicale ugandese nell’ultimo secolo, a partire dall’influenza di musiche esterne, dall’insegnamento della musica tradizionale nelle scuole e dall’istituzione di festival scolastici e di gruppi folklorici: diverse performance attuali di canti e di danza sotto sottoposte a studio analitico. Nel complesso, si rileva una generale rifunzionalizzazione di musiche e idee di genere che si rifanno al passato, ma hanno valore soprattutto per il recupero della cultura locale nel presente,connotato dal contesto multiculturale dell’Uganda contemporanea e dalle politiche, promosse dal Governo, che favoriscono l’emancipazione femminile.

Cinchona alkaloids and BINOL derivatives as privileged catalysts or ligands in asymmetric synthesis

During the last fifteen years organocatalysis emerged as a powerful tool for the enantioselective functionalization of the most different organic molecules. Both C-C and C-heteroatom bonds can be formed in an enantioselective fashion using many types of catalyst and the field is always growing. Many kind of chiral catalysts have emerged as privileged, but among them Proline, cinchona alkaloids, BINOL, and their derivatives showed to be particularly useful chiral scaffolds. This thesis, after a short presentation of many organocatalysts and activation modes, focuses mainly on cinchona alkaloid derived primary amines and BINOL derived chiral Brønsted acids, describing their properties and applications. Then, in the experimental part, these compounds are used for the catalysis of new transformations. The enantioselective Friedel-Crafts alkylation of cyclic enones with naphthols using cinchona alkaloid derived primary amines as catalysts is presented and discussed. The results of this work were very good and this resulted also in a publication. The same catalysts are then used to accomplish the enantioselective addition of indoles to cyclic enones. Many catalysts in combination with many acids as co-catalysts were tried and the reaction was fully studied. Selective N-alkylation was obtained in many cases, in combination with quite good to good enantioselectivities. Also other kind of catalysis were tried for this reaction, with interesting results. Another aza-Michael reaction between OH-free hydroxylamines and nitrostyrene using cinchona alkaloid derived thioureas is briefly discussed. Then our attention focused on Brønsted acid catalyzed transformations. With this regard, the Prins cyclization, a reaction never accomplished in an enantioselective fashion until now, is presented and developed. The results obtained are promising. In the last part of this thesis the work carried out abroad is presented. In Prof. Rueping laboratories, an enantioselective Nazarov cyclization using cooperative catalysis and the enantioselective desymmetrization of meso-hydrobenzoin catalyzed by Brønsted acid were studied.

Au(I) Catalyzed Manipulation of Propargylic Alcohols: A New Route Towards the Synthesis of Indole Alkaloids

In this work we presented several aspects regarding the possibility to use readily available propargylic alcohols as acyclic precursors to develop new stereoselective [Au(I)]-catalyzed cascade reactions for the synthesis of highly complex indole architectures. The use of indole-based propargylic alcohols of type 1 in a stereoselective [Au(I)]-catalyzed hydroindolynation/immiun trapping reactive sequence opened access to a new class of tetracyclic indolines, dihydropyranylindolines A and furoindolines B. An enantioselective protocol was futher explored in order to synthesize this molecules with high yields and ee. The suitability of propargylic alcohols in [Au(I)]-catalyzed cascade reactions was deeply investigated by developing cascade reactions in which was possible not only to synthesize the indole core but also to achieve a second functionalization. Aniline based propargylic alcohols 2 were found to be modular acyclic precursors for the synthesis of [1,2-a] azepinoindoles C. In describing this reactivity we additionally reported experimental evidences for an unprecedented NHCAu(I)-vinyl specie which in a chemoselective fashion, led to the annulation step, synthesizing the N1-C2-connected seven membered ring. The chemical flexibility of propargylic alcohols was further explored by changing the nature of the chemical surrounding with different preinstalled N-alkyl moiety in propargylic alcohols of type 3. Particularly, in the case of a primary alcohol, [Au(I)] catalysis was found to be prominent in the synthesis of a new class of [4,3-a]-oxazinoindoles D while the use of an allylic alcohol led to the first example of [Au(I)] catalyzed synthesis and enantioselective functionalization of this class of molecules (D*). With this work we established propargylic alcohols as excellent acyclic precursor to developed new [Au(I)]-catalyzed cascade reaction and providing new catalytic synthetic tools for the stereoselective synthesis of complex indole/indoline architectures.

Self-Assembled Monolayers (SAMs) in Organic Field-Effect Transistors

Organic printed electronics is attracting an ever-growing interest in the last decades because of its impressive breakthroughs concerning the chemical design of π-conjugated materials and their processing. This has an impact on novel applications, such as flexible-large-area displays, low- cost printable circuits, plastic solar cells and lab-on-a-chip devices. The organic field-effect transistor (OFET) relies on a thin film of organic semiconductor that bridges source and drain electrodes. Since its first discovery in the 80s, intensive research activities were deployed in order to control the chemico-physical properties of these electronic devices and consequently their charge. Self-assembled monolayers (SAMs) are a versatile tool for tuning the properties of metallic, semi-conducting, and insulating surfaces. Within this context, OFETs represent reliable instruments for measuring the electrical properties of the SAMs in a Metal/SAM/OS junction. Our experimental approach, named Charge Injection Organic-Gauge (CIOG), uses OTFT in a charge-injection controlled regime. The CIOG sensitivity has been extensively demonstrated on different homologous self-assembling molecules that differ in either chain length or in anchor/terminal group. One of the latest applications of organic electronics is the so-called “bio-electronics” that makes use of electronic devices to encompass interests of the medical science, such as biosensors, biotransducers etc… As a result, thee second part of this thesis deals with the realization of an electronic transducer based on an Organic Field-Effect Transistor operating in aqueous media. Here, the conventional bottom gate/bottom contact configuration is replaced by top gate architecture with the electrolyte that ensures electrical contact between the top gold electrode and the semiconductor layer. This configuration is named Electrolyte-Gated Field-Effect Transistor (EGOFET). The functionalization of the top electrode is the sensing core of the device allowing the detection of dopamine as well as of protein biomarkers with ultra-low sensitivity.

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.

Electrospun Polymeric Scaffolds with Enhanced Biomimetic Properties for Tissue Engineering Applications

This PhD Thesis is focused on the development of fibrous polymeric scaffolds for tissue engineering applications and on the improvement of scaffold biomimetic properties. Scaffolds were fabricated by electrospinning, which allows to obtain scaffolds made of polymeric micro or nanofibers. Biomimetism was enhanced by following two approaches: (1) the use of natural biopolymers, and (2) the modification of the fibers surface chemistry. Gelatin was chosen for its bioactive properties and cellular affinity, however it lacks in mechanical properties. This problem was overcome by adding poly(lactic acid) to the scaffold through co-electrospinning and mechanical properties of the composite constructs were assessed. Gelatin effectively improves cell growth and viability and worth noting, composite scaffolds of gelatin and poly(lactic acid) were more effective than a plain gelatin scaffold. Scaffolds made of pure collagen fibers were fabricated. Modification of collagen triple helix structure in electrospun collagen fibers was studied. Mechanical properties were evaluated before and after crosslinking. The crosslinking procedure was developed and optimized by using - for the first time on electrospun collagen fibers - the crosslinking reactant 1,4-butanediol diglycidyl ether, with good results in terms of fibers stabilization. Cell culture experiments showed good results in term of cell adhesion and morphology. The fiber surface chemistry of electrospun poly(lactic acid) scaffold was modified by plasma treatment. Plasma did not affect thermal and mechanical properties of the scaffold, while it greatly increased its hydrophilicity by the introduction of carboxyl groups at the fiber surface. This fiber functionalization enhanced the fibroblast cell viability and spreading. Surface modifications by chemical reactions were conducted on electrospun scaffolds made of a polysophorolipid. The aim was to introduce a biomolecule at the fiber surface. By developing a series of chemical reactions, one oligopeptide every three repeating units of polysophorolipid was grafted at the surface of electrospun fibers.

Electrochemical surface modification of Single walled carbon nanotubes and graphene-based electrodes for (bio)sensing applications

Sensors are devices that have shown widespread use, from the detection of gas molecules to the tracking of chemical signals in biological cells. Single walled carbon nanotube (SWCNT) and graphene based electrodes have demonstrated to be an excellent material for the development of electrochemical biosensors as they display remarkable electronic properties and the ability to act as individual nanoelectrodes, display an excellent low-dimensional charge carrier transport, and promote surface electrocatalysis. The present work aims at the preparation and investigation of electrochemically modified SWCNT and graphene-based electrodes for applications in the field of biosensors. We initially studied SWCNT films and focused on their topography and surface composition, electrical and optical properties. Parallel to SWCNTs, graphene films were investigated. Higher resistance values were obtained in comparison with nanotubes films. The electrochemical surface modification of both electrodes was investigated following two routes (i) the electrografting of aryl diazonium salts, and (ii) the electrophylic addition of 1, 3-benzodithiolylium tetrafluoroborate (BDYT). Both the qualitative and quantitative characteristics of the modified electrode surfaces were studied such as the degree of functionalization and their surface composition. The combination of Raman, X-ray photoelectron spectroscopy, atomic force microscopy, electrochemistry and other techniques, has demonstrated that selected precursors could be covalently anchored to the nanotubes and graphene-based electrode surfaces through novel carbon-carbon formation.

Silk Fibroin: a biopolymer platform for innovative pharmaceutical formulation and biomedical devices.

The protein silk fibroin (SF) from the silkworm Bombyx mori is a FDA-approved biomaterial used over centuries as sutures wire. Importantly, several evidences highlighted the potential of silk biomaterials obtained by using so-called regenerated silk fibroin (RSF) in biomedicine, tissue engineering and drug delivery. Indeed, by a water-based protocol, it is possible to obtain protein water-solution, by extraction and purification of fibroin from silk fibres. Notably, RSF can be processed in a variety of biomaterials forms used in biomedical and technological fields, displaying remarkable properties such as biocompatibility, controllable biodegradability, optical transparency, mechanical robustness. Moreover, RSF biomaterials can be doped and/or chemical functionalized with drugs, optically active molecules, growth factors and/or chemicals In this view, activities of my PhD research program were focused to standardize the process of extraction and purification of protein to get the best physical and chemical characteristics. The analysis of the chemo-physical properties of the fibroin involved both the RSF water-solution and the protein processed in film. Chemo-physical properties have been studied through: vibrational (FT-IR and Raman-FT) and optical (absorption and emission UV-VIS) spectroscopy, nuclear magnetic resonance (1H and 13C NMR), thermal analysis and thermo-gravimetric scan (DSC and TGA). In the last year of my PhD, activities were focused to study and define innovative methods of functionalization of the silk fibroin solution and films. Indeed, research program was the application of different methods of manufacturing approaches of the films of fibroin without the use of harsh treatments and organic solvents. New approaches to doping and chemical functionalization of the silk fibroin were studied. Two different methods have been identified: 1) biodoping that consists in the doping of fibroin with optically active molecules through the addition of fluorescent molecules in the standard diet used for the breeding of silkworms; 2) chemical functionalization via silylation.

Tailoring properties and functionalities of TiO2 and Ag nanoparticles involved in surfaces engineering processes

The functionalization of substrates through the application of nanostructured coatings allows to create new materials, with enhanced properties. In this work, the development of self-cleaning and antibacterial textiles, through the application of TiO2 and Ag based nanostructured coatings was carried out. The production of TiO2 and Ag functionalized materials was achieved both by the classical dip-padding-curing method and by the innovative electrospinning process to obtain nanofibers doped with nano-TiO2 and nano-Ag. In order to optimize the production of functionalized textiles, the study focused on the comprehension of mechanisms involved in the photocatalytic and antibacterial processes and on the real applicability of the products. In particular, a deep investigation on the relationship between nanosol physicochemical characteristics, nanocoating properties and their performances was accomplished. Self-cleaning textiles with optimized properties were obtained by properly purifying and applying commercial TiO2 nanosol while the studies on the photocatalytic mechanism operating in self-cleaning application demonstrated the strong influence of hydrophilic properties and of interaction surface/radicals on final performance. Moreover, a study about the safety in handling of nano-TiO2 was carried out and risk remediation strategies, based on “safety by design” approach, were developed. In particular, the coating of TiO2 nanoparticles by a SiO2 shell was demonstrated to be the best risk remediation strategy in term of biological response and preserving of photoreactivity. The obtained results were confirmed determining the reactive oxygen species production by a multiple approach. Antibacterial textiles for biotechnological applications were also studied and Ag-coated cotton materials, with significant anti-bacterial properties, were produced. Finally, composite nanofibers were obtained merging biopolymer processing and sol-gel techniques. Indeed, electrospun nanofibers embedded with TiO2 and Ag NPs, starting from aqueous keratin based formulation were produced and the photocatalytic and antibacterial properties were assessed. The results confirmed the capability of electrospun keratin nanofibers matrix to preserve nanoparticle properties.

Contribution of Non-Covalent Interactions and Electronic Effects on the Conformational Landscape and Tautomeric Equilibria of Molecules and Molecular Complexes: Structural and Dynamical Data from Rotational Spectroscopy

This thesis concerns the study of complex conformational surfaces and tautomeric equilibria of molecules and molecular complexes by quantum chemical methods and rotational spectroscopy techniques. In particular, the focus of this research is on the effects of substitution and noncovalent interactions in determining the energies and geometries of different conformers, tautomers or molecular complexes. The Free-Jet Absorption Millimeter Wave spectroscopy and the Pulsed-Jet Fourier Transform Microwave spectroscopy have been applied to perform these studies and the obtained results showcase the suitability of these techniques for the study of conformational surfaces and intermolecular interactions. The series of investigations of selected medium-size molecules and complexes have shown how different instrumental setups can be used to obtain a variety of results on molecular properties. The systems studied, include molecules of biological interest such as anethole and molecules of astrophysical interest such as N-methylaminoethanol. Moreover halogenation effects have been investigated on halogen substituted tautomeric systems (5-chlorohydroxypyridine and 6-chlorohydroxypyridine), where it has shown that the position of the inserted halogen atom affects the prototropic equilibrium. As for fluorination effects, interesting results have been achieved investigating some small complexes where a molecule of water is used as a probe to reveal the changes on the electrostatic potential of different fluorinated compounds: 2-fluoropyridine, 3-fluoropyridine and penta-fluoropyridine. While in the case of the molecular complex between water and 2-fluoropyridine and 3-fluoropyridine the geometry of the complex with one water molecule is analogous to that of pyridine with the water molecule linked to the pyridine nitrogen, the case of pentafluoropyridine reveals the effect of perfluorination and the water oxygen points towards the positive center of the pyridine ring. Additional molecular adducts with a molecule of water have been analyzed (benzylamine-water and acrylic acid-water) in order to reveal the stabilizing driving forces that characterize these complexes.

Photoactive nanodevices for potential biological applications

Biological systems are complex and highly organized architectures governed by noncovalent interactions, which are responsible for molecular recognition, self-assembly, self-organization, adaptation and evolution processes. These systems provided the inspiration for the development of supramolecular chemistry, that aimed at the design of artificial multicomponent molecular assemblies, namely supramolecular systems, properly designed to perform different operations: each constituting unit performs a single act, whereas the entire supramolecular system is able to execute a more complex function, resulting from the cooperation of the constituting components. Supramolecular chemistry deals with the development of molecular systems able to mimic naturally occurring events, for example complexation and self-assembly through the establishment of noncovalent interactions. Moreover, the application of external stimuli, such as light, allows to perform these operations in a time- and space-controlled manner. These systems can interact with biological systems and, thus, can be applied for bioimaging, therapeutic and drug delivery purposes. In this work the study of biocompatible supramolecular species able to interact with light is presented. The first part deals with the photophysical, photochemical and electrochemical characterization of water-soluble blue emitting triazoloquinolinium and triazolopyridinium salts. Moreover, their interaction with DNA has been explored, in the perspective of developing water-soluble systems for bioimaging applications. In the second part, the effect exerted by the presence of azobenzene-bearing supramolecular species in liposomes, inserted both in the phospholipid bilayer and in the in the aqueous core of vesicles has been studied, in order to develop systems able to deliver small molecules and ions in a photocontrolled manner. Moreover, the versatility of azobenzene and its broad range of applications have been highlighted, since conjugated oligoazobenzene derivatives proved not to be adequate to be inserted in the phospholipid bilayer of liposomes, but their electrochemical properties made them interesting candidates as electron acceptor materials for photovoltaic applications.

Modelling, diagnostics and experimental analysis of plasma assisted processes for material treatment

This work presents results from experimental investigations of several different atmospheric pressure plasmas applications, such as Metal Inert Gas (MIG) welding and Plasma Arc Cutting (PAC) and Welding (PAW) sources, as well as Inductively Coupled Plasma (ICP) torches. The main diagnostic tool that has been used is High Speed Imaging (HSI), often assisted by Schlieren imaging to analyse non-visible phenomena. Furthermore, starting from thermo-fluid-dynamic models developed by the University of Bologna group, such plasma processes have been studied also with new advanced models, focusing for instance on the interaction between a melting metal wire and a plasma, or considering non-equilibrium phenomena for diagnostics of plasma arcs. Additionally, the experimental diagnostic tools that have been developed for industrial thermal plasmas have been used also for the characterization of innovative low temperature atmospheric pressure non equilibrium plasmas, such as dielectric barrier discharges (DBD) and Plasma Jets. These sources are controlled by few kV voltage pulses with pulse rise time of few nanoseconds to avoid the formation of a plasma arc, with interesting applications in surface functionalization of thermosensitive materials. In order to investigate also bio-medical applications of thermal plasma, a self-developed quenching device has been connected to an ICP torch. Such device has allowed inactivation of several kinds of bacteria spread on petri dishes, by keeping the substrate temperature lower than 40 degrees, which is a strict requirement in order to allow the treatment of living tissues.

To Evaluate the Synergistic Effect of Different Crosslinking Strategies on Collagen Derivatives to Develop Funcional Biomimetic Scaffolds

The preliminary objective of this work was to study how the effect of different crosslinking methodologies can functionally modify various characteristics of biological macromolecules relevant for scaffold development in bone tissue engineering. The research study was classified and studied in three different phases: (i) different crosslinking strategies in gelatin functionalization, (ii) ribose mediated crosslinking in collagen-hydroxyapatite scaffold (iii) different crosslinking mechanisms in functional modification of bone-like scaffold. The obtained results were highly positive in all the three investigated studies. Though the core aim of this research was to explore the available crosslinking strategies in different biological macromolecules, the present study generated significant findings, largely contributing to provide optimum solutions in understanding how the crosslinking density can fine-tune the overall performance of a scaffold, relevant for its functioning in vivo. In particular, this study demonstrated that different crosslinkers at different conditions (pH and temperature) can modify the functional properties of the scaffolds differently, therefore this optimization strategies on these crosslinkers as obtained from this study results will help material scientists in the design and development of bioactive hybrid biomaterials for hard tissue regeneration.

Design and characterization of Electrochemical Sensors for Organic Bioelectronics

This Ph.D. Thesis concerns the design and characterisation of functional electrochemical interfaces in organic electronic devices for bioelectronic applications. The Thesis is structured as follows: Chapter I – Technological context that has inspired the research, introduction to Organic Bioelectronics and literature review concerning Organic Electrochemical Transistors (OECTs) for sensing applications. Chapter II – Working principle of an all-polymeric OECT and operando microscopic characterization using scanning electrochemical techniques. Chapter III – Dopamine detection with all-polymeric OECT sensors. Development of a potentiodynamic approach to address selectivity issues in the presence of interfering species and design of a needle-type, sub-micrometric OECT sensor for spatially resolved detection of biological Dopamine concentrations. Chapter IV – Development of an OECT pH sensor. Characterization of the electrochemical transducer and functionalization of the OECT gate electrode with the sensing material. Potentiodynamic and potentiostatic operation modalities are explored and the sensing performances are assessed in both cases. The final device is realized on a flexible substrate and tested in Artificial Sweat. Chapter V – Study of two-terminal, electrochemically gated sensors inspired by the OECT configuration. Design and characterization of novel functional materials showing a potentiometric transduction of the chemical signal that can be exploited in the realization of electrochemical sensors with simplified geometry for wearable applications. Chapter VI – Conclusion.

Non-ambient solid-state characterization of crystalline molecular organic semiconductors

The research project is focused on the investigation of the polymorphism of crystalline molecular material for organic semiconductor applications under non-ambient conditions, and the solid-state characterization and crystal structure determination of the different polymorphic forms. In particular, this research project has tackled the investigation and characterization of the polymorphism of perylene diimides (PDIs) derivatives at high temperatures and pressures, in particular N,N’-dialkyl-3,4,9,10-perylendiimide (PDI-Cn, with n = 5, 6, 7, 8). These molecules are characterized by excellent chemical, thermal, and photostability, high electron affinity, strong absorption in the visible region, low LUMO energies, good air stability, and good charge transport properties, which can be tuned via functionalization; these features make them promising n-type organic semiconductor materials for several applications such as OFETs, OPV cells, laser dye, sensors, bioimaging, etc. The thermal characterization of PDI-Cn was carried out by a combination of differential scanning calorimetry, variable temperature X-ray diffraction, hot-stage microscopy, and in the case of PDI-C5 also variable temperature Raman spectroscopy. Whereas crystal structure determination was carried out by both Single Crystal and Powder X-ray diffraction. Moreover, high-pressure polymorphism via pressure-dependent UV-Vis absorption spectroscopy and high-pressure Single Crystal X-ray diffraction was carried out in this project. A data-driven approach based on a combination of self-organizing maps (SOM) and principal component analysis (PCA) is also reported was used to classify different π-stacking arrangements of PDI derivatives into families of similar crystal packing. Besides the main project, in the framework of structure-property analysis under non-ambient conditions, the structural investigation of the water loss in Pt- and Pd- based vapochromic potassium/lithium salts upon temperature, and the investigation of structure-mechanical property relationships in polymorphs of a thienopyrrolyldione endcapped oligothiophene (C4-NT3N) are reported.