Preparation of new crystal forms via photochemical, mechanochemical and sol-gel methods

This work of thesis involves various aspects of crystal engineering. Chapter 1 focuses on crystals containing crown ether complexes. Aspects such as the possibility of preparing these materials by non-solution methods, i.e. by direct reaction of the solid components, thermal behavior and also isomorphism and interconversion between hydrates are taken into account. In chapter 2 a study is presented aimed to understanding the relationship between hydrogen bonding capability and shape of the building blocks chosen to construct crystals. The focus is on the control exerted by shape on the organization of sandwich cations such as cobalticinium, decamethylcobalticinium and bisbenzenchromium(I) and on the aggregation of monoanions all containing carboxylic and carboxylate groups, into 0-D, 1-D, 2-D and 3-D networks. Reactions conducted in multi-component molecular assemblies or co-crystals have been recognized as a way to control reactivity in the solid state. The [2+2] photodimerization of olefins is a successful demonstration of how templated solid state synthesis can efficiently synthesize unique materials with remarkable stereoselectivity and under environment-friendly conditions. A demonstration of this synthetic strategy is given in chapter 3. The combination of various types of intermolecular linkages, leading to formation of high order aggregation and crystalline materials or to a random aggregation resulting in an amorphous precipitate, may not go to completeness. In such rare cases an aggregation process intermediate between crystalline and amorphous materials is observed, resulting in the formation of a gel, i.e. a viscoelastic solid-like or liquid-like material. In chapter 4 design of new Low Molecular Weight Gelators is presented. Aspects such as the relationships between molecular structure, crystal packing and gelation properties and the application of this kind of gels as a medium for crystal growth of organic molecules, such as APIs, are also discussed.

Il teatro di Sarah Kane fra biografia, performance e scrittura

Il presente studio si propone come una rilettura del profilo drammaturgico e teatrale di Sarah Kane a partire dalla ricostruzione e integrazione dei dati biografici e delle interazioni artistiche e personali dell’autrice. Lo studio si articola in due sezioni: in un primo momento esso inquadra contestualmente la drammaturgia inglese del secondo dopoguerra, origine della prima generazione dei Giovani Arrabbiati e sostrato della trasformazione teatrale britannica degli anni Novanta. La seconda sezione, invece, si articola come un’indagine biografica della vita della Kane scandita da documenti e immagini inediti. Tali immagini restituiscono una preziosa testimonianza dei primi spettacoli giovanili, delle prime regie e del percorso professionale maturo della drammaturga/regista, oltre a far luce sulla sua vita personale e famigliare e sugli influssi della stessa sul suo teatro. Inoltre, lo studio approfondito delle vicende biografiche dell’autrice ridisegna le caratteristiche fondanti dell'universo teatrale britannico comprendendo il valore che hanno: i teatri, la critica giornalistica e le strutture universitarie, per la configurazione del sistema teatrale.

El país de Juan di María Teresa Andruetto: un “crinale inesplorato” tra sfide e conquiste

Il presente elaborato si propone di analizzare il racconto dalla scrittrice argentina María Teresa Andruetto (Premio Hans Christian Andersen 2012) El país de Juan, nell’edizione pubblicata dalla casa editrice spagnola Anaya nel 2003. Nel 2014 ne è stata proposta la traduzione in italiano con il titolo Il paese di Juan, ad opera di Ilide Carmignani. La storia, che narra di due bambini costretti a migrare dalla campagna alle favelas argentine (Villas), si presenta come una vera e propria sfida traduttiva per il contrasto tra la poeticità del linguaggio e il realismo del mondo raccontato ed il forte legame con il contesto locale in cui è inserita. Lo studio consta di tre capitoli principali: nel primo si approfondiscono la vita, le opere, lo stile e la concezione della letteratura della Andruetto. Dopo aver impostato tale cornice stilistica e contestuale, si prosegue, nel secondo capitolo, con l’analisi del testo originale, dove vengono messi in luce gli aspetti formali e stilistici della scrittura, le tematiche, gli elementi grafici, le illustrazioni e il contesto storico-sociale. Si passa poi, nel terzo ed ultimo capitolo, ad un’analisi della traduzione italiana del libro rispetto alla capacità di ricreare un tipo di linguaggio altamente innovativo, la salvaguardia delle figure retoriche, degli aspetti grafici e dei riferimenti culturali, elementi di fondamentale importanza per creare una traduzione in grado di aprire gli orizzonti del giovane lettore. Inoltre, si confrontano i glossari della versioni spagnola e italiana evidenziandone differenze e affinità. Si pone infine l’accento sull’indiscutibile abilità della Carmignani nel saper mantenere la dicotomia testuale tra realismo e mistero, riferendosi anche all’importanza della collaborazione tra lo scrittore e il traduttore, legame che senza dubbio è possibile cogliere nella traduzione Il paese di Juan.

Coatings ibridi organici-inorganici ottenuti mediante processo sol-gel e contenenti assorbitori di radiazioni uv

In questo progetto di tesi si è cercato il modo di rendere più efficace la resistenza dei materiali plastici alla fotodegradazione indotta dai raggi ultravioletti, attraverso l’utilizzo di coatings ibridi organici-inorganici preparati utilizzando il processo sol-gel. Tali rivestimenti in grado di migliorare la resistenza superficiale potrebbero essere applicati a diversi materiali ed in particolare ai policarbonati che per le loro eccellenti proprietà di trasparenza vengono molto utilizzati in illuminotecnica ed altre applicazioni per l’esterno. In particolare il lavoro ha riguardato lo studio e l’utilizzo di due assorbitori UV di tipo fenolico, il 2,2’-diidrossi-4-metossibenzofenone e il 2,2’,4,4’-tetraidrossibenzofenone. Si è provato a non collocare semplicemente tali assorbitori all’interno del coating sol-gel ma a legarli covalentemente al network tridimensionale di silani auspicando una migliore resistenza alla fotodegradazione UV-indotta. Il nostro interesse si è concentrato soprattutto sul 2,2’,4,4’-tetraidrossibenzofenone, in quanto abbiamo visto che una sua funzionalizzazione rispetto all’altro assorbitore UV risulta più semplice ed efficace.

Contribution à l’étude de l’influence des caractères physico-chimiques du sol sur la stabilité structurale ; cas de la plaine de Sidi Bel Abbes

The aim of the study is to contribute to the knowledge and the identification of the main physical and chemical characteristics of the soil that affect the structural stability of soil types forming the soil cover of the plain of Sidi Bel Abbes region for agricultural use by excellence. Structural stability is an indicator of the cohesion of soil aggregates. This is a parameter that expresses the ability of soil aggregates to resist degradation in general the impact of rain or excess water. Measuring the structural stability makes it possible to evaluate the sensitivity a soil crusting and erosion. The results showed that soils subject of our study are stable and very stable with a slight difference. We have a statistical study made it possible to establish a correlation between the structural stability and other physical and chemical soil parameters measured )fersiallitic red soil and brown calcareous soil( such as organic matter content, the rate of total limestone and soil texture, to better explain the stability or instability of the soil structure and to establish a relationship between these parameters and the structural stability. // Keywords: Sidi Bel Abbes, chemical characteristics, physical, structural stability, soil, plain, fersiallitic red soil, brown calcareous soil

Osteoblast responses to different oxide coatings produced by the sol-gel process on titanium substrates

In order to improve the osseointegration of endosseous implants made from titanium, the structure and composition of the surface were modified. Mirror-polished commercially pure (cp) titanium substrates were coated by the sol-gel process with different oxides: TiO(2), SiO(2), Nb(2)O(5) and SiO(2)-TiO(2). The coatings were physically and biologically characterized. Infrared spectroscopy confirmed the absence of organic residues. Ellipsometry determined the thickness of layers to be approximately 100nm. High resolution scanning electron microscopy (SEM) and atomice force microscopy revealed a nanoporous structure in the TiO(2) and Nb(2)O(5) layers, whereas the SiO(2) and SiO(2)-TiO(2) layers appeared almost smooth. The R(a) values, as determined by white-light interferometry, ranged from 20 to 50nm. The surface energy determined by the sessile-drop contact angle method revealed the highest polar component for SiO(2) (30.7mJm(-2)) and the lowest for cp-Ti and 316L stainless steel (6.7mJm(-2)). Cytocompatibility of the oxide layers was investigated with MC3T3-E1 osteoblasts in vitro (proliferation, vitality, morphology and cytochemical/immunolabelling of actin and vinculin). Higher cell proliferation rates were found in SiO(2)-TiO(2) and TiO(2), and lower in Nb(2)O(5) and SiO(2); whereas the vitality rates increased for cp-Ti and Nb(2)O(5). Cytochemical assays showed that all substrates induced a normal cytoskeleton and well-developed focal adhesion contacts. SEM revealed good cell attachment for all coating layers. In conclusion, the sol-gel-derived oxide layers were thin, pure and nanostructured; consequent different osteoblast responses to those coatings are explained by the mutual action and coadjustment of different interrelated surface parameters.

Synthesis of PDMS-metal oxide hybrid nanocomposites using an in situ sol-gel route

Organic-inorganic hybrid nanocomposites are widely studied and applied in broad areas because of their ability to combine the flexibility, low density of the organic materials with the hardness, strength, thermal stability, good optical and electronic properties of the inorganic materials. Polydimethylsiloxane (PDMS) due to its excellent elasticity, transparency, and biocompatibility has been extensively employed as the organic host matrix for nanocomposites. For the inorganic component, titanium dioxide and barium titanate are broadly explored as they possess outstanding physical, optical and electronic properties. In our experiment, PDMS-TiO2 and PDMS-BaTiO3 hybrid nanocomposites were fabricated based on in-situ sol-gel technique. By changing the amount of metal precursors, transparent and homogeneous PDMS-TiO2 and PDMS-BaTiO3 hybrid films with various compositions were obtained. Two structural models of these two types of hybrids were stated and verified by the results of characterization. The structures of the hybrid films were examined by a conjunction of FTIR and FTRaman. The morphologies of the cross-sectional areas of the films were characterized by FESEM. An Ellipsometer and an automatic capacitance meter were utilized to evaluate the refractive index and dielectric constant of these composites respectively. A simultaneous DSC/TGA instrument was applied to measure the thermal properties. For PDMS-TiO2 hybrids, the higher the ratio of titanium precursor added, the higher the refractive index and the dielectric constant of the composites are. The highest values achieved of refractive index and dielectric constant were 1.74 and 15.5 respectively for sample PDMS-TiO2 (1-6). However, when the ratio of titanium precursor to PDMS was as high as 20 to 1, phase separation occurred as evidenced by SEM images, refractive index and dielectric constant decreased. For PDMS-BaTiO3 hybrids, with the increase of barium and titanium precursors in the system, the refractive index and dielectric constant of the composites increased. The highest value was attained in sample PDMS-BaTiO3 (1-6) with a refractive index of 1.6 and a dielectric constant of 12.2. However, phase separation appeared in SEM images for sample PDMS-BaTiO3 (1-8), the refractive index and dielectric constant reduced to lower values. Different compositions of PDMS-TiO2 and PDMS-BaTiO3 hybrid films were annealed at 60 °C and 100 °C, the influences on the refractive index, dielectric constant, and thermal properties were investigated.

Development of Vapor Deposited Silica Sol-Gel Particles for a Bioactive Materials System to Direct Osteoblast Behavior

Tissue engineering and regenerative medicine have emerged in an effort to generate replacement tissues capable of restoring native tissue structure and function, but because of the complexity of biologic system, this has proven to be much harder than originally anticipated. Silica based bioactive glasses are popular as biomaterials because of their ability to enhance osteogenesis and angiogenesis. Sol-gel processing methods are popular in generating these materials because it offers: 1) mild processing conditions; 2) easily controlled structure and composition; 3) the ability to incorporate biological molecules; and 4) inherent biocompatibility. The goal of this work was to develop a bioactive vaporization system for the deposition of silica sol-gel particles as a means to modify the material properties of a substrate at the nano- and micro- level to better mimic the instructive conditions of native bone tissue, promoting appropriate osteoblast attachment, proliferation, and differentiation as a means for supporting bone tissue regeneration. The size distribution, morphology and degradation behavior of the vapor deposited sol-gel particles developed here were found to be dependent upon formulation (H2O:TMOS, pH, Ca/P incorporation) and manufacturing (substrate surface character, deposition time). Additionally, deposition of these particles onto substrates can be used to modify overall substrate properties including hydrophobicity, roughness, and topography. Deposition of Ca/P sol particles induced apatite-like mineral formation on both two- and three-dimensional materials when exposed to body fluids. Gene expression analysis suggests that Ca/P sol particles induce upregulation osteoblast gene expression (Runx2, OPN, OCN) in preosteoblasts during early culture time points. Upon further modification-specifically increasing particle stability-these Ca/P sol particles possess the potential to serve as a simple and unique means to modify biomaterial surface properties as a means to direct osteoblast differentiation.