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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
31

Atom Transfer Radical Polymerization of Polar Monomers and Synthesis of Block Copolymers for Industrial and Biomedical Applications

Mazzotti, Giovanni <1988> January 1900 (has links)
The aim of this thesis is to push forward the synthesis of well-defined materials containing polar monomers. The ATRP of polar monomers was investigated with the aim to obtain living and well-defined materials. Block copolymers with pre-determinable composition and unimodal distribution of molecular weight were synthesized. Furthermore, the Atom Transfer Radical Co-Polymerization of NVCL and NVP with non-polar monomers was investigated with the aim to obtain amphiphilic material with tunable polarity. The ATRP of vinyl acetate (VAc), which was poorly optimized, was studied trying to obtain poly(VAc) with low polydispersity (<1.25), pre-determinable molecular weight and living character. The optimization of the ATRP of VAc and the synthesis of several block copolymers, synthesized in presence of different experimental conditions, can significantly expand the field of materials and applications of poly(VAc) and poly(vinyl alcohol)-based products. Moreover, the synthesis of pH and temperature polymers was investigated with the aim to obtain products suitable for the development of drug-delivery systems which can be applied in anti-cancer applications. For this purpose Pluronic F127, which is thermosensitive, and poly(ethylene glycol)s were modified with pH poly[2-(N,N-dimethylamino)ethyl methacrylate] (PDMAEMA), poly[2-(N,N-diethylamino)ethyl methacrylate] (PDEAEMA) and poly[2-(N,N-diisopropylamino)ethyl methacrylate] (PDIAEMA). The methacrylic moieties have different pKa, and they give to the synthesized materials the desired pH responsiveness. The gelation behavior of the obtained products was investigated by rheological measurements; the dimension of the polymeric aggregates in water solutions at different pH was studied by DLS and the drug-incorporation as a function of pH was determined in systems with stable pH and in systems in which the pH was decreased progressively. All the cited investigation allowed to well-characterized the behavior and the structure of polymeric aggregates in water solution and they also allowed to determine their pH and temperature responsiveness.
32

Design and Synthesis of New Luminescent Materials: from Light Sources to Biological Applications

Matteucci, Elia <1988> January 1900 (has links)
The synthesis of luminescent metal complexes is a very challenging task since they can be regarded as the starting point for many different areas. Luminescent complexes, in fact, can be used for technological, industrial, medical and biological applications. They consist of two main parts: the central core of the complex, a metal atom, and various organic ligands bonded to it. Among all the transition metal complexes, Iridium(III) ones show the best photophysical properties: generally, they have high quantum yields, very long lifetimes and possess easily tunable emissions throughout the visible range. During my PhD I prepared different families of Ir(III) complexes suitable for various applications. In detail, my thesis deals with the synthesis of new functionalized chelating ligands that have been used to obtain phosphorescent Ir(III) complexes. In particular I synthesised isocyanides, phenyltetrazole and pyridiltriazolylidene derivatives and various corresponding Ir(III) complexes with peculiar photophysical properties, suitable for the preparation of electroluminescent devices. Moreover, I synthesized pyridiltriazole chelating ligands for the preparation of Ir(III) complexes able to be embebbed in nanoparticles. At the same time, I set up the synthesis of various carbazole-terpyridines systems containing substituent of different length and aromatic character. During my studies, I enhanced my knowledges about the techniques for the spectroscopical characterization of the obtained compounds, such as mono- and bidimensional and VT- NMR, UV-vis and spectrofluorimetry.
33

Sustainable Catalytic Processes for the Valorisation of Light Alcohols

Malmusi, Andrea <1988> January 1900 (has links)
During my PhD I carried out three main research works, which are described in this thesis. The topics of my research were dealt with the development of more sustainable processes through the exploitation of renewable sources and the replacement of hazardous chemicals with safer ones. Two of the three research topics I carried out dealt with ethanol as a renewable source for the development of more sustainable processes. Another research topic concerned isobutene alkylation with methanol, as a substitute for formaldehyde. First research project was regarding ethanol transformation over V-based catalysts. Fe/V and Cu/V mixed oxides were tested as catalysts for the transformation of ethanol both in aerobic and anaerobic conditions. Both catalysts were active in ethanol dehydrogenation to acetaldehyde. Anyway the presence of Fe or Cu had an influence on catalytic performance. The reason of these different behaviours were investigated by means of characterization techniques. Another research work, regarding ethanol as raw material, was carried out during my stage at the Lieibniz Institute für Katalyse (Germany), under the supervision of Dr. Habil. Evgenii Kondratenko. The research topic dealt with ethanol conversion to H2 and CO2 by means of partial oxidation carried out over supported Pt, Rh and Ru nanoparticles. The greater part of the research work dealt with isobutene alkylation with methanol, in place of formaldehyde, for the production of isoprene via the Prins reaction. The reaction was carried out over different metal phosphates. Main products were isoprene, 2-methylbutenes and dimethyl ether. An investigation on the reaction scheme showed that these products are kinetically primary compounds. Data and investigations shown in this thesis probably will not lead soon to the development of new chemical processes, but they enrich that scientific background that is the pool from which it is possible to design a more sustainable industrial chemistry.
34

Sustainable Catalytic Process for the Synthesis of Niacin

Mari, Massimiliano <1988> January 1900 (has links)
Nicotinic acid (niacin) is an important vitamin of the B group, with an annual production close to 40,000 tons. It is used in medicine, food industry, agriculture and in production of cosmetics. Older industrial processes have drawbacks such as a low atomic efficiency and the use of toxic catalysts or stoichiometric oxidants. Several studies were carried out during latest years on new technologies for the synthesis of niacin and nicotinate precursors, such as 3-picoline and pyridine-3-nitrile. This thesis reports about the results of three different research projects; the first was aimed at the study of the one-step production of pyridine-3-nitrile starting from 2-methylglutaronitrile, the second at acetaldehyde/acetonitrile condensation for 3-picoline synthesis, and the third at investigating the reactivity of supported vanadium oxide catalysts for the direct gas-phase oxidation of 3-picoline with air; this process would be more sustainable compared to both older ones and some of those currently used for niacin production. For the first two research projects, a catalysts screening was carried out; however, results were not satisfactory. The third project involved the preparation, characterisation and reactivity testing of different zirconia-supported V2O5 catalysts. The effect of parameters, such as the Vanadium oxide loading and specific surface area, on catalytic performance were studied. Operative conditions such as temperature, contact time and feed composition were optimized. Yields to nicotinic acid close to the best ones reported in the literature were achieved; moreover, catalysts based on V2O5/ZrO2 were found to be remarkably active. Catalysts were characterized by means of XRD and in-situ Raman spectroscopy in the aim of finding correlations between catalytic performances and physic-chemical properties. In some cases, ZrV2O7 formed during the reaction. Vanadyl-pyrophosphate was also tested as the catalyst for 3-picoline oxidation, but its performance was lower compared to that one shown by V2O5/ZrO2.
35

Production and Characterization of New 2D Materials for Technological Applications in Composites and Surface Coatings

Kouroupis-agalou, Konstantinos <1985> January 1900 (has links)
In this dissertation, we firstly developed a new method to evaluate the exfoliation results of Graphene and other 2D materials (Graphene Oxide, Boron Nitride).This was essential to understand the fundamental processes behind the production of 2D materials. Additionally, that helped us to understand the production development of 2D-based composite materials and bio- compatible materials, such as gelatin fibers. We evaluated the processed 2D nanomaterials with commonly used characterization techniques used in the scientific and industrial world, which are the Atomic Force Microscope. Furthermore, we developed this method by using Fluorescence Optical Microscopy (FOM), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Based on AFM analysis of thousands samples, the exfoliation of 2D nanomaterials, like the distributions recognized in the fields of biology, astronomy and mineralogy. We demonstrated a new way to produce stable graphene solutions in low boiling point solvents and how the exfoliated material can interpret into polymer surface such as Polyvinylchloride (PVC) and natural rubber. Overall, the uniqueness of this work is that we developed a new method that has not been studied before and gives the opportunity to materials scientists that are researching on the growing field of Graphene and other 2D materials to have a method in order to control, quantify and evaluate the exfoliation results of nanomaterials that are produced through the most well-known methods of liquid phase exfoliation and ball milling, both of which are applied in scientific and industrial level. Thus, the results presented in this work may offer insight into the polymer composites where the size and shape of nanosheets can be rationally optimized.
36

Conformational equilibria, non-bonding interactions and chirality from rotational spectroscopy

Spada, Lorenzo <1983> January 1900 (has links)
The aim of this thesis is to characterize the genuine nature of the non-bonding interactions, such as hydrogen, weak hydrogen and halogen bonding as well as the lone pair•••π interaction, in an environment free from solvent or matrix effects, by using rotational spectroscopy in supersonic expansion. Fluorination and methylation effects, competition between different non-covalent interactions, isomeric preferences are described in the molecular system studied as well as the proton transfer process, the Ubbelohde and the reverse Ubbelohde effects, the internal rotations, and quadrupole couplings which take place. The dissociation energies of the molecular adducts are also estimated and the structural determination of molecules and/or molecular complexes is performed by using isotopologue spectra. Conformational and tautomeric equilibria are investigated for molecules of biological interests, occasionally using the laser ablation technique. Studies have been performed in order to differentiate the enantiomers of chiral molecules, based on opposite phase detection in double quantum coherence experiments.
37

Fighting Cancer through Designed and Natural Products: Discovery of New LDH-A Inhibitors and Route to the Total Synthesis of Rakicidin A

Rupiani, Sebastiano <1988> 19 April 2016 (has links)
The present work aimed to synthesizing new biologically active small molecules as innovative antitumor lead candidates and to the total synthesis of a natural compound with selectivity towards cancer hypoxia. In this context, a first project involved the design and synthesis of N-acylhydrazone based inhibitors of lactate dehydrogenase A (LDH-A). The structures of the new molecules where designed by means of virtual screening and synthesized to obtain a library of analogs which were evaluated on the enzyme. Active compounds were also screened on cells of non-Hodgkins lymphoma and one of them proved to be a promising inhibitor, suggesting that the N-acylhydrazone as suitable scaffolds for LDH-A inhibitors. The second project aimed to the synthesis of Galloflavin (GF) analogs and to the study of the compound’s SAR. GF is an LDH-A inhibitor which was previously identified and synthesized by our group. Its poor solubility and stability prevented us from studying its SAR maintaining the core structure. Therefore, the synthesis of three potential classes of structural analogs was devised and carried out. One compound was found to reproduce GF’s behaviour on the enzyme and in cell, therefore being a good starting point for the study. A small library of analogs was synthesized and biological tests are ongoing to acquire in-depth knowledge about the key pharmacophores of this interesting inhibitor. The third project was carried out at Aarhus University in the group of Prof. Thomas Poulsen. The work focused on the total synthesis of Rakicidin A, a macrolide of natural origin which was identified and isolated from soil samples and is known for its interesting properties in selectively inducing cell death in hypoxic environments and being also active on cancer stem cells. The total synthesis involved several steps including key enantioselective reactions to build the 5 stereocenters on the molecule.
38

Geopolymers with tailored porosity

Papa, Elettra <1987> January 1900 (has links)
Geopolymers are synthetic materials formed by alkali-activation of aluminosilicate particles. They have attracted increasing attention as sustainable materials, being obtained from different raw materials, including industrial by-products, and by production processes at low temperature. Thanks to the good properties showed by these materials (thermal stability, fire-resistance, etc.), and the intrinsic mesoporosity, geopolymers have been studied as new materials for applications in many industrially relevant fields. To achieve full advantage of their porous structure, it is necessary to control its formation. The geopolymer production process in aqueous medium allows to tailor the porosity from nanometric to millimetric range since water acts as pore former. Moreover, ultra-macroporosity may be induced in the materials exploiting different techniques, commonly used for the production of porous ceramics, determining the possibility to obtain materials with different architectures, pore size and shape, etc. Hierarchical pore systems, where the mesopores of the geopolymer skeletal materials are directly connected to macro- and finally to ultra-macropores, may be constructed in this way. The main goal of this research project was to investigate the use of different process techniques applied to geopolymer matrices to generate porous structures characterized by peculiar porosities able to determine specific properties and functionalize the materials. In detail, the porosity was induced by direct foaming or addition of lightweight aggregates. Furthermore, geopolymers with main unidirectional anisotropic macropores were produced, for the first time, using a freeze-casting technique. All the materials produced were deeply investigated to optimize the production processes and evaluate the final properties, many of which arising from the intrinsic and induced porosity generated, in order to address the materials for potential applications as, for example, thermal insulating panels or heat transfer devices.
39

Hyphenated Approaches for the Analysis of Bioactive Natural Compounds in Complex Matrices

Protti, Michele <1986> January 1900 (has links)
Plants, animals and micro-organisms represent a reservoir of natural products, the so called “natural source-derived compounds”. This is particularly true for the plant kingdom, as it offers a variety of species still used as remedies for several diseases in many parts of the world. Nevertheless, the bioactive potential of many plant species remains largely unexplored. Thus, biodiversity represents an unlimited source of chemical entities with potential beneficial effects on human health. These compounds are usually secondary metabolites often present in low quantity in plant material and their extraction, purification and quantitation still remain a great challenge for analytical scientists. The research activity carried out during these three years of PhD Programme was focused on the development, validation and application of original methods aimed at the quali-quantitative analysis of compounds with potential bioactive interest in plant matrices, foods, drinks and related products, as well as the analytical screening of plant by-products from cosmetic manufacture. Bioactive substances, belonging to the classes of polyphenols, aminoacids, coumarins, triterpenes and phytohormones, have been investigated as authenticity markers, in order to identify high quality products and to valorise niche products. The study regarded herbs (Argania spinosa), fruits (Citrus × myrtifolia, Punica granatum) and berries (Myrtus communis) mainly used as folk medicines for their broad spectrum of supposed pharmacological and therapeutic effects. The analytical methods developed within this study are based on high performance liquid chromatography and ultra-high performance liquid chromatography coupled to spectrofluorometric detection, triple quadrupole and high-resolution triple quadrupole mass spectrometry (HPLC-F, LC-MS/MS and UHPLC-HRMS). Significant efforts have been put also into the development and optimisation of miniaturised sample pretreatment strategies, such as micro-solid phase extraction (µSPE) and micro-extraction by packed sorbent (MEPS), able to purify complex matrices of natural origin (whole fruits, fruit parts, leaves and their extracts) and derived commercial products.
40

Simulation of Smart Materials

Matta, Micaela <1987> January 1900 (has links)
The aim of this thesis is the elucidation of structure-properties relationship of molecular semiconductors for electronic devices. This involves the use of a comprehensive set of simulation techniques, ranging from quantum-mechanical to numerical stochastic methods, and also the development of ad-hoc computational tools. In more detail, the research activity regarded two main topics: the study of electronic properties and structural behaviour of liquid crystalline (LC) materials based on functionalised oligo(p-phenyleneethynylene) (OPE), and the investigation on the electric field effect associated to OFET operation on pentacene thin film stability. In this dissertation, a novel family of substituted OPE liquid crystals with applications in stimuli-responsive materials is presented. In more detail, simulations can not only provide evidence for the characterization of the liquid crystalline phases of different OPEs, but elucidate the role of charge transfer states in donor-acceptor LCs containing an endohedral metallofullerene moiety. Such systems can be regarded as promising candidates for organic photovoltaics. Furthermore, exciton dynamics simulations are performed as a way to obtain additional information about the degree of order in OPE columnar phases. Finally, ab initio and molecular mechanics simulations are used to investigate the influence of an applied electric field on pentacene reactivity and stability. The reaction path of pentacene thermal dimerization in the presence of an external electric field is investigated; the results can be related to the fatigue effect observed in OFETs, that show significant performance degradation even in the absence of external agents. In addition to this, the effect of the gate voltage on a pentacene monolayer are simulated, and the results are then compared to X-ray diffraction measurements performed for the first time on operating OFETs.

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