Tesi di Dottorato
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Item Hydrophilic Ir(III) complexes suitable for the construction of functional mesoporous materials(2012-11-27) Yadav, Yogesh Jivajirao; Versace, Carlo; Ghedini, Mauro; Bartolino, RobertoNowadays, intensive efforts have been carried out on the design of novel advanced molecular materials, which can self-assemble in a strong, directional and reversible way to construct supramolecular materials with specific properties. The rational design and preparation of supramolecular assemblies through the coordination of metal ions with organic ligands has attracted attention for developing novel crystalline materials with interesting structural topologies and promising applications, and has evolved as an interesting research. The metals used in these complexes can serve as structural components and/or as a source of properties (e.g., magnetic, catalytic, optoelectronic, etc). Cyclometallated Ir(III) octahedral complexes possess fascinating properties used in various applications such as luminescent and electrochemiluminescent labeling reagents for biological substrates1, sensors2, or electronic devices3,4. Recently, the interest in ionic Ir(III) complexes is growing rapidly because not only high internal quantum efficiency (~100%) can be achieved in principle, but also tunable emission wavelengths over the entire visible spectrum can be successfully obtained through ingenious modification of ligands. In particular, Ir(III) complexes based on the chelating ligand 2,2’-bipyridine (bpy) have been successfully applied in light-emitting electrochemical cells (LECs) and sensors.5 The theoretically calculated phosphorescence yield (Fp) of the Ir(III) complexes are close to unity in solution.6 The solution investigations have made great contributions to the fundamental understanding of luminescence processes at molecular level. The conclusions drawn from the dilute solution data, however, cannot commonly be extended to the concentrated solutions. Indeed, many Ir(III) complexes show very different light-emitting behaviors in dilute and concentrated solutions and respectively in the solid state. The luminescence is often weakened or quenched at high concentrations, a phenomenon widely known as “concentration quenching”. A main cause for the quenching process is mechanistically associated with the “formation of aggregates”, which is probably why the concentration quenching effect has frequently been referred to as “aggregationcaused quenching” (ACQ). On the other hand “aggregation-induced phosphorescent emission” (AIPE) is an unusual phenomenon existing also in transition metal complexes, which have no emission in solution but enhanced emission in the solid state.7 There are some examples of AIPE, most of them in neutral Ir(III) complexes.8, 9, 10, 11, 12 The main strategies to avoid unpleasant quenching phenomena are based on the dispersion of the chromophore. Mainly, two strategies are employed: engineering at molecular level by introducing functionalities able to electronically disconnect the chromophores (bulky groups or functionalities capable to construct hard crystalline or soft dynamic supramolecular assemblies) or isolating the active molecules in different host matrices (host-guest systems).13 In particular, the dispersion of a chromophore into mesoporous materials not only prevents the aggregation phenomena but also provides increased thermal, chemical and mechanical stability to the final materials. Mesoporous materials are ordered porous materials with periodic distribution of pores, high surface area, controllable large pore sizes in the range of 2 – 50 nm and variable topology of the pores. The inorganic matrixes may be made up of SiO2, TIO2, ZrO2, Al2O3, Nb2O5 etc. Basically, the synthesis of ordered functional mesoporous materials is based on the condensation of an inorganic scaffold on the organised structure formed in water by surfactant molecules. Two different strategies may be employed, the cooperative self-assembly mechanism (CSA) and the true liquid crystal templating’ (TLCT) mechanism.14 The functionalization of the mesoporous material may be done in both cases by inserting the chromophore into the primarily water solution. Therefore, water soluble chromophores may guarantee a better compatibility with the surfactant/water system, whereas a proper functionalization on the molecular structure of the chromophore that permit the self-assembly into supramolecular ordered water assemblies, will allow to use the chromophores directly as structure directing agents (SDAs). Since the photophysical properties of the ionic complexes are influenced profoundly by the surroundings of the molecule both in solution and in condensed states, it is fundamental to study the behavior of such complexes in these different states, in order to achieve a fine tuning of the properties as a function of their structure and order in the final material. The knowledge gained in the assembling of supramolecular materials using non-covalent bonds may be used for the construction of ordered systems in water. This strategy will permit the one-step synthesis of functional mesoporous materials, and to control the order of the final material controlling the order in water of the functional Ir(III) complexes. In particular, the molecular fragments that one can change to achieve the desired properties in the final ionic Ir(III) complexes are the cyclometallating or coordinating ligands, and respectively the counterion. My research therefore is focused on the design and synthesis of hydrophilic ionic Ir(III) complexes with flexible or rigid ancillary ligands and use of different counterions, all suitable for controlling the supramolecular assembly in the solid state, and to transfer the knowledge gained into obtaining ordered structures in water, or water-surfactant systems, necessary for the synthesis of mesoporous materials with defined properties. The ionic octahedral Ir(III) complexes synthesised during this thesis and their classification in different classes are presented in the figure S1Item Synthesis of molecules of pharmaceutical interest by organometallic catalysis(2012-11-20) Maltese, Vito; Gabriele, Bartolo; Salerno, Giuseppe; Bartolino, RobertoNel presente lavoro di tesi, è riportato un nuovo approccio alla sintesi di furani-3-carbossilati tramite reazione di carbonilazione ossidativa palladiocatalizzata di composti 3-in-1,2-diolici, aventi un gruppo alcolico primario o secondario sul C-1. Tutte le reazioni sono state condotte in solvente alcolico (metanolo o etanolo) in condizioni relativamente blande (100°C e 40 atm di una miscela CO-aria 4:1). I rispettivi furani carbonilati sono stati ottenuti con rese eccellenti (56-93%) attraverso un processo di etero ciclizzazione-alcossicarbonilazione-deidratazione 5-endo-dig sequenziale, usando l’ossigeno come ossidante esterno. In condizioni simili, i derivati 2- metil-3-in-1,2-diolici, aventi un gruppo alcolico terziario, permettono la sintesi di 4-metilene-4,5-diidrofurani-3-carbossilati con rese soddisfacenti (58-60%). I tiofeni sono una classe molto importante di composti eterociclici. Molte molecule contenenti il nucleo tiofenico mostrano una grande varietà di attività biologiche e trovano applicazione in campo farmaceutico e cosmetico. Inoltre, sono degli intermedi sintetici molto utili nella preparazione di nuovi materiali polimerici. Nel presente lavoro è stato realizzato un nuovo percorso sintetico per la sintesi di tiofeni sostituiti a partire da 1-mercapto-3-in-2-oli, tramite S-eterociclizzazione PdI2/KIcatalizzata. Il sistema catalitico PdI2/KI, sviluppato dal gruppo di ricerca in cui è stato svolto il Dottorato, ha già dimostrato la sua efficacia nel favorire reazioni simili. La reazione di amminocarbonilazione ossidativa di alchini funzionalizzati è uno dei metodi più versatili per la sintesi diretta di eterocicli e carbocicli carbonilati. In particolare, il sistema catalitico PdI2/KI è un ottimo promotore per queste reazioni, in presenza di ossigeno come ossidante. Nell’ultima parte del lavoro è stata sviluppata una nuova sintesi di indanilideni carbossilati, applicando la reazione di amminocarbonilazione ossidativa a esteri 2-etinilbenzilmalonici, per l’ottenimento di prodotti indanilidenici carbonilati con un alto grado di selettività nei confronti del diastereoisomero E che, in alcuni casi, è stato isolato in maniera totalmente selettiva.Item Properties of biomolecules at the interfaces: studies and characterization of chromonic mesogens, from the basis to applications(2013-11-28) Tone, Caterina; Bartolino, Roberto; Versace, Carlo; Ciuchi, FedericaThe study of the interaction between molecules, in particular biological molecules and liquid crystals (LC), has experienced a huge growth in the recent years because of the development in devices engineering applied not only in photonics but also in the biomedical eld. In order to design more e cient LC devices, it is rst necessary to understand the behavior and properties of newly-synthesized liquid crystals and to garner a more indepth understanding of currently-existing LCs in order to answer pending questions about them. The aim of this thesis work, is to better understand the interactions involved at the interface between liquid crystals and other materials, whatever is their nature, i.e. polymeric or biological. We started studying the e ect of di erent con ning surfaces on the alignment of a special class of lyotropic liquid crystals, called \chromonics", which, in addition of LC properties, are biocompatible. Di erently from the most common liquid crystals, i.e. thermotropic LC, the mesogens that constitute the chromonic LC phases are not amphiphilic, but they are \plan-like" aromatic compound. This class of molecules embraces not only dyes and drugs, but also DNA and its bases. Using the knowledge acquired with chromonic mesogen, we tried to understand a more complicate system, such as the phenomena involved at the biomolecules decorated-liquid crystals lms interfaces. More speci cally, it is possible to divide the work in two macro-parts. The rst part concerns the alignment of a chromonic molecule, \disodium cromoglycate" (DSCG). The study of chromonic LC behaviour in con ned geometries and its physical properties, could be a model for more complex biological assemblies. Hence, we demonstrated the role of alignment layer's surface energy in the alignment of nematic phase of DSCG, achieving both alignments and for the rst time, a stable-in-time homeotropic anchoring of this LC solution. With the knowledge acquired from DSCG, we were able to align also DNA bases liquid crystal solutions. In particular, guanosine monophosphate in pre-cholesteric and cholesteric liquid crystals phases were perfectly aligned homeotropically without means of external elds, as was done until now, and partially planar aligned. Moreover, we observed that if ionic and/or silver doped solutions are added to the LC guanosine phases, it is possible to control the pitch of the cholesteric phase, modifying the helix structure. Instead, varying the nature of the con ning surfaces, in such conditions, it is possible to obtain guanosine vesicles. Other studies have been carried out on new chromonic complexes, synthesized at Chemistry Department of UNICAL, with possible application as anticancer drugs. A complete characterization of these compounds were done (XRD, phase diagrams, etc) and also for these compounds, we developed a\route"to drive the alignment, particularly important for future application in biophotonic devices. The second part of the work is focused on LC based biosensors. From the biotechnological and biomedical applications point of view, the studies on interactions of proteins with lipids are an area of fundamental interest, due to enormous biological importance. In fact, studies on biosensor devices are tremendously increased in recent years, focusing the attention also on nding low cost raw materials with high e ciency: liquid crystals, thanks to their high sensitivity to the external conditions, represent the best candidate. It has been demonstrated that aqueous interface of LC has an instantaneous response when exposed to phospholipids. This is a good base to study the interaction between biomolecules using LC as probe. Starting from the results found in literature, we studied the e ect of phospholipids on protein decoratede-liquid crystal interfaces by means of optical microscopy and FT-IR measurements. The rst technique allowed us to observe the response of decorated LC lm when exposed to phospholipids vesicles, while the second, gave us insight on conformational changes involved in secondary structure of the protein in function of the time of interaction between protein and LC, and the pH of the surrounding environment. The results obtained show a new methods to report speci c binding of vesicles on protein decorated interfaces.