Tetrafenilciclopentadienon-derivati ed analoghi: sintesi, "self-assembly" e caratterizzazione reologica

Gels are materials that are easier to recognize than to define. For all practical purpose, a material is termed a gel if the whole volume of liquid is completely immobilized as usually tested by the ‘tube inversion’ method. Recently, supramolecular gels obtained from low molecular weight gelators (LMWGs) have attracted considerable attention in materials science since they represent a new class of smart materials sensitive to external stimuli, such as temperature, ultrasounds, light, chemical species and so on. Accordingly, during the past years a large variety of potentialities and applications of these soft materials in optoelectronics, as electronic devices, light harvesting systems and sensors, in bio-materials and in drug delivery have been reported. Spontaneous self-assembly of low molecular weight molecules is a powerful tool that allows complex supramolecular nanoscale structures to be built. The weak and non-covalent interactions such as hydrogen bonding, π–π stacking, coordination, electrostatic and van der Waals interactions are usually considered as the most important features for promoting sol-gel equilibria. However, the occurrence of gelation processes is ruled by further “external” factors, among which the temperature and the nature of the solvents that are employed are of crucial importance. For example, some gelators prefer aromatic or halogenated solvents and in some cases both the gelation temperature and the type of the solvent affect the morphologies of the final aggregation. Functionalized cyclopentadienones are fascinating systems largely employed as building blocks for the synthesis of polyphenylene derivatives. In addition, it is worth noting that structures containing π-extended conjugated chromophores with enhanced absorption properties are of current interest in the field of materials science since they can be used as “organic metals”, as semiconductors, and as emissive or absorbing layers for OLEDs or photovoltaics. The possibility to decorate the framework of such structures prompted us to study the synthesis of new hydroxy propargyl arylcyclopentadienone derivatives. Considering the ability of such systems to give π–π stacking interactions, the introduction on a polyaromatic structure of polar substituents able to generate hydrogen bonding could open the possibility to form gels, although any gelation properties has been never observed for these extensively studied systems. we have synthesized a new class of 3,4-bis (4-(3-hydroxy- propynyl) phenyl) -2, 5-diphenylcyclopentadienone derivatives, one of which (1a) proved to be, for the first time, a powerful organogelator. The experimental results indicated that the hydroxydimethylalkynyl substituents are fundamental to guarantee the gelation properties of the tetraarylcyclopentadienone unit. Combining the results of FT-IR, 1H NMR, UV-vis and fluorescence emission spectra, we believe that H-bonding and π–π interactions are the driving forces played for the gel formation. The importance of soft materials lies on their ability to respond to external stimuli, that can be also of chemical nature. In particular, high attention has been recently devoted to anion responsive properties of gels. Therefore the behaviour of organogels of 1a in toluene, ACN and MeNO2 towards the addition of 1 equivalent of various tetrabutylammonium salts were investigated. The rheological properties of gels in toluene, ACN and MeNO2 with and without the addition of Bu4N+X- salts were measured. In addition a qualitative analysis on cation recognition was performed. Finally the nature of the cyclic core of the gelator was changed in order to verify how the carbonyl group was essential to gel solvents. Until now, 4,5-diarylimidazoles have been synthesized.

Implementation of a non ground meta interpreter for defeasible logic

Human reasoning is a fascinating and complex cognitive process that can be applied in different research areas such as philosophy, psychology, laws and financial. Unfortunately, developing supporting software (to those different areas) able to cope such as complex reasoning it’s difficult and requires a suitable logic abstract formalism. In this thesis we aim to develop a program, that has the job to evaluate a theory (a set of rules) w.r.t. a Goal, and provide some results such as “The Goal is derivable from the KB5 (of the theory)”. In order to achieve this goal we need to analyse different logics and choose the one that best meets our needs. In logic, usually, we try to determine if a given conclusion is logically implied by a set of assumptions T (theory). However, when we deal with programming logic we need an efficient algorithm in order to find such implications. In this work we use a logic rather similar to human logic. Indeed, human reasoning requires an extension of the first order logic able to reach a conclusion depending on not definitely true6 premises belonging to a incomplete set of knowledge. Thus, we implemented a defeasible logic7 framework able to manipulate defeasible rules. Defeasible logic is a non-monotonic logic designed for efficient defeasible reasoning by Nute (see Chapter 2). Those kind of applications are useful in laws area especially if they offer an implementation of an argumentation framework that provides a formal modelling of game. Roughly speaking, let the theory is the set of laws, a keyclaim is the conclusion that one of the party wants to prove (and the other one wants to defeat) and adding dynamic assertion of rules, namely, facts putted forward by the parties, then, we can play an argumentative challenge between two players and decide if the conclusion is provable or not depending on the different strategies performed by the players. Implementing a game model requires one more meta-interpreter able to evaluate the defeasible logic framework; indeed, according to Göedel theorem (see on page 127), we cannot evaluate the meaning of a language using the tools provided by the language itself, but we need a meta-language able to manipulate the object language8. Thus, rather than a simple meta-interpreter, we propose a Meta-level containing different Meta-evaluators. The former has been explained above, the second one is needed to perform the game model, and the last one will be used to change game execution and tree derivation strategies.

The Complex Monge-Ampère Equation

In questa trattazione si studia la regolarità delle soluzioni viscose plurisubarmoniche dell’equazione di Monge-Ampère complessa. Si tratta di un’equazione alle derivate parziali del secondo ordine completamente non lineare il cui termine del secondo ordine è il determinante della matrice hessiana complessa di una funzione incognita a valori reali u. Il principale risultato della tesi è un nuovo controesempio di tipo Pogorelov per questa equazione. Si prova cioè l’esistenza di soluzioni viscose plurisubarmoniche e non classiche per un equazione di Monge-Ampère complessa.