Sintesi di PNA a libertà conformazionale ridotta

The present work started a research project aimed at the synthesis of conformationally “locked” PNA (Peptide Nucleic Acids) monomers. Compared to classic aeg-PNA, this structural modification would result in an improvement in the pairing properties with natural nucleic acids, due to entropic variations in the process. Specifically, an attempt was made to build a PNA monomer around a β-lactam ring. That ring could be imagined as obtained by linking the methylene groups in α position of both the nucleobase and the carboxyl function. These structural properties would imply pre-organization of the final oligomer, improving the pairing process in biological systems. The first step of this work was the investigation of the Staudinger reaction for the ciclization of the lactam ring, and in particular the activation method of the carboxylic group of the nucleobase derivatives. Use of triazine chloride led to the synthesis of the adenine-based β-lactam-PNA. Attempts to synthesize the same monomer based on cytosine, guanine and thymine were unsuccessful, so alternative methods for carboxylic group activation were investigated. Conversion of carboxylic acids to acyl chlorides led to a partial result: despite the method worked well with analogues of the final reactants, it didn’t worked with substrates needed for lactam based PNAs. Search for a valid activation process continued involving carbonyl diimidazole, Mukayama reagent, and LDA (with methylester derivative of nucelobase) without good results. Last, it was investigated a different synthetic approach by first synthesizing a proper backbone with a chlorine in the β- lactam ring. This chlorine ring should undergo substitution by a nucleobase anion to give the desired PNA monomer. Unluckily also this synthetic route didn’t lead to the desired monomers.

Inverse and regular phenyl-azole ligands for luminescent Iridium(III) complexes

In the modern society, light is mostly powered by electricity which lead to a significant increase of the global energy consumption. In order to reduce it, different kinds of electric lamps have been developed over the years; it is now accepted that phosphorescence-based OLEDs offer many advantages over existing light technologies. Iridium complexes are considered excellent candidates for bright materials by virtue of the possibility to easily tune the wavelength of the emitted radiation, by appropriate modifications of the nature of the ligands. It is important to note that the synthesis of Ir(III) blue-emitting complexes is a very challenging goal, because of wide HOMO-LUMO gaps needed for produce a deep blue emission. During my thesis I planned the synthesis of two different series of new Ir(III) heteroleptic complexes, the C and the N series, using cyclometalating ligands containing an increasing number of nitrogens in inverse and regular position. I successfully performed in the synthesis of the required four ligands, i.e. 1-methyl-4-phenyl-1H-imidazole (2), 4-phenyl-1-methyl-1,2,3-triazole (3), 1-phenyl-1H-1,2,3-triazole (6) and 1-phenyl-1H-tetrazole (7), that differ in the number of nitrogens present in the heterocyclic ring and in the position of the phenyl ring. Therefore the cyclometalation of the obtained ligands to get the corresponding Ir(III)-complexes was attempted. I succeeded in the synthesis of two Ir(III)-complexes of the C series, and I carried out various attempts to set up the appropriate reaction conditions to get the remaining desired derivatives. The work is still in progress, and once all the desired complexes will be synthesized and characterized, a correlation between their structure and their emitting properties could be formulated analysing and comparing the photophysical data of the real compounds.

Indoor position, localizzazione e tracciamento in ambienti chiusi

Le grandi catene di distribuzione, per sviluppare strategie commerciali sempre più efficaci, sono interessate a comprendere il percorso che ogni cliente effettua all’interno del punto vendita, che reparti visita, il tempo di permanenza in un’area specifica ecc… Quindi è stato necessario trovare un sistema per localizzare e tracciare un cliente all’interno di un ambiente chiuso (indoor position). Prima di tutto ci si è concentrati sulla ricerca e sviluppo di una nuova idea che potesse superare gli ostacoli delle soluzioni attualmente in commercio. Si è pensato di sostituire le tessere punti del punto vendita con delle tessere bluetoothLE e di creare un sistema di posizionamento al chiuso utilizzando la stessa logica di funzionamento del GPS per gli ambienti aperti. Il ricevitore è la tessera BLE posseduta dal cliente e i satelliti sono tre device Android dotati di un’app specifica per rilevare il segnale radio (RSSI) emesso dalla tessera ogni secondo. Le rilevazioni dei tre device Android sono successivamente trasferite all’interno di una web application che si occupa di elaborare i dati tramite il processo di trilaterazione. L’output sono le coordinate x,y di ciascuna tessera in ogni secondo di visita all’interno del punto vendita. Questi dati sono infine utilizzati per mostrare graficamente il percorso effettuato dal cliente, l’orario di ingresso e di uscita e il tempo di permanenza. Riepilogando, il progetto comprende una fase di ricerca e intuizione di una nuova idea, una fase di progettazione per traslare i meccanismi del funzionamento GPS all’utilizzo in un ambiente chiuso, una fase di implementazione dell’app e della web application e infine una fase di sperimentazioni sul campo che si concluderà dopo la laurea con test reali in un supermercato della zona.