The activity carried out during my PhD was principally addressed to the development and characterization of new detection systems based on chemical luminescence (CL) for the implementation into smartphone based-biosensors for point of care (POC) and point of need applications. The aim of this research has been to determine the feasibility of combining smartphone detection capabilities with CL dependent assay results. In particular, my work has concerned the development of two smartphone-based assays to image and quantify chemiluminescence coupled biospecific enzymatic reactions to detect total cholesterol in serum and lactate in oral fluid and sweat. The devices were produced using a low-cost 3D printing technology and include a disposable analytical minicartridge, a mini dark box to avoid interference from ambient light measurement, and a holder to connect the dark box to a smartphone. The performances of these systems were compared with those obtained with a reference laboratory instrumentation (thermoelectrically cooled MZ-2PRO CCD camera). Finally, it was developed an alternative non-invasive smartphone-based assay to quantify lactate in oral fluid using a reagentless bioactive paper-based solid-phase biosensor integrated in smartphone-based device, employing light reflectance to measure an end-point enzymatic chemical reaction. The quantitative information is obtained from the change of color, due to variability of amount, intensity and brightness of light reflected from surface where assay has occurred. The proposed approaches based on the use of smartphone as detector paves the way for a new generation of analytical devices in the clinical diagnostic field. Moreover, the connectivity and data processing offered by smartphones can be exploited to perform analysis directly at home with simple procedures. The extreme simplicity of the device widens it applicability and makes it suitable for the detection of many analytes of clinical interest, for instance H2O2 producing all kind of oxidases.

In this dissertation thermal and catalytic pyrolysis of protein-rich biomass was investigated. The study was focused on the liquid and solid products. This thesis was aimed to gather chemical information on the thermal behavior of proteinaceous substrates in the presence of zeolite and compare with lignocellulosic biomass. Furthermore, the thesis was focused on the development of reliable analytical methods by means of Py-GC-MS in order to predicting bio-oil composition and to investigating biochar structure and its correlation with thermal stability. In addition a sampling procedure for the direct analysis of pyrolysis vapours based on absorption onto a microfiber (SPME) was developed. Py-GC-MS was applied as screening method to study the effect of different catalysts (H-ZSM5, MCM-41) and biomass-catalyst weight ratio on aromatic hydrocarbons production. The obtained results demonstrated that Py-GC-MS enable the selection of pyrolysis conditions. H-ZSM5 confirmed to be the catalyst with the best performance in terms of hydrocarbon production. In addition, the chemical composition observed by Py-GC-MS significantly reflects that obtained on bench scale. However, some difference has been found. Indeed, formation of high molecular weight PAHs have been observed only on bench scale and nitrogen-containing compounds and oxygenated compounds exhibited some difference related to condensation step. Problems during condensation step led to using SPME as at-line monitoring technique during the process capable of hot gas phase analysis. Strong similarity between GC-MS analysis of hot vapours and bio-oil from condensation traps were found. Finally, Py-GC-MS was applied to the chemical characterization of biochars obtained under different pyrolysis conditions or from different feedstock. Py-GC-MS can provide molecular indices useful to gather information on biochar thermal stability and to predicting the biochar carbonization degree. Furthermore, the molecular pattern resulting from Py-GC-MS could be utilized to infer information on the nature of the initial substrate and differentiate biochars.

During my PhD I was involved in many studies concerning the nucleophilic (SNAr) and electrophilic (SEAr) aromatic substitution reactions. My research activity was focused on the study of different electrophile/nucleophile combinations between strongly activated species, with the purpose to investigate on their reactivity, to detect new intermediates of the aromatic substitution reaction and to obtain new higly conjugated structures bearing contemporaneously electron donor and acceptor moieties on the same unit for application in different fields. Different reactions between both neutral or charged electrophilic and nucleophilic species were performed and from their combinations new products for applications in different fields (e.g. medicine, biology and materials) were obtained and new intermediates of the aromatic substitution reactions [e.g. Wheland (W), Meisenheimer (M), and even Wheland-Meisenheimer (WM)], were detected and characterized, mainly using NMR spectroscopic techniques. In particular the involved nucleophilic species were: tri- and diaminobenzene derivatives, trihydroxybenzene, trimethoxybenzene, anisole derivatives and aminothiazole derivatives; whereas the selected electrophilic species were: aryldiazonium ions, benzofuroxan and benzofurazan derivatives, thiophene derivatives and benzhydrylium ions. Furthermore, the last year of my PhD course, I spent a period in the Department of Chemistry, Ludwig-Maximilians-University of Munich, in collaboration with Prof. Herbert Mayr’s group, with the aim to investigate on the nucleophilic reactivities of di- and triaminobenzene derivatives performing their combination with different reference electrophiles, selected from the Mayr’s reactivity scales.

Questa tesi è mirata ad essere un lavoro che racchiude alcuni dei vari aspetti rilevanti che collegano la Green Chemistry alla sostenibilità ambientale. La tesi riguarda lo sviluppo sostenibile attraverso capitoli che concorrono alla progettazione di processi chimici eco-compatibili innovativi e approcci verdi per ridurre al minimo e/o rimediare l'inquinamento ambientale. In questo contesto, il mio progetto di dottorato ha affrontato tre temi principali: 1. Progettazione, sintesi e caratterizzazione di nuove molecole di tensioattivo che impiegano materie prime rinnovabili, acido itaconico e ammine lipofile, come materiali di partenza; il Capitolo 2 descrive questo argomento. 2. Sviluppo di una procedura sostenibile finalizzata alla sintesi multicomponente a cascata di biarilcalconi in acqua pura o in condizioni di catalisi micellare; in quest'ultimo caso, uno dei tensioattivi precedentemente sintetizzati è stato ampiamente impiegato; il Capitolo 5 descrive questo argomento. Capitolo 3 e Capitolo 4 descrivono il contesto scientifico e le innovazioni più importanti che hanno aperto la strada a i risultati conseguiti durante il 2 ° anno del corso di dottorato; il primo è una panoramica sull'uso dell'acqua come solvente per reazioni organiche; il secondo è una panoramica sulle reazioni di cross-coupling e lo sfruttamento in questo contesto della catalisi micellare. 3. Progettazione, sintesi e impiego di ligandi di tipo fenantrolinico deuterati per l'ossidazione aerobica palladio catalizzata del metil-glucoside, consentendo un elevato miglioramento della prestazione in questa reazione impegnativa; il Capitolo 7 raccoglie i risultati ottenuti, mentre il capitolo 6 riassume i più importanti progressi ottenuti negli ultimi anni nelle ossidazioni aerobiche di alcoli palladio-catalizzate. / This thesis is intended to be a work that encompasses some of the various relevant aspects linking the Green Chemistry practice to environmental sustainability. The thesis covers sustainable development through chapters that contribute to the design of novel environmentally benign chemical processes and green approaches to minimize and/or remediate environmental pollution. In this context, my PhD project has faced three main topics: 1. Design, synthesis and characterization of new surfactant molecules employing renewable feedstocks, itaconic acid and fatty amines, as starting materials; Chapter 2 describes this topic. 2. Development of a sustainable procedure aimed to the multicomponent cascade synthesis of biaryl-based chalcones in pure water or under micellar catalysis conditions; in the latter case, one of the surfactants previously synthesized has been widely employed; Chapter 5 describes this topic. Chapter 3 and Chapter 4 describe the scientific context and the most important innovations that have paved the way to the results achieved during the 2nd year of PhD course; the former is an overview on the use of water as solvent for organic reactions; the latter is an overview on cross-coupling reactions and the exploitation in this context of micellar catalysis. 3. Design, synthesis and exploitation of deuterated phenanthroline-type ligands for the aerobic palladium-catalyzed oxidation of methyl glucoside, allowing a high performance improvement in this challenging reaction; Chapter 7 collects the obtained results, while Chapter 6 summarizes the most important advances obtained in the last years in the palladium-catalyzed aerobic oxidations of alcohols.

Ce manuscrit détaille différentes méthodes de synthèse des sulfoxydes vinyliques ainsi que leurs utilisations dans une réaction d'addition conjuguée intramoléculaire pour obtenir des 1,3-diols syn. Ces derniers sont employés pour la synthèse de précurseurs d'analogues de nucléosides. Dans le premier chapitre, nous montrerons différents aspects importants de la chimie des nucléosides et de leurs analogues; nous présenterons leur mécanisme d'action, ainsi que des médicaments à structure nucléosidique utilisés pour traiter différentes maladies virales. Par la suite, nous décrirons quelques méthodes de synthèses décrites dans la littérature pour ce type de molécules, ainsi que quelques exemples pour la synthèse des motifs 1,3-diols syn, sans vouloir être exhaustif ni trop entrer dans les détails. Le deuxième chapitre présente les différentes méthodes de synthèse que nous avons utilisées pour la synthèse des sulfoxydes vinyliques. Ces derniers sont les précurseurs de la réaction d'addition conjuguée intramoléculaire que nous utilisons pour la mise en place du motif 1,3-diol syn, cette réaction ainsi que les résultats obtenus seront discutés dans le chapitre 3. Finalement, nous exposerons les résultats obtenus pour la réaction de Pummerer et la réaction de cyclisation en milieu acide, qui nous a permis d'obtenir les analogues du 3-désoxyribose et ses analogues.

La dégradation rapide des huiles moteurs et la formation accrue de dépôts dans les moteurs Diesel sont une des conséquences majeures de l'utilisation de la technologie de Recirculation des Gaz d'Echappement (EGR, pour

L'objectif de ce projet scientifique réalisé dans le Laboratoire de Synthèse Organique (DCSO) de l'Ecole Polytechnique sous la direction du Dr. Fabien Gagosz et Pr. Samir Zard a été l'étude de nouvelles transformations catalysées par des complexes d'or (I) développées au laboratoire. Ces catalyseurs agissent comme des acides de Lewis "soft" vis à vis des liaisons carbone-carbone multiples permettant la formation de nouvelles liaisons carbone-carbone ou carbone-hétéroatome. De nouvelles méthodes permettant la synthèse des hétérocycles: des carbonates et des carbamates cycliques (Chapitres II et III), des oxazolones (Chapitre IV), des 2,5-dihydrofuranes (Chapitre V) ou bien des cycles carbonés: des bicyclo[3.1.0]hexènes (Chapitre VII) et des cyclopentènes (Chapitres VIII and IX) ont été développées.

Dans les dernières années, les complexes d'or se sont avérés des excellents catalyseurs pour des nombreuses transformations homogènes impliquant l'activation des liaisons carbon-carbon multiples vis-à-vis de l'attaque des différents nucléophiles (Chapitre 1). Suite à la découverte par le Dr. Fabien L. Gagosz d'une nouvelle classe de catalyseurs cationiques d'or(I), cristallins, stables à l'air et très réactifs, ayant un groupement triflimide comme contre-anion (Chapitre 2), notre équipe s'est intéressée au développement de nouvelles transformations catalysées par ces complexes. Ce manuscrit présente une partie du travail effectué dans ce domaine qui a mené à la découverte de nouvelles méthodes pour la synthèse des différents dérivés hétéro- et carbocycliques, tels que les 4-alkylidène-1,3-dioxolan-2-ones (Chapitre 3), les 4-oxazolin-2-ones (Chapitre 4), les 2,5-dihydrofuranes (Chapitre 5), les pyrroles et les furanes (Chapitre 6), les esters de 1,3-butadièn-2-ol (Chapitre 7), les cyclopentènes (Chapitre 8) ou bien les 1,3-oxazinan-2-ones (Chapitre 9).

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L'objectif de cette étude consiste à élaborer des couches d'oxydes qui seront utilisées dans des dispositifs fonctionnant à haute température. Les oxydes synthétisés répondent bien aux propriétés recherchées dans les piles à combustible à électrolyte solide et les barrières thermiques. Cet objectif a été atteint grâce à l'utilisation d'un plasma hors-équilibre généré dans un réacteur à tuyère convergente supersonique. Un aérosol contenant les précurseurs nitrés est introduit, à l'aide du système d'injection adapté, dans le réacteur plasma en vue d'obtenir les dépôts d'oxydes recherchés. La mise au point d'un nouveau système d'injection a rendu possible la réalisation des dépôts réputés difficiles à élaborer. L'étude hydrodynamique de l'écoulement des gaz et des particules dans le réacteur a été réalisée de deux façons. D'une part, le modèle développé sous FLUENT a indiqué que la vitesse des gaz plasmagènes en sortie de la tuyère peut atteindre 700 m.s-1. D'autre part, l'anémométrie laser-Doppler a montré le rôle important de la tuyère convergente qui accélère l'écoulement des particules. La spectroscopie d'émission optique a révélé l'importance de cette tuyère sur la concentration des espèces réactives dans le plasma et sa contribution sur la dissociation de l'eau par la présence des radicaux OH° et des H atomiques. Un code développé dans notre laboratoire a permis d'étudier l'évolution des fractions molaires des espèces réactives le long du réacteur en fonction de la puissance et du diamètre du col de la tuyère. La microscopie électronique à balayage a mis en évidence la morphologie des dépôts synthétisés. La spectrophotométrie infrarouge à transformée de Fourier a été employée pour quantifier l'influence des différents paramètres sur le taux de conversion des précurseurs en oxydes. La diffraction des rayons X a confirmé la pureté des dépôts et la structure cristalline correspondante.