Studio di un nuovo processo per la sintesi di acido adipico.

Obiettivo del mio lavoro di tesi è stato quello di verificare la fattibilità di un nuovo processo per la produzione di acido adipico da cicloesene con due stadi di reazione. Il primo stadio di reazione prevede l’ossidazione del cicloesene con soluzione acquosa di acqua ossigenata a formare l’epossido, che idrata a 1,2-cicloesandiolo, mentre nel secondo stadio il glicole viene ossidato con ossigeno ad acido adipico. Il lavoro è stato focalizzato sullo studio del meccanismo di reazione per l’ossidazione del 1,2-cicloesandiolo ad acido adipico, utilizzando catalizzatori a base di Ru(OH)3/Al2O3, Ru(OH)3-Bi(OH)3/Al2O3, Cu/C e Cu/TiO2. Le prove condotte hanno dimostrato che i catalizzatori usati sono attivi nell’ossidazione di 1,2-cicloesandiolo, ma sono caratterizzati da scarsa selettività ad acido adipico. Dall’analisi dei risultati ottenuti si desume che la reazione richiede condizioni fortemente basiche per potere avvenire. In queste condizioni però si vengono a formare degli intermedi che reagiscono rapidamente con l’acqua e con l’ossigeno, dando luogo alla formazione di una serie di prodotti primari e secondari.

Studio della metilazione del fenolo in fase gas su catalizzatori a base di ossidi metallici

È stata studiata la reattività di sistemi catalitici a base di ossidi misti di V e Fe per la reazione di metilazione del fenolo in fase gas con metanolo. Questi sistemi promuovono efficacemente la deidrogenazione del metanolo a formaldeide, ciò conferisce loro una grande attività e non è stata osservata alcuna disattivazione nei tempi di reazione tenuti. I principali prodotti ottenuti sono 2,6-xilenolo e o-cresolo. Il catalizzatore, inizialmente costituito da FeVO4 subisce, durante le prime fasi di reazione, una progressiva riduzione, fino all’ottenimento di una fase spinello stabile costituita da coulsonite FeV2O4 e magnetite.

Biodiesel ottenuto da olio di babassu e sue miscele: studio di produzione e controllo di qualità

Il contributo all’innalzamento del riscaldamento globale, prodotto dai combustibili fossili è un dei principali problemi ambientali. Le bioenergie potrebbero contribuire enormemente alla riduzione di questo fenomeno, sostituendo in parte i combustibili tradizionali di origine fossile. In questo contesto, può collocarsi il biodiesel prodotto a partire da oli vegetali, rappresentando una valida e strategica alternativa. Il biodiesel è una miscela di metil esteri di acidi grassi, [fatty acids methyl esters (FAME)], normalmente ottenuta tramite reazione di transesterificazione tra oli vegetali e alcol a catena corta in presenza di un catalizzatore acido o basico in catalisi sia omogena che eterogenea. Il biodiesel si colloca tra le materie prime di seconda generazione e può risultare una buona base di partenza per ottenere un biodiesel performante e con un basso costo finale.

Studio ed ottimizzazione di una via di sintesi di idrossitirosolo a ridotto impatto ambientale

In questo progetto di tesi abbiamo lavorato all’ottimizzazione di un nuovo processo di sintesi di idrossitirosolo eco-compatibile e di possibile applicazione industriale. Il processo, che risulta una via molto competitiva per ottenere idrossitirosolo, si compone di due step: una prima sintesi di un intermedio acetalico e la successiva riduzione di questo al prodotto di interesse. In particolare il lavoro di tesi ha riguardato lo studio di catalizzatori e delle condizioni per le due reazioni al fine di aumentare le selettività dei prodotti target, analizzando la formazione dei sottoprodotti. Si è cercato, inoltre, di intraprendere una strada alternativa, provando la sintesi di un intermedio acetalico ciclico (possibilmente più stabile dell’altro intermedio acetalico) e, quindi, la sua riduzione, ritenendo di poter così evitare la formazione dei sottoprodotti. In this project we worked on the optimization of a new and industrially applicable process for the synthesis of hydroxytyrosol. Furthermore, we devised a process according to the principles of green chemistry. The process, that is a competitive way to obtain hydroxytyrosol, consists of two steps: first the synthesis of an acetalic precursor and then its reduction. Particularly the work was focused on the study of the catalysts and the conditions for the two reactions in order to increase the selectivity of target products, also analyzing the formation of the by-products. At last, we tried to take an alternative route with the synthesis of another acetalic precursor: a cyclic one. This because we thought that a cyclic acetal should be more stable than not cyclic one and maybe the reduction on this second precursor could not pass by the formation of the by-products already saw.

Embedding environmental sustainability in the undergraduate chemistry curriculum : a case study

In spite of increasing attention devoted to the importance of embedding sustainability in university curricula, few Australian universities include specific green chemistry units, and there is no mention of green or sustainable chemistry concepts in the majority of units. In this paper, an argument is posited that all universities should embed sustainable chemistry within all Chemistry courses because it is the morally correct stance to minimise the harm of climate change. Attitudes of chemistry lecturers towards integrating sustainability into their teaching have been probed and it was found, using an established model, that personal environmental perspectives are critical to their attitude. Importantly, academic staff whose research has an environmental component were more likely to incorporate sustainability into their teaching while others struggled to find ways to do so even when they believed it to be important. This paper will recommend that resources are required to assist academic staff without a green chemistry research program to incorporate sustainability into their teaching and several suggestions are provided.

Glycerol carbonate as green solvent for pretreatment of sugarcane bagasse

Background Pretreatment of lignocellulosic biomass is a prerequisite for effective saccharification to produce fermentable sugars. We have previously reported an effective low temperature (90 °C) process at atmospheric pressure for pretreatment of sugarcane bagasse with acidified mixtures of ethylene carbonate (EC) and ethylene glycol (EG). In this study, “greener” solvent systems based on acidified mixtures of glycerol carbonate (GC) and glycerol were used to treat sugarcane bagasse and the roles of each solvent in deconstructing biomass were determined. Results Pretreatment of sugarcane bagasse at 90 °C for only 30 min with acidified GC produced a solid residue having a glucan digestibility of 90% and a glucose yield of 80%, which were significantly higher than a glucan digestibility of 16% and a glucose yield of 15% obtained for bagasse pretreated with acidified EC. Biomass compositional analyses showed that GC pretreatment removed more lignin than EC pretreatment (84% vs 54%). Scanning electron microscopy (SEM) showed that fluffy and size-reduced fibres were produced from GC pretreatment whereas EC pretreatment produced compact particles of reduced size. The maximal glucan digestibility and glucose yield of GC/glycerol systems were about 7% lower than those of EC/ethylene glycol (EG) systems. Replacing up to 50 wt% of GC with glycerol did not negatively affect glucan digestibility and glucose yield. The results from pretreatment of microcrystalline cellulose (MCC) showed that (1) pretreatment with acidified alkylene glycol (AG) alone increased enzymatic digestibility compared to pretreatments with acidified alkylene carbonate (AC) alone and acidified mixtures of AC and AG, (2) pretreatment with acidified GC alone slightly increased, but with acidified EC alone significantly decreased, enzymatic digestibility compared to untreated MCC, and (3) there was a good positive linear correlation of enzymatic digestibility of treated and untreated MCC samples with congo red (CR) adsorption capacity. Conclusions Acidified GC alone was a more effective solvent for pretreatment of sugarcane bagasse than acidified EC alone. The higher glucose yield obtained with GC-pretreated bagasse is possibly due to the presence of one hydroxyl group in the GC molecular structure, resulting in more significant biomass delignification and defibrillation, though both solvent pretreatments reduced bagasse particles to a similar extent. The maximum glucan digestibility of GC/glycerol systems was less than that of EC/EG systems, which is likely attributed to glycerol being less effective than EG in biomass delignification and defibrillation. Acidified AC/AG solvent systems were more effective for pretreatment of lignin-containing biomass than MCC.

Green synthesis of 1-2 nm gold nanoparticles stabilized by amine-terminated ionic liquid and their electrocatalytic activity in oxygen reduction

Stable gold nanoparticles with average size 1.7 nm synthesized by an amine-terminated ionic liquid showed enhanced electrocatalytic activity and high stability.

Green synthesis of nanowire-like Pt nanostructures and their catalytic properties

We reported a simple and effective green chemistry route for facile synthesis of nanowire-like Pt nanostructures atone step. In the reaction, dextran acted as a reductive agent as well as a protective agent for the synthesis of Pt nanostructures. Simple mixing of precursor aqueous solutions of dextran and K2PtCl4 at 80 degrees C could result in spontaneous formation of the Pt nanostructures. Optimization of the experiment condition could yield nanowire-like Pt nanostructures at 23:1 molar ratio of the dextran repeat unit to K2PtCl4.

Ionic liquids are not always green: hydrolysis of 1-butyl-3-methylimidazolium hexafluorophosphate

1-Butyl-3-methylimidazolium fluoride hydrate has been identified crystallographically as a decomposition product created during purification of the hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. This highlights the need to treat ionic liquids much as one would any other research chemical with potentially hazardous properties, unknown toxicity and/or stability, particularly when searching for 'green solvents'.

Green photochemistry: photo-Friedel-Crafts acylations of 1,4-naphthoquinone in room temperature ionic liquids

The photo-Friedel-Crafts acylation of 1,4-naphthoquinone with various aldehydes was investigated in a series of room temperature ionic liquids. High conversions and selectivities were achieved in [C(2)mim](+)-based ionic liquids with the highest isolated yields found in [C(2)mim][NTf2]. The developed procedure allowed for a replacement of hazardous solvents such as benzene and acetonitrile which are commonly used for this transformation.

Simple green approach to reinforce natural rubber with bacterial cellulose nanofibers

Natural rubber (NR) is a renewable polymer with a wide range of applications, which is constantly tailored, further increasing its utilizations. The tensile strength is one of its most important properties susceptible of being enhanced by the simple incorporation of nanofibers. The preparation and characterization of natural-rubber based nanocomposites reinforced with bacterial cellulose (BC) and bacterial cellulose coated with polystyrene (BCPS), yielded high performance materials. The nanocomposites were prepared by a simple and green process, and characterized by tensile tests, dynamical mechanical analysis (DMA), scanning electron microscopy (SEM), and swelling experiments. The effect of the nanofiber content on morphology, static, and dynamic mechanical properties was also investigated. The results showed an increase in the mechanical properties, such as Young's modulus and tensile strength, even with modest nanofiber loadings. © 2013 American Chemical Society.

Green synthesis of gold nanoparticles with self-sustained natural rubber membranes

Green chemistry is an innovative way to approach the synthesis of metallic nanostructures employing eco-friendly substances (natural compounds) acting as reducing agents. Usually, slow kinetics are expected due to, use of microbiological materials. In this report we study composites of natural rubber (NR) membranes fabricated using latex from Hevea brasiliensis trees (RRIM 600) that works as reducing agent for the synthesis of gold nanoparticles. A straight and clean method is presented, to produce gold nanoparticles (AuNP) in a flexible substrate or in solution, without the use of chemical reducing reagents, and at the same time providing good size's homogeneity, reproducibility, and stability of the composites. Copyright © 2013 Flávio C. Cabrera et al.

Design and development of new green catalytic methodologies for the synthesis of enantiomerically enriched molecules

The following Ph.D work was mainly focused on catalysis, as a key technology, to achieve the objectives of sustainable (green) chemistry. After introducing the concepts of sustainable (green) chemistry and an assessment of new sustainable chemical technologies, the relationship between catalysis and sustainable (green) chemistry was briefly discussed and illustrated via an analysis of some selected and relevant examples. Afterwards, as a continuation of the ongoing interest in Dr. Marco Bandini’s group on organometallic and organocatalytic processes, I addressed my efforts to the design and development of novel catalytic green methodologies for the synthesis of enantiomerically enriched molecules. In the first two projects the attention was focused on the employment of solid supports to carry out reactions that still remain a prerogative of omogeneous catalysis. Firstly, particular emphasis was addressed to the discovery of catalytic enantioselective variants of nitroaldol condensation (commonly termed Henry reaction), using a complex consisting in a polyethylene supported diamino thiopene (DATx) ligands and copper as active species. In the second project, a new class of electrochemically modified surfaces with DATx palladium complexes was presented. The DATx-graphite system proved to be efficient in promoting the Suzuki reaction. Moreover, in collaboration with Prof. Wolf at the University of British Columbia (Vancouver), cyclic voltammetry studies were reported. This study disclosed new opportunities for carbon–carbon forming processes by using heterogeneous, electrodeposited catalyst films. A straightforward metal-free catalysis allowed the exploration around the world of organocatalysis. In fact, three different and novel methodologies, using Cinchona, Guanidine and Phosphine derivatives, were envisioned in the three following projects. An interesting variant of nitroaldol condensation with simple trifluoromethyl ketones and also their application in a non-conventional activation of indolyl cores by Friedel-Crafts-functionalization, led to two novel synthetic protocols. These approaches allowed the preparation of synthetically useful trifluoromethyl derivatives bearing quaternary stereocenters. Lastly, in the sixth project the first γ-alkylation of allenoates with conjugated carbonyl compounds was envisioned. In the last part of this Ph.D thesis bases on an extra-ordinary collaboration with Prof. Balzani and Prof. Gigli, I was involved in the synthesis and characterization of a new type of heteroleptic cyclometaled-Ir(III) complexes, bearing bis-oxazolines (BOXs) as ancillary ligands. The new heteroleptic complexes were fully characterized and in order to examine the electroluminescent properties of FIrBOX(CH2), an Organic Light Emitting Device was realized.

Derivati naturali dell'acido difenolico per la sostituzione del bisfenolo A

La produzione di materie plastiche da fonti rinnovabili è oggi uno dei principali obiettivi della chimica dei polimeri. Anche se i materiali termoplastici da fonte “bio” sono stati già ampiamente studiati, non si può affermare lo stesso per i termoidurenti. Le resine epossidiche sono ampiamente usate come rivestimenti, adesivi e materiali strutturali grazie alle loro eccezionali proprietà meccaniche e alla buona resistenza al calore. Nonostante ciò, la ricerca svolta in questo campo su tali materiali è molto limitata e la loro produzione deriva ancora dalla reazione tra epicloridrina, cancerogena, e bisfenolo A, sospettato di avere effetti sul sistema ormonale. Per questo, la possibilità di trovare un sostituto per il bisfenolo A è un punto cruciale della chimica per dare una risposta eco-sostenibile alla domanda dei consumatori. L’acido difenolo è stato identificato come un buon canditato per la sostituzione del bisfenolo A, grazie alla similarità delle loro strutture. Dal momento che esso deriva dalla reazione tra acido levulinico, derivante da biomassa e fenolo, è possibile considerarlo un reagente di origine bio. Lo scopo di questo lavoro è quello di sostituire il fenolo con composti fenolici di origine naturale come m-cresolo, guaiacolo, catecolo e resorcinolo. Le molecole risultanti saranno confrontate con il bisfenolo A per ciò che concerne la possibilità di formare i rispettivi glicidil eteri tramite reazione con epicloridrina. Questo permetterebbe la formazione di un pre-polimero epossidico proveniente da fonte rinnovabile in un prossimo futuro.