Use of solvents and environmental friendly materials for applications in Green Chemistry

The present Thesis studies three alternative solvent groups as sustainable replacement of traditional organic solvents. Some aspects of fluorinated solvents, supercritical fluids and ionic liquids, have been analysed with a critical approach and their effective “greenness” has been evaluated from the points of view of the synthesis, the properties and the applications. In particular, the attention has been put on the environmental and human health issues, evaluating the eco-toxicity, the toxicity and the persistence, to underline that applicability and sustainability are subjects with equal importance. The “green” features of fluorous solvents and supercritical fluids are almost well-established; in particular supercritical carbon dioxide (scCO2) is probably the “greenest” solvent among the alternative solvent systems developed in the last years, enabling to combine numerous advantages both from the point of view of industrial/technological applications and eco-compatibility. In the Thesis the analysis of these two classes of alternative solvents has been mainly focused on their applicability, rather than the evaluation of their environmental impact. Specifically they have been evaluated as alternative media for non-aqueous biocatalysis. For this purpose, the hydrophobic ion pairing (HIP), which allows solubilising enzymes in apolar solvents by an ion pairing between the protein and a surfactant, has been investigated as effective enzymatic derivatisation technique to improve the catalytic activity under homogeneous conditions in non conventional media. The results showed that the complex enzyme-surfactant was much more active both in fluorous solvents and in supercritical carbon dioxide than the native form of the enzyme. Ionic liquids, especially imidazolium salts, have been proposed some years ago as “fully green” alternative solvents; however this epithet does not take into account several “brown” aspects such as their synthesis from petro-chemical starting materials, their considerable eco-toxicity, toxicity and resistance to biodegradation, and the difficulty of clearly outline applications in which ionic liquids are really more advantageous than traditional solvents. For all of these reasons in this Thesis a critical analysis of ionic liquids has been focused on three main topics: i) alternative synthesis by introducing structural moieties which could reduce the toxicity of the most known liquid salts, and by using starting materials from renewable resources; ii) on the evaluation of their environmental impact through eco-toxicological tests (Daphnia magna and Vibrio fischeri acute toxicity tests, and algal growth inhibition), toxicity tests (MTT test, AChE inhibition and LDH release tests) and fate and rate of aerobic biodegradation in soil and water; iii) and on the demonstration of their effectiveness as reaction media in organo-catalysis and as extractive solvents in the recovery of vegetable oil from terrestrial and aquatic biomass. The results about eco-toxicity tests with Daphnia magna, Vibrio fischeri and algae, and toxicity assay using cultured cell lines, clearly indicate that the difference in toxicity between alkyl and oxygenated cations relies in differences of polarity, according to the general trend of decreasing toxicity by decreasing the lipophilicity. Independently by the biological approach in fact, all the results are in agreement, showing a lower toxicity for compounds with oxygenated lateral chains than for those having purely alkyl lateral chains. These findings indicate that an appropriate choice of cation and anion structures is important not only to design the IL with improved and suitable chemico-physical properties but also to obtain safer and eco-friendly ILs. Moreover there is a clear indication that the composition of the abiotic environment has to be taken into account when the toxicity of ILs in various biological test systems is analysed, because, for example, the data reported in the Thesis indicate a significant influence of salinity variations on algal toxicity. Aerobic biodegradation of four imidazolium ionic liquids, two alkylated and two oxygenated, in soil was evaluated for the first time. Alkyl ionic liquids were shown to be biodegradable over the 6 months test period, and in contrast no significant mineralisation was observed with oxygenated derivatives. A different result was observed in the aerobic biodegradation of alkylated and oxygenated pyridinium ionic liquids in water because all the ionic liquids were almost completely degraded after 10 days, independently by the number of oxygen in the lateral chain of the cation. The synthesis of new ionic liquids by using renewable feedstock as starting materials, has been developed through the synthesis of furan-based ion pairs from furfural. The new ammonium salts were synthesised in very good yields, good purity of the products and wide versatility, combining low melting points with high decomposition temperatures and reduced viscosities. Regarding the possible applications as surfactants and biocides, furan-based salts could be a valuable alternative to benzyltributylammonium salts and benzalkonium chloride that are produced from non-renewable resources. A new procedure for the allylation of ketones and aldehydes with tetraallyltin in ionic liquids was developed. The reaction afforded high yields both in sulfonate-containing ILs and in ILs without sulfonate upon addition of a small amount of sulfonic acid. The checked reaction resulted in peculiar chemoselectivity favouring aliphatic substrates towards aromatic ketones and good stereoselectivity in the allylation of levoglucosenone. Finally ILs-based systems could be easily and successfully recycled, making the described procedure environmentally benign. The potential role of switchable polarity solvents as a green technology for the extraction of vegetable oil from terrestrial and aquatic biomass has been investigated. The extraction efficiency of terrestrial biomass rich in triacylglycerols, as soy bean flakes and sunflower seeds, was comparable to those of traditional organic solvents, being the yield of vegetable oils recovery very similar. Switchable polarity solvents as been also exploited for the first time in the extraction of hydrocarbons from the microalga Botryococcus braunii, demonstrating the efficiency of the process for the extraction of both dried microalgal biomass and directly of the aqueous growth medium. The switchable polarity solvents exhibited better extraction efficiency than conventional solvents, both with dried and liquid samples. This is an important issue considering that the harvest and the dewatering of algal biomass have a large impact on overall costs and energy balance.

Partnership fra terzo Settore e Istituzioni Locali nelle Politiche Family Friendly: Il "Distretto famiglia"

L’idea fondamentale da cui prende avvio la presente tesi di dottorato è che sia possibile parlare di una svolta nel modo di concettualizzare e implementare le politiche sociali, il cui fuoco diviene sempre più la costruzione di reti di partnership fra attori pubblici e privati, in cui una serie di soggetti sociali plurimi (stakeholders) attivano fra loro una riflessività relazionale. L’ipotesi generale della ricerca è che, dopo le politiche improntate a modelli statalisti e mercatisti, o un loro mix, nella politica sociale italiana emerga l’esigenza di una svolta riflessiva e relazionale, verso un modello societario, sussidiario e plurale, e che di fatto – specie a livello locale – stiano sorgendo molte iniziative in tal senso. Una delle idee più promettenti sembra essere la creazione di distretti sociali per far collaborare tra loro attori pubblici, privati e di Terzo settore al fine di creare forme innovative di servizi per la famiglia e la persona. La presente tesi si focalizza sul tentativo della Provincia di Trento di distrettualizzare le politiche per la famiglia. Tramite l’analisi del progetto “Trentino – Territorio Amico della Famiglia” e di una sua verticalizzazione, il Distretto Famiglia, si è studiato l’apporto delle partnership pubblico-privato nella formazione di strumenti innovativi di governance che possano determinare una svolta morfogenetica nell’elaborazione di politiche per la famiglia. Le conclusioni del lavoro, attraverso una comparazione tra esperienze territoriali, presentano la differenziazione delle partnership sociali, in base ad alcuni variabili (pluralità di attori, pluralità di risorse, shared project, capitale sociale, decision making, mutual action, logiche di lavoro relazionale, sussidiarietà). Le diverse modalità di gestione delle partnership (capacitante, professionale e generativa) sintetizzano i portati culturali, strutturali e personali coinvolti nelle singole costruzioni. Solo le partnership che interpretano il loro potenziale regolativo e promozionale secondo la riflessività relazionale tendono a generare beni comuni nel contesto sociale.

New eco-friendly polyesters from renewable resources

Nowadays the development of sustainable polymers, with convenient properties to substitute the traditional petroleum-based materials, is one of the major issues for material science. The utilization of renewable resources as feedstock for biopolyesters is a challenging target.The research work described in the present thesis is strictly connected to these urgent necessities and is focused mainly in finding new biopolymers, in particular biopolyesters, which are obtainable from biomass and characterized by a wide range of properties, in order to potentially substitute polyolefins and aromatic polyesters (for example, poly(ethylene terephthalate))

Logiche modali e logiche independence friendly

Analisi di logiche modali con quantificatori parzialmente ordinati.

Bex: un ambiente user-friendly per esplorare articoli scientifici e bibliografie

Un'applicazione web user-friendly di supporto ai ricercatori per l'esecuzione efficiente di specifici tasks di ricerca e analisi di articoli scientifici

KrigInv: An efficient and user-friendly implementation of batch-sequential inversion strategies based on kriging

Several strategies relying on kriging have recently been proposed for adaptively estimating contour lines and excursion sets of functions under severely limited evaluation budget. The recently released R package KrigInv 3 is presented and offers a sound implementation of various sampling criteria for those kinds of inverse problems. KrigInv is based on the DiceKriging package, and thus benefits from a number of options concerning the underlying kriging models. Six implemented sampling criteria are detailed in a tutorial and illustrated with graphical examples. Different functionalities of KrigInv are gradually explained. Additionally, two recently proposed criteria for batch-sequential inversion are presented, enabling advanced users to distribute function evaluations in parallel on clusters or clouds of machines. Finally, auxiliary problems are discussed. These include the fine tuning of numerical integration and optimization procedures used within the computation and the optimization of the considered criteria.

White matter in aphasia: a historical review of the Dejerines' studies

The Objective was to describe the contributions of Joseph Jules Dejerine and his wife Augusta Dejerine-Klumpke to our understanding of cerebral association fiber tracts and language processing. The Dejerines (and not Constantin von Monakow) were the first to describe the superior longitudinal fasciculus/arcuate fasciculus (SLF/AF) as an association fiber tract uniting Broca's area, Wernicke's area, and a visual image center in the angular gyrus of a left hemispheric language zone. They were also the first to attribute language-related functions to the fasciculi occipito-frontalis (FOF) and the inferior longitudinal fasciculus (ILF) after describing aphasia patients with degeneration of the SLF/AF, ILF, uncinate fasciculus (UF), and FOF. These fasciculi belong to a functional network known as the Dejerines' language zone, which exceeds the borders of the classically defined cortical language centers. The Dejerines provided the first descriptions of the anatomical pillars of present-day language models (such as the SLF/AF). Their anatomical descriptions of fasciculi in aphasia patients provided a foundation for our modern concept of the dorsal and ventral streams in language processing.

Headache and transient aphasia in a 35-year-old female patient

We describe the case of a 35-year-old female patient who suffered from fulminant tick-borne encephalitis and subsequently died. Remarkable about this case was that the woman was not living in an endemic area and that the disease occurred outside the usual season. Furthermore, this indicates that an increase in transmission of tick-borne encephalitis can be expected outside the classical endemic areas in higher altitudes, possibly as a consequence of climate changes.