Dipartimento di Chimica e Tecnologie Chimiche - Tesi di Dottorato
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Questa collezione raccoglie le Tesi di Dottorato afferenti al Dipartimento di Chimica e Tecnologie Chimiche dell'Università della Calabria.
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Item New Catalyzed Approaches For The One-Step Synthesis Of High Value-Added Products(Università della Calabria, 2021-10-28) Amuso, Roberta; Critelli, Salvatore; Gabrele, Bartolo; Veltri, LuciaHeterocyclic compounds play an important role in synthetic and bioorganic chemistry, as they represent a structural motif in a large number of biologically active natural and non-natural compounds. The synthesis of new heterocycles possessing biological activity and the development of innovative and accessible synthetic pathways are currently a very widespread research area. In the present PhD thesis is reported the development of new synthetic, simple and innovative methodologies in one step for the direct formation of high value-added compounds by the catalytic activation of simple building blocks, CO and CO2. CO is a simplest and most available C-1 unit, which meets the requirements of “atom economy”, step economy and “green chemistry”; the possibility to synthesize molecules of important pharmacological interest by a direct carbonylation procedure involving the use of carbon monoxide represent a very attractive alternative synthetic approach. CO2 is the main component of greenhouse gases, responsible for the increase in the earth's temperature and anomalous climate changes. Thus, post-combustion COIn fact, carbon dioxide can be considered as a ubiquitous, cheap, abundant, non-toxic, non-flammable and renewable C1 source, which has great importance from the viewpoint of both environmental protection and resource utilization. In the first chapter is reported a new example of an additive cyclocarbonylation process leading to 1-thia-4a,9-diazafluoren-4-ones, an important class of polyheterocyclic compounds known to possess important pharmacological activities. Part of this PhD was spent at Leibniz Institute for Catalysis in Rostock University. Here, ruthenium PNP pincer complexes bearing supplementary cyclometalated C,N-bound ligands have been prepared and fully characterized for the first time. The advantages of the new catalysts are demonstrated in the general green α-alkylation of ketones with alcohols following a hydrogen autotransfer protocol. Furthermore, other cyclometalated ruthenium complexes bearing bidentate ligand were obtained for methylation of anilines with methanol to selectively give N-methylanilines. The hydrogen autotransfer procedure has been applied under mild conditions (60 °C) in a practical manner (NaOH as base).2 capture and its conversion into high value-added chemicals are integral parts of today’s green energy industry.Item Green biomaterials and advanced technologies for road pavements(Università della Calabria, 2021-04-08) Ashimova, Saltanat Zhandarbekovna; Cerra, Maria Carmela; Rossi, Cesare Oliverio; Burkhanbaevich, Teltayev BagdatThe main objective aims at developing methodologies and new biomaterials for the sustainability assessment of “green bituminous mixtures”. “Green bituminous mixtures” is used in the context as a general term for all types of bituminous mixtures in which specific materials or technologies are used with the aim of reducing the environmental impact and of reducing health risks of workers. In the present research new bioadditives were developed and tested to improve the adhesion between bitumen and stones, to modify the rheological characteristic of the bitumen as well as rejuvenating properties of the bitumen.Item Production of new bituminous materials (ecobinders)by recycling waste oil and rubber from end-of-life tire ("Crumb Rubber")(Università della Calabria, 2021) Porto, Michele; Cerra, Maria Carmela; Rossi, CesareNowadays the main problems faced by applied research and industry are towards environmental issues such as global warming, carbon footprint, reduction of greenhouse gas emission amongst others. The Kyoto Treaty was developed as a result in 1997 to setting the objective for European countries to develop policies and technologies in order to meet greenhouse gas reduction requirements. In this light, the asphalt industry accordingly implemented measures to facilitate eco-friendly operations. Examples of some of these measures include the introduction of the use of Warm Mix Asphalt (WMA) and Reclaimed Asphalt Pavement (RAP) which reduce production costs and reduce CO2 emissions. Another initiative used to address environmental problems is resource conservation which has made the use, recovery and recycling of resources more practical and effective in not only reducing production costs but also in making a regenerative circular economy. An example of this initiative is an innovation called End of Waste (EoW) product through which waste is converted into a new product and it is proving very practical and effective in recent times. The End of Waste (EoW) criteria means recovery and treatment processes under which waste could be converted in a new potential product. In particular, according to the European normative the main requirements for a given waste - possibly treated by industrial processes - to satisfy the EoW qualification are the following: a) the substance or object is intended to be used for specific purposes; b) there is a market or demand for this substance or object; c) the substance or object meets the technical requirements for the specific purposes and complies with the existing legislation and standards applicable to the products; d) the use of the substance or object will not lead to overall negative impacts on the environment or human health (in accordance with the Substance of Very High Concern (SVHC) list) From this perspective, the reuse of opportunely re-refined exhausted oils from automobile and industrial hydraulic applications - that have become unfit for the use for which they were originally intended - completely fulfil the circular economy goals. This PhD thesis deals with the conversion of End of Waste Product (EoW) in the form of Re-refined Engine Oil Bottom (REOB) obtained from exhausted oil regeneration processes – through the addition of recycled industrial waste materials - to high performing bituminous binder suitable for use in asphalt mix production. This can save the asphalt industry an even larger amount of resources if it is normalized to practice using this new potentially revolutionary binder together with Reclaimed Asphalt Pavement (RAP) which reduces the need for virgin aggregates in asphalt mix production. Indeed, in the present work asphalt concrete samples have been obtained by using 100 % Reclaimed Asphalt Pavement (RAP) aggregates. The asphalt concrete samples thus obtained underwent testing in order to study their behaviour with the goal to substitute virgin aggregates that are commonly employed in asphalt pavement. This would allow to reach the standards of most of the European countries where RAP is already used in the range of 70-90%, while up to now in Italy a maximum of 30% of RAP is used in the Hot Mix Asphalt (HMA) and Warm Mix Asphalt (WMA). The aged and more brittle bituminous binder that coats the aggregates limits the use of RAP material as it stiffens the resulting asphalt mixtures making the pavements more brittle and sometimes more prone to cracking especially at low temperatures. To overcome this problem a rejuvenating agent could be used.Item Design and development of a flexible and low-cost electrochromic device for smart windows(Università della Calabria, 2022-05-10) Parisi, Francesco; Cipparrone, Gabriella; La Deda, MassimoItem Development of new bio-materials and technologies for the green regeneration of RAP(Università della Calabria, 2021) Loise, Valeria; Cerra, Maria Carmela; Oliverio Rossi, CesareIl presente lavoro di ricerca ha avuto come scopo lo sviluppo di nuovi rigeneranti green per il fresato d’asfalto, noto anche come reclaimed asphalt pavement (RAP). Questa ricerca nasce dalla necessità di aumentare l’uso del RAP nelle pavimentazioni stradali. L’uso del RAP ha sia un impatto economico positivo, infatti non è necessario usare inerti e bitume fresco, ma soprattutto ha un alto un impatto in termini di ecosostenibilità, il RAP da rifiuto da smaltire diventa di fatto materia prima, implementando l’economia circolare e l’end waste. Infatti il riuso del fresato d’asfalto consentirebbe di non trattare più questo materiale come uno scarto, con tutti le relative problematiche ambientali derivabili, ma bensì come una risorsa. Inoltre sono state sviluppate ed implementate tecniche di indagine chimico-fisiche e nuove metodologie per determinare i meccanismi di azione di un rigenerante sulla struttura del bitume e distinguere in modo univoco un rigenerante da un semplice flussante. Tale tesi è stata la base scientifica che ha permesso di definire una norma europea e nazionale da seguire per le aziende che commercializzano rigeneranti bituminosi. Spesso infatti il fresato d’asfalto viene trattato con agenti che non modificano la struttura colloidale del bitume riportandola alla loro struttura originaria, ma che semplicemente hanno una mera attività flussante (abbassare la viscosità del sistema). Le “classiche” metodologie di indagine generalmente basate su parametri fisici-meccanici ed ingegneristici, non sono sufficienti per discriminare l’azione di un rigenerante da quella di un flussante. Tale approccio finora comunemente usato ha avuto un forte impatto sulla durata e qualità delle pavimentazioni stradali, effetto devastante dal punto di vista economico, sociale e soprattutto ambientale. The present research aimed to develop a procedure and methodologies that could uniquely distinguish between a fluxing agent and a rejuvenating agent. Recently, it has been realized that the reclaimed asphalt pavement (RAP) was a resource of considerable importance. In fact, it contains an appreciable amount of binder, which under certain conditions can be recycled for the construction of new pavements, thus reducing not only costs but also the use of raw materials. Therefore, this allows to consider the RAP more as a resource than a waste. Most of the time, the bitumen obtained from the RAP is treated with agents that have a mere flux function (lowering the viscosity of the system). These agents do not modify the colloidal structure of the bitumen. Therefore, they are not able to restore the structure of the aged bitumen to that of the neat bitumen. Furthermore, the investigation methodologies generally used to counter the regenerating effect of an additive are based on physical-mechanical and engineering parameters. These parameters are almost always insufficient to discriminate the action of a regenerant from that of a flux. For this reason, chemical-physical investigation techniques have been developed and implemented to determine the action mechanisms of a rejuvenator on the inner structure of the bitumen. In this way, it was possible to uniquely discriminate between a real rejuvenator and a fluxing agent. Finally, this thesis was the scientific basis that allowed the definition of a new European and National standard to be followed for companies that market bituminous regenerants.Item A computational mechanistic study of potentially evolving platinum based anticancer drugs(Università della Calabria, 2021) Dabbish, Eslam; Andò, Sebastiano; Sicilia, EmiliaMetals are known to play a fundamental physiological role inside human body affecting many of the biological functions. Analogously, metal based drugs can also have a similar impact. Cisplatin, a simple platinum complex, is well known to be a cytotoxic agent and the first approved and most widely used metal based drug for fighting cancer. Currently, used platinum containing anticancer agents namely cisplatin, carboplatin and oxaliplatin suffer from serious toxic side effects as well as acquired and inherent drug resistance against many types of cancer. Consequently, new platinum anticancer drug families evolved to overcome the current limitations of traditional platinum drugs. Monofunctional platinum complexes, Pt(IV) complexes, platinum complexes targeting mitochondria, platinum idodio derivatives and photoactivated platinum compounds are examples of some of such newly developed platinum based cytotoxic families. Computational chemistry has strongly grown over the past years with both the increase in computers capabilities and the development of new theories and efficient algorithms that can allow to handle bigger models in a reasonable time. Molecular modelling can give a wealth of information about the studied systems in terms of energies, electronic properties, geometries, conformations, structure/activity relationships, reaction mechanisms and many others. By using quantum mechanical methods like Density Functional Theory (DFT) and its time-dependant formulation TD-DFT and molecular dynamics (MD) computational tools, the mechanism of action of some selected examples of non-traditional platinum anticancer drug families have been studied in this thesis. Phenanthriplatin is the most effective member of a new class of platinum anticancer agents (7-40 times more active than cisplatin) known as monofunctional platinum anticancer drugs. In addition, it has started its clinical trials phase. Our computational mechanistic study of phenanthriplatin highlighted the importance of the role played by its unique chemical structure in the drug activation, interaction with DNA and transcription blockage. Targeting of mitochondrial DNA by means of platinum drugs can lead to mitochondrial dysfunction in cancer cells that causes tumour cells growth inhibition and apoptosis. We have undertaken a comparative study between three different isomers of a recently prepared triphenyl phosphonium modified monofunctional platinum complexes for their mechanism of action. Pt(IV) complexes are prodrugs that are reduced inside the body by means of abundant biological reducing agents like ascorbic acid to release the equivalent cytotoxic Pt(II) complexes. This reduction step is considered to be the limiting step for the activity of such class of drugs. In a series of studies, we have carried out a detailed mechanistic study to understand the relation between the nature of Pt(IV) complexes axial and equatorial ligands and the extent and mechanism of reduction by means of ascorbic acid at physiological pH. We highlighted the particular importance and impact of the nature of axial ligands on the reduction process. Photoactivated chemotherapy (PACT) technique allows the localized activation of drugs by means of specific wavelength light. A recently synthesized complex named platicur is a cis-diammineplatinum(II) complex of curcumin in which the Pt(II) centre is bound to a curcumin molecule as the leaving ligand. Upon light irradiation curcumin molecule is released together with the doubly aquated Pt(II) complex that can exert the required cytotoxic effect. In our study, we have provided a deep insight in the photoactivated excited states and their role in the photocleavage mechanism with the release of curcumin.Item Dinamiche fisiologiche e molecolari in Arthrospira maxima durante il trattamento con glifosato e microplastiche(2021-12-12) Nisticò, Dante; Angelone, Tommaso; Mazzuca, Silvia; Calabrò, Vincenza