From Lignocellulosic Biomass to Rare Sugars: Hydrolisis and Isomerization with Heterogeneous Catalysts

The PhD project presented in this thesis focused on two research topics turned to contribute to the development of a modern model of production, that is able to reduce the environmental impact of the chemical industry. For this purpose, preparation and characterization of heterogeneous catalysts for the transformation of renewable raw materials into valuable chemicals has been studied. The first part of the work concerned the conversion of lignocellulosic biomass, the most abundant renewable source presents on Earth, into monosaccharides and bio-building blocks, such as HMF, furfural and levulinic acid. Solid acid metal phosphate catalysts were synthetized for lignocellulose transformation; the catalytic behaviors shown by prepared metal phosphates were correlated to their physical-chemical properties: in particular, the role of acid features on the hydrolysis reaction has been studied. The synthesis of interesting industrial monosaccharides that cannot be obtained in appreciable amount from natural resources, called rare sugars, was the topic of the second part of the work. For this purpose, the rearrangement of glucose by the use of heterogeneous catalysts containing titanium was studied: especially, the influence of the different Ti species on products distribution has been investigated

Microalgae as a Nutraceutical Tool to Antagonize the Impairment of Redox Status Induced by SNPs: Implications on Insulin Resistance

Microalgae represent a growing innovative source of nutraceuticals such as carotenoids and phenolic compound which are naturally present within these single-celled organisms or can be induced in response to specific growth conditions. The presence of the unfavourable allelic variant in genes involved in the control of oxidative stress, due to one or more SNPs in gene encoding protein involved in the regulation of redox balance, can lead to pathological conditions such as insulin resistance, which, in turn, is directly involved in the pathogenesis of type 2 diabetes mellitus. In this review we provide an overview of the main SNPs in antioxidant genes involved in the promotion of insulin resistance with a focus on the potential role of microalgae-derived antioxidant molecules as novel nutritional tools to mitigate oxidative stress and improve insulin sensitivity

Growth Inhibition of Retinoblastoma Cell Line by Exosome-Mediated Transfer of miR-142-3p

Retinoblastoma (Rb) is the most common ocular paediatric malignancy and is caused by a mutation of the two alleles of the tumor suppressor gene, RB1. The tumor microenvironment (TME) represents a complex system whose function is not yet well defined and where microvesicles, such as exosomes, play a key role in intercellular communication. Micro-RNAs (mRNAs) have emerged as important modifiers of biological mechanisms involved in cancer and been able to regulate tumor progression. Methods: Co-culture of monocytes with retinoblastoma cell lines, showed a significant growth decrease. Given the interaction between Rb cells and monocytes, we investigated the role of the supernatant in the cross-talk between cell lines, by taking the product of the co-culture and then using it as a culture medium for Rb cells. Results: miR-142-3p showed to be particularly over-expressed both in the Rb cell line and in the medium used for their culture, comparing to control cell line and the normal supernatant, respectively. Therefore, we provided evidence that miR-142-3p is released by monocytes in the co-culture medium's exosomes and that it is subsequently up-taken by Rb cells, causing the inhibition of proliferation of Rb cell line by affecting cell cycle progression. Conclusion: This study highlights the role of exosomic miR-142-3p in the TME of Rb and identifies new molecular targets, which are able to control tumor growth aiming the development of a forward-looking miR-based strategy

INSPEcT: a computational tool to infer mRNA synthesis, processing and degradation dynamics from RNA- and 4sU-seq time course experiments.

Abstract Motivation: Cellular mRNA levels originate from the combined action of multiple regulatory processes, which can be recapitulated by the rates of pre-mRNA synthesis, pre-mRNA processing and mRNA degradation. Recent experimental and computational advances set the basis to study these intertwined levels of regulation. Nevertheless, software for the comprehensive quantification of RNA dynamics is still lacking. Results: INSPEcT is an R package for the integrative analysis of RNA- and 4sU-seq data to study the dynamics of transcriptional regulation. INSPEcT provides gene-level quantification of these rates, and a modeling framework to identify which of these regulatory processes are most likely to explain the observed mRNA and pre-mRNA concentrations. Software performance is tested on a synthetic dataset, instrumental to guide the choice of the modeling parameters and the experimental design. Availability and implementation: INSPEcT is submitted to Bioconductor and is currently available as Supplementary Additional File S1. Contact: [email protected] Supplementary Information: Supplementary data are available at Bioinformatics online

Principle of non-discrimination in article III of GATT and the GATT/WTO jurisprudence of "Like Products"

The analysis of non-discrimination under Article III of GATT has shown weakness or flaws throughout more than fifty years. The language used by GATT/WTO panels and the Appellate Body in interpreting the two prongs of non-discrimination in the national treatment clause, namely, likeness and protection, lagged behind economic reality. The critical legal analysis carried out in here reveals, to some extent, this while offering a clearer and sounder analysis to non-discrimination based more on market analysis and its economic indicators.Doctorat en droitinfo:eu-repo/semantics/nonPublishe

Nuovi catalizzatori e processi per la produzione industriale di anidride maleica

La sintesi industriale di anidride maleica (AM) è realizzata mediante ossidazione selettiva di n-butano con un catalizzatore a base di ossidi misti di vanadio e fosforo, il pirofosfato di vanadile, (VO)2P2O7. Allo stesso tempo però, la necessità di sviluppare nuovi processi per la sintesi di molecole piattaforma a partire da fonti rinnovabili, ha portato a sviluppare un processo di produzione di AM a partire da 1-butanolo. Lo studio condotto nel seguente lavoro di tesi, prenderà in considerazione aspetti relativi ad entrambi i processi di produzione di AM: sintesi a partire da n-butano e sintesi a partire da 1-butanolo. Per quanto riguarda l’utilizzo di 1-butanolo, ci si concentrerà sullo studio della prima fase della reazione di sintesi di AM, ossia la disidratazione di 1-butanolo a dare buteni, primi intermedi nella reazione di sintesi della AM, mediante l’utilizzo di catalizzatori a base di composti poliossometallati di tipo Keggin supportati a diversa composizione. Per quello che è invece il processo industriale attuale, ossia la sintesi a partire da n-butano, si studieranno e confronteranno le prestazioni di due sistemi catalitici che vengono comunemente utilizzati in impianto industriale, con lo scopo di ottenere, in laboratorio, informazioni utili al miglioramento del processo industriale stesso

Optical tissue clearing associated with 3D imaging: application in preclinical and clinical studies

Understanding the inner morphology of intact tissues is one of the most competitive challenges in modern biology. Since the beginning of the twentieth century, optical tissue clearing (OTC) has provided solutions for volumetric imaging, allowing the microscopic visualization of thick sections of tissue, organoids, up to whole organs and organisms (for example, mouse or rat). Recently, tissue clearing has also been introduced in clinical settings to achieve a more accurate diagnosis with the support of 3D imaging. This review aims to give an overview of the most recent developments in OTC and 3D imaging and to illustrate their role in the field of medical diagnosis, with a specific focus on clinical applications

Catalyst and process for the synthesis of fatty acids esters

The oresent invention relates to an heterogeneous catalyst comprising silica and a metal oxide from the group consisting of magnesium oxide, CaO, BaO and ZnO. The invention also relates to a process for preparing esters of one or more fatty acidswith one or more alcohol

Integrated catalytic process for biomass hydrolysis: a comparison of different pretreatments and catalysts

The conversion of lignocellulose biomass into valuable chemicals is one of the pillars of the biorefinery, the aim of which is to develop integrated processes for the transformation of renewables collected from agricultural, forestry and urban waste into “bio-platform molecules”. For these reasons, there is a great interest in developing reusable solid acid catalysts, which are effective in cellulose transformation, in place of the traditional processes that make use of mineral acids. The starting point of the transformation chain is the deconstruction of the lignocellulose and depolymerization of the hemicellulose and cellulose to give monosaccharides, or even transform sugars into other valuable bio-based building blocks. The aim of this work is to compare the performance of metal phosphates catalysts, zirconium and niobium phosphates, in cellulose and lignocellulose (conifer wood sawdust) hydrolysis, after pretreatment of the biomass with different procedures. Two different types of pretreatment were investigated: a mechanical pretreatment, in which the substrate was subjected to a 48-hours treatment in a high-energy ball mill, and a thermal pretreatment, in which biomass was autohydrolyzed at 180°C for 1 hour in a monomodal microwave reactor. Results of tests conducted with metal phosphate catalysts on cellulose and lignocellulose, either as such or after the two different treatments, showed that pretreatments were effective in facilitating the hydrolysis: in particular, with pretreated substrates, we observed an important improvement of catalytic performance. As regards catalytic behaviors, the differences of performances between the two metal phosphates can be explained by invoking both the different total concentration and type of acid sites

Le iniziative dell'Unione europea sul lavoro tramite piattaforme digitali

l dibattito svoltosi il 30 maggio 2022 offre un confronto aperto tra giuristi, donne e uomini, esperti nei diversi campi interessati dalla proposta di Direttiva del 2021 volta a regolare l’attività di lavoro inter- mediata dalle piattaforme: dal diritto del lavoro a quello della concorrenza, dall’intelligenza artificiale al rispetto della privacy. Si è discusso sull’idoneità della proposta di Direttiva ad assicurare a tutti i lavo- ratori i diritti sociali fondamentali (lavoristici e previdenziali) ed a realizzare criteri di trasparenza e con- trollo sulle decisioni adottate in via algoritmica dalle piattaforme, sul ruolo che i sindacati potrebbero ave- re in questo processo, sul rapporto tra questa iniziativa e quella connessa di formulazione di guidelines della Commissione europea in ordine all’ammissibilità della contrattazione collettiva da parte di lavora- tori autonomi in situazione di disparità negoziale con le controparti, in modo da superare o circoscrivere la giurisprudenza della Corte di Giustizia in questa materia. Ancora si è affrontato il tema delle ricadute della futura Direttiva sulle legislazioni interne e sulla possibilità che questa offra un orientamento più saldo ed univoco ai giudici nazionali per qualificare i rapporti di lavoro