14 resultados para High-value solutes

em AMS Tesi di Dottorato - Alm@DL - Università di Bologna


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This PhD thesis describes set up of technological models for obtaining high health value foods and ingredients that preserve the final product characteristics as well as enrich with nutritional components. In particular, the main object of my research has been Virgin Olive Oil (VOO) and its important antioxidant compounds which differentiate it from all other vegetables oils. It is well known how the qualitative and quantitative presence of phenolic molecules extracted from olives during oil production is fundamental for its oxidative and nutritional quality. For this purpose, agronomic and technological conditions of its production have been investigated. It has also been examined how this fraction can be better preserved during storage. Moreover, its relation with VOO sensorial characteristics and its interaction with a protein in emulsion foods have also been studied. Finally, an experimental work was carried out to determine the antioxidative and heat resistance properties of a new antioxidant (EVS-OL) when used for high temperature frying such as is typically employed for the preparation of french fries. Results of the scientific research have been submitted for a publication and some data has already been published in national and international scientific journals.

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The olive oil extraction industry is responsible for the production of high quantities of vegetation waters, represented by the constitutive water of the olive fruit and by the water used during the process. This by-product represent an environmental problem in the olive’s cultivation areas because of its high content of organic matter, with high value of BOD5 and COD. For that reason the disposal of the vegetation water is very difficult and needs a previous depollution. The organic matter of vegetation water mainly consists of polysaccharides, sugars, proteins, organic acids, oil and polyphenols. This last compounds are the principal responsible for the pollution problems, due to their antimicrobial activity, but, at the same time they are well known for their antioxidant properties. The most concentrate phenolic compounds in waters and also in virgin olive oils are secoiridoids like oleuropein, demethyloleuropein and ligstroside derivatives (the dialdehydic form of elenolic acid linked to 3,4-DHPEA, or p-HPEA (3,4-DHPEA-EDA or p-HPEA-EDA) and an isomer of the oleuropein aglycon (3,4-DHPEA-EA). The management of the olive oil vegetation water has been extensively investigated and several different valorisation methods have been proposed, such as the direct use as fertilizer or the transformation by physico-chemical or biological treatments. During the last years researchers focused their interest on the recovery of the phenolic fraction from this waste looking for its exploitation as a natural antioxidant source. At the present only few contributes have been aimed to the utilization for a large scale phenols recovery and further investigations are required for the evaluation of feasibility and costs of the proposed processes. The present PhD thesis reports a preliminary description of a new industrial scale process for the recovery of the phenolic fraction from olive oil vegetation water treated with enzymes, by direct membrane filtration (microfiltration/ultrafiltration with a cut-off of 250 KDa, ultrafiltration with a cut-off of 7 KDa/10 KDa and nanofiltration/reverse osmosis), partial purification by the use of a purification system based on SPE analysis and by a liquid-liquid extraction system (LLE) with contemporary reduction of the pollution related problems. The phenolic fractions of all the samples obtained were qualitatively and quantitatively by HPLC analysis. The work efficiency in terms of flows and in terms of phenolic recovery gave good results. The final phenolic recovery is about 60% respect the initial content in the vegetation waters. The final concentrate has shown a high content of phenols that allow to hypothesize a possible use as zootechnic nutritional supplements. The purification of the final concentrate have garanteed an high purity level of the phenolic extract especially in SPE analysis by the use of XAD-16 (73% of the total phenolic content of the concentrate). This purity level could permit a future food industry employment such as food additive, or, thanks to the strong antioxidant activity, it would be also use in pharmaceutical or cosmetic industry. The vegetation water depollutant activity has brought good results, as a matter of fact the final reverse osmosis permeate has a low pollutant rate in terms of COD and BOD5 values (2% of the initial vegetation water), that could determinate a recycling use in the virgin olive oil mechanical extraction system producing a water saving and reducing thus the oil industry disposal costs .

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“Cartographic heritage” is different from “cartographic history”. The second term refers to the study of the development of surveying and drawing techniques related to maps, through time, i.e. through different types of cultural environment which were background for the creation of maps. The first term concerns the whole amount of ancient maps, together with these different types of cultural environment, which the history has brought us and which we perceive as cultural values to be preserved and made available to many users (public, institutions, experts). Unfortunately, ancient maps often suffer preservation problems of their analog support, mostly due to aging. Today, metric recovery in digital form and digital processing of historical cartography allow preserving map heritage. Moreover, modern geomatic techniques give us new chances of using historical information, which would be unachievable on analog supports. In this PhD thesis, the whole digital processing of recovery and elaboration of ancient cartography is reported, with a special emphasis on the use of digital tools in preservation and elaboration of cartographic heritage. It is possible to divide the workflow into three main steps, that reflect the chapter structure of the thesis itself: • map acquisition: conversion of the ancient map support from analog to digital, by means of high resolution scanning or 3D surveying (digital photogrammetry or laser scanning techniques); this process must be performed carefully, with special instruments, in order to reduce deformation as much as possible; • map georeferencing: reproducing in the digital image the native metric content of the map, or even improving it by selecting a large number of still existing ground control points; this way it is possible to understand the projection features of the historical map, as well as to evaluate and represent the degree of deformation induced by the old type of cartographic transformation (that can be unknown to us), by surveying errors or by support deformation, usually all errors of too high value with respect to our standards; • data elaboration and management in a digital environment, by means of modern software tools: vectorization, giving the map a new and more attractive graphic view (for instance, by creating a 3D model), superimposing it on current base maps, comparing it to other maps, and finally inserting it in GIS or WebGIS environment as a specific layer. The study is supported by some case histories, each of them interesting from the point of view of one digital cartographic elaboration step at least. The ancient maps taken into account are the following ones: • three maps of the Po river delta, made at the end of the XVI century by a famous land-surveyor, Ottavio Fabri (he is single author in the first map, co-author with Gerolamo Pontara in the second map, co-author with Bonajuto Lorini and others in the third map), who wrote a methodological textbook where he explains a new topographical instrument, the squadra mobile (mobile square) invented and used by himself; today all maps are preserved in the State Archive of Venice; • the Ichnoscenografia of Bologna by Filippo de’ Gnudi, made in the 1702 and today preserved in the Archiginnasio Library of Bologna; it is a scenographic view of the city, captured in a bird’s eye flight, but also with an icnographic value, as the author himself declares; • the map of Bologna by the periti Gregorio Monari and Antonio Laghi, the first map of the city derived from a systematic survey, even though it was made only ten years later (1711–1712) than the map by de’ Gnudi; in this map the scenographic view was abandoned, in favor of a more correct representation by means of orthogonal projection; today the map is preserved in the State Archive of Bologna; • the Gregorian Cadastre of Bologna, made in 1831 and updated until 1927, now preserved in the State Archive of Bologna; it is composed by 140 maps and 12 brogliardi (register volumes). In particular, the three maps of the Po river delta and the Cadastre were studied with respect to their acquisition procedure. Moreover, the first maps were analyzed from the georeferencing point of view, and the Cadastre was analyzed with respect to a possible GIS insertion. Finally, the Ichnoscenografia was used to illustrate a possible application of digital elaboration, such as 3D modeling. Last but not least, we must not forget that the study of an ancient map should start, whenever possible, from the consultation of the precious original analogical document; analysis by means of current digital techniques allow us new research opportunities in a rich and modern multidisciplinary context.

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The most relevant thermo-mechanical properties of SiC or C based CFCCs are high strength, high toughness, low weight, high reliability, thermal shock and fatigue resistance. Thanks to these special characteristics, the CFCCs are the best candidates to substitute metals and monolithic ceramics, traditionally employed to realize components in energy, aeronautic and nuclear fields. Among the commonly techniques for the CFCCs production, CVI still represents the most significant one. Its main advantages are the versatility, the high quality deposits and the fact that it is conducted under mild temperature conditions. On the other hand, this technique is quite complex, therefore the set up of all process parameters needs long development time. The main purpose of the present study was to analyze the parameters controlling the CVD and CVI processes. Specifically, deposition and infiltration of SiC and Py-C tests were conducted on non-porous and porous substrates. The experiments were performed with a pilot size Isothermal/Isobaric CVI plant, designed and developed by ENEA. To guarantee the control of the process parameters, a previously optimization of the plant was needed. Changing temperature, pressure, flow rates and methane/hydrogen ratio, the Py-C deposition rate value, for an optimal fibre/matrix interphase thickness, was determined. It was also underlined the hydrogen inhibiting effect over the Py-C deposition rate. Regarding SiC morphologies, a difference between the inner and outer substrate surfaces was observed, as a consequence of a flow rate non-uniformity. In the case of the Cf/C composites development, the key parameter of the CVI process was the gas residence time. In fact, the hydrogen inhibiting effect was evident only with high value of residence time. Furthermore, lower the residence time more homogeneous the Py-C deposition rate was obtained along the reaction chamber axis. Finally, a CVD and CVI theoretical modelling was performed.

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Agri-food supply chains extend beyond national boundaries, partially facilitated by a policy environment that encourages more liberal international trade. Rising concentration within the downstream sector has driven a shift towards “buyer-driven” global value chains (GVCs) extending internationally with global sourcing and the emergence of multinational key economic players that compete with increase emphasis on product quality attributes. Agri-food systems are thus increasingly governed by a range of inter-related public and private standards, both of which are becoming a priori mandatory, especially in supply chains for high-value and quality-differentiated agri-food products and tend to strongly affect upstream agricultural practices, firms’ internal organization and strategic behaviour and to shape the food chain organization. Notably, increasing attention has been given to the impact of SPS measures on agri-food trade and notably on developing countries’ export performance. Food and agricultural trade is the vital link in the mutual dependency of the global trade system and developing countries. Hence, developing countries derive a substantial portion of their income from food and agricultural trade. In Morocco, fruit and vegetable (especially fresh) are the primary agricultural export. Because of the labor intensity, this sector (especially citrus and tomato) is particularly important in terms of income and employment generation, especially for the female laborers hired in the farms and packing houses. Hence, the emergence of agricultural and agrifood product safety issues and the subsequent tightening of market requirements have challenged mutual gains due to the lack of technical and financial capacities of most developing countries.

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La demolizione idrolitica delle pareti cellulari delle piante tramite enzimi lignocellulosici è quindi uno degli approcci più studiati della valorizzazione di scarti agricoli per il recupero di fitochimici di valore come secondary chemical building block per la chimica industriale. White rot fungi come il Pleurotus ostreatus producono una vasta gamma di enzimi extracellulari che degradano substrati lignocellulosici complessi in sostanze solubili per essere utilizzati come nutrienti. In questo lavoro abbiamo studiato la produzione di diversi tipi di enzimi lignocellulosici quali cellulase, xilanase, pectinase, laccase, perossidase e arylesterase (caffeoilesterase e feruloilesterase), indotte dalla crescita di Pleurotus ostreatus in fermentazione allo stato solido (SSF) di sottoprodotti agroalimentari (graspi d’uva, vinaccioli, lolla di riso, paglia di grano e crusca di grano) come substrati. Negli ultimi anni, SSF ha ricevuto sempre più interesse da parte dei ricercatori, dal momento che diversi studi per produzioni di enzimi, aromi, coloranti e altre sostanze di interesse per l' industria alimentare hanno dimostrato che SSF può dare rendimenti più elevati o migliorare le caratteristiche del prodotto rispetto alla fermentazione sommersa. L’utilizzo dei sottoprodotti agroalimentari come substrati nei processi SSF, fornisce una via alternativa e di valore, alternativa a questi residui altrimenti sotto/o non utilizzati. L'efficienza del processo di fermentazione è stato ulteriormente studiato attraverso trattamenti meccanici di estrusione del substrato , in grado di promuovere il recupero dell’enzima e di aumentare l'attività prodotta. Le attività enzimatiche prodotte dalla fermentazione sono strettamente dipendente della rimozione periodica degli enzimi prodotti. Le diverse matrici vegetali utilizzate hanno presentato diversi fenomeni induttivi delle specifiche attività enzimatiche. I processi SSF hanno dimostrato una buona capacità di produrre enzimi extracellulari in grado di essere utilizzati successivamente nei processi idrolitici di bioraffinazione per la valorizzazione dei prodotti agroalimentari.

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Driven by environmental reasons and the expected depletion of crude oil, bio-based polymers are currently undergoing a renaissance in the attempt to replace fossil-based ones. The present work aims at contributing in the development of the steps that start from biomass and move to new polymeric multifunctional materials. The study focuses on two bio-based building blocks (itaconic and vanillic acids) characterized by exploitable functionalities, i.e. a lateral double bond and a substituted aromatic ring respectively, able to confer interesting properties to the final polymers. The lateral double bond of dimethyl itaconate was functionalized via thia-Michael addition reaction obtaining a thermo-stable building block that can undergo polycondensation under classical conditions of reaction. The addition of a long lateral chain allows the polymer to express antimicrobial activity against Staphylococcus aureus making it attractive for packaging and targeting antimicrobial applications. Moreover, the architecture of the homopolymer was modified by means of copolymerization with dimethyl 2,5-furandicarboxylate thus improving the rigidity and obtaining a thermo-processable material. Potential applications as thermoset or thermoplastic material have been discussed. As concerns vanillic acid, the presence of aromatic rings on the polymer backbone imparts high thermal stability, but brittle behaviour in the homopolymer. Therefore, the architecture of the polyester was successfully tuned by means of copolymerization with a flexible bio-based comonomer, i.e. ω-pentadecalactone, providing processable random copolymers. An in depth investigation of water transport mechanism has been undertaken on the synthesized polyesters. Since the copolymers present a succession of aromatic and aliphatic units, as a consequence of the chemical structure water vapor permeability interposes between polyethylene and poly(ethylene terephthalate) proving that the copolyesters are suitable for packaging applications. Moving towards a sustainable model of development, novel sustainable synthetic pathways for the eco-design of new bio-based polymeric structures with high value functionalities and different potential applications have been successfully developed.

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The increasing environmental global regulations have directed scientific research towards more sustainable materials, even in the field of composite materials for additive manufacturing. In this context, the presented research is devoted to the development of thermoplastic composites for FDM application with a low environmental impact, focusing on the possibility to use wastes from different industrial processes as filler for the production of composite filaments for FDM 3D printing. In particular carbon fibers recycled by pyro-gasification process of CFRP scraps were used as reinforcing agent for PLA, a biobased polymeric matrix. Since the high value of CFs, the ability to re-use recycled CFs, replacing virgin ones, seems to be a promising option in terms of sustainability and circular economy. Moreover, wastes from different agricultural industries, i.e. wheat and rice production processes, were valorised and used as biofillers for the production of PLA-biocomposites. The integration of these agricultural wastes into PLA bioplastic allowed to obtain biocomposites with improved eco-sustainability, biodegradability, lightweight, and lower cost. Finally, the study of novel composites for FDM was extended towards elastomeric nanocomposite materials, in particular TPU reinforced with graphene. The research procedure of all projects involves the optimization of production methods of composite filaments with a particular attention on the possible degradation of polymeric matrices. Then, main thermal properties of 3D printed object are evaluated by TGA, DSC characterization. Additionally, specific heat capacity (CP) and Coefficient of Linear Thermal Expansion (CLTE) measurements are useful to estimate the attitude of composites for the prevention of typical FDM issues, i.e. shrinkage and warping. Finally, the mechanical properties of 3D printed composites and their anisotropy are investigated by tensile test using distinct kinds of specimens with different printing angles with respect to the testing direction.

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The world grapples with climate change from fossil fuel reliance, prompting Europe to pivot to renewable energy. Among renewables, biomass is a bioenergy and bio-carbon source, used to create high-value biomolecules, replacing fossil-based products. Alkyl levulinates, derived from biomass, hold promise as bio-additives and biofuels, especially via acid solvolysis of hexose sugars, necessitating further exploration. Alkyl levulinate's potential extends to converting into γ-valerolactone (GVL), a bio-solvent produced via hydrogenation with molecular-hydrogen. Hydrogen, a key reagent and energy carrier, aids renewable energy integration. This thesis delves into a biorefinery system study, aligning with sustainability goals, integrating biomass valorization, energy production, and hydrogen generation. It investigates optimizing technologies for butyl levulinate production and subsequent GVL hydrogenation. Sustainability remains pivotal, reflecting the global shift towards renewable and carbon bio-resources. The research initially focuses on experimenting with the optimal technology for producing butyl levulinate from biomass-derived hexose fructose. It examines the solvolysis process, investigating optimal conditions, kinetic modeling, and the impact of solvents on fructose conversion. The subsequent part concentrates on the technological aspect of hydrogenating butyl levulinate into GVL. It includes conceptual design, simulation, and optimization of the fructose-to-GVL process scheme based on process intensification. In the final part, the study applies the process to a real case study in Normandy, France, adapting it to local biomass availability and wind energy. It defines a methodology for designing and integrating the energy-supply system, evaluating different scenarios. Sustainability assessment using economic, environmental, and social indicators culminates in an overall sustainability index, indicating scenarios integrating the GVL biorefinery system with wind power and hydrogen energy storage as promising due to high profitability and reduced environmental impact. Sensitivity analyses validate the methodology's reliability, potentially extending to other technological systems.

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Mollusk shells are often found in archeological sites, given their great preservation potential and high value as a multipurpose resource. They are often the only available material to use for radiocarbon dating, due to a lack of well-preserved bones in many archeological sites, especially for the key period of the Middle to Upper Paleolithic transition. However, radiocarbon dating on mollusk shells is often regarded as less reliable compared to bones, wood, or charcoals due to the various factors influencing their radiocarbon content (e.g., Isotope fractionation, marine reservoir effect etc.). For the development of more accurate chronologies using shells, it is fundamental to continue improving the precision of the techniques applied, as has been done for other materials (wood and bones). Thus, improving the chemical pretreatment on mollusk shells might allow researchers to obtain more reliable radiocarbon determinations allowing for the construction of new radiocarbon chronologies in archeological sites where so far it has not been possible. Furthermore, mollusk shells can provide information on the climatic and environmental variables present during their growth. Using shells for paleoclimatic reconstruction adds more evidence helpful for the interpretation of scenarios of human migration, adaptation, and behavior. Standard methods for both radiocarbon and stable isotope studies use the carbonate fraction of the shell. However, being biogenic structures, mollusk shells also consist of a minor organic fraction. The shell organic matrix has an important role in the formation of the calcium carbonate structure and is still not fully understood. This thesis explores the potential of using the shell organic matrix for radiocarbon dating and paleoenvironmental studies. The results of the work performed for this thesis represent a starting point for future research to build on, and further develop the approach and methodology proposed here.

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In this thesis the impact of R&D expenditures on firm market value and stock returns is examined. This is performed in a sample of European listed firms for the period 2000-2009. I apply different linear and GMM econometric estimations for testing the impact of R&D on market prices and construct country portfolios based on firms’ R&D expenditure to market capitalization ratio for studying the effect of R&D on stock returns. The results confirm that more innovative firms have a better market valuation,investors consider R&D as an asset that produces long-term benefits for corporations. The impact of R&D on firm value differs across countries. It is significantly modulated by the financial and legal environment where firms operate. Other firm and industry characteristics seem to play a determinant role when investors value R&D. First, only larger firms with lower financial leverage that operate in highly innovative sectors decide to disclose their R&D investment. Second, the markets assign a premium to small firms, which operate in hi-tech sectors compared to larger enterprises for low-tech industries. On the other hand, I provide empirical evidence indicating that generally highly R&D-intensive firms may enhance mispricing problems related to firm valuation. As R&D contributes to the estimation of future stock returns, portfolios that comprise high R&D-intensive stocks may earn significant excess returns compared to the less innovative after controlling for size and book-to-market risk. Further, the most innovative firms are generally more risky in terms of stock volatility but not systematically more risky than low-tech firms. Firms that operate in Continental Europe suffer more mispricing compared to Anglo-Saxon peers but the former are less volatile, other things being equal. The sectors where firms operate are determinant even for the impact of R&D on stock returns; this effect is much stronger in hi-tech industries.

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Compared to other, plastic materials have registered a strong acceleration in production and consumption during the last years. Despite the existence of waste management systems, plastic_based materials are still a pervasive presence in the environment, with negative consequences on marine ecosystem and human health. The recycling is still challenging due to the growing complexity of product design, the so-called overpackaging, the insufficient and inadequate recycling infrastructure, the weak market of recycled plastics and the high cost of waste treatment and disposal. The Circular economy package, the European Strategy for plastics in a circular economy and the recent European Green Deal include very ambitious programmes to rethink the entire plastic value chain. As regards packaging, all plastic packaging will have to be 100% recyclable (or reusable) and 55% recycled by 2030. Regions are consequently called upon to set up a robust plan able to fit the European objectives. It takes on greater importance in Emilia Romagna where the Packaging valley is located. This thesis supports the definition of a strategy aimed to establish an after-use plastics economy in the region. The PhD work has set the basis and the instruments to establish the so-called Circularity Strategy with the aim to turn about 92.000t of plastic waste into profitable secondary resources. System innovation, life cycle thinking and participative backcasting method have allowed to deeply analyse the current system, orientate the problem and explore sustainable solutions through a broad stakeholder participation. A material flow analysis, accompanied by a barrier analysis, has supported the identification of the gaps between the present situation and the 2030 scenario. Eco-design for and from recycling (and a mass _based recycling rate (based on the effective amount of plastic wastes turned into secondary plastics), valorized by a value_based indicator, are the key-points of the action plan.

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This work deals with the development of calibration procedures and control systems to improve the performance and efficiency of modern spark ignition turbocharged engines. The algorithms developed are used to optimize and manage the spark advance and the air-to-fuel ratio to control the knock and the exhaust gas temperature at the turbine inlet. The described work falls within the activity that the research group started in the previous years with the industrial partner Ferrari S.p.a. . The first chapter deals with the development of a control-oriented engine simulator based on a neural network approach, with which the main combustion indexes can be simulated. The second chapter deals with the development of a procedure to calibrate offline the spark advance and the air-to-fuel ratio to run the engine under knock-limited conditions and with the maximum admissible exhaust gas temperature at the turbine inlet. This procedure is then converted into a model-based control system and validated with a Software in the Loop approach using the engine simulator developed in the first chapter. Finally, it is implemented in a rapid control prototyping hardware to manage the combustion in steady-state and transient operating conditions at the test bench. The third chapter deals with the study of an innovative and cheap sensor for the in-cylinder pressure measurement, which is a piezoelectric washer that can be installed between the spark plug and the engine head. The signal generated by this kind of sensor is studied, developing a specific algorithm to adjust the value of the knock index in real-time. Finally, with the engine simulator developed in the first chapter, it is demonstrated that the innovative sensor can be coupled with the control system described in the second chapter and that the performance obtained could be the same reachable with the standard in-cylinder pressure sensors.

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This research activity aims at providing a reliable estimation of particular state variables or parameters concerning the dynamics and performance optimization of a MotoGP-class motorcycle, integrating the classical model-based approach with new methodologies involving artificial intelligence. The first topic of the research focuses on the estimation of the thermal behavior of the MotoGP carbon braking system. Numerical tools are developed to assess the instantaneous surface temperature distribution in the motorcycle's front brake discs. Within this application other important brake parameters are identified using Kalman filters, such as the disc convection coefficient and the power distribution in the disc-pads contact region. Subsequently, a physical model of the brake is built to estimate the instantaneous braking torque. However, the results obtained with this approach are highly limited by the knowledge of the friction coefficient (μ) between the disc rotor and the pads. Since the value of μ is a highly nonlinear function of many variables (namely temperature, pressure and angular velocity of the disc), an analytical model for the friction coefficient estimation appears impractical to establish. To overcome this challenge, an innovative hybrid solution is implemented, combining the benefit of artificial intelligence (AI) with classical model-based approach. Indeed, the disc temperature estimated through the thermal model previously implemented is processed by a machine learning algorithm that outputs the actual value of the friction coefficient thus improving the braking torque computation performed by the physical model of the brake. Finally, the last topic of this research activity regards the development of an AI algorithm to estimate the current sideslip angle of the motorcycle's front tire. While a single-track motorcycle kinematic model and IMU accelerometer signals theoretically enable sideslip calculation, the presence of accelerometer noise leads to a significant drift over time. To address this issue, a long short-term memory (LSTM) network is implemented.