Food safety in wine: optimization of analytical controls and evaluation of production technologies

This PhD thesis has been proposed to validate and then apply innovative analytical methodologies for the determination of compounds with harmful impact on human health, such as biogenic amines and ochratoxin A in wines. Therefore, the influence of production technology (pH, amino acids precursor and use of different malolactic starters) on biogenic amines content in wines was evaluated. An HPLC method for simultaneous determination of amino acids and amines with precolumnderivatization with 9-Fluorenyl-methoxycarbonyl chloride (FMOC-Cl) and UV detection was developed. Initially, the influence of pH, time of derivatization, gradient profile were studied. In order to improve the separation of amino acids and amines and reduce the time of analysis, it was decided to study the influence of different flows and the use of different columns in the chromatographic method. Firstly, a C18 Luna column was used and later two monolithic columns Chromolith in series. It appeared to be suitable for an easy, precise and accurate determination of a relatively large number of amino acids and amines in wines. This method was then applied on different wines produced in the Emilia Romagna region. The investigation permitted to discriminate between red and white wines. Amino acids content is related to the winemaking process. Biogenic amines content in these wines does not represent a possible toxicological problem for human health. The results of the study of influence of technologies and wine composition demonstrated that pH of wines and amino acids content are the most important factors. Particularly wines with pH > 3,5 show higher concentration of biogenic amines than wines with lower pH. The enrichment of wines by nutrients also influences the content of some biogenic amines that are higher in wines added with amino acids precursors. In this study, amino acids and biogenic amines are not statistically affected by strain of lactic acid bacteria inoculated as a starter for malolactic fermentation. An evaluation of different clean-up (SPE-MycoSep; IACs and LLE) and determination methods (HPLC and ELISA) of ochratoxin A was carried out. The results obtained proved that the SPE clean-up are reliable at the same level while the LLE procedures shows lowest recovery. The ELISA method gave a lower determination and a low reproducibility than HPLC method.

Unlocking the Potential of Women in the Rural Development Process of Republic of Srpska: The Role of Extension Service

In Bosnia Herzegovina the development of clear policy objectives and endorsement of a long-term, coherent and mutual agricultural and rural development policy have also been affected by structural problems: a lack of reliable information on population and other relevant issues, the absence of an adequate land registry system and cadastre. Moreover in BiH the agricultural and rural sectors are characterized by many factors that have typically affected transition countries such as land fragmentation, lack of agricultural mechanization and outdated production technologies, and rural aging, high unemployment and out-migration. In such a framework the condition and role of women in rural areas suffered for the lack of gender disaggregated data and a consequent poor information that lead to the exclusion of gender related questions in the agenda of public institutions and to the absence of targeted policy interventions. The aim of the research is to investigate the role and condition of women in the rural development process of Republic of Srpska and to analyze the capacity of extension services to stimulate their empowerment. Specific research questions include the status of women in the rural areas of Republic of Srpska, the role of government in fostering the empowerment of rural women, and the role of the extension service in supporting rural women. The methodology - inspired by the case study method developed by R. Yin - is designed along the three specific research questions that are used as building blocks. Each of the three research questions is investigated with a combination of methodological tools - including surveys, experts interviews and focus groups - aimed to overcome the lack of data and knowledge that characterize the research objectives.

Copper(I) phenanthroline complexes and supramolecular systems containing fullerenes: Photophysics, photochemistry and potential applications in sustainable energy technologies.

Chemistry can contribute, in many different ways to solve the challenges we are facing to modify our inefficient and fossil-fuel based energy system. The present work was motivated by the search for efficient photoactive materials to be employed in the context of the energy problem: materials to be utilized in energy efficient devices and in the production of renewable electricity and fuels. We presented a new class of copper complexes, that could find application in lighting techhnologies, by serving as luminescent materials in LEC, OLED, WOLED devices. These technologies may provide substantial energy savings in the lighting sector. Moreover, recently, copper complexes have been used as light harvesting compounds in dye sensitized photoelectrochemical solar cells, which offer a viable alternative to silicon-based photovoltaic technologies. We presented also a few supramolecular systems containing fullerene, e.g. dendrimers, dyads and triads.The most complex among these arrays, which contain porphyrin moieties, are presented in the final chapter. They undergo photoinduced energy- and electron transfer processes also with long-lived charge separated states, i.e. the fundamental processes to power artificial photosynthetic systems.

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

La nutrizione-idratazione artificiale è terapia? All'interfaccia tra scienza, diritto e bioetica, il fine vita in Italia, secondo una prospettiva di comunicazione della scienza post-accademica e Science&Technologies Studies (STS)

The question “artificial nutrition and hydration (ANH) is therapy or not?” is one of the key point of end-of-life issues in Italy, since it was (and it is also nowadays) a strategic and crucial point of the Italian Bioethics discussion about the last phases of human life: determining if ANH is therapy implies the possibility of being included in the list of treatments that could be mentioned for refusal within the living will document. But who is entitled to decide and judge if ANH is a therapy or not? Scientists? The Legislator? Judges? Patients? This issue at first sight seems just a matter of science, but at stake there is more than a scientific definition. According to several scholars, we are in the era of post-academic Science, in which Science broaden discussion, production, negotation and decision to other social groups that are not just the scientific communities. In this process, called co-production, on one hand scientific knowledge derives from the interaction between scientists and society at large. On the other hand, science is functional to co-production of social order. The continuous negotation on which science has to be used in social decisions is just the evidence of the mirroring negotation for different way to structure and interpret society. Thus, in the interaction between Science and Law, deciding what kind of Science could be suitable for a specific kind of Law, envisages a well defined idea of society behind this choice. I have analysed both the legislative path (still in progress) in the living will act production in Italy and Eluana Englaro’s judicial case (that somehow collapsed in the living will act negotiation), using official documents (hearings, texts of the official conference, committees comments and ruling texts) and interviewing key actors in the two processes from the science communication point of view (who talks in the name of science? Who defines what is a therapy? And how do they do?), finding support on the theoretical framework of the Science&Technologies Studies (S&TS).

Technology Development and Consumer Acceptance of Innovation in Fruit Production

Precision Agriculture (PA) and the more specific branch of Precision Horticulture are two very promising sectors. They focus on the use of technologies in agriculture to optimize the use of inputs, so to reach a better efficiency, and minimize waste of resources. This important objective motivated many researchers and companies to search new technology solutions. Sometimes the effort proved to be a good seed, but sometimes an unfeasible idea. So that PA, from its birth more or less 25 years ago, is still a “new” management, interesting for the future, but an actual low adoption rate is still reported by experts and researchers. This work aims to give a contribution in finding the causes of this low adoption rate and proposing a methodological solution to this problem. The first step was to examine prior research about Precision Agriculture adoption, by ex ante and ex post approach. It was supposed as important to find connections between these two phases of a purchase experience. In fact, the ex ante studies dealt with potential consumer’s perceptions before a usage experience occurred, therefore before purchasing a technology, while the ex post studies described the drivers which made a farmer become an end-user of PA technology. Then, an example of consumer research is presented. This was an ex ante research focused on pre-prototype technology for fruit production. This kind of research could give precious information about consumer acceptance before reaching an advanced development phase of the technology, and so to have the possibility to change something with the least financial impact. The final step was to develop the pre-prototype technology that was the subject of the consumer acceptance research and test its technical characteristics.

Development of methodologies supporting the sustainable and safe integration of offshore conventional and renewable energy production

Against a backdrop of rapidly increasing worldwide population and growing energy demand, the development of renewable energy technologies has become of primary importance in the effort to reduce greenhouse gas emissions. However, it is often technically and economically infeasible to transport discontinuous renewable electricity for long distances to the shore. Another shortcoming of non-programmable renewable power is its integration into the onshore grid without affecting the dispatching process. On the other hand, the offshore oil & gas industry is striving to reduce overall carbon footprint from onsite power generators and limiting large expenses associated to carrying electricity from remote offshore facilities. Furthermore, the increased complexity and expansion towards challenging areas of offshore hydrocarbons operations call for higher attention to safety and environmental protection issues from major accident hazards. Innovative hybrid energy systems, as Power-to-Gas (P2G), Power-to-Liquid (P2L) and Gas-to-Power (G2P) options, implemented at offshore locations, would offer the opportunity to overcome challenges of both renewable and oil & gas sectors. This study aims at the development of systematic methodologies based on proper sustainability and safety performance indicators supporting the choice of P2G, P2L and G2P hybrid energy options for offshore green projects in early design phases. An in-depth analysis of the different offshore hybrid strategies was performed. The literature reviews on existing methods proposing metrics to assess sustainability of hybrid energy systems, inherent safety of process routes in conceptual design stage and environmental protection of installations from oil and chemical accidental spills were carried out. To fill the gaps, a suite of specific decision-making methodologies was developed, based on representative multi-criteria indicators addressing technical, economic, environmental and societal aspects of alternative options. A set of five case-studies was defined, covering different offshore scenarios of concern, to provide an assessment of the effectiveness and value of the developed tools.

Additive Manufacturing by LPBF and WAAM of metals: correlation between production process, microstructure and mechanical properties

In the most recent years, Additive Manufacturing (AM) has drawn the attention of both academic research and industry, as it might deeply change and improve several industrial sectors. From the material point of view, AM results in a peculiar microstructure that strictly depends on the conditions of the additive process and directly affects mechanical properties. The present PhD research project aimed at investigating the process-microstructure-properties relationship of additively manufactured metal components. Two technologies belonging to the AM family were considered: Laser-based Powder Bed Fusion (LPBF) and Wire-and-Arc Additive Manufacturing (WAAM). The experimental activity was carried out on different metals of industrial interest: a CoCrMo biomedical alloy and an AlSi7Mg0.6 alloy processed by LPBF, an AlMg4.5Mn alloy and an AISI 304L austenitic stainless steel processed by WAAM. In case of LPBF, great attention was paid to the influence that feedstock material and process parameters exert on hardness, morphological and microstructural features of the produced samples. The analyses, targeted at minimizing microstructural defects, lead to process optimization. For heat-treatable LPBF alloys, innovative post-process heat treatments, tailored on the peculiar hierarchical microstructure induced by LPBF, were developed and deeply investigated. Main mechanical properties of as-built and heat-treated alloys were assessed and they were well-correlated to the specific LPBF microstructure. Results showed that, if properly optimized, samples exhibit a good trade-off between strength and ductility yet in the as-built condition. However, tailored heat treatments succeeded in improving the overall performance of the LPBF alloys. Characterization of WAAM alloys, instead, evidenced the microstructural and mechanical anisotropy typical of AM metals. Experiments revealed also an outstanding anisotropy in the elastic modulus of the austenitic stainless-steel that, along with other mechanical properties, was explained on the basis of microstructural analyses.

Investigation of innovative combustion systems for reduced fuel consumption and increased specific power production

This work resumes a wide variety of research activities carried out with the main objective of increasing the efficiency and reducing the fuel consumption of Gasoline Direct Injection engines, especially under high loads. For this purpose, two main innovative technologies have been studied, Water Injection and Low-Pressure Exhaust Gas Recirculation, which help to reduce the temperature of the gases inside the combustion chamber and thus mitigate knock, being this one of the main limiting factors for the efficiency of modern downsized engines that operate at high specific power. A prototypal Port Water Injection system was developed and extensive experimental work has been carried out, initially to identify the benefits and limitations of this technology. This led to the subsequent development and testing of a combustion controller, which has been implemented on a Rapid Control Prototyping environment, capable of managing water injection to achieve knock mitigation and a more efficient combustion phase. Regarding Low-Pressure Exhaust Gas Recirculation, a commercial engine that was already equipped with this technology was used to carry out experimental work in a similar fashion to that of water injection. Another prototypal water injection system has been mounted to this second engine, to be able to test both technologies, at first separately to compare them on equal conditions, and secondly together in the search of a possible synergy. Additionally, based on experimental data from several engines that have been tested during this study, including both GDI and GCI engines, a real-time model (or virtual sensor) for the estimation of the maximum in-cylinder pressure has been developed and validated. This parameter is of vital importance to determine the speed at which damage occurs on the engine components, and therefore to extract the maximum performance without inducing permanent damages.

Development of sexing systems functional to mass production of Aedes albopictus sterile males

Aedes albopictus is a vector able to transmit several arboviruses. Due to its high impact on human health, it is important to develop an efficient control strategy for this pest. Nowadays, control based on chemical insecticides is limited by the number of available active principles and the occurrence of resistance. A valuable alternative to the conventional control strategies is the sterile insect technique (SIT) which relies on releasing sterile males of the target insect. Mating between wild females and sterile males results in no viable offspring. A crucial aspect of SIT is the production of a large number of sterile males with a low presence of females that can bite and transmit viruses. The present thesis aimed to find, implement and study the most reliable mechanical sex sorter and protocol to implement male productivity and reduce female contamination. In addition, I evaluated different variables and sorting protocols to enable female recovery for breeding purposes. Furthermore, I studied the creation of a hyper-protandric strain potentially able to produce only males. I also assessed the integration of artificial intelligence with an optical unit to identify sexes at the adult stage. All these applications helped to realise a mass production model in Italy with a potential weekly production of 1 million males. Moreover, I studied and applied for aerial sterile male release in an urban environment. This technology could allow the release of males in a wide area, overcoming environmental and urban obstacles. However, the development and application of drone technologies in a metropolitan area close to airports, such as in Bologna area, must fit specific requirements. Lastly, at Réunion Island, during a Short Term Scientific Mission France (AIM-COST Action), Indian Ocean, I studied the Boosted SIT application. Coating sterile males with Pyriproxyfen may help spread the insecticide into the larval breeding sites.

Technologies for urban and rural internet of things

Nowadays, application domains such as smart cities, agriculture or intelligent transportation, require communication technologies that combine long transmission ranges and energy efficiency to fulfill a set of capabilities and constraints to rely on. In addition, in recent years, the interest in Unmanned Aerial Vehicles (UAVs) providing wireless connectivity in such scenarios is substantially increased thanks to their flexible deployment. The first chapters of this thesis deal with LoRaWAN and Narrowband-IoT (NB-IoT), which recent trends identify as the most promising Low Power Wide Area Networks technologies. While LoRaWAN is an open protocol that has gained a lot of interest thanks to its simplicity and energy efficiency, NB-IoT has been introduced from 3GPP as a radio access technology for massive machine-type communications inheriting legacy LTE characteristics. This thesis offers an overview of the two, comparing them in terms of selected performance indicators. In particular, LoRaWAN technology is assessed both via simulations and experiments, considering different network architectures and solutions to improve its performance (e.g., a new Adaptive Data Rate algorithm). NB-IoT is then introduced to identify which technology is more suitable depending on the application considered. The second part of the thesis introduces the use of UAVs as flying Base Stations, denoted as Unmanned Aerial Base Stations, (UABSs), which are considered as one of the key pillars of 6G to offer service for a number of applications. To this end, the performance of an NB-IoT network are assessed considering a UABS following predefined trajectories. Then, machine learning algorithms based on reinforcement learning and meta-learning are considered to optimize the trajectory as well as the radio resource management techniques the UABS may rely on in order to provide service considering both static (IoT sensors) and dynamic (vehicles) users. Finally, some experimental projects based on the technologies mentioned so far are presented.