Preparation and assessment of immobilized laccase-based micro- and nanocatalysts for the degradation of anthropogenic compounds

Since the dawn of its presence on earth, the human being has been able to exploit the enzymes for its subsistence. More recent is the meeting between the enzymatic processes and the urgent need for technologies that aim to preserve our planet. In this field nowadays enzymatic catalysis is tested either to depollution/remediation as well as waste disposal. The work presented in this thesis, regarding both these two topics, is tailored on two European projects (EU 2020), MADFORWATER and TERMINUS respectively. Firstly, production of micro- and nanocatalysts via immobilization of laccases (a lignin-degrader enzyme) is performed. In the second part of the thesis laccase is applied to a tertiary treatment of wastewater with the aim to degrade 9 pharmaceutical active compounds in batch reactors. Despite several optimizations, poor degradation is reached and we did not proceed with the study of different bioreactor setups. Therefore, the focus is moved to a project concerning the production of smart multi-layer plastic packaging containing enzymes to improve the possibilities of recycling. In this field shielded nanocatalysts produced via coating techniques able to interact with redox mediators are investigated. The target substrate in this second project is produced in laboratory (i.e. polyurethane like compounds), starting from monomers whose degradation had already been tested, as a proof of concept. The first enzyme studied is still the laccase.

A distributed middleware for IT/OT convergence in modern industrial environments

The modern industrial environment is populated by a myriad of intelligent devices that collaborate for the accomplishment of the numerous business processes in place at the production sites. The close collaboration between humans and work machines poses new interesting challenges that industry must overcome in order to implement the new digital policies demanded by the industrial transition. The Industry 5.0 movement is a companion revolution of the previous Industry 4.0, and it relies on three characteristics that any industrial sector should have and pursue: human centrality, resilience, and sustainability. The application of the fifth industrial revolution cannot be completed without moving from the implementation of Industry 4.0-enabled platforms. The common feature found in the development of this kind of platform is the need to integrate the Information and Operational layers. Our thesis work focuses on the implementation of a platform addressing all the digitization features foreseen by the fourth industrial revolution, making the IT/OT convergence inside production plants an improvement and not a risk. Furthermore, we added modular features to our platform enabling the Industry 5.0 vision. We favored the human centrality using the mobile crowdsensing techniques and the reliability and sustainability using pluggable cloud computing services, combined with data coming from the crowd support. We achieved important and encouraging results in all the domains in which we conducted our experiments. Our IT/OT convergence-enabled platform exhibits the right performance needed to satisfy the strict requirements of production sites. The multi-layer capability of the framework enables the exploitation of data not strictly coming from work machines, allowing a more strict interaction between the company, its employees, and customers.

Laser cladding and its potential to reduce particulate matter emissions from the automotive and locomotive sector

Laser Cladding (LC) is an emerging technology which is used both for coating applications as well as near-net shape fabrication. Despite its significant advantages, such as low dilution and metallurgical bond with the substrate, it still faces issues such as process control and repeatability, which restricts the extension to its applications. The following thesis evaluates the LC technology and tests its potential to be applied to reduce particulate matter emissions from the automotive and locomotive sector. The evaluation of LC technology was carried out for the deposition of multi-layer and multi-track coatings. 316L stainless steel coatings were deposited to study the minimisation of geometric distortions in thin-walled samples. Laser power, as well as scan strategy, were the main variables to achieve this goal. The use of constant power, reduction at successive layers, a control loop control system, and two different scan strategies were studied. The closed-loop control system was found to be practical only when coupled with the correct scan strategy for the deposition of thin walls. Three overlapped layers of aluminium bronze were deposited onto a structural steel pipe for multitrack coatings. The effect of laser power, scan speed and hatch distance on the final geometry of coating were studied independently, and a combined parameter was established to effectively control each geometrical characteristic (clad width, clad height and percentage of dilution). LC was then applied to coat commercial GCI brake discs with tool steel. The optical micrography showed that even with preheating, the cracks that originated from the substrate towards the coating were still present. The commercial brake discs emitted airborne particles whose concentration and size depended on the test conditions used for simulation in the laboratory. The contact of LC cladded wheel with rail emitted significantly less ultra-fine particles while maintaining the acceptable values of coefficient of friction.

The predictive role of the human gut microbiota in covid-19: implications for disease severity and post-covid syndrome

The COVID-19 pandemic, sparked by the SARS-CoV-2 virus, stirred global comparisons to historical pandemics. Initially presenting a high mortality rate, it later stabilized globally at around 0.5-3%. Patients manifest a spectrum of symptoms, necessitating efficient triaging for appropriate treatment strategies, ranging from symptomatic relief to antivirals or monoclonal antibodies. Beyond traditional approaches, emerging research suggests a potential link between COVID-19 severity and alterations in gut microbiota composition, impacting inflammatory responses. However, most studies focus on severe hospitalized cases without standardized criteria for severity. Addressing this gap, the first study in this thesis spans diverse COVID-19 severity levels, utilizing 16S rRNA amplicon sequencing on fecal samples from 315 subjects. The findings highlight significant microbiota differences correlated with severity. Machine learning classifiers, including a multi-layer convoluted neural network, demonstrated the potential of microbiota compositional data to predict patient severity, achieving an 84.2% mean balanced accuracy starting one week post-symptom onset. These preliminary results underscore the gut microbiota's potential as a biomarker in clinical decision-making for COVID-19. The second study delves into mild COVID-19 cases, exploring their implications for ‘long COVID’ or Post-Acute COVID-19 Syndrome (PACS). Employing longitudinal analysis, the study unveils dynamic shifts in microbial composition during the acute phase, akin to severe cases. Innovative techniques, including network approaches and spline-based longitudinal analysis, were deployed to assess microbiota dynamics and potential associations with PACS. The research suggests that even in mild cases, similar mechanisms to hospitalized patients are established regarding changes in intestinal microbiota during the acute phase of the infection. These findings lay the foundation for potential microbiota-targeted therapies to mitigate inflammation, potentially preventing long COVID symptoms in the broader population. In essence, these studies offer valuable insights into the intricate relationships between COVID-19 severity, gut microbiota, and the potential for innovative clinical applications.

Study of high-quality ALD gate dielectrics in radiation sensitive oxide field effect transistors

Radiation dosimetry is crucial in many fields, where the exposure of ionizing radiation must be precisely controlled to avoid health and environmental safety issues. Radiotherapy and radioprotection are two examples in which fast and reliable detectors are needed. Compact and large area wearable detectors are being developed to address real-life radiation dosimetry applications, their ideal properties include flexibility, lightness, and low-cost. This thesis contributed to the development of Radiation sensitive OXide Field Effect Transistors (ROXFETs), which are detectors able to provide fast and real-time radiation read out. ROXFETs are based on thin film transistors fabricated with high-mobility amorphous oxide semiconductor, making them compatible with large area, flexible, and low cost production over plastic substrates. The gate dielectric material has high dielectric constant and high atomic number, which results in high performances and high radiation sensitivity, respectively. The aim of this work was to establish a stable and reliable fabrication process for ROXFETs made with atomic layer deposited gate dielectric. A study on the effect of gate dielectric materials was performed, focusing the attention on the properties of the dielectric-semiconductor interface. Single and multi layer dielectric structures were compared during this work. Furthermore, the effect of annealing temperature was studied. The device performances were tested to understand the underlying physical processes. In this way, it was possible to determine a reliable fabrication procedure and an optimal structure for ROXFETs. An outstanding sensitivity of (65±3)V/Gy was measured in detectors with a bi-layer Ta₂O₅-Al₂O₃ gate dielectric with low temperature annealing performed at 180°C.

Outbreak of infectious laryngotracheitis in large multi-age egg layer chicken flocks in Minas Gerais, Brazil

A recent (November 2010) outbreak of infectious laryngotracheitis (ILT) in a multi-age laying hen facility in Minas Gerais state, Brazil, is described. Previous ILT outbreak in laying hens was only notified in São Paulo state, Brazil, in 2002. In the outbreak described here, the affected population was approximately eight million hens, with flock sizes ranging from 100,000 to 2,900,000 chickens. The average mortality ranged from 1 to 6%, and morbidity was around 90% (most of the twenty seven farms of the area were positive for ILT virus). Three multi-age laying farms from one company were selected for this report. Clinical signs included prostration, dyspnea, conjunctivitis, occasional swelling of the paranasal sinuses and bloody mucous nasal discharge. Severely affected chickens presented with dyspnea, gasping and became cyanotic before death. At necropsy, these chickens had fibrinous exudate blocking the larynx and the lumen of cranial part of the trachea. In addition, conjunctivitis with intense hyperemia, edema and sinuses with caseous exudate were present. On histopathology, there were marked necrosis and desquamation of respiratory ephitelium and conjunctiva with numerous syncytial cells formation and fibrinous exudate. Moderate to marked non suppurative (especially lymphocytes and plasma cells) infiltration in the lamina propria also was observed. Sixteen out of 20 examined chickens, eosinophilic intranuclear inclusion bodies were observed in the syncytial cells. The DNA extracted from larynx and trachea produced positive PCR results for ILT virus (ILTV) DNA using formalin-fixed, paraffin embedded (FFPE) samples. Amplicons from a small region of ICP4 gene were submitted to sequencing and showed 100% identity with ILTV EU104910.1 (USA strain), 99% with ILTV JN596963.1 (Australian strain) and 91% with ILTV JN580316.1 (Gallid herpesvirus 1 CEO vaccine strain) and JN580315.1 (Gallid herpesvirus 1 TCO vaccine strain).

Cross-layer optimizations in multi-hop ad hoc networks

Unlike traditional wireless networks, characterized by the presence of last-mile, static and reliable infrastructures, Mobile ad Hoc Networks (MANETs) are dynamically formed by collections of mobile and static terminals that exchange data by enabling each other's communication. Supporting multi-hop communication in a MANET is a challenging research area because it requires cooperation between different protocol layers (MAC, routing, transport). In particular, MAC and routing protocols could be considered mutually cooperative protocol layers. When a route is established, the exposed and hidden terminal problems at MAC layer may decrease the end-to-end performance proportionally with the length of each route. Conversely, the contention at MAC layer may cause a routing protocol to respond by initiating new routes queries and routing table updates. Multi-hop communication may also benefit the presence of pseudo-centralized virtual infrastructures obtained by grouping nodes into clusters. Clustering structures may facilitate the spatial reuse of resources by increasing the system capacity: at the same time, the clustering hierarchy may be used to coordinate transmissions events inside the network and to support intra-cluster routing schemes. Again, MAC and clustering protocols could be considered mutually cooperative protocol layers: the clustering scheme could support MAC layer coordination among nodes, by shifting the distributed MAC paradigm towards a pseudo-centralized MAC paradigm. On the other hand, the system benefits of the clustering scheme could be emphasized by the pseudo-centralized MAC layer with the support for differentiated access priorities and controlled contention. In this thesis, we propose cross-layer solutions involving joint design of MAC, clustering and routing protocols in MANETs. As main contribution, we study and analyze the integration of MAC and clustering schemes to support multi-hop communication in large-scale ad hoc networks. A novel clustering protocol, named Availability Clustering (AC), is defined under general nodes' heterogeneity assumptions in terms of connectivity, available energy and relative mobility. On this basis, we design and analyze a distributed and adaptive MAC protocol, named Differentiated Distributed Coordination Function (DDCF), whose focus is to implement adaptive access differentiation based on the node roles, which have been assigned by the upper-layer's clustering scheme. We extensively simulate the proposed clustering scheme by showing its effectiveness in dominating the network dynamics, under some stressing mobility models and different mobility rates. Based on these results, we propose a possible application of the cross-layer MAC+Clustering scheme to support the fast propagation of alert messages in a vehicular environment. At the same time, we investigate the integration of MAC and routing protocols in large scale multi-hop ad-hoc networks. A novel multipath routing scheme is proposed, by extending the AOMDV protocol with a novel load-balancing approach to concurrently distribute the traffic among the multiple paths. We also study the composition effect of a IEEE 802.11-based enhanced MAC forwarding mechanism called Fast Forward (FF), used to reduce the effects of self-contention among frames at the MAC layer. The protocol framework is modelled and extensively simulated for a large set of metrics and scenarios. For both the schemes, the simulation results reveal the benefits of the cross-layer MAC+routing and MAC+clustering approaches over single-layer solutions.

Achievable performance gain of IEEE 802.11 multi-rate link adaptation algorithm with cross-layer design

Link quality-based rate adaptation has been widely used for IEEE 802.11 networks. However, network performance is affected by both link quality and random channel access. Selection of transmit modes for optimal link throughput can cause medium access control (MAC) throughput loss. In this paper, we investigate this issue and propose a generalised cross-layer rate adaptation algorithm. It considers jointly link quality and channel access to optimise network throughput. The objective is to examine the potential benefits by cross-layer design. An efficient analytic model is proposed to evaluate rate adaptation algorithms under dynamic channel and multi-user access environments. The proposed algorithm is compared to link throughput optimisation-based algorithm. It is found rate adaptation by optimising link layer throughput can result in large performance loss, which cannot be compensated by the means of optimising MAC access mechanism alone. Results show cross-layer design can achieve consistent and considerable performance gains of up to 20%. It deserves to be exploited in practical design for IEEE 802.11 networks.

Monitoring of active layer dynamics at two transects on Svalbard using multi-channel ground-penetrating radar

Multi-channel ground-penetrating radar is used to investigate the late-summer evolution of the thaw depth and the average soil water content of the thawed active layer at a high-arctic continuous permafrost site on Svalbard, Norway. Between mid of August and mid of September 2008, five surveys have been conducted over transect lengths of 130 and 175 m each. The maximum thaw depths range from 1.6 m to 2.0 m, so that they are among the deepest thaw depths recorded for Svalbard so far. The thaw depths increase by approximately 0.2 m between mid of August and beginning of September and subsequently remain constant until mid of September. The thaw rates are approximately constant over the entire length of the transects within the measurement accuracy of about 5 to 10 cm. The average volumetric soil water content of the thawed soil varies between 0.18 and 0.27 along the investigated transects. While the measurements do not show significant changes in soil water content over the first four weeks of the study, strong precipitation causes an increase in average soil water content of up to 0.04 during the last week. These values are in good agreement with evapotranspiration and precipitation rates measured in the vicinity of the the study site. While we cannot provide conclusive reasons for the detected spatial variability of the thaw depth at the study site, our measurements show that thaw depth and average soil water content are not directly correlated. The study demonstrates the potential of multi-channel ground-penetrating radar for mapping thaw depth in permafrost areas. The novel non-invasive technique is particularly useful when the thaw depth exceeds 1.5 m, so that it is hardly accessible by manual probing. In addition, multi-channel ground-penetrating radar holds potential for mapping the latent heat content of the active layer and for estimating weekly to monthly averages of the ground heat flux during the thaw period.

Physical Layer Security with Threshold-Based Multiuser Scheduling in Multi-antenna Wireless Networks

In this paper, we consider a multiuser downlink wiretap network consisting of one base station (BS) equipped with AA antennas, NB single-antenna legitimate users, and NE single-antenna eavesdroppers over Nakagami-m fading channels. In particular, we introduce a joint secure transmission scheme that adopts transmit antenna selection (TAS) at the BS and explores threshold-based selection diversity (tSD) scheduling over legitimate users to achieve a good secrecy performance while maintaining low implementation complexity. More specifically, in an effort to quantify the secrecy performance of the considered system, two practical scenarios are investigated, i.e., Scenario I: the eavesdropper’s channel state information (CSI) is unavailable at the BS, and Scenario II: the eavesdropper’s CSI is available at the BS. For Scenario I, novel exact closed-form expressions of the secrecy outage probability are derived, which are valid for general networks with an arbitrary number of legitimate users, antenna configurations, number of eavesdroppers, and the switched threshold. For Scenario II, we take into account the ergodic secrecy rate as the principle performance metric, and derive novel closed-form expressions of the exact ergodic secrecy rate. Additionally, we also provide simple and asymptotic expressions for secrecy outage probability and ergodic secrecy rate under two distinct cases, i.e., Case I: the legitimate user is located close to the BS, and Case II: both the legitimate user and eavesdropper are located close to the BS. Our important findings reveal that the secrecy diversity order is AAmA and the slope of secrecy rate is one under Case I, while the secrecy diversity order and the slope of secrecy rate collapse to zero under Case II, where the secrecy performance floor occurs. Finally, when the switched threshold is carefully selected, the considered scheduling scheme outperforms other well known existing schemes in terms of the secrecy performance and complexity tradeoff