10081 research outputs found
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Electrochemistry of polycyclic aromatic molecules for advanced carbon nanostructures: luminescence and transistor applications
Get PDFPolycyclic aromatic hydrocarbons (PAHs) are a large class of π-conjugated organic molecules with fused aromatic rings, which can be considered as fragments of 2D-graphene and have been extensively studied for their unique optical and electronic properties. The aim of this study is to understand the complex electrochemical behaviour of planar, curved, and heteroatom doped polycyclic aromatic molecules, particularly focusing on the oxidative coupling of their radical cations and the electrochemically induced cyclodehydrogenation reactions.
In the first part of this thesis, the class of PAHs and aromatic nanostructures are introduced, and the reactivity of electrogenerated species is discussed, focusing on the electrochemical approach for the synthesis of extended π-conjugated structures. Subsequently, the electrochemical properties and reactivity of electrogenerated radical ions of planar and curved polyaromatics are correlated to their structures. In the third chapter, electrochemical cyclodehydrogenation of hexaphenylbenzene is used to prepare self-assembled hexabenzocoronene, directly deposited on an interdigitated electrode, which was characterised as organic electrochemical transistor. In the fourth chapter, the electrochemical behaviour of a family of azapyrene derivatives has been carefully investigated together with the electrogenerated chemiluminescence (ECL), both by ion-annihilation and co-reactant methods. Two structural azapyrene isomers with different nitrogen positions are thoroughly discussed in terms of redox and ECL properties. Interestingly, the ECL of only one of them showed a double emission with excimer formation. A detailed mechanism is discussed for the ECL by co-reactant benzoyl peroxide, to rationalise the different ECL behaviours of the two isomers on the basis of their topologically modulated electronic properties.
In conclusion, the different electrochemical behaviours of PAHs were shown, focussing on the chemical reactivity of the electrogenerated species and taking advantage of it for important processes spanning from unconventional synthesis methods for carbon nanostructures to the exploitation of self-assembled nanostructured systems in organic electronics, to novel organic emitters in ECL
Role of CARM1 (PRMT4) in high grade serous ovarian cancer metabolism and function of PRMT5 in ARID1A- deficient endometrial cancer invasion
Get PDFThe arginine methyltransferase CARM1 (PRMT4) is amplified and overexpressed in ~20% of high-grade serous ovarian cancer (HGSOC) and correlates with a poor survival. Therapeutic approaches based on CARM1 expression remain to be an unmet need. Here we show that fatty acid metabolism represents a metabolic vulnerability for HGSOC in a CARM1 expression status dependent manner. CARM1 promotes the de novo synthesis of fatty acids and monounsaturated fatty acids (MUFAs). The disruption of MUFAs synthesis by inhibition of SCD1 results in excessive accumulation of cytotoxic saturated fatty acids and it is synthetic lethal with CARM1 expression. Collectively, our data show that the pharmacological inhibition of MUFAs synthesis via SCD1 inhibition represents a therapeutic strategy for CARM1-high HGSOC.
Another arginine methyltransferase, PRMT5, has been identified by our CRISPR screening analysis as a promising candidate for invasive ARID1A-deficient endometrial cancer. Endometrial Cancer frequently harbor somatic inactivating mutation of ARID1A that can promote an invasive phenotype. Our in vitro approach validated the CRISPR screening showing that both PRTM5 knock down and its pharmaceutical inhibition specifically hamper the invasion of ARID1A inactivated cells. Mechanistically, PRMT5 directly regulates the epithelia to mesenchymal transition pathway genes interacting with the SWI/SNF complexes. Moreover, in vivo experiments showed that PRMT5 inhibition contrasted the myometrium invasion highlighting PRMT5 inhibition as promising therapeutic strategy for ARID1A- inactivated aggressive endometrial cancer
Response times in computerized adaptive testing: a method for cheating detection
Get PDFIn the field of educational and psychological measurement, the shift from paper-based to computerized tests has become a prominent trend in recent years. Computerized tests allow for more complex and personalized test administration procedures, like Computerized Adaptive Testing (CAT).
CAT, following the Item Response Theory (IRT) models, dynamically generates tests based on test-taker responses, driven by complex statistical algorithms. Even if CAT structures are complex, they are flexible and convenient, but concerns about test security should be addressed. Frequent item administration can lead to item exposure and cheating, necessitating preventive and diagnostic measures.
In this thesis a method called "CHeater identification using Interim Person fit Statistic" (CHIPS) is developed, designed to identify and limit cheaters in real-time during test administration. CHIPS utilizes response times (RTs) to calculate an Interim Person fit Statistic (IPS), allowing for on-the-fly intervention using a more secret item bank. Also, a slight modification is proposed to overcome situations with constant speed, called Modified-CHIPS (M-CHIPS).
A simulation study assesses CHIPS, highlighting its effectiveness in identifying and controlling cheaters. However, it reveals limitations when cheaters possess all correct answers. The M-CHIPS overcame this limitation. Furthermore, the method has shown not to be influenced by the cheaters’ ability distribution or the level of correlation between ability and speed of test-takers.
Finally, the method has demonstrated flexibility for the choice of significance level and the transition from fixed-length tests to variable-length ones.
The thesis discusses potential applications, including the suitability of the method for multiple-choice tests, assumptions about RT distribution and level of item pre-knowledge. Also limitations are discussed to explore future developments such as different RT distributions, unusual honest respondent behaviors, and field testing in real-world scenarios. In summary, CHIPS and M-CHIPS offer real-time cheating detection in CAT, enhancing test security and ability estimation while not penalizing test respondents
Medial Artery Calcification (MAC) and Small Artery Disease (SAD) in patients with critical limb ischemia: definition of predisposing factors, development of a prognostic score, histopathological definition, and evaluation of lower limb vein arterialization outcomes as a revascularization technique.
Get PDFQuesto studio si concentra sull'ischemia critica cronica dell'arto inferiore (CLTI), una patologia globale con gravi complicanze e impatto sociale elevato. Recentemente, la "Medial Artery Calcification" (MAC) è emersa come fattore prognostico significativo nei pazienti con CLTI e malattia grave dei vasi del piede, ma le informazioni sono principalmente retrospettive. Questa tesi esplora la relazione tra MAC e CLTI in tre sezioni. Nella sezione clinica, 248 pazienti sono stati divisi in gruppi MAC per valutare l'impatto prospettico sulla guarigione e sul salvataggio dell'arto. Nella sezione isto-patologica, campioni arteriosi di 26 pazienti sottoposti ad amputazione maggiore sono stati analizzati per comprendere la relazione tra MAC, aterosclerosi e occlusione vascolare. Nella sezione di arterializzazione, 16 pazienti sottoposti all'arterializzazione delle vene del piede (AVP) sono stati esaminati per valutare i risultati clinici prospettici. I risultati della sezione clinica indicano che la presenza di MAC severa è associata a risultati clinici peggiori nei pazienti affetti da CLTI. L'analisi isto-patologica mostra una prevalenza elevata di MAC rispetto all'aterosclerosi, con una associazione importante tra MAC e iperplasia intimale. L'AVP presenta risultati promettenti nei pazienti affetti da CLTI. In conclusione, la MAC influisce sui risultati clinici della CLTI, e l'AVP potrebbe essere una strategia efficace di trattamento.This study focuses on chronic limb-threatening ischemia (CLTI), a global pathology with severe complications and significant societal impact. Recently, Medial Artery Calcification (MAC) has emerged as a significant prognostic factor in patients with CLTI and severe foot vessel disease, but the information is primarily retrospective. This thesis explores the relationship between MAC and CLTI in three sections. In the clinical section, 248 patients were divided into MAC groups to prospectively assess the impact on limb healing and salvage. In the histopathological section, arterial samples from 26 patients undergoing major amputation were analyzed to understand the relationship between MAC, atherosclerosis, and vascular occlusion. In the arterialization section, 16 patients undergoing foot vein arterialization (AVP) were examined to prospectively evaluate clinical outcomes. Results from the clinical section indicate that the presence of severe MAC is associated with worse clinical outcomes in CLTI patients. Histopathological analysis reveals a high prevalence of MAC compared to atherosclerosis, with a significant association between MAC and intimal hyperplasia. AVP shows promising outcomes in CLTI patients. In conclusion, MAC influences CLTI clinical outcomes, and AVP may be an effective treatment strategy
Integrating the age factor in designing industrial environments and workstations in the workforce ageing era
Get PDFAs people spend a third of their lives at work and, in most cases, indoors, the work environment assumes crucial importance. The continuous and dynamic interaction between people and the working environment surrounding them produces physiological and psychological effects on operators.
Recognizing the substantial impact of comfort and well-being on employee satisfaction and job performance, the literature underscores the need for industries to implement indoor environment control strategies to ensure long-term success and profitability.
However, managing physical risks (i.e., ergonomic and microclimate) in industrial environments is often constrained by production and energy requirements.
In the food processing industry, for example, the safety of perishable products dictates storage temperatures that do not allow for operator comfort. Conversely, warehouses dedicated to non-perishable products often lack cooling systems to limit energy expenditure, reaching high temperatures in the summer period.
Moreover, exceptional events, like the COVID-19 pandemic, introduce new constraints, with recommendations impacting thermal stress and respiratory health. Furthermore, the thesis highlights how workers' variables, particularly the aging process, reduce tolerance to environmental stresses. Consequently, prolonged exposure to environmental stress conditions at work results in cardiovascular disease and musculoskeletal disorders. In response to the global trend of an aging workforce, the thesis bridges a literature gap by proposing methods and models that integrate the age factor into comfort assessment. It aims to present technical and technological solutions to mitigate microclimate risks in industrial environments, ultimately seeking innovative ways to enhance the aging workforce's comfort, performance, experience, and skills. The research outlines a logical-conceptual scheme with three main areas of focus: analyzing factors influencing the work environment, recognizing constraints to worker comfort, and designing solutions. The results significantly contribute to science by laying the foundation for new research in worker health and safety in an ageing working population's extremely current industrial context
Teaching italian L2 for study purposes: a proposal of graded readers for chinese students
Get PDFDati i problemi di comprensione linguistica riscontrati dagli studenti cinesi nel contesto accademico e la crescente necessità della didattica dell’italiano L2 per fini di studio, il presente lavoro ha come obiettivo finale la creazione di letture graduate, proposte come materiali didattici comprensibili e mirati agli studenti cinesi di italiano L2, in modo da agevolare il loro approccio ai testi impegnativi richiesti per gli studi artistico-professionali.
In particolare, nei primi due capitoli si discute il ruolo significativo della distanza linguistica tra italiano e cinese nell’acquisizione della L2 da parte degli studenti cinesi e nello sviluppo della loro abilità di lettura in L2. In seguito, per capire come debba essere un input ideale per l’acquisizione linguistica a fini di studio, vengono esaminati vari approcci glottodidattici basati sull’input, e si osservano i tratti delle varietà di italiano presenti nel contesto accademico. Il lavoro procede poi con un’analisi delle specifiche caratteristiche linguistiche riscontrate in manuali universitari di storia dell’arte, utilizzando sia un approccio quantitativo che qualitativo, con l’obiettivo di avere un “panorama” delle complessità linguistiche che uno studente L2 deve affrontare nello studio. Successivamente, verrà presentata una sperimentazione di riscrittura con due gruppi, i quali sono stati sottoposti rispettivamente al testo originale e a quello riscritto secondo i criteri formulati dallo studio teorico sul confronto tipologico. I risultati ottenuti confermano sia le interferenze del cinese nella lettura in italiano, sia l’efficacia degli approcci linguistici individuati nel facilitare la comprensibilità del testo per gli studenti cinesi di livello A2-B1. Di conseguenze, viene proposto un percorso di letture graduate per gli studenti cinesi di belle arti; oltre a essere comprensibili, le letture mirano anche all’acquisizione delle varietà di italiano necessarie per lo studio accademico-professionale. L’ultima parte del lavoro è dedicata alle riflessioni teoriche e didattiche sviluppate nel corso della ricerca.Considering the comprehension challenges faced by Chinese students in academic contexts and the increasing demand for teaching Italian as a second language (L2) for study purposes, this work aims to develop a series of graded readers, which are proposed as comprehensible and tailor-made teaching materials for Chinese learners studying Italian as a second language, in order to ease their engagement with challenging texts required for art-professional studies.
Specifically, the first two chapters discuss the significant role of language distance between Italian and Chinese in the L2 acquisition of Chinese students and the development of their L2 reading skills. Following that, to comprehend what constitutes an ideal input for language acquisition for study purposes, various input-based language teaching approaches are examined, and linguistic traits present in the academic context are observed. The work then advances with an analysis of the specific linguistic features present in university art history textbooks, employing both quantitative and qualitative approaches to gain a comprehensive understanding of the linguistic complexities faced by an L2 learner in their studies. Subsequently, a rewriting experiment will be introduced, involving two groups. Each group was exposed to either the original or the rewritten text based on the criteria formulated in the theoretical study on language typology comparison. The results obtained confirm both the interference of Chinese in reading Italian and the effectiveness of the identified linguistic approaches in facilitating text comprehensibility for A2-B1 level Chinese students. Consequently, a series of graded readers is proposed for Chinese fine arts students. In addition to promoting comprehensibility, these readings also aim at the acquisition of the varieties of Italian necessary for academic-professional study. The final part of the paper is dedicated to the theoretical and practical teaching reflections that emerged during the research
Retrospective assessment of fracture risk through opportunistic radiological screening in a large modern cohort of liver transplant recipients
Get PDFObjective:
Liver transplantation has been associated with a high prevalence of osteoporosis, although most data rely on single-center studies with limited sample size, with most of them dating back to late 1990s and early 2000s. The present thesis aims to assess the prevalence of fragility fractures and contributing factors in a large modern cohort of liver transplant recipients managed in a referral Italian Liver Transplant Center.
Design and Methods:
Paper and electronic medical records of 429 consecutive patients receiving liver transplantation from 1/1/2010 to 31/12/2015 were reviewed, and 366 patients were selected. Clinically obtained electronic radiological images within 6 months from the date of liver transplant surgery, such as lateral views of spine X-rays or CT abdominal scans, were opportunistically reviewed in a blinded fashion to screen for morphometric vertebral fractures. Clinical fragility fractures reported in the medical records, along with information on etiology of cirrhosis and biochemistries at the time of liver surgery were also recorded.
Results:
Prevalence of fragility fractures in the whole cohort was 155/366 (42.3%), with no significant differences between sexes. Of patients with fractures, most sustained vertebral fractures (145/155, 93.5%), the majority of which were mild or moderate wedges. Multiple vertebral fractures were common (41.3%). Fracture rates were similar across different etiologies of cirrhosis and were also comparable in patients with diabetes or exposed to glucocorticoids. Kidney function was significantly worse in women with fractures. Independent of age, sex, alcohol use, eGFR, etiology of liver disease, lower BMI was the only independent risk factor for fractures (adjusted OR 1,058, 95%CI 1,001-1,118, P=0.046) in this study population.
Conclusions:
A considerable fracture burden was shown in a large and modern cohort of liver transplant recipients. Given the remarkably high prevalence of fractures, a metabolic bone disease screening should be implemented in every patient awaiting liver transplantation
Directly training spiking neural networks for cyber-physical systems: from supervised to reinforcement learning
Get PDFSpiking Neural Networks (SNNs) are bio-inspired Artificial Neural Networks (ANNs) utilizing discrete spiking signals, akin to neuron communication in the brain, making them ideal for real-time and energy-efficient Cyber-Physical Systems (CPSs). This thesis explores their potential in Structural Health Monitoring (SHM), leveraging low-cost MEMS accelerometers for early damage detection in motorway bridges.
The study focuses on Long Short-Term SNNs (LSNNs), although their complex learning processes pose challenges. Comparing LSNNs with other ANN models and training algorithms for SHM, findings indicate LSNNs' effectiveness in damage identification, comparable to ANNs trained using traditional methods. Additionally, an optimized embedded LSNN implementation demonstrates a 54% reduction in execution time, but with longer pre-processing due to spike-based encoding.
Furthermore, SNNs are applied in UAV obstacle avoidance, trained directly using a Reinforcement Learning (RL) algorithm with event-based input from a Dynamic Vision Sensor (DVS). Performance evaluation against Convolutional Neural Networks (CNNs) highlights SNNs' superior energy efficiency, showing a 6x decrease in energy consumption.
The study also investigates embedded SNN implementations' latency and throughput in real-world deployments, emphasizing their potential for energy-efficient monitoring systems. This research contributes to advancing SHM and UAV obstacle avoidance through SNNs' efficient information processing and decision-making capabilities within CPS domains
Tectonics of the wedge-top Epiligurian basins and implications for the syn-to-post orogenic evolution of the Northern Apennines fold-and-thrust belt (Italy)
Get PDFThis thesis has the aim to give an overview about the tectonic history of the Epiligurian units, which crop out in the axial portion of the Northern Apennines fold-and-thrust belt, from a structural and thermal point of view, through a multiscalar and multitecnique approach. I focused on a key example of Epiligurian wedge-top basin, (Marzabotto Basin) proceeding from macro-to-microscale approach. The study started from a remote sensing analysis of the lineaments and morphostructures which affected the study area to obtain the regional faulting pattern and an overview about the main tectonic structures, used as basis for the structural investigation at the mesoscale. On the basis of this, it was possible to reconstruct the succession of tectonic events that affected the Marzabotto Basin, consisting in: i) two sets of thrusts indicating a NE-SW and NW-SE shortening of the sedimentary succession; ii) NE-SW-left lateral transtensional faults related to a strike-slip tectonic phase; iii) three main sets of extensional structures which cut and displace the previous thrusts. Normal faults are related to the post-orogenic evolution and have been dated with U-Th method, getting an age of Middle-Late Pleistocene. From a thermal point of view, apatite fission-tracks and (U-Th)/He analyses of detrital minerals and thermal modelling on the middle-upper Eocene siliciclastic deposits allowed me to better constrain the local exhumation history and correlate it with the large-scale tectonic evolution of the Northern Apennines. In particular, the Marzabotto Basin experienced a complex burial-exhumation history, consisting in two cooling cooling phases related to the growth of the Northern Apennines belt (Oligo-Miocene in age) and a later cooling which tracks the accretion in the orogenic wedge concomitant with rollback-driven extension (late Miocene-Pliocene in age). In conclusion it is possible to affirm that the study shed new light on poorly constrained elements of fold-and-thrust belt
Regularization meets GreenAI: a new framework for image reconstruction in life sciences applications
Get PDFIll-conditioned inverse problems frequently arise in life sciences, particularly in the context of image deblurring and medical image reconstruction. These problems have been addressed through iterative variational algorithms, which regularize the reconstruction by adding prior knowledge about the problem's solution. Despite the theoretical reliability of these methods, their practical utility is constrained by the time required to converge. Recently, the advent of neural networks allowed the development of reconstruction algorithms that can compute highly accurate solutions with minimal time demands. Regrettably, it is well-known that neural networks are sensitive to unexpected noise, and the quality of their reconstructions quickly deteriorates when the input is slightly perturbed. Modern efforts to address this challenge have led to the creation of massive neural network architectures, but this approach is unsustainable from both ecological and economic standpoints. The recently introduced GreenAI paradigm argues that developing sustainable neural network models is essential for practical applications.
In this thesis, we aim to bridge the gap between theory and practice by introducing a novel framework that combines the reliability of model-based iterative algorithms with the speed and accuracy of end-to-end neural networks. Additionally, we demonstrate that our framework yields results comparable to state-of-the-art methods while using relatively small, sustainable models.
In the first part of this thesis, we discuss the proposed framework from a theoretical perspective. We provide an extension of classical regularization theory, applicable in scenarios where neural networks are employed to solve inverse problems, and we show there exists a trade-off between accuracy and stability. Furthermore, we demonstrate the effectiveness of our methods in common life science-related scenarios.
In the second part of the thesis, we initiate an exploration extending the proposed method into the probabilistic domain. We analyze some properties of deep generative models, revealing their potential applicability in addressing ill-posed inverse problems