Purification, biochemical characterization and localization at single cell resolution of Matrix Gla Protein (MGP) and Bone Gla Protein (BGP) in the teleost fish Argyrosomus regius

Tese de dout. em Química, Faculdade de Ciências do Mar e do Ambiente, Univ. do Algarve, 2002

Electrochemical Immunosensing of Cortisol in an Automated Microfluidic System Towards Point-of-Care Applications

This dissertation describes the development of a label-free, electrochemical immunosensing platform integrated into a low-cost microfluidic system for the sensitive, selective and accurate detection of cortisol, a steroid hormone co-related with many physiological disorders. Abnormal levels of cortisol is indicative of conditions such as Cushing’s syndrome, Addison’s disease, adrenal insufficiencies and more recently post-traumatic stress disorder (PTSD). Electrochemical detection of immuno-complex formation is utilized for the sensitive detection of Cortisol using Anti-Cortisol antibodies immobilized on sensing electrodes. Electrochemical detection techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) have been utilized for the characterization and sensing of the label-free detection of Cortisol. The utilization of nanomaterial’s as the immobilizing matrix for Anti-cortisol antibodies that leads to improved sensor response has been explored. A hybrid nano-composite of Polyanaline-Ag/AgO film has been fabricated onto Au substrate using electrophoretic deposition for the preparation of electrochemical immunosening of cortisol. Using a conventional 3-electrode electrochemical cell, a linear sensing range of 1pM to 1µM at a sensitivity of 66µA/M and detection limit of 0.64pg/mL has been demonstrated for detection of cortisol. Alternately, a self-assembled monolayer (SAM) of dithiobis(succinimidylpropionte) (DTSP) has been fabricated for the modification of sensing electrode to immobilize with Anti-Cortisol antibodies. To increase the sensitivity at lower detection limit and to develop a point-of-care sensing platform, the DTSP-SAM has been fabricated on micromachined interdigitated microelectrodes (µIDE). Detection of cortisol is demonstrated at a sensitivity of 20.7µA/M and detection limit of 10pg/mL for a linear sensing range of 10pM to 200nM using the µIDE’s. A simple, low-cost microfluidic system is designed using low-temperature co-fired ceramics (LTCC) technology for the integration of the electrochemical cortisol immunosensor and automation of the immunoassay. For the first time, the non-specific adsorption of analyte on LTCC has been characterized for microfluidic applications. The design, fabrication technique and fluidic characterization of the immunoassay are presented. The DTSP-SAM based electrochemical immunosensor on µIDE is integrated into the LTCC microfluidic system and cortisol detection is achieved in the microfluidic system in a fully automated assay. The fully automated microfluidic immunosensor hold great promise for accurate, sensitive detection of cortisol in point-of-care applications.

Collaborative filtering and deep learning based recommendation system for cold start items

Recommender system is a specific type of intelligent systems, which exploits historical user ratings on items and/or auxiliary information to make recommendations on items to the users. It plays a critical role in a wide range of online shopping, e-commercial services and social networking applications. Collaborative filtering (CF) is the most popular approaches used for recommender systems, but it suffers from complete cold start (CCS) problem where no rating record are available and incomplete cold start (ICS) problem where only a small number of rating records are available for some new items or users in the system. In this paper, we propose two recommendation models to solve the CCS and ICS problems for new items, which are based on a framework of tightly coupled CF approach and deep learning neural network. A specific deep neural network SADE is used to extract the content features of the items. The state of the art CF model, timeSVD++, which models and utilizes temporal dynamics of user preferences and item features, is modified to take the content features into prediction of ratings for cold start items. Extensive experiments on a large Netflix rating dataset of movies are performed, which show that our proposed recommendation models largely outperform the baseline models for rating prediction of cold start items. The two proposed recommendation models are also evaluated and compared on ICS items, and a flexible scheme of model retraining and switching is proposed to deal with the transition of items from cold start to non-cold start status. The experiment results on Netflix movie recommendation show the tight coupling of CF approach and deep learning neural network is feasible and very effective for cold start item recommendation. The design is general and can be applied to many other recommender systems for online shopping and social networking applications. The solution of cold start item problem can largely improve user experience and trust of recommender systems, and effectively promote cold start items.

Hybrid Monte Carlo algorithm for the double exchange model

The Hybrid Monte Carlo algorithm is adapted to the simulation of a system of classical degrees of freedom coupled to non self-interacting lattices fermions. The diagonalization of the Hamiltonian matrix is avoided by introducing a path-integral formulation of the problem, in d + 1 Euclidean space–time. A perfect action formulation allows to work on the continuum Euclidean time, without need for a Trotter–Suzuki extrapolation. To demonstrate the feasibility of the method we study the Double Exchange Model in three dimensions. The complexity of the algorithm grows only as the system volume, allowing to simulate in lattices as large as 163 on a personal computer. We conclude that the second order paramagnetic–ferromagnetic phase transition of Double Exchange Materials close to half-filling belongs to the Universality Class of the three-dimensional classical Heisenberg model.

A novel latent factor model for recommender system

Matrix factorization (MF) has evolved as one of the better practice to handle sparse data in field of recommender systems. Funk singular value decomposition (SVD) is a variant of MF that exists as state-of-the-art method that enabled winning the Netflix prize competition. The method is widely used with modifications in present day research in field of recommender systems. With the potential of data points to grow at very high velocity, it is prudent to devise newer methods that can handle such data accurately as well as efficiently than Funk-SVD in the context of recommender system. In view of the growing data points, I propose a latent factor model that caters to both accuracy and efficiency by reducing the number of latent features of either users or items making it less complex than Funk-SVD, where latent features of both users and items are equal and often larger. A comprehensive empirical evaluation of accuracy on two publicly available, amazon and ml-100 k datasets reveals the comparable accuracy and lesser complexity of proposed methods than Funk-SVD.

The role of cancer related inflammation, Src family kinases and matrix metalloproteinase 9 in colorectal cancer

Colorectal cancer (CRC) is the third most common cancer in the UK with 41,000 new cases diagnosed in 2011. Despite undergoing potentially curative resection, a significant amount of patients develop recurrence. Biomarkers that aid prognostication or identify patients who are suitable for adjuvant treatments are needed. The TNM staging system does a reasonably good job at offering prognostic information to the treating clinician, but it could be better and identifying methods of improving its accuracy are needed. Tumour progression is based on a complex relationship between tumour behaviour and the hosts’ inflammatory responses. Sustained tumour cell proliferation, evading growth suppressors, resisting apoptosis, replicative immortality, sustained angiogenesis, invasion & metastasis, avoiding immune destruction, deregulated cellular energetics, tumour promoting inflammation and genomic instability & mutation have been identified as hallmarks. These hallmarks are malignant behaviors are what makes the cell cancerous and the more extreme the behaviour the more aggressive the cancer the more likely the risk of a poor outcome. There are two primary genomic instability pathways: Microsatellite Instability (MSI) and Chromosomal Instability (CI) also referred to as Microsatellite Stability (MSS). Tumours arising by these pathways have a predilection for specific anatomical, histological and molecular biological features. It is possible that aberrant molecular expression of genes/proteins that promote malignant behaviors may also act as prognostic and predictive biomarkers, which may offer superior prognostic information to classical prognostic features. Cancer related inflammation has been described as a 7th hallmark of cancer. Despite the systemic inflammatory response (SIR) being associated with more aggressive malignant disease, infiltration by immune cells, particularly CD8+ lymphocytes, at the advancing edge of the tumour have been associated with improved outcome and tumour MSI. It remains unknown if the SIR is associated with tumour MSI and this requires further study. The mechanisms by which colorectal cancer cells locally invade through the bowel remain uncertain, but connective tissue degradation by matrix metalloproteinases (MMPs) such as MMP-9 have been implicated. MMP-9 has been found in the cancer cells, stromal cells and patient circulation. Although tumoural MMP-9 has been associated with poor survival, reports are conflicting and contain relatively small sample sizes. Furthermore, the influence of high serum MMP-9 on survival remains unknown. Src family kinases (SFKs) have been implicated in many adverse cancer cell behaviors. SFKs comprise 9 family members BLK, C-SRC, FGR, FYN, HCK, LCK, LYN, YES, YRK. C-SRC has been the most investigated of all SFKs, but the role of other SFKs in cellular behaviors and their prognostic value remains largely unknown. The development of Src inhibitors, such as Dasatinib, has identified SFKs as a potential therapeutic target for patients at higher risk of poor survival. Unfortunately, clinical trials so far have not been promising but this may reflect inadequate patient selection and SFKs may act as useful prognostic and predictive biomarkers. In chapter 3, the association between cancer related inflammation, tumour MSI, clinicopathological factors and survival was tested in two independent cohorts. A training cohort consisting of n=182 patients and a validation cohort of n=677 patients. MSI tumours were associated with a raised CRP (p=0.003). Hypoalbuminaemia was independently associated with poor overall survival in TNM stage II cancer (HR 3.04 (95% CI 1.44 – 6.43);p=0.004), poor recurrence free survival in TNM stage III cancer (HR 1.86 (95% 1.03 – 3.36);p=0.040) and poor overall survival in CI colorectal cancer (HR 1.49 (95% CI 1.06 – 2.10);p=0.022). Interestingly, MSI tumours were associated with poor overall survival in TNM stage III cancer (HR 2.20 (95% CI 1.10 – 4.37);p=0.025). In chapter 4, the role of MMP-9 in colorectal cancer progression and survival was examined. MMP-9 in the tissue was assessed using IHC and serum expression quantified using ELISA. Serum MMP-9 was associated with cancer cell expression (Spearman’s Correlation Coefficient (SCC) 0.393, p<0.001)) and stromal expression (SCC 0.319, p=0.002). Serum MMP-9 was associated with poor recurrence-free (HR 3.37 (95% CI 1.20 – 9.48);p=0.021) and overall survival (HR 3.16 (95% CI 1.22 – 8.15);p=0.018), but tumour MMP-9 was not survival or MSI status. In chapter 5, the role of SFK expression and activation in colorectal cancer progression and survival was studied. On PCR analysis, although LYN, C-SRC and YES were the most highly expressed, FGR and HCK had higher expression profiles as tumours progressed. Using IHC, raised cytoplasmic FAK (tyr 861) was independently associated with poor recurrence free survival in all cancers (HR 1.48 (95% CI 1.02 – 2.16);p=0.040) and CI cancers (HR 1.50 (95% CI 1.02 – 2.21);p=0.040). However, raised cytoplasmic HCK (HR 2.04 (95% CI 1.11 – 3.76);p=0.022) was independently associated with poor recurrence-free survival in TNM stage II cancers. T84 and HT29 cell lines were used to examine the cellular effects of Dasatinib. Cell viability was assessed using WST-1 assay and apoptosis assessed using an ELISA cell death detection assay. Dasatinib increased T84 tumour cell apoptosis in a dose dependent manner and resulted in reduced expression of nuclear (p=0.008) and cytoplasmic (p=0.016) FAK (tyr 861) expression and increased nuclear FGR expression (p=0.004). The results of this thesis confirm that colorectal cancer is a complex disease that represents several subtypes of cancer based on molecular biological behaviors. This thesis concentrated on features of the disease related to inflammation in terms of genetic and molecular characterisation. MSI cancers are closely associated with systemic inflammation but despite this observation, they retain their relatively improved survival. MMP-9 is a feature of tissue remodeling during inflammation and is also associated with degradation of connective tissue, advanced T-stage and poor outcome when measured in the serum. The lack of stromal quantification due to TMA use rather than full sections makes the value of tumoural MMP-9 immunoreactivity in the prognostication and its association with MSI unknown and requires further study. Finally, SFK activation was also associated with SIR, however, only cytoplasmic HCK was independently associated with poor survival in patients with TNM stage II disease, the group of patients where identifying a novel biomarker is most needed. There is still some way to go before these biomarkers are translated into clinical practice and future work needs to focus on obtaining a reliable and robust scientific technique with validation in an adequately powered independent cohort.

Determination of subclinical metabolic disorders in transition dairy cows

Das Gesundheitsmanagement von Milchkühen hat in den vergangenen Jahren auf den landwirtschaftlichen Betrieben an Bedeutung gewonnen. Neben Präventionsmaßnahmen zur Gesunderhaltung der Tiere ist die frühzeitige und systematische Erkennung von Erkrankungen hierbei der Hauptbestandteil. Es zeigt sich vermehrt, dass vor allem Transitkühe verstärkt an Stoffwechselerkrankungen in sowohl klinischer als auch subklinischer Form erkranken. Letztere stellen ein hohes Risiko dar, zum einen weil subklinische Erkrankungen oftmals nur schwer oder gar nicht erkannt werden und zum anderen, weil sie in vielen Fällen die Grundlage für meist schwerwiegendere Folgeerkrankungen sind. In der vorliegenden Studie wird das Thema der Früherkennung von subklinischen Ketosen und der subakuten Pansenazidose behandelt. Verschiedene Methoden wurden unter praktischen Versuchsbedingungen auf ihre Tauglichkeit zur Krankheitserkennung hin geprüft. In einer ersten Studie wurde auf einem konventionellen Milchviehbetrieb ein Ketose-Monitoring bei frischlaktierenden Kühen ab Tag 3 postpartum durchgeführt. Insgesamt 15 Tiere waren an einer subklinischen Ketose erkrankt, was eine Aufkommensrate von 26% in den untersuchten Tieren bedeutete. Die Blutproben von insgesamt 24 Tieren wurden auf ihren IL-6-Gehalt untersucht. Von den untersuchten Tieren waren 14 Tiere erkrankt, 10 Tiere bildeten die gesunde Kontrollgruppe. Interleukin-6 wurde bestimmt, da dem Zytokin IL-6 in anderen Studien in Bezug auf Ketosen eine Rolle zugesprochen wurde. Die erwartete Erhöhung von IL-6 bei erkrankten Tieren konnte nicht festgestellt werden; die erkrankten Kühe zeigten vielmehr die niedrigsten IL-6 Werte der Studiengruppe. Insgesamt waren die IL-6 Konzentrationen auf einem niedrigen Niveau mit 27.2 pg/m l± 10.2. Es zeigte sich, dass die IL-6 Bestimmung im Blut hinsichtlich der Erkennung von subklinischen Ketosen nur eingeschränkt nutzbar ist. Es konnte ausschließlich eine schwache negative Korrelation zwischen Beta- Hydroxybutyrat (BHBA, Goldstandard für den Nachweis einer Ketose) und IL-6 detektiert werden. Zusätzlich zu den Blutanalysen wurde ebenfalls die tägliche Wiederkauaktivität mit dem „DairyCheck“ System bestimmt, welches kontinuierlich die charakteristischen Kaumuskelkontraktionen aufzeichnet und somit die Dauer des Wiederkäuens bestimmt werden kann. Es wurde geprüft, ob sich ketotische Tiere von nicht ketotischen Tieren hinsichtlich der täglichen Wiederkäuzeit unterscheiden. Milchkühe mit einer Ketose kauten im Schnitt 475 min/d ± 56 wieder, nach Genesung 497 min/d ± 48. Sie befanden sich somit im Durchschnitt immer unterhalb der gesunden Kontrollgruppe, welche 521 min/d ± 76 wiederkaute. Eine Korrelation zwischen der Wiederkauzeit und dem BHBA- Gehalt im Blut war nur sehr schwach ausgeprägt, nicht zuletzt da die Tiere generell eine hohe Variabilität in der Wiederkauaktivität zeigten. Bei einer weiteren Studie, ebenfalls auf einem Praxisbetrieb durchgeführt, wurde auf die Erkennung der subakuten Pansensazidose (SARA) fokussiert. Hierbei kam ein drahtloses, kommerziell verfügbares Bolussystem zum Einsatz, welches den pH Wert kontinuierlich im Retikulorumen misst. Es macht die Erkennung einer SARA auch unter Praxisbedingungen ohne invasive Methoden wie der Punktion möglich. Das Bolussystem wurde 24 Milchkühen kurz vor der Abkalbung oral eingegeben, um den pH-Wert während der gesamten Transitphase messen und überwachen zu können. Während in der Trockenstehphase nur vereinzelte SARA Fälle auftraten, erlitt ein Großteil der untersuchten Tiere in der Frühlaktation eine SARA. Auf Grundlage von pH-Werten von laktierenden Milchkühen, wurde zusätzlich eine Sensitivitätsanalyse von verschieden, bereits eingesetzten Nachweismethoden durchgeführt, um die Tauglichkeit für die SARA-Diagnostik zu untersuchen. Es handelte sich hierbei zum einen um einen SARA-Nachweis unter Heranziehung von Einzelwerten, Fress- und Wiederkäuzeiten, sowie ausgewählten Milchinhaltsstoffen und der Milchmenge. Die Analyse ergab, dass nahezu alle Nachweismethoden im Vergleich zur Langzeitmessung nur eingeschränkt zur SARA-Diagnostik nutzbar sind. In einem weiteren Teil der Studie wurde eine Kotfraktionierung bei den gleichen Tieren durchgeführt, um damit SARA-Tiere auch mittels der Kotanalyse erkennen kann. Es konnte gezeigt werden, dass zum einen die Ration einen Einfluss auf die Kotzusammensetzung hat (Trockensteherration versus Ration für Laktierende) zum anderen aber auch, dass eine SARA die Zusammensetzung des Kotes verändert. Hierfür wurden Kotproben ausschließlich von laktierenden Kühen untersucht, sodass der Einfluss der Ration ausgeschlossen werden konnte. Erhöhte Faseranteile im Kot von SARA - Kühen gaben Hinweis auf eine verminderte Verdaulichkeit. Dabei erwies sich vor allem die Hemizellulose als guter Parameter, um auf eine SARA schließen zu können. Die Versuchsbedingungen ließen es ebenfalls zu, die pH-Verläufe der Tiere in der Frühlaktation zu untersuchen. Eine Clusteranalyse von pH-Werten der ersten 12 Tage postpartum zeigte, dass die untersuchten Tiere trotz gleicher Haltungs- und Fütterungsbedingungen unterschiedliche pH-Wert Verläufe entwickelten. So gab es eine Gruppe von Milchkühen, die den pH-Wert stabil halten konnte, während die restlichen pH-Abfälle in verschiedenen Verläufen und Intensitäten aufzeigten. Es konnte ebenfalls aufgezeigt werden, dass Tiere innerhalb der Testherde unterschiedliche Schweregrade der SARA entwickelten. Auch in dieser Studie wurde deutlich, dass Tiere scheinbar unterschiedliche Möglichkeiten haben, auf ihre Umwelt zu reagieren, bzw. suboptimalen Bedingungen entgegenwirken zu können. Zusammengefasst wurden verschiedene Methoden zur Ketose- und SARA- Erkennung geprüft, von denen nur einzelne für die Praxis zu empfehlen sind. Die Variabilität der Tiere, sowohl bei der Ausprägung der Erkrankungen als auch bei den gemessenen Parametern verdeutlicht die Notwendigkeit, diese im Herden- und Gesundheitsmanagement in Zukunft stärker zu berücksichtigen.

Hierarchical spatial segregation of two Mediterranean vole species: the role of patch‑network structure and matrix composition

According to ecological theory, the coexistence of competitors in patchy environments may be facilitated by hierarchical spatial segregation along axes of environmental variation, but empirical evidence is limited. Cabrera and water voles show a metapopulation-like structure in Mediterranean farmland, where they are known to segregate along space, habitat, and time axes within habitat patches. Here, we assess whether segregation also occurs among and within landscapes, and how this is influenced by patch-network and matrix composition. We surveyed 75 landscapes, each covering 78 ha, where we mapped all habitat patches potentially suitable for Cabrera and water voles, and the area effectively occupied by each species (extent of occupancy). The relatively large water vole tended to be the sole occupant of landscapes with high habitat amount but relatively low patch density (i.e., with a few large patches), and with a predominantly agricultural matrix, whereas landscapes with high patch density (i.e.,many small patches) and low agricultural cover, tended to be occupied exclusively by the small Cabrera vole. The two species tended to co-occur in landscapes with intermediate patch-network and matrix characteristics, though their extents of occurrence were negatively correlated after controlling for environmental effects. In combination with our previous studies on the Cabrera-water vole system, these findings illustrated empirically the occurrence of hierarchical spatial segregation, ranging from withinpatches to among-landscapes. Overall, our study suggests that recognizing the hierarchical nature of spatial segregation patterns and their major environmental drivers should enhance our understanding of species coexistence in patchy environments.

Can birds play a role as High Nature Value indicators of montado system?

Montados form a heterogeneous landscape of wooded matrix dominated by cork and/or holm oak with open areas characterized by fuzzy boundaries. Montado supports a high biological diversity associated to low intensity management and a landscape diversity provided by a continuous gradient of land cover. Among other features this permits the classification of montados as a High Nature Value (HNV) system. We assessed the role of birds as HNV indicators for montado, and tested several bird groups—farmland, edge, forest generalists and forest specialists species; and some universal indicators such as species conservation status, Shannon’s diversity index and species richness. Our study areas covered the North–South distribution of cork oak in Portugal, and we surveyed the breeding bird communities across 117 sampling sites. In addition to variables related to management and sanitary status, we considered variables that characterize the landscape heterogeneity inside the montado—trees and shrub density and richness of woody vegetation. Our results suggest that specific bird guilds can be used as HNV indicators of particular typologies of montado, and highlight the need to develop an indicator that could be transversally applied to all types of montado.

Smart Farming in Italian agriculture: essays on adoption and diffusion dynamics shaping the agricultural digital transition

Smart Farming Technologies (SFT) is a term used to define the set of digital technologies able not only to control and manage the farm system, but also to connect it to the many disruptive digital applications posed at multiple links along the value chain. The adoption of SFT has been so far limited, with significant differences at country-levels and among different types of farms and farmers. The objective of this thesis is to analyze what factors contributes to shape the agricultural digital transition and to assess its potential impacts in the Italian agri-food system. Specifically, this overall research objective is approached under three different perspectives. Firstly, we carry out a review of the literature that focuses on the determinants of adoption of farm-level Management Information Systems (MIS), namely the most adopted smart farming solutions in Italy. Secondly, we run an empirical analysis on what factors are currently shaping the adoption of SFT in Italy. In doing so, we focus on the multi-process and multi-faceted aspects of the adoption, by overcoming the one-off binary approach often used to study adoption decisions. Finally, we adopt a forward-looking perspective to investigate what the socio-ethical implications of a diffused use of SFT might be. On the one hand, our results indicate that bigger, more structured farms with higher levels of commercial integration along the agri-food supply chain are those more likely to be early adopters. On the other hand, they highlight the need for the institutional and organizational environment around farms to more effectively support farmers in the digital transition. Moreover, the role of several other actors and actions are discussed and analyzed, by highlighting the key role of specific agri-food stakeholders and ad-hoc policies, with the aim to propose a clearer path towards an efficient, fair and inclusive digitalization of the agrifood sector.

Transition Matters. Il ruolo del designer nella transizione sostenibile e circolare dei materiali polimerici

La ricerca indaga il ruolo del designer nella transizione sostenibile e circolare all’uso di materiali polimerici. Nel contesto contemporaneo la plastica è utilizzata in quasi ogni settore merceologico ma la sua futura applicazione è messa in forte discussione a causa dei visibili impatti ambientali del suo uso irresponsabile. Un passaggio netto dalla totale dipendenza alla liberazione dei polimeri è difficile; è necessario un periodo di transizione che permetta di coesistere responsabilmente con i polimeri in attesa di trovare dei validi sostituti. L’obiettivo della ricerca è lavorare su questo periodo ponendo il designer e le sue competenze come soggetti chiave del movimento. La tesi di ricerca propone un approccio per calare le pratiche del Transition Design nella progettazione di sistemi-prodotto, nutrendosi degli attributi anticipatori dell’Advanced Design e puntando agli obiettivi del Circular Design, lavorando a partire dalle merci più critiche nel contesto contemporaneo: quelle in polimero fossile non riciclabile. Contributo della tesi è la figura del Transition Matter Designer, un progettista di transizioni dei materiali che prevede metamorfosi di sistemi-prodotto nel tempo grazie alle sue competenze a diverse scale del progetto: forma l’utente agli atteggiamenti circolari e sostenibili, caratterizza i materiali per individuarne nuovi usi, seleziona i processi produttivi adatti a prevenire scarti e ne anticipa i cicli di vita nei prodotti. I Knitted Fasteners sono il risultato della simulazione del lavoro del Transition Matter Designer nel tessile: un sistema di elementi di fissaggio, personalizzabili dallo stilista e integrati negli abiti a maglia, che permettono di eliminare l’uso di fashion fasteners in plastica e metallo, elementi che rendono difficile il riciclo dei capi. Dalla sperimentazione è emerso il modello concettuale della Transindustrial Production: un lavoro di collaborazione fra Transition Matter Designer e creativo per dare identità ai materiali polimerici circolari attraverso l’ibridazione fra artigianato e industria, tipico del Made in Italy.

Enhancing predictive capability of models for solubility and permeability in polymers and composites

The interpretation of phase equilibrium and mass transport phenomena in gas/solvent - polymer system at molten or glassy state is relevant in many industrial applications. Among tools available for the prediction of thermodynamics properties in these systems, at molten/rubbery state, is the group contribution lattice-fluid equation of state (GCLF-EoS), developed by Lee and Danner and ultimately based on Panayiotou and Vera LF theory. On the other side, a thermodynamic approach namely non-equilibrium lattice-fluid (NELF) was proposed by Doghieri and Sarti to consistently extend the description of thermodynamic properties of solute polymer systems obtained through a suitable equilibrium model to the case of non-equilibrium conditions below the glass transition temperature. The first objective of this work is to investigate the phase behaviour in solvent/polymer at glassy state by using NELF model and to develop a predictive tool for gas or vapor solubility that could be applied in several different applications: membrane gas separation, barrier materials for food packaging, polymer-based gas sensors and drug delivery devices. Within the efforts to develop a predictive tool of this kind, a revision of the group contribution method developed by High and Danner for the application of LF model by Panayiotou and Vera is considered, with reference to possible alternatives for the mixing rule for characteristic interaction energy between segments. The work also devotes efforts to the analysis of gas permeability in polymer composite materials as formed by a polymer matrix in which domains are dispersed of a second phase and attention is focused on relation for deviation from Maxwell law as function of arrangement, shape of dispersed domains and loading.

Radiocarbon and stable isotopes in the shell organic matrix: a new approach for the use of mollusk shells in the study of human evolution

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.

Synthesis of Na-PSS geopolymers and analysis of the H2O/Na2O molar ratio influence over their mechanical properties

Geopolymers are solid aluminosilicate material made by mixing an activating solution and a solid precursor. This work studied the mechanisms of synthesis of metakaolin-based geopolymers and the influence of water content, described by the molar ratio H2O/Na2O, on the final product. The samples were tested using a Uniaxial Compressive Test (UCT) to define their compressive resistance. Two geopolymers series were synthetized and let them rest for 7- days and 28-days, each of them composed by six different sets. 7-day rest series showed that water addition had no relevant effect over its resistance while the 28-day rest series almost doubled the compressive resistance, although those with the highest H2O/Na2O molar ratio showed instead a drastic reduction. Two other series were synthesized by adding silt aggregate, a waste material obtained in the production of aggregate for concrete, corresponding to 10wt% and 20wt%of the metakaolin used. After 28 days of aging, these samples were tested via UCT to measure the variation of the compressive resistance after the silt addition. The aggregate has disruptive effects over the compressive resistance, but the 20wt% samples achieved a higher compressive resistance. Samples with highest and lowest compressive resistance have been chosen to carry out an XRD analysis. In all the samples it has been recognized the presence of Anatase (TiO2), a titanium oxide found in the metakaolin and Thermonatrite, a hydrated sodium carbonate [Na2CO3 • (H2O)]. Scanning Electron Microscopy was carried out on the samples with the highest compressive resistance and showed that the samples with lower water content developed a homogeneous geopolymeric texture, while those with higher water content showed instead a spongy-like texture and a higher air or pore solution bubbles presence. Silt/geopolymer composites showed a fracture system developing across the interstitial transition zone between the geopolymer matrix and the aggregate particle.

Ultracold Bose-Fermi mixtures with pairing: quantum phase transition, mechanical stability, and trap confinement

Ultracold dilute gases occupy an important role in modern physics and they are employed to verify fundamental quantum theories in most branches of theoretical physics. The scope of this thesis work is the study of Bose-Fermi (BF) mixtures at zero temperature with a tunable pairing between bosons and fermions. The mixtures are treated with diagrammatic quantum many-body methods based on the so-called T-matrix formalism. Starting from the Fermi-polaron limit, I will explore various values of relative concentrations up to mixtures with a majority of bosons, a case barely considered in previous works. An unexpected quantum phase transition is found to occur in a certain range of BF coupling for mixture with a slight majority of bosons. The mechanical stability of mixtures has been analysed, when the boson-fermion interaction is changed from weak to strong values, in the light of experimental results recently obtained for a double-degenerate Bose-Fermi mixture of 23 Na - 40 K. A possible improvement in the description of the boson-boson repulsion based on Popov's theory is proposed. Finally, the effects of a harmonic trapping potential are described, with a comparison with the experimental data for the condensate fraction recently obtained for a trapped 23 Na - 40 K mixture.