Development of Zirconia based phosphors for application in lighting and as luminescent bioprobes

The strong progress evidenced in photonic and optoelectronic areas, accompanied by an exponential development in the nanoscience and nanotechnology, gave rise to an increasing demand for efficient luminescent materials with more and more exigent characteristics. In this field, wide band gap hosts doped with lanthanide ions represent a class of luminescent materials with a strong technological importance. Within wide band gap material, zirconia owns a combination of physical and chemical properties that potentiate it as an excellent host for the aforementioned ions, envisaging its use in different areas, including in lighting and optical sensors applications, such as pressure sensors and biosensors. Following the demand for outstanding luminescent materials, there is also a request for fast, economic and an easy scale-up process for their production. Regarding these demands, laser floating zone, solution combustion synthesis and pulsed laser ablation in liquid techniques are explored in this thesis for the production of single crystals, nanopowders and nanoparticles of lanthanides doped zirconia based hosts. Simultaneously, a detailed study of the morphological, structural and optical properties of the produced materials is made. The luminescent characteristics of zirconia and yttria stabilized zirconia (YSZ) doped with different lanthanide ions (Ce3+ (4f1), Pr3+ (4f2), Sm3+ (4f5), Eu3+ (4f6), Tb3+ (4f8), Dy3+ (4f9), Er3+ (4f11), Tm3+ (4f12), Yb3+ (4f13)) and co-doped with Er3+,Yb3+ and Tm3+,Yb3+ are analysed. Besides the Stokes luminescence, the anti- Stokes emission upon infrared excitation (upconversion and black body radiation) is also analysed and discussed. The comparison of the luminescence characteristics in materials with different dimensions allowed to analyse the effect of size in the luminescent properties of the dopant lanthanide ions. The potentialities of application of the produced luminescent materials in solid state light, biosensors and pressure sensors are explored taking into account their studied characteristics.

Detection of mesoscale thermal fronts from 4km data using smoothing techniques: Gradient-based fronts classification and basin scale application

In order to optimize frontal detection in sea surface temperature fields at 4 km resolution, a combined statistical and expert-based approach is applied to test different spatial smoothing of the data prior to the detection process. Fronts are usually detected at 1 km resolution using the histogram-based, single image edge detection (SIED) algorithm developed by Cayula and Cornillon in 1992, with a standard preliminary smoothing using a median filter and a 3 × 3 pixel kernel. Here, detections are performed in three study regions (off Morocco, the Mozambique Channel, and north-western Australia) and across the Indian Ocean basin using the combination of multiple windows (CMW) method developed by Nieto, Demarcq and McClatchie in 2012 which improves on the original Cayula and Cornillon algorithm. Detections at 4 km and 1 km of resolution are compared. Fronts are divided in two intensity classes (“weak” and “strong”) according to their thermal gradient. A preliminary smoothing is applied prior to the detection using different convolutions: three type of filters (median, average and Gaussian) combined with four kernel sizes (3 × 3, 5 × 5, 7 × 7, and 9 × 9 pixels) and three detection window sizes (16 × 16, 24 × 24 and 32 × 32 pixels) to test the effect of these smoothing combinations on reducing the background noise of the data and therefore on improving the frontal detection. The performance of the combinations on 4 km data are evaluated using two criteria: detection efficiency and front length. We find that the optimal combination of preliminary smoothing parameters in enhancing detection efficiency and preserving front length includes a median filter, a 16 × 16 pixel window size, and a 5 × 5 pixel kernel for strong fronts and a 7 × 7 pixel kernel for weak fronts. Results show an improvement in detection performance (from largest to smallest window size) of 71% for strong fronts and 120% for weak fronts. Despite the small window used (16 × 16 pixels), the length of the fronts has been preserved relative to that found with 1 km data. This optimal preliminary smoothing and the CMW detection algorithm on 4 km sea surface temperature data are then used to describe the spatial distribution of the monthly frequencies of occurrence for both strong and weak fronts across the Indian Ocean basin. In general strong fronts are observed in coastal areas whereas weak fronts, with some seasonal exceptions, are mainly located in the open ocean. This study shows that adequate noise reduction done by a preliminary smoothing of the data considerably improves the frontal detection efficiency as well as the global quality of the results. Consequently, the use of 4 km data enables frontal detections similar to 1 km data (using a standard median 3 × 3 convolution) in terms of detectability, length and location. This method, using 4 km data is easily applicable to large regions or at the global scale with far less constraints of data manipulation and processing time relative to 1 km data.

Development of paper-based color test-strip for drug detection in aquatic environment: Application to oxytetracycline

The wide use of antibiotics in aquaculture has led to the emergence of resistant microbial species. It should be avoided/minimized by controlling the amount of drug employed in fish farming. For this purpose, the present work proposes test-strip papers aiming at the detection/semi-quantitative determination of organic drugs by visual comparison of color changes, in a similar analytical procedure to that of pH monitoring by universal pH paper. This is done by establishing suitable chemical changes upon cellulose, attributing the paper the ability to react with the organic drug and to produce a color change. Quantitative data is also enabled by taking a picture and applying a suitable mathematical treatment to the color coordinates given by the HSL system used by windows. As proof of concept, this approach was applied to oxytetracycline (OXY), one of the antibiotics frequently used in aquaculture. A bottom-up modification of paper was established, starting by the reaction of the glucose moieties on the paper with 3-triethoxysilylpropylamine (APTES). The so-formed amine layer allowed binding to a metal ion by coordination chemistry, while the metal ion reacted after with the drug to produce a colored compound. The most suitable metals to carry out such modification were selected by bulk studies, and the several stages of the paper modification were optimized to produce an intense color change against the concentration of the drug. The paper strips were applied to the analysis of spiked environmental water, allowing a quantitative determination for OXY concentrations as low as 30 ng/mL. In general, this work provided a simple, method to screen and discriminate tetracycline drugs, in aquaculture, being a promising tool for local, quick and cheap monitoring of drugs.

Application of mathematical models to mycotoxins children risk assessment: a case study of Portuguese children exposure to co-occurring mycotoxins in processed cereal-based foods

People, animals and the environment can be exposed to multiple chemicals at once from a variety of sources, but current risk assessment is usually carried out based on one chemical substance at a time. In human health risk assessment, ingestion of food is considered a major route of exposure to many contaminants, namely mycotoxins, a wide group of fungal secondary metabolites that are known to potentially cause toxicity and carcinogenic outcomes. Mycotoxins are commonly found in a variety of foods including those intended for consumption by infants and young children and have been found in processed cereal-based foods available in the Portuguese market. The use of mathematical models, including probabilistic approaches using Monte Carlo simulations, constitutes a prominent issue in human health risk assessment in general and in mycotoxins exposure assessment in particular. The present study aims to characterize, for the first time, the risk associated with the exposure of Portuguese children to single and multiple mycotoxins present in processed cereal-based foods (CBF). Portuguese children (0-3 years old) food consumption data (n=103) were collected using a 3 days food diary. Contamination data concerned the quantification of 12 mycotoxins (aflatoxins, ochratoxin A, fumonisins and trichothecenes) were evaluated in 20 CBF samples marketed in 2014 and 2015 in Lisbon; samples were analyzed by HPLC-FLD, LC-MS/MS and GC-MS. Daily exposure of children to mycotoxins was performed using deterministic and probabilistic approaches. Different strategies were used to treat the left censored data. For aflatoxins, as carcinogenic compounds, the margin of exposure (MoE) was calculated as a ratio of BMDL (benchmark dose lower confidence limit) to the aflatoxin exposure. The magnitude of the MoE gives an indication of the risk level. For the remaining mycotoxins, the output of exposure was compared to the dose reference values (TDI) in order to calculate the hazard quotients (ratio between exposure and a reference dose, HQ). For the cumulative risk assessment of multiple mycotoxins, the concentration addition (CA) concept was used. The combined margin of exposure (MoET) and the hazard index (HI) were calculated for aflatoxins and the remaining mycotoxins, respectively. 71% of CBF analyzed samples were contaminated with mycotoxins (with values below the legal limits) and approximately 56% of the studied children consumed CBF at least once in these 3 days. Preliminary results showed that children exposure to single mycotoxins present in CBF were below the TDI. Aflatoxins MoE and MoET revealed a reduced potential risk by exposure through consumption of CBF (with values around 10000 or more). HQ and HI values for the remaining mycotoxins were below 1. Children are a particularly vulnerable population group to food contaminants and the present results point out an urgent need to establish legal limits and control strategies regarding the presence of multiple mycotoxins in children foods in order to protect their health. The development of packaging materials with antifungal properties is a possible solution to control the growth of moulds and consequently to reduce mycotoxin production, contributing to guarantee the quality and safety of foods intended for children consumption.

Characterization of a biodegradable starch based film. Application on the preservation of fresh spinach

Mestrado em Engenharia Alimentar - Instituto Superior de Agronomia - UL

Brazilian multifaceted ecologically-based agriculture: Between conventionalization and agroecological principles application.

2009

Application-Based Analysis of Register File Criticality for Reliability Assessment in Embedded Microprocessors

There is an increasing concern to reduce the cost and overheads during the development of reliable systems. Selective protection of most critical parts of the systems represents a viable solution to obtain a high level of reliability at a fraction of the cost. In particular to design a selective fault mitigation strategy for processor-based systems, it is mandatory to identify and prioritize the most vulnerable registers in the register file as best candidates to be protected (hardened). This paper presents an application-based metric to estimate the criticality of each register from the microprocessor register file in microprocessor-based systems. The proposed metric relies on the combination of three different criteria based on common features of executed applications. The applicability and accuracy of our proposal have been evaluated in a set of applications running in different microprocessors. Results show a significant improvement in accuracy compared to previous approaches and regardless of the underlying architecture.

Development of hydroxyapatite-based nanomaterials to enhance biological response of osteoblast cells for clinical application

Purpose: To develop a novel chitosan/gelatin-hydroxyapatite (CGHaP) microspheres for evaluating the biological response of pre-osteoblast cells. Methods: The microsphere was prepared by water-in-oil emulsion method. Cell proliferation was studied using AlamarBlue colorimetric assay and DAPI staining while alkaline phosphatase assay was carried out by colorimetric assay method. Chitosan microspheres as well as chitosan-hydroxyapatite microspheres was prepared and tested for biological response from MC3T3-E1 cell line. Results: The results showed that CGHaP promotes MC3T3-E1 cell proliferation and spread on the surface of microspheres. The cells were clustered with more actin filaments and well-linked with neighbouring cells or adjacent cells when cultured in CGHaP microspheres whereas fewer cells were spread on chitosan (CH) microspheres. CGHaP microspheres significantly (p < 0.05) promoted cell attachment, proliferation and extracellular matrix mineralization. CGHaP microspheres presented significantly (p < 0.02) higher calcium deposition (0.5 ng) than CH microspheres (0.28 ng). Specifically, CGHaP microspheres exhibited high ALP activity (8 units; 2-fold) compared to CH with 3 units, after 7 days of incubation. The results suggest that CGHaP possesses a great ability to facilitate bone ingrowth formation and possibility of good osteointegration in vivo. Conclusion: The nanomaterial enhances the proliferation of pre-osteoblast cells in tissue engineering microspheres. The outcome of this study may have a major impact on the development of novel nanomaterials for bone tissue engineering.

Acceptance of smartphone-based mobile shopping:mobile benefits, customer characteristics, perceived risk and the impact of application context

Despite their generally increasing use, the adoption of mobile shopping applications often differs across purchase contexts. In order to advance our understanding of smartphone-based mobile shopping acceptance, this study integrates and extends existing approaches from technology acceptance literature by examining two previously underexplored aspects. Firstly, the study examines the impact of different mobile and personal benefits (instant connectivity, contextual value and hedonic motivation), customer characteristics (habit) and risk facets (financial, performance, and security risk) as antecedents of mobile shopping acceptance. Secondly, it is assumed that several acceptance drivers differ in relevance subject to the perception of three mobile shopping characteristics (location sensitivity, time criticality, and extent of control), while other drivers are assumed to matter independent of the context. Based on a dataset of 410 smartphone shoppers, empirical results demonstrate that several acceptance predictors are associated with ease of use and usefulness, which in turn affect intentional and behavioral outcomes. Furthermore, the extent to which risks and benefits impact ease of use and usefulness is influenced by the three contextual characteristics. From a managerial perspective, results show which factors to consider in the development of mobile shopping applications and in which different application contexts they matter.

Computer-based monitoring platform for renewable energy systems: Four experimental application cases using NI LabVIEW

Sustainability and responsible environmental behaviour constitute a vital premise in the development of the humankind. In fact, during last decades, the global energetic scenario is evolving towards a scheme with increasing relevance of Renewable Energy Sources (RES) like photovoltaic, wind, biomass and hydrogen. Furthermore, hydrogen is an energy carrier which constitutes a mean for long-term energy storage. The integration of hydrogen with local RES contributes to distributed power generation and early introduction of hydrogen economy. Intermittent nature of many of RES, for instance solar and wind sources, impose the development of a management and control strategy to overcome this drawback. This strategy is responsible of providing a reliable, stable and efficient operation of the system. To implement such strategy, a monitoring system is required.The present paper aims to contribute to experimentally validate LabVIEW as valuable tool to develop monitoring platforms in the field of RES-based facilities. To this aim, a set of real systems successfully monitored is exposed.

Emerging plant-based proteins: comparison from extraction to functional properties and food application

The increasing demand for alternatives to meat food products, which is linked to ethical and environmental reasons, highlights the necessity of using different protein sources. Plant proteins provide a valid option, thanks to the relative low costs, high availability and wide supply sources. The current process used to produce plant concentrates and isolates is the alkaline extraction followed by isoelectric precipitation. However, despite the high purity of the proteins, it presents some drawbacks. Innovative protein extraction processes are emerging, with the aim of reducing the environmental impact and the costs, as well as improving the functional properties. In this study, the traditional wet protein extraction and another simplified wet process were used to obtain protein-rich extracts out of different plants. The sources considered in the project were de-oiled sunflower and canola, chickpea, lentils, and the camelina meal, an emerging oleaginous seed interesting for its high content of omega 3. The extracts obtained from the two processes were then analysed for their capacities to hold water and fat, to form gel and a stable foam. Results highlighted strong differences concerning the protein content, yield and functionalities. The extracts obtained with the alkaline process confirmed the literature data about the four plant sources (sunflower, canola, chickpea and lentils) and allow to obtain a camelina concentrate with a protein content of 63 % and a protein recovery of 41 %. The second easiest process was not effective to obtain a protein enrichment in oleaginous sources, whereas an enrichment of 10 and 15 % was obtained in chickpea and lentils, respectively. The functional properties were also completely different: the easiest process produced protein ingredients completely water-soluble at pH 7, with a discrete foaming capacity compared to the extracts obtained with alkaline process. These characteristics could make these extracts suitable for the plant milk-analogue products.

Synthesis, characterization, and application of PHB-based gels for cultural heritage conservation

The aim of my master thesis is developing novel, greener approaches for the cleaning of artworks: such treatment consists in the removal of old varnish layers which tend to discolor or darken with time, thus allowing replacement with a new protecting coat. While protocols presently applied can be effective in the cleaning of the artworks, none of them take into account conservators’ health safety and environmental issues. Thus, using biomass-derived components, which are non-toxic and reusable and/or compostable might bring into the heritage conservation an additional awareness about safety and environmental claiming. The laboratory work for the thesis is a collaborative work between different groups. The biggest part of the work was at the Polymer group where gels were synthesized using Polyhydroxybutyrate (PHB) from sustainable resources and green solvents. The use of the gels might help to reduce the volatilization of solvents and contributes to the localization of the cleaning action. After the preparation of the gels, different characterization methods were used in order to estimate their properties and shelf-life. Finally, the work was completed on the application of the gels on sculpture, coated with undesired layers to be removed. Here, pre-mapping of the areas of interest was realized with different optical techniques, followed by the application of the gels for the cleaning and analyzing the effectiveness of cleaning.

Spatial based approach to fisheries management. An application to bottom trawling in the strait of Sicily

At the beginning of my thesis project, considering that some stocks are in overfishing status due to both high fishing effort and high level of juveniles in the catch, my main purpose was to understand how to contribute to improving the state of the fishery resources of the Mediterranean Sea. To mitigate the overfishing, the General Fisheries Commission for the Mediterranean (GFCM) adopted several Fishery Restricted Areas, which are geographically defined areas where some specific fishing activities are temporarily or permanently banned or restricted in order to reduce the exploitation patterns and conservation of specific stocks as well as of habitats and deep-sea ecosystems, including the Essential Fish Habitats (EFH) and the Vulnerable Marine Ecosystems (VME). Considering that GFCM established 3 Fisheries Restricted Areas (FRAs) in the Strait of Sicily (SoS) in 2016 aimed at protecting the nursery areas of the deep-water rose shrimp (DPS, Parapenaeus longirostris – Lucas, 1846) and the European hake (HKE, Merluccius merluccius – Linnaeus, 1758) to reduce the exploitation pattern of undersized species, in my thesis project I devoted myself to evaluate the effect of the FRAs on the status stock and the fishery performance using a spatial bio-economic model.

Development and application of a computer-based methodology for design for additive manufacturing of automotive components

The research project aims to improve the Design for Additive Manufacturing of metal components. Firstly, the scenario of Additive Manufacturing is depicted, describing its role in Industry 4.0 and in particular focusing on Metal Additive Manufacturing technologies and the Automotive sector applications. Secondly, the state of the art in Design for Additive Manufacturing is described, contextualizing the methodologies, and classifying guidelines, rules, and approaches. The key phases of product design and process design to achieve lightweight functional designs and reliable processes are deepened together with the Computer-Aided Technologies to support the approaches implementation. Therefore, a general Design for Additive Manufacturing workflow based on product and process optimization has been systematically defined. From the analysis of the state of the art, the use of a holistic approach has been considered fundamental and thus the use of integrated product-process design platforms has been evaluated as a key element for its development. Indeed, a computer-based methodology exploiting integrated tools and numerical simulations to drive the product and process optimization has been proposed. A validation of CAD platform-based approaches has been performed, as well as potentials offered by integrated tools have been evaluated. Concerning product optimization, systematic approaches to integrate topology optimization in the design have been proposed and validated through product optimization of an automotive case study. Concerning process optimization, the use of process simulation techniques to prevent manufacturing flaws related to the high thermal gradients of metal processes is developed, providing case studies to validate results compared to experimental data, and application to process optimization of an automotive case study. Finally, an example of the product and process design through the proposed simulation-driven integrated approach is provided to prove the method's suitability for effective redesigns of Additive Manufacturing based high-performance metal products. The results are then outlined, and further developments are discussed.

Development of a relationship between physical parameters of tsunami waves and tsunami intensity based on macroscopic effects and its application to the Italian tsunami database

Tsunamis are rare events. However, their impact can be devastating and it may extend to large geographical areas. For low-probability high-impact events like tsunamis, it is crucial to implement all possible actions to mitigate the risk. The tsunami hazard assessment is the result of a scientific process that integrates traditional geological methods, numerical modelling and the analysis of tsunami sources and historical records. For this reason, analysing past events and understanding how they interacted with the land is the only way to inform tsunami source and propagation models, and quantitatively test forecast models like hazard analyses. The primary objective of this thesis is to establish an explicit relationship between the macroscopic intensity, derived from historical descriptions, and the quantitative physical parameters measuring tsunami waves. This is done first by defining an approximate estimation method based on a simplified 1D physical onshore propagation model to convert the available observations into one reference physical metric. Wave height at the coast was chosen as the reference due to its stability and independence of inland effects. This method was then implemented for a set of well-known past events to build a homogeneous dataset with both macroseismic intensity and wave height. By performing an orthogonal regression, a direct and invertible empirical relationship could be established between the two parameters, accounting for their relevant uncertainties. The target relationship is extensively tested and finally applied to the Italian Tsunami Effect Database (ITED), providing a homogeneous estimation of the wave height for all existing tsunami observations in Italy. This provides the opportunity for meaningful comparison for models and simulations, as well as quantitatively testing tsunami hazard models for the Italian coasts and informing tsunami risk management initiatives.