Application of different instrumental techniques to the selective evaluation of bio-sensible compounds in foodstuff of animal and vegetable origin

This PhD thesis describes the application of some instrumental analytical techniques suitable to the study of fundamental food products for the human diet, such as: extra virgin olive oil and dairy products. These products, widely spread in the market and with high nutritional values, are increasingly recognized healthy properties although their lipid fraction might contain some unfavorable components to the human health. The research activity has been structured in the following investigations: “Comparison of different techniques for trans fatty acids analysis” “Fatty acids analysis of outcrop milk cream samples, with particular emphasis on the content of Conjugated Linoleic Acid (CLA) and trans Fatty Acids (TFA), by using 100m high-polarity capillary column” “Evaluation of the oxidited fatty acids (OFA) content during the Parmigiano-Reggiano cheese seasoning” “Direct analysis of 4-desmethyl sterols and two dihydroxy triterpenes in saponified vegetal oils (olive oil and others) using liquid chromatography-mass spectrometry” “Quantitation of long chain poly-unsatured fatty acids (LC-PUFA) in base infant formulas by Gas Chromatography, and evaluation of the blending phases accuracy during their preparation” “Fatty acids composition of Parmigiano Reggiano cheese samples, with emphasis on trans isomers (TFA)”

Genomic characterization of the italian wolf (Canis lupus): the genes involved in black coat colour determination and application of microarray technique for snps detection.

This study provides a comprehensive genetic overview on the endangered Italian wolf population. In particular, it focuses on two research lines. On one hand, we focalised on melanism in wolf in order to isolate a mutation related with black coat colour in canids. With several reported black individuals (an exception at European level), the Italian wolf population constituted a challenging research field posing many unanswered questions. As found in North American wolf, we reported that melanism in the Italian population is caused by a different melanocortin pathway component, the K locus, in which a beta-defensin protein acts as an alternative ligand for the Mc1r. This research project was conducted in collaboration with Prof. Gregory Barsh, Department of Genetics and Paediatrics, Stanford University. On the other hand, we performed analysis on a high number of SNPs thanks to a customized Canine microarray useful to integrate or substitute the STR markers for genotyping individuals and detecting wolf-dog hybrids. Thanks to DNA microchip technology, we obtained an impressive amount of genetic data which provides a solid base for future functional genomic studies. This study was undertaken in collaboration with Prof. Robert K. Wayne, Department of Ecology and Evolutionary Biology, University of California, Los Angeles (UCLA).

Supporting semantic web technologies in the pervasive service ecosystems middleware

Semantic Web technologies are strategic in order to fulfill the openness requirement of Self-Aware Pervasive Service Ecosystems. In fact they provide agents with the ability to cope with distributed data, using RDF to represent information, ontologies to describe relations between concepts from any domain (e.g. equivalence, specialization/extension, and so on) and reasoners to extract implicit knowledge. The aim of this thesis is to study these technologies and design an extension of a pervasive service ecosystems middleware capable of exploiting semantic power, and deepening performance implications.

Application of comprehensive gas chromatography (GCxGC) to measurements of volatile organic species in ambient air

The focus of this thesis was the in-situ application of the new analytical technique "GCxGC" in both the marine and continental boundary layer, as well as in the free troposphere. Biogenic and anthropogenic VOCs were analysed and used to characterise local chemistry at the individual measurement sites. The first part of the thesis work was the characterisation of a new set of columns that was to be used later in the field. To simplify the identification, a time-of-flight mass spectrometer (TOF-MS) detector was coupled to the GCxGC. In the field the TOF-MS was substituted by a more robust and tractable flame ionisation detector (FID), which is more suitable for quantitative measurements. During the process, a variety of volatile organic compounds could be assigned to different environmental sources, e.g. plankton sources, eucalyptus forest or urban centers. In-situ measurements of biogenic and anthropogenic VOCs were conducted at the Meteorological Observatory Hohenpeissenberg (MOHP), Germany, applying a thermodesorption-GCxGC-FID system. The measured VOCs were compared to GC-MS measurements routinely conducted at the MOHP as well as to PTR-MS measurements. Furthermore, a compressed ambient air standard was measured from three different gas chromatographic instruments and the results were compared. With few exceptions, the in-situ, as well as the standard measurements, revealed good agreement between the individual instruments. Diurnal cycles were observed, with differing patterns for the biogenic and the anthropogenic compounds. The variability-lifetime relationship of compounds with atmospheric lifetimes from a few hours to a few days in presence of O3 and OH was examined. It revealed a weak but significant influence of chemistry on these short-lived VOCs at the site. The relationship was also used to estimate the average OH radical concentration during the campaign, which was compared to in-situ OH measurements (1.7 x 10^6 molecules/cm^3, 0.071 ppt) for the first time. The OH concentration ranging from 3.5 to 6.5 x 10^5 molecules/cm^3 (0.015 to 0.027 ppt) obtained with this method represents an approximation of the average OH concentration influencing the discussed VOCs from emission to measurement. Based on these findings, the average concentration of the nighttime NO3 radicals was estimated using the same approach and found to range from 2.2 to 5.0 x 10^8 molecules/cm^3 (9.2 to 21.0 ppt). During the MINATROC field campaign, in-situ ambient air measurements with the GCxGC-FID were conducted at Tenerife, Spain. Although the station is mainly situated in the free troposphere, local influences of anthropogenic and biogenic VOCs were observed. Due to a strong dust event originating from Western Africa it was possible to compare the mixing ratios during normal and elevated dust loading in the atmosphere. The mixing ratios during the dust event were found to be lower. However, this could not be attributed to heterogeneous reactions as there was a change in the wind direction from northwesterly to southeasterly during the dust event.

Non linear application of an in-house finite elements software

Questa tesi si pone come obiettivo l'analisi delle componenti di sollecitazione statica di un serbatoio, in acciaio API 5L X52, sottoposto a carichi di flessione e pressione interna attraverso il programma agli elementi finiti PLCd4, sviluppato presso l'International Center for Numerical Methods in Engineering (CIMNE - Barcelona). Questo tipo di analisi rientra nel progetto europeo ULCF, il cui traguardo è lo studio della fatica a bassissimo numero di cicli per strutture in acciaio. Prima di osservare la struttura completa del serbatoio è stato studiato il comportamento del materiale per implementare all'interno del programma una nuova tipologia di curva che rappresentasse al meglio l'andamento delle tensioni interne. Attraverso il lavoro di preparazione alla tesi è stato inserito all'interno del programma un algoritmo per la distribuzione delle pressioni superficiali sui corpi 3D, successivamente utilizzato per l'analisi della pressione interna nel serbatoio. Sono state effettuate analisi FEM del serbatoio in diverse configurazioni di carico ove si è cercato di modellare al meglio la struttura portante relativa al caso reale di "full scale test". Dal punto di vista analitico i risultati ottenuti sono soddisfacenti in quanto rispecchiano un corretto comportamento del serbatoio in condizioni di pressioni molto elevate e confermano la bontà del programma nell'analisi computazionale.

Soil application of Meliaceae derivatives: effect on carbon and nitrogen dynamics in the soil-plant system

The effect of soil incorporation of 7 Meliaceae derivatives (6 commercial neem cakes and leaves of Melia azedarach L.) on C and N dynamics and on nutrient availability to micropropagated GF677 rootstock was investigated. In a first laboratory incubation experiment the derivatives showed different N mineralization dynamics, generally well predicted by their C:N ratio and only partly by their initial N concentration. All derivatives increased microbial biomass C, thus representing a source of C for the soil microbial population. Soil addition of all neem cakes (8 g kg-1) and melia leaves (16 g kg-1) had a positive effect on plant growth and increased root N uptake and leaf green colour of micropropagated plants of GF677. In addition, the neem cakes characterized by higher nutrient concentration increased P and K concentration in shoot and leaves 68 days after the amendment. In another experiment, soil incorporation of 15N labeled melia leaves (16 g kg-1) had no effect on the total amount of plant N, however the percentage of melia derived-N of treated plants ranged between 0.8% and 34% during the experiment. At the end of the growing season, about 7% of N added as melia leaves was recovered in plant, while 70% of it was still present in soil. Real C mineralization and the priming effect induced by the addition of the derivatives were quantified by a natural 13C abundance method. The real C mineralization of the derivatives ranged between 22% and 40% of added-C. All the derivatives studied induced a positive priming effect and, 144 days after the amendment, the amount of C primed corresponded to 26% of added-C, for all the derivatives. Despite this substantial priming effect, the C balance of the soil, 144 days after the amendment, always resulted positive.

Applications of infrared thermography in the food industry

In the last 20-30 years, the implementation of new technologies from the research centres to the food industry process was very fast. The infrared thermography is a tool used in many fields, including agriculture and food science technology, because of it's important qualities like non-destructive method, it is fast, it is accurate, it is repeatable and economical. Almost all the industrial food processors have to use the thermal process to obtain an optimal product respecting the quality and safety standards. The control of temperature of food products during the production, transportation, storage and sales is an essential process in the food industry network. This tool can minimize the human error during the control of heat operation, and reduce the costs with personal. In this thesis the application of infrared thermography (IRT) was studies for different products that need a thermal process during the food processing. The background of thermography was presented, and also some of its applications in food industry, with the benefits and limits of applicability. The measurement of the temperature of the egg shell during the heat treatment in natural convection and with hot-air treatment was compared with the calculated temperatures obtained by a simplified finite element model made in the past. The complete process shown a good results between calculated and observed temperatures and we can say that this technique can be useful to control the heat treatments for decontamination of egg using the infrared thermography. Other important application of IRT was to determine the evolution of emissivity of potato raw during the freezing process and the control non-destructive control of this process. We can conclude that the IRT can represent a real option for the control of thermal process from the food industry, but more researches on various products are necessary.

Application of innovative methods of source apportionment in air contamination assessment

In this work, new tools in atmospheric pollutant sampling and analysis were applied in order to go deeper in source apportionment study. The project was developed mainly by the study of atmospheric emission sources in a suburban area influenced by a municipal solid waste incinerator (MSWI), a medium-sized coastal tourist town and a motorway. Two main research lines were followed. For what concerns the first line, the potentiality of the use of PM samplers coupled with a wind select sensor was assessed. Results showed that they may be a valid support in source apportionment studies. However, meteorological and territorial conditions could strongly affect the results. Moreover, new markers were investigated, particularly focusing on the processes of biomass burning. OC revealed a good biomass combustion process indicator, as well as all determined organic compounds. Among metals, lead and aluminium are well related to the biomass combustion. Surprisingly PM was not enriched of potassium during bonfire event. The second research line consists on the application of Positive Matrix factorization (PMF), a new statistical tool in data analysis. This new technique was applied to datasets which refer to different time resolution data. PMF application to atmospheric deposition fluxes identified six main sources affecting the area. The incinerator’s relative contribution seemed to be negligible. PMF analysis was then applied to PM2.5 collected with samplers coupled with a wind select sensor. The higher number of determined environmental indicators allowed to obtain more detailed results on the sources affecting the area. Vehicular traffic revealed the source of greatest concern for the study area. Also in this case, incinerator’s relative contribution seemed to be negligible. Finally, the application of PMF analysis to hourly aerosol data demonstrated that the higher the temporal resolution of the data was, the more the source profiles were close to the real one.

Percieved Organizational Efficacy in Internationalized Companies: Application of Competing Values Approach and Collective Efficacy

This dissertation focuses on “organizational efficacy”, in particular on employees’ beliefs of organizational capacity to be efficacious. Organizational efficacy is considered from two perspectives – competing values approach and collective efficacy, and evaluated in internationalized companies. The dissertation is composed of three studies. The data were collected in thirteen Italian companies on different stages of internationalization for a total number of respondents is 358. In the first study the factorial validity of the competing values instrument (Rohrbaugh, 1981) was investigated and confirmed. Two scales were used to measure collective efficacy: a general collective efficacy scale (Bohn, 2010), and a specific collective efficacy scale, developed following suggestions of Borgogni et al. (2001), it evaluates employees’ beliefs of efficacy of organizations in the international market. The findings suggest that competing values and collective organizational efficacy instruments may provide a multi-faceted measurement of employees’ beliefs of organizational efficacy. The second study examined the relationship between organizational efficacy and collective work engagement. To measure collective work engagement the UWES-9 (Schaufeli & Bakker, 2003) was adapted at the group level; its factor structure and reliability were similar to the standard UWES-9. The findings suggest that organizational efficacy fully predicts collective work engagement. Also we investigated whether leadership moderates the relationship between organizational efficacy and collective work engagement. We operationalized leadership style with MLQ (Bass & Avolio, 1995); the results suggest that intellectual stimulation and idealized influence (transformational leadership) and contingent reward (transactional leadership) enhance the impact of organizational efficacy on collective work engagement. In the third study we investigated organizational efficacy and collective work engagement in internationalized companies. The findings show that beliefs of organizational efficacy vary across companies in different stages of internationalization, while no significant difference was found for collective work engagement. Limitations, practical implications and future studies are discussed in the conclusion.

The application of a new psychotherapeutic strategy for enhancing eudaimonic well-being in children with mood and anxiety disorders

The aim of the dissertation was to test the feasibility of a new psychotherapeutic protocol for treating children and adolescents with mood and anxiety disorders: Child-Well-Being Therapy (CWBT). It originates from adult Well-Being Therapy protocol (WBT) and represents a conceptual innovation for treating affective disorders. WBT is based on the multidimensional model of well-being postulated by Ryff (eudaimonic perspective), in sequential combination with cognitive-behavioral therapy (CBT). Results showed that eudaimonic well-being was impaired in children with affective disorders in comparison with matched healthy students. A first open investigation aimed at exploring the feasibility of a 8-session CWBT protocol in a group of children with emotional and behavioural disorders has been implemented. Data showed how CWBT resulted associated to symptoms reduction, together with the decrease of externalizing problems, maintained at 1-year follow-up. CWBT triggered also an improvement in psychological well-being as well as an increasing flourishing trajectory over time. Subsequently, a modified and extended version of CWBT (12-sessions) has been developed and then tested in a controlled study with 34 patients (8 to 16 years) affected by mood and anxiety disorders. They were consecutively randomized into 3 different groups: CWBT, CBT, 6-month waiting list (WL). Both treatments resulted effective in decreasing distress and in improving well-being. Moreover, CWBT was associated with higher improvement in anxiety and showed a greater recovery rate (83%) than CBT (54%). Both groups maintained beneficial effects and CWBT group displayed a lower level of distress as well as a higher positive trend in well-being scores over time. Findings need to be interpret with caution, because of study limitations, however important clinical implications emerged. Further investigations should determine whether the sequential integration of well-being and symptom-oriented strategies could play an important role in children and adolescents’ psychotherapeutic options, fostering a successful adaptation to adversities during the growth process.

Spatial Disparity and Dynamic Trajectory of Convergence in China: Construction and Application of a Composite Index of Regional Development

China is a large country characterized by remarkable growth and distinct regional diversity. Spatial disparity has always been a hot issue since China has been struggling to follow a balanced growth path but still confronting with unprecedented pressures and challenges. To better understand the inequality level benchmarking spatial distributions of Chinese provinces and municipalities and estimate dynamic trajectory of sustainable development in China, I constructed the Composite Index of Regional Development (CIRD) with five sub pillars/dimensions involving Macroeconomic Index (MEI), Science and Innovation Index (SCI), Environmental Sustainability Index (ESI), Human Capital Index (HCI) and Public Facilities Index (PFI), endeavoring to cover various fields of regional socioeconomic development. Ranking reports on the five sub dimensions and aggregated CIRD were provided in order to better measure the developmental degrees of 31 or 30 Chinese provinces and municipalities over 13 years from 1998 to 2010 as the time interval of three “Five-year Plans”. Further empirical applications of this CIRD focused on clustering and convergence estimation, attempting to fill up the gap in quantifying the developmental levels of regional comprehensive socioeconomics and estimating the dynamic convergence trajectory of regional sustainable development in a long run. Four clusters were benchmarked geographically-oriented in the map on the basis of cluster analysis, and club-convergence was observed in the Chinese provinces and municipalities based on stochastic kernel density estimation.

Application of Submerged Grouted Anchors in Sheet Pile Quay Walls

Sheet pile walls are one of the oldest earth retention systems utilized in civil engineering projects. They are used for various purposes; such as excavation support system, cofferdams, cut-off walls under dams, slope stabilization, waterfront structures, and flood walls. Sheet pile walls are one of the most common types of quay walls used in port construction. The worldwide increases in utilization of large ships for transportation have created an urgent need of deepening the seabed within port areas and consequently the rehabilitation of its wharfs. Several methods can be used to increase the load-carrying capacity of sheet-piling walls. The use of additional anchored tie rods grouted into the backfill soil and arranged along the exposed wall height is one of the most practical and appropriate solutions adopted for stabilization and rehabilitation of the existing quay wall. The Ravenna Port Authority initiated a project to deepen the harbor bottom at selected wharves. An extensive parametric study through the finite element program, PLAXIS 2D, version 2012 was carried out to investigate the enhancement of using submerged grouted anchors technique on the load response of sheet-piling quay wall. The influence of grout-ties area, length of grouted body, anchor inclination and anchor location were considered and evaluated due to the effect of different system parameters. Also a comparative study was conducted by Plaxis 2D and 3D program to investigate the behavior of these sheet pile quay walls in terms of horizontal displacements induced along the sheet pile wall and ground surface settlements as well as the anchor force and calculated factor of safety. Finally, a comprehensive study was carried out by using different constitutive models to simulate the mechanical behavior of the soil to investigate the effect of these two models (Mohr-Coulomb and Hardening Soil) on the behavior of these sheet pile quay walls.

Application of a hybrid blocking layer in dye-sensitized solar cells

In dye-sensitized solar cells a blocking layer between the transparent electrode and the mesoporous titanium dioxide film is used to prevent short-circuits between the hole-conductor and the front electrode. The conventional approach is to use a compact layer of titanium dioxide prepared by spin coating or spray pyrolysis. The thickness of the blocking layer is critical. On one hand, the layer has to be thick enough to cover the rough substrate completely. On the other hand, the serial resistance increases with increasing film thickness, because the layer acts as an ohmic resistance itself. In this thesis an amphiphilic diblock copolymer is used as a functional template to produce an alternative, hybrid blocking layer. The hybrid blocking layer is thinner than the conventional, compact titanium dioxide film and thereby possesses a higher conductivity. Still, this type of blocking layer covers the rough electrode material completely and avoids current loss through charge recombination. The novel blocking layer is prepared using a tailored, amphiphilic block copolymer in combination with sol-gel chemistry. While the hydrophilic poly(ethylene oxide) part of the polymer coordinates a titanium dioxide precursor to form a percolating network of titania particles, the hydrophobic poly(dimethylsiloxane) part turns into an insulating ceramic layer. With this technique, crack-free films with a thickness down to 24 nm are obtained. The presence of a conductive titanium dioxide network for current flow, which is embedded in an insulating ceramic material, is validated by conductive scanning force microscopy. This is the first time that such a hybrid blocking layer is implemented in a solar cell. With this approach the efficiency could be increased up to 27 % compared to the conventional blocking layer. Thus, it is demonstrated that the hybrid blocking layer represents a competitive alternative to the classical approach.

The Application of European Competition Law in Arbitration Proceedings

This work provides several policy proposals capable to strengthen the private enforcement of EU competition law in arbitration. It focuses on the procedural law aspects that are permeated by legal uncertainty and that have not yet fallen under the scrutiny of the law and economics debate. The policy proposals described herein are based on the functional approach to law and economics and aim to promote a more qualified decision making process by: adjudicators, private parties and lawmakers. The resulting framework of procedural rules would be a cost-effective policy tool that could sustain the European Commission’s effort to guarantee a workable level of competition in the EU internal market. This project aims to answer the following broad research question: which procedural rules can improve the efficiency of antitrust arbitration by decreasing litigation costs for private parties on the one hand, and by increasing private parties’ compliance with competition law on the other hand?Throughout this research project, such broad question has been developed into research sub-questions revolving around several key legal issues. The chosen sub-research questions result from a vacuum in the European enforcement system that leaves several key legal issues in antitrust arbitration unresolved. The legal framework proposed in this research project could prevent such a blurry scenario from impairing the EU private enforcement of competition law in arbitration. Therefore, our attention was triggered by those legal issues whose proposed solutions lead to relevant uncertainties and that are most suitable for a law and economics analysis.

Data management and data analysis in the large European projects GEHA (GEnetics of Healthy Aging) and NU-AGE (NUtrition and AGEing): a bioinformatic approach

The aging process is characterized by the progressive fitness decline experienced at all the levels of physiological organization, from single molecules up to the whole organism. Studies confirmed inflammaging, a chronic low-level inflammation, as a deeply intertwined partner of the aging process, which may provide the “common soil” upon which age-related diseases develop and flourish. Thus, albeit inflammation per se represents a physiological process, it can rapidly become detrimental if it goes out of control causing an excess of local and systemic inflammatory response, a striking risk factor for the elderly population. Developing interventions to counteract the establishment of this state is thus a top priority. Diet, among other factors, represents a good candidate to regulate inflammation. Building on top of this consideration, the EU project NU-AGE is now trying to assess if a Mediterranean diet, fortified for the elderly population needs, may help in modulating inflammaging. To do so, NU-AGE enrolled a total of 1250 subjects, half of which followed a 1-year long diet, and characterized them by mean of the most advanced –omics and non –omics analyses. The aim of this thesis was the development of a solid data management pipeline able to efficiently cope with the results of these assays, which are now flowing inside a centralized database, ready to be used to test the most disparate scientific hypotheses. At the same time, the work hereby described encompasses the data analysis of the GEHA project, which was focused on identifying the genetic determinants of longevity, with a particular focus on developing and applying a method for detecting epistatic interactions in human mtDNA. Eventually, in an effort to propel the adoption of NGS technologies in everyday pipeline, we developed a NGS variant calling pipeline devoted to solve all the sequencing-related issues of the mtDNA.