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Study of the importance of the catalysis in organic synthesis and industrial applications in Thermoplastic Polyurethane (TPU)\ud production
My PhD work thesis is divided in two sections, the first one is an academic part and the second one is an industrial part.\ud
The first part of my thesis represents a contribution to the program of the research group of the Department of Organic Chemistry of the University of Camerino, that has for a long time been studying the cerium chemistry and has dedicated itself particularly to the study of new\ud
methodologies involving the use of system CeCl3·7H2O with NaI.\ud
In many trials good results have been achieved and the procedures developed are characterized not only by the efficiency of the reactions, but also by chemoselective\ud
processes, by a good stereochemical control, by reacting available and inexpensive reagents and in some cases, from the possibility of recovering the catalytic promoter system used through simple procedures of work-up. One of the objectives of the modern organic synthesis concern the substitution of the chemical processes that use substances dangerous for the environment with eco-friendly methodologies. The system CeCl3·7H2O-NaI is inexpensive,\ud
non-toxic, very stable when exposed to water and air, it is able to work under solvent-free conditions and it can be recycled. This means that it is an excellent catalyst in various reactions, contributing in this way to the development of green chemistry, in response to the\ud
problem of environmental pollution caused by the difficulty eliminating of the organic solvents. This also means the development of new strategies for the synthesis of natural\ud
substances and unnatural with important biological activities, it represents a field of remarkable interest and in continuing development in organic chemistry.\ud
In the academic part of this work, we are employed about the synthesis of (+)-Furanomycin, specifically we proposed a new short synthesis of a useful intermediate, a 1,2-diprotected 2-amino-pent-4-ene-1,3-diol, starting from the inexpensive natural amino acid L-serine, and via a Gamer-type aldehyde.\ud
In the last part, that is completely different, is performed in Goldenplast spa. This company is located in Potenza Picena (MC) and it works in the manufacturing of polymer blend for footwear market and grain as infill in artificial turf.\ud
Goldenplast spa was founded in 1993 by Germano Ercoli, the managing director, Gianni Perozzi, the technical manager and Massimo Vallesi, the sales manager, with the scope of\ud
thermoplastic, SBS compounds production. The production started in 1994.\ud
The scope of Goldenplast spa is to provide footwear industry with solutions for moulding applications of soles.\ud
During its activity, in fact, Goldenplast spa has periodically created and introduced on the market new materials which has opened to customers new work opportunities and new markets. This innovating attitude is recognised both from Goldenplast’s customers and\ud
competitors.\ud
From 1996, with the first innovation material, called Superlight®, a low density thermoplastic rubber compound, the company introduced many other new materials up to produce a grain used like infill in artificial football fields. In 2004 this grade called Runplast® and in 2008\ud
Runplast-2S®, with an improving formulation awards with two stars FIFA homologation.\ud
Cause the increasing demand of high performance compounds like GPU and XP series, two family of TPU based thermoplastic rubber compounds modified with rubber resins, in 2008, the management takes decision to produce on your own TPU (Thermoplastic Poly Urethane), with the commercial name HIPUR® that begun in first months of 2009.\ud
Nowadays, Goldenplast spa it's able to achieve a productive capacity about 150 tons a day and about 50% of this material is exported all over the world.\ud
When plant's management begun to work on TPU project, they understood the importance they need external resources to develop this new business, completely different to the existing work activity done until now. Since the proximity of the University of Camerino, they thought to propose a long-range collaboration to solve possible problems and find out new solutions. Union among university and industry lead to a doctorate with main purpose to follow the new project until the completion and implementation in the factory.\ud
To sum up, the second part of this PhD thesis have to be understood like not classical research approach, but in this case like a problem solving approach
Investigating into South Ethiopian folklore medicine employed for malaria intervention and a quantitative method for screening drugs/vaccines acting on pre-erythrocytic stages of Plasmodia
Un diario tra le pagine. La raccolta libraria del magister e predicatore Giuseppe Paci da Sarnano OFMConv (1629-1697).
Un aspetto strutturale della Consolatio boeziana: la collocazione del carme IX del III libro tra quadrivium e geometrica medietas.
Genetic basis of coat color: agouti signalling protein and melanocortin 1 receptor genes in coat color variation in alpaca (Vicugna pacos)
Coat color is an easily recognizable trait, making it simple to follow the inheritance from generation to generation. Domestic animals have a valuable resources of coat color diversity compared to limited variation in natural population, providing excellent models to decipher the genetic basis of coat color. In mammals, pigmentation is known to be influenced by more than 350 genes. Among those, agouti signaling protein (agouti) and melanocortin 1 receptor (MC1R) are well known in the regulation of the eumelanin and pheomelanin synthesis, which is conserved in most of the mammals.\ud
In alpaca, the coat color variation has been very poorly explored at the biological and genetic levels. The modification of coat color frequencies by selection or crossing supposes a correct knowledge of biological and genetic aspects of pigmentation. The ability to determine the mechanisms of coat color inheritance in alpacas would be highly valuable to the industry allowing precise breeding programmes for desired colors. Hence, the broad aim of this thesis has been to investigate the genetic mechanism causing coat color variation in alpaca with respect to agouti and MC1R genes.\ud
The mutations which affect eumelanic and pheomelanic coat colors were identified in both the genes. The exon-4 in the agouti gene contain the causative mutations (g.3836C>T and g.3896G>A and g.3866_3923del57). In specific, two agouti genetic background for black phenotypes and a possible partial dominance/haploinsufficiency in the brown coat colored phenotypes were identified. The reverse transcription analysis of alpaca skin from black, brown and white animals revealed three transcripts with different 5‟untranslated regions (UTR). In particular, one form is common for all the analysed phenotypes and two show a phenotype specific expression (white and black). Interestingly, the 5‟UTR of the transcript specific to white phenotype, possibly originating from a duplicated copy of agouti gene (intra-chromosomal recombination event), contains a 142 bp sequence belonging to the NCOA6 gene In MC1R, specific combinations of mutations were observed in pheomelanic and eumelanic phenotypes. The animals homozygous to the mutations A82/A259/A376/C901 combination were observed to have black phenotypes. The combination of G82/G259/G376/T901 observed to have white phenotypes. And the brown phenotypes were observed to have the heterozygous condition for the mutations (A82G/A259G/A376G/C901T). Moreover, two different MC1R transcripts with respect to 5‟UTR were identified from the skin. The semi-quantitative RT-PCR analysis indicated that the agouti and MC1R gene expressions were inversely proportional with respect to pheomelanic and eumelanic phenotypes.\ud
All together, the data I gathered during my PhD thesis gave a strong contribution to the understanding of the possible genetic mechanisms behind black and brown phenotypes in alpaca. Moreover, the present findings refine the structure of agouti, MC1R locus and its transcripts, which provide additional information for better understanding of the role of agouti and MC1R in the pigmentation of alpaca as well as other mammals. Apart from all, these finding could provide the basis for marker assisted breeding programme to get the desired phenotypes and also sheds further light on the intriguing molecular processes of pigmentation development in alpaca
Tectonic-sedimentary burial history and exhumation of the\ud Southern sector of the Central-Western Pyrenees, Spain
The main objective of this thesis is the reconstruction of thermal evolution of the stratigraphical-structural units forming the backbones of the central-western Pyrenees,\ud
Spain. This study employs an integrated approach to answer questions concerning the thermal and diagenetic history of a foreland basin. In particular, this study focuses on\ud
the area comprised between the Axial Zone and External Sierras of the Pyrenees, which comprises both Internal Sierras and Jaca Basin. Due to the type of sedimentary rocks\ud
cropping out, the study area represents an ideal natural laboratory where to apply a methodological approach usually pertaining to basin analysis to solve structural problems related to mountain building and exhumation. In fact, the published stratigraphic-structural data concerning the central-western Pyrenees are integrated with paleothermal data obtained in this Ph.D. thesis in order to better constrain both timing and modalities of contractional and extensional deformation.\ud
The central-western sector of the Pyrenees chain consists of a doubly-vergent, E-W oriented fold-and-thrust belt which formed, since the Late Cretaceous, as a result of\ud
convergence between the European and Iberian plates along a section of previously thinned continental crust. The whole Pyrenean orogen extends, for about 1,500 km, from southern France to the Cantabrian ranges of northern Spain. The range consists of a central Axial Zone of uplifted Variscan basement rocks flanked, both to the north and south, by fold-thrust belts made up of Mesozoic-Cenozoic sedimentary covers. The northern limit of the Axial Zone is marked by the North Pyrenean Fault, which regarded as the Iberian-European plate suture. The thrust belts are, in turn, flanked by foreland basins which consist on the Aquitaine basin to the north and the Ebro basin to the south.\ud
The experimental work carried out in this study consists on an integrated analysis of organic and inorganic thermal indicators usually employed in diagenesis and very low\ud
grade metamorphism (fluid inclusions microthermometry, Kübler Index, illite content in mixed layers illite-smectite, vitrinite reflectance and apatite fission tracks). This data, together with mesostrusctural analyses, shed new lights on the thermal and tectonic evolution of studied sedimentary successions of Permian to Oligocene ages.\ud
In particular in the Axial Zone (CHAPTER 4), this methodological approach in the Aragón-Béarn pull-apart Basin allowed to discriminate between regional and local\ud
causes of different thermal signatures throughout the succession. Paleo-temperatures distribution indicates a two-step sequential evolution of the basin. The first stage of\ud
strong and localised subsidence ruled by deep rooted strike-slip faults, high heat flux and diffused contact metamorphism records maximum temperatures between 220 and\ud
170°C from bottom to top as detected by vitrinite reflectance (about 2.5%), clay mineral assemblages (KI between 0.44 and 0.54 °2, conversion of mixed layers illite-smectite to discrete illite) and homogenization temperatures from quartz cements.\ud
The second stage with transgressive sedimentation overlapping the previous basin limits ruled by shallower strike-slip faults and lower heat flux and contact metamorphism records maximum temperatures between 100 and 150°C as indicated by fluid inclusions in cements, KI between 0.57 and 0.94°Delta2theta and illite content in mixed layers illitesmectite of 85-92%. Local thermal anomalies are the result of the influence of intrusions due to two different magmatic events which affected organic matter and clay minerals both in the lower (Ro%: 4.2-4.7% and KI up to 0.32°Delta2theta) and upper sequence Ro%:2.9%). Whereas, homogenization temperatures of about 110-120°C from calcite veins parallel and perpendicular to bedding and/or foliation trace the last stages of the thermal evolution of the basin.\ud
In the Internal Sierras (CHAPTER 5), the comparison among such indicators, together with mesostructural analyses, mainly evidenced that the upper portion of the preorogenic\ud
sequence (Alveolina limestones, Paleocene in age) was deformed by two conjugate sets of normal faults and two related sets of en-echelon veins where calcite vein filling records trapping temperatures of primary fluid inclusions never exceeding 70°C. They are dramatically lower than maximum paleo-temperatures (up to 189°C) experienced by younger syn-orogenic deposits (Hecho Group, Lower Eocene in age)and older pre-orogenic units (Marboré Fm, Maastrichtian in age) where field evidences of extension due to flexure are not preserved. Thus, through basin modelling, fluid\ud
inclusion constraints allowed to record the maximum depths of 2-3 km extensional deformation that affected the peripheral bulge; whereas vitrinite reflectance, XRD on\ud
clay minerals assemblages and apatite fission tracks allowed to define the amount of subsequent sedimentary and/or tectonic burial and exhumation in the syn-orogenic\ud
succession of the Hecho Group (CHAPTER 6), in the Jaca Basin, with amounts decreasing from hinterland to foreland from 9 km to 2.5 km. In this chapter higher values of thermal maturity are shown. They are concentrated along the inner outcrops of the Hecho Group (Ro% between 1.90 and 1.12%; I-S mixed layers stacking order long range R3; percentage of illite in I-S between 90 and 85%; KI between 0.57 and 0.80°Delta2theta) with lower values recorded only along the Aragón valley (Ro% between 0.45 and 0.4%; I-S mixed layers stacking order short range R1; percentage of illite in I-S between 77 and 73%; KI between 0.67 and 0.83°Delta2theta), mainly suggesting a contribution of\ud
sedimentary burial with respect to tectonics load along the strike of the chain.\ud
Finally, the distribution of paleothermal and structural features throughout the sedimentary succession cropping out in the Internal Sierras and inner portion of Jaca Basin helped to provide a quantitative contribution for further speculations on the geometry, kinematics and dynamics of the Iberian Plate flexure in Cenozoic times.\ud
\ud
L'obiettivo principale di questa tesi e' la ricostruzione dell'evoluzione termica delle unita' stratigrafiche e strutturali che formano la dorsale dei Pirenei centro-occidentali, in Spagna. Questo studio e' finalizzato a rispondere alle domande relative alla storia termica e diagenetica di un bacino di avanfossa. In particolare, il lavoro svolto in questa tesi si concentra nella zona compresa tra la Zona Assiale e la Sierras Esteriores dei\ud
Pirenei, all’interno della quale si trovano la dorsale Meso-Cenozoica della Sierras Interiores e il bacino di avanfossa Eocenico di Jaca.\ud
In virtu' del tipo di rocce sedimentarie che affiorano, l'area di studio rappresenta un laboratorio naturale ideale in cui applicare un approccio metodologico multidisciplinare, di solito appartenente all’Analisi di Bacino, per risolvere i problemi strutturali legati alla\ud
formazione degli orogeni e alla loro esumazione.\ud
Inoltre, la presenza di dati stratigrafico-strutturali, relativi al settore centro-occidentale dei Pirenei e disponibili in letteratura, vengono integrati con i dati ottenuti in questa tesi di dottorato, al fine di vincolare quantitativamente sia i tempi che le modalità di deformazione ed esumazione delle unità sedimentarie studiate.\ud
Il settore centro-occidentale dei Pirenei e' costituito da una serie di thrust e pieghe doppio-vergenti orientati E-W che, a partire dal Cretaceo sup., si sono sviluppati a causa\ud
della collisione continentale tra le placche Iberica ad Europea\ud
L'intero orogene, che si estende per circa 1,500 km dalla Francia meridionale fino alla Cantabria nel nord della Spagna, è costituito da una Zona Assiale centrale, caratterizzata da rocce di basamento Varisico affiancate, sia a nord che a sud, dalla copertura sedimentaria meso-cenozoica piegata. Il limite settentrionale della Zona Assiale e' segnato dalla faglia Nord-Pirenaica, considerata la sutura della collisione continentale iberico-europea. L’intera catena e' limitata da due bacini di avanfossa, il bacino di Aquitania a nord e il bacino dell’Ebro a sud.\ud
Il lavoro sperimentale, condotto in questo studio, e' costituito da un'analisi integrata di indicatori termici organici e inorganici (studio microtermometrico delle inclusioni fluide, contenuto di Illite negli strati misti Illite-Smectite, cristallinità dell’Illite tramite\ud
l’indice di Kübler, riflettanza vitrinite e tracce di fissione in apatite) che, di solito, sono utilizzati nel campo della diagenesi e del metamorfismo di grado molto basso. Questi dati, insieme ad un’analisi mesostrutturale, fornicono nuova luce sull’evoluzione termica e tettonica, dal Permiano all’Oligocene, delle successioni sedimentarie studiate.\ud
In particolare nella Zona Assiale (Capitolo 4), questo approccio metodologico, focalizzato nel bacino di pull-apart di Aragón-Béarn (Carbonifero Sup.-Permiano), ha\ud
consentito di discriminare le cause regionali da quelle locali che hanno prodotto anomalie termiche in tutta la successione. La distribuzione delle paleotemperature\ud
ottenute indica due fasi evolutive del bacino. La prima fase, caratterizzata da una forte e localizzata subsidenza, e' governata da faglie trascorrenti profonde che hanno prodotto un flusso di calore elevato e un metamorfismo di contatto diffuso. Questa fase registra, dal basso verso l’alto, temperature massime tra i 220 e i 170 °C, come rilevato dallo studio della riflettenza della vitrinite (Ro circa 2.5%), dalla mineralogia delle argille (I% fino al 99% e KI tra 0.44 e 0.54°Delta2theta) e dalle temperature di omogeneizzazione nelle inclusioni fluide nei cementi silicatici.\ud
La seconda fase, con sedimentazione trasgressiva che si sovrappone in discordanza sulle unita' precedentemente deposte, e' governata da faglie trascorrenti poco profonde che hanno prodotto un flusso di calore inferiore e metamorfismo di contatto. Le temperature massime registrate vanno da 100 ai 150 °C come indicato dalle inclusioni fluide nei cementi, dal KI tra 0,57 e 0,94°Delta2theta e dal contenuto dell’Illite negli strati misti I-S del\ud
85-92%.\ud
La presenza di anomalie termiche locali, invece, sono il risultato dell'influenza di intrusioni causati dai due eventi magmatici che hanno interessato la materia organica e\ud
minerali argillosi sia nella parte inferiore (Ro% compreso tra 4,2 e 4,7% e KI fino a 0,32°Delta2theta) che nella parte superiore del bacino (Ro% di 2,9%). Infine, le temperature di omogeneizzazione, ottenute dall’analisi delle inclusioni fluide nelle vene parallele e/o\ud
perpendicolari alla stratificazione/foliazione, mostrano valori tra 110-120°C indicando una fase tardiva dell'evoluzione termica del bacino.\ud
Nella Sierras Interiores (Capitolo 5), il confronto tra i vari indicatori termici ha evidenziato soprattutto che la parte superiore della sequenza pre-orogenica,\ud
caratterizzata da calcari Paleocenici ad Alveolina, e' deformata da due sistemi di faglie normali coniugate e due sistemi di vene en-echelon correlate ad essi. Lo studio\ud
microtermometrico delle inclusioni fluide, effettuato nel riempimento calcitico delle vene, registra temperature non superiori ai 70°C.\ud
Questi valori di temperatura sono assai inferiori rispetto a quelli riscontrati sia nella successione pre-orogenica Cretacica sottostante (Formazione di Marboré) che in quella\ud
sin-orogenica Eocenica del Gruppo dell’Hecho sovrastante (fino a 189°C).\ud
Cosi', grazie ad un’analisi strutturale delle successioni affioranti, lo studio microtermometrico delle inclusioni fluide ha permesso di registrare la profondita'\ud
massima della deformazione estensionale di 2-3 km che ha interessato il peripheral bulge durante l’Eocene inferiore.\ud
Lo studio della riflettenza della vitrinite, della mineralogia delle argille negli strati misti I-S e delle tracce di fissione nelle apatiti hanno, invece, consentito di definire la quantita' di carico sedimentario e/o tettonico presenti nella successione sin-orogenia del Gruppo\ud
dell’Hecho (Capitolo 6), nel bacino di Jaca, con contributi di circa 9 km di spessore decrescenti dalla parte interna fino a 2,5 km nella parte esterna.\ud
In questo capitolo vengono presentati sia gli alti valori di maturita' termica dei sedimenti concentrati nella parte interna della successione torbiditica, lungo le valli dell’Hecho e della Tena (Ro% compresi tra 1.90 e 1.12%; % dell’Illite negli strati misti I-S tra 90 e\ud
85%; KI compresi tra 0.57 e 0.80 °Delta2theta), che i bassi valori registrati lungo la valle dell’Aragón (Ro% compresi tra 0.45 e 0.4%; % di Illite in I-S tra 77 e 73%; KI tra 0.67 e 0.83 °Delta2theta). Questi valori differenti, riscontrati longitudinalmente in tutta l’area di\ud
studio, suggeriscono un diverso contributo del carico sedimentario rispetto a quello tettonico.\ud
Infine, la distribuzione dei dati paleotermici e strutturali presenti in tutte le successione sedimentarie studiate, tra le Sierras Interiores e la parte interna della Bacino di Jaca, ha permesso di dare un contributo quantitativo per ulteriori studi sulla geometria, la\ud
cinematica e la dinamica della flessurazione della placca iberica durante il Cenozoico
Marine magnetic anomalies and plate motions in the central Atlantic region during the Oligocene and early Miocene
Although the plate kinematics associated with the opening of the central Atlantic ocean after the break-up of Pangaea has been the subject of several studies since the late 1960s, there are still open problems and debated solutions to the tectonic evolution of this area. In particular, the initial fit of Pangaea, the spreading directions during the early stages of opening, the existence of ridge jumps, and the entity of intraplate deformation processes in northwest\ud
Africa are still subject to different interpretations by different research groups. The objective of this study is a reassessment of the central Atlantic plate kinematics since the early Jurassic through a re-examination of marine magnetic anomalies, fracture zone trends and geologic data.\ud
A total of 215 magnetic ship-tracks from the NGDC GEODAS database for the time interval from 1964 through 1994, in the area comprised between the Atlantis FZ and the Azores\ud
triple junction, were analyzed. The data quality was assessed through an examination of Kp indices. Magnetic data collected during disturbed days were filtered away. Thus, 29 reliable magnetic profiles were extracted having an azimuth that differed from the fracture zones trend\ud
by less than 30° and did not cross any fracture zone. The ship-track segments were projected onto flow lines that parallel existing fracture zones in order to avoid shape distortion and possible misinterpretation of the magnetic anomalies. Finally, the magnetic data were high-pass\ud
filtered to remove trends.\ud
A new advanced software tool for the analysis and interpretation of the anomalies was used improving the reliability of magnetic anomaly identifications.\ud
The main result of this work has been the assessment that an independent Moroccan plate existed during the Oligocene and early Miocene, which moved eastward relative to\ud
northwest Africa. This event has significant implications for the fit of central Pangea during the early Mesozoic.\ud
A new map of the magnetic lineations in the central Atlantic is proposed, which is based on an analysis of magnetic anomaly profiles and fracture zone geometry in the zone north of the Atlantis FZ. This map overcomes the flaws of previous compilations, even if it retains much of\ud
the classic works.\ud
The structural pattern that results from this study evidences that: 1) the whole set of North American isochrons are shifted to the west in the area north of the Atlantis FZ with respect to the classical compilations; 2) a unique spreading direction existed during the early and middle Jurassic, and until the M25 – M21 time interval in the late Jurassic. Such a spreading direction is compatible with that proposed in a recent model of opening of the proto-Atlantic, but extends the trend well beyond the early Jurassic
THE STRUCTURAL FORM: Topology Optimization in Architecture and Industrial Design
The expression Structural Form is used to define the co-existence of two aspects: Form and Structure.\ud
In the constructive practice, form and structure are not always integrated and can appear separately; the skin of a building can hide a different inner structure or the style of an object is often independent from its structural system. In many cases the Structural Form is the result of man’s adaptation to special conditions: climatic, historical, economical, cultural.\ud
In nature that definition is adopted by the life forms following the evolutionary principles that rule the development of biological forms. In mostly of life-forms,\ud
structure and form tend to be coincident. Branches of trees and skeleton bones have a specific Structural Form which define their function and design. In this sense Structural Form has a natural meaning.\ud
The natural meaning of Structural Form can be adopted in special forms of structural elements, created to build specific architectures. This concept was applied in the past to build architectures based on empirical knowledge and it has been abandoned in the last century to follow abstract forms.\ud
The experiences shown in the present work have demonstrated how structural optimization procedures, like topology optimization, are able to mimic natural processes in defining architectural structures and industrial design\ud
objects with an aesthetic added-value that might represent an alternative and attractive vision