Biomimetic Materials for Biomedical Applications

Objects with complex shape and functions have always attracted attention and interest. The morphological diversity and complexity of naturally occurring forms and patterns have been a motivation for humans to copy and adopt ideas from Nature to achieve functional, aesthetic and social value. Biomimetics is addressed to the design and development of new synthetic materials using strategies adopted by living organisms to produce biological materials. In particular, biomineralized tissues are often sophisticate composite materials, in which the components and the interfaces between them have been defined and optimized, and that present unusual and optimal chemical-physical, morphological and mechanical properties. Moreover, biominerals are generally produced by easily traceable raw materials, in aqueous media and at room pressure and temperature, that is through cheap process and materials. Thus, it is not surprising that the idea to mimic those strategies proper of Nature has been employed in several areas of applied sciences, such as for the preparation of liquid crystals, ceramic thin films computer switches and many other advanced materials. On this basis, this PhD thesis is focused on the investigation of the interaction of biologically active ions and molecules with calcium phosphates with the aim to develop new materials for the substitution and repair of skeletal tissue, according to the following lines: I. Modified calcium phosphates. A relevant part of this PhD thesis has been addressed to study the interaction of Strontium with calcium phosphates. It was demonstrated that strontium ion can substitute for calcium into hydroxyapatite, causing appreciable structural and morphological modifications. The detailed structural analysis carried out on the nanocrystals at different strontium content provided new insight into its interaction with the structure of hydroxyapatite. At variance with the behaviour of Sr towards HA, it was found that this ion inhibits the synthesis of octacalcium phosphate. However, it can substitute for calcium in this structure up to 15 atom %, in agreement with the increase of the cell parameters observed on increasing ion concentration. A similar behaviour was found for Magnesium ion, whereas Manganese inhibits the synthesis of octacalcium phosphate and it promotes the precipitation of dicalcium phosphate dehydrate. It was also found that Strontium affects the kinetics of the reaction of hydrolysis of α-TCP. It inhibits the conversion from α-TCP to hydroxyapatite. However, the resulting apatitic phase contains significant amounts of Sr2+ suggesting that the addition of Sr2+ to the composition of α-TCP bone cements could be successfully exploited for its local delivery in bone defects. The hydrolysis of α-TCP has been investigated also in the presence of increasing amounts of gelatin: the results indicated that this biopolymer accelerates the hydrolysis reaction and promotes the conversion of α-TCP into OCP, suggesting that its addition in the composition of calcium phosphate cements can be employed to modulate the OCP/HA ratio, and as a consequence the solubility, of the set cement. II. Deposition of modified calcium phosphates on metallic substrates. Coating with a thin film of calcium phosphates is frequently applied on the surface of metallic implants in order to combine the high mechanical strength of the metal with the excellent bioactivity of the calcium phosphates surface layers. During this PhD thesis, thank to the collaboration with prof. I.N. Mihailescu, head of the Laser-Surface-Plasma Interactions Laboratory (National Institute for Lasers, Plasma and Radiation Physics – Laser Department, Bucharest) Pulsed Laser Deposition has been successfully applied to deposit thin films of Sr substituted HA on Titanium substrates. The synthesized coatings displayed a uniform Sr distribution, a granular surface and a good degree of crystallinity which slightly decreased on increasing Sr content. The results of in vitro tests carried out on osteoblast-like and osteoclast cells suggested that the presence of Sr in HA thin films can enhance the positive effect of HA coatings on osteointegration and bone regeneration, and prevent undesirable bone resorption. The possibility to introduce an active molecule in the implant site was explored using Matrix Assisted Pulsed Laser Evaporation to deposit hydroxyapatite nanocrystals at different content of alendronate, a bisphosphonate widely employed in the treatments of pathological diseases associated to bone loss. The coatings displayed a good degree of crystallinity, and the results of in vitro tests indicated that alendronate promotes proliferation and differentiation of osteoblasts even when incorporated into hydroxyapatite. III. Synthesis of drug carriers with a delayed release modulated by a calcium phosphate coating. A core-shell system for modulated drug delivery and release has been developed through optimization of the experimental conditions to cover gelatin microspheres with a uniform layer of calcium phosphate. The kinetics of the release from uncoated and coated microspheres was investigated using aspirin as a model drug. It was shown that the presence of the calcium phosphate shell delays the release of aspirin and allows to modulate its action.

Provenienza dei sedimenti arenitici nel bacino di Tracia (eo-oligocene, Turchia nord-occidentale e Grecia nord-orientale)

The Thrace Basin is the largest and thickest Tertiary sedimentary basin of the eastern Balkans region and constitutes an important hydrocarbon province. It is located between the Rhodope-Strandja Massif to the north and west, the Marmara Sea and Biga Peninsula to the south, and the Black Sea to the est. It consists of a complex system of depocenters and uplifts with very articulate paleotopography indicated by abrupt lateral facies variations. Its southeastern margin is widely deformed by the Ganos Fault, a segment of the North Anatolian strike-slip fault system . Most of the Thrace Basin fill ranges from the Eocene to the Late Oligocene. Maximum total thickness, including the Neogene-Quaternary succession, reaches 9.000 meters in a few narrow depocenters. This sedimentary succession consists mainly of basin plain turbiditic deposits with a significant volcaniclastic component which evolves upwards to shelf deposits and continental facies, with deltaic bodies prograding towards the basin center in the Oligocene. This work deals with the provenance of Eocene-Oligocene clastic sediments of the southern and western part of Thrace Basin in Turkey and Greece. Sandstone compositional data (78 gross composition analyses and 40 heavy minerals analyses) were used to understand the change in detrital modes which reflects the provenance and geodinamic evolution of the basin. Samples were collected at six localities, which are from west to est: Gökçeada, Gallipoli and South-Ganos (south of Ganos Fault), Alexandroupolis, Korudağ and North-Ganos (north of Ganos Fault). Petrologic (framework composition and heavy-mineral analyses) and stratigraphic-sedimentologic data, (analysis of sedimentologic facies associations along representative stratigraphic sections, paleocurrents) allowed discrimination of six petrofacies; for each petrofacies the sediment dispersal system was delineated. The Thrace Basin fill is made mainly of lithic arkoses and arkosic litharenites with variable amount of low-grade metamorphic lithics (also ophiolitic), neovolcanic lithics, and carbonate grains (mainly extrabasinal). Picotite is the most widespread heavy mineral in all petrofacies. Petrological data on analyzed successions show a complex sediment dispersal pattern and evolution of the basin, indicating one principal detrital input from a source area located to the south, along both the İzmir-Ankara and Intra-Pontide suture lines, and a possible secondary source area, represented by the Rhodope Massif to the west. A significant portion of the Thrace Basin sediments in the study area were derived from ophiolitic source rocks and from their oceanic cover, whereas epimetamorphic detrital components came from a low-grade crystalline basement. An important penecontemporaneous volcanic component is widespread in late Eocene-Oligocene times, indicating widespread post-collisional (collapse?) volcanism following the closure of the Vardar ocean. Large-scale sediment mass wasting from south to north along the southern margin of the Thrace Basin is indicated (i) in late Eocene time by large olistoliths of ophiolites and penecontemporaneous carbonates, and (ii) in the mid-Oligocene by large volcaniclastic olistoliths. The late Oligocene paleogeographic scenario was characterized by large deltaic bodies prograding northward (Osmancik Formation). This clearly indicates that the southern margin of the basin acted as a major sediment source area throughout its Eocene-Oligocene history. Another major sediment source area is represented by the Rhodope Massif, in particolar the Circum-Rhodopic belt, especially for plutonic and metamorphic rocks. Considering preexisting data on the petrologic composition of Thrace Basin, silicilastic sediments in Greece and Bulgaria (Caracciolo, 2009), a Rhodopian provenance could be considered mostly for areas of the Thrace Basin outside our study area, particularly in the northern-central portions of the basin. In summary, the most important source area for the sediment of Thrace Basin in the study area was represented by the exhumed subduction-accretion complex along the southern margin of the basin (Biga Peninsula and western-central Marmara Sea region). Most measured paleocurrent indicators show an eastward paleoflow but this is most likely the result of gravity flow deflection. This is possible considered a strong control due to the east-west-trending synsedimentary transcurrent faults which cuts the Thrace Basin, generating a series of depocenters and uplifts which deeply influenced sediment dispersal and the areal distribution of paleoenvironments. The Thrace Basin was long interpreted as a forearc basin between a magmatic arc to the north and a subduction-accretion complex to the south, developed in a context of northward subduction. This interpretation was challenged by more recent data emphasizing the lack of a coeval magmatic arc in the north and the interpretation of the chaotic deposit which outcrop south of Ganos Fault as olistoliths and large submarine slumps, derived from the erosion and sedimentary reworking of an older mélange unit located to the south (not as tectonic mélange formed in an accretionary prism). The present study corroborates instead the hypothesis of a post-collisional origin of the Thrace Basin, due to a phase of orogenic collapse, which generated a series of mid-Eocene depocenters all along the İzmir-Ankara suture (following closure of the Vardar-İzmir-Ankara ocean and the ensuing collision); then the slab roll-back of the remnant Pindos ocean played an important role in enhancing subsidence and creating additional accommodation space for sediment deposition.

Slope stability analysis by multi-temporal DEMs and 3D modelling: The 2002 and 2007 Stromboli landslide events

Natural hazard related to the volcanic activity represents a potential risk factor, particularly in the vicinity of human settlements. Besides to the risk related to the explosive and effusive activity, the instability of volcanic edifices may develop into large landslides often catastrophically destructive, as shown by the collapse of the northern flank of Mount St. Helens in 1980. A combined approach was applied to analyse slope failures that occurred at Stromboli volcano. SdF slope stability was evaluated by using high-resolution multi-temporal DTMMs and performing limit equilibrium stability analyses. High-resolution topographical data collected with remote sensing techniques and three-dimensional slope stability analysis play a key role in understanding instability mechanism and the related risks. Analyses carried out on the 2002–2003 and 2007 Stromboli eruptions, starting from high-resolution data acquired through airborne remote sensing surveys, permitted the estimation of the lava volumes emplaced on the SdF slope and contributed to the investigation of the link between magma emission and slope instabilities. Limit Equilibrium analyses were performed on the 2001 and 2007 3D models, in order to simulate the slope behavior before 2002-2003 landslide event and after the 2007 eruption. Stability analyses were conducted to understand the mechanisms that controlled the slope deformations which occurred shortly after the 2007 eruption onset, involving the upper part of slope. Limit equilibrium analyses applied to both cases yielded results which are congruent with observations and monitoring data. The results presented in this work undoubtedly indicate that hazard assessment for the island of Stromboli should take into account the fact that a new magma intrusion could lead to further destabilisation of the slope, which may be more significant than the one recently observed because it will affect an already disarranged deposit and fractured and loosened crater area. The two-pronged approach based on the analysis of 3D multi-temporal mapping datasets and on the application of LE methods contributed to better understanding volcano flank behaviour and to be prepared to undertake actions aimed at risk mitigation.

The stratigraphic record of the quaternary sea level fluctuations and the impact of the post-glacial sea level rise (Termination I) in the Adriatic basin (Mediterranean sea)

The modern stratigraphy of clastic continental margins is the result of the interaction between several geological processes acting on different time scales, among which sea level oscillations, sediment supply fluctuations and local tectonics are the main mechanisms. During the past three years my PhD was focused on understanding the impact of each of these process in the deposition of the central and northern Adriatic sedimentary successions, with the aim of reconstructing and quantifying the Late Quaternary eustatic fluctuations. In the last few decades, several Authors tried to quantify past eustatic fluctuations through the analysis of direct sea level indicators, among which drowned barrier-island deposits or coral reefs, or indirect methods, such as Oxygen isotope ratios (δ18O) or modeling simulations. Sea level curves, obtained from direct sea level indicators, record a composite signal, formed by the contribution of the global eustatic change and regional factors, as tectonic processes or glacial-isostatic rebound effects: the eustatic signal has to be obtained by removing the contribution of these other mechanisms. To obtain the most realistic sea level reconstructions it is important to quantify the tectonic regime of the central Adriatic margin. This result has been achieved integrating a numerical approach with the analysis of high-resolution seismic profiles. In detail, the subsidence trend obtained from the geohistory analysis and the backstripping of the borehole PRAD1.2 (the borehole PRAD1.2 is a 71 m continuous borehole drilled in -185 m of water depth, south of the Mid Adriatic Deep - MAD - during the European Project PROMESS 1, Profile Across Mediterranean Sedimentary Systems, Part 1), has been confirmed by the analysis of lowstand paleoshorelines and by benthic foraminifera associations investigated through the borehole. This work showed an evolution from inner-shelf environment, during Marine Isotopic Stage (MIS) 10, to upper-slope conditions, during MIS 2. Once the tectonic regime of the central Adriatic margin has been constrained, it is possible to investigate the impact of sea level and sediment supply fluctuations on the deposition of the Late Pleistocene-Holocene transgressive deposits. The Adriatic transgressive record (TST - Transgressive Systems Tract) is formed by three correlative sedimentary bodies, deposited in less then 14 kyr since the Last Glacial Maximum (LGM); in particular: along the central Adriatic shelf and in the adjacent slope basin the TST is formed by marine units, while along the northern Adriatic shelf the TST is represented by costal deposits in a backstepping configuration. The central Adriatic margin, characterized by a thick transgressive sedimentary succession, is the ideal site to investigate the impact of late Pleistocene climatic and eustatic fluctuations, among which Meltwater Pulses 1A and 1B and the Younger Dryas cold event. The central Adriatic TST is formed by a tripartite deposit bounded by two regional unconformities. In particular, the middle TST unit includes two prograding wedges, deposited in the interval between the two Meltwater Pulse events, as highlighted by several 14C age estimates, and likely recorded the Younger Dryas cold interval. Modeling simulations, obtained with the two coupled models HydroTrend 3.0 and 2D-Sedflux 1.0C (developed by the Community Surface Dynamics Modeling System - CSDMS), integrated by the analysis of high resolution seismic profiles and core samples, indicate that: 1 - the prograding middle TST unit, deposited during the Younger Dryas, was formed as a consequence of an increase in sediment flux, likely connected to a decline in vegetation cover in the catchment area due to the establishment of sub glacial arid conditions; 2 - the two-stage prograding geometry was the consequence of a sea level still-stand (or possibly a fall) during the Younger Dryas event. The northern Adriatic margin, characterized by a broad and gentle shelf (350 km wide with a low angle plunge of 0.02° to the SE), is the ideal site to quantify the timing of each steps of the post LGM sea level rise. The modern shelf is characterized by sandy deposits of barrier-island systems in a backstepping configuration, showing younger ages at progressively shallower depths, which recorded the step-wise nature of the last sea level rise. The age-depth model, obtained by dated samples of basal peat layers, is in good agreement with previous published sea level curves, and highlights the post-glacial eustatic trend. The interval corresponding to the Younger Dyas cold reversal, instead, is more complex: two coeval coastal deposits characterize the northern Adriatic shelf at very different water depths. Several explanations and different models can be attempted to explain this conundrum, but the problem remains still unsolved.

Rituali indigeni in Mesoamerica. La festa di Petición de Lluvias nella Montaña di Guerrero (Messico)

Questa tesi di carattere antropologico in ambito dottorale riguarda i rituali comunitari nelle comunità indigene messicane. Il principale oggetto della ricerca è il rituale della pioggia o di Petición de Lluvia, caratterizzato sia dal sacrificio animale che da una specifica relazione di causa-effetto con l’ambiente circostante. La ricerca etnografica è cominciata dall’ipotesi di voler verificare la persistenza nel tempo, e dunque nell’attualità, di procedure cerimoniali non appartenenti, almeno nella loro forma più lineare, alla religione cattolico-cristiana. Il luogo nel quale è avvenuta tale ricerca è la regione La Montaña di Guerrero, situata nel Messico sud-occidentale, e più precisamente la zona in cui vivono le comunità di etnia Nahua di San Pedro Petlacala, Acuilpa, e Xalpatláhuac che si trovano nelle vicinanze della cittadina di Tlapa de Comonfort. In un contesto ambientale profondamente rurale come quello della Montaña di Guerrero, la persistenza dei rituali evidenzia come le risorse naturali e gli agenti atmosferici - pioggia, vento, nubi - continuino a rappresentare gli elementi centrali che condizionano le variabili economiche di sussistenza e della riproduzione sociale. Il rituale di Petición de Lluvia rappresenta il momento di congiunzione tra la stagione secca e quella piovosa, tra la semina ed il raccolto del mais. Definito come una pratica religiosa nella quale il gruppo si identifica e partecipa con varie donazioni (ofrenda o deposito rituale), suddivisibili in alimenti/oggetti/preghiere ed azioni rituali, la cerimonia esprime l’auspicio di piogge abbondanti, con le quali irrigare i campi e continuare le attività umane. Il destinatario dell’offerta è la stessa divinità della pioggia, Tlaloc per le antiche civiltà mesoamericane, invocato sotto le mentite spoglie del santo patrono del 25 aprile, San Marcos. Il rituale è contraddistinto per tutta la sua durata dalla presenza del principale specialista religioso, sacerdote in lingua spagnola oppure «Tlahmáquetl» in lingua náhuatl.

Paleosecular variation of the magnetic field recorded in Pleistocene-holocene volcanics from Pantelleria (italy) and Azores archipelago (portugal): implications for local volcanic history

The primary goal of volcanological studies is to reconstruct the eruptive history of active volcanoes, by correlating and dating volcanic deposits, in order to depict a future scenario and determine the volcanic hazard of an area. However, alternative methods are necessary where the lack of outcrops, the deposit variability and discontinuity make the correlation difficult, and suitable materials for an accurate dating lack. In this thesis, paleomagnetism (a branch of Geophysics studying the remanent magnetization preserved in rocks) is used as a correlating and dating tool. The correlation is based on the assumption that coeval rocks record similar paleomagnetic directions; the dating relies upon the comparison between paleomagnetic directions recorded by rocks with the expected values from references Paleo-Secular Variation curves (PSV, the variation of the geomagnetic field along time). I first used paleomagnetism to refine the knowledge of the pre – 50 ka geologic history of the Pantelleria island (Strait of Sicily, Italy), by correlating five ignimbrites and two breccias deposits emplaced during that period. Since the use of the paleomagnetic dating is limited by the availability of PSV curves for the studied area, I firstly recovered both paleomagnetic directions and intensities (using a modified Thellier method) from radiocarbon dated lava flows in São Miguel (Azores Islands, Portugal), reconstructing the first PSV reference curve for the Atlantic Ocean for the last 3 ka. Afterwards, I applied paleomagnetism to unravel the chronology and characteristics of Holocene volcanic activity at Faial (Azores) where geochronological age constraints lack. I correlated scoria cones and lava flows yielded by the same eruption on the Capelo Peninsula and dated eruptive events (by comparing paleomagnetic directions with PSV from France and United Kingdom), finding that the volcanics exposed at the Capelo Peninsula are younger than previously believed, and entirely comprised in the last 4 ka.

Fabrication, Electrical Characterization and Simulation of Thin Film Solar Cells: CdTe and CIGS Materials

CdTe and Cu(In,Ga)Se2 (CIGS) thin film solar cells are fabricated, electrically characterized and modelled in this thesis. We start from the fabrication of CdTe thin film devices where the R.F. magnetron sputtering system is used to deposit the CdS/CdTe based solar cells. The chlorine post-growth treatment is modified in order to uniformly cover the cell surface and reduce the probability of pinholes and shunting pathways creation which, in turn, reduces the series resistance. The deionized water etching is proposed, for the first time, as the simplest solution to optimize the effect of shunt resistance, stability and metal-semiconductor inter-diffusion at the back contact. In continue, oxygen incorporation is proposed while CdTe layer deposition. This technique has been rarely examined through R.F sputtering deposition of such devices. The above experiments are characterized electrically and optically by current-voltage characterization, scanning electron microscopy, x-ray diffraction and optical spectroscopy. Furthermore, for the first time, the degradation rate of CdTe devices over time is numerically simulated through AMPS and SCAPS simulators. It is proposed that the instability of electrical parameters is coupled with the material properties and external stresses (bias, temperature and illumination). Then, CIGS materials are simulated and characterized by several techniques such as surface photovoltage spectroscopy is used (as a novel idea) to extract the band gap of graded band gap CIGS layers, surface or bulk defect states. The surface roughness is scanned by atomic force microscopy on nanometre scale to obtain the surface topography of the film. The modified equivalent circuits are proposed and the band gap graded profiles are simulated by AMPS simulator and several graded profiles are examined in order to optimize their thickness, grading strength and electrical parameters. Furthermore, the transport mechanisms and Auger generation phenomenon are modelled in CIGS devices.

El depósito irregular de dinero: una aproximación teórica, histórica y ética

El análisis económico de las instituciones jurídicas ha adquirido una importancia considerable en los últimos años. Precisamente, el objetivo esencial de este trabajo se centra en el estudio del análisis económico del contrato de depósito irregular de dinero mediante tres enfoques metodológicos diferentes. El primer capítulo de este trabajo analiza la naturaleza jurídica del contrato de depósito irregular de dinero, examinando las principales características respecto al contrato de préstamo o mutuo. Igualmente, este capítulo estudiará la lógica jurídica propia de ambas instituciones, y cómo los principios generales del derecho fueron descubiertos desde el derecho romano clásico. El segundo capítulo trata de analizar la historia de los hechos económicos y, en particular, el proceso histórico de la violación de los principios tradicionales del derecho en relación al contrato de depósito irregular de dinero. Por último, el capítulo tercero examina los distintos intentos doctrinales realizados para elaborar un nuevo tipo de contrato de depósito bancario de dinero, con el único objetivo de legitimar un sistema bancario con un coeficiente de caja de reserva fraccionaria.