Chemistry of Fe(II) in the presence of organic exudates from phytoplankton and of copper in seawater

Programa de doctorado de Oceanografía ; 2006-2008

New polymeric materials for vascular surgery

The dramatic impact that vascular diseases have on human life quality and expectancy nowadays is the reason why both medical and scientific communities put great effort in discovering new and effective ways to fight vascular pathologies. Among the many different treatments, endovascular surgery is a minimally-invasive technique that makes use of X-ray fluoroscopy to obtain real-time images of the patient during interventions. In this context radiopaque biomaterials, i.e. materials able to absorb X-ray radiation, play a fundamental role as they are employed both to enhance visibility of devices during interventions and to protect medical staff and patients from X-ray radiations. Organic-inorganic hybrids are materials that combine characteristics of organic polymers with those of inorganic metal oxides. These materials can be synthesized via the sol-gel process and can be easily applied as thin coatings on different kinds of substrates. Good radiopacity of organic-inorganic hybrids has been recently reported suggesting that these materials might find applications in medical fields where X-ray absorption and visibility is required. The present PhD thesis aimed at developing and characterizing new radiopaque organic-inorganic hybrid materials that can find application in the vascular surgery field as coatings for the improvement of medical devices traceability as well as for the production of X-ray shielding objects and garments. Novel organic-inorganic hybrids based on different polyesters (poly-lactic acid and poly-ε-caprolactone) and polycarbonate (poly-trimethylene carbonate) as the polymeric phase and on titanium oxide as the inorganic phase were synthesized. Study of the phase interactions in these materials allowed to demonstrate that Class II hybrids (where covalent bonds exists between the two phases) can be obtained starting from any kind of polyester or polycarbonate, without the need of polymer pre-functionalization, thanks to the occurrence of transesterification reactions operated by inorganic molecules on ester and carbonate moieties. Polyester based hybrids were successfully coated via dip coating on different kinds of textiles. Coated textiles showed improved radiopacity with respect to the plain fabric while remaining soft to the touch. The hybrid was able to coat single fibers of the yarn rather than coating the yarn as a whole. Openings between yarns were maintained and therefore fabric breathability was preserved. Such coatings are promising for the production of light-weight garments for X-ray protection of medical staff during interventional fluoroscopy, which will help preventing pathologies that stem from chronic X-ray exposure. A means to increase the protection capacity of hybrid-coated fabrics was also investigated and implemented in this thesis. By synthesizing the hybrid in the presence of a suspension of radiopaque tantalum nanoparticles, PDMS-titania hybrid materials with tunable radiopacity were developed and were successfully applied as coatings. A solution for enhancing medical device radiopacity was also successfully investigated. High metal radiopacity was associated with good mechanical and protective properties of organic-inorganic hybrids in the form of a double-layer coating. Tantalum was employed as the constituent of the first layer deposited on sample substrates by means of a sputtering technique. The second layer was composed of a hybrid whose constituents are well-known biocompatible organic and inorganic components, such as the two polymers PCL and PDMS, and titanium oxide, respectively. The metallic layer conferred to the substrate good X-ray visibility. A correlation between radiopacity and coating thickness derived during this study allows to tailor radiopacity simply by controlling the metal layer sputtering deposition time. The applied metal deposition technique also permits easy shaping of the radiopaque layer, allowing production of radiopaque markers for medical devices that can be unambiguously identified by surgeons during implantation and in subsequent radiological investigations. Synthesized PCL-titania and PDMS-titania hybrids strongly adhered to substrates and show good biocompatibility as highlighted by cytotoxicity tests. The PDMS-titania hybrid coating was also characterized by high flexibility that allows it to stand large substrate deformations without detaching nor cracking, thus being suitable for application on flexible medical devices.

Vortex dynamics in superconductors in the presence of anisotropic pinning

Vortex dynamics in two different classes of superconductors with anisotropic unidirected pinning sites was experimentally investigated by magnetoresistivity measurements: YBCO−films with unidirected twins and Nb-films deposited on faceted $mathrm Al_2O_3$ substrate surfaces. For the interpretation of the experimental results a theoretical model based on the Fokker-Planck equation was used. It was proved by X-ray measurements that YBCO films prepared on (001) $mathrm NdGaO_3$ substrates exhibit only one twin orientation in contrast to YBCO films grown on (100) $mathrm SrTiO_$3 substrates. The magnetoresistivity measurements of the YBCO films with unidirected twin boundaries revealed the existence of two new magnetoresistivity components, which is a characteristic feature of a guided vortex motion: an odd longitudinal component with respect to the magnetic field sign reversal and an even transversal component. However, due to the small coherence length in YBCO and the higher density of point-like defects comparing to high-quality YBCO single crystals, the strength of the isotropic point pinning was comparable with the strength of the pinning produced by twins. This smeared out all effects caused by the pinning anisotropy. The behaviour of the odd longitudinal component was found to be independent of the transport current direction with respect to the twin planes. The magnetoresistivity measurements of faceted Nb films demonstrated the appearance of an odd longitudinal and even transversal component of the magnetoresistivity. The temperature and magnetic field dependences of all relevant magnetoresistivity components were measured. The angles between the average vortex velocity vector and the transport current direction calculated from the experimental data for the different transport current orientations with respect to the facet ridges showed that the vortices moved indeed along the facet ridges. An anomalous Hall effect, i.e. a sign change of the odd transversal magnetoresistivity, has been found in the temperature and magnetic field dependences of the Hall resisitivity of the samples. The theory developed by V.~A.~Shklovskij was used for the explanation of the experimental data. It shows very good agreement with the experiment. The temperature dependence of the even longitudinal magnetoresistivity component of the samples could be very well fitted within the theoretical approach, using for the isotropic and anisotropic pinning potential simple potential with a symmetric triangular potential wells whose depths were estimated from the experimental data.

Oxylipins biosynthesis in Lactobacillus helveticus in the presence of oxidative stress

This PhD thesis is aimed at studying the possible pathways and the mechanisms that can trigger oxylipins biosynthesis, and particularly that of short chain aldehydes and alcohols, in Lactobacillus helveticus, also in the presence of oxidative stress, using a totally labelled linoleic acid as precursor. In plants and fungi these molecules, involved in defence mechanisms against pathogens and in communication systems, derive from the oxidation of cellular unsaturated fatty acids (UFAs) and their accumulation is associated with stress exposure. Since some oxylipins are produced also by lactobacilli, it is possible to hypothesize that a metabolic pathway from UFAs to oxylipins, similar to what happens in plants and fungi, is present also in lactic acid bacteria. The results obtained pointed out that some volatile molecules are the result of UFAs catabolism, since they appear only when cells are incubated in their presence. Labelled linoleic acid is integrated in the membrane and subsequently transformed into aldehydes and alcohols, whose extent and carbon atoms number depend on stress exposure. The enzymes responsible for this metabolic pathway in plants and fungi (e.g. lipoxygenase, dioxygenase) seem to be absent in Lactobacillus helveticus and in other lactobacilli. Proteomic analyses show the over expression of many proteins, including thioredoxin reductase (part of the bacterial oxidative defence system), mainly in cells grown with linoleic acid without oxidative stress exposure, confirming that linoleic acid itself induces oxidative stress. 6 general oxidoreductases (class including dioxygenases and peroxidase) were found and therefore a deeper investigation on them could be productive in elucidating all steps involved in oxylipins biosynthesis in bacteria. Due to the multiple role of oxylipins (flavouring agents, antimicrobial compounds and interspecific signalling molecules) the identification of genes involved and regulating factors should have an important biotechnological impact, also allowing the overproduction of selected bioactive molecules.

Experimental characterization of backscattering properties of UWB antennas in the presence of close objects

RTLS and RFID systems are becoming more and more important in several fields. When these systems meet the UWB technology, they can take advantage of each other strengths. Since nowadays a strong importance is given to the "green" technology, we chose to adopt a passive solution. In this case the backscattering modulation can be used to carry data. Therefore it is necessary to analyze the behavior of the antennas used as tags, when they are closed to dierent material objects. In particular, the antenna mode part has been deeply observed, as it is the crucial part of the signal regarding the backscatter modulation.

General effective medium model for the complex permittivity extraction with an open-ended coaxial probe in presence of a multilayer material under test

The work presented in this thesis is focused on the open-ended coaxial-probe frequency-domain reflectometry technique for complex permittivity measurement at microwave frequencies of dispersive dielectric multilayer materials. An effective dielectric model is introduced and validated to extend the applicability of this technique to multilayer materials in on-line system context. In addition, the thesis presents: 1) a numerical study regarding the imperfectness of the contact at the probe-material interface, 2) a review of the available models and techniques, 3) a new classification of the extraction schemes with guidelines on how they can be used to improve the overall performance of the probe according to the problem requirements.

Investigation of the dipole response of nickel isotopes in the presence of a high-frequency electromagnetic field

The electric dipole response of neutron-rich nickel isotopes has been investigated using the LAND setup at GSI in Darmstadt (Germany). Relativistic secondary beams of 56−57Ni and 67−72Ni at approximately 500 AMeV have been generated using projectile fragmentation of stable ions on a 4 g/cm2 Be target and subsequent separation in the magnetic dipole fields of the FRagment Separator (FRS). After reaching the LAND setup in Cave C, the radioactive ions were excited electromagnetically in the electric field of a Pb target. The decay products have been measured in inverse kinematics using various detectors. Neutron-rich 67−69Ni isotopes decay by the emission of neutrons, which are detected in the LAND detector. The present analysis concentrates on the (gamma,n) and (gamma,2n) channels in these nuclei, since the proton and three-neutron thresholds are unlikely to be reached considering the virtual photon spectrum for nickel ions at 500 AMeV. A measurement of the stable 58Ni isotope is used as a benchmark to check the accuracy of the present results with previously published data. The measured (gamma,n) and (gamma,np) channels are compared with an inclusive photoneutron measurement by Fultz and coworkers, which are consistent within the respective errors. The measured excitation energy distributions of 67−69Ni contain a large portion of the Giant Dipole Resonance (GDR) strength predicted by the Thomas-Reiche-Kuhn energy-weighted sum rule, as well as a significant amount of low-lying E1 strength, that cannot be attributed to the GDR alone. The GDR distribution parameters are calculated using well-established semi-empirical systematic models, providing the peak energies and widths. The GDR strength is extracted from the chi-square minimization of the model GDR to the measured data of the (gamma,2n) channel, thereby excluding any influence of eventual low-lying strength. The subtraction of the obtained GDR distribution from the total measured E1 strength provides the low-lying E1 strength distribution, which is attributed to the Pygmy Dipole Resonance (PDR). The extraction of the peak energy, width and strength is performed using a Gaussian function. The minimization of trial Gaussian distributions to the data does not converge towards a sharp minimum. Therefore, the results are presented by a chi-square distribution as a function of all three Gaussian parameters. Various predictions of PDR distributions exist, as well as a recent measurement of the 68Ni pygmy dipole-resonance obtained by virtual photon scattering, to which the present pygmy dipole-resonance distribution is also compared.

Designing Electricity Auctions in the Presence of Transmission Constraints

This paper analyzes the effect that different designs in the access to fnancial transmission rights has on spot electricity auctions. In particular, I characterize the equilibrium in the spot electricity market when financial transmission rights are assigned to the grid operator and when financial transmission rights are assigned to the firm that submits the lowest bid in the spot electricity auction. When financial transmission rights are assigned to the grid operator, my model, in contrast with the models available in the literature, works out the equilibrium for any transmission capacity. Moreover, I have found that an increase in transmission capacity not only increases competition between markets but also within a single market. When financial transmission rights are assigned to the firm that submits the lowest bid in the spot electricity auction, firms compete not only for electricity demand, but also for transmission rights and the arbitrage profits derived from its hold. I have found that introduce competition for transmission rights reduces competition in spot electricity auctions.

The Presence of Words in Visual Art from Surrealism to Conceptualism

Without a doubt, one of the biggest changes that affected XXth century art is the introduction of words into paintings and, in more recent years, in installations. For centuries, if words were part of a visual composition, they functioned as reference; strictly speaking, they were used as a guideline for a better perception of the subject represented. With the developments of the XXth century, words became a very important part of the visual composition, and sometimes embodied the composition itself. About this topic, American art critic and collector Russell Bowman wrote an interesting article called Words and images: A persistent paradox, in which he examines the American and the European art of the XXth century in almost its entirety, dividing it up in six “categories of intention”. The aforementioned categories are not based on the art history timeline, but on the role that language played for specific artists or movements. Taking inspiration from Bowman's article, this paper is structured in three chapters, respectively: words in juxtaposition and free association, words as means of exploration of language structures, and words as means for political and personal messages. The purpose of this paper is therefore to reflect on the role of language in contemporary art and on the way it has changed from artist to artist.

Human Presence Detection: analisi comparativa e caso di studio in Home Manager

La possibilità di monitorare l’attività degli utenti in un sistema domotico, sia considerando le azioni effettuate direttamente sul sistema che le informazioni ricavabili da strumenti esterni come la loro posizione GPS, è un fattore importante per anticipare i bisogni e comprendere le preferenze degli utenti stessi, rendendo sempre più intelligenti ed autonomi i sistemi domotici. Mentre i sistemi attualmente disponibili non includono o non sfruttano appieno queste potenzialità, l'obiettivo di sistemi prototipali sviluppati per fini di ricerca, quali ad esempio Home Manager, è invece quello di utilizzare le informazioni ricavabili dai dispositivi e dal loro utilizzo per abilitare ragionamenti e politiche di ordine superiore. Gli obiettivi di questo lavoro sono: - Classificare ed elencare i diversi sensori disponibili al fine di presentare lo stato attuale della ricerca nel campo dello Human Sensing, ovvero del rilevamento di persone in un ambiente. - Giustificare la scelta della telecamera come sensore per il rilevamento di persone in un ambiente domestico, riportando metodi per l’analisi video in grado di interpretare i fotogrammi e rilevare eventuali figure in movimento al loro interno. - Presentare un’architettura generica per integrare dei sensori in un sistema di sorveglianza, implementando tale architettura ed alcuni algoritmi per l’analisi video all’interno di Home Manager con l’aiuto della libreria OpenCV .

An angiographic analysis of atherosclerosis progression in below-the-knee arteries after femoropopliteal angioplasty in claudicants

Purpose: To report an angiographic investigation of midterm atherosclerotic disease progression in below-the-knee (BTK) arteries of claudicants. Methods: Angiograms were performed in 58 consecutive claudicants (35 men; mean age 68.3±8.7 years) with endovascular treatment of femoropopliteal arteries in 58 limbs after a mean follow-up of 3.6±1.2 years. Angiograms were reviewed in consensus by 2 experienced readers blinded to clinical data. Progression of atherosclerosis in 4 BTK arterial segments (tibioperoneal trunk, anterior and posterior tibial arteries, and peroneal artery) was assessed according to the Bollinger score. The composite per calf Bollinger score represented the average of the 4 BTK arterial segment scores. The association of the Bollinger score with cardiovascular risk factors and gender was scrutinized. Results: A statistically significant increase in atherosclerotic burden was observed for the mean composite per calf Bollinger score (5.7±8.3 increase, 95% CI 3.5 to 7.9, p<0.0001), as well as for each single arterial segment analyzed. In multivariate linear regression analysis, diabetes mellitus was associated with a more pronounced progression of atherosclerotic burden in crural arteries (β: 5.6, p=0.035, 95% CI 0.398 to 10.806). Conclusion: Progression of infrapopliteal atherosclerotic lesions is common in claudicants during midterm follow-up. Presence of diabetes mellitus was confirmed as a major risk factor for more pronounced atherosclerotic BTK disease progression.

Renal insufficiency is independently associated with a distal distribution pattern of symptomatic lower-limb atherosclerosis

Objectives The purpose of this study was to assess the impact of renal insufficiency (RI) on the distribution pattern of peripheral arterial disease (PAD). We hypothesised that RI is associated with a distally accentuated involvement of the peripheral arterial tree. Design This is a retrospective analysis. Materials and Methods Analysis was based on a consecutive series of 2709 patients with chronic PAD of atherosclerotic origin undergoing primary endovascular treatment of lower-extremity arteries. Atherosclerotic pattern was grouped into femoropopliteal (n = 2085) and infragenicular (n = 892) disease according to target lesions treated while using iliac disease (n = 1133) as reference. Univariable and multivariable multinomial regression analyses were performed to assess relation with RI. Results are shown as relative risk ratio (RRRs) with 95% confidence intervals (95% CIs). A p < 0.05 was considered statistically significant. RI was defined as glomerular filtration rate (GFR) < 60 ml min−1 1.73 m−2. Results Presence of RI was an independent risk factor for a centrifugal lesion pattern (RRR 1.48, 95% CI: 1.17–1.86, p = 0.001). Moreover, a decrease in GFR by 10 ml min−1 1.73 m−2 was associated with an RRR of 1.08 for below-the-knee arterial disease (95% CI: 1.03–1.13, p = 0.003). Conclusion Presence and severity of RI are independent predictors of a distal obstructive pattern in patients with symptomatic PAD.

Endovascular treatment of popliteal artery aneurysms: a single-center experience

PURPOSE: To evaluate the use of covered stent-grafts in the endovascular treatment (ET) of popliteal artery aneurysms (PAAs). MATERIALS AND METHODS: A retrospective analysis was conducted over a period of 52 months in 18 consecutive patients (17 men; mean age +/- SD, 70 years +/- 11) undergoing ET of PAAs with the Viabahn endograft in a single center. Patient symptoms, aneurysm characteristics, technical outcomes, complications, and follow-up were assessed. RESULTS: Aneurysm diameters ranged from 12 to 51 mm with a mean of 30 mm (+/-11). Thirteen aneurysms (72.2%) were partially thrombosed and 12 patients (66.6%) had symptoms of lower limb ischemia at presentation (11 chronic and one acute). The technical success rate was 94%. Intraprocedural emboli and endoleak occurred in one and two patients, respectively. Fourteen patients were available for follow-up after successful treatment, with a mean follow-up time of 15 months (range, 7-37 months). All stent-grafts were patent after 1 month, with no mortality or limb loss. The primary patency rate with complete exclusion of the aneurysm at 6 months was 86%. Pre- and postprocedural noninvasive arterial studies were available in 10 patients, demonstrating improvement of the ankle-brachial index from 0.96 +/- 0.41 to 1.17 +/- 0.18, respectively (P = .06). CONCLUSIONS: Endovascular stent-graft repair of PAAs is a feasible treatment option. However, further follow-up studies regarding the durability of results are required.

Endovascular treatment of a traumatic direct carotid-cavernous fistula using the Amplatzer Vascular Plug II

To report the use of the second-generation Amplatzer Vascular Plug II (AVP II) for the treatment of a posttraumatic type A carotid-cavernous fistula (CCF).

Endovascular treatment for chronic atherosclerotic occlusive mesenteric disease: is stenting superior to balloon angioplasty?

Endovascular treatment is an increasingly used therapeutic option in patients with chronic atherosclerotic occlusive mesenteric disease. Purpose of this study was evaluation of patency and mortality in patients treated with visceral artery percutaneous transluminal angioplasty (PTA) or stenting including follow-up.