957 resultados para QUIMICA BIO-INORGANICA
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Objective: We investigated the relation between duration of dual antiplatelet therapy (DAPT) and clinical outcomes up to 12 months after Genous (TM) endothelial progenitor cell capturing R stent (TM) placement in patients from the e-HEALING registry. Background: Cessation of (DAPT) has been shown to be associated with the occurrence of stent thrombosis (ST). After Genous placement, 1 month of DAPT is recommended. Methods: Patients were analyzed according to continuation or discontinuation of DAPT at a 30-day and 6-month landmark, excluding patients with events before the landmark. Each landmark was a new baseline, and outcomes were followed up to 12 months after stenting. The main outcome for our current analysis was target vessel failure (TVF), defined as target vessel-related cardiac death or myocardial infarction and target vessel revascularization. Secondary outcomes included ST. (Un)adjusted hazard ratios (HR) for TVF were calculated with Cox regression. Results: No difference was observed in the incidence of TVF [HR: 1.03; 95% confidence intervals (CI): 0.651.65, P = 0.89] in patients continuing DAPT (n = 4,249) at 30 days versus patients stopped (n = 309), and HR: 0.82 (95% CI: 0.551.23, P = 0.34) in patients continuing DAPT (n = 2,654) at 6 months versus patients stopped [n = 1,408] DAPT). Furthermore, no differences were observed in ST. Even after addition of identified independent predictors for TVF, adjusted TVF hazards were comparable. Conclusions: In a post-hoc analysis of e-HEALING, duration of DAPT was not associated with the occurrence of the outcomes TVF or ST. The Genous stent may be an attractive treatment especially in patients at increased risk for (temporary) cessation of DAPT or bleeding. (C) 2011 Wiley Periodicals, Inc.
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Rhodoliths are nodules of non-geniculate coralline algae that occur in shallow waters (<150 m depth) subjected to episodic disturbance. Rhodolith beds stand with kelp beds, seagrass meadows, and coralline algal reefs as one of the world's four largest macrophyte-dominated benthic communities. Geographic distribution of rhodolith beds is discontinuous, with large concentrations off Japan, Australia and the Gulf of California, as well as in the Mediterranean, North Atlantic, eastern Caribbean and Brazil. Although there are major gaps in terms of seabed habitat mapping, the largest rhodolith beds are purported to occur off Brazil, where these communities are recorded across a wide latitudinal range (2 degrees N - 27 degrees S). To quantify their extent, we carried out an inter-reefal seabed habitat survey on the Abrolhos Shelf (16 degrees 50' - 19 degrees 45'S) off eastern Brazil, and confirmed the most expansive and contiguous rhodolith bed in the world, covering about 20,900 km(2). Distribution, extent, composition and structure of this bed were assessed with side scan sonar, remotely operated vehicles, and SCUBA. The mean rate of CaCO3 production was estimated from in situ growth assays at 1.07 kg m(-2) yr(-1), with a total production rate of 0.025 Gt yr(-1), comparable to those of the world's largest biogenic CaCO3 deposits. These gigantic rhodolith beds, of areal extent equivalent to the Great Barrier Reef, Australia, are a critical, yet poorly understood component of the tropical South Atlantic Ocean. Based on the relatively high vulnerability of coralline algae to ocean acidification, these beds are likely to experience a profound restructuring in the coming decades.
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The National Institute for Clinical Excellence (NICE) guidelines recommend the use of bare-metal stents (BMS) in non-complex lesions with a low risk of restenosis (diameter a parts per thousand yen3 mm and lesion length a parts per thousand currency sign15 mm) and the use of drug-eluting stents (DES) in more complex lesions with a high risk of restenosis (diameter < 3.0 mm or lesion length > 15 mm). However, the guidelines were created based on studies evaluating BMS and DES only. We performed an analysis of patients undergoing non-urgent percutaneous coronary intervention with the novel endothelial cell capturing stent (ECS). The ECS is coated with CD34(+) antibodies that attract circulating endothelial progenitor cells to the stent surface, thereby accelerating the endothelialization of the stented area. We analyzed all patients enrolled in the worldwide e-HEALING registry that met the NICE criteria for either low-risk or high-risk lesions and were treated with a parts per thousand yen1 ECS. The main study outcome was target vessel failure (TVF) at 12-month follow-up, defined as the composite of cardiac death or MI and target vessel revascularization (TVR). A total of 4,241 patients were assessed in the current analysis. At 12-month follow-up, TVF occurred in 7.0% of the patients with low-risk lesions and in 8.8% of the patients with high-risk lesions (p = 0.045). When evaluating the diabetic patients versus the non-diabetic patients per risk group, no significant differences were found in TVF, MI or TVR in either risk group. The ECS shows good clinical outcomes in lesions carrying either a high or a low risk of restenosis according to the NICE guidelines with comparable rates of cardiac death, myocardial infarction, and stent thrombosis. The TVF rate with ECS was slightly higher in patients with high-risk lesions, driven by higher clinically driven TLR. The risk of restenosis with ECS in patients carrying high-risk lesions needs to be carefully considered relative to other risks associated with DES. Furthermore, the presence of diabetes mellitus did not influence the incidence of TVF in either risk group.
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Máster en Oceanografía
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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)”
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Organotin compounds have found in the last few decades a wide variety of applications. Indeed, they are used successfully as antifouling paints, PVC stabilizers and ion carriers, as well as homogeneous catalysts. In this context, it has been proved that the Lewis acidity of the metal centre allows these compounds to promote the reaction between alcohol and ester. However their use is now limited by their well-known toxicity, moreover they are hardly removable from the reaction mixture. This problem can be overcome by grafting the organotin derivative onto a polymeric cross-linked support. In this way the obtained heterogeneous catalyst can be easily filtered off from the reaction mixture, thus creating the so-called "clean organotin reagents", avoiding the presence of toxic organotin residues in solution and the tin release in the environment. In the last few years several insoluble polystyrene resins containing triorganotin carboxylate moieties have been synthesized with the aim of improving their catalytic activity: in particular we have investigated and opportunely modified their chemical structure in order to optimize the accessibility to the metal centre and its Lewis acidity. Recently, we replaced the polymeric matrix with an inorganic one, in order to dispose of a relatively cheaper and easily available support. For this purpose an ordered mesoporous silica, characterized by 2D-hexagonal pores, named MCM-41, and an amorphous silica have been selected. In the present work two kinds of MCM-41 silica containing the triorganotin carboxylate moiety have been synthesized starting from a commercial Cab-O-Sil M5 silica. These catalysts have two different spacers between the core and the tin-carboxylate moiety, namely a polyaliphatic chain (compound FT29) or a poliethereal one (compound FT6), with the aim to improve the interaction between catalyst and reacting ester. Three catalysts supported onto an amorphous silica have been also synthesized: the structure is the same as silica FT29, i.e. a compound having a polialiphatic chain, and they have different percentage of organotin derivative grafted on the silica surface (10, 30, 50% respectively for silica MB9, SU27 and SU28). The performances of the above silica as heterogeneous catalysts in transesterification reactions have been tested in a model reaction between ethyl acetate and 1-octanol, a primary alcohol sensitive to the reaction conditions. The alcohol conversion was assessed by gas-chromatography, determining the relative amount of transesterified product and starting alcohol after established time intervals.
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La presente ricerca si inquadra nell’ambito della risoluzione dei problemi legati alla chirurgia ossea, per la cura e la sostituzione di parti di osso in seguito a fratture, lesioni gravi, malformazioni e patologie quali osteoporosi, tumori, etc… Attualmente la progettazione di impianti per le sostituzioni/rigenerazioni ossee richiede che i materiali sviluppati siano in grado di “mimare” la composizione e la morfologia dei tessuti naturali, in modo da generare le specifiche interazioni chimiche esistenti nei tessuti dell’organismo con cui vengono a contatto e quindi di biointegrarsi e/o rigenerare l’osso mancante nel miglior modo possibile, in termini qualitativi e quantitativi. Per lo sviluppo di sostituti ossei porosi sono state sperimentate 2 tecnologie innovative: il freeze-casting ed il foaming. Gli impianti ceramici realizzati hanno presentano una dimensione dei pori ed un’interconnessione adeguata sia per l’abitazione cellulare che per la penetrazione dei fluidi fisiologici e la vascolarizzazione. In particolare l’elevata unidirezionalità nei campioni ottenuti mediante freeze-casting si presenta molto promettente poiché fornisce cammini guida che migliorano la vascolarizzazione dell’impianto e l’abitazione cellulare in tempi rapidi e nella parte più interna dello scaffold. D’altra parte, la tecnologia del foaming ha permesso l’ottenimento di materiali apatitici ad alta porosità multidimensionale ed interconnessa con proprietà meccaniche implementate rispetto a tipologie precedenti e, lavorabili dopo sinterizzazione mediante prototipazione rapida. Per questo motivo, questi materiali sono attualmente in corso di sperimentazione, con risultati preliminari adeguati promettenti per un’applicazione clinica, come sostituti ossei di condilo mandibolare, sito estremamente critico per gli sforzi meccanici presenti. È stata dimostrata la possibilità di utilizzare lo scaffold ceramico biomimetico con la duplice funzione di sostituto osseo bioattivo e sistema di rilascio in situ di ioni specifici e di antibiotico, in cui la cinetica di rilascio risulta fortemente dipendente dalle caratteristiche chimico-fisico morfologiche del dispositivo (solubilità, area di superficie specifica,…). Per simulare sempre di più la composizione del tessuto osseo e per indurre specifiche proprietà funzionali, è stata utilizzata la gelatina come fase proteica con cui rivestire/impregnare dispositivi porosi 3D a base di apatite, con cui miscelare direttamente la fase inorganica calcio-fosfatica e quindi realizzare materiali bio-ibridi in cui le due fasi contenenti siano intimamente interagenti. Inoltre al fine di ridurre gli innumerevoli problemi legati alle infezioni ossee alcuni dei materiali sviluppati sono stati quindi caricati con antibiotico e sono state valutate le cinetiche di rilascio. In questa maniera, nel sito dell’impianto sono state associate le funzioni di trasporto e di rilascio di farmaco, alla funzione di sostituzione/rigenerazione ossee. La sperimentazione con la gelatina ha messo in luce proprietà posatamente sfruttabili della stessa. Oltre a conferire allo scaffold un implementata mimesi composizionale del tessuto osseo, ha infatti consentito di aumentare le proprietà meccaniche, sia come resistenza a compressione che deformazione. Unitamente a quanto sopra, la gelatina ha consentito di modulare la funzionalità di dispensatore di farmaco; mediante controllo della cinetica di rilascio, tramite processi di reticolazione più o meno spinti.
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This PhD thesis addresses the topic of large-scale interactions between climate and marine biogeochemistry. To this end, centennial simulations are performed under present and projected future climate conditions with a coupled ocean-atmosphere model containing a complex marine biogeochemistry model. The role of marine biogeochemistry in the climate system is first investigated. Phytoplankton solar radiation absorption in the upper ocean enhances sea surface temperatures and upper ocean stratification. The associated increase in ocean latent heat losses raises atmospheric temperatures and water vapor. Atmospheric circulation is modified at tropical and extratropical latitudes with impacts on precipitation, incoming solar radiation, and ocean circulation which cause upper-ocean heat content to decrease at tropical latitudes and to increase at middle latitudes. Marine biogeochemistry is tightly related to physical climate variability, which may vary in response to internal natural dynamics or to external forcing such as anthropogenic carbon emissions. Wind changes associated with the North Atlantic Oscillation (NAO), the dominant mode of climate variability in the North Atlantic, affect ocean properties by means of momentum, heat, and freshwater fluxes. Changes in upper ocean temperature and mixing impact the spatial structure and seasonality of North Atlantic phytoplankton through light and nutrient limitations. These changes affect the capability of the North Atlantic Ocean of absorbing atmospheric CO2 and of fixing it inside sinking particulate organic matter. Low-frequency NAO phases determine a delayed response of ocean circulation, temperature and salinity, which in turn affects stratification and marine biogeochemistry. In 20th and 21st century simulations natural wind fluctuations in the North Pacific, related to the two dominant modes of atmospheric variability, affect the spatial structure and the magnitude of the phytoplankton spring bloom through changes in upper-ocean temperature and mixing. The impacts of human-induced emissions in the 21st century are generally larger than natural climate fluctuations, with the phytoplankton spring bloom starting one month earlier than in the 20th century and with ~50% lower magnitude. This PhD thesis advances the knowledge of bio-physical interactions within the global climate, highlighting the intrinsic coupling between physical climate and biosphere, and providing a framework on which future studies of Earth System change can be built on.