Sintesi e caratterizzazione di carboni per applicazioni in catalisi

I materiali a base di carbone vengono utilizzati in catalisi come supporti per fasi attive, ma anche direttamente come catalizzatori essi stessi, grazie soprattutto alla versatilità delle loro proprietà di massa e superficiali. L’attività catalitica dei carboni è influenzata soprattutto dalla natura, dalla concentrazione e dall’accessibilità dei siti attivi tra cui i più comuni sono: gruppi funzionali superficiali, difetti, ed eteroatomi inseriti nella struttura. Per ridurre i problemi diffusionali legati alla microporosità dei carboni attivi sono in corso numerosi studi sulla sintesi di carboni mesoporosi, i quali possono fornire benefici unici come alta area superficiale ed elevato volume dei pori, uniti a buone proprietà chimiche e stabilità meccanica. Nel corso di questa tesi, sono state svolte diverse attività finalizzate principalmente alla preparazione e alla caratterizzazione di carboni mesoporosi da utilizzare in ambito catalitico. La sintesi di carboni porosi è stata eseguita con la metodologia soft-templating, un metodo basato sulla replica di un agente templante polimerico che si organizza in micelle attorno alle quali avviene la reticolazione di un precursore polimerico termoindurente. Precursore e templante vengono pirolizzati ad elevate temperature per rimuovere in un primo momento l’agente templante e successivamente carbonizzare il precursore. Sono state scelte due metodologie di sintesi riportate in letteratura con lo scopo di sintetizzare due tipologie di carboni. La sintesi Mayes è stata utilizzata per sintetizzare carboni mesoporosi classici, mentre la sintesi Hao è stata utilizzata per ottenere carboni porosi contenenti azoto. Le due sintesi sono state ottimizzate variando diversi parametri, tra cui il tempo di reticolazione (curing) e la temperatura di pirolisi. Sui diversi carboni ottenuti sono stati effettuati alcuni trattamenti superficiali di ossidazione al fine di modificarne la funzionalità. In particolare si sono utilizzati agenti ossidanti come HNO3, H2O2 e N2O.

Estudi de l'estabilitat tèrmica de l'espinel·la NiCo2O4 mesoporosa

Els materials mesoporos (amb una mida controlada de porus entre els 2 i 50 nm) tenen com a tret diferencial la seva gran superfície específica, la qual els fa aptes per a aplicacions molt diverses. L’espinel·la de NiCo2O4 és aplicable com a sensor de gasos, com a catalitzador de les reaccions d’evolució i reducció d’oxigen o com a elèctrode en electrosíntesi inorgànica i orgànica. Hom preveu que l’obtenció de NiCo2O4 mesoporós podria ampliar el ventall d’aplicacions d’aquest material o millorar les prestacions de les ja existents. L’objectiu del projecte és el de determinar el rang de temperatures d’ús dels dispositius que incorporin l’espinel·la de NiCo2O4 mesoporosa. Per tal d’analitzar l’estabilitat tèrmica d’aquest material, es realitza un procés de síntesi complet de mostres d’aquestes característiques. S’inicia un procés d’obtenció de nanomotlles de sílice amb mesoestructura SBA-15 i KIT-6 pel mètode de soft-templating. Aquests templates es validen per TEM i EDX i són els emprats per a la síntesi de mostres de NiCo2O4 per hard-templating. Un cop sintetitzades les mostres de NiCo2O4 SBA-15 i KIT-6, es procedeix a validar la qualitat de la seva mesoestructura per TEM, i la seva composició química per EDX i de fases per XRD. Aquestes dues mostres as-prepared passen a ser sotmeses a un seguit de tractaments tèrmics a temperatures de 400ºC, 450ºC, 500ºC, 550ºC i 600ºC. Això permetrà observar per TEM el col·lapse de la mesoestructura i per XRD serà possible detectar i quantificar la segregació de NiO que podria malmetre les propietats del material en qualsevol de les seves aplicacions. Segons l’aparició d’aquests dos efectes negatius, es determinarà una temperatura crítica de funcionalitat del NiCo2O4 mesoporós. També es farà una anàlisi termogravimètrica dels precursors emprats per a la síntesi del NiCo2O4 confinats en templates de sílice: nitrat de cobalt i nitrat de níquel per separat, i una mescla d’ambdós amb proporcions 0,5:1 Ni(II):Co(II). Es podrà observar en quines temperatures tenen lloc el processos físicoquímics patits per aquests precursors, quan té lloc la formació dels òxids pertinents i com afecta la presència dels nanomotlles a cada un d’ells. Finalment, aquest projecte també incideix en l’estudi de la reproductibilitat per hard-templating de l’espinel·la de FeCo2O4, un material força desconegut en format mesoporós. I la caracterització de les mostres as-prepared per TEM, EDX i XRD.

Realizzazione e caratterizzazione chimico-fisica di una sorgente di plasma di non equilibrio operante a pressione atmosferica per la modifica superficale di materiali polimerici in ambiente controllato

Il plasma, quarto stato della materia, rappresenta un gas ionizzato in cui ioni ed elettroni si muovono a diverse energie sotto l’azione di un campo elettro-magnetico applicato dall’esterno. I plasmi si dividono in plasmi di equilibrio e di non equilibrio termodinamico, quest’ultimi sono caratterizzati da un’alta temperatura elettronica (oltre 10000 K) e da una bassa temperatura traslazionale degli ioni e delle specie neutre (300-1000 K). I plasmi di non equilibrio trovano largo impiego nella microelettronica, nei processi di polimerizzazione, nell’industria biomedicale e del packaging, consentendo di effettuare trattamenti di sterilizzazione e attivazione superficiale. Il lavoro di tesi è incentrato sui processi di funzionalizzazione e polimerizzazione superficiale con l’obbiettivo di realizzare e caratterizzare sorgenti di plasma di non equilibrio a pressione atmosferica operanti in ambiente controllato. È stata realizzata una sorgente plasma operante a pressione atmosferica e in ambiente controllato per realizzare trattamenti di modifica superficiale e di polimerizzazione su substrati polimerici. L’efficacia e l’omogeneità dei trattamenti eseguiti sono stati valutati tramite misura dell’angolo di contatto. La caratterizzazione elettrica ha consentito di determinare i valori di densità di energia superficiale trasferita sui substrati al variare delle condizioni operative. Lo strato depositato durante il processo di polimerizzazione è stato analizzato qualitativamente tramite l’analisi chimica in spettroscopia infrarossa. L’analisi delle prove di funzionalizzazione dimostra l’uniformità dei processi plasma eseguiti; inoltre i valori dell’angolo di contatto misurati in seguito ai trattamenti risultano confrontabili con la letteratura esistente. Lo studio dei substrati trattati in atmosfera satura d’azoto ha rivelato una concentrazione superficiale di azoto pari al 3% attribuibile alla presenza di ammine, ammine protonate e gruppi ammidici; ciò conferma la bontà della soluzione realizzata e dei protocolli operativi adottati per la funzionalizzazione delle superfici. L’analisi spettroscopica dei trattamenti di polimerizzazione, ha fornito spettri IR confrontabili con la letteratura esistente indicando una buona qualità del polimero depositato (PEG). I valori misurati durante la caratterizzazione elettrica della sorgente realizzata risulteranno fondamentali in futuro per l’ottimizzazione del dispositivo. I dati raccolti infatti, determineranno le linee guida per il tailoring dei trattamenti plasma e per lo sviluppo della sorgente. Il presente lavoro di tesi, pur prendendo in esame una piccola parte delle applicazioni industriali dei plasmi non termici, conferma quanto queste siano pervasive nei comuni processi industriali evidenziandone le potenzialità e i numerosi campi d’applicazione. La tecnologia plasma è destinata ad essere imprescindibile per la ricerca di soluzioni innovative ai limiti dei processi tradizionali.

Determinants of biological activity of nanomaterials in innate immunity cells: the role of aspect ratio, environmental contaminants and protein corona

As defined by the European Union, “ ’Nanomaterial’ (NM) means a natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or agglomerate, where, for 50 % or more of the particles in the number size distribution, one or more external dimensions is in the size range 1 nm-100 nm ” (2011/696/UE). Given their peculiar physico-chemical features, nanostructured materials are largely used in many industrial fields (e.g. cosmetics, electronics, agriculture, biomedical) and their applications have astonishingly increased in the last fifteen years. Nanostructured materials are endowed with very large specific surface area that, besides making them very useful in many industrial processes, renders them very reactive towards the biological systems and, hence, potentially endowed with significant hazard for human health. For these reasons, in recent years, many studies have been focused on the identification of toxic properties of nanostructured materials, investigating, in particular, the mechanisms behind their toxic effects as well as their determinants of toxicity. This thesis investigates two types of nanostructured TiO2 materials, TiO2 nanoparticles (NP), which are yearly produced in tonnage quantities, and TiO2 nanofibres (NF), a relatively novel nanomaterial. Moreover, several preparations of MultiWalled Carbon Nanotubes (MWCNT), another nanomaterial widely present in many products, are also investigated.- Although many in vitro and in vivo studies have characterized the toxic properties of these materials, the identification of their determinants of toxicity is still incomplete. The aim of this thesis is to identify the structural determinants of toxicity, using several in vitro models. Specific fields of investigation have been a) the role of shape and the aspect ratio in the determination of biological effects of TiO2 nanofibres of different length; b) the synergistic effect of LPS and TiO2 NP on the expression of inflammatory markers and the role played therein by TLR-4; c) the role of functionalization and agglomeration in the biological effects of MWCNT. As far as biological effects elicited by TiO2 NF are concerned, the first part of the thesis demonstrates that long TiO2 nanofibres caused frustrated phagocytosis, cytotoxicity, hemolysis, oxidative stress and epithelial barrier perturbation. All these effects were mitigated by fibre shortening through ball-milling. However, short TiO2 NF exhibited enhanced ability to activate acute pro-inflammatory effects in macrophages, an effect dependent on phagocytosis. Therefore, aspect ratio reduction mitigated toxic effects, while enhanced macrophage activation, likely rendering the NF more prone to phagocytosis. These results suggest that, under in vivo conditions, short NF will be associated with acute inflammatory reaction, but will undergo a relatively rapid clearance, while long NF, although associated with a relatively smaller acute activation of innate immunity cells, are not expected to be removed efficiently and, therefore, may be associated to chronic inflammatory responses. As far as the relationship between the effects of TiO2 NP and LPS, investigated in the second part of the thesis, are concerned, TiO2 NP markedly enhanced macrophage activation by LPS through a TLR-4-dependent intracellular pathway. The adsorption of LPS onto the surface of TiO2 NP led to the formation of a specific bio-corona, suggesting that, when bound to TiO2 NP, LPS exerts a much more powerful pro-inflammatory effect. These data suggest that the inflammatory changes observed upon exposure to TiO2 NP may be due, at least in part, to their capability to bind LPS and, possibly, other TLR agonists, thus enhancing their biological activities. Finally, the last part of the thesis demonstrates that surface functionalization of MWCNT with amino or carboxylic groups mitigates the toxic effects of MWCNT in terms of macrophage activation and capability to perturb epithelial barriers. Interestingly, surface chemistry (in particular surface charge) influenced the protein adsorption onto the MWCNT surface, allowing to the formation of different protein coronae and the tendency to form agglomerates of different size. In particular functionalization a) changed the amount and the type of proteins adsorbed to MWCNT and b) enhanced the tendency of MWCNT to form large agglomerates. These data suggest that the different biological behavior of functionalized and pristine MWCNT may be due, at least in part, to the different tendency to form large agglomerates, which is significantly influenced by their different capability to interact with proteins contained in biological fluids. All together, these data demonstrate that the interaction between physico-chemical properties of nanostructured materials and the environment (cells + biological fluids) in which these materials are present is of pivotal importance for the understanding of the biological effects of NM. In particular, bio-persistence and the capability to elicit an effective inflammatory response are attributable to the interaction between NM and macrophages. However, the interaction NM-cells is heavily influenced by the formation at the nano-bio interface of specific bio-coronae that confer a novel biological identity to the nanostructured materials, setting the basis for their specific biological activities.

New analytical methodologies for doping control – detection of anabolic androgenic steroids in human urine

Dissertation submitted to Faculdade de Ciências e Tecnologia - Universidade Nova de Lisboa in fulfilment of the requirements for the degree of Doctor of Philosophy (Biochemistry - Biotechnology)

Compact saloplastic membranes of natural polysaccharides for soft tissue engineering

The regeneration of soft biological tissues requires new substitutes that exhibit mechanical properties similar to the native tissue. Herein, thin saloplastic membranes with tunable physical properties are prepared by complexation of chitosan and alginate solutions containing different concentrations of sodium chloride. Polyelectrolyte complexes (PECs) are transferred to flat Petri dishes for compaction into membrane shapes by sedimentation and solvent evaporation. All membranes are resistant to degradation by lysozyme and are stable in solutions with pH values between 1 and 13. Immersing the different membranes in new doping solutions of increasing salt concentrations triggers the typical saloplastic behavior, with a high water absorption and decrease of the rigidity and ultimate tensile strength. The range of such variations is tuned by the sodium chloride amount used in the synthesis: high salt concentrations increase water uptake and tensile moduli, while decreasing the ultimate strength. Cellular assays demonstrate high proliferation rates and viability of L929 fibroblasts seeded onto the most rigid membranes. The results validate the use of saloplastic membranes as soft tissue substitutes for future biomedical applications.

Silica templating of a self-assembling peptide amphiphile that forms nanotapes

The peptide amphiphile C16-KTTKS templates silica polymerization, enabling the production of silica nanotape structures, imaged via electron microscopy (TEM and SEM). X-ray scattering shows that the nanotapes comprise stacked layers, as for the parent peptide amphiphile, but with a substantially increased layer spacing resulting from silica polymerization.

Characterization of BaTi1-xZrxO3 thin films obtained by a soft chemical spin-coating technique

Single-phase perovskite structure BaZrxTi1-xO3 (BZT) (0.05less than or equal toxless than or equal to0.25) thin films were deposited on Pt-Ti-SiO2-Si substrates by the spin-coating technique. The structural modifications in the thin films were studied using x-ray diffraction and micro-Raman scattering techniques. Lattice parameters calculated from x-ray data indicate an increase in lattice (a axis) with the increasing content of zirconium in these films. Such Zr substitution also result in variations of the phonon mode wave numbers, especially those of lower wave numbers, for BaZrxTi1-xO3 thin films, corroborate to the structural change caused by the zirconium doping. on the other hand, Raman modes persist above structural phase transition, although all optical modes should be Raman inactive in the cubic phase. The origin of these modes must be interpreted as a function of a local breakdown of the cubic symmetry, which could be a result of some kind of disorder. The BZT thin films exhibited a satisfactory dielectric constant close to 181-138, and low dielectric loss tan delta<0.03 at the frequency of 1 kHz. The leakage current density of the BZT thin films was studied at elevated temperatures and the data obey the Schottky emission model. Through this analysis the Schottky barrier height values 0.68, 1.39, and 1.24 eV were estimated to the BZT5, BZT15, and BZT25 thin films, respectively. (C) 2004 American Institute of Physics.

Development of metal oxide nanoparticles by soft chemical method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Zirconia foams prepared by integration of the sol-gel method and dual soft template techniques

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural phase evolution of strontium-doped lead titanate thin films prepared by the soft chemical technique

Strontium-modified lead titanate thin films with composition Pb1-xSrxTiO3 were grown on Pt/Ti/SiO2/Si substrates using the polymeric precursor method. The structural phase evolution as a function of the Sr contents was studied using micro-Raman scattering, specular reflectance infrared Fourier transform spectroscopy, and x-ray diffraction. The results showed a gradual change from tetragonal to cubic structure, the transition occurring at about x = 0.58. The infrared reflectance spectra showed that the frequency of several peaks decreases as the strontium concentration increases. These features are correlated with a decrease in the tetragonal distortion of the TiO6 octahedra as the strontium concentration increases.

Comparative Study Of Planned And Unplanned Excisions For The Treatment Of Soft Tissue Sarcoma Of The Extremities.

Unplanned excision of soft tissue sarcomas is common because benign soft tissue lesions are very frequent. This study evaluated the impact of unplanned resections on overall survival, local recurrence and distant metastasis in patients with soft tissue sarcomas of the extremities. In total, 52 patients who were diagnosed with soft tissue sarcomas between May 2001 and March 2011 were analyzed in a retrospective study. Of these patients, 29 (55.8%) had not undergone previous treatment and the remaining 23 (44.2%) patients had undergone prior resection of the tumor without oncological planning. All subsequent surgical procedures were performed at the same cancer referral center. The follow-up ranged from 6 to 122 months, with a mean of 39.89 months. Age, lesion size and depth, histological grade, surgical margins, overall survival, local and distant recurrence and adjuvant therapies were compared. Residual disease was observed in 91.3% of the re-resected specimens in the unplanned excision group, which exhibited greater numbers of superficial lesions, low histological grades and contaminated surgical margins compared with the re-resected specimens in the planned excision group. No differences were observed in local recurrence and 5-year overall survival between the groups, but distant metastases were significantly associated with planned excision after adjustment for the variables. There was no difference between patients undergoing unplanned excision and planned excision regarding local recurrence and overall survival. The planned excision group had a higher risk of distant metastasis, whereas there was a high rate of residual cancer in the unplanned excision group.

Evaluation Of Soft-tissue Lesions With (18)f-fdg Pet/ct: Initial Results Of A Prospective Trial.

Although MRI is utilized for planning the resection of soft-tissue tumors, it is not always capable of differentiating benign from malignant lesions. The risk of local recurrence of soft-tissue sarcomas is increased when biopsies are performed before resection and by inadequate resections. PET associated with computed tomography using fluorodeoxyglucose labeled with fluorine-18 ((18)F-FDG PET/CT) may help differentiate between benign and malignant tumors, thus avoiding inadequate resections and making prior biopsies unnecessary. The purpose of this study was to evaluate the usefulness of (18)F-FDG PET/CT in differentiating benign from malignant solid soft-tissue lesions. Patients with solid lesions of the limbs or abdominal wall detected by MRI were submitted to (18)F-FDG PET/CT. The maximum standardized uptake value (SUVmax) cutoff was determined to differentiate malignant from benign tumors. Regardless of the (18)F-FDG PET/CT results all patients underwent biopsy and surgery. MRI was performed in 54 patients, and 10 patients were excluded because of purely lipomatose or cystic lesions. (18)F-FDG PET/CT was performed in the remaining 44 patients. Histopathology revealed 26 (59%) benign and 18 (41%) malignant soft-tissue lesions. A significant difference in SUVmax was observed between benign and malignant soft-tissue lesions. The SUVmax cutoff of 3.0 differentiated malignant from benign lesions with 100% sensitivity, 83.3% specificity, 89.6% accuracy, 78.3% positive predictive value, and 100% negative predictive value. (18)F-FDG PET/CT seems to be able to differentiate benign from malignant soft-tissue lesions with good accuracy and very high negative predictive value. Incorporating (18)F-FDG PET/CT into the diagnostic algorithm of these patients may prevent inadequate resections and unnecessary biopsies.

A comparison of skeletal, dentoalveolar and soft tissue characteristics in white and black Brazilian subjects

OBJECTIVE: This study aimed to compare skeletal, dentoalveolar and soft tissue characteristics in white and black Brazilian subjects presenting normal occlusions. MATERIAL AND METHODS: The sample comprised the lateral cephalograms of 106 untreated Brazilian subjects with normal occlusion, divided into two groups: Group 1- 50 white subjects (25 of each gender), at a mean age of 13.17 years (standard deviation 1.07); and Group 2- 56 black subjects (28 of each gender), at a mean age of 13.24 years (standard deviation 0.56). Variables studied were obtained from several cephalometric analyses. Independent t tests were used for intergroup comparison and to determine sexual dimorphism. RESULTS: black subjects presented a more protruded maxilla and mandible, a smaller chin prominence and a greater maxillomandibular discrepancy than white subjects. Blacks presented a more horizontal craniofacial growth pattern than whites. Maxillary and mandibular incisors presented more protruded and proclined in black subjects. The nasolabial angle was larger in whites. Upper and lower lips were more protruded in blacks than in whites. CONCLUSIONS: The present study found a bimaxillary skeletal, dentoalveolar and soft tissue protrusion in black Brazilian subjects compared to white Brazilian subjects, both groups with normal occlusion. Upper and lower lips showed to be more protruded in blacks, but lip thickness was similar in both groups.