Estudo de metodologias de controle de qualidade do Mo-99 utilizado no preparo de geradores de Mo-99/Tc-99m

Dissertação (Mestrado em Tecnologia Nuclear)

Obtenção de polímeros de LCC para aplicação como antioxidante de biodiesel de soja

Biodiesel is a fuel obtained from vegetable oils, such as soy, castorbean, among others. The monoester of fatty acid of these oils have chains with mono, di and tri double connections. The presence of these insaturations are susceptible to oxidization. Antioxidants are substances able to prevent oxidization from oils, fats, fat foods, as well as esters of Alquila( biodiesel). The objective of this work is to summarize a new antioxidant from the Cashew Nut Shell Liquid (CNSL) using the electrolysis technique. A current of 2 amperes was used in a single cell of only one group and two eletrodos of stainless steel 304 in a solution of methanol, together with the eletrolits: acetic acid, sodium chloride and sodium hydroxide, for two hours of agitation. The electrolysis products are characterized by the techniques of cromatography in a thin layer, spectroscopy of infrared and gravimetric analysis. The material was submitted to tests of oxidative stability made by the techniques of spectropy of impendancy and Rancimat (EN 14112). The analyses of characterization suggest that the polimerization of the electrolytic material ocurred. The application results of these materials as antioxidants of soy biodiesel showed that the order of the oxidative stability was obtained by both techniques used

Efecto antiinflamatorio de extractos metanólicos de plantas de Azuay y Loja (Ecuador) a través del modelo de peces cebra

Los peces cebra son utilizados como modelo biológico para screening primario de extractos de plantas con potencial bioactividad, aprovechando sus similitudes: genética, fisiológica y respuesta farmacológica con los mamíferos. En el estudio se empleó este modelo para valorar la actividad antiinflamatoria de 36 extractos metanólicos de plantas medicinales utilizadas en las provincias de Azuay y Loja (Ecuador). Parte del material vegetal fue recolectado con el aporte de una hierbatera de etnia Saraguro. Los extractos fueron preparados por percolación y su toxicidad fue evaluada en peces cebra en concentraciones variables de 400 a 3,125 μg/ml, determinándose la máxima concentración tolerada para cada uno de ´estos. La actividad antiinflamatoria se evaluó a través del ensayo de migración leucocitaria inducida por lipopolisacárido de Sallmonella typhi. Los extractos de: Cestrum aff. peruvianum, Galinsoga parviflora, Galium sp., Oenothera tetraptera, Peperomia aff. galioides , Passiflora ampullaceae y Ambrosia arborescens, correspondientes al 18,92% de los analizados, mostraron un potencial antiinflamatorio comparable con indometacina y dexametasona; siendo el extracto metanólico de Cestrum aff. peruvianum el más relevante a 50 g/ml. El análisis fitoquímico básico de los extractos se realizó por cromatografía de capa fina, evidenciándose la presencia de saponinas y terpenoidoes como compuestos principales en la mayoría de los extractos.

Phytochemical screening and evaluation of cytotoxicity of stem bark extracts of Genus dolichocarpa and Duguetia chrysocarpa (Annonaceae)

Purpose: To investigate the phytochemistry and cytotoxic activity of stem bark extracts from Genus dolichocarpa and Duguetia chrysocarpa - two species of the Annonaceae family. Methods: The crude ethanol bark extracts (EtOH) of the plants were obtained by maceration. The crude extracts were suspended in a mixture of methanol (MeOH) and water (H2O) (proportion 3:7 v/v) and partitioned with hexane, chloroform (CHCl3) and ethyl acetate (AcOEt) in ascending order of polarity to obtain the respective fractions. The extracts were evaluated on thin layer chromatography (TLC) plates of silica gel to highlight the main groups of secondary metabolites. Cytotoxicity was tested against human tumor cell lines - OVCAR-8 (ovarian), SF-295 (brain) and HCT-116 (colon) - using 3- (4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. Results: The screening results demonstrated that all the extracts were positive for the presence of flavonoids and tannins. The presence of alkaloids also was detected in some extracts. The hexane extract of A. dolichocarpa showed the strongest cytotoxicity against HCT-116 with cell growth inhibition of 89.02 %. Conclusion: The findings demonstrate for the first time the cytotoxic activity of the extracts of A. dolichocarpa and D. chrysocarpa, thus providing some evidence that plants of the Annonaceae family are a source of active secondary metabolites with cytotoxic activity.

Pirólise de borras oleosas de petroleo utilizando nanomateriais

The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery

Sensor psychrometric approaches to mitigating aflatoxins in maize dried on farms in Kenya

Kenia liegt in den Äquatorialtropen von Ostafrika und ist als ein weltweiter Hot-Spot für Aflatoxinbelastung insbesondere bei Mais bekannt. Diese toxischen und karzinogenen Verbindungen sind Stoffwechselprodukte von Pilzen und so insbesondere von der Wasseraktivität abhängig. Diese beeinflusst sowohl die Trocknung als auch die Lagerfähigkeit von Nahrungsmitteln und ist somit ein wichtiger Faktor bei der Entwicklung von energieeffizienten und qualitätsorientierten Verarbeitungsprozessen. Die vorliegende Arbeit hat sich zum Ziel gesetzt, die Veränderung der Wasseraktivität während der konvektiven Trocknung von Mais zu untersuchen. Mittels einer Optimierungssoftware (MS Excel Solver) wurde basierend auf sensorerfassten thermo-hygrometrischen Daten der gravimetrische Feuchteverlust von Maiskolben bei 37°C, 43°C und 53°C vorausberechnet. Dieser Bereich stellt den Übergang zwischen Niedrig- und Hochtemperaturtrocknung dar. Die Ergebnisse zeigen deutliche Unterschiede im Verhalten der Körner und der Spindel. Die Trocknung im Bereich von 35°C bis 45°C kombiniert mit hohen Strömungsgeschwindigkeiten (> 1,5 m / s) begünstigte die Trocknung der Körner gegenüber der Spindel und kann daher für eine energieeffiziente Trocknung von Kolben mit hohem Anfangsfeuchtegehalt empfohlen werden. Weitere Untersuchungen wurden zum Verhalten unterschiedlicher Schüttungen bei der bei Mais üblichen Satztrocknung durchgeführt. Entlieschter und gedroschener Mais führte zu einem vergrößerten Luftwiderstand in der Schüttung und sowohl zu einem höheren Energiebedarf als auch zu ungleichmäßigerer Trocknung, was nur durch einen erhöhten technischen Aufwand etwa durch Mischeinrichtungen oder Luftumkehr behoben werden könnte. Aufgrund des geringeren Aufwandes für die Belüftung und die Kontrolle kann für kleine landwirtschaftliche Praxisbetriebe in Kenia daher insbesondere die Trocknung ganzer Kolben in ungestörten Schüttungen empfohlen werden. Weiterhin wurde in der Arbeit die Entfeuchtung mittels eines Trockenmittels (Silikagel) kombiniert mit einer Heizquelle und abgegrenztem Luftvolumen untersucht und der konventionellen Trocknung gegenüber gestellt. Die Ergebnisse zeigten vergleichbare Entfeuchtungsraten während der ersten 5 Stunden der Trocknung. Der jeweilige Luftzustand bei Verwendung von Silikagel wurde insbesondere durch das eingeschlossene Luftvolumen und die Temperatur beeinflusst. Granulierte Trockenmittel sind bei der Maistrocknung unter hygienischen Gesichtspunkten vorteilhaft und können beispielsweise mit einfachen Öfen regeneriert werden, so dass Qualitätsbeeinträchtigungen wie bei Hochtemperatur- oder auch Freilufttrocknung vermieden werden können. Eine hochwertige Maistrocknungstechnik ist sehr kapitalintensiv. Aus der vorliegenden Arbeit kann aber abgeleitet werden, dass einfache Verbesserungen wie eine sensorgestützte Belüftung von Satztrocknern, der Einsatz von Trockenmitteln und eine angepasste Schüttungshöhe praktikable Lösungen für Kleinbauern in Kenia sein können. Hierzu besteht, ggf. auch zum Aspekt der Verwendung regenerativer Energien, weiterer Forschungsbedarf.

Caracterização cromatográfica em camada delgada do extrato fluido de guaco: Mikania glomerata Sprengel.

As frações hexanicas, clorofórmicas, em acetato de etila e etanólica do extrato fluido de guaco - Mikania glomerata foram analisadas por cromatografia em camada delgada frente a padrões de ácido caurenóico, ácido cinamoilgrandiflorico, estigmasterol e cumarina visando o estabelecimento de perfil cromatográfico que permita identificar este insumo farmacêutico.

Determination of bioactive amines in tropical wines produced at Brazilian's Northeast.

The wine production in the region of the Sub-middle São Francisco river Valley has started there are few years ago.The region has a climate variability that allows to obtain two or three harvests per year, which influences significantly the composition of the grapes. This work aimed to evaluate the amount of amines present in white and red tropical wines produced in the Northeast of Brazil. The winemaking was done by the traditional method. After stabilizing the wines were bottled and then analyzed for the determination of the amines putrescine, spermidine and spermine, by thin layer chromatography (TLC). The harvests were in June (harvest I) and November (harvest II) 2009. The results showed that the edaphoclimatic conditions of the two harvests had significant influence (p> 0.05) on bioactive amines concentration, with high values for red wines. In addition, tropical wines from Sub-middle São Francisco river Valley showed adequate correlation between bioactive amines as compared to other wines in the world.

Advanced Spectroscopy for the Study of Colourants in Cultural Heritage

Colourants are substances used to change the colour of something, and are classified in three typology of colorants: a) pigments, b) dyes, and c) lakes and hybrid pigments. Their identification is very important when studying cultural heritage; it gives information about the artistic technique, can help in dating, and offers insights on the condition of the object. Besides, the study of the degradation phenomena constitutes a framework for the preventive conservation strategies, provides evidence of the object's original appearance, and contributes to the authentication of works of art. However, the complexity of these systems makes it impossible to achieve a complete understanding using a single technique, making necessary a multi-analytical approach. This work focuses on the set-up and application of advanced spectroscopic methods for the study of colourants in cultural heritage. The first chapter presents the identification of modern synthetic organic pigments using Metal Underlayer-ATR (MU-ATR), and the characterization of synthetic dyes extracted from wool fibres using a combination of Thin Layer Chromatography (TLC) coupled to MU-ATR using AgI@Au plates. The second chapter presents the study of the effect of metallic Ag in the photo-oxidation process of orpiment, and the influence of the different factors, such as light and relative humidity. We used a combination of vibrational and synchrotron radiation-based X-ray microspectroscopy techniques: µ-ATR-FT-IR, µ-Raman, SR-µ-XRF, µ-XANES at S K-, Ag L3- and As K-edges and SR-µ-XRD. The third chapter presents the study of metal carboxylates in paintings, specifically on the formation of Zn and Pb carboxylates in three different binders: stand linseed oil, whole egg, and beeswax. We used micro-ATR-FT-IR, macro FT-IR in total reflection (rMA-FT-IR), portable Near-Infrared spectroscopy (NIR), macro X-ray Powder Diffraction (MA-XRPD), XRPD, and Gas Chromatography Mass-Spectrometry (GC-MS). For the data processing, we explored the data from rMA-FT-IR and NIR with the Principal Component Analysis (PCA).

Wireless Power Link Design for Both High-Power Inductive Coupling and Smart Metasurfaces Exploitation

As future technologies are going to be autonomous under the umbrella of the Internet of things (IoT) we can expect WPT to be the solution for intelligent devices. WPT has many industrial and medical applications both in the near-field and far-field domains. Considering the impact of WPT, this thesis is an attempt to design and realize both near-field and far-field WPT solutions for different application scenarios. A 27 MHz high frequency inductive wireless power link has been designed together with the Class-E switching inverter to compensate for the efficiency loss because of the varying weak coupling between transmitter and receiver because of their mutual misalignment. Then a system of three coils was introduced for SWIPT. The outer coil for WPT and the inner two coils were designed to fulfil the purpose of communication and testing, operating at frequencies different from the WPT coil. In addition to that, a trapping filter technique has also been adopted to ensure the EM isolation of the coils. Moreover, a split ring resonator-based dual polarization converter has been designed with good efficiency over a wide frequency range. The gap or cuts have been introduced in the adjacent sides of the square ring to make it a dual-polarization converter. The converter is also stable over a wide range of incident angles. Furthermore, a meta-element based intelligent surface has been designed to work in the reflection mode at 5 GHz. In this research activity, interdigital capacitors (IDCs) instead of ICs are introduced and a thin layer of the HfZrO between substrate and meta elements is placed whose response can be tuned and controlled with the applied voltage to achieve IRS.

Inkjet-printed poly(N-isopropylacrylamide)/graphene electrodes for selective electroanalytical sensing

The main research topic of the present master thesis consisted in the modification and electrochemical testing of inkjet printed graphene electrodes with a thin polymeric hydrogel layer made of cross-linked poly(N-isopropylacrylamide) (PNIPAAM) acting as a functional layer to fabricate selective sensors. The first experimental activities dealt with the synthesis of the polymeric hydrogel and the modification of the active surface of graphene sensors through photopolymerization. Simultaneous inkjet printing and photopolymerization of the hydrogel precursor inks onto graphene demonstrated to be the most effective and reproducible technique for the modification of the electrode with PNIPAAM. The electrochemical performance of the modified electrodes was tested through cyclic voltammetry. Voltammograms with standard redox couples with either positive, neutral or negative charges, suggested an electrostatic filtering effect by the hydrogel blocking negatively charged redox species in near neutral pH electrolyte solutions from reaching the electrode surface. PNIPAAM is a known thermo-responsive polymer, but the variation of temperature did not influence the filtering properties of the hydrogels for the redox couples studied. However, a variation of the filter capacity of the material was observed at pH 2 in which the PNIPAAM hydrogel, most likely in protonated form, became impermeable to positively charged redox species and permeable to negatively charged species. Finally, the filtering capacity of the electrodes modified with PNIPAAM was evaluated for the electrochemical determination of analytes in presence of negatively charge potential interferents, such as antioxidants like ascorbic acid. The outcome of the final experiments suggested the possibility to use the inkjet-printed PNIPAAM thin layer for electroanalytical applications as an electrostatic filter against interferents of opposite charges, typically present in complex matrices, such as food and beverages.

Fabrication by magnetron sputtering and characterization of electrodes based on CuIn0.7Ga0.3Se2 (CIGS)

This thesis work aims to produce and test multilayer electrodes for their use as photocathode in a PEC device. The electrode developed is based on CIGS, a I-III-VI2 semiconductor material composed of copper (Cu), indium (In), Gallium (Ga) and selenium (Se). It has a bandgap in the range of 1.0-2.4 eV and an absorption coefficient of about 105cm−1, which makes it a promising photocathode for PEC water splitting. The idea of our multilayer electrode is to deposit a thin layer of CdS on top of CIGS to form a solid-state p–n junction and lead to more efficient charge separation. In addition another thin layer of AZO (Aluminum doped zinc oxide) is deposit on top of CdS since it would form a better alignment between the AZO/CdS/CIGS interfaces, which would help to drive the charge transport further and minimize charge recombination. Finally, a TiO2 layer on top of the electrodes is used as protective layer during the H2 evolution. FTO (Fluorine doped tin oxide) and Molybdenum are used as back-contact. We used the technique of RF magnetron sputtering to deposit the thin layers of material. The structural characterization performed by XDR measurement confirm a polycrystalline chalcopyrite structural with a preferential orientation along the (112) direction for the CIGS. From linear fit of the Tauc plot, we get an energy gap of about 1.16 eV. In addition, from a four points measurements, we get a resistivity of 0.26 Ωcm. We performed an electrochemical characterization in cell of our electrodes. The results show that our samples have a good stability but produce a photocurrent of the order of μA, three orders of magnitude smaller than our targets. The EIS analysis confirm a significant depletion of the species in front of the electrode causing a lower conversion of the species and less current flows.

Non-line-of-sight localization with frequency-selective metasurfaces

An emerging technology, that Smart Radio Environments rely on to improve wireless link quality, are Reconfigurable Intelligent Surfaces (RISs). A RIS, in general, can be understood as a thin layer of EM composite material, typically mounted on the walls or ceilings of buildings, which can be reconfigured even after its deployment in the network. RISs made by composing artificial materials in an engineered way, in order to obtain unconventional characteristics, are called metasurfaces. Through the programming of the RIS, it is possible to control and/or modify the radio waves that affect it, thus shaping the radio environment. To overcome the limitations of RISs, the metaprism represents an alternative: it is a passive and non-reconfigurable frequency-selective metasurface that acts as a metamirror to improve the efficiency of the wireless link. In particular, using an OFDM (Orthogonal Frequency-Division Multiplexing) signaling it is possible to control the reflection of the signal, suitably selecting the sub-carrier assigned to each user, without having to interact with the metaprism or having to estimate the CSI. This thesis investigates how OFDM signaling and metaprism can be used for localization purposes, especially to extend the coverage area at low cost, in a scenario where the user is in NLoS (Non-line-of-sight) conditions with respect to the base station, both single antenna. In particular, the paper concerns the design of the analytical model and the corresponding Matlab implementation of a Maximum Likelihood (ML) estimator able to estimate the unknown position, behind an obstacle, from which a generic user transmits to a base station, exploiting the metaprism.

Modelling adhesive joints with cohesive zone models: effect of the cohesive law shape of the adhesive layer

Adhesively-bonded joints are extensively used in several fields of engineering. Cohesive Zone Models (CZM) have been used for the strength prediction of adhesive joints, as an add-in to Finite Element (FE) analyses that allows simulation of damage growth, by consideration of energetic principles. A useful feature of CZM is that different shapes can be developed for the cohesive laws, depending on the nature of the material or interface to be simulated, allowing an accurate strength prediction. This work studies the influence of the CZM shape (triangular, exponential or trapezoidal) used to model a thin adhesive layer in single-lap adhesive joints, for an estimation of its influence on the strength prediction under different material conditions. By performing this study, guidelines are provided on the possibility to use a CZM shape that may not be the most suited for a particular adhesive, but that may be more straightforward to use/implement and have less convergence problems (e.g. triangular shaped CZM), thus attaining the solution faster. The overall results showed that joints bonded with ductile adhesives are highly influenced by the CZM shape, and that the trapezoidal shape fits best the experimental data. Moreover, the smaller is the overlap length (LO), the greater is the influence of the CZM shape. On the other hand, the influence of the CZM shape can be neglected when using brittle adhesives, without compromising too much the accuracy of the strength predictions.

High-Speed Laser Processing of Thin Single and Multi-Layer Films

Theoretical models are developed for the continuous-wave and pulsed laser incision and cut of thin single and multi-layer films. A one-dimensional steady-state model establishes the theoretical foundations of the problem by combining a power-balance integral with heat flow in the direction of laser motion. In this approach, classical modelling methods for laser processing are extended by introducing multi-layer optical absorption and thermal properties. The calculation domain is consequently divided in correspondence with the progressive removal of individual layers. A second, time-domain numerical model for the short-pulse laser ablation of metals accounts for changes in optical and thermal properties during a single laser pulse. With sufficient fluence, the target surface is heated towards its critical temperature and homogeneous boiling or "phase explosion" takes place. Improvements are seen over previous works with the more accurate calculation of optical absorption and shielding of the incident beam by the ablation products. A third, general time-domain numerical laser processing model combines ablation depth and energy absorption data from the short-pulse model with two-dimensional heat flow in an arbitrary multi-layer structure. Layer removal is the result of both progressive short-pulse ablation and classical vaporisation due to long-term heating of the sample. At low velocity, pulsed laser exposure of multi-layer films comprising aluminium-plastic and aluminium-paper are found to be characterised by short-pulse ablation of the metallic layer and vaporisation or degradation of the others due to thermal conduction from the former. At high velocity, all layers of the two films are ultimately removed by vaporisation or degradation as the average beam power is increased to achieve a complete cut. The transition velocity between the two characteristic removal types is shown to be a function of the pulse repetition rate. An experimental investigation validates the simulation results and provides new laser processing data for some typical packaging materials.