Síntese e caracterização de ferritas de níquel dopadas com cobalto e efeito da substituição nas suas propriedades magnéticas

The ferrite composition Ni1 - xCoxFe2O4 (0 ≤ x ≤ 0.75) were obtained by the method of microwave assisted synthesis and had their structural and magnetic properties evaluated due to the effect of the substitution of Ni by Co. The compounds were prepared: according to the concept of chemical propellants and heated in the microwave oven with power 7000kw. The synthesized material was characterized by absorption spectroscopy in the infrared (FTIR), Xray diffraction (XRD) using the Rietveld refinement, specific surface area (BET) , scanning electron microscopy (SEM) with aid of energy dispersive analysis (EDS) and magnetic measurements (MAV). The results obtained from these techniques confirmed the feasibility of the method of synthesis employed to obtain the desired spinel structure, the ferrite, nickel ferrite as for nickel doped with cobalt. The results from XRD refinement ally showed the formation of secondary phases concerning stages α - Fe2O3, FeO, (FeCo)O e Ni0. On the other hand, there is an increase in crystallite size with the increase of cobalt in systems, resulting in an increased crystallinity. The results showed that the BET systems showed a reduction in specific surface area with the increase of cobalt and from the SEM, the formation of irregular porous blocks and that the concentration of cobalt decreased the agglomerative state of the system. The magnetic ferrites studied showed different characteristics according to the amount of dopant used, ranging from a very soft magnetic material (easy magnetization and demagnetization ) - for the system without cobalt - a magnetic material with a little stiffer behavior - for systems containing cobalt. The values of the coercive field increased with the increasing growth of cobalt, and the values of saturation magnetization and remanence increased up to x = 0,25 and then reduced. The different magnetic characteristics presented by the systems according to the amount of dopant used, allows the use of these materials as intermediates magnetic

Síntese de catalisadores nanoporosos na ausência total e parcial de direcionadores orgânicos para pirólise catalítica de óleos pesados e intermediários

The processing of heavy oil produced in Brazil is an emergency action and a strategic plan to obtain self-sufficiency and economic surpluses. Seen in these terms, it is indispensable to invest in research to obtain new catalysts for obtaining light fraction of hydrocarbons from heavy fractions of petroleum. This dissertation for the degree of Doctor of Philosophy reports the materials preparation that combine the high catalytic activity of zeolites with the greater accessibility of the mesoporosity, more particularly the HZSM-5/MCM-41 hybrid, done by synthesis processes with less environmental impact than conventional ones. Innovative methodologies were developed for the synthesis of micro-mesoporous hybrid material by dual templating mechanism and from crystalline zeolitic aluminosilicate in the absence of organic template. The synthesis of hybrid with pore bimodal distribution took place from one-single organic directing agent aimed to eliminate the use of organic templates, acids of any kind or organic solvents like templating agent of crystalline zeolitic aluminosilicate together with temperature-programmed microwave-assisted, making the experimental procedures of preparation most practical and easy, with good reproducibility and low cost. The study about crystalline zeolitic aluminosilicate in the absence of organic template, especially MFI type, is based on use of H2O and Na+ cation playing a structural directing role in place of an organic template. Advanced characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Highresolution Transmission Electron Microscopy (HRTEM), Adsorption of N2 and CO2, kinetic studies by Thermogravimetric Analysis (TGA) and Pyrolysis coupled to Gas Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) were employed in order to evaluate the synthesized materials. Achieve the proposed objectives, has made available a set of new methodologies for the synthesis of zeolite and hybrid micro-mesoporous material, these suitable for catalytic pyrolysis of heavy oils aimed at producing light fraction

Effect of processing route on the phase formation and properties of Bi4Ti3O12 ceramics

Our efforts were directed to the preparation of bismuth titanate-Bi4Ti3O12 (BIT) by two procedures: mechanically assisted synthesis and polymeric precursor method to display a variety of their advantages. To follow the nucleation and phase formation of BIT, XRD and Rietveld refinement analysis were used and it was shown that Bi4Ti3O12 ceramic can been successfully prepared from nano-sized powders obtained by both methods. The ferroelectric properties were determined and the loops from BIT obtained by polymeric precursor method were not fully saturated with a remnant polarization of 20 mu C/cm(2) and coercitive field of 1500 kV/cm. BIT obtained from powders prepared by mechanically assisted synthesis shows a remnant polarization of 0.65 mu C/cm(2) and coercitive field of 1050 kV/cm. The grain morphology may be the factor causing the observed differences. (C) 2005 Published by Elsevier Ltd and Techna Group S.r.l.

The role of hierarchical morphologies in the superior gas sensing performance of CuO-based chemiresistors

The development of gas sensors with innovative designs and advanced functional materials has attracted considerable scientific interest given their potential for addressing important technological challenges. This work presents new insight towards the development of high-performance p-type semiconductor gas sensors. Gas sensor test devices, based on copper (II) oxide (CuO) with innovative and unique designs (urchin-like, fiber-like, and nanorods), are prepared by a microwave-assisted synthesis method. The crystalline composition, surface area, porosity, and morphological characteristics are studied by X-ray powder diffraction, nitrogen adsorption isotherms, field-emission scanning electron microscopy and high-resolution transmission electron microscopy. Gas sensor measurements, performed simultaneously on multiple samples, show that morphology can have a substantial influence on gas sensor performance. An assembly of urchin-like structures is found to be most effective for hydrogen detection in the range of parts-per-million at 200 °C with 300-fold larger response than the previously best reported values for semiconducting CuO hydrogen gas sensors. These results show that morphology plays an important role in the gas sensing performance of CuO and can be effectively applied in the further development of gas sensors based on p-type semiconductors. High-performance gas sensors based on CuO hierarchical morphologies with in situ gas sensor comparison are reported. Urchin-like morphologies with high hydrogen sensitivity and selectivity that show chemical and thermal stability and low temperature operation are analyzed. The role of morphological influences in p-type gas sensor materials is discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efeito do ultrassom de alta intensidade na extração e difusão da cafeína nos grãos de café (Coffea arabica)

Pós-graduação em Engenharia e Ciência de Alimentos - IBILCE

Cristalização convencional de zeólitas e induzida por sementes

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

Efeito do processo de descafeinação de café arábica em meio aquoso auxiliado por ultrassom sobre a composição química e o perfil sensorial

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The ultra-sonication of minerals in swine feed

A sample preparation method based on ultrasound assisted-extraction (UAE) of Ca, Mg and P from swine feed has been described. The experiment was performed to cover the variables influencing the sonication process and, the method validation using standard reference material. Final solutions obtained upon sonication were analyzed by flame atomic absorption spectrometry (for Ca and Mg) and by UV-vis spectrophotometry (for P). The best conditions for metal extraction were as follows: sample mass: 100 mg in 20 mL 0.10 mol/L HCl, a particle size: <60 μm, sonication time: 5 cycles of 10 s and ultrasound power: 102 W. The UAE method was applied in digestibility assays in different piglet feeds and their results showed that it is highly comparable (P > 0.05) to the other methods used for such purposes, as block digestion, and offered a Ca, Mg and P method of quantification limit of 10.6, 12.4 and 14 mg/kg, respectively. The major advantages of the UAE method compared to other methods are the high treatment rate, low reagent usage in the extracts and, it does not generate toxic residues that might negatively affect human health and the environment, accompanied by good precision and accuracy.

Structural refinement, growth process, photoluminescence and photocatalytic properties of (Ba1-xPr2x/3)WO4 crystals synthesized by the coprecipitation method

Barium praseodymium tungstate (Ba1-xPr2x/3)WO4 crystals with (x = 0, 0.01, and 0.02) were prepared by the coprecipitation method. These crystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinements, Fourier-transform Raman (FT-Raman) and Fourier-transform infrared (FT-IR) spectroscopies. The shape and size of these crystals were observed by field emission scanning electron microcopy (FE-SEM). Their optical properties were investigated by ultraviolet visible (UV-vis) absorption and photoluminescence (PL) measurements. Moreover, we have studied the photocatalytic (PC) activity of crystals for degradation of rhodamine B (RhB) dye. XRD patterns, Rietveld refinements data, FT-Raman and FT-IR spectroscopies indicate that all crystals exhibit a tetragonal structure without deleterious phases. FT-Raman spectra exhibited 13 Raman-active modes in a range from 50 to 1000 cm(-1), while FT-IR spectra have 8 infrared active modes in a range from 200 to 1050 cm(-1). FE-SEM images showed different shapes (bonbon-, spindle-, rice-and flake-like) as well as a reduction in the crystal size with an increase in Pr3+ ions. A possible growth process was proposed for these crystals. UV-vis absorption measurements revealed a decrease in optical band gap values with an increase of Pr3+ into the matrix. An intense green PL emission was noted for (Ba1-xPr2x/3)WO4 crystals (x = 0), while crystals with (x = 0.01 and 0.02) produced a reduction in the wide band PL emission and the narrow band PL emission which is related to f-f transitions from Pr3+ ions. High photocatalytic efficiency was verified for the bonbon-like BaWO4 crystals as a catalyst in the degradation of the RhB dye after 25 min under UV-light. Finally, we discuss possible mechanisms for PL and PC properties of these crystals.

Development of instrumental and sensory analytical methods of food obtained by traditional and emerging technologies

The consumer demand for natural, minimally processed, fresh like and functional food has lead to an increasing interest in emerging technologies. The aim of this PhD project was to study three innovative food processing technologies currently used in the food sector. Ultrasound-assisted freezing, vacuum impregnation and pulsed electric field have been investigated through laboratory scale systems and semi-industrial pilot plants. Furthermore, analytical and sensory techniques have been developed to evaluate the quality of food and vegetable matrix obtained by traditional and emerging processes. Ultrasound was found to be a valuable technique to improve the freezing process of potatoes, anticipating the beginning of the nucleation process, mainly when applied during the supercooling phase. A study of the effects of pulsed electric fields on phenol and enzymatic profile of melon juice has been realized and the statistical treatment of data was carried out through a response surface method. Next, flavour enrichment of apple sticks has been realized applying different techniques, as atmospheric, vacuum, ultrasound technologies and their combinations. The second section of the thesis deals with the development of analytical methods for the discrimination and quantification of phenol compounds in vegetable matrix, as chestnut bark extracts and olive mill waste water. The management of waste disposal in mill sector has been approached with the aim of reducing the amount of waste, and at the same time recovering valuable by-products, to be used in different industrial sectors. Finally, the sensory analysis of boiled potatoes has been carried out through the development of a quantitative descriptive procedure for the study of Italian and Mexican potato varieties. An update on flavour development in fresh and cooked potatoes has been realized and a sensory glossary, including general and specific definitions related to organic products, used in the European project Ecropolis, has been drafted.

Folic acid derivatives for PET imaging and therapy addressing folate receptor positive tumors

Folic acid, also known as vitamin B9, is the oxidized form of 5,6,7,8-tetrahydrofolate, which serves as methyl- or methylene donor (C1-building blocks) during DNA synthesis. Under physiological conditions the required amount of 5,6,7,8-tetrahydrofolate for survival of the cell is accomplished through the reduced folate carrier (RFC). In contrast, the supply of 5,6,7,8-tetrahydrofolate is insufficient under pathophysiological conditions of tumors due to an increased proliferation rate. Consequently, many tumor cells exhibit an (over)expression of the folate receptor. This phenomenon has been applied to diagnostics (PET, SPECT, MR) to image FR-positive tumors and on the other hand to treat malignancies related to a FR (over)expression. Based on this concept, a new 18F-labeled folate for PET imaging has been developed and was evaluated in vivo using tumor-bearing mice. The incorporation of oligoethylene spacers into the molecular structure led to a significant enhancement of the pharmacokinetics in comparison to previously developed 18F-folates. The liver uptake could be reduced by one sixth by remaining a tumor uptake of 3%ID/g leading to better contrast ratios. Encouraged by these results, a clickable 18F-labeled serine-based prosthetic group has been synthesized, again with the idea to improve the metabolic and pharmacokinetic profile of hydrophilic radiotracers. Therefore, an alkyne-carrying azido-functionalized serine derivative for coupling to biomolecules was synthesized and a chlorine leaving group for 18F-labeling, which could be accomplished using a microwave-assisted synthesis, a [K⊂2.2.2]+/carbonate system in DMSO. Radiochemical yields of 77±6% could be achieved.rnThe promising results obtained from the FR-targeting concept in the diagnostic field have been transferred to the boron neutron capture therapy. Therefore, a folate derivative was coupled to different boron clusters and cell uptake studies were conducted. The synthesis of the folate-boron clusters was straightforward. At first, a linker molecule based on maleic acid was synthesized, which was coupled to the boron cluster via Michael Addition of a thiol and alkene and subsequently coupled to the targeting moiety using CuAAC. The new conjugates of folate and boron clusters led to a significant increase of boron concentration in the cell of about 5-times compared to currently used and approved boron pharmaceuticals. rnMoreover, azido-folate derivatives were coupled to macromolecular carrier systems (pHPMA), which showed an enhanced and specific accumulation at target sites (up to 2.5-times) during in vivo experiments. A specific blockade could be observed up to 30% indicating an efficient targeting effect. A new kind of nanoparticles consisting of a PDLLA core and p((HPMA)-b-LMA)) as surfactants were developed and successfully radiolabeled via 18F-click chemistry in good RCYs of 8±3%rnThe nanoparticles were obtained via the miniemulsion technique in combination with solvent evaporation. The 18F-labeled nanoparticles were applied to in vivo testing using a mouse model. PET imaging showed a “mixed” biodistribution of low molecular weight as well as high molecular weight systems, indicating a partial loss of the 18F-labeled surfactant.rnIn conclusion, the presented work successfully utilized the FR-targeting concept in both, the diagnostic field (PET imaging) and for therapeutic approaches (BNCT, drug delivery systems). As a result, the high potential of FR-targeting in oncological applications has been shown and was confirmed by small animal PET imaging.rn

Occurrence and analysis of selected pharmaceutical compounds in soil from Spanish agricultural fields

This work describes the analysis of 15 pharmaceutical compounds, belonging to different therapeutic classes (anti-inflammatory/analgesics, lipid regulators, antiepileptics, ?-blockers and antidepressants) and with diverse physical?chemical properties, in Spanish soils with different farmland uses. The studied compounds were extracted from soil by ultrasound-assisted extraction (UAE) and determined, after derivatization, by gas chromatography with mass spectrometric detection (GC?MS). The limits of detection (LODs) ranged from 0.14 ng g?1 (naproxen) to 0.65 ng g?1 (amitriptyline). At least two compounds where detected in all samples, being ibuprofen, salicylic acid, and paracetamol, the most frequently detected compounds. The highest levels found in soil were 47 ng g?1 for allopurinol and 37 ng g?1 for salicylic acid. The influence of the type of crop and the sampling area on the levels of pharmaceuticals in soil, as well as their relationship with soil physical?chemical properties, was studied. The frequent and widespread detection of some of these compounds in agricultural soils show a diffuse contamination, although the low levels found do not pose a risk to the environment or the human health.

Spatio-temporal distribution of pyrethroids in soil in Mediterranean paddy fields

Purpose The demand of rice by the increase in population in many countries has intensified the application of pesticides and the use of poor quality water to irrigate fields. The terrestrial environment is one compartment affected by these situations, where soil is working as a reservoir, retaining organic pollutants. Therefore, it is necessary to develop methods to determine insecticides in soil and monitor susceptible areas to be contaminated, applying adequate techniques to remediate them. Materials and methods This study investigates the occurrence of ten pyrethroid insecticides (PYs) and its spatio-temporal variance in soil at two different depths collected in two periods (before plow and during rice production), in a paddy field area located in the Mediterranean coast. Pyrethroids were quantified using gas chromatography?mass spectrometry (GC?MS) after ultrasound-assisted extraction with ethyl acetate. The results obtained were assessed statistically using non-parametric methods, and significant statistical differences (p < 0.05) in pyrethroids content with soil depth and proximity to wastewater treatment plants were evaluated. Moreover, a geographic information system (GIS) was used to monitor the occurrence of PYs in paddy fields and detect risk areas. Results and discussion Pyrethroids were detected at concentrations ?57.0 ng g?1 before plow and ?62.3 ng g?1 during rice production, being resmethrin and cyfluthrin the compounds found at higher concentrations in soil. Pyrethroids were detected mainly at the top soil, and a GIS program was used to depict the obtained results, showing that effluents from wastewater treatment plants (WWTPs) were the main sources of soil contamination. No toxic effects were expected to soil organisms, but it is of concern that PYs may affect aquatic organisms, which represents the worst case scenario. Conclusions A methodology to determine pyrethroids in soil was developed to monitor a paddy field area. The use of water fromWWTPs to irrigate rice fields is one of the main pollution sources of pyrethroids. It is a matter of concern that PYs may present toxic effects on aquatic organisms, as they can be desorbed from soil. Phytoremediation may play an important role in this area, reducing the possible risk associated to PYs levels in soil.

Propriedades físico-químicas e mecânicas de membranas porosas de carboximetilquitosana e hidrogéis de quitosana para aplicação em engenharia de tecidos

Este trabalho teve como principal objetivo produzir membranas porosas de carboximetilquitosana e hidrogéis de quitosana com propriedades físico-químicas e mecânicas adequadas para aplicações em Engenharia de Tecidos. Para isso, quitosanas com diferentes graus de acetilação (4,0%<GA<40%) e de elevada massa molar média viscosimétrica (Mv>750.000 g.mol-1) foram produzidas através da aplicação de processos consecutivos de desacetilação assistida por irradiação de ultrassom de alta intensidade (DAIUS) à beta-quitina extraída de gládios de lulas Doryteuthis spp. A carboximetilação de quitosana extensivamente desacetilada (Qs-3; GA=4%) foi realizada pela reação com ácido monocloroacético em meio isopropanol/solução aquosa de NaOH, gerando a amostra CMQs-0 (GS≈0,98; Mv≈190.000 g.mol-1). A irradiação de ultrassom de alta intensidade foi empregada para tratar solução aquosa de CMQs-0 durante 1 h e 3 h, resultando nas amostras CMQs-1 (Mv≈94.000 g.mol-1) e CMQs-3 (Mv≈43.000 g.mol-1), respectivamente. Para a produção de membranas reticuladas, genipina foi adicionada em diferentes concentrações (1,0x10-4 mol.L-1, 3,0x10-4 mol.L-1 ou 5,0x10-4 mol.L-1) às soluções aquosas das CMQs, que foram vertidas em placas de Petri e a reação de reticulação procedeu por 24 h. Em seguida, as membranas reticuladas (M-CMQs) foram liofilizadas, neutralizadas, lavadas e liofilizadas novamente, resultando em nove amostras, que foram caracterizadas quanto ao grau médio de reticulação (GR), grau médio de hidratação (GH), morfologia, propriedades mecânicas e quanto à susceptibilidade à degradação por lisozima. O grau médio de reticulação (GR) foi tanto maior quanto maior a concentração de genipina empregada na reação, variando de GR≈3,3% (M-CMQs-01) a GR≈17,8% (M-CMQs-35). As análises de MEV revelaram que as membranas reticuladas M-CMQs são estruturas porosas que apresentam maior densidade de poros aparentes quanto maiores os valores de Mve GR. Entretanto, as membranas preparadas a partir de CMQs de elevada massa molar (Mv>94.000 g.mol-1) e pouco reticuladas (GR<10%), apresentaram propriedades mecânicas superiores em termos de resistência máxima à tração (>170 kPa) e elongação máxima à ruptura (>40%). Por outro lado, as membranas mais susceptíveis à degradação enzimática foram aquelas preparadas a partir de CMQs de baixa massa molar (Mv≈43.000 g.mol-1) e que exibiram baixos graus de reticulação (GR<11%). Hidrogéis estáveis de quitosana sem o uso de qualquer agente de reticulação externo foram produzidos a partir da gelificação de soluções aquosas de quitosana com solução de NaOH ou vapor de NH3. Os hidrogéis produzidos a partir de soluções de quitosana de elevada massa molar média ponderal (Mw≈640.000 g.mol-1) e extensivamente desacetilada (DA≈2,8%) em concentrações poliméricas acima 2,0%, exibiram melhores propriedades mecânicas com o aumento da concentração polimérica, devido à formação de numerosos emaranhamentos físicos das cadeias poliméricas em solução. Os resultados mostram que as propriedades físico-químicas e mecânicas dos hidrogéis de quitosana podem ser controladas variando a concentração do polímero e o processo de gelificação. A avaliação biológica de tais hidrogéis para a regeneração de miocárdio infartado de ratos revelou que os hidrogéis de quitosana preparados a partir de soluções de polímero a 1,5% foram perfeitamente incorporados sobre a superfície do epicárdio do coração e apresentaram degradação parcial acompanhada por infiltração de células mononucleares.

Screen-printed electrode based electrochemical detector coupled with ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction for determination of mercury in water samples

A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid–liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbamate is extracted from sample solution into the water-immiscible IL formed in-situ. Then, an ultrasound-assisted procedure is employed to back-extract the mercury into 10 µL of a 4 M HCl aqueous solution, which is finally analyzed using SPCnAuEs. Sample preparation methodology was optimized using a multivariate optimization strategy. Under optimized conditions, a linear range between 0.5 and 10 µg L−1 was obtained with a correlation coefficient of 0.997 for six calibration points. The limit of detection obtained was 0.2 µg L−1, which is lower than the threshold value established by the Environmental Protection Agency and European Union (i.e., 2 µg L−1 and 1 µg L−1, respectively). The repeatability of the proposed method was evaluated at two different spiking levels (3 and 10 µg L−1) and a coefficient of variation of 13% was obtained in both cases. The performance of the proposed methodology was evaluated in real-world water samples including tap water, bottled water, river water and industrial wastewater. Relative recoveries between 95% and 108% were obtained.