Síntese, caracterização e estudo fotofísico de complexos de 4,4- diaminoestilbeno-2,2-dissulfonato com íons lantanídeos

This is a work involving fundamental studies of chemistry where the synthesis and structural characterization, as well as a possible future application of these new compounds as luminescent sensors or sunscreen agents, complexes with 4,4 diaminostilbene-2,2-disulfonic (DSD) and trivalent lanthanide ions La3+, Nd3+, Eu3+, Gd3+ and Yb3+, were synthesized in the ratio of 3 mmol: 1 mmol (DSD: lanthanides). The complexes obtained with these ions were present in powder form and were characterized by complexometric titration with EDTA CHN Elemental analysis, molecular absorption spectroscopy in the ultraviolet region, the absorption spectroscopy in the infrared, thermal analysis (TG / DTG), Nuclear Magnetic Resonance - NMR 1H and Luminescence Spectroscopy. The complexometric titration and CHN analysis, confirmed the TG / DTG which suggest that these complexes have the following general chemical formulas: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O,[Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O,[Eu2(C14 H12S2O6N2)2(H2O)2Cl2].7H2O,[Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. The disappearance of the bands in the infrared spectrum at 2921 cm-1 and 2623 cm-1 and the displacement of the bands in the spectra of the amine complex indicate that the lanthanide ion is coordinated to the oxygen atoms and the sulfonate groups of the nitrogens amines, suggesting the formation of the dimer. The disappearance of the signal and the displacement signal SO3H amines in the 1H NMR spectrum of this complex are also indicative coordination and dimer formation. The Thermogravimetry indicates that the DSD is thermally stable in the range of 40º to 385°C and their complexes with lanthanide ions exhibit weight loss between 4 and 5 stages. The Uv-visible spectra indicated that the DSD and complexes exhibit cis isomers. The analysis of luminescence indicates that the complexes do not exhibit emission in the region of the lanthanides but an intense emission part of the binder. This is related to the triplet states of the ligand, which are in the lowest energy state emitting lanthanide ions, and also the formation of the dimer that suppress the luminescence of ion Eu3+. The formation of dimer was also confirmed by calculating the europium complex structure using the model Hamiltonian PM6 and Sparkle

Estudo de materiais mesoporosos funcionalizados com diferentes aminas para captura do dióxido de carbono através do processo de adsorção

Intensive use of machinery and engines burning fuel dumps into the atmosphere huge amounts of carbon dioxide (CO2), causing the intensification of the greenhouse effect. Climate changes that are occurring in the world are directly related to emissions of greenhouse gases, mainly CO2, gases, mainly due to the excessive use of fossil fuels. The search for new technologies to minimize the environmental impacts of this phenomenon has been investigated. Sequestration of CO2 is one of the alternatives that can help minimize greenhouse gas emissions. The CO2 can be captured by the post-combustion technology, by adsorption using adsorbents selective for this purpose. With this objective, were synthesized by hydrothermal method at 100 °C, the type mesoporous materials MCM - 41 and SBA-15. After the synthesis, the materials were submitted to a calcination step and subsequently functionalized with different amines (APTES, MEA, DEA and PEI) through reflux method. The samples functionalized with amines were tested for adsorption of CO2 in order to evaluate their adsorption capacities as well, were subjected to various analyzes of characterization in order to assess the efficiency of the method used for functionalization with amines. The physic-chemical techniques were used: X- ray diffraction (XRD), nitrogen adsorption and desorption (BET/BJH), scanning electron microscopy (SEM), transmission electron microscopy (TEM), CNH Analysis, Thermogravimetry (TG/DTG) and photoelectron spectroscopy X-ray (XPS). The CO2 adsorption experiments were carried out under the following conditions: 100 mg of adsorbent, at 25 °C under a flow of 100 ml/min of CO2, atmospheric pressure and the adsorption variation in time 10-210 min. The X-ray diffraction with the transmission electron micrographs for the samples synthesized and functionalized, MCM-41 and SBA-15 showed characteristic peaks of hexagonal mesoporous structure formation, showing the structure thereof was obtained. The method used was efficient reflux according to XPS and elemental analysis, which showed the presence of amines in the starting materials. The functionalized SBA -15 samples were those that had potential as best adsorbent for CO2 capture when compared with samples of MCM-41, obtaining the maximum adsorption capacity for SBA-15-P sample

Estudo integrado do potencial fitorremediador da Eichhornia crassipes em ambientes naturais e sua utilização para obtenção de extratos proteicos

This study aimed to analyze the phytoremediation potential of Eichhornia crassipes in natural environments, optimize the extraction process of crude protein from plant tissue and, obtain and characterize this process in order to determine its viability of use instead of the protein sources of animal and/or human feed. For this, it has been determined in Apodi/Mossoró river water the concentration of ammonium ions, nitrite, nitrate, calcium, magnesium, potassium, iron, copper, manganese, zinc, nickel, cobalt, sodium, aluminum, cádmium, lead, and total chromium; It was determined in plant tissue of aquatic macrophytes of Eichhornia crassipes species present in Apodi/Mossoró River the moisture content, ash, calcium, magnesium, potassium, iron, copper, manganese, zinc, nickel, cobalt, sodium, aluminum, cadmium, lead, total chromium, total nitrogen and crude protein. It was also determined the translocation factor and bioaccumulation of all the quantified elements; It was developed and optimized the extraction procedure of crude protein based on the isoelectric method and a factorial design 24 with repetition; It was extracted and characterized the extract obtained by determining the moisture content, ash, magnesium, potassium, iron, copper, manganese, zinc, nickel, cobalt, sodium, cadmium, total nitrogen and crude protein. And finally, it was also characterized the protein extract using Thermogravimetric Analysis (TG), Derived Thermogravimetric (DTG), Differential Scanning Calorimetry (DSC), Infrared Spectroscopy (FT-IR) and jelly-like electrophoresis of polyacrylamide (SDS -PAGE) to assess the their molecular weights/mass. Thus, from the results obtained for the translocation and bioaccumulation factors was found that the same can be used as phytoremediation agent in natural environments of all quantified elements. It was also found that the developed method of extraction and protein precipitation was satisfactory for the purpose of the work, which gave the best conditions of extraction and precipitation of proteins as: pH extraction equal to 13.0, extraction temperature equals 60 ° C, reaction time equals to 30 minutes, and pH precipitation equals to 4.0. As for the extract obtained, the total nitrogen and crude protein were quantified higher than those found in the plant, increasing the crude protein content approximately 116.88% in relation to the quantified contente in the vegetal tissue of macrophyte. The levels of nickel and cadmium were the unique that were found below the detection limit of used the equipment. The electrophoretic analysis allowed us to observe that the protein extract obtained is composed of low polypeptide chains by the molecular and phytochelatins, with 6 and 15 kDa bands. Analysis of TG, DTG, DSC and FT-IR showed similarities in protein content of the obtained extracts based on different collection points and 9 parts of the plant under study, as well as commercial soy protein and casein. Finally, based on all these findings, it was concluded that the obtained extract in this work can be used instead of the protein sources of animal feed should, before that, test its digestibility. As human supplementation, it is necessary to conduct more tests associated with the optimization process in the sense of removing undesirable components and constant monitoring of the water body and the raw material used

Desenvolvimento de metodologia capaz de detectar e quantificar misturas de corantes em sucos artificiais em pó

Foi desenvolvido um método para detectar e quantificar misturas de corantes em sucos artificiais em pó fabricados no Brasil, de diferentes marcas e sabores. Foram estudados 6 corantes artificiais: amarelo tartrazina, amarelo crepúsculo, vermelho ponceau 4R, vermelho bordeaux S, vermelho 40 e azul brilhante presentes de forma unitária ou em misturas nos sucos com sabores laranja, tangerina, maracujá, abacaxi, limão e uva. A identificação dos corantes nas amostras foi feita através da comparação com os espectros dos padrões, utilizando-se a análise por infravermelho médio e pelos respectivos valores de absorção máxima nos comprimentos de onda relativos aos padrões e valores de referência na literatura. Também foram estudados os perfis de decomposição térmica por termogravimetria, termogravimetria derivada e calorimetria diferencial exploratória dos corantes e dos sucos em pó, sendo determinados os teores de umidade, de matéria orgânica e de cinzas. O teor de umidade encontrado não ultrapassou 4% para todas as amostras de suco analisadas. Com relação ao teor de matéria orgânica obteve-se para 57% dos sucos analisados um teor médio de 51,3% e para 43% das outras amostras obteve-se uma média de 67,2 %. Os resultados obtidos para o teor de cinzas indicaram que 29% das amostras apresentaram um teor de 26,7% para esse parâmetro enquanto 71% das amostras apresentaram um teor de cinzas de 46,4%. Os resultados obtidos por análise térmica mostraram-se adequados considerando-se que para obter os resultados pelo método tradicional há um investimento maior de tempo, de pessoal envolvido e de material, além da proteção ao meio ambiente. Para a análise por espectroscopia de absorção molecular foi proposta uma equação simplificada para a determinação de cada corante na mistura utilizando-se a lei de Beer. Para validação, empregou-se a espectroscopia de absorção molecular no visível, onde foi investigada a influência dos interferentes (TiO2 e açúcar) presentes nas amostras de sucos, os testes de fotodegradação e a avaliação do efeito do pH. Para quantificação tomou-se como referência 512 amostras sintéticas contendo um e dois corantes (1,5625 a 25,000 mg L-1) para obtenção das curvas analíticas que foram aplicadas à análise dos sucos em pó. Os resultados indicaram que o teor máximo do amarelo crepúsculo foi encontrado nos sucos com os sabores laranja, tangerina e manga que correspondeu a 25,6% da ingestão diária aceitável (para ser ultrapassada corresponderia a ingestão de 4 copos). O teor máximo encontrado para o amarelo tartrazina nos sucos foi para o sabor maracujá que correspondeu a 8,5% da ingestão diária aceitável, (para ser alcançado corresponderia a ingestão de 12 copos). O método proposto foi testado e validado com sucesso para amostras de sucos em pó sendo de simples execução e de rapidez na obtenção dos resultados

Desenvolvimento de catalisadores bifuncionais de óxido de zircônio modificado por óxidos de tungstênio e molibdênio contendo platina para a reação de isomerização de n-parafinas

Bifunctional catalysts based on zircon oxide modified by tungsten (W = 10, 15 and 20 %) and by molybdenum oxide (Mo= 10, 15 e 20 %) containg platinum (Pt = 1%) were prepared by the polymeric precursor method. For comparison, catalysts the tungsten base was also prepared by the impregnation method. After calcinations at 600, 700 and 800 ºC, the catalysts were characterized by X-ray diffraction, fourier-transform infrared spectroscopy, thermogravimetric and differential thermal analysis, nitrogen adsorption and scanning electron microscopy. The profile of metals reduction was determined by temperature programmed reduction. The synthesized catalysts were tested in n-heptane isomerization. X-ray diffractogram of the Pt/WOx-ZrO2 and Pt/MoOx-ZrO2 catalysts revealed the presence of tetragonal ZrO2 and platinum metallic phases in all calcined samples. Diffraction peaks due WO3 and ZrO2 monoclinic also were observed in some samples of the Pt/WOx-ZrO2 catalysts. In the Pt/MoOx-ZrO2 catalysts also were observed diffraction peaks due ZrO2 monoclinic and Zr(MoO4)2 oxide. These phases contained on Pt/WOx-ZrO2 and Pt/MoOx-ZrO2 catalysts varied in accordance with the W or Mo loading and in accordance with the calcination temperature. The infrared spectra showed absorption bands due O-W-O and W=O bonds in the Pt/WOx-ZrO2 catalysts and due O-Mo-O, Mo=O and Mo-O bonds in the Pt/MoOx-ZrO2 catalysts. Specific surface area for Pt/WOx-ZrO2 catalysts varied from 30-160 m2 g-1 and for the Pt/MoOx-ZrO2 catalysts varied from 10-120 m2 g-1. The metals loading (W or Mo) and the calcination temperature influence directly in the specific surface area of the samples. The reduction profile of Pt/WOx-ZrO2 catalysts showed two peaks at lower temperatures, which are attributed to platinum reduction. The reduction of WOx species was evidenced by two reduction peak at high temperatures. In the case of Pt/MoOx-ZrO2 catalysts, the reduction profile showed three reduction events, which are attributed to reduction of MoOx species deposited on the support and in some samples one of the peak is related to the reduction of Zr(MoO4)2 oxide. Pt/WOx-ZrO2 catalysts were active in the n-heptane isomerization with high selectivity to 3-methyl-hexane, 2,3- dimethyl-pentane, 2-methyl-hexane among other branched hydrocarbons. The Pt/MoOx-ZrO2 catalysts practically didn't present activity for the n-heptane isomerization, generating mainly products originating from the catalytic cracking

Síntese e caracterização estrutural e magnética da ferrita de cálcio

The calcium ferrite (Ca2Fe2O5) has a perovskite-type structure with oxygen deficiency and is used as a chemical catalyst. With the advent of nanoscience and nanotechnology, methods of preparation, physical and chemical characterizations, and the technological applications of nanoparticles have attracted great scientific interest. Calcium nanostructured ferrites were produced via high-energy milling, with subsequent heat treatment. The milling products were characterized by X-ray diffraction, magnetization and Mössbauer spectroscopy. Samples of the type Ca2Fe2O5 were obtained from the CaCO3 and Fe2O3 powder precursors, which were mixed stoichiometrically and milled for 10h and thermally treated at 700ºC, 900ºC and 1100ºC. The Mössbauer spectra of the treated samples were adjusted three subespectros: calcium ferrite (octahedral and tetrahedral sites) and a paramagnetic component, related to very small particles of calcium ferrite, which are in a superparamagnetic state. For samples beats in an atmosphere of methyl alcohol, there is a significant increase in area associated with the paramagnetic component. Hysteresis curves obtained are characteristic of a weak ferromagnetic-like material

Parâmetros físico-químicos de estrelas com planetas na missão CoRoT

In the present study we compute the atmospheric parameters (Teff , log g and vmic, [Fe/H]) and chemical abundance of 16 ions (Fe I, Fe II, O I, Si I, Na I, Mg I, Al I, Ca I, Ti I, Co I, Ni I, Rb I, Zr I, Ba II, La II and Cr I) for 16 solar-like stars with masses between 0:8 and 1:2 Mfi aproximatedly, including 10 planet-host stars detected by the CoRoT Space Mission. For this study, we use data from the ESO public archive: (i) high resolution spectra (R 47000) from the UVES spectrograph on the VLT/UT2-ESO (for 7 stars, covering the wavelength range 3450-4515 Å and 5500-9400 Å) and (ii) high resolution spectra from HARPS spectrograph on the La Silla-ESO 3.60 m telescope (for 9 stars, covering the wavelength range 4200-6865 Å). Our spectral analysis is based on MARCS models of atmosphere and Turbospectrum spectroscopic tools. On the base of the computed parameters, the referred abundances appears to follow the same behavior of the solar curve abundances. Further, one observes a signifficant correlation between the abundance ratio [m/Fe] and condensation temperature (Tc) of refractory elements (Tc > 900 K). The behavior of the projected rotational velocity (v sin i) versus the computed abundances [m/Fe] is also analyzed, presenting no clear trends. This study oers additional constraints to trace the evolutive history of solar-like stars with planets, including the search for chemical dierences between stars with and without transit planets and anomalies in the studied abundances

Superparamagnetismo em Jacobsitas sintéticas

In this experimental study sintetic samples of Jacobsites (MnFe2O4) were synthesized by the Pechini method and calcined within ambient atmosphere and afterwards in the vacuum from 400 to 700ºC, the range of calcination temperatures. The X-Ray Diffraction (XRD) and the Scanning Electronic Microscopy (SEM) analysis have shown that the samples treated at 400ºC temperature are composed by a simple type of spinel phase, with a crystallite size of 8:8nm for the sample calcined in ambient atmosphere and 20; 1nm for the sample treated in the vacuum, showing that the cristallite average size can be manipulated by the atmosphere control. The hysteresis loops for the sample calcined at 400ºC in ambient atmosphere reveal features of superparamagnetic behavior with magnetization 29:3emu=g at the maximum field of 1:2T. The sample calcined in 400oC under vacuum show magnetization = 67emu=g at the maximum field of 1:5T. The sample treated at 500oC, under ambient atmosphere, has shown besides the spinel phase, secondary phases of hematite (Fe2O3) and bixbyite (FeMnO3). The hysteresis loops demonstrate a sharp drop of the magnetization compared to the previous sample. The analysis has revealed that for the samples treated in higher temperatures (600ºC and 700ºC) its observed the absence of the spinel phase and the maintenance of the bixbyite and hematite. The hysteresis loops for those samples in accordance to the external magnetic field are straight lines crossing the origin, consistent with the antiferromagnetic behavior of the phases.The Mössbauer espectroscopy show to the sample calcined at 400ºC within ambiente atmosphere two sextet and one doublet. The two sextets are assigned to the hyperfine fields related to the magnetic deployment in the nuclei of Fe3+ ions, at the tetraedric and octaedric sites. The doublet is assigned to superparamagnetic behavior of the particles with smaller diameter than dc . Now the sample calcined at 400ºC under vacuum only show two sextet

Propriedades magnéticas de ortoferritas de lantânio dopadas com estrôncio

Samples of lanthanum Ortoferrites doped with strontium were synthesized in a single phase by the sol-gel method. Two samples were prepared, one by varying the concentration of strontium in lanthanum ortoferrites La1−xSrxFeO3−δ with (0 ≤ x ≤ 0.5), and another batch of samples of type, La1/3Sr2/3FeO3−δ, now varying only the temperature of calcination. Our samples were obtained by Pechini method and sintered in air and oxygen atmospheric. Their crystal structures were determined by x-ray diraction (XRD), scanning electron microscopy (SEM), where we observed that the samples (0 ≤ x ≤ 0.3) have orthorhombic symmetry and the volume of the single cell decreases with the increasing of concentration of strontium. For x = 0.5 it is only observed the simple phase when that is sintered in O2 atmospheric. Their magnetic characteristics were obtained by the Mössbauer spectroscopy and magnetic measurements. The magnetization measurements for samples La1−xSrxFeO3−δ with (0 ≤ x ≤ 0.5) revealed that the magnetization decreases with increasing concentration of strontium, but for the sample x = 0.4 the magnetization shows a high coercive field and a ferrimagnetic behavior, which is attributed to a small amount of strontium hexaferrite. As for the samples La1/3Sr2/3FeO3−δ calcined between 800 oC e 1200 oC. The hysteresis curves revealed two distinct behaviors: an declined antiferromagnetic behavior (Canted) for samples calcined between 800 oC and 1000 oC and a paramagnetic behavior for the samples calcined at 1100 oC e 1200 o C. Thermal hysteresis and sharp peaks around the Néel temperature (TN), over the curves of specific heat as a function of temperature was only observed in calcined samples with 1100 oC and 1200 oC. This eect is attributed to the charge ordering. These results indicate that the charge ordering occurs only in the samples without oxygen deficiency. Magnetic measurements as a function of temperature are also in agreement with this interpretation

Propriedades fisicas do monocristal fe/mgo(100) e estudo da expansao termica da superficie da ag(100)

In this work we have developed a way to grow Fe/MgO(100) monocrystals by magnetron sputtering DC. We investigated the growing in a temperature range among 100 oC and 300 oC. Structural and magneto-crystalline properties were studied by different experimental techniques. Thickness and surface roughness of the films were investigated by atomic force microscopy, while magneto-crystalline properties were investigated by magneto-optical Kerr effect and ferromagnetic resonance. Our results show that as we increase the deposition temperature, the magneto-crystalline anisotropy of the films also increases, following the equation of Avrami. The best temperature value to make a film is 300 oC. As the main result, we built a base of magnetoresistence devices and as an aplication, we present measurements of Fe/Cr/Fe trilayer coupling. In a second work we investigated the temperature dependence of the first three interlayer spacings of Ag(100) surface using low energy electron diffraction. A linear expansion model of crystal surface was used and the values of Debye temperatures of the first two layers and thermal expansion coefficient were determinated. A relaxation of 1% was found for Ag(100) surface and these results are matched with faces (110) and (111) of the silver. iv

Síntese, sinterização e caracterização de ferrita de níquel

In this work we obtain nickel ferrite by the combustion synthesis method whcih involves synthesising in an oven at temperatures of 750oC, 950oC and 125oC. The precursors oxidizing used were nickel nitrate, ferric as an oxidizing and reducing urea (fuel). After obtaining the mixture, the product was deagglomerated and past through a 270 mesh sieve. To assess the structure, morphology, particle size, magnetic and electrical properties of nanoparticles obtained the samples were sintered and characterized by x-ray distraction (XRD), x-ray fluorescence spectroscopy (FRX); scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), vibrating sample magnetometer (MAV ) and electrical permittivity. The results indicated the majority of phase inverse spinel ferrite and Hematite secondary phase nickel and nickel oxide. Through the intensity of the distraction, the average size of the crystallization peaks were half-height width which was calculated using the Scherrer equation. From observing the peaks of all the reflections, it appears that samples are crystal clear with the formation of nanoparticles. Morphologically, the nanoferritas sintered nickel pellet formation was observed with three systems of particle size below 100mn, which favored the formation of soft pellets. The average size of the grains in their micrometric scale. FRX and EDS showed qualitatively the presence of iron elements nickel and oxygen, where through quantitative data we can observe the presence of the secondary phase. The magnetic properties and the saturation magnetization and the coercive field are in accordance with the nickel, ferrite where the curve of hysteresis has aspects of a soft material. Dielectric constant values are below 10 and low tangent loss