Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes

fac-[MBr(CO)(3)(pypzH)] (M = Mn, Re; pypzH = (3-(2-pyridyl) pyrazole) complexes are prepared from fac[ MBr(CO)(3)(NCMe)(2)] and pypzH. The result of their deprotonation depends on the metallic substrate: the rhenium complex affords cleanly the bimetallic compound [fac-{Re(CO)(3)(mu(2)-pypz)}] 2 (mu(2)-pypz = mu(2)-3-(2pyridyl-. 1N) pyrazolate-2. 1N), which was crystallographically characterized, whereas a similar manganese complex was not detected. When two equivalents of pyridylpyrazolate are used, polymetallic species [fac-M(CO) 3(mu(2)-pypz)(mu(3)-pypz) M'] (mu(3)-pypz = mu(3)-3-(2-pyridyl-kappa N-1) pyrazolate-1 kappa 2N, N: 2. 1N:; M = Mn, M' = Li, Na, K; M = Re, M' = Na) are obtained. The crystal structures of the manganese carbonylate complexes were determined. The lithium complex is a monomer containing one manganese and one lithium atom, whereas the sodium and potassium complexes are dimers and reveal an unprecedented coordination mode for the bridging 3-(2-pyridyl) pyrazolate ligand, where the nitrogen of the pyridyl fragment and the nitrogen-1 of pyrazolate are chelated to manganese atoms, and each nitrogen-2 of pyrazolate is coordinated to two alkaline atoms. The polymetallic carbonylate complexes are unstable in solution and evolve spontaneously to [fac-{Re(CO) 3(mu(2)-pypz)}](2) or to the trimetallic paramagnetic species [MnII(mu(2)-pypz) 2{fac-{MnI(CO) 3(mu(2)-pypz)}(2)}]. The related complex cis-[MnCl2(pypzH)(2)] was also synthesized and structurally characterized. The electrochemical behavior of the new homo-and heteropolymetallic 3-(2-pyridyl) pyrazolate complexes has been studied and details of their redox properties are reported.

Synthesis and characterization of COPPER(II) 4´-phenyl-terpyridine compounds and catalytic application for aerobic oxidation of benzylic alcohols

The reactions between 4'-phenyl-terpyridine (L) and nitrate, acetate or chloride Cu(II) salts led to the formation of [Cu(NO3)(2)L] (1), [Cu(OCOCH3)(2)L]center dot CH2Cl2 (2 center dot CH2Cl2)and [CuCl2L]center dot[Cu(Cl)(mu-Cl)L](2) (3), respectively. Upon dissolving 1 in mixtures of DMSO-MeOH or EtOH-DMF the compounds [Cu(H2O){OS(CH3)(2)}L]-(NO3)(2) (4) and [Cu(HO)(CH3CH2OH)L](NO3) (5) were obtained, in this order. Reaction of 3 with AgSO3CF3 led to [CuCl(OSO2CF3)L] (6). The compounds were characterized by ESI-MS, IR, elemental analysis, electrochemical techniques and, for 2-6, also by single crystal X-ray diffraction. They undergo, by cyclic voltammetry, two single-electron irreversible reductions assigned to Cu(II) -> Cu(I)and Cu(I) -> Cu(0) and, for those of the same structural type, the reduction potential appears to correlate with the summation of the values of the Lever electrochemical EL ligand parameter, which is reported for the first time for copper complexes. Complexes 1-6 in combination with TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl radical) can exhibit a high catalytic activity, under mild conditions and in alkaline aqueous solution, for the aerobic oxidation of benzylic alcohols. Molar yields up to 94% (based on the alcohol) with TON values up to 320 were achieved after 22 h.

Anti-Corrosion performance of a new silane coating for corrosion protection of AZ31 Magnesium alloy in Hank’s solution

Mg alloys can be used as bioresorsable metallic implants. However, the high corrosion rate of magnesium alloys has limited their biomedical applications. Although Mg ions are essential to the human body, an excess may cause undesirable health effects. Therefore, surface treatments are required to enhance the corrosion resistance of magnesium parts, decreasing its rate to biocompatible levels and allowing its safe application as bioresorbable metallic implants. The application of biocompatible silane coatings is envisaged as a suitable strategy for retarding the corrosion process of magnesium alloys. In the current work, a new glycidoxypropyltrimethoxysilane (GPTMS) based coating was tested on AZ31 magnesium substrates subjected to different surface conditioning procedures before coating deposition. The surface conditioning included a short etching with hydrofluoric acid (HF) or a dc polarisation in alkaline electrolyte. The silane coated samples were immersed in Hank's solution and the protective performance of the coating was studied through electrochemical impedance spectroscopy (EIS). The EIS data was treated by new equivalent circuit models and the results revealed that the surface conditioning process plays a key role in the effectiveness of the silane coating. The HF treated samples led to the highest impedance values and delayed the coating degradation, compared to the mechanically polished samples or to those submitted to dc polarisation.

Modifications of MCM-22 zeolite through sequential post-synthesis treatments. Implications on the acidic and catalytic behaviour

Desilication and a combination of alkaline followed by acid treatment were applied to MCM-22 zeolite using two different base concentrations. The samples were characterised by powder X-ray diffraction, Al-27 and Si-29 MAS-NMR spectroscopy, SEM, TEM and low temperature N-2 adsorption. The acidity of the samples was study through pyridine adsorption followed by FTIR spectroscopy and by the analyses of the hydroxyl region. The catalytic behaviour, anticipated by the effect of post-synthesis treatments on the acidity and space available inside the two internal pore systems was evaluated by using the model reaction of m-xylene transformation. The generation of mesoporosity was achieved upon alkaline treatment with 0.05 M NaOH solution and practically no additional gain was obtained when the more concentrate solution, 0.1 M, was used. Instead, Al extraction takes place along with Si, as shown by Si-29 and Al-27 MAS-NMR data, followed by Al deposition as extraframework species. Samples submitted to alkaline plus acid treatments present distinct behaviour. When the lowest NaOH solution was used no relevant effect was observed on the textural characteristics. Additionally, when the acid treatment was performed on an already fragilized MCM-22 structure, due to previous desilication with 0.1 M NaOH solution, the extraction of Al from both internal pore systems promotes their interconnection, evolving from a 2-D to a 3-D porous structure. This transformation has a marked effect in the catalytic behaviour, allowing an increase of m-xylene conversion as a consequence of an easier and faster molecular traffic in the 3-D structure. On the other hand, the continuous deposition of extraframework Al species inside the pores leads to a shape selective effect that privileges the formation of the more valuable isomer p-xylene.

Aplicação de zeólitos hierárquicos a reacções de acilação de Friedel-Crafts

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química

A high throughput colorimetric assay of beta-1,3-D-glucans by Congo red dye

Mushroom strains contain complex nutritional biomolecules with a wide spectrum of therapeutic and prophylactic properties. Among these compounds, β-d-glucans play an important role in immuno-modulating and anti-tumor activities. The present work involves a novel colorimetric assay method for β-1,3-d-glucans with a triple helix tertiary structure by using Congo red. The specific interaction that occurs between Congo red and β-1,3-d-glucan was detected by bathochromic shift from 488 to 516 nm (> 20 nm) in UV–Vis spectrophotometer. A micro- and high throughput method based on a 96-well microtiter plate was devised which presents several advantages over the published methods since it requires only 1.51 μg of polysaccharides in samples, greater sensitivity, speed, assay of many samples and very cheap. β-d-Glucans of several mushrooms (i.e., Coriolus versicolor, Ganoderma lucidum, Pleurotus ostreatus, Ganoderma carnosum, Hericium erinaceus, Lentinula edodes, Inonotus obliquus, Auricularia auricular, Polyporus umbellatus, Cordyseps sinensis, Agaricus blazei, Poria cocos) were isolated by using a sequence of several extractions with cold and boiling water, acidic and alkaline conditions and quantified by this microtiter plate method. FTIR spectroscopy was used to study the structural features of β-1,3-d-glucans in these mushroom samples as well as the specific interaction of these polysaccharides with Congo red. The effect of NaOH on triple helix conformation of β-1,3-d-glucans was investigated in several mushroom species.

Syngas production by water electrolysis: preliminary tests on methane production

Master Thesis to obtain the Master degree in Chemical Engineering - Branch Chemical Processes

Behaviour and fate of metals in urban wastewater treatment plants: a review

The concerns on metals in urban wastewater treatment plants (WWTPs) are mainly related to its contents in discharges to environment, namely in the final effluent and in the sludge produced. In the near future, more restrictive limits will be imposed to final effluents, due to the recent guidelines of the European Water Framework Directive (EUWFD). Concerning the sludge, at least seven metals (Cd, Cr, Cu, Hg, Ni, Pb and Zn) have been regulated in different countries, four of which were classified by EUWFD as priority substances and two of which were also classified as hazardous substances. Although WWTPs are not designed to remove metals, the study of metals behaviour in these systems is a crucial issue to develop predictive models that can help more effectively the regulation of pre-treatment requirements and contribute to optimize the systems to get more acceptable metal concentrations in its discharges. Relevant data have been published in the literature in recent decades concerning the occurrence/fate/behaviour of metals in WWTPs. However, the information is dispersed and not standardized in terms of parameters for comparing results. This work provides a critical review on this issue through a careful systematization, in tables and graphs, of the results reported in the literature, which allows its comparison and so its analysis, in order to conclude about the state of the art in this field. A summary of the main consensus, divergences and constraints found, as well as some recommendations, is presented as conclusions, aiming to contribute to a more concerted action of future research. © 2015, Islamic Azad University (IAU).

Hydrogen evolution on nanostructured Ni-Cu foams

Three-dimensional (3D) nickel-copper (Ni-Cu) nanostructured foams were prepared by galvanostatic electrodeposition, on stainless steel substrates, using the dynamic hydrogen bubble template. These foams were tested as electrodes for the hydrogen evolution reaction (HER) in 8 M KOH solutions. Polarisation curves were obtained for the Ni-Cu foams and for a solid Ni electrode, in the 25-85 degrees C temperature range, and the main kinetic parameters were determined. It was observed that the 3D foams have higher catalytic activity than pure Ni. HER activation energies for the Ni-Cu foams were lower (34-36 kJ mol(-1)) than those calculated for the Ni electrode (62 kJ mol(-1)). The foams also presented high stability for HER, which makes them potentially attractive cathode materials for application in industrial alkaline electrolysers.

Magma flow pattern in dykes of the Azores revealed by ansiotropy of magnetic susceptibility

The localization of magma melting areas at the lithosphere bottom in extensional volcanic domains is poorly understood. Large polygenetic volcanoes of long duration and their associated magma chambers suggest that melting at depth may be focused at specific points within the mantle. To validate the hypothesis that the magma feeding a mafic crust, comes from permanent localized crustal reservoirs, it is necessary to map the fossilized magma flow within the crustal planar intrusions. Using the AMS, we obtain magmatic flow vectors from 34 alkaline basaltic dykes from São Jorge, São Miguel and Santa Maria islands in the Azores Archipelago, a hot-spot related triple junction. The dykes contain titanomagnetite showing a wide spectrum of solid solution ranging from Ti-rich to Ti-poor compositions with vestiges of maghemitization. Most of the dykes exhibit a normal magnetic fabric. The orientation of the magnetic lineation k1 axis is more variable than that of the k3 axis, which is generally well grouped. The dykes of São Jorge and São Miguel show a predominance of subhorizontal magmatic flows. In Santa Maria the deduced flow pattern is less systematic changing from subhorizontal in the southern part of the island to oblique in north. These results suggest that the ascent of magma beneath the islands of Azores is predominantly over localized melting sources and then collected within shallow magma chambers. According to this concept, dykes in the upper levels of the crust propagate laterally away from these magma chambers thus feeding the lava flows observed at the surface.