12 resultados para BIS-1:11 MOLYBDOSLLICATE HETEROPOLYANION WITH DYSPROSIUM
em Repositório Científico do Instituto Politécnico de Lisboa - Portugal
Resumo:
The present work deals with preliminary studies concerning a new synthesis approach to prepare SAPO materials with AEL structure and evaluate their catalytic behavior in the hydroisomerization of long paraffins. The new SAPO-11 catalysts were synthesized with the help of a small amine (methylamine, MA) added during the preparation of the initial gel. As MA incorporates into the structure of the final materials, it contributes, together with DPA (dipropylamine), to an increase in Si incorporation as isolated species, which results in Bronsted acid sites. Thus, this new and original synthesis strategy allows to obtain materials with enhanced Bronsted acidity when compared with free MA materials. The catalysts were tested in n-decane hydroisomerization (n-decane was used as a model molecule) and confirmed the effect of MA on the acidic properties of the catalysts. The samples synthesized with MA present a higher number of acid sites that increase the catalytic conversion but have a negative effect in the isomerization selectivity, i.e. a more significant amount of cracking products is formed.
Resumo:
The water-soluble copper(II) complex [Cu(H2R)(HL)]center dot H2O (1) was prepared by reaction of copper(II) nitrate hydrate with (E)-2-(((1-hydroxynaphthalen-2-yl)methylene)amino) benzenesulfonic acid (H2L) and diethanolamine (H3R). It was characterized by IR and ESI-MS spectroscopies, elemental and X-ray crystal structural analyses. 1 shows a high catalytic activity for the solvent-free microwave (MW) assisted oxidation of 1-phenylethanol with tert-butylhydroperoxide, leading, in the presence of TEMPO, to yields up to 85% (TON = 850) in a remarkably short reaction time (15 min, with the corresponding TOE value of 3.40 x 10(3) h(-1)) under low power (25W) MW irradiation. Crown Copyright (C) 2014 Published by Elsevier B.V. All rights reserved.
Resumo:
[RuCl(arene)(-Cl)](2) dimers were treated in a 1:2 molar ratio with sodium or thallium salts of bis- and tris(pyrazolyl)borate ligands [Na(BpBr3)], [Tl(TpBr3)], and [Tl(Tp(iPr,4Br))]. Mononuclear neutral complexes [RuCl(arene)((2)-BpBr3)] (1: arene=p-cymene (cym); 2: arene=hexamethylbenzene (hmb); 3: arene=benzene (bz)), [RuCl(arene)((2)-TpBr3)] (4: arene=cym; 6: arene=bz), and [RuCl(arene)((2)-Tp(iPr,4Br))] (7: arene=cym, 8: arene=hmb, 9: arene=bz) have been always obtained with the exception of the ionic [Ru-2(hmb)(2)(-Cl)(3)][TpBr3] (5), which formed independently of the ratio of reactants and reaction conditions employed. The ionic [Ru(CH3OH)(cym)((2)-BpBr3)][X] (10: X=PF6, 12: X=O3SCF3) and the neutral [Ru(O2CCF3)(cym)((2)-BpBr3)] (11) have been obtained by a metathesis reaction with corresponding silver salts. All complexes 1-12 have been characterized by analytical and spectroscopic data (IR, ESI-MS, H-1 and (CNMR)-C-13 spectroscopy). The structures of the thallium and calcium derivatives of ligand TpBr3, [Tl(TpBr3)] and [Ca(dmso)(6)][TpBr3](2)2DMSO, of the complexes 1, 4, 5, 6, 11, and of the decomposition product [RuCl(cym)(Hpz(iPr,4Br))(2)][Cl] (7) have been confirmed by using single-crystal X-ray diffraction. Electrochemical studies showed that 1-9 and 11 undergo a single-electron (RuRuIII)-Ru-II oxidation at a potential, measured by cyclic voltammetry, which allows comparison of the electron-donor characters of the bis- and tris(pyrazol-1-yl)borate and arene ligands, and to estimate, for the first time, the values of the Lever E-L ligand parameter for BpBr3, TpBr3, and Tp(iPr,4Br). Theoretical calculations at the DFT level indicated that both oxidation and reduction of the Ru complexes under study are mostly metal-centered with some involvement of the chloride ligand in the former case, and also demonstrated that the experimental isolation of the (3)-binuclear complex 5 (instead of the mononuclear 5) is accounted for by the low thermodynamic stability of the latter species due to steric reasons.
Resumo:
A 10 kJ electromagnetic forming (EMF) modulator with energy recovery based on two resonant power modules, each containing a 4.5 kV/30-kA silicon controlled rectifier, a 1.11-mF capacitor bank and an energy recovery circuit, working in parallel to allow a maximum actuator discharge current amplitude and rate of 50 kA and 2 kA/mu s was successfully developed and tested. It can be plugged in standard single phase 230 V/16 A mains socket and the circuit is able to recover up to 32% of its initial energy, reducing the charging time of conventional EMF systems by up to 68%.
Resumo:
The synthesis of two new inherently chiral calix[4]arenes (ICCs, 1 and 2), endowed with electron-rich concave surfaces, has been achieved through the desymmetrization of a lower rim distal-bridged oxacyclophane (OCP) macrocycle. The new highly emissive ICCs were resolved by chiral HPLC, and the enantiomeric nature of the isolated antipodes proved by electronic circular dichroism (CD). Using time-dependent density functional calculations of CD spectra, their absolute configurations were established. NMR studies with (S)-Pirkle's alcohol unequivocally showed that the host-guest interactions occur in the chiral pocket comprehending the calix-OCP exo cavities and the carbazole moieties.
Resumo:
The concept of explaining the use of an old tool like the Smith chart, using modern tools like MATLAB [1] scripts in combination with e-learning facilities, is exemplified by two MATLAB scripts. These display, step by step, the graphical procedure that must be used to solve the double-stub impedance-matching problem. These two scripts correspond to two different possible ways to analyze this matching problem, and they are important for students to learn by themselves.
Resumo:
In order to study the impact of premature birth and low income on mother–infant interaction, four Portuguese samples were gathered: full-term, middle-class (n=99); premature, middle-class (n=63); full-term, low income (n=22); and premature, low income (n=21). Infants were filmed in a free play situation with their mothers, and the results were scored using the CARE Index. By means of multinomial regression analysis, social economic status (SES) was found to be the best predictor of maternal sensitivity and infant cooperative behavior within a set of medical and social factors. Contrary to the expectations of the cumulative risk perspective, two factors of risk (premature birth together with low SES) were as negative for mother–infant interaction as low SES solely. In this study, as previous studies have shown, maternal sensitivity and infant cooperative behavior were highly correlated, as was maternal control with infant compliance. Our results further indicate that, when maternal lack of responsiveness is high, the infant displays passive behavior, whereas when the maternal lack of responsiveness is medium, the infant displays difficult behavior. Indeed, our findings suggest that, in these cases, the link between types of maternal and infant interactive behavior is more dependent on the degree of maternal lack of responsiveness than it is on birth status or SES. The results will be discussed under a developmental and evolutionary reasoning
Resumo:
Chromia (Cr2O3) has been extensively explored for the purpose of developing widespread industrial applications, owing to the convergence of a variety of mechanical, physical and chemical properties in one single oxide material. Various methods have been used for large area synthesis of Cr2O3 films. However, for selective area growth and growth on thermally sensitive materials, laser-assisted chemical vapour deposition (LCVD) can be applied advantageously. Here we report on the growth of single layers of pure Cr2O3 onto sapphire substrates at room temperature by low pressure photolytic LCVD, using UV laser radiation and Cr(CO)(6) as chromium precursor. The feasibility of the LCVD technique to access selective area deposition of chromia thin films is demonstrated. Best results were obtained for a laser fluence of 120 mJ cm(-2) and a partial pressure ratio of O-2 to Cr(CO)(6) of 1.0. Samples grown with these experimental parameters are polycrystalline and their microstructure is characterised by a high density of particles whose size follows a lognormal distribution. Deposition rates of 0.1 nm s(-1) and mean particle sizes of 1.85 mu m were measured for these films. (C) 2011 Elsevier B.V. All rights reserved.
Resumo:
This paper addresses the voltage droop compensation associated with long pulses generated by solid-stated based high-voltage Marx topologies. In particular a novel design scheme for voltage droop compensation in solid-state based bipolar Marx generators, using low-cost circuitry design and control, is described. The compensation consists of adding one auxiliary PWM stage to the existing Marx stages, without changing the modularity and topology of the circuit, which controls the output voltage and a LC filter that smoothes the voltage droop in both the positive and negative output pulses. Simulation results are presented for 5 stages Marx circuit using 1 kV per stage, with 1 kHz repetition rate and 10% duty cycle.
Resumo:
The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.
Resumo:
The aim of this study is to examine the implications of the IPPA in the perception of illness and wellbeing in MS patients. Methods - This is a quasi experimental study non-randomized study with 24 MS patients diagnosed at least 1 year before, and with an EDSS score of under 7. We used the IPPA in 3 groups of eight people in 3 Portuguese hospitals (Lisbon, Coimbra, and Porto). The sessions were held once a week for 90 minutes, over a period of 7 weeks. The instruments used were: We asked the subjects the question “Please classify the severity of your disease?” and used the Personal Wellbeing Scale (PWS) at the beginning (time A) and end (time B) of the IPPA. We used the SPSS version 20. A non-parametric statistical hypothesis test (Wilcoxon test) was used for the variable analysis. The intervention followed the recommendations of the Helsinki Declaration. Results – The results suggest that there are differences between time A and B, the perception of illness decreased (p<0.08), while wellbeing increased (p<0.01). Conclusions: The IPPA can play an important role in modifying the perception of disease severity and personal wellbeing.
Resumo:
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.