Synthesis, crystal structures and magnetic properties of a phenoxo-bridged dinuclear Cu(II) complex and a dicyanamide bridged novel molecular rectangle based on it

The phenoxo-bridged dinuclear Cu-II complex [Cu2L2-(NCNCN)(2)] (1) and the dicyanamide-bridged molecular rectangle [Cu4L4{mu(1,5)-(NCNCN)(2)}]center dot(ClO4)(2)(H2O)(2) (2) were synthesized using the tridentate reduced Schiff-base ligand HL {2-[(2-dimethylamino-ethylamino) methyl] phenol}. The complexes were characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Complex 2 was formed through the joining of the phenoxo-bridged dinuclear Cu2O2 cores of 1 via the mu(1,5)-bridging mode of dicyanamide. The structural properties of the Cu2O2 cores in two complexes are significantly different. The geometry of the copper ions is distorted trigonal bipyramid in 1 but is nearly square-pyramidal in 2. These differences have a marked effect on the magnetic properties of two compounds. Although both are antiferromagnetically coupled, the coupling constants (J = -185.2 and -500.9 cm(-1) for 1 and 2, respectively) differ considerably.

Understanding advances in the simulation of intraseasonal variability in the ECMWF model. Part II: the application of process-based diagnostics

In Part I of this study it was shown that moving from a moisture-convergent- to a relative-humidity-dependent organized entrainment rate in the formulation for deep convection was responsible for significant advances in the simulation of the Madden – Julian Oscillation (MJO) in the ECMWF model. However, the application of traditional MJO diagnostics were not adequate to understand why changing the control on convection had such a pronounced impact on the representation of the MJO. In this study a set of process-based diagnostics are applied to the hindcast experiments described in Part I to identify the physical mechanisms responsible for the advances in MJO simulation. Increasing the sensitivity of the deep convection scheme to environmental moisture is shown to modify the relationship between precipitation and moisture in the model. Through dry-air entrainment, convective plumes ascending in low-humidity environments terminate lower in the atmosphere. As a result, there is an increase in the occurrence of cumulus congestus, which acts to moisten the mid troposphere. Due to the modified precipitation – moisture relationship more moisture is able to build up, which effectively preconditions the tropical atmosphere for the t ransition t o d eep convection. R esults from this study suggest that a tropospheric moisture control on convection is key to simulating the interaction between the convective heating and the large-scale wave forcing associated with the MJO.

Calixarene and Resorcarene Based Receptors: From Structural and Thermodynamic Studies to the Synthesis of a New Mercury(II) Selective Material

Materials used in current technological approaches for the removal of mercury lack selectivity. Given that this is one of the main features of supramolecular chemistry, receptors based on calix[4]arene and calix[4]resorcarene containing functional groups able to interact selectively with polluting ions while discriminating against biologically essential ones were designed. Thus two receptors, a partially functionalized calix[4]arene derivative, namely, 5,11,17,23-tetra-tert-butyl [25-27-bis(diethyl thiophosphate amino)dihydroxy] calix[4]arene (1) and a fully functionalized calix[4]resorcarene, 4,6,10,12,16,18,22,24-diethyl thiophosphate calix[4]resorcarene (2) are introduced. Mercury(II) was the identified target due to the environmental and health problems associated with its presence in water Thus following the synthesis and characterization of 1 and 2 in solution ((1)HNMR) and in the solid state (X-ray crystallography) the sequence of experimental events leading to cation complexation studies in acetonitrile and methanol ((1)H NMR, conductance, potentiometric, and calorimetric measurements) with the aim of assessing their behavior as mercury selective receptors are described. The cation selectivity pattern observed in acetonitrile follows the sequence Hg(II) > Cu(II) > Ag(I). In methanol 1 is also selective for Hg(II) relative to Ag(I) but no interaction takes place between this receptor and Cu(II) in this solvent. Based on previous results and experimental facts shown in this paper, it is concluded that the complexation observed with Cu(II) in acetonitrile occurs through the acetonitrile-receptor adduct rather than through the free ligand. Receptor 2 has an enhanced capacity for uptaking Hg(II) but forms metalate complexes with Cu(II). These studies in solution guided the inmobilization of receptor 1 into a silica support to produce a new and recyclable material for the removal of Hg(II) from water. An assessment on its capacity to extract this cation from water relative to Cu(II) and Ag (I) shows that the cation selectivity pattern of the inmobilized receptor is the same as that observed for the free receptor in methanol. These findings demonstrate that fundamental studies play a critical role in the selection of the receptor to be attached to silicates as well as in the reaction medium used for the synthesis of the new decontaminating agent.

Nickel catalysts supported on ZrO2, Y2O3-stabilized ZrO2 and CaO-stabilized ZrO2 for the steam reforming of ethanol: Effect of the support and nickel load

Catalysts with various nickel loads were prepared on supports of ZrO2, ZrO2-Y2O3 and ZrO2-CaO, characterized by XRD and TPR and tested for activity in ethanol steam reforming. XRD of the supports identified the monoclinic crystalline phase in the ZrO2 and cubic phases in the ZrO2-Y2O3 and ZrO2-CaO supports. In the catalysts, the nickel impregnated on the supports was identified as the NiO phase. In the TPR analysis, peaks were observed showing the NiO phase having different interactions with the supports. In the catalytic tests, practically all the catalysts achieved 100% ethanol conversion, H-2 yield was near 70% and the gaseous concentrations of the other co-products varied in accordance with the equilibrium among them, affected principally by the supports. It was observed that when the ZrO2 was modified with Y2O3 and CaO, there were big changes in the CO and CO2 concentrations, which were attributed to the rise in the number of oxygen vacancies, permitting high-oxygen mobility and affecting the gaseous equilibrium. The liquid products analysis showed a low selectivity to liquid co-products during the reforming reactions. (c) 2007 Published by Elsevier B.V.

Homogenization of Precipitation Hardening Nickel Based Superalloys

Allvac 718 Plus and Haynes 282 are relatively new precipitation hardening nickel based superalloys with good high temperature mechanical properties. In addition, the weldability of these superalloys enhances easy fabrication. The combination of high temperature capabilities and superior weldability is unmatched by other precipitation hardening superalloys and linked to the amount of the γ’ hardening precipitates in the materials. Hence, it is these properties that make Allvac 718 Plus and Haynes 282 desirable in the manufacture of hot sections of aero engine components. Studies show that cast products are less weldable than wrought products. Segregation of elements in the cast results in inhomogeneous composition which consequently diminishes weldability. Segregation during solidification of the cast products results in dendritic microstructure with the segregating elements occupying interdendritic regions. These segregating elements are trapped in secondary phases present alongside γ matrix. Studies show that in Allvac 718Plus, the segregating phase is Laves while in Haynes 282 the segregating phase is not yet fully determined. Thus, the present study investigated the effects of homogenization heat treatments in eliminating segregation in cast Allvac 718 Plus and Haynes 282. Paramount to the study was the effect of different homogenization temperatures and dwell time in the removal of the segregating phases. Experimental methods used to both qualify and quantify the segregating phases included SEM, EDX analysis, manual point count and macro Vickers hardness tests. Main results show that there is a reduction in the segregating phases in both materials as homogenization proceeds hence a disappearance of the dendritic structure. In Allvac 718 Plus, plate like structures is observed to be closely associated with the Laves phase at low temperatures and dwell times. In addition, Nb is found to be segregating in the interdendritic areas. The expected trend of increase in Laves as a result of the dissolution of the plate like structures at the initial stage of homogenization is only detectable for few cases. In Haynes 282, white and grey phases are clearly distinguished and Mo is observed to be segregating in interdendritic areas.

Activity of Mo(II) allylic complexes supported in MCM-41 as oxidation catalysts precursors

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

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica for differential pulse adsorptive stripping analysis of nickel in ethanol fuel

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica (SiAt-SPCPE) was applied to Ni2+ determination in commercial ethanol fuel samples. The proposed method comprised four steps: (1) Ni2+ preconcentration at open circuit potential directly in the ethanol fuel sample, (2) transference of the electrode to an electrochemical cell containing DMG, (3) differential pulse voltammogram registering and (4) surface regeneration by polishing the electrode. The proposed method combines the high Ni2+ adsorption capacity presented by 2-aminothiazole organofunctionalized silica with the electrochemical properties of the Ni(DMG)2 complex, whose electrochemical reduction provides the analytical signal.All experimental parameters involved in the proposed method were optimized. Using a preconcentration time of 20 min, it was obtained a linear range from 7.5 x 10(-9) to 1.0 x 10(-6) mol L-1 with detection limit of 2.0 x 10(-9) mol L-1. Recovery values between 96.5 and 102.4% were obtained for commercial samples spiked with 1.0 mu mol L-1 Ni2+ and the developed electrode was totally stable in ethanolic solutions. The contents of Ni2+ found in the commercial samples using the proposed method were compared to those obtained by graphite furnace atomic absorption spectroscopy by using the F- and t-test. Neither the F- nor t-values exceeded the critical values at 95% confidence level, confirming that there are not statistical differences between the results obtained by both methods. These results indicate that the developed electrode can be successfully employed to reliable Ni2+ determination in commercial ethanol fuel samples without any sample pretreatment or dilution step. (c) 2006 Elsevier B.V. All rights reserved.

Influence of support on catalytic behavior of nickel catalysts in the steam reforming of ethanol for hydrogen production

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Study of alternative schemes for the parameterization step of the continuation power flow method based on physical parameters, part II: Performance evaluation

New parameterization schemes have been proposed by the authors in Part I of this paper. In this part these new options for the parameterization of power flow equations are tested, namely, the total power losses (real and reactive), the power at the slack bus (real or reactive), the reactive power at generation buses, and the transmission line power losses (real and reactive). These different parameterization schemes can be used to obtain the maximum loading point without ill-conditioning problems, once the singularity of Jacobian matrix is avoided. The results obtained with the new approach for the IEEE test systems (14, 30, 57, and 118 buses) show that the characteristics of the conventional method are not only preserved but also improved. In addition, it is shown that the proposed method and the conventional one can be switched during the tracing of PV curves to determine, with few iterations, all points of the PV curve. Several tests were also carried out to compare the performance of the proposed parameterization schemes for the continuation power flow method with the use of both the secant and tangent predictors.

DEVELOPMENT OF A CHEMICALLY MODIFIED ELECTRODE BASED ON CARBON PASTE AND FUNCTIONALIZED SILICA-GEL FOR PRECONCENTRATION AND VOLTAMMETRIC DETERMINATION OF MERCURY(II)

A mercury-sensitive chemically modified electrode (CME) based on modified silica gel-containing carbon paste was developed. The functional group attached to the silica gel surface was 3-(2-thiobenzimidazolyl)propyl, which is able to complex mercury ions. This electrode was applied to the determination of mercury(II) ions in aqueous solution. The mercury was chemically preconcentrated on the CME prior to voltammetric determination by anodic stripping in the differential-pulse mode. A calibration graph covering the concentration range from 0.08 to 2 mg l-1 was constructed. The precision for six determinations of 0.122 and 0.312 mg l-1 Hg(II) was 3.2 and 2.9% (relative standard deviation), respectively. The detection limit for a 5-min preconcentration period was 0.013 mg l-1. A study for foreign ions was also made.

Estudo e desenvolvimento de sensores biomiméticos baseados em materiais carbonáceos modificados com ftalocianinacobalto (II) para detecção amperométrica de metribuzin

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Compostos de paládio (II): síntese, caracterização e investigação da atividade antitumoral

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of the balance between Co(II) and Co(0) oxidation states on the catalytic activity of cobalt catalysts for Ethanol Steam Reforming

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Electrochemical investigation of the voltammetric determination of hydrochlorothiazide using a nickel hydroxide modified nickel electrode

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

Direct Access to Oxidation-Resistant Nickel Catalysts through an Organometallic Precursor

The synthesis of nickel catalysts for industrial applications is relatively simple; however, nickel oxidation is usually difficult to avoid, which makes it challenging to optimize catalytic activities, metal loadings, and high-temperature activation steps. A robust, oxidation-resistant and very active nickel catalyst was prepared by controlled decomposition of the organometallic precursor [bis(1,5-cyclooctadiene)nickel(0)], Ni(COD)(2), over silica-coated magnetite (Fe3O4@SiO2). The sample is mostly Ni(0), and surface oxidized species formed after exposure to air are easily reduced in situ during hydrogenation of cyclohexene under mild conditions recovering the initial activity. This unique behavior may benefit several other reactions that are likely to proceed via Ni heterogeneous catalysis.