Origin of Ferromagnetism and Magnetic Anisotropy in a Family of Copper(II) Triangles

Previously reported ferromagnetic triangles (NnBu₄)₂[Cu₃(μ₃-Cl)₂(μ-4-NO₂-pz)₃Cl₃] ( 1 ), (PPN)₂[Cu₃(μ₃-Cl)₂(μ-pz)₃Cl₃] ( 2 ), (bmim)₂[Cu₃(μ₃-Cl)₂(μ-pz)₃Cl₃] ( 3 ) and newly reported (PPh₄)₂[Cu₃(μ₃-Cl)₂(μ-4-Ph-pz)₃Cl₃] ( 4 ) were studied by magnetic susceptometry, electron paramagnetic resonance (EPR) spectroscopy and ab initio calculations to assess the origins of their ferromagnetism and of the magnetic anisotropy of their ground S=3/2 state (PPN⁺=bis(triphenylphosphine)iminium, bmim⁺=1-butyl-3-methylbenzimidazolium, pz⁻=pyrazolate). Ab initio studies revealed the d character of the magnetic orbitals of the compressed trigonal bipyramidal copper(II) ions. Ferromagnetic interactions were attributed to weak orbital overlap via the pyrazolate bridges. From the wavefunctions expansions, the ratios of the magnetic couplings were determined, which were indeterminate by magnetic susceptometry. Single-crystal EPR studies of 1 were carried out to extend the spin Hamiltonian with terms which induce zero-field splitting (zfs), namely dipolar interactions, anisotropic exchange and Dzyaloshinskii–Moriya interactions (DMI). The data were treated through both a giant-spin model and through a multispin exchange-coupled model. The latter indicated that ≈62 % of the zfs is due to anisotropic and ≈38 % due to dipolar interactions. The powder EPR data of all complexes were fitted to a simplified form of the multispin model and the anisotropic and dipolar contributions to the ground state zfs were estimated.     

Novel nano-zeolite modified carbon paste electrode for electrocatalytic oxidation of methanol

Abstract  

Methanol is used as a fuel in the direct methanol fuel cell. Direct oxidation of methanol encounters large overvoltages at most unmodified electrode surfaces. The development of new procedures for electrocatalytic oxidation of methanol to decrease this overvoltage is therefore very desirable. In this paper, we report a new zeolite-modified carbon paste electrode based on Ni-ZSM-5 for methanol electrooxidation. Nanocrystallites of ZSM-5 (Si/Al of 50) with average particle size of 58 nm were synthesized using clear solutions at low temperature (90 °C) under atmospheric pressure. Ni(II) ions were incorporated into the zeolite by immersion of the modified carbon paste electrode with synthesized zeolite in a 1.0 M nickel chloride solution. Cyclic voltammetry showed that by using nano-sized zeolite, the oxidation current increased compared with that of micron-sized zeolite crystallites.     

Oxidation of secondary amines to nitrones using magnetically separable tungstophosphoric acid supported on silica-encapsulated γ-Fe2O3 nanoparticles

Superparamagnetic tungstophosphoric acid supported on silica-encapsulated γ-Fe₂O₃ was used as an efficient catalyst for the direct oxidation of secondary amines to nitrones with hydrogen peroxide as the oxidant. The catalyst could be recycled up to four times without significant loss of activity.     

On the Hilbert 2-class field tower of some abelian 2-extensions over the field of rational numbers

It is well known by results of Golod and Shafarevich that the Hilbert 2-class field tower of any real quadratic number field, in which the discriminant is not a sum of two squares and divisible by eight primes, is infinite. The aim of this article is to extend this result to any real abelian 2-extension over the field of rational numbers. So using genus theory, units of biquadratic number fields and norm residue symbol, we prove that for every real abelian 2-extension over ? in which eight primes ramify and one of theses primes ≡ ?1 (mod 4), the Hilbert 2-class field tower is infinite.     

Enhanced hydrogen selectivity from catalytic decomposition of formic acid over FeZnIr nanocatalyst at room temperature

Research on Chemical Intermediates - Hydrogen is considered a promising energy carrier for the future, especially for clean energy generation via fuel cell technologies. Formic acid is one of the...     

Influence of clay suspensions on the precipitation of CaCO3 in seawater

The effect of montmorillonite and kaolinite, most common clay in marine water, on nucleation and growth of calcium carbonate in standard sea water was studied. Crystallization was induced by the degasification of the dissolved carbonic gas. It was shown by XRD and SEM analysis that CaCO₃ crystallize under its aragonite polymorph some either the clay concentration or type. It was also found that tested clays inhibited significantly the crystallization of calcium carbonate, especially for concentrations higher than 25 mgL^–1. From the fine analyses of the formed solid, it was suggested that the tested clays have an indirect effect on nucleation and growth of aragonite by increasing the Mg ions concentration, strong inhibitor of CaCO₃ formation, in the neighbourhood of clay particles where supersaturation is the higher and than crystallization can occur. In addition to its indirect role, kaolinite can interact with aragonite by adsorbing on their faces and blocking growth sites (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the choice of explicit stabilizing terms in column generation

Column generation algorithms are instrumental in many areas of applied optimization, where linear programs with an enormous number of columns need to be solved. Although successfully employed in many applications, these approaches suffer from well-known instability issues that somewhat limit their efficiency. Building on the theory developed for nondifferentiable optimization algorithms, a large class of stabilized column generation algorithms can be defined which avoid the instability issues by using an explicit stabilizing term in the dual; this amounts at considering a (generalized) augmented Lagrangian of the primal master problem. Since the theory allows for a great degree of flexibility in the choice and in the management of the stabilizing term, one can use piecewise-linear or quadratic functions that can be efficiently dealt with using off-the-shelf solvers. The practical effectiveness of this approach is demonstrated by extensive computational experiments on large-scale Vehicle and Crew Scheduling problems. Also, the results of a detailed computational study on the impact of the different choices in the stabilization term (shape of the function, parameters), and their relationships with the quality of the initial dual estimates, on the overall effectiveness of the approach are reported, providing practical guidelines for selecting the most appropriate variant in different situations.     

Removal of numerical instability in the solution of an inverse heat conduction problem

In this paper, we consider an inverse heat conduction problem (IHCP). A set of temperature measurements at a single sensor location inside the heat conduction body is required. Using a transformation, the ill-posed IHCP becomes a Cauchy problem. Since the solution of Cauchy problem, exists and is unique but not always stable, the ill-posed problem is closely approximated by a well-posed problem. For this new well-posed problem, the existence, uniqueness, and stability of the solution are proved.