Structural and equilibrium studies on mixed ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) with N-(2-benzimidazolyl)methyliminodiacetic acid and typical N,N donor ligands

Mixed ligand complexes: [Co(L)(bipy)] (.) 3H(2)O (1), [Ni(L)(phen)] (.) H2O (2), [Cu(L)(phen)] (.) 3H(2)O (3) and [Zn(L)(bipy)] (.) 3H(2)O (4), where L2- = two -COOH deprotonated dianion of N-(2-benzimidazolyl)methyliminodiacetic acid (H(2)bzimida, hereafter, H,L), bipy = 2,2' bipyridine and phen = 1,10-phenanthroline have been isolated and characterized by elemental analysis, spectral and magnetic measurements and thermal studies. Single crystal X-ray diffraction studies show octahedral geometry for 1, 2 and 4 and square pyramidal geometry for 3. Equilibrium studies in aqueous solution (ionic strength I = 10(-1) mol dm(-3) (NaNO3), at 25 +/- 1 degrees C) using different molar proportions of M(II):H2L:B, where M = Co, Ni, Cu and Zn and B = phen, bipy and en (ethylene diamine), however, provides evidence of formation of mononuclear and binuclear binary and mixed ligand complexes: M(L), M(H-1L)(-), M(B)(2+), M(L)(B), M(H-1L)(B)(-), M-2(H-1L)(OH), (B)M(H-1L)M(B)(+), where H-1L3- represents two -COOH and the benzimidazole NI-H deprotonated quadridentate (O-, N, O-, N), or, quinquedentate (O-, N, O-, N, N-) function of the coordinated ligand H,L. Binuclear mixed ligand complex formation equilibria: M(L)(B) + M(B)(2+) = (B)M(H-1L)M(B)(+) + H+ is favoured with higher pi-acidity of the B ligands. For Co(II), Ni(II) and Cu(II), these equilibria are accompanied by blue shift of the electronic absorption maxima of M(II) ions, as a negatively charged bridging benzimidazolate moiety provides stronger ligand field than a neutral one. Solution stability of the mixed ligand complexes are in the expected order: Co(II) < Ni(II) < Cu(II) > Zn(II). The Delta logK(M) values are less negetive than their statistical values, indicating favoured formation of the mixed ligand complexes over the binary ones. (c) 2005 Elsevier B.V. All rights reserved.

Equilibrium studies on mixed ligand complex formation of Co(II), Ni(II), Cu(II) and Zn(II) with N-(2-hydroxybenzyl)-L-histidine (H(2)hb-L-his) and typical N,N donor ligands: Crystal structure of [Ni(hb-L-his)(bipyridine)]center dot H2O complex

Equilibrium study on complex formation of Co(II), Ni(II), Cu(II) and Zn(II), hereafter M(II), with the quadridentate (O-, N, O-, N) donor ligand, N-(2-hydroxybenzyl)-L-histidine (H(2)hb-L-his, hereafter H2L), in the absence and in the presence of typical (N, N) donor bidentate ligands, 1,10 phenanthroline(phen), 2, 2'-bipyridine(bipy), ethylenediamine(en), hereafter B, in aqueous solution at 25 +/- 1 degrees C was done at a fixed ionic strength, I = 0.1 mol dm(-3) (NaNO3) by combined pH-metric, UV-Vis and EPR measurements provide evidence for the formation of mononuclear and dinuclear binary and mixed ligand complexes of the types: M(L), M(L)(2)(2-), M-2(L)(2+), M-2(H-1L)(+), M(L)(B), (B)M(H-1L)M(B)(+). The imidazole moiety of the ligand is found to act as a bridging bidentate ligand in the dinuclear M-2(L)(2+), M-2(H-1L)(+) and (B)M(H-1L)M(B)(+) complexes, using its N-3 atom and N1-H deprotonated moiety. Stability constants of the complexes provide evidence of discrimination of Cu(II) from the other M(II) ions by this ligand. Solid complexes: [Ni(L)(H2O)(2)] (1), [Cu(L)(H2O)] (2), and [Ni(L)(bipy)] (.) H2O (3) have been isolated and characterized by various physicochemical studies. Single crystal X-ray diffraction of the ternary complex, 3, shows an octahedral [(O-,N,N,O-)(N,N)] geometry with extensive pi-pi stacking of the aromatic rings and H-bonding with imidazole (N1-H), secondary amino N-atom, the lattice H2O molecule, and the carboxylate and phenolate O-atoms. (c) 2006 Elsevier B.V. All rights reserved.

Synthesis, crystal structure and hydrolysis of a dinuclear copper(II) complex constructed by N2O donor Schiff base and 4,4 '-bipyridine: discrete supra-molecular ensembles vs. oligomers

The tridentate Schiff base ligand, 7-amino-4-methyl-5-aza-3-hepten-2-one (HAMAH), prepared by the mono-condensation of 1,2diaminoethane and acetylacetone, reacts with Cu(BF4)(2) center dot 6H(2)O to produce initially a dinuclear Cu(II) complex, [{Cu(AMAH)}(2) (mu-4,4'-bipyJ](BF4)(2) (1) which undergoes hydrolysis in the reaction mixture and finally produces a linear polymeric chain compound, [Cu(acac)(2)(mu-4,4'-bipy)](n) (2). The geometry around the copper atom in compound 1 is distorted square planar while that in compound 2 is essentially an elongated octahedron. On the other hand, the ligand HAMAH reacts with Cu(ClO4)(2) center dot 6H(2)O to yield a polymeric zigzag chain, [{Cu(acac)(CH3OH)(mu-4,4'-bipy)}(ClO4)](n) (3). The geometry of the copper atom in 3 is square pyramidal with the two bipyridine molecules in the cis equatorial positions. All three complexes have been characterized by elemental analysis, IR and UV-Vis spectroscopy and single crystal X-ray diffraction studies. A probable explanation for the different size and shape of the reported polynuclear complexes formed by copper(II) and 4,4'-bipyridine has been put forward by taking into account the denticity and crystal field strength of the blocking ligand as well as the Jahn-Teller effect in copper(II). (c) 2007 Elsevier Ltd. All rights reserved.

A new theory of educational change - punctuated equilibrium: the case of the internationalisation of Higher Education institutions

This article argues for a new theoretical paradigm for the analysis of change in educational institutions that is able to deal with such issues as readiness for change, transformational change and the failure of change strategies. Punctuated equilibrium (Tushman and Romanelli, 1985) is a theory which has wide application. It envisages long-term change as being made up of a succession of long periods of relative stability interspersed by brief periods of rapid profound change. In the periods of stability only relatively small incremental changes are possible. The periods of transformational change may be triggered by external or internal influences. A recent study of the long-term process of internationalisation in higher education institutions shows evidence to support the theory: long periods of incremental change, events precipitating profound change and the failure of externally imposed attempts to change. Also, as the theory predicts, changes in collegial organisations are slower and more uncertain than changes in managed organisations.

Investigation into low power of a 2D Inverse Discrete CosineTransform (IDCT) in FPGAs

Design for low power in FPGA is rather limited since technology factors affecting power are either fixed or limited for FPGA families. This paper investigates opportunities for power savings of a pipelined 2D IDCT design at the architecture and logic level. We report power consumption savings of over 25% achieved in FPGA circuits obtained from clock gating implementation of optimizations made at the algorithmic level(1).

Comparison of extrasystolic ECG signal classifiers using discrete wavelet transforms

This work compares and contrasts results of classifying time-domain ECG signals with pathological conditions taken from the MITBIH arrhythmia database. Linear discriminant analysis and a multi-layer perceptron were used as classifiers. The neural network was trained by two different methods, namely back-propagation and a genetic algorithm. Converting the time-domain signal into the wavelet domain reduced the dimensionality of the problem at least 10-fold. This was achieved using wavelets from the db6 family as well as using adaptive wavelets generated using two different strategies. The wavelet transforms used in this study were limited to two decomposition levels. A neural network with evolved weights proved to be the best classifier with a maximum of 99.6% accuracy when optimised wavelet-transform ECG data wits presented to its input and 95.9% accuracy when the signals presented to its input were decomposed using db6 wavelets. The linear discriminant analysis achieved a maximum classification accuracy of 95.7% when presented with optimised and 95.5% with db6 wavelet coefficients. It is shown that the much simpler signal representation of a few wavelet coefficients obtained through an optimised discrete wavelet transform facilitates the classification of non-stationary time-variant signals task considerably. In addition, the results indicate that wavelet optimisation may improve the classification ability of a neural network. (c) 2005 Elsevier B.V. All rights reserved.

A novel radix-3/9 algorithm for type-III generalized discrete Hartley transform

A novel radix-3/9 algorithm for type-III generalized discrete Hartley transform (GDHT) is proposed, which applies to length-3(P) sequences. This algorithm is especially efficient in the case that multiplication is much more time-consuming than addition. A comparison analysis shows that the proposed algorithm outperforms a known algorithm when one multiplication is more time-consuming than five additions. When combined with any known radix-2 type-III GDHT algorithm, the new algorithm also applies to length-2(q)3(P) sequences.

Insights into redox cycling of sulfur and iron in peatlands using high-resolution diffusive equilibrium thin film (DET) gel probe sampling

High spatial resolution vertical profiles of pore-water chemistry have been obtained for a peatland using diffusive equilibrium in thin films (DET) gel probes. Comparison of DET pore-water data with more traditional depth-specific sampling shows good agreement and the DET profiling method is less invasive and less likely to induce mixing of pore-waters. Chloride mass balances as water tables fell in the early summer indicate that evaporative concentration dominates and there is negligible lateral flow in the peat. Lack of lateral flow allows element budgets for the same site at different times to be compared. The high spatial resolution of sampling also enables gradients to be observed that permit calculations of vertical fluxes. Sulfate concentrations fall at two sites with net rates of 1.5 and 5.0nmol cm− 3 day− 1, likely due to a dominance of bacterial sulfate reduction, while a third site showed a net gain in sulfate due to oxidation of sulfur over the study period at an average rate of 3.4nmol cm− 3 day− 1. Behaviour of iron is closely coupled to that of sulfur; there is net removal of iron at the two sites where sulfate reduction dominates and addition of iron where oxidation dominates. The profiles demonstrate that, in addition to strong vertical redox related chemical changes, there is significant spatial heterogeneity. Whilst overall there is evidence for net reduction of sulfate within the peatland pore-waters, this can be reversed, at least temporarily, during periods of drought when sulfide oxidation with resulting acid production predominates.

Flux difference splitting for inviscid, real gases with non-equilibrium chemistry

A flux-difference splitting method is presented for the inviscid terms of the compressible flow equations for chemical non-equilibrium gases

An efficient finite difference scheme for three-dimensional, non-equilibrium flows using operator splitting

An efficient finite difference scheme is presented for the inviscid terms of the three-dimensional, compressible flow equations for chemical non-equilibrium gases. This scheme represents an extension and an improvement of one proposed by the author, and includes operator splitting.

Error estimates for a fully discrete spectral scheme for a class of nonlinear, nonlocal dispersive wave equations

We analyze a fully discrete spectral method for the numerical solution of the initial- and periodic boundary-value problem for two nonlinear, nonlocal, dispersive wave equations, the Benjamin–Ono and the Intermediate Long Wave equations. The equations are discretized in space by the standard Fourier–Galerkin spectral method and in time by the explicit leap-frog scheme. For the resulting fully discrete, conditionally stable scheme we prove an L2-error bound of spectral accuracy in space and of second-order accuracy in time.

On a class of nonselfadjoint periodic boundary value problems with discrete real spectrum

In a previous paper (J. of Differential Equations, Vol. 249 (2010), 3081-3098) we examined a family of periodic Sturm-Liouville problems with boundary and interior singularities which are highly non-self-adjoint but have only real eigenvalues. We now establish Schatten class properties of the associated resolvent operator.

Idealized model for changes in equilibrium temperature, mixed layer depth, and boundary layer cloud over land in a doubled CO2 climate

An idealized equilibrium model for the undisturbed partly cloudy boundary layer (BL) is used as a framework to explore the coupling of the energy, water, and carbon cycles over land in midlatitudes and show the sensitivity to the clear‐sky shortwave flux, the midtropospheric temperature, moisture, CO2, and subsidence. The changes in the surface fluxes, the BL equilibrium, and cloud cover are shown for a warmer, doubled CO2 climate. Reduced stomatal conductance in a simple vegetation model amplifies the background 2 K ocean temperature rise to an (unrealistically large) 6 K increase in near‐surface temperature over land, with a corresponding drop of near‐surface relative humidity of about 19%, and a rise of cloud base of about 70 hPa. Cloud changes depend strongly on changes of mean subsidence; but evaporative fraction (EF) decreases. EF is almost uniquely related to mixed layer (ML) depth, independent of background forcing climate. This suggests that it might be possible to infer EF for heterogeneous landscapes from ML depth. The asymmetry of increased evaporation over the oceans and reduced transpiration over land increases in a warmer doubled CO2 climate.

Time-dependent orientation coupling in equilibrium polymer melts

The motion in concentrated polymer systems is described by either the Rouse or the reptation model, which both assume that the relaxation of each polymer chain is independent of the surrounding chains. This, however, is in contradiction with several experiments. In this Letter, we propose a universal description of orientation coupling in polymer melts in terms of the time-dependent coupling parameter κ(t). We use molecular dynamics simulations to show that the coupling parameter increases with time, reaching about 50% at long times, independently of the chain length or blend composition. This leads to predictions of component dynamics in mixtures of different molecular weights from the knowledge of monodisperse dynamics for unentangled melts. Finally, we demonstrate that entanglements do not play a significant role in the observed coupling. © 2010 The American Physical Society