Dioxadiaza- and trioxadiaza-macrocycles containing one dibenzofuran unit selective for cadmium

The binding properties of dioxadiaza-([17](DBF) N2O2) and trioxadiaza- ([22](DBF)N2O3), macrocyclic ligands containing a rigid dibenzofuran group ( DBF), to metal cations and structural studies of their metal complexes have been carried out. The protonation constants of these two ligands and the stability constants of their complexes with Ca2+, Ba2+, and Mn2+, Co2+, Ni2+, Cu2+, Zn2+ and Cd2+, were determined at 298.2 K in methanol-water ( 1 : 1, v/v), and at ionic strength 0.10 mol dm(-3) in KNO3. The values of the protonation constants of both ligands are similar, indicating that no cavity size effect is observed. Only mononuclear complexes of these ligands with the divalent metal ions studied were found, and their stability constants are lower than expected, especially for the complexes of the macrocycle with smaller cavity size. However, the Cd2+ complex with [ 17]( DBF) N2O2 exhibits the highest value of stability constant for the whole series of metal ions studied, indicating that this ligand reveals a remarkable selectivity for cadmium(II) in the presence of all the metal ions studied, except copper( II), indicating that this ligand reveals a remarkable selectivity for cadmium( II) in the presence of the mentioned metal ions. The crystal structures of H-2[17](DBF)N2O32+ (diprotonated form of the ligand) and of its cadmium complex were determined by X-ray diffraction. The Cd2+ ion fits exactly inside the macrocyclic cavity exhibiting coordination number eight by coordination to all the donor atoms of the ligand, and additionally to two oxygen atoms from one nitrate anion and one oxygen atom from a water molecule. The nickel( II) and copper( II) complexes with the two ligands were further studied by UV-vis-NIR and the copper( II) complexes also by EPR spectroscopic techniques in solution indicating square-pyramidal structures and suggesting that only one nitrogen and oxygen donors of the ligands are bound to the metal. However an additional weak interaction of the second nitrogen cannot be ruled out.

New dioxadiaza- and trioxadiaza-macrocycles containing one dibenzofuran unit with two amino pendant arms: synthesis, protonation and complexation studies

New dioxadiaza- and trioxadiaza-macrocycles containing one rigid dibenzofuran unit (DBF) and N-(2-aminoethyl) pendant arms were synthesized, N,N'-bis(2-aminoethyl)-[17]( DBF) N2O2 (L-1) and N,N'-bis(2-aminoethyl)-[22](DBF)N2O3 (L-2), respectively. The binding properties of both macrocycles to metal ions and structural studies of their metal complexes were carried out. The protonation constants of both compounds and the stability constants of their complexes with Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Pb2+ were determined at 298.2 K, in aqueous solutions, and at ionic strength 0.10 mol dm(-3) in KNO3. Mononuclear complexes with both ligands were formed, and dinuclear complexes were only found for L-2. The thermodynamic binding affinities of the metal complexes of L-2 are lower than those of L-1 as expected, but the Pb2+ complexes of both macrocycles exhibit close stability constant values. On the other hand, the binding affinities of Cd2+ and Pb2+ for L-1 are very high, when compared to those of Co2+, Ni2+ and Zn2+. These interesting properties were explained by the presence of the rigid DBF moiety in the backbone of the macrocycle and to the special match between the macrocyclic cavity size and the studied larger metal ions. To elucidate the adopted structures of complexes in solution, the nickel(II) and copper( II) complexes with both ligands were further studied by UV-vis-MR spectroscopy in DMSO-H2O 1 : 1 (v/v) solution. The copper(II) complexes were also studied by EPR spectroscopy in the same mixture of solvents. The crystal structure of the copper complex of L-1 was also determined. The copper(II) displays an octahedral geometry, the four nitrogen atoms forming the equatorial plane and two oxygen atoms, one from the DBF unit and the other one from the ether oxygen, in axial positions. One of the ether oxygens of the macrocycle is out of the coordination sphere. Our results led us to suggest that this geometry is also adopted by the Co2+ to Zn2+ complexes, and only the larger Cd2+ and Pb2+ manage to form complexes with the involvement of all the oxygen atoms of the macrocyclic backbone.

Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2′:6′,2′′-terpyridine ligand: implications for actinide(III)/lanthanide(III) partitioning

The quadridentate N-heterocyclic ligand 6-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin- 3-yl)-2,2′ : 6′,2′′-terpyridine (CyMe4-hemi-BTBP) has been synthesized and its interactions with Am(III),U(VI), Ln(III) and some transition metal cations have been evaluated by X-ray crystallographic analysis, Am(III)/Eu(III) solvent extraction experiments, UVabsorption spectrophotometry, NMR studies and ESI-MS. Structures of 1 : 1 complexes with Eu(III), Ce(III) and the linear uranyl (UO2 2+) ion were obtained by X-ray crystallographic analysis, and they showed similar coordination behavior to related BTBP complexes. In methanol, the stability constants of the Ln(III) complexes are slightly lower than those of the analogous quadridentate bis-triazine BTBP ligands, while the stability constant for the Yb(III)complex is higher. 1H NMR titrations and ESI-MS with lanthanide nitrates showed that the ligand forms only 1 : 1 complexes with Eu(III), Ce(III) and Yb(III), while both 1 : 1 and 1 : 2 complexes were formed with La(III) and Y(III) in acetonitrile. A mixture of isomeric chiral 2 : 2 helical complexes was formed with Cu(I), with a slight preference (1.4 : 1) for a single directional isomer. In contrast, a 1 : 1 complex was observed with the larger Ag(I) ion. The ligand was unable to extract Am(III) or Eu(III) from nitric acid solutions into 1-octanol, except in the presence of a synergist at low acidity. The results show that the presence of two outer 1,2,4-triazine rings is required for the efficient extraction and separation of An(III)from Ln(III) by quadridentate N-donor ligands.

Trefftz discontinuous Galerkin methods for acoustic scattering on locally refined meshes

We extend the a priori error analysis of Trefftz-discontinuous Galerkin methods for time-harmonic wave propagation problems developed in previous papers to acoustic scattering problems and locally refined meshes. To this aim, we prove refined regularity and stability results with explicit dependence of the stability constant on the wave number for non convex domains with non connected boundaries. Moreover, we devise a new choice of numerical flux parameters for which we can prove L2-error estimates in the case of locally refined meshes near the scatterer. This is the setting needed to develop a complete hp-convergence analysis.

Effects of chlorogenic acid and bovine serum albumin on the oxidative stability of low density lipoproteins in vitro

The ability of chlorogenic acid to inhibit oxidation of human low-density lipoprotein (LDL) was studied by in vitro copper-induced LDL oxidation. The effect of chlorogenic acid on the lag time before LDL oxidation increased in a dose dependent manner by up to 176% of the control value when added at concentrations of 0.25 -1.0 μM. Dose dependent increases in lag time of LDL oxidation were also observed, but at much higher concentrations, when chlorogenic acid was incubated with LDL (up to 29.7% increase in lag phase for 10 μM chlorogenic acid) or plasma (up to 16.6% increase in lag phase for 200 μM chlorogenic acid) prior to isolation of LDL, and this indicated that chlorogenic acid was able to bind, at least weakly, to LDL. Bovine serum albumin (BSA) increased the oxidative stability of LDL in the presence of chlorogenic acid. Fluorescence spectroscopy showed that chlorogenic acid binds to BSA with a binding constant of 3.88 x 104 M-1. BSA increased the antioxidant effect of chlorogenic acid, and this was attributed to copper ions binding to BSA, thereby reducing the amount of copper available for inducing lipid peroxidation.

Extensional rheology and stability of gas cell walls in bread doughs at elevated temperatures in relation to breadmaking performance

The rheological properties of gas cell walls in bread doughs are considered to be important in relation to their stability and gas retention during proof and baking. Large deformation rheological properties of gas cell walls were measured using biaxial extension for a number of doughs of varying breadmaking quality at constant strain rate and elevated temperatures of 25-60degreesC. Strain hardening and failure strain of cell walls both decreased with temperature, with cell walls in good breadmaking doughs remaining stable and retaining their strain hardening properties at higher temperatures (60degreesC), while the cell walls of poor breadmaking doughs became unstable at lower temperatures (45-50degreesC) and had lower strain hardening. Strain hardening measured at 50degreesC gave good correlations with baking volume, with the best correlations achieved between rheological measurements and baking tests that used similar mixing conditions. As predicted by the considered failure criterion, a strain hardening value of I defines a region below which gas cell walls become unstable, and discriminates well between the baking quality of a range of commercial flour blends of varying quality. This indicates that the stability of gas cell walls during baking is strongly related to strain hardening properties, and that extensional rheological measurements can be used as indicators of baking quality.

Stability results for the time-harmonic Maxwell equations with impedance boundary conditions

We consider the time-harmonic Maxwell equations with constant coefficients in a bounded, uniformly star-shaped polyhedron. We prove wavenumber-explicit norm bounds for weak solutions. This result is pivotal for convergence proofs in numerical analysis and may be a tool in the analysis of electromagnetic boundary integral operators.

Comment on ``Conditional Exceedance Probabilities''

In a recent paper, Mason et al. propose a reliability test of ensemble forecasts for a continuous, scalar verification. As noted in the paper, the test relies on a very specific interpretation of ensembles, namely, that the ensemble members represent quantiles of some underlying distribution. This quantile interpretation is not the only interpretation of ensembles, another popular one being the Monte Carlo interpretation. Mason et al. suggest estimating the quantiles in this situation; however, this approach is fundamentally flawed. Errors in the quantile estimates are not independent of the exceedance events, and consequently the conditional exceedance probabilities (CEP) curves are not constant, which is a fundamental assumption of the test. The test would reject reliable forecasts with probability much higher than the test size.

Some numerical experiments on the effect of the variation of static stability in two-layer quasi-geostrophic models

A method to solve a quasi-geostrophic two-layer model including the variation of static stability is presented. The divergent part of the wind is incorporated by means of an iterative procedure. The procedure is rather fast and the time of computation is only 60–70% longer than for the usual two-layer model. The method of solution is justified by the conservation of the difference between the gross static stability and the kinetic energy. To eliminate the side-boundary conditions the experiments have been performed on a zonal channel model. The investigation falls mainly into three parts: The first part (section 5) contains a discussion of the significance of some physically inconsistent approximations. It is shown that physical inconsistencies are rather serious and for these inconsistent models which were studied the total kinetic energy increased faster than the gross static stability. In the next part (section 6) we are studying the effect of a Jacobian difference operator which conserves the total kinetic energy. The use of this operator in two-layer models will give a slight improvement but probably does not have any practical use in short periodic forecasts. It is also shown that the energy-conservative operator will change the wave-speed in an erroneous way if the wave-number or the grid-length is large in the meridional direction. In the final part (section 7) we investigate the behaviour of baroclinic waves for some different initial states and for two energy-consistent models, one with constant and one with variable static stability. According to the linear theory the waves adjust rather rapidly in such a way that the temperature wave will lag behind the pressure wave independent of the initial configuration. Thus, both models give rise to a baroclinic development even if the initial state is quasi-barotropic. The effect of the variation of static stability is very small, qualitative differences in the development are only observed during the first 12 hours. For an amplifying wave we will get a stabilization over the troughs and an instabilization over the ridges.

Symmetric stability of compressible zonal flows on a generalized equatorial β plane

Sufficient conditions are derived for the linear stability with respect to zonally symmetric perturbations of a steady zonal solution to the nonhydrostatic compressible Euler equations on an equatorial � plane, including a leading order representation of the Coriolis force terms due to the poleward component of the planetary rotation vector. A version of the energy–Casimir method of stability proof is applied: an invariant functional of the Euler equations linearized about the equilibrium zonal flow is found, and positive definiteness of the functional is shown to imply linear stability of the equilibrium. It is shown that an equilibrium is stable if the potential vorticity has the same sign as latitude and the Rayleigh centrifugal stability condition that absolute angular momentum increase toward the equator on surfaces of constant pressure is satisfied. The result generalizes earlier results for hydrostatic and incompressible systems and for systems that do not account for the nontraditional Coriolis force terms. The stability of particular equilibrium zonal velocity, entropy, and density fields is assessed. A notable case in which the effect of the nontraditional Coriolis force is decisive is the instability of an angular momentum profile that decreases away from the equator but is flatter than quadratic in latitude, despite its satisfying both the centrifugal and convective stability conditions.

The stability of a two-dimensional vorticity filament under uniform strain

The quantitative effects of uniform strain and background rotation on the stability of a strip of constant vorticity (a simple shear layer) are examined. The thickness of the strip decreases in time under the strain, so it is necessary to formulate the linear stability analysis for a time-dependent basic flow. The results show that even a strain rate γ (scaled with the vorticity of the strip) as small as 0.25 suppresses the conventional Rayleigh shear instability mechanism, in the sense that the r.m.s. wave steepness cannot amplify by more than a certain factor, and must eventually decay. For γ < 0.25 the amplification factor increases as γ decreases; however, it is only 3 when γ e 0.065. Numerical simulations confirm the predictions of linear theory at small steepness and predict a threshold value necessary for the formation of coherent vortices. The results help to explain the impression from numerous simulations of two-dimensional turbulence reported in the literature that filaments of vorticity infrequently roll up into vortices. The stabilization effect may be expected to extend to two- and three-dimensional quasi-geostrophic flows.