A rare case of solution and solid state inter-conversion of two copper(II) dimers and a copper(II) chain

Three Cu(II)-azido complexes of formula [Cu2L2(N-3)(2)] (1), [Cu2L2(N-3)(2)]center dot H2O (2) and [CuL(N-3)](n) (3) have been synthesized using the same tridentate Schiff base ligand HL (2-[(3-methylaminopropylimino)-methyl]-phenol), the condensation product of N-methyl-1,3-propanediamine and salicyldehyde). Compounds 1 and 2 are basal-apical mu-1,1 double azido bridged dimers. The dimeric structure of 1 is centro-symmetric but that of 2 is non-centrommetric. Compound 3 is a mu-1,1 single azido bridged 1D chain. The three complexes interconvert in solution and can be obtained in pure form by carefully controlling the synthetic conditions. Compound 2 undergoes an irreversible transformation to 1 upon dehydration in the solid state. The magnetic properties of compounds 1 and 2 show the presence of weak antiferromagnetic exchange interactions mediated by the double 1,1-N-3 azido bridges (J = -2.59(4) and -0.10(1) cm-(1), respectively). The single 1,1-N-3 bridge in compound 3 mediates a negligible exchange interaction.

Structural and magnetic studies of Schiff base complexes of nickel(ii) nitrite: change in crystalline state, ligand rearrangement and a very rare μ-nitrito-1κO:2κN:3κO′ bridging mode

Four new nickel(II) complexes, [Ni2L2(NO2)2]·CH2Cl2·C2H5OH, 2H2O (1), [Ni2L2(DMF)2(m-NO2)]ClO4·DMF (2a), [Ni2L2(DMF)2(m-NO2)]ClO4 (2b) and [Ni3L¢2(m3-NO2)2(CH2Cl2)]n·1.5H2O (3) where HL = 2-[(3-amino-propylimino)-methyl]-phenol, H2L¢ = 2-({3-[(2-hydroxy-benzylidene)-amino]-propylimino}-methyl)-phenol and DMF = N,N-dimethylformamide, have been synthesized starting with the precursor complex [NiL2]·2H2O, nickel(II) perchlorate and sodium nitrite and characterized structurally and magnetically. The structural analyses reveal that in all the complexes, NiII ions possess a distorted octahedral geometry. Complex 1 is a dinuclear di-m2-phenoxo bridged species in which nitrite ion acts as chelating co-ligand. Complexes 2a and 2b also consist of dinuclear entities, but in these two compounds a cis-(m-nitrito-1kO:2kN) bridge is present in addition to the di-m2-phenoxo bridge. The molecular structures of 2a and 2b are equivalent; they differ only in that 2a contains an additional solvated DMF molecule. Complex 3 is formed by ligand rearrangement and is a one-dimensional polymer in which double phenoxo as well as m-nitrito-1kO:2kN bridged trinuclear units are linked through a very rare m3-nitrito-1kO:2kN:3kO¢ bridge. Analysis of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the nickel(II) ions in four complexes, with exchange parameters J of -5.26, -11.45, -10.66 and -5.99 cm-1 for 1, 2a, 2b and 3, respectively

On the difficulties of present theoretical models to predict the oxidation state of atomic Au adsorbed on regular sites of CeO2(111)

The electronic structure and oxidation state of atomic Au adsorbed on a perfect CeO2(111) surface have been investigated in detail by means of periodic density functional theory-based calculations, using the LDA+U and GGA+U potentials for a broad range of U values, complemented with calculations employing the HSE06 hybrid functional. In addition, the effects of the lattice parameter a0 and of the starting point for the geometry optimization have also been analyzed. From the present results we suggest that the oxidation state of single Au atoms on CeO2(111) predicted by LDA+U, GGA+U, and HSE06 density functional calculations is not conclusive and that the final picture strongly depends on the method chosen and on the construction of the surface model. In some cases we have been able to locate two well-defined states which are close in energy but with very different electronic structure and local geometries, one with Au fully oxidized and one with neutral Au. The energy difference between the two states is typically within the limits of the accuracy of the present exchange-correlation potentials, and therefore, a clear lowest-energy state cannot be identified. These results suggest the possibility of a dynamic distribution of Au0 and Au+ atomic species at the regular sites of the CeO2(111) surface.

Mechanisms of motivation-cognition interaction: challenges and opportunities

There has been a recent rejuvenation of interest in studies of motivation-cognition interactions arising from many different areas of psychology and neuroscience. The current issue of Cognitive, Affective, and Behavioral Neuroscience provides a sampling of some of the latest research from a number of these different areas. In this introductory paper, we provide an overview of the current state of the field, in terms of key research developments and candidate neural mechanisms receiving focused investigation as potential sources of motivation-cognition interaction. However, our primary goal is conceptual: to highlight the distinct perspectives taken by different research areas in terms of how motivation is defined, the relevant dimensions and dissociations that are emphasized, and the theoretical questions being targeted. Together, these distinctions present both challenges and opportunities for efforts aiming towards a more unified and cross-disciplinary approach. We identify a set of pressing research questions calling out for this sort of cross-disciplinary approach, with the explicit goal of encouraging integrative and collaborative investigations directed towards them.

Solution calorimetry as a tool for investigating drug interaction with intestinal fluid

Solution calorimetry offers a reproducible technique for measuring the enthalpy of solution (ΔsolH) of a solute dissolving into a solvent. The ΔsolH of two solutes, propranolol HCl and mannitol were determined in simulated intestinal fluid (SIF) solutions designed to model the fed and fasted states within the gut, and in Hanks’ balanced salt solution (HBSS) of varying pH. The bile salt and lipid within the SIF solutions formed mixed micelles. Both solutes exhibited endothermic reactions in all solvents. The ΔsolH for propranolol HCl in the SIF solutions differed from those in the HBSS and was lower in the fed state than the fasted state SIF solution, revealing an interaction between propranolol and the micellar phase in both SIF solutions. In contrast, for mannitol the ΔsolH was constant in all solutions indicating minimal interaction between mannitol and the micellar phases of the SIF solutions. In this study, solution calorimetry proved to be a simple method for measuring the enthalpy associated with the dissolution of model drugs in complex biological media such as SIF solutions. In addition, the derived power–time curves allowed the time taken for the powdered solutes to form solutions to be estimated.

Propagation of the Madden–Julian Oscillation and scale interaction with the diurnal cycle in a high-resolution GCM

The Madden–Julian Oscillation (MJO) is the chief source of tropical intra-seasonal variability, but is simulated poorly by most state-of-the-art GCMs. Common errors include a lack of eastward propagation at the correct frequency and zonal extent, and too small a ratio of eastward- to westward-propagating variability. Here it is shown that HiGEM, a high-resolution GCM, simulates a very realistic MJO with approximately the correct spatial and temporal scale. Many MJO studies in GCMs are limited to diagnostics which average over a latitude band around the equator, allowing an analysis of the MJO’s structure in time and longitude only. In this study a wider range of diagnostics is applied. It is argued that such an approach is necessary for a comprehensive analysis of a model’s MJO. The standard analysis of Wheeler and Hendon (Mon Wea Rev 132(8):1917–1932, 2004; WH04) is applied to produce composites, which show a realistic spatial structure in the MJO envelopes but for the timing of the peak precipitation in the inter-tropical convergence zone, which bifurcates the MJO signal. Further diagnostics are developed to analyse the MJO’s episodic nature and the “MJO inertia” (the tendency to remain in the same WH04 phase from one day to the next). HiGEM favours phases 2, 3, 6 and 7; has too much MJO inertia; and dies out too frequently in phase 3. Recent research has shown that a key feature of the MJO is its interaction with the diurnal cycle over the Maritime Continent. This interaction is present in HiGEM but is unrealistically weak.

The slowly evolving background state of the atmosphere

The theory of wave–mean flow interaction requires a partition of the atmospheric flow into a notional background state and perturbations to it. Here, a background state, known as the Modified Lagrangian Mean (MLM), is defined as the zonally symmetric state obtained by requiring that every potential vorticity (PV) contour lying within an isentropic layer encloses the same mass and circulation as in the full flow. For adiabatic and frictionless flow, these two integral properties are time-invariant and the MLM state is a steady solution of the primitive equations. The time dependence in the adiabatic flow is put into the perturbations, which can be described by a wave-activity conservation law that is exact even at large amplitude. Furthermore, the effects of non-conservative processes on wave activity can be calculated from the conservation law. A new method to calculate the MLM state is introduced, where the position of the lower boundary is obtained as part of the solution. The results are illustrated using Northern Hemisphere ERA-Interim data. The MLM state evolves slowly, implying that the net non-conservative effects are weak. Although ‘adiabatic eddy fluxes’ cannot affect the MLM state, the effects of Rossby-wave breaking, PV filamentation and subsequent dissipation result in sharpening of the polar vortex edge and meridional shifts in the MLM zonal flow, both at tropopause level and on the winter stratospheric vortex. The rate of downward migration of wave activity during stratospheric sudden warmings is shown to be given by the vertical scale associated with polar vortex tilt divided by the time-scale for wave dissipation estimated from the wave-activity conservation law. Aspects of troposphere–stratosphere interaction are discussed. The new framework is suitable to examine the climate and its interactions with disturbances, such as midlatitude storm tracks, and makes a clean partition between adiabatic and non-conservative processes.

The importance of anisotropic Coulomb interaction in LaMnO3

In low-temperature anti-ferromagnetic LaMnO3, strong and localized electronic interactions among Mn 3d electrons prevent a satisfactory description from standard local density and generalized gradient approximations in density functional theory calculations. Here we show that the strong on-site electronic interactions are described well only by using direct and exchange corrections to the intra-orbital Coulomb potential. Only DFT+U calculations with explicit exchange corrections produce a balanced picture of electronic, magnetic and structural observables in agreement with experiment. To understand the reason, a rewriting of the functional form of the +U corrections is presented that leads to a more physical and transparent understanding of the effect of these correction terms. The approach highlights the importance of Hund’s coupling (intra-orbital exchange) in providing anisotropy across the occupation and energy eigenvalues of the Mn d states. This intra-orbital exchange is the key to fully activating the Jahn-Teller distortion, reproducing the experimental band gap and stabilizing the correct magnetic ground state in LaMnO3. The best parameter values for LaMnO3 within the DFT(PBEsol)+U framework are determined to be U = 8 eV and J = 1.9 eV.

Interaction of equatorial waves through resonance with the diurnal cycle of tropical heating

In this work, a new theoretical mechanism is presented in which equatorial Rossby and inertio-gravity wave modes may interact with each other through resonance with the diurnal cycle of tropical deep convection. We have adopted the two-layer incompressible equatorial primitive equations forced by a parametric heating that roughly represents deep convection activity in the tropical atmosphere. The heat source was parametrized in the simplest way according to the hypothesis that it is proportional to the lower-troposphere moisture convergence, with the background moisture state function mimicking the structure of the ITCZ. In this context, we have investigated the possibility of resonant interaction between equatorially trapped Rossby and inertio-gravity modes through the diurnal cycle of the background moisture state function. The reduced dynamics of a single resonant duo shows that when this diurnal variation is considered, a Rossby wave mode can undergo significant amplitude modulations when interacting with an inertio-gravity wave mode, which is not possible in the context of the resonant triad non-linear interaction. Therefore, the results suggest that the diurnal variation of the ITCZ can be a possible dynamical mechanism that leads the Rossby waves to be significantly affected by high frequency modes.

Interaction of strangelets with ordinary nuclei

Strangelets (hypothetical stable lumps of strange quarkmatter) of astrophysical origin may be ultimately detected in specific cosmic ray experiments. The initial mass distribution resulting from the possible astrophysical production sites would be subject to reprocessing in the interstellar medium and in the earth`s atmosphere. In order to get a better understanding of the claims for the detection of this still hypothetic state of hadronic matter, we present a study of strangelet-nucleus interactions including several physical processes of interest (abrasion, fusion, fission, excitation and de-excitation of the strangelets), to address the fate of the baryon number along the strangelet path. It is shown that, although fusion may be important for low-energy strangelets in the interstellar medium (thus increasing the initial baryon number A), in the earth`s atmosphere the loss of the baryon number should be the dominant process. The consequences of these findings are briefly addressed.

Interaction with calmodulin is important for the secretion of thimet oligopeptidase following stimulation

Thimet oligopeptidase (EC 3.4.24.15; EP24.15) was originally described as a neuropeptide-metabolizing enzyme, highly expressed in the brain, kidneys and neuroendocrine tissue. EP24.15 lacks a typical signal peptide sequence for entry into the secretory pathway and is secreted by cells via an unconventional and unknown mechanism. In this study, we identified a novel calcium-dependent interaction between EP24.15 and calmodulin, which is important for the stimulated, but not constitutive, secretion of EP24.15. We demonstrated that, in vitro, EP24.15 and calmodulin physically interact only in the presence of Ca(2+), with an estimated K(d) value of 0.52 mu m. Confocal microscopy confirmed that EP24.15 colocalizes with calmodulin in the cytosol of resting HEK293 cells. This colocalization markedly increases when cells are treated with either the calcium ionophore A23187 or the protein kinase A activator forskolin. Overexpression of calmodulin in HEK293 cells is sufficient to greatly increase the A23187-stimulated secretion of EP24.15, which can be inhibited by the calmodulin inhibitor calmidazolium. The specific inhibition of protein kinase A with KT5720 reduces the A23187-stimulated secretion of EP24.15 and inhibits the synergistic effects of forskolin with A23187. Treatment with calmidazolium and KT5720 nearly abolishes the stimulatory effects of A23187 on EP24.15 secretion. Together, these data suggest that the interaction between EP24.15 and calmodulin is regulated within cells and is important for the stimulated secretion of EP24.15 from HEK293 cells.

Structural characterization of the interaction of the polyene antibiotic Amphotericin B with DODAB bicelles and vesicles

Amphotericin B (AmB) is widely used in the treatment of systemic fungal infections, despite its toxic effects. Nephrotoxicity, ascribed as the most serious toxic effect, has been related to the state of aggregation of the antibiotic. In search of the increase in AmB antifungal activity associated with low toxicity, several AmB-amphiphile formulations have been proposed. This work focuses on the structural characterization of a specific AmB formulation: AmB associated with sonicated dioctadecyl dimethylammonium bromide (DODAB) aggregates. Here, it was confirmed that sonicated DODAB dispersion is constituted by DODAB bicelles, and that monomeric AmB is much more soluble in bicelles than in DODAB vesicles. A new optical parameter is proposed for the estimation of the relative amount of amphiphile-bound monomeric AmB. With theoretical simulations of the spectra of spin labels incorporated in DODAB bicelles it was possible to prove that monomeric AmB binds preferentially to lipids located at the edges of DODAB bicelles, rigidifying them, and decreasing the polarity of the region. That special binding of monomeric AmB along the borders of bicelles, where the lipids are highly disorganized, could be used in the formulation of other carriers for the antibiotic, including mixtures of natural lipids which are known to form bicelles. (C) 2011 Elsevier B.V. All rights reserved.

Excited state electronic polarization and reappraisal of the n <- pi* emission of acetone in water

Electronic polarization of the acetone molecule in the excited n -> pi* state is considered and its influence on the solvent shift in the emission spectrum is analyzed. Using an iterative procedure the electronic polarizations of both the ground and the excited states are included and compared with previous results obtained with Car-Parrinello dynamics. Analysis of the emission transition obtained using CIS(D)/aug-cc-pVDZ on statistically uncorrelated solute-solvent structures, composed of acetone and twelve explicit water molecules embedded in the electrostatic field of remaining 263 water molecules, corroborates that the solvent effect is mild, calculated here between 80 and 380 cm (1). (c) 2010 Published by Elsevier B.V.

(85)Rb Bose-Einstein condensate with tunable interaction: A quantum many body approach

We present a quantum many body approach with van der Waal type of interaction to achieve (85)Rb Bose-Einstein condensate with tunable interaction which has been produced by magnetic field induced Feshbach resonance in the JILA experiment. (C) 2008 Elsevier B.V. All rights reserved.

Signature of the interaction between dark energy and dark matter in galaxy clusters

We investigate the influence of ail interaction between dark energy and dark matter upon the dynamics of galaxy clusters. We obtain file general Layser-Irvine equation in the presence of interactions, and find how, in that case. the virial theorem stands corrected. Using optical, X-ray and weak lensing data from 33 relaxed galaxy clusters, we put constraints on the strength of the coupling between the dark sectors. Available data Suggests that this coupling is small but positive, indicating that dark energy might be decaying into dark matter. Systematic effects between the several mass estimates, however, should be better known, before definitive conclusions oil the magnitude and significance of this coupling could be established. (C) 2009 Published by Elsevier B.V.