Structure and magnetic properties of a tetranuclear Cu(II) complex containing the 2-(pyridine-2-yliminomethyl)-phenol ligand

A tetranuclear Cu(II) complex [Cu4L4(H2O)4](ClO4)4 has been synthesized using the terdentate Schiff base 2-(pyridine-2-yliminomethyl)-phenol (HL) (the condensation product of salicylaldehyde and 2-aminopyridine) and copper perchlorate. Chemical characterizations such as IR and UV/Vis of the complex have been carried out. A single-crystal diffraction study shows that the complex contains a nearly planar tetranuclear core containing four copper atoms, which occupy four equivalent five-coordinate sites with a square pyramidal environment. Magnetic measurements have been carried out over the temperature range 2–300K and with 100Oe field strengths. Analysis of magnetic susceptibility data indicates a strong antiferromagnetic (J1=−638cm−1) exchange interaction between diphenoxo-bridged Cu(II) centers and a moderate antiferromagnetic (J2=−34cm−1) interaction between N–C–N bridged Cu(II) centers. Magnetic exchange interactions (J’s) are also discussed on the basis of a computational study using DFT methodology. The spin density distribution (singlet ground state) is calculated to visualize the effect of delocalization of spin density through bridging groups.

Using coordinated observations in polarized white light and Faraday rotation to probe the spatial position and magnetic field of an interplanetary sheath

Coronal mass ejections (CMEs) can be continuously tracked through a large portion of the inner heliosphere by direct imaging in visible and radio wavebands. White light (WL) signatures of solar wind transients, such as CMEs, result from Thomson scattering of sunlight by free electrons and therefore depend on both viewing geometry and electron density. The Faraday rotation (FR) of radio waves from extragalactic pulsars and quasars, which arises due to the presence of such solar wind features, depends on the line-of-sight magnetic field component B ∥ and the electron density. To understand coordinated WL and FR observations of CMEs, we perform forward magnetohydrodynamic modeling of an Earth-directed shock and synthesize the signatures that would be remotely sensed at a number of widely distributed vantage points in the inner heliosphere. Removal of the background solar wind contribution reveals the shock-associated enhancements in WL and FR. While the efficiency of Thomson scattering depends on scattering angle, WL radiance I decreases with heliocentric distance r roughly according to the expression Ir –3. The sheath region downstream of the Earth-directed shock is well viewed from the L4 and L5 Lagrangian points, demonstrating the benefits of these points in terms of space weather forecasting. The spatial position of the main scattering site r sheath and the mass of plasma at that position M sheath can be inferred from the polarization of the shock-associated enhancement in WL radiance. From the FR measurements, the local B ∥sheath at r sheath can then be estimated. Simultaneous observations in polarized WL and FR can not only be used to detect CMEs, but also to diagnose their plasma and magnetic field properties.

Synthesis, characterisation and magnetic properties of a one-dimensional Iron(II) coordination polymer

A new iron(II) coordination polymer, [FeCl2(NC7H9)2(N2C12H12)], has been synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction. This material crystallizes in the monoclinic space group C2/c, with a = 11.2850(6), b = 13.8925(7), c = 17.0988(9) Å and β = 94.300(3)º (Z = 4). The crystal structure consists of neutral zig-zag chains, in which the iron(II) ions are octahedrally coordinated. The infinite polymer chains are packed into a three-dimensional structure through C–H···Cl interactions. Magnetic susceptibility measurements reveal the existence of weak antiferromagnetic interactions between the iron(II) ions. The effective magnetic moment, μ eff = 5.33 μ B , is consistent with a high-spin iron(II) configuration.

A comparison of cross-hole electrical and seismic data in fractured rock

Cross-hole anisotropic electrical and seismic tomograms of fractured metamorphic rock have been obtained at a test site where extensive hydrological data were available. A strong correlation between electrical resistivity anisotropy and seismic compressional-wave velocity anisotropy has been observed. Analysis of core samples from the site reveal that the shale-rich rocks have fabric-related average velocity anisotropy of between 10% and 30%. The cross-hole seismic data are consistent with these values, indicating that observed anisotropy might be principally due to the inherent rock fabric rather than to the aligned sets of open fractures. One region with velocity anisotropy greater than 30% has been modelled as aligned open fractures within an anisotropic rock matrix and this model is consistent with available fracture density and hydraulic transmissivity data from the boreholes and the cross-hole resistivity tomography data. However, in general the study highlights the uncertainties that can arise, due to the relative influence of rock fabric and fluid-filled fractures, when using geophysical techniques for hydrological investigations.

An observing system simulation experiment to evaluate the scientific merit of wind and ozone measurements from the future SWIFT instrument

(from author) One of the first papers in the peer-review literature to discuss an OSSE to evaluate future wind observations in the stratosphere. Provides key evidence to justify the construction of the SWIFT instrument (currently planned to be built by the Canadian Space Agency for launch on ~ 2010).

Coronal mass ejections and magnetic flux buildup in the heliosphere

To test for magnetic flux buildup in the heliosphere from coronal mass ejections (CMEs), we simulate heliospheric flux as a constant background open flux with a time-varying interplanetary CME (ICME) contribution. As flux carried by ejecta can only contribute to the heliospheric flux budget while it remains closed, the ICME flux opening rate is an important factor. Two separate forms for the ICME flux opening rate are considered: (1) constant and (2) exponentially decaying with time. Coronagraph observations are used to determine the CME occurrence rates, while in situ observations are used to estimate the magnetic flux content of a typical ICME. Both static equilibrium and dynamic simulations, using the constant and exponential ICME flux opening models, require flux opening timescales of ∼50 days in order to match the observed doubling in the magnetic field intensity at 1 AU over the solar cycle. Such timescales are equivalent to a change in the ICME closed flux of only ∼7–12% between 1 and 5 AU, consistent with CSE signatures; no flux buildup results. The dynamic simulation yields a solar cycle flux variation with high variability that matches the overall variability of the observed magnetic field intensity remarkably well, including the double peak forming the Gnevyshev gap.

Retrieval of effective ice crystal size in the infrared: sensitivity study and global measurements from TIROS-N Operational Vertical Sounder

The difference between cirrus emissivities at 8 and 11 μm is sensitive to the mean effective ice crystal size of the cirrus cloud, De. By using single scattering properties of ice crystals shaped as planar polycrystals, diameters of up to about 70 μm can be retrieved, instead of up to 45 μm assuming spheres or hexagonal columns. The method described in this article is used for a global determination of mean effective ice crystal sizes of cirrus clouds from TOVS satellite observations. A sensitivity study of the De retrieval to uncertainties in hypotheses on ice crystal shape, size distributions, and temperature profiles, as well as in vertical and horizontal cloud heterogeneities shows that uncertainties can be as large as 30%. However, the TOVS data set is one of few data sets which provides global and long-term coverage. Having analyzed the years 1987–1991, it was found that measured effective ice crystal diameters De are stable from year to year. For 1990 a global median De of 53.5 μm was determined. Averages distinguishing ocean/land, season, and latitude lie between 23 μm in winter over Northern Hemisphere midlatitude land and 64 μm in the tropics. In general, larger Des are found in regions with higher atmospheric water vapor and for cirrus with a smaller effective emissivity.

Validating ECMWF forecasts for the occurrence of ice supersaturation using visual observations of persistent contrails and radiosonde measurements over England

One of the largest uncertainties in quantifying the impact of aviation on climate concerns the formation and spreading of persistent contrails. The inclusion of a cloud scheme that allows for ice supersaturation into the integrated forecast system (IFS) of the European Centre for Medium-Range Weather Forecasts (ECMWF) can be a useful tool to help reduce these uncertainties. This study evaluates the quality of the ECMWF forecasts with respect to ice super saturation in the upper troposphere by comparing them to visual observations of persistent contrails and radiosonde measurements of ice supersaturation over England. The performance of 1- to 3-day forecasts is compared including also the vertical accuracy of the supersaturation forecasts. It is found that the operational forecasts from the ECMWF are able to predict cold ice supersaturated regions very well. For the best cases Peirce skill scores of 0.7 are obtained, with hit rates at times exceeding 80% and false-alarm rates below 20%. Results are very similar for comparisons with visual observations and radiosonde measurements, the latter providing the better statistical significance.

Forest fire plumes over the North Atlantic: p-TOMCAT model simulations with aircraft and satellite measurements from the ITOP/ICARTT campaign

Intercontinental Transport of Ozone and Precursors (ITOP) (part of International Consortium for Atmospheric Research on Transport and Transformation (ICARTT)) was an intense research effort to measure long-range transport of pollution across the North Atlantic and its impact on O3 production. During the aircraft campaign plumes were encountered containing large concentrations of CO plus other tracers and aerosols from forest fires in Alaska and Canada. A chemical transport model, p-TOMCAT, and new biomass burning emissions inventories are used to study the emissions long-range transport and their impact on the troposphere O3 budget. The fire plume structure is modeled well over long distances until it encounters convection over Europe. The CO values within the simulated plumes closely match aircraft measurements near North America and over the Atlantic and have good agreement with MOPITT CO data. O3 and NOx values were initially too great in the model plumes. However, by including additional vertical mixing of O3 above the fires, and using a lower NO2/CO emission ratio (0.008) for boreal fires, O3 concentrations are reduced closer to aircraft measurements, with NO2 closer to SCIAMACHY data. Too little PAN is produced within the simulated plumes, and our VOC scheme's simplicity may be another reason for O3 and NOx model-data discrepancies. In the p-TOMCAT simulations the fire emissions lead to increased tropospheric O3 over North America, the north Atlantic and western Europe from photochemical production and transport. The increased O3 over the Northern Hemisphere in the simulations reaches a peak in July 2004 in the range 2.0 to 6.2 Tg over a baseline of about 150 Tg.

Cyclins, cyclin-dependent kinases, and cyclin-dependent kinase inhibitors: detection methods and activity measurements

The cyclin/cyclin-dependent kinase (Cdk) complexes and the Cdk inhibitors (CDKI) are crucial regulators of cell cycle progression in all eukaryotic cells. Using rat cardiac myocytes as a model system, this chapter provides a detailed account of methods that can be employed to measure both cyclin/Cdk activity in cells and the extent of CDKI inhibitory activity present in a particular cell type.

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.

Dinuclear complexes of M-II thiocyanate (M = Ni and Cu) containing a tridentate Schiff-base ligand: synthesis, structural diversity and magnetic properties

A dinuclear Ni-II complex, [Ni-2(L)(2)(H2O)(NCS)(2)]center dot 3H(2)O (1) in which the metal atoms are bridged by one water molecule and two mu(2)-phenolate ions, and a thiocyanato-bridged dimeric Cull complex, [Cu(L)NCS](2) (2) [L = tridentate Schiff-base ligand, N-(3-aminopropyl)salicylaldimine, derived from 1:1 condensation of salicylaldehyde and 1,3-diaminopropane], have been synthesized and characterized by IR and UV/Vis spectroscopy, cyclic voltammetry and single-crystal X-ray diffraction studies. The structure of 1 consists of dinuclear units with crystallographic C-2 symmetry in which each Ni-II atom is in a distorted octahedral environment. The Ni-O distance and the Ni-O-Ni angle, through the bridged water molecule, are 2.240(11) angstrom and 82.5(5)degrees, respectively. The structure of 2 consists of dinuclear units bridged asymmetrically by di-mu(1,3)-NCS ions; each Cull ion is in a square-pyramidal environment with tau = 0.25. Variable-temperature magnetic susceptibility studies indicate the presence of dominant ferromagnetic exchange coupling in complex 1 with J = 3.1 cm(-1), whereas complex 2 exhibits weak antiferromagnetic coupling between the Cu-II centers with J = -1.7 cm(-1). ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)