Synthesis, characterization and molecular structure of 1,1′ bis (diphenyl phosphino ferrocene) dioxide complex of the cis-uranyl dichloride

A 1,1' bis(diphenyl phosphino ferrocene) dioxide complex of the uranyl dichloride was synthesized and characterized by elemental analysis, H-1, P-31{H-1} NMR and X-ray diffraction methods. The structure of the compound shows that the uranium(VI) ion is surrounded by four oxygen and two chlorine atoms in an octahedral geometry. Two oxygen atoms from the bis (diphenyl phosphino ferrocene) dioxide and two chlorine atoms form a square planar arrangement. Two uranyl oxygen atoms occupy the axial positions. The bis(diphenyl phosphino ferrocene) dioxide ligand acts as a bidentate chelating ligand with a bite angle of 82.90(16)degrees around the uranyl group. The two chlorine atoms are mutually cis with a CI-U-Cl angle of 97.75(7)degrees.

The effects of explicit versus parameterized convection on the MJO in a large-domain high-resolution tropical case study. Part I: Characterization of large-scale organization and propagation

High-resolution simulations over a large tropical domain (∼20◦S–20◦N and 42◦E–180◦E) using both explicit and parameterized convection are analyzed and compared to observations during a 10-day case study of an active Madden-Julian Oscillation (MJO) event. The parameterized convection model simulations at both 40 km and 12 km grid spacing have a very weak MJO signal and little eastward propagation. A 4 km explicit convection simulation using Smagorinsky subgrid mixing in the vertical and horizontal dimensions exhibits the best MJO strength and propagation speed. 12 km explicit convection simulations also perform much better than the 12 km parameterized convection run, suggesting that the convection scheme, rather than horizontal resolution, is key for these MJO simulations. Interestingly, a 4 km explicit convection simulation using the conventional boundary layer scheme for vertical subgrid mixing (but still using Smagorinsky horizontal mixing) completely loses the large-scale MJO organization, showing that relatively high resolution with explicit convection does not guarantee a good MJO simulation. Models with a good MJO representation have a more realistic relationship between lower-free-tropospheric moisture and precipitation, supporting the idea that moisture-convection feedback is a key process for MJO propagation. There is also increased generation of available potential energy and conversion of that energy into kinetic energy in models with a more realistic MJO, which is related to larger zonal variance in convective heating and vertical velocity, larger zonal temperature variance around 200 hPa, and larger correlations between temperature and ascent (and between temperature and diabatic heating) between 500–400 hPa.

Optical characterization of the growth and spatial structure of a substorm onset arc

We present a detailed case study of the characteristics of auroral forms that constitute the first ionospheric signatures of substorm expansion phase onset. Analysis of the optical frequency and along-arc (azimuthal) wave number spectra provides the strongest constraint to date on the potential mechanisms and instabilities in the near-Earth magnetosphere that accompany auroral onset and which precede poleward arc expansion and auroral breakup. We evaluate the frequency and growth rates of the auroral forms as a function of azimuthal wave number to determine whether these wave characteristics are consistent with current models of the substorm onset mechanism. We find that the frequency, spatial scales, and growth rates of the auroral forms are most consistent with the cross-field current instability or a ballooning instability, most likely triggered close to the inner edge of the ion plasma sheet. This result is supportive of a near-Earth plasma sheet initiation of the substorm expansion phase. We also present evidence that the frequency and phase characteristics of the auroral undulations may be generated via resonant processes operating along the geomagnetic field. Our observations provide the most powerful constraint to date on the ionospheric manifestation of the physical processes operating during the first few minutes around auroral substorm onset.

Interaction of anthocyanins with human serum albumin: influence of pH and chemical structure on binding

The affinity of anthocyanins for human serum albumin (HSA) was determined by a fluorescence quenching method. The effects of pH and structure of anthocyanins on the binding constants were studied. The constants for binding of anthocyanins to HSA ranged from 1.08 x 10^5 M-1 to 13.16 x 10^5 M-1. A hydrophobic effect at acidic pH was shown by the relatively high positive entropy values under the conditions studied. Electrostatic interactions including hydrogen bonding contributed to the binding at pH 7.4. The effect of structure of anthocyanins on the affinity was pH dependent, particularly the effect of additional hydroxyl substituents. Hydroxyl substituents and glycosylation of anthocyanins decreased the affinity for binding to HSA at lower pH (especially pH 4), but increased the strength of binding at pH 7.4. In contrast, methylation of a hydroxyl group enhanced the binding at acidic pH, while this substitution reduced the strength of binding at pH 7.4. This paper has shown that changes in anthocyanin structure or reductions in pH, which may occur in the region of inflammatory sites, have an effect of the binding of anthocyanins to HSA.

Nonlinear wave-activity conservation laws and Hamiltonian structure for the two-dimensional anelastic equations

Exact, finite-amplitude, local wave-activity conservation laws are derived for disturbances to steady flows in the context of the two-dimensional anelastic equations. The conservation laws are expressed entirely in terms of Eulerian quantities, and have the property that, in the limit of a small-amplitude, slowly varying, monochromatic wave train, the wave-activity density A and flux F, when averaged over phase, satisfy F = cgA where cg is the group velocity of the waves. For nonparallel steady flows, the only conserved wave activity is a form of disturbance pseudoenergy; when the steady flow is parallel, there is in addition a conservation law for the disturbance pseudomomentum. The above results are obtained not only for isentropic background states (which give the so-called “deep form” of the anelastic equations), but also for arbitrary background potential-temperature profiles θ0(z) so long as the variation in θ0(z) over the depth of the fluid is small compared with θ0 itself. The Hamiltonian structure of the equations is established in both cases, and its symmetry properties discussed. An expression for available potential energy is also derived that, for the case of a stably stratified background state (i.e., dθ0/dz > 0), is locally positive definite; the expression is valid for fully three-dimensional flow. The counterparts to results for the two-dimensional Boussinesq equations are also noted.

Local and average structure in zinc cyanide: towards an understanding of the atomistic origin of negative thermal expansion

Neutron diffraction at 11.4 and 295 K and solid-state 67Zn NMR are used to determine both the local and average structures in the disordered, negative thermal expansion (NTE) material, Zn(CN)2. Solid-state NMR not only confirms that there is head-to-tail disorder of the C≡N groups present in the solid, but yields information about the relative abundances of the different Zn(CN)4-n(NC)n tetrahedral species, which do not follow a simple binomial distribution. The Zn(CN)4 and Zn(NC)4 species occur with much lower probabilities than are predicted by binomial theory, supporting the conclusion that they are of higher energy than the other local arrangements. The lowest energy arrangement is Zn(CN)2(NC)2. The use of total neutron diffraction at 11.4 K, with analysis of both the Bragg diffraction and the derived total correlation function, yields the first experimental determination of the individual Zn−N and Zn−C bond lengths as 1.969(2) and 2.030(2) Å, respectively. The very small difference in bond lengths, of ~0.06 Å, means that it is impossible to obtain these bond lengths using Bragg diffraction in isolation. Total neutron diffraction also provides information on both the average and local atomic displacements responsible for NTE in Zn(CN)2. The principal motions giving rise to NTE are shown to be those in which the carbon and nitrogen atoms within individual Zn−C≡N−Zn linkages are displaced to the same side of the Zn···Zn axis. Displacements of the carbon and nitrogen atoms to opposite sides of the Zn···Zn axis, suggested previously in X-ray studies as being responsible for NTE behavior, in fact make negligible contribution at temperatures up to 295 K.

Horizontal and vertical structure of the Eyjafjallajökull ash cloud over the UK: a comparison of airborne lidar observations and simulations

During April and May 2010 the ash cloud from the eruption of the Icelandic volcano Eyjafjallajökull caused widespread disruption to aviation over northern Europe. The location and impact of the eruption led to a wealth of observations of the ash cloud were being obtained which can be used to assess modelling of the long range transport of ash in the troposphere. The UK FAAM (Facility for Airborne Atmospheric Measurements) BAe-146-301 research aircraft overflew the ash cloud on a number of days during May. The aircraft carries a downward looking lidar which detected the ash layer through the backscatter of the laser light. In this study ash concentrations derived from the lidar are compared with simulations of the ash cloud made with NAME (Numerical Atmospheric-dispersion Modelling Environment), a general purpose atmospheric transport and dispersion model. The simulated ash clouds are compared to the lidar data to determine how well NAME simulates the horizontal and vertical structure of the ash clouds. Comparison between the ash concentrations derived from the lidar and those from NAME is used to define the fraction of ash emitted in the eruption that is transported over long distances compared to the total emission of tephra. In making these comparisons possible position errors in the simulated ash clouds are identified and accounted for. The ash layers seen by the lidar considered in this study were thin, with typical depths of 550–750 m. The vertical structure of the ash cloud simulated by NAME was generally consistent with the observed ash layers, although the layers in the simulated ash clouds that are identified with observed ash layers are about twice the depth of the observed layers. The structure of the simulated ash clouds were sensitive to the profile of ash emissions that was assumed. In terms of horizontal and vertical structure the best results were obtained by assuming that the emission occurred at the top of the eruption plume, consistent with the observed structure of eruption plumes. However, early in the period when the intensity of the eruption was low, assuming that the emission of ash was uniform with height gives better guidance on the horizontal and vertical structure of the ash cloud. Comparison of the lidar concentrations with those from NAME show that 2–5% of the total mass erupted by the volcano remained in the ash cloud over the United Kingdom.

Synthesis and Electronic Structure of Dissymmetrical, Naphthalene-Bridged Sandwich Complexes [Cp′Fe(μ‑C10H8)MCp*]x (x = 0, +1; M =Fe, Ru; Cp′ = η5‑C5H2‑1,2,4‑tBu3; Cp* = η5‑C5Me5)

The dissymmetrical naphthalene-bridged complexes [Cp′Fe(μ-C10H8)FeCp*] (3; Cp* = η5-C5Me5, Cp′ = η5-C5H2-1,2,4-tBu3) and [Cp′Fe(μ-C10H8)RuCp*] (4) were synthesized via a one-pot procedure from FeCl2(thf)1.5, Cp′K, KC10H8, and [Cp* FeCl(tmeda)] (tmeda = N,N,N′,N′- tetramethylethylenediamine) or [Cp*RuCl]4, respectively. The symmetrically substituted iron ruthenium complex [Cp*Fe(μ-C10H8)RuCp*] (5) bearing two Cp* ligands was prepared as a reference compound. Compounds 3−5 are diamagnetic and display similar molecular structures, where the metal atoms are coordinated to opposite sides of the bridging naphthalene molecule. Cyclic voltammetry and UV/vis spectroelectrochemistry studies revealed that neutral 3−5 can be oxidized to monocations 3+−5+ and dications 32+−52+. The chemical oxidation of 3 and 4 with [Cp2Fe]PF6 afforded the paramagnetic hexafluorophosphate salts [Cp′Fe(μ-C10H8)FeCp*]PF6 ([3]PF6) and [Cp′Fe(μ-C10H8)RuCp*]PF6 ([4]PF6), which were characterized by various spectroscopic techniques, including EPR and 57Fe Mössbauer spectroscopy. The molecular structure of [4]PF6 was determined by X-ray crystallography. DFT calculations support the structural and spectroscopic data and determine the compositions of frontier molecular orbitals in the investigated complexes. The effects of substituting Cp* with Cp′ and Fe with Ru on the electronic structures and the structural and spectroscopic properties are analyzed.

Futures trading, spot price volatility and market efficiency: evidence from European real estate securities futures

In 2007 futures contracts were introduced based upon the listed real estate market in Europe. Following their launch they have received increasing attention from property investors, however, few studies have considered the impact their introduction has had. This study considers two key elements. Firstly, a traditional Generalized Autoregressive Conditional Heteroskedasticity (GARCH) model, the approach of Bessembinder & Seguin (1992) and the Gray’s (1996) Markov-switching-GARCH model are used to examine the impact of futures trading on the European real estate securities market. The results show that futures trading did not destabilize the underlying listed market. Importantly, the results also reveal that the introduction of a futures market has improved the speed and quality of information flowing to the spot market. Secondly, we assess the hedging effectiveness of the contracts using two alternative strategies (naïve and Ordinary Least Squares models). The empirical results also show that the contracts are effective hedging instruments, leading to a reduction in risk of 64 %.

'Doctor, Doctor...' entrepreneurial diagnosis and market making

Doctor-patient jokes are universally popular because of the information asymmetries within the diagnostic relationship. We contend that entrepreneurial diagnosis is present in markets where consumers are unable to diagnose their own problems and, instead, may rely on the entrepreneur to diagnose them. Entrepreneurial diagnosis is a cognitive skill possessed by the entrepreneur. It is an identifiable subset of entrepreneurial judgment and can be modeled – which we attempt to do. In order to overcome the information asymmetries and exploit opportunities, we suggest that entrepreneurs must invest in market making innovations (as distinct from product innovations) such as trustworthy reputations. The diagnostic entrepreneur described in this paper represents a creative response to difficult diagnostic problems and helps to explain the success of many firms whose products are not particularly innovative but which are perceived as offering high standards of service. These firms are trusted not only for their truthfulness about the quality of their product, but for their honesty, confidentiality and understanding in helping customers identify the most appropriate product to their needs.