Synthesis, characterization, crystal structure, and DNA-binding of ruthenium(II) complexes of heterocyclic nitrogen ligands resulting from a benzimidazole-based quinazoline derivative

The reaction of cis-[RuCl2(dmso)(4)] with [6-(2-pyridinyl)-5,6-dihydrobenzimidazo[1,2-c] quinazoline] (L) afforded in pure form a blue ruthenium(II) complex, [Ru(L-1)(2)] (1), where the original L changed to [2-(1H-benzoimidazol-2-yl)-phenyl]-pyridin-2-ylmethylene-amine (HL1). Treatment of RuCl3 center dot 3H(2)O with L in dry tetrahydrofuran in inert atmosphere led to a green ruthenium(II) complex, trans-[RuCl2(L-2)(2)] (2), where L was oxidized in situ to the neutral species 6-pyridin-yl-benzo[4,5]imidazo[1,2-c] quinazoline (L-2). Complex 2 was also obtained from the reaction of RuCl3 center dot 3H(2)O with L-2 in dry ethanol. Complexes 1 and 2 have been characterized by physico-chemical and spectroscopic tools, and 1 has been structurally characterized by single-crystal X-ray crystallography. The electrochemical behavior of the complexes shows the Ru(III)/Ru(II) couple at different potentials with quasi-reversible voltammograms. The interaction of these complexes with calf thymus DNA by using absorption and emission spectral studies allowed determination of the binding constant K-b and the linear Stern-Volmer quenching constant K-SV

Correlations between two sets of angular relation equations

It is shown here that the angular relation equations between direct and reciprocal vectors are very similar to the angular relation equations in Euler's theorem. These two sets of equations are usually treated separately as unrelated equations in different fields. In this careful study, the connection between the two sets of angular equations is revealed by considering the cosine rule for the spherical triangle. It is found that understanding of the correlation is hindered by the facts that the same variables are defined differently and different symbols are used to represent them in the two fields. Understanding the connection between different concepts is not only stimulating and beneficial, but also a fundamental tool in innovation and research, and has historical significance. The background of the work presented here contains elements of many scientific disciplines. This work illustrates the common ground of two theories usually considered separately and is therefore of benefit not only for its own sake but also to illustrate a general principle that a theory relevant to one discipline can often be used in another. The paper works with chemistry related concepts using mathematical methodologies unfamiliar to the usual audience of mainstream experimental and theoretical chemists.

Angular momentum conservation and gravity wave drag parameterization: implications for climate models

The robustness of the parameterized gravity wave response to an imposed radiative perturbation in the middle atmosphere is examined. When momentum is conserved and for reasonable gravity wave drag parameters, the response to a polar cooling induces polar downwelling above the region of the imposed cooling, with consequent adiabatic warming. This response is robust to changes in the gravity wave source spectrum, background flow, gravity wave breaking criterion, and model lid height. When momentum is not conserved, either in the formulation or in the implementation of the gravity wave drag parameterization, the response becomes sensitive to the above-mentioned factors—in particular to the model lid height. The spurious response resulting from nonconservation is found to be nonnegligible in terms of the total gravity wave drag–induced downwelling.

The angular momentum constraint on climate sensitivity and downward influence in the middle atmosphere

It is shown that under reasonable assumptions, conservation of angular momentum provides a strong constraint on gravity wave drag feedbacks to radiative perturbations in the middle atmosphere. In the time mean, radiatively induced temperature perturbations above a given altitude z cannot induce changes in zonal mean wind and temperature below z through feedbacks in gravity wave drag alone (assuming an unchanged gravity wave source spectrum). Thus, despite the many uncertainties in the parameterization of gravity wave drag, the role of gravity wave drag in middle-atmosphere climate perturbations may be much more limited than its role in climate itself. This constraint limits the possibilities for downward influence from the mesosphere. In order for a gravity wave drag parameterization to respect the momentum constraint and avoid spurious downward influence, any nonzero parameterized momentum flux at a model lid must be deposited within the model domain, and there must be no zonal mean sponge layer. Examples are provided of how violation of these conditions leads to spurious downward influence. For planetary waves, the momentum constraint does not prohibit downward influence, but it limits the mechanisms by which it can occur: in the time mean, downward influence from a radiative perturbation can only arise through changes in reflection and meridional propagation properties of planetary waves.

The domain derivative in rough-surface scattering and rigorous estimates for first-order perturbation theory

We investigate Fréchet differentiability of the scattered field with respect to variation in the boundary in the case of time–harmonic acoustic scattering by an unbounded, sound–soft, one–dimensional rough surface. We rigorously prove the differentiability of the scattered field and derive a characterization of the Fréchet derivative as the solution to a Dirichlet boundary value problem. As an application of these results we give rigorous error estimates for first–order perturbation theory, justifying small perturbation methods that have a long history in the engineering literature. As an application of our rigorous estimates we show that a plane acoustic wave incident on a sound–soft rough surface can produce an unbounded scattered field.

Simulations of angular momentum evolution in wind-fed CV precursors

It is thought that the secondary stars in cataclysmic variables (CVs) may undergo a period of mass loss in the form of a wind during the evolution of the system (Mullan et al. 1992). This wind is thought to magnetically brake the secondary star with a time-scale ~ 10^8 yr (e.g. van Paradijs 1986). When the secondary’s spin has been brought close to synchronism with the orbit it is possible for tidal torques to lock the secondary in synchronous rotation.

Synergistic angular and spectral estimation of aerosol properties using CHRIS/PROBA-1 and simulated Sentinel-3~data

A method has been developed to estimate Aerosol Optical Depth (AOD), Fine Mode Fraction (FMF) and Single Scattering Albedo (SSA) over land surfaces using simulated Sentinel-3 data. The method uses inversion of a coupled surface/atmosphere radiative transfer model, and includes a general physical model of angular surface reflectance. An iterative process is used to determine the optimum value of the aerosol properties providing the best fit of the corrected reflectance values for a number of view angles and wavelengths with those provided by the physical model. A method of estimating AOD using only angular retrieval has previously been demonstrated on data from the ENVISAT and PROBA-1 satellite instruments, and is extended here to the synergistic spectral and angular sampling of Sentinel-3 and the additional aerosol properties. The method is tested using hyperspectral, multi-angle Compact High Resolution Imaging Spectrometer (CHRIS) images. The values obtained from these CHRIS observations are validated using ground based sun-photometer measurements. Results from 22 image sets using the synergistic retrieval and improved aerosol models show an RMSE of 0.06 in AOD, reduced to 0.03 over vegetated targets.

Synergistic angular and spectral estimation of aerosol properties using CHRIS/PROBA-1 and simulated Sentinel-3 data

We develop a method to derive aerosol properties over land surfaces using combined spectral and angular information, such as available from ESA Sentinel-3 mission, to be launched in 2015. A method of estimating aerosol optical depth (AOD) using only angular retrieval has previously been demonstrated on data from the ENVISAT and PROBA-1 satellite instruments, and is extended here to the synergistic spectral and angular sampling of Sentinel-3. The method aims to improve the estimation of AOD, and to explore the estimation of fine mode fraction (FMF) and single scattering albedo (SSA) over land surfaces by inversion of a coupled surface/atmosphere radiative transfer model. The surface model includes a general physical model of angular and spectral surface reflectance. An iterative process is used to determine the optimum value of the aerosol properties providing the best fit of the corrected reflectance values to the physical model. The method is tested using hyperspectral, multi-angle Compact High Resolution Imaging Spectrometer (CHRIS) images. The values obtained from these CHRIS observations are validated using ground-based sun photometer measurements. Results from 22 image sets using the synergistic retrieval and improved aerosol models show an RMSE of 0.06 in AOD, reduced to 0.03 over vegetated targets.

Hydrodynamics with spin angular momentum from systematic coarse graining: a tutorial example

The derivation of time evolution equations for slow collective variables starting from a micro- scopic model system is demonstrated for the tutorial example of the classical, two-dimensional XY model. Projection operator techniques are used within a nonequilibrium thermodynamics framework together with molecular simulations in order to establish the building blocks of the hydrodynamics equations: Poisson brackets that determine the deterministic drift, the driving forces from the macroscopic free energy and the friction matrix. The approach is rather general and can be applied for deriving the equations of slow variables for a broad variety of systems.

Cloud information content analysis of multi-angular measurements in the oxygen A-band: application to 3MI and MSPI

The vertical distribution of cloud cover has a significant impact on a large number of meteorological and climatic processes. Cloud top altitude and cloud geometrical thickness are then essential. Previous studies established the possibility of retrieving those parameters from multi-angular oxygen A-band measurements. Here we perform a study and comparison of the performances of future instruments. The 3MI (Multi-angle, Multi-channel and Multi-polarization Imager) instrument developed by EUMETSAT, which is an extension of the POLDER/PARASOL instrument, and MSPI (Multi-angles Spectro-Polarimetric Imager) develoloped by NASA's Jet Propulsion Laboratory will measure total and polarized light reflected by the Earth's atmosphere–surface system in several spectral bands (from UV to SWIR) and several viewing geometries. Those instruments should provide opportunities to observe the links between the cloud structures and the anisotropy of the reflected solar radiation into space. Specific algorithms will need be developed in order to take advantage of the new capabilities of this instrument. However, prior to this effort, we need to understand, through a theoretical Shannon information content analysis, the limits and advantages of these new instruments for retrieving liquid and ice cloud properties, and especially, in this study, the amount of information coming from the A-Band channel on the cloud top altitude (CTOP) and geometrical thickness (CGT). We compare the information content of 3MI A-Band in two configurations and that of MSPI. Quantitative information content estimates show that the retrieval of CTOP with a high accuracy is possible in almost all cases investigated. The retrieval of CGT seems less easy but possible for optically thick clouds above a black surface, at least when CGT > 1–2 km.

Small states, great power? Gaining influence through intrinsic, derivative, and collective power

In recent years, scholars have devoted increased attention to the agency of small states in International Relations. However, the conventional wisdom remains that while not completely powerful, small states are unlikely to achieve much of significance when faced by great power opposition. This argument, however, implicitly rests on resource-based and compulsory understandings of power. This article explores the implicit connections between the concept of "small state" and diverse concepts of power, asking how we should understand these states' attempts to gain influence and achieve their international political objectives. By connecting the study of small states with additional understandings of power, the article elaborates the broader avenues for influence that are open to many states but are particularly relevant for small states. The article argues that small states' power can be best understood as originating in three categories: “derivative,” collective, and particular-intrinsic. Derivative power, coined by Michael Handel, relies upon the relationship with a great power. Collective power involves building coalitions of supportive states, often through institutions. Particular-intrinsic power relies on the assets of the small state trying to do the influencing. Small states specialize in the bases and means of these types of power, which may have unconventional compulsory, institutional, structural, and productive aspects.