A hexadecanuclear copper(I)-copper(II) mixed-valence compound: structure, magnetic properties, intervalence charge transfer, EPR, and NMR

Hexadecanuclear copper mixed-valence complex 2 containing 10 Cu-II, centers and 6 Cu-I centers was isolated with N,O donor ligands. From the X-ray crystal structure, 2 was found to contain a centrosymmetric dimeric cation - each monomeric unit composed of eight copper centers. It displays a very broad and weak intervalence charge-transfer band around 1100 nm at room temperature in the solid state. Variable-temperature magnetic susceptibility measurements indicate an S = 1/2 ground state for half of 2, explicitly, each Cu-8 moiety has a g value around 2.26. Complex 2 was examined by NMR spectroscopy at room temperature in solution and by EPR at low temperature; the data indicates that the valence is delocalized in 2 at room temperature but localized at low temperature. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Novel charge transfer supramolecular assemblies with Keggin anions and 2-amino-5-nitropyridine

Several novel compounds with the non-linear optical chromophore 2-amino-5-nitropyridine (2A5NP) and Keggin polyoxoanions (alpha-isomers), having the general formula (2A5NP)(m)H-n[XM12O40]center dot xH(2)O, M = Mo, W, were synthesised. Compounds were obtained with X = P, n = 3, m = 3 and 4 and X = Si, n = m = 4 ( x = 2 - 6). Thus, for each of the anions [PMo12O40](3-) and [PW12O40](3-) two different compounds were obtained, with the same anion and organic counterpart but with a different stoichiometric ratio. These presented different charge transfer properties and thermal stability. All compounds were characterised by spectroscopic and analytical techniques. The single crystal X-ray diffraction structure of (2A5NP)(4)H-3[PMo12O40]center dot 2.5H(2)O center dot 0.5C(2)H(5)OH showed that the water solvent molecules and the organic chromophores are assembled via infinite one-dimensional chains of hydrogen bonds with formation of open channels, which accommodate [ PMo12O40] 3- and ethanol solvent molecules.

Facile photoinduced charge separation through a cyanoacetylide bridge in a heterobimetallic Fe(II)-Re(I) complex

Photoinduced Fe-to-bpy charge transfer in [{Cp(dppe)Fe}-(mu-C CC N){Re(CO)(3)(bpy)}]PF6 has been observed by ps-TRIR spectroscopy, supported by UV-Vis/IR spectroelectrochemistry and DFT calculations.

An investigation and comparison of the bioactivity of selected essential oils on human lice and house dust mites

The insecticidal potency of some essential oils suggests that they may find an application in the control of house dust mites, but current in vitro assays for mites do not appear to give consistent results. A simple, novel, mite chamber assay was therefore developed to carry out testing. Different species of insects are susceptible to different essential oil components, so we compared the relative acaricidal and pediculicidal activity of three essential oils: tea tree, lavender and lemon, because the activity of their constituents on lice ranges from highly active to virtually inactive. The most effective essential oil against both lice and mites was tea tree oil; lavender was the second most effective, and lemon oil the least, although it did show activity against mites, unlike lice. The assay proved simple and effective and gave reproducible results. (c) 2007 Elsevier B.V. All rights reserved.

U.K. HiGEM: Simulations of desert dust and biomass burning aerosols with a high-resolution atmospheric GCM

The atmospheric component of the United Kingdom’s new High-resolution Global Environmental Model (HiGEM) has been run with interactive aerosol schemes that include biomass burning and mineral dust. Dust emission, transport, and deposition are parameterized within the model using six particle size divisions, which are treated independently. The biomass is modeled in three nonindependent modes, and emissions are prescribed from an external dataset. The model is shown to produce realistic horizontal and vertical distributions of these aerosols for each season when compared with available satellite- and ground-based observations and with other models. Combined aerosol optical depths off the coast of North Africa exceed 0.5 both in boreal winter, when biomass is the main contributor, and also in summer, when the dust dominates. The model is capable of resolving smaller-scale features, such as dust storms emanating from the Bode´ le´ and Saharan regions of North Africa and the wintertime Bode´ le´ low-level jet. This is illustrated by February and July case studies, in which the diurnal cycles of model variables in relation to dust emission and transport are examined. The top-of-atmosphere annual mean radiative forcing of the dust is calculated and found to be globally quite small but locally very large, exceeding 20 W m22 over the Sahara, where inclusion of dust aerosol is shown to improve the model radiative balance. This work extends previous aerosol studies by combining complexity with increased global resolution and represents a step toward the next generation of models to investigate aerosol–climate interactions. 1. Introduction Accurate modeling of mineral dust is known to be important because of its radiative impact in both numerical weather prediction models (Milton et al. 2008; Haywood et

Charge transfer in Cr adsorption and reaction at the rutile TiO2(110) surface

The rutile TiO2(110) surface has been doped with sub-monolayer metallic Cr, which oxidises and donates charge to specific surface Ti ions. X-Ray and ultra violet photoemission spectroscopy and first principles density functional theory with Hubbard U are used to assign the oxidation states of Cr and surface Ti and we find that Cr2+ forms on bridging oxygen ions and a 5-fold coordinated surface Ti atom is reduced to Ti3+ and the Cr ions readily react with oxygen (to Cr3+), which leads to depletion of surface Ti3+ 3d electrons.

Ultrafast charge separation in a photoreactive rhenium-appended porphyrin assembly monitored by picosecond transient infrared spectroscopy

Rhenium(bipyridine)(tricarbonyl)(picoline) units have been linked covalently to tetraphenylmetalloporphyrins of magnesium and zinc via an amide bond between the bipyridine and one phenyl substituent of the porphyrin. The resulting complexes, abbreviated as [Re(CO)(3)(Pic)Bpy-MgTPP][OTf] and [Re(CO)(3)(Pic)Bpy-ZnTPP][OTf], exhibit no signs of electronic interaction between the Re(CO)(3)(bpy) units and the metalloporphyrin units in their ground states. However, emission spectroscopy reveals solvent-dependent quenching of porphyrin emission on irradiation into the long-wavelength absorption bands localized on the porphyrin. The characteristics of the excited states have been probed by picosecond time-resolved absorption (TRVIS) spectroscopy and time-resolved infrared (TRIR) spectroscopy in nitrile solvents. The presence of the charge-separated state involving electron transfer from MgTPP or ZnTPP to Re(bpy) is signaled in the TRIR spectra by a low-frequency shift in the nu(CO) bands of the Re(CO)(3) moiety similar to that observed by spectroelectrochemical reduction. Long-wavelength excitation of [Re(CO)(3)(Pic)Bpy-MTPP][OTf] results in characteristic TRVIS spectra of the S-1 state of the porphyrin that decay with a time constant of 17 ps (M = Mg) or 24 ps (M = Zn). The IR bands of the CS state appear on a time scale of less than 1 ps (Mg) or ca. 5 ps (Zn) and decay giving way to a vibrationally excited (i.e., hot) ground state via back electron transfer. The IR bands of the precursors recover with a time constant of 35 ps (Mg) or 55 ps (Zn). The short lifetimes of the charge-transfer states carry implications for the mechanism of reaction in the presence of triethylamine.

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Effect of headgroup size, charge, and solvent structure on polymer−micelle interactions, studied by molecular dynamics simulations

We performed atomistic molecular dynamics simulations of anionic and cationic micelles in the presence of poly(ethylene oxide) (PEO) to understand why nonionic water-soluble polymers such as PEO interact strongly with anionic micelles but only weakly with cationic micelles. Our micelles include sodium n-dodecyl sulfate (SDS), n-dodecyl trimethylammonium chloride (DTAC), n-dodecyl ammonium chloride (DAC), and micelles in which we artificially reverse the sign of partial charges in SDS and DTAC. We observe that the polymer interacts hydrophobically with anionic SDS but only weakly with cationic DTAC and DAC, in agreement with experiment. However, the polymer also interacts with the artificial anionic DTAC but fails to interact hydrophobically with the artificial cationic SDS, illustrating that large headgroup size does not explain the weak polymer interaction with cationic micelles. In addition, we observe through simulation that this preference for interaction with anionic micelles still exists in a dipolar "dumbbell" solvent, indicating that water structure and hydrogen bonding alone cannot explain this preferential interaction. Our simulations suggest that direct electrostatic interactions between the micelle and polymer explain the preference for interaction with anionic micelles, even though the polymer overall carries no net charge. This is possible given the asymmetric distribution of negative charges on smaller atoms and positive charges oil larger units in the polymer chain.

Correlation between regioselectivity and site charge in propene polymerisation catalysed by metallocene

The reactions of propene with [Zr(cyclopentadienyl)(2)Me](+) have been investigated using density functional theory in order to study the correlation between regioselectivity and site charge in propene polymerisation. The reaction paths of the 1,2 and 2,1 additions of the methyl group to propene have been established. The geometries and energies of the reactants, transition states and products have been obtained using both PBEPBE/LANL2DZ and B3LYP/LANL2DZ methodologies. The results with both density functionals show that the activation energy for 1,2-insertion is lower than that for 2,1-insertion (Fig. 5) and this is consistent with the experiment results. Also for both density functionals, the difference of the thermal dynamic driving forces between the 2,1 product named 2-21 and the 1,2 product named 2-12 is significantly lower than the difference between the energy barriers. It is noted that in the reactants, the Mulliken partial charge on the central carbon atom C2 is positive and it can be concluded that 1,2-insertion is favoured because it can proceed via a cationic reaction.

Motivation, rationale and key results from the GERBILS Saharan dust measurement campaign

The Geostationary Earth Radiation Budget Intercomparison of Longwave and Shortwave radiation (GERBILS) was an observational field experiment over North Africa during June 2007. The campaign involved 10 flights by the FAAM BAe-146 research aircraft over southwestern parts of the Sahara Desert and coastal stretches of the Atlantic Ocean. Objectives of the GERBILS campaign included characterisation of mineral dust geographic distribution and physical and optical properties, assessment of the impact upon radiation, validation of satellite remote sensing retrievals, and validation of numerical weather prediction model forecasts of aerosol optical depths (AODs) and size distributions. We provide the motivation behind GERBILS and the experimental design and report the progress made in each of the objectives. We show that mineral dust in the region is relatively non-absorbing (mean single scattering albedo at 550 nm of 0.97) owing to the relatively small fraction of iron oxides present (1–3%), and that detailed spectral radiances are most accurately modelled using irregularly shaped particles. Satellite retrievals over bright desert surfaces are challenging owing to the lack of spectral contrast between the dust and the underlying surface. However, new techniques have been developed which are shown to be in relatively good agreement with AERONET estimates of AOD and with each other. This encouraging result enables relatively robust validation of numerical models which treat the production, transport, and deposition of mineral dust. The dust models themselves are able to represent large-scale synoptically driven dust events to a reasonable degree, but some deficiencies remain both in the Sahara and over the Sahelian region, where cold pool outflow from convective cells associated with the intertropical convergence zone can lead to significant dust production.

Last charge of the knights? Iraq, Afghanistan and the special relationship

At the heart of the ‘special relationship’ ideology, there is supposed to be a grand bargain. In exchange for paying the ‘blood price’ as America's ally, Britain will be rewarded with exceptional influence over American foreign policy and its strategic behaviour. Soldiers and statesman continue to articulate this idea. Since 9/11, the notion of Britain playing ‘Greece’ to America's ‘Rome’ gained new life thanks to Anglophiles on both sides of the Atlantic. One potent version of this ideology was that the more seasoned British would teach Americans how to fight ‘small wars’ in Iraq and Afghanistan, thereby bolstering their role as tutor to the superpower. Britain does derive benefits from the Anglo-American alliance and has made momentous contributions to the wars in Afghanistan and Iraq. Yet British solidarity and sacrifices have not purchased special influence in Washington. This is partly due to Atlanticist ideology, which sets Britain unrealistic standards by which it is judged, and partly because the notion of ‘special influence’ is misleading as it loses sight of the complexities of American policy-making. The overall result of expeditionary wars has been to strain British credibility in American eyes and to display its lack of consistent influence both over high policy and the design and execution of US military campaigns. While there may be good arguments in favour of the UK continuing its efforts in Afghanistan, the notion that the war fortifies Britain's vicarious world status is a dangerous illusion that leads to repeated overstretch and disappointment. Now that Britain is in the foothills of a strategic defence review, it is important that the British abandon this false consciousness.

Service charge management

Service Charge Management is an area of concern to property managers acting for both property occupiers and investors. This paper reviews the background to service charge management in the UK, and examines, by means of a survey, the current state of service charge practice in the surveying profession.