Photochromic dithienylethene derivatives containing Ru(II) or Os(II) metal units. Sensitized photocyclization from a triplet state

Efficient photocyclization from a low-lying triplet state is reported for a photochromic dithienylperfluorocyclopentene with Ru(bpy)(3) units attached via a phenylene linker to the thiophene rings. The ring-closure reaction in the nanosecond domain is sensitized by the metal complexes. Upon photoexcitation into the lowest Ru-to-bpy (MLCT)-M-1 state followed by intersystem crossing to emitting (MLCT)-M-3 states, photoreactive (IL)-I-3 states are populated by an efficient energy-transfer process. The involvement of these (IL)-I-3 states explains the quantum yield of the photocyclization, which is independent of the excitation wavelength but decreases strongly in the presence of dioxygen. This behavior differs substantially from the photocyclization of the nonemissive dithienylperfluorocyclopentene free ligand, which occurs from the lowest (IL)-I-1 state on a picosecond time scale and is insensitive to oxygen quenching. Cyclic voltammetric studies have also been performed to gain further insight into the energetics of the system. The very high photocyclization quantum yields, far above 0.5 in both cases, are ascribed to the strong steric repulsion between the bulky substituents on the dithienylperfluorocyclopentene bridge bearing the chelating bipyridine sites or the Ru(bpy)(3) moieties, forcing the system to adopt nearly exclusively the reactive antiparallel conformation. In contrast, replacement of both Ru(II) centers by Os(II) completely prevents the photocyclization reaction upon light excitation into the low-lying Os-to-bpy (MLCT)-M-1 state. The photoreaction can only be triggered by optical population of the higher lying (IL)-I-1 excited state of the central photochromic unit, but its yield is low due to efficient energy transfer to the luminescent lowest (MLCT)-M-3 state.

Synthesis, spectroscopy and spectroelectrochemistry of chlorocarbonyl {1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene-kappa(2)-N,N '}rhodium (I)

Reaction of the dinuclear complex [{Rh(CO)(2)}(2) (mu-Cl)(2)]with an alpha-diimine ligand, 1,2- bis[(2,6-diisopropylphenyl) imino] acenaphthene (iPr(2)Ph-bian), produces square-planar [RhCl(CO)(iPr(2)Ph-bian)]. For the first time, 2: 1 and 1: 1 alpha-diimine/dimer reactions yielded the same product. The rigidity of iPr(2)Ph-bian together with its flexible electronic properties and steric requirements of the 2,6-diisopropyl substituents on the benzene rings allow rapid closure of a chelate bond and replacement of a CO ligand instead of chloride. A resonance Raman study of [RhCl(CO)(iPr(2)Ph-bian)] has revealed a predominant Rh-to-bian charge transfer (MLCT) character of electronic transitions in the visible spectral region. The stabilisation of [RhCl(CO)(iPr(2)Ph-bian)] in lower oxidation states by the pi-acceptor iPr(2)Ph-bian ligand was investigated in situ by UV-VIS, IR and EPR spectroelectrochemistry at variable temperatures. The construction of the novel UV-VIS-NIR-IR low-temperature OTTLE cell used in these studies is described in the last part of the paper.

Kinetic studies of reactions of organosilylenes: what have they taught us?

Rate constants for bimolecular reactions, obtained through time-resolved kinetic studies both in the gas and liquid phases are reviewed. Data for reactions of MeSiH, PhSiH, ClSiH, SiCl2, SiMe2, MeSiPh, SiPh2 and SiMes(2) are covered. Where possible, substituent effects relative to SiH2 have been obtained. These demonstrate widely varying effects between different types of reaction, which aids mechanistic understanding. Reactivities are high for all silylenes, but substituents can reduce them by both electronic and steric effects. The gas and liquid phase data (mainly for SiMe2) are compared and appear to be reasonably consistent. This review, although detailed, is not comprehensive.

Proof of concept of automated mapping of weeds in arable fields

The project investigated whether it would be possible to remove the main technical hindrance to precision application of herbicides to arable crops in the UK, namely creating geo-referenced weed maps for each field. The ultimate goal is an information system so that agronomists and farmers can plan precision weed control and create spraying maps. The project focussed on black-grass in wheat, but research was also carried out on barley and beans and on wild-oats, barren brome, rye-grass, cleavers and thistles which form stable patches in arable fields. Farmers may also make special efforts to control them. Using cameras mounted on farm machinery, the project explored the feasibility of automating the process of mapping black-grass in fields. Geo-referenced images were captured from June to December 2009, using sprayers, a tractor, combine harvesters and on foot. Cameras were mounted on the sprayer boom, on windows or on top of tractor and combine cabs and images were captured with a range of vibration levels and at speeds up to 20 km h-1. For acceptability to farmers, it was important that every image containing black-grass was classified as containing black-grass; false negatives are highly undesirable. The software algorithms recorded no false negatives in sample images analysed to date, although some black-grass heads were unclassified and there were also false positives. The density of black-grass heads per unit area estimated by machine vision increased as a linear function of the actual density with a mean detection rate of 47% of black-grass heads in sample images at T3 within a density range of 13 to 1230 heads m-2. A final part of the project was to create geo-referenced weed maps using software written in previous HGCA-funded projects and two examples show that geo-location by machine vision compares well with manually-mapped weed patches. The consortium therefore demonstrated for the first time the feasibility of using a GPS-linked computer-controlled camera system mounted on farm machinery (tractor, sprayer or combine) to geo-reference black-grass in winter wheat between black-grass head emergence and seed shedding.

A simplified, high-yield synthesis, and crystal structure of [tris{bis(2,4,6-triisopropylphenyl)tin}]

The species [{Sn(C2H2iPr3-2,4,6)2}3] has been obtained in a simple, essentially quantitative, synthesis from SnCl2 and ArLi in diethyl ether at low temperature. The crystal structure analysis confirms the trimeric nature of the molecular units but reveals some unusual features. The crystal contains the unusual feature of an asymmetric unit that consists of three units of [{SnAr2}3] in P21/c; the molecular unit is a scalene triangle, showing high consistency between the three molecules, in contrast to analogous trimeric species of silicon or germanium. The SnSn bonds are lengthened (average value 2.942 Å) owing to steric crowding.

Discerning policy and drivers for sustainable facilities management practice

Due to the changing nature of the facilities management (FM) profession, facilities managers are increasingly engaged with the evolving sustainability agenda in the UK and the development or uptake of sustainability policies within their organisations. This study investigates how facilities managers are engaging with the sustainability agenda and the drivers, policy issues and information they use to improve their sustainability performance management. A web based self-administered questionnaire survey of facilities managers in the UK was conducted to identify drivers and issues that influence and support good sustainable practices. A total of 268 facilities managers responded. The results indicate that legislation is the most important driver for the implementation of sustainable practices. Corporate image and Organisational ethos are also recognised. However demand for efficient monitoring, management and reporting on environmental impact is not highly rated even though the top three issues of sustainability managed by facilities managers are energy management, waste and recycling management and carbon footprint. In addition, facilities managers are expected to take ownership of activities assigned to the reduction of carbon emission. Government industries and organisation with high turnover are more likely to have a sustainability policy. Financial constraints are the main barriers while legislations are the main driver for implementing sustainability. For non-profit organisations and the charitable sector, financial constraints are no hindrance to implementing a sustainability policy. The conclusion drawn is that sustainability agendas continue to be influenced by regulated environmental issues rather than a balanced approach which takes into consideration the wider social and economic aspects of sustainability. While this scenario is far from ideal, the expectation is that the organisation will trust FM to take a vital role in delivering a comprehensive sustainability policy due to the rising tide of legislation, public scrutiny, as well as the needed business case for genuinely embracing sustainability. However, as the integration of sustainability with core business strategies is continuously evolving the emphasis on different drivers will vary from organisation to organisation as well as the responsibilities of facilities managers.

Effect of a methyl group on the spontaneous resolution of a square-pyramidal coordination compound: crystal packing and conglomerate formation

Reaction of [Cu(pic)2]·2H2O (where pic stands for 2-picolinato) with 2-({[2-(dimethylamino)ethyl]amino}methyl)phenol (HL1) produces the square-pyramidal complex [CuL1(pic)] (1), which crystallizes as a conglomerate (namely a mixture of optically pure crystals) in the Sohncke space group P212121. The use of the methylated ligand at the benzylic position, i.e. (±)-2-(1-{[2-(dimethylamino)ethyl]amino}ethyl)phenol (HL2), yields the analogous five-coordinate complex [CuL2(pic)] (2) that crystallizes as a true racemate (namely the crystals contain both enantiomers) in the centrosymmetric space group P21/c. Density functional theory (DFT) calculations indicate that the presence of the methyl group indeed leads to a distinct crystallization behaviour, not only by intramolecular steric effects, but also because its involvement in non-covalent C–H···π and hydrophobic intermolecular contacts appears to be an important factor contributing to the crystal-lattice (stabilizing) energy of 2

Foreword: International Space Science Institute (ISSI) workshop on the Earth’s cryosphere and sea level change

Rising sea level is perhaps the most severe consequence of climate warming, as much of the world’s population and infrastructure is located near current sea level (Lemke et al. 2007). A major rise of a metre or more would cause serious problems. Such possibilities have been suggested by Hansen and Sato (2011) who pointed out that sea level was several metres higher than now during the Holsteinian and Eemian interglacials (about 250,000 and 120,000 years ago, respectively), even though the global temperature was then only slightly higher than it is nowadays. It is consequently of the utmost importance to determine whether such a sea level rise could occur and, if so, how fast it might happen. Sea level undergoes considerable changes due to natural processes such as the wind, ocean currents and tidal motions. On longer time scales, the sea level is influenced by steric effects (sea water expansion caused by temperature and salinity changes of the ocean) and by eustatic effects caused by changes in ocean mass. Changes in the Earth’s cryosphere, such as the retreat or expansion of glaciers and land ice areas, have been the dominant cause of sea level change during the Earth’s recent history. During the glacial cycles of the last million years, the sea level varied by a large amount, of the order of 100 m. If the Earth’s cryosphere were to disappear completely, the sea level would rise by some 65 m. The scientific papers in the present volume address the different aspects of the Earth’s cryosphere and how the different changes in the cryosphere affect sea level change. It represents the outcome of the first workshop held within the new ISSI Earth Science Programme. The workshop took place from 22 to 26 March, 2010, in Bern, Switzerland, with the objective of providing an in-depth insight into the future of mountain glaciers and the large land ice areas of Antarctica and Greenland, which are exposed to natural and anthropogenic climate influences, and their effects on sea level change. The participants of the workshop are experts in different fields including meteorology, climatology, oceanography, glaciology and geodesy; they use advanced space-based observational studies and state-of-the-art numerical modelling.

Pairwise assembly of organopalladium(II) units with cyanurato(3-) and trithiocyanurato(3-) ligands: formation of chiral Pd12, Pd10 and Pd9 cage-molecules

The o-palladated, chloro-bridged dimers [Pd{2-phenylpyridine(-H)}-μ-Cl]2 and [Pd{N,N-dimethylbenzylamine(-H)}-μ-Cl]2 react with cyanuric acid in the presence of base to afford closed, chiral cage-molecules in which twelve organo-Pd(II) centers, located in pairs at the vertices of an octahedron, are linked by four tetrahedrally-arranged cyanurato(3-) ligands. Incomplete (Pd10) cages, having structures derived from the corresponding Pd12 cages by replacing one pair of organopalladium centers with two protons, have also been isolated. Reaction of [Pd{2-phenylpyridine(-H)}-μ-Cl]2 with trithiocyanuric acid gives an entirely different and more open type of cage-complex, comprising only nine organopalladium centers and three thiocyanurato(3-) ligands: cage-closure in this latter system appears to be inhibited by steric crowding of the thiocarbonyl groups.

The drivers of projected North Atlantic sea level change

Sea level change predicted by the CMIP5 atmosphere–ocean general circulation models (AOGCMs) is not spatially homogeneous. In particular, the sea level change in the North Atlantic is usually characterised by a meridional dipole pattern with higher sea level rise north of 40°N and lower to the south. The spread among models is also high in that region. Here we evaluate the role of surface buoyancy fluxes by carrying out simulations with the FAMOUS low-resolution AOGCM forced by surface freshwater and heat flux changes from CO2-forced climate change experiments with CMIP5 AOGCMs, and by a standard idealised surface freshwater flux applied in the North Atlantic. Both kinds of buoyancy flux change lead to the formation of the sea level dipole pattern, although the effect of the heat flux has a greater magnitude, and is the main cause of the spread of results among the CMIP5 models. By using passive tracers in FAMOUS to distinguish between additional and redistributed buoyancy, we show that the enhanced sea level rise north of 40°N is mainly due to the direct steric effect (the reduction of sea water density) caused by adding heat or freshwater locally. The surface buoyancy forcing also causes a weakening of the Atlantic meridional overturning circulation, and the consequent reduction of the northward ocean heat transport imposes a negative tendency on sea level rise, producing the reduced rise south of 40°N. However, unlike previous authors, we find that this indirect effect of buoyancy forcing is generally less important than the direct one, except in a narrow band along the east coast of the US, where it plays a major role and leads to sea level rise, as found by previous authors.

Another look at family adjustment

This chapter argues that in the international career context there is a need to conceptualise the adjustment of the family unit holistically. We discuss what that means and how it can be done. We note that to date the family has almost always been conceptualised as a hindrance to or a support for the working expatriate. However, in international assignments the family as a whole is expatriated and the family may become part of the expatriate resources with the line between work and family/personal life blurring. We draw on the Family Adjustment and Adaptation Response (FAAR) literature to argue that previous conceptions of adjustment have failed to capture the complexity of the process from the family perspective and we use that literature to develop our understanding of the process of adjustment of the family unit and suggest ways forward.

Spatial and temporal variations of the seasonal sea level cycle in the northwest Pacific

The seasonal sea level variations observed from tide gauges over 1900-2013 and gridded satellite altimeter product AVISO over 1993-2013 in the northwest Pacific have been explored. The seasonal cycle is able to explain 60-90% of monthly sea level variance in the marginal seas, while it explains less than 20% of variance in the eddy-rich regions. The maximum annual and semi-annual sea level cycles (30cm and 6cm) are observed in the north of the East China Sea and the west of the South China Sea respectively. AVISO was found to underestimate the annual amplitude by 25% compared to tide gauge estimates along the coasts of China and Russia. The forcing for the seasonal sea level cycle was identified. The atmospheric pressure and the steric height produce 8-12cm of the annual cycle in the middle continental shelf and in the Kuroshio Current regions separately. The removal of the two attributors from total sea level permits to identify the sea level residuals that still show significant seasonality in the marginal seas. Both nearby wind stress and surface currents can explain well the long-term variability of the seasonal sea level cycle in the marginal seas and the tropics because of their influence on the sea level residuals. Interestingly, the surface currents are a better descriptor in the areas where the ocean currents are known to be strong. Here, they explain 50-90% of inter-annual variability due to the strong links between the steric height and the large-scale ocean currents.

Defining key structural determinants for the pro-osteogenic activity of flavonoids

Epidemiological studies suggest that fruits and vegetables may play a role in promoting bone growth and preventing age-related bone loss, attributable, at least in part, to phytochemicals such as flavonoids stimulating osteoblastogenesis. Through systematically screening the effect of flavonoids on the osteogenic differentiation of human mesenchymal stem cells in vitro, and correlating activity with chemical structure using comparative molecular field analysis, we have successfully identified important structural features which relate to their activity, as well as reliably predicting the activity of compounds with unknown activity. Contour maps emphasised the importance of electronegativity, steric bulk, and a 2-C-3-C double bond at the flavonoid C-ring, as well as overall electropositivity and reduced steric bulk at the flavonoid B-ring. These results support a role for certain flavonoids in promoting osteogenic differentiation, thus their potential for preventing skeletal deterioration, as well as providing a foundation for the lead optimisation of novel bone anabolics.

CONSIDERATIONS ON THE REINTRODUCTION AND RECOVERY OF THE ALAGOAS CURASSOW MITU MITU (LINNAEUS, 1766) FROM EXTINCTION USING A POTENTIALLY HYBRID CAPTIVE STOCK

The Alagoas Curassow Mitu mitu is considered extinct in the wild. Since 1979, two females and a male caught in the wild have bred successfully in captivity, and, in 1990, hybridizations between M. mitu and Razor-billed Mitu M. tuberosum were performed. By June 2008, there were around 130 living birds in two different aviaries. We sequenced two regions of the mitochondrial DNA of both captive stocks of Alagoas Curassows. We unequivocally identified hybrids that have haplotype typical of M. tuberosum. However, unless the original studbook can be recovered there is no confident way to discriminate ""pure"" M. mitu birds for breeding and reintroduction purposes. Allied with morphological data gathered in an independent study, we suggest that conservation actions need to focus on specimens with diagnostic phenotypic characters of M. mitu, and avoid birds with mitochondria, genetic contribution of M. tuberosum. Although we have detected low levels of genetic variability among captive birds, the steady increase of the captive population suggests that inbreeding depression and hybridization are not a reproductive hindrance. Reintroduction of some of these potential hybrid birds in the original area of occurrence of the Alagoas Curassow may be the only hope to fill in the ecological niche left vacant. An educational program involving local communities to conserve future reintroduction of curassows and their restored habitat is highly recommended. Accepted 12 November 2009.

Sub-barrier fusion of two-neutron halo nuclei

The tunneling of composite systems, where breakup may occur during the barrier penetration process, is considered in connection with the fusion of halo-like radioactive, neutron- and proton-rich nuclei, on heavy targets. The large amount of recent and new data clearly indicates that breakup hinders the fusion at energies near and below the Coulomb barrier. However, clear evidence for enhancement due to halo properties seems to over ride the breakup hindrance at lower energies, owing, to a large extent, to the extended matter density distribution. In particular we report here that at sub-barrier energies the fusion cross section of the Borromean two-neutron halo nucleus (6)He with the actinide nucleus (238)U is significantly enhanced as compared to the fusion of a similar projectile with no halo. This conclusion differs from that of the original work, where it was claimed that no such enhancement ensues. This sub-barrier fusion enhancement is also observed in the (6)He + (209)Bi system. (C) 2010 Elsevier B.V. All rights reserved.