Rhodium cationic complexes using dithioethers as chiral ligands. Application in styrene hydroformylation

Addition of the dithioethers (−)-DIOSR2 (R=Me, iPr) (2,3-O-isopropylidene-1,4-dimethyl (and diisopropyl) thioether-L-threitol) to a dichloromethane solution of [Rh(COD)2]ClO4 (COD=1,5-cyclooctadiene) yielded the mononuclear complexes [Rh(COD)(DIOSR2)]ClO4. X-ray diffraction methods showed that the [Rh(COD)(DIOSiPr2)]ClO4 complex had an square-planar coordination geometry at the rhodium atom with the iPr groups in anti position. Cyclooctadiene complexes react with carbon monoxide to form dinuclear tetracarbonylated complexes [(CO)2Rh(μ-DIOSR2)2(CO)2](ClO4)2. [Rh(COD)(DIOSR2)]ClO4 are active catalyst precursors in styrene hydroformylation at 30 atm and 65°C which give conversions of up to 99% with a regioselectivity in 2-phenylpropanal as high as 74%. In all cases enantioselectivities are low.

Structures, reactivity, and catalytic activity of dithiolato-bridged heterobimetallic MRh (M = Pt, Pd) complexes

Heterobimetallic complexes [(P−P)Pt(μ-S−S)Rh(cod)]ClO4 (P−P = (PPh3)2, Ph2P(CH2)3PPh2 (dppp), and Ph2P(CH2)4PPh2 (dppb); S−S = -S(CH2)2S- (EDT), -S(CH2)3S- (PDT), -S(CH2)4S- (BDT), cod = 1,5-cyclooctadiene) reacted with CO to form the carbonyl complexes [(P−P)Pt(μ-S−S)Rh(CO)2]ClO4 and then with PR3 ligands to give [(P−P)Pt(μ-S−S)Rh(CO)(PR3)]ClO4. The binuclear framework of these cod complexes was maintained in the reactions reported. The cod complexes were tested as catalyst precursors in the hydroformylation of styrene. HPNMR in situ studies showed that mononuclear species formed under catalytic conditions.

Amphioxus type I keratin cDNA and the evolution of intermediate filament genes

We report the cloning of an intermediate filament (IF) cDNA from the cephalochordate amphioxus that encodes a protein assignable to the type I keratin group. This is the first type I keratin reported from an invertebrate. Molecular phylogenetic analyses reveal that amphioxus also possesses a type II keratin, and that the genes encoding short-rod IF proteins underwent different patterns of duplication in vertebrates and their closest relatives, the cephalochordates. Extensive IF gene duplication and divergence may have facilitated the origin of new specialised cell types in vertebrates.

The diurnal cycle in the tropics

A global archive of high-resolution (3-hourly, 0.58 latitude–longitude grid) window (11–12 mm) brightness temperature (Tb) data from multiple satellites is being developed by the European Union Cloud Archive User Service (CLAUS) project. It has been used to construct a climatology of the diurnal cycle in convection, cloudiness, and surface temperature for all regions of the Tropics. An example of the application of the climatology to the evaluation of the climate version of the U.K. Met. Office Unified Model (UM), version HadAM3, is presented. The characteristics of the diurnal cycle described by the CLAUS data agree with previous observational studies, demonstrating the universality of the characteristics of the diurnal cycle for land versus ocean, clear sky versus convective regimes. It is shown that oceanic deep convection tends to reach its maximum in the early morning. Continental convection generally peaks in the evening, although there are interesting regional variations, indicative of the effects of complex land–sea and mountain–valley breezes, as well as the life cycle of mesoscale convective systems. A striking result from the analysis of the CLAUS data has been the extent to which the strong diurnal signal over land is spread out over the adjacent oceans, probably through gravity waves of varying depths. These coherent signals can be seen for several hundred kilometers and in some instances, such as over the Bay of Bengal, can lead to substantial diurnal variations in convection and precipitation. The example of the use of the CLAUS data in the evaluation of the Met. Office UM has demonstrated that the model has considerable difficulty in capturing the observed phase of the diurnal cycle in convection, which suggests some fundamental difficulties in the model’s physical parameterizations. Analysis of the diurnal cycle represents a powerful tool for identifying and correcting model deficiencies.

The equatorial response to higher latitude forcing

The classic view, following Charney and Webster and Holton, is that significant midlatitude forcing of the Tropics can be expected only in regions with westerly winds in the upper troposphere because it is only in these regions that stationary Rossby waves will be able to propagate toward the equator. Here it is shown that higherlatitude forcing can project directly onto equatorial waves and give a significant tropical response in both easterly and westerly tropical flow. The equatorial response to higher-latitude forcing is considered in the context of a dry atmosphere and a localized higher-latitude forcing with eastward or westward phase speed. Previous ideas of the Doppler shifting of equatorial waves by zonal flows are extended to include consideration of a forcing involving a range of zonal wavenumbers. A Gill-type model suggests that there can be significant forcing of equatorial waves by either vorticity forcing or heating in higher latitudes. In agreement with the theory, the Kelvin wave response to eastward forcing is peaked at high frequencies/short periods but reduces only slowly with decreasing frequency. Primitive-equation experiments confirm the strong equatorial response associated with a deep Kelvin wave for forcing in midlatitudes. The response is strongest in the Eastern Hemisphere with its equatorial, upper-tropospheric easterlies. The possible importance of this equatorial response in the organization of large-scale, deep tropical convection and the initiation of the Madden–Julian oscillation is discussed. The ability of westward forcing in higher latitudes to trigger Rossby–gravity and Rossby waves is found in the primitive-equation model to be significant but rather less robust. These wave signatures are clearest in the lower troposphere. For shorter periods the Rossby–gravity wave dominates, and for upper-tropospheric forcing, downward and eastward wave activity propagation is seen. Upper-tropospheric westerlies are found to enhance the response.

Integrating pests and pathogens into the climate change/food security debate

While many studies have demonstrated the sensitivities of plants and of crop yield to a changing climate, a major challenge for the agricultural research community is to relate these findings to the broader societal concern with food security. This paper reviews the direct effects of climate on both crop growth and yield and on plant pests and pathogens and the interactions that may occur between crops, pests, and pathogens under changed climate. Finally, we consider the contribution that better understanding of the roles of pests and pathogens in crop production systems might make to enhanced food security. Evidence for the measured climate change on crops and their associated pests and pathogens is starting to be documented. Globally atmospheric [CO(2)] has increased, and in northern latitudes mean temperature at many locations has increased by about 1.0-1.4 degrees C with accompanying changes in pest and pathogen incidence and to farming practices. Many pests and pathogens exhibit considerable capacity for generating, recombining, and selecting fit combinations of variants in key pathogenicity, fitness, and aggressiveness traits that there is little doubt that any new opportunities resulting from climate change will be exploited by them. However, the interactions between crops and pests and pathogens are complex and poorly understood in the context of climate change. More mechanistic inclusion of pests and pathogen effects in crop models would lead to more realistic predictions of crop production on a regional scale and thereby assist in the development of more robust regional food security policies.

Elevated atmospheric carbon dioxide impairs the performance of root-feeding vine weevils by modifying root growth and secondary metabolites

Predicting how insect crop pests will respond to global climate change is an important part of increasing crop production for future food security, and will increasingly rely on empirically based evidence. The effects of atmospheric composition, especially elevated carbon dioxide (eCO(2)), on insect herbivores have been well studied, but this research has focussed almost exclusively on aboveground insects. However, responses of root-feeding insects to eCO(2) are unlikely to mirror these trends because of fundamental differences between aboveground and belowground habitats. Moreover, changes in secondary metabolites and defensive responses to insect attack under eCO(2) conditions are largely unexplored for root herbivore interactions. This study investigated how eCO(2) (700 mu mol mol-1) affected a root-feeding herbivore via changes to plant growth and concentrations of carbon (C), nitrogen (N) and phenolics. This study used the root-feeding vine weevil, Otiorhynchus sulcatus and the perennial crop, Ribes nigrum. Weevil populations decreased by 33% and body mass decreased by 23% (from 7.2 to 5.4 mg) in eCO(2). Root biomass decreased by 16% in eCO(2), which was strongly correlated with weevil performance. While root N concentrations fell by 8%, there were no significant effects of eCO(2) on root C and N concentrations. Weevils caused a sink in plants, resulting in 8-12% decreases in leaf C concentration following herbivory. There was an interactive effect of CO(2) and root herbivory on root phenolic concentrations, whereby weevils induced an increase at ambient CO(2), suggestive of defensive response, but caused a decrease under eCO(2). Contrary to predictions, there was a positive relationship between root phenolics and weevil performance. We conclude that impaired root-growth underpinned the negative effects of eCO(2) on vine weevils and speculate that the plant's failure to mount a defensive response at eCO(2) may have intensified these negative effects.

Coupled atmosphere-biophysics-hydrology models for environmental modeling

The formulation and implementation of LEAF-2, the Land Ecosystem–Atmosphere Feedback model, which comprises the representation of land–surface processes in the Regional Atmospheric Modeling System (RAMS), is described. LEAF-2 is a prognostic model for the temperature and water content of soil, snow cover, vegetation, and canopy air, and includes turbulent and radiative exchanges between these components and with the atmosphere. Subdivision of a RAMS surface grid cell into multiple areas of distinct land-use types is allowed, with each subgrid area, or patch, containing its own LEAF-2 model, and each patch interacts with the overlying atmospheric column with a weight proportional to its fractional area in the grid cell. A description is also given of TOPMODEL, a land hydrology model that represents surface and subsurface downslope lateral transport of groundwater. Details of the incorporation of a modified form of TOPMODEL into LEAF-2 are presented. Sensitivity tests of the coupled system are presented that demonstrate the potential importance of the patch representation and of lateral water transport in idealized model simulations. Independent studies that have applied LEAF-2 and verified its performance against observational data are cited. Linkage of RAMS and TOPMODEL through LEAF-2 creates a modeling system that can be used to explore the coupled atmosphere–biophysical–hydrologic response to altered climate forcing at local watershed and regional basin scales.

An analytical model of mountain wave drag for wind profiles with shear and curvature

An analytical model is developed to predict the surface drag exerted by internal gravity waves on an isolated axisymmetric mountain over which there is a stratified flow with a velocity profile that varies relatively slowly with height. The model is linear with respect to the perturbations induced by the mountain, and solves the Taylor–Goldstein equation with variable coefficients using a Wentzel–Kramers–Brillouin (WKB) approximation, formally valid for high Richardson numbers, Ri. The WKB solution is extended to a higher order than in previous studies, enabling a rigorous treatment of the effects of shear and curvature of the wind profile on the surface drag. In the hydrostatic approximation, closed formulas for the drag are derived for generic wind profiles, where the relative magnitude of the corrections to the leading-order drag (valid for a constant wind profile) does not depend on the detailed shape of the orography. The drag is found to vary proportionally to Ri21, decreasing as Ri decreases for a wind that varies linearly with height, and increasing as Ri decreases for a wind that rotates with height maintaining its magnitude. In these two cases the surface drag is predicted to be aligned with the surface wind. When one of the wind components varies linearly with height and the other is constant, the surface drag is misaligned with the surface wind, especially for relatively small Ri. All these results are shown to be in fairly good agreement with numerical simulations of mesoscale nonhydrostatic models, for high and even moderate values of Ri.

Contribution of N Species and P Fractions to Stream Water Quality in Agricultural Catchments

The contribution from agricultural catchments to stream nitrogen and phosphorus concentrations was assessed by evaluation of the chemical composition of these nutrients in agricultural runoff for both surface and subsurface flow pathways. A range of land uses (grazed and ungrazed grassland, cereals, roots) in intensive agricultural systems was studied at scales from hillslope plots (0.5m2) to large catchment (>300km2). By fractionating the total nutrient load it was possible to establish that most of the phosphorus was transported in the unreactive (particulate and organic) fraction via surface runoff. This was true regardless of the scale of measurement. The form of the nitrogen load varied with land use and grazing intensity. High loads of dissolved inorganic nitrogen (with >90% transported as NH4-N) were recorded in surface runoff from heavily grazed land. In subsurface flow from small (2km2) subcatchments and in larger (>300 km2) catchments, organic nitrogen was found to be an important secondary constituent of the total nitrogen load, comprising 40% of the total annual load.