Divinyldisiloxane and divinylsilane complexes of rhodium(I)

Reaction of the tetrakis(cyclooctene)rhodium(I) complex [{Rh(C8H14-c)2(μ-Cl)}2] with the appropriate divinyldisiloxane molecules (ViSiR2)2O (R=Me or Ph) yields, by displacement of the cycloctene ligands, the complexes [{Rh(ViSiR2)2O(μ-Cl)}2] (R=Me (1) or Ph (2)). These react further with a tertiary phosphine PR3 to give cis-[Rh{(ViSiR2)2O}(PR′3)Cl] (R′=Ph or C6H4Me-p). The complex cis-[{Rh(Vi2SiMe2)(μ-Cl)}2] (7) was similarly prepared by the displacement of ethylene from [{Rh(C2H4)2(μ-Cl)}2] by the divinyldimethylsilane Vi2SiMe2. X-ray molecular structures of the crystalline complexes 1, 2 and 7 show a distorted square planar Rh(I) environment, the CH2CH groups being orthogonal to this plane; 1 and 2 have the Rh–(ViSiR2)2O metallacycle in the chair conformation, but differ in the nature of the central Rh(Cl)RhCl core, which is planar for 1 and puckered for 2, but each of 1 and 2 is the rac-diastereoisomer, whereas 7 has the meso-configuration. In solution 1 and 2 exist as a mixture of isomers, probably the rac- and meso-pairs as established by multinuclear NMR spectral studies. A series of saturation transfer NMR spectroscopic experiments showed that the divinyldisiloxane ligands in [{Rh(ViSiPh2)2O(μ-Cl)}2] underwent a dynamic process involving the dissociation, rotation and then reassociation of the vinyl groups.

Integrated cytokine and metabolic analysis of pathological responses to parasite exposure in rodents

Parasitic infections cause a myriad of responses in their mammalian hosts, on immune as well as on metabolic level. A multiplex panel of cytokines and metabolites derived from four parasite-rodent models, namely, Plasmodium berghei-mouse, Trypanosoma brucei brucei-mouse, Schistosoma mansoni-mouse, and Fasciola hepatica-rat were statistically coanalyzed. 1H NMR spectroscopy and multivariate statistical analysis were used to characterize the urine and plasma metabolite profiles in infected and noninfected animals. Each parasite generated a unique metabolic signature in the host. Plasma cytokine concentrations were obtained using the ‘Meso Scale Discovery’ multi cytokine assay platform. Multivariate data integration methods were subsequently used to elucidate the component of the metabolic signature which is associated with inflammation and to determine specific metabolic correlates with parasite-induced changes in plasma cytokine levels. For example, the relative levels of acetyl glycoproteins extracted from the plasma metabolite profile in the P. berghei-infected mice were statistically correlated with IFN-γ, whereas the same cytokine was anticorrelated with glucose levels. Both the metabolic and the cytokine data showed a similar spatial distribution in principal component analysis scores plots constructed for the combined murine data, with samples from all infected animals clustering according to the parasite species and whereby the protozoan infections (P. berghei and T. b. brucei) grouped separately from the helminth infection (S. mansoni). For S. mansoni, the main infection-responsive cytokines were IL-4 and IL-5, which covaried with lactate, choline, and D-3-hydroxybutyrate. This study demonstrates that the inherently differential immune response to single and multicellular parasites not only manifests in the cytokine expression, but also consequently imprints on the metabolic signature, and calls for in-depth analysis to further explore direct links between immune features and biochemical pathways.

A new method for the determination of Holocene palaeohydrology

This paper describes a new method for the assessment of palaeohydrology through the Holocene. A palaeoclimate model was linked with a hydrological model, using a weather generator to correct bias in the rainfall estimates, to simulate the changes in the flood frequency and the groundwater response through the late Pleistocene and Holocene for the Wadi Faynan in southern Jordan, a site considered internationally important due to its rich archaeological heritage spanning the Pleistocene and Holocene. This is the first study to describe the hydrological functioning of the Wadi Faynan, a meso-scale (241 km2) semi-arid catchment, setting this description within the framework of contemporary archaeological investigations. Historic meteorological records were collated and supplemented with new hydrological and water quality data. The modelled outcomes indicate that environmental changes, such as deforestation, had a major impact on the local water cycle and this amplified the effect of the prevailing climate on the flow regime. The results also show that increased rainfall alone does not necessarily imply better conditions for farming and highlight the importance of groundwater. The discussion focuses on the utility of the method and the importance of the local hydrology to the sustained settlement of the Wadi Faynan through pre-history and history.

Considering heteroglossia in language and development in Sub-Saharan Africa

Countries throughout the sub-Saharan (SSA) region have a complex linguistic heritage having their origins in opportunistic boundary changes effected by Western colonial powers at the Berlin Conference 1884-85. Postcolonial language-in-education policies valorizing ex-colonial languages have contributed at least in part to underachievement in education and thus the underdevelopment of human resources in SSA countries. This situation is not likely to improve whilst unresolved questions concerning the choice of language(s) that would best support social and economic development remain. Whilst policy attempts to develop local languages have been discussed within the framework of the African Union, and some countries have experimented with models of multilingual education during the past decade, the goalposts have already changed as a result of migration and trade. This paper argues that language policy makers need to be cognizant of changing language ecologies and their relationship with emerging linguistic and economic markets. The concept of language, within such a framework, has to be viewed in relation to the multiplicity of language markets within the shifting landscapes of people, culture, economics and the geo-politics of the 21st Century. Whilst, on the one hand, this refers to the hegemony of dominant powerful languages and the social relations of disempowerment, on the other hand, it also refers to existing and evolving social spaces and local language capabilities and choices. Within this framework the article argues that socially constructed dominant macro language markets need to be viewed also in relation to other, self-defined, community meso- and individual micro- language markets and their possibilities for social, economic and political development. It is through pursuing this argument that this article assesses the validity of Omoniyi’s argument in this volume, for the need to focus on the concept of language capital within multilingual contexts in the SSA region as compared to Bourdieu’s concept of linguistic capital.  

Electrochromic and electrofluorochromic properties of a new boron dipyrromethene–ferrocene conjugate

A new boron dipyrromethene–ferrocene (BODIPY–Fc) conjugate with pentafluorophenyl as the meso substituent and two Fc termini was synthesized and its spectroscopic and electrochemical features were analyzed. An intramolecular charge transfer from the donor Fc to the acceptor BODIPY has been predicted by theory and confirmed experimentally, leading to efficient fluorescence quenching when the dyad is in the neutral state. Fluorescence can be triggered by oxidizing both ferrocenyl units either chemically or electrochemically. Eventually, a fully reversible fluorescence switch is evidenced by coupling TIRF microscopy with electrolysis in an electrochemical cell.

Assessment of a 1 hour gridded precipitation dataset to drive a hydrological model: a case study of the summer 2007 floods in the Upper Severn, UK

In this study a gridded hourly 1-km precipitation dataset for a meso-scale catchment (4,062 km2) of the Upper Severn River, UK was constructed using rainfall radar data to disaggregate a daily precipitation (rain gauge) dataset. The dataset was compared to an hourly precipitation dataset created entirely from rainfall radar data. Results found that when assessed against gauge readings and as input to the Lisflood-RR hydrological model, the rain gauge/radar disaggregated dataset performed the best suggesting that this simple method of combining rainfall radar data with rain gauge readings can provide temporally detailed precipitation datasets for calibrating hydrological models.

Climate and more sustainable cities: climate information for improved planning and management of cities (producers/capabilities perspective)

In the last two decades substantial advances have been made in the understanding of the scientific basis of urban climates. These are reviewed here with attention to sustainability of cities, applications that use climate information, and scientific understanding in relation to measurements and modelling. Consideration is given from street (micro) scale to neighbourhood (local) to city and region (meso) scale. Those areas where improvements are needed in the next decade to ensure more sustainable cities are identified. High-priority recommendations are made in the following six strategic areas: observations, data, understanding, modelling, tools and education. These include the need for more operational urban measurement stations and networks; for an international data archive to aid translation of research findings into design tools, along with guidelines for different climate zones and land uses; to develop methods to analyse atmospheric data measured above complex urban surfaces; to improve short-range, high-resolution numerical prediction of weather, air quality and chemical dispersion through improved modelling of the biogeophysical features of the urban land surface; to improve education about urban meteorology; and to encourage communication across scientific disciplines at a range of spatial and temporal scales.

Can polar lows be objectively identified and tracked in the ECMWF operational analysis and the ERA-Interim reanalysis?

Polar lows are maritime meso-cyclones associated with intense surface wind speeds and oceanic heat fluxes at high latitudes. The ability of the ERA-Interim (ERAI) reanalysis to represent polar lows in the North Atlantic is assessed by comparing ERAI and the ECMWF operational analysis for the period 2008-2011. First, the representation of a set of satellite observed polar lows over the Norwegian and Barents Seas in the operational analysis and ERAI is analysed. Then, the possibility of directly identifying and tracking the polar lows in the operational analysis and ERAI is explored using a tracking algorithm based on 850 hPa vorticity with objective identification criteria on cyclone dynamical intensity and atmospheric static stability. All but one of the satellite observed polar lows with a lifetime of at least 6 hours have an 850 hPa vorticity signature of a co-located mesocyclone in both the operational analysis and ERAI for most of their life cycles. However, the operational analysis has vorticity structures that better resemble the observed cloud patterns and stronger surface wind speed intensities compared to those in ERAI. By applying the objective identification criteria, about 55% of the satellite observed polar lows are identified and tracked in ERAI, while this fraction increases to about 70% in the operational analysis. Particularly in ERAI, the remaining observed polar lows are mainly not identified because they have too weak wind speed and vorticity intensity compared to the tested criteria. The implications of the tendency of ERAI to underestimate the polar low dynamical intensity for future studies of polar lows is discussed.

Urban integrated meteorological observations: practice and experience in Shanghai, China

Observations of atmospheric conditions and processes in citiesare fundamental to understanding the interactions between the urban surface and weather/climate, improving the performance of urban weather, air quality and climate models, and providing key information for city end-users (e.g. decision-makers, stakeholders, public). In this paper, Shanghai's urban integrated meteorological observation network (SUIMON) and some examples of intended applications are introduced. Its characteristics include being: multi- purpose (e.g. forecast, research, service), multi-function (high impact weather, city climate, special end-users), multi-scale (e.g. macro/meso-, urban-, neighborhood, street canyon), multi-variable (e.g. thermal, dynamic, chemical, bio-meteorological, ecological), and multi- platform (e.g. radar, wind profiler, ground-based, satellite based, in-situ observation/ sampling). Underlying SUIMON is a data management system to facilitate exchange of data and information. The overall aim of the network is to improve coordination strategies and instruments; to identify data gaps based on science and user driven requirements; and to intelligently combine observations from a variety of platforms by using a data assimilation system that is tuned to produce the best estimate of the current state of the urban atmosphere.

Daytime CO2 urban surface fluxes from airborne measurements, eddy-covariance observations and emissions inventory in Greater London

Airborne measurements within the urban mixing layer (360 m) over Greater London are used to quantify CO2 emissions at the meso-scale. Daytime CO2 fluxes, calculated by the Integrative Mass Boundary Layer (IMBL) method, ranged from 46 to 104 μmol CO2 m−2 s−1 for four days in October 2011. The day-to-day variability of IMBL fluxes is at the same order of magnitude as for surface eddy-covariance fluxes observed in central London. Compared to fluxes derived from emissions inventory, the IMBL method gives both lower (by −37%) and higher (by 19%) estimates. The sources of uncertainty of applying the IMBL method in urban areas are discussed and guidance for future studies is given.

nor-Mevaldic acid surrogates as selective antifungal agent leads against Botrytis cinerea. Enantioselective preparation of 4-hydroxy-6-(1-phenylethoxy)tetrahydro-2H-pyran-2-one

Solvent-free desymmetrisation of meso-dialdehyde 1 with chiral 1-phenylethan-1-ol, led to preparation of 4-silyloxy-6-alkyloxytetrahydro-2H-pyran-2-one (+)-3a with a 96:4 d.r. Deprotected lactone (+)-19a and the related racemic lactones 16a-18a present a lactone moiety resembling the natural substrate of HMG-CoA reductase and their antifungal properties have been evaluated against the phytopathogenic fungi Botrytis cinerea and Colletotrichum gloeosporioides. These compounds were selectively active against B. cinerea, while inactive against C. gloeosporioides.

Tracking the uncertainty in flood alerts driven by grand ensemble weather predictions

The incorporation of numerical weather predictions (NWP) into a flood warning system can increase forecast lead times from a few hours to a few days. A single NWP forecast from a single forecast centre, however, is insufficient as it involves considerable non-predictable uncertainties and can lead to a high number of false or missed warnings. Weather forecasts using multiple NWPs from various weather centres implemented on catchment hydrology can provide significantly improved early flood warning. The availability of global ensemble weather prediction systems through the ‘THORPEX Interactive Grand Global Ensemble’ (TIGGE) offers a new opportunity for the development of state-of-the-art early flood forecasting systems. This paper presents a case study using the TIGGE database for flood warning on a meso-scale catchment (4062 km2) located in the Midlands region of England. For the first time, a research attempt is made to set up a coupled atmospheric-hydrologic-hydraulic cascade system driven by the TIGGE ensemble forecasts. A probabilistic discharge and flood inundation forecast is provided as the end product to study the potential benefits of using the TIGGE database. The study shows that precipitation input uncertainties dominate and propagate through the cascade chain. The current NWPs fall short of representing the spatial precipitation variability on such a comparatively small catchment, which indicates need to improve NWPs resolution and/or disaggregating techniques to narrow down the spatial gap between meteorology and hydrology. The spread of discharge forecasts varies from centre to centre, but it is generally large and implies a significant level of uncertainties. Nevertheless, the results show the TIGGE database is a promising tool to forecast flood inundation, comparable with that driven by raingauge observation.

Limitations to recording larger mammalian predators in savannah using camera traps and spoor

Traditionally, spoor (tracks, pug marks) have been used as a cost effective tool to assess the presence of larger mammals. Automated camera traps are now increasingly utilized to monitor wildlife, primarily as the cost has greatly declined and statistical approaches to data analysis have improved. While camera traps have become ubiquitous, we have little understanding of their effectiveness when compared to traditional approaches using spoor in the field. Here, we a) test the success of camera traps in recording a range of carnivore species against spoor; b) ask if simple measures of spoor size taken by amateur volunteers is likely to allow individual identification of leopards and c) for a trained tracker, ask if this approach may allow individual leopards to be followed with confidence in savannah habitat. We found that camera traps significantly under-recorded mammalian top and meso-carnivores, with camera traps more likely under-record the presence of smaller carnivores (civet 64%; genet 46%, Meller’s mongoose 45%) than larger (jackal sp. 30%, brown hyena 22%), while leopard was more likely to be recorded by camera trap (all recorded by camera trap only). We found that amateur trackers could be beneficial in regards to collecting presence data; however the large variance in measurements of spoor taken in the field by volunteers suggests that this approach is unlikely to add further data. Nevertheless, the use of simple spoor measurements in the field by a trained field researcher increases their ability to reliably follow a leopard trail in difficult terrain. This allows researchers to glean further data on leopard behaviour and habitat utilisation without the need for complex analysis.

Climatology of polar lows over the Sea of Japan using the JRA-55 reanalysis

Polar lows are intense meso- a -scale cyclones that develop over the oceans poleward of the main baroclinic zone. A number of previous studies have reported polar low formation over the Sea of Japan within the East Asian winter monsoon. To understand the climatology of polar lows over the Sea of Japan, a tracking al- gorithm for polar lows is applied to the recent JRA-55 reanalysis. The polar low tracking is applied to 36 cold seasons (October–March) from October 1979 to March 2015. The polar lows over the Sea of Japan reach their maximum intensity on the southeastern side of the midline between the Japanese islands and the Asian continent. Consistent with previous case studies, composite analysis demonstrates that the polar low devel- opment is associated with the enhanced northerly flow on the western side of a synoptic-scale extratropical cyclone, with the cold trough in the midtroposphere and with increased heat fluxes from the sea surface. Furthermore, the present climatological study has revealed two dominant directions of motion of the polar lows: southward and eastward. Southward-moving polar lows are steered by a strong northerly flow in the lower troposphere, which is enhanced on the western side of synoptic-scale extratropical cyclones, while the eastward-moving polar lows occur within a planetary-scale westerly flow in the midlatitudes. Thus, the di- rection of polar low motion reflects the difference in planetary- and synoptic-scale conditions.

Diastereoselective and enantioselective preparation of nor-mevaldic acid surrogates through desymmetrisation methodology. Enantioselective synthesis of (+) and (-) nor-mevalonic lactones

Solvent-free desymmetrisation of a meso-dialdehyde with chiral alcohols, led to preparation of 4-silyloxy-6-alkyloxytetrahydro-2H-pyran-2-one derivatives with a 96% de. This methodology, which yields the corresponding methyl nor-mevaldates with 99% ee, has been applied to the enantioselective synthesis of the (-)-(R) and (+)-(S) nor-mevalonic acid lactones.