Structure determination, magnetic and optical properties of a new chromium(II) thioantimonate, [Cr((NH2CH2CH2)(3)N)]Sb4S7

The chromium(II) antimony(III) sulphicle, [Cr((NH2CH2CH2)(3)N)]Sb4S7, was synthesised under solvothermal conditions from the reaction of Sb2S3. Cr and S dissolved in tris(2-aminoethyl)amine (tren) at 438 K. The products were characterised by single-crystal X-ray diffraction. elemental analysis, SQUID magnetometry and diffuse reflectance spectroscopy. The compound crystallises in the monoclinic space group P2(1)/n with a = 7.9756(7), b = 10.5191(9), c = 25.880(2) angstrom and beta = 90.864(5)degrees. Alternating SbS33- trigonal pyramids and Sb36 semi-cubes generate Sb4S72- chains which are directly bonded to Cr(tren pendant units. The effective magnetic moment of 4.94(6)mu(B) shows a negligible orbital contribution, in agreement with expectations for Cr(II):d(4) in a (5)A ground state. The measured band gap of 2.14(3) eV is consistent with a correlation between optical band gap and framework density that is established from analysis of a wide range of antimony sulphides. (C) 2007 Elsevier Ltd. All rights reserved.

Potential energy surface and MULTIMODE vibrational analysis of C2H3+

A full dimensional, ab initio-based semiglobal potential energy surface for C2H3+ is reported. The ab initio electronic energies for this molecule are calculated using the spin-restricted, coupled cluster method restricted to single and double excitations with triples corrections [RCCSD(T)]. The RCCSD(T) method is used with the correlation-consistent polarized valence triple-zeta basis augmented with diffuse functions (aug-cc-pVTZ). The ab initio potential energy surface is represented by a many-body (cluster) expansion, each term of which uses functions that are fully invariant under permutations of like nuclei. The fitted potential energy surface is validated by comparing normal mode frequencies at the global minimum and secondary minimum with previous and new direct ab initio frequencies. The potential surface is used in vibrational analysis using the "single-reference" and "reaction-path" versions of the code MULTIMODE. (c) 2006 American Institute of Physics.

Adsorption of frog foam nest proteins at the air-water interface

The surfactant properties of aqueous protein mixtures ( ranaspumins) from the foam nests of the tropical frog Physalaemus pustulosus have been investigated by surface tension, two-photon excitation. uorescence microscopy, specular neutron reflection, and related biophysical techniques. Ranaspumins lower the surface tension of water more rapidly and more effectively than standard globular proteins under similar conditions. Two- photon excitation. uorescence microscopy of nest foams treated with fluorescent marker ( anilinonaphthalene sulfonic acid) shows partitioning of hydrophobic proteins into the air-water interface and allows imaging of the foam structure. The surface excess of the adsorbed protein layers, determined from measurements of neutron reflection from the surface of water utilizing H2O/D2O mixtures, shows a persistent increase of surface excess and layer thickness with bulk concentration. At the highest concentration studied ( 0.5 mg ml(-1)), the adsorbed layer is characterized by three distinct regions: a protruding top layer of similar to20 Angstrom, a middle layer of similar to30 Angstrom, and a more diffuse submerged layer projecting some 25 Angstrom into bulk solution. This suggests a model involving self-assembly of protein aggregates at the air-water interface in which initial foam formation is facilitated by specific surfactant proteins in the mixture, further stabilized by subsequent aggregation and cross-linking into a multilayer surface complex.

Methods for comparing and constraining models of dendritic spines

Physiological evidence using Infrared Video Microscopy during the uncaging of glutamate has proven the existence of excitable calcium ion channels in spine heads, highlighting the need for reliable models of spines. In this study we compare the three main methods of simulating excitable spines: Baer & Rinzel's Continuum (B&R) model, Coombes' Spike-Diffuse-Spike (SDS) model and paired cable and ion channel equations (Cable model). Tests are done to determine how well the models approximate each other in terms of speed and heights of travelling waves. Significant quantitative differences are found between the models: travelling waves in the SDS model in particular are found to travel at much lower speeds and sometimes much higher voltages than in the Cable or B&R models. Meanwhile qualitative differences are found between the B&R and SDS models over realistic parameter ranges. The cause of these differences is investigated and potential solutions proposed.

Multiple-scattering in radar systems: a review

Although extensively studied within the lidar community, the multiple scattering phenomenon has always been considered a rare curiosity by radar meteorologists. Up to few years ago its appearance has only been associated with two- or three-body-scattering features (e.g. hail flares and mirror images) involving highly reflective surfaces. Recent atmospheric research aimed at better understanding of the water cycle and the role played by clouds and precipitation in affecting the Earth's climate has driven the deployment of high frequency radars in space. Examples are the TRMM 13.5 GHz, the CloudSat 94 GHz, the upcoming EarthCARE 94 GHz, and the GPM dual 13-35 GHz radars. These systems are able to detect the vertical distribution of hydrometeors and thus provide crucial feedbacks for radiation and climate studies. The shift towards higher frequencies increases the sensitivity to hydrometeors, improves the spatial resolution and reduces the size and weight of the radar systems. On the other hand, higher frequency radars are affected by stronger extinction, especially in the presence of large precipitating particles (e.g. raindrops or hail particles), which may eventually drive the signal below the minimum detection threshold. In such circumstances the interpretation of the radar equation via the single scattering approximation may be problematic. Errors will be large when the radiation emitted from the radar after interacting more than once with the medium still contributes substantially to the received power. This is the case if the transport mean-free-path becomes comparable with the instrument footprint (determined by the antenna beam-width and the platform altitude). This situation resembles to what has already been experienced in lidar observations, but with a predominance of wide- versus small-angle scattering events. At millimeter wavelengths, hydrometeors diffuse radiation rather isotropically compared to the visible or near infrared region where scattering is predominantly in the forward direction. A complete understanding of radiation transport modeling and data analysis methods under wide-angle multiple scattering conditions is mandatory for a correct interpretation of echoes observed by space-borne millimeter radars. This paper reviews the status of research in this field. Different numerical techniques currently implemented to account for higher order scattering are reviewed and their weaknesses and strengths highlighted. Examples of simulated radar backscattering profiles are provided with particular emphasis given to situations in which the multiple scattering contributions become comparable or overwhelm the single scattering signal. We show evidences of multiple scattering effects from air-borne and from CloudSat observations, i.e. unique signatures which cannot be explained by single scattering theory. Ideas how to identify and tackle the multiple scattering effects are discussed. Finally perspectives and suggestions for future work are outlined. This work represents a reference-guide for studies focused at modeling the radiation transport and at interpreting data from high frequency space-borne radar systems that probe highly opaque scattering media such as thick ice clouds or precipitating clouds.

A simplified mathematical model for urban microclimate simulation

Techniques for modelling urban microclimates and urban block surfaces temperatures are desired by urban planners and architects for strategic urban designs at the early design stages. This paper introduces a simplified mathematical model for urban simulations (UMsim) including urban surfaces temperatures and microclimates. The nodal network model has been developed by integrating coupled thermal and airflow model. Direct solar radiation, diffuse radiation, reflected radiation, long-wave radiation, heat convection in air and heat transfer in the exterior walls and ground within the complex have been taken into account. The relevant equations have been solved using the finite difference method under the Matlab platform. Comparisons have been conducted between the data produced from the simulation and that from an urban experimental study carried out in a real architectural complex on the campus of Chongqing University, China in July 2005 and January 2006. The results show a satisfactory agreement between the two sets of data. The UMsim can be used to simulate the microclimates, in particular the surface temperatures of urban blocks, therefore it can be used to assess the impact of urban surfaces properties on urban microclimates. The UMsim will be able to produce robust data and images of urban environments for sustainable urban design.

Boundary layer dynamics over London, UK, as observed using Doppler lidar during REPARTEE-II

Urban boundary layers (UBLs) can be highly complex due to the heterogeneous roughness and heating of the surface, particularly at night. Due to a general lack of observations, it is not clear whether canonical models of boundary layer mixing are appropriate in modelling air quality in urban areas. This paper reports Doppler lidar observations of turbulence profiles in the centre of London, UK, as part of the second REPARTEE campaign in autumn 2007. Lidar-measured standard deviation of vertical velocity averaged over 30 min intervals generally compared well with in situ sonic anemometer measurements at 190 m on the BT telecommunications Tower. During calm, nocturnal periods, the lidar underestimated turbulent mixing due mainly to limited sampling rate. Mixing height derived from the turbulence, and aerosol layer height from the backscatter profiles, showed similar diurnal cycles ranging from c. 300 to 800 m, increasing to c. 200 to 850 m under clear skies. The aerosol layer height was sometimes significantly different to the mixing height, particularly at night under clear skies. For convective and neutral cases, the scaled turbulence profiles resembled canonical results; this was less clear for the stable case. Lidar observations clearly showed enhanced mixing beneath stratocumulus clouds reaching down on occasion to approximately half daytime boundary layer depth. On one occasion the nocturnal turbulent structure was consistent with a nocturnal jet, suggesting a stable layer. Given the general agreement between observations and canonical turbulence profiles, mixing timescales were calculated for passive scalars released at street level to reach the BT Tower using existing models of turbulent mixing. It was estimated to take c. 10 min to diffuse up to 190 m, rising to between 20 and 50 min at night, depending on stability. Determination of mixing timescales is important when comparing to physico-chemical processes acting on pollutant species measured simultaneously at both the ground and at the BT Tower during the campaign. From the 3 week autumnal data-set there is evidence for occasional stable layers in central London, effectively decoupling surface emissions from air aloft.

Conformational polymorphism of the molecular complex of 3-fluorobenzoic acid with 4-acetylpyridine

Two polymorphs of the molecular complex formed between 3-fluorobenzoic acid with 4-acetylpyridine are described and found to be based upon the same dimeric supramolecular construct. The conformational freedom around the hydrogen bond results in a 180 degrees rotation about this intermolecular link, distinguishing the polymorphs and affecting the packing of the dimeric units. The two polymorphs are fully characterised by single crystal X-ray and neutron diffraction and quantum mechanical calculations. There is evidence of structured crystal growth defects in both polymorphic crystals via observation of diffuse scattering and a disorder model for the average structure of Form I, which can be interpreted as a mixing of the two dimer conformations. The similarity of energy of the distinct dimeric units, supporting their likely co-existence, has been verified by periodic quantum chemical calculations.

Hillslope scale surface runoff, sediment, and nutrient losses associated with tramline wheelings

Research on arable sandy loam and silty clay loam soils on 4° slopes in England has shown that tramlines (i.e. the unseeded wheeling areas used to facilitate spraying operations in cereal crops) can represent the most important pathway for phosphorus and sediment loss from moderately sloping fields. Detailed monitoring over the October–March period in winters 2005–2006 and 2006–2007 included event-based sampling of surface runoff, suspended and particulate sediment, and dissolved and particulate phosphorus from hillslope segments (each ∼300–800 m2) established in a randomized block design with four replicates of each treatment at each of two sites on lighter and heavier soils. Experimental treatments assessed losses from the cropped area without tramlines, and from the uncropped tramline area, and were compared to losses from tramlines which had been disrupted once in the autumn with a shallow tine. On the lighter soil, the effects of removal or shallow incorporation of straw residues was also determined. Research on both sandy and silty clay loam soils across two winters showed that tramline wheelings represented the dominant pathway for surface runoff and transport of sediment, phosphorus and nitrogen from cereal crops on moderate slopes. Results indicated 5·5–15·8% of rainfall lost as runoff, and losses of 0·8–2·9 kg TP ha−1 and 0·3–4·8 t ha−1 sediment in tramline treatments, compared to only 0·2–1·7% rainfall lost as runoff, and losses of 0·0–0·2 kg TP ha−1 and 0·003–0·3 t ha−1 sediment from treatments without tramlines or those where tramlines had been disrupted. The novel shallow disruption of tramline wheelings using a tine once following the autumn spray operation consistently and dramatically reduced (p < 0·001) surface runoff and loads of sediment, total nitrogen and total phosphorus to levels similar to those measured in cropped areas between tramlines. Results suggest that options for managing tramline wheelings warrant further refinement and evaluation with a view to incorporating them into spatially-targeted farm-level management planning using national or catchment-based agri-environment policy instruments aimed at reducing diffuse pollution from land to surface water systems. Copyright © 2010 John Wiley & Sons, Ltd.

Contributing understanding of mitigation options for phosphorus and sediment to a review of the efficacy of contemporary agricultural stewardship measures

Experiences from the Mitigation Options for Phosphorus and Sediment (MOPS) projects, which aim to determine the effectiveness of measures to reduce pollutant loading from agricultural land to surface waters, have been used to contribute to the findings of a recent paper (Kay et al., 2009, Agricultural Systems, 99, 67–75), which reviewed the efficacy of contemporary agricultural stewardship measures for ameliorating the water pollution problems of key concern to the UK water industry. MOPS1 is a recently completed 3-year research project on three different soil types in the UK, which focused on mitigation options for winter cereals. MOPS1 demonstrated that tramlines can be the major pathway for sediment and nutrient transfer from arable hillslopes, and that although minimum tillage, crop residue incorporation, contour cultivation, and beetle banks also have potential to be cost-effective mitigation options, tramline management is the one of the most promising treatments for mitigating diffuse pollution losses, as it was able to reduce sediment and nutrient losses by 72–99% in four out of five site years trialled. Using information from the MOPS projects, this paper builds on the findings of Kay et al. to provide an updated picture of the evidence available and the immediate needs for research in this area.

Modulation of neuroinflammation by dietary flavonoids

There is increasing evidence to suggest neuroinflammatory processes contribute to the cascade of events that lead to the progressive neuronal damage observed in neurodegenerative disorders such as Parkinson’s disease and Alzheimer’s disease. The molecular mechanisms underlying such neurodegenerative processes are rather complex and involve modulation of the mitogen-activated protein kinase (MAPK) and NF-κB pathways leading to the generation of nitric oxide (NO). Such a small molecule may diffuse to the neighbouring neurons and trigger neuronal death through the inhibition of mitochondrial respiration and increases in the reactive oxygen and nitrogen species. Recently, attention has focused on the neuroprotective effects of flavonoids which have been effective in protecting against both age-related cognitive and motor decline in vivo. Although, the precise mechanisms by which flavonoids may exert their neuroprotective effects remain unclear, accumulating evidence suggest that they may exert their neuroprotective effects through the modulation of the MAP Kinase and PI3 Kinase signaling pathways. The aim of the present chapter is to highlight the potential neuroprotective role of dietary flavonoids in terms of their ability to modulate neuroinflammation in the central nervous system. We will provide an outline of the role glial cells play in neuroinflammation and describe the involvement of inflammatory mediators, produced by glia, in the cascade of events leading to neuronal degeneration. We will then present the evidence that flavonoids may modulate neuroinflammation by inhibiting the production of these inflammatory agents and summarise their potential mechanisms of action.

Sediment fingerprinting as an environmental forensics tool explaining cyanobacteria blooms in lakes

Cyanobacteria (blue-green algae) blooms in water bodies present serious public health issues with attendant economic and ecological impacts. Llyn Tegid (Lake Bala) is an important conservation and amenity asset within Snowdonia National Park, Wales which since the mid-1990s has experienced multiple toxic cyanobacteria blooms threatening the ecology and tourism-dependent local economy. Multiple working hypotheses explain the emergence of this problem, including climate change, land management linked to increased nutrient flux, hydromorphological alterations or changing trophic structure - any of which may operate individually or cumulatively to impair lake function. This paper reports the findings of a sedimentfingerprinting study using dated lake cores to explore the linkages between catchment and lake management practices and the emergence of the algal blooms problem. Since 1900 AD lake bed sedimentation rates have varied from 0.06 to 1.07 g cm−2 yr−1, with a pronounced acceleration since the early 1980s. Geochemical analysis revealed increases in the concentrations of total phosphorus (TP), calcium and heavy metals such as zinc and lead consistent with eutrophication and a rising pollution burden, particularly since the late 1970s. An uncertainty-inclusive sedimentfingerprinting approach was used to apportion the relative fluxes from the major catchment land cover types of improved pasture, rough grazing, forestry and channel banks. This showed improved pasture and channel banks are the dominant diffuse sources of sediment in the catchment, though forestry sources were important historically. Conversion of rough grazing to improved grassland, coupled with intensified land management and year-round livestock grazing, is concluded to provide the principal source of rising TP levels. Lake Habitat Survey and particle size analysis of lake cores demonstrate the hydromorphological impact of the River Dee Regulation Scheme, which controls water level and periodically diverts flow into Llyn Tegid from the adjacent Afon Tryweryn catchment. This hydromorphological impact has also been most pronounced since the late 1970s. It is concluded that an integrated approach combining land management to reduce agricultural runoff allied to improved water level regulation enabling recovery of littoral macrophytes offers the greatest chance halting the on-going cyanobacteria issue in Llyn Tegid.

An overview of domestic energy models and a new approach with agent based modelling

Government targets for CO2 reductions are being progressively tightened, the Climate Change Act set the UK target as an 80% reduction by 2050 on 1990 figures. The residential sector accounts for about 30% of emissions. This paper discusses current modelling techniques in the residential sector: principally top-down and bottom-up. Top-down models work on a macro-economic basis and can be used to consider large scale economic changes; bottom-up models are detail rich to model technological changes. Bottom-up models demonstrate what is technically possible. However, there are differences between the technical potential and what is likely given the limited economic rationality of the typical householder. This paper recommends research to better understand individuals’ behaviour. Such research needs to include actual choices, stated preferences and opinion research to allow a detailed understanding of the individual end user. This increased understanding can then be used in an agent based model (ABM). In an ABM, agents are used to model real world actors and can be given a rule set intended to emulate the actions and behaviours of real people. This can help in understanding how new technologies diffuse. In this way a degree of micro-economic realism can be added to domestic carbon modelling. Such a model should then be of use for both forward projections of CO2 and to analyse the cost effectiveness of various policy measures.

Understanding the early stages of the innovation diffusion process: awareness, influence and communication networks

The themes of awareness and influence within the innovation diffusion process are addressed. The innovation diffusion process is typically represented as stages, yet awareness and influence are somewhat under-represented in the literature. Awareness and influence are situated within the contextual setting of individual actors but also within the broader institutional forces. Understanding how actors become aware of an innovation and then how their opinion is influenced is important for creating a more innovation-active UK construction sector. Social network analysis is proposed as one technique for mapping how awareness and influence occur and what they look like as a network. Empirical data are gathered using two modes of enquiry. This is done through a pilot study consisting of chartered professionals and then through a case study organization as it attempted to diffuse an innovation. The analysis demonstrates significant variations across actors’ awareness and influence networks. It is argued that social network analysis can complement other research methods in order to present a richer picture of how actors become aware of innovations and where they draw their influences regarding adopting innovations. In summarizing the findings, a framework for understanding awareness and influence associated with innovation within the UK construction sector is presented. Finally, with the UK construction sector continually being encouraged to be innovative, understanding and managing an actor’s awareness and influence network will be beneficial. The overarching conclusion thus describes the need not only to build research capacity in this area but also to push the boundaries related to the research methods employed.

Balloon-borne disposable radiometer for cloud detection

A low cost, disposable instrument for measuring solar radiation during meteorological balloon flights through cloud layers is described. Using a photodiode detector and low thermal drift signal conditioning circuitry, the device showed less than 1% drift for temperatures varied from +20 °C to −35 °C. The angular response to radiation, which declined less rapidly than the cosine of the angle between the incident radiation and normal incidence, is used for cloud detection exploiting the motion of the platform. Oriented upwards, the natural motion imposed by the balloon allows cloud and clear air to be distinguished by the absence of radiation variability within cloud, where the diffuse radiation present is isotropic. The optical method employed by the solar radiation instrument has also been demonstrated to provide higher resolution measurements of cloud boundaries than relative humidity measurements alone.