Synthesis, crystal structure and reactivity of copper(II) complexes of tetradentate N2S2 donor ligands

Two new hexa-coordinated mononuclear copper(II) complexes of two ligands L-1 and L-2 containing NSSN donor sets formulated as [Cu(L)(H2O)(2)](NO3)(2) [1a, L = 1,2-bis(2-pyridylmethylthio)ethane (L-1), 1b L = 1,3-bis(2-pyridyl-methylthio)propane (L-2)] were synthesized and characterized by physico-chemical and spectroscopic methods. In 1a the single crystal X-ray crystallography analysis showed a distorted octahedral geometry about copper(II) ion. The crystal packing evidences pairs of complexes arranged about a center of symmetry and connected through a H-bond occurring between aquo ligands and nitrate anions. On reaction with chloride and pseudohalides (N-3(-) and SCN-), in acetonitrile at ambient temperature. complexes 1 changed to monocationic penta-coordinated mononuclear copper(H) species formulated as [Cu(L)(Cl)]NO3 (2), [Cu(L)(N-3)]NO3 (3). and [Cu(L)(SCN)]NO3 (4). These copper(II) complexes have been isolated in pure form from the reaction mixtures and characterized by physico-chemical and spectroscopic tools. The solid-state structure of 2a, established by X-ray crystallography, shows a trigonal bipyramidal geometry about the metal ion with a trigonality index (tau) of 0.561. (C) 2009 Elsevier B.V. All rights reserved.

Lean construction: Arenas of enactment, models of diffusion and the meaning of 'leanness'

The existing literature on lean construction is overwhelmingly prescriptive with little recognition of the social and politicised nature of the diffusion process. The prevailing production-engineering perspective too often assumes that organizations are unitary entities where all parties strive for the common goal of 'improved performance'. An alternative perspective is developed that considers the diffusion of lean construction across contested pluralistic arenas. Different actors mobilize different storylines to suit their own localized political agendas. Multiple storylines of lean construction continuously compete for attention with other management fashions. The conceptualization and enactment of lean construction therefore differs across contexts, often taking on different manifestations from those envisaged. However, such localized enactments of lean construction are patterned and conditioned by pre-existing social and economic structures over which individual managers have limited influence. Taking a broader view, 'leanness' can be conceptualized in terms of a quest for structural flexibility involving restructuring, downsizing and outsourcing. From this perspective, the UK construction industry can be seen to have embarked upon leaner ways of working in the mid-1970s, long before the terminology of lean thinking came into vogue. Semi-structured interviews with construction sector policy-makers provide empirical support for the view that lean construction is a multifaceted concept that defies universal definition.

Qualitative modelling of sustainable energy scenarios: An application and extension of the Bon Qualitative Input-Output model

Climate change is one of the major challenges facing economic systems at the start of the 21st century. Reducing greenhouse gas emissions will require both restructuring the energy supply system (production) and addressing the efficiency and sufficiency of the social uses of energy (consumption). The energy production system is a complicated supply network of interlinked sectors with 'knock-on' effects throughout the economy. End use energy consumption is governed by complex sets of interdependent cultural, social, psychological and economic variables driven by shifts in consumer preference and technological development trajectories. To date, few models have been developed for exploring alternative joint energy production-consumption systems. The aim of this work is to propose one such model. This is achieved in a methodologically coherent manner through integration of qualitative input-output models of production, with Bayesian belief network models of consumption, at point of final demand. The resulting integrated framework can be applied either (relatively) quickly and qualitatively to explore alternative energy scenarios, or as a fully developed quantitative model to derive or assess specific energy policy options. The qualitative applications are explored here.

The integration of figurative language and static depictions: an eye movement study of fictive motion

Do we view the world differently if it is described to us in figurative rather than literal terms? An answer to this question would reveal something about both the conceptual representation of figurative language and the scope of top-down influences oil scene perception. Previous work has shown that participants will look longer at a path region of a picture when it is described with a type of figurative language called fictive motion (The road goes through the desert) rather than without (The road is in the desert). The current experiment provided evidence that such fictive motion descriptions affect eye movements by evoking mental representations of motion. If participants heard contextual information that would hinder actual motion, it influenced how they viewed a picture when it was described with fictive motion. Inspection times and eye movements scanning along the path increased during fictive motion descriptions when the terrain was first described as difficult (The desert is hilly) as compared to easy (The desert is flat); there were no such effects for descriptions without fictive motion. It is argued that fictive motion evokes a mental simulation of motion that is immediately integrated with visual processing, and hence figurative language can have a distinct effect on perception. (c) 2005 Elsevier B.V. All rights reserved.

A review and implementation of swarm pattern formation and transformation models

Purpose: The purpose of this paper is to address a classic problem – pattern formation identified by researchers in the area of swarm robotic systems – and is also motivated by the need for mathematical foundations in swarm systems. Design/methodology/approach: The work is separated out as inspirations, applications, definitions, challenges and classifications of pattern formation in swarm systems based on recent literature. Further, the work proposes a mathematical model for swarm pattern formation and transformation. Findings: A swarm pattern formation model based on mathematical foundations and macroscopic primitives is proposed. A formal definition for swarm pattern transformation and four special cases of transformation are introduced. Two general methods for transforming patterns are investigated and a comparison of the two methods is presented. The validity of the proposed models, and the feasibility of the methods investigated are confirmed on the Traer Physics and Processing environment. Originality/value: This paper helps in understanding the limitations of existing research in pattern formation and the lack of mathematical foundations for swarm systems. The mathematical model and transformation methods introduce two key concepts, namely macroscopic primitives and a mathematical model. The exercise of implementing the proposed models on physics simulator is novel.

Porcine models for the metabolic syndrome, digestive and bone disorders: a general overview

The aim of this review article is to provide an overview of the role of pigs as a biomedical model for humans. The usefulness and limitations of porcine models have been discussed in terms of metabolic, cardiovascular, digestive and bone diseases in humans. Domestic pigs and minipigs are the main categories of pigs used as biomedical models. One drawback of minipigs is that they are in short supply and expensive compared with domestic pigs, which in contrast cost more to house, feed and medicate. Different porcine breeds show different responses to the induction of specific diseases. For example, ossabaw minipigs provide a better model than Yucatan for the metabolic syndrome as they exhibit obesity, insulin resistance and hypertension, all of which are absent in the Yucatan. Similar metabolic/physiological differences exist between domestic breeds (e.g. Meishan v. Pietrain). The modern commercial (e.g. Large White) domestic pig has been the preferred model for developmental programming due to the 2- to 3-fold variation in body weight among littermates providing a natural form of foetal growth retardation not observed in ancient (e.g. Meishan) domestic breeds. Pigs have been increasingly used to study chronic ischaemia, therapeutic angiogenesis, hypertrophic cardiomyopathy and abdominal aortic aneurysm as their coronary anatomy and physiology are similar to humans. Type 1 and II diabetes can be induced in swine using dietary regimes and/or administration of streptozotocin. Pigs are a good and extensively used model for specific nutritional studies as their protein and lipid metabolism is comparable with humans, although pigs are not as sensitive to protein restriction as rodents. Neonatal and weanling pigs have been used to examine the pathophysiology and prevention/treatment of microbial-associated diseases and immune system disorders. A porcine model mimicking various degrees of prematurity in infants receiving total parenteral nutrition has been established to investigate gut development, amino acid metabolism and non-alcoholic fatty liver disease. Endoscopic therapeutic methods for upper gastrointestinal tract bleeding are being developed. Bone remodelling cycle in pigs is histologically more similar to humans than that of rats or mice, and is used to examine the relationship between menopause and osteoporosis. Work has also been conducted on dental implants in pigs to consider loading; however with caution as porcine bone remodels slightly faster than human bone. We conclude that pigs are a valuable translational model to bridge the gap between classical rodent models and humans in developing new therapies to aid human health.

Energetics of climate models: net energy balance and meridional enthalpy transport

We analyze the publicly released outputs of the simulations performed by climate models (CMs) in preindustrial (PI) and Special Report on Emissions Scenarios A1B (SRESA1B) conditions. In the PI simulations, most CMs feature biases of the order of 1 W m −2 for the net global and the net atmospheric, oceanic, and land energy balances. This does not result from transient effects but depends on the imperfect closure of the energy cycle in the fluid components and on inconsistencies over land. Thus, the planetary emission temperature is underestimated, which may explain the CMs' cold bias. In the PI scenario, CMs agree on the meridional atmospheric enthalpy transport's peak location (around 40°N/S), while discrepancies of ∼20% exist on the intensity. Disagreements on the oceanic transport peaks' location and intensity amount to ∼10° and ∼50%, respectively. In the SRESA1B runs, the atmospheric transport's peak shifts poleward, and its intensity increases up to ∼10% in both hemispheres. In most CMs, the Northern Hemispheric oceanic transport decreases, and the peaks shift equatorward in both hemispheres. The Bjerknes compensation mechanism is active both on climatological and interannual time scales. The total meridional transport peaks around 35° in both hemispheres and scenarios, whereas disagreements on the intensity reach ∼20%. With increased CO 2 concentration, the total transport increases up to ∼10%, thus contributing to polar amplification of global warming. Advances are needed for achieving a self-consistent representation of climate as a nonequilibrium thermodynamical system. This is crucial for improving the CMs' skill in representing past and future climate changes.

Gas-phase kinetics of chlorosilylene reactions II. ClSiH + C2H4: absolute rate measurements and quantum chemical and RRKM calculations for the prototype pi addition reaction

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1-silacyclopent-3-ene, are carried out to obtain rate constants for its bimolecular reaction with ethene, C2H4, in the gas-phase. The reaction is studied over the pressure range 0.13-13.3 kPa (with added SF6) at five temperatures in the range 296-562 K. The second order rate constants, obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equation: log(k(infinity)/cm(3) molecule(-1) s(-1))=(-10.55 +/- 0.10) + (3.86 +/- 0.70) kJ mol(-1)/RT ln10. The Arrhenius parameters correspond to a loose transition state and the rate constant at room temperature is 43% of that for SiH2 + C2H4, showing that the deactivating effect of Cl-for-H substitution in the silylene is not large. Quantum chemical calculations of the potential energy surface for this reaction at the G3MP2//B3LYP level show that, as well as 1-chlorosilirane, ethylchlorosilylene is a viable product. The calculations reveal how the added effect of the Cl atom on the divalent state stabilisation of ClSiH influences the course of this reaction. RRKM calculations of the reaction pressure dependence suggest that ethylchlorosilylene should be the main product. The results are compared and contrasted with those of SiH2 and SiCl2 with C2H4.

Fabrication and characterization of micromachined rectangular waveguide components for use at millimeter-wave and terahertz frequencies

The fabrication and characterization of micromachined reduced-height air-filled rectangular waveguide components suitable for integration is reported in this paper. The lithographic technique used permits structures with heights of up to 100 μm to be successfully constructed in a repeatable manner. Waveguide S-parameter measurements at frequencies between 75-110 GHz using a vector network analyzer demonstrate low loss propagation in the TE10 mode reaching 0.2 dB per wavelength. Scanning electron microscope photographs of conventional and micromachined waveguides show that the fabrication technique can provide a superior surface finish than possible with commercially available components. In order to circumvent problems in efficiently coupling free-space propagating beams to the reduced-height G-band waveguides, as well as to characterize them using quasi-optical techniques, a novel integrated micromachined slotted horn antenna has been designed and fabricated, E-, H-, and D-plane far-field antenna pattern measurements at different frequencies using a quasi-optical setup show that the fabricated structures are optimized for 180-GHz operation with an E-plane half-power beamwidth of 32° elevated 35° above the substrate, a symmetrical H-plane pattern with a half-power beamwidth of 23° and a maximum D-plane cross-polar level of -33 dB. Far-field pattern simulations using HFSS show good agreement with experimental results.

Synthesis and characterization of Cu(II) complexes of tetradentate and tridentate symmetrical Schiff base ligands involving o-phenelenediamine, salicylaldehyde and diacetylmonoxime

A mononuclear complex [CuL] (1), a binuclear complex [Cu2LCl2(H2O)] (2), a trinuclear complex [Cu3L2](ClO4)(2) (3) involving o-phenylenediamine and salicylaldehyde and another binuclear complex of a tridentate ligand (H2L1) [Cu2L (2) (1) ](CH3COO)(2) (4) involving o-phenylenediamine and diacetylmonoxime have been synthesized, where H2L = N,N'-o-phenylenebis(salicylideneimine) and H2L1 = 3-(2-aminophenylimino)butan-2-one oxime. All the complexes have been characterized by elemental analyses, spectral and magnetic studies. The binuclear complex (2) was characterized structurally where the two Cu(II) centers are connected via an oxygen-bridged arrangement.

A comparative analysis of projected impacts of climate change on river runoff from global and catchment-scale hydrological models

We present a comparative analysis of projected impacts of climate change on river runoff from two types of distributed hydrological model, a global hydrological model (GHM) and catchment-scale hydrological models (CHM). Analyses are conducted for six catchments that are global in coverage and feature strong contrasts in spatial scale as well as climatic and development conditions. These include the Liard (Canada), Mekong (SE Asia), Okavango (SW Africa), Rio Grande (Brazil), Xiangu (China) and Harper's Brook (UK). A single GHM (Mac-PDM.09) is applied to all catchments whilst different CHMs are applied for each catchment. The CHMs typically simulate water resources impacts based on a more explicit representation of catchment water resources than that available from the GHM, and the CHMs include river routing. Simulations of average annual runoff, mean monthly runoff and high (Q5) and low (Q95) monthly runoff under baseline (1961-1990) and climate change scenarios are presented. We compare the simulated runoff response of each hydrological model to (1) prescribed increases in global mean temperature from the HadCM3 climate model and (2)a prescribed increase in global-mean temperature of 2oC for seven GCMs to explore response to climate model and structural uncertainty. We find that differences in projected changes of mean annual runoff between the two types of hydrological model can be substantial for a given GCM, and they are generally larger for indicators of high and low flow. However, they are relatively small in comparison to the range of projections across the seven GCMs. Hence, for the six catchments and seven GCMs we considered, climate model structural uncertainty is greater than the uncertainty associated with the type of hydrological model applied. Moreover, shifts in the seasonal cycle of runoff with climate change are presented similarly by both hydrological models, although for some catchments the monthly timing of high and low flows differs.This implies that for studies that seek to quantify and assess the role of climate model uncertainty on catchment-scale runoff, it may be equally as feasible to apply a GHM as it is to apply a CHM, especially when climate modelling uncertainty across the range of available GCMs is as large as it currently is. Whilst the GHM is able to represent the broad climate change signal that is represented by the CHMs, we find, however, that for some catchments there are differences between GHMs and CHMs in mean annual runoff due to differences in potential evaporation estimation methods, in the representation of the seasonality of runoff, and in the magnitude of changes in extreme monthly runoff, all of which have implications for future water management issues.

Integration of remote sensing and GIS for modelling flash floods in Wadi Hudain catchment, Egypt

This paper presents a new approach to modelling flash floods in dryland catchments by integrating remote sensing and digital elevation model (DEM) data in a geographical information system (GIS). The spectral reflectance of channels affected by recent flash floods exhibit a marked increase, due to the deposition of fine sediments in these channels as the flood recedes. This allows the parts of a catchment that have been affected by a recent flood event to be discriminated from unaffected parts, using a time series of Landsat images. Using images of the Wadi Hudain catchment in southern Egypt, the hillslope areas contributing flow were inferred for different flood events. The SRTM3 DEM was used to derive flow direction, flow length, active channel cross-sectional areas and slope. The Manning Equation was used to estimate the channel flow velocities, and hence the time-area zones of the catchment. A channel reach that was active during a 1985 runoff event, that does not receive any tributary flow, was used to estimate a transmission loss rate of 7·5 mm h−1, given the maximum peak discharge estimate. Runoff patterns resulting from different flood events are quite variable; however the southern part of the catchment appears to have experienced more floods during the period of study (1984–2000), perhaps because the bedrock hillslopes in this area are more effective at runoff production than other parts of the catchment which are underlain by unconsolidated Quaternary sands and gravels. Due to high transmission loss, runoff generated within the upper reaches is rarely delivered to the alluvial fan and Shalateen city situated at the catchment outlet. The synthetic GIS-based time area zones, on their own, cannot be relied on to model the hydrographs reliably; physical parameters, such as rainfall intensity, distribution, and transmission loss, must also be considered.