Tuning of redox potential and visible absorption band of ruthenium(II) complexes of (benzimidazolyl) derivatives: synthesis, characterization, spectroscopic and redox properties, X-ray structures and DFT calculations

Six ruthenium(II) complexes have been prepared using the tridentate ligands 2,6-bis(benzimidazolyl) pyridine and bis(2-benzimidazolyl methyl) amine and having 2,2'-bipyridine, 2,2':6',2 ''-terpyridine, PPh3, MeCN and chloride as coligands. The crystal structures of three of the complexes trans-[Ru(bbpH(2))(PPh3)(2)(CH3CN)I(ClO4)(2) center dot 2H(2)O (2), [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy)](ClO4)(2) (4) are also reported. The complexes show visible region absorption at 402-517 nm, indicating that it is possible to tune the visible region absorption by varying the ancillary ligand. Luminescence behavior of the complexes has been studied both at RT and at liquid nitrogen temperature (LNT). Luminescence of the complexes is found to be insensitive to the presence of dioxygen. Two of the complexes [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy]ClO4)(2) (4) show RT emission in the NIR region, having lifetime, quantum yield and radiative constant values suitable for their application as NIR emitter in the solid state devices. The DFT calculations on these two complexes indicate that the metal t(2g) electrons are appreciably delocalized over the ligand backbone. (C) 2006 Elsevier B.V. All rights reserved.

Global radiative and climate effect of the water vapour continuum at visible and near-infrared wavelengths

Recent laboratory measurements show that absorption by the water vapour continuum in near-infrared windows may be about an order of magnitude higher than assumed in many radiation codes. The radiative impact of the continuum at visible and near-infrared wavelengths is examined for the present day and for a possible future warmer climate (with a global-mean total column water increase of 33%). The calculations use a continuum model frequently used in climate models (‘CKD’) and a continuum model where absorption is enhanced at wavelengths greater than 1 µm based on recent measurements (‘CAVIAR’). The continuum predominantly changes the partitioning between solar radiation absorbed by the surface and the atmosphere; changes in top-of-atmosphere net irradiances are smaller. The global-mean clear-sky atmospheric absorption is enhanced by 1.5 W m−2 (about 2%) and 2.8 W m−2 (about 3.5%) for CKD and CAVIAR respectively, relative to a hypothetical no-continuum case, with all-sky enhancements about 80% of these values. The continuum is, in relative terms, more important for radiation budget changes between the present day and a possible future climate. Relative to the no-continuum case, the increase in global-mean clear-sky absorption is 8% higher using CKD and almost 20% higher using CAVIAR; all-sky enhancements are about half these values. The effect of the continuum is estimated for the solar component of the water vapour feedback, the reduction in downward surface irradiance and precipitation change in a warmer world. For CKD and CAVIAR respectively, and relative to the no-continuum case, the solar component of the water vapour feedback is enhanced by about 4 and 9%, the change in clear-sky downward surface irradiance is 7 and 18% more negative, and the global-mean precipitation response decreases by 1 and 4%. There is a continued need for improved continuum measurements, especially at atmospheric temperatures and at wavelengths below 2 µm.

Improvements to the accuracy of measurements of NO2 by zenith-sky visible spectrometers II: errors in zero using a more complete chemical model

Using a flexible chemical box model with full heterogeneous chemistry, intercepts of chemically modified Langley plots have been computed for the 5 years of zenith-sky NO2 data from Faraday in Antarctica (65°S). By using these intercepts as the effective amount in the reference spectrum, drifts in zero of total vertical NO2 were much reduced. The error in zero of total NO2 is ±0.03×1015 moleccm−2 from one year to another. This error is small enough to determine trends in midsummer and any variability in denoxification between midwinters. The technique also suggests a more sensitive method for determining N2O5 from zenith-sky NO2 data.

Detection of flood extent in urban areas using high resolution TerraSAR-X data

Flooding is a major hazard in both rural and urban areas worldwide, but it is in urban areas that the impacts are most severe. An investigation of the ability of high resolution TerraSAR-X data to detect flooded regions in urban areas is described. An important application for this would be the calibration and validation of the flood extent predicted by an urban flood inundation model. To date, research on such models has been hampered by lack of suitable distributed validation data. The study uses a 3m resolution TerraSAR-X image of a 1-in-150 year flood near Tewkesbury, UK, in 2007, for which contemporaneous aerial photography exists for validation. The DLR SETES SAR simulator was used in conjunction with airborne LiDAR data to estimate regions of the TerraSAR-X image in which water would not be visible due to radar shadow or layover caused by buildings and taller vegetation, and these regions were masked out in the flood detection process. A semi-automatic algorithm for the detection of floodwater was developed, based on a hybrid approach. Flooding in rural areas adjacent to the urban areas was detected using an active contour model (snake) region-growing algorithm seeded using the un-flooded river channel network, which was applied to the TerraSAR-X image fused with the LiDAR DTM to ensure the smooth variation of heights along the reach. A simpler region-growing approach was used in the urban areas, which was initialized using knowledge of the flood waterline in the rural areas. Seed pixels having low backscatter were identified in the urban areas using supervised classification based on training areas for water taken from the rural flood, and non-water taken from the higher urban areas. Seed pixels were required to have heights less than a spatially-varying height threshold determined from nearby rural waterline heights. Seed pixels were clustered into urban flood regions based on their close proximity, rather than requiring that all pixels in the region should have low backscatter. This approach was taken because it appeared that urban water backscatter values were corrupted in some pixels, perhaps due to contributions from side-lobes of strong reflectors nearby. The TerraSAR-X urban flood extent was validated using the flood extent visible in the aerial photos. It turned out that 76% of the urban water pixels visible to TerraSAR-X were correctly detected, with an associated false positive rate of 25%. If all urban water pixels were considered, including those in shadow and layover regions, these figures fell to 58% and 19% respectively. These findings indicate that TerraSAR-X is capable of providing useful data for the calibration and validation of urban flood inundation models.

The retrieval of ice water content from radar reflectivity factor and temperature and its use in evaluating a mesoscale model

Ice clouds are an important yet largely unvalidated component of weather forecasting and climate models, but radar offers the potential to provide the necessary data to evaluate them. First in this paper, coordinated aircraft in situ measurements and scans by a 3-GHz radar are presented, demonstrating that, for stratiform midlatitude ice clouds, radar reflectivity in the Rayleigh-scattering regime may be reliably calculated from aircraft size spectra if the "Brown and Francis" mass-size relationship is used. The comparisons spanned radar reflectivity values from -15 to +20 dBZ, ice water contents (IWCs) from 0.01 to 0.4 g m(-3), and median volumetric diameters between 0.2 and 3 mm. In mixed-phase conditions the agreement is much poorer because of the higher-density ice particles present. A large midlatitude aircraft dataset is then used to derive expressions that relate radar reflectivity and temperature to ice water content and visible extinction coefficient. The analysis is an advance over previous work in several ways: the retrievals vary smoothly with both input parameters, different relationships are derived for the common radar frequencies of 3, 35, and 94 GHz, and the problem of retrieving the long-term mean and the horizontal variance of ice cloud parameters is considered separately. It is shown that the dependence on temperature arises because of the temperature dependence of the number concentration "intercept parameter" rather than mean particle size. A comparison is presented of ice water content derived from scanning 3-GHz radar with the values held in the Met Office mesoscale forecast model, for eight precipitating cases spanning 39 h over Southern England. It is found that the model predicted mean I WC to within 10% of the observations at temperatures between -30 degrees and - 10 degrees C but tended to underestimate it by around a factor of 2 at colder temperatures.

Conventions for writing the values of quantities in the SI

Possible improvements to the conventional rules for using and writing the values of quantities in the International System of Units (SI) are discussed in the light of recent suggestions for improving the system with a view to making it more adaptable to use in computer codes.

Public values for badgers, bovine TB reduction and management strategies

This paper applies an attribute-based stated choice experiment approach to estimate the value that society places on changes to the size of the badger population in England and Wales. The study was undertaken in the context of a rising incidence of bovine tuberculosis (bTB) in cattle and the government's review of current bTB control policy. This review includes consideration of culling badgers to reduce bTB in cattle, since badgers are thought to be an important wildlife reservoir for the disease. The design of the CE involved four attributes (size of badger population, cattle slaughtered due to bTB, badger management strategy and household tax) at four levels with eight choice sets of two alternatives presented to respondents. Telephone interviews were undertaken with over 400 respondents, which elicited their attitudes and preferences concerning badgers, bTB in cattle and badger management strategies. The study estimated a willingness to pay of 0.10 pound per household per year per 100,000 badgers and 1.52 pound per household per year per 10,000 cattle slaughtered due to bTB which aggregated to 22 per badger and 3298 pound per bTB slaughtered animal for all households in England and Wales. Management strategy toward badgers had a very high valuation, highlighting the emotive issue of badger culling for respondents and the importance of government policy towards badgers.

Evaluation of NRC, UC Davis and ADAS approaches to estimate the metabolizable energy values of feeds at maintenance energy intake from equations utilizing chemical assays and in vitro determinations

Feed samples received by commercial analytical laboratories are often undefined or mixed varieties of forages, originate from various agronomic or geographical areas of the world, are mixtures (e.g., total mixed rations) and are often described incompletely or not at all. Six unified single equation approaches to predict the metabolizable energy (ME) value of feeds determined in sheep fed at maintenance ME intake were evaluated utilizing 78 individual feeds representing 17 different forages, grains, protein meals and by-product feedstuffs. The predictive approaches evaluated were two each from National Research Council [National Research Council (NRC), Nutrient Requirements of Dairy Cattle, seventh revised ed. National Academy Press, Washington, DC, USA, 2001], University of California at Davis (UC Davis) and ADAS (Stratford, UK). Slopes and intercepts for the two ADAS approaches that utilized in vitro digestibility of organic matter and either measured gross energy (GE), or a prediction of GE from component assays, and one UC Davis approach, based upon in vitro gas production and some component assays, differed from both unity and zero, respectively, while this was not the case for the two NRC and one UC Davis approach. However, within these latter three approaches, the goodness of fit (r(2)) increased from the NRC approach utilizing lignin (0.61) to the NRC approach utilizing 48 h in vitro digestion of neutral detergent fibre (NDF:0.72) and to the UC Davis approach utilizing a 30 h in vitro digestion of NDF (0.84). The reason for the difference between the precision of the NRC procedures was the failure of assayed lignin values to accurately predict 48 h in vitro digestion of NDF. However, differences among the six predictive approaches in the number of supporting assays, and their costs, as well as that the NRC approach is actually three related equations requiring categorical description of feeds (making them unsuitable for mixed feeds) while the ADAS and UC Davis approaches are single equations, suggests that the procedure of choice will vary dependent Upon local conditions, specific objectives and the feedstuffs to be evaluated. In contrast to the evaluation of the procedures among feedstuffs, no procedure was able to consistently discriminate the ME values of individual feeds within feedstuffs determined in vivo, suggesting that the quest for an accurate and precise ME predictive approach among and within feeds, may remain to be identified. (C) 2004 Elsevier B.V. All rights reserved.

Synthesis, structure and solution chemistry of mixed-ligand oxovanadium(IV) and oxovanadium(V) complexes incorporating tridentate ONO donor hydrazone ligands

In the title family, the ONO donor ligands are the acetylhydrazones of salicylaidehyde (H2L1) and 2-hydroxyacetophenone (H2L2) (general abbreviation, H2L). The reaction of bis(acetylacetonato)oxovanadium(IV) with a mixture of tridentate H2L and a bidentate NN donor [e.g., 2,2'-bipyridine(bpy) or 1,10-phenanthroline(phen), hereafter B] ligands in equimolar ratio afforded the tetravalent complexes of the type [(VO)-O-IV(L)(B)]; complexes (1)-(4) whereas, if B is replaced by 8-hydroxyquinoline(Hhq) (which is a bidentate ON donor ligand), the above reaction mixture yielded the pentavalent complexes of the type [(VO)-O-V(L)(hq)]; complexes (5) and (6). Aerial oxygen is most likely the oxidant (for the oxidation of V-IV -> V-V) in the synthesis of pentavalent complexes (5) and (6). [(VO)-O-IV(L)(B)] complexes are one electron paramagnetic and display axial EPR spectra, while the [(VO)-O-V(L)(hq)] complexes are diamagnetic. The X-ray structure of [(VO)-O-V(L-2)(hq)] (6) indicates that H2L2 ligand is bonded with the vanadium meridionally in a tridentate dinegative fashion through its phenolic-O, enolic-O and imine-N atoms. The general bond length order is: oxo < phenolato < enolato. The V-O (enolato) bond is longer than V-O (phenolato) bond by similar to 0.07 angstrom and is identical with V-O (carboxylate) bond. H-1 NMR spectrum of (6) in CDCl3 solution indicates that the binding nature in the solid state is also retained in solution. Complexes (1)(4) display two ligand-field transitions in the visible region near 820 and 480 nm in DMF solution and exhibit irreversible oxidation peak near +0.60 V versus SCE in DMSO solution, while complexes (5) and (6) exhibit only LMCT band near 535 nm and display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. The VO3+-VO2+ E-1/2 values shift considerably to more negative values when neutral NN donor is replaced by anionic ON donor species and it also provides better VO3+ binding via phenolato oxygen. For a given bidentate ligand, E-1/2 increases in the order: (L-2)(2-) < (L-1)(2-). (c) 2004 Elsevier B.V. All rights reserved.

Chemical, physical and electrical properties of aged dodecylbenzene: thermal ageing of mixed isomers in air

A commercial dodecylbenzene (DDB) cable oil was aged at temperatures between 90 and 135 degrees C in air and was analyzed using various analytical techniques including optical and infra-red spectroscopy and dielectric analysis. On ageing, the oil darkened, significant oxidation features were found by infra-red spectroscopy and the acid number, water content and dielectric loss all increased. Ageing in the presence of paper or aluminum did not affect the ageing process, whereas ageing was significantly modified by the presence of copper. An absorption at 680 nm ("red absorbers") was detected by ultra-violet/visible spectroscopy followed by the production of an opaque precipitate. A reaction between copper and the acid generated on ageing is thought to produce copper carboxylates, and X-ray fluorescence confirmed that copper was indeed present in both the aged oil and the precipitate. Significantly, once red absorbers were detected, the dielectric loss increased to catastrophically high values and, therefore, the appearance of these compounds may serve as a useful diagnostic indicator. The development of acidity on ageing appears to be key in initiating the destructive copper conversion reaction and hence the control of oil acidity may be key to prolonging the life of DDB cable oils.