Hydrogen-bond assisted stabilization of the less favored conformation of a tridentate Schiff base ligand in dinuclear nickel(II) complex: an experimental and theoretical study

The Schiff base ligand, HL (2-[1-(3-methylamino-propylimino)-ethyl]-phenol), the 1:1 condensation product of 2-hydroxy acetophenone and N-methyl-1,3-diaminopropane, has been synthesized and characterized by X-ray crystallography as the perchlorate salt [H2L]ClO4 (1). The structure consists of discrete [H2L](+) cations and perchlorate anions. Two dinuclear Ni-II complexes, [Ni2L2(NO2)(2)] (2), [Ni2L2(NO3)(2)] (3) have been synthesized using this ligand and characterized by single crystal X-ray analyses. Complexes 2 and 3 are centrosymmetric dimers in which the Ni-II ions are in distorted fac- and mer-octahedral environments, respectively, bridged by two mu(2)-phenolate ions of deprotonated ligand, L. The plane of the phenyl rings and the Ni2O2 basal plane are nearly coplanar in 2 but almost perpendicular in 3. We have studied and explained this different behavior using high level DFT calculations (RI-BP86/def2-TZVP level of theory). The conformation observed in 3, which is energetically less favorable, is stabilized via intermolecular non-covalent interactions. Under the excitation of ultraviolet light, characteristic fluorescence of compound 1 was observed; by comparison fluorescence intensity decreases in case of compound 3 and completely quenched in compound 2.

Boundaries and Bridges: the influence of James Cooksey Culwick on the development of the teaching and learning of music in nineteenth century Ireland

James Cooksey Culwick (1845-1907) was born in England. Trained as chorister and organist in Lichfield Cathedral, he moved to Ireland at twenty- one and remained until his death in 1907. Although his reputation as scholar, musician and teacher was acknowledged widely during his lifetime - he received an honorary doctorate from University of Dublin (1893) - little is known about the contribution he made to music education. This paper addresses this gap in the literature and argues that it was Culwick's singular achievement to pay attention to music pedagogy at secondary level, by recognizing that music could be seen as a serious career option for girls, and by providing resources for teachers which emphasised the development of an 'art-feeling' in pupils of all abilities. In addition, he considered Irish music as an art which had significance as music first, and Irish music second, and advocated a 'laudable tolerance' for opposing views on matters of cultural identity to Ireland at the end of the nineteenth century.

Hurricanes and climate: the U.S. CLIVAR working group on hurricanes

While a quantitative climate theory of tropical cyclone formation remains elusive, considerable progress has been made recently in our ability to simulate tropical cyclone climatologies and understand the relationship between climate and tropical cyclone formation. Climate models are now able to simulate a realistic rate of global tropical cyclone formation, although simulation of the Atlantic tropical cyclone climatology remains challenging unless horizontal resolutions finer than 50 km are employed. This article summarizes published research from the idealized experiments of the Hurricane Working Group of U.S. CLIVAR (CLImate VARiability and predictability of the ocean-atmosphere system). This work, combined with results from other model simulations, has strengthened relationships between tropical cyclone formation rates and climate variables such as mid-tropospheric vertical velocity, with decreased climatological vertical velocities leading to decreased tropical cyclone formation. Systematic differences are shown between experiments in which only sea surface temperature is increased versus experiments where only atmospheric carbon dioxide is increased, with the carbon dioxide experiments more likely to demonstrate the decrease in tropical cyclone numbers previously shown to be a common response of climate models in a warmer climate. Experiments where the two effects are combined also show decreases in numbers, but these tend to be less for models that demonstrate a strong tropical cyclone response to increased sea surface temperatures. Further experiments are proposed that may improve our understanding of the relationship between climate and tropical cyclone formation, including experiments with two-way interaction between the ocean and the atmosphere and variations in atmospheric aerosols.

Uptake of agri-environmental schemes in the Less-Favoured Areas of Greece: The role of corruption and farmers' responses to the financial crisis

Vine-growing in the Less-Favoured Areas of Greece is facing multiple challenges that might lead to its abandonment. In an attempt to maintain rural populations, Rural Development Schemes have been created that offer the opportunity to rural households to maintain or expand their farming businesses including vine-growing. This paper stems from a study that used data from a cross-sectional survey of 204 farmers to investigate how farming systems and farmers’ perception of corruption, amongst other socio-economic factors, affected their decisions to continue vine-growing through participation in Rural Development Schemes, in three remote Less-Favoured Areas of Greece. The Theory of Planned Behaviour was used to frame the research problem with the assumption being that an individual’s intention to participate in a Scheme is based on their prior beliefs about it. Data from the survey were reduced and simplified by the use of non-linear principal component analysis. The ensuing variables were used in selectivity corrected ordered probit models to reveal farmers’ attitudes towards viticulture and rural development. It was found that economic factors, perceived corruption and farmers’ attitudes were significant determinants on whether to participate in the Schemes. The research findings highlight the important role of perceived corruption and the need for policies that facilitate farmers’ access to decision making centres.

Combining 3D and 2D for less constrained periocular recognition

Periocular recognition has recently become an active topic in biometrics. Typically it uses 2D image data of the periocular region. This paper is the first description of combining 3D shape structure with 2D texture. A simple and effective technique using iterative closest point (ICP) was applied for 3D periocular region matching. It proved its strength for relatively unconstrained eye region capture, and does not require any training. Local binary patterns (LBP) were applied for 2D image based periocular matching. The two modalities were combined at the score-level. This approach was evaluated using the Bosphorus 3D face database, which contains large variations in facial expressions, head poses and occlusions. The rank-1 accuracy achieved from the 3D data (80%) was better than that for 2D (58%), and the best accuracy (83%) was achieved by fusing the two types of data. This suggests that significant improvements to periocular recognition systems could be achieved using the 3D structure information that is now available from small and inexpensive sensors.

The Representative Soil Sampling Scheme of England and Wales: the spatial variation of topsoil nutrient status and pH between 1971 and 2001

The Representative Soil Sampling Scheme (RSSS) has monitored the soil of agricultural land in England and Wales since 1969. Here we describe the first spatial analysis of the data from these surveys using geostatistics. Four years of data (1971, 1981, 1991 and 2001) were chosen to examine the nutrient (available K, Mg and P) and pH status of the soil. At each farm, four fields were sampled; however, for the earlier years, coordinates were available for the farm only and not for each field. The averaged data for each farm were used for spatial analysis and the variograms showed spatial structure even with the smaller sample size. These variograms provide a reasonable summary of the larger scale of variation identified from the data of the more intensively sampled National Soil Inventory. Maps of kriged predictions of K generally show larger values in the central and southeastern areas (above 200 mg L-1) and an increase in values in the west over time, whereas Mg is fairly stable over time. The kriged predictions of P show a decline over time, particularly in the east, and those of pH show an increase in the east over time. Disjunctive kriging was used to examine temporal changes in available P using probabilities less than given thresholds of this element. The RSSS was not designed for spatial analysis, but the results show that the data from these surveys are suitable for this purpose. The results of the spatial analysis, together with those of the statistical analyses, provide a comprehensive view of the RSSS database as a basis for monitoring the soil. These data should be taken into account when future national soil monitoring schemes are designed.

A comparative study of the effects of metal contamination on collembola in the field and in the laboratory

We examined the species diversity and abundance of Collembola at 32 sampling points along a gradient of metal contamination in a rough grassland site ( Wolverhampton, England), formerly used for the disposal of metal-rich smelting waste. Differences in the concentrations of Cd, Cu, Pb and Zn between the least and most contaminated part of the 35 metre transect were more than one order of magnitude. A gradient of Zn concentrations from 597 to 9080 mug g(-1) dry soil was found. A comparison between field concentrations of the four metals and previous studies on their relative toxicities to Collembola, suggested that Zn is likely to be responsible for any ecotoxicological effects on springtails at this site. Euedaphic ( soil dwelling) Collembola were extracted by placing soil cores into Tullgren funnels and epedaphic ( surface dwelling) species were sampled using pitfall traps. There was no obvious relationship between the total abundance, or a range of commonly used diversity indices, and Zn levels in soils. However, individual species showed considerable differences in abundance. Metal "tolerant'' (e.g., Ceratophysella denticulata) and metal "sensitive'' (e.g., Cryptopygus thermophilus) species could be identified. Epedaphic species appeared to be influenced less by metal contamination than euedaphic species. This difference is probably due to the higher mobility and lower contact with the soil pore water of epedaphic springtails in comparison to euedaphic Collembola. In an experiment exposing the standard test springtail, Folsomia candida, to soils from all 32 sampling points, adult survival and reproduction showed small but significant negative relationships with total Zn concentrations. Nevertheless, juveniles were still produced from eggs laid by females in the most contaminated soils with 9080 mug g(-1) Zn. Folsomia candida is much more sensitive to equivalent concentrations of Zn in the standard OECD soil. Thus, care should be taken in extrapolating the results of laboratory toxicity tests on metals in OECD soil to field soils, in which, the biological availability of contaminants is likely to be lower. Our studies have shown the importance of ecotoxicological effects at the species level. Although there may be no differences in overall abundance, sensitive species that are numerous in contaminated sites, and which may play important roles in decomposition("keystone species'') can be greatly reduced in numbers by pollution.

Variation in the ability of human influenza A viruses to induce and inhibit the IFN-beta pathway

We investigated the ability of a selection of human influenza A viruses, including recent clinical isolates, to induce IFN-beta production in cultured cell lines. In contrast to the well-characterized laboratory strain A/PR/8/34, several, but not all, recent isolates of H3N2 viruses resulted in moderate IFN-beta stimulation. Through the generation of recombinant viruses, we were able to show that this is not due to a loss of the ability of the NS1 genes to suppress IFN-beta induction; indeed, the NS1 genes behaved similarly with respect to their abilities to block dsRNA signaling. Interestingly, replication of A/Sydney/5/97 virus was less Susceptible to pre-treatment with IFN-alpha than the other viruses. In contrast to the universal effect on dsRNA signaling, we noted differences in the effect of NS1 proteins on expression of interferon stimulated genes and also genes induced by a distinct pathway. The majority of NS1 proteins blocked expression From both IFN-dependent and TNF-dependent promoters by an apparent post-transcriptional mechanism. The NS1 gene of A/PR/8/34 NS1 did not confer these blocks. We noted striking differences in the Cellular localization of different influenza A virus NS1 proteins during infection, which might explain differences in biological activity. (C) 2005 Elsevier Inc. All rights reserved.

A comparative study of the effects of metal contamination on collembola in the field and in the laboratory

We examined the species diversity and abundance of Collembola at 32 sampling points along a gradient of metal contamination in a rough grassland site ( Wolverhampton, England), formerly used for the disposal of metal-rich smelting waste. Differences in the concentrations of Cd, Cu, Pb and Zn between the least and most contaminated part of the 35 metre transect were more than one order of magnitude. A gradient of Zn concentrations from 597 to 9080 mug g(-1) dry soil was found. A comparison between field concentrations of the four metals and previous studies on their relative toxicities to Collembola, suggested that Zn is likely to be responsible for any ecotoxicological effects on springtails at this site. Euedaphic ( soil dwelling) Collembola were extracted by placing soil cores into Tullgren funnels and epedaphic ( surface dwelling) species were sampled using pitfall traps. There was no obvious relationship between the total abundance, or a range of commonly used diversity indices, and Zn levels in soils. However, individual species showed considerable differences in abundance. Metal "tolerant'' (e.g., Ceratophysella denticulata) and metal "sensitive'' (e.g., Cryptopygus thermophilus) species could be identified. Epedaphic species appeared to be influenced less by metal contamination than euedaphic species. This difference is probably due to the higher mobility and lower contact with the soil pore water of epedaphic springtails in comparison to euedaphic Collembola. In an experiment exposing the standard test springtail, Folsomia candida, to soils from all 32 sampling points, adult survival and reproduction showed small but significant negative relationships with total Zn concentrations. Nevertheless, juveniles were still produced from eggs laid by females in the most contaminated soils with 9080 mug g(-1) Zn. Folsomia candida is much more sensitive to equivalent concentrations of Zn in the standard OECD soil. Thus, care should be taken in extrapolating the results of laboratory toxicity tests on metals in OECD soil to field soils, in which, the biological availability of contaminants is likely to be lower. Our studies have shown the importance of ecotoxicological effects at the species level. Although there may be no differences in overall abundance, sensitive species that are numerous in contaminated sites, and which may play important roles in decomposition("keystone species'') can be greatly reduced in numbers by pollution.

Power, nature and neoliberalism: the political ecology of water in Chile

Since the 1990s, international water sector reforms have centred heavily on economic and market approaches. In regard to water resources management, tradable water rights have been promoted, often supported by the neoliberal model adopted in Chile. Chile's 1981 Water Code was reformed to comprise a system of water rights that could be freely traded with few restrictions. International financial institutions have embraced the Chilean model, claiming that it results in more efficient water use, and potentially fosters social and environmental benefits. However, in Chile the Water Code is deeply contested. It has been criticised for being too permissive and has produced a number of problems in practice. Moreover, attempts to modify it have become the focus of a lengthy polemic debate. This paper employs a political ecology perspective to explore the socio-environmental outcomes of water management in Chile, drawing on a case study of agriculture in the semi-arid Norte Chico. The case illustrates how large-scale farmers exert greater control over water, while peasant farmers have increasingly less access. I argue that these outcomes are facilitated by the mode of water management implemented within the framework of the Water Code. Through this preliminary examination of social equity and the environmental aspects of water resources management in Chile, I suggest that the omission of these issues from the international debates on water rights markets is a cause for concern.

Gut microbial activity, implications for health and disease: the potential role of metabolite analysis

Microbial metabolism of proteins and amino acids by human gut bacteria generates a variety of compounds including phenol, indole, and sulfur compounds and branched chain fatty acids, many of which have been shown to elicit a toxic effect on the lumen. Bacterial fermentation of amino acids and proteins occurs mainly in the distal colon, a site that is often fraught with symptoms from disorders including ulcerative colitis (UC) and colorectal cancer (CRC). In contrast to carbohydrate metabolism by the gut microbiota, proteolysis is less extensively researched. Many metabolites are low molecular weight, volatile compounds. This review will summarize the use of analytical methods to detect and identify compounds in order to elucidate the relationship between specific dietary proteinaceous substrates, their corresponding metabolites, and implications for gastrointestinal health.

A mixture of trans-galactooligosaccharides reduces markers of metabolic syndrome and modulates the fecal microbiota and immune function of overweight adults

Metabolic syndrome is a set of disorders that increases the risk of developing cardiovascular disease. The gut microbiota is altered toward a less beneficial composition in overweight adults and this change can be accompanied by inflammation. Prebiotics such as galactooligosaccharides can positively modify the gut microbiota and immune system; some may also reduce blood lipids. We assessed the effect of a galactooligosaccharide mixture [Bi2 muno (B-GOS)] on markers of metabolic syndrome, gut microbiota, and immune function in 45 overweight adults with $3 risk factors associated with metabolic syndrome in a double-blind, randomized, placebo (maltodextrin)-controlled, crossover study (with a 4-wk wash-out period between interventions). Whole blood, saliva, feces, and anthropometric measurements were taken at the beginning, wk 6, and end of each 12-wk intervention period. Predominant groups of fecal bacteria were quantified and full blood count, markers of inflammation and lipid metabolism, insulin, and glucose were measured. B-GOS increased the number of fecal bifidobacteria at the expense of less desirable groups of bacteria. Increases in fecal secretory IgA and decreases in fecal calprotectin, plasma C-reactive protein, insulin, total cholesterol (TC), TG, and the TC:HDL cholesterol ratio were also observed. Administration of B-GOS to overweight adults resulted in positive effects on the composition of the gut microbiota, the immune response, and insulin, TC, and TG concentrations. B-GOSmay be a useful candidate for the enhancement of gastrointestinal health, immune function, and the reduction of metabolic syndrome risk factors in overweight adults.