Synthesis, structure, solution chemistry and the electronic effect of para substituents on the vanadium center in a family of mixed-ligand [(VO)-O-V(ONO)(ON)] compexes

Four tridentate dibasic ONO donor hydrazone ligands derived from the condensation of benzoylhydrazine with either 2-hydroxyacetophenone or its para substituted derivatives (H2L1-4, general abbreviation H2L) have been used as primary ligands and 8-hydroxyquinoline (Hhq, a bidentate monobasic ON donor species) has been used as auxiliary ligand. The reaction of [(VO)-O-IV(acac)21 with H2L in methanol followed by the addition of Hhq in equimolar ratio under aerobic condition afforded the mixed-ligand oxovanadium(V) complexes of the type [(VO)-O-V(L)(hq)] (1-4) in excellent yield. The X-ray structure of the compound [(VO)-O-V(L-4)(hq)] (4) indicates that the H2L4 ligand is bonded with vanadium meridionally in a tridentate dinegative fashion through its deprotonated phenolic-O, deprotonated enolic-O and imine-N atoms. The V-O bond length order is: oxo < phenolato < enolato. H-1 NMR spectra of 4 in CDCl3 solution indicates that it's solid-state structure is retained in solution. Complexes are diamagnetic and exhibit only ligand to metal charge transfer (LMCT) transition band near 530 nm in CH2Cl2 solution in addition to intra-ligand pi-pi* transition band near 335 rim and they display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. lambda(max) (for LMCT transition) and the reduction peak potential (E-p(c)) values of the complexes are found to be linearly related with the Hammett (sigma) constants of the substituents in the aryloxy ring of the hydrazone ligands. lambda(max) and E-p(c) values show large dependence d lambda(max)/d sigma = 32.54 nm and dE(p)(c)/d sigma = 0.19 V, respectively, on the Hammett constant. (c) 2006 Elsevier B.V. All rights reserved.

Effect of small, acid-soluble proteins on spore resistance and germination under a combination of pressure and heat treatment

To find the range of pressure required for effective high-pressure inactivation of bacterial spores and to investigate the role of alpha/beta-type small, acid-soluble proteins (SASP) in spores under pressure treatment, mild heat was combined with pressure (room temperature to 65 degrees C and 100 to 500 MPa) and applied to wild-type and SASP-alpha(-/)beta(-) Bacillus subtilis spores. On the one hand, more than 4 log units of wild-type spores were reduced after pressurization at 100 to 500 MPa and 65 degrees C, On the other hand, the number of surviving mutant spores decreased by 2 log units at 100 MPa and by more than 5 log units at 500 MPa. At 500 MPa and 65 degrees C, both wild-type and mutant spore survivor counts were reduced by 5 log units. Interestingly, pressures of 100, 200, and 300 MPa at 65 degrees C inactivated wild-type SASP-alpha(+)/beta(+) spores more than mutant SASP-alpha(-)/beta(-) spores, and this was attributed to less pressure-induced germination in SASP-alpha(-)/beta(-) spores than in wild-type SASP-alpha(+)/beta(+) spores. However, there was no difference in the pressure resistance between SASP-alpha(+)/beta(+) and SASP-alpha(-)/beta(-) spores at 100 MPa and ambient temperature (approximately 22 degrees C) for 30 min. A combination of high pressure and high temperature is very effective for inducing spore germination, and then inactivation of the germinated spore occurs because of the heat treatment. This study showed that alpha/beta-type SASP play a role in spore inactivation by increasing spore germination under 100 to 300 MPa at high temperature.

Effect of headgroup size, charge, and solvent structure on polymer−micelle interactions, studied by molecular dynamics simulations

We performed atomistic molecular dynamics simulations of anionic and cationic micelles in the presence of poly(ethylene oxide) (PEO) to understand why nonionic water-soluble polymers such as PEO interact strongly with anionic micelles but only weakly with cationic micelles. Our micelles include sodium n-dodecyl sulfate (SDS), n-dodecyl trimethylammonium chloride (DTAC), n-dodecyl ammonium chloride (DAC), and micelles in which we artificially reverse the sign of partial charges in SDS and DTAC. We observe that the polymer interacts hydrophobically with anionic SDS but only weakly with cationic DTAC and DAC, in agreement with experiment. However, the polymer also interacts with the artificial anionic DTAC but fails to interact hydrophobically with the artificial cationic SDS, illustrating that large headgroup size does not explain the weak polymer interaction with cationic micelles. In addition, we observe through simulation that this preference for interaction with anionic micelles still exists in a dipolar "dumbbell" solvent, indicating that water structure and hydrogen bonding alone cannot explain this preferential interaction. Our simulations suggest that direct electrostatic interactions between the micelle and polymer explain the preference for interaction with anionic micelles, even though the polymer overall carries no net charge. This is possible given the asymmetric distribution of negative charges on smaller atoms and positive charges oil larger units in the polymer chain.

Effects of non-host plant odour on Meligethes aeneus during immigration to oilseed rape

The use of semiochemicals for the manipulation of the pollen beetle, Meliethes aeneus (Fabricius) (Coleoptera: Nitidulidae), is being investigated for potential incorporation into a push-pull strategy for this pest, which damages oilseed rape, Brassica napus L. (Brassicaceae), throughout Europe. Previous laboratory behavioural studies using volatiles from non-host plants showed that M. aeneus is repelled by the odour of lavender, Lavendula angustifolia Mill. (Lamiaceae), essential oil. This article reports on semi-field and field trials to investigate this behaviour under more realistic conditions. Semi-field experiments were conducted to assess the relative importance of olfaction at different points in host location behaviour by M. aeneus. The results showed that oilseed rape plants treated with lavender odour were less colonised by M. aeneus in comparison with an untreated control, but that the treatment effect was much reduced if the lavender odour was applied after colonisation. The field experiment demonstrated that lavender odour caused a significant reduction in the number of adultM. aeneus infesting the oilseed rape plants in the treatment plots compared to the control plots. Overall, these findings are very encouraging for the future development of a push-pull pest control system.

The global-scale impacts of climate change on water resources and flooding under new climate and socio-economic scenarios

This paper presents a preliminary assessment of the relative effects of rate of climate change (four Representative Concentration Pathways - RCPs), assumed future population (five Shared Socio-economic Pathways - SSPs), and pattern of climate change (19 CMIP5 climate models) on regional and global exposure to water resources stress and river flooding. Uncertainty in projected future impacts of climate change on exposure to water stress and river flooding is dominated by uncertainty in the projected spatial and seasonal pattern of change in climate. There is little clear difference in impact between RCP2.6, RCP4.5 and RCP6.0 in 2050, and between RCP4.5 and RCP6.0 in 2080. Impacts under RCP8.5 are greater than under the other RCPs in 2050 and 2080. For a given RCP, there is a difference in the absolute numbers of people exposed to increased water resources stress or increased river flood frequency between the five SSPs. With the ‘middle-of-the-road’ SSP2, climate change by 2050 would increase exposure to water resources stress for between approximately 920 and 3400 million people under the highest RCP, and increase exposure to river flood risk for between 100 and 580 million people. Under RCP2.6, exposure to increased water scarcity would be reduced in 2050 by 22-24%, compared to impacts under the RCP8.5, and exposure to increased flood frequency would be reduced by around 16%. The implications of climate change for actual future losses and adaptation depend not only on the numbers of people exposed to changes in risk, but also on the qualitative characteristics of future worlds as described in the different SSPs. The difference in ‘actual’ impact between SSPs will therefore be greater than the differences in numbers of people exposed to impact.

Participatory scenarios as a tool to link science and policy on food security under climate change in East Africa

How effective are multi-stakeholder scenarios building processes to bring diverse actors together and create a policy-making tool to support sustainable development and promote food security in the developing world under climate change? The effectiveness of a participatory scenario development process highlights the importance of ‘boundary work’ that links actors and organizations involved in generating knowledge on the one hand, and practitioners and policymakers who take actions based on that knowledge on the other. This study reports on the application of criteria for effective boundary work to a multi-stakeholder scenarios process in East Africa that brought together a range of regional agriculture and food systems actors. This analysis has enabled us to evaluate the extent to which these scenarios were seen by the different actors as credible, legitimate and salient, and thus more likely to be useful. The analysis has shown gaps and opportunities for improvement on these criteria, such as the quantification of scenarios, attention to translating and communicating the results through various channels and new approaches to enable a more inclusive and diverse group of participants. We conclude that applying boundary work criteria to multi-stakeholder scenarios processes can do much to increase the likelihood of developing sustainable development and food security policies that are more appropriate.

The effects of retinoic acid on human corneal stromal keratocytes cultured in vitro under serum-free conditions

Purpose: Retinoic acid (RA) is a metabolite of vitamin A that plays a fundamental role in the development and function of the human eye. The purpose of this study was to investigate the effects of RA on the phenotype of corneal stromal keratocytes maintained in vitro for extended periods under serum-free conditions. Methods: Keratocytes isolated from human corneas were cultured up to 21 days in serum-free media supplemented with RA or DMSO vehicle. The effects of RA and of its removal after treatment on cell proliferation and morphology were evaluated. In addition, the expression of keratocyte markers was quantified at the transcriptional and protein levels by quantitative PCR and immunoblotting or ELISA, respectively. Furthermore, the effects of RA on keratocyte migration were tested using scratch assays. Results: Keratocytes cultured with RA up to 10×10-6 M showed enhanced proliferation and stratification, and reduced mobility. RA also promoted the expression of keratocyte-characteristic proteoglycans such as keratocan, lumican, and decorin, and increased the amounts of collagen type-I in culture while significantly reducing the expression of matrix metalloproteases 1, 3, and 9. RA effects were reversible, and cell phenotype reverted to that of control after removal of RA from media. Conclusions: RA was shown to control the phenotype of human corneal keratocytes cultured in vitro by regulating cell behaviour and extracellular matrix composition. These findings contribute to our understanding of corneal stromal biology in health and disease, and may prove useful in optimizing keratocyte cultures for applications in tissue engineering, cell biology, and medicine.

An interdisciplinary modelling approach asessing the cost-effectiveness of agri-environmental measures on reducing nutrient concentration to WFD thresholds under climate change: the case of the Louros catchment

The application of the Water Framework Directive (WFD) in the European Union (EU) targets certain threshold levels for the concentration of various nutrients, nitrogen and phosphorous being the most important. In the EU, agri-environmental measures constitute a significant component of Pillar 2—Rural Development Policies in both financial and regulatory terms. Environmental measures also are linked to Pillar 1 payments through cross-compliance and the greening proposals. This paper drawing from work carried out in the REFRESH FP7 project aims to show how an INtegrated CAtchment model of plant/soil system dynamics and instream biogeochemical and hydrological dynamics can be used to assess the cost-effectiveness of agri-environmental measures in relation to nutrient concentration targets set by the WFD, especially in the presence of important habitats. We present the procedures (methodological steps, challenges and problems) for assessing the cost-effectiveness of agri-environmental measures at the baseline situation, and climate and land use change scenarios. Furthermore, we present results of an application of this methodology to the Louros watershed in Greece and discuss the likely uses and future extensions of the modelling approach. Finally, we attempt to reveal the importance of this methodology for designing and incorporating alternative environmental practices in Pillar 1 and 2 measures.

Intensified impact of tropical Atlantic SST on the western North Pacific summer climate under a weakened Atlantic thermohaline circulation

The tropical North Atlantic (TNA) sea surface temperature (SST) has been identified as one of regulators on the boreal summer climate over the western North Pacific (WNP), in addition to SSTs in the tropical Pacific and Indian Oceans. The major physical process proposed is that the TNA warming induces a pair of cyclonic circulation anomaly over the eastern Pacific and negative precipitation anomalies over the eastern to central tropical Pacific, which in turn lead to an anticyclonic circulation anomaly over the western to central North Pacific. This study further demonstrates that the modulation of the TNA warming to the WNP summer climate anomaly tends to be intensified under background of the weakened Atlantic thermohaline circulation (THC) by using a water-hosing experiment. The results suggest that the weakened THC induces a decrease in thermocline depth over the TNA region, resulting in the enhanced sensitivity of SST variability to wind anomalies and thus intensification of the interannual variation of TNA SST. Under the weakened THC, the atmospheric responses to the TNA warming are westward shifted, enhancing the anticyclonic circulation and negative precipitation anomaly over the WNP. This study supports the recent finding that the negative phase of the Atlantic multidecadal oscillation after the late 1960s has been favourable for the strengthening of the connection between TNA SST variability and WNP summer climate and has important implications for seasonal prediction and future projection of the WNP summer climate.

Subsurface urban heat island and its effects on horizontal ground-source heat pump potential under climate change

Recent urban air temperature increase is attributable to the climate change and heat island effects due to urbanization. This combined effects of urbanization and global warming can penetrate into the underground and elevate the subsurface temperature. In the present study, over-100 years measurements of subsurface temperature at a remote rural site were analysed, and an increasing rate of 0.17⁰C per decade at soil depth of 30cm due to climate change was identified in the UK, but the subsurface warming in an urban site showed a much higher rate of 0.85⁰C per decade at a 30cm depth and 1.18⁰C per decade at 100cm. The subsurface urban heat island (SUHI) intensity obtained at the paired urban-rural stations in London showed an unique 'U-shape', i.e. lowest in summer and highest during winter. The maximum SUHII is 3.5⁰C at 6:00 AM in December, and the minimum UHII is 0.2⁰C at 18:00PM in July. Finally, the effects of SUHI on the energy efficiency of the horizontal ground source heat pump (GSHP) were determined. Provided the same heat pump used, the installation at an urban site will maintain an overall higher COP compared with that at a rural site in all seasons, but the highest COP improvement can be achieved in winter.

Interacting controls on innate sources of CO2 efflux from a calcareous arid zone soil under experimental acidification and wetting

More than half of global soil carbon is stored as carbonates, primarily in arid and semi-arid zones. Climate change models predict more frequent and severe rainfall events in some parts of the globe, many of which are dominated by calcareous soils. Such events trigger substantial increases in soil CO2 efflux. We hypothesised that the primary source of CO2 emissions from calcareous, arid zone soil during a single wetting event is abiotic and that soil acidification and wetting have a positive, potentially interacting, effect. We manipulated soil pH, soil moisture, and controlled soil respiration by gamma irradiating half of an 11 day incubation experiment. All manipulated experimental treatments had a rapid and enormous effect on CO2 emission. Respiration contributed ca. 5% of total CO2 efflux; the major source (carbonate buffering) varied depending on the extent of acidification and wetting. Maximum CO2 efflux occurred when pH was lowest and at intermediate matric potential. CO2 efflux was lowest at native pH when soil was air dry. Our data suggest that there may be an underestimate of soil-atmosphere carbon fluxes in arid ecosystems with calcareous soils. There is also a clear potential that these soils may become net carbon sources depending on changes in rainfall patterns, rainfall acidity, and future land management. Our findings have major implications for carbon cycling in arid zone soil and further study of carbon dynamics in these terrestrial systems at a landscape level will be required if we are to improve global climate and carbon cycling models.