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.

Language support for immigrant children: a study of state schools in the UK and US

In recent decades, immigrants, refugees and asylum seekers have sought a new way of life in large numbers, often leaving their countries of origin behind in search of places that offer a better way of life. The purpose of this study was to investigate how elementary and middle school students in state schools in Reading, England (primarily speakers of Asian languages), and Richmond, Virginia (primarily speakers of Spanish), were supported academically, when most children's first language was not English. The authors were interested in exploring whether or not there were cultural or structural differences in the way each country helped or hindered these students as they progressed through the school systems. Three UK schools in a district of approximately 100,000 and three US schools in a district of approximately 250,000 were the focus of this exploration from 2000 to 2003. Findings indicated that there were cultural and legislative differences and similarities. Teachers and administrators in both countries attempted to provide services with limited and sometimes diminishing resources. Community support varied based on resources, attitudes toward various ethnic groups, and the coping strategies adopted by these groups in their new environments. Marked differences appeared with regard to the manner in which assessments took place and how the results were made available to the public.

Security, trust and privacy supported by context-aware middleware

Driven by new network and middleware technologies such as mobile broadband, near-field communication, and context awareness the so-called ambient lifestyle will foster innovative use cases in building automation, healthcare and agriculture. In the EU project Hydra1 highlevel security, trust and privacy concerns such as loss of control, profiling and surveillance are considered at the outset. At the end of this project the Hydra middleware development platform will have been designed so as to enable developers to realise secure ambient scenarios especially in the user domains of building automation, healthcare, and agriculture. This paper gives a short introduction to the Hydra project, its user domains and its approach to ensure security by design. Based on the results of a focus group analysis of the building automation domain typical threats are evaluated and their risks are assessed. Then, specific security requirements with respect to security, privacy, and trust are derived in order to incorporate them into the Hydra Security Meta Model. How concepts such as context security, semantic security, and virtualisation support the overall Hydra approach will be introduced and illustrated on the basis of a technical building automation scenario.

Global retrieval of ATSR cloud parameters and evaluation (GRAPE): dataset assessment

The Along-Track Scanning Radiometers (ATSRs) provide a long time-series of measurements suitable for the retrieval of cloud properties. This work evaluates the freely-available Global Retrieval of ATSR Cloud Parameters and Evaluation (GRAPE) dataset (version 3) created from the ATSR-2 (1995�2003) and Advanced ATSR (AATSR; 2002 onwards) records. Users are recommended to consider only retrievals flagged as high-quality, where there is a good consistency between the measurements and the retrieved state (corresponding to about 60% of converged retrievals over sea, and more than 80% over land). Cloud properties are found to be generally free of any significant spurious trends relating to satellite zenith angle. Estimates of the random error on retrieved cloud properties are suggested to be generally appropriate for optically-thick clouds, and up to a factor of two too small for optically-thin cases. The correspondence between ATSR-2 and AATSR cloud properties is high, but a relative calibration difference between the sensors of order 5�10% at 660 nm and 870 nm limits the potential of the current version of the dataset for trend analysis. As ATSR-2 is thought to have the better absolute calibration, the discussion focusses on this portion of the record. Cloud-top heights from GRAPE compare well to ground-based data at four sites, particularly for shallow clouds. Clouds forming in boundary-layer inversions are typically around 1 km too high in GRAPE due to poorly-resolved inversions in the modelled temperature profiles used. Global cloud fields are compared to satellite products derived from the Moderate Resolution Imaging Spectroradiometer (MODIS), Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) measurements, and a climatology of liquid water content derived from satellite microwave radiometers. In all cases the main reasons for differences are linked to differing sensitivity to, and treatment of, multi-layer cloud systems. The correlation coefficient between GRAPE and the two MODIS products considered is generally high (greater than 0.7 for most cloud properties), except for liquid and ice cloud effective radius, which also show biases between the datasets. For liquid clouds, part of the difference is linked to choice of wavelengths used in the retrieval. Total cloud cover is slightly lower in GRAPE (0.64) than the CALIOP dataset (0.66). GRAPE underestimates liquid cloud water path relative to microwave radiometers by up to 100 g m�2 near the Equator and overestimates by around 50 g m�2 in the storm tracks. Finally, potential future improvements to the algorithm are outlined.

Development of colour and firmness in strawberry crops is UV light sensitive, but colour is not a good predictor of several quality parameters

BACKGROUND: Strawberry (Fragaria × ananassa Duchesne var. Elsanta) plants were grown in polytunnels covered with three polythene films that transmitted varying levels of ultraviolet (UV) light. Fruit were harvested under near-commercial conditions and quality and yield were measured. During ripening, changes in the colour parameters of individual fruit were monitored, and the accuracy of using surface colour to predict other quality parameters was determined by analysing the correlation between colour and quality parameters within UV treatments. RESULTS: Higher exposure to UV during growth resulted in the fruit becoming darker at harvest and developing surface colour more quickly; fruit were also firmer at harvest, but shelf life was not consistently affected by the UV regime. Surface colour measurements were poorly correlated to firmness, shelf life or total phenolics, anthocyanins and ellagic acid contents. CONCLUSION: Although surface colour of strawberry fruits was affected by the UV regime during growth, and this parameter is an important factor in consumer perception, we concluded that the surface colour at the time of harvest was, contrary to consumer expectations, a poor indicator of firmness, potential shelf life or anthocyanin content. Copyright © 2011 Society of Chemical Industry

Reaping the benefits: science and the sustainable intensification of global agriculture

Food security is one of this century’s key global challenges. By 2050 the world will require increased crop production in order to feed its predicted 9 billion people. This must be done in the face of changing consumption patterns, the impacts of climate change and the growing scarcity of water and land. Crop production methods will also have to sustain the environment, preserve natural resources and support livelihoods of farmers and rural populations around the world. There is a pressing need for the ‘sustainable intensifi cation’ of global agriculture in which yields are increased without adverse environmental impact and without the cultivation of more land. Addressing the need to secure a food supply for the whole world requires an urgent international effort with a clear sense of long-term challenges and possibilities. Biological science, especially publicly funded science, must play a vital role in the sustainable intensifi cation of food crop production. The UK has a responsibility and the capacity to take a leading role in providing a range of scientifi c solutions to mitigate potential food shortages. This will require signifi cant funding of cross-disciplinary science for food security. The constraints on food crop production are well understood, but differ widely across regions. The availability of water and good soils are major limiting factors. Signifi cant losses in crop yields occur due to pests, diseases and weed competition. The effects of climate change will further exacerbate the stresses on crop plants, potentially leading to dramatic yield reductions. Maintaining and enhancing the diversity of crop genetic resources is vital to facilitate crop breeding and thereby enhance the resilience of food crop production. Addressing these constraints requires technologies and approaches that are underpinned by good science. Some of these technologies build on existing knowledge, while others are completely radical approaches, drawing on genomics and high-throughput analysis. Novel research methods have the potential to contribute to food crop production through both genetic improvement of crops and new crop and soil management practices. Genetic improvements to crops can occur through breeding or genetic modifi cation to introduce a range of desirable traits. The application of genetic methods has the potential to refi ne existing crops and provide incremental improvements. These methods also have the potential to introduce radical and highly signifi cant improvements to crops by increasing photosynthetic effi ciency, reducing the need for nitrogen or other fertilisers and unlocking some of the unrealised potential of crop genomes. The science of crop management and agricultural practice also needs to be given particular emphasis as part of a food security grand challenge. These approaches can address key constraints in existing crop varieties and can be applied widely. Current approaches to maximising production within agricultural systems are unsustainable; new methodologies that utilise all elements of the agricultural system are needed, including better soil management and enhancement and exploitation of populations of benefi cial soil microbes. Agronomy, soil science and agroecology—the relevant sciences—have been neglected in recent years. Past debates about the use of new technologies for agriculture have tended to adopt an either/or approach, emphasising the merits of particular agricultural systems or technological approaches and the downsides of others. This has been seen most obviously with respect to genetically modifi ed (GM) crops, the use of pesticides and the arguments for and against organic modes of production. These debates have failed to acknowledge that there is no technological panacea for the global challenge of sustainable and secure global food production. There will always be trade-offs and local complexities. This report considers both new crop varieties and appropriate agroecological crop and soil management practices and adopts an inclusive approach. No techniques or technologies should be ruled out. Global agriculture demands a diversity of approaches, specific to crops, localities, cultures and other circumstances. Such diversity demands that the breadth of relevant scientific enquiry is equally diverse, and that science needs to be combined with social, economic and political perspectives. In addition to supporting high-quality science, the UK needs to maintain and build its capacity to innovate, in collaboration with international and national research centres. UK scientists and agronomists have in the past played a leading role in disciplines relevant to agriculture, but training in agricultural sciences and related topics has recently suffered from a lack of policy attention and support. Agricultural extension services, connecting farmers with new innovations, have been similarly neglected in the UK and elsewhere. There is a major need to review the support for and provision of extension services, particularly in developing countries. The governance of innovation for agriculture needs to maximise opportunities for increasing production, while at the same time protecting societies, economies and the environment from negative side effects. Regulatory systems need to improve their assessment of benefits. Horizon scanning will ensure proactive consideration of technological options by governments. Assessment of benefi ts, risks and uncertainties should be seen broadly, and should include the wider impacts of new technologies and practices on economies and societies. Public and stakeholder dialogue—with NGOs, scientists and farmers in particular—needs to be a part of all governance frameworks.

Considering heteroglossia in language and development in Sub-Saharan Africa

Countries throughout the sub-Saharan (SSA) region have a complex linguistic heritage having their origins in opportunistic boundary changes effected by Western colonial powers at the Berlin Conference 1884-85. Postcolonial language-in-education policies valorizing ex-colonial languages have contributed at least in part to underachievement in education and thus the underdevelopment of human resources in SSA countries. This situation is not likely to improve whilst unresolved questions concerning the choice of language(s) that would best support social and economic development remain. Whilst policy attempts to develop local languages have been discussed within the framework of the African Union, and some countries have experimented with models of multilingual education during the past decade, the goalposts have already changed as a result of migration and trade. This paper argues that language policy makers need to be cognizant of changing language ecologies and their relationship with emerging linguistic and economic markets. The concept of language, within such a framework, has to be viewed in relation to the multiplicity of language markets within the shifting landscapes of people, culture, economics and the geo-politics of the 21st Century. Whilst, on the one hand, this refers to the hegemony of dominant powerful languages and the social relations of disempowerment, on the other hand, it also refers to existing and evolving social spaces and local language capabilities and choices. Within this framework the article argues that socially constructed dominant macro language markets need to be viewed also in relation to other, self-defined, community meso- and individual micro- language markets and their possibilities for social, economic and political development. It is through pursuing this argument that this article assesses the validity of Omoniyi’s argument in this volume, for the need to focus on the concept of language capital within multilingual contexts in the SSA region as compared to Bourdieu’s concept of linguistic capital.  

Does tool use extend peripersonal space? A review and re-analysis

The fascinating idea that tools become extensions of our body appears in artistic, literary, philosophical, and scientific works alike. In the last fifteen years, this idea has been re-framed into several related hypotheses, one of which states that tool use extends the neural representation of the multisensory space immediately surrounding the hands (variously termed peripersonal space, peri-hand space, peri-cutaneous space, action space, or near space). This and related hypotheses have been tested extensively in the cognitive neurosciences, with evidence from molecular, neurophysiological, neuroimaging, neuropsychological, and behavioural fields. Here, I briefly review the evidence for and against the hypothesis that tool use extends a neural representation of the space surrounding the hand, concentrating on neurophysiological, neuropsychological, and behavioural evidence. I then provide a re-analysis of data from six published and one unpublished experiments using the crossmodal congruency task to test this hypothesis. While the re-analysis broadly confirms the previously-reported finding that tool use does not literally extend peripersonal space, the overall effect-sizes are small and statistical power is low. I conclude by questioning whether the crossmodal congruency task can indeed be used to test the hypothesis that tool use modifies peripersonal space.

Separating the dynamical effects of climate change and ozone depletion. Part II: Southern Hemisphere troposphere

The separate effects of ozone depleting substances (ODSs) and greenhouse gases (GHGs) on forcing circulation changes in the Southern Hemisphere extratropical troposphere are investigated using a version of the Canadian Middle Atmosphere Model (CMAM) that is coupled to an ocean. Circulation-related diagnostics include zonal wind, tropopause pressure, Hadley cell width, jet location, annular mode index, precipitation, wave drag, and eddy fluxes of momentum and heat. As expected, the tropospheric response to the ODS forcing occurs primarily in austral summer, with past (1960-99) and future (2000-99) trends of opposite sign, while the GHG forcing produces more seasonally uniform trends with the same sign in the past and future. In summer the ODS forcing dominates past trends in all diagnostics, while the two forcings contribute nearly equally but oppositely to future trends. The ODS forcing produces a past surface temperature response consisting of cooling over eastern Antarctica, and is the dominant driver of past summertime surface temperature changes when the model is constrained by observed sea surface temperatures. For all diagnostics, the response to the ODS and GHG forcings is additive: that is, the linear trend computed from the simulations using the combined forcings equals (within statistical uncertainty) the sum of the linear trends from the simulations using the two separate forcings. Space time spectra of eddy fluxes and the spatial distribution of transient wave drag are examined to assess the viability of several recently proposed mechanisms for the observed poleward shift in the tropospheric jet.

The dependence of contrail formation on the weather pattern and altitude in the North Atlantic

Aircraft flying through cold ice-supersaturated air produce persistent contrails which contribute to the climate impact of aviation. Here, we demonstrate the importance of the weather situation, together with the route and altitude of the aircraft through this, on estimating contrail coverage. The results have implications for determining the climate impact of contrails as well as potential mitigation strategies. Twenty-one years of re-analysis data are used to produce a climatological assessment of conditions favorable for persistent contrail formation between 200 and 300 hPa over the north Atlantic in winter. The seasonal-mean frequency of cold ice-supersaturated regions is highest near 300 hPa, and decreases with altitude. The frequency of occurrence of ice-supersaturated regions varies with large-scale weather pattern; the most common locations are over Greenland, on the southern side of the jet stream and around the northern edge of high pressure ridges. Assuming aircraft take a great circle route, as opposed to a more realistic time-optimal route, is likely to lead to an error in the estimated contrail coverage, which can exceed 50% for westbound north Atlantic flights. The probability of contrail formation can increase or decrease with height, depending on the weather pattern, indicating that the generic suggestion that flying higher leads to fewer contrails is not robust.

Two macrocyclic pentaaza compounds containing pyridine evaluated as novel chelating agents in copper(II) and nickel(II) overload

Two pentaaza macrocycles containing pyridine in the backbone, namely 3,6,9,12,18-pentaazabicyclo[12.3.1] octadeca-1(18),14,16-triene ([15]pyN(5)), and 3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),15,17-triene ([16]pyN(5)), were synthesized in good yields. The acid-base behaviour of these compounds was studied by potentiometry at 298.2 K in aqueous solution and ionic strength 0.10 M in KNO3. The protonation sequence of [15]pyN(5) was investigated by H-1 NMR titration that also allowed the determination of protonation constants in D2O. Binding studies of the two ligands with Ca2+, Ni2+, Cu2+, Zn2+, Cd2+, and Pb2+ metal ions were performed under the same experimental conditions. The results showed that all the complexes formed with the 15-membered ligand, particularly those of Cu2+ and especially Ni2+, are thermodynamically more stable than with the larger macrocycle. Cyclic voltammetric data showed that the copper(II) complexes of the two macrocycles exhibited analogous behaviour, with a single quasi-reversible one-electron transfer reduction process assigned to the Cu(II)/Cu(I) couple. The UV-visible-near IR spectroscopic and magnetic moment data of the nickel(II) complexes in solution indicated a tetragonal distorted coordination geometry for the metal centre. X-band EPR spectra of the copper(II) complexes are consistent with distorted square pyramidal geometries. The crystal structure of [Cu([15]pyN(5))](2+) determined by X-ray diffraction showed the copper(II) centre coordinated to all five macrocyclic nitrogen donors in a distorted square pyramidal environment.

Did the RAI buy it? The role and limits of American broadcasting in Italy in the Cold War

With a 20 million dollar budget and 1,900 staff Voice of America broadcasted in 45 different languages and Italy was one of its main targets. By looking into what went on behind the microphone, this article addresses the extent to which cultural change was planned and structured transnationally, the interactions and interdependencies operating between Washington and Rome, and how a cooperation was achieved despite the fierce resistance of some of RAI’s executives. This allowed to air programmes produced in New York, and led to the launch of the most popular character of Italian radio and television: Mike Bongiorno.

Alverata: Latin, Greek and Cyrillic typeface

Alverata: a typeface design for Europe This typeface is a response to the extraordinarily diverse forms of letters of the Latin alphabet in manuscripts and inscriptions in the Romanesque period (c. 1000–1200). While the Romanesque did provide inspiration for architectural lettering in the nineteenth century, these letterforms have not until now been systematically considered and redrawn as a working typeface. The defining characteristic of the Romanesque letterform is variety: within an individual inscription or written text, letters such as A, C, E and G might appear with different forms at each appearance. Some of these forms relate to earlier Roman inscriptional forms and are therefore familiar to us, but others are highly geometric and resemble insular and uncial forms. The research underlying the typeface involved the collection of a large number of references for lettering of this period, from library research and direct on-site ivestigation. This investigation traced the wide dispersal of the Romanesque lettering tradition across the whole of Europe. The variety of letter widths and weights encountered, as well as variant shapes for individual letters, offered both direct models and stylistic inspiration for the characters and for the widths and weight variants of the typeface. The ability of the OpenType format to handle multiple stylistic variants of any one character has been exploited to reflect the multiplicity of forms available to stonecutters and scribes of the period. To make a typeface that functions in a contemporary environment, a lower case has been added, and formal and informal variants supported. The pan-European nature of the Romanesque design tradition has inspired an pan-European approach to the character set of the typeface, allowing for text composition in all European languages, and the typeface has been extended into Greek and Cyrillic, so that the broadest representation of European languages can be achieved.