Catalytic oxidation of alcohols using molecular oxygen mediated by poly(ethylene glycol)-supported nitroxyl radicals

The selective catalytic oxidation of alcohols over a mixture of copper(l) chloride and a number of linear 'linker-less' or 'branched' poly(ethylene glycol)-supported nitroxyl radicals of the 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) family as a catalyst system has been investigated in the presence of molecular oxygen in a batch reactor. It is found that the activity profile of the polymer-supported nitroxyl radicals is in good agreement with that of low-molecular weight nitroxyl catalysts, for example, allylic and benzylic alcohols are oxidised faster than aliphatic alcohols. The oxidations can be tuned to be highly selective such that aldehydes are the only oxidation products observed in the oxidation of primary alcohols and the oxidations of secondary alcohols yield the corresponding ketones. A strong structural effect of the polymeric nitroxyl species on catalytic activity that is dependent upon their spatial orientation of the nitroxyl radicals is particularly noted. The new soluble macromolecular catalysts can be recovered readily from the reaction mixture by solvent precipitation and filtration. In addition, the recycled catalysts demonstrate a similar selectivity with only a small decrease in activity compared to the fresh catalyst even after five repetitive cycles. (c) 2005 Elsevier B.V. All rights reserved.

Preparation of consistent soil data sets for modelling purposes: Secondary SOTER data for four case study areas

The common GIS-based approach to regional analyses of soil organic carbon (SOC) stocks and changes is to define geographic layers for which unique sets of driving variables are derived, which include land use, climate, and soils. These GIS layers, with their associated attribute data, can then be fed into a range of empirical and dynamic models. Common methodologies for collating and formatting regional data sets on land use, climate, and soils were adopted for the project Assessment of Soil Organic Carbon Stocks and Changes at National Scale (GEFSOC). This permitted the development of a uniform protocol for handling the various input for the dynamic GEFSOC Modelling System. Consistent soil data sets for Amazon-Brazil, the Indo-Gangetic Plains (IGP) of India, Jordan and Kenya, the case study areas considered in the GEFSOC project, were prepared using methodologies developed for the World Soils and Terrain Database (SOTER). The approach involved three main stages: (1) compiling new soil geographic and attribute data in SOTER format; (2) using expert estimates and common sense to fill selected gaps in the measured or primary data; (3) using a scheme of taxonomy-based pedotransfer rules and expert-rules to derive soil parameter estimates for similar soil units with missing soil analytical data. The most appropriate approach varied from country to country, depending largely on the overall accessibility and quality of the primary soil data available in the case study areas. The secondary SOTER data sets discussed here are appropriate for a wide range of environmental applications at national scale. These include agro-ecological zoning, land evaluation, modelling of soil C stocks and changes, and studies of soil vulnerability to pollution. Estimates of national-scale stocks of SOC, calculated using SOTER methods, are presented as a first example of database application. Independent estimates of SOC stocks are needed to evaluate the outcome of the GEFSOC Modelling System for current conditions of land use and climate. (C) 2007 Elsevier B.V. All rights reserved.

Exploring other childhoods through quantitative secondary analyses of large scale surveys: opportunities and challenges for children's geographers

This paper considers the potential contribution of secondary quantitative analyses of large scale surveys to the investigation of 'other' childhoods. Exploring other childhoods involves investigating the experience of young people who are unequally positioned in relation to multiple, embodied, identity locations, such as (dis)ability, 'class', gender, sexuality, ethnicity and race. Despite some possible advantages of utilising extensive databases, the paper outlines a number of methodological problems with existing surveys which tend to reinforce adultist and broader hierarchical social relations. It is contended that scholars of children's geographies could overcome some of these problematic aspects of secondary data sources by endeavouring to transform the research relations of large scale surveys. Such endeavours would present new theoretical, ethical and methodological complexities, which are briefly considered.

Temporal patterns of nutrient availability around nests of leaf-cutting ants (Atta colombica) in secondary moist tropical forest

Leaf-cutting ants consume up to 10% of canopy leaves in the foraging area of their colony and therefore represent a key perturbation in the nutrient cycle of tropical forests. We used a chronosequence of nest sites on Barro, Colorado Island, Panama, to assess the influence of leaf-cutting ants (Atta colombica) on nutrient availability in a neotropical rainforest. Twelve nest sites were sampled, including active nests, recently abandoned nests (<1 year) and long-abandoned nests (>1 year). Waste material discarded by the ants down-slope from the nests contained large concentrations of nitrogen and phosphorus in both total and soluble forms, but decomposed within one year after the nests were abandoned. Despite this, soil under the waste material contained high concentrations of nitrate and ammonium that persisted after the disappearance of the waste, although soluble phosphate returned to background concentrations within one year of nest abandonment. Fine roots were more abundant in soil under waste than control soils up to one year after nest abandonment, but were not significantly different for older sites. In contrast to the waste dumps, soil above the underground nest chambers consistently contained lower nutrient concentrations than control soils, although this was not statistically significant. We conclude that the 'islands of fertility' created by leaf-cutting ants provide a nutritional benefit to nearby plants for less than one year after nest abandonment in the moist tropical environment of Barro Colorado Island. Published by Elsevier Ltd.

Children's lives, children's futures: A study of children starting secondary school

This title presents a fascinating analysis of how children in their first year of high school feel about their schools, its place in their lives and its role in their futures. This highly topical monograph focuses on how children in their first year of high school feel about school, its place in their lives and its role in their futures. The theoretical context of the study is the focus in educational studies on children's voice and children's active role in education, together with the focus in the sociology of childhood on children as active constructors of their lives and childhood as a subject of serious study. The importance of young people's life plans and the alignment between education and ambitions was recognized in the Sloan Foundation study of American teenagers. In many Western societies there is concern that children from less advantaged social backgrounds have limited aspirations, and are disproportionately unlikely to go to university. This book is highly relevant to understanding the nature of children's engagement with education, the choices and constraints they experience and the reasons some young people fail to take advantage of educational opportunities. "Continuum Studies in Educational Research" (CSER) is a major new series in the field of educational research. Written by experts and scholars for experts and scholars, this ground-breaking series focuses on research in the areas of comparative education, history, lifelong learning, philosophy, policy, post-compulsory education, psychology and sociology. Based on cutting edge research and written with lucidity and passion, the CSER series showcases only those books that really matter in education - studies that are major, that will be remembered for having made a difference.

Use of secondary somatic embryos promotes genetic fidelity in cryopreservation of cocoa (Theobroma cacao L.)

The inability to conserve cocoa (Theobroma cacao L.) germplasm via sced storage and the vulnerability of field collections make the establishment of cryopreserved genebanks for the crop a priority. An effective encapsulation-dehydration based cryopreservation system has been developed for cocoa but because the somatic embryos used for freezing arise after a protracted period of callus culture there is concern about maintenance of genetic fidelity during the process. Microsatellite markers for seven of the 10 cocoa linkage groups were used to screen a population of 189 primary somatic embryo-derived emblings and the 43 secondary somatic embryos they gave rise to. Of the primary somatic embryos, 38.1% exhibited polymorphic microsatellite profiles while for secondary somatic embryos the frequency was 23.3%. The same microsatellite markers used to screen another population of 44 secondary somatic embryos cryopreserved through encapsulation-dehydration revealed no polymorphisms. Scanning electron microscopy showed the secondary somatic embryos were derived from cotyledonary epidermal cells rather than callus. The influence of embryo ontogeny on somaclonal variation is discussed.

The cell wall and secretory proteome of a tobacco cell line synthesising secondary wall

The utility of plant secondary cell wall biomass for industrial and biofuel purposes depends upon improving cellulose amount, availability and extractability. The possibility of engineering such biomass requires much more knowledge of the genes and proteins involved in the synthesis, modification and assembly of cellulose, lignin and xylans. Proteomic data are essential to aid gene annotation and understanding of polymer biosynthesis. Comparative proteomes were determined for secondary walls of stem xylem and transgenic xylogenic cells of tobacco and detected peroxidase, cellulase, chitinase, pectinesterase and a number of defence/cell death related proteins, but not marker proteins of primary walls such as xyloglucan endotransglycosidase and expansins. Only the corresponding detergent soluble proteome of secretory microsomes from the xylogenic cultured cells, subjected to ion-exchange chromatography, could be determined accurately since, xylem-specific membrane yields were of poor quality from stem tissue. Among the 109 proteins analysed, many of the protein markers of the ER such as BiP, HSP70, calreticulin and calnexin were identified, together with some of the biosynthetic enzymes and associated polypeptides involved in polymer synthesis. However 53% of these endomembrane proteins failed identification despite the use of two different MS methods, leaving considerable possibilities for future identification of novel proteins involved in secondary wall polymer synthesis once full genomic data are available.

UV irradiance as a major influence on growth, development and secondary products of commercial importance in Lollo Rosso lettuce 'Revolution' grown under polyethylene films

The growth and production of anthocyanin, flavonoid and phenolic compounds were evaluated in Lollo Rosso lettuce 'Revolution' grown continuously under films varying in their ability to transmit LTV radiation (completely transparent to IN, transparent above 320, 350, 370 and 3 80 nm and completely opaque to LTV radiation). Plants were grown from seed under UV transparent and UV blocking films and destructively harvested 3-4 weeks after transplanting. Plants under a complete UV blocking film (UV400) produced up to 2.2 times more total above ground dry weight than plants under the UV transparent film. In contrast, anthocyanin content in plants under the UV blocking film was approximately eight times lower than in plants under a UV transparent film. Furthermore, there was a curvilinear relationship between the anthocyanin content and LTV wavelength cutoff such that above 370 run there was no further reduction in anthocyanin content. Fluorescence measurements indicated that photosynthetic performance index was 15% higher under the presence of UVB and UVA (UV280) than under the presence of UVA (UV320) and 53% higher than in the absence of UV radiation suggesting protection of the photosynthetic apparatus possibly by phenolic compounds. These findings are of particular importance as the potential of UV transmitting films to increase secondary compounds may offer the opportunity to produce plants commercially with increased health benefits compared to those grown under conventional films.

An evaluation of the costs of making specific secondary metabolites: does the yield penalty incurred by host plant resistance to insects due to competition for resources?

The presumption that the synthesis of 'defence' compounds in plants must incur some 'trade-off' or penalty in terms of annual crop yields has been used to explain observed inverse correlations between resistance to herbivores and rates of growth or photosynthesis. An analysis of the cost of making secondary compounds suggests that this accounts for only a small part of the overall carbon budget of annual crop plants. Even the highest reported amounts of secondary metabolites found in different crop species (flavonoids, allylisothiocyanates, hydroxamic acids, 2-tridecanone) represent a carbon demand that can be satisfied by less than an hour's photosynthesis. Similar considerations apply to secondary compounds containing nitrogen or sulphur, which are unlikely to represent a major investment compared to the cost of making proteins, the major demand for these elements. Decreases in growth and photosynthesis in response to stress are more likely the result of programmed down-regulation. Observed correlations between yield and low contents of unpalatable or toxic compounds may be the result of parallel selection during the refinement of crop species by humans.