Surface modification of TiO2 with copper clusters for band gap narrowing

Surface modification of photocatalytic materials to give better activity, and potentially extending the response into the visible spectrum, is an area of active research. In this work, DFT modelling suggests that surface modification of rutile and anatase TiO2 with partially oxidised copper clusters can induce a red shift in the photo-action spectrum. Copper clusters were synthesised and characterised separately before TiO2 nanoparticle surface modification. Characterisation of copper clusters and photocatalysts modified with copper clusters showed that ex-situ synthesis can control the size of surface clusters. Sub-nanometre clusters of copper maintained their size and morphology upon attachment to the photocatalyst surface. The copper clusters we determined to be a mixture of Cu(0) and Cu(I), and no significant change in the oxidation state was observed following surface modification or following photoelectrochemical measurements. Experimental measurements including UV–vis spectroscopy and valence band XPS showed a small red shift the band gap correlating to the DFT predictions. Photoelectrochemical characterisation showed an enhancement in the UV photocurrent response and a small red shift in the effective band gap for the surface modified TiO2

Formal Quantum Efficiencies for the Photocatalytic Reduction of CO2 in a Gas Phase Batch Reactor

The photocatalytic reduction of CO2 to fuels, or useful products, is an area of active research. In this work, nanoengineering and surface modification of titania were investigated as approaches for improving the CO2 reduction efficiency in a fixed-bed gas phase batch photoreactor under UV–vis irradiation. Titania nanotubes were prepared by a hydrothermal method, and TiO2 (P25) was surface modified with copper clusters. Unmodified TiO2 (P25) was used as the bench-mark comparison. The titania nanotubes and Cu-TiO2 materials showed higher efficiency for the photocatalytic reduction of CO2 to yield CH4 as compared to P25. Carbon monoxide yields were similar for all photocatalysts tested. The photocatalytic reduction of CO2 was observed on all photocatalyst tested, with the nanotubes proving to be the most efficient for the production of CH4. The product yields per mass of catalyst observed in this work are similar to those reported in the literature (with similar reactor parameters) but the calculated formal quantum efficiencies for CO2 reduction are very low (4.41 × 10−5 to 5.95 × 10-4)

Multifunctional photo/thermal catalysts for the reduction of carbon dioxide

The photochemical fixation of CO2 to energy rich products for solar energy storage or feedstock chemicals is an attractive, albeit daunting, challenge. The overall feasibility of CO2 conversion is limited by the availability of efficient photo-active materials that meet the energetic requirements for CO2 reduction and are optically matched to the solar spectrum. Surface modification of TiO2 with earth abundant metal oxides presents one approach to develop visible active photocatalysts through band gap narrowing, while providing catalytic sites to lower the activation energy for CO2 reduction. In this work density functional theory was used to model the effect of surface modification of rutile and anatase using MnOx nanoclusters. The results indicate the formation of inter-band gap states following surface modification with MnOx, but surface water can change this. Oxygen vacancies are predicted to form in supported MnOx and the interaction with CO2 was investigated. MnOx-TiO2 was synthesized and characterised using surface analytical methods and photoelectrochemistry. The interaction of CO2 with the materials under irradiation was probed using in-situ FTIR to interrogate the role of oxygen vacancies in CO2 binding and reaction. These results provide insights into the requirements of a multifunctional catalyst for CO2 conversion

Beef production from feedstuffs conserved using new technologies to reduce negative environmental impacts

End of project reportMost (ca. 86%) Irish farms make some silage. Besides directly providing feed for livestock, the provision of grass silage within integrated grassland systems makes an important positive contribution to effective grazing management and improved forage utilisation by grazing animals, and to effective feed budgeting by farmers. It can also contribute to maintaining the content of desirable species in pastures, and to livestock not succumbing to parasites at sensitive times of the year. Furthermore, the optimal recycling of nutrients collected from housed livestock can often be best achieved by spreading the manures on the land used for producing the conserved feed. On most Irish farms, grass silage will remain the main conserved forage for feeding to livestock during winter for the foreseeable future. However, on some farms high yields of whole-crop (i.e. grain + straw) cereals such as wheat, barley and triticale, and of forage maize, will be an alternative option provided that losses during harvesting, storage and feedout are minimised and that input costs are restrained. These alternative forages have the potential to reliably support high levels of animal performance while avoiding the production of effluent. Their production and use however will need to advantageously integrate into ruminant production systems. A range of technologies can be employed for crop production and conservation, and for beef production, and the optimal options need to be identified. Beef cattle being finished indoors are offered concentrate feedstuffs at rates that range from modest inputs through to ad libitum access. Such concentrates frequently contain high levels of cereals such as barley or wheat. These cereals are generally between 14% to 18% moisture content and tend to be rolled shortly before being included in coarse rations or are more finely processed prior to pelleting. Farmers thinking of using ‘high-moisture grain’ techniques for preserving and processing cereal grains destined for feeding to beef cattle need to know how the yield, conservation efficiency and feeding value of such grains compares with grains conserved using more conventional techniques. European Union policy strongly encourages a sustainable and multifunctional agriculture. Therefore, in addition to providing European consumers with quality food produced within approved systems, agriculture must also contribute positively to the conservation of natural resources and the upkeep of the rural landscape. Plastics are widely used in agriculture and their post-use fate on farms must not harm the environment - they must be managed to support the enduring sustainability of farming systems. There is an absence of information on the efficacy of some new options for covering and sealing silage with plastic sheeting and tyres, and an absence of an inventory of the use, re-use and post-use fate of plastic film on farms. Irish cattle farmers operate a large number of beef production systems, half of which use dairy bred calves. In the current, continuously changing production and market conditions, new beef systems must be considered. A computer package is required that will allow the rapid, repeatable simulation and assessment of alternate beef production systems using appropriate, standardised procedures. There is thus a need to construct, evaluate and utilise computer models of components of beef production systems and to develop mathematical relationships to link system components into a network that would support their integration into an optimal system model. This will provide a framework to integrate physical and financial on-farm conditions with models for estimating feed supply and animal growth patterns. Cash flow and profit/loss results will be developed. This will help identify optimal systems, indicate the cause of failure of imperfect systems and identify areas where applied research data are currently lacking, or more basic research is required

Determining the effects of an evidence-based after school program on objectively measured physical ability in urban children

This study determined whether improvements occurred in participant objectively measured physical activity (Actigraph, wGT3X-BT, Pensacola, FL) during the MANE (Methodical Approach to Activity and Nutrition Education) after-school program

Will the US Economy Recover in 2010? A Minimal Spanning Tree Study

We calculated the cross correlations between the half-hourly times series of the ten Dow Jones US economic sectors over the period February 2000 to August 2008, the two-year intervals 2002--2003, 2004--2005, 2008--2009, and also over 11 segments within the present financial crisis, to construct minimal spanning trees (MSTs) of the US economy at the sector level. In all MSTs, a core-fringe structure is found, with consumer goods, consumer services, and the industrials consistently making up the core, and basic materials, oil and gas, healthcare, telecommunications, and utilities residing predominantly on the fringe. More importantly, we find that the MSTs can be classified into two distinct, statistically robust, topologies: (i) star-like, with the industrials at the center, associated with low-volatility economic growth; and (ii) chain-like, associated with high-volatility economic crisis. Finally, we present statistical evidence, based on the emergence of a star-like MST in Sep 2009, and the MST staying robustly star-like throughout the Greek Debt Crisis, that the US economy is on track to a recovery.Comment: elsarticle class, includes amsmath.sty, graphicx.sty and url.sty. 68 pages, 16 figures, 8 tables. Abridged version of the manuscript presented at the Econophysics Colloquim 2010, incorporating reviewer comment

Host galaxies of luminous quasars: population synthesis of optical off-axis spectra

There is increasing evidence of a connection between AGN activity and galaxy evolution. To obtain further insight into this potentially important evolutionary phase, we analyse the properties of quasar host galaxies. In this paper, we present a population synthesis modeling technique for off-axis spectra, the results of which constrain host colour and the stellar ages of luminous quasars (M_V(nuc)<-23). Our technique is similar to well established quiescent-galaxy models, modified to accommodate scattered nuclear light (a combination of atmospheric, instrumental and host galaxy scattered light) observed off axis. In our model, subtraction of residual scattered quasar light is performed, while simultaneously modeling the constituent stellar populations of the host galaxy. The reliability of this technique is tested via a Monte-Carlo routine in which the correspondence between synthetic spectra with known parameters and the model output is determined. Application of this model to a preliminary sample of 10 objects is presented and compared to previous studies. Spectroscopic data was obtained via long-slit and integral-field unit observations on the Keck and WIYN telescopes. We confirm that elliptical quasar hosts are distinguishable (bluer) from inactive ellipticals in rest frame B-V colour. Additionally, we note a trend for radio luminous (L_5GHz > 10^40 erg s^-1) quasars to be located in redder host galaxies in comparison to their less luminous radio counterparts. While the host colour and age of our radio luminous sample is in close proximity to the green valley, our radio faint sample is consistent with quiescent star-forming galaxies. However, further observations are needed to confirm these results. Finally, we discuss future applications for our technique on a larger sample of objects being obtained via SALT and WIYN telescope observing campaigns.Comment: 18 pages, 10 figures, accepted for publication in MNRA

Perceptions of dementia and use of services in minority ethnic communities: a scoping exercise.

-Despite the rapidly ageing population and a predicted sevenfold increase in the prevalence of dementia in minority ethnic communities, people from these communities remain under-represented in specialist dementia services. Leventhal’s Model of Self-Regulation suggests perceptions ofillness facilitate help-seeking behaviours such as the use of services. Thisscoping exercise makes use of the model to explore perceptions ofdementia in British Indian, African and Caribbean, and East and CentralEuropean communities in the United Kingdom. Between August 2013and April 2014, culturally specific dementia awareness roadshows wereattended by people living with dementia, carers and members of thepublic. During the roadshows, 62 British Indian, 50 African and Caribbean, and 63 East and Central European attenders participated indiscussion groups and a dementia knowledge quiz. Thematic andframework analysis were conducted on the discussion group data. Threemain themes are presented: Perceptions of dementia, awareness ofdementia in the wider family and community, and awareness and use ofservices. The findings suggest that although groups attributed a biologicalbasis for memory loss, a number of misconceptions prevailed regardingthe cause of dementia. Groups also made use of religion, as opposed tomedical healthcare services, as a form of personal and treatment control. Seeking help from healthcare services was hindered by lack of awarenessof services, and culturally specific barriers such as language. The findingshave a number of implications for policy and practice including thedevelopment of public health interventions and the need to focus further on reducing barriers to accessing services

Border sequences of Medicago truncatula CLE36 are specifically cleaved by endoproteases common to the extracellular fluids of Medicago and soybean

CLE (CLAVATA3/ESR-related) peptides are developmental regulators that are secreted into the apoplast. Little is known about the role of the sequences that flank CLE peptides in terms of their biological activity or how they are targeted by proteases that are known to liberate the final active CLE peptides from their precursor sequences. The biological activity of Medicago truncatula CLE36, which possesses broadly conserved border sequences flanking the putative final active CLE36 peptide product, was assessed. Using in vitro root growth assays and an in vitro root and callus formation assay it is shown that CLE36 peptides of different lengths possess differential biological activities. Using mass spectrometry, Glycine max and Medicago extracellular fluids were each shown to possess an endoproteolytic activity that recognizes and cleaves at border sequences in a synthetic 31 amino acid CLE36 ‘propeptide bait’ to liberate biologically active peptide products. Inhibitor studies suggest that a subtilisin, in combination with a carboxypeptidase, liberated and trimmed CLE36, respectively, to form biologically relevant 11–15 amino acid cleavage products. The 15 amino acid cleavage product is more biologically potent on Arabidopsis than shorter or longer CLE peptides. In situ hybridization shows that the soybean orthologue of CLE36 (GmCLE34) is expressed in the provascular tissue. The results suggest that secreted subtilisins can specifically recognize the border sequences of CLE36 propeptides and liberate biologically active cleavage products. These secreted proteases may affect the stability and biological activity of CLE peptides in the apoplast or be involved in CLE36 processing

Gender and Medieval archaeology: storming the castle

Despite feminist critiques over three decades, Archaeological scholarship remains predominantly focused on exploring patriarchal narratives and is thereby complicit in reinforcing structural inequalities. Questions must be asked of how the construction of archaeological knowledge affects representation and impacts on our ‘archaeologies’. This paper explores the relative absence of gendered approaches within Archaeology through the lens of Later Medieval Archaeology in particular, and with a micro-focus on Castle-studies in Britain and Ireland. Is there a reason for the silence in relation to gender in the archaeology of the later middle ages