A more direct way to make catalysts: one-pot ligand-assisted aerobic stripping and electrodeposition of copper on graphite

Electrodeposition of metals onto conductive supports such as graphite potentially provides a lower-waste method to form heterogeneous catalysts than the standard methods such as wet impregnation. Copper electrodeposition onto pressed graphite disc electrodes was investigated from aqueous CuSO4-ethylenediamine solutions by chronoamperometry with scanning electron microscopy used to ascertain the particle sizes obtained by this method. The particle size was studied as a function of pH, CuSO4-ethylenediamine concentration, and electrodeposition time. It was observed that decreasing the pH, copper-ethylenediamine concentration and time each decreased the size of the copper particles observed, with the smallest obtained being around 5-20 nm. Furthermore, electroless aerobic oxidation of copper metal in the presence of ethylenediamine was successfully coupled with the electrodeposition in the same vessel. In this way, deposition was achieved sequentially on up to twenty different graphite discs using the same ethylenediamine solution, demonstrating the recyclability of the ligand. The materials thus prepared were shown to be catalytically active for the mineralisation of phenol by hydrogen peroxide. Overall, the results provide a proof-of-principle that by making use of aerobic oxidation coupled with electrochemical deposition, elemental base metals can be used directly as starting materials to form heterogeneous catalysts without the need to use metal salts as catalyst precursors.

Rapid changes in the level of Kluane Lake in Yukon Territory over the last millennium

The level of Kluane Lake, the largest lake in Yukon Territory, was lower than at present during most of the Holocene. The lake rose rapidly in the late seventeenth century to a level 12 m above present, drowning forest and stranding driftwood on a conspicuous high-stand beach, remnants of which are preserved at the south end of the lake. Kluane Lake fell back to near its present level by the end of the eighteenth century and has fluctuated within a range of about 3 m over the last 50 yr. The primary control on historic fluctuations in lake level is the discharge of Slims River, the largest source of water to the lake. We use tree ring and radiocarbon ages, stratigraphy and sub-bottom acoustic data to evaluate two explanations for the dramatic changes in the level of Kluane Lake. Our data support the hypothesis of Hugh Bostock, who suggested in 1969 that the maximum Little Ice Age advance of Kaskawulsh Glacier deposited large amounts of sediment in the Slims River valley and established the present course of Slims River into Kluane Lake. Bostock argued that these events caused the lake to rise and eventually overflow to the north. The overflowing waters incised the Duke River fan at the north end of Kluane Lake and lowered the lake to its present level. This study highlights the potentially dramatic impacts of climate change on regional hydrology during the Little Ice Age in glacierised mountains. © 2006 University of Washington.

Ancient DNA reveals late survival of mammoth and horse in interior Alaska

Causes of late Quaternary extinctions of large mammals (" megafauna") continue to be debated, especially for continental losses, because spatial and temporal patterns of extinction are poorly known. Accurate latest appearance dates (LADs) for such taxa are critical for interpreting the process of extinction. The extinction of woolly mammoth and horse in northwestern North America is currently placed at 15,000-13,000 calendar years before present (yr BP), based on LADs from dating surveys of macrofossils (bones and teeth). Advantages of using macrofossils to estimate when a species became extinct are offset, however, by the improbability of finding and dating the remains of the last-surviving members of populations that were restricted in numbers or con-fined to refugia. Here we report an alternative approach to detect 'ghost ranges' of dwindling populations, based on recovery of ancient DNA from perennially frozen and securely dated sediments (sedaDNA). In such contexts, sedaDNA can reveal the molecular presence of species that appear absent in the macrofossil record. We show that woolly mammoth and horse persisted in interior Alaska until at least 10,500 yr BP, several thousands of years later than indicated from macrofossil surveys. These results contradict claims that Holocene survival of mammoths in Beringia was restricted to ecologically isolated high-latitude islands. More importantly, our finding that mammoth and horse overlapped with humans for several millennia in the region where people initially entered the Americas challenges theories that megafaunal extinction occurred within centuries of human arrival or were due to an extraterrestrial impact in the late Pleistocene.

TP53 R249S Mutations, Exposure to Aflatoxin, and Occurrence of Hepatocellular Carcinoma in a Cohort of Chronic Hepatitis B Virus Carriers from Qidong, China

Hepatocellular carcinoma (HCC) has a high mortality in East Asia and Sub-Saharan Africa, two regions where the main etiologic factors are chronic infections with hepatitis B vir-us and dietary exposure to aflatoxin. A single base substitution at the third nucleotide of codon 249 of TP53 (R249S) is common in HCC in these regions and has been associated with aflatoxin-DNA adducts. To determine whether R249S may be detected in plasma DNA before HCC diagnosis, we conducted a case-control study nested in a cohort of adult chronic hepatitis B virus carriers from Qidong County, People's Republic of China. Of the 234 plasma specimens that yielded adequate DNA, only 2 (0.9%) were positive for R249S by restriction fragment length polymorphisms, and both of them were controls. Of the 249 subjects tested for aflatoxin-albumin adducts, 168 (67%) were positive, with equal distribution between cases and controls. Aflatoxin-albumin adduct levels were low in the study, suggesting an overall low ongoing exposure to aflatoxin in this cohort. The R249S mutation was detected in 11 of 18 (61%) available tumor tissues. To assess whether low levels of mutant DNA were detectable in pre-diagnosis plasma, 14 plasma specimens from these patients were analyzed by short oligonucleotide mass analysis. Nine of them (64%) were found to be positive. Overall, these results suggest that HCC containing R249S can occur in the absence of significant recent exposure to aflatoxins. The use of short oligonucleotide mass analysis in the context of low ongoing aflatoxin exposure may allow the detection of R249S in plasma several months ahead of clinical diagnosis. (Cancer Epidemiol Biomarkers Prev 2009;18(5):1638-43)

A 2300 yr record of sago and rice use from the southern Kelabit Highlands of Sarawak, Malaysian Borneo

Rice and sago are today important staples for many subsistence farmers and nomadic hunter-gatherers living in interior Borneo, but the cultural antiquity of these staples remains poorly understood. This study examines a 2300 yr sedimentary record from a palaeochannel near the village of Pa’Dalih in the southern Kelabit Highlands. Pollen and phytolith evidence indicate significant use of the sago palm Eugeissona near the channel during this period. Oryza phytoliths likely belonging to domesticated rice varieties are also recorded, although rice may have been used to a lesser extent than the sago palms. A rise in cultural activity takes place between c. 1715 and 1600 cal. BP, shown by increased frequency of fires.

Asprich Peptides Are Occluded in Calcite and Permanently Disorder Biomineral Crystals

Macromolecules are a minority but important component of the minerals formed by living organisms, or biominerals. The role these macromolecules play at the early stages of biomineral formation, as well as their long-term and long-range effects on the mature biomineral, is poorly understood. A 42-amino acid peptide, asp2, was derived from the Asprich family of proteins. In this study we present X-ray absorption near-edge structure spectroscopy and X-ray photoelectron emission microscopy data from the asp2 peptide, the calcite (CaCO3) crystals, and the peptide + crystal composites. The results clearly show that asp2 is occluded in fully formed biomineral crystals and slightly but permanently disorders the crystal structure at short- and long-range distances.

The accuracy of accredited glaucoma optometrists in the diagnosis and treatment recommendation for glaucoma

Aim: To compare the diagnostic performance of accredited glaucoma optometrists (AGO) for both the diagnosis of glaucoma and the decision to treat with that of routine hospital eye care, against a reference standard of expert opinion (a consultant ophthalmologist with a special interest in glaucoma). Methods: A directly comparative, masked, performance study was undertaken in Grampian, Scotland. Of 165 people invited to participate, 100 (61%) were examined. People suspected of having glaucoma underwent, within one month, a full ophthalmic assessment in both a newly established community optometry led glaucoma management scheme and a consultant led hospital eye service. Results: Agreement between the AGO and the consultant ophthalmologist in diagnosing glaucoma was substantial (89%; ? = 0.703, SE = 0.083). Agreement over the need for treatment was also substantial (88%; ? = 0.716, SE = 0.076). The agreement between the trainee ophthalmologists and the consultant ophthalmologist in the diagnosis of glaucoma and treatment recommendation was moderate (83%, ? = 0.541, SE = 0.098, SE = 0.98; and 81%, ? = 0.553, SE = 0.90, respectively). The diagnostic accuracy of the optometrists in detecting glaucoma in this population was high for specificity (0.93 (95% confidence interval, 0.85 to 0.97)) but lower for sensitivity (0.76 (0.57 to 0.89)). Performance was similar when accuracy was assessed for treatment recommendation (sensitivity 0.73 (0.57 to 0.85); specificity 0.96 (0.88 to 0.99)). The differences in sensitivity and specificity between AGO and junior ophthalmologist were not statistically significant. Conclusions: Community optometrists trained in glaucoma provided satisfactory decisions regarding diagnosis and initiation of treatment for glaucoma. With such additional training in glaucoma, optometrists are at least as accurate as junior ophthalmologists but some cases of glaucoma are missed.

LDL-containing immune complexes in the DCCT/EDIC cohort:associations with lipoprotein subclasses

Immune complexes containing modified LDL (LDL-IC) and NMR-determined Total LDL particle concentrations are significantly associated with intima-media thickness (IMT). We analyzed the associations between concentrations of NMR-determined lipoprotein subclasses and LDL-IC in the DCCT/EDIC cohort. LDL-IC concentrations in women and men of the DCCT/EDIC cohort did not differ significantly and were positively associated with Total LDL particle concentrations in men and women (r=0.34, r=0.32, respectively; P

Risk factors related to inflammation and endothelial dysfunction in the DCCT/EDIC cohort and their relationship with nephropathy and macrovascular complications

Because endothelial cell dysfunction and inflammation are key contributors to the development of complications in type 1 diabetes, we studied risk factors related to endothelial dysfunction and inflammation (C-reactive protein and fibrinogen, soluble vascular cell adhesion molecule-1, intracellular adhesion molecule-1, and E-selectin, and fibrinolytic markers) in a subgroup of patients from the Diabetes Control and Complications Trial (DCCT)/Epidemiology of Diabetes Intervention and Complications (EDIC) study cohort.

Distal Deposition of Tephra from the Eyjafjallajökull 2010 Summit Eruption

The 2010 Eyjafjallajökull lasted 39 days and had 4 different phases, of which the first and third (14–18 April and 5–6 May) were most intense. Most of this period was dominated by winds with a northerly component that carried tephra toward Europe, where it was deposited in a number of locations and was sampled by rain gauges or buckets, surface swabs, sticky-tape samples and air filtering. In the UK, tephra was collected from each of the Phases 1–3 with a combined range of latitudes spanning the length of the country. The modal grain size of tephra in the rain gauge samples was 25 um, but the largest grains were 100 um in diameter and highly vesicular. The mass loading was equivalent to 8–218 shards cm2, which is comparable to tephra layers from much larger past eruptions. Falling tephra was collected on sticky tape in the English Midlands on 19, 20 and 21st April (Phase 2), and was dominated by aggregate clasts (mean diameter 85 um, component grains <10 um). SEM-EDS spectra for aggregate grains contained an extra peak for sulphur, when compared to control samples from the volcano, indicating that they were cemented by sulphur-rich minerals e.g. gypsum (CaSO4⋅H2O). Air quality monitoring stations did not record fluctuations in hourly PM10 concentrations outside the normal range of variability during the eruption, but there was a small increase in 24-hour running mean concentration from 21–24 April (Phase 2). Deposition of tephra from Phase 2 in the UK indicates that transport of tephra from Iceland is possible even for small eruption plumes given suitable wind conditions. The presence of relatively coarse grains adds uncertainty to concentration estimates from air quality sensors, which are most sensitive to grain sizes <10 um. Elsewhere, tephra was collected from roofs and vehicles in the Faroe Islands (mean grain size 40 um, but 100 um common), from rainwater in Bergen in Norway (23–91 um) and in air filters in Budapest, Hungary (2–6 um). A map is presented summarizing these and other recently published examples of distal tephra deposition from the Eyjafjallajökull eruption. It demonstrates that most tephra deposited on mainland Europe was produced in the highly explosive Phase 1 and was carried there in 2–3 days.

M level Inquiry Across Disciplinary Boundaries: Using Reflective Sketchbooks

Debates unfolding around the recent development of M Level programmes for teacher education are not unfamiliar to those being addressed in other professional disciplines such as business. A strong theme in our analysis is that reflective practitioners could be provided with a wider range of tools and methods to support them in their reflection. Considerable energies have been expended on e portfolios, but our experience of use of paper based reflective
sketchbooks suggests that they may have some distinct advantages over text-dominated electronic media. In fact such sketchbooks challenge typed text as the dominant route to learning and communication (Gilbert 1998), (New, 2005), (Hickman, 2007). Professionals in teacher education are currently exploring ways in which M level can be conceived in terms of professional learning. This is also important terrain in other professions. For example, best practice in business management involves constant innovation so that students do not experience a split between the research context of the business faculty and the experience of operating in the business situation. This is paralleled in education by the concern that trainees do not experience a split between the research or scholarly informed approach of university tutors, and the experience of practical teaching in school. Our research question is concerned with how a consciously developed reflective sketchbook method can generate levels of critical thought that are both postgraduate and professionally valued in the workplace. We are also interested in the contribution this form of enquiry at M Level can make in terms of life long learning.

"No Artist has Ethical Sympathies": Oscar Wilde, Aesthetics, and Moral Evolution

“There is no mode of action, no form of emotion, that we do not share with the lower animals” (137). This evolutionary claim is not attributable to Darwin, but to Oscar Wilde, who allows Gilbert to voice this bold assertion in “The True Function of Criticism.” While critics have long wrestled with the ethical stance and coherence of Wilde's writings, they have overlooked a significant influence on his work: debates concerning the evolution of morality that animated the periodicals in which he was writing. Wilde was fascinated by the proposition that complex human behaviours, including moral and aesthetic responses, might be traced back to evolutionary impulses. Significantly, he also wrote for a readership already engaged with these controversies.

The PREDICTS database: a global database of how local terrestrial biodiversity responds to human impacts

Biodiversity continues to decline in the face of increasing anthropogenic pressures such as habitat destruction, exploitation, pollution and introduction of alien species. Existing global databases of species' threat status or population time series are dominated by charismatic species. The collation of datasets with broad taxonomic and biogeographic extents, and that support computation of a range of biodiversity indicators, is necessary to enable better understanding of historical declines and to project - and avert - future declines. We describe and assess a new database of more than 1.6 million samples from 78 countries representing over 28,000 species, collated from existing spatial comparisons of local-scale biodiversity exposed to different intensities and types of anthropogenic pressures, from terrestrial sites around the world. The database contains measurements taken in 208 (of 814) ecoregions, 13 (of 14) biomes, 25 (of 35) biodiversity hotspots and 16 (of 17) megadiverse countries. The database contains more than 1% of the total number of all species described, and more than 1% of the described species within many taxonomic groups - including flowering plants, gymnosperms, birds, mammals, reptiles, amphibians, beetles, lepidopterans and hymenopterans. The dataset, which is still being added to, is therefore already considerably larger and more representative than those used by previous quantitative models of biodiversity trends and responses. The database is being assembled as part of the PREDICTS project (Projecting Responses of Ecological Diversity In Changing Terrestrial Systems - http://www.predicts.org.uk). We make site-level summary data available alongside this article. The full database will be publicly available in 2015.

The effect of level of straw bale provision on the behaviour and leg health of commercial broiler chickens

This study aimed to assess the effect of the number of straw bales (SBs) provided on the behaviour and leg health of commercial broiler chickens. Houses containing ~23 000 broiler chickens were assigned to one of two treatments: (1) access to 30 SBs per house, ‘30SB’ or (2) access to 45 SB per house, ‘45SB’. This equated to bale densities of 1 bale/44 m2 and 1 bale/29 m2 of floor space within houses, respectively. Treatments were applied in one of two houses on a commercial farm, and were replicated over six production cycles. Both houses had windows and were also artificially lit. Behaviour was observed in weeks 3 to5 of the cycle. This involved observations of general behaviour and activity, gait scores (0: perfect to 5: unable to walk) and latency to lie (measured in seconds from when a bird had been encouraged to stand). Production performance and environmental parameters were also measured. SB density had no significant effect on activity levels (P>0.05) or walking ability (P>0.05). However, the average latency to lie was greater in 30SB birds compared with 45SB birds (P<0.05). The incidence of hock burn and podo dermatitis, average BW at slaughter and levels of mortality and culling were unaffected by SB density (P>0.05). The results from this study suggest that increasing SB levels from 1 bale/44 m2 to 1 bale/29 m2 floor space does not lead to significant improvements in the welfare of commercial broiler chickens in windowed houses.