The effect of alkyl substitution on the extraction properties of BTPhen ligands for the partitioning of trivalent minor actinides and lanthanides in spent nuclear fuels

Bis-triazinylphenanthroline ligands (BTPhens), which contain additional alkyl (n-butyl and sec-butyl) groups attached to the triazine rings, have been synthesized, and the effects of this alkyl substitution on their extraction properties with Ln(III) and An(III) cations in simulated nuclear waste solutions have been studied. The speciation of n-butyl-substituted ligand (C4- BTPhen) with some trivalent lanthanide nitrates was elucidated by 1 H-NMR spectroscopic titrations. These experiments have shown that the dominant species in solution were the 1:2 complexes [Ln(III)(BTPhen)2], even at higher Ln(III) concentrations, and the relative stability of 2:1 to 1:1 BTPhen-Ln(III) complexes varied with different lanthanides. As expected, sec-butylsubstituted ligand (sec-C4 BTPhen) showed higher solubility than C4-BTPhen in certain diluents. A greater separation factor (SFAm/Eu = ca. 210) was observed for sec-C4-BTPhen compared to C4-BTPhen (SFAm/Eu = ca. 125) in 1-octanol at 4 M HNO3 solutions. The greater separation factor may be due to the higher solubility of the 2:1 complex for sec-C4-BTPhen at the interface than the 1:1 complex of C4-BTPhen.

The impact of Rhinanthus minor in newly established meadows on a productive site

Question: What is the impact of the presence of Rhinanthus minor on forb abundance in newly established swards? Location: Wetherby, West Yorkshire, UK (53 degrees 55' N, 1 degrees 22(1) W). Method: A standard meadow mix containing six forbs and six grasses was sown on an ex-arable field and immediately over-sown using a randomised plot design with three densities of Rhinanthus minor (0, 600, and 1000 seeds per m(2)). Above-ground biomass was analysed over a period of three years, while detailed assessments of sward composition were performed during the first two years. Results: Values of grass biomass were reduced in the presence of Rhinanthus, especially at the higher sowing density. The ratio of grass: forb biomass was also lower in association with Rhinanthus, but only at the higher sowing density. The presence of Rhinanthus, had no effect on species number or diversity, which decreased between years regardless of treatment. Conclusions: Although not tested in a multi-site experiment, the benefit of introducing Rhinanthus into newly established swards to promote for abundance was determined. The efficacy of Rhinanthus presence is likely to depend on whether species not susceptible to the effects of parasitism are present.

Experimental comparison of the comprehensibility of a Z specification and its implementation in Java

Comprehensibility is often raised as a problem with formal notations, yet formal methods practitioners dispute this. In a survey, one interviewee said 'formal specifications are no more difficult to understand than code'. Measurement of comprehension is necessarily comparative and a useful comparison for a specification is against its implementation. Practitioners have an intuitive feel for the comprehension of code. A quantified comparison will transfer this feeling to formal specifications. We performed an experiment to compare the comprehension of a Z specification with that of its implementation in Java. The results indicate there is little difference in comprehensibility between the two. (C) 2004 Elsevier B.V. All rights reserved.

Challenges and opportunities facing contractors in Ghana

The main aim of this study was to ascertain and discuss the current challenges and opportunities facing construction contractors in Ghana. This involved a review of the economic, legal and political environments in which contractors in Ghana operate; a review of published studies on construction in developing countries generally and Ghana specifically; and in-depth interviews and discussions with seven building and civil engineering contractors in Ghana in 2009 and 2010. Six road contractors were also interviewed. The findings indicate significant challenges relating mainly to financing for projects and a harsh business environment. However, most contractors interviewed admitted to significant problems in their own organisations. It is clear that the contracting environment in Ghana is harsh particularly for local contractors who are often not paid on time and without compensation for late payment. However, local construction firms in Ghana who want to breakthrough ought to formulate the right strategic plans, develop innovative business strategies, develop professionalism, and merge with local firms with similar organisational values and characteristics. In short, local or indigenous Ghanaian contractors ought to face up to the reality of competition and the dynamics of modern business in order to survive, grow and become major players in the construction industry in Ghana.

Uniqueness in chess studies

Van der Heijden’s ENDGAME STUDY DATABASE IV, HhdbIV, is the definitive collection of 76,132 chess studies. In each one, White is to achieve the stipulated goal, win or draw: study solutions should be essentially unique with minor alternatives at most. In this second note on the mining of the database, we use the definitive Nalimov endgame tables to benchmark White’s moves in sub-7-man chess against this standard of uniqueness. Amongst goal-compatible mainline positions and goal-achieving moves, we identify the occurrence of absolutely unique moves and analyse the frequency and lengths of absolutely-unique-move sequences, AUMSs. We identify the occurrence of equi-optimal moves and suboptimal moves and refer to a defined method for classifying their significance.

On the evaluation of temperature trends in the tropical troposphere

A series of model experiments with the coupled Max-Planck-Institute ECHAM5/OM climate model have been investigated and compared with microwave measurements from the Microwave Sounding Unit (MSU) and re-analysis data for the period 1979–2008. The evaluation is carried out by computing the Temperature in the Lower Troposphere (TLT) and Temperature in the Middle Troposphere (TMT) using the MSU weights from both University of Alabama (UAH) and Remote Sensing Systems (RSS) and restricting the study to primarily the tropical oceans. When forced by analysed sea surface temperature the model reproduces accurately the time-evolution of the mean outgoing tropospheric microwave radiation especially over tropical oceans but with a minor bias towards higher temperatures in the upper troposphere. The latest reanalyses data from the 25 year Japanese re-analysis (JRA25) and European Center for Medium Range Weather Forecasts Interim Reanalysis are in very close agreement with the time-evolution of the MSU data with a correlation of 0.98 and 0.96, respectively. The re-analysis trends are similar to the trends obtained from UAH but smaller than the trends from RSS. Comparison of TLT, computed from observations from UAH and RSS, with Sea Surface Temperature indicates that RSS has a warm bias after 1993. In order to identify the significance of the tropospheric linear temperature trends we determined the natural variability of 30-year trends from a 500 year control integration of the coupled ECHAM5 model. The model exhibits natural unforced variations of the 30 year tropospheric trend that vary within ±0.2 K/decade for the tropical oceans. This general result is supported by similar results from the Geophysical Fluid Dynamics Laboratory (GFDL) coupled climate model. Present MSU observations from UAH for the period 1979–2008 are well within this range but RSS is close to the upper positive limit of this variability. We have also compared the trend of the vertical lapse rate over the tropical oceans assuming that the difference between TLT and TMT is an approximate measure of the lapse rate. The TLT–TMT trend is larger in both the measurements and in the JRA25 than in the model runs by 0.04–0.06 K/decade. Furthermore, a calculation of all 30 year TLT–TMT trends of the unforced 500-year integration vary between ±0.03 K/decade suggesting that the models have a minor systematic warm bias in the upper troposphere.

Glucokinase Regulatory Protein genetic variant interacts with omega-3 PUFA to influence insulin resistance and inflammation in metabolic syndrome

Glucokinase Regulatory Protein (GCKR) plays a central role regulating both hepatic triglyceride and glucose metabolism. Fatty acids are key metabolic regulators, which interact with genetic factors and influence glucose metabolism and other metabolic traits. Omega-3 polyunsaturated fatty acids (n-3 PUFA) have been of considerable interest, due to their potential to reduce metabolic syndrome (MetS) risk. Objective To examine whether genetic variability at the GCKR gene locus was associated with the degree of insulin resistance, plasma concentrations of C-reactive protein (CRP) and n-3 PUFA in MetS subjects. Design Homeostasis model assessment of insulin resistance (HOMA-IR), HOMA-B, plasma concentrations of C-peptide, CRP, fatty acid composition and the GCKR rs1260326-P446L polymorphism, were determined in a cross-sectional analysis of 379 subjects with MetS participating in the LIPGENE dietary cohort. Results Among subjects with n-3 PUFA levels below the population median, carriers of the common C/C genotype had higher plasma concentrations of fasting insulin (P = 0.019), C-peptide (P = 0.004), HOMA-IR (P = 0.008) and CRP (P = 0.032) as compared with subjects carrying the minor T-allele (Leu446). In contrast, homozygous C/C carriers with n-3 PUFA levels above the median showed lower plasma concentrations of fasting insulin, peptide C, HOMA-IR and CRP, as compared with individuals with the T-allele. Conclusions We have demonstrated a significant interaction between the GCKR rs1260326-P446L polymorphism and plasma n-3 PUFA levels modulating insulin resistance and inflammatory markers in MetS subjects. Further studies are needed to confirm this gene-diet interaction in the general population and whether targeted dietary recommendations can prevent MetS in genetically susceptible individuals.

Contested institutions? Traditional leaders and land access and control in communal areas of Eastern Cape Province, South Africa

The South African government has endeavoured to strengthen property rights in communal areas and develop civil society institutions for community-led development and natural resource management. However, the effectiveness of this remains unclear as the emergence and operation of civil society institutions in these areas is potentially constrained by the persistence of traditional authorities. Focusing on the former Transkei region of Eastern Cape Province, three case study communities are used examine the extent to which local institutions overlap in issues of land access and control. Within these communities, traditional leaders (chiefs and headmen) continue to exercise complete and sole authority over land allocation and use this to entrench their own positions. However, in the absence of effective state support, traditional authorities have only limited power over how land is used and in enforcing land rights, particularly over communal resources such as rangeland. This diminishes their local legitimacy and encourages some groups to contest their authority by cutting fences, ignoring collective grazing decisions and refusing to pay ‘fees’ levied on them. They are encouraged in such activities by the presence of democratically elected local civil society institutions such as ward councillors and farmers’ organisations, which have broad appeal and are increasingly responsible for much of the agrarian development that takes place, despite having no direct mandate over land. Where it occurs at all, interaction between these different institutions is generally restricted to approval being required from traditional leaders for land allocated to development projects. On this basis it is argued that a more radical approach to land reform in communal areas is required, which transfers all powers over land to elected and accountable local institutions and integrates land allocation, land management and agrarian development more effectively.

Lanthanide speciation in potential SANEX and GANEX actinide/ 2 lanthanide separations using Tetra-N-Donor extractants

Lanthanide(III) complexes with N-donor ex-tractants, which exhibit the potential for the separation of minor actinides from lanthanides in the management of spent nuclear fuel, have been directly synthesized and characterized in both solution and solid states. Crystal structures of the Pr3+, Eu3+, Tb3+, and Yb3+ complexes of 6,6′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin3-yl)-1,10-phenanthroline(CyMe4-BTPhen) and the Pr3+, Eu3+, and Tb3+ complexes of 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotria-zin-3-yl)-2,2′-bypyridine (CyMe4-BTBP) were obtained. The majority of these structures displayed coordination of two ofthe tetra-N-donor ligands to each Ln3+ ion, even when in some cases the complexations were performed with equimolar amounts of lanthanide and N-donor ligand. The structures showed that generally the lighter lanthanides had their coordination spheres completed by a bidentate nitrate ion, giving a 2+ charged complex cation, whereas the structures of the heavier lanthanides displayed tricationic complex species with a single water molecule completing their coordination environments. Electronic absorption spectroscopic titrations showed formation of the 1:2 Ln3+/LN4‑donor species (Ln = Pr3+, Eu3+, Tb3+) in methanol when the N-donor ligand was in excess. When the Ln3+ ion was in excess, evidence for formation of a 1:1 Ln3+/LN4‑donor complex species was observed. Luminescent lifetime studies of mixtures of Eu3+ with excess CyMe4-BTBP and CyMe4-BTPhen in methanol indicated that the nitrate-coordinated species is dominant in solution. X-ray absorption spectra of Eu3+ and Tb3+ species, formed by extraction from an acidic aqueous phase into an organic solution consisting of excess N-donor extractant in pure cyclohexanone or 30% tri-n-butyl phosphate (TBP) in cyclohexanone, were obtained. The presence of TBP in the organic phase did not alter lanthanide speciation. Extended X-ray absorption fine structure data from these spectra were fitted using chemical models established by crystallography and solution spectroscopy and showed the dominant lanthanide species in the bulk organic phase was a 1:2 Ln3+/LN‑donor species.

Antioxidant properties of three aromatic herbs (rosemary, thyme and lavender) in oil-in-water emulsions

Lipid oxidation is the major form of deterioration in foods because it decreases food quality and nutritional value, and may have negative health implications. Selected aromatic plant extracts from leaves, flowers and stems of rosemary, thyme and lavender were investigated for their antioxidant activity. The total polyphenol content was determined by the Folin-Ciocalteu assay and the antioxidant capacity was determined by the Trolox equivalent antioxidant capacity, 1,1-diphenyl-2-picrylhydrazyl, oxygen radical absorbance capacity and ferric-reducing antioxidant power assays. For all four antioxidant assays, the extracts from thyme flowers, lavender leaves and thyme leaves had the highest antioxidant activity, followed by rosemary stems, rosemary leaves, and lavender stems, and the lavender flowers and thyme stems had the lowest antioxidant activity. The antioxidant activity was correlated with the polyphenol content, although minor deviations were observed. In oil-in-water emulsion, extracts from rosemary leaves and thyme leaves were most effective at retarding oxidation followed by the rosemary stems and thyme flowers. Extracts from thyme flowers and lavender leaves were less effective in the emulsion than predicted by the homogeneous antioxidant assays. This study demonstrated the potential use of plants extract as substitutes for synthetic antioxidants.

Robustness despite uncertainty: regional climate data reveal the dominant role of humans in explaining global extinctions of Late Quaternary megafauna

Debate over the late Quaternary megafaunal extinctions has focussed on whether human colonisation or climatic changes were more important drivers of extinction, with few extinctions being unambiguously attributable to either. Most analyses have been geographically or taxonomically restricted and the few quantitative global analyses have been limited by coarse temporal resolution or overly simplified climate reconstructions or proxies. We present a global analysis of the causes of these extinctions which uses high-resolution climate reconstructions and explicitly investigates the sensitivity of our results to uncertainty in the palaeological record. Our results show that human colonisation was the dominant driver of megafaunal extinction across the world but that climatic factors were also important. We identify the geographic regions where future research is likely to have the most impact, with our models reliably predicting extinctions across most of the world, with the notable exception of mainland Asia where we fail to explain the apparently low rate of extinction found in in the fossil record. Our results are highly robust to uncertainties in the palaeological record, and our main conclusions are unlikely to change qualitatively following minor improvements or changes in the dates of extinctions and human colonisation.