Speciation of Rare-Earth Metal Complexes in Ionic Liquids: A Multiple-Technique Approach

The dissolution process of metal complexes in ionic liquids was investigated by a multiple-technique approach to reveal the solvate species of the metal in solution. The task-specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) is able to dissolve stoichiometric amounts of the oxides of the rare-earth elements. The crystal structures of the compounds [Eu-2(bet)(8)(H2O)(4)][Tf2N](6), [Eu-2(bet)(8)(H2O)(2)][Tf2N](6)center dot 2H(2)O, and [Y-2(bet)(6)(H2O)(4)][Tf2N](6) were found to consist of dimers. These rare-earth complexes are well soluble in the ionic liquids [Hbet][Tf2N] and [C(4)mim]- [Tf2N] (C(4)mim = 1-butyl-3-methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, H-1, C-13, and Y-89 NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X-ray absorption fine structure) and HEXS (high-energy X-ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry.

Speciation of uranyl complexes in ionic liquids by optical spectroscopy

Uranyl complexes dissolved in room-temperature ionic liquids have diagnostic absorption and emission spectra which reflect the molecular symmetry and geometry. In particular, the characteristic vibrational fine structure of the absorption spectra allows identification of the molecular symmetry of a uranyl complex. The concept of speciation of. uranyl complexes is illustrated for the hydrated uranyl ion, the tetrachloro complex [UO2Cl4](2-), the trinitrato complex [UO2(NO3)(3)](-), the triacetato complex [UO2(CH3COO)(3)](-) and the crown ether complex [UO2(18-crown-6)](2+) in imidazolium and pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids. The competition between 18- crown-6 and small inorganic ligands for coordination to the uranyl ion was investigated. The crystal structures of the hydrolysis product [(UO2)(2)(mu(2)-OH)(2)(H2O)(6)] [UO2Br4](18-crown-6)(4) and imidazolium salt [C(6)mim](2)[UO2Br4] are described.

Speciation of chloroindate(III) ionic liquids

A range of chloroindate(III) ionic liquid systems was prepared by mixing of 1-alkyl-3-methylimidazolium chloride with indium(III) chloride in various ratios, expressed as the mol fraction of indium(III) chloride, chi(InCl3). For chi(InCl3) 0.50, the products were biphasic (suspensions of a solid in an ionic liquid). Speciation of these chloroindate(III) systems was carried out using a wide range of techniques: differential scanning calorimetry (DSC), polarised optical microscopy (POM), liquid-state and solid-state In-115 NMR spectroscopy, X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS). Ionic liquids prepared using an excess of the organic chloride (chi(InCl3) 0.5) contained indium(III) chloride powder suspended in a neutral tetrachloroindate ionic liquid.

Parasite diversity, patterns of MHC II variation and olfactory based mate choice in diverging three-spined stickleback ecotypes

Ecological speciation has been the subject of intense research in evolutionary biology but the genetic basis of the actual mechanism driving reproductive isolation has rarely been identified. The extreme polymorphism of the major histocompatibility complex (MHC), probably maintained by parasite-mediated selection, has been proposed as a potential driver of population divergence. We performed an integrative field and experimental study using three-spined stickleback river and lake ecotypes. We characterized their parasite load and variation at MHC class II loci. Fish from lakes and rivers harbor contrasting parasite communities and populations possess different MHC allele pools that could be the result of a combined action of genetic drift and parasite-mediated selection. We show that individual MHC class II diversity varies among populations and is lower in river ecotypes. Our results suggest the action of homogenizing selection within habitat type and diverging selection between habitat types. Finally, reproductive isolation was suggested by experimental evidence: in a flow channel design females preferred assortatively the odor of their sympatric male. This demonstrates the role of olfactory cues in maintaining reproductive isolation between diverging fish ecotypes.

Biodiversity loss and ecosystem functioning: Distinguishing between number and identity of species

Given currently high rates of extinction, it is critical to be able to predict how ecosystems will respond to loss of species and consequent changes in community structure. Much previous research in this area has been based on terrestrial systems, using synthetically assembled communities. There has beer! much less research on inter-trophic effects in different systems, using in situ removal experiments. Problems with the design of early experiments have made it difficult to determine whether reductions in ecosystem functioning in low diversity treatments were due to the number of species present or merely to the reduced likelihood of including particular (

Predatory fish loss affects the structure and functioning of a model marine food web

The rate of species loss is increasing on a global scale and predators are most at risk from human-induced extinction. The effects of losing predators are difficult to predict, even with experimental single species removals, because different combinations of species interact in unpredictable ways. We tested the effects of the loss of groups of common predators on herbivore and algal assemblages in a model benthic marine system. The predator groups were fish, shrimp and crabs. Each group was represented by at least two characteristic species based on data collected at local field sites. We examined the effects of the loss of predators while controlling for the loss of predator biomass. The identity, not the number of predator groups, affected herbivore abundance and assemblage structure. Removing fish led to a large increase in the abundance of dominant herbivores, such as Ampithoids and Caprellids. Predator identity also affected algal assemblage structure. It did not, however, affect total algal mass. Removing fish led to an increase in the final biomass of the least common taxa (red algae) and reduced the mass of the dominant taxa (brown algae). This compensatory shift in the algal assemblage appeared to facilitate the maintenance of a constant total algal biomass. In the absence of fish, shrimp at higher than ambient densities had a similar effect on herbivore abundance, showing that other groups could partially compensate for the loss of dominant predators. Crabs had no effect on herbivore or algal populations, possibly because they were not at carrying capacity in our experimental system. These findings show that contrary to the assumptions of many food web models, predators cannot be classified into a single functional group and their role in food webs depends on their identity and density in 'real' systems and carrying capacities.

Extinction risk from climate change

Climate change over the past ,30 years has produced numerous shifts in the distributions and abundances of species1,2 and has been implicated in one species-level extinction3. Using projections of species’ distributions for future climate scenarios, we assess extinction risks for sample regions that cover some 20% of the Earth’s terrestrial surface. Exploring three approaches in which the estimated probability of extinction shows a powerlaw relationship with geographical range size, we predict, on the basis of mid-range climate-warming scenarios for 2050, that 15–37% of species in our sample of regions and taxa will be ‘committed to extinction’. When the average of the three methods and two dispersal scenarios is taken, minimal climate-warming scenarios produce lower projections of species committed to extinction (,18%) than mid-range (,24%) and maximum change (,35%) scenarios. These estimates show the importance of rapid implementation of technologies to decrease greenhouse

Deforestation and apparent extinctions of endemic forest beetles in Madagascar

Madagascar has lost about half of its forest cover since 1953 with much regional variation, for instance most of the coastal lowland forests have been cleared. We sampled the endemic forest dwelling Helictopleurini dung beetles across Madagascar during 2002–2006. Our samples include 29 of the 51 previously known species for which locality information is available. The most significant factor explaining apparent extinctions (species not collected by us) is forest loss within the historical range of the focal species, suggesting that deforestation has already caused the extinction, or effective extinction, of a large number of insect species with small geographical ranges, typical for many endemic taxa in Madagascar. Currently, roughly 10% of the original forest cover remains. Species–area considerations suggest that this will allow roughly half of the species to persist. Our results are consistent with this prediction.

Palaeobiology of an extinct Ice Age mammal: Stable isotope and cementum analysis of giant deer teeth

The extinct giant deer, Megaloceros giganteus, is among the largest and most famous of the cervids. Megaloceros remains have been uncovered across Europe and western Asia. but the highest concentrations come from Irish bogs and caves Although Megaloceros has enjoyed a great deal of attention over the centuries, paleobiological study has focused oil morphometric and distributional work until now. This paper presents quantitative data that have implications for understanding its sudden extirpation in western Europe during a period of global climate change approximately 10.600 C-14 years ago (ca 12,500 calendar years BP). We report here the first stable isotope analysis of giant deer teeth. which we combine with dental cementum accretion in order to document age, diet and life-history seasonality from birth until death Enamel delta C-13 and delta O-18 measured in the second and third molars from seven individual giant deer Suggest a grass and forbbased diet supplemented with browse in a deteriorating. possibly water-stressed, environment, and a season of birth around spring/early summer Cementurm data indicate that the ages of the specimens ranged from 6.5 to 14 years and that they possessed mature antlers by autumn, similar to extant cervids. In addition. the possibility for combining these two techniques in future mammalian paleoccological studies is considered. The data presented in this study imply that Megoloceros would have indeed been vulnerable to extirpation during the terminal Pleistocene in Ireland. and this information is relevant to understanding the broader pattern of its extinction.

Optical transmission properties and electric field distribution of interacting 2D silver nanorod Arrays

Silver nanorods have been grown by electrodeposition into thin film porous alumina templates (AAO). Optical transmission measurements using p-polarized incident white light shows clear plasmon resonance extinction peaks. We successfully model the dependence on angle in incidence of extinction peak height and position using a multiple-multipoles (MMP) approach with the different spectral features being clearly associated with the effective electric field distribution and coupling between individual nanorods.

Anomalous extinction behaviour towards the type Ia SN 2003cg

We present optical and near-infrared photometry and spectroscopy of the Type Ia SN 2003cg, which exploded in the nearby galaxy NGC 3169. The observations cover a period between -8.5 and +414 d post-maximum. SN 2003cg is a normal but highly reddened Type Ia event. Its B magnitude at maximum B-max = 15.94 +/- 0.04 and Delta m(15)(B)(obs) = 1.12 +/- 0.04 [Delta m(15)(B)(intrinsic) = 1.25 +/- 0.05]. Allowing R-V to become a free parameter within the Cardelli et al. extinction law, simultaneous matches to a range of colour curves of normal SNe Ia yielded E(B - V) = 1.33 +/- 0.11, and RV = 1.80 +/- 0.19. While the value obtained for R-V is small, such values have been invoked in the past, and may imply a grain size which is small compared with the average value for the local interstellar medium.

Assessing the conservation status of the freshwater pearl mussel in the North of Ireland - Relevance of growth and age characteristics

In order to conserve the freshwater pearl mussel in Ireland, populations that have a high risk of extinction must he identified and given priority for conservation. Growth of freshwater pearl mussels has been found to vary among populations on a wide geographic scale as well as on a local scale. Populations having a high growth constant (k), because of the small size of individuals and their shorter life-span and thus lower reproductive output, may be more likely to become extinct than those which have a low k and hence larger size and greater reproductive output. This study attempts to estimate the growth constant (k) in rivers in Donegal and Northern Ireland based on measuring lire largest shell in each population. Large differences in values of k were found among rivers and these are discussed in relation to catchment bedrock types and the identification of conservation priorities. Appropriate conservation strategies are recommended for Margaritifera margaritifera populations in the north of Ireland.

Does the freshwater pearl mussel, Margaritifera margaritifera L., face extinction in Northern Ireland?

1. Until recently the status of Margaritifera margaritifera L. in Northern Ireland was not well documented. This paper presents the results of field surveys conducted in 1990/'91 and in 1996 at over 200 sites covering all major river systems in Northern Ireland. 2.Margaritifera populations in Northern Ireland were recorded at just 20 sites mainly located in the west of the province. Formerly many rivers supported vast numbers of mussels but anecdotal evidence points to periods of major declines in mussel populations since the turn of the century. 3. The absence of mussels smaller than 30 mm in length at most sites suggests very little or no recruitment during the past decade. During the surveys, deteriorating water quality, habitat disturbance and pearl fishing were recorded and are the major causes of the decline of the freshwater pearl mussel in Northern Ireland. 4. Unless the above problems are alleviated in the very near future, M.margaritifera will probably become extinct in Northern Ireland. © 1998 John Wiley & Sons, Ltd.

‘Marxism and Ecology: From Political Economy to Political Ecology’

One of the reasons for the 'fin de seicle' angst within western liberal capitalist societies is the rise in prominance of ecological concerns within these societies. Long before the New Right declared the post-war welfare state to be untenable, early green critics had claimed it to be ecologically unsustainable. The addiction of the welfare state on ever increasing levels of economic growth was pronounced to be simply impossible within the context of a finite planet. Although it was not expressed in this manner, what these early ecological concerns with Limits to Growth were in effect saying was that the accumulation of capital rendered capitalism unsustainable. Yet the ecological critique of capitalism has not found much favour within the Marxist critique untile recently. Early Marxist analyses of the ecology movement dismissed them as ‘petty bourgeios radicals’ while many greens still view Marxism as ‘fair shares in extinction’. The lack of positive engagement and dialogue between Marxism and ecology has in recent years been put right with a discernable overlap between the two critiques of capitalism. This article seeks to present the areas of disagreement and agreement between the two and seeks to provide an ‘environmental audit’ on both the Marxist method and political project.

Determination of the molar extinction coefficient for the ferric reducing/antioxidant power assay

The FRAP reagent contains 2,4,6-tris(2-pyridyl)-s-triazine, which forms a blue-violet complex ion in the presence of ferrous ions. Although the FRAP (ferric reducing/antioxidant power) assay is popular and has been in use for many years, the correct molar extinction coefficient of this complex ion under FRAP assay conditions has never been published, casting doubt on the validity of previous calibrations. A previously reported value of 19.800 is an underestimate. We determined that the molar extinction coefficient was 21,140. The value of the molar extinction coefficient was also shown to depend on the type of assay and was found to be 22,230 under iron assay conditions, in good agreement with published data. Redox titration indicated that the ferrous sulfate heptahydrate calibrator recommended by Benzie and Strain, the FRAP assay inventors, is prone to efflorescence and, therefore, is unreliable. Ferrous ammonium sulfate hexahydrate in dilute sulfuric acid was a more stable alternative. Few authors publish their calibration data, and this makes comparative analyses impossible. A critical examination of the limited number of examples of calibration data in the published literature reveals only that Benzie and Strain obtained a satisfactory calibration using their method. (C) 2011 Elsevier Inc. All rights reserved.