Synthesis, X-ray crystal structures and properties of complex salts and sterically crowded heteroleptic complexes of group 10 metal ions with aromatic sulfonyl dithiocarbimates and triphenylphosphine ligand

Two new complex salts of the form (Bu4N)(2)[Ni(L)(2)] (1) and (Ph4P)(2)[Ni(L)(2)] (2) and four heteroleptic complexes cis-M(PPh3)(2)(L) [M = Ni(II) (3), Pd(II) (4), L = 4-CH3OC6H4SO2N=CS2] and cis-M(PPh3)(2)(L') [M = Pd(II) (5), Pt(II) (6), L' = C6H5SO2N=CS2] were prepared and characterized by elemental analyses, IR, H-1, C-13 and P-31 NMR and UV-Vis spectra, solution and solid phase conductivity measurements and X-ray crystallography. A minor product trans-Pd(PPh3)(2)(SH)(2), 4a was also obtained with the synthesis of 4. The NiS4 and MP2S2 core in the complex salts and heteroleptic complexes are in the distorted square-plane whereas in the trans complex, 4a the centrosymmetric PdS2P2 core is perforce square planar. X-ray crystallography revealed the proximity of the ortho phenyl proton of the PPh3 ligand to Pd(II) showing rare intramolecular C-H center dot center dot center dot Pd anagostic binding interactions in the palladium cis-5 and trans-4a complexes. The complex salts with sigma(rt) values similar to 10 (5) S cm (1) show semi-conductor behaviors. The palladium and platinum complexes show photoluminescence properties in solution at room temperature.

An analysis of verbal responses to music in a group of adult non-specialists

In a workshop setting, two pieces of recorded music were presented to a group of adult non-specialists; a key feature was to set up structured discussion within which the respondents considered each piece of music as a whole and not in its constituent parts. There were two areas of interest, namely to explore whether the respondents were likely to identify the musical features or to make extra-musical associations and, to establish the extent to which there would be commonality and difference in their approach to formulating the verbal responses. An inductive approach was used in the analysis of data to reveal some of the working theories underpinning the intuitive musicianship of the adult non-specialist listener. Findings have shown that, when unprompted by forced choice responses, the listeners generated responses that could be said to be information-poor in terms of musical features but rich in terms of the level of personal investment they made in formulating their responses. This is evidenced in a number of connections they made between the discursive and the non-discursive, including those which are relational and mediated by their experiences. Implications for music education are considered.

Attaching and effacing lesions in the large intestine of an eight-month-old heifer associated with Escherichia coli O26 infection in a group of animals with dysentery

Escherichia coli O26:K60, with genetic attributes consistent with a potentially human enterohaemorrhagic E coli was isolated from the faeces of an eight-month-old heifer with dysentery. Attaching and effacing lesions were identified in the colon of a similarly affected heifer examined postmortem, and shown to be associated with E coli O26 by specific immunolabelling.

Monometallic salts derived from complex anions of group 10 metal ions with p-tolylsulfonyldithiocarbimate ligand: Synthesis, characterization and properties

New monometallic complex salts of the form X-2[M(L)(2)] [M = Ni2+, X = (CH3)(2)NH2+(1); M = Ni2+, X = (CH3)(4)N+ (2); M = Ni2+, X = (C2H5)(4)N+(3); M = Ni2+, X = (C3H7)(4)N+(4); M = Ni2+; X = (C6H13)(4)N+) (5); M = Pd2+,X = (CH3)(2)NH2+(6); M = Pd2+, X= (C2H5)(4)N+(7); M = Pd2+, X= (C3H7)(4)N+(8); M = Pd2+, X = (C6H13)(4)N+ (9); M = Pt2+, X = (CH3)(2)NH2+(10); L = p-tolylsulfonyldithiocarbimate (CH3C6H4SO2N=CS22 )] have been prepared and characterized by elemental analysis, IR, H-1 and C-13 NMR and UV-Vis spectroscopy; 1, 3, 4 and 5 by X-ray crystallography. In 1, 3, 4 and 5, the Ni atom is four coordinate with a square planar environment being bonded to four sulfur atoms from two bidentate ligands. All the salts are weakly conducting (sigma(rt) = 10 (7) to 10 (14) Scm (1)) because of the lack of significant S center dot center dot center dot S intermolecular interactions between complex anions [M(L)(2)](2) in the solid state however, they show behavior of semiconductors in the temperature range 353-453 K. All the Pd(II) and Pt(II) salts exhibited phtotolumeniscent emissions near visible region in solution at room temperature.

Syntheses, crystal structures and properties of sterically congested heteroleptic complexes of group 10 metal ions with p-tolylsulfonyl dithiocarbimate and 1,2-bis (diphenylphosphino) ethane

Three novel heteroleptic complexes of the type cis- [ML(dppe)] [M = Ni(II), Pd(II), Pt(II); L = p-tolylsulfonyl dithiocarbimate; dppe = 1,2-bis(diphenylphosphino)ethane] have been prepared and characterized. X-ray crystallography revealed the close proximity of one of the ortho phenyl protons of the dppe ligand to the metal in the Ni(II) complex showing existence of the less common C-H center dot center dot center dot Ni anagostic interactions observed for the first time in the dithio-phosphine mixed-ligand systems. The platinum complex showed a strong photoluminescence emission near visible region in CH(2)Cl(2) solution.

Pollen-based differentiation of Amazonian rainforest communities and implications for lowland palaeoecology in tropical South America

An ongoing controversy in Amazonian palaeoecology is the manner in which Amazonian rainforest communities have responded to environmental change over the last glacial–interglacial cycle. Much of this controversy results from an inability to identify the floristic heterogeneity exhibited by rainforest communities within fossil pollen records. We apply multivariate (Principal Components Analysis) and classification (Unweighted Pair Group with Arithmetic Mean Agglomerative Classification) techniques to floral-biometric, modern pollen trap and lake sediment pollen data situated within different rainforest communities in the tropical lowlands of Amazonian Bolivia. Modern pollen rain analyses from artificial pollen traps show that evergreen terra firme (well-drained), evergreen terra firme liana, evergreen seasonally inundated, and evergreen riparian rainforests may be readily differentiated, floristically and palynologically. Analogue matching techniques, based on Euclidean distance measures, are employed to compare these pollen signatures with surface sediment pollen assemblages from five lakes: Laguna Bella Vista, Laguna Chaplin, and Laguna Huachi situated within the Madeira-Tapajós moist forest ecoregion, and Laguna Isirere and Laguna Loma Suarez, which are situated within forest patches in the Beni savanna ecoregion. The same numerical techniques are used to compare rainforest pollen trap signatures with the fossil pollen record of Laguna Chaplin.

Building the niche through time: using 13,000 years of data to predict the effects of climate change on three tree species in Europe

Aim  Species distribution models (SDMs) based on current species ranges underestimate the potential distribution when projected in time and/or space. A multi-temporal model calibration approach has been suggested as an alternative, and we evaluate this using 13,000 years of data. Location  Europe. Methods  We used fossil-based records of presence for Picea abies, Abies alba and Fagus sylvatica and six climatic variables for the period 13,000 to 1000 yr bp. To measure the contribution of each 1000-year time step to the total niche of each species (the niche measured by pooling all the data), we employed a principal components analysis (PCA) calibrated with data over the entire range of possible climates. Then we projected both the total niche and the partial niches from single time frames into the PCA space, and tested if the partial niches were more similar to the total niche than random. Using an ensemble forecasting approach, we calibrated SDMs for each time frame and for the pooled database. We projected each model to current climate and evaluated the results against current pollen data. We also projected all models into the future. Results  Niche similarity between the partial and the total-SDMs was almost always statistically significant and increased through time. SDMs calibrated from single time frames gave different results when projected to current climate, providing evidence of a change in the species realized niches through time. Moreover, they predicted limited climate suitability when compared with the total-SDMs. The same results were obtained when projected to future climates. Main conclusions  The realized climatic niche of species differed for current and future climates when SDMs were calibrated considering different past climates. Building the niche as an ensemble through time represents a way forward to a better understanding of a species' range and its ecology in a changing climate.

Pollen, plant macrofossil and charcoal records for palaeovegetation reconstruction in the Mediterranean-Black Sea Corridor since the Last Glacial Maximum

New reconstructions of changing vegetation patterns in the Mediterranean-Black Sea Corridor since the Last Glacial Maximum are being produced by an improved biomisation scheme that uses both pollen and plant macrofossil data, in conjunction. Changes in fire regimes over the same interval will also be reconstructed using both microscopic and macroscopic charcoal remains. These reconstructions will allow a diagnosis of the interactions between climate, fire and vegetation on millennial timescales, and will also help to clarify the role of coastline and other geomorphic changes, salinity and impacts of human activities in this region. These new data sets are being produced as a result of collaboration between the Palynology Working Group (WG-2) within the IGCP-521 project and the international Palaeovegetation Mapping Project (BIOME 6000). The main objective of this paper is to present the goals of this cooperation, methodology, including limitations and planned improvements, and to show the initial results of some applications.

Hurricanes and climate: the U.S. CLIVAR working group on hurricanes

While a quantitative climate theory of tropical cyclone formation remains elusive, considerable progress has been made recently in our ability to simulate tropical cyclone climatologies and understand the relationship between climate and tropical cyclone formation. Climate models are now able to simulate a realistic rate of global tropical cyclone formation, although simulation of the Atlantic tropical cyclone climatology remains challenging unless horizontal resolutions finer than 50 km are employed. This article summarizes published research from the idealized experiments of the Hurricane Working Group of U.S. CLIVAR (CLImate VARiability and predictability of the ocean-atmosphere system). This work, combined with results from other model simulations, has strengthened relationships between tropical cyclone formation rates and climate variables such as mid-tropospheric vertical velocity, with decreased climatological vertical velocities leading to decreased tropical cyclone formation. Systematic differences are shown between experiments in which only sea surface temperature is increased versus experiments where only atmospheric carbon dioxide is increased, with the carbon dioxide experiments more likely to demonstrate the decrease in tropical cyclone numbers previously shown to be a common response of climate models in a warmer climate. Experiments where the two effects are combined also show decreases in numbers, but these tend to be less for models that demonstrate a strong tropical cyclone response to increased sea surface temperatures. Further experiments are proposed that may improve our understanding of the relationship between climate and tropical cyclone formation, including experiments with two-way interaction between the ocean and the atmosphere and variations in atmospheric aerosols.

A new calibrated sunspot group series since 1749: statistics of active day fractions

Although the sunspot-number series have existed since the mid-19th century, they are still the subject of intense debate, with the largest uncertainty being related to the "calibration" of the visual acuity of individual observers in the past. Daisy-chain regression methods are applied to inter-calibrate the observers which may lead to significant bias and error accumulation. Here we present a novel method to calibrate the visual acuity of the key observers to the reference data set of Royal Greenwich Observatory sunspot groups for the period 1900-1976, using the statistics of the active-day fraction. For each observer we independently evaluate their observational thresholds [S_S] defined such that the observer is assumed to miss all of the groups with an area smaller than S_S and report all the groups larger than S_S. Next, using a Monte-Carlo method we construct, from the reference data set, a correction matrix for each observer. The correction matrices are significantly non-linear and cannot be approximated by a linear regression or proportionality. We emphasize that corrections based on a linear proportionality between annually averaged data lead to serious biases and distortions of the data. The correction matrices are applied to the original sunspot group records for each day, and finally the composite corrected series is produced for the period since 1748. The corrected series displays secular minima around 1800 (Dalton minimum) and 1900 (Gleissberg minimum), as well as the Modern grand maximum of activity in the second half of the 20th century. The uniqueness of the grand maximum is confirmed for the last 250 years. It is shown that the adoption of a linear relationship between the data of Wolf and Wolfer results in grossly inflated group numbers in the 18th and 19th centuries in some reconstructions.

Glacial lake drainage in Patagonia (13-8 kyr) and response of the adjacent Pacific Ocean

Large freshwater lakes formed in North America and Europe during deglaciation following the Last Glacial Maximum. Rapid drainage of these lakes into the Oceans resulted in abrupt perturbations in climate, including the Younger Dryas and 8.2 kyr cooling events. In the mid-latitudes of the Southern Hemisphere major glacial lakes also formed and drained during deglaciation but little is known about the magnitude, organization and timing of these drainage events and their e ect on regional climate. We use 16 new single-grain optically stimulated luminescence (OSL) dates to de ne three stages of rapid glacial lake drainage in the Lago General Carrera/Lago Buenos Aires and Lago Cohrane/ Pueyrredón basins of Patagonia and provide the rst assessment of the e ects of lake drainage on the Paci c Ocean. Lake drainage occurred between 13 and 8 kyr ago and was initially gradual eastward into the Atlantic, then subsequently reorganized westward into the Paci c as new drainage routes opened up during Patagonian Ice Sheet deglaciation. Coupled ocean-atmosphere model experiments using HadCM3 with an imposed freshwater surface “hosing” to simulate glacial lake drainage suggest that a negative salinity anomaly was advected south around Cape Horn, resulting in brief but signi cant impacts on coastal ocean vertical mixing and regional climate.

Structural and magnetic properties and hyperfine interaction in La(3.5)Ru(4)O(13) compound

Structural, magnetic and hyperfine interaction measurements have been carried out on the novel compound La(3.5)Ru(4)O(13) prepared under two different atmospheres (air and oxygen flow). This compound is formed in the orthorhombic structure (space group Pmmm, # 47). The coexistence of the triple-layered perovskite-type planes (quasi-2D structure) and the rutile-like slabs (1D structure) leads to interesting magnetic and electronic properties in this compound. The magnetic susceptibility of this system shows a peak at T similar to 47 K associated with antiferromagnetic interactions. The Curie-Weiss behaviour of the susceptibility provides an effective magnetic moment consistent with Ru ions in low-spin state. Perturbed angular correlation measurements carried out with (111)Cd probe in the temperature range 10-60 K reveal only quadrupole interactions and indicate the occurrence of structural distortions for T<40K. (C) 2009 Elsevier B.V. All rights reserved.

Chemostratigraphy of the Tamengo Formation (Corumba Group, Brazil) A contribution to the calibration of the Ediacaran carbon-isotope curve

The Corumba Group cropping out in the southern Paraguay Belt in Brazil is one of the most complete Ediacaran sedimentary archives of palaeogeographic climatic biogeochemical and biotic evolution in southwestern Gondwana The unit hosts a rich fossil record including acritarchs vendotaenids (Vendo taenia Eoholynia) soft-bodied metazoans (Corumbella) and skeletal fossils (Cloudina Titanotheca) The Tamengo Formation made up mainly of limestones and marls provides a rich bio- and chemostratigraphic record Several outcrops formerly assigned to the Cuiaba Group are here included in the Tamengo Formation on the basis of lithological and chemostratigraphical criteria High-resolution carbon isotopic analyses are reported for the Tamengo Formation showing (from base to top) (1) a positive delta(13)C excursion to +4 parts per thousand PDB above post-glacial negative values (2) a negative excursion to -3 5 parts per thousand associated with a marked regression and subsequent transgression (3) a positive excursion to +5 5 parts per thousand and (4) a plateau characterized by delta(13)C around +3 parts per thousand A U-Pb SHRIMP zircon age of an ash bed Interbedded in the upper part of the delta(13)C positive plateau yielded 543 +/- 3 Ma which is considered as the depositional age (Babinski et al 2008a) The positive plateau in the upper Tamengo Formation and the preceding positive excursion are ubiquitous features in several successions worldwide including the Nama Group (Namibia) the Dengying Formation (South China) and the Nafun and Ara groups (Oman) This plateau is constrained between 542 and 551 Ma thus consistent with the age of the upper Tamengo Formation The negative excursion of the lower Tamengo Formation may be correlated to the Shuram-Wonoka negative anomaly although delta(13)C values do not fall beyond -3 5 parts per thousand in the Brazilian sections Sedimentary breccias occur just beneath this negative excursion in the lower Tamengo Formation One possible interpretation of the origin of these breccias is a glacioeustatic sea-level fall but a tectonic interpretation cannot be completely ruled out Published by Elsevier B V

Bendadaite, a new iron arsenate mineral of the arthurite group

Bendadaite, ideally Fe(2+)Fe(2)(3+)(AsO(4))(2)(OH)(2 center dot).4H(2)O, is a new member of the arthurite group It was found as a weathering product of arsenopyrite on a single hand specimen from the phosphate pegmatite Bendada. central Portugal (type locality) Co-type locality is the granite pegmatite of La via do Almerindo (Almerindo mine), Linopolis, Divmo das Laranjeiras county, Minas Gerais, Brazil Further localities are the Vein Negra mine, Copiapo province, Chile, mid-East, Bou Azzer district, Morocco, and Para Inferida yard, Fenugu Sibirt mine, Gonnosfanadiga, Medio Campidano Province, Sardinia. Italy Type bendadaite occurs as blackish green to dark brownish tufts (<0 1 mm long) and flattened radiating aggregates. in intimate association with an intermediate member of the scorodite-mansfieldite series It is monoclinic. space group P2(l/c). with a = 10 239(3) angstrom. b = 9 713(2) angstrom, c = 5 552(2) angstrom. beta = 94 11(2)degrees. = 550 7(2) angstrom(3). Z = 2 Electron-microprobe analysis yielded (wt %). CaO 0 04, MnO 0 03. CuO 006, ZnO 004. Fe(2)O(3) (total) 43 92, Al(2)O(3) 115. SnO(2) 0 10, As(2)O(5) 43 27. P(2)O(5) 1 86, SO(3) 0.03 The empirical formula is (Fe(0 52)(2+)Fe(0 32)(3+)rectangle(0 16))(Sigma 1 00)(Fe(1 89)(3+)Al(0 11))(Sigma 2 00)(As(1 87)P(0 13))(Sigma 2 00)O(8)(OH)(2 00) 4H(2)O based. CM 2(As,P) and assuming ideal 80, 2(OH), 4H2O and complete occupancy of the ferric on site by Fe(3+) and Al Optically, bendadaite is biaxial, positive, 2V(est) = 85+/-4 degrees, 2V(eale) = 88 degrees, with alpha 1 734(3). 13 1 759(3), 7 1 787(4) Pleochrosim is medium strong X pale reddish brown. Y yellowish brown, Z dark yellowish brown. absorption Z > V > X, optical dispersion weak, r > v. Optical axis plane Is parallel to (010), with X approximately parallel to a and Z nearly parallel to c Bendadaite has vitreous to sub-adamantine luster, is translucent and non-fluorescent It is brittle, shows irregular fracture and a good cleavage parallel to 1010} 3 15 0 10 g/cm(3), 3 193 g/cm3 (for the empirical formula) The five strongest powder diffraction lines [d in angstrom (I)(hkl] are 10 22 (10)(100), 7 036 (8)(110), 4 250 (5)(11 I), 2 865 (4)(311), 4 833 (3)(020,011) The d spacings are very similar to those of its Zn analogue, ojelaite The crystal structure of bendadaite was solved and refined using a crystal from the co-type locality with the composition (Fe(0 95)(2+)rectangle(0 05))(Sigma 1 00)(Fe(1 80)(3+)Al(0 20))Sigma(2 00)(As(1 48)P(0 52))(Sigma 2 00)O(8)) (OH)(2) 4H(2)O (R = 16%) and confirms an arthurite-type atomic arrangement

Footemineite, the Mn-analog of atencioite, from the Foote mine, Kings Mountain, Cleveland County, North Carolina, USA, and its relationship with other roscherite-group minerals

Footemineite, ideally Ca2Mn2+square Mn22+Be4(PO4)(6)(OH)(4)-6H(2)O, triclinic, is a new member of the roscherite group. It occurs on thin fractures crossing quartz-microcline-spodumene pegmatite at the Foote mine, Kings Mountain, Cleveland County, North Carolina, U.S.A. Associated minerals are albite, analcime, eosphorite, siderite/rhodochrosite, fairfieldite, fluorapatite, quartz, milarite, and pyrite. Footemineite forms prismatic to bladed generally rough to barrel-shaped crystals up to about 1.5 mm long and I mm in diameter. Its color is yellow, the streak is white, and the luster is vitreous to slightly pearly. Footemineite is transparent and non-fluorescent. Twinning is simple, by reflection, with twin boundaries across the length of the crystals. Cleavage is good on {0 (1) over bar1}) and {100}. Density (calc.) is 2.873 g/cm(3). Footemineite is biaxial (-), n(alpha) = 1.620(2), n(beta) = 1.627(2), n(gamma) = 1.634(2) (white light). 2V(obs) = 80 degrees, 2V(calc) = 89.6 degrees. Orientation: X boolean AND b similar to 12 degrees, Y boolean AND c similar to 15 degrees, Z boolean AND a similar to 15 degrees. Elongation direction is c, dispersion: r > v or r < v, weak. Pleochroism: beta (brownish yellow) > alpha = gamma (yellow). Mossbauer and IR spectra are given. The chemical composition is (EDS mode electron microprobe, Li and Be by ICP-OES, Fe3+:Fe2+ y Mossbauer, H2O by TG data, wt%): Li2O 0.23, BeO 9.54, CaO 9.43, SrO 0.23, BaO 0.24, MgO 0.18, MnO 26.16, FeO 2.77, Fe2O3 0.62, Al2O3 0.14, P2O5 36.58, SiO2 0.42, H2O 13.1, total 99.64. The empirical formula is (Ca1.89Sr0.03Ba0.02)Sigma(1.94)(Mn-0.90(2+)square(0.10))Sigma(1.00)(square 0.78Li0.17Mg0.05) Sigma(1.00)(Mn3.252+Fe0.432+ Fe0.093+Al0.03)Sigma(3.80) Be-4.30(P5.81Si0.08O24)[(OH)3.64(H2O)0.36]Sigma(4.00)center dot 6.00H(2)O . The strongest reflection peaks of the powder diffraction pattern [d, angstrom (1, %) (hkl)] are 9.575 (53) (010), 5.998 (100) (0 (1) over bar1), 4.848 (26) (021), 3.192 (44) (210), 3.003 (14) (0 (2) over bar2), 2.803 (38) ((1) over bar 03), 2.650 (29) ((2) over bar 02), 2.424 (14) (231). Single-crystal unit-cell parameters are a = 6.788(2), b = 9.972(3), c = 10.014(2) A, (x = 73.84(2), beta = 85.34(2), gamma = 87.44(2)degrees,V = 648.74 angstrom(3), Z = 1. The space group is P (1) over bar. Crystal structure was refined to R = 0.0347 with 1273 independent reflections (F > 2(5). Footemineite is dimorphous with roscherite, and isostructural with atencioite. It is identical with the mineral from Foote mine described as ""triclinic roscherite."" The name is for the Foote mine, type locality for this and several other minerals.