Structure and spectroelectrochemical response of arene− ruthenium and arene−osmium complexes with potentially hemilabile noninnocent ligands

Nine of the compounds [M(L2−)(p-cymene)] (M = Ru, Os, L2− = 4,6-di-tert-butyl-N-aryl-o-amidophenolate) were prepared and structurally characterized (Ru complexes) as coordinatively unsaturated, formally 16 valence electron species. On L2−-ligand based oxidation to EPR-active iminosemiquinone radical complexes, the compounds seek to bind a donor atom (if available) from the N-aryl substituent, as structurally certified for thioether and selenoether functions, or from the donor solvent. Simulated cyclic voltammograms and spectroelectrochemistry at ambient and low temperatures in combination with DFT results confirm a square scheme behavior (ECEC mechanism) involving the Ln ligand as the main electron transfer site and the metal with fractional (δ) oxidation as the center for redox-activated coordination. Attempts to crystallize [Ru(Cym)(QSMe)](PF6) produced single crystals of [RuIII(QSMe •−)2](PF6) after apparent dissociation of the arene ligand.

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.

Yield and nitrogen accumulation and partitioning in winter wheat under elevated CO2: A 3-year free-air CO2 enrichment experiment

Fossil fuel combustion and deforestation have resulted in a rapid increase in atmospheric [CO2] since the 1950’s, and it will reach about 550 μmol mol−1 in 2050. Field experiments were conducted at the Free-air CO2 Enrichment facility in Beijing, China. Winter wheat was grown to maturity under elevated [CO2] (550 ± 17 μmol mol−1) and ambient [CO2] (415 ± 16 μmol mol−1), with high nitrogen (N) supply (HN, 170 kg N ha−1) and low nitrogen supply (LN, 100 kg N ha−1) for three growing seasons from 2007 to 2010. Elevated [CO2] increased wheat grain yield by 11.4% across the three years. [CO2]-induced yield enhancements were 10.8% and 11.9% under low N and high N supply, respectively. Nitrogen accumulation under elevated [CO2] was increased by 12.9% and 9.2% at the half-way anthesis and ripening stage across three years, respectively. Winter wheat had higher nitrogen demand under elevated [CO2] than ambient [CO2], and grain yield had a stronger correlation with plant N uptake after anthesis than before anthesis at high [CO2]. Our results suggest that regulating on the N application rate and time, is likely important for sustainable grain production under future CO2 climate.

Fat composition of organic and conventional retail milk in northeast England

This study of UK retail milk identified highly significant variations in fat composition. The survey, conducted over 2 yr replicating summer and winter, sampled 22 brands, 10 of which indicated organic production systems. Results corroborate earlier farm-based findings considering fat composition of milk produced under conventional and organic management. Organic milk had higher concentrations of beneficial fatty acids (FA) than conventional milk, including total polyunsaturated fatty acids (PUFA; 39.4 vs. 31.8 g/kg of total FA), conjugated linoleic acid cis-9,trans-11 (CLA9; 7.4 v 5.6 g/kg of FA), and α-linolenic acid (α-LN; 6.9 vs. 4.4 g/kg of FA). As expected, purchase season had a strong effect on fat composition: compared with milk purchased in winter, summer milk had a lower concentration of saturated fatty acids (682 vs. 725 g/kg of FA) and higher concentrations of PUFA (37.6 vs. 32.8 g/kg of FA), CLA9 (8.1 vs. 4.7 g/kg of FA), and α-LN (6.5 vs. 4.6 g/kg of FA). Differences identified between sampling years were more surprising: compared with that in yr 2, milk purchased in year 1 had higher concentrations of PUFA (37.5 vs. 32.9 g/kg of FA), α-LN (6.0 vs. 5.1 g/kg of FA), and linoleic acid (19.9 vs. 17.5 g/kg of FA) and lower concentrations of C16:0 and C14:0 (332 vs. 357 and 110 vs. 118 g/kg of FA, respectively). Strong interactions were identified between management and season as well as between season and year of the study. As in the earlier farm studies, differences in fat composition between systems were greater for summer compared with winter milk. Large between-year differences may be due to changes in weather influencing milk composition through forage availability, quality, and intake. If climate change predictions materialize, both forage and dairy management may have to adapt to maintain current milk quality. Considerable variation existed in milk fat composition between brands.

Third language acquisition in adulthood

In recent years, researchers have acknowledged that the study of third language acquisition cannot simply be viewed as an extension of the study of bilingualism, and the present volume’s authors agree that a point of departure that embraces the unique properties that differentiate L2 acquisition from L3/Ln acquisition is essential. From linguistic, sociological, psychological, educational and cognitive viewpoints, it has become increasingly apparent that the study of L3/Ln acquisition can provide new evidence to help resolve ongoing debates in these areas of study. This volume uniquely provides a wide-ranging overview of current trends in the study of adult additive multilingualism from formal, psycholinguistic and sociolinguistic perspectives, adding new insights into adult multilingual epistemology. This collection includes critical reviews of L3/Ln morphosyntax, phonology, and the lexicon, as well as individual studies with unique language pairings including Romance, Germanic, Slavic, and Asian languages.

ENSO related variation of equatorial MRG and Rossby waves and forcing from higher latitudes

The contrasting behaviour of westward-moving mixed Rossby-gravity (WMRG) and the first Rossby (R1) waves in El Niño (EN) and La Niña (LN) seasons is documented with a focus on the Northern Hemisphere winter. The eastward-moving variance in the upper troposphere is dominated by WMRG and R1 structures that appear to be Doppler-shifted by the flow and are referred to as WMRG-E and R1-E. In the East Pacific and Atlantic the years with stronger equatorial westerly winds have the stronger WMRG and WMRG- E. In the East Pacific, R1 is also a maximum in LN. However, R1-E exhibits an eastward-shift between LN and EN. The changes with ENSO phase provide a test-bed for the understanding of these waves. In the East Pacific and Atlantic, the stronger WMRG-E and WMRG with stronger westerlies are in accord with the dispersion relation with simple Doppler-shifting by the zonal flow. The possible existence of free waves can also explain stronger R1 in EN in the Eastern Hemisphere. 1-D free wave propagation theory based on wave activity conservation is also important for R1. However, this theory is unable to explain the amplitude maxima for other waves observed in the strong equatorial westerly regions in the Western Hemisphere, and certainly not their ENSO-related variation. The forcing of equatorial waves by higher latitude wave activity and its variation with ENSO phase is therefore examined. Propagation of extratropical eastward-moving Rossby wave activity through the westerly ducts into the equatorial region where it triggers WMRG-E is favoured in the stronger westerlies, in LN in the East Pacific and EN in the Atlantic. It is also found that WMRG is forced by Southern Hemisphere westward-moving wavetrains arching into the equatorial region where they are reflected. The most significant mechanism for both R1 and R1-E appear to be lateral forcing by subtropical wavetrains.

CMB and LSS constraints on a single-field model of inflation

A new inflationary scenario whose exponential potential V (Phi) has a quadratic dependence on the field Phi in addition to the standard linear term is confronted with the five-year observations of the Wilkinson-Microwave Anisotropy Probe and the Sloan Digital Sky Survey data. The number of e-folds (N), the ratio of tensor-to-scalar perturbations (r), the spectral scalar index of the primordial power spectrum (n(s)) and its running (dn(s)/d ln k) depend on the dimensionless parameter a multiplying the quadratic term in the potential. In the limit a. 0 all the results of the exponential potential are fully recovered. For values of alpha not equal 0, we find that the model predictions are in good agreement with the current observations of the Cosmic Microwave Background (CMB) anisotropies and Large-Scale Structure (LSS) in the Universe. Copyright (C) EPLA, 2008.

Frequency of extreme rainfall events in Southern Brazil modulated by interannual and interdecadal variability

The frequency of extreme rainfall events in Southern Brazil is impacted by Ell Nino - Southern Oscillation (ENSO) episodes, especially in austral spring. There are two areas in which this impact is more significant: one is on the coast, where extreme events are more frequent during El Nino (EN) and the other one extends inland, where extreme events increase during EN and decrease during La Nina (LN). Atmospheric circulation patterns associated with severe rainfall in those areas are similar (opposite) to anomalous patterns characteristic of EN (LN) episodes, indicating why increase (decrease) of extreme events in EN (LN) episodes is favoured. The most recurrent precipitation patterns during extreme rainfall events in each of these areas are disclosed by Principal Component Analysis (PCA) and evidence the separation between extreme events in these areas: a severe precipitation event generally does not occur simultaneously in the coast and inland, although they may Occur inland and in the coastal region in sequence. Although EN predominantly enhances extreme rainfall, there are EN years in which fewer severe events occur than the average of neutral years, and also the enhancement of extreme rainfall is not uniform for different EN episodes, because the interdecadal non-ENSO variability also modulates significantly the frequency of extreme events in Southern Brazil. The inland region, which is more affected, shows increase (decrease) of extreme rainfall in association with the negative (positive) phase of the Atlantic Multidecadal Variability, with the negative (positive) phase of the Pacific Multidecadal Variability and with the positive (negative) phase of the Pacific Interdecadal Variability. Copyright (C) 2008 Royal Meteorological Society

The role of citrate precursors on the morphology of lanthanide oxides obtained by thermal decomposition

Two series of lanthanide oxides with different morphologies were synthesized through calcinations of two types of citrate polymeric precursors. These oxides were characterized by XRD patterns, SEM electronic microscopy, and N(2) adsorption isotherms. SEM microscopy analysis showed that the calcination of crystalline fibrous precursors [Ln(2)(LH)(3)center dot 2H(2)O] (L = citrate) originated fibrous shaped particles. On the other hand, the calcination of irregular shaped particles of precursors [LnL center dot xH(2)O] originated irregular shaped particles of oxide, pointing out a morphological template effect of precursors on the formation of the respective oxides.

Examples of Self-Iterating Lie Algebras, 2

We study properties of self-iterating Lie algebras in positive characteristic. Let R = K[t(i)vertical bar i is an element of N]/(t(i)(p)vertical bar i is an element of N) be the truncated polynomial ring. Let partial derivative(i) = partial derivative/partial derivative t(i), i is an element of N, denote the respective derivations. Consider the operators v(1) = partial derivative(1) + t(0)(partial derivative(2) + t(1)(partial derivative(3) + t(2)(partial derivative(4) + t(3)(partial derivative(5) + t(4)(partial derivative(6) + ...))))); v(2) = partial derivative(2) + t(1)(partial derivative(3) + t(2)(partial derivative(4) + t(3)(partial derivative(5) + t(4)(partial derivative(6) + ...)))). Let L = Lie(p)(v(1), v(2)) subset of Der R be the restricted Lie algebra generated by these derivations. We establish the following properties of this algebra in case p = 2, 3. a) L has a polynomial growth with Gelfand-Kirillov dimension lnp/ln((1+root 5)/2). b) the associative envelope A = Alg(v(1), v(2)) of L has Gelfand-Kirillov dimension 2 lnp/ln((1+root 5)/2). c) L has a nil-p-mapping. d) L, A and the augmentation ideal of the restricted enveloping algebra u = u(0)(L) are direct sums of two locally nilpotent subalgebras. The question whether u is a nil-algebra remains open. e) the restricted enveloping algebra u(L) is of intermediate growth. These properties resemble those of Grigorchuk and Gupta-Sidki groups.

SYNTHESIS, CHARACTERIZATION AND THERMAL ANALYSIS OF 1:1 AND 2:3 LANTHANIDE(III) CITRATES

The synthesis and characterization of lanthanide(III) citrates with stoichiometries 1:1 and 2:3; [LnL center dot xH(2)O] and [Ln(2)(LH)(3)center dot 2H(2)O], Ln=La, Ce, Pr, Nd, Sm and Eu are reported. L stands for (C6O7H5)(3-) and LH for (C6O7H6)(2-). Infrared absorption spectra of both series evidence coordination of carboxylate groups through symmetric bridges or chelation. X-ray powder patterns show the amorphous character of [LnL center dot xH(2)O]. The compounds [Ln(2)LH(3)center dot 2H(2)O] are crystalline and isomorphous. Emission spectra of Eu compounds suggest C-2v symmetry for the coordination polyhedron of [LnL center dot xH(2)O] and C-4v for [Ln(2)(LH)(3)center dot 2H(2)O]. Thermal analyses (TG-DTG-DTA) were carried out for both series. The thermal analysis patterns of the two series are quite different and both fit in a 4-step model of thermal decomposition, with lanthanide oxides as final products.

Metabotropic glutamate receptors transduce signals for neurite outgrowth after binding of the prion protein to laminin gamma 1 chain

The prion protein (PrP(C)) is highly expressed in the nervous system, and its abnormal conformer is associated with prion diseases. PrP(C) is anchored to cell membranes by glycosylphosphatidylinositol, and transmembrane proteins are likely required for PrP(C)-mediated intracellular signaling. Binding of laminin (Ln) to PrP(C) modulates neuronal plasticity and memory. We addressed signaling pathways triggered by PrP(C)-Ln interaction in order to identify transmembrane proteins involved in the transduction of PrP(C)-Ln signals. The Ln gamma 1-chain peptide, which contains the Ln binding site for PrP(C), induced neuritogenesis through activation of phospholipase C (PLC), Ca(2+) mobilization from intracellular stores, and protein kinase C and extracellular signal-regulated kinase (ERK1/2) activation in primary cultures of neurons from wild-type, but not PrP(C)-null mice. Phage display, coimmunoprecipitation, and colocalization experiments showed that group I metabotropic glutamate receptors (mGluR1/5) associate with PrP(C). Expression of either mGluR1 or mGluR5 in HEK293 cells reconstituted the signaling pathways mediated by PrP(C)-Ln gamma 1 peptide interaction. Specific inhibitors of these receptors impaired PrP(C)-Ln gamma 1 peptide-induced signaling and neuritogenesis. These data show that group I mGluRs are involved in the transduction of cellular signals triggered by PrP(C)-Ln, and they support the notion that PrP(C) participates in the assembly of multiprotein complexes with physiological functions on neurons.-Beraldo, F. H., Arantes, C. P., Santos, T. G., Machado, C. F., Roffe, M., Hajj, G. N., Lee, K. S., Magalhaes, A. C., Caetano, F. A., Mancini, G. L., Lopes, M. H., Americo, T. A., Magdesian, M. H., Ferguson, S. S. G., Linden, R., Prado, M. A. M., Martins, V. R. Metabotropic glutamate receptors trans-duce signals for neurite outgrowth after binding of the prion protein to laminin gamma 1 chain. FASEB J. 25, 265-279 (2011). www.fasebj.org

Den hvita stadens tjänare : En studie över fackligt arbete och arbetsvilkor bland mentalskötare vid Säters sjukhus åren 1912 till 1952

källor: fackliga protokoll från 1912 till 1952, årsberättelser från 1927 till 1952.Metod: en kvalitativ textläsningSyfte: att undersöka skötarnas arbetssituation, med särskilt hänsyn till kvinnornas situation på Säters sjukhus åren 1912 till 1952 utifrån ett fackligt perspektiv.Frågeställninigar: Hur arbetade och organiserade sig personalen i den fackliga organisationen för bättre arbetsvillkor på Säters sjukhus. Vilka övergripande förändringar skedde för personalen på Säters sjukhus med avseende på arbetsmiljö och utbildning, speciellt med avseende på genus. Hur gestaltade sig kvinnornas fackliga arbete och villkor på Säters sjukhus jämfört med männens.Resultat: Det skedde tydliga förändringar i fackföreningens medlemsantal under perioden, föreningens viktigaste arbete var kampen för 48 timmars arbetsvecka. Under periodens senare del tillkom arbetarskyddslagstiftning som innebar en förbättring i arbetsmiljön. Lön och utbildning var andra frågor för fackföreningen, särskilt under 1940-talet förbättrades kvinnornas utbildningsmöjligheter. Sjukhuset var starkt uppdelat i en manlig och en kvinnlig del, där fackföreningen var en övervägande manlig aktivitet.

Kolerahanteringen i Falun år 1834 & 1853 : En studie av sundhetsnämndens agerande

Syftet med uppsatsen är att undersöka vilka åtgärder som Falu stad, genom sundhetsnämnden, vidtog när farsoten kolera spreds i Sverige år 1834 respektive år 1853 samt om dessa åtgärder skiljer sig över tid. Frågeställningarna som används är: Vilka förebyggande åtgärder mot kolera vidtog staden genom sundhetsnämnden år 1834 och år 1853? Hur agerade läkarna i Falun mot kolerahotet? Skiljer sig Falu sundhetsnämnds åtgärder i jämförelse med andra städers sundhetsnämnder? Skiljer sig sundhetsnämndens åtgärder mellan åren 1834 och 1853? Materialet som används består av sundhetsnämndens mötesprotokoll från åren 1834 och år 1853, kolerakungörelser från de båda tidpunkterna, stadsläkare- och gruvläkarapporter samt utdrag från Tidning för Falu län och stad. Resultatet visar, att Falun vid båda tillfällena spärrades av genom att vaktstationer upprättades vid vägarna och vid stadens gräns. En karantänsstation upprättades vid stadens hälsobrunn för att ta om hand personer som inte vistats på kolerafri ort de 10 senaste dagarna. Staden delades in i tio distrikt som bemannades med en distriktschef samt några uppsyningsmän, som kontrollerade att staden hölls ren och att invånarna var rena. Stadens läkare var väldigt aktiva under sundhetsnämndens möten år 1834 och gav flera förslag på vad som behövdes göras medan de år 1853 intog en mer passiv roll. Åtgärderna i Stockholm år 1834 är snarlika de åtgärder som genomfördes i Falun samma år, huvudstaden delades också in i distrikt och det tillsattes även distriktschefer och uppsyningsmän. En annan likhet är att både Falun och Stockholm beställde färdiga likkistor för att ha i beredskap. Såväl sundhetsnämnderna i Karlskrona, Ystad och Arboga liksom Falun år 1853 vidtog i stort sett samma åtgärder som gjordes redan år 1834 t ex spärrningsåtgärder, karantänsskydd, införandet av kolerasjukhus och extra insatser för de mest utsatta i samhället.

Folkskoleseminariet i Falun : En geografisk rekryteringsstudie av folkskoleseminarister 1875-1950

Denna studie ska undersöka den geografiska rekryteringen av de antagna eleverna vid det kvinnliga folkskoleseminariet i Falun från 1875 till 1950. Resultaten jämförs med två liknade studier samt ställs mot den urbanisering och befolkningsökning som skedde under den studerade perioden. Resultaten visar små förändringar över tiden, där rekryteringen var nära nog rikstäckande med en majoritet från nuvarande Dalarnas län och närliggande län. De antagna var i huvudsak från landsbygden, där det inte skedde några förändringar trots befolkningsökning och urbanisering under den studerade perioden. Detta visar på att Faluns seminarium var betydelsefullt för den lokala bildningen, och då framför allt på landsbygden. Resultatet visar dessutom på en kontinuitet i den geografiska rekryteringen.