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.