Electron spectroscopic investigation of the semiconductor-metal transition in La1-xSrxMnO3

We study the electronic structure of La1-xSrxMnO3+δ, x=0, 0.1, 0.2, 0.3, and 0.4, across the semiconductor-metal transition, using various electron spectroscopy techniques. The negligible intensity seen at EF using ultraviolet photoemission spectroscopy and bremsstrahlung isochromat spectroscopy (BIS) indicate an unusual semiconductor-metal transition observed for x≥0.2, consistent with the resistivity data. The BIS spectra show doped hole states developing about 1.4 eV above EF as a function of x. Auger electron spectroscopy gives an estimate of the intra-atomic Coulomb energy in the O 2p manifold to be about 6.8 eV. The Mn 2p core-level spectrum of LaMnO3, analyzed in terms of a configuration-interaction calculation, gives parameter values of the charge-transfer energy Δ=5.0 eV, the hybridization strength between Mn 3d and O 2p states, t=3.8 eV, and the on-site Coulomb energy in Mn 3d states Udd=4.0 eV, suggesting a mixed character for the ground state of LaMnO3.

The nature of charge ordering in rare earth manganates and its strong dependence on the size of the A-site cations

Charge ordering in rare earth manganates of the type Ln(0.5)A(0.5)MnO(3) (Ln = rare earth, A = alkaline earth) is highly sensitive to the average radius of the A-site cations, [r(A)]. Tn the small [r(A)] regime (e.g., Y0.5Ca0.5MnO3), charge ordering occurs in the paramagnetic state, the transformation to an antiferromagnetic state occurring at still lower temperatures. At moderate [r(A)] values (e.g., Nd0.5Sr0.5MnO3), a ferromagnetic metallic state transforms to a charge-ordered antiferromagnetic state with cooling. These two distinct types of charge ordering and associated properties are explained in terms of the variation of the exchange couplings J(FM) and J(AFM) with [r(A)] and the invariance of the single-ion Jahn-Teller energy with [r(A)]. A qualitative temperature-[r(A)] phase diagram, consistent with the experimental observations, has been constructed to describe the properties of the manganates in the different [r(A)] regimes. (C) 1997 Academic Press.

Potentiometric determination of the Gibbs energies of formation of lead aluminates

The Gibbs energies of formation of three compounds in the PbO-Al2O3 system—2PbO · Al2O3, PbO · Al2O3, andPbO· 6Al2O3—have been determined from potentiometric measurements on reversible solid-state galvanic cells [dformula Pt, Ir | Pb, alpha-Al[sub 2]O[sub 3], PbO [center-dot] 6Al[sub 2]O[sub 3] | ZrO[sub 2]-CaO | NiO, Ni | Pt] [dformula Pt | NiO, Ni | ZrO[sub 2]-CaO | Pb, PbO [center-dot] 6Al[sub 2]O[sub 3], PbO [center-dot] Al[sub 2]O[sub 3] | Ir, Pt] and [dformula Pt | NiO, Ni | ZrO[sub 2]-CaO | Pb, PbO [center-dot] Al[sub 2]O[sub 3], 2PbO [center-dot] Al[sub 2]O[sub 3] | Ir, Pt] in the temperature range 850–1375 K. The results are discussed in the light of reported phase diagrams for the PbO-Al2O3system. The partial pressures of different lead oxide species, PbnOn, n = 1–6, in the gas phase in equilibrium withthe aluminates are calculated by combining the results of this study with the mass-spectrometric data of Drowart et al.(1) for polymerization equilibria in the gas phase. The concentration of oxygen in lead in equilibrium with the aluminatesare also derived from the results and the literature data on the Gibbs energy of solution of oxygen in liquid lead.

Preparation of zinc oxide coatings by using newly designed metal-organic complexes of Zn: Effect of molecular structure of the precursor and surfactant over the crystallization, growth and luminescence

We report large scale deposition of tapered zinc oxide (ZnO) nanorods on Si(100) substrate by using newly designed metal-organic complex of zinc (Zn) as the precursor, and microwave irradiation assisted chemical synthesis as a process. The coatings are uniform and high density ZnO nanorods (similar to 1.5 mu m length) grow over the entire area (625 mm(2)) of the substrate within 1-5 min of microwave irradiation. ZnO coatings obtained by solution phase deposition yield strong UV emission. Variation of the molecular structure/molecular weight of the precursors and surfactants influence the crystallinity, morphology, and optical properties of ZnO coatings. The precursors in addition with the surfactant and the solvent are widely used to obtain desired coating on any substrate. The growth mechanism and the schematics of the growth process of ZnO coatings on Si(100) are discussed. (c) 2013 Elsevier B.V. All rights reserved.

The impact of the great recession on employment polarization in Spain

This article analyzes changes in the occupational employment share in Spain for the period 1997-2012 and the way particular sociodemographic groups adapt to those changes. There seems to be clear evidence of employment polarization between 1997 and 2012 that accelerates over the recession. Changes in the composition of the labour supply cannot explain the increase in the share of occupations at the low end of the wage distribution. Sector reallocation may have partially contributed to explain the polarization process in Spain during the years of expansion (1997-2007) but it is a minor factor during the recession. The polarization of occupations within sectors observed, especially during the recession, appears to be related to a decline in routine tasks which is compensated by an increase in occupations with non-routine service contents, which are found both in the low and high end of the wage distribution. Instead, jobs with a higher degree of abstract contents do not appear to increase their share in total employment during these 15 years. The paper finds that this process has affected males more strongly than females because of their higher concentration in occupations more focused on routine tasks. Among males, for workers under 30 years old, we find a decrease in the share of occupations with more routine tasks which turns into increases in those with more abstract content and particularly with more non-routine service content. Instead, male workers over 30 years old seem to remain in declining occupations to a greater extent. Females of different ages are not affected by the abovementioned changes.

Phylogeographic analysis of mitochondrial DNA haplogroup F2 in China reveals T12338C in the initiation codon of the NDS gene not to be pathogenic

In this report, we studied on a homoplasmic T12338C change in mitochondrial DNA (mtDNA), which substituted methionine in the translational initiation codon of the NADH dehydrogenase subunit 5 gene (ND5) with threonine. This nucleotide change was originall

Solid-state MAS NMR studies on the hydrothermal stability of the zeolite catalysts for residual oil selective catalytic cracking

By using the solid-state MAS NMR technique, the hydrothermal stabilities (under 100% steam at 1073 K) of HZSM-5 zeolites modified by lanthanum and phosphorus have been studied. They are excellent zeolite catalysts for residual oil selective catalytic cracking (RSCC) processes. It was indicated that the introduction of phosphorus to the zeolite via impregnation with orthophosphoric acid led to dealumination as well as formation of different Al species, which were well distinguished by Al-27 3Q MAS NMR. Meanwhile, the hydrothermal stabilities of the zeolites (P/HZSM-5, La-P/HZSM-5) were enhanced even after the samples were treated under severe conditions for a prolonged time. It was found that the Si-O-Al bonds were broken under hydrothermal conditions, while at the same time the phosphorous compounds would occupy the silicon sites to form (SiO)(x)Al(OP)(4 - x) species. With increasing time, more silicon sites around the tetrahedral coordinated Al in the lattice can be replaced till the aluminum is completely expelled from the framework. The existence of lanthanum can partially restrict the breaking of the Si-O-Al bonds and the replacement of the silicon sites by phosphorus, thus preventing dealumination under hydrothermal conditions. This was also proved by P-31 MAS NMR spectra. (C) 2004 Elsevier Inc. All rights reserved.

Examination of the present state of the Grimsby trawl fishery Part 1

Part 1 covers the North Sea fisheries, a voyage on a steam trawler, an outline of the rise of trawling in the North Sea and the introduction of trawling at a northern fishing station and its influence on the fishery.

Examination of the present state of the Grimsby trawl fishery Part 2

Part 2 covers the definition of an immature fish, evidence of deterioration in the North Sea trade, life history of North Sea food fish, discussion on and proposed measures to counter the destruction of immature fish.

Position and structure of the subtropical/Azores front region from combined Lagrangian and remote sensing (IR/altimeter/SeaWIFS) measurements

The position and structure of the North Atlantic Subtropical Front is studied using Lagrangian flow tracks and remote sensing (AVHRR imagery: TOPEX/POSEIDON altimetry: SeaWiFS) in a broad region ( similar to 31 degree to similar to 36 degree N) of marked gradient of dynamic height (Azores Current) that extends from the Mid-Atlantic Ridge (MAR), near similar to 40 degree W, to the Eastern Boundary ( similar to 10 degree W). Drogued Argos buoy and ALACE tracks are superposed on infrared satellite images in the Subtropical Front region. Cold (cyclonic) structures, called storms, and warm (anticyclonic) structures of 100-300 km in size can be found on the south side of the Subtropical Front outcrop, which has a temperature contrast of about 1 degree C that can be followed for similar to 2500 km near 35 degree N. Warmer water adjacent to the outcrop is flowing eastward (Azores Current) but some warm water is returned westward about 300 km to the south (southern Counterflow). Estimates of horizontal diffusion in a Storm (D=2.2t10 super(2) m super(2) s super(-1)) and in the Subtropical Front region near 200 m depth (D sub(x)=1.3t10 super(4) m super(2) s super(-1), D sub(y)=2.6t10 super(3) m super(2) s super(-1)) are made from the Lagrangian tracks. Altimeter and in situ measurements show that Storms track westwards. Storms are separated by about 510 km and move westward at 2.7 km d super(-1). Remote sensing reveals that some initial structures start evolving as far east as 23 degree W but are more organized near 29 degree W and therefore Storms are about 1 year old when they reach the MAR (having travelled a distance of 1000 km). Structure and seasonality in SeaWiFS data in the region is examined.

The Absolute Configuration for Inthomycin C: Revision of Previously Published Work with a Reinstatement of the (3R)-Configuration for (-)-Inthomycin C

Abstract Image

Stereochemical evidence is presented to demonstrate that (−)-inthomycin C has (3R)- and not (3S)-stereochemistry. Careful reappraisal of the previously published work2−5 now indicates that the Hatakeyama, Hale, Ryu, and Taylor teams all have synthesized (−)-(3R)-inthomycin C. The newly measured [α]D of pure (−)-(3R)-inthomycin C (98% ee) is −7.9 (c 0.33, CHCl3) and not −41.5 (c 0.1, CHCl3) as was previously reported in 2012.