Reconstruction of deglacial sea surface temperatures in the tropical Pacific from selective analysis of a fossil coral

The Sr/Ca of coral skeletons demonstrates potential as an indicator of sea surface temperatures (SSTs). However, the glacial-interglacial SST ranges predicted from Sr/Ca of fossil corals are usually higher than from other marine proxies. We observed infilling of secondary aragonite, characterised by high Sr/Ca ratios, along intraskeletal pores of a fossil coral from Papua New Guinea that grew during the penultimate deglaciation (130 +/- 2 ka). Selective microanalysis of unaltered areas of the fossil coral indicates that SSTs at similar to 130 ka were &lt;= 1 degrees C cooler than at present in contrast with bulk measurements ( combining infilled and unaltered areas) which indicate a difference of 6-7 degrees C. The analysis of unaltered areas of fossil skeletons by microprobe techniques may offer a route to more accurate reconstruction of past SSTs.</p

Step by step capping and strain state of GaN/AlN quantum dots studied by grazing incidence diffraction anomalous fine structure

The investigation of small size embedded nanostructures, by a combination of complementary anomalous diffraction techniques, is reported. GaN Quantum Dots (QDs), grown by molecular beam epitaxy in a modified Stranski-Krastanow mode, are studied in terms of strain and local environment, as a function of the AlN cap layer thickness, by means of grazing incidence anomalous diffraction. That is, the X-ray photons energy is tuned across the Ga absorption K-edge which makes diffraction chemically selective. Measurement of \textit{hkl}-scans, close to the AlN (30-30) Bragg reflection, at several energies across the Ga K-edge, allows the extraction of the Ga partial structure factor, from which the in-plane strain of GaN QDs is deduced. From the fixed-Q energy-dependent diffracted intensity spectra, measured for diffraction-selected iso-strain regions corresponding to the average in-plane strain state of the QDs, quantitative information regarding composition and the out-of-plane strain has been obtained. We recover the in-plane and out-of-plane strains in the dots. The comparison to the biaxial elastic strain in a pseudomorphic layer indicates a tendency to an over-strained regime.Comment: submitted to PR

Structure and Morphology of Silver Nanoparticles on the (111) Surface of Cerium Oxide

The structure of Ag nanoparticles of different size, supported on the cerium oxide (111) surface, was investigated by X-ray absorption fine structure at the Ag K-edge. The results of the data analysis in the near and extended energy range are interpreted with the help of the results obtained by X-ray photoelectron spectroscopy and scanning tunneling microscopy measurements and allow to obtain a detailed atomic scale description of the model system investigated. The Ag nanoparticles have an average size of a few tens of angstroms, which increases with increasing deposited Ag amount. The nanoparticles show a slight tendency to nucleate at the step edges between different cerium oxide layers and they have a face centered cubic structure with an Ag-Ag interatomic distance contracted by 3-4% with respect to the bulk value. The interatomic distance contraction is mainly ascribed to dimensionality induced effects, while epitaxial effects have a minor role. The presence of Ag-O bonds at the interface between the nanoparticles and the supporting oxide is also detected. The Ag-O interatomic distance decreases with decreasing nanoparticle size

Stable amorphous georgeite as a precursor to a high-activity catalyst .

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable—and hence little known and largely ignored1—georgeite. The first three of these minerals are widely used as catalyst precursors2, 3, 4 for the industrially important methanol-synthesis and low-temperature water–gas shift (LTS) reactions5, 6, 7, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase2, 3, 8, 9, 10 is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite11; with few exceptions12 it uses sodium carbonate as the carbonate source, but this also introduces sodium ions—a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts

Activation and Deactivation of a Robust Immobilized Cp*Ir-Transfer Hydrogenation Catalyst: A Multielement in Situ X-ray Absorption Spectroscopy Study

A highly robust immobilized [Cp*IrCl2]2 precatalyst on Wang resin for transfer hydrogenation, which can be recycled up to 30 times, was studied using a novel combination of X-ray absorption spectroscopy (XAS) at Ir L3-edge, Cl K-edge, and K K-edge. These culminate in in situ XAS experiments that link structural changes of the Ir complex with its catalytic activity and its deactivation. Mercury poisoning and “hot filtration” experiments ruled out leached Ir as the active catalyst. Spectroscopic evidence indicates the exchange of one chloride ligand with an alkoxide to generate the active precatalyst. The exchange of the second chloride ligand, however, leads to a potassium alkoxide–iridate species as the deactivated form of this immobilized catalyst. These findings could be widely applicable to the many homogeneous transfer hydrogenation catalysts with Cp*IrCl substructure

A New Heterobinuclear FeIIICuII Complex with a Single Terminal FeIII–O(phenolate) Bond. Relevance to Purple Acid Phosphatases and Nucleases

A novel heterobinuclear mixed valence complex [Fe^IIICu^II(BPBPMP)(OAc)_2]ClO_4, 1, with the unsymmetrical N_5O_2 donor ligand 2-bis[{(2-pyridylmethyl)aminomethyl}-6-{(2-hydroxybenzyl)(2-pyridylmethyl)} aminomethyl]-4-methylphenol (H_2BPBPMP) has been synthesized and characterized. A combination of data from mass spectrometry, potentiometric titrations, X-ray absorption and electron paramagnetic resonance spectroscopy, as well as kinetics measurements indicates that in ethanol/water solutions an [Fe^III-(nu)OH-Cu^IIOH_2]+ species is generated which is the likely catalyst for 2,4-bis(dinitrophenyl)phosphate and DNA hydrolysis. Insofar as the data are consistent with the presence of an Fe_III-bound hydroxide acting as a nucleophile during catalysis, 1 presents a suitable mimic for the hydrolytic enzyme purple acid phosphatase. Notably, 1 is significantly more reactive than its isostructural homologues with different metal composition (Fe^IIIM^II, where M^II is Zn^II, Mn^II, Ni^II,or Fe^II). Of particular interest is the observation that cleavage of double-stranded plasmid DNA occurs even at very low concentrations of 1 (2.5 nuM), under physiological conditions (optimum pH of 7.0), with a rate enhancement of 2.7 x 10^7 over the uncatalyzed reaction. Thus, 1 is one of the most effective model complexes to date, mimicking the function of nucleases

Spectral energy distribution and radio halo of NGC253 at low radio frequencies

A. D. Kapinska, 'Spectral Energy Distribution and Radio Halo of NGC 253 at Low Radio Frequencies', The Astrophysical Journal, Vol. 838(68), 15 pp, March 2017. The version of record is available online at doi: https://doi.org/10.3847/1538-4357/aa5f5d. © 2017. The American Astronomical Society. All rights reserved.We present new radio continuum observations of NGC253 from the Murchison Widefield Array at frequencies between 76 and 227 MHz. We model the broadband radio spectral energy distribution for the total flux density of NGC253 between 76 MHz and 11 GHz. The spectrum is best described as a sum of central starburst and extended emission. The central component, corresponding to the inner 500pc of the starburst region of the galaxy, is best modelled as an internally free-free absorbed synchrotron plasma, with a turnover frequency around 230 MHz. The extended emission component of the NGC253 spectrum is best described as a synchrotron emission flattening at low radio frequencies. We find that 34% of the extended emission (outside the central starburst region) at 1 GHz becomes partially absorbed at low radio frequencies. Most of this flattening occurs in the western region of the SE halo, and may be indicative of synchrotron self-absorption of shock re-accelerated electrons or an intrinsic low-energy cut off of the electron distribution. Furthermore, we detect the large-scale synchrotron radio halo of NGC253 in our radio images. At 154 - 231 MHz the halo displays the well known X-shaped/horn-like structure, and extends out to ~8kpc in z-direction (from major axis).Peer reviewedFinal Published versio