Theoretical and experimental evidence for a post-perovskite phase of MgSiO3 in Earth's D" layer

The Earth's lower mantle is believed to be composed mainly of (Mg,Fe)SiO3 perovskite, with lesser amounts of (Mg,Fe)O and CaSiO3). But it has not been possible to explain many unusual properties of the lowermost 150 km of the mantle (the D" layer) with this mineralogy. Here, using ab initio simulations and high-pressure experiments, we show that at pressures and temperatures of the D" layer, MgSiO3 transforms from perovskite into a layered CaIrO3-type post-perovskite phase. The elastic properties of the post-perovskite phase and its stability field explain several observed puzzling properties of the D" layer: its seismic anisotropy, the strongly undulating shear-wave discontinuity at its top and possibly the anticorrelation between shear and bulk sound velocities.Comment: PUBLISHED IN Nature 430, 445-448 (2004

DNA Copy Number Changes in Human Malignant Fibrous Histiocytomas by Array Comparative Genomic Hybridisation

BACKGROUND: Malignant fibrous histiocytomas (MFHs), or undifferentiated pleomorphic sarcomas, are in general high-grade tumours with extensive chromosomal aberrations. In order to identify recurrent chromosomal regions of gain and loss, as well as novel gene targets of potential importance for MFH development and/or progression, we have analysed DNA copy number changes in 33 MFHs using microarray-based comparative genomic hybridisation (array CGH). PRINCIPAL FINDINGS: In general, the tumours showed numerous gains and losses of large chromosomal regions. The most frequent minimal recurrent regions of gain were 1p33-p32.3, 1p31.3-p31.2 and 1p21.3 (all gained in 58% of the samples), as well as 1q21.2-q21.3 and 20q13.2 (both 55%). The most frequent minimal recurrent regions of loss were 10q25.3-q26.11, 13q13.3-q14.2 and 13q14.3-q21.1 (all lost in 64% of the samples), as well as 2q36.3-q37.2 (61%), 1q41 (55%) and 16q12.1-q12.2 (52%). Statistical analyses revealed that gain of 1p33-p32.3 and 1p21.3 was significantly associated with better patient survival (P = 0.021 and 0.046, respectively). Comparison with similar array CGH data from 44 leiomyosarcomas identified seven chromosomal regions; 1p36.32-p35.2, 1p21.3-p21.1, 1q32.1-q42.13, 2q14.1-q22.2, 4q33-q34.3, 6p25.1-p21.32 and 7p22.3-p13, which were significantly different in copy number between the MFHs and leiomyosarcomas. CONCLUSIONS: A number of recurrent regions of gain and loss have been identified, some of which were associated with better patient survival. Several specific chromosomal regions with significant differences in copy number between MFHs and leiomyosarcomas were identified, and these aberrations may be used as additional tools for the differential diagnosis of MFHs and leiomyosarcomas

Magnetic Frustration Driven by Itinerancy in Spinel CoV2O4

Localized spins and itinerant electrons rarely coexist in geometrically-frustrated spinel lattices. They exhibit a complex interplay between localized spins and itinerant electrons. In this paper, we study the origin of the unusual spin structure of the spinel CoV2O4, which stands at the crossover from insulating to itinerant behavior using the first principle calculation and neutron diffraction measurement. In contrast to the expected paramagnetism, localized spins supported by enhanced exchange couplings are frustrated by the effects of delocalized electrons. This frustration produces a non-collinear spin state even without orbital orderings and may be responsible for macroscopic spin-glass behavior. Competing phases can be uncovered by external perturbations such as pressure or magnetic field, which enhances the frustration

Ferroelectric polarization switching with a remarkably high activation energy in orthorhombic GaFeO3 thin films

This work was supported by the National Research Foundation (NRF) Grants funded by the Korea Government (MSIP) (Grant No. 2012R 1A1A2041628 and 2013R 1A2A2A01068274). The work at Cambridge was supported by the Engineering and Physical Sciences Research Council (EPSRC). AG and RG thank the Department of Science and Technology for the financial support (Grant No. SB/S3/ME/29/2013).Orthorhombic GaFeO3 (o-GFO) with the polar Pna21 space group is a prominent ferrite owing to its piezoelectricity and ferrimagnetism, coupled with magnetoelectric effects. Herein, we demonstrate large ferroelectric remanent polarization in undoped o-GFO thin films by adopting either a hexagonal strontium titanate (STO) or a cubic yttrium-stabilized zirconia (YSZ) substrate. The polarization-electric-field hysteresis curves of the polar c-axis-grown o-GFO film on a SrRuO3/STO substrate show the net switching polarization of ~35 μC cm−2 with an unusually high coercive field (Ec) of ±1400 kV cm−1 at room temperature. The positive-up and negative-down measurement also demonstrates the switching polarization of ~26 μC cm−2. The activation energy for the polarization switching, as obtained by density-functional theory calculations, is remarkably high, 1.05 eV per formula unit. We have theoretically shown that this high value accounts for the extraordinary high Ec and the stability of the polar Pna21 phase over a wide range of temperatures up to 1368 K.Publisher PDFPeer reviewe

Influence of surface atomic structure demonstrated on oxygen incorporation mechanism at a model perovskite oxide

Perovskite oxide surfaces catalyze oxygen exchange reactions that are crucial for fuel cells, electrolyzers, and thermochemical fuel synthesis. Here, by bridging the gap between surface analysis with atomic resolution and oxygen exchange kinetics measurements, we demonstrate how the exact surface atomic structure can determine the reactivity for oxygen exchange reactions on a model perovskite oxide. Two precisely controlled surface reconstructions with (4 × 1) and (2 × 5) symmetry on 0.5 wt.% Nb-doped SrTiO3(110) were subjected to isotopically labeled oxygen exchange at 450 °C. The oxygen incorporation rate is three times higher on the (4 × 1) surface phase compared to the (2 × 5). Common models of surface reactivity based on the availability of oxygen vacancies or on the ease of electron transfer cannot account for this difference. We propose a structure-driven oxygen exchange mechanism, relying on the flexibility of the surface coordination polyhedra that transform upon dissociation of oxygen molecules.Austrian Science Fund (SFB “ Functional Oxide Surfaces and Interfaces ” - FOXSI, Project F 45)European Research Council Advanced Grant (“OxideSurfaces” (Project ERC-2011-ADG_20110209))National Science Foundation (U.S.). Division of Materials Research (CAREER Award Grant No. 1055583

Unusual synergistic effect in layered Ruddlesden-Popper oxide enables ultrafast hydrogen evolution

Efficient electrocatalysts for hydrogen evolution reaction are key to realize clean hydrogen production through water splitting. As an important family of functional materials, transition metal oxides are generally believed inactive towards hydrogen evolution reaction, although many of them show high activity for oxygen evolution reaction. Here we report the remarkable electrocatalytic activity for hydrogen evolution reaction of a layered metal oxide, Ruddlesden-Popper-type Sr2RuO4 with alternative perovskite layer and rock-salt SrO layer, in an alkaline solution, which is comparable to those of the best electrocatalysts ever reported. By theoretical calculations, such excellent activity is attributed mainly to an unusual synergistic effect in the layered structure, whereby the (001) SrO-terminated surface cleaved in rock-salt layer facilitates a barrier-free water dissociation while the active apical oxygen site in perovskite layer promotes favorable hydrogen adsorption and evolution. Moreover, the activity of such layered oxide can be further improved by electrochemistry-induced activation

Electrical half-wave rectification at ferroelectric domain walls

Ferroelectric domain walls represent multifunctional 2D-elements with great potential for novel device paradigms at the nanoscale. Improper ferroelectrics display particularly promising types of domain walls, which, due to their unique robustness, are the ideal template for imposing specific electronic behavior. Chemical doping, for instance, induces p- or n-type characteristics and electric fields reversibly switch between resistive and conductive domain-wall states. Here, we demonstrate diode-like conversion of alternating-current (AC) into direct-current (DC) output based on neutral 180$^{\circ}$ domain walls in improper ferroelectric ErMnO$_3$. By combining scanning probe and dielectric spectroscopy, we show that the rectification occurs for frequencies at which the domain walls are fixed to their equilibrium position. The practical frequency regime and magnitude of the output is controlled by the bulk conductivity. Using density functional theory we attribute the transport behavior at the neutral walls to an accumulation of oxygen defects. Our study reveals domain walls acting as 2D half-wave rectifiers, extending domain-wall-based nanoelectronic applications into the realm of AC technology

Familial Adenomatous Polyposis-Associated Desmoids Display Significantly More Genetic Changes than Sporadic Desmoids

Desmoid tumours (also called deep or aggressive fibromatoses) are potentially life-threatening fibromatous lesions. Hereditary desmoid tumours arise in individuals affected by either familial adenomatous polyposis (FAP) or hereditary desmoid disease (HDD) carrying germline mutations in APC. Most sporadic desmoids carry somatic mutations in CTNNB1. Previous studies identified losses on 5q and 6q, and gains on 8q and 20q as recurrent genetic changes in desmoids. However, virtually all genetic changes were derived from sporadic tumours. To investigate the somatic alterations in FAP-associated desmoids and to compare them with changes occurring in sporadic tumours, we analysed 17 FAP-associated and 38 sporadic desmoids by array comparative genomic hybridisation and multiple ligation-dependent probe amplification. Overall, the desmoids displayed only a limited number of genetic changes, occurring in 44% of cases. Recurrent gains at 8q (7%) and 20q (5%) were almost exclusively found in sporadic tumours. Recurrent losses were observed for a 700 kb region at 5q22.2, comprising the APC gene (11%), a 2 Mb region at 6p21.2-p21.1 (15%), and a relatively large region at 6q15-q23.3 (20%). The FAP-associated desmoids displayed a significantly higher frequency of copy number abnormalities (59%) than the sporadic tumours (37%). As predicted by the APC germline mutations among these patients, a high percentage (29%) of FAP-associated desmoids showed loss of the APC region at 5q22.2, which was infrequently (3%) seen among sporadic tumours. Our data suggest that loss of region 6q15-q16.2 is an important event in FAP-associated as well as sporadic desmoids, most likely of relevance for desmoid tumour progression

Unlocking the potential of weberite-type metal fluorides in electrochemical energy storage

Sodium-ion batteries (NIBs) are a front-runner among the alternative battery technologies suggested for substituting the state-of-the-art lithium-ion batteries (LIBs). The specific energy of Na-ion batteries is significantly lower than that of LIBs, which is mainly due to the lower operating potentials and higher molecular weight of sodium insertion cathode materials. To compete with the high energy density of LIBs, high voltage cathode materials are required for NIBs. Here we report a theoretical investigation on weberite-type sodium metal fluorides (SMFs), a new class of high voltage and high energy density materials which are so far unexplored as cathode materials for NIBs. The weberite structure type is highly favorable for sodium-containing transition metal fluorides, with a large variety of transition metal combinations (M, M’) adopting the corresponding Na2MM’F7 structure. A series of known and hypothetical compounds with weberite-type structure were computationally investigated to evaluate their potential as cathode materials for NIBs. Weberite-type SMFs show two-dimensional pathways for Na+ diffusion with surprisingly low activation barriers. The high energy density combined with low diffusion barriers for Na+ makes this type of compounds promising candidates for cathode materials in NIBs