Structural and magnetic properties of isovalently substituted multiferroic BiFeO3: Insights from Raman spectroscopy

Raman spectra, supplemented by powder x-ray diffraction and magnetization data of isovalently A- and B-site substituted BiFeO3 in the Bi1−xLaxFeO3 (0≤x≤1), Bi1−xTbxFeO3 (0≤x≤0.2), and Bi0.9Sm0.1Fe1−xMnxO3 (0≤x≤0.3) series, are presented. A good agreement between the structural transitions observed by x-ray diffraction and the vibrational modes observed in the Raman spectra is found over the whole substitutional ranges, and in particular we find spectroscopic signatures of a PbZrO3-type structure for Bi0.8La0.2FeO3. Mode assignments in the substituted materials are made based on Raman spectra of the end-members BiFeO3 and LaFeO3. Moreover, by comparing spectra from all samples with R3c structure, the phonon assignment in BiFeO3 is revisited. A close connection between the degree of octahedral tilt and the Raman shift of the A1 oxygen a−a−a− tilt mode is established. An explanation for the strong second-order scattering observed in Bi1−xLaxFeO3 and Bi1−xTbxFeO3 is suggested, including the assignment of the previously mysterious BiFeO3 mode at 620 cm−1. Finally, the magnetization data indicates a transition from a cycloidal modulated state towards a canted antiferromagnet with increasing A-site substitution, while Bi0.9Sm0.1Fe1−xMnxO3 with x=0 and 0.15 exhibit an anomalous closing of the hysteresis loop at low temperatures. For low A-site substitution levels (x≤0.1) the decreasing Raman intensity of the Fe derived modes correlates with the partial destruction of the spin cycloid as the substitution level increases

Crystal structure and proton conductivity of BaZr0.9Sc0

Solid-state sintering has been used to prepare the perovskite BaZr0.9Sc0.1O3-delta. Analysis of X-ray powder diffraction data shows that an increase of the unit cell parameter, a, was observed after deuteration. Rietveld analysis of room-temperature neutron powder diffraction data confirmed cubic symmetry (space group Pm-3m). Dynamic thermogravimetric analysis indicates that the hydration process occurs below 335 degrees C and approximately 58% of the theoretical number of protonic defects can be filled. The presence of protons/deutrons is seen from the strong O-H/O-D stretch band in the infrared spectrum of the hydrated/deuterated samples. The proton conductivity of a prehydrated sample was investigated under dry and wet Ar atmosphere

Crystallographic and Magnetic Properties of the Spinel-type Ferrites ZnxCo1-xFe2O4 (0.0 <= x <= 0.75)

Ultrahigh frequencies (UHF) have applications in signal and power electronics to minimize product sizes, increase production quantity and lower manufacturing cost. In the UHF range of 300 MHz to 3 GHz, ferrimagnetic iron oxides (ferrites) are especially useful because they combine the properties of a magnetic material with that of an electrical insulator. Ferrites have much higher electrical resistivity than metallic ferromagnetic materials, resulting in minimization of the eddy current losses, and total penetration of the electromagnetic (EM) field. Hence ferrites are frequently applied as circuit elements, magnetic storage media like read/write heads, phase shifters and Faraday rotators. The electromagnetic properties of ferrites are affected by operating conditions such as field strength, temperature and frequency. The spinel system ZnxCo1-xFe2O4 (x= 0.0, 0.25, 0.50 and 0.75) has been prepared by the standard solid state sintering method. X-ray and neutron powder diffraction measurements were performed at room temperature. Neutron diffraction data analysis confirms the cubic symmetry corresponding to the space group Fd3m. The distribution of three cations Zn2+, Co2+ and Fe3+ over the spinel lattice and other crystallographic parameters like lattice constant, oxygen position parameter, overall temperature factor and occupancies of different ions in different lattice sites for the samples have been determined from the analysis of neutron diffraction data. The lattice constant increases with increasing Zn content in the system. The magnetic structure was found to be ferrimagnetic for the samples with x <= 0.50. Magnetization measurements show that with the increase of Zn content in the system the value of saturation magnetization first increases and then decreases. The variation of the magnetic moment with Zn substitution has been discussed in terms of the distribution of magnetic and non-magnetic ions over the A and B sub-lattices and their exchange coupling

Crystal structure and proton conductivity of BaSn0.6Sc0.4O3-delta: insights from neutron powder diffraction and solid-state NMR spectroscopy

The solid-state synthesis and structural characterisation of perovskite BaSn(1–x)Sc(x)O(3–δ) (x = 0.0, 0.1, 0.2, 0.3, 0.4) and its corresponding hydrated ceramics are reported. Powder and neutron X-ray diffractions reveal the presence of cubic perovskites (space group Pm3m) with an increasing cell parameter as a function of scandium concentration along with some indication of phase segregation. (119)Sn and (45)Sc solid-state NMR spectroscopy data highlight the existence of oxygen vacancies in the dry materials, and their filling upon hydrothermal treatment with D(2)O. It also indicates that the Sn(4+) and Sc(3+) local distribution at the B-site of the perovskite is inhomogeneous and suggests that the oxygen vacancies are located in the scandium dopant coordination shell at low concentrations (x ≤ 0.2) and in the tin coordination shell at high concentrations (x ≥ 0.3). (17)O NMR spectra on (17)O enriched BaSn(1–x)Sc(x)O(3–δ) materials show the existence of Sn–O–Sn, Sn–O–Sc and Sc–O–Sc bridging oxygen environments. A further room temperature neutron powder diffraction study on deuterated BaSn(0.6)Sc(0.4)O(3–δ) refines the deuteron position at the 24k crystallographic site (x, y, 0) with x = 0.579(3) and y = 0.217(3) which leads to an O–D bond distance of 0.96(1) Å and suggests tilting of the proton towards the next nearest oxygen. Proton conduction was found to dominate in wet argon below 700 °C with total conductivity values in the range 1.8 × 10(–4) to 1.1 × 10(–3) S cm(–1) between 300 and 600 °C. Electron holes govern the conduction process in dry oxidizing conditions, whilst in wet oxygen they compete with protonic defects leading to a wide mixed conduction region in the 200 to 600 °C temperature region, and a suppression of the conductivity at higher temperature

Highly dense and chemically stable proton conducting electrolyte sintered at 1200 °C

The authors S. Hossain and A. M. Abdalla are grateful to the graduate studies office of Universiti Brunei Darussalam for graduate research scholarship (GRS) for funding this research. The authors are thankful to Professor John T. S. Irvine for managing a visiting scholarship for SH and AMA at Center for Advanced Materials at School of Chemistry in University of St Andrews, UK for the research works done.The BaCe0.7Zr0.1Y0.2−xZnxO3−δ (x = 0.05, 0.10, 0.15, 0.20) has been synthesized by the conventional solid state reaction method for application in protonic solid oxide fuel cell. The phase purity and lattice parameters of the materials have been studied by the room temperature X-ray diffraction (XRD). Scanning electron microscopy (SEM) has been done for check the morphology and grain growth of the samples. The chemical and mechanical stabilities have been done using thermogravimetric analysis (TGA) in pure CO2 environment and thermomechanical analysis (TMA) in Argon atmosphere. The XRD of the materials show the orthorhombic crystal symmetry with Pbnm space group. The SEM images of the pellets show that the samples sintered at 1200 °C are highly dense. The XRD after TGA in CO2 and thermal expansion measurements confirm the stability. The particles of the samples are in micrometer ranges and increasing Zn content decreases the size. The conductivity measurements have been done in 5% H2 with Ar in dry and wet atmospheres. All the materials show high proton conductivity in the intermediate temperature range (400–700 °C). The maximum proton conductivity was found to be 1.0 × 10−2 S cm−1 at 700 °C in wet atmosphere for x = 0.10. From our study, 10 wt % of Zn seems to be optimum at the B-site of the perovskite structure. All the properties studied here suggest it can be a promising candidate of electrolyte for IT-SOFCs.PostprintPeer reviewe

Genome-wide association meta-analysis in 269,867 individuals identifies new genetic and functional links to intelligence

Intelligence is highly heritable(1) and a major determinant of human health and well-being(2). Recent genome-wide meta-analyses have identified 24 genomic loci linked to variation in intelligence3-7, but much about its genetic underpinnings remains to be discovered. Here, we present a large-scale genetic association study of intelligence (n = 269,867), identifying 205 associated genomic loci (190 new) and 1,016 genes (939 new) via positional mapping, expression quantitative trait locus (eQTL) mapping, chromatin interaction mapping, and gene-based association analysis. We find enrichment of genetic effects in conserved and coding regions and associations with 146 nonsynonymous exonic variants. Associated genes are strongly expressed in the brain, specifically in striatal medium spiny neurons and hippocampal pyramidal neurons. Gene set analyses implicate pathways related to nervous system development and synaptic structure. We confirm previous strong genetic correlations with multiple health-related outcomes, and Mendelian randomization analysis results suggest protective effects of intelligence for Alzheimer's disease and ADHD and bidirectional causation with pleiotropic effects for schizophrenia. These results are a major step forward in understanding the neurobiology of cognitive function as well as genetically related neurological and psychiatric disorders.Peer reviewe

Genome-wide association analysis of more than 120,000 individuals identifies 15 new susceptibility loci for breast cancer.

Genome-wide association studies (GWAS) and large-scale replication studies have identified common variants in 79 loci associated with breast cancer, explaining ∼14% of the familial risk of the disease. To identify new susceptibility loci, we performed a meta-analysis of 11 GWAS, comprising 15,748 breast cancer cases and 18,084 controls together with 46,785 cases and 42,892 controls from 41 studies genotyped on a 211,155-marker custom array (iCOGS). Analyses were restricted to women of European ancestry. We generated genotypes for more than 11 million SNPs by imputation using the 1000 Genomes Project reference panel, and we identified 15 new loci associated with breast cancer at P < 5 × 10(-8). Combining association analysis with ChIP-seq chromatin binding data in mammary cell lines and ChIA-PET chromatin interaction data from ENCODE, we identified likely target genes in two regions: SETBP1 at 18q12.3 and RNF115 and PDZK1 at 1q21.1. One association appears to be driven by an amino acid substitution encoded in EXO1.BCAC is funded by Cancer Research UK (C1287/A10118, C1287/A12014) and by the European Community's Seventh Framework Programme under grant agreement 223175 (HEALTH-F2-2009-223175) (COGS). Meetings of the BCAC have been funded by the European Union COST programme (BM0606). Genotyping on the iCOGS array was funded by the European Union (HEALTH-F2-2009-223175), Cancer Research UK (C1287/A10710, C8197/A16565), the Canadian Institutes of Health Research (CIHR) for the CIHR Team in Familial Risks of Breast Cancer program and the Ministry of Economic Development, Innovation and Export Trade of Quebec, grant PSR-SIIRI-701. Combination of the GWAS data was supported in part by the US National Institutes of Health (NIH) Cancer Post-Cancer GWAS initiative, grant 1 U19 CA148065-01 (DRIVE, part of the GAME-ON initiative). For a full description of funding and acknowledgments, see the Supplementary Note.This is the author accepted manuscript. The final version is available from NPG via http://dx.doi.org/10.1038/ng.324

Polygenic Risk Scores for Prediction of Breast Cancer and Breast Cancer Subtypes

Stratification of women according to their risk of breast cancer based on polygenic risk scores (PRSs) could improve screening and prevention strategies. Our aim was to develop PRSs, optimized for prediction of estrogen receptor (ER)-specific disease, from the largest available genome-wide association dataset and to empirically validate the PRSs in prospective studies. The development dataset comprised 94,075 case subjects and 75,017 control subjects of European ancestry from 69 studies, divided into training and validation sets. Samples were genotyped using genome-wide arrays, and single-nucleotide polymorphisms (SNPs) were selected by stepwise regression or lasso penalized regression. The best performing PRSs were validated in an independent test set comprising 11,428 case subjects and 18,323 control subjects from 10 prospective studies and 190,040 women from UK Biobank (3,215 incident breast cancers). For the best PRSs (313 SNPs), the odds ratio for overall disease per 1 standard deviation in ten prospective studies was 1.61 (95%CI: 1.57-1.65) with area under receiver-operator curve (AUC) = 0.630 (95%CI: 0.628-0.651). The lifetime risk of overall breast cancer in the top centile of the PRSs was 32.6%. Compared with women in the middle quintile, those in the highest 1% of risk had 4.37- and 2.78-fold risks, and those in the lowest 1% of risk had 0.16- and 0.27-fold risks, of developing ER-positive and ER-negative disease, respectively. Goodness-of-fit tests indicated that this PRS was well calibrated and predicts disease risk accurately in the tails of the distribution. This PRS is a powerful and reliable predictor of breast cancer risk that may improve breast cancer prevention programs.NovartisEli Lilly and CompanyAstraZenecaAbbViePfizer UKCelgeneEisaiGenentechMerck Sharp and DohmeRocheCancer Research UKGovernment of CanadaArray BioPharmaGenome CanadaNational Institutes of HealthEuropean CommissionMinistère de l'Économie, de l’Innovation et des Exportations du QuébecSeventh Framework ProgrammeCanadian Institutes of Health Researc