Second-harmonic-generation of [(Se,Te)Cl3_{3}]+^{+} [GaCl4_{4}]–^{–} with aligned ionic tetrahedra

[SeCl$_{3}$][GaCl$_{4}$] (1) and [TeCl$_{3}$][GaCl$_{4}$] (2) are prepared via Lewis-acid–base reaction of SeCl$_{4}$ or TeCl$_{4}$ with GaCl$_{3}$ at 50 °C (1) and 140 °C (2) in quantitative yield. The ionic compounds contain pseudo-tetrahedral [SeCl$_{3}$]$^{+}$/[TeCl$_{3}$]$^{+}$ cations with a prominent stereochemically active electron lone pair at Se(IV)/Te(IV) as well as tetrahedral [GaCl$_{4}$]$^{–}$ anions. Both compounds crystallize in the polar chiral space group P1 with an unidirectional alignment of all tetrahedral building units. They can be considered as the first examples of a much larger group of ionic compounds [MX$_{3}$]$^{+}$[M′X$_{4}$]$^{–}$ (M, M′: metal or main-group element, X: halogen) showing nonlinear optical effects. Material characterization is performed by X-ray structure analysis based on single crystals and powder samples, thermogravimetry, optical spectroscopy, infrared and Raman spectroscopy. Second harmonic generation (SHG) is observed with intensities about 3-times stronger than for potassium dihydrogen phosphate (KDP) in the visible spectral regime with narrow-band-gap materials (2.8, 3.2 eV). Density functional theory calculations are employed to complement the experimental findings, interpret the Raman spectra, visualize the stereochemically active lone electron pair, and compute the SHG tensor

New insights into the lattice dynamics of α-quartz

The lattice dynamics of α-quartz has been studied in great details by combining inelastic X-ray scattering (IXS) from single- and polycrystalline samples, 3D mapping of thermal diffuse scattering (TDS) and ab initio calculations. Pronounced features in TDS patterns have been identified and the origin of first peak in vibrational density of states is unambiguously reveale

High-pressure polymeric nitrogen allotrope with the black phosphorus structure

Studies of polynitrogen phases are of great interest for fundamental science and for the design of novel high energy density materials. Laser heating of pure nitrogen at 140 GPa in a diamond anvil cell led to the synthesis of a polymeric nitrogen allotrope with the black phosphorus structure, bp-N. The structure was identified in situ using synchrotron single-crystal X-ray diffraction and further studied by Raman spectroscopy and density functional theory calculations. The discovery of bp-N brings nitrogen in line with heavier pnictogen elements, resolves incongruities regarding polymeric nitrogen phases and provides insights into polynitrogen arrangements at extreme densities

Synthesis, crystal structure and structure-property relations of strontium orthocarbonate, Sr₂CO₄

Carbonates containing CO4 groups as building blocks have recently been discovered. A new orthocarbonate, Sr2CO4 is synthesized at 92 GPa and at a temperature of 2500 K. Its crystal structure was determined by in situ synchrotron single-crystal X-ray diffraction, selecting a grain from a polycrystalline sample. Strontium orthocarbonate crystallizes in the orthorhombic crystal system (space group Pnma) with CO4, SrO9 and SrO11 polyhedra as the main building blocks. It is isostructural to Ca2CO4. DFT calculations reproduce the experimental findings very well and have, therefore, been used to predict the equation of state, Raman and IR spectra, and to assist in the discussion of bonding in this compound.Funding Agencies|Alexander von Humboldt-StiftungAlexander von Humboldt Foundation; Bundesministerium fur Bildung und ForschungFederal Ministry of Education &amp; Research (BMBF) [05K19WC1]; Deutsche ForschungsgemeinschaftGerman Research Foundation (DFG) [DU 954-11/1, DU 393-9/2, DU 393-13/1, FOR2125, WI1232]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]</p

Genome-Wide Association Study Identifies Genetic Loci Associated with Iron Deficiency

The existence of multiple inherited disorders of iron metabolism in man, rodents and other vertebrates suggests genetic contributions to iron deficiency. To identify new genomic locations associated with iron deficiency, a genome-wide association study (GWAS) was performed using DNA collected from white men aged ≥25 y and women ≥50 y in the Hemochromatosis and Iron Overload Screening (HEIRS) Study with serum ferritin (SF) ≤ 12 µg/L (cases) and iron replete controls (SF>100 µg/L in men, SF>50 µg/L in women). Regression analysis was used to examine the association between case-control status (336 cases, 343 controls) and quantitative serum iron measures and 331,060 single nucleotide polymorphism (SNP) genotypes, with replication analyses performed in a sample of 71 cases and 161 controls from a population of white male and female veterans screened at a US Veterans Affairs (VA) medical center. Five SNPs identified in the GWAS met genome-wide statistical significance for association with at least one iron measure, rs2698530 on chr. 2p14; rs3811647 on chr. 3q22, a known SNP in the transferrin (TF) gene region; rs1800562 on chr. 6p22, the C282Y mutation in the HFE gene; rs7787204 on chr. 7p21; and rs987710 on chr. 22q11 (GWAS observed P<1.51×10−7 for all). An association between total iron binding capacity and SNP rs3811647 in the TF gene (GWAS observed P = 7.0×10−9, corrected P = 0.012) was replicated within the VA samples (observed P = 0.012). Associations with the C282Y mutation in the HFE gene also were replicated. The joint analysis of the HEIRS and VA samples revealed strong associations between rs2698530 on chr. 2p14 and iron status outcomes. These results confirm a previously-described TF polymorphism and implicate one potential new locus as a target for gene identification