The local structure of self-doped BiS2-based layered systems as a function of temperature.

We have studied the local structure of layered Eu(La,Ce)FBiS2 compounds by Bi L3-edge extended X-ray absorption fine structure (EXAFS) measurements as a function of temperature. We find that the BiS2 sub-lattice is largely distorted in EuFBiS2, characterized by two different in-plane Bi-S1 distances. The distortion is marginally affected by partial substitutions of Ce (Eu0.5Ce0.5FBiS2) and La (Eu0.5La0.5FBiS2). The temperature dependence of the local structure distortion reveals an indication of possible charge density wave like instability in the pristine self-doped EuFBiS2 and Ce substituted Eu0.5Ce0.5FBiS2 while it is suppressed in La substituted Eu0.5La0.5FBiS2. In compounds with higher superconducting transition temperature, the axial Bi-S2 bond distance is elongated and the related bond stiffness decreased, suggesting some important role of this in the charge transfer mechanism for self-doping in the active BiS2-layer. In-plane Bi-S1 distances are generally softer than the axial Bi-S2 distance and they suffer further softening by the substitutions. The results are discussed in relation to an important role of the Bi defect chemistry driven asymmetric local environment in the physical properties of these materials.

Temperature dependent local atomic displacements in NaSn2As2 system.

NaSn2As2 is mechanically exfoliable layered van der Waals (vdW) Zintl phase that is getting interesting due to its low thermal conductivity and recently observed superconductivity. Here, we have investigated the temperature dependent local structure of NaSn2As2 by a combined analysis of As K-edge and Sn K-edge extended x-ray absorption fine structure measurements. The system is intrinsically disordered with the interatomic distances largely consistent to those estimated by average structure measurements. The stretching force constants of different bond distances have been determined using temperature dependent mean square relative displacements. The Sn-As distance is the strongest bond in this system, having covalent nature, unlike the weaker interlayer distances which are characterized by vdW type bonding. Among them, As-Na distance is slightly weaker than Sn-Sn(i) below ∼200 K and tends to get stronger above this temperature. The anomalous behavior of As-Na bond suggests that the mechanical exfoliation in this system is likely to be temperature dependent. The anomaly in the interlayer atomic correlations may be due to a charge density wave-like instability around this temperature, indicated by earlier experiments. The local structure and disorder are discussed in relation to the physical properties of NaSn2As2.

Suppression of structural instability in LaOBiS2-x Se x by Se substitution.

Isovalent substitution of S by Se in LaOBiS2-x Se x has a substantial effect on its electronic structure and thermoelectric properties. To investigate the possible role of BiS2 structural instability, we have studied the local structure of LaOBiS2-x Se x ([Formula: see text]) using temperature dependent Bi L3-edge extended x-ray absorption fine structure measurements. The results reveal that the local structure of the two compounds is significantly different. The BiS2 sub-lattice is largely distorted in LaOBiS2 (x = 0.0), with two in-plane Bi-S1 distances separated by ∼0.4 Å instead LaOBiSSe (x = 1.0) showing much smaller local disorder with two in-plane Bi-Se distances in the plane being separated by ∼0.2 Å. Temperature dependent study shows that the two Bi-S1 distances are characterized by different bond strength in LaOBiS2 (x = 0.0) while it is similar for the Bi-Se distances in LaOBiSSe (x = 1.0). The out of plane Bi-S2 bond is harder in LaOBiSSe indicating that the structural instability of BiS2 layer has large effect on the out-of-plane atomic correlations. The results suggest that the local structure of LaOBiS2-x Se x is an important factor to describe differing electronic and thermal transport of the two compounds.

Effect of Te substitution on crystal structure and transport properties of AgBiSe2 thermoelectric material.

Silver bismuth diselenide (AgBiSe2) has attracted much attention as an efficient thermoelectric material, owing to its intrinsically low lattice thermal conductivity. While samples synthesized using a solid-state reaction showed n-type conductivity and their dimensionless figure of merit (ZT) reached ∼1 by electron doping, theoretical calculations predicted that a remarkably high thermoelectric performance can be achieved in p-type AgBiSe2. In this paper, we present the effect of Te substitution on the crystal structure and thermoelectric properties of AgBiSe2, expecting p-type conductivity due to the shallowing of the energy potential of the valence band. We found that all AgBiSe2-xTex (x = 0-0.8) prepared using a solid-state reaction exhibits n-type conductivity from 300 to 750 K. The room-temperature lattice thermal conductivity decreased to as low as 0.3 W m-1 K-1 by Te substitution, which was qualitatively described using the point defect scattering model for the solid solution. We show that ZT reaches ∼0.6 for x = 0.8 at a broad range of temperatures, from 550 to 750 K, due to the increased power factor, although the carrier concentration has not been optimized yet.

Role of the local structure in superconductivity of LaO0.5F0.5BiS2-x Se x system.

We have studied the local structure of LaO0.5F0.5BiS2-x Se x by Bi L1-edge extended x-ray absorption fine structure (EXAFS). We find a significant effect of Se substitution on the local atomic correlations with a gradual elongation of average in-plane Bi-S bondlength. The associated mean square relative displacement, measuring average local distortions in the BiS2 plane, hardly shows any change for small Se substitution, but decreases significantly for [Formula: see text]. The Se substitution appears to suppress the local distortions within the BiS2 plane that may optimize in-plane orbital hybridization and hence the superconductivity. The results suggest that the local structure of the BiS2-layer is one of the key ingredients to control the physical properties of the BiS2-based dichalcogenides.

The effect of RE substitution in layered REO(0.5)F(0.5)BiS2: chemical pressure, local disorder and superconductivity.

We have studied the effect of RE substitution on the structure and the local atomic disorder in REO0.5F0.5BiS2 (RE = rare-earth) to understand their correlation with the bulk superconductivity in these materials. The mean RE size, affecting the chemical pressure, has been varied in two series namely Ce1-xNdxO0.5F0.5BiS2 and Nd1-ySmyO0.5F0.5BiS2. The lattice parameters evolve anomalously, showing an anisotropic shrinkage (elongation) of the c-axis (a-axis) to an isotropic expansion of the lattice with increasing mean RE size. The Bi L3-edge extended X-ray absorption fine structure (EXAFS) measurements are performed to investigate local displacements in the BiS2 lattice, revealing a large disorder and a sharp boundary between the Ce-containing and Sm-containing series with a distinct local structure. The results suggest that the bulk superconductivity in REO0.5F0.5BiS2 is correlated with anomalous atomic displacements in the Bi-S1 network, likely to be a combined effect of active Bi 6s electronic states and a possible Jahn-Teller-like instability of the Bi 6px/6py electrons.

Determination of local atomic displacements in CeO(1-x)F(x)BiS2 system.

We have used Bi and Ce L3-edges extended x-ray absorption fine structure measurements to study local structure of CeO(1-x)F(x)BiS2 system as a function of F-substitution. The local structure of both BiS2 active layer and CeO1-xFx spacer layer changes systematically. The in-plane Bi-S1 distance decreases (ΔRmax ∼ 0.08 Å) and the out-of-plane Bi-S2 distance increases (ΔRmax ∼ 0.12 Å) with increasing F-content. On the other hand, the Ce-O/F distance increases (ΔRmax ∼ 0.2 Å) with a concomitant decrease of the Ce-S2 distance (ΔRmax ∼ 0.15 Å). Interestingly, the Bi-S1 distance is characterized by a large disorder that increases with F-content. The results provide useful information on the local atomic displacements in CeO(1-x)F(x)BiS2, that should be important for the understanding of the coexistence of superconductivity and low temperature ferromagnetism in this system.

Spectromicroscopy of electronic phase separation in KxFe2-ySe2 superconductor.

Structural phase separation in AxFe2-ySe2 system has been studied by different experimental techniques, however, it should be important to know how the electronic uniformity is influenced, on which length scale the electronic phases coexist, and what is their spatial distribution. Here, we have used novel scanning photoelectron microscopy (SPEM) to study the electronic phase separation in KxFe2-ySe2, providing a direct measurement of the topological spatial distribution of the different electronic phases. The SPEM results reveal a peculiar interconnected conducting filamentary phase that is embedded in the insulating texture. The filamentary structure with a particular topological geometry could be important for the high Tc superconductivity in the presence of a phase with a large magnetic moment in AxFe2-ySe2 materials.

Transcriptional activation of a geranylgeranyl diphosphate synthase gene, GGPPS2, isolated from Scoparia dulcis by treatment with methyl jasmonate and yeast extract.

A cDNA clone, designated SdGGPPS2, was isolated from young seedlings of Scoparia dulcis. The putative amino acid sequence of the translate of the gene showed high homology with geranylgeranyl diphosphate synthase (GGPPS) from various plant sources, and the N-terminal residues exhibited the characteristics of chloroplast targeting sequence. An appreciable increase in the transcriptional level of SdGGPPS2 was observed by exposure of the leaf tissues of S. dulcis to methyl jasmonate, yeast extract or Ca(2+) ionophore A23187. In contrast, SdGGPPS1, a homologous GGPPS gene of the plant, showed no or only negligible change in the expression level upon treatment with these stimuli. The truncated protein heterologously expressed in Escherichia coli in which the putative targeting domain was deleted catalyzed the condensation of farnesyl diphosphate and isopentenyl diphosphate to liberate geranylgeranyl diphosphate. These results suggested that SdGGPPS2 plays physiological roles in methyl jasmonate and yeast extract-induced metabolism in the chloroplast of S. dulcis cells.

Electronic properties of FeSe(1-x)Te(x) probed by x-ray emission and absorption spectroscopy.

The electronic structure of FeSe(1-x)Te(x) chalcogenide superconductors has been studied by x-ray emission (XES) and x-ray absorption (XAS) as a function of Te substitution. The Fe Kß XES spectra reveal a relatively low spin state for Fe in FeSe(1-x)Te(x) superconductors, persisting in the whole range of Te substitution. The Fe K-edge high-resolution XAS shows systematic spectral changes due to the evolving hybridization between the Fe 3d (4p) and chalcogen p (d) orbitals. The resonant inelastic x-ray scattering (RIXS) spectra hardly show any feature except the one due to charge transfer from occupied to unoccupied bands, that changes substantially from FeSe to FeTe. The results provide important information on the electronic states and their evolution in the FeSe(1-x)Te(x) chalcogenides.

Large local disorder in superconducting K(0.8)Fe(1.6)Se2 studied by extended x-ray absorption fine structure.

We have measured the local structure of superconducting K(0.8)Fe(1.6)Se(2) chalcogenide (T(c) = 31.8 K) by temperature dependent polarized extended x-ray absorption fine structure (EXAFS) at the Fe and Se K-edges. We find that the system is characterized by a large local disorder. The Fe-Se and Fe-Fe distances are found to be shorter than the distances measured by diffraction, while the corresponding mean square relative displacements reveal large Fe-site disorder and relatively large c-axis disorder. The local force constant for the Fe-Se bondlength (k ~ 5.8 eV Å(-2)) is similar to the one found in the binary FeSe superconductor, however, the Fe-Fe bondlength appears to be flexible (k ~ 2.1 eV Å(-2)) in comparison to the binary FeSe (k ~ 3.5 eV Å(-2)), an indication of partly relaxed Fe-Fe networks in K(0.8)Fe(1.6)Se(2). The results suggest a glassy nature for the title system, with the superconductivity being similar to that in the granular materials.

Random alloy-like local structure of Fe(Se, S)(1-x)Te(x) superconductors revealed by extended x-ray absorption fine structure.

The local structure of Fe(Se, S)(1-x)Te(x) ternary (11-type) chalcogenides has been studied by temperature dependent Fe K-edge extended x-ray absorption fine structure measurements. We find that the Fe-Se and Fe-Te distances in ternary FeSe(1-x)Te(x) are closer to the respective distances in the binary systems, revealing significant divergence of the local structure from the average one. The mean square relative displacements show a systematic change with Te content, consistent with bond relaxation in the inhomogeneous ternary phases. Also, the Fe-Te and Fe-S distances in the FeS(0.2)Te(0.8) ternary system are found to be different in the crystallographically homogeneous structure. The observed features are characteristic of ternary random alloys, suggesting that a proper consideration should be given to the atomic distribution for describing the complex electronic structure of these multi-band Fe-based chalcogenides.

A study of the electronic structure of FeSe(1-x)Te(x) chalcogenides by Fe and Se K-edge x-ray absorption near edge structure measurements.

Fe K-edge and Se K-edge x-ray absorption near edge structure (XANES) measurements are used to study the FeSe(1 - x)Te(x) electronic structure of chalcogenides. An intense Fe K-edge pre-edge peak due to Fe 1s --> 3d (and admixed Se/Te p states) is observed, showing substantial change with Te substitution and x-ray polarization. The main white line peak in the Se K-edge XANES due to Se 1s --> 4p transition appears similar to the one expected for Se(2-) systems and changes with Te substitution. Polarization dependence reveals that unoccupied Se orbitals near the Fermi level have predominant p(x, y) character. The results provide key information on the hybridization of Fe 3d and chalcogen p states in the Fe-based chalcogenide superconductors.

Splenic artery embolization before laparoscopic splenectomy in children.

BACKGROUND: This study assessed the safety and utility of preoperative splenic artery embolization before laparoscopic splenectomy in children. METHODS: Five young girls with a mean age of 13.2 years underwent laparoscopic splenectomies at the authors' institution from August 1998 to April 2003. Three of the patients had idiopathic thrombocytopenic purpura, and two had hereditary spherocytosis. Preoperative splenic artery embolization was performed the day before the surgery in all cases. The laparoscopic splenectomy was performed using traditional laparoscopic procedures and standard laparoscopic instruments with the patient in the right semilateral position. RESULTS: The mean spleen weight was 252.6 g, and the mean length was 11.6 cm. All the patients reported postembolic pain, but not to a level unmanageable by intravascular narcotics. There were no severe complications in the splenic artery embolization. The laparoscopic splenectomies were completed in a mean of 211 min, with a mean estimated blood loss of 9 ml. None of the operations required conversion to traditional open laparotomy, and none of the patients died or experienced operative complications. CONCLUSION: The authors concluded that splenic artery embolization is safe and useful as an adjuvant procedure performed before elective laparoscopic splenectomy in children.

Acute cholecystitis caused by a cholesterol polyp.

A 39-year-old man hospitalized with upper abdominal pain had been found to have a 3mm polyp in the body of the gallbladder 3 years previously. Laboratory tests on admission showed mild liver dysfunction. Ultrasonography depicted a dilated gallbladder with increased wall thickness; the polyp could no longer be seen. Computed tomography with drip infusion cholangiography again showed a dilated gallbladder, and also stenosis of the distal cystic duct. The resected specimen obtained by laparoscopic cholecystectomy showed disappearance of the polyp from the body of the gallbladder. A cholesterol stone was incarcerated in the cystic duct, representing an impacted detached cholesterol polyp causing acute cholecystitis. Spontaneous detachment of a cholesterol polyp from the gallbladder mucosa, then, can result in acute cholecystitis.

Incidentally discovered giant renal arteriovenous malformation.

A case is presented of giant renal arteriovenous malformation (AVM). A 61-year-old woman was admitted to the National Defense Medical College Hospital for further evaluation of a renal cyst. Doppler ultrasonography and magnetic resonance imaging revealed a giant renal AVM, although the patient had no history nor clinical sign suggesting an AVM. Under the diagnosis of a right renal AVM, the patient underwent AVM resection.