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Solvent-free mechanochemical synthesis of two Pt complexes: cis-(Ph3P)2PtCl2 and cis-(Ph3P)2PtCO3.

Cis-(Ph3P)2PtCl2 and cis-(Ph3P)2PtCO3 were prepared mechanochemically from solid reactants in the absence of a solvent; cis-(Ph3P)2PtCl2 was obtained in 98% yield after ball-milling of polycrystalline PtCl2 and Ph3P; the mechanically induced solid-state reaction of cis-(Ph3P)2PtCl2 with an excess of anhydrous K2CO3 produced cis-(Ph3P)2PtCO3 in 70% yield; the formation of transition metal complexes as a result of mechanochemical solvent-free reactions has been confirmed by means of solid-state 31P MAS NMR spectroscopy, X-ray powder diffraction and differential thermal analysis.

Journal Article↗

Fractionation of elements by particle size of ashes ejected from Copahue Volcano, Argentina.

The volcano Copahue, Neuquén province, Argentina has shown infrequent explosive eruptions since the 18th century. Recently, eruptive activity and seismicity were registered in the period July-October, 2000. As a consequence, ash clouds were dispersed by winds and affected Caviahue village located at about 9 km east of the volcano. Samples of deposited particles from this area were collected during this episode for their chemical analysis to determine elements of concern with respect to the health of the local population and its environment. Different techniques were used to evaluate the distribution of elements in four particle size ranges from 36 to 300 microm. X-ray powder diffraction (XRD) was selected to detect major components namely, minerals, silicate glass, fragments of rocks and sulfurs. Major and minor elements (Al, Ca, Cl, Fe, K, Mg, Mn, Na, S, Si and Ti), were detected by energy dispersive X ray analysis (EDAX). Trace element (As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, U, V and Zn) content was quantified by inductively coupled plasma-mass spectrometry (ICP-MS). Nuclear activation analysis (NAA) was employed for the determination of Ce, Co, Cs, Eu, Hf, La, Lu, Rb, Sc, Sm, Ta and Yb. An enrichment was observed in the smallest size fraction of volcanic ashes for four elements (As, Cd, Cu and Sb) of particular interest from the environmental and human health point of view.

Argentina↗

The structure of poly(ethylene oxide)8: NaBPh4 from a single crystal oligomer and polycrystalline polymer.

We show that the structure of a polymer electrolyte may be solved by growing single crystals of an oligomeric (short chain) complex which provided an adequate starting model for refinement of the equivalent polymeric structure using powder diffraction: the efficacy of this method has been demonstrated by determining for the first time the structure of an 8 : 1 complex, poly(ethylene oxide)(8) : NaBPh(4).

Journal Article↗

Location of H+ sites in the fast proton-conductor (H3O)SbTeO6 pyrochlore.

The defect pyrochlore (H3O)SbTeO6 oxide is an excellent proton conductor, showing a conductivity value of 10(-1) S cm(-1) at 30 degrees C under saturated water vapor partial pressure. It can be prepared by ion exchange from KTeSbO6 pyrochlore in sulfuric acid at 453 K for 12 h. The full characterization of the structure of the (H3O)SbTeO6 pyrochlore, including the location of the H3O+ units within the three-dimensional framework, has been carried out by neutron powder diffraction. A first Rietveld refinement of the [SbTeO6]- framework was performed in the Fd3m space group (a= 10.1510(1) A); a difference Fourier map enabled the unambiguous location of the O2 atoms from the H3O+ ions at 32e (x,x,x) positions, and subsequently the H atoms at 96g (x,x,z). The (H3O)SbTeO6 crystal structure is constituted by a network of randomly distributed Sb(V)O6 and Te(VI)O6 octahedra linked by their corners with (Sb,Te)-O1-(Sb,Te) angles of 136.2 degrees. Hydronium ions are located off-center around the large 8a cages of the pyrochlore. The geometry of the (O2)-H3 units is that of an almost regular tetrahedron, with O2 atoms at the center and the three H atoms in three of the vertices; the fourth vertex is supposed to be occupied by the O2 lone pair. The three O2-H bonds have equal distances of 1.020(8)A. The H3O+ units are linked to the O1 framework oxygens by weaker hydrogen bonds, with O1-H bond lengths of 1.649(7) A. The relatively large thermal factors of O2 and H, of 2.5 and 3.7 A2, respectively, suggest that both kinds of atoms are not static at fixed positions but could be dynamically fluctuating between crystallographically equivalent sites.

Antimony↗

Calcium sulfate hemihydrate is the inorganic mineral in statoliths of Scyphozoan medusae (Cnidaria).

Scyphomedusae use inorganic crystals (statoliths) for gravity sensing. The organs which contain the statoliths are called rhopalia. Rhopalia of five different species of the three different orders of the class Scyphozoa were studied with high-end solid-state chemical methods to elucidate the crystallographic nature of the biomineral: synchrotron powder diffraction, synchrotron single-crystal diffraction, synchrotron microtomography, scanning electron microscopy, and energy dispersive X-ray spectroscopy. Each rhopalium contains a large number of statoliths in an ordered way. The statoliths of all species consist of calcium sulfate hemihydrate, a water-deficient phase. This is remarkable for sea-living organisms consisting mostly of water. The phylogenetic relationships within the class Scyphozoa are discussed.

Animals↗

Structure, magnetism and optical properties of achiral and chiral two-dimensional oxalate-bridged anionic networks with symmetric and asymmetric ammonium cations.

A series of two-dimensional (2D) oxalate-based compounds, namely [N(n-C4H9)4][M(II)Cr(III)(ox)3] (M(II) = Mn, Fe; ox = C2O4(2-)) and [N(C2H5)(n-C3H7)(n-C4H9)(n-C5H11)][M(II)M(III)(ox)(3)] ((M(II), M(III)) =(Mn, Cr), (Fe, Cr), (Mn, Fe)) were synthesised starting from racemic tris(oxalato)metalate: rac-[M(III)(ox)3]3- (M(III) = Cr, Fe). For Cr(III), the synthesis has been undertaken starting from resolved (Delta)- or (Lambda)-[Cr(III)(ox)3]3-. The natural circular dichroism measurements assess the enantioselectivity of the synthesis. X-Ray powder diffraction analysis has revealed that, when racemic reagents are used to synthesise Mn(II) containing compounds, a R3c achiral space group is found. In contrast a P6(3) chiral space group is found when starting from (Delta)- or (Lambda)-[Cr(III)(ox)3]3-. Surprisingly, whatever the optical purity of the starting building block, all Fe(II) containing compounds crystallise in the P6(3) chiral space group. The magnetic properties of the synthesised compounds confirm that these compounds are ferromagnets for M(III)= Cr. For M(II)= Mn, Theta ranges between 9 and 11 K and T(c) equals 6 K. For M(II)= Fe, Theta ranges between 14 and 16 K and Tc between 11 and 12 K. [N(C2H5)(n-C3H7)(n-C4H9)(n-C5H11)][Mn(II)Fe(III)(ox)3] is an antiferromagnet with Theta = - 107 K and T(N) = 29 K.

Journal Article↗

Nuclear and magnetic structures and magnetic properties of synthetic brochantite, Cu4(OH)6SO4.

Cu4(OH)6SO4 (1) and Cu4(OD)6SO4 (2) were obtained by hydrothermal syntheses from copper sulfate and sodium hydroxide in H2O and D2O, respectively. They crystallize in the monoclinic system, space group P2(1)/a (14), a = 13.1206(5), b = 9.8551(3), c = 6.0295(2) Angstroms, beta = 103.432(3) degrees, V = 758.3(1) Angstroms(3), Z = 4 and a = 13.1187(5), b = 9.8552(3), c = 6.0293(2) Angstroms, beta = 103.410(3) degrees, V = 758.3(1) Angstroms(3), Z = 4, respectively. They are iso-structural to the mineral brochantite and consist of double chains of edge-sharing copper octahedra that are connected to one another by corners to form corrugated planes along bc; these planes are in-turn bridged by the unprecedented mu7-sulfate tetrahedra to give a 3D-structure. All the hydrogen atoms were precisely located from refinement of the neutron powder diffraction data of the deuterated sample. Magnetic susceptibility data reveal a low-dimensional behavior at high temperature and the presence of both ferromagnetic and antiferromagnetic super-exchanges resulting in a 3D long-range antiferromagnetic ordering at 7.5 K accompanied by a small canting of the moments. The transition is confirmed by a lambda-peak in the specific heat. The magnetic structure at 1.4 K shows the moments are oriented perpendicular to the corrugated planes with alternation along +/-a for neighboring chains within the double chains. The enhanced incoherent scattering at low-angle suggests the existence of short-range ferromagnetic clusters.

Journal Article↗

Electronic and local structural changes in Li(2+x)Ti3O7 ramsdellite compounds upon electrochemical Li-ion insertion reactions by X-ray absorption spectroscopy.

Electronic and local structural changes in ramsdellite-type Li(2+x)Ti3O7 compound were investigated by X-ray absorption spectroscopy (XAS) measurements. Upon electrochemical Li-ion insertions, the host lattice with ramsdellite structure is retained, indicated by X-ray powder diffraction. Ti K-edge extended X-ray absorption fine structure (EXAFS) analysis shows, however, slight local structural distortions around Ti ions. The energy shifts and the changes in the peak intensity of Ti K-edge and Ti L-edge XAS reveal the reducing oxidation states of Ti ions as the amount of electrochemically-inserted Li-ion increases. Equally important, oxide ions have a significant effect on the electronic transfer process, suggested by O K-edge XAS. These results on electronic structural changes were interpreted using the Zaanen-Sawatzky-Allen scheme.

Journal Article↗

Pressure induced octahedral tilting distortion in Ba2YTaO6.

Herein we communicate the first example of a pressure induced octahedral tilting distortion in a double perovskite phase, which was observed during the structural characterization of Ba2YTaO6 using high-pressure synchrotron X-ray powder diffraction.

Journal Article↗

VUV photoelectron imaging of biological nanoparticles: ionization energy determination of nanophase glycine and phenylalanine-glycine-glycine.

The ionization energies of biological nanoparticles are determined using the velocity map photoelectron imaging technique. A beam of nanoparticles produced by aerosol methods is photoionized with tunable vacuum ultraviolet (VUV) synchrotron radiation. The resulting photoelectrons are detected and their angular and energy distributions are measured, yielding an angle-resolved photoelectron spectrum. The ionization energies of the nanoparticles are derived from plots of the photoelectron spectrum versus incident photon energy. The ionization energies of nanophase glycine and phenylalanine-glycine-glycine are 7.6 +/- 0.2 eV, and 7.5 +/- 0.2 eV, respectively. X-Ray powder diffraction studies on the glycine nanoparticles indicate that they are crystalline in nature. The reduced ionization energy when compared to gas phase results suggests that the polarization energy in the solid is significant. The difference in the ionization energy between the nano and gas phase reflects this polarization energy and is derived to be 1.7 +/- 0.2 eV and 1.6 +/- 0.2 eV for glycine and phenylalanine-glycine-glycine, respectively. Using these results the molecular polarizability of glycine is estimated to be 4.7 +/- 0.3 A3 (31.9 +/- 1.9 au).

Glycine↗

The crystallization kinetics and morphology of nitric acid trihydrate.

Crystallization kinetics of stable and metastable nitric acid trihydrate (NAT) were investigated by time dependent X-ray powder diffraction (XRD) measurements. Kinetic conversion curves were evaluated adopting the Avrami model. The growth and morphology of the respective crystallites were monitored in situ on the cryo-stage of an environmental scanning electron microscope (ESEM) under a partial pressure of nitrogen gas (0.3 Torr, 40 Pa). The results show a close relationship between the presence of ice in the sample and the crystallization mechanism of NAT, which results in different shapes and sizes of NAT crystal particles.

Computer Simulation↗

Simulation of the pressure-driven wurtzite to rock salt phase transition in nanocrystals.

Nanocrystals in the size range 12-21 nm of a model binary ionic material in the wurtzite (B4) structure were constructed with morphologies which minimize the surface energy. These were then embedded in a pressurization medium, consisting of a binary Lennard-Jones-type fluid and progressively pressurized in "constant pressure" molecular dynamics simulation runs. Phase transitions to the rocksalt (B1) phase were confirmed by examining calculated powder diffraction patterns, which show the same changes in features as seen for experimental systems. By directly observing the atomic trajectories throughout the duration of the transition the local mechanism has been identified. The transition proceeds via a trigonal bipyramidal intermediate, denoted as the h-MgO structure. It is initiated by a single nucleation event at a [1120]B4 surface with subsequent growth of the B1 region throughout the remainder of the nanocrystal. The consequences of this mechanism for the particle shape of the product phase are detailed and contrasted with those previously found for initially zincblende (B3) structured nanoparticles, using the same interaction potential. The observed transition pressures are elevated relative to the thermodynamically predicted pressure for the bulk, but there is no observable system size effect on the transition pressure across the size range of nanocrystals investigated.

Computer Simulation↗

Effect of Sr content on the crystal structure and electrical properties of the system La2-xSrxNiO4+delta (0 <or=x<or= 1).

Materials formulated as La(2-x)Sr(x)NiO(4+delta) (0 <or=x<or= 1) have been prepared and investigated by high-resolution neutron powder diffraction in order to correlate the structural variation induced by the incorporation of Sr into the crystal lattice with the electronic and thermal properties of each material. The evolution of the electrical conductivity and thermal expansion coefficients with temperature have been determined in order to study the potential use of these compounds as cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFC). These oxides show a good thermal expansion coefficient (TEC = 11-13 x 10(-6) K(-1)), and high electronic conductivity up to 273 S cm(-1). It is noticeable that a great enhancement of the electrical conductivity with the Sr content is concomitant with the shortening of the Ni-O1 bond length.

Journal Article↗

High-pressure synthesis and study of the crystal and magnetic structure of the distorted SeNiO3 and SeMnO3 perovskites.

We describe the preparation of SeMO(3) (M = Ni, Mn) under high pressure conditions (3.5 GPa), starting from reactive H(2)SeO(3) and MO mixtures, contained in sealed gold capsules under the reaction conditions 850 degrees C for 1 h. The polycrystalline samples have been studied by neutron powder diffraction (NPD) data and magnetization measurements. SeMO(3) (M = Ni, Mn) are orthorhombically distorted perovskites (space group Pnma). Below T(N) approximately 104 K (M = Ni) and T(N) approximately 53.5 K (M = Mn) these oxides experience an antiferromagnetic ordering, as demonstrated by susceptibility and NPD measurements. The magnetic reflections observed in the neutron patterns can be indexed with a propagation vector k = 0. Both compounds present the same magnetic structure, which is given by the basis vector (0, 0, A(z)). It can be described as antiferromagnetic (010) layers of magnetic moments lying along the c direction, which are antiferromagnetically coupled along the b direction. For the Ni(2+) ions, the ordered magnetic moment at T = 2.3 K is 2.11(3) micro(B), whereas for Mn(2+) at T = 2.6 K, |m| = 4.64(2) micro(B), consistent with the electronic configurations te (Ni(2+)) and te (Mn(2+)).

Journal Article↗

Dissolved urate promotes calcium oxalate crystallization: epitaxy is not the cause.

1. Increasing the concentration of dissolved urate promotes the crystallization of calcium oxalate from urine. The possibility was investigated that this effect may be caused by heterogeneous nucleation of calcium oxalate by particles of crystalline urate. 2. Urine samples were collected from 10 healthy men, centrifuged and filtered, and a solution of sodium urate was added to increase the medium urate concentration from 2.2 to 5.6 mmol/l. Calcium oxalate crystallization was induced by the addition of oxalate, followed by incubation for 90 min in a shaking waterbath at 37 degrees C. The crystalline material was filtered out and the urate concentration was determined in the filtrate. 3. No difference in the urate concentration before and after induction of calcium oxalate crystallization was observed. These findings were confirmed by infra-red spectroscopy, X-ray powder diffraction and ultraviolet wet chemical analysis with detection limits of 5-10, 1.0 and 0.055%, respectively; urate was not detected in the calcium oxalate crystals. 4. In addition, three urine samples were collected and passed through 10 kDa ultrafiltration membranes to remove any colloidal particles which might have been present. The urate concentration was increased and an oxalate load was added as before, prior to incubation at 37 degrees C in a shaking water bath for 5 min, followed by passage through 10 kDa ultrafiltration membranes. Scanning electron microscopy revealed no particles on the membranes thereby indicating that colloidal or crystalline urate was not formed early in the crystallization experiments.(ABSTRACT TRUNCATED AT 250 WORDS)

Adult↗

Foreign material as a cause of choledocholithiasis.

BACKGROUND AND STUDY AIMS: There are sporadic reports concerning foreign material as a cause of choledocholithiasis. Gallstones obtained endoscopically from the biliary duct were analyzed to determine their structure and the presence of foreign material. The possible correlation between foreign material in gallstones and clinical data was investigated. PATIENTS AND METHODS: Gallstones were examined qualitatively using a crystallographic analysis by X-ray powder diffraction, and the foreign material which was found was subjected to morphological analysis using polarization microscopy. Patients' clinical data were obtained from clinical records, physical examination and documentation. RESULTS: Out of a group of 54 patients, foreign material was found in CBD stones of six individuals (11.1%). Four of these patients were from the group who had undergone a previous cholecystectomy (29/54, 13.8%), and surgical suturing material was found in these four. On the other hand, in the group who had not undergone the operation, foreign material was found in two patients out of 25 (8%); in one case it was cellulose and in the other case the fibre was not identified. CONCLUSIONS: Foreign material can account for lithiasis in the biliary duct. In contrast to present reports in the literature, we have proved that this is possible even in patients without previous surgical intervention in the pancreatobiliary region.

Adult↗