Self-Assembly of n-Alkyl Thiols as Disulfides on Au(111)

A grazing incidence x-ray diffraction study of CH(3)(CH(2))(9)SH self-assembled on the (111) surface of gold revealed a disulfide head group structure, which provides a context in which to understand the structure and self-assembly process of this widely studied system. The structure consists of a nearly hexagonal two-dimensional arrangement of the hydrocarbon chains with a dimerization of the sulfur head groups (accommodated through a gauche bond), resulting in a S-S spacing of 2.2 angstroms. These results demonstrate the importance of internal molecular degrees of freedom in the templating of "soft" organic materials on inorganic substrates.     

High-Pressure Polymorph of Thulium: An X-ray Diffraction Study

An x-ray diffractiotn study of thulium at room temperature and high pressure by means of a diamond-anvil press has shown that thulium transforms from a hexagonal close-packed structure to the samarium type, as other rareearth elements (gadolinium, terbium, dysprosium, and holmium) do. Unlike the other rare-earth elements, thulium (hexagonal close-packed) has an axial ratio (c/a) that is independent of pressure within experimental error and the transition is reversible. The transition occurs with increasing pressure in the range of 60 to 116 kilobars. The lattice paralieters of the samarium-type phase of thulium at about 116 kilobars are a = 3.327 +/- 0.005 angstroms and c = 23.48 +/- 0.04 angstroms, and the volume change at the transition is estimated to be - 0.5 percent of the volume of the hexagonal close-packed phase at the transition.     

Single crystals of transfer RNA: an x-ray diffraction study

Large single crystals of formylmethionyl transfer RNA have been prepared. An x-ray diffraction study shows that the material crystallizes in a hexagonal lattice with a equal to 170 angstroms, c equal to 234 angstroms. The diffraction pattern extends to spacings just under 20 angstroms at present. The crystals are heavily hydrated, containing 88 percent water.     

A Fluorite Isotype of SnO2 and a New Modification of TiO2: Implications for the Earth's Lower Mantle

The existence of a cubic fluorite-type SnO(2) and a hexagonal TiO(2) (which may be related to the fluorite structure) have been demonstrated by an in situ x-ray diffraction study in which a diamond-anvil pressure cell was used after the samples had been heated by a continuous yttrium-aluminum-garnet laser. At room temperature, the lattice parameter for SnO(2) (fluorite) is a = 4.925 +/- 0.005 angstroms and those for TiO(2) (fluorite-related) are a = 9.22 +/- 0.01 angstroms and c = 5.685 +/- 0.006 angstroms at about 250 kilobars. The volume change associated with the transition from rutile to fluorite (or related structure) is about -8 percent for SnO(2) and -10.5 percent for TiO(2) at transition. Upon release of pressure, both the fluorite-type SnO(2) and the TiO(2) reverted to the alpha-PbO(2) structure at room temperature. The hypothesis that the earth's lower mantle is composed of oxide phases might be feasible if it were possible for SiO(2) to possess the fluorite structure or its related forms at high pressure, as shown for SnO(2) and TiO(2) in this study. The oxide hypothesis proposed here differs from that postulated by Birch in that the primary coordination of silicon is 6 for Birch's hypothesis and 8 for the hypothesis presented here.     

A new allotropic form of carbon from the ries crater

A new allotropic form of carbon occurs in shock-fused graphite gneisses in the Ries Crater, Bavaria. The assemblage in which it occurs consists of hexagonal graphite, rutile, pseudobrookite, magnetite, nickeliferous pyrrhotite, and baddeleyite. Electron-probe analyses indicate that the new phase is pure carbon. It is opaque and much more strongly reflecting than hexagonal graphite. Measurement of x-ray diffraction powder patterns leads to cell dimensions a = 8.948 +/- 0.009, c = 14.078 +/- 0.017 angstroms, with a primitive hexagonal lattice.     

Hexagonal pattern in cell walls of Escherichia coli B

Cell walls, isolated from Escherichia coli B, as examined by electron microscopy and optical diffraction contain a hexagonal lattice structure, the (1,0) planes of which are separated by 140 +/- 8 angstroms. Unless the walls are briefly heated (10 minutes, 90 degrees C) early in the isolation, the hexagonal array cannot always be observed. Enzymatic digestion with pancreatin and amylase improves visualization of the lattice; subsequent treatment with pepsin and sodium dodecylsulfate removes the hexagonal pattern. Protein or lipoprotein globular units within the wall may thus be arranged in a hexagonal array uponthe mucopeptide layer.     

Crystal Structure and Optical Properties of Cd32S14(SC6H5)36. DMF4, a Cluster with a 15 Angstrom CdS Core

Recrystallization of the solid Cd(10)S(4)(SC(6)H(5))(12) from a solution of pyridine and N, N-di-methylformamide (DMF) results in the formation of the cluster Cd(32)S(14)(SC(6)H(5))(36)-DMF(4) as pale yellow cubes. The structure consists of an 82-atom CdS core that is a roughly spherical piece of the cubic sphalerite lattice approximately 12 angstroms in diameter. The four corners of the lattice are capped by hexagonal wurtzite-like CdS units, which results in an overall tetrahedral cluster approximately 15 angstroms in diameter. This cluster dissolves intact in tetrahydrofuran where its absorption spectrum reveals a sharp peak at 358 nanometers at room temperature and its emission spectra show a strong broad band at 500 nanometers.     

Crystallinity of the double layer of cadmium arachidate films at the water surface

A crystalline counterionic layer at the interface between an electrolyte solution and a charged layer of insoluble amphiphilic molecules was observed with grazing incidence synchrotron x-ray diffraction. Uncompressed arachidic films spread over 10(-3) molar cadmium chloride solution (pH 8.8) spontaneously form crystalline clusters with coherence lengths of approximately 1000 angstroms at 9 degrees C. Ten distinct diffraction peaks were observed, seven of which were attributed to scattering only from a crystalline Cd(2+) layer and the other three to scattering primarily from the arachidate layer. The reflections from the Cd(2+) layer were indexed according to a 2 x 3 supercell of the arachidate lattice with three Cd(2+) ions per cadmium unit cell.     

First occurrence of the garnet-ilmenite transition in silicates

Pyrope garnet (Mg(3)Al(2)Si(3)O(12)) has been found to transform to an ilmenite-type phase at a loading pressure between 240 and 250 kilobars and at about 1000 degrees to 1400 degrees C in a diamond-anvil press coupled with laser heating. The lattice parameters for the ilmenite-type phase of (Mg(.75) Al(.25))(Si(.75) Al(.25))O(3) are a(0) = 4.755 +/- 0.002 and c(0) = 13.360 +/- 0.005 angstroms. The zero-pressure volume change associated with the garnet-ilmenite transition is calculated to be -7.1 percent. This result verifies the prediction that pyrope garnet would transform to the ilmenite structure at high pressure first suggested in 1962 by Clark et al. and Ringwood.     

In Situ Determination of the NiAs Phase of FeO at High Pressure and Temperature

In situ synchrotron x-ray diffraction measurements of FeO at high pressures and high temperatures revealed that the high-pressure phase of FeO has the NiAs structure (B8). The lattice parameters of this NiAs phase at 96 gigapascals and 800 kelvin are a = 2.574(2) angstroms and c = 5.172(4) angstroms (the number in parentheses is the error in the last digit). Metallic behavior of the high-pressure phase is consistent with a covalently and metallically bonded NiAs structure of FeO. Transition to the NiAs structure of FeO would enhance oxygen solubility in molten iron. This transition thus provides a physiochemical basis for the incorporation of oxygen into the Earth's core.     

Precision Lattice-Parameter Determination of (Mg,Fe)SiO3 Tetragonal Garnets

The tetragonal garnet (Mg,Fe)SiO(3) is a high-pressure phase of pyroxene that is thought to be a major constituent of the earth's upper mantle. Its crystal structure is similar to that of cubic garnet, but it is slightly distorted to tetragonal symmetry so that its x-ray powder diffraction pattern shows a very small line splitting. A suite of tetragonal garnets with different compositions in the MgSiO(3)-rich portion of the MgSiO(3)-FeSiO(3) system was synthesized at about 20 gigapascals and 2000 degrees C. The lattice parameters a and c of quenched samples were determined by whole-powder-pattern decomposition analysis of Fe Kalpha x-ray powder diffraction data, which has the capacity to resolve to a high degree heavily overlapping reflections. It was found that the lattice parameters can be obtained from the following equations; a (in angstroms) = 11.516 + 0.088x and c (in angstroms) = 11.428 + 0.157x, where x, teh mole fraction of FeSiO(3), is 0.0 相似文献   

A monoclinic post-stishovite polymorph of silica in the shergotty meteorite

A post-stishovite phase of silica was identified in the Shergotty meteorite by x-ray diffraction and field emission scanning electron microscopy. The diffraction pattern revealed a monoclinic lattice, similar to the baddeleyite-structured polymorph with the cell parameters a = 4.375(1) angstroms, b = 4.584(1) angstroms, c = 4. 708(1) angstroms, beta= 99.97(3), rho = 4.30(2) grams per cubic centimeter, where the numbers in parentheses are the maximum deviations. Transmission electron microscopy investigations indicate the presence of the alpha-lead dioxide-like polymorph, stishovite, and secondary cristobalite in the same silica grain. The mixture of high-density polymorphs suggests that several post-stishovite phases were formed during the shock event on the Shergotty parent body.     

New phases of c60 synthesized at high pressure

The fullerene C(60) can be converted into two different structures by high pressure and temperature. They are metastable and revert to pristine C(60) on reheating to 300 degrees C at ambient pressure. For synthesis temperatures between 300 degrees and 400 degrees C and pressures of 5 gigapascals, a nominal face-centered-cubic structure is produced with a lattice parameter a(o) = 13.6 angstroms. When treated at 500 degrees to 800 degrees C at the same pressure, C(60) transforms into a rhombohedral structure with hexagonal lattice parameters of a(o) = 9.22 angstroms and c(o) = 24.6 angstroms. The intermolecular distance is small enough that a chemical bond can form, in accord with the reduced solubility of the pressure-induced phases. Infrared, Raman, and nuclear magnetic resonance studies show a drastic reduction of icosahedral symmetry, as might occur if the C(60) molecules are linked.     

X-ray Structure of the Cygnus Loop

X-ray emission from the Cygnus Loop was observed in the energy region around 0.2 to 1 kiloelectronvolt with a collector that focused x-rays along one dimension while scanning across the nebula. The total integrated intensity is 1.3x 10(-8) erg per square centimeter per second. The one-dimensional x-ray structure has the same angular size-about 3 degrees-as the outermost boundaries of the optical filaments. There is no increase in x-ray emission at the center of the nebula nor at the strong feature that is seen in certain radio maps. The x-ray spectrum is consistent with thermal radiation from a hot plasma at a temperature of about 4 x 10(6) degrees K with evidence for a line at 19 angstroms corresponding to the 2p-->1s transition of O VIII.     

Crystal Structure of the High-Pressure Phase of Solid CO2

X-ray diffraction study of solid CO(2) at room temperature has shown that the powder pattern of the high-pressure phase, which supersedes the low-pressure cubic Pa3 phase at about 10 gigapascals, is consistently interpreted in terms of an orthorhombic Cmca structure. The orthorhombic cell at 11.8 gigapascals has dimensions of 4.330 +/- 0.015, 4.657 +/- 0.005, 5.963 +/- 0.009 angstroms for its a, b, and c faces, respectively, and a volume of 120.3 +/- 0.5 cubic angstroms. Four molecules contained in the unit cell are located at the base-centered positions with their molecular axes inclined at about 52 degrees with respect to the crystallographic c axis. The volume change associated with the Pa3-Cmca transition is close to zero. The structural dimensions obtained for the high-pressure crystalline phase of CO(2) are of great importance for a theoretical understanding of the role of intermolecular interactions, including quadrupole-quadrupole interactions, in molecular condensation.     

An ultradense polymorph of rutile with seven-coordinated titanium from the Ries crater

We report the discovery of an ultradense post-rutile polymorph of titanium dioxide in shocked gneisses of the Ries crater in Germany. The microscopic diagnostic feature is intense blue internal reflections in crossed polarizers in reflected light. X-ray diffraction studies revealed a monoclinic lattice, isostructural with the baddeleyite ZrO2 polymorph, and the titanium cation is coordinated with seven oxygen anions. The cell parameters are as follows: a = 4.606(2) angstroms, b = 4.986(3) angstroms, c = 4.933(3) angstroms, beta (angle between c and a axes) = 99.17(6) degrees; space group P2(1)/c; density = 4.72 grams per cubic centimeter, where the numbers in parentheses are standard deviations in the last significant digits. This phase is 11% denser than rutile. The mineral is sensitive to x-ray irradiation and tends to invert to rutile. The presence of baddeleyite-type TiO2 in the shocked rocks indicates that the peak shock pressure was between 16 and 20 gigapascals, and the post-shock temperature was much lower than 500 degrees C.     

Friction anisotropy and asymmetry of a compliant monolayer induced by a small molecular tilt

Lateral force microscopy in the wearless regime was used to study the friction behavior of a lipid monolayer on mica. In the monolayer, condensed domains with long-range orientational order of the lipid molecules were present. The domains revealed unexpectedly strong friction anisotropies and non-negligible friction asymmetries. The angular dependency of these effects correlated well with the tilt direction of the alkyl chains of the monolayer, as determined by electron diffraction and Brewster angle microscopy. The molecular tilt causing these frictional effects was less than 15 degrees, demonstrating that even small molecular tilts can make a major contribution to friction.     

Synthesis and structure of a terminal uranium nitride complex

The terminal uranium nitride linkage is a fundamental target in the study of f-orbital participation in metal-ligand multiple bonding but has previously eluded characterization in an isolable molecule. Here, we report the preparation of the terminal uranium(V) nitride complex [UN(Tren(TIPS))][Na(12-crown-4)(2)] {in which Tren(TIPS) = [N(CH(2)CH(2)NSiPr(i)(3))(3)](3-) and Pr(i) = CH(CH(3))(2)} by reaction of the uranium(III) complex [U(Tren(TIPS))] with sodium azide followed by abstraction and encapsulation of the sodium cation by the polydentate crown ether 12-crown-4. Single-crystal x-ray diffraction reveals a uranium-terminal nitride bond length of 1.825(15) angstroms (where 15 is the standard uncertainty). The structural assignment is supported by means of (15)N-isotopic labeling, electronic absorption spectroscopy, magnetometry, electronic structure calculations, elemental analyses, and liberation of ammonia after treatment with water.     

Monoclinic hydroxyapatite

The existence of a monoclinic phase of hydroxyapatite, Ca(2)(PO(4))(4)OH, has been confirmed, by single-crystal structure analysis (weighted "reliability" factor = 3.9 percent on |F|(2)). The structure has space group P21/b, a = 9.4214(8) angstroms, b = 2a, c = 6.8814(7) angstroms, and gamma = 120 degrees , and is analogous to that of chlorapatite. The distortions from the hexagonal structure with which the monoclinic structure is pseudosymmetric are similar to those in chlorapatite, including enlargement of that triangular array of oxygen atoms in which the chlorine ion or, in hydroxyapatite, the hydroxyl hydrogen ion is approximately centered. The hydroxyapatite specimen was prepared by the conversion of a single crystal of chlorapatite in steam at 1200 degrees C, was mimetically twinned, and was approximately 37 percent monoclinic.     

Phosphide from metorites: barringerite, a new iron-nickel mineral

Schreibersite, (Fe,Ni)(3)P, and a higher phosphide, barringerite, occur in the Ollague pallasite. The composition of the higher phosphide, determined by electron probe microanalysis, is (Fe(0.58)Ni(0.42)Co(0.003))(1.95)P. It is hexagonal, with space group P62m and a = 5.87 +/- 0.07 angstroms and c = 3.44 +/- 0.04 angstroms. If we assume a primary origin, the new mineral indicates that troilite and schreibersite crystallized at high temperatures. The occurrence of a higher phosphide in a pallasite indicates local nonequilibria within a group of meteorites that are remarkable for their overall degree of equilibrium crystallization.