Interpenetrating As20 fullerene and Ni12 icosahedra in the onion-skin [As@Ni12@As20]3- ion

The [As@Ni12@As20]3- ion was prepared from As7(3-) and Ni(COD)2 in ethylenediamine solutions and isolated as the Bu4P+ salt (As, arsenic; Ni, nickel; COD, cyclooctadiene; Bu, butyl; P, phosphorus). The anion contains an icosahedral [Ni12(mu12-As)]3- fragment that resides at the center of an As20 dodecahedral (fullerene) cage to give an onion-skin-like [As@Ni12@As20]3- cluster with Ih point symmetry. The icosahedron and pentagonal dodecahedron are reciprocal platonic solids, and the 32 surface atoms form a dimpled geodesic sphere composed of 60 triangular faces. In the gas phase, the [As@Ni12@As20]3- ion sequentially loses all 21 As atoms to form a series of Ni12As(21-x) clusters where 0 相似文献   

Djurleite (Cu1.94S) and Low Chalcocite (Cu2S): New Crystal Structure Studies

Additional x-ray structure studies on low chalcocite generally confirm the previously reported structure but show that either disorder is present or the true space group is not P2(1)/c but Pc, four of the 96 copper atoms in the monoclinic unit cell taking on twofold (linear) coordination. The crystal structure of djurleite has been solved in space group P2(1)/n, the monoclinic cell having parameters a = 26.897, b = 15.745, and c = 13.565 angstroms; beta = 90.13 degrees ; and a content of 248 copper and 128 sulfur atoms. Of the 62 different copper atoms in the structure, 52 are in threefold, triangular coordination with sulfur, nine in tetrahedral, and one in linear coordination.     

Atomic resolution imaging of adsorbates on metal surfaces in air: iodine adsorption on pt(111)

The adsorption of iodine on platinum single crystals was studied with the scanning tunneling microscope (STM) to define the limits of resolution that can be obtained while imaging in air and to set a target resolution for STM imaging of metal surfaces immersed in an electrochemical cell. Two iodine adlattice unit cells of slightly different iodine packing density were clearly imaged: ( radical7 x radical7) R19.1 degrees -I, surface coverage ?(I) = 3/7; and (3 x 3)-I, ?(I) = 4/9. The three iodine atoms in the ( radical7 x radical7) unit cell form a regular hexagonal lattice interatomic distance d(I) = 0.424 nanometer, with two atoms adsorbed in threefold hollow sites and one atom adsorbed at an atop site. The (3 x 3) unit cell showed two different packing arrangements of the four iodine atoms exit. In one of the (3 x 3) structures, the iodine atoms pack to form a hexagonal lattice, d(I) = 0.417 nanometer, with three of the iodine atoms at twofold adsorption sites and one atom at an atop site. Another packing arrangement of iodine into the (3 x 3) unit cell was imaged in which the iodine atoms are not arranged symmetrically.     

Shattuckite and plancheite: a crystal chemical study

The orthorhombic crystal structures of shattuckite, Cu(5)( SiO(3))(4)(OH)(2) and planchétite, Cu(8)(Si(4)0(11))(2)(OH)(4) H(2)O, have been solved. Shattuckite contains silicate chains similar to pyroxene in a complex association with copper atoms, while the closely related planchéite contains silicate chains similar to amphibole.     

Ti8C12+-Metallo-Carbohedrenes: A New Class of Molecular Clusters?

During the course of studying the dehydrogenation reactions of hydrocarbons by titanium atoms, ions, and clusters, an exceptionally stable and abundant cluster which contains 8 titaniums and 12 carbons was discovered. "Titration" reactions with ND(3) reveal the uptake of eight molecules, pointing to the fact that the titanium atoms are at exposed positions of similar coordination. A dodecahedral structure of T(h) point group symmetry is proposed to account for the unusual stability of this molecular cluster. The Ti(8)C(12)(+) dodecahedron has 12 pentagonal rings and each of the rings is formed by two titanium and three carbon atoms, where each titanium is bound to three carbons. Based on the model, it is expected that neutral Ti(8)C(12) would be a stable metallo-carbododecahedral molecule and may comprise one member of a new class of molecules, namely metallo-carbohedrenes.     

Silacalix-

The synthesis of polyphosphinine macrocycles, which consist of a 16-membered ring with four phosphorus atoms (P4) and a 12-membered ring with three phosphorus atoms (P3), is described. Their high coordination ability is demonstrated by the quantitative synthesis of the rhodium and iridium cation complexes of the P4 macrocycle and by quantitative synthesis of the W(CO)3 complex of the P3 compound. Unlike the other available macrocyclic ligands bearing oxygen, sulfur, di- or tricoordinate nitrogen, and even tricoordinate phosphorus as ligating atoms, which are all essentially final sigma donors, these dicoordinate phosphorus-based macrocycles have strong pi-acceptor properties. Their use can be envisaged for the stabilization of negative oxidation states of transition metals or in reductive catalysis.     

Crystal Structure of the Solid Electrolyte, RbAg4I5

The crystal structure of the solid electrolyte RbAg(4)I(5) has been determined from single-crystal x-ray diffraction counter data. There are four RbAg(4)I(5) in a cubic unit cell with a = 11.24 A. The structure refinement, by least squares, is based on space group P4(1)3 (O(7)). The arrangement of the iodide ions is similar to that of the manganese atoms in beta-manganese, and provides 56 iodide tetrahedra per unit cell, which share faces in such manner as to provide diffusion paths for the silver ions. The occurrence of the two low-temperature phases of RbAg(4)I(5) has been established by x-ray diffraction and optical examination.     

Pressure-induced phases of sulfur

At least three phases of sulfur may be induced at pressures between 16 and 65 kilobars. A fibrous form obtained at pressures of 27 kilobars and higher appears to be closely related to the form obtained when plastic sulfur is chilled and stretched. Crystals of the fibrous form are orthorhombic with a = 13.8, b = 32.4, and c = 9.25 A. Thus far the results are in accord with deductions made by Prins and co-workers that the sulfur atoms are arranged in helices with ten atoms and three turns per 13.8-A period, and that these helices are essentially close-packed. The unit cell contains 16 ten-atom chain lengths. The probable space groups to which the crystal may belong are C c m m, C c 2 m, or C c m 2(1). These imply that the structure must contain both right- and left-handed helices and that at least half the helices have some disorder about their axes. The other two phases appear to have structures related to that of the fibrous form, but analyses of them has not progressed as far. One of these phases appears to be uomegasulfur.     

MCM-22: A Molecular Sieve with Two Independent Multidimensional Channel Systems

The molecular sieve MCM-22 contains structural features previously unobserved in this class of materials. Its framework topology, derived from high-resolution electron micrographs and refined with synchrotron x-ray diffraction powder data, contains two independent pore systems, both of which are accessed through rings composed of ten tetrahedral (T) atoms (such as Si, Al, and B). One of these pore systems is defined by two-dimensional, sinusoidal channels. The other consists of large supercages whose inner free diameter, 7.1 angstroms, is defined by 12 T-O species (12-rings) and whose inner height is 18.2 angstroms. These coexisting pore systems may provide opportunities for a wide variety of catalytic applications in the petrochemical and refining industries. Another structural feature is an unusual -T-O-T- chain that passes through the center of a modified dodecasil-1H [4(3)5(6)6(3)] cage.     

Anomalous scattering study of the bi distribution in the 2212 superconductor: implications for cu valency

The distribution of the bismuth atoms over the cation sites in the 2212 Bi-Sr-Ca-Cu-O superconductor has been determined by anomalous scattering synchrotron crystallography. The analysis of reflection pairs measured at wavelengths of 0.9243 and 0.9600 angstrom shows a delocalization of the bismuth atoms over the calcium and strontium sites. The "mixed" plane between the CuO(2) layers contains 6.0(1.4) percent bismuth (where the number in brackets represents the statistical standard deviation derived from the least-squares refinement of the data), and a much smaller amount of strontium than often assumed. The strontium deficiency is charge-compensated by the creation of electron holes in the CuO(2) layer. The result supports the view that neither extra oxygen nor overlap of the bismuth 6p and copper 3d bands is needed to account for the holes, which are an essential feature of the superconductivity mechanism.     

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]{middle dot}4H2O

Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH(3))(2)NH(2)]K(4)[V(10)O(10)(H(2)O)(2)(OH)(4)(PO(4))(7)].4H(2)O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P(5+). These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH(3))(2)NH(2)(+) and K(+) cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P4(3) with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.     

A functional model for O-O bond formation by the O2-evolving complex in photosystem II

The formation of molecular oxygen from water in photosynthesis is catalyzed by photosystem II at an active site containing four manganese ions that are arranged in di-mu-oxo dimanganese units (where mu is a bridging mode). The complex [H2O(terpy)Mn(O)2Mn(terpy)OH2](NO3)3 (terpy is 2,2':6', 2"-terpyridine), which was synthesized and structurally characterized, contains a di-mu-oxo manganese dimer and catalyzes the conversion of sodium hypochlorite to molecular oxygen. Oxygen-18 isotope labeling showed that water is the source of the oxygen atoms in the molecular oxygen evolved, and so this system is a functional model for photosynthetic water oxidation.     

X-ray diffraction and computation yield the structure of alkanethiols on gold(111)

The structure of self-assembled monolayers (SAMs) of long-chain alkyl sulfides on gold(111) has been resolved by density functional theory-based molecular dynamics simulations and grazing incidence x-ray diffraction for hexanethiol and methylthiol. The analysis of molecular dynamics trajectories and the relative energies of possible SAM structures suggest a competition between SAM ordering, driven by the lateral van der Waals interaction between alkyl chains, and disordering of interfacial Au atoms, driven by the sulfur-gold interaction. We found that the sulfur atoms of the molecules bind at two distinct surface sites, and that the first gold surface layer contains gold atom vacancies (which are partially redistributed over different sites) as well as gold adatoms that are laterally bound to two sulfur atoms.     

葡萄糖酸钠和植酸酶对肉鸡营养利用和屠宰性能的影响

用300只1周龄的Arbor Acres(AA)商品肉公鸡,采用2×3试验设计,研究了玉米豆粕型低磷饲粮中添加葡萄糖酸钠(0和2%)和植酸酶(0、500、1 000 U/kg)对肉鸡营养物质利用、胃肠道pH值和屠宰性能的影响.结果表明:在低磷饲粮中添加葡萄糖酸钠提高了肉鸡前期的干物质表观存留率(P<0.000 1)和腹脂率(P=0.063);添加植酸酶提高了肉鸡的全净膛率(P=0.065)、腿肌率(P=0.093)、腹脂率(P=0.001),降低了回肠pH值(P=0.07);葡萄糖酸钠和植酸酶在腹脂率提高上存在互作效应(P=0.043).     

Large first hyperpolarizabilities in push-pull polyenes by tuning of the bond length alternation and aromaticity

Conjugated organic compounds with 3-phenyl-5-isoxazolone or N,N'-diethylthiobarbituric acid acceptors have large first molecular hyperpolarizabilities (beta) in comparison with compounds with 4-nitrophenyl acceptors. For example, julolidinyl-(CH=CH)(3)-CH=N,N'- diethylthiobarbituric acid, which has 12 atoms between the donor and acceptor, has a beta(0) of 911 x 10(-30) electrostatic units, whereas (CH(3))(2)NC(6)H(4),-(CH=CH)(4)-C(6)H(4)NO(2), with 16 atoms between its donor and acceptor, has a beta(0) of 133 x 10(-30) electrostatic units. The design strategies demonstrated here have resulted in chromophores that when incorporated into poled-polymer electrooptic modulators exhibited significant enhancements in electrooptic coefficients relative to polymers containing the commonly used dye Disperse Red-1. Poled polymer devices based on these or related chromophores may ultimately lead to high-speed electrooptic switching elements with low drive-power requirements, suitable for telecommunications applications.     

A cationic cesium continuum in zeolite x

A cesium continuum that fills the channels and cavities of zeolite X has been prepared, and its structure has been determined by single-crystal x-ray crystallography. The three-dimensional continuum is cationic to balance the negative charge of the zeolite framework. Its valence electrons, only 0.3 per Cs(+) ion, are widely delocalized over 95 percent of the cesium ions in the crystal. The continuum has a unit cell formula of (Cs(122))(86+) and contains Cs(13) and Cs(14) clusters (one per supercage) arranged like the atoms in diamond, with one Cs(2) appendix (in the sodalite cavity) per cluster.     

The manganese site of the photosynthetic water-splitting enzyme

As the originator of the oxygen in our atmosphere, the photosynthetic water-splitting enzyme of chloroplasts is vital for aerobic life on the earth. It has a manganese cluster at its active site, but it is poorly understood at the molecular level. Polarized synchrotron radiation was used to examine the x-ray absorption of manganese in oriented chloroplasts. The manganese site, in the "resting" (S1) state, is an asymmetric cluster, which probably contains four manganese atoms, with interatomic separations of 2.7 and 3.3 angstroms; the vector formed by the 3.3-angstrom manganese pair is oriented perpendicular to the membrane plane. Comparisons with model compounds suggest that the cluster contains bridging oxide or hydroxide ligands connecting the manganese atoms, perhaps with carboxylate bridges connecting the 3.3-angstrom manganese pair.     

枣雄性不育种质半同胞子代的遗传多样性分析

以280份种质,包括枣的雄性不育种质JMS2、‘交城五号’枣、‘邢16’酸枣、JMS2ב交城五号’的56个子代、JMS2ב邢16’的96个子代以及JMS2自然授粉获得的125个子代为材料,采用SSR分子标记技术研究枣半同胞家系的遗传多样性。10对SSR引物在277份子代中检测出35个等位基因,观测等位基因数量(Na)、有效等位基因数量(Ne)、香侬指数(I)、观测杂合度(Ho)、期望杂合度(He)、基因遗传多样性(h)和基因分化系数(Fst)分别为3.500,2.108 7,0.819 2,0.573 1,0.471 4,0.470 5和0.096 0,表明277个子代的遗传多样性水平一般。在以JMS2为母本的3个子代群体中,未知父本的自然杂交子代群体遗传多样性最为丰富,I、Na和Ne分别为0.749 5,3.500 0,2.029 2。JMS2ב邢16’子代群体的遗传多样性(Na=2.30,Ne=2.067 8,I=0.722 0)小于自然杂交子代群体,但大于JMS2ב交城五号’子代群体(Na=2.3,Ne=1.829 3,I=0.615 9)。JMS2自然授粉子代可能存在多个父本,JMS2与酸枣‘邢16’较JMS2和‘交城五号’的亲缘关系远,双亲亲缘关系远和多个父本授粉可增加JMS2半同胞子代的遗传多样性。本研究可以为进一步评价和利用枣半同胞家系提供借鉴参考。     

Synthesis and Characterization of Molybdenum Carbide Clusters MonC4n, (n = 1 to 4)

Laser radiation (XeCl laser, 308-nanometer wavelength) focused into a cell containing Mo(CO)(6) vapor produced ultrafine particles in the extended waist of the laser beam. Negative ion mass spectrometry revealed molybdenum carbide cluster ions with a stoichiometry MonC4n (n = 1 to 4). The MonC4n(-) (n = 2 to 4) ions are completely unreactive with NH(3), H(2)O, and O(2), suggesting structures in which the molybdenum atoms are unavailable for coordination to additional ligands. Collision-induced dissociation studies of these anions show the loss of MoC(4) units as the main fragmentation pathway. This observation, together with the lack of addition reactions, provides a basis for structures in which a planar cluster of two, three, or four molybdenum atoms is surrounded by, and bonded to, carbon dimers.     

The structure of ferrihydrite, a nanocrystalline material

Despite the ubiquity of ferrihydrite in natural sediments and its importance as an industrial sorbent, the nanocrystallinity of this iron oxyhydroxide has hampered accurate structure determination by traditional methods that rely on long-range order. We uncovered the atomic arrangement by real-space modeling of the pair distribution function (PDF) derived from direct Fourier transformation of the total x-ray scattering. The PDF for ferrihydrite synthesized with the use of different routes is consistent with a single phase (hexagonal space group P6(3)mc; a = approximately 5.95 angstroms, c = approximately 9.06 angstroms). In its ideal form, this structure contains 20% tetrahedrally and 80% octahedrally coordinated iron and has a basic structural motif closely related to the Baker-Figgis delta-Keggin cluster. Real-space fitting indicates structural relaxation with decreasing particle size and also suggests that second-order effects such as internal strain, stacking faults, and particle shape contribute to the PDFs.