Monodisperse metal clusters 10 angstroms in diameter in a polymeric host: the "monomer as solvent' approach

A general methodology is presented for the dispersion of an inorganic compound within an organic polymer host through the use of solubilizing and polymerizable ligands. The dispersion of metal cluster cations 10 angstroms in diameter within a polymer host is achieved by free-radical polymerization of the hexafunctional metal cluster [Mo(6)Cl(8)(NVI)(6)](triflate)(4) with bound polymerizable ligands in N-vinylimidazole (NVI) solutions. Copolymerization of the activated cluster-bound ligands with the surrounding medium probably plays a key role in preventing aggregation and produces near monodisperse molecular clusters within the polymer matrix.     

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.     

Controlling molecular order in "hairy-rod" langmuir-blodgett films: a polarization-modulation microscopy study

The interplay of molecular weight, layer thickness, and thermal annealing in controlling molecular order in ultrathin Langmuir-Blodgett films is characterized with the use of polarization-modulation laser-scanning microscopy. The degree and direction of molecular alignment can be imaged rapidly and sensitively through the magnitude and orientation of linear dichroism in Langmuir-Blodgett films of rodlike poly(phthalocyaninatosiloxane) (PcPS). Images are presented for films as thin as two molecular layers ( approximately 44 angstroms). Molecular alignment along the transfer direction is much stronger for films of PcPS with approximately 25 repeat units ( approximately 10 nanometers long) than for those with approximately 50 repeat units ( approximately 20 nanometers long). Enhancement of alignment by thermal annealing is also much greater for PcPS-25 than PcPS-50. Intimate interaction with the substrate suppresses improvement in alignment by annealing, evident by an anomalously small increase in anisotropic absorption of the first two layers.     

Crystalline Ropes of Metallic Carbon Nanotubes

Fullerene single-wall nanotubes (SWNTs) were produced in yields of more than 70 percent by condensation of a laser-vaporized carbon-nickel-cobalt mixture at 1200degreesC. X-ray diffraction and electron microscopy showed that these SWNTs are nearly uniform in diameter and that they self-organize into "ropes," which consist of 100 to 500 SWNTs in a two-dimensional triangular lattice with a lattice constant of 17 angstroms. The x-ray form factor is consistent with that of uniformly charged cylinders 13.8 +/- 0.2 angstroms in diameter. The ropes were metallic, with a single-rope resistivity of <10(-4) ohm-centimeters at 300 kelvin. The uniformity of SWNT diameter is attributed to the efficient annealing of an initial fullerene tubelet kept open by a few metal atoms; the optimum diameter is determined by competition between the strain energy of curvature of the graphene sheet and the dangling-bond energy of the open edge, where growth occurs. These factors strongly favor the metallic (10,10) tube with C5v symmetry and an open edge stabilized by triple bonds.     

Crystallographic structure of the octameric histone core of the nucleosome at a resolution of 3.3 A

The structure of the (H2A-H2B-H3-H4)2 histone octamer has been determined by means of x-ray crystallographic techniques at a resolution of 3.3 angstroms. The octamer is a prolate ellipsoid 110 angstroms long and 65 to 70 angstroms in diameter, and its general shape is that of a rugby ball. The size and shape are radically different from those determined in earlier studies. The most striking feature of the histone octamer is its tripartite organization, that is, a central (H3-H4)2 tetramer flanked by two H2A-H2B dimers. The DNA helix, placed around the octamer in a path suggested by the features on the surface of the protein, appears like a spring holding the H2A-H2B dimers at either end of the (H3-H4)2 tetramer.     

Paramyosin: molecular length and assembly

Paratnyosin paracrystails formned with divalent cations have a 725-angstrom axial period and show simple negative staining patterns in the electron microscope. The structure of the aggregates is interpreted in terms of an array of polar molecules about 1275 angstroms long, with "gaps" and "overlaps" in the molecular assembly. Antiparallel relatiotns between molecules lead to the assembly of paracrystals with opposite polarity at either end. Implications of the in vitro structure for filaments containing paramyosin in muscle are discussed.     

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.     

Synthesis of inorganic fullerene-like molecules

The reaction of [Cp*Fe(eta5-P5)] with Cu(I)Cl in solvent mixtures of CH2Cl2/CH3CN leads to the formation of entirely inorganic fullerene-like molecules of the formula [[Cp*Fe(eta5:eta1:eta1:eta1:eta1:eta1-P5)]12[CuCl]10[Cu2Cl3]5[Cu(CH3CN)2]5] (1) possessing 90 inorganic core atoms. This compound represents a structural motif similar to that of C60: cyclo-P5 rings of [Cp*Fe(eta5-P5)] molecules are surrounded by six-membered P4Cu2 rings that result from the coordination of each of the phosphorus lone pairs to CuCl metal centers, which are further coordinated by P atoms of other cyclo-P5 rings. Thus, five- and six-membered rings alternate in a manner comparable to that observed in the fullerene molecules. The so-formed half shells are joined by [Cu2Cl3]- as well as by [Cu(CH3CN)2]+ units. The spherical body has an inside diameter of 1.25 nanometers and an outside diameter of 2.13 nanometers, which is about three times as large as that of C60.     

Matrix-Mediated Synthesis of Nanocrystalline ggr-Fe2O3: A New Optically Transparent Magnetic Material

A new magnetic material with appreciable optical transmission in the visible region at room temperature has been isolated as a gamma-Fe(2)O(3)/polymer nanocomposite. The synthesis is carried out in an ion-exchange resin at 60 degrees C. Magnetization and susceptibility data demonstrate loading-dependent saturation moments as high as 46 electromagnetic units per gram and superparamagnetism for lower loadings where particle sizes are less than 100 angstroms. Optical absorption studies show that the small-particle form of gamma-Fe(2)O(3) is considerably more transparent to visible light than the single-crystal form. The difference in absorption ranges from nearly an order of magnitude in the "red" spectral region to a factor of 3 at 5400 angstroms. The magnetization of the nanocomposite is greater by more than an order of magnitude than those of the strongest room-temperature transparent magnets, FeBO(3) and FeF(3).     

Thyroglobulin: evidence for crystallization and association

Crystals of thyroglobulin have been obtained from ammonium sulfate solutions and have been examined by electron microscopy as shadowed carbon replicas. Unit size in the crystal is 228 +/- 9 angstroms, which corresponds to a molecular weight of 5,300,000. Data are in accord with the possibility that this unit represents a polymer of thyroglobulin.     

X-Ray Photoconductive Nanocomposites

The successful development of digital radiography depends, to a large extent, on the availability of suitable x-ray photoconductors. The x-ray photoconductive nanocomposites reported here combine the advantages of both inorganic and organic compounds. An inorganic compound was finely dispersed in an organic polymer. The inorganic compound, with its large x-ray absorption efficiency, functioned as the x-ray absorber, and the polymer provided good dielectric properties and ease of thin-film preparation. The preparation procedures and the x-ray photoconductive properties of a specific example, a 50 percent by weight nanocomposite of bismuth triiodide and nylon-11, are discussed in detail.     

Tabashir: an opal of plant origin

A specimen of tabashir, a variety of opal found in bamboo, contained more water but smaller amounts of alkalis and alkaline earths than most opals. It consisted of particles of about 100 angstroms in diameter, linked together in clumps, which appeared in fractured surfaces as irregularities. The tabashir was amorphous, but its microstructure differed from that of silicagel and amorphous opal of inorganic origin.     

Ring closure of carbon nanotubes

Lightly etched single-walled carbon nanotubes are chemically reacted to form rings. The rings appear to be fully closed as opposed to open coils, as ring-opening reactions did not change the structure of the observed rings. The average diameter of the rings was 540 nanometers with a narrow size distribution. The nanotubes in solution were modeled as wormlike polymer chains, yielding a persistence length of 800 nanometers. Nanotubes shorter than this length behave stiffly and stay nearly straight in solution. However, nanotubes longer than the Kuhn segment length of 1600 nanometers undergo considerable thermal fluctuation, suggesting a greater flexibility of these materials than is generally assumed.     

不同硒处理对大蒜含硒量及产量和品质的影响

采用不同浓度Na2SeO3进行大蒜叶面喷施的田间试验,以研究大蒜对硒的吸收、转化和硒对大蒜产量、品质等的影响规律。结果表明,叶面施硒可明显提高大蒜中总硒、有机硒和无机硒含量,并且有机硒转化率与硒浓度增加呈正比,其总硒、有机硒和无机硒在最高硒浓度(1000mg/kg)达最高,分别是CK的6.5、7.8和2.0倍。大蒜产量在0.5、10mg/kg浓度较CK增加,其后产量降低。施硒促进大蒜对Mg的吸收,而K、P、Fe在一定硒浓度(0.5、10mg/kg)有不同程度提高。因此,在此试验条件下,既能增加大蒜有机硒含量和产量,又可适当提高其营养品质的叶面施硒浓度,以不超过10mg/kg为宜。     

Molecular structure of DNA by scanning tunneling microscopy

Uncoated DNA molecules marked with an activated tris(l-aziridinyl) phosphine oxide (TAPO) solution were deposited on gold substrates and imaged in air with the use of a high-resolution scanning tunneling microscope (STM). Constant-current and gap-modulated STM images show clear evidence of the helicity of the DNA structure: pitch periodicity ranges from 25 to 35 angstroms, whereas the average diameter is 20 angstroms. Molecular structure within a single helix turn was also observed.     

Interwoven metal-organic framework on a periodic minimal surface with extra-large pores

Interpenetration (catenation) has long been considered a major impediment in the achievement of stable and porous crystalline structures. A strategy for the design of highly porous and structurally stable networks makes use of metal-organic building blocks that can be assembled on a triply periodic P-minimal geometric surface to produce structures that are interpenetrating-more accurately considered as interwoven. We used 4,4',4"-benzene-1,3,5-triyl-tribenzoic acid (H(3)BTB), copper(II) nitrate, and N,N'-dimethylformamide (DMF) to prepare Cu(3)(BTB)(2)(H(2)O)(3).(DMF)(9)(H(2)O)(2) (MOF-14), whose structure reveals a pair of interwoven metal-organic frameworks that are mutually reinforced. The structure contains remarkably large pores, 16.4 angstroms in diameter, in which voluminous amounts of gases and organic solvents can be reversibly sorbed.     

Experiments and simulations of ion-enhanced interfacial chemistry on aqueous NaCl aerosols

A combination of experimental, molecular dynamics, and kinetics modeling studies is applied to a system of concentrated aqueous sodium chloride particles suspended in air at room temperature with ozone, irradiated at 254 nanometers to generate hydroxyl radicals. Measurements of the observed gaseous molecular chlorine product are explainable only if reactions at the air-water interface are dominant. Molecular dynamics simulations show the availability of substantial amounts of chloride ions for reaction at the interface, and quantum chemical calculations predict that in the gas phase chloride ions will strongly attract hydroxl radicals. Model extrapolation to the marine boundary layer yields daytime chlorine atom concentrations that are in good agreement with estimates based on field measurements of the decay of selected organics over the Southern Ocean and the North Atlantic. Thus, ion-enhanced interactions with gases at aqueous interfaces may play a more generalized and important role in the chemistry of concentrated inorganic salt solutions than was previously recognized.     

施用硫肥和硒肥对茎瘤芥产量及抗氧化作用的影响

【目的】了解不同硫、硒肥施用量对茎瘤芥(Brassica juncea var.tumida)干物质量,硫、硒含量及叶片保护酶活性和代谢物质含量的影响,以探明茎瘤芥对硫、硒肥的生理响应机制。【方法】以茎瘤芥“涪杂1号”为供试品种,采用盆栽试验研究了硫(S) (0,50,100 mg/kg)、硒(Se) (0,1,3 mg/kg)不同用量处理组合(S₀Se₀(CK)、S₅₀Se₁、S₅₀Se₃、S₁₀₀Se₁、S₁₀₀Se₃)对茎瘤芥不同部位干物质量和硫、硒积累及叶片抗氧化能力的影响。【结果】与S₀Se₀相比,施用硫、硒肥能明显提高茎瘤芥根、膨大茎和叶片及单株干物质量。施用硫、硒的处理均能明显提高茎瘤芥各部位对硫、硒的吸收与积累,且硫和硒主要积累在茎瘤芥地上部分膨大茎和叶中。施用硫、硒的处理明显提高了各部位的有机硒和无机硒含量,其中膨大茎和叶中的有机硒含量明显高于无机硒;5个处理中,S₅₀Se₃处理根、膨大茎和叶中的有机硒与无机硒含量均最高。超氧化物歧化酶(SOD)活性以S₁₀₀Se₁处理最高,谷胱甘肽过氧化酶(GSH-Px)活性以S₅₀Se₃处理最高;而抗坏血酸过氧化酶(APX)和过氧化氢酶(CAT)活性随着硫、硒肥用量的增加变化不大。施用硫、硒肥后,茎瘤芥叶片中MDA含量较高,抗坏血酸（AsA）和过氧化氢（H₂O₂）含量较低。【结论】施用硫、硒肥能提高茎瘤芥单株干物质量,促进硒的吸收与积累,对SOD和GSHPx活性及MDA含量有明显影响。综合分析认为,50 mg/kg S+3 mg/kg Se是硫、硒肥施用的最佳组合。     

Oxidation-resistant gold-55 clusters

Gold nanoparticles ranging in diameter from 1 to 8 nanometers were prepared on top of silicon wafers in order to study the size dependence of their oxidation behavior when exposed to atomic oxygen. X-ray photoelectron spectroscopy showed a maximum oxidation resistance for "magic-number" clusters containing 55 gold atoms. This inertness is not related to electron confinement leading to a size-induced metal-to-insulator transition, but rather seems to be linked to the closed-shell structure of such magic clusters. The result additionally suggests that gold-55 clusters may act as especially effective oxidation catalysts, such as for oxidizing carbon monoxide.     

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.