Reactivity of organic compounds in hot water: geochemical and technological implications

Understanding of the reactivity of organic molecules in hot water is developing from studies aimed at explaining how organic matter (kerogen) forms in natural environments and then breaks down into energy source materials. In natural systems where kerogens are depolymerized, hot water is ubiquitous and usually contains salt and minerals. Reactions such as ionic condensation, cleavage, and hydrolysis are facilitated by changes in the chemical and physical properties of water as temperature increases. These changes make the solvent properties of water at high temperature similar to those of polar organic solvents at room temperature, thus facilitating reactions with organic compounds. An understanding of aqueous organic chemistry may lead to potential applications in areas as diverse as the recycling of plastics, the synthesis of chemicals, and coal liquefaction.     

Chemical waves

Spatial structures may occur in nonlinear systems far from equilibrium. Chemical waves, which are concentration variations of chemical species propagating in a system, are an example of such structures. A survey is given of some experiments on chemical waves by spectroscopic and microphotographic techniques, arranged according to different types of waves, different geometries, and various properties.     

Reversible reduction of oxygen to peroxide facilitated by molecular recognition

Generation of soluble sources of peroxide dianion (O(2)(2-)) is a challenge in dioxygen chemistry. The oxidizing nature of this anion renders its stabilization in organic media difficult. This Report describes the chemically reversible reduction of oxygen (O(2)) to cryptand-encapsulated O(2)(2-). The dianion is stabilized by strong hydrogen bonds to N-H groups from the hexacarboxamide cryptand. Analogous stabilization of peroxide by hydrogen bonding has been invoked recently in crystalline saccharide and protein systems. The present peroxide adducts are stable at room temperature in dimethyl sulfoxide (DMSO) and N,N'-dimethylformamide (DMF). These adducts can be obtained in gram quantities from the cryptand-driven disproportionation reaction of potassium superoxide (KO(2)) at room temperature.     

High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt

The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non-precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non-precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%).     

Laminar growth of ultrathin metal films on metal oxides: Co on hydroxylated alpha-Al2O3(0001)

Metals deposited in vacuum on metal oxides such as alumina normally grow as three-dimensional clusters because of weak adatom-substrate interactions. This tendency hinders our ability to form interfaces of ultrathin, laminar metal films on oxides for use in microelectronics and other technologies where nanostructural control is desired. We present experimental and theoretical results showing that room temperature Co deposition on fully hydroxylated clean sapphire (alpha-Al2O3) produces a surface chemical reaction that leads to laminar growth, despite a large mismatch in lattice constants. This process should be applicable to a wide range of metals and metal oxides.     

高分子乳化剂在啶虫脒水乳剂中的应用

[目的]研制环境友好、稳定的新型啶虫脒水乳剂。[方法]选用高分子乳化剂,制备环境友好型新型啶虫脒水乳剂,并检测其理化性能指标。[结果]5%啶虫脒水乳剂的优化配方为:溶剂环己酮+二甲苯为10%+10%,助溶剂N-N-二甲基甲酰胺为2%;高分子乳化剂N-100+G-100为5%+3.5%,添加1%硼砂和柠檬酸的缓冲体系,抗冻剂乙二醇为5%,自来水补足。该配方在室温、冷贮、热贮下稳定,各项技术指标均符合水乳剂的质量技术指标要求,且防治大白菜蚜虫的速效性与持效性均优于对照乳油产品。[结论]该研究成功研制出的新型啶虫脒水乳剂具有广阔的市场应用前景,值得进一步推广。     

Chemically derived, ultrasmooth graphene nanoribbon semiconductors

We developed a chemical route to produce graphene nanoribbons (GNR) with width below 10 nanometers, as well as single ribbons with varying widths along their lengths or containing lattice-defined graphene junctions for potential molecular electronics. The GNRs were solution-phase-derived, stably suspended in solvents with noncovalent polymer functionalization, and exhibited ultrasmooth edges with possibly well-defined zigzag or armchair-edge structures. Electrical transport experiments showed that, unlike single-walled carbon nanotubes, all of the sub-10-nanometer GNRs produced were semiconductors and afforded graphene field effect transistors with on-off ratios of about 10(7) at room temperature.     

A late-transition metal oxo complex: K7Na9[O=PtIV(H2O)L2], L = [PW9O34]9-

Terminal mono-oxo complexes of the late transition metal elements have long been considered too unstable to synthesize because of repulsion between the oxygen electrons and the mostly filled metal d orbitals. A platinum(IV)-oxo compound flanked by two polytungstate ligands, K7Na9[O=Pt(H2O)L2], L = [PW9O34(9-)], has now been prepared and isolated at room temperature as air-stable brown crystals. X-ray and neutron diffraction at 30 kelvin revealed a very short [1.720(18) angstrom] Pt-O bond and no evidence of a hydrogen atom at the terminal oxygen, ruling out a better precedented Pt-OH complex. Density functional theory and spectroscopic data account for the stability of the Pt(IV)-oxo unit by electron withdrawal into delocalized orbitals of the polytungstates.     

Large electrocaloric effect in ferroelectric polymers near room temperature

Applying an electrical field to a polar polymer may induce a large change in the dipolar ordering, and if the associated entropy changes are large, they can be explored in cooling applications. With the use of the Maxwell relation between the pyroelectric coefficient and the electrocaloric effect (ECE), it was determined that a large ECE can be realized in the ferroelectric poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] copolymer at temperatures above the ferroelectric-paraelectric transition (above 70 degrees C), where an isothermal entropy change of more than 55 joules per kilogram per kelvin degree and adiabatic temperature change of more than 12 degrees C were observed. We further showed that a similar level of ECE near room temperature can be achieved by working with the relaxor ferroelectric polymer of P(VDF-TrFE-chlorofluoroethylene).     

Air pollution: remote detection of several pollutant gases with a laser heterodyne radiometer

An infrared heterodyne radiometer with a spectral resolution of 0.04 reciprocal centimeters has been used to remotely detect samples of ozone, sulfur dioxide, ammonia, and ethylene at room temperature, and samples of nitric oxide at 390K. Each gas was observed in a background of nitrogen or oxygen at atmospheric pressure. Sensitivities to some of these gases are adequate for detection of ambient concentrations as low as a few parts per billion.     

Electrodeposited defect chemistry superlattices

Nanometer-scale layered structures based on thallium(III) oxide were electrodeposited in a beaker at room temperature by pulsing the applied potential during deposition. The conducting metal oxide samples were superlattices, with layers as thin as 6.7 nanometers. The defect chemistry was a function of the applied overpotential: High overpotentials favored oxygen vacancies, whereas low overpotentials favored cation interstitials. The transition from one defect chemistry to another in this nonequilibrium process occurred in the same potential range (100 to 120 millivolts) in which the rate of the back electron transfer reaction became significant. The epitaxial structures have the high carrier density and low electronic dimensionality of high transition temperature superconductors.     

超干红花种子耐藏性及抗老化作用

红花种子经超干处理能显著提高耐藏性及抗老化能力.红花未超干种子(MC=9.01％)经室温贮藏3年,其发芽率,活力指数,脱氢酶活性,过氧化氢酶(CAT)活力和超氧物岐化酶(SOD)活力均有明显下降,而同期室温下贮藏的超干种子(MC=2.18％)其发芽力和活力指数仍保持在原来水平;脱氢酶、CAT、SOD活力保持与低温贮藏种子的同等水平.未超干种子在老化过程中其营养贮藏物较多被消耗,而超干种子保存较好.     

Chemical reactions of anions in the gas phase

Anions of many types, both organic and inorganic, farmiliar and exotic, can be generated in the gas phase by rational chemical synthesis in a flowing afterglow apparatus. Once formed, the rates, products, and mechanisms of their reactions with neutral species of all kinds can be studied, not only at room temperature but at higher energies in a drift field. These completely unsolvated ions undergo a large number of reactions that are analogous to those they undergo in solution, as well as some that are less familiar. New types of ions, for which there are no counterparts in solution, can be produced and their chemical reactions explored.     

Sulfide solubilities in alteration-controlled systems

Solubilities of sphalerite (ZnS) and galena (PbS) were determined at 300 degrees to 500 degrees C and 1000 bars total pressure in a chemical environment buffered by silicate mineral equilibria. Chloride solutions and muscovite-bearing assemblages characteristic of hydrothermal wall-rock alteration were used; weak acidities at temperature were therefore involved. The metal concentrations encountered tended to be higher than those observed in high bisulfide-H(2)S systems at neutral to weakly basic pH used in most previous experimentation; the chemical conditions of the work, although not completely satisfactory, are geologically more realistic than previous experimentation done in the basic-pH region.     

A three-dimensional synthetic metallic crystal composed of single-component molecules

Molecular metals normally require charge transfer between two different chemical species. We prepared crystals of [Ni(tmdt)2] (tmdt, trimethylenetetrathiafulvalenedithiolate) and carried out crystal structure analyses and resistivity measurements. The analyses and measurements revealed that these single-component molecular crystals are metallic from room temperature down to 0.6 kelvin. Ab initio molecular orbital calculations suggested that pi molecular orbitals form conduction bands. The compact molecular arrangement, intermolecular overlap integrals of the highest occupied and lowest unoccupied molecular orbitals, and tight-binding electronic band structure calculation revealed that [Ni(tmdt)2] is a three-dimensional synthetic metal composed of planar molecules.     

Toxic potential of materials at the nanolevel

Nanomaterials are engineered structures with at least one dimension of 100 nanometers or less. These materials are increasingly being used for commercial purposes such as fillers, opacifiers, catalysts, semiconductors, cosmetics, microelectronics, and drug carriers. Materials in this size range may approach the length scale at which some specific physical or chemical interactions with their environment can occur. As a result, their properties differ substantially from those bulk materials of the same composition, allowing them to perform exceptional feats of conductivity, reactivity, and optical sensitivity. Possible undesirable results of these capabilities are harmful interactions with biological systems and the environment, with the potential to generate toxicity. The establishment of principles and test procedures to ensure safe manufacture and use of nanomaterials in the marketplace is urgently required and achievable.     

Total alignment of calcite at acidic polydiacetylene films: cooperativity at the organic-inorganic interface

Biological matrices can direct the absolute alignment of inorganic crystals such as calcite. Cooperative effects at an organic-inorganic interface resulted in similar co-alignment of calcite at polymeric Langmuir-Schaefer films of 10,12-pentacosadiynoic acid (p-PDA). The films nucleated calcite at the (012) face, and the crystals were co-aligned with respect to the polymer's conjugated backbone. At the same time, the p-PDA alkyl side chains reorganized to optimize the stereochemical fit to the calcite structure, as visualized by changes in the optical spectrum of the polymer. These results indicate the kinds of interactions that may occur in biological systems where large arrays of crystals are co-aligned.     

Singlet molecular oxygen from superoxide anion and sensitized fluorescence of organic molecules

The superoxide anion, O(2)-, evolves singlet molecular oxygen in dimethylsulfoxide solution. Pronounced water quenching of superoxide-sensitized luminescence is indicative of the preferential generation of the (1)sigma(g)+ state. Recent identification of O(2)- in the xanthine oxidase system suggests that the generation of singlet oxygen may also occur in enzymatic systems.     

Time-Resolved X-ray Diffraction Study of Solid Combustion Reactions

Real-time synchrotron diffraction has been used to monitor the phase transformations of highly exothermic, fast self-propagating solid combustion reactions on a subsecond time scale down to 100 milliseconds and in some instances to 10 milliseconds. Three systems were investigated: Ti + C --> TiC; Ti + C + xNi --> TiC + Ni-Ti alloy; and Al + Ni --> AlNi. In all three reactions, the first step was the melting of the metal reactants. Formation of TiC in the first two reactions was completed within 400 milliseconds of the melting of the Ti metal, indicating that the formation of TiC took place during the passage of the combustion wave front. In the Al + Ni reaction, however, passage of the wave front was followed by the appearance and disappearance of at least one intermediate in the afterburn region. The final AlNi was formed some 5 seconds later and exhibited a delayed appearance of the (210) reflection, which tends to support a phase transformation from a disordered AlNi phase at high temperature to an ordered CsCl structure some 20 seconds later. This new experimental approach can be used to study the chemical dynamics of high-temperature solid-state phenomena and to provide the needed database to test various models for solid combustion.     

Nanophase transition metal oxides show large thermodynamically driven shifts in oxidation-reduction equilibria

Knowing the thermodynamic stability of transition metal oxide nanoparticles is important for understanding and controlling their role in a variety of industrial and environmental systems. Using calorimetric data on surface energies for cobalt, iron, manganese, and nickel oxide systems, we show that surface energy strongly influences their redox equilibria and phase stability. Spinels (M(3)O(4)) commonly have lower surface energies than metals (M), rocksalt oxides (MO), and trivalent oxides (M(2)O(3)) of the same metal; thus, the contraction of the stability field of the divalent oxide and expansion of the spinel field appear to be general phenomena. Using tabulated thermodynamic data for bulk phases to calculate redox phase equilibria at the nanoscale can lead to errors of several orders of magnitude in oxygen fugacity and of 100 to 200 kelvin in temperature.