Visualizing gas molecules interacting with supported nanoparticulate catalysts at reaction conditions

Understanding how molecules can restructure the surfaces of heterogeneous catalysts under reaction conditions requires methods that can visualize atoms in real space and time. We applied a newly developed aberration-corrected environmental transmission electron microscopy to show that adsorbed carbon monoxide (CO) molecules caused the {100} facets of a gold nanoparticle to reconstruct during CO oxidation at room temperature. The CO molecules adsorbed at the on-top sites of gold atoms in the reconstructed surface, and the energetic favorability of this reconstructed structure was confirmed by ab initio calculations and image simulations. This atomic-scale visualizing method can be applied to help elucidate reaction mechanisms in heterogeneous catalysis.     

Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene

The removal of trace acetylene from ethylene is performed industrially by palladium hydrogenation catalysts (often modified with silver) that avoid the hydrogenation of ethylene to ethane. In an effort to identify catalysts based on less expensive and more available metals, density functional calculations were performed that identified relations in heats of adsorption of hydrocarbon molecules and fragments on metal surfaces. This analysis not only verified the facility of known catalysts but identified nickel-zinc alloys as alternatives. Experimental studies demonstrated that these alloys dispersed on an oxide support were selective for acetylene hydrogenation at low pressures.     

Linear metal nanostructures and size effects of supported metal catalysts

Nickel metal catalysts composed of nanometer by micrometer strips have been produced with solid-state microfabrication techniques. The strips are actually the edges of nickelcatalyst thin films, which are sandwiched between separating support layers, which are also nanometers thick. These linear nanostructures constitute well-defined and well-controlled catalytic entities that reproduce the size of traditional supported metal clusters in one dimension, thus separating size from total number of atoms in the catalyst. Examination of their catalytic activity showed that they duplicate the behavior of conventional supported clusters. A specific rate maximum was observed for the hydrogenolysis of ethane at a nanoscale dimension similar to the cluster size at which the rate is maximum in the case of the supported cluster studies, whereas the hydrogenation of ethylene shows no such size dependency. The results suggest that the surface-to-volume ratio or the number of atoms in the catalytic entity cannot be the source of these size effects and that either support effects or nonequilibrium surface structures are the determining factors.     

Antiarthritic gold compounds effectively quench electronically excited singlet oxygen

Although certain gold [Au(I)] compounds have been used effectively in the treatment of rheumatoid arthritis for some years, the molecular basis for such therapeutic action has been unclear. One possible mechanism of the action of Au(I) compounds is that they protect unsaturated membrane lipids and proteins against oxidative degradation caused by activated phagocytes that are not properly regulated. In this study it has been shown that superoxide ion (O-2.), a product of activated phagocytes, can be oxidized to electronically excited singlet oxygen (O1(2)delta g), an agent that is capable of peroxidation of unsaturated fatty acid derivatives. It has also been shown that antiarthritic Au(I) compounds are effective deactivators of O1(2)delta g with quenching constants on the order of 10(7) M-1 sec-1.     

Mechanism of the relation between the content of nitro and nitroso compounds in amnion and allantois of chicken embryos and rate of posthatch chick growth

It is established that metabolism of nitric oxide (NO) in the chicken embryo and posthatch growth rate of chicks have a direct relation which is determined both by the genotype and by external factors influencing posthatch growth rate.     

NMR imaging of catalytic hydrogenation in microreactors with the use of para-hydrogen

Catalysis is vital to industrial chemistry, and the optimization of catalytic reactors attracts considerable resources. It has proven challenging to correlate the active regions in heterogeneous catalyst beds with morphology and to monitor multistep reactions within the bed. We demonstrate techniques, using magnetic resonance imaging and para-hydrogen (p-H2) polarization, that allow direct visualization of gas-phase flow and the density of active catalyst in a packed-bed microreactor, as well as control over the dynamics of the polarized state in space and time to facilitate the study of subsequent reactions. These procedures are suitable for characterizing reactors and reactions in microfluidic devices where low sensitivity of conventional magnetic resonance would otherwise be the limiting factor.     

Biomineralization of gold: biofilms on bacterioform gold

Bacterial biofilms are associated with secondary gold grains from two sites in Australia. 16S ribosomal DNA clones of the genus Ralstonia that bear 99% similarity to the bacterium Ralstonia metallidurans-shown to precipitate gold from aqueous gold(III) tetrachloride-were present on all DNA-positive gold grains but were not detected in the surrounding soils. These results provide evidence for the bacterial contribution to the authigenic formation of secondary bacterioform gold grains and nuggets.     

Mechanism and stereoselectivity of asymmetric hydrogenation

Rhodium complexes containing chiral phosphine ligands catalyze the hydrogenation of olefinic substrates such as alpha-aminoacrylic acid derivatives, producing chiral products with very high optical yields. Elucidation of the mechanisms of such reactions leads to the conclusion that the stereoselection is dictated not by the preferred initial binding of the substrate to the chiral catalyst, but rather by the much higher reactivity of the minor diastereomer of the catalyst-substrate adduct corresponding to the less favored binding mode.     

Enhanced ethylene and ethane production with free-radical cracking catalysts

A series of free-radical catalysts have been discovered that increase the yield of highly valuable olefins from the cracking of low molecular weight paraffins. For example, catalytic cracking of n-butane, isobutane, and propane over manganese or iron supported on magnesium oxide (MgO) gave product distributions different from those given by thermal (free-radical) cracking or cracking over traditional acid catalysts. With n-butane and propane feeds, the products from catalytic cracking included large amounts of ethylene and ethane; with isobutane feed, propylene was the major product. Physical characterization of the MgO-supported catalyst showed the manganese to be in a 2+ oxidation state in the reduced catalyst and a 4+ oxidation state in the fully oxidized catalyst. Manganese was also shown to be uniformly distributed in the support material with very little enrichment at the surface. Matrix isolation of the gasphase radicals from n-butane feed showed that ethyl and methyl radicals were produced over the active catalysts. In the thermal process, only methyl radicals were produced. The mechanism of the catalytic reaction appears to be selective formation of primary carbanions at the catalyst surface followed by electron transfer and release of primary hydrocarbon radicals to the gas phase.     

镉离子在三正辛胺为载体的支撑液膜中的传输

用三正辛胺为载体，聚丙烯微孔膜为支撑体的支撑液膜体系处理含镉料液，得出影响镉离子传输的参数。     

Asymmetric hydrogenation of unfunctionalized, purely alkyl-substituted olefins

Asymmetric hydrogenation of olefins is one of the most useful reactions for the synthesis of optically active compounds, especially in industry. However, the application range of the catalysts developed so far is limited to alkenes with a coordinating functional group or an aryl substituent next to the double bond. We have found a class of chiral iridium catalysts that give high enantioselectivity in the hydrogenation of unfunctionalized, trialkyl-substituted olefins. Because these catalysts do not require the presence of any particular functional group or aryl substituent in the substrate, they considerably broaden the scope of asymmetric hydrogenation.     

Atmospheric reactions of polycyclic aromatic hydrocarbons: facile formation of mutagenic nitro derivatives

Directly active mutagens are formed on exposure of the promutagen benzo[a]pyrene to gaseous pollutants in smog. In simulated atmospheres containing 1 part per million nitrogen dioxide and traces of nitric acid, directly mutagenic nitro derivatives are readily formed from both benzo[a]pyrene and perylene, a non-mutagen in the Ames reversion assay. Possible formation of direct mutagens by such reactions on sample collection filters, in exhaust effluents, and in the atmosphere should be recognized.     

Spectroscopy of biological compounds with inelastic electron tunneling

Metal-insulator-metal electron tunnel junctions can be doped with a solution of an organic compound by placing a drop of the solution on the insulator and spinning of the excess. Electrical measurement of the second derivative of voltage with respect to current, as a function of applied voltage, then gives a spectrum of vibrational modes equivalent to an infrared or Raman spectrum, but with the use of only micrograms of sample.     

Cytogenetic studies with cyclamate and related compounds

Cyclamate, cyclohexylamine, N-hydroxycyclohexylamine, and dicyclohexylamine can induce chromosomal damage in human leukocyte cultures.     

New quaternary ammonium compounds with adrenomimetic action

Quaternary salts of two triesters of p-dimethylaminothiophenol and phosphoric acid or thiophosphoric acid have effects similar to epinephrine on blood pressure, heart rate, and the nictitating membrane of the anesthetized cat. Two analogous compounds derived from phenol are depressor. None is a potent anticholinesterase. Further investigation is desirable because of the possibility of a relatively specific action on sympathetic ganglia.     

2—甲氧基—5—硝基苯酚合成工艺及其应用的研究

探讨了２－甲氧基－５－硝基苯酚合成新工艺和其在农业上应用，以２－甲氧基苯酚为原料，经４步反应，在６ｈ内合成２－甲氧基－５－硝基苯酚，经测试表明，其产物收率６３％，纯度大于９９％，将２－甲氧基－５－硝基苯酚和其它原料一起配制的ＮＭＰ植物制剂进行应用试验，对蔬菜具有促进发芽，提早开花，延长生育期，提高蔬菜产量的功效，使用浓度以５０００～６０００倍液为宜。     

加氢反应器裙座支撑结构的有限元分析

加氢反应器裙座支撑结构部位的机械应力和温差应力均较大,应力状况较为恶劣。对加氢反应器裙座支撑局部结构进行了温度场分析,采用间接分析法将所得温度场施加到结构上进行热应力分析。根据不同温度点的单向拉伸试验得到材料在各温度点下的应力一应变曲线,采用线弹性和弹塑性两种材料本构分别对加氢反应器裙座支撑结构进行有限元计算。将计算结果进行对比分析,表明弹塑性有限元计算结果更加精确。此外,根据ASMEVIII-22007关于两种方法的失效评定内容对该结构局部失效的可能性进行了评定计算。对比研究表明,基于线弹性有限元计算结果虽可用于工程设计,但其最大应力部位与实际情况并不一致,因此分析设计计算方法仍有改进的空间。（图6,表1,参10）     

Low-temperature synthesis of zintl compounds with a single-source molecular precursor

Thermolysis of the heterobimetallic phosphinidene complex [Sb(PCy)3]2- Li6.6HNMe2 (Cy = C6H11) at 303 to 313 kelvin gives Zintl compounds containing (Sb7)3- anions. The complex thus constitutes a stable molecular single-source precursor to Zintl compounds and provides a potential low-temperature route to photoactive alkali metal antimonates. The new chemical reaction involved, which is driven thermodynamically by the formation of P-P bonds, has implications in the low-temperature synthesis of other technologically important materials (such as gallium arsenide).