Iron catalysts for selective anti-Markovnikov alkene hydrosilylation using tertiary silanes

Alkene hydrosilylation, the addition of a silicon hydride (Si-H) across a carbon-carbon double bond, is one of the largest-scale industrial applications of homogeneous catalysis and is used in the commercial production of numerous consumer goods. For decades, precious metals, principally compounds of platinum and rhodium, have been used as catalysts for this reaction class. Despite their widespread application, limitations such as high and volatile catalyst costs and competing side reactions have persisted. Here, we report that well-characterized molecular iron coordination compounds promote the selective anti-Markovnikov addition of sterically hindered, tertiary silanes to alkenes under mild conditions. These Earth-abundant base-metal catalysts, coordinated by optimized bis(imino)pyridine ligands, show promise for industrial application.     

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.     

钙钛矿催化剂用于氨选择性还原氮氧化物的研究进展

氨选择性催化还原氮氧化物(NO_x)技术是目前应用较为广泛的催化脱硝技术,钙钛矿材料因其独特的结构、良好的稳定性且环保无害的特点成为选择性催化还原NO_x领域的研究热点。本文综述了近年来国内外关于钙钛矿NH_3-SCR催化剂的研究进展,较为全面地对钙钛矿催化剂的主要类型、脱硝活性、构效关系进行了论述,同时介绍了钙钛矿在光辅助SCR技术这一全新领域的研究进展,并总结了钙钛矿催化剂的NH_3-SCR反应机制,对该领域未来可能的发展方向和研究目标进行了展望。     

Platinum catalysts for the high-yield oxidation of methane to a methanol derivative

Platinum catalysts are reported for the direct, low-temperature, oxidative conversion of methane to a methanol derivative at greater than 70 percent one-pass yield based on methane. The catalysts are platinum complexes derived from the bidiazine ligand family that are stable, active, and selective for the oxidation of a carbon-hydrogen bond of methane to produce methyl esters. Mechanistic studies show that platinum(II) is the most active oxidation state of platinum for reaction with methane, and are consistent with reaction proceeding through carbon-hydrogen bond activation of methane to generate a platinum-methyl intermediate that is oxidized to generate the methyl ester product.     

A predictably selective aliphatic C-H oxidation reaction for complex molecule synthesis

Realizing the extraordinary potential of unactivated sp3 C-H bond oxidation in organic synthesis requires the discovery of catalysts that are both highly reactive and predictably selective. We report an iron (Fe)-based small molecule catalyst that uses hydrogen peroxide (H2O2) to oxidize a broad range of substrates. Predictable selectivity is achieved solely on the basis of the electronic and steric properties of the C-H bonds, without the need for directing groups. Additionally, carboxylate directing groups may be used to furnish five-membered ring lactone products. We demonstrate that these three modes of selectivity enable the predictable oxidation of complex natural products and their derivatives at specific C-H bonds with preparatively useful yields. This type of general and predictable reactivity stands to enable aliphatic C-H oxidation as a method for streamlining complex molecule synthesis.     

Inorganic pyrophosphate: formation in bacterial photophosphorylation

Inorganic pyrophosphate is identified as the major product of photophosphorylation by isolated chromatophores from Rhodospirillum rubrum in the absence of added nucleotides.     

低温空气氧化生物炭吸附苯系污染物的作用机制

为进一步明晰低温空气氧化生物炭吸附苯系污染物的作用机制,以竹屑为原料、CaCl₂为活化剂,通过两步活化法制备低温空气氧化生物炭,并综合吸附试验、炭结构表征和密度泛函理论（density functional theory, DFT）计算,解析低温空气氧化生物炭吸附苯酚、苯胺、对苯二酚、对硝基苯酚等4种苯系污染物的过程与行为。结果表明：低温空气氧化生物炭对苯系污染物的吸附性能受生物炭孔隙结构和表面官能团的协同作用影响,生物炭通过微孔结构的孔隙填充作用在空间几何尺度调控苯系污染物的吸附存储过程。低温空气氧化生物炭后,氧原子以羟基、醛基和羧基的形式赋存于生物炭碳骨架表面,从电子尺度影响碳骨架的电子结构排布、改变碳骨架与苯系污染物间的吸附位置及作用类型,通过静电引力及氢键等作用,显著增强生物炭对苯系污染物的吸附能力,其中,羟基和羧基的氢原子作为氢键的供体,醛基的氧原子作为氢键的受体。     

Inorganic pyrophosphate: energy source for sulfate-reducing bacteria of the genus desulfotomaculum

Sulfate-reducing bacteria belonging to the genus Desulfotomaculum utilized inorganic pyrophosphate as a source of energy for growth in the presence of fixed carbon (acetate and yeast extract) and sulfate. Pyrophosphate does not support the growth of Desulfovibrio under the same growth conditions. Over a limited range of concentrations, growth is proportional to pyrophosphate, and extracts of bacteria grown on pyrophosphate medium have enzymatic activities similar to extracts prepared from bacteria grown on medium containing lactate plus sulfate. The variety of cell types observed in crude anaerobic pyrophosphate-enrichment cultures from a marine environment suggests that this unique type of energy metabolism is not restricted to the sulfate-reducing bacteria of the genus Desulfotomaculum.     

Nitric oxide reduction coupled with carbon monoxide oxidation in the presence of soluble metal catalysts

Solutions of RhCl(3).xH(2)O in ethanol and Ru(NO)(2)[P(C(6)H(5))(3)](2) in benzene catalyze the reduction of nitric oxide to nitrous oxide concomitant with the oxidation of carbon monoxide to carbon dioxide at ambient temperature and atmospheric pressure. The reaction, which is followed by gas chromatography and by the decrease in pressure of the system, proceeds to 47 percent conversion of the reactants after 63 hours.     

Stereoselective organic reactions: catalysts for carbonyl addition processes

Important advances are being made in the development of stereoselective organic reactions. Some of the emerging research directions that hold forth great promise in this area deal with the development of chiral catalysts for these processes. This review attempts to unify one aspect of this field, the development of catalysts and catalyst models for the enantioselective addition of hydride and carbon nucleophiles to carbonyl substrates. Mechanistic constructs for the stereodifferentiating transition states are provided.     

Freon consumption: implications for atmospheric ozone

Freons are a potential source of stratospheric chlorine and may indirectly cause serious reductions in the concentration of ozone. The reduction could be as large as 3 percent by 1980, or 16 percent by 2000, if Freon consumption were to grow at 10 percent per year. Even if Freon use were terminated as early as 1990, it could leave a significant effect which might endure for several hundred years.     

赤霉素高产菌株选育及其固态发酵研究进展

目前,工业大规模赤霉素生产采用液体深层发酵技术,但存在成本高、能耗大、环境不友好等突出问题。选育赤霉素高产菌株是提高赤霉素产量、降低生产成本的重要手段。同时,固态发酵技术以其独特优势在近30 a来重获关注,赤霉素固态发酵研究因此取得很大进展。综述了赤霉素产生菌的单一诱变、复合诱变、原生质体诱变手段,以及筛选稳定高产突变株的方法,总结了赤霉素固态发酵培养基种类以及固态发酵控制条件,并展望赤霉素固态发酵的巨大潜力。     

Sex differences in the brain: implications for explaining autism

Empathizing is the capacity to predict and to respond to the behavior of agents (usually people) by inferring their mental states and responding to these with an appropriate emotion. Systemizing is the capacity to predict and to respond to the behavior of nonagentive deterministic systems by analyzing input-operation-output relations and inferring the rules that govern such systems. At a population level, females are stronger empathizers and males are stronger systemizers. The "extreme male brain" theory posits that autism represents an extreme of the male pattern (impaired empathizing and enhanced systemizing). Here we suggest that specific aspects of autistic neuroanatomy may also be extremes of typical male neuroanatomy.     

University-industry research relationships in biotechnology: implications for the university

The growth of university-industry research relationships in biotechnology has raised questions concerning their effects, both positive and negative, on universities. A survey of over 1200 faculty members at 40 major universities in the United States reveals that biotechnology researchers with industrial support publish at higher rates, patent more frequently, participate in more administrative and professional activities and earn more than colleagues without such support. At the same time, faculty with industry funds are much more likely than other biotechnology faculty to report that their research has resulted in trade secrets and that commercial considerations have influenced their choice of research projects. Although the data do not establish a causal connection between industrial support and these faculty behaviors, our findings strongly suggest that university-industry research relationships have both benefits and risks for academic institutions. The challenge for universities is to find ways to manage these relationships that will preserve the benefits while minimizing the risks.     

Field-based evidence for devolatilization in subduction zones: implications for arc magmatism

Metamorphic rocks on Santa Catalina Island, California, afford examination of fluid-related processes at depths of 15 to 45 kilometers in an Early Cretaceous subduction zone. A combination of field, stable isotope, and volatile content data for the Catalina Schist indicates kilometer-scale transport of large amounts of water-rich fluid with uniform oxygen and hydrogen isotope compositions. The fluids were liberated in devolatilizing, relatively low-temperature (400 degrees to 600 degrees C) parts of the subduction zone, primarily by chlorite-breakdown reactions. An evaluation of pertinent phase equilibria indicates that chlorite in mafic and sedimentary rocks and melange may stabilize a large volatile component to great depths (perhaps >100 kilometers), depending on the thermal structure of the subduction zone. This evidence for deep volatile subduction and large-scale flow of slab-derived, water-rich fluids lends credence to models that invoke fluid addition to sites of arc magma genesis.     

Copper: relation to penicillamine-induced defect in collagen

When rats were depleted of copper by administration of a copperdeficient diet, no abnormalities developed in dermal collagen. In contrast, marked changes were produced by penicillamine although the degree of copperdeficiency induced by the drug was less. Large additions of copper to the diet failed to prevent the penicillamine-induced collagen defect when the drug was given parenterally. The effect of penicillamine on soft-tissue collagen appears to be unrelated to its copper-chelating properties.     

Exhaust catalysts: appropriate conditions for comparing platinum and base metal

There are fundamental differences in the behavior of alumina-supported samples of a platinum and a copper-chromium catalyst for oxidation of carbon monoxide in a simulated automotive exhaust stream. Ignoring such differences can result in inappropriate comparisons between oxidation catalysts for automotive application.