Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions

Oxidation is an important method for the synthesis of chemical intermediates in the manufacture of high-tonnage commodities, high-value fine chemicals, agrochemicals and pharmaceuticals: but oxidations are often inefficient. The introduction of catalytic systems using oxygen from air is preferred for 'green' processing. Gold catalysis is now showing potential in selective redox processes, particularly for alcohol oxidation and the direct synthesis of hydrogen peroxide. However, a major challenge that persists is the synthesis of an epoxide by the direct electrophilic addition of oxygen to an alkene. Although ethene is epoxidized efficiently using molecular oxygen with silver catalysts in a large-scale industrial process, this is unique because higher alkenes can only be effectively epoxidized using hydrogen peroxide, hydroperoxides or stoichiometric oxygen donors. Here we show that nanocrystalline gold catalysts can provide tunable active catalysts for the oxidation of alkenes using air, with exceptionally high selectivity to partial oxidation products ( approximately 98%) and significant conversions. Our finding significantly extends the discovery by Haruta that nanocrystalline gold can epoxidize alkenes when hydrogen is used to activate the molecular oxygen; in our case, no sacrificial reductant is needed. We anticipate that our finding will initiate attempts to understand more fully the mechanism of oxygen activation at gold surfaces, which might lead to commercial exploitation of the high redox activity of gold nanocrystals.     

The suppression of star formation by powerful active galactic nuclei

The old, red stars that constitute the bulges of galaxies, and the massive black holes at their centres, are the relics of a period in cosmic history when galaxies formed stars at remarkable rates and active galactic nuclei (AGN) shone brightly as a result of accretion onto black holes. It is widely suspected, but unproved, that the tight correlation between the mass of the black hole and the mass of the stellar bulge results from the AGN quenching the surrounding star formation as it approaches its peak luminosity. X-rays trace emission from AGN unambiguously, whereas powerful star-forming galaxies are usually dust-obscured and are brightest at infrared and submillimetre wavelengths. Here we report submillimetre and X-ray observations that show that rapid star formation was common in the host galaxies of AGN when the Universe was 2-6 billion years old, but that the most vigorous star formation is not observed around black holes above an X-ray luminosity of 10(44) ergs per second. This suppression of star formation in the host galaxy of a powerful AGN is a key prediction of models in which the AGN drives an outflow, expelling the interstellar medium of its host and transforming the galaxy's properties in a brief period of cosmic time.     

湖南丫江桥花岗岩中锆石的Hf同位素地球化学

在丫江桥过铝花岗岩中, 锆石可以分作两期, 分别形成于岩浆定位前的深部岩浆房内和岩浆定位后的侵入部位. 这两期锆石的原位Hf同位素分析揭示, 该花岗岩浆主要来自地壳物质的深部熔融. 然而, 部分较高的¹⁷⁶Hf/¹⁷⁷Hf数据表明, 这些花岗质锆石中可能包裹了形成于幔源岩浆的细小锆石(其粒径小于激光束斑). 事实上, 背散射电子图像和电子探针分析显示, 在部分第1期锆石内部存在着另一种形态和成分不同的锆石晶体, 它们可能是在花岗质岩浆形成初期混入的幔源岩浆中的结晶产物. 因此, 推测丫江桥过铝花岗岩的产生与地幔岩浆的底侵作用有联系.     

Grenvillian orogeny in the Southern Cathaysia Block: Constraints from U-Pb ages and Lu-Hf isotopes in zircon from metamorphic basement

Metamorphic basement rocks in the Cathaysia Block are composed mainly of meta-sediments with different ages. New zircon U-Pb geochronological results from the meta-sedimentary rocks exposed in the Zengcheng and Hezi areas, southern Cathaysia Block, show that they consist dominantly of early Neoproterozoic （1.0-0.9 Ga） materials with minor Paleo- to Mesoproterozoic and late Neoproterozoic （0.8-0.6 Ga） components, suggesting that the detritus mostly come from a Grenvillian orogen. The youngest detrital zircon ages place a constraint on the deposition time of these sediments in Late Neoproterozoic. Zircon Hf isotopic compositions indicate that the Grenvillian zircons were derived from the reworking of Mesoproterozoic arc magmatic rocks and Paleoproterozoic continental crust, implying an arc-continent collisional setting. Single-peak age spectra and the presence of abundant euhedral Grenvillian zircons suggest that the sedimentary provenance is not far away from the sample location. Thus, the Grenvillian orogen probably preexisted along the southern margin of the Cathaysia Block, or very close to the south. Similarity in the ages of Grenvillian orogeny and the influence of the assembly of Gondwana in South China with India and East Antarctic are discussed, with suggestion that South China was more likely linked with the India-East Antarctica continents in Early Neoproterozoic rather than between western Laurentia and eastern Australia.