Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes

Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal

Modifying Polyester Surfaces with Incompatible Polymer Additives

Surface modification of amorphous PET in incompatible blends is demonstrated using fluorocarbon end-functional polystyrenes. Contact angles with water and decane were consistent with high levels of surface fluorocarbon, even for spin-cast films with no further processing required. Hydrophobicity and lipophobicity were further increased by annealing above the glass transition temperature. High resolution depth profiling using complementary ion beam analysis and specular neutron reflectometry has enabled accurate characterisation of the composition profile of the additive including the minimum in additive concentration found just below the surface enriched layer. This analysis quantified the very low compatibility between the modifying polymer and the amorphous PET and was consistent with the highly segregated nature of the adsorbing species and its sharp interface with the subphase. For these incompatible polymer blends, surfaces enriched with the surface active polymer could coexist at equilibrium with extremely low (∼0.4%) bulk loadings of the additive. This suggests that for thicker films at even lower additive concentrations than the minimum 1% that we studied, it may be possible to achieve efficient surface modification. However, at this concentration, the efficiency of surface modification is limited by the processing conditions. Finally we note that in higher loadings of surface active additive there is clear evidence for lateral phase separation into patterned domains of differing composition. The enhancement in surface properties is due to local reorganisation rather than bulk redistribution of the components within the film, as the composition versus depth distributions of the polymer blend components was observed to be relatively unaffected by annealing

A Pair of Compact Red Galaxies at Redshift 2.38, Immersed in a 100 kpc Scale Ly-alpha Nebula

We present Hubble Space Telescope (HST) and ground-based observations of a pair of galaxies at redshift 2.38, which are collectively known as 2142-4420 B1 (Francis et al. 1996). The two galaxies are both luminous extremely red objects (EROs), separated by 0.8 arcsec. They are embedded within a 100 kpc scale diffuse Ly-alpha nebula (or blob) of luminosity ~10^44 erg/s. The radial profiles and colors of both red objects are most naturally explained if they are young elliptical galaxies: the most distant yet found. It is not, however, possible to rule out a model in which they are abnormally compact, extremely dusty starbursting disk galaxies. If they are elliptical galaxies, their stellar populations have inferred masses of ~10^11 solar masses and ages of ~7x10^8 years. Both galaxies have color gradients: their centers are significantly bluer than their outer regions. The surface brightness of both galaxies is roughly an order of magnitude greater than would be predicted by the Kormendy relation. A chain of diffuse star formation extending 1 arcsec from the galaxies may be evidence that they are interacting or merging. The Ly-alpha nebula surrounding the galaxies shows apparent velocity substructure of amplitude ~ 700 km/s. We propose that the Ly-alpha emission from this nebula may be produced by fast shocks, powered either by a galactic superwind or by the release of gravitational potential energy.Comment: 33 pages, 9 figures, ApJ in press (to appear in Jun 10 issue

The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site

Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology

The Structure of the Accretion Disk in the ADC X-Ray Binary 4U 1822-371 at Optical and Ultraviolet Wavelengths

The eclipsing low-mass X-ray binary 4U 1822-371 is the prototypical accretion disk corona (ADC) system. We have obtained new time-resolved UV spectroscopy of 4U 1822-371 with the Advanced Camera for Surveys/Solar Blind Channel (ACS/SBC) on the Hubble Space Telescope (HST) and new V- and J-band photometry with the 1.3-m SMARTS telescope at CTIO. We use the new data to construct its UV/optical spectral energy distribution and its orbital light curve in the UV, V, and J bands. We derive an improved ephemeris for the optical eclipses and confirm that the orbital period is changing rapidly, indicating extremely high rates of mass flow in the system; and we show that the accretion disk in the system has a strong wind with projected velocities up to 4000 km/s. We show that the disk has a vertically-extended, optically-thick component at optical wavelengths.This component extends almost to the edge of the disk and has a height equal to ~0.5 of the disk radius. As it has a low brightness temperature, we identify it as the optically-thick base of a disk wind, not as the optical counterpart of the ADC. Like previous models of 4U 1822-371, ours needs a tall obscuring wall near the edge of the accretion disk, but we interpret the wall as a layer of cooler material at the base of the disk wind, not as a tall, luminous disk rim.Comment: 37 pages, 12 figures, submitted to Ap

Efficient green methanol synthesis from glycerol

The production of biodiesel from the transesterification of plant-derived triglycerides with methanol has been commercialized extensively. Impure glycerol is obtained as a by-product at roughly one-tenth the mass of the biodiesel. Utilization of this crude glycerol is important in improving the viability of the overall process. Here we show that crude glycerol can be reacted with water over very simple basic or redox oxide catalysts to produce methanol in high yields, together with other useful chemicals, in a one-step low-pressure process. Our discovery opens up the possibility of recycling the crude glycerol produced during biodiesel manufacture. Furthermore, we show that molecules containing at least two hydroxyl groups can be converted into methanol, which demonstrates some aspects of the generality of this new chemistry

El signo verbal y no verbal: punto de partida del proceso integrador y totalizador de la enseñanza de la lengua materna

Based on the principle that the teaching-learning process requires the integration of all the elements that participate in the process, we propose here to offer an explanation based on didactic semiotics as to the need to consider gestures, voice tones, contact and other signs as part of this integrative, totalizing and contextual process on which the teaching of the mother tongue should be based. This paper is based on observation made in class rooms which utilized an instrument developed to observe whether the non-verbal sign was taken into account in the teaching process. The purpose of this study is to demonstrate that neither the verbal nor the non-verbal sign is considered in the class room when language or any other subject is taught, since they transmit explicit and implicit messages received by the students which influence learning.Sustentado en el principio de que el proceso de enseñar y aprender necesita de la integración de todos los elementos que participan en dicho proceso se pretende, a través de este trabajo, dar una explicación sustentada en la semiótica didáctica sobre la necesidad de considerar los gestos, el tono de voz, el contacto y otros signos como parte de ese proceso integrador, totalizador y contextualizado en que debe fundamentarse la enseñanza de la lengua materna. Este trabajo se desarrolla a partir de las observaciones realizadas en las aulas de clases donde mediante la aplicación de un instrumento se pudo observar que el signo no verbal no es tomado en cuenta en el proceso de enseñanza. Se propone en este estudio demostrar que tanto el signo verbal como el signo no verbal deben ser considerados en el salón de clase al momento de enseñar lengua u otra asignatura, puesto que transmiten mensajes explícitos e implícitos que son recibidos por los alumnos e inciden en el aprendizaj

The FIRST-2MASS Red Quasar Survey II: An anomalously high fraction of LoBALs in searches for dust-reddened quasars

We present results on a survey to find extremely dust-reddened Type-1 Quasars. Combining the FIRST radio survey, the 2MASS Infrared Survey and the Sloan Digital Sky Survey, we have selected a candidate list of 122 potential red quasars. With more than 80% spectroscopically identified objects, well over 50% are classified as dust-reddened Type 1 quasars, whose reddenings (E(B-V)) range from approximately 0.1 to 1.5 magnitudes. They lie well off the color selection windows usually used to detect quasars and many fall within the stellar locus, which would have made it impossible to find these objects with traditional color selection techniques. The reddenings found are much more consistent with obscuration happening in the host galaxy rather than stemming from the dust torus. We find an unusually high fraction of Broad Absorption Line (BAL) quasars at high redshift, all but one of them belonging to the Low Ionization BAL (LoBAL) class and many also showing absorption the metastable FeII line (FeLoBAL). The discovery of further examples of dust-reddened LoBAL quasars provides more support for the hypothesis that BAL quasars (at least LoBAL quasars) represent an early stage in the lifetime of the quasar. The fact that we see such a high fraction of BALs could indicate that the quasar is in a young phase in which quasar feedback from the BAL winds is suppressing star formation in the host galaxy.Comment: 17 pages, 7 figures, accepted for publication in Ap