Halodehydroxylation of alcohols to yield benzylic and alkyl halides in ionic liquids

Background: Alcohols are widely used, and sometimes renewable, reagents but the hydroxyl moiety is a relatively poor leaving group under mild conditions. Direct nucleophilic substitution of alcohols is a desirable reaction for synthetic and process chemists. Results: Synthesis of twelve alkyl and benzyl halides was achieved in [Bmim]PF6 (Bmim = 1-butyl-3 methylimidazolium) from their parent alcohols using ammonium halides as the halogenating agents. Trends in reactivity based on the alcohol and halide were discovered. Mechanistic evidence suggests that the reaction proceeds via SN2 substitution of the hydroxyl group, which is activated via hydrogen-bonding with the acidic proton of the imidazolium cation. Also, for benzyl substrates, equilibria involving formation of dibenzyl ether complicate the reactions and reduce optimum yields. Conclusions: Ammonium halides are useful, solid and relatively safe reagents for the conversion of some primary alcohols to organohalides in ionic liquids (yields up to 81 %). Indanol under the same conditions yields biindenylidene (GC yield 63 %)

Multi-wavelength analysis of the dust emission in the Small Magellanic Cloud

We present an analysis of dust grain emission in the diffuse interstellar medium of the Small Magellanic Cloud (SMC). This study is motivated by the availability of 170 microns ISOPHOT data covering a large part of the SMC, with a resolution enabling to disentangle the diffuse medium from the star forming regions. After data reduction and subtraction of Galactic foreground emission, we used the ISOPHOT data together with HiRes IRAS data and ATCA/Parkes combined HI column density maps to determine dust properties for the diffuse medium. We found a far infrared emissivity per hydrogen atom 30 times lower than the Solar Neighborhood value. The modeling of the spectral energy distribution of the dust, taking into account the enhanced interstellar radiation field, gives a similar conclusion for the smallest grains (PAHs and very small grains) emitting at shorter wavelength. Assuming Galactic dust composition in the SMC, this result implies a difference in the gas-to-dust ratio (GDR) 3 times larger than the difference in metallicity. This low depletion of heavy elements in dust could be specific of the diffuse ISM and not apply for the whole SMC dust if it results from efficient destruction of dust by supernovae explosions.Comment: 11 pages, 10 figures. Accepted for publication in Astronomy & Astrophysic

The HII Region KR 140: Spontaneous Formation of a High Mass Star

We have used a multiwavelength data set from the Canadian Galactic Plane Survey (CGPS) to study the Galactic HII region KR 140, both on the scale of the nebula itself and in the context of the star forming activity in the nearby W3/W4/W5 complex of molecular clouds and HII regions. From both radio and infrared data we have found a covering factor of about 0.5 for KR 140 and we interpret the nebula as a bowl-shaped region viewed close to face on. Extinction measurements place the region on the near side of its parent molecular cloud. The nebula is kept ionized by one O8.5 V(e) star, VES 735, which is less than a few million years old. CO data show that VES 735 has disrupted much of the original molecular cloud for which the estimated mass and density are about 5000 $M_{\odot}$ and 100 cm$^{-3}$, respectively. KR 140 is isolated from the nearest star forming activity, in W3. Our data suggest that KR 140 is an example of spontaneous (i.e., non-triggered) formation of, unusually, a high mass star.Comment: 46 pages; includes 15 figures; accepted by the Ap

The SPECFIND V2.0 catalogue of radio cross-identifications and spectra. SPECFIND meets the Virtual Observatory

The new release of the SPECFIND radio cross-identification catalogue, SPECFIND V2.0, is presented. It contains 107488 cross-identified objects with at least three radio sources observed at three independent frequencies. Compared to the previous release the number of entry radio catalogues is increased from 20 to 97 containing 115 tables. This large increase was only made possible by the development of four tools at CDS which use the standards and infrastructure of the Virtual Observatory (VO). This was done in the framework of the VO-TECH European Design Study of the Sixth Framework Program. We give an overview of the different classes of radio sources that a user can encounter. Due to the increase of frequency coverage of the input radio catalogues, this release demonstrates that the SPECFIND algorithm is able to detect spectral breaks around a frequency of ~1 GHz.Comment: 11 pages, 10 figures, accepted for publication in A&

The faint supernova remnant G 116.5+1.1 and the detection of a new candidate remnant

The extended supernova remnant G 116.5+1.1 was observed in the optical emission lines of Halpha+[N II], [S II] and [O III]; deep long-slit spectra were also obtained. The morphology of the remnant's observed emission is mainly diffuse and patchy in contrast to the known filamentary emission seen along the western limb. The bulk of the detected emission in the region appears unrelated to the remnant but there is one area of emission in the south-east which is characterized by a [S II]/Halpha ratio of ~0.5, implying a possible relation to G 116.5+1.1. If this is actually the case, it would imply a more extended remnant than previously realized. Emission in the [O III] 5007 A line image is not detected, excluding moderate or fast velocity shocks running into ionized interstellar clouds. Our current estimate of the distance to G 116.5+1.1 of ~3 kpc is in agreement with earlier estimates and implies a very extended remnant (69 pc x 45 pc). Observations further to the north-east of G 116.5+1.1 revealed a network of filamentary structures prominent in Halpha+[N II] and [S II] but failed to detect [O III] line emission. Long-slit spectra in a number of positions provide strong evidence that this newly detected emission arises from shock heated gas. Typical Halpha fluxes lie in the range of 9 to 17 x10^{-17} erg/s/cm^2/ arcsec^2, while low electron densities are implied by the intensities of the sulfur lines. Weak emission from the medium ionization line at 5007 A is detected in only one spectrum. Cool dust emission at 60 and 100 microns may be correlated with the optical emission in a limited number of positions. Surpisingly, radio emission is not detected in published surveys suggesting that the new candidate remnant may belong to the class of "radio quiet" supernova remnants.Comment: 10 pages, 5 figures, accepted for publication in A&

Assessment of F/HN-Pseudotyped Lentivirus as a Clinically Relevant Vector for Lung Gene Therapy

RATIONALE: Ongoing efforts to improve pulmonary gene transfer thereby enabling gene therapy for the treatment of lung diseases, such as cystic fibrosis (CF), has led to the assessment of a lentiviral vector (simian immunodeficiency virus [SIV]) pseudotyped with the Sendai virus envelope proteins F and HN. OBJECTIVES: To place this vector onto a translational pathway to the clinic by addressing some key milestones that have to be achieved. METHODS: F/HN-SIV transduction efficiency, duration of expression, and toxicity were assessed in mice. In addition, F/HN-SIV was assessed in differentiated human air-liquid interface cultures, primary human nasal epithelial cells, and human and sheep lung slices. MEASUREMENTS AND MAIN RESULTS: A single dose produces lung expression for the lifetime of the mouse (~2 yr). Only brief contact time is needed to achieve transduction. Repeated daily administration leads to a dose-related increase in gene expression. Repeated monthly administration to mouse lower airways is feasible without loss of gene expression. There is no evidence of chronic toxicity during a 2-year study period. F/HN-SIV leads to persistent gene expression in human differentiated airway cultures and human lung slices and transduces freshly obtained primary human airway epithelial cells. CONCLUSIONS: The data support F/HN-pseudotyped SIV as a promising vector for pulmonary gene therapy for several diseases including CF. We are now undertaking the necessary refinements to progress this vector into clinical trials

GASKAP -- The Galactic ASKAP Survey

A survey of the Milky Way disk and the Magellanic System at the wavelengths of the 21-cm atomic hydrogen (HI) line and three 18-cm lines of the OH molecule will be carried out with the Australian Square Kilometre Array Pathfinder telescope. The survey will study the distribution of HI emission and absorption with unprecedented angular and velocity resolution, as well as molecular line thermal emission, absorption, and maser lines. The area to be covered includes the Galactic plane (|b|< 10deg) at all declinations south of delta = +40deg, spanning longitudes 167deg through 360deg to 79deg at b=0deg, plus the entire area of the Magellanic Stream and Clouds, a total of 13,020 square degrees. The brightness temperature sensitivity will be very good, typically sigma_T ~ 1 K at resolution 30arcsec and 1 km/s. The survey has a wide spectrum of scientific goals, from studies of galaxy evolution to star formation, with particular contributions to understanding stellar wind kinematics, the thermal phases of the interstellar medium, the interaction between gas in the disk and halo, and the dynamical and thermal states of gas at various positions along the Magellanic Stream.Comment: 45 pages, 8 figures, Pub. Astron. Soc. Australia (in press

Star formation in the Vela Molecular Ridge. Large scale mapping of cloud D in the mm continuum

The Vela Molecular Ridge is one of the nearest intermediate-mass star forming regions, located within the galactic plane and outside the solar circle. Cloud D, in particular, hosts a number of small embedded young clusters. We present the results of a large-scale map in the dust continuum at 1.2 mm of a ~ 1deg x 1deg area within cloud D. The main aim of the observations was to obtain a complete census of cluster-forming cores and isolated (both high- and low-mass) young stellar objects in early evolutionary phases. The bolometer array SIMBA at SEST was used to map the dust emission in the region with a typical sensitivity of ~ 20 mJy/beam. This allows a mass sensitivity of ~ 0.2 Msun. The resolution is 24 arcsec, corresponding to ~ 0.08 pc, roughly the radius of a typical young embedded cluster in the region. The continuum map is also compared to a large scale map of CO(1-0) integrated emission. Using the CLUMPFIND algorithm, a robust sample of 29 cores has been obtained, spanning the size range 0.03 - 0.25 pc and the mass range 0.4 - 88 Msun. The most massive cores are associated both with red IRAS sources and with embedded young clusters, and coincide with CO(1-0) integrated emission peaks. The cores are distributed according to a mass spectrum ~ M^{-alpha} and a mass-versus-size relation ~ D^{x}, with alpha ~ 1.45 - 1.9 and x ~ 1.1 - 1.7. They appear to originate in the fragmentation of gas filaments seen in CO(1-0) emission and their formation is probably induced by expanding shells of gas. The core mass spectrum is flatter than the Initial Mass Function of the associated clusters in the same mass range, suggesting further fragmentation within the most massive cores. A threshold A_V ~ 12 mag seems to be required for the onset of star formation in the gas.Comment: 13 pages, 11 figures, to be published in Astronomy and Astrophysic

Ultrafast All-Polymer Paper-Based Batteries

Conducting polymers for battery applications have been subject to numerous investigations during the last two decades. However, the functional charging rates and the cycling stabilities have so far been found to be insufficient for practical applications. These shortcomings can, at least partially, be explained by the fact that thick layers of the conducting polymers have been used to obtain sufficient capacities of the batteries. In the present letter, we introduce a novel nanostructured high-surface area electrode material for energy storage applications composed of cellulose fibers of algal origin individually coated with a 50 nm thin layer of polypyrrole. Our results show the hitherto highest reported charge capacities and charging rates for an all polymer paper-based battery. The composite conductive paper material is shown to have a specific surface area of 80 m2 g-1 and batteries based on this material can be charged with currents as high as 600 mA cm-2 with only 6 % loss in capacity over 100 subsequent charge and discharge cycles. The aqueous-based batteries, which are entirely based on cellulose and polypyrrole and exhibit charge capacities between 25 and 33 mAh g-1 or 38-50 mAh g-1 per weight of the active material, open up new possibilities for the production of environmentally friendly, cost efficient, up-scalable and lightweight energy storage systems. There is currently a great interest in the development of thin, flexible, lightweight, and environmentally friendly batteries and supercapacitors.1 In this process, the preparation of novel redox polymer and electronically conducting polymer-base

Tools and techniques for solvent selection: green solvent selection guides

Driven by legislation and evolving attitudes towards environmental issues, establishing green solvents for extractions, separations, formulations and reaction chemistry has become an increasingly important area of research. Several general purpose solvent selection guides have now been published with the aim to reduce use of the most hazardous solvents. This review serves the purpose of explaining the role of these guides, highlighting their similarities and differences. How they can be used most effectively to enhance the greenness of chemical processes, particularly in laboratory organic synthesis and the pharmaceutical industry, is addressed in detail