Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium

The reversible reaction of H(2)with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H(2)and yields a spectroscopically detectable phosphenium-stabilized (sigma-H-2)-complex, readily showing exchange with gaseous H(2)and D-2. Further reaction of this complex affords a phosphine-functionalized metal hydride, representing a unique example of reversible H(2)cleavage across a 3d MP bond. The same species is also accessibleviastepwise H+/H(-)transfer to the bis-phosphenium complex, and releases H(2)upon heating or irradiation. Dihydrogen transfer from the H-2-complex to styrene is exploited to demonstrate the first example of promoting hydrogenation with a phosphenium complex.Peer reviewe

Using Raman Spectroscopy to Improve Hyperpolarized Noble Gas Production for Clinical Lung Imaging Techniques

Spin-exchange optical pumping (SEOP) can be used to “hyperpolarize” 129Xe for human lung MRI. SEOP involves transfer of angular momentum from light to an alkali metal (Rb) vapor, and then onto 129Xe nuclear spins during collisions; collisions between excited Rb and N2 ensure that incident optical energy is nonradiatively converted into heat. However, because variables that govern SEOP are temperature-dependent, the excess heat can complicate efforts to maximize spin polarization—particularly at high laser fluxes and xenon densities. Ultra-low frequency Raman spectroscopy may be used to perform in situ gas temperature measurements to investigate the interplay of energy thermalization and SEOP dynamics. Experimental configurations include an “orthogonal” pump-and-probe design and a newer “inline” design (with source and detector on the same axis) that has provided a >20-fold improvement in SNR. The relationship between 129Xe polarization and the spatiotemporal distribution of N2 rotational temperatures has been investigated as a function of incident laser flux, exterior cell temperature, and gas composition. Significantly elevated gas temperatures have been observed—hundreds of degrees hotter than exterior cell surfaces—and variances with position and time can indicate underlying energy transport, convection, and Rb mass-transport processes that, if not controlled, can negatively impact 129Xe hyperpolarization

A test of coding procedures for lexical data with Tup i-Guaran i and Chapacuran languages

Recent phylogenetic studies in historical linguistics have focused on lexical data. However, the way that such data are coded into characters for phylogenetic analysis has been approached in different ways, without investigating how coding methods may affect the results. In this paper, we compare three different coding methods for lexical data (multistate meaning-based characters, binary root-meaning characters, and binary cognate characters) in a Bayesian framework, using data from the Tup ́ı-Guaran ́ı and Chapacuran language families as case studies. We show that, contrary to prior expectations, different coding methods can have a significant impact on the topology of the resulting trees

The Sydney-AAO Multi-object Integral field spectrograph (SAMI)

We demonstrate a novel technology that combines the power of the multi-object spectrograph with the spatial multiplex advantage of an integral field spectrograph (IFS). The Sydney-AAO Multi-object IFS (SAMI) is a prototype wide-field system at the Anglo-Australian Telescope (AAT) that allows 13 imaging fibre bundles ("hexabundles") to be deployed over a 1-degree diameter field of view. Each hexabundle comprises 61 lightly-fused multimode fibres with reduced cladding and yields a 75 percent filling factor. Each fibre core diameter subtends 1.6 arcseconds on the sky and each hexabundle has a field of view of 15 arcseconds diameter. The fibres are fed to the flexible AAOmega double-beam spectrograph, which can be used at a range of spectral resolutions (R=lambda/delta(lambda) ~ 1700-13000) over the optical spectrum (3700-9500A). We present the first spectroscopic results obtained with SAMI for a sample of galaxies at z~0.05. We discuss the prospects of implementing hexabundles at a much higher multiplex over wider fields of view in order to carry out spatially--resolved spectroscopic surveys of 10^4 to 10^5 galaxies.Comment: 24 pages, 16 figures. Accepted by MNRA

Anti-confocal versus confocal assessment of the middle ear simulated by Monte Carlo methods

The ability to monitor the inflammatory state of the middle ear mucosa would provide clinical utility. To enable spectral measurements on the mucosa whilst rejecting background signal from the eardrum an anti-confocal system is investigated. In contrast to the central pinhole in a confocal system the anti-confocal system uses a central stop to reject light from the in-focus plane, the eardrum, with all other light detected. Monte Carlo simulations of this system show an increase in detected signal and improved signal-to-background ratio compared to a conventional confocal set-up used to image the middle ear mucosa. System parameters are varied in the simulation and their influence on the level of background rejection are presented

A model for reactive porous transport during re-wetting of hardened concrete

A mathematical model is developed that captures the transport of liquid water in hardened concrete, as well as the chemical reactions that occur between the imbibed water and the residual calcium silicate compounds residing in the porous concrete matrix. The main hypothesis in this model is that the reaction product -- calcium silicate hydrate gel -- clogs the pores within the concrete thereby hindering water transport. Numerical simulations are employed to determine the sensitivity of the model solution to changes in various physical parameters, and compare to experimental results available in the literature.Comment: 30 page

High-resolution survey for planetary companions to young stars in the Taurus molecular cloud

Direct imaging in the infrared at the diffraction limit of large telescopes is a unique probe of the properties of young planetary systems. We survey 55 single class I and class II stars in Taurus in the L’ filter using natural and laser guide star adaptive optics and the near-infrared camera (NIRC2) of the Keck II telescope, in order to search for planetary-mass companions. We use both reference star differential imaging and kernel phase techniques, achieving typical 5σ contrasts of ∼6 mag at separations of 0.2 arcsec and ∼8 mag beyond 0.5 arcsec. Although, we do not detect any new faint companions, we constrain the frequency of wide separation massive planets, such as HR 8799 analogues. We find that, assuming hot-start models and a planet distribution with power-law mass and semimajor axis indices of −0.5 and −1, respectively, less than 20 per cent of our target stars host planets with masses >2 MJ at separations >10 au.The observatory was made possible by the generous financial support of the W. M. Keck Foundation. ALW would like to thank the Australian Government for their support through the Australian Postgraduate Award Scholarship and the Research School of Astronomy and Astrophysics at the Australian National University for the ANU Supplementary PhD Scholarship