Proton location in acid⋯pyridine hydrogen bonds of multi-component crystals

YesThe design of new functional crystalline materials requires an understanding of the factors that control salt and co-crystal formation. These states often only differ in the location of the proton and are influenced by chemical and crystallographic factors. The interaction between a carboxylic acid and a pyridine is a frequently used supramolecular synthon in crystal engineering which can exist as either a co-crystal (CO2H⋯N) or salt (CO2−⋯HN+). The results of a Cambridge Structure Database search indicate that the nature of the functional groups on the pyridine play a stronger role in selection of the phase than those of the acid. However, the nature of the local hydrogen bonding of the interaction also adjusts the potential for proton transfer. This was demonstrated by ab initio modelling of the energy landscape for binary and ternary co-crystals by inclusion of varying components of the local environment

Winter foraging ecology of moose in the Tanana Flats and Alaska Range foothills

Thesis (M.S.) University of Alaska Fairbanks, 2002I studied woody browse distribution, production, removal, species composition, twig size, moose diets, and predicted daily intake of resident and migratory moose in the Tanana Flats and adjacent Alaska Range Foothills, Alaska, 1999-2000. Density of moose in these areas was high (1.1 moose/km²). Moose were experiencing density-dependent effects on reproduction and growth, exhibited by low adult twinning rate (6%) and absence of pregnant yearlings, yet 17.5 kg higher 10-month-old calf body weights in the migratory segment. Of all willow, poplar, and paper birch plants sampled, 74% had a broomed architecture, which I attributed to heavy use by moose. Using a model of daily moose intake based on bite mass and bite density, I estimated that 1) migratory moose met expected intake during winter while intake of resident moose was marginal, 2) moose could not meet their expected daily intake with the mean twig dry mass (0.26 g) remaining unbrowsed at end of winter, and 3) higher predicted intake by migratory moose than resident moose was consistent with their higher 10-month-old calf weights

OPserver: interactive online-computations of opacities and radiative accelerations

Codes to compute mean opacities and radiative accelerations for arbitrary chemical mixtures using the Opacity Project recently revised data have been restructured in a client--server architecture and transcribed as a subroutine library. This implementation increases efficiency in stellar modelling where element stratification due to diffusion processes is depth dependent, and thus requires repeated fast opacity reestimates. Three user modes are provided to fit different computing environments, namely a web browser, a local workstation and a distributed grid.Comment: 5 pages, 1 figur

Closed-form solutions of the Schroedinger equation for a class of smoothed Coulomb potentials

An infinite family of closed-form solutions is exhibited for the Schroedinger equation for the potential $V(r) = -Z/\sqrt{|r|^{2} + a^{2}}$. Evidence is presented for an approximate dynamical symmetry for large values of the angular momentum $l$.Comment: 13 pages LaTeX, uses included Institute of Physics style files, 3 PostScript figures. In press at J. Phys. B: At. Mol. Opt. Phys. (1997

Simulation study of the effect of the chemical heterogeneity of activated carbon on water adsorption

In this paper we present results from the molecular simulation of water adsorption in slit-shaped activated carbon pores. We calculate adsorption isotherms by grand canonical Monte Carlo (GCMC) simulation, Henry's constants by Monte Carlo integration, and vapor-liquid equilibrium data by the gauge-cell Monte Carlo method, to investigate the chemical heterogeneity of activated carbon adsorbents. Several types of polar oxygen-containing sites are placed on the surface of the carbon with different densities and local distributions, in order to determine the individual effects of each of these factors on the adsorption of water. Our results confirm the role of surface sites in the enhancement of water adsorption, Furthermore, we show that the local distribution of these sites has a strong effect on low-pressure adsorption, while the overall site density affects mainly the vapor-liquid phase transition. The type of oxygen-containing group is shown not to be of critical importance, since more complex groups can effectively be represented by simpler sites. This study forms the basis for the development of a model for activated carbon that is able to represent the chemical heterogeneity of this type of material

Near-Infrared Spectroscopy of 0.4<z<1.0 CFRS Galaxies: Oxygen Abundances, SFRs and Dust

Using new J-band VLT-ISAAC and Keck-NIRSPEC spectroscopy, we have measured Halpha and [NII] line fluxes for 0.47<z<0.92 CFRS galaxies which have [OII], Hbeta and [OIII]a line fluxes available from optical spectroscopy, to investigate how the properties of the star forming gas in galaxies evolve with redshift. We derive the extinction and oxygen abundances for the sample using a method based on a set of ionisation parameter and oxygen abundance diagnostics, simultaneously fitting the [OII], Hbeta,[OIII], Halpha, and [NII] line fluxes. The individual reddening measurements allow us to accurately correct the Halpha-based star formation rate (SFR) estimates for extinction. Our most salient conclusions are: a) in all 30 CFRS galaxies the source of gas ionisation is not due to AGN activity; b) we find a range of 0<AV<3, suggesting that it is important to determine the extinction for every single galaxy in order to reliably measure SFRs and oxygen abundances in high redshift galaxies; c) high values of [NII]/Halpha >0.1 for most (but not all) of the CFRS galaxies indicate that they lie on the high-metallicity branch of the R23 calibration; d) about one third of the 0.47<z<0.92 CFRS galaxies in our sample have lower metallicities than local galaxies with similar luminosities and star formation rates; e) comparison with a chemical evolution model indicates that these low metallicity galaxies are unlikely to be the progenitors of metal-poor dwarf galaxies at z~0.Comment: Accepted for publication in the Astrophysical Journa

Updated opacities from the opacity project

Using the code autostructure, extensive calculations of inner-shell atomic data have been made for the chemical elements He, C, N, O, Ne, Na, Mg, Al, Si, S, Ar, Ca, Cr, Mn, Fe and Ni. The results are used to obtain updated opacities from the Opacity Project (OP). A number of other improvements on earlier work have also been included. Rosseland-mean opacities from the OP are compared with those from OPAL. Differences of 5-10 per cent occur. The OP gives the 'Z-bump', at log(T) 5.2, to be shifted to slightly higher temperatures. The opacities from the OP, as functions of temperature and density, are smoother than those from OPAL. The accuracy of the integrations used to obtain mean opacities can depend on the frequency mesh used. Tests involving variation of the numbers of frequency points show that for typical chemical mixtures the OP integrations are numerically correct to within 0.1 per cent. The accuracy of the interpolations used to obtain mean opacities for any required values of temperature and density depends on the temperature-density meshes used. Extensive tests show that, for all cases of practical interest, the OP interpolations give results correct to better than 1 per cent. Prior to a number of recent investigations which have indicated a need for downward revisions in the solar abundances of oxygen and other elements, there was good agreement between properties of the Sun deduced from helioseismology and from stellar evolution models calculated using OPAL opacities. The revisions destroy that agreement. In a recent paper, Bahcall et al. argue that the agreement would be restored if opacities for the regions of the Sun with 2 × 106T 5 × 106 K (0.7-0.4 R) were larger than those given by OPAL by about 10 per cent. In the region concerned, the present results from the OP do not differ from those of OPAL by more than 2.5 per cent

Restrictive antibiotic stewardship associated with reduced hospital mortality in gram-negative infection

Introduction: Antimicrobial stewardship has an important role in the control of Clostridium difficile infection (CDI) and antibiotic resistance. An important component of UK stewardship interventions is the restriction of broad-spectrum beta-lactam antibiotics and promotion of agents associated with a lower risk of CDI such as gentamicin. Whilst the introduction of restrictive antibiotic guidance has been associated with improvements in CDI and antimicrobial resistance evidence of the effect on outcome following severe infection is lacking. Methods: In 2008, Glasgow hospitals introduced a restrictive antibiotic guideline. A retrospective before/after study assessed outcome following gram-negative bacteraemia in the 2-year period around implementation. Results: Introduction of restrictive antibiotic guidelines was associated with a reduction in utilisation of ceftriaxone and co-amoxiclav and an increase in amoxicillin and gentamicin. 1593 episodes of bacteraemia were included in the study. The mortality over 1 year following gram-negative bacteraemia was lower in the period following guideline implementation (RR 0.852, P = 0.045). There was no evidence of a difference in secondary outcomes including ITU admission, length of stay, readmission, recurrence of bacteraemia and need for renal replacement therapy. There was a fall in CDI (RR 0.571, P = 0.014) and a reduction in bacterial resistance to ceftriaxone and co-amoxiclav but no evidence of an increase in gentamicin resistance after guideline implementation. Conclusion: Restrictive antibiotic guidelines were associated with a reduction in CDI and bacterial resistance but no evidence of adverse outcomes following gram-negative bacteraemia. There was a small reduction in one year mortality

Winter habitat use of New Zealand falcons (Falco novaeseelandiae ferox) in an intensively managed pine plantation, central North Island, New Zealand

Copyright and source must be acknowledgedPublishe

Building up co-crystals: structural motif consistencies across families of co-crystals

YesThe creation of co-crystals as a route to creating new pharmaceutical phases with modified or defined physicochemical properties is an area of intense research. Much of the current research has focused on creating new phases for numerous active pharmaceutical ingredients (APIs) to alter physical properties such as low solubilities, enhancing processability or stability. Such studies have identified suitable co-formers and common bonding motifs to aid with the design of new co-crystals but understanding how the changes in the molecular structure of the components are reflected in the packing and resulting properties is still lacking. This lack of insight means that the design and growth of new co-crystals is still a largely empirical process with co-formers selected and then attempts to grow the different materials undertaken to evaluate the resulting properties. This work will report on the results of a combination of crystal structure database analysis with computational chemistry studies to identify what structural features are retained across a selection of families of co-crystals with common components. The competition between different potential hydrogen bonding motifs was evaluated using ab initio quantum mechanical calculations and this was related to the commonality in the packing motifs when observed. It is found while the stronger local bonding motifs are often retained within systems, the balance of weaker long-range packing forces gives rise to many subtle shifts in packing leading to greater challenges in the prediction of final crystal structures