Infrared and Raman Spectroscopy of the Dirhodium Tetraacetate Complexes Rh2(O2CCH3)4, Rh2(18O2CCH3)4, Rh2(O2CCD3)4 and Rh2(O2CCH3)4(H2O)2

The infrared (3500-50 cm-I), and Raman (3550-30 cm-I) spectra of the dirhodium tetraacetate species Rh2(02CCHs)4, Rh2(IB02CCHs)4, Rh2(02CCDS)4, and Rh2(02CCHs)4(H20)2 have been recorded and the key bands assigned, The oxygen-18 and deuteration studies, in particular, assisted with ma king the important band assignments for the anhydrous complex, for which 11 (RhRh) occurs at 355-351 cm-I, and 11 (RhO) at 389-319 cm-I (Raman) and 398-341 cm-I (infrared). The band attributed to 11 (RhRh) is typically intense, sharp, and relatively insensitive to either IBO_ or CDs-substitution. Thus 11 (RhRh) shifts only 4 cm-Ion either IBO or CDs substitution whereas 11 (RhO) shifts 4-6 cm-I in the Raman and 3-7 cm-I in the infrared spectra on IBO substitution but 12 cm-I in the Raman and 11-18 cm-I in the infrared spectra on CDs substitution. Some preliminary isotopic work for the complex Rh2(02CCHS)4(H20l2 is also presented

T-cell production of matrix metalloproteinases and inhibition of parasite clearance by TIMP-1 during chronic Toxoplasma infection in the brain

Chronic infection with the intracellular protozoan parasite Toxoplasma gondii leads to tissue remodelling in the brain and a continuous requirement for peripheral leucocyte migration within the CNS (central nervous system). In the present study, we investigate the role of MMPs (matrix metalloproteinases) and their inhibitors in T-cell migration into the infected brain. Increased expression of two key molecules, MMP-8 and MMP-10, along with their inhibitor, TIMP-1 (tissue inhibitor of metalloproteinases-1), was observed in the CNS following infection. Analysis of infiltrating lymphocytes demonstrated MMP-8 and -10 production by CD4+ and CD8+ T-cells. In addition, infiltrating T-cells and CNS resident astrocytes increased their expression of TIMP-1 following infection. TIMP-1-deficient mice had a decrease in perivascular accumulation of lymphocyte populations, yet an increase in the proportion of CD4+ T-cells that had trafficked into the CNS. This was accompanied by a reduction in parasite burden in the brain. Taken together, these findings demonstrate a role for MMPs and TIMP-1 in the trafficking of lymphocytes into the CNS during chronic infection in the brain

p53-mediated redox control promotes liver regeneration and maintains liver function in response to CCl4

The p53 transcription factor coordinates wide-ranging responses to stress that contribute to its function as a tumour suppressor. The responses to p53 induction are complex and range from mediating the elimination of stressed or damaged cells to promoting survival and repair. These activities of p53 can modulate tumour development but may also play a role in pathological responses to stress such as tissue damage and repair. Using a p53 reporter mouse, we have previously detected strong induction of p53 activity in the liver of mice treated with the hepatotoxin carbon tetrachloride (CCl ). Here, we show that p53 functions to support repair and recovery from CCl -mediated liver damage, control reactive oxygen species (ROS) and limit the development of hepatocellular carcinoma (HCC), in part through the activation of a detoxification cytochrome P450, CYP2A5 (CYP2A6 in humans). Our work demonstrates an important role for p53-mediated redox control in facilitating the hepatic regenerative response after damage and identifies CYP2A5/CYP2A6 as a mediator of this pathway with potential prognostic utility in human HCC

Simulations of the Milky Way's central molecular zone -- I. Gas dynamics

We use hydrodynamical simulations to study the Milky Way's central molecular zone (CMZ). The simulations include a non-equilibrium chemical network, the gas self-gravity, star formation and supernova feedback. We resolve the structure of the interstellar medium at sub-parsec resolution while also capturing the interaction between the CMZ and the bar-driven large-scale flow out to R\sim 5\kpc. Our main findings are as follows: (1) The distinction between inner ($R\lesssim120$~pc) and outer ($120\lesssim R\lesssim450$~pc) CMZ that is sometimes proposed in the literature is unnecessary. Instead, the CMZ is best described as single structure, namely a star-forming ring with outer radius $R\simeq 200$~pc which includes the 1.3$^\circ$ complex and which is directly interacting with the dust lanes that mediate the bar-driven inflow. (2) This accretion can induce a significant tilt of the CMZ out of the plane. A tilted CMZ might provide an alternative explanation to the $\infty$-shaped structure identified in Herschel data by Molinari et al. 2011. (3) The bar in our simulation efficiently drives an inflow from the Galactic disc ($R\simeq 3$~kpc) down to the CMZ ($R\simeq200$~pc) of the order of $1\rm\,M_\odot\,yr^{-1}$, consistent with observational determinations. (4) Supernova feedback can drive an inflow from the CMZ inwards towards the circumnuclear disc of the order of $\sim0.03\,\rm M_\odot\,yr^{-1}$. (5) We give a new interpretation for the 3D placement of the 20 and 50 km s$^{-1}$ clouds, according to which they are close ($R\lesssim30$~pc) to the Galactic centre, but are also connected to the larger-scale streams at $R\gtrsim100$~pc.Comment: Accepted for publication in MNRAS. Movies of the simulations can be found at: https://www.youtube.com/channel/UCwnzfO-xLxzRDz9XsexfPo

UWISH2 -- The UKIRT Widefield Infrared Survey for H2

We present the goals and preliminary results of an unbiased, near-infrared, narrow-band imaging survey of the First Galactic Quadrant (10deg<l<65deg ; -1.3deg<b<+1.3deg). This area includes most of the Giant Molecular Clouds and massive star forming regions in the northern hemisphere. The survey is centred on the 1-0S(1) ro-vibrational line of H2, a proven tracer of hot, dense molecular gas in star-forming regions, around evolved stars, and in supernova remnants. The observations complement existing and upcoming photometric surveys (Spitzer-GLIMPSE, UKIDSS-GPS, JCMT-JPS, AKARI, Herschel Hi-GAL, etc.), though we probe a dynamically active component of star formation not covered by these broad-band surveys. Our narrow-band survey is currently more than 60% complete. The median seeing in our images is 0.73arcsec. The images have a 5sigma detection limit of point sources of K=18mag and the surface brightness limit is 10^-19Wm^-2arcsec^-2 when averaged over our typical seeing. Jets and outflows from both low and high mass Young Stellar Objects are revealed, as are new Planetary Nebulae and - via a comparison with earlier K-band observations acquired as part of the UKIDSS GPS - numerous variable stars. With their superior spatial resolution, the UWISH2 data also have the potential to reveal the true nature of many of the Extended Green Objects found in the GLIMPSE survey.Comment: 14pages, 8figures, 2tables, accepted for publication by MNRAS, a version with higher resolution figures can be found at http://astro.kent.ac.uk/~df

A Sweet Killer: Mesoporous Polysaccharide Confined Silver Nanoparticles for Antibacterial Applications

Silver nanoparticles (AgNP) confined within porous starch have been prepared in a simple, green and efficient manner, utilising the nanoporous structure of predominantly mesoporous starch (MS) to act as nanoparticle stabiliser, support and reducing surface. MS/AgNP materials present high surface areas (SBET > 150 m2 g−1) and mesopore volumes (Vmeso > 0.45 cm3 g−1). The interaction of the AgNP precursor and forming nanoparticle nuclei with the mesoporous domains of the porous polysaccharide, direct porosity to increasingly narrower and more defined pore size distributions, indicative of a degree of cooperative assembly. Transmission electron microscopy images indicated the presence of spherical AgNP of a size reflective of the porous polysaccharide mesopore diameter (e.g., 5–25 nm), whilst XPS analysis confirmed the metallic Ag0 state. Materials were prepared at relatively low Ag loadings (<0.18 mmol g−1), demonstrating excellent antimicrobial activity in solid and liquid phase testing against Gram negative (E. coli) and positive (S. aureus) model bacteria. The resulting materials are biocompatible and present a useful solid porous carbohydrate-based polymer vehicle to control the AgNP size regime and facilitate transference to a biological environment

Implications of climate change for agricultural productivity in the early twenty-first century

This paper reviews recent literature concerning a wide range of processes through which climate change could potentially impact global-scale agricultural productivity, and presents projections of changes in relevant meteorological, hydrological and plant physiological quantities from a climate model ensemble to illustrate key areas of uncertainty. Few global-scale assessments have been carried out, and these are limited in their ability to capture the uncertainty in climate projections, and omit potentially important aspects such as extreme events and changes in pests and diseases. There is a lack of clarity on how climate change impacts on drought are best quantified from an agricultural perspective, with different metrics giving very different impressions of future risk. The dependence of some regional agriculture on remote rainfall, snowmelt and glaciers adds to the complexity. Indirect impacts via sea-level rise, storms and diseases have not been quantified. Perhaps most seriously, there is high uncertainty in the extent to which the direct effects of CO2 rise on plant physiology will interact with climate change in affecting productivity. At present, the aggregate impacts of climate change on global-scale agricultural productivity cannot be reliably quantified

Ernst Freund as Precursor of the Rational Study of Corporate Law

Gindis, David, Ernst Freund as Precursor of the Rational Study of Corporate Law (October 27, 2017). Journal of Institutional Economics, Forthcoming. Available at SSRN: https://ssrn.com/abstract=2905547, doi: https://dx.doi.org/10.2139/ssrn.2905547The rise of large business corporations in the late 19th century compelled many American observers to admit that the nature of the corporation had yet to be understood. Published in this context, Ernst Freund's little-known The Legal Nature of Corporations (1897) was an original attempt to come to terms with a new legal and economic reality. But it can also be described, to paraphrase Oliver Wendell Holmes, as the earliest example of the rational study of corporate law. The paper shows that Freund had the intuitions of an institutional economist, and engaged in what today would be called comparative institutional analysis. Remarkably, his argument that the corporate form secures property against insider defection and against outsiders anticipated recent work on entity shielding and capital lock-in, and can be read as an early contribution to what today would be called the theory of the firm.Peer reviewe

The DYMECS project: a statistical approach for the evaluation of convective storms in high-resolution NWP models

A new frontier in weather forecasting is emerging by operational forecast models now being run at convection-permitting resolutions at many national weather services. However, this is not a panacea; significant systematic errors remain in the character of convective storms and rainfall distributions. The DYMECS project (Dynamical and Microphysical Evolution of Convective Storms) is taking a fundamentally new approach to evaluate and improve such models: rather than relying on a limited number of cases, which may not be representative, we have gathered a large database of 3D storm structures on 40 convective days using the Chilbolton radar in southern England. We have related these structures to storm life-cycles derived by tracking features in the rainfall from the UK radar network, and compared them statistically to storm structures in the Met Office model, which we ran at horizontal grid length between 1.5 km and 100 m, including simulations with different subgrid mixing length. We also evaluated the scale and intensity of convective updrafts using a new radar technique. We find that the horizontal size of simulated convective storms and the updrafts within them is much too large at 1.5-km resolution, such that the convective mass flux of individual updrafts can be too large by an order of magnitude. The scale of precipitation cores and updrafts decreases steadily with decreasing grid lengths, as does the typical storm lifetime. The 200-m grid-length simulation with standard mixing length performs best over all diagnostics, although a greater mixing length improves the representation of deep convective storms