Infrared spectroscopic studies of hydrogen bonding in substituted nitrophenols: substituent and solvent effects

A detailed infrared spectroscopic study of the substituted phenols 2-cyano-4,6-dinitrophenol and 4-cyano-2,6-dinitrophenol has been carried out (in several different solvents) in order to investigate the substituent and solvent effects on their intra- and inter-molecular hydrogen bonding properties. In benzene or dichloromethane it is found that both isomers form strong intramolecular hydrogen bonds with the 2-cyano (2CN) isomer having a stronger intramolecular interaction (in accordance with the higher pKa). The 4-cyano (4CN) isomer shows two distinct NO2 groups and exchange between the two possible hydrogen bonding sites is probably slow on the infrared time-scale. In protic solvents such as methanol the intramolecular hydrogen bonds are broken (more easily for the 4CN isomer) by intermolecular hydrogen bonding to the solvent. The differential “reactivity” towards methanol may be associated with steric congestion in the 4CN isomer leading to the forcing of at least one of the NO2 groups out of the aromatic plane. The use of mixed solvents (benzene-methanol) has established that the two hydrogen bonded species are observed together and that a high concentration of methanol is required to drive the equilibrium towards the intermolecular hydrogen bonded species. In dimethyl sulphoxide the behaviour of the two isomers is even more interesting. The 4CN isomer is ionised to produce the corresponding phenolate. However the 2CN isomer remains neutral (but highly solvated). We attribute this difference to the requirement for the 4CN isomer to allow the 2- and 6-NO2 groups to recover planarity with the aromatic ring. The energy compensation involved in this process is clearly sufficient to break a stronger intramolecular hydrogen bond.info:eu-repo/semantics/publishedVersio

The basicity of alkali metal methoxides in methanol. The effects of ion association on methoxide additions to activated anisoles

The formation of adducts with 1 :2 and 1:3 stoichiometry by methoxide addition to nitro-activated anisoles has been examined spectrophotometrically. For these equilibria the ‘basicity’ of sodium methoxide solutions in methanol is appreciably greater than that of corresponding potassium methoxide solutions. This is in contrast with other measures of basicity and is attributed to the association of the multi-charged adducts with cations which is stronger with sodium than with potassium ions.info:eu-repo/semantics/publishedVersio

Multiple Sources toward the High-mass Young Star S140 IRS1

S140 IRS1 is a remarkable source where the radio source at the center of the main bipolar molecular outflow in the region is elongated perpendicular to the axis of the outflow, an orientation opposite to that expected if the radio source is a thermal jet exciting the outflow. We present results of 1.3 cm continuum and H2O maser emission observations made with the VLA in its A configuration toward this region. In addition, we also present results of continuum observations at 7 mm and re-analyse observations at 2, 3.5 and 6 cm (previously published). IRS 1A is detected at all wavelengths, showing an elongated structure. Three water maser spots are detected along the major axis of the radio source IRS 1A. We have also detected a new continuum source at 3.5 cm (IRS 1C) located ~0.6'' northeast of IRS 1A. The presence of these two YSOs (IRS 1A and 1C) could explain the existence of the two bipolar molecular outflows observed in the region. In addition, we have also detected three continuum clumps (IRS 1B, 1D and 1E) located along the major axis of IRS 1A. We discuss two possible models to explain the nature of IRS 1A: a thermal jet and an equatorial wind.Comment: 17 pages, 4 figures, to be published in A

Hubble Space Telescope imaging of the CFRS and LDSS redshift surveys - IV. Influence of mergers in the evolution of faint field galaxies from z~1

HST images of a sample of 285 galaxies with measured z from the CFRS and Autofib-LDSS redshift surveys are analysed to derive the evolution of the merger fraction out to z~1. We have performed visual and machine-based merger identifications, as well as counts of bright pairs of galaxies with magnitude differences less than 1.5 mag. We find that the pair fraction increases with z, with up to ~20% of the galaxies being in physical pairs at z~0.75-1. We derive a merger fraction varying with z as (1+z)^{3.2 +/- 0.6}, after correction for line-of-sight contamination, in excellent agreement with the merger fraction derived from the visual classification of mergers for which m = 3.4 +/- 0.6. After correcting for seeing effects on the ground-based selection of survey galaxies, we conclude that the pair fraction evolves as (1+z)^{2.7 +/- 0.6}. This implies that an average L* galaxy will have undergone 0.8 to 1.8 merger events from z=1 to 0, with 0.5 to 1.2 merger events occuring in a 2 Gyr time span at z~0.9. This result is consistent with predictions from semi-analytical models of galaxy formation. From the simple co-addition of the observed luminosities of the galaxies in pairs, physical mergers are computed to lead to a brightening of 0.5 mag for each pair on average, and a boost in star formation rate of a factor of 2, as derived from the average [O II] equivalent widths. Mergers of galaxies are therefore contributing significantly to the evolution of both the luminosity function and luminosity density of the Universe out to z~1.Comment: 14 pages, 6 PS figures included. Accepted for publication in MNRA

A realist evaluation of a London general practitioner trainer course

Clinicians with teaching and training roles should be adequately trained and assessed. However, some debate exists as to what the nature of this training should be. Historically, a postgraduate certificate in education was a pre-requisite to becoming a GP trainer but this is changing with growing concern that such a pre-requisite might act as a deterrent to potential GP trainers. This research examines the impact of a scheme designed to provide an alternative, more practical and focused, pathway to becoming a GP trainer. We interviewed 26 course participants and stakeholders of the London GP Training Course (LGPTC), observed teaching sessions, and analysed course materials. We asked what elements of the course were and weren’t effective, for whom, and under what circumstances. Here, we present a summary of our main findings–that GP trainers want to know practically, not theoretically, how to be a trainer; formative assessment boosts trainees’ confidence in their own skills and abilities; short, practical GP training courses can help enhance the numbers of GP trainers; important questions remain about the role and value of educational theory in education faculty development

Protostars and Outflows in the NGC7538 - IRS9 Cloud Core

New high resolution observations of HCO+ J=1-0, H13CN J=1-0, SO 2,2 - 1,1, and continuum with BIMA at 3.4 mm show that the NGC7538 - IRS9 cloud core is a site of active ongoing star formation. Our observations reveal at least three young bipolar molecular outflows, all ~ 10,000 -- 20,000 years old. IRS9 drives a bipolar, extreme high velocity outflow observed nearly pole on. South of IRS9 we find a cold, protostellar condensation with a size of ~ 14" x 6" with a mass > 250 Msun. This is the center of one of the outflows and shows deep, red-shifted self absorption in HCO+, suggesting that there is a protostar embedded in the core, still in a phase of active accretion. This source is not detected in the far infrared, suggesting that the luminosity < 10^4 Lsun; yet the mass of the outflow is ~ 60 Msun. The red-shifted HCO+ self-absorption profiles observed toward the southern protostar and IRS9 predict accretion rates of a few times 10^-4 to 10^-3 Msun/yr. Deep VLA continuum observations at 3.6 cm show that IRS9 coincides with a faint thermal VLA source, but no other young star in the IRS9 region has any detectable free-free emission at a level of ~ 60 microJy at 3.6 cm. The HCO+ abundance is significantly enhanced in the hot IRS9 outflow. A direct comparison of mass estimates from HCO+ and CO for the well-characterized red-shifted IRS9 outflow predicts an HCO+ enhancement of more than a factor of 30, or [HCO+/H2] >= 6 10^-8.Comment: 40 pages, 3 tables and 10 figures included; to appear in Ap

The infrared imaging spectrograph (IRIS) for TMT: the science case

The InfraRed Imaging Spectrograph (IRIS) is a first-light instrument being designed for the Thirty Meter Telescope (TMT). IRIS is a combination of an imager that will cover a 16.4" field of view at the diffraction limit of TMT (4 mas sampling), and an integral field unit spectrograph that will sample objects at 4-50 mas scales. IRIS will open up new areas of observational parameter space, allowing major progress in diverse fields of astronomy. We present the science case and resulting requirements for the performance of IRIS. Ultimately, the spectrograph will enable very well-resolved and sensitive studies of the kinematics and internal chemical abundances of high-redshift galaxies, shedding light on many scenarios for the evolution of galaxies at early times. With unprecedented imaging and spectroscopy of exoplanets, IRIS will allow detailed exploration of a range of planetary systems that are inaccessible with current technology. By revealing details about resolved stellar populations in nearby galaxies, it will directly probe the formation of systems like our own Milky Way. Because it will be possible to directly characterize the stellar initial mass function in many environments and in galaxies outside of the the Milky Way, IRIS will enable a greater understanding of whether stars form differently in diverse conditions. IRIS will reveal detailed kinematics in the centers of low-mass galaxies, allowing a test of black hole formation scenarios. Finally, it will revolutionize the characterization of reionization and the first galaxies to form in the universe.Comment: to appear in Proc. SPIE 773

Geographies of the COVID-19 pandemic

The spread of the novel coronavirus (SARS-CoV-2) has resulted in the most devastating global public health crisis in over a century. At present, over 10 million people from around the world have contracted the Coronavirus Disease 2019 (COVID-19), leading to more than 500,000 deaths globally. The global health crisis unleashed by the COVID-19 pandemic has been compounded by political, economic, and social crises that have exacerbated existing inequalities and disproportionately affected the most vulnerable segments of society. The global pandemic has had profoundly geographical consequences, and as the current crisis continues to unfold, there is a pressing need for geographers and other scholars to critically examine its fallout. This introductory article provides an overview of the current special issue on the geographies of the COVID-19 pandemic, which includes 42 commentaries written by contributors from across the globe. Collectively, the contributions in this special issue highlight the diverse theoretical perspectives, methodological approaches, and thematic foci that geographical scholarship can offer to better understand the uneven geographies of the Coronavirus/COVID-19. </jats:p

The Gemini Deep Deep Survey: II. Metals in Star-Forming Galaxies at Redshift 1.3<z<2

The goal of the Gemini Deep Deep Survey (GDDS) is to study an unbiased sample of K<20.6 galaxies in the redshift range 0.8<z<2.0. Here we determine the statistical properties of the heavy element enrichment in the interstellar medium (ISM) of a subsample of 13 galaxies with 1.34<z<1.97 and UV absolute magnitude M_2000 < -19.65. The sample contains 38% of the total number of identified galaxies in the first two fields of the survey with z>1.3. The selected objects have colors typical of irregular and Sbc galaxies. Strong [OII] emission indicates high star formation activity in the HII regions (SFR~13-106 M_sun/yr). The high S/N composite spectrum shows strong ISM MgII and FeII absorption, together with weak MnII and MgI lines. The FeII column density, derived using the curve of growth analysis, is logN_FeII = 15.54^{+0.23}_{-0.13}. This is considerably larger than typical values found in damped Ly-alpha systems (DLAs) along QSO sight lines, where only 10 out of 87 (~11%) have logN_FeII > 15.2. High FeII column densities are observed in the z=2.72 Lyman break galaxy cB58 (logN_FeII ~ 15.25) and in gamma-ray burst host galaxies (logN_FeII ~ 14.8-15.9). Given our measured FeII column density and assuming a moderate iron dust depletion (delta_Fe ~ 1 dex), we derive an optical dust extinction A_V ~ 0.6. If the HI column density is log N(HI)<21.7 (as in 98% of DLAs), then the mean metallicity is Z/Z_sun > 0.2. The high completeness of the GDDS sample implies that these results are typical of star-forming galaxies in the 1<z<2 redshift range, an epoch which has heretofore been particularly challenging for observational programs.Comment: ApJ in press, corrected HI column density estimat