Clustering and Micro-immiscibility in Alcohol-Water Mixtures: Evidence from Molecular Dynamics Simulations

We have investigated the hydrogen-bonded structures in liquid methanol and a 7:3 mole fraction aqueous solution using classical Molecular Dynamics simulations at 298K and ambient pressure. We find that, in contrast to recent predictions from X-ray emission studies, the hydrogen-bonded structure in liquid methanol is dominated by chain and small ring structures. In the methanol-rich solution, we find evidence of micro-immiscibility, supporting recent conclusions derived from neutron diffraction data.Comment: 5 pages, 4 figure

Freedom of Information Act: scalpel or just a sharp knife?

The concluding statement of the Burns Commission, established to evaluate whether changes are needed to the Freedom of Information Act (FOIA), ruled no major legislative changes were required. As such Freedom of Information (FOI) legislation still enables anyone to obtain information from public authorities. In this brief report article we explore arguments regarding FOI as an instrument for healthcare research using an international research programme as a case study

Inhibition and young children's performance on the Tower of London task

Young children, when performing problem solving tasks, show a tendency to break task rules and produce incomplete solutions. We propose that this tendency can be explained by understanding problem solving within the context of the development of “executive functions” – general cognitive control functions, which serve to regulate the operation of the cognitive system. This proposal is supported by the construction of two computational models that simulate separately the performance of 3–4 year old and 5–6 year old children on the Tower of London planning task. We seek in particular to capture the emerging role of inhibition in the older group. The basic framework within which the models are developed is derived from Fox and Das’ Domino model [Fox, J., & Das, S. (2000). Safe and sound: Artificial intelligence in hazardous applications. Cambridge, MA: MIT Press] and Norman and Shallice’s [Norman, D.A., & Shallice, T. (1986). Attention to action: Willed and automatic control of behaviour. In R. Davidson, G. Schwartz, & D. Shapiro (Eds.), Consciousness and Self Regulation (Vol. 4). New York: Plenum] theory of willed and automatic action. Two strategies and a simple perceptual bias are implemented within the models and comparisons between model and child performance reveal a good fit for the key dependent measures (number of rule breaks and percentage of incomplete solutions) of the two groups

Spectroscopic Discovery of the Broad-Lined Type Ic Supernova 2010bh Associated with the Low-Redshift GRB 100316D

We present the spectroscopic discovery of a broad-lined Type Ic supernova (SN 2010bh) associated with the nearby long-duration gamma-ray burst (GRB) 100316D. At z = 0.0593, this is the third-nearest GRB-SN. Nightly optical spectra obtained with the Magellan telescopes during the first week after explosion reveal the gradual emergence of very broad spectral features superposed on a blue continuum. The supernova features are typical of broad-lined SNe Ic and are generally consistent with previous supernovae associated with low-redshift GRBs. However, the inferred velocities of SN 2010bh at 21 days after explosion are a factor of ~2 times larger than those of the prototypical SN 1998bw at similar epochs, with v ~ 26,000 km/s, indicating a larger explosion energy or a different ejecta structure. A near-infrared spectrum taken 13.8 days after explosion shows no strong evidence for He I at 1.083 microns, implying that the progenitor was largely stripped of its helium envelope. The host galaxy is of low luminosity (M_R ~ -18.5 mag) and low metallicity (Z < 0.4 Z_solar), similar to the hosts of other low-redshift GRB-SNe.Comment: 6 pages, 4 figures, 1 table, submitted to ApJ Letter

Helimeric porphyrinoids: Stereostructure and chiral resolution of meso -tetraarylmorpholinochlorins

The synthesis and chiral resolution of free-base and Ni(II) complexes of a number of derivatives of meso-tetraphenylmorpholinochlorins, with and without direct β-carbon-to-o-phenyl linkages to the flanking phenyl groups, is described. The morpholinochlorins, a class of stable chlorin analogues, were synthesized in two to three steps from meso-tetraphenylporphyrin. The conformations and the relative stereostructures of a variety of free-base and Ni(II) complexes of these morpholinochlorins were elucidated by X-ray diffractometry. Steric and stereoelectronic arguments explain the relative stereoarray of the morpholino-substituents, which differ in the free-base and Ni(II) complexes, and in the monoalkoxy, β-carbon-to-o-phenyl linked morpholinochlorins, and the dialkoxy derivatives. The Ni(II) complexes were all found to be severely ruffled whereas the free-base chromophores are more planar. As a result of the helimeric distortion of their porphyrinoid chromophores, the ruffled macrocycles possess a stable inherent element of chirality. Most significantly, resolution of the racemic mixtures was achieved, both by classical methods via diastereomers and by HPLC on a chiral phase. Full CD spectra were recorded and modeled using quantum-chemical computational methods, permitting, for the first time, an assignment of the absolute configurations of the chromophores. The report expands the range of known pyrrole-modified porphyrins. Beyond this, it introduces large chiral porphyrinoid π-systems that exist in the form of two enantiomeric, stereochemically stable helimers that can be resolved. This forms the basis for possible future applications, for example, in molecular-recognition systems or in materials with chiroptic properties. © 2011 American Chemical Society

Fabrication, characterization and modeling of functionally graded synthetic graphite/polymer nanocomposites

In this chapter, the fabrication, characterization, and modeling of functionally graded nanocomposites (FGNs) are presented. FGNs with phenolic matrix and synthetic graphite (SG) as nanofillers were fabricated using a combined powder stacking and compression molding techniques. Ball milling was used to homogeneously distribute nanofillers within the phenolic matrix. The process allowed FGNs with four different microstructure gradient patterns of the same geometry and SG content, as well as non-graded nanocomposites (NGNs), to be fabricated. The surface morphology of FGNs and SG distribution were examined. The transient thermal behavior of FGNs subjected to sudden temperature changes was numerically investigated to examine the effect of compositional patterns on the temperature gradient field in these materials. Temperature-dependent thermal conductivity and heat capacity of the FGN components were measured and used in finite element-based transient thermal analysis developed based on the experimental procedure. A controlled microstructure and composition was achieved in microscale. Thermomechanical and viscoelastic properties of nanocomposites were highly affected by the distribution patterns of SG within the matrix. The transient thermal analysis results showed that the transient time and temperature field in nanocomposite structures were highly influenced by the compositional gradient configurations. The FGN with a gradual decrease in reinforcing content from the exposed side to the other side had the lowest temperature gradient field (about 11 °C less than the other gradient patterns) and transient time (about 56 seconds less than the other gradient patterns)

500 Days of SN 2013dy: spectra and photometry from the ultraviolet to the infrared

SN 2013dy is a Type Ia supernova for which we have compiled an extraordinary dataset spanning from 0.1 to ~ 500 days after explosion. We present 10 epochs of ultraviolet (UV) through near-infrared (NIR) spectra with HST/STIS, 47 epochs of optical spectra (15 of them having high resolution), and more than 500 photometric observations in the BVrRiIZYJH bands. SN 2013dy has a broad and slowly declining light curve (delta m(B) = 0.92 mag), shallow Si II 6355 absorption, and a low velocity gradient. We detect strong C II in our earliest spectra, probing unburned progenitor material in the outermost layers of the SN ejecta, but this feature fades within a few days. The UV continuum of SN 2013dy, which is strongly affected by the metal abundance of the progenitor star, suggests that SN 2013dy had a relatively high-metallicity progenitor. Examining one of the largest single set of high-resolution spectra for a SN Ia, we find no evidence of variable absorption from circumstellar material. Combining our UV spectra, NIR photometry, and high-cadence optical photometry, we construct a bolometric light curve, showing that SN 2013dy had a maximum luminosity of 10.0^{+4.8}_{-3.8} * 10^{42} erg/s. We compare the synthetic light curves and spectra of several models to SN 2013dy, finding that SN 2013dy is in good agreement with a solar-metallicity W7 model.Comment: 22 pages, 18 figures, replaced with version accecpted for publication in MNRA

Maximising response to postal questionnaires – A systematic review of randomised trials in health research

Background Postal self-completion questionnaires offer one of the least expensive modes of collecting patient based outcomes in health care research. The purpose of this review is to assess the efficacy of methods of increasing response to postal questionnaires in health care studies on patient populations. Methods The following databases were searched: Medline, Embase, CENTRAL, CDSR, PsycINFO, NRR and ZETOC. Reference lists of relevant reviews and relevant journals were hand searched. Inclusion criteria were randomised trials of strategies to improve questionnaire response in health care research on patient populations. Response rate was defined as the percentage of questionnaires returned after all follow-up efforts. Study quality was assessed by two independent reviewers. The Mantel-Haenszel method was used to calculate the pooled odds ratios. Results Thirteen studies reporting fifteen trials were included. Implementation of reminder letters and telephone contact had the most significant effect on response rates (odds ratio 3.7, 95% confidence interval 2.30 to 5.97 p = <0.00001). Shorter questionnaires also improved response rates to a lesser degree (odds ratio 1.4, 95% confidence interval 1.19 to 1.54). No evidence was found that incentives, re-ordering of questions or including an information brochure with the questionnaire confer any additional advantage. Conclusion Implementing repeat mailing strategies and/or telephone reminders may improve response to postal questionnaires in health care research. Making the questionnaire shorter may also improve response rates. There is a lack of evidence to suggest that incentives are useful. In the context of health care research all strategies to improve response to postal questionnaires require further evaluation