Phosphorothioate Anti-sense Oligonucleotides: The Kinetics and Mechanism of the Generation of the Sulfurising Agent from Phenylacetyl Disulfide (PADS)

The synthesis of phosphorothioate oligonucleotides is often accomplished in the pharmaceutical industry by the sulfurisation of the nucleotide-phosphite using phenylacetyl disulfide (PADS) which has an optimal combination of properties. This is best achieved by an initial ‘ageing’ of PADS for 48 hrs in acetonitrile with 3-picoline to generate polysulfides. The initial base-catalysed degradation of PADS occurs by an E1cB-type elimination to generate a ketene and acyldisulfide anion. Proton abstraction to reversibly generate a carbanion is demonstrated by H/D exchange, the rate of which is greatly increased by electron-withdrawing substituents in the aromatic ring of PADS. The ketene can be trapped intramolecularly by an o-allyl group. The disulfide anion generated subsequently attacks unreacted PADS on sulfur to give polysulfides, the active sulfurising agent. The rate of degradation of PADS is decreased by less basic substituted pyridines and is only first order in PADS indicating that the rate-limiting step is formation of the disulfide anion from the carbanion

Designing pseudocubic perovskites with enhanced nanoscale polarization

A crystal-chemical framework has been proposed for the design of pseudocubic perovskites with nanoscale ferroelectric order, and its applicability has been demonstrated using a series of represen- tative solid solutions that combined ferroelectric (K 0.5 Bi 0.5 TiO 3 , BaTiO 3 , and PbTiO 3 ) and antifer- roelectric (Nd-substituted BiFeO 3 ) end members. The pseudocubic structures obtained in these systems exhibited distortions that were coherent on a scale ranging from sub-nanometer to tens of nanometers, but, in all cases, the macroscopic distortion remained unresolvable even if using high- resolution X-ray powder diffraction. Different coherence lengths for the local atomic displacements account for the distinctly different dielectric, ferroelectric, and electromechanical properties exhib- ited by the samples. The guidelines identified provide a rationale for chemically tuning the coher- ence length to obtain the desired functional response

Effective temperatures and radii of planet-hosting stars from IR photometry

In this paper we present and analyse determinations of effective temperatures of planet-hosting stars using infrared (IR) photometry. One of our goals is the comparison with spectroscopic temperatures to evaluate the presence of systematic effects that could alter the determination of metal abundances. To estimate the stellar temperatures we have followed a new approach based on fitting the observed 2MASS IR photometry with accurately calibrated synthetic photometry. Special care has been put in evaluating all sources of possible errors and incorporating them in the analysis. A comparison of our temperature determinations with spectroscopic temperatures published by different groups reveals the presence of no systematic trends and a scatter compatible with the quoted uncertainties of 0.5-1.3%. This mutual agreement strengthens the results of both the spectroscopic and IR photometry analyses. Comparisons with other photometric temperature calibrations, generally with poorer performances, are also presented. In addition, the method employed of fitting IR photometry naturally yields determinations of the stellar semi-angular diameters, which, when combined with the distances, results in estimations of the stellar radii with remarkable accuracies of ~2-4%. A comparison with the only star in the sample with an empirically determined radius (HD 209458 -- from transit photometry) indicates excellent agreement.Comment: 4 pages, 1 figure, accepted for publication as a letter in A&

Blogging in the physics classroom: A research-based approach to shaping students' attitudes towards physics

Even though there has been a tremendous amount of research done in how to help students learn physics, students are still coming away missing a crucial piece of the puzzle: why bother with physics? Students learn fundamental laws and how to calculate, but come out of a general physics course without a deep understanding of how physics has transformed the world around them. In other words, they get the "how" but not the "why". Studies have shown that students leave introductory physics courses almost universally with decreased expectations and with a more negative attitude. This paper will detail an experiment to address this problem: a course weblog or "blog" which discusses real-world applications of physics and engages students in discussion and thinking outside of class. Specifically, students' attitudes towards the value of physics and its applicability to the real-world were probed using a 26-question Likert scale survey over the course of four semesters in an introductory physics course at a comprehensive Jesuit university. We found that students who did not participate in the blog study generally exhibited a deterioration in attitude towards physics as seen previously. However, students who read, commented, and were involved with the blog maintained their initially positive attitudes towards physics. Student response to the blog was overwhelmingly positive, with students claiming that the blog made the things we studied in the classroom come alive for them and seem much more relevant.Comment: 20 pages, 6 figure

Nanoscale polar heterogeneities and branching Bi-displacement directions in K0.5Bi0.5TiO3

K0.5Bi0.5TiO3 (KBT)—one of the few perovskite-like ferroelectric compounds with room-temperature tetragonal symmetry—differs from other members of its family (BaTiO3 and PbTiO3) by the presence of a disordered mixture of K and Bi on cuboctahedral sites. This disorder is expected to affect local atomic displacements and their response to an applied electric field. We have derived nanoscale atomistic models of KBT by refining atomic coordinates to simultaneously fit neutron/X-ray total scattering and extended X-ray absorption fine-structure data. Both Bi and Ti ions were found to be offset relative to their respective oxygen cages in the high-temperature cubic phase; in contrast, the coordination environment of K remained relatively undistorted. In the cubic structure, Bi displacements prefer the ⟨100⟩ directions and the probability density distribution of Bi features six well-separated sites; a similar preference exists for the much smaller Ti displacements, although the split sites for Ti could not be resolved. The cation displacements are correlated, yielding polar nanoregions, whereas on average, the structure appears as cubic. The cubic ↔ tetragonal phase transition involves both order/disorder and displacive mechanisms. A qualitative change in the form of the Bi probability density distribution occurs in the tetragonal phase on cooling to room temperature because Bi displacements “branch off” to ⟨111⟩ directions. This change, which preserves the average symmetry, is accompanied by the development of nanoscale polar heterogeneities that exhibit significant deviations of their polarization vectors from the average polar axis

Hypoxia PET/CT and Colorectal Cancer : A Case Report

Funding: Funding for the pilot study was provided by the Colorectal Study Fund, a NHSG endowment fund number: NER 11482.Peer reviewedPublisher PD

The formation and habitability of terrestrial planets in the presence of hot jupiters

`Hot jupiters,' giant planets with orbits very close to their parent stars, are thought to form farther away and migrate inward via interactions with a massive gas disk. If a giant planet forms and migrates quickly, the planetesimal population has time to re-generate in the lifetime of the disk and terrestrial planets may form (Armitage 2003). We present results of simulations of terrestrial planet formation in the presence of hot jupiters, broadly defined as having orbital radii <= 0.5 AU. We show that terrestrial planets similar to those in the Solar System can form around stars with hot jupiters, and can have water contents equal to or higher than the Earth's. For small orbital radii of hot jupiters (e.g. 0.15, 0.25 AU) potentially habitable planets can form, but for semi-major axes of 0.5 AU or greater their formation is suppressed. We show that the presence of an outer giant planet such as Jupiter does not enhance the water content of the terrestrial planets, but rather decreases their formation and water delivery timescales. We speculate that asteroid belts may exist interior to the terrestrial planets in systems with hot jupiters.Comment: 5 pages, 2 color figures in emulate ApJ style submitted to Icaru

Decisions to consent for autopsy after stillbirth: Aboriginal and Torres Strait Islander women’s experiences

Abstract Background: The stillbirth rate for Australian Aboriginal and Torres Strait Islander infants is twice that for non-Indigenous infants. Autopsy is the gold standard for fetal investigation, however, parental consent is low. There is little research investigating the drivers of parents’ decision-making for autopsy after stillbirth. Aims: The current study explored the reasons why Aboriginal and Torres Strait Islander women did or did not give permission to autopsy after stillbirth. Materials and Methods: Five Aboriginal and/or Torres Strait Islander women participated in semi-structured interviews. Thematic analysis was conducted within a phenomenological framework. Results: Five themes were identified as reasons for giving permission – to find out why baby died; confirm diagnosis; understand future risk; help others; and doubt about maternal causes. Four themes were identified as reasons for declining permission – not asked in a sensitive manner; not enough time to think; distress about the autopsy procedure; and unwilling to agree. There was a lack of acceptability of the lengthy timeframe for the availability of autopsy results as families usually wait between three and nine months. This lengthy waiting period negatively impacted upon families’ health and wellbeing. Conclusions: It is important for health professionals to understand the factors that parents consider when giving permission for autopsy after stillbirth. It is hoped that an increase in autopsy rate will enhance the understanding of the causes of stillbirth and ultimately decrease the stillbirth rate for Aboriginal and Torres Strait Islander families

Elemental abundance differences in the 16 Cygni binary system: a signature of gas giant planet formation?

The atmospheric parameters of the components of the 16Cygni binary system, in which the secondary has a gas giant planet detected, are measured accurately using high quality observational data. Abundances relative to solar are obtained for 25 elements with a mean error of 0.023 dex. The fact that 16CygA has about four times more lithium than 16CygB is normal considering the slightly different masses of the stars. The abundance patterns of 16CygA and B, relative to iron, are typical of that observed in most of the so-called solar twin stars, with the exception of the heavy elements (Z>30), which can, however, be explained by Galactic chemical evolution. Differential (A-B) abundances are measured with even higher precision (0.018 dex, on average). We find that 16CygA is more metal-rich than 16CygB by 0.041+/-0.007 dex. On an element-to-element basis, no correlation between the A-B abundance differences and dust condensation temperature (Tc) is detected. Based on these results, we conclude that if the process of planet formation around 16CygB is responsible for the observed abundance pattern, the formation of gas giants produces a constant downwards shift in the photospheric abundance of metals, without a Tc correlation. The latter would be produced by the formation of terrestrial planets instead, as suggested by other recent works on precise elemental abundances. Nevertheless, a scenario consistent with these observations requires the convective envelopes of 1 Msun stars to reach their present-day sizes about three times quicker than predicted by standard stellar evolution models.Comment: ApJ, in pres

Searching for the signatures of terrestial planets in solar analogs

We present a fully differential chemical abundance analysis using very high-resolution (R >~ 85,000) and very high signal-to-noise (S/N~800 on average) HARPS and UVES spectra of 7 solar twins and 95 solar analogs, 24 are planet hosts and 71 are stars without detected planets. The whole sample of solar analogs provide very accurate Galactic chemical evolution trends in the metalliciy range -0.3<[Fe/H]<0.5. Solar twins with and without planets show similar mean abundance ratios. We have also analysed a sub-sample of 28 solar analogs, 14 planet hosts and 14 stars without known planets, with spectra at S/N~850 on average, in the metallicity range 0.14<[Fe/H]<0.36 and find the same abundance pattern for both samples of stars with and without planets. This result does not depend on either the planet mass, from 7 Earth masses to 17.4 Jupiter masses, or the orbital period of the planets, from 3 to 4300 days. In addition, we have derived the slope of the abundance ratios as a function of the condensation temperature for each star and again find similar distributions of the slopes for both stars with and without planets. In particular, the peaks of these two distributions are placed at a similar value but with opposite sign as that expected from a possible signature of terrestial planets. In particular, two of the planetary systems in this sample, containing each of them a Super-Earth like planet, show slope values very close to these peaks which may suggest that these abundance patterns are not related to the presence of terrestial planets.Comment: Accepted for publication in The Astrophysical Journa