Epoxidation of Strained Alkenes Catalysed by (1,2-dimethyl-4(1H)pyridinone-3-olate)2MnIIICl

The mild epoxidation of strained alkenes using (DMPO)2MnCl catalyst (DMPO = 1,2-dimethyl-4(1H)-pyridinone-3-olate) in the presence of various oxidants was studied. Hydrogen peroxide and monopersulfate were found to be the best oxidants when used with imidazole in acetonitrile at 4 °C, with up to 94% conversion. Dismutation of hydrogen peroxide was also observed when used as an oxidant. The epoxidation using hydrogen peroxide or monoperoxysulfate appears to be mild and very selective for strained alkenes. A mechanism is proposed where imidazole is required for activation of the oxidant and where a detected MnV = O species is proposed as the active species. Competitive reaction between H2O2 and the substrate for the active species is proposed and homolytic vs heterolytic scissions of the Osingle bondO bond of the oxidant are discussed

Accomplishing Technical and Investigative Expertise in Everyday Crime Scene Investigation

This research, situated at the intersection of sociology, science and technology studies and police studies, provides the first sociological account of Crime Scene Investigator (CSI) training in England and Wales. Focusing on the acquisition and everyday enactment of CSI expertise, this qualitative, ethnographic investigation asks (1) what are the roles, practices and expertise of the CSI and (2) how is the CSI’s expertise developed in training and enacted in everyday work. These questions are explored through participant observation at the main training centre for UK CSIs, observation at crime scenes, interviews with trainees during and after their training and visual methods. By unpicking the visible and invisible components of CSI work, I analyse how CSIs are trained to document crime scenes and explore the practices of transforming a potentially relevant object from these locations into artefacts that meet the requirements of courtroom scrutiny. I demonstrate how CSIs engage actively and reflexively with the requirements of different conceptions of objectivity and the changing demands placed on them. They continually and performatively negotiate and delimit multiple boundaries, from the very literal in demarcating a crime scene to claiming their position within the investigative hierarchy in each interaction. Unlike other discussions of boundary work, for the CSI this is iterative, requires constant effort and is embedded in their routine practice. Within police environments, the CSI has scope for such boundary work. In the courtroom, however, crime scene investigation is narrowly defined. This thesis develops our understanding of the CSI and crime scene investigation as a practice. It stresses the significance of taking this actor seriously in any account of forensic science and investigative practices. By viewing the CSI as simply an evidence collector, or not considering her work at all, the expertise and pivotal role of this actor in the meaningful and efficient use of science in policing is blackboxed. My detailed qualitative analysis of the CSI’s role, work and specialist expertise contributes a necessary account of a key actor in the police and criminal justice system.ESR

Resolved Debris Discs Around A Stars in the Herschel DEBRIS Survey

The majority of debris discs discovered so far have only been detected through infrared excess emission above stellar photospheres. While disc properties can be inferred from unresolved photometry alone under various assumptions for the physical properties of dust grains, there is a degeneracy between disc radius and dust temperature that depends on the grain size distribution and optical properties. By resolving the disc we can measure the actual location of the dust. The launch of Herschel, with an angular resolution superior to previous far-infrared telescopes, allows us to spatially resolve more discs and locate the dust directly. Here we present the nine resolved discs around A stars between 20 and 40 pc observed by the DEBRIS survey. We use these data to investigate the disc radii by fitting narrow ring models to images at 70, 100 and 160 {\mu}m and by fitting blackbodies to full spectral energy distributions. We do this with the aim of finding an improved way of estimating disc radii for unresolved systems. The ratio between the resolved and blackbody radii varies between 1 and 2.5. This ratio is inversely correlated with luminosity and any remaining discrepancies are most likely explained by differences to the minimum size of grain in the size distribution or differences in composition. We find that three of the systems are well fit by a narrow ring, two systems are borderline cases and the other four likely require wider or multiple rings to fully explain the observations, reflecting the diversity of planetary systems.Comment: 19 pages, 13 figures, 6 tables. Accepted for publication in MNRA

The debris disk around gamma Doradus resolved with Herschel

We present observations of the debris disk around gamma Doradus, an F1V star, from the Herschel Key Programme DEBRIS (Disc Emission via Bias-free Reconnaissance in the Infrared/Submillimetre). The disk is well-resolved at 70, 100 and 160 micron, resolved along its major axis at 250 micron, detected but not resolved at 350 micron, and confused with a background source at 500 micron. It is one of our best resolved targets and we find it to have a radially broad dust distribution. The modelling of the resolved images cannot distinguish between two configurations: an arrangement of a warm inner ring at several AU (best-fit 4 AU) and a cool outer belt extending from ~55 to 400 AU or an arrangement of two cool, narrow rings at ~70 AU and ~190 AU. This suggests that any configuration between these two is also possible. Both models have a total fractional luminosity of ~10^{-5} and are consistent with the disk being aligned with the stellar equator. The inner edge of either possible configuration suggests that the most likely region to find planets in this system would be within ~55 AU of the star. A transient event is not needed to explain the warm dust's fractional luminosity.Comment: 12 pages, 6 figures, accepted for publication in Ap

Maternal alcohol ingestion reduces SP-A expression by pre-term fetal lung epithelia

In addition to neurodevelopmental effects, alcohol consumption at high levels during pregnancy is associated with immunomodulation and premature birth. Premature birth, in turn, is associated with increased susceptibility to various infectious agents such as Respiratory Syncytial Virus (RSV). The initial line of pulmonary innate defense includes the mucociliary apparatus, which expels microorganisms trapped within the airway secretions. Surfactant proteins A and D (SP-A and SP-D, respectively) are additional components of pulmonary innate immunity and have an important role in pulmonary defense against inhaled pathogens. The purpose of this study was to determine if chronic alcohol consumption during the third trimester of pregnancy alters the function of the mucociliary apparatus and expression of SP-A and SP-D of fetal lung epithelia. Sixteen, date-mated ewes were assigned to two different groups; an ethanol exposed group in which ewes received ethanol through surgically implanted intra-abomasal cannula during the third trimester of pregnancy, and a control group in which ewes received the equivalent amount of water instead of ethanol. Within these two groups, ewes were further randomly assigned to a full-term group in which the lambs were naturally delivered, and a pre-term group in which the lambs were delivered prematurely via an abdominal incision and uterotomy. Ethanol was administered 5 times a week as a 40% solution at 1gr/kg of body weight. The mean maternal serum alcohol concentration (SAC) measured 6 hr post administration was 16.3 +/− 4.36 mg/dL. Tracheas from 6 full-term lambs were collected to assess ciliary beat frequency (CBF). The lung tissue from all (24) lambs was collected for immunohistochemistry (IHC) analysis of SP-A and SP-D protein production and fluorogenic real-time quantitative polymerase chain reaction analysis (qPCR) of SP-A and SP-D mRNA levels. Exposure to ethanol during pregnancy significantly blocked stimulated increase in CBF though ethanol-mediated desensitization of cAMP-dependant protein kinase (PKA). In addition, pre-term born/ethanol-exposed lambs showed significantly decreased SP-A m-RNA expression when compared to the pre-term born/control group (p=0.004); no significant changes were seen with SP-D. The full-term/ethanol exposed lambs had no significant alterations in mRNA levels, but had significantly less detectable SP-A protein when compared to the full-term/control lambs (p=0.02). These findings suggest that chronic maternal ethanol consumption during the third trimester of pregnancy alters innate immune gene expression in fetal lung. These alterations may underlie increased susceptibility of pre-term infants, exposed to ethanol in utero, to RSV and other microbial agents

Confirming the Primarily Smooth Structure of the Vega Debris Disk at Millimeter Wavelengths

Clumpy structure in the debris disk around Vega has been previously reported at millimeter wavelengths and attributed to concentrations of dust grains trapped in resonances with an unseen planet. However, recent imaging at similar wavelengths with higher sensitivity has disputed the observed structure. We present three new millimeter wavelength observations that help to resolve the puzzling and contradictory observations. We have observed the Vega system with the Submillimeter Array (SMA) at a wavelength of 880 μm and an angular resolution of 5"; with the Combined Array for Research in Millimeter-wave Astronomy (CARMA) at a wavelength of 1.3 mm and an angular resolution of 5"; and with the Green Bank Telescope (GBT) at a wavelength of 3.3 mm and angular resolution of 10". Despite high sensitivity and short baselines, we do not detect the Vega debris disk in either of the interferometric data sets (SMA and CARMA), which should be sensitive at high significance to clumpy structure based on previously reported observations. We obtain a marginal (3σ) detection of disk emission in the GBT data; the spatial distribution of the emission is not well constrained.We analyze the observations in the context of several different models, demonstrating that the observations are consistent with a smooth, broad, axisymmetric disk with inner radius 20–100 AU and width ≾50 AU. The interferometric data require that at least half of the 860 μm emission detected by previous single-dish observations with the James Clerk Maxwell Telescope be distributed axisymmetrically, ruling out strong contributions from flux concentrations on spatial scales of ≾100 AU. These observations support recent results from the Plateau de Bure Interferometer indicating that previous detections of clumpy structure in the Vega debris disk were spurious

A novel diagnostic gene region for distinguishing between two pest fruit flies: Bactrocera tryoni (Froggatt) and Bactrocera neohumeralis (Hardy) (Diptera: Tephritidae)

Bactrocera tryoni and Bactrocera neohumeralis are morphologically similar sibling pest fruit fly species that possess different biological attributes, geographic distributions, and host ranges. The need to differentiate between the two species is critical for accurate pest status assessment, management, biosecurity, and maintenance of reference colonies. While morphologically similar, adults may be separated based on subtle characters; however, some characters exhibit intraspecific variability, creating overlap between the two species. Additionally, there is currently no single molecular marker or rapid diagnostic assay that can reliably distinguish between B. neohumeralis and B. tryoni; therefore, ambiguous samples remain undiagnosed. Here we report the first molecular marker that can consistently distinguish between B. tryoni and B. neohumeralis. Our diagnostic region consists of two adjacent single nucleotide polymorphisms (SNPs) within the pangolin (pan) gene region. We confirmed the genotypes of each species are consistent across their distributional range, then developed a tetra-primer amplification refractory mutation system (ARMS) PCR assay for rapid diagnosis of the species. The assay utilizes four primers in multiplex, with two outer universal primers, and two internal primers: one designed to target two adjacent SNPs (AA) present in B. tryoni and the other targeting adjacent SNPs present in B. neohumeralis (GG). The assay accurately discriminates between the two species, but their SNP genotypes are shared with other nontarget tephritid fruit fly species. Therefore, this assay is most suited to adult diagnostics where species confirmation is necessary in determining ambiguous surveillance trap catches; maintaining pure colony lines; and in Sterile Insect Technique management responses