High-velocity features: A ubiquitous property of Type Ia supernovae

Evidence of high-velocity features (HVFs) such as those seen in the near-maximum spectra of some Type Ia supernovae (SNe Ia; e. g., SN 2000cx) has been searched for in the available SN Ia spectra observed earlier than 1 week before B maximum. Recent observational efforts have doubled the number of SNe Ia with very early spectra. Remarkably, all SNe Ia with early data ( seven in our Research Training Network sample and 10 from other programs) show signs of such features, to a greater or lesser degree, in Ca II IR and some also in the Si II lambda 6355 line. HVFs may be interpreted as abundance or density enhancements. Abundance enhancements would imply an outer region dominated by Si and Ca. Density enhancements may result from the sweeping up of circumstellar material (CSM) by the highest velocity SN ejecta. In this scenario, the high incidence of HVFs suggests that a thick disk and/or a high-density companion wind surrounds the exploding white dwarf, as may be the case in single degenerate systems. Large-scale angular fluctuations in the radial density and abundance distribution may also be responsible: this could originate in the explosion and would suggest a deflagration as the more likely explosion mechanism. CSM interaction and surface fluctuations may coexist, possibly leaving different signatures on the spectrum. In some SNe, the HVFs are narrowly confined in velocity, suggesting the ejection of blobs of burned material.

Forensic examination of multilayer white paint by lateral scanning Raman spectroscopy

Multilayer samples of white architectural paint potentially have very high evidential value in forensic casework, because the probability that two unrelated samples will have the same sequence of layers is extremely low. However, discrimination between the different layers using optical microscopy is often difficult or impossible. Here, lateral scanning Raman spectroscopy has been used to chemically map the cross-sections of multilayer white paint chips. It was found that the spectra did allow the different layers to be delineated on the basis of their spectral features. The boundaries between different layers were not as sharp as expected, with transitions occurring over length scales of > 20 µm, even with laser spot diameters <4 µm. However, the blurring of the boundaries was not so large as to prevent recording and identification of spectra from each of the layers in the samples. This method clearly provides excellent discrimination between different multilayer white paint samples and can readily be incorporated into existing procedures for examination of paint transfer evidence.

RESONANCE RAMAN INVESTIGATION OF PH-DEPENDENT EQUILIBRIA OF WATER-SOLUBLE IRON PORPHYRINS

Resonance Raman spectroscopy has been used to probe the structures of; tetrakis(1-methylpyridinium-4-yl)-porphinatoiron(III), FeIII (T4MPyP); tetrakis(1-methylpyridium-2-yl)porphinatoiron(III), FeIII (T2MPyP); tetrakis(4-sulphonatophkenyl)porphinatoir(III), FeIII(TSPP); and tetrakis(4-carboxylatophenyl)porphinatoiron(III), FeIII(TCPP), over a wide pH range. The anionic complexes FeIII (TSPP) and FeIII (TCPP) contain high-spin iron(III) at all pHs. Both these complexes exhibit marked spectral changes at ca. pH 6 which correspond to conversion from the diaquo species, in acid solution, to hydroxy- or mu-oxo dimer complexes. Both cationic complexes show similar diaquo to high-spin hydroxy, or mu-oxo dimer, transitions at ca. pH 6. However, at pH > 11.5 for FeIII (T4MPyP) and pH > 9 for FeIII (T2MPyP) a second equilibrium process is observed, leading to two new species. One of these is readily assigned as the low-spin iron(III) dihydroxy complex by analogy with spectra of the dicyano complex. The second species is assigned to the hydroxy iron(II) complex by comparison with photo-chemically generated FeII (T4MPyP) (OH). The formation of iron(II) species in alkaline solutions of FeIII (T4MPyP) and FeIII (T2MPyP) is entirely unexpected and the significance of the observation to previous investigations of the pH-dependent behaviour of these complexes is discussed.

Reactivity difference between protolytic forms of some macrocyclic chromium(III) complexes in ligand substitution and electron transfer processes

The review provides insight into the mechanism of ligand substitution and electron transfer (from chromium(III) to iron(III)) by comparison of the reactivity of some tetraazamacrocyclic chromium(III) complexes in the conjugate acid-base forms. Use of two geometrical isomers made possible to estimate the influence of geometry and protolytic reactions in trans and cis position towards the leaving group on the rate enhancement. Studies on the reaction rates in different media demonstrated the role played by outer sphere interactions in a monodentate ligand substitution. (C) 2009 Published by Elsevier B.V.

OXIDATIVE DISSOLUTION OF CHROMIUM(III) OXIDES BY METAPERIODATE IONS IN PERCHLORIC-ACID

The kinetics of oxidative dissolution of a number of different samples of chromium(III) oxide by periodate ions in 1 mol dm-3 HClO4 solution have been studied and the results interpreted using the inverse-cubic rate law. The metaperiodate acts as a two-electron oxidant and the overall reaction stoichiometry involves the reaction of 3 mol of periodate with 1 mol of Cr(III) oxide. From a detailed study of the kinetics of dissolution the rate-determining step appears to be the reaction between an adsorbed periodate ion and its associated Cr(III) oxide surface site, with inhibition by one of the reaction products, iodate, through competitive adsorption. Analysis of the kinetic data generates values for the Langmuir adsorption coefficients for periodate and iodate ions on highly hydrated Cr(III) oxide of 84 +/- 8 and 2600 +/- 370 dm3 mol-1, respectively. The Cr(III) oxide-periodate reaction has a high overall activation energy, 82 +/- 6 kJ mol-1. The kinetics of dissolution of highly hydrated Cr(III) oxide under conditions in which the simple inverse-cubic rate law function does not apply can be successfully predicted using a simple kinetic model.

Aerobactin iron transport genes commonly encoded by certain ColV plasmids occur in the chromosome of a human invasive strain of Escherichia coli K1

The aerobactin-mediated iron uptake system encoded by pColV-K30 and other ColV plasmids has been associated with the ability of Escherichia coli strains to cause disease. We investigated whether the pColV-K30 aerobactin system is present in E. coli K1 VW187 isolated from a human neonate with meningitis. This strain exhibited a functional aerobactin-mediated iron uptake system, as assessed by a cross-feeding bioassay and by its sensitivity to cloacin, a bacteriocin that recognizes the outer membrane receptor for iron-aerobactin complexes. By using a variety of techniques, we could not find any plasmid harboring the aerobactin genes. Hybridization of restriction endonuclease-cleaved chromosomal DNA from strain VW187 with various clones containing subsets of the pColV-K30 aerobactin region showed that the aerobactin genes were located on a 10.5-kilobase-pair chromosomal HindIII restriction fragment which also contained IS1-like insertion sequences. The chromosomal aerobactin region showed a high degree of conservation when compared with the homologous region in plasmid pColV-K30, although it was located on a different restriction endonuclease site environment.

Modeling colloid deposition on a protein layer adsorbed to iron-oxide-coated sand

Our recent study reported that conformation change of granule-associated Bovine Serum Albumin (BSA) may influence the role of the protein controlling colloid deposition in porous media (Flynn et al., 2012). The present study conceptualized the observed phenomena with an ellipsoid morphology model, describing BSA as an ellipsoid taking a side-on or end-on conformation on granular surface, and identified the following processes: (1) at low adsorbed concentrations, BSA exhibited a side-on conformation blocking colloid deposition; (2) at high adsorbed concentrations, BSA adapted to an end-on conformation promoted colloid deposition; and (3) colloid deposition on the BSA layer may progressively generate end-on molecules (sites) by conformation change of side-on BSA, resulting in sustained increasing deposition rates. Generally, the protein layer lowered colloid attenuation by the porous medium, suggesting the overall effect of BSA was inhibitory at the experimental time scale. A mathematical model was developed to interpret the ripening curves. Modeling analysis identified the site generation efficiency of colloid as a control on the ripening rate (declining rate in colloid concentrations), and this efficiency was higher for BSA adsorbed from a more dilute BSA solution. © 2012 Elsevier B.V.

Cooking rice in a high water to rice ratio reduces inorganic arsenic content

Total arsenic and arsenic speciation was performed on different rice types (basmati, long-grain, polished ([white] and wholegrain [brown]) that had undergone various forms of cooking. The effect of rinse washing, low volume (2.5 : 1 water : rice) and high volume (6 : 1 water : rice) cooking, as well as steaming, were investigated. Rinse washing was effective at removing circa. 10% of the total and inorganic arsenic from basmati rice, but was less effective for other rice types. While steaming reduced total and inorganic arsenic rice content, it did not do so consistently across all rice types investigated. Low volume water cooking did not remove arsenic. High volume water : rice cooking did effectively remove both total and inorganic arsenic for the long-grain and basmati rice (parboiled was not investigated in high volume cooking water experiment), by 35% and 45% for total and inorganic arsenic content, respectively, compared to uncooked (raw) rice. To reduce arsenic content of cooked rice, specifically the inorganic component, rinse washing and high volume of cooking water are effective.

Speciation and localization of arsenic in white and brown rice grains

Synchrotron-based X-ray fluorescence (S-XRF) was utilized to locate arsenic (As) in polished (white) and unpolished (brown) rice grains from the United States, China, and Bangladesh. In white rice As was generally dispersed throughout the grain, the bulk of which constitutes the endosperm. In brown rice As was found to be preferentially localized at the surface, in the region corresponding to the pericarp and aleurone layer. Copper, iron, manganese, and zinc localization followed that of arsenic in brown rice, while the location for cadmium and nickel was distinctly different, showing relatively even distribution throughout the endosperm. The localization of As in the outer grain of brown rice was confirmed by laser ablation ICP-MS. Arsenic speciation of all grains using spatially resolved X-ray absorption near edge structure (micro-XANES) and bulk extraction followed by anion exchange HPLC-ICP-MS revealed the presence of mainly inorganic As and dimethylarsinic acid (DMA). However, the two techniques indicated different proportions of inorganic:organic As species. A wider survey of whole grain speciation of white (n=39) and brown (n=45) rice samples from numerous sources (field collected, supermarket survey, and pot trials) showed that brown rice had a higher proportion of inorganic arsenic present than white rice. Furthermore, the percentage of DMA present in the grain increased along with total grain arsenic.

Lead isotopes and lead shot ingestion in the globally threatened marbled teal (Marmaronetta angustirostris) and white-headed duck (Oxyura leucocephala)

Lead isotope ratios ((206)Pb/(207)Pb and (208)Pb/(207)Pb) and concentrations in the livers and bones of marbled teal and white-headed duck found dead or moribund were determined in order to establish the main lead source in these waterfowl species. Lead concentrations in bone (dry weight) and liver (wet weight) were found to be very high in many of the white-headed ducks (bone: geometric mean=88.9 ppm, maximum=419 ppm; liver: geometric mean=16.8 ppm, maximum=57.0 ppm). Some of the marbled teal had high lead levels in the bones but liver lead levels were all low (bone: geometric mean=6.13 ppm, maximum=112 ppm; liver: geometric mean=0.581 ppm, maximum=4.77 ppm). Ingested lead shot were found in 71% of the white-headed duck and 20% of the marbled teal. The (206)Pb/(207)Pb ratio in livers and bones of white-headed ducks and marbled teals showed no significant differences compared to the ratios obtained from lead shot. The (206)Pb/(207)Pb ratio in bones of marbled teal ducklings with the highest lead concentrations tended to resemble the ratios of lead shot, which supports our hypothesis that the lead was derived from the hens. We also found that the lead ratios of lead shot and lead ratios described for soils in the area overlapped, but also that the isotopic ratio (206)Pb/(207)Pb in lead shot used in Spain has a narrow range compared with those used in North America. The principal source of lead in many of these birds was, however, most likely lead shot, as supported by the similar isotopic ratios, high lead concentrations in tissues and evidence of ingested shot.

HIGH SPEED CMOS/SOS IMPLEMENTATION OF A BIT LEVEL SYSTOLIC CORRELATOR.

The fabrication and performance of the first bit-level systolic correlator array is described. The application of systolic array concepts at the bit level provides a simple and extremely powerful method for implementing high-performance digital processing functions. The resulting structure is highly regular, facilitating yield enhancement through fault-tolerant redundancy techniques and therefore ideally suited to implementation as a VLSI chip. The CMOS/SOS chip operates at 35 MHz, is fully cascadable and exhibits 64-stage correlation for 1-bit reference and 4-bit data. 7 refs.

Oxidative dehydrogenation of propane with N2O over Fe-ZSM-5 and Fe-SiO2: Influence of the iron species and acid sites

A series of iron containing zeolites with varying Si/Al ratios (11.5-140) and low iron content (similar to 0.9 wt.% Fe) have been synthesised by solid-state ion exchange with commercially available zeolites and tested, for the first time, in the oxidative dehydrogenation of propane (ODHP) with N2O. The samples were characterised by XRD, N-2-Adsorption, NH3-TPD and DR-UV-vis spectroscopy. The acidity of the Fe-ZSM-5 can be controlled by high temperature and steam treatments and Si/Al ratio. The selectivity and yield of propene were found to be the highest over Fe-ZSM-5 with low Al contents and reduced acidity. The initial propene yield over Fe-ZSM-5 was significantly higher than that of Fe-SiO2 since the presence of weak and/or medium acid sites together with oligonuclear iron species and iron oxides on the ZSM-5 are found to enhance the N2O activation. The coking of Fe-ZSM-5 catalysts could also be controlled by reduction of the surface acidity of ZSM-5 and by the use of O-2 in addition to N2O as the oxidant. Fe-ZSM-5 zeolites prepared with solid-state method have been shown to have comparable activity and better stability towards coking compared with Fe-ZSM-5 zeolites prepared by liquid ion exchange and hydrothermal synthesis methods. (C) 2012 Elsevier B.V. All rights reserved.

Collectives of diagnostic biomarkers identify high-risk subpopulations of hematuria patients: exploiting heterogeneity in large-scale biomarker data

Background: Ineffective risk stratification can delay diagnosis of serious disease in patients with hematuria. We applied a systems biology approach to analyze clinical, demographic and biomarker measurements (n = 29) collected from 157 hematuric patients: 80 urothelial cancer (UC) and 77 controls with confounding pathologies.

Methods: On the basis of biomarkers, we conducted agglomerative hierarchical clustering to identify patient and biomarker clusters. We then explored the relationship between the patient clusters and clinical characteristics using Chi-square analyses. We determined classification errors and areas under the receiver operating curve of Random Forest Classifiers (RFC) for patient subpopulations using the biomarker clusters to reduce the dimensionality of the data.

Results: Agglomerative clustering identified five patient clusters and seven biomarker clusters. Final diagnoses categories were non-randomly distributed across the five patient clusters. In addition, two of the patient clusters were enriched with patients with ‘low cancer-risk’ characteristics. The biomarkers which contributed to the diagnostic classifiers for these two patient clusters were similar. In contrast, three of the patient clusters were significantly enriched with patients harboring ‘high cancer-risk” characteristics including proteinuria, aggressive pathological stage and grade, and malignant cytology. Patients in these three clusters included controls, that is, patients with other serious disease and patients with cancers other than UC. Biomarkers which contributed to the diagnostic classifiers for the largest ‘high cancer- risk’ cluster were different than those contributing to the classifiers for the ‘low cancer-risk’ clusters. Biomarkers which contributed to subpopulations that were split according to smoking status, gender and medication were different.

Conclusions: The systems biology approach applied in this study allowed the hematuric patients to cluster naturally on the basis of the heterogeneity within their biomarker data, into five distinct risk subpopulations. Our findings highlight an approach with the promise to unlock the potential of biomarkers. This will be especially valuable in the field of diagnostic bladder cancer where biomarkers are urgently required. Clinicians could interpret risk classification scores in the context of clinical parameters at the time of triage. This could reduce cystoscopies and enable priority diagnosis of aggressive diseases, leading to improved patient outcomes at reduced costs. © 2013 Emmert-Streib et al; licensee BioMed Central Ltd.

2D simulations of the double-detonation model for thermonuclear transients from low-mass carbon-oxygen white dwarfs

Thermonuclear explosions may arise in binary star systems in which a carbon-oxygen (CO) white dwarf (WD) accretes helium-rich material from a companion star. If the accretion rate allows a sufficiently large mass of helium to accumulate prior to ignition of nuclear burning, the helium surface layer may detonate, giving rise to an astrophysical transient. Detonation of the accreted helium layer generates shock waves that propagate into the underlying CO WD. This might directly ignite a detonation of the CO WD at its surface (an edge-lit secondary detonation) or compress the core of the WD sufficiently to trigger a CO detonation near the centre. If either of these ignition mechanisms works, the two detonations (helium and CO) can then release sufficient energy to completely unbind the WD. These 'double-detonation' scenarios for thermonuclear explosion of WDs have previously been investigated as a potential channel for the production of Type Ia supernovae from WDs of ~ 1 M . Here we extend our 2D studies of the double-detonation model to significantly less massive CO WDs, the explosion of which could produce fainter, more rapidly evolving transients. We investigate the feasibility of triggering a secondary core detonation by shock convergence in low-mass CO WDs and the observable consequences of such a detonation. Our results suggest that core detonation is probable, even for the lowest CO core masses that are likely to be realized in nature. To quantify the observable signatures of core detonation, we compute spectra and light curves for models in which either an edge-lit or compression-triggered CO detonation is assumed to occur. We compare these to synthetic observables for models in which no CO detonation was allowed to occur. If significant shock compression of the CO WD occurs prior to detonation, explosion of the CO WD can produce a sufficiently large mass of radioactive iron-group nuclei to significantly affect the light curves. In particular, this can lead to relatively slow post-maximum decline. If the secondary detonation is edge-lit, however, the CO WD explosion primarily yields intermediate-mass elements that affect the observables more subtly. In this case, near-infrared observations and detailed spectroscopic analysis would be needed to determine whether a core detonation occurred. We comment on the implications of our results for understanding peculiar astrophysical transients including SN 2002bj, SN 2010X and SN 2005E. © 2012 The Authors Monthly Notices of the Royal Astronomical Society © 2012 RAS.