First-principles calculation of carrier-phonon scattering in n-type Si1−xGex alloys

First-principles electronic structure methods are used to find the rates of inelastic intravalley and intervalley n-type carrier scattering in Si1-xGex alloys. Scattering parameters for all relevant Delta and L intra- and intervalley scattering are calculated. The short-wavelength acoustic and the optical phonon modes in the alloy are computed using the random mass approximation, with interatomic forces calculated in the virtual crystal approximation using density functional perturbation theory. Optical phonon and intervalley scattering matrix elements are calculated from these modes of the disordered alloy. It is found that alloy disorder has only a small effect on the overall inelastic intervalley scattering rate at room temperature. Intravalley acoustic scattering rates are calculated within the deformation potential approximation. The acoustic deformation potentials are found directly and the range of validity of the deformation potential approximation verified in long-wavelength frozen phonon calculations. Details of the calculation of elastic alloy scattering rates presented in an earlier paper are also given. Elastic alloy disorder scattering is found to dominate over inelastic scattering, except for almost pure silicon (x approximate to 0) or almost pure germanium (x approximate to 1), where acoustic phonon scattering is predominant. The n-type carrier mobility, calculated from the total (elastic plus inelastic) scattering rate, using the Boltzmann transport equation in the relaxation time approximation, is in excellent agreement with experiments on bulk, unstrained alloys..

[N]pT ensemble and finite-size-scaling study of the critical isostructural transition in the generalized exponential model of index 4.

First-order transitions of system where both lattice site occupancy and lattice spacing fluctuate, such as cluster crystals, cannot be efficiently studied by traditional simulation methods, which necessarily fix one of these two degrees of freedom. The difficulty, however, can be surmounted by the generalized [N]pT ensemble [J. Chem. Phys. 136, 214106 (2012)]. Here we show that histogram reweighting and the [N]pT ensemble can be used to study an isostructural transition between cluster crystals of different occupancy in the generalized exponential model of index 4 (GEM-4). Extending this scheme to finite-size scaling studies also allows us to accurately determine the critical point parameters and to verify that it belongs to the Ising universality class.

Statistical methods for polyhedral shape classification with incomplete data - application to cryo-electron tomographic images

A certain type of bacterial inclusion, known as a bacterial microcompartment, was recently identified and imaged through cryo-electron tomography. A reconstructed 3D object from single-axis limited angle tilt-series cryo-electron tomography contains missing regions and this problem is known as the missing wedge problem. Due to missing regions on the reconstructed images, analyzing their 3D structures is a challenging problem. The existing methods overcome this problem by aligning and averaging several similar shaped objects. These schemes work well if the objects are symmetric and several objects with almost similar shapes and sizes are available. Since the bacterial inclusions studied here are not symmetric, are deformed, and show a wide range of shapes and sizes, the existing approaches are not appropriate. This research develops new statistical methods for analyzing geometric properties, such as volume, symmetry, aspect ratio, polyhedral structures etc., of these bacterial inclusions in presence of missing data. These methods work with deformed and non-symmetric varied shaped objects and do not necessitate multiple objects for handling the missing wedge problem. The developed methods and contributions include: (a) an improved method for manual image segmentation, (b) a new approach to 'complete' the segmented and reconstructed incomplete 3D images, (c) a polyhedral structural distance model to predict the polyhedral shapes of these microstructures, (d) a new shape descriptor for polyhedral shapes, named as polyhedron profile statistic, and (e) the Bayes classifier, linear discriminant analysis and support vector machine based classifiers for supervised incomplete polyhedral shape classification. Finally, the predicted 3D shapes for these bacterial microstructures belong to the Johnson solids family, and these shapes along with their other geometric properties are important for better understanding of their chemical and biological characteristics.

New methods for the asymmetric synthesis of α-alkylated ketones and 1,3-amino alcohols

A large number of optically active drugs and natural products contain α-functionalised ketones or simple derivatives thereof. Furthermore, chiral α-alkylated ketones are useful synthons and have found widespread use in total synthesis. The asymmetric alkylation of ketones represents one of the most powerful and longstanding procedures in organic chemistry. Surprisingly, however, only one effective methodology is available, and this involves the use of chiral auxiliaries. This is discussed in Chapter 1, which also provides a background of other key topics discussed throughout the thesis. Expanding on the existing methodology of chiral auxiliaries, Chapter 2 details the synthesis of a novel chiral auxiliary containing a pyrrolidine ring and its use in the asymmetric preparation of α-alkylated ketones with good enantioselectivity. The synthesis of racemic α-alkylated ketones as reference standards for GC chromatography is also reported in this chapter. Chapter 3 details a new approach to chiral α-alkylated ketones using an intermolecular chirality transfer methodology. This approach employs the use of simple non-chiral dimethylhydrazones and their asymmetric alkylation using the chiral diamine ligands, (+)- and (-)-sparteine. The methodology described represents the first example of an asymmetric alkylation of non-chiral azaenolates. Enantiomeric ratios up to 83 : 17 are observed. Chapter 4 introduces the first aldol-Tishchenko reaction of an imine derivative for the preparation of 1,3-aminoalcohol precursors. 1,3-Aminoalcohols can be synthesised via indirect routes involving various permutations of stepwise construction with asymmetric induction. Our approach offers an alternative highly diastereomeric route to the synthesis of this important moiety utilising N-tert-butanesulfinyl imines in an aldol-Tishchenko-type reaction. Chapter 5 details the experimental procedures for all of the above work. Chapter 6 discusses the results of a separate research project undertaken during this PhD. 2-alkyl-quinolin-4-ones and their N-substituted derivatives have several important biological functions such as the role of Pseudomonas quinolone signal (PQS) in quorum sensing. Herein, we report the synthesis of its biological precursor, 2-heptyl-4-hydroxy-quinoline (HHQ) and possible isosteres of PQS; the C-3 Cl, Br and I analogues. N-Methylation of the iodide was also feasible and the usefulness of this compound showcased in Pd-catalysed cross-coupling reactions, thus allowing access to a diverse set of biologically important molecules.

Risk factors for macro- and microvascular complications among older adults with diagnosed type 2 diabetes: findings from The Irish Longitudinal Study on Ageing

Objective. To explore risk factors for macro- and microvascular complications in a nationally representative sample of adults aged 50 years and over with type 2 diabetes in Ireland. Methods. Data from the first wave of The Irish Longitudinal Study on Ageing (TILDA) (2009–2011) was used in cross-sectional analysis. The presence of doctor diagnosis of diabetes, risk factors, and macro and microvascular complications were determined by self-report. Gender-specific differences in risk factor prevalence were assessed with the chi-squared test. Binomial regression analysis was conducted to explore independent associations between established risk factors and diabetes-related complications. Results. Among 8175 respondents, 655 were classified as having type 2 diabetes. Older age, being male, a history of smoking, a lower level of physical activity, and a diagnosis of high cholesterol were independent predictors of macrovascular complications. Diabetes diagnosis of 10 or more years, a history of smoking, and a diagnosis of hypertension were associated with an increased risk of microvascular complications. Older age, third-level education, and a high level of physical activity were protective factors (

Chemical composition of manganese nodules and a ferromanganese crust using different methods

In the 1960s and 1970s, the Kennecott Corporation conducted a number of activities in the evaluation of manganese nodule deposits as well as in their possible hydrometallurgy.

Chemical composition of nodules from two locations in the Pacific Ocean using different methods

Manganese nodules recovered in the Pacific Ocean by the U. S. Bureau of Mines and by DeepSea Ventures Ltd. are studied for their chemical composition using X microprobe and X-ray fluorescence methods.

Efficacy and Safety of Cannabidiol and Tetrahydrocannabivarin on Glycemic and Lipid Parameters in Patients With Type 2 Diabetes: A Randomized, Double-Blind, Placebo-Controlled, Parallel Group Pilot Study

OBJECTIVE Cannabidiol (CBD) and D9-tetrahydrocannabivarin (THCV) are nonpsychoactive phytocannabinoids affecting lipid and glucose metabolism in animal models. This study set out to examine the effects of these compounds in patients with type 2 diabetes. RESEARCH DESIGN AND METHODS In this randomized, double-blind, placebo-controlled study, 62 subjects with noninsulin-treated type 2 diabetes were randomized to five treatment arms: CBD (100 mg twice daily), THCV (5 mg twice daily), 1:1 ratio of CBD and THCV (5 mg/5 mg, twice daily), 20:1 ratio of CBD and THCV (100 mg/5 mg, twice daily), or matched placebo for 13 weeks. The primary end point was a change in HDL-cholesterol concentrations from baseline. Secondary/tertiary end points included changes in glycemic control, lipid profile, insulin sensitivity, body weight, liver triglyceride content, adipose tissue distribution, appetite, markers of inflammation, markers of vascular function, gut hormones, circulating endocannabinoids, and adipokine concentrations. Safety and tolerability end points were also evaluated. RESULTS Compared with placebo, THCV significantly decreased fasting plasma glucose (estimated treatment difference [ETD] = 21.2 mmol/L; P < 0.05) and improved pancreatic b-cell function (HOMA2 b-cell function [ETD = 244.51 points; P < 0.01]), adiponectin (ETD = 25.9 3 106 pg/mL; P < 0.01), and apolipoprotein A (ETD = 26.02 mmol/L; P < 0.05), although plasma HDL was unaffected. Compared with baseline (but not placebo), CBD decreased resistin (2898 pg/ml; P < 0.05) and increased glucose-dependent insulinotropic peptide (21.9 pg/ml; P < 0.05). None of the combination treatments had a significant impact on end points. CBD and THCV were well tolerated. CONCLUSIONS THCV could represent a newtherapeutic agent in glycemic control in subjects with type 2 diabetes.

Type Ia supernovae from violent mergers of carbon-oxygen white dwarfs: polarization signatures

The violent merger of two carbon-oxygen white dwarfs has been proposed as a viable progenitor for some Type Ia supernovae. However, it has been argued that the strong ejecta asymmetries produced by this model might be inconsistent with the low degree of polarization typically observed in Type Ia supernova explosions. Here, we test this claim by carrying out a spectropolarimetric analysis for the model proposed by Pakmor et al. for an explosion triggered during the merger of a 1.1 and 0.9 M⊙ carbon-oxygen white dwarf binary system. Owing to the asymmetries of the ejecta, the polarization signal varies significantly with viewing angle. We find that polarization levels for observers in the equatorial plane are modest (≲1 per cent) and show clear evidence for a dominant axis, as a consequence of the ejecta symmetry about the orbital plane. In contrast, orientations out of the plane are associated with higher degrees of polarization and departures from a dominant axis. While the particular model studied here gives a good match to highly polarized events such as SN 2004dt, it has difficulties in reproducing the low polarization levels commonly observed in normal Type Ia supernovae. Specifically, we find that significant asymmetries in the element distribution result in a wealth of strong polarization features that are not observed in the majority of currently available spectropolarimetric data of Type Ia supernovae. Future studies will map out the parameter space of the merger scenario to investigate if alternative models can provide better agreement with observations.

The peculiar Type Ia supernova iPTF14atg: Chandrasekhar-mass explosion or violent merger?

iPTF14atg, a subluminous peculiar Type Ia supernova (SN Ia) similar to SN 2002es, is the first SN Ia for which a strong UV flash was observed in the early-time light curves. This has been interpreted as evidence for a single-degenerate (SD) progenitor system, where such a signal is expected from interactions between the SN ejecta and the non-degenerate companion star. Here, we compare synthetic observables of multidimensional state-of-the-art explosion models for different progenitor scenarios to the light curves and spectra of iPTF14atg. From our models, we have difficulties explaining the spectral evolution of iPTF14atg within the SD progenitor channel. In contrast, we find that a violent merger of two carbon-oxygen white dwarfs with 0.9 and 0.76 M⊙, respectively, provides an excellent match to the spectral evolution of iPTF14atg from 10 d before to several weeks after maximum light. Our merger model does not naturally explain the initial UV flash of iPTF14atg. We discuss several possibilities like interactions of the SN ejecta with the circumstellar medium and surface radioactivity from an He-ignited merger that may be able to account for the early UV emission in violent merger models.

Mechanical stretch up-regulates the B-type natriuretic peptide system in human cardiac fibroblasts:a possible defense against transforming growth factor-β mediated fibrosis

BACKGROUND: Mechanical overload of the heart is associated with excessive deposition of extracellular matrix proteins and the development of cardiac fibrosis. This can result in reduced ventricular compliance, diastolic dysfunction, and heart failure. Extracellular matrix synthesis is regulated primarily by cardiac fibroblasts, more specifically, the active myofibroblast. The influence of mechanical stretch on human cardiac fibroblasts' response to pro-fibrotic stimuli, such as transforming growth factor beta (TGFβ), is unknown as is the impact of stretch on B-type natriuretic peptide (BNP) and natriuretic peptide receptor A (NPRA) expression. BNP, acting via NPRA, has been shown to play a role in modulation of cardiac fibrosis.

METHODS AND RESULTS: The effect of cyclical mechanical stretch on TGFβ induction of myofibroblast differentiation in primary human cardiac fibroblasts and whether differences in response to stretch were associated with changes in the natriuretic peptide system were investigated. Cyclical mechanical stretch attenuated the effectiveness of TGFβ in inducing myofibroblast differentiation. This finding was associated with a novel observation that mechanical stretch can increase BNP and NPRA expression in human cardiac fibroblasts, which could have important implications in modulating myocardial fibrosis. Exogenous BNP treatment further reduced the potency of TGFβ on mechanically stretched fibroblasts.

CONCLUSION: We postulate that stretch induced up-regulation of the natriuretic peptide system may contribute to the observed reduction in myofibroblast differentiation.

Long-term statin therapy in patients with systolic heart failure and normal cholesterol:effects on elevated serum markers of collagen turnover, inflammation, and B-type natriuretic peptide

BACKGROUND: The role of statin therapy in heart failure (HF) is unclear. The amino-terminal propeptide of procollagen type III (PIIINP) predicts outcome in HF, and yet there are conflicting reports of statin therapy effects on PIIINP.

OBJECTIVES: This study determined whether there was an increase in serum markers of inflammation, fibrosis (including PIIINP), and B-type natriuretic peptide (BNP) in patients with systolic HF and normal total cholesterol and determined the effects of long-term treatment with atorvastatin on these markers.

METHODS: Fifty-six white patients with systolic HF and normal cholesterol levels (age 72 [13] years; 68% male; body mass index 27.0 [7.3] kg/m(2); ejection fraction 35 [13]%; 46% with history of smoking) were randomly allocated to atorvastatin treatment for 6 months, titrated to 40 mg/d (A group) or not (C group). Age- and/or sex-matched subjects without HF (N group) were also recruited. Biomarkers were measured at baseline (all groups) and 6 months (A and C groups).

RESULTS: Serum markers of collagen turnover, inflammation, and BNP were significantly elevated in HF patients compared with normal participants (all P < 0.05). There were correlations between these markers in HF patients but not in normal subjects. Atorvastatin treatment for 6 months caused a significant reduction in the following biomarkers compared with baseline: BNP, from median (interquartile range) 268 (190-441) pg/mL to 185 (144-344) pg/mL; high-sensitivity C-reactive protein (hs-CRP), from 5.26 (1.95 -9.29) mg/L to 3.70 (2.34-6.81) mg/L; and PIIINP, from 4.65 (1.86) to 4.09 (1.25) pg/mL (all P < 0.05 baseline vs 6 months). Between-group differences were significant for PIIINP only (P = 0.027). There was a positive interaction between atorvastatin effects and baseline hs-CRP and PIIINP (P < 0.01).

CONCLUSIONS: Long-term statin therapy reduced PIIINP in this small, selected HF population with elevated baseline levels. Further evaluation of statin therapy in the management of HF patients with elevated PIIINP is warranted.

The VLT-FLAMES Tarantula Survey XXI. Stellar spin rates of O-type spectroscopic binaries

Context: The initial distribution of spin rates of massive stars is a fingerprint of their elusive formation process. It also sets a key initial condition for stellar evolution and is thus an important ingredient in stellar population synthesis. So far, most studies have focused on single stars. Most O stars are, however, found in multiple systems. 

Aims: By establishing the spin-rate distribution of a sizeable sample of O-type spectroscopic binaries and by comparing the distributions of binary subpopulations with one another and with that of presumed-single stars in the same region, we aim to constrain the initial spin distribution of O stars in binaries, and to identify signatures of the physical mechanisms that affect the evolution of the spin rates of massive stars. 

Methods: We use ground-based optical spectroscopy obtained in the framework of the VLT-FLAMES Tarantula Survey (VFTS) to establish the projected equatorial rotational velocities (ν_esini) for components of 114 spectroscopic binaries in 30 Doradus. The ν_esini values are derived from the full width at half maximum (FWHM) of a set of spectral lines, using a FWHM vs. ν_esini calibration that we derive based on previous line analysis methods applied to single O-type stars in the VFTS sample. 

Results: The overall ν_esini distribution of the primary stars resembles that of single O-type stars in the VFTS, featuring a low-velocity peak (at ν_esini<200 kms^-1) and a shoulder at intermediate velocities (200 <ν_esini<300 kms^-1). The distributions of binaries and single stars, however, differ in two ways. First, the main peak at ν_esini ~ 100kms^-1 is broader and slightly shifted towards higher spin rates in the binary distribution than that of the presumed-single stars. This shift is mostly due to short-period binaries (P_orb~<10 d). Second, the ν_esini distribution of primaries lacks a significant population of stars spinning faster than 300 kms^-1, while such a population is clearly present in the single-star sample. The ν_esini distribution of binaries with amplitudes of radial velocity variation in the range of 20 to 200 kms^-1 (mostly binaries with P_orb ~ 10-1000 d and/or with q<0.5) is similar to that of single O stars below ν_esini_~<170kms^-1. 

Conclusions: Our results are compatible with the assumption that binary components formed with the same spin distribution as single stars, and that this distribution contains few or no fast-spinning stars. The higher average spin rate of stars in short-period binaries may either be explained by spin-up through tides in such tight binary systems, or by spin-down of a fraction of the presumed-single stars and long-period binaries through magnetic braking (or by a combination of both mechanisms). Most primaries and secondaries of SB2 systems with P_orb~<10 d appear to have similar rotational velocities. This is in agreement with tidal locking in close binaries where the components have similar radii. The lack of very rapidly spinning stars among binary systems supports the idea that most stars with ν_esini_~> 300kms^-1 in the single-star sample are actually spun-up post-binary interaction products. Finally, the overall similarities (low-velocity peak and intermediate-velocity shoulder) of the spin distribution of binary and single stars argue for a massive star formation process in which the initial spin is set independently of whether stars are formed as single stars or as components of a binary system.

The VLT-FLAMES Tarantula Survey: XIX. B-type supergiants: Atmospheric parameters and nitrogen abundances to investigate the role of binarity and the width of the main sequence

Context: Model atmosphere analyses have been previously undertaken for both Galactic and extragalactic B-type supergiants. By contrast, little attention has been given to a comparison of the properties of single supergiants and those that are members of multiple systems. 

Aims: Atmospheric parameters and nitrogen abundances have been estimated for all the B-type supergiants identified in the VLT-FLAMES Tarantula survey. These include both single targets and binary candidates. The results have been analysed to investigate the role of binarity in the evolutionary history of supergiants. 

Methods: tlusty non-local thermodynamic equilibrium (LTE) model atmosphere calculations have been used to determine atmospheric parameters and nitrogen abundances for 34 single and 18 binary supergiants. Effective temperatures were deduced using the silicon balance technique, complemented by the helium ionisation in the hotter spectra. Surface gravities were estimated using Balmer line profiles and microturbulent velocities deduced using the silicon spectrum. Nitrogen abundances or upper limits were estimated from the Nii spectrum. The effects of a flux contribution from an unseen secondary were considered for the binary sample. Results. We present the first systematic study of the incidence of binarity for a sample of B-type supergiants across the theoretical terminal age main sequence (TAMS). To account for the distribution of effective temperatures of the B-type supergiants it may be necessary to extend the TAMS to lower temperatures. This is also consistent with the derived distribution of mass discrepancies, projected rotational velocities and nitrogen abundances, provided that stars cooler than this temperature are post-red supergiant objects. For all the supergiants in the Tarantula and in a previous FLAMES survey, the majority have small projected rotational velocities. The distribution peaks at about 50 km s^-1 with 65% in the range 30 km s^-1 ≤ ν_e sin i ≤ 60 km s^-1. About ten per cent have larger ve sin i (≥100 km s^-1), but surprisingly these show little or no nitrogen enhancement. All the cooler supergiants have low projected rotational velocities of ≤70 km s^-1 and high nitrogen abundance estimates, implying that either bi-stability braking or evolution on a blue loop may be important. Additionally, there is a lack of cooler binaries, possibly reflecting the small sample sizes. Single-star evolutionary models, which include rotation, can account for all of the nitrogen enhancement in both the single and binary samples. The detailed distribution of nitrogen abundances in the single and binary samples may be different, possibly reflecting differences in their evolutionary history. 

Conclusions: The first comparative study of single and binary B-type supergiants has revealed that the main sequence may be significantly wider than previously assumed, extending to T_eff = 20 000 K. Some marginal differences in single and binary atmospheric parameters and abundances have been identified, possibly implying non-standard evolution for some of the sample. This sample as a whole has implications for several aspects of our understanding of the evolutionary status of blue supergiants.

The VLT-FLAMES tarantula survey:XII. Rotational velocities of the single O-type stars

Context. The 30 Doradus (30 Dor) region of the Large Magellanic Cloud, also known as the Tarantula nebula, is the nearest starburst region. It contains the richest population of massive stars in the Local Group, and it is thus the best possible laboratory to investigate open questions on the formation and evolution of massive stars. Aims. Using ground-based multi-object optical spectroscopy obtained in the framework of the VLT-FLAMES Tarantula Survey (VFTS), we aim to establish the (projected) rotational velocity distribution for a sample of 216 presumably single O-type stars in 30 Dor. The sample is large enough to obtain statistically significant information and to search for variations among subpopulations - in terms of spectral type, luminosity class, and spatial location - in the field of view. Methods. We measured projected rotational velocities, 3e sin i, by means of a Fourier transform method and a profile fitting method applied to a set of isolated spectral lines. We also used an iterative deconvolution procedure to infer the probability density, P(3e), of the equatorial rotational velocity, 3e. Results. The distribution of 3e sin i shows a two-component structure: a peak around 80 km s1 and a high-velocity tail extending up to 600 km s^-1 This structure is also present in the inferred distribution P(3e) with around 80% of the sample having 0 <3e ≤ 300 km s^-1 and the other 20% distributed in the high-velocity region. The presence of the low-velocity peak is consistent with what has been found in other studies for late O- and early B-type stars. Conclusions. Most of the stars in our sample rotate with a rate less than 20% of their break-up velocity. For the bulk of the sample, mass loss in a stellar wind and/or envelope expansion is not efficient enough to significantly spin down these stars within the first few Myr of evolution. If massive-star formation results in stars rotating at birth with a large portion of their break-up velocities, an alternative braking mechanism, possibly magnetic fields, is thus required to explain the present-day rotational properties of the O-type stars in 30 Dor. The presence of a sizeable population of fast rotators is compatible with recent population synthesis computations that investigate the influence of binary evolution on the rotation rate of massive stars. Even though we have excluded stars that show significant radial velocity variations, our sample may have remained contaminated by post-interaction binary products. That the highvelocity tail may be populated primarily (and perhaps exclusively) by post-binary interaction products has important implications for the evolutionary origin of systems that produce gamma-ray bursts. © 2013 Author(s).