Clusters, liquids and crystals of dialkylimidazolium salts. A combined perspective from ab initio computer simulations

We summarize results obtained by a combination of ab initio and classical computer simulations of dialkylimidazolium ionic liquids in different states of aggregation, from crystals to liquids and clusters. Unusual features arising from the competition between electrostatic, dispersion, and hydrogen-bonding interactions are identified at the origin of observed structural patterns. We also discuss the way Brønsted acids interact with ionic liquids leading to the formation of hydrogen-bonded anions.

Interleukin-8 signaling promotes androgen-independent proliferation of prostate cancer cells via induction of androgen receptor expression and activation

The aim of our study was to assess the importance of the CXC chemokine and interleukin (IL)-8 in promoting the transition of prostate cancer (CaP) to the androgen-independent state. Stimulation of the androgen-dependent cell lines, LNCaP and 22Rv1, with exogenous recombinant human interleukin-8 (rh-IL-8) increased androgen receptor (AR) gene expression at the messenger RNA (mRNA) and protein level, assessed by quantitative polymerase chain reaction and immunoblotting, respectively. Using an androgen response element-luciferase construct, we demonstrated that rh-IL-8 treatment also resulted in increased AR transcriptional activity in both these cell lines, and a subsequent upregulation of prostate-specific antigen and cyclin-dependent kinase 2 mRNA transcript levels in LNCaP cells. Blockade of CXC chemokine receptor-2 signaling using a small molecule antagonist (AZ10397767) attenuated the IL-8-induced increases in AR expression and transcriptional activity. Furthermore, in 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assays, coadministration of AZ10397767 reduced the viability of LNCaP and 22Rv1 cells exposed to bicalutamide. Our data show that IL-8 signaling increases AR expression and promotes ligand-independent activation of this receptor in two androgen-dependent cell lines, describing two mechanisms by which this chemokine may assist in promoting the transition of CaP to the androgen-independent state. In addition, our data show that IL-8-promoted regulation of the AR attenuates the effectiveness of the AR antagonist bicalutamide in reducing CaP cell viability.

Friedel-Crafts Benzoylation of Anisole in Ionic Liquids: Catalysis, Separation, and Recycle Studies

The comparison of three ionic liquid-mediated catalytic processes for the benzoylation of anisole with benzoic anhydride is presented. A detailed understanding of the mechanism by which the zeolite and metal triflate reactions in bis{trifluoromethanesulfonyl}imide-based ionic liquids has been reported previously, and these routes are considered together with an indium chloride-based ionic liquid system. Solvent extraction and vacuum/steam distillation have been assessed as possible workup procedures, and an overall preliminary economic evaluation of each overall process is reported. Although the predominant activity is associated with the in situ formation of a homogeneous acid catalyst, the low cost and facile separation of the zeolite-catalysed process leads to this route being the most economically viable overall option. The results of a continuous flow miniplant based on the zeolite catalyst are also presented and compared with the reaction using a small plug How reactor.

Heart Rhythm UK position statement on clinical indications for implantable cardioverter defibrillators in adult patients with familial sudden cardiac death syndromes

Whilst the decision regarding defibrillator implantation in a patient with a familial sudden cardiac death syndrome is likely to be most significant for any particular individual, the clinical decision-making process itself is complex and requires interpretation and extrapolation of information from a number of different sources. This document provides recommendations for adult patients with the congenital Long QT syndromes, Brugada syndrome, catecholaminergic polymorphic ventricular tachycardia, hypertrophic cardiomyopathy, and arrhythmogenic right ventricular cardiomyopathy. Although these specific conditions differ in terms of clinical features and prognosis, it is possible and logical to take an approach to determining a threshold for implantable cardioveter-defibrillator implantation that is common to all of the familial sudden cardiac death syndromes based on estimates of absolute risk of sudden death. Published on behalf of the European Society of Cardiology. © The Author 2010.

Three-dimensional delayed-detonation models with nucleosynthesis for type ia supernovae

We present results for a suite of 14 three-dimensional, high-resolution hydrodynamical simulations of delayed-detonation models of Type Ia supernova (SN Ia) explosions. This model suite comprises the first set of three-dimensional SN Ia simulations with detailed isotopic yield information. As such, it may serve as a data base for Chandrasekhar-mass delayed-detonation model nucleosynthetic yields and for deriving synthetic observables such as spectra and light curves. We employ aphysically motivated, stochastic model based on turbulent velocity fluctuations and fuel density to calculate in situ the deflagration-to-detonation transition probabilities. To obtain different strengths of the deflagration phase and thereby different degrees of pre-expansion, we have chosen a sequence of initial models with 1, 3, 5, 10, 20, 40, 100, 150, 200, 300 and 1600 (two different realizations) ignition kernels in a hydrostatic white dwarf with a central density of 2.9 × 10 g cm, as well as one high central density (5.5 × 10 g cm) and one low central density (1.0 × 10 g cm) rendition of the 100 ignition kernel configuration. For each simulation, we determined detailed nucleosynthetic yields by postprocessing10 tracer particles with a 384 nuclide reaction network. All delayed-detonation models result in explosions unbinding thewhite dwarf, producing a range of 56Ni masses from 0.32 to 1.11M. As a general trend, the models predict that the stableneutron-rich iron-group isotopes are not found at the lowest velocities, but rather at intermediate velocities (~3000×10 000 km s) in a shell surrounding a Ni-rich core. The models further predict relatively low-velocity oxygen and carbon, with typical minimum velocities around 4000 and 10 000 km s, respectively. © 2012 The Authors. Published by Oxford University Press on behalf of the Royal Astronomical Society.

Influence of concrete composition on anchorage bond behavior of prestressing reinforcement

An experimental research addressing the effects of concrete composition and strength on anchorage bond behavior of prestressing reinforcement is presented to clarify the effect of material properties that have appeared contradictory in previous literature. Bond stresses and anchorage lengths have been obtained in twelve concrete mixes made up of different cement contents (C) – 350 to 500 kg/m3 – and water/cement (w/c) ratios – 0.3 to 0.5 – with compressive strength at 24 h ranging from 24 to 55 MPa. A testing technique based on measuring the prestressing force in specimens with different embedment lengths has been used. The results show that anchorage length increases when w/c increases, more significantly when C is higher; the effect of C reveals different trends based on w/c. The obtained anchorage bond stresses are greater for higher concrete compressive strength, and their average ratio of 1.45 with respect to transmission bond stresses implies a potential bond capacity.

Tephra from andesitic Shiveluch volcano, Kamchatka, NW Pacific: chronology of explosive eruptions and geochemical fingerprinting of volcanic glass

The ~16-ka-long record of explosive eruptions from Shiveluch volcano (Kamchatka, NW Pacific) is refined using geochemical fingerprinting of tephra and radiocarbon ages. Volcanic glass from 77 prominent Holocene tephras and four Late Glacial tephra packages was analyzed by electron microprobe. Eruption ages were estimated using 113 radiocarbon dates for proximal tephra sequence. These radiocarbon dates were combined with 76 dates for regional Kamchatka marker tephra layers into a single Bayesian framework taking into account the stratigraphic ordering within and between the sites. As a result, we report ~1,700 high-quality glass analyses from Late Glacial–Holocene Shiveluch eruptions of known ages. These define the magmatic evolution of the volcano and provide a reference for correlations with distal fall deposits. Shiveluch tephras represent two major types of magmas, which have been feeding the volcano during the Late Glacial–Holocene time: Baidarny basaltic andesites and Young Shiveluch andesites. Baidarny tephras erupted mostly during the Late Glacial time (~16–12.8 ka BP) but persisted into the Holocene as subordinate admixture to the prevailing Young Shiveluch andesitic tephras (~12.7 ka BP–present). Baidarny basaltic andesite tephras have trachyandesite and trachydacite (SiO₂ < 71.5 wt%) glasses. The Young Shiveluch andesite tephras have rhyolitic glasses (SiO₂ > 71.5 wt%). Strongly calc-alkaline medium-K characteristics of Shiveluch volcanic glasses along with moderate Cl, CaO and low P₂O₅ contents permit reliable discrimination of Shiveluch tephras from the majority of other large Holocene tephras of Kamchatka. The Young Shiveluch glasses exhibit wave-like variations in SiO₂ contents through time that may reflect alternating periods of high and low frequency/volume of magma supply to deep magma reservoirs beneath the volcano. The compositional variability of Shiveluch glass allows geochemical fingerprinting of individual Shiveluch tephra layers which along with age estimates facilitates their use as a dating tool in paleovolcanological, paleoseismological, paleoenvironmental and archeological studies. Electronic tables accompanying this work offer a tool for statistical correlation of unknown tephras with proximal Shiveluch units taking into account sectors of actual tephra dispersal, eruption size and expected age. Several examples illustrate the effectiveness of the new database. The data are used to assign a few previously enigmatic wide-spread tephras to particular Shiveluch eruptions. Our finding of Shiveluch tephras in sediment cores in the Bering Sea at a distance of ~600 km from the source permits re-assessment of the maximum dispersal distances for Shiveluch tephras and provides links between terrestrial and marine paleoenvironmental records.