Telechelic polyisobutylene with unsaturated end groups and with anhydride end groups

Anhydride terminated polyisobutylene (PIB) oligomers were synthesized in a one- or two-step process from chlorine terminated oligomers. In the one-step process, chlorine functional oligomers were just heated in the presence of maleic anhydride (MA) for 12 h at 190°C without a catalyst. In the two-step process, the chlorine end functional groups were first converted by selective dehydrochlorination to isopropenylpoly-isobutylene end groups with t-BuOK in refluxing tetrahydrofuran during 16 h. In a second step, MA was coupled to the PIB with unsaturated end groups by reacting the oligomer with MA for 12 h at 190°C. These reactions could be followed by i.r. and n.m.r. The PIB-MA obtained had a functionality between 30% and 100%. In order to study the formation of amine functionalities, the PIB-MA was reacted with diamines. The coupling gave an imide bonding

Synthesis and properties of poly(butylene terephthalate)-b-polyisobutylene segmented block copolymers

Segmented block copolymers of polyisobutylene (PIB) and poly(butylene terephthalate) (PBT) were made by condensation polymerization of α,θ-di-anhydride telechelic PIB, with 1,4-butanediol and dimethyl terephthalate. The inherent viscosity of the polymers was between 0.35 and 2.0 dl g−1. The extractability of the polymers with hexane was studied. The thermal behaviour of these polymers was studied by differential scanning calorimetry and dynamic mechanical thermal analysis. PBT-b-PIB had a glass transition temperature of −62°C and a melting temperature of 200–220°C. A shear modulus was found which, at room temperature, increased from 0.4 to 900 MPa with increasing PBT content in the block copolymer. The degradation was followed by measuring the change of inherent viscosity during thermal and hydrolytic treatment. The PBT-b-PIB showed good resistance to thermal and hydrolytic degradation

Probing 3D Density and Velocity Fields of ISM in Centers of Galaxies with Future X-Ray Observations

Observations of bright and variable "reflected" X-ray emission from molecular clouds located within inner hundred parsec of our Galaxy have demonstrated that the central supermassive black hole, Sgr A*, experienced short and powerful flares in the past few hundred years. These flares offer a truly unique opportunity to determine 3D location of the illuminated clouds (with ~10 pc accuracy) and to reveal their internal structure (down to 0.1 pc scales). Short duration of the flare(s), combined with X-rays high penetration power and insensitivity of the reflection signal to thermo- and chemo-dynamical state of the gas, ensures that the provided diagnostics of the density and velocity fields is unbiased and almost free of the projection and opacity effects. Sharp and sensitive snapshots of molecular gas accessible with aid of future X-ray observatories featuring large collecting area and high angular (arcsec-level) and spectral (eV-level) resolution cryogenic bolometers will present invaluable information on properties of the supersonic turbulence inside the illuminated clouds, map their shear velocity field and allow cross-matching between X-ray data and velocity-resolved emission of various molecular species provided by ALMA and other ground-based facilities. This will highlight large and small-scale dynamics of the dense gas and help uncovering specifics of the ISM lifecycle and high-mass star formation under very extreme conditions of galactic centers. While the former is of particular importance for the SMBH feeding and triggering AGN feedback, the latter might be an excellent test case for star formation taking place in high-redshift galaxies.Comment: White paper submitted to the Astro2020 Decadal Surve

Expression of a catalytically inactive mutant form of glutathione peroxidase 4 (Gpx4) confers a dominant-negative effect in male fertility.

The selenoenzyme Gpx4 is essential for early embryogenesis and cell viability for its unique function to prevent phospholipid oxidation. Recently, the cytosolic form of Gpx4 was identified as an upstream regulator of a novel form of non-apoptotic cell death, called ferroptosis, whereas the mitochondrial isoform of Gpx4 (mGpx4) was previously shown to be crucial for male fertility. Here, we generated and analyzed mice with targeted mutation of the active site selenocysteine (Sec) of Gpx4 (Gpx4_U46S). Mice homozygous for Gpx4_U46S died at the same embryonic stage (E7.5) as Gpx4-/- embryos as expected. Surprisingly, male mice heterozygous for Gpx4_U46S presented subfertility. Subfertility was manifested in a reduced number of litters from heterozygous breedings and an impairment of spermatozoa to fertilize oocytes in vitro. Morphologically, sperm isolated from heterozygous Gpx4_U46S mice revealed many structural abnormalities particularly in the spermatozoan midpiece due to improper oxidation and polymerization of sperm capsular proteins and malformation of the mitochondrial capsule surrounding and stabilizing sperm mitochondria. These findings are reminiscent of sperm isolated from selenium-deprived rodents or from mice specifically lacking mGpx4. Due to a strongly facilitated incorporation of Ser in the polypeptide chain as compared to Sec at the UGA codon, expression of the catalytically inactive Gpx4_U46S was found to be strongly increased. Since the stability of the mitochondrial capsule of mature spermatozoa depends on the moonlighting function of Gpx4 both as an enzyme oxidizing capsular protein thiols and being a structural protein, tightly controlled expression of functional Gpx4 emerges being key for full male fertility

Spatio-Temporal Variability of Suspended Particulate Matter in a High-Arctic Estuary (Adventfjorden, Svalbard) Using Sentinel-2 Time-Series

Arctic coasts, which feature land-ocean transport of freshwater, sediments, and other terrestrial material, are impacted by climate change, including increased temperatures, melting glaciers, changes in precipitation and runoff. These trends are assumed to affect productivity in fjordic estuaries. However, the spatial extent and temporal variation of the freshwater-driven darkening of fjords remain unresolved. The present study illustrates the spatio-temporal variability of suspended particulate matter (SPM) in the Adventfjorden estuary, Svalbard, using in-situ field campaigns and ocean colour remote sensing (OCRS) via high-resolution Sentinel-2 imagery. To compute SPM concentration (CSPMsat), a semi-analytical algorithm was regionally calibrated using local in-situ data, which improved the accuracy of satellite-derived SPM concentration by ~20% (MRD). Analysis of SPM concentration for two consecutive years (2019, 2020) revealed strong seasonality of SPM in Adventfjorden. Highest estimated SPM concentrations and river plume extent (% of fjord with CSPMsat > 30 mg L−1) occurred during June, July, and August. Concurrently, we observed a strong relationship between river plume extent and average air temperature over the 24 h prior to the observation (R2 = 0.69). Considering predicted changes to environmental conditions in the Arctic region, this study highlights the importance of the rapidly changing environmental parameters and the significance of remote sensing in analysing fluxes in light attenuating particles, especially in the coastal Arctic Ocean.publishedVersio

Massive stars in massive clusters - IV. Disruption of clouds by momentum-driven winds

We examine the effect of momentum-driven OB-star stellar winds on a parameter space of simulated turbulent giant molecular clouds using smoothed particle hydrodynamic simulations. By comparison with identical simulations in which ionizing radiation was included instead of winds, we show that momentum-driven winds are considerably less effective in disrupting their host clouds than are H ii regions. The wind bubbles produced are smaller and generally smoother than the corresponding ionization-driven bubbles. Winds are roughly as effective in destroying the very dense gas in which the O stars are embedded, and thus shutting down the main regions of star-forming activity in the model clouds. However, their influence falls off rapidly with distance from the sources, so they are not as good at sweeping up dense gas and triggering star formation further out in the clouds. As a result, their effect on the star formation rate and efficiency is generally more negative than that of ionization, if they exert any effect at all.Peer reviewe

ZnAlMg hot-dip galvanised steel sheets Tribology and tool wear

For the last few years zinc magnesium alloys on cold rolled steel were investigated in detail because of theirpotential to provide better corrosion protection than pure zinc coatings [1]. However, for introduction into theautomotive industry, it is also necessary to learn more about their tribological behavior. In the present workthe tribological potential of ZnAlMg hot dip galvanized steel sheets (HDG/ZM) was studied in terms of slidingproperties, adhesive and abrasive tool wear and compared to hot dip galvanized reference material (HDG/Z).Different tribological tests were performed. The friction coefficient was determined directly by doing strip drawtests at constant contact pressure. The deep drawing property was tested by forming model cups. Two differentoils, a pure corrosion protection oil and a prelube, were tested in each of the tribological tests. Abrasive toolwear was studied according to the SEP1160 standard. Adhesive tool wear (galling) was characterized ondifferent tool material and compared to the results for hot dip galvanized reference material. HDG/ZM stripsshowed improved friction behavior in the strip draw test when compared to classical hot dip galvanizedreference material. The abrasive tool wear is comparable to HDG/Z material, however, the galling was found tobe less than for pure zinc, and the morphology of the coating material transferred to the tool during deepdrawing is also different. This makes HDG//ZM an interesting system not only with respect to corrosion butalso in terms of tribology, thus providing clear advantages in formability