Preparation, Structure, and Reactivity of Nonstabilized Organoiron Compounds. Implications for Iron-Catalyzed Cross Coupling Reactions

A series of unprecedented organoiron complexes of the formal oxidation states −2, 0, +1, +2, and +3 is presented, which are largely devoid of stabilizing ligands and, in part, also electronically unsaturated (14-, 16-, 17- and 18-electron counts). Specifically, it is shown that nucleophiles unable to undergo β-hydride elimination, such as MeLi, PhLi, or PhMgBr, rapidly reduce Fe(3+) to Fe(2+) and then exhaustively alkylate the metal center. The resulting homoleptic organoferrate complexes [(Me4Fe)(MeLi)][Li(OEt2)]2 (3) and [Ph4Fe][Li(Et2O)2][Li(1,4-dioxane)] (5) could be characterized by X-ray crystal structure analysis. However, these exceptionally sensitive compounds turned out to be only moderately nucleophilic, transferring their organic ligands to activated electrophiles only, while being unable to alkylate (hetero)aryl halides unless they are very electron deficient. In striking contrast, Grignard reagents bearing alkyl residues amenable to β-hydride elimination reduce FeXn (n = 2, 3) to clusters of the formal composition [Fe(MgX)2]n. The behavior of these intermetallic species can be emulated by structurally well-defined lithium ferrate complexes of the type [Fe(C2H4)4][Li(tmeda)]2 (8), [Fe(cod)2][Li(dme)]2 (9), [CpFe(C2H4)2][Li(tmeda)] (7), [CpFe(cod)][Li(dme)] (11), or [Cp*Fe(C2H4)2][Li(tmeda)] (14). Such electron-rich complexes, which are distinguished by short intermetallic Fe−Li bonds, were shown to react with aryl chlorides and allyl halides; the structures and reactivity patterns of the resulting organoiron compounds provide first insights into the elementary steps of low valent iron-catalyzed cross coupling reactions of aryl, alkyl, allyl, benzyl, and propargyl halides with organomagnesium reagents. However, the acquired data suggest that such C−C bond formations can occur, a priori, along different catalytic cycles shuttling between metal centers of the formal oxidation states Fe(+1)/Fe(+3), Fe(0)/Fe(+2), and Fe(−2)/Fe(0). Since these different manifolds are likely interconnected, an unambiguous decision as to which redox cycle dominates in solution remains difficult, even though iron complexes of the lowest accessible formal oxidation states promote the reactions most effectively

Kinematics of massive star ejecta in the Milky Way as traced by 26^26Al

Context. Massive stars form in groups and their winds and supernova explosions create superbubbles up to kpc in size. The fate of their ejecta is of vital importance for the dynamics of the interstellar medium, for chemical evolution models, and the chemical enrichment of galactic halos and the intergalactic medium. However, ejecta kinematics and the characteristic scales in space and time have not been explored in great detail beyond ~10 Ka. Aims: Through measurement of radioactive 26Al with its decay time constant at ~106 years, we aim to trace the kinematics of cumulative massive-star and supernova ejecta independent of the uncertain gas parameters over million-year time scales. Our goal is to identify the mixing time scale and the spatio-kinematics of such ejecta from the pc to kpc scale in our Milky Way. Methods: We use the SPI spectrometer on the INTEGRAL observatory and its observations along the Galactic ridge to trace the detailed line shape systematics of the 1808.63 keV gamma-ray line from 26Al decay. We determine line centroids and compare these to Doppler shift expectations from large-scale systematic rotation around the Galaxy centre, as observed in other Galactic objects. Results: We measure the radial velocities of gas traced by 26Al, averaged over the line of sight, as a function of Galactic longitude. We find substantially higher velocities than expected from Galactic rotation, the average bulk velocity being ~200 km s-1 larger than predicted from Galactic rotation. The observed radial velocity spread implies a Doppler broadening of the gamma-ray line that is consistent with our measurements of the overall line width. We can reproduce the observed characteristics with 26Al sources located along the inner spiral arms, when we add a global blow-out preference into the forward direction away from arms into the inter-arm region, as is expected when massive stars are offset towards the spiral-arm leading edge. With the known connection of superbubbles to the gaseous halo, this implies angular-momentum transfer in the disk-halo system and consequently also radial gas flows. The structure of the interstellar gas above the disk affects how ionizing radiation may escape and ionize intergalactic gas.Peer reviewe

Comparing simulated 26^{26}Al maps to gamma-ray measurements

© ESO 2019.Context. The diffuse gamma-ray emission of $^{26}{\rm Al}$ at 1.8 MeV reflects ongoing nucleosynthesis in the Milky Way, and traces massive-star feedback in the interstellar medium due to its 1 Myr radioactive lifetime. Interstellar-medium morphology and dynamics are investigated in astrophysics through 3D hydrodynamic simulations in fine detail, as only few suitable astronomical probes are available. Aims. We compare a galactic-scale hydrodynamic simulation of the Galaxy's interstellar medium, including feedback and nucleosynthesis, with gamma-ray data on $^{26}{\rm Al}$ emission in the Milky Way extracting constraints that are only weakly dependent on the particular realisation of the simulation or Galaxy structure. Methods. Due to constraints and biases in both the simulations and the gamma-ray observations, such comparisons are not straightforward. For a direct comparison, we perform maximum likelihood fits of simulated sky maps as well as observation-based maximum entropy maps to measurements with INTEGRAL/SPI. To study general morphological properties, we compare the scale heights of $^{26}{\rm Al}$ emission produced by the simulation to INTEGRAL/SPI measurements.} Results. The direct comparison shows that the simulation describes the observed inner Galaxy well, but differs significantly from the observed full-sky emission morphology. Comparing the scale height distribution, we see similarities for small scale height features and a mismatch at larger scale heights. We attribute this to the prominent foreground emission sites that are not captured by the simulation.Peer reviewedFinal Accepted Versio

Becoming the Synthi-Fou: Stockhausen and the new keyboardism

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Karlheinz Stockhausen embraced the potential of electronic music to generate new timbres and acoustic typologies early in his career. After first experimenting with magnetic tape in works such as Gesang der Jünglinge (1955) and Kontakte (1958–60), he later embraced other synthesis technologies for the production of large-scale spatial electro-acoustic works such as Sirius (1970) and Oktophonie (1990–91). His interest in technological advances in sound design and sound diffusion also managed to penetrate his highly evolved Klavierstücke

High-speed Civil Transport Aircraft Emissions

Estimates are given for the emissions from a proposed high speed civil transport (HSCT). This advanced technology supersonic aircraft would fly in the lower stratosphere at a speed of roughly Mach 1.6 to 3.2 (470 to 950 m/sec or 920 to 1850 knots). Because it would fly in the stratosphere at an altitude in the range of 15 to 23 km commensurate with its design speed, its exhaust effluents could perturb the chemical balance in the upper atmosphere. The first step in determining the nature and magnitude of any chemical changes in the atmosphere resulting from these proposed aircraft is to identify and quantify the chemically important species they emit. Relevant earlier work is summarized, dating back to the Climatic Impact Assessment Program of the early 1970s and current propulsion research efforts. Estimates are provided of the chemical composition of an HSCT's exhaust, and these emission indices are presented. Other aircraft emissions that are not due to combustion processes are also summarized; these emissions are found to be much smaller than the exhaust emissions. Future advances in propulsion technology, in experimental measurement techniques, and in understanding upper atmospheric chemistry may affect these estimates of the amounts of trace exhaust species or their relative importance

Human antimicrobial peptide, LL-37, induces non-inheritable reduced susceptibility to vancomycin in <i>Staphylococcus aureus</i>

Abstract Antimicrobial peptides (AMPs) are central components of the innate immune system providing protection against pathogens. Yet, serum and tissue concentrations vary between individuals and with disease conditions. We demonstrate that the human AMP LL-37 lowers the susceptibility to vancomycin in the community-associated methicillin-resistant S. aureus (CA-MRSA) strain FPR3757 (USA300). Vancomycin is used to treat serious MRSA infections, but treatment failures occur despite MRSA strains being tested susceptible according to standard susceptibility methods. Exposure to physiologically relevant concentrations of LL-37 increased the minimum inhibitory concentration (MIC) of S. aureus towards vancomycin by 75%, and resulted in shortened lag-phase and increased colony formation at sub-inhibitory concentrations of vancomycin. Computer simulations using a mathematical antibiotic treatment model indicated that a small increase in MIC might decrease the efficacy of vancomycin in clearing a S. aureus infection. This prediction was supported in a Galleria mellonella infection model, where exposure of S. aureus to LL-37 abolished the antimicrobial effect of vancomycin. Thus, physiological relevant concentrations of LL-37 reduce susceptibility to vancomycin, indicating that tissue and host specific variations in LL-37 concentrations may influence vancomycin susceptibility in vivo

Use of serum lactate levels to predict survival for patients with out-of-hospital cardiac arrest: A cohort study

Objectives: We examined the association of serum lactate levels and early lactate clearance with survival to hospital discharge for patients suffering an out-of-hospital cardiac arrest (OHCA). Methods: A retrospective cohort analysis was performed of patients with OHCA transported by ambulance to two adult tertiary hospitals in Perth, Western Australia. Exclusion criteria were traumatic cardiac arrest, return of spontaneous circulation prior to the arrival of the ambulance, age less than 18 years and no serum lactate levels recorded. Serum lactate levels recorded for up to 48h post-arrest were obtained from the hospital clinical information system, and lactate clearance over 48h was calculated. Descriptive and logistic regression analyses were conducted. Results: There were 518 patients with lactate values, of whom 126 (24.3%) survived to hospital discharge. Survivors and non-survivors had different mean initial lactate levels (mean±SD 6.9±4.7 and 12.2±5.5mmol/L, respectively; P&lt;0.001). Lactate clearance was higher in survivors. Lactate levels for non-survivors did not decrease below 2mmol/L until at least 30h after the ambulance call. Conclusion: In OHCA patients who had serum lactate levels measured, both lower initial serum lactate and early lactate clearance in the first 48h following OHCA were associated with increased likelihood of survival. However, the use of lactate in isolation as a predictor of survival or neurological outcome is not recommended. Prospective studies that minimise selection bias are required to determine the clinical utility of serum lactate levels in OHCA patients. © 2016 Australasian College for Emergency Medicine and Australasian Society for Emergency Medicine

The Small Heat Shock Protein Hsp27 Affects Assembly Dynamics and Structure of Keratin Intermediate Filament Networks

AbstractThe mechanical properties of living cells are essential for many processes. They are defined by the cytoskeleton, a composite network of protein fibers. Thus, the precise control of its architecture is of paramount importance. Our knowledge about the molecular and physical mechanisms defining the network structure remains scarce, especially for the intermediate filament cytoskeleton. Here, we investigate the effect of small heat shock proteins on the keratin 8/18 intermediate filament cytoskeleton using a well-controlled model system of reconstituted keratin networks. We demonstrate that Hsp27 severely alters the structure of such networks by changing their assembly dynamics. Furthermore, the C-terminal tail domain of keratin 8 is shown to be essential for this effect. Combining results from fluorescence and electron microscopy with data from analytical ultracentrifugation reveals the crucial role of kinetic trapping in keratin network formation

eROSITA studies of the Carina Nebula

© 2024 The Author(s). Published by EDP Sciences. This is an open access article distributed under the terms of the Creative Commons Attribution License (CC BY), https://creativecommons.org/licenses/by/4.0/Context. During the first four all-sky surveys eRASS:4, which was carried out from December 2019 to 2021, the extended Roentgen Survey with an Imaging Telescope Array (eROSITA) on board the Spektrum-Roentgen-Gamma (Spektr-RG, SRG) observed the Galactic H II region, the Carina nebula. Aims. We analysed the eRASS:4 data to study the distribution and spectral properties of the hot interstellar plasma and the bright stellar sources in the Carina nebula. Methods. The spectral extraction regions of the diffuse emission were defined based on the X-ray spectral morphology and multi-wavelength data. The spectra were fit with a combination of thermal and non-thermal emission models. The X-ray bright point sources in the Carina nebula are the colliding wind binary η Car, several O stars, and Wolf–Rayet (WR) stars. We extracted the spectra of the brightest stellar sources, which can be well fit with a multi-component thermal plasma model. Results. The spectra of the diffuse emission in the brighter parts of the Carina nebula are well reproduced by two thermal models, a lower-temperature component (~0.2 keV) and a higher-temperature component (0.6–0.8 keV). An additional non-thermal component dominates the emission above ~1 keV in the Central region around η Car and the other massive stars. Significant orbital variation in the X-ray flux was measured for η Car, WR 22, and WR 25. η Car requires an additional time-variable thermal component in the spectral model, which is associated with the wind-wind collision zone. Conclusions. Properties such as temperature, pressure, and luminosity of the X-ray emitting plasma in the Carina nebula derived from the eROSITA data are consistent with theoretical calculations of emission from superbubbles. This confirms that the X-ray emission is caused by the hot plasma inside the Carina nebula that has been shocked-heated by the stellar winds of the massive stars, in particular, of η Car.Peer reviewe