A pendant proton shuttle on [Fe4N(CO)12]- alters product selectivity in formate vs. H2 production via the hydride [H-Fe4N(CO)12].

Proton relays are known to increase reaction rates for H2 evolution and lower overpotentials in electrocatalytic reactions. In this report we describe two electrocatalysts, [Fe4N(CO)11(PPh3)]- (1-) which has no proton relay, and hydroxyl-containing [Fe4N(CO)11(Ph2P(CH2)2OH)]- (2-). Solid state structures indicate that these phosphine-substituted clusters are direct analogs of [Fe4N(CO)12]- where one CO ligand has been replaced by a phosphine. We show that the proton relay changes the selectivity of reactions: CO2 is reduced selectively to formate by 1- in the absence of a relay, and protons are reduced to H2 under a CO2 atmosphere by 2-. These results implicate a hydride intermediate in the mechanism of the reactions and demonstrate the importance of controlling proton delivery to control product selectivity. Thermochemical measurements performed using infrared spectroelectrochemistry provided pKa and hydricity values for [HFe4N(CO)11(PPh3)]-, which are 23.7, and 45.5 kcal mol-1, respectively. The pKa of the hydroxyl group in 2- was determined to fall between 29 and 41, and this suggests that the proximity of the proton relay to the active catalytic site plays a significant role in the product selectivity observed, since the acidity alone does not account for the observed results. More generally, this work emphasizes the importance of substrate delivery kinetics in determining the selectivity of CO2 reduction reactions that proceed through metal-hydride intermediates

Photorefractive properties of lithium niobate crystals doped with manganese

The photorefractive properties of lithium niobate crystals doped with manganese (Mn) have been investigated. It is found that the effect of dark decay due to electron tunneling, which is the limiting factor of the highest practical doping level, is less in LiNbO3:Mn than in LiNbO3:Fe, and higher doping levels can be used in LiNbO3:Mn to achieve larger dynamic range and sensitivity for holographic applications. The highest practical doping level in LiNbO3: Mn has been found to be similar to0.5 wt.% MnCO3, and refractive-index changes and sensitivities up to 1.5 X 10(-3) and 1.3 cm/J are measured for extraordinarily polarized light of the wavelength 458 nm. It has been found that, in terms of both dynamic range (or refractive-index change) and sensitivity, the optimal oxidation state is highly oxidized. The distribution coefficient of Mn has been determined to be similar to1. Absorption measurements are used to obtain more information about charge-transport parameters. The material is excellently suited for holographic recording with blue light. The hologram quality is outstanding because holographic scattering is much weaker compared with that in, e.g., iron-doped lithium niobate. Thermal fixing has been successfully demonstrated in LiNbO3:Mn crystals. (C) 2003 Optical Society of America

Evidence of Isotopic Fractionation During Vapor Exchange Between the Atmosphere and the Snow Surface in Greenland

Several recent studies from both Greenland and Antarctica have reported significant changes in the water isotopic composition of near‐surface snow between precipitation events. These changes have been linked to isotopic exchange with atmospheric water vapor and sublimation‐induced fractionation, but the processes are poorly constrained by observations. Understanding and quantifying these processes are crucial to both the interpretation of ice core climate proxies and the formulation of isotope‐enabled general circulation models. Here, we present continuous measurements of the water isotopic composition in surface snow and atmospheric vapor together with near‐surface atmospheric turbulence and snow‐air latent and sensible heat fluxes, obtained at the East Greenland Ice‐Core Project drilling site in summer 2016. For two 4‐day‐long time periods, significant diurnal variations in atmospheric water isotopologues are observed. A model is developed to explore the impact of this variability on the surface snow isotopic composition. Our model suggests that the snow isotopic composition in the upper subcentimeter of the snow exhibits a diurnal variation with amplitudes in δ18O and δD of ~2.5‰ and ~13‰, respectively. As comparison, such changes correspond to 10–20% of the magnitude of seasonal changes in interior Greenland snow pack isotopes and of the change across a glacial‐interglacial transition. Importantly, our observation and model results suggest, that sublimation‐induced fractionation needs to be included in simulations of exchanges between the vapor and the snow surface on diurnal timescales during summer cloud‐free conditions in northeast Greenland

The characteristics and pre-hospital management of blunt trauma patients with suspected spinal column injuries:a retrospective observational study

Background Pre-hospital spinal immobilisation by emergency medical services (EMS) staff is currently the standard of care in cases of suspected spinal column injuries. There is, however, a lack of data on the characteristics of patients who received spinal immobilisation during the pre-hospital phase and on the adverse effects of immobilisation. The objectives of this study were threefold. First, we determined the pre-hospital characteristics of blunt trauma patients with suspected spinal column injuries who were immobilised by EMS staff. Second, we assessed the choices made by EMS staff regarding spinal immobilisation techniques and reasons for immobilisation. Third, we researched the possible adverse effects of immobilisation. Design A retrospective observational study in a cohort of blunt trauma patients. Study method Data of blunt trauma patients with suspected spinal column injuries were collected from one EMS organisation between January 2008 and January 2013. Coded data and free text notes were analysed. Results A total of 1082 patients were included in this study. Spinal immobilisation was applied in 96.3 % of the patients based on valid pre-hospital criteria. In 2.1 % of the patients immobilisation was not based on valid criteria. Data of 1.6 % patients were missing. Main reasons for spinal immobilisation were posterior midline spinal tenderness (37.2 % of patients) and painful distracting injuries (13.5 % of patients). Spinal cord injury (SCI) was suspected in 5.7 % of the patients with posterior midline spinal tenderness. A total of 15.8 % patients were immobilised using non-standard methods. The reason for departure from the standard method was explained for 3 % of these patients. Reported adverse effects included pain (n = 10, 0.9 %,); shortness of breath (n = 3, 0.3 %); combativeness or anxiety (n = 6, 0.6 %); and worsening of pain when supine (n = 1, 0.1 %). Conclusion/recommendation Spinal immobilisation was applied in 96.3 % of all included patients based on pre-hospital criteria. We found that consensus among EMS staff on how to interpret the criterion 'distracting injury' was lacking. Furthermore, the adverse effects of spinal immobilisation were incompletely documented in pre-hospital care reports. To provide validated information on potential symptoms of SCI, a uniform EMS scoring system for motoric assessment should be developed

Стратегічне планування як основний інструмент ефективності підприємства

Наук. кер.: А.Ю. Жулавськи

Evidence for Strong Electron Correlations in a Nonsymmorphic Dirac Semimetal

Metallic iridium oxides (iridates) provide a fertile playground to explore new phenomena resulting from the interplay between topological protection, spin-orbit and electron-electron interactions. To date, however, few studies of the low energy electronic excitations exist due to the difficulty in synthesising crystals with sufficiently large carrier mean-free-paths. Here, we report the observation of Shubnikov-de Haas quantum oscillations in high-quality single crystals of monoclinic SrIrO3 in magnetic fields up to 35 T. Analysis of the oscillations reveals a Fermi surface comprising multiple small pockets with effective masses up to 4.5 times larger than the calculated band mass. Ab-initio calculations reveal robust linear band-crossings at the Brillouin zone boundary, due to its non-symmorphic symmetry, and overall we find good agreement between the angular dependence of the oscillations and the theoretical expectations. Further evidence of strong electron correlations is realized through the observation of signatures of non-Fermi liquid transport as well as a large Kadowaki-Woods ratio. These collective findings, coupled with knowledge of the evolution of the electronic state across the Ruddlesden-Popper iridate series, establishes monoclinic SrIrO3 as a topological semimetal on the boundary of the Mott metal-insulator transition. © 2021, The Author(s).We gratefully acknowledge useful discussions with A. Rost and D. F. McMorrow. We would also like to thank G. Stenning and D. Nye for help with the instruments in the Materials Characterisation Laboratory at the ISIS Neutron and Muon Source, Kuang-Yu Samuel Chang and Roos Leenen for technical assistance with the DFT calculations, and Sebastian Bette for XRD characterizations. We acknowledge the support of the HFML-Radboud University (RU)/Netherlands Organisation for Scientific Research (NWO), a member of the European Magnetic Field Laboratory. This work is part of the research program Strange Metals (Grant 16METL01) of the former Foundation for Fundamental Research on Matter, which is financially supported by the NWO and the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (Grant Agreement No. 835279-Catch-22). We gratefully acknowledge support from the UK Engineering and Physical Sciences research council, grant EP/N034694/1. We acknowledge collaborative support from A.S. Gibbs, D. Fortes and the ISIS Crystallography Group for making available the 193Ir for the isotope work. Experiments at the ISIS Neutron and Muon Source were supported by a beamtime allocation RB1990395, DOI:10.5286/ISIS.E.RB1990395, from the Science and Technology Facilities Council. The work of D. P. and V. M. was supported by Act 211 Government of the Russian Federation, contract 02.A03.21.0006

DNA bending by bHLH charge variants

We wish to understand the role of electrostatics in DNA stiffness and bending. The DNA charge collapse model suggests that mutual electrostatic repulsions between neighboring phosphates significantly contribute to DNA stiffness. According to this model, placement of fixed charges near the negatively charged DNA surface should induce bending through asymmetric reduction or enhancement of these inter-phosphate repulsive forces. We have reported previously that charged variants of the elongated basic-leucine zipper (bZIP) domain of Gcn4p bend DNA in a manner consistent with this charge collapse model. To extend this result to a more globular protein, we present an investigation of the dimeric basic-helix–loop–helix (bHLH) domain of Pho4p. The 62 amino acid bHLH domain has been modified to position charged amino acid residues near one face of the DNA double helix. As observed for bZIP charge variants, DNA bending toward appended cations (away from the protein:DNA interface) is observed. However, unlike bZIP proteins, DNA is not bent away from bHLH anionic charges. This finding can be explained by the structure of the more globular bHLH domain which, in contrast to bZIP proteins, makes extensive DNA contacts along the binding face