Geometries of third-row transition-metal complexes from density-functional theory

A set of 41 metal-ligand bond distances in 25 third-row transition-metal complexes, for which precise structural data are known in the gas phase, is used to assess optimized and zero-point averaged geometries obtained from DFT computations with various exchange-correlation functionals and basis sets. For a given functional (except LSDA) Stuttgart-type quasi-relativistic effective core potentials and an all-electron scalar relativistic approach (ZORA) tend to produce very similar geometries. In contrast to the lighter congeners, LSDA affords reasonably accurate geometries of 5d-metal complexes, as it is among the functionals with the lowest mean and standard deviations from experiment. For this set the ranking of some other popular density functionals, ordered according to decreasing standard deviation, is BLYP > VSXC > BP86 approximate to BPW91 approximate to TPSS approximate to B3LYP approximate to PBE > TPSSh > B3PW91 approximate to B3P86 approximate to PBE hybrid. In this case hybrid functionals are superior to their nonhybrid variants. In addition, we have reinvestigated the previous test sets for 3d- (Buhl M.; Kabrede, H. J. Chem. Theory Comput. 2006, 2, 1282-1290) and 4d- (Waller, M. P.; Buhl, M. J. Comput. Chem. 2007,28,1531-1537) transition-metal complexes using all-electron scalar relativistic DFT calculations in addition to the published nonrelativistic and ECP results. For this combined test set comprising first-, second-, and third-row metal complexes, B3P86 and PBE hybrid are indicated to perform best. A remarkably consistent standard deviation of around 2 pm in metal-ligand bond distances is achieved over the entire set of d-block elements.PostprintPeer reviewe

Temperature dependence of the ``0.7'' 2(e^2)/h quasi plateau in strongly confined quantum point contacts

We present new results of the ``0.7'' 2(e^2)/h structure or quasi plateau in some of the most strongly confined point contacts so far reported. This strong confinement is obtained by a combination of shallow etching and metal gate deposition on modulation doped GaAs/GaAlAs heterostructures. The resulting subband separations are up to 20 meV, and as a consequence the quantized conductance can be followed at temperatures up to 30 K, an order of magnitude higher than in conventional split gate devices. We observe pronounced quasi plateaus at several of the lowest conductance steps all the way from their formation around 1 K to 30 K, where the entire conductance quantization is smeared out thermally. We study the deviation of the conductance from ideal integer quantization as a function of temperature, and we find an activated behavior, exp(-T_a/T), with a density dependent activation temperature T_a of the order of 2 K. We analyze our results in terms of a simple theoretical model involving scattering against plasmons in the constriction.Comment: RevTex (4 pages) including 2 postscript figures. To appear in Physica B, 199

Sudden Cardiac Arrest in Football

Background: Sudden Cardiac Arrest (SCA) is defined as the abrupt loss of heart function as an occurrence without physical contact (absent commotio cordis). SCA's morbidity ratio is 1:50,000 of all deaths. The published estimates on SCA suggest that 11% of all victims have a normal heart. Current screening investigations include electrocardiography (ECG), echography, 24-hour ECG monitoring, eliciting stress history, and cardiac Magnetic Resonance Imaging. Some cardiac pathologies screened have never been detected. Athletes who experienced SCA had a survival rate of 50-60% over 30-days, and this rate might reach up to 80-89% in some cohort studies. The survival factors are based on regular and thorough screening checks, and better observation that enables quicker pickups. Players vary in cardiopulmonary resuscitation (CPR) performance and are emotionally involved, as was reported recently with footballer Christian Eriksen in the 2021 European Championship 1 . However, anyone trained in CPR, not just medical professionals, can assist in resuscitation (Figure 1). Evidence-based studies show that Basic Cardiac Life Support (BCLS) is more effective on the sports field than Advanced Cardiac Life Support 2 . The objective of this literature review is to make recommendations to effectively respond to SCA during football tournaments. Methods: PubMed database was used to retrieve articles published in English between 2018 and 2021 related to SCA during football games. Results: There are limited publications in this specific domain. Reports from 67 countries account for 617 players (mean age 34 ± 16 years, 96% men) suffering from SCA or traumatic sudden death during football activities between 2014 - 2018, of whom 142 players (23%) survived 1 . CPR resulted in a survival rate of 85% with the use of an automated external defibrillator (AED) compared to 35% without. Conclusion: Key recommendations from this literature review are listed in Table 1. These are important steps needed to improve survival chance from SCA 3 . Qatar, hosting the Football World Cup 2022, can put in place additional measures to promote effective SCA resuscitation and ensure the safety of all players

Pre-exposure prophylaxis with OspA-specific human monoclonal antibodies protects mice against tick transmission of Lyme disease spirochetes

Background. Tick transmission of Borrelia spirochetes to humans results in significant morbidity from Lyme disease worldwide. Serum concentrations of antibodies against outer surface protein A (OspA) were shown to correlate with protection from infection with Borrelia burgdorferi, the primary cause of Lyme disease in the United States. Methods. Mice transgenic for human immunoglobulin genes were immunized with OspA protein of B. burgdorferi to generate human monoclonal antibodies (HuMabs) against OspA. HuMabs were generated and tested in in vitro borreliacidal assays and animal protection assays. Results. Nearly 100 unique OspA specific HuMabs were generated and four HuMabs (221-7, 857-2, 319-44, and 212-55) were selected as lead candidates based on borreliacidal activity. HuMab 319-44, 857-2 and 212-55 were borreliacidal against one or two Borrelia genospecies, whereas 221-7 was borreliacidal (IC50 \u3c 1nM) against B. burgdorferi, B. afzelii and B. garinii, the three main genospecies endemic in the US, Europe and Asia. All four HuMabs completely protected mice from infection at 10 mg/kg in a murine model of tick-mediated transmission of B. burgdorferi. Conclusions. Our study indicates that OspA-specific HuMabs can prevent the transmission of Borrelia and administration of these antibodies could be employed as pre-exposure prophylaxis for Lyme disease

Experimental study of the role of physicochemical surface processing on the IN ability of mineral dust particles

During the measurement campaign FROST 2 (FReezing Of duST 2), the Leipzig Aerosol Cloud Interaction Simulator (LACIS) was used to investigate the influence of various surface modifications on the ice nucleating ability of Arizona Test Dust (ATD) particles in the immersion freezing mode. The dust particles were exposed to sulfuric acid vapor, to water vapor with and without the addition of ammonia gas, and heat using a thermodenuder operating at 250 °C. Size selected, quasi monodisperse particles with a mobility diameter of 300 nm were fed into LACIS and droplets grew on these particles such that each droplet contained a single particle. Temperature dependent frozen fractions of these droplets were determined in a temperature range between −40 °C ≤T≤−28 °C. The pure ATD particles nucleated ice over a broad temperature range with their freezing behavior being separated into two freezing branches characterized through different slopes in the frozen fraction vs. temperature curves. Coating the ATD particles with sulfuric acid resulted in the particles' IN potential significantly decreasing in the first freezing branch (T>−35 °C) and a slight increase in the second branch (T≤−35 °C). The addition of water vapor after the sulfuric acid coating caused the disappearance of the first freezing branch and a strong reduction of the IN ability in the second freezing branch. The presence of ammonia gas during water vapor exposure had a negligible effect on the particles' IN ability compared to the effect of water vapor. Heating in the thermodenuder led to a decreased IN ability of the sulfuric acid coated particles for both branches but the additional heat did not or only slightly change the IN ability of the pure ATD and the water vapor exposed sulfuric acid coated particles. In other words, the combination of both sulfuric acid and water vapor being present is a main cause for the ice active surface features of the ATD particles being destroyed. A possible explanation could be the chemical transformation of ice active metal silicates to metal sulfates. The strongly enhanced reaction between sulfuric acid and dust in the presence of water vapor and the resulting significant reductions in IN potential are of importance for atmospheric ice cloud formation. Our findings suggest that the IN concentration can decrease by up to one order of magnitude for the conditions investigated

Simultaneous ultrafast probing of intramolecular vibrations and photoinduced charge carriers in rubrene using broadband time-domain THz spectroscopy

Mattijs Koeberg, Euan Hendry, Juleon M. Schins, Hendrik A. van Laarhoven, Cees F. J. Flipse, Klaus Reimann, Michael Woerner, Thomas Elsaesser, and Mischa Bonn, Physical Review B, Vol. 75, article 195216 (2007). "Copyright © 2007 by the American Physical Society."We determine the ultrafast frequency- and time-resolved complex dielectric responses of photoexcited, single-crystal rubrene in the frequency range of 10–30 THz (330–1000 cm−1) using ultrafast broadband THz spectroscopy. In this frequency range, we observe the response of both photogenerated mobile charges and intramolecular vibrational modes simultaneously, both of which vary with time after excitation. The data in conjunction with a theoretical model indicate a dynamic blueshift of the 15.5 THz phonon

Evolution of electronic and ionic structure of Mg-clusters with the growth cluster size

The optimized structure and electronic properties of neutral and singly charged magnesium clusters have been investigated using ab initio theoretical methods based on density-functional theory and systematic post-Hartree-Fock many-body perturbation theory accounting for all electrons in the system. We have systematically calculated the optimized geometries of neutral and singly charged magnesium clusters consisting of up to 21 atoms, electronic shell closures, binding energies per atom, ionization potentials and the gap between the highest occupied and the lowest unoccupied molecular orbitals. We have investigated the transition to the hcp structure and metallic evolution of the magnesium clusters, as well as the stability of linear chains and rings of magnesium atoms. The results obtained are compared with the available experimental data and the results of other theoretical works.Comment: 30 pages, 10 figures, 3 table

Electrochemical activation of molecular nitrogen at the Ir/YSZ interface.

Nitrogen is often used as an inert background atmosphere in solid state studies of electrode and reaction kinetics, of solid state studies of transport phenomena, and in applications e.g. solid oxide fuel cells (SOFC), sensors and membranes. Thus, chemical and electrochemical reactions of oxides related to or with dinitrogen are not supposed and in general not considered. We demonstrate by a steady state electrochemical polarisation experiments complemented with in situphotoelectron spectroscopy (XPS) that at a temperature of 450 °C dinitrogen can be electrochemically activated at the three phase boundary between N2, a metal microelectrode and one of the most widely used solid oxide electrolytes—yttria stabilized zirconia (YSZ)—at potentials more negative than E = −1.25 V. The process is neither related to a reduction of the electrolyte nor to an adsorption process or a purely chemical reaction but is electrochemical in nature. Only at potentials more negative than E = −2 V did new components of Zr 3d and Y 3d signals with a lower formal charge appear, thus indicating electrochemical reduction of the electrolyte matrix. Theoretical model calculations suggest the presence of anionic intermediates with delocalized electrons at the electrode/electrolyte reaction interface. The ex situSIMS analysis confirmed that nitrogen is incorporated and migrates into the electrolyte beneath the electrode

Chimeric 2C10R4 anti-CD40 antibody therapy is critical for long-term survival of GTKO.hCD46.hTBM pig-to-primate cardiac xenograft

Preventing xenograft rejection is one of the greatest challenges of transplantation medicine. Here, we describe a reproducible, long-term survival of cardiac xenografts from alpha 1-3 galactosyltransferase gene knockout pigs, which express human complement regulatory protein CD46 and human thrombomodulin (GTKO.hCD46.hTBM), that were transplanted into baboons. Our immunomodulatory drug regimen includes induction with anti-thymocyte globulin and alpha CD20 antibody, followed by maintenance with mycophenolate mofetil and an intensively dosed alpha CD40 (2C10R4) antibody. Median (298 days) and longest (945 days) graft survival in five consecutive recipients using this regimen is significantly prolonged over our recently established survival benchmarks (180 and 500 days, respectively). Remarkably, the reduction of aCD40 antibody dose on day 100 or after 1 year resulted in recrudescence of anti-pig antibody and graft failure. In conclusion, genetic modifications (GTKO.hCD46.hTBM) combined with the treatment regimen tested here consistently prevent humoral rejection and systemic coagulation pathway dysregulation, sustaining long-term cardiac xenograft survival beyond 900 days

Entropy production for mechanically or chemically driven biomolecules

Entropy production along a single stochastic trajectory of a biomolecule is discussed for two different sources of non-equilibrium. For a molecule manipulated mechanically by an AFM or an optical tweezer, entropy production (or annihilation) occurs in the molecular conformation proper or in the surrounding medium. Within a Langevin dynamics, a unique identification of these two contributions is possible. The total entropy change obeys an integral fluctuation theorem and a class of further exact relations, which we prove for arbitrarily coupled slow degrees of freedom including hydrodynamic interactions. These theoretical results can therefore also be applied to driven colloidal systems. For transitions between different internal conformations of a biomolecule involving unbalanced chemical reactions, we provide a thermodynamically consistent formulation and identify again the two sources of entropy production, which obey similar exact relations. We clarify the particular role degenerate states have in such a description