Microscopic insights into the partial oxidation of methanol on gold using Au(332) as a model system

Nanoporous gold (np-Au) is a pure metal-based catalyst, which forms methyl formate very selectively in the partial oxidation of methanol. Although several model studies under ultrahigh vacuum as well as quantum mechanical calculations attempted to provide insight into the structural and catalytic properties of np-Au, the understanding of the factors leading to the high activity and selectivity remain incomplete. In this work, a single crystalline Au(332) surface was used to model structural properties like low index (111) facets as well as low coordinated Au atoms. The experiments were conducted under well-defined UHV conditions by pulsed, isothermal molecular beam (MB) experiments combined with in situ infrared reflection adsorption spectroscopy (IRAS) as well as temperature programmed reaction (TPR) experiments. Using CO as a probe molecule applying isotopically diluted gas mixtures to prevent dipolar coupling between CO molecules, the several adsorption sites on Au(332) were spectroscopically evidenced and assigned by a combination with DFT calculations. In isothermal MB experiments on the partial methanol oxidation to methyl formate, varying the surface temperature as well as the methanol and oxygen fluxes revealed two distinct surface deactivation processes for methyl formate formation due to the formation of formate and due to impurities in the used methanol. Low coordinated sites were found to form methyl formate at a higher rate compared to other sites on the Au(332), while other reaction steps, e.g. formation of methoxy proceed also effectively on terrace sites and with gold-oxygen (AuOx) phases. TPR results demonstrated unwanted oxidation of methyl formate, the desired partial oxidation product in methanol oxidation, to occur on Au(332) already at low temperatures and even for low oxygen coverages, as expected for typical reaction conditions on np-Au. Three different reaction mechanisms for CO2 formation from methyl formate were identified by isotopic labeling experiments, which were connected to specific oxygen species on minority sites. Due to its dependence on oxygen at special sites, the methyl formate oxidation is slow under isothermal conditions compared to the oxidation of methanol which provides a microscopic understanding of the high selectivity of np-Au on the formation of methyl formate

Heterogeneity of oxygen reactivity: key for selectivity of partial methanol oxidation on gold surfaces

Recent evidence for low-temperature oxidation of methyl formate on Au(332) may affect the selectivity of gold catalysts during partial oxidation of methanol. Under isothermal conditions, overoxidation of methyl formate is significantly slower than methanol oxidation which can be attributed to special oxygen species required for overoxidation

Methanol oxidation on Au(332): methyl formate selectivity and surface deactivation under isothermal conditions

Methanol oxidation on the stepped Au(332) surface was investigated by pulsed isothermal molecular beam (MB) experiments. The effect of the surface temperature as well as the influence of changes in the methanol and atomic oxygen flux on the partial oxidation to methyl formate was studied. A maximum in methyl formate formation is observed at 250 K under the applied single collision conditions. Increasing the methanol to oxygen ratio was found to increase the selectivity to methyl formate and decrease unwanted overoxidation to surface deactivating formate detected by in situ infrared reflection absorption spectroscopy (IRAS). The results show evidence for the importance of an additional deactivation mechanism for methyl formate formation connected to methanol which is active under oxygen-deficient conditions at low temperatures. Moreover, the measurements suggest a small number of sites to be highly reactive for methyl formate formation which are preferentially blocked under oxygen-deficient conditions

The VLTI/MIDI survey of massive young stellar objects - Sounding the inner regions around intermediate- and high-mass young stars using mid-infrared interferometry

We aim to characterize the distribution and composition of circumstellar material around young massive stars, and to investigate exactly which physical structures in these objects are probed by long-baseline mid-infrared interferometric observations. We used the two-telescope interferometric instrument MIDI of the Very Large Telescope Interferometer of the European Southern Observatory to observe a sample of 24 intermediate- and high-mass young stellar objects in the N band (8-13 micron). We had successful fringe detections for 20 objects, and present spectrally-resolved correlated fluxes and visibility levels for projected baselines of up to 128 m. We fit the visibilities with geometric models to derive the sizes of the emitting regions, as well as the orientation and elongation of the circumstellar material. Fourteen objects in the sample show the 10 micron silicate feature in absorption in the total and correlated flux spectra. For 13 of these objects, we were able to fit the correlated flux spectra with a simple absorption model, allowing us to constrain the composition and absorptive properties of the circumstellar material. Nearly all of the massive young stellar objects observed show significant deviations from spherical symmetry at mid-infrared wavelengths. In general, the mid-infrared emission can trace both disks and outflows, and in many cases it may be difficult to disentangle these components on the basis of interferometric data alone, because of the sparse spatial frequency coverage normally provided by current long-baseline interferometers. For the majority of the objects in this sample, the absorption occurs on spatial scales larger than those probed by MIDI. Finally, the physical extent of the mid-infrared emission around these sources is correlated with the total luminosity, albeit with significant scatter.Comment: 36 pages, 22 figures. Accepted to Astronomy and Astrophysic

SPOTS: The Search for Planets Orbiting Two Stars. I. Survey description and first observations

Direct imaging surveys for exoplanets commonly exclude binary stars from their target lists, leaving a large part of the overall planet demography unexplored. To address this gap in our understanding of planet formation and evolution, we have launched the first direct imaging survey dedicated to circumbinary planets: SPOTS, the Search for Planets Orbiting Two Stars. In this paper, we discuss the theoretical context, scientific merit, and technical feasibility of such observations, describe the target sample and observational strategy of our survey, and report on the first results from our pilot survey of 26 targets with the VLT NaCo facility. While we have not found any confirmed substellar companions to date, a number of promising candidate companions remain to be tested for common proper motion in upcoming follow-up observations. We also report on the astrometry of the three resolved binaries in our target sample. This pilot survey constitutes a successful proof of concept for our survey strategy and paves the way for a second stage of exploratory observations with VLT SPHERE.Comment: 12 pages, 4 figures, 3 tables. Accepted for publication in A&

Scanning X-ray nanodiffraction from ferroelectric domains in strained K0.75Na0.25NbO3 epitaxial films grown on (110) TbScO3

Scanning X-ray nanodiffraction on a highly periodic ferroelectric domain pattern of a strained K0.75Na0.25NbO3 epitaxial layer has been performed by using a focused X-ray beam of about 100 14;nm probe size. A 90°-rotated domain variant which is aligned along [1 2]TSO has been found in addition to the predominant domain variant where the domains are aligned along the [12]TSO direction of the underlying (110) TbScO3 (TSO) orthorhombic substrate. Owing to the larger elastic strain energy density, the 90°-rotated domains appear with significantly reduced probability. Furthermore, the 90°-rotated variant shows a larger vertical lattice spacing than the 0°-rotated domain variant. Calculations based on linear elasticity theory substantiate that this difference is caused by the elastic anisotropy of the K0.75Na0.25NbO3 epitaxial layer

Machine learning based prediction of COVID-19 mortality suggests repositioning of anticancer drug for treating severe cases

Despite available vaccinations COVID-19 case numbers around the world are still growing, and effective medications against severe cases are lacking. In this work, we developed a machine learning model which predicts mortality for COVID-19 patients using data from the multi-center ‘Lean European Open Survey on SARS-CoV-2-infected patients’ (LEOSS) observational study (>100 active sites in Europe, primarily in Germany), resulting into an AUC of almost 80%. We showed that molecular mechanisms related to dementia, one of the relevant predictors in our model, intersect with those associated to COVID-19. Most notably, among these molecules was tyrosine kinase 2 (TYK2), a protein that has been patented as drug target in Alzheimer's Disease but also genetically associated with severe COVID-19 outcomes. We experimentally verified that anti-cancer drugs Sorafenib and Regorafenib showed a clear anti-cytopathic effect in Caco2 and VERO-E6 cells and can thus be regarded as potential treatments against COVID-19. Altogether, our work demonstrates that interpretation of machine learning based risk models can point towards drug targets and new treatment options, which are strongly needed for COVID-19

Convalescent plasma treatment for SARS-CoV-2 infected high-risk patients: a matched pair analysis to the LEOSS cohort

Establishing the optimal treatment for COVID-19 patients remains challenging. Specifically, immunocompromised and pre-diseased patients are at high risk for severe disease course and face limited therapeutic options. Convalescent plasma (CP) has been considered as therapeutic approach, but reliable data are lacking, especially for high-risk patients. We performed a retrospective analysis of 55 hospitalized COVID-19 patients from University Hospital Duesseldorf (UKD) at high risk for disease progression, in a substantial proportion due to immunosuppression from cancer, solid organ transplantation, autoimmune disease, dialysis. A matched-pairs analysis (1:4) was performed with 220 patients from the Lean European Open Survey on SARS-CoV-2-infected Patients (LEOSS) who were treated or not treated with CP. Both cohorts had high mortality (UKD 41.8%, LEOSS 34.1%). A matched-pairs analysis showed no significant effect on mortality. CP administration before the formation of pulmonary infiltrates showed the lowest mortality in both cohorts (10%), whereas mortality in the complicated phase was 27.8%. CP administration during the critical phase revealed the highest mortality: UKD 60.9%, LEOSS 48.3%. In our cohort of COVID-19 patients with severe comorbidities CP did not significantly reduce mortality in a retrospective matched-pairs analysis. However, our data supports the concept that a reduction in mortality is achievable by early CP administration

End-to-end simulations of the E-ELT/METIS coronagraphs

The direct detection of low-mass planets in the habitable zone of nearby stars is an important science case for future E-ELT instruments such as the mid-infrared imager and spectrograph METIS, which features vortex phase masks and apodizing phase plates (APP) in its baseline design. In this work, we present end-to-end performance simulations, using Fourier propagation, of several METIS coronagraphic modes, including focal-plane vortex phase masks and pupil-plane apodizing phase plates, for the centrally obscured, segmented E-ELT pupil. The atmosphere and the AO contributions are taken into account. Hybrid coronagraphs combining the advantages of vortex phase masks and APPs are considered to improve the METIS coronagraphic performance

Empirical Standards for Software Engineering Research

Empirical Standards are natural-language models of a scientific community's expectations for a specific kind of study (e.g. a questionnaire survey). The ACM SIGSOFT Paper and Peer Review Quality Initiative generated empirical standards for research methods commonly used in software engineering. These living documents, which should be continuously revised to reflect evolving consensus around research best practices, will improve research quality and make peer review more effective, reliable, transparent and fair.Comment: For the complete standards, supplements and other resources, see https://github.com/acmsigsoft/EmpiricalStandard