Representing molecule-surface interactions with symmetry-adapted neural networks

The accurate description of molecule-surface interactions requires a detailed knowledge of the underlying potential-energy surface (PES). Recently, neural networks (NNs) have been shown to be an efficient technique to accurately interpolate the PES information provided for a set of molecular configurations, e.g. by first-principles calculations. Here, we further develop this approach by building the NN on a new type of symmetry functions, which allows to take the symmetry of the surface exactly into account. The accuracy and efficiency of such symmetry-adapted NNs is illustrated by the application to a six-dimensional PES describing the interaction of oxygen molecules with the Al(111) surface.Comment: 13 pages including 8 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Das digitale wissenschaftliche Informationssystem der WWU:Integrierte Bereitstellung, einheitlicher Zugang und individuelle Verteilung

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Strong and ductile platelet-reinforced polymer films inspired by nature: Microstructure and mechanical properties

The unique structure and mechanical properties of platelet-reinforced biological materials such as bone and seashells have motivated the development of artificial composites exhibiting new, unusual mechanical behavior. On the basis of designing principles found in these biological structures, we combined high-performance artificial building blocks to fabricate platelet-reinforced polymer matrix composites that exhibit simultaneously high tensile strength and ductility. The mechanical properties are correlated with the underlying microstructure of the composites before and after mechanical loading using transmission electron microscopy. The critical role of the strength of the platelet-polymer interface and its dependence on the platelet surface chemistry and the type of matrix polymer are studied. Thin multilayered films with highly oriented platelets were produced through the bottom-up layer-by-layer assembly of submicrometer-thin alumina platelets and either polyimide or chitosan as polymer matrix. The tensile strength and strain at rupture of the prepared composites exceeded that of nacre, whereas the elastic modulus reached values similar to that of lamellar bones. In contrast to the brittle failure of clay-reinforced composites of similar or higher strength and stiffness, our composites exhibit plastic deformation in the range of 2-90% before failure. In addition to the high reinforcing efficiency and ductility achieved, several toughening mechanisms were identified in fractured composites, namely friction, debonding, and formation of microcracks at the platelet-polymer interface, as well as plastic deformation and void formation within the continuous polymeric phase. The combination of high strength, ductility, and toughness was achieved by selecting platelets that exhibit an aspect ratio high enough to carry significant load but small enough to allow for fracture under the platelet pull-out mode. At high concentrations of platelets, the ductility gets lost because of out-of-plane misalignment of the platelets and incorporation of voids in the microstructure during processing. The designing principles applied in this study can potentially be extended to other types of platelets and polymers to obtain new, hybrid materials with tunable mechanical propertie

Integrierte Bereitstellung, einheitlicher Zugang und individuelle Verteilung:Informations-Management einer großen Universität

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Informationsmanagement

Programm: Wilhelm Held: Zur Bedeutung des Informationsmanagements Christian Schild: Unternehmensinterne Suchmaschine Jörg Lorenz: Portale zum zentralen Einstieg in die Arbeitsumgebung Reinhard Mersch: Identitätsmanagement Georg Richter: Informationsverarbeitung in sicheren Infrastrukturen Ludger Elkemann: Kundenfreundliche Telefonauskunf

Protein S-Bacillithiolation Functions in Thiol Protection and Redox Regulation of the Glyceraldehyde-3-Phosphate Dehydrogenase Gap in Staphylococcus aureus Under Hypochlorite Stress

Aims: Bacillithiol (BSH) is the major low-molecular-weight thiol of the human pathogen Staphylococcus aureus. In this study, we used OxICAT and Voronoi redox treemaps to quantify hypochlorite-sensitive protein thiols in S. aureus USA300 and analyzed the role of BSH in protein S-bacillithiolation.  Results: The OxICAT analyses enabled the quantification of 228 Cys residues in the redox proteome of S. aureus USA300. Hypochlorite stress resulted in >10% increased oxidation of 58 Cys residues (25.4%) in the thiol redox proteome. Among the highly oxidized sodium hypochlorite (NaOCl)-sensitive proteins are five S-bacillithiolated proteins (Gap, AldA, GuaB, RpmJ, and PpaC). The glyceraldehyde-3-phosphate (G3P) dehydrogenase Gap represents the most abundant S-bacillithiolated protein contributing 4% to the total Cys proteome. The active site Cys151 of Gap was very sensitive to overoxidation and irreversible inactivation by hydrogen peroxide (H2O2) or NaOCl in vitro. Treatment with H2O2 or NaOCl in the presence of BSH resulted in reversible Gap inactivation due to S-bacillithiolation, which could be regenerated by the bacilliredoxin Brx (SAUSA300_1321) in vitro. Molecular docking was used to model the S-bacillithiolated Gap active site, suggesting that formation of the BSH mixed disulfide does not require major structural changes.  Conclusion and Innovation: Using OxICAT analyses, we identified 58 novel NaOCl-sensitive proteins in the pathogen S. aureus that could play protective roles against the host immune defense and include the glycolytic Gap as major target for S-bacillithiolation. S-bacillithiolation of Gap did not require structural changes, but efficiently functions in redox regulation and protection of the active site against irreversible overoxidation in S. aureus. Antioxid. Redox Signal. 28, 410–430

Holocene changes in vegetation composition in northern Europe: why quantitative pollen-based vegetation reconstructions matter

International audienceWe present pollen-based reconstructions of the spatio-temporal dynamics of northern European regional vegetation abundance through the Holocene. We apply the Regional Estimates of VEgetation Abundance from Large Sites (REVEALS) model using fossil pollen records from eighteen sites within five modern biomes in the region. The eighteen sites are classified into four time-trajectory types on the basis of principal components analysis of both the REVEALS-based vegetation estimates (RVs) and the pollen percentage (PPs). The four trajectory types are more clearly separated for RVs than PPs. Further, the timing of major Holocene shifts, rates of compositional change, and diversity indices (turnover and evenness) differ between RVs and PPs. The differences are due to the reduction by REVEALS of biases in fossil pollen assemblages caused by different basin size, and inter-taxonomic differences in pollen productivity and dispersal properties. For example, in comparison to the PPs, the RVs show an earlier increase in Corylus and Ulmus in the early-Holocene and a more pronounced increase in grassland and deforested areas since the mid-Holocene. The results suggest that the influence of deforestation and agricultural activities on plant composition and abundance from Neolithic times was stronger than previously inferred from PPs. Relative to PPs, RVs show a more rapid compositional change, a largest decrease in turnover, and less variable evenness in most of northern Europe since 5200 cal yr BP. All these changes are primarily related to the strong impact of human activities on the vegetation. This study demonstrates that RV-based estimates of diversity indices, timing of shifts, and rates of change in reconstructed vegetation provide new insights into the timing and magnitude of major humandisturbance on Holocene regional vegetation, features that are critical in the assessment of humanimpact on vegetation, land-cover, biodiversity, and climate in the past

Fungal iron availability during deep seated candidiasis is defined by a complex interplay involving systemic and local events

Peer reviewedPublisher PD

The InSight-HP³ mole on Mars: Lessons learned from attempts to penetrate to depth in the Martian soil

The NASA InSight lander mission to Mars payload includes the Heat Flow and Physical Properties Package HP3 to measure the surface heat flow. The package was designed to use a small penetrator - nicknamed the mole - to implement a vertical string of temperature sensors in the soil to a depth of 5 m. The mole itself is equipped with sensors to measure a thermal conductivity-depth profile as it proceeds to depth. The heat flow is calculated from the product of the temperature gradient and the thermal conductivity. To avoid the perturbation caused by annual surface temperature variations, the measurements need to be taken at a depth between 3 m and 5 m. The mole is designed to penetrate cohesionless soil similar in rheology to quartz sand which is expected to provide a good analogue material for Martian sand. The sand would provide friction to the buried mole hull to balance the remaining recoil of the mole hammer mechanism that drives the mole forward. Unfortunately, the mole did not penetrate more than 40 cm, roughly a mole length. The failure to penetrate deeper is largely due to a cohesive duricrust of a few tens of centimeter thickness that failed to provide the required friction. Although a suppressor mass and spring as part of the mole hammer mechanism absorb much of the recoil, the available mass did not allow designing a system that fully eliminated the recoil. The mole penetrated to 40 cm depth benefiting from friction provided by springs in the support structure from which it was deployed and from friction and direct support provided by the InSight Instrument Deployment Arm. In addition, the Martian soil provided unexpected levels of penetration resistance that would have motivated designing a more powerful mole. The low weight of the mole support structure was not sufficient to guide the mole penetrating vertically. Roughly doubling the overall mass of the instrument package would have allowed to design a more robust system with little or no recoil, more energy of the mole hammer mechanism and a more massive support structure. In addition, to cope with duricrust a mechanism to support the mole to a depth of about two mole lengths should be considered

Acute Beneficial Hemodynamic Effects of a Novel 3D-Echocardiographic Optimization Protocol in Cardiac Resynchronization Therapy

Post-implantation therapies to optimize cardiac resynchronization therapy (CRT) focus on adjustments of the atrio-ventricular (AV) delay and ventricular-to-ventricular (VV) interval. However, there is little consensus on how to achieve best resynchronization with these parameters. The aim of this study was to examine a novel combination of doppler echocardiography (DE) and three-dimensional echocardiography (3DE) for individualized optimization of device based AV delays and VV intervals compared to empiric programming.25 recipients of CRT (male: 56%, mean age: 67 years) were included in this study. Ejection fraction (EF), the primary outcome parameter, and left ventricular (LV) dimensions were evaluated by 3DE before CRT (baseline), after AV delay optimization while pacing the ventricles simultaneously (empiric VV interval programming) and after individualized VV interval optimization. For AV delay optimization aortic velocity time integral (AoVTI) was examined in eight different AV delays, and the AV delay with the highest AoVTI was programmed. For individualized VV interval optimization 3DE full-volume datasets of the left ventricle were obtained and analyzed to derive a systolic dyssynchrony index (SDI), calculated from the dispersion of time to minimal regional volume for all 16 LV segments. Consecutively, SDI was evaluated in six different VV intervals (including LV or right ventricular preactivation), and the VV interval with the lowest SDI was programmed (individualized optimization).EF increased from baseline 23±7% to 30±8 (p<0.001) after AV delay optimization and to 32±8% (p<0.05) after individualized optimization with an associated decrease of end-systolic volume from a baseline of 138±60 ml to 115±42 ml (p<0.001). Moreover, individualized optimization significantly reduced SDI from a baseline of 14.3±5.5% to 6.1±2.6% (p<0.001).Compared with empiric programming of biventricular pacemakers, individualized echocardiographic optimization with the integration of 3-dimensional indices into the optimization protocol acutely improved LV systolic function and decreased ESV and can be used to select the optimal AV delay and VV interval in CRT