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Background: Acute mountain sickness (AMS) is the most common disease caused by hypobaric hypoxia (HH) in high-altitude (HA) associated with high mortality when progressing to high-altitude pulmonary edema (HAPE) and/or high-altitude cerebral edema (HACE). There is evidence for a role of pro- and anti-inflammatory cytokines in development of AMS, but biological pathways and molecular mechanisms underlying AMS remain elusive. We aimed to measure changes in blood cytokine levels and their possible association with the development of AMS.Method: 15 healthy mountaineers were included into this prospective clinical trial. All participants underwent baseline normoxic testing with venous EDTA blood sampling at the Bangor University in United Kingdom (69 m). The participants started from Beni at an altitude of 869 m and trekked same routes in four groups the Dhaulagiri circuit in the Nepali Himalaya. Trekking a 14-day route, the mountaineers reached the final HA of 5,050 m at the Hidden Valley Base Camp (HVBC). Venous EDTA blood sampling was performed after active ascent to HA the following morning after arrival at 5,050 m (HVBC). A panel of 21 cytokines, chemokines and growth factors were assessed using Luminex system (IL-1β, IL-2, IL-4, IL-6, IL-8, IL-10, IL-12p40, IL-1ra, sIL-2Rα, IFN-γ, TNF-α, MCP-1, MIP-1α, MIP-1β, IP-10, G-CSF, GM-CSF, EGF, FGF-2, VEGF, and TGF-β1).Results: There was a significant main effect for the gradual ascent from sea-level (SL) to HA on nearly all cytokines. Serum levels for TNF-α, sIL-2Rα, G-CSF, VEGF, EGF, TGF-β1, IL-8, MCP-1, MIP-1β, and IP-10 were significantly increased at HA compared to SL, whereas levels for IFN-γ and MIP-1α were significantly decreased. Serum VEGF was higher in AMS susceptible versus AMS resistant subjects (p < 0.027, main effect of AMS) and increased after ascent to HA in both AMS groups (p < 0.011, main effect of HA). Serum VEGF increased more from SL values in the AMS susceptible group than in the AMS resistant group (p < 0.049, interaction effect).Conclusion: Cytokine concentrations are significantly altered in HA. Within short interval after ascent, cytokine concentrations in HH normalize to values at SL. VEGF is significantly increased in mountaineers suffering from AMS, indicating its potential role as a biomarker for AMS.

The pull-out resistance of fully threaded, self-tapping screws under axial loading has been investigated intensively in the past. Actual design models are based mainly on empirical data because the detailed interaction between the screw thread and the surrounding timber member remains unclear and might depend on the test set-up. An innovative screw sensor with 19 internal fibre Bragg gratings (FBGs) was developed to measure the forces along the screw axis. The screw diameter was 12 mm and the maximum embedding length was 360 mm. The FBG measurement screw was applied in pull-out tests under different support conditions. The results carried out show details of the axial forces along fully threaded screws depending on the magnitude of the screw axis to grain angle, the embedding length, the material and the support conditions. Load transfer between the screw and the surrounding timber was determined by means of the change of axial forces along the screw axis. A comparison of the experimental results with Volkersen’s theory points out the decisive dependency of the support conditions on the axial forces in fully threaded self-tapping screws. Additionally, the experimental test results show indications of shear and compressive stresses in the interface of the measurement screw.

Chemical functionalization of molecular 2D materials toward the assembly of hierarchical functional nanostructures is of great importance for nanotechnology including areas like artificial photocatalytic systems, nanobiosensors, or ultrafiltration. To achieve the desired functionality of 2D materials, these need to be characterized down to the nanoscale. However, obtaining the respective chemical information is challenging and generally requires the application of complementary experimental techniques. Here, the synthesis and chemical characterization of hierarchically assembled molecular nanosheets based on ≈1 nm thin, molecular carbon nanomembrane (CNM) and covalently grafted, single‐molecule layer cobalt(III) catalysts for the light‐driven hydrogen evolution reaction (HER) is demonstrated. X‐ray photoelectron spectroscopy (XPS) and tip‐enhanced Raman spectroscopy (TERS) to access both the transversal and longitudinal chemical information of the synthesized nanosheets with nanometer resolution are employed. TERS and XPS data provide detailed information on the average and local surface distribution of the catalyst as well as mechanistic details of the grafting reaction. The proposed approach represents a general route toward a nanoscale structural analysis for a variety of molecular 2D materials—a rapidly growing materials class with broad prospects for fundamental science and applications., Hierarchically assembled nanosheets with ultimate molecular thickness, bearing functional cobalt(III) complexes are investigated by X‐ray photoelectron spectroscopy and tip‐enhanced Raman scattering. The combination of both techniques provides detailed insights into the structure of the formed 2D materials down to the nanoscale., publishedVersion

Cobaloximes are promising, earth-abundant catalysts for the light-driven hydrogen evolution reaction. Typically, these cobalt(III) complexes are prepared in situ or employed in their neutral form, e.g. [Co(dmgH 2 )(py)Cl], even though related complex salts have been reported previously and could in principle offer improved catalytic activity as well as more efficient immobilization on solid support. Here we report an interdisciplinary investigation into complex salts [Co(dmgH) 2 (py) 2 ] + [Co(dmgBPh 2 ) 2 Cl 2 ] - , TBA + [Co(dmgBPh 2 ) 2 Cl 2 ] - and [Co(dmgH) 2 (py) 2 ] + BArF - . We describe their strategic syntheses from commercially available complex [Co(dmgH) 2 (py)Cl] and demonstrate that these double and single complex salts are potent catalysts for the light-driven hydrogen evolution reaction. We also show that scanning electrochemical cell microscopy can be used to deposit arrays of catalysts [Co(dmgH) 2 (py) 2 ] + [Co(dmgBPh 2 ) 2 Cl 2 ] - and [Co(dmgH) 2 (py)Cl] on supported and free-standing amino-terminated ~ 1 nm thick carbon nanomembranes (CNMs). Photocatalytic H 2 evolution at such arrays was quantified with Pd microsensors using scanning electrochemical microscopy, thus providing a new approach for catalytic evaluation and opening up novel routes for the creation and analysis of “designer catalyst arrays”, nano-printed in a desired pattern on a solid support.

Cyclophellitols are potent inhibitors of exo- and endoglycosidases. Efficient synthetic methodologies are needed to fully capitalize on this intriguing class of mechanism-based enzyme deactivators. We report the synthesis of an orthogonally protected cyclitol from d-glucal (19% yield over 12 steps) and its use in the synthesis of α-(1,3)-linked di- and trisaccharide dextran mimetics. These new glycomimetics may find use as Dextranase inhibitors, and the developed chemistries in widening the palette of glycoprocessing enzyme-targeting glycomimetics.

Aromatic self-assembled monolayers (SAMs) can be cross-linked into molecular nanosheets  carbon nanomembranes (CNMs)  via low-energy electron irradiation. Due to their favorable mechanical stability and tunable functional properties, they possess a high potential for various applications including nanosensors, separation membrane for osmosis or energy conversion devices. Despite this potential, the mechanistic details of the electron irradiation induced cross-linking process still need to be understood in more detail. Here we studied the cross-linking of 4'-nitro-1,1 ́-biphenyl-4-thiol SAM on gold. The SAM samples were irradiated with different electron energies ranging from 2.5 to 100 eV in ultra-high vacuum and subsequently analysed by complementary techniques. We present results obtained via spectroscopy and microscopy characterization by high-resolution X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction with micrometre sized electron beams (LEED) and low-energy electron microscopy (LEEM). To demostrate the formation of CNMs, the formed two-dimensional molecular materials were transferred onto grids and oxidized wafer and analyzed by optical, scanning electron (SEM) and atomic force microscopy (AFM). We found a strong energy dependence for the cross section for the cross-linking process, which rates decrease exponentially towards lower electron energies by about four orders of magnitude. We conduct a comparative analysis of the cross sections for the C-H bond scission via electron impact ionization and dissociative electron attachment and find out that these different ionization mechnisms are responsible for the variation of the cross-linking cross section with electron energy.

The spatiotemporally-controlled perturbation of cellular function using photopharmacology has facilitated the elucidation of biological networks and opens up new opportunities for precision medicine. Here, we introduce cell- permeable photoswitchable small molecules, termed optojasps, to optically control the dynamics of the actin cytoskeleton and cellular functions that depend on it. These light-dependent effectors were designed from the F-actin-stabilizing marine depsipeptide jasplakinolide by functionalizing them with azobenzene photoswitches. We demonstrate that optojasps can be employed to control cell viability, cell motility, and cytoskeletal signalling with the high spatial and temporal resolution that light affords. We expect that optojasps will find applications in diverse areas of cell biological research. They may also provide a template for the development of chemotherapeutics targeting the ubiquitous actin cytoskeleton with precision control in the μm range.

The lattice Boltzmann method is a modern approach to simulate fluid flow. In its original formulation, it is restricted to regular grids, second-order discretizations, and a unity CFL number. This paper describes our new off-lattice Boltzmann solver NATriuM, an extensible and parallel C++ code to perform lattice Boltzmann simulations on irregular grids. NATriuM also allows high-order spatial discretizations and non-unity CFL numbers to be used. We demonstrate how these features can efficiently decrease the number of grid points required in a simulation and thus reduce the computational time, compared to the standard lattice Boltzmann method. We detail the implementation of a recently proposed semi-Lagrangian lattice Boltzmann method and prove its efficiency in comparisons to other state-of-the-art off-lattice Boltzmann schemes.

This paper presents a framework for incorporating arbitrary implicit multistep schemes into the lattice Boltzmann method. While the temporal discretization of the lattice Boltzmann equation is usually derived using a second-order trapezoidal rule, it appears natural to augment the time discretization by using multistep methods. The effect of incorporating multistep methods into the lattice Boltzmann method is studied in terms of accuracy and stability. Numerical tests for the third-order accurate Adams-Moulton method and the second-order backward differentiation formula show that the temporal order of the method can be increased when the stability properties of multistep methods are considered in accordance with the second Dahlquist barrier.

The lattice Boltzmann method (LBM) facilitates efficient simulations of fluid turbulence based on advection and collision of local particle distribution functions. To ensure stable simulations on underresolved grids, the collision operator must prevent drastic deviations from local equilibrium. This can be achieved by various methods, such as the multirelaxation time, entropic, quasiequilibrium, regularized, and cumulant schemes. Complementing a part of a unified theoretical framework of these schemes, the present work presents a derivation of the regularized lattice Boltzmann method (RLBM), which follows a recently introduced entropic multirelaxation time LBM by Karlin, Bösch, and Chikatamarla (KBC). It is shown that both methods can be derived by locally maximizing a quadratic Taylor expansion of the entropy function. While KBC expands around the local equilibrium distribution, the RLBM is recovered by expanding entropy around a global equilibrium. Numerical tests were performed to elucidate the role of pseudoentropy maximization in these models. Simulations of a two-dimensional shear layer show that the RLBM successfully reproduces the largest eddies even on a 16×16 grid, while the conventional LBM becomes unstable for grid resolutions of 128×128 and lower. The RLBM suppresses spurious vortices more effectively than KBC. In contrast, simulations of the three-dimensional Taylor-Green and Kida vortices show that KBC performs better in resolving small scale vortices, outperforming the RLBM by a factor of 1.8 in terms of the effective Reynolds number.