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The sliding performance of cross country skis is mainly influenced by the ability of the ski base to minimize capillary forces and contact area. Whereas, the first condition depends on hydrophobicity, the second one is controlled by the ski grinding structure and the morphology of snow. In this contribution the results of sliding tests with five typical grinding structures will be presented and compared to calculations of the real area of contact. Surface topographies were measured and corresponding roughness features were analyzed by 3D optical microscopy. The measured ski base profiles and the measured grain size distribution of granular snow at −2°C were employed within a bearing model for a rough surface in contact with loose and freely-moving snow grains treated as ice spheres. For the five grinding structures, this model revealed a good correlation of the real area of contact between ski and snow with run times in lab-condition sliding tests. The results indicate that the snow-containing volume of the grinding structure is pivotal for tailoring the sliding behavior.

Background Glutaredoxins (GRXs) are oxidoreductases involved in diverse cellular processes through their capacity to reduce glutathionylated proteins and/or to coordinate iron‑sulfur (Fe-S) clusters. Among class II GRXs, the plant-specific GRXS16 is a bimodular protein formed by an N-terminal endonuclease domain fused to a GRX domain containing a 158CGFS signature. Methods The biochemical properties (redox activity, sensitivity to oxidation, pKa of cysteine residues, midpoint redox potential) of Arabidopsis thaliana GRXS16 were investigated by coupling oxidative treatments to alkylation shift assays, activity measurements and mass spectrometry analyses. Results Activity measurements using redox-sensitive GFP2 (roGFP2) as target protein did not reveal any significant glutathione-dependent reductase activity of A. thaliana GRXS16 whereas it was able to catalyze the oxidation of roGFP2 in the presence of glutathione disulfide. Accordingly, Arabidopsis GRXS16 reacted efficiently with oxidized forms of glutathione, leading to the formation of an intramolecular disulfide between Cys158 and the semi-conserved Cys215, which has a midpoint redox potential of - 298 mV at pH 7.0 and is reduced by plastidial thioredoxins (TRXs) but not GSH. By promoting the formation of this disulfide, Cys215 modulates GRXS16 oxidoreductase activity. Conclusion The reduction of AtGRXS16, which is mandatory for its oxidoreductase activity and the binding of Fe-S clusters, depends on light through the plastidial FTR/TRX system. Hence, disulfide formation may constitute a redox switch mechanism controlling GRXS16 function in response to day/night transition or oxidizing conditions. General significance From the in vitro data obtained with roGFP2, one can postulate that GRXS16 would mediate protein glutathionylation/oxidation in plastids but not their deglutathionylation.

Iron–sulfur (Fe–S) clusters are ubiquitous cofactors in all life and are used in a wide array of diverse biological processes, including electron transfer chains and several metabolic pathways. Biosynthesis machineries for Fe–S clusters exist in plastids, the cytosol, and mitochondria. A single monothiol glutaredoxin (GRX) is involved in Fe–S cluster assembly in mitochondria of yeast and mammals. In plants, the role of the mitochondrial homolog GRXS15 has only partially been characterized. Arabidopsis (Arabidopsis thaliana) grxs15 null mutants are not viable, but mutants complemented with the variant GRXS15 K83A develop with a dwarf phenotype similar to the knockdown line GRXS15amiR. In an in-depth metabolic analysis of the variant and knockdown GRXS15 lines, we show that most Fe–S cluster-dependent processes are not affected, including biotin biosynthesis, molybdenum cofactor biosynthesis, the electron transport chain, and aconitase in the tricarboxylic acid (TCA) cycle. Instead, we observed an increase in most TCA cycle intermediates and amino acids, especially pyruvate, glycine, and branched-chain amino acids (BCAAs). Additionally, we found an accumulation of branched-chain α-keto acids (BCKAs), the first degradation products resulting from transamination of BCAAs. In wild-type plants, pyruvate, glycine, and BCKAs are all metabolized through decarboxylation by mitochondrial lipoyl cofactor (LC)-dependent dehydrogenase complexes. These enzyme complexes are very abundant, comprising a major sink for LC. Because biosynthesis of LC depends on continuous Fe–S cluster supply to lipoyl synthase, this could explain why LC-dependent processes are most sensitive to restricted Fe–S supply in grxs15 mutants.

The development of epitaxy techniques for localized growth of crystalline silicon nanofilms and nanostructures has been crucial to recent advances in electronics and photonics. A precise definition of the crystal growth location, however, requires elaborate pre-epitaxy processes for substrate patterning. Our molecular dynamics simulations reveal that homoepitaxial silicon nanofilms can be directly deposited by a crystalline silicon tip rubbing against the substrate, thus enabling geometrically controlled crystal growth with no need for substrate pre-patterning. We name this solid-phase epitaxial growth triboepitaxy as it solely relies on shear-induced amorphization and recrystallization that occur even at low temperature at the sliding interface between two silicon crystals. The interplay between the two concomitant, shear-induced processes is responsible for the formation of an amorphous sliding interface with constant nanometric thickness. If the two elastically anisotropic crystals slide along different crystallographic orientations, the amorphous layer can move unidirectionally perpendicular to the sliding plane, causing the crystal with lowest elastic energy per atom to grow at the expenses of the other crystal. As triboepitaxial growth is governed by the shear elastic response of the two crystals along the sliding direction, it can be implemented as a mechanical scanning-probe lithography method in which epitaxial growth is controlled by tuning the crystallographic misorientation between tip and substrate, the tip's size or the normal force. These results suggest a radically new way to conceive nanofabrication techniques that are based on tribologically induced materials transformations., 35 pages, 13 figures, 1 table

The formation of a persulfide group (-SSH) on cysteine residues has gained attention as a reversible posttranslational modification contributing to protein regulation or protection. The widely distributed 3-mercaptopyruvate sulfurtransferases (MSTs) are implicated in the generation of persulfidated molecules and H2S biogenesis through transfer of a sulfane sulfur atom from a suitable donor to an acceptor. Arabidopsis has two MSTs, named STR1 and STR2, but they are poorly characterized. To learn more about these enzymes, we conducted a series of biochemical experiments including a variety of possible reducing systems. Our kinetic studies, which used a combination of sulfur donors and acceptors revealed that both MSTs use 3-mercaptopyruvate efficiently as a sulfur donor while thioredoxins, glutathione, and glutaredoxins all served as high-affinity sulfane sulfur acceptors. Using the redox-sensitive GFP (roGFP2) as a model acceptor protein, we showed that the persulfide-forming MSTs catalyze roGFP2 oxidation and more generally trans-persulfidation reactions. However, a preferential interaction with the thioredoxin system and glutathione was observed in case of competition between these sulfur acceptors. Moreover, we observed that MSTs are sensitive to overoxidation but are protected from an irreversible inactivation by their persulfide intermediate and subsequent reactivation by thioredoxins or glutathione. This work provides significant insights into Arabidopsis STR1 and STR2 catalytic properties and more specifically emphasizes the interaction with cellular reducing systems for the generation of H2S and glutathione persulfide and reactivation of an oxidatively modified form.

A combination of atomistic simulations and vacuum tribometry allows atomic-scale insights into the chemical structure of superlubricious hydrogenated diamond-like carbon (a-C:H) interfaces in vacuum. Quantum molecular dynamics shearing simulations provide a structure-property map of the friction regimes that characterize the dry sliding of a-C:H. Shear stresses and structural properties at the sliding interfaces are crucially determined by the hydrogen content CH in the shear zone of the a-C:H coating. Extremely small CH&nbsp, (below 3 at.%) cause cold welding, mechanical mixing and high friction. At intermediate CH (ranging approximately from 3 to 20 at.%), cold welding in combination with mechanical mixing remains the dominant sliding mode, but some a-C:H samples undergo aromatization, resulting in a superlubricious sliding interface. A further increase in CH (above 20 at.%) prevents cold welding completely and changes the superlubricity mechanism from aromatic to hydrogen passivation. The hydrogen-passivated surfaces are composed of short hydrocarbon chains hinting at a tribo-induced oligomerization reaction. In the absence of cold welding, friction strongly correlates with nanoscale roughness, measured by the overlap of colliding protrusions at the sliding interface. Finally, the atomistic friction map is related to reciprocating friction experiments in ultrahigh vacuum. Accompanying X-ray photoelectron and Auger electron spectroscopy (XPS, XAES) analyses elucidate structural changes during vacuum sliding of a hydrogen-rich a-C:H with 36 at.% hydrogen. Initially, the a-C:H is covered by a nanometer-thick hydrogen-depleted surface layer. After a short running-in phase that results in hydrogen accumulation, superlubricity is established. XPS and XAES indicate a non-aromatic 1–2-nm-thick surface layer with polyethylene-like composition in agreement with our simulations.

Tribology letters 69(4), 136 (2021). doi:10.1007/s11249-021-01508-9, Published by Springer Science Business Media B.V., Dordrecht

This work elucidates friction in Poly-Ether-Ether-Ketone (PEEK) sliding contacts through multiscale simulations. At the nanoscale, non-reactive classical molecular dynamics (MD) simulations of dry and water-lubricated amorphous PEEK-PEEK interfaces are performed. During a short running-in phase, we observe structural transformations at the sliding interface that result in flattening of the initial nanotopographies accompanied by strong polymer chain alignment in the shearing direction. Our MD simulations reveal a linear pressure-dependence of the shear stress τMD (P,σH2o) [MPa]=0.18P + 50.5 - 1.25σH2o, where σH2o [nm-2] is the surface number density of adsorbed water molecules. This constitutive law is of central importance for our multiscale approach, since it forms a link between MD and elastoplastic contact mechanics calculations. An integration of τMD (P,σH2o) over the real area of contact yields a macroscopic friction coefficient μmacro (σH2o) that allows for a meaningful comparison with friction coefficients μexp≈0.5-0.7 which are in good agreement with the calculated dry friction coefficients μmacro(σH2o=0).For milder experimental loads, our multiscale model suggests that the lower friction states with μexp≈0.2 originate in the presence of physisorbed molecules (e.g. water), which significantly reduce interfacial adhesion.

Social media has long established itself in everyday marketing. In the field of B2B content marketing, social media channels are rated with 95% approval as almost as important as the companies website with 98% approval according to the Statista Content Marketing Trend Study 2020. Facebook, Instagram, Twitter, Snapchat, TikTok, and the like are regarded as the social media classics or newcomers and are currently used much more in the B2C than in the B2B environment.

International audience; The increasing demand for sustainable tribology has accelerated the development of environmentally friendly lubrication solutions such as water or water-related lubricants. Earlier works have reported on water-lubricated sliding of silicon nitride (Si3N4) at high speeds, which can result in a superlow friction (m < 0.01) owing to the formation of hydrodynamic water films on hydrophilic surface layers. Here, combined boundary-lubrication experiments at low sliding speeds and atomistic simulations reveal an alternative superlubricity mechanism for glycerol-lubricated Si3N4. X-ray photoelectron and time-of-flight secondary ion mass spectrometry performed inside and outside the wear track as well as high-resolution mass spectroscopy of the used lubricant strongly suggest that sub-nanometer-thick graphene nitride layers form at the very top of Si3N4. In the accompanying atomistic simulations, glycerol molecules undergo tribochemical decomposition and react with surface-bound nitrogen atoms to form carbon nitrides. Further shearing promotes the formation of 2D graphene nitrides that passivate the ceramic surfaces and induce a superlow friction under boundary lubrication. Thus, glycerol-lubricated Si3N4 has a high potential for use in green superlubricity enabled by in situ synthesis of disordered graphene nitride species.

Social Media hat sich im Marketing-Alltag schon langst etabliert. Im Bereich des B2B Content Marketings werden Social Media Kanale mit 95 % Zustimmung als fast so wichtig, wie die eigene Website mit 98 % Zustimmung laut der Statista Content Marketing Trendstudie 2020 eingestuft. Facebook, Instagram, Twitter, Snapchat, TikTok o. a. gelten als die Social Media Klassiker bzw. Newcomer und werden aktuell wesentlich starker im B2C- als im B2B-Umfeld eingesetzt.

Friction and wear reduction by diamond-like carbon (DLC) in automotive applications can be affected by zinc-dialkyldithiophosphate (ZDDP), which is widely used in engine oils. Our experiments show that DLC’s tribological behaviour in ZDDP-additivated oils can be optimised by tailoring its stiffness, surface nano-topography and hydrogen content. An optimal combination of ultralow friction and negligible wear is achieved using hydrogen-free tetrahedral amorphous carbon (ta-C) with moderate hardness. Softer coatings exhibit similarly low wear and thin ZDDP-derived patchy tribofilms but higher friction. Conversely, harder ta-Cs undergo severe wear and sub-surface sulphur contamination. Contact-mechanics and quantum-chemical simulations reveal that shear combined with the high local contact pressure caused by the contact stiffness and average surface slope of hard ta-Cs favour ZDDP fragmentation and sulphur release. In absence of hydrogen, this is followed by local surface cold welding and sub-surface mechanical mixing of sulphur resulting in a decrease of yield stress and wear., Wear reduction in diamond-like carbon interacting with ZDDP-additivated oils is essential for current automotive applications. Here, the authors present an atomic-scale study revealing that this can be achieved by tailoring diamond-like carbon’s stiffness, surface nano-topography, and hydrogen content.

The biosynthesis of many sulfur-containing molecules depends on cysteine as a sulfur source. Cysteine desulfurase (CD) and rhodanese (Rhd) domain-containing protein families participate in the trafficking of sulfur for various metabolic pathways in bacteria and human, but their connection is not yet described in plants. The existence of natural chimeric proteins, however, containing both CD and Rhd domains in specific bacterial genera suggests a general interaction between both proteins. We report here the biochemical relationships between two cytosolic proteins from Arabidopsis thaliana, a Rhd domain containing protein, the sulfurtransferase 18 (STR18), and a CD isoform referred to as ABA3, and compare these biochemical features to those of a natural CD-Rhd fusion protein from the bacterium Pseudorhodoferax sp.. We observed that the bacterial enzyme is bifunctional exhibiting both CD and STR activities using L-cysteine and thiosulfate as sulfur donors but preferentially uses L-cysteine to catalyze trans-persulfidation reactions. In vitro activity assays and mass spectrometry analyses revealed that STR18 stimulates the CD activity of ABA3 by reducing the intermediate persulfide on its catalytic cysteine thereby accelerating the overall transfer reaction. Both proteins interact in planta and form an efficient sulfur relay system whereby STR18 catalyzes trans-persulfidation reactions from ABA3 to the model acceptor protein roGFP2. In conclusion, the ABA3-STR18 couple likely represents an uncharacterized pathway of sulfur trafficking in the cytosol of plant cells, independent of ABA3 function in molybdenum cofactor maturation.

Iron-sulfur (Fe-S) clusters are ubiquitous cofactors in all life and are used in a wide array of diverse biological processes, including electron transfer chains and several metabolic pathways. Biosynthesis machineries for Fe-S clusters exist in plastids, the cytosol and mitochondria. A single monothiol glutaredoxin (GRX) has been shown to be involved in Fe-S cluster assembly in mitochondria of yeast and mammals. In plants, the role of the mitochondrial homologue GRXS15 has only partially been characterized. Arabidopsisgrxs15null mutants are not viable, but mutants complemented with the variantGRXS15 K83Adevelop with a dwarf phenotype. In an in-depth metabolic analysis, we show that most Fe-S cluster-dependent processes are not affected, including biotin biosynthesis, molybdenum cofactor biosynthesis and the electron transport chain. Instead, we observed an increase in most TCA cycle intermediates and amino acids, especially pyruvate, 2-oxoglutarate, glycine and branched-chain amino acids (BCAAs). The most pronounced accumulation occurred in branched-chain α-keto acids (BCKAs), the first degradation products resulting from deamination of BCAAs. In wild-type plants, pyruvate, 2-oxoglutarate, glycine and BCKAs are all metabolized through decarboxylation by four mitochondrial lipoyl cofactor-dependent dehydrogenase complexes. Because these enzyme complexes are very abundant and the biosynthesis of the lipoyl cofactor depends on continuous Fe-S cluster supply to lipoyl synthase, this could explain why lipoyl cofactor-dependent processes are most sensitive to restricted Fe-S supply inGRXS15 K83Amutants.One-sentence summaryDeficiency in GRXS15 restricts protein lipoylation and causes metabolic defects in lipoyl cofactor-dependent dehydrogenase complexes, with branched-chain amino acid catabolism as dominant bottleneck.

Seeds preserve a far developed plant embryo in a quiescent state. Seed metabolism relies on stored resources and is reactivated to drive germination when the external conditions are favorable. Since the switchover from quiescence to reactivation provides a remarkable case of a cell physiological transition we investigated the earliest events in energy and redox metabolism of Arabidopsis seeds at imbibition. By developing fluorescent protein biosensing in intact seeds, we observed ATP accumulation and oxygen uptake within minutes, indicating rapid activation of mitochondrial respiration, which coincided with a sharp transition from an oxidizing to a more reducing thiol redox environment in the mitochondrial matrix. To identify individual operational protein thiol switches, we captured the fast release of metabolic quiescence in organello and devised quantitative iodoacetyl tandem mass tag (iodoTMT)-based thiol redox proteomics. The redox state across all Cys peptides was shifted toward reduction from 27.1% down to 13.0% oxidized thiol. A large number of Cys peptides (412) were redox switched, representing central pathways of mitochondrial energy metabolism, including the respiratory chain and each enzymatic step of the tricarboxylic acid (TCA) cycle. Active site Cys peptides of glutathione reductase 2, NADPH-thioredoxin reductase a/b, and thioredoxin-o1 showed the strongest responses. Germination of seeds lacking those redox proteins was associated with markedly enhanced respiration and deregulated TCA cycle dynamics suggesting decreased resource efficiency of energy metabolism. Germination in aged seeds was strongly impaired. We identify a global operation of thiol redox switches that is required for optimal usage of energy stores by the mitochondria to drive efficient germination.

A stable passivation of surface dangling bonds underlies the outstanding friction properties of diamond and diamond-like carbon (DLC) coatings in boundary lubrication. While hydrogen is the simplest termination of a carbon dangling bond, fluorine can also be used as a monoatomic termination, providing an even higher chemical stability. However, whether and under which conditions a substitution of hydrogen with fluorine can be beneficial to friction is still an open question. Moreover, which of the chemical differences between C-H and C-F bonds are responsible for the change in friction has not been unequivocally understood yet. In order to shed light on this problem, we develop a density functional theory-based, nonreactive force field that describes the relevant properties of hydrogen- and fluorine-terminated diamond and DLC tribological interfaces. Molecular dynamics and nudged elastic band simulations reveal that the frictional stress at such interfaces correlates with the corrugation of the contact potential energy, thus ruling out a significant role of the mass of the terminating species on friction. Furthermore, the corrugation of the contact potential energy is almost exclusively determined by steric factors, while electrostatic interactions only play a minor role. In particular, friction between atomically flat diamond surfaces is controlled by the density of terminations, by the C-H and C-F bond lengths, and by the H and F atomic radii. For sliding DLC/DLC interfaces, the intrinsic atomic-scale surface roughness plays an additional role. While surface fluorination decreases the friction of incommensurate diamond contacts, it can negatively affect the friction performance of carbon surfaces that are disordered and not atomically flat. This work provides a general framework to understand the impact of chemical structure of surfaces on friction and to generate design rules for optimally terminated low-friction systems.

Within the project the electronic structure and chemical reactions at interfaces are investigated by using the quantum chemical methods density functional theory (DFT) and density-functional tight binding (DFTB). The research covers a broad spectrum of topics ranging from sustainable energy materials for solar hydrogen production to the wear and friction in tribological contacts including mechanically induced chemical reactions of lubricant and additive molecules at surfaces. A common feature of the different studies are surface reactions of molecules induced by different driving forces such as excited charge carriers or external mechanical load. Here, selected examples of our studies are presented where the splitting of water molecules at surfaces and interfaces plays a key role. We start with the ab initio DFT investigation of unconventional U3O8//Fe2O3 heterostructures which are used to split water molecules with the purpose of solar hydrogen production and conclude with DFTB simulations of water lubricated carbon coatings where water splitting can lead to extremely low friction, also known as superlubricity.

This work discusses the use of slipping domains to improve load support in water-lubricated microsystems through a multi-scale approach. A semi-analytical continuum formulation is developed to calculate changes in pressure distribution for a line contact with added slip. It is found that the slipping region maximizing hydrodynamic lift should favor inlet flow, but not be located at the contact outlet. Estimations for its positioning are provided. Slip on flat surfaces gives the largest gains in load support and friction reduction, but moderate improvements are also possible on circular geometries featuring high convergence ratios. Finally, Molecular Dynamics simulations are employed to quantify slip on hydrophobic surfaces. Among the considered topologies, graphene is an excellent candidate to generate slip in water-lubricated microsystems.