Importance of the catalytic effect of the substrate in the functionality of lubricant additives: the case of MoDTC

Molybdenum dithiocarbamates (MoDTCs) are lubricant additives very efficient in reducing the friction of steel and they are employed in a number of industrial applications. The functionality of these additives is ruled by the chemical interactions occurring at the buried sliding interface, which are of key importance for the improvement of the lubrication performance. Yet, these tribochemical processes are very difficult to monitor in real time. Ab initio molecular dynamics simulations are the ideal tool to shed light into such a complicated reactivity. In this work we perform ab initio simulations, both in static and tribological conditions, to understand the effect of surface oxidation on the tribochemical reactivity of MoDTC and we find that when the surfaces are covered by oxygen, the first dissociative steps of the additives are significantly hindered. Our preliminary tribological tests on oxidized steel discs support these results. Bare metallic surfaces are necessary for a stable adsorption of the additives, their quick decomposition, and the formation of a durable MoS$_2$ tribolayer. This work demonstrates the importance of the catalytic role of the substrate and confirms the full capability of the computational protocol in the pursuit of materials and compounds more efficient in reducing friction

Experimental and Ab Initio Characterization of Mononuclear Molybdenum Dithiocarbamates in Lubricant Mixtures

Molybdenum dithiocarbamates (MoDTCs) are a class of lubricant additives widely employed in automotives. Most of the studies concerning MoDTC take into account the dimeric structures because of their industrial relevance, with the mononuclear compounds usually neglected, because isolating and characterizing subgroups of MoDTC molecules are generally difficult. However, the byproducts of the synthesis of MoDTC can impact the friction reduction performance at metallic interfaces, and the effect of mononuclear MoDTC (mMoDTC) compounds in the lubrication has not been considered yet in the literature. In this study, we consider for the first time the impurities of MoDTC consisting of mononuclear compounds and combine experimental and computational techniques to elucidate the interaction of these impurities with binuclear MoDTC in commercial formulations. We present a preliminary strategy to separate a commercial MoDTC product in chemically different fractions. These fractions present different tribological behaviors depending on the relative amount of mononuclear and binuclear complexes. The calculations indicate that the dissociation mechanism of mMoDTC is similar to the one observed for the dimeric structures. However, the different chemical properties of mMoDTC impact the kinetics for the formation of the beneficial molybdenum disulfide (MoS2) layers, as shown by the tribological experiments. These results help to understand the functionality of MoDTC lubricant additives, providing new insights into the complex synergy between the different chemical structures

Proteostasis During Cerebral Ischemia

Cerebral ischemic is a complex pathology involving a cascade of cellular mechanisms, which deregulate proteostasis and lead to neuronal death. Proteostasis refers to the equilibrium between protein synthesis, folding, transport, and protein degradation. Within the brain proteostasis plays key roles in learning and memory by controlling protein synthesis and degradation. Two important pathways are implicated in the regulation of proteostasis: the unfolded protein response (UPR) and macroautophagy (called hereafter autophagy). Both are necessary for cell survival, however, their over-activation in duration or intensity can lead to cell death. Moreover, UPR and autophagy can activate and potentiate each other to worsen the issue of cerebral ischemic. A better understanding of autophagy and ER stress will allow the development of therapeutic strategies for stroke, both at the acute phase and during recovery. This review summarizes the latest therapeutic advances implicating ER stress or autophagy in cerebral ischemic. We argue that the processes governing proteostasis should be considered together in stroke, rather than focusing either on ER stress or autophagy in isolation

Tye7 regulates yeast Ty1 retrotransposon sense and antisense transcription in response to adenylic nucleotides stress

Transposable elements play a fundamental role in genome evolution. It is proposed that their mobility, activated under stress, induces mutations that could confer advantages to the host organism. Transcription of the Ty1 LTR-retrotransposon of Saccharomyces cerevisiae is activated in response to a severe deficiency in adenylic nucleotides. Here, we show that Ty2 and Ty3 are also stimulated under these stress conditions, revealing the simultaneous activation of three active Ty retrotransposon families. We demonstrate that Ty1 activation in response to adenylic nucleotide depletion requires the DNA-binding transcription factor Tye7. Ty1 is transcribed in both sense and antisense directions. We identify three Tye7 potential binding sites in the region of Ty1 DNA sequence where antisense transcription starts. We show that Tye7 binds to Ty1 DNA and regulates Ty1 antisense transcription. Altogether, our data suggest that, in response to adenylic nucleotide reduction, TYE7 is induced and activates Ty1 mRNA transcription, possibly by controlling Ty1 antisense transcription. We also provide the first evidence that Ty1 antisense transcription can be regulated by environmental stress conditions, pointing to a new level of control of Ty1 activity by stress, as Ty1 antisense RNAs play an important role in regulating Ty1 mobility at both the transcriptional and post-transcriptional stages

Modelling the response to vaccine in non-human primates to define SARS-CoV-2 mechanistic correlates of protection

The definition of correlates of protection is critical for the development of next-generation SARS-CoV-2 vaccine platforms. Here, we propose a model-based approach for identifying mechanistic correlates of protection based on mathematical modelling of viral dynamics and data mining of immunological markers. The application to three different studies in non-human primates evaluating SARS-CoV-2 vaccines based on CD40-targeting, two-component spike nanoparticle and mRNA 1273 identifies and quantifies two main mechanisms that are a decrease of rate of cell infection and an increase in clearance of infected cells. Inhibition of RBD binding to ACE2 appears to be a robust mechanistic correlate of protection across the three vaccine platforms although not capturing the whole biological vaccine effect. The model shows that RBD/ACE2 binding inhibition represents a strong mechanism of protection which required significant reduction in blocking potency to effectively compromise the control of viral replication.Initiative for the creation of a Vaccine Research InstituteInfrastructure nationale pour la modélisation des maladies infectieuses humaine

PDRs4All III: JWST's NIR spectroscopic view of the Orion Bar

(Abridged) We investigate the impact of radiative feedback from massive stars on their natal cloud and focus on the transition from the HII region to the atomic PDR (crossing the ionisation front (IF)), and the subsequent transition to the molecular PDR (crossing the dissociation front (DF)). We use high-resolution near-IR integral field spectroscopic data from NIRSpec on JWST to observe the Orion Bar PDR as part of the PDRs4All JWST Early Release Science Program. The NIRSpec data reveal a forest of lines including, but not limited to, HeI, HI, and CI recombination lines, ionic lines, OI and NI fluorescence lines, Aromatic Infrared Bands (AIBs including aromatic CH, aliphatic CH, and their CD counterparts), CO2 ice, pure rotational and ro-vibrational lines from H2, and ro-vibrational lines HD, CO, and CH+, most of them detected for the first time towards a PDR. Their spatial distribution resolves the H and He ionisation structure in the Huygens region, gives insight into the geometry of the Bar, and confirms the large-scale stratification of PDRs. We observe numerous smaller scale structures whose typical size decreases with distance from Ori C and IR lines from CI, if solely arising from radiative recombination and cascade, reveal very high gas temperatures consistent with the hot irradiated surface of small-scale dense clumps deep inside the PDR. The H2 lines reveal multiple, prominent filaments which exhibit different characteristics. This leaves the impression of a "terraced" transition from the predominantly atomic surface region to the CO-rich molecular zone deeper in. This study showcases the discovery space created by JWST to further our understanding of the impact radiation from young stars has on their natal molecular cloud and proto-planetary disk, which touches on star- and planet formation as well as galaxy evolution.Comment: 52 pages, 30 figures, submitted to A&

Perceptions et attentes des patients vis-à-vis de leur médecin traitant (étude qualitative réalisée auprès d'habitants du Nord de la France)

LILLE2-BU Santé-Recherche (593502101) / SudocSudocFranceF

Response of Macrophyte Traits to Herbivory and Neighboring Species Integration of the Functional Trait Framework in the Context of Ecological Invasions

German Research Foundation (DFG), Leipzig University within the program of Open Access Publishing; German Centre for Integrative Biodiversity Research (iDiv) Halle-Jena-Leipzig - German Research Foundation [FZT 118] We acknowledge support from the German Research Foundation (DFG), Leipzig University within the program of Open Access Publishing. LT and BG gratefully acknowledge the support of the German Centre for Integrative Biodiversity Research (iDiv) Halle-Jena-Leipzig funded by the German Research Foundation (FZT 118).International audienceWith the increase in the number of introduced species each year, biological invasions are considered as one of the most important environmental problems for native biodiversity. In invaded habitats, the establishment of exotic plant species depends on the abiotic and biotic environment. Herbivores and neighboring plants (native or exotic) comprise an important part of the latter. Herbivores cause trophic and non-trophic damage to focal plants, which respond to herbivory by varying their different traits quantitatively (e.g., growth rate and biomass changes) and qualitatively (e.g., variation in morphological and chemical defenses strategies affecting plant palatability). Neighboring plant species also affect functional traits and the fitness of focal plant species, thus herbivore effects on a focal plant could also depend indirectly on the palatability and defensive traits of the neighboring species inside the community. Here, in a first step toward the integration of associational susceptibility/resistance theories in the field of ecological invasion, we performed a microcosm experiment to consider the effects of an exotic crayfish on the growth rate, morphological traits and damage level of three macrophytes (two exotic, one native) growing in pairwise combinations. We found that (i) the response to herbivore presence and to neighboring species identity seemed to be species specific, and (ii) crayfish enhance the fragmentation rate of the two exotic macrophytes Ludwigia grandiflora and Egeria densa in the presence of the native macrophyte Myriophyllum spicatum, which could indirectly facilitate their invasion success. Indeed, fragmentation can increase dispersal abilities of the exotic macrophytes considered in this study as they are able to generate new plants from their fragments. However, our results showed that the interaction herbivore-neighbor species was hardly significant. Our paper presents some first results on associational resistance/susceptibility and lays the foundation for developing a general framework that combines plant community ecology and biological invasion ecology to explain invasive species success