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International audience; Serpentinization and carbonation of ultramafic formations is a ubiquitous phenomenon, which deeply influences the biogeochemical cycles of water, hydrogen, carbon…while supporting the particular biosphere around the oceanic hydrothermal vents. Carbonation of peridotites and other mafic and ultramafic rocks is also a hot topic in the current energy landscape as the engineered sequestration of mineral CO2 in these formations could help reduce the atmospheric emissions and cope with climate change. In this study, we present two reactive percolation experiments performed on a natural serpentinite dredged from the ultraslow South-West Indian Oceanic Ridge. The serpentinite cores (length 3-4 cm and dia. 5.6 mm) were subjected for about 10 days to the continuous injection of a NaHCO3-saturated brine at respectively 160°C and 280°C. Petrographic and petrophysical results as well as outlet fluid compositions were compared to numerical batch simulations performed with the PHREEQC open software allowing to reconstruct the mineralogical evolution of both cores. The most striking observation is the fast and dramatic decrease of the permeability for both experiments principally due to the precipitation of carbonates. On the contrary, serpentine was found to be less impacting as it precipitates in low-flow zones, out of the main percolation paths. In total, about 5.6% of the total injected CO2 was retained in the core, at 280°C. In the same time, hydrogen was consistently produced with a total recovered H2 corresponding to 0.8% of the maximum H2 possible. The global behavior of the cores is interpreted as the result from an interplay between interacting spatio-temporal lengthscales controlled by the Damköhler number.

International audience; Solubility experiments were performed on a trachyte and a pantellerite from Pantelleria. The trachyte has SiO 2 = 65.2 wt%, Al 2 O 3 = 15.2 wt% and a peralkaline index (P.I. = molar[(Na 2 O + K 2 O)/Al 2 O 3 ]) ∼ 1 while the pantellerite has SiO 2 = 72.2 wt%, Al 2 O 3 = 11 wt% and a P.I. = 1.3. Solubility experiments were performed in the pressure range of 50-300 MPa at T = 950°C for the trachyte and 50-200 MPa at T = 850°C for the pantellerite. The water content of experimental glasses was determined by Karl Fischer titration, elemental analyser and FT-IR spectroscopy. Water content appears similar in both compositions for analogous pressure conditions, varying from ∼2.5 wt% at 50 MPa to ∼5.8 at 200 MPa. Comparison of the experimental data with the thermodynamic models shows that the empirical model of Moore et al. [1998] better matches the experimental data for both compositions, while the thermodynamic models of Papale et al. [2006] and Ghiorso and Gualda [2015] tend to overestimate melt water content, probably due to the paucity of peralkaline melt compositions used for calibration. One inference of these new solubility data is on MI-derived depth of felsic reservoirs at Pantelleria which deepens from 2.4 to 3.5 km.

International audience; Gold-(I) catalysis was used for the intramolecular cyclization of tertiary alcohols with terminal alkynes to form diverse aza-spirocycles. The reaction was carried out with low catalyst loading under microwave irradiation to give both sulfonylated and acylated spirocyclic nitrogen derivatives. Gram scale spirocyclization was carried out and demonstrates the robustness of the reaction. An intramolecular Mizoroki-Heck reaction was performed to give several tetracyclic spirocycles. Double bond reduction and selective protecting group manipulation gave spiropiperazine and spiromorpholine derivatives. These compounds were incorporated into biologically relevant scaffolds to give the first selective spirocyclic inhibitors of LIMK.

An investigation performed on the interactions of silty soil treated with cement or lime demonstrates the strong relationship between microstructural phenomena and their engineering behavior. Cement hydration induces a rapid improvement in soil properties while the progressive pozzolanic reaction of lime leads to long-term improvement. Moreover, the cement-treated soil presents better mechanical properties (California bearing ratio and unconfined compressive strength). X-ray diffraction tests and thermo-gravimetric analyses show calcium aluminate hydrates in lime-treated soil and ettringite in cement-treated soil. Mineralogical changes and new hydrates formed in the treated soil demonstrate their positive effect on the engineering behavior of the soil. Swelling and indirect tensile strength indicate the soil suitability for treatment with specific amounts of binders. Cement-treated soil resists the immersion test, as ettringite and new calcium aluminate hydrate are detected by XRD after immersion, whereas dissolution of the unreacted lime and part of the calcium hydrates during the immersion test imply a low resistance to immersion of lime-treated soil.

The formation of iron- and/or manganese-rich dark patinas on sandstones is a common natural phenomenon that occurs also on building stones. Lunéville château, in eastern France, presents such patinas that developed either under natural conditions (rain and time) or after an accidental fire and exposure to significant amounts of water as part of attempts to extinguish the fire. The present study aimed at characterizing both types of patinas in an effort to determine their formation mechanisms and Mn sources. In both cases, Mn required for patina formation likely derives from the reductive dissolution of Mn-rich minerals present in pristine sandstones, as suggested by the contrasting mineralogy and chemistry of Mn-rich phases present in the bulk and in the patina of a given building block. Reduced Mn species then migrate to the exposed surface of building blocks where they are re-oxidized via undetermined processes. Patinas developing “naturally” over time result from the alternation of wetting-reducing and drying-oxidizing cycles and appear to be composed of birnessite. Patinas formed after the 2003 fire result from this single accidental event and form a much thinner, heterogeneous, and discontinuous layer of poorly crystalline lithiophorite at the sandstone surface (∼ 0–150 µm compared to ∼ 300–600 µm for “natural” patinas). The lack of Mn-rich patinas on areas of Lunéville château is likely related to the lower Mn content of pristine sandstone blocks.

We present radio observations of the most slowly rotating known radio pulsar PSR J0250+5854. With a 23.5 s period, it is close, or even beyond, the $P$-$\dot{P}$ diagram region thought to be occupied by active pulsars. The simultaneous observations with FAST, the Chilbolton and Effelsberg LOFAR international stations, and NenuFAR represent a five-fold increase in the spectral coverage of this object, with the detections at 1250 MHz (FAST) and 57 MHz (NenuFAR) being the highest- and lowest-frequency published respectively to date. We measure a flux density of $4\pm2$ $\mu$Jy at 1250 MHz and an exceptionally steep spectral index of $-3.5^{+0.2}_{-1.5}$, with a turnover below $\sim$95 MHz. In conjunction with observations of this pulsar with the GBT and the LOFAR Core, we show that the intrinsic profile width increases drastically towards higher frequencies, contrary to the predictions of conventional radius-to-frequency mapping. We examine polarimetric data from FAST and the LOFAR Core and conclude that its polar cap radio emission is produced at an absolute height of several hundreds of kilometres around 1.5 GHz, similar to other rotation-powered pulsars across the population. Its beam is significantly underfilled at lower frequencies, or it narrows because of the disappearance of conal outriders. Finally, the results for PSR J0250+5854 and other slowly spinning rotation-powered pulsars are contrasted with the radio-detected magnetars. We conclude that magnetars have intrinsically wider radio beams than the slow rotation-powered pulsars, and that consequently the latter's lower beaming fraction is what makes objects such as PSR J0250+5854 so scarce., Comment: 14 pages, 6 figures

20200316 H2020-NMBP‐35‐2017 CORES-PD/00253/2012 PD/BD/136678/2018 UIDB/ 50006/2020 UIDP/50006/2020 Cellulose nitrate (CN) is an intrinsically unstable material that puts at risk the preservation of a great variety of objects in heritage collections, also posing threats to human health. For this reason, a detailed investigation of its degradation mechanisms is necessary to develop sustainable conservation strategies. To investigate novel probes of degradation, we implemented deep UV photoluminescence micro spectral-imaging, for the first time, to characterize a corpus of historical systems composed of cellulose nitrate. The analysis of cinematographic films and everyday objects dated from the nineteenth c./early twentieth c. (Perlov's collection), as well as of photo-aged CN and celluloid references allowed the identification of novel markers that correlate with different stages of CN degradation in artworks, providing insight into the role played by plasticizers, fillers, and other additives in stability. By comparison with photoaged references of CN and celluloid (70% CN and 30% camphor), it was possible to correlate camphor concentration with a higher rate of degradation of the cinematographic films. Furthermore, the present study investigates, at the sub-microscale, materials heterogeneity that correlates to the artworks' history, associating the different emission profiles of zinc oxide to specific color formulations used in the late nineteenth and early twentieth centuries. publishersversion published

International audience; Fluids in magmas play a key role in magma differentiation and transportation of economic metals for ore deposits. As a chalcophile and incompatible element, zinc and its isotopes have been increasingly applied to study the magmatic-hydrothermal processes. However, zinc isotopic fractionation between aqueous fluids and magmas has not been well constrained. Here we experimentally determined equilibrium fractionation factors of Zn isotopes between aqueous fluids and silicate magmas (Δ66Znfluid-magma= δ66Znfluid - δ66Znmagma). The results reveal that aqueous fluids are isotopically heavier than the coexisting silicate magmas. No correlation between Δ66Znfluid-magma and temperature or chlorine contents in fluids is observed under our experimental conditions. Instead, Δ66Znfluid-magma is negatively corresponded with NBO/T of the melt (the ratio of non-bridge oxygen and tetrahedron ions), and positively correlated with the molar ratio of Al/(0.5K+Ca+Fe) in the bulk magmas, suggesting the controlling of silicate composition on Zn isotope fractionation. Our data therefore indicate that the isotopically heavier Zn in the fluids exsolved from magmas may account for the higher δ66Zn of pegmatites and high-silica granitic rocks. Moreover, involvement of magmatic fluids can explain the highly variable and remarkably heavier Zn isotopic signatures of fumaroles, thermal spring waters, and seafloor hydrothermal fluids compared to the igneous rocks. This study provides information that can be used to guide research using Zn isotopes to trace fluid activity and magmatism.

International audience; Drug-loaded liposomes are typical examples of nanomedicine. We show here that doxorubicin, the anti-cancer agent in the liposomal drug Doxil ® , can sensitize Ytterbium (Yb 3+ ) and generate its near infrared (NIR) emission. When doxorubicin and amphiphilic Yb 3+ chelates are incorporated into liposomes, the sensitized emission of Yb 3+ is dependent on the integrity of the particles which can be used to monitor drug release. We also established the first demonstration that the NIR Yb 3+ emission signal is observable in living mice following intratumoral injection of the Yb 3+ -doxorubicin-liposomes, using a commercial macroscopic setup equipped with a near-infrared camera.

Understanding diagenetic reactions in accreted sediments is critical for establishing the balance of fluid sources and sinks in accretionary prisms, which is in turn important for assessing the fluid pressure field and the ability for faults to host seismic slip. For this reason, we studied diagenetic reactions in deformation bands (shear zones and veins) within deep mud sediments from the Nankai accretionary prism (SW Japan) drilled at site C0001 during IODP Expedition 315, by means of microscopic observation, X-ray diffraction, and major- and trace-element analyses. Deformation bands are not only more compacted than the host sediment but are also enriched in framboidal pyrite, as observed under microscopy and confirmed by chalcophile-element enrichments (Fe, S, Cu, As, Sb, Pb). In tandem, one shear zone sample displays a destabilization of smectite or illite–smectite mixed layers and a slight crystallization of illite relative to its sediment matrix, and another sample shows correlated increases in B and Li in shear zones and veins compared to the host sediment, both effects suggesting a transformation of smectite into illite in deformation bands. The two diagenetic reactions of sulfide precipitation and smectite-to-illite transformation are explained by a combined action of sulfate-reducing and methanogen bacteria, which strongly suggests an increased activity of anaerobic microbial communities localized in deformation bands. This local bacterial proliferation was possibly enhanced by the liberation of hydrogen from strained phyllosilicates. We suggest that the proliferation of anoxic bacteria, boosted by deformation, may contribute to the pore water freshening observed at depth in accretionary prisms. Deformation-enhanced metabolic reactions may also explain the illitization observed in major faults of accretionary prisms. Care is therefore needed before interpreting illitization, and other diagenetic reactions as well, as evidence of shear heating, as these might be biogenic instead of thermogenic.

International audience; We establish small-time asymptotic expansions for heat kernels of hypoelliptic Hörmander operators in a neighborhood of the diagonal, generalizing former results obtained in particular by Métivier and by Ben Arous. The coefficients of our expansions are identified in terms of the nilpotentization of the underlying sub-Riemannian structure. Our approach is purely analytic and relies in particular on local and global subelliptic estimates as well as on the local nature of small-time asymptotics of heat kernels. The fact that our expansions are valid not only along the diagonal but in an asymptotic neighborhood of the diagonal is the main novelty, useful in view of deriving Weyl laws for subelliptic Laplacians. In turn, we establish a number of other results on hypoelliptic heat kernels that are interesting in themselves, such as Kac's principle of not feeling the boundary, asymptotic results for singular perturbations of hypoelliptic operators, global smoothing properties for selfadjoint heat semigroups.

The Couriège prospect (French Guiana) provides key examples of the diversity of gold distribution related to supergene processes. The nature of gold in two contrasted weathering profiles is examined as a function of the weathering lithofacies. The autochthonous profile hosts weathered Au-bearing quartz veins whereas the pediment profile is enriched in free gold issued from dismantled gold-bearing quartz veins. The gold distribution is controlled by: (1) the preservation of primary gold as free gold in both transported and autochthonous horizons and as electrum inclusions in detrital pyrite; and (2) the formation of secondary gold through dissolution/precipitation processes, expressed as gold spherulites on the free gold grain surface, an Ag-depleted rim around transported free gold grains and Ag-depleted gold micro-inclusions hosted by oxidized autochthonous pyrite. Gold enrichment through supergene chemical processes remains limited within the truncated autochthonous profile. A new conceptual model is proposed for the area, defining the role of chemical and physical processes in gold endowment and accounting for the geomorphological context. The overall evolution includes (1) deep weathering and peneplenation, (2) dismantlement and transport of lateritic material and (3) the development of a latosol cover. This study highlights that gold exploration in tropical environments must consider the residual v. transported nature and the inheritance of targeted pedogenic horizons.

International audience; SrREGa3O7 melilite ceramics with large rare-earth elements (RE = La to Y) are famous materials especially known for their luminescence properties. Using an innovative approach, the full and congruent crystallization from glass process, SrREGa3O7 transparent polycrystalline ceramics with small rare earth elements (RE = Dy-Lu and Y) have been successfully synthesized and characterized. Interestingly, compared to the classic tetragonal (P-421m) melilite structure composed of mixed Sr/RE cationic sites, these compositions can crystallize in a 3 x 1 x 1 orthorhombic (P21212) superstructure. A detailed study of the superstructure, investigated by different techniques (synchrotron and neutron powder diffraction, STEM-HAADF imaging and EDS mapping), highlights the existence of a Sr/RE cation ordering favored by a large Sr/RE size mismatch and a sufficiently small RE cation. An appropriate control of the synthesis conditions through glass crystallization enables the formation of the desired polymorphs, either ordered or disordered. The influence of this tailored cationic ordering/disordering on the RE luminescent spectroscopic properties have been investigated. A stronger structuration of the RE emission band is observed in the ordered ceramic compared to the disordered ceramic and the glass, whose band shapes are very similar, indicating that the RE environment in the glass and disordered ceramic are close.

Volcanoes emit halogens into the atmosphere that undergo complex chemical cycling in plumes and cause destruction of ozone. We present a case study of the Mount Etna plume in the summer of 2012, when the volcano was passively degassing, using aircraft observations and numerical simulations with a new 3D model “WRF-Chem Volcano” (WCV), incorporating volcanic emissions and multi-phase halogen chemistry. Measurements of SO2 – an indicator of plume intensity – and ozone were made in the plume a few tens of kilometres from Etna, revealing a strong negative correlation between ozone and SO2 levels. From these observations, using SO2 as a tracer species, we estimate a mean in-plume ozone loss rate of 1.3×10−5 molecules of O3 per second per molecule of SO2. This value is similar to observation-based estimates reported very close to Etna's vents, indicating continual ozone loss in the plume up to at least tens of kilometres downwind. The WCV model is run with nested grids to simulate the plume close to the volcano at 1 km resolution. The focus is on the early evolution of passively degassing plumes aged less than 1 h and up to tens of kilometres downwind. The model is able to reproduce the so-called “bromine explosion”: the daytime conversion of HBr into bromine radicals that continuously cycle in the plume. These forms include the radical BrO, a species whose ratio with SO2 is commonly measured in volcanic plumes as an indicator of halogen ozone-destroying chemistry. The species BrO is produced in the ambient-temperature chemistry, with in-plume BrO / SO2 ratios on the order of 10−4 mol/mol, similar to those observed previously in Etna plumes. Wind speed and time of day are identified as non-linear controls on this ratio. Sensitivity simulations confirm the importance of near-vent radical products from high-temperature chemistry in initiating the ambient-temperature plume halogen cycling. Heterogeneous reactions that activate bromine also activate a small fraction of the emitted chlorine; the resulting production of chlorine radical Cl strongly enhances the methane oxidation and hence the formation of formaldehyde (HCHO) in the plume. Modelled rates of ozone depletion are found to be similar to those derived from aircraft observations. Ozone destruction in the model is controlled by the processes that recycle bromine, with about three-quarters of this recycling occurring via reactions between halogen oxide radicals. Through sensitivity simulations, a relationship between the magnitude of halogen emissions and ozone loss is established. Volcanic halogen cycling profoundly impacts the overall plume chemistry in the model, notably hydrogen oxide radicals (HOx), nitrogen oxides (NOx), sulfur, and mercury chemistry. In the model, it depletes HOx within the plume, increasing the lifetime of SO2 and hence slowing sulfate aerosol formation. Halogen chemistry also promotes the conversion of NOx into nitric acid (HNO3). This, along with the displacement of nitrate out of background aerosols in the plume, results in enhanced HNO3 levels and an almost total depletion of NOx in the plume. The halogen–mercury model scheme is simple but includes newly identified photo-reductions of mercury halides. With this set-up, the mercury oxidation is found to be slow and in near-balance with the photo-reduction of the plume. Overall, the model findings demonstrate that halogen chemistry has to be considered for a complete understanding of sulfur, HOx, reactive nitrogen, and mercury chemistry and of the formation of sulfate particles in volcanic plumes.

In this paper, we prove sharp pointwise kernel estimates and dispersive properties for the linear wave equation on noncompact Riemannian symmetric spaces G/K of any rank with G complex. As a consequence, we deduce Strichartz inequalities for a large family of admissible pairs and prove global well-posedness results for the corresponding semilinear equation with low regularity data as on hyperbolic spaces., Comment: To appear in Pure and Applied Analysis

We present a statistical survey of large-amplitude, asymmetric plasma and magnetic field enhancements detected outside the diamagnetic cavity at comet 67P/Churyumov–Gerasimenko from December 2014 to June 2016. Based on the concurrent observations of plasma and magnetic field enhancements, we interpret them to be magnetosonic waves. The aim is to provide a general overview of these waves' properties over the mission duration. As the first mission of its kind, the ESA Rosetta mission was able to study the plasma properties of the inner coma for a prolonged time and during different stages of activity. This enables us to study the temporal evolution of these waves and their characteristics. In total, we identified ∼ 70 000 steepened waves in the magnetic field data by means of machine learning. We observe that the occurrence of these steepened waves is linked to the activity of the comet, where steepened waves are primarily observed at high outgassing rates. No clear indications of a relationship between the occurrence rate and solar wind conditions were found. The waves are found to propagate predominantly perpendicular to the background magnetic field, which indicates their compressional nature. Characteristics like amplitude, skewness, and width of the waves were extracted by fitting a skew normal distribution to the magnetic field magnitude of individual steepened waves. With increasing mass loading, the average amplitude of the waves decreases, while the skewness increases. Using a modified 1D magnetohydrodynamic (MHD) model, we investigated if the waves can be described by the combination of nonlinear and dissipative effects. By combining the model with observations of amplitude, width and skewness, we obtain an estimate of the effective plasma diffusivity in the comet–solar wind interaction region and compare it with suitable reference values as a consistency check. At 67P/Churyumov–Gerasimenko, these steepened waves are of particular importance as they dominate the innermost interaction region for intermediate to high activity.

In this contribution we introduce LoopStructural, a new open-source 3D geological modelling Python package (http://www.github.com/Loop3d/LoopStructural, last access: 15 June 2021). LoopStructural provides a generic API for 3D geological modelling applications harnessing the core Python scientific libraries pandas, numpy and scipy. Six different interpolation algorithms, including three discrete interpolators and 3 polynomial trend interpolators, can be used from the same model design. This means that different interpolation algorithms can be mixed and matched within a geological model allowing for different geological objects, e.g. different conformable foliations, fault surfaces and unconformities to be modelled using different algorithms. Geological features are incorporated into the model using a time-aware approach, where the most recent features are modelled first and used to constrain the geometries of the older features. For example, we use a fault frame for characterising the geometry of the fault surface and apply each fault sequentially to the faulted surfaces. In this contribution we use LoopStructural to produce synthetic proof of concepts models and a 86 km × 52 km model of the Flinders Ranges in South Australia using map2loop.

The centralizer of the image of the diagonal embedding of $U_q(\mathfrak{sl}_2)$ in the tensor product of three irreducible representations is examined in a Schur-Weyl duality spirit. The aim is to offer a description in terms of generators and relations. A conjecture in this respect is offered with the centralizers presented as quotients of the Askey-Wilson algebra. Support for the conjecture is provided by an examination of the representations of the quotients. The conjecture is also shown to be true in a number of cases thereby exhibiting in particular the Temperley-Lieb, Birman-Murakami-Wenzl and one-boundary Temperley-Lieb algebras as quotients of the Askey-Wilson algebra., 26 pages

In Liquid Composite Molding (LCM), a fabric can be formed by highly double curved punch geometries. During the forming step, various types of defects can appear and may have a significant influence on the mechanical properties of the final composite materials. Till now, these defects have not been fully studied and/or understood. The aim of this study was to understand the mechanisms leading to the forming of mesoscopic defects (buckles and sliding), as well as their effect on the behavior of composite materials. To achieve this goal, an experimental machine was designed and built. The machine generates different types of defects, with controlled and adjusted amplitudes (calibrated defects) in samples of a fabric. These samples were then used to manufacture composite samples with calibrated defects, by an LCM process, in order to test and compare them with composite samples without defects. Thanks to this machine, calibrated forming defects that simulate the defects of an LCM process were generated, and the experimental parameters corresponding to the appearance of these defects were defined for two types of fabrics based on glass and carbon fibers. This work provides insight into the forming mechanisms of the buckle and sliding defects that occur during an LCM process.

The present paper proposes a novel way to unify Rough Set Theory and Formal Concept Analysis. Our method stems from results and insights developed in the algebraic theory of modal logic, and is based on the idea that Pawlak's original approximation spaces can be seen as special instances of enriched formal contexts, i.e. relational structures based on formal; contexts from Formal Concept Analysis.

International audience; Purpose: The results of studies of sporadic radio emission of several types of space radio sources, including neutron stars and planets of the Solar System, are presented. The aim of this work is to review the latest achievements in the study of low-frequency radio emission of the Solar System planets and transient signals similar to pulsar pulses using the UTR-2 radio telescope. The importance of the development of the verification methods of the spaceborne radio emission in the study of sporadic signals from various sources is shown. Design/methodology/approach: The studies of sporadic signals of different nature are based on the common set of procedures for cleaning records from the terrestrial radio frequency interference (RFI) in the frequency-time pattern using the information on the nature of the particular type of sporadic radio emission, possible types of interference and signal distortion. Characteristic features of sporadic radio emission of different sources are given, and for each of them the optimal method of signal extraction is developed. The efficiency of the developed procedures for cleaning from noise using adjustable parameters is shown. This is done on the basis of observations of diverse types of space radio sources, such as lightnings in the atmospheres of planets, single pulses of neutron stars and sporadic radio emission of Jupiter. Findings: The developed methods of signal extraction detection in the presence of radio-interference have allowed obtaining the unique results such as: the distribution of the total intensity of single pulses of neutron stars depending on the galactic latitude; the automatic search of lightnings in the Saturn’s atmosphere in data due to the carefully elaborated RFI mitigation procedures, which made it possible to obtain the Saturn electrostatic discharge (SED) emission parameters based on the most complete set of events. Increased efficiency of the selection of Jupiter’s S-radiation signals despite the data corruption by the presence of radio-interference, which was reached due to the carefully chosen parameters of data cleaning procedures, have allowed us to detect short and intensive bursts, being the most informative for determining the physical parameters of radio emission in the area of their generation. Conclusions: The large effective area and high sensitivity of the UTR-2 radio telescope allow making the sporadic radio emission study with high temporal and frequency resolutions. Due to these factors we can apply a wide range of methods of space signals’ detection in the presence of terrestrial radio-frequency interference of natural and artificial origin. The data cleaning parameters allow accounting for the characteristic features of space signals and to obtain important and even unique scientific results. Key words: decameter wavelength range; UTR-2; sporadic radio emission; transients; lightning in the atmospheres of planets; Jupiter S-bursts

The mechanisms behind the plant litter mixture effect on decomposition are still difficult to disentangle. To tackle this issue, we used a model that specifically addresses the role of the litter moisture content. Our model predicts that when two litters interact in terms of water flow, the difference of evaporation rate between two litters can trigger a nonadditive mixture effect on decomposition. Water flows from the wettest to the driest litter, changing the reaction rates without changing the overall litter water content. The reaction rate of the litter receiving the water increases relatively more than the decrease in the reaction rate of the litter supplying the water, leading to a synergistic effect. Such water flow can keep the microbial biomass of both litter in a water content domain suitable to maintain decomposition activity. When applied to experimental data (Sphagnum rubellum and Molinia caerulea litters), the model is able to assess whether any nonadditive effect originates from water content variation alone or whether other factors have to be taken into account., The mechanisms behind the plant litter mixture effect on decomposition are still difficult to disentangle. The model proposed in this article predicts that when two litters interact in terms of water flow, the difference of evaporation rate between two litters can trigger a nonadditive mixture effect on decomposition. Water flows from the wettest to the driest litter, changing the reaction rates without changing the overall litter water content.

The development of recombinant COVID-19 vaccines has resulted from scientific progress made at an unprecedented speed during 2020. The recombinant spike glycoprotein monomer, its trimer, and its recombinant receptor-binding domain (RBD) induce a potent anti-RBD neutralizing antibody response in animals. In COVID-19 convalescent sera, there is a good correlation between the antibody response and potent neutralization. In this review, we summarize with a critical view the molecular aspects associated with the interaction of SARS-CoV-2 RBD with its receptor in human cells, the angiotensin-converting enzyme 2 (ACE2), the epitopes involved in the neutralizing activity, and the impact of virus mutations thereof. Recent trends in RBD-based vaccines are analyzed, providing detailed insights into the role of antigen display and multivalence in the immune response of vaccines under development., SARS-CoV-2 receptor-binding domain (RBD)-specific antibodies are crucial for neutralizing efficacy. Emerging mutations, the quality of the IgG response, and the benefit of multivalent display are analyzed here for RBD subunit vaccines.

International audience; Fluid–mineral and fluid–rock interfaces are key parameters controlling the reactivity and fate of fluids in reservoir rocks and aquifers. The interface dynamics through space and time results from complex processes involving a tight coupling between chemical reactions and transport of species as well as a strong dependence on the physical, chemical, mineralogical and structural properties of the reacting solid phases. In this article, we review the recent advances in pore-scale imaging and reactive flow modelling applied to interface dynamics. Digital rocks derived from time-lapse X-ray micro-tomography imaging gives unprecedented opportunity to track the interface evolution during reactive flow experiments in porous or fractured media, and evaluate locally mineral reactivity. The recent improvements in pore-scale reactive transport modelling allow for a fine description of flow and transport that integrates moving fluid–mineral interfaces inherent to chemical reactions. Combined with three-dimensional digital images, pore-scale reactive transport modelling complements and augments laboratory experiments. The most advanced multi-scale models integrate sub-voxel porosity and processes which relate to imaging instrument resolution and improve upscaling possibilities. Two example applications based on the solver porousMedia4Foam illustrate the dynamics of the interface for different transport regimes (i.e., diffusive- to advective-dominant) and rock matrix properties (i.e., permeable vs. impermeable, and homogeneous vs. polymineralic). These parameters affect both the interface roughness and its geometry evolution, from sharp front to smeared (i.e., diffuse) interface. The paper concludes by discussing the challenges associated with precipitation processes in porous media, rock texture and composition (i.e., physical and mineralogical heterogeneity), and upscaling to larger scales.

International audience; Persistent luminescence and photochromism are two fascinating optical properties that involve charge trapping via defects and their release due to an external stimulation. In both processes, it is possible to define 1 (or on) and 0 (or off) optical states. Consequently, materials with one of these phenomena find major interest in view of designing smart, anticounterfeiting, and optical information storage devices. Combining both processes within a single material can lead to a new generation of information storage phosphors, in which it may be possible to obtain three different optical states by playing on the external stimulations applied on the material. For that purpose, the elaboration of nickel-doped ZnGa2O4 spinet transparent nano-glassceramics is presented in this work. The short-wave infrared (SWIR) emission, a broad band located at ca. 1275 nm, arises from Ni2+ cations located in gallium octahedral sites. SWIR persistent luminescence, arising from the same doping ion transition, can also be monitored after UV charging. Interestingly, UV irradiation not only leads to persistent luminescence charging but also to a reversible photochromism effect. By means of a complete optical characterization study combined with electron paramagnetic resonance measurements, the origins of both the persistent luminescence emission and the photochromism are explored. Finally, a discussion on the advantages of such a material combining both persistent luminescence and photochromism properties, leading to three possible optical states of the material, is dressed in view of possible optical memory systems.

The success of luminescence dating as a chronological tool in Quaternary science builds upon innovative methodological approaches, providing new insights into past landscapes. Infrared radiofluorescence (IR-RF) on K-feldspar is such an innovative method that was already introduced two decades ago. IR-RF promises considerable extended temporal range and a simple measurement protocol, with more dating applications being published recently. To date, all applications have used multi-grain measurements. Herein, we take the next step by enabling IR-RF measurements on a single grain level. Our contribution introduces spatially resolved infrared radiofluorescence (SR IR-RF) on K-feldspars and intends to make SR IR-RF broadly accessible as a geochronological tool. In the first part of the article, we detail equipment, CCD camera settings and software needed to perform and analyse SR IR-RF measurements. We use a newly developed ImageJ macro to process the image data, identify IR-RF emitting grains and obtain single-grain IR-RF signal curves. For subsequent analysis, we apply the statistical programming environment R and the package Luminescence. In the second part of the article, we test SR IR-RF on two K-feldspar samples. One sample was irradiated artificially; the other sample received a natural dose. The artificially irradiated sample renders results indistinguishable from conventional IR-RF measurements with the photomultiplier tube. The natural sample seems to overestimate the expected dose by ca. 50 % on average. However, it also shows a lower dose component, resulting in ages consistent with the same sample's quartz fraction. Our experiments also revealed an unstable signal background due to our cameras' degenerated cooling system. Besides this technical issue specific to the system we used, SR IR-RF is ready for application. Our contribution provides guidance and software tools for methodological and applied luminescence (dating) studies on single-grain feldspars using radiofluorescence.

International audience; Interactions of paramagnetic metal complexes with their biological environment can modulate their magnetic resonance imaging (MRI) contrast-enhancing properties in different ways, and this has been widely exploited to create responsive probes that can provide biochemical information. We survey progress in two rapidly growing areas: the MRI detection of biologically important metal ions, such as calcium, zinc, and copper, and the use of transition metal complexes as smart MRI agents. In both fields, new imaging technologies, which take advantage of other nuclei (19F) and/or paramagnetic contact shift effects, emerge beyond classical, relaxation-based applications. Most importantly, in vivo imaging is gaining ground, and the promise of molecular MRI is becoming reality, at least for preclinical research.

International audience; A better understanding and use of molten carbonate fuel cells (MCFCs) requires more detailed consideration on transport properties in melt. The combination of different methodological developments can be one solution to improve our comprehension. Here we present 23 Na and 7 Li self-diffusion coefficients measured by pulsed field gradient (PFG) NMR technique combined with electrical conductivity obtained by a 4-electrod set up, in the eutectic mixture Li2CO3-Na2CO3 (52:48 %mol) at high temperature (up to 1050 K), and under pure CO2 atmosphere. The results were compared with known experimental data from literature obtained by radiotracers techniques and 2-electrod set up and also with some calculations of the transport properties.

International audience; The conserved 3 '-5 ' exoribonuclease EXOSC10/Rrp6 processes and degrades RNA, regulates gene expression and participates in DNA double-strand break repair and control of telomere maintenance via degradation of the telomerase RNA component. EXOSC10/Rrp6 is part of the multimeric nuclear RNA exosome and interacts with numerous proteins. Previous clinical, genetic, biochemical and genomic studies revealed the protein's essential functions in cell division and differentiation, its RNA substrates and its relevance to autoimmune disorders and oncology. However, little is known about the regulatory mechanisms that control the transcription, translation and stability of EXOSC10/Rrp6 during cell growth, development and disease and how these mechanisms evolved from yeast to human. Herein, we provide an overview of the RNA- and protein expression profiles of EXOSC10/Rrp6 during cell division, development and nutritional stress, and we summarize interaction networks and post-translational modifications across species. Additionally, we discuss how known and predicted protein interactions and post-translational modifications influence the stability of EXOSC10/Rrp6. Finally, we explore the idea that different EXOSC10/Rrp6 alleles, which potentially alter cellular protein levels or affect protein function, might influence human development and disease progression. In this review we interpret information from the literature together with genomic data from knowledgebases to inspire future work on the regulation of this essential protein's stability in normal and malignant cells.

International audience; In water-bearing porous rocks, pore pressure variations play a major role in deformation, through dissolution−precipitation and fracturing processes. An often-overlooked variation where pressure falls to negative pressure or tension can operate whenever aquifer formations dry out, for instance, in deep storage (nuclear or industrial wastes, long-term CO 2 mitigation, short-term energetic resources, etc.). This can generate capillary tension within the aquifers. This study investigates the mechanical effect of such in-pore tension in the surrounding crystal field, through laboratory experiments at the one-pore scale. Microthermometric procedures were carried out on synthetic fluid inclusions to generate large tensile stress and were combined with Raman microspectrometry to visualize the resulting stress fields in the host quartz. For comparison, we numerically modeled the stress field by linear elasticity theory. The experiments demonstrate that significant damage is produced in crystalline materials by the pore tension. Despite the induced stress measured by micro-Raman spectrometry to remain moderate, it is able to fracture the quartz. The volume of the cavity is a prominent controlling parameter for the stress amplitude. The crystalline heterogeneities of the solid are another major parameter for localizing the mean weak stress and accumulating overstress. Our results call for bringing pore-scale micromechanics into the safety assessment of the geological storage of various wastes inside depleted aquifers. They also show the magnifying effect of heterogeneities on propagating stress and localizing it along certain directions, promoting the final failure of water-bearing minerals, rocks, or pore networks.

International audience; Summertime HONO concentrations were synchronously measured at two (agricultural and nonagricultural) sites in the North China Plain (NCP). Daytime HONO (1.4 ± 0.6 ppbv) and HONO/NO2 ((12 ± 8)%) over the agricultural field after fertilization were found to be remarkably higher than those before fertilization, implying strong HONO emission from the fertilized fields. Synchronous enhancements of HONO and O3 after fertilization at both sites suggested that the emitted HONO accelerated the local and the regional O3 pollution. HONO budget analysis further revealed that its emission was significantly enhanced after fertilization. Soil HONO emission flux and its uncertainty were estimated and discussed. The estimated emission flux exhibited a distinct diurnal variation with a noontime maximum. The net OH production rate from HONO photolysis greatly exceeded that from O3 photolysis over the agricultural field, and their maximum ratio of 4.7 was obtained after fertilization. We provide field evidence that fertilized fields in the NCP act as a strong HONO source, which accelerates daytime photochemistry, leading to an increase of regional photo-oxidants such as O3. Considering the severe O3 pollution in the summer NCP and that the large area of the agricultural field is regularly treated with high fertilization amount in this region, HONO emission should be taken into account in the regional air quality deterioration.

Ion acoustic waves were observed between 15 and 30 km from the centre of comet 67P/Churyumov–Gerasimenko by the Rosetta spacecraft during its close flyby on 28 March 2015. There are two electron populations: one cold at kBTe≈0.2 eV and one warm at kBTe≈2 eV. The ions are dominated by a cold (a few hundredths of electronvolt) distribution of water group ions with a bulk speed of (3–3.7) km s−1. A warm kBTe≈6 eV ion population, which also is present, has no influence on the ion acoustic waves due to its low density of only 0.25 % of the plasma density. Near closest approach the propagation direction was within 50∘ from the direction of the bulk velocity. The waves, which in the plasma frame appear below the ion plasma frequency fpi≈2 kHz, are Doppler-shifted to the spacecraft frame where they cover a frequency range up to approximately 4 kHz. The waves are detected in a region of space where the magnetic field is piled up and draped around the inner part of the ionised coma. Estimates of the current associated with the magnetic field gradient as observed by Rosetta are used as input to calculations of dispersion relations for current-driven ion acoustic waves, using kinetic theory. Agreement between theory and observations is obtained for electron and ion distributions with the properties described above. The wave power decreases over cometocentric distances from 24 to 30 km. The main difference between the plasma at closest approach and in the region where the waves are decaying is the absence of a significant current in the latter. Wave observations and theory combined supplement the particle measurements that are difficult at low energies and complicated by spacecraft charging.

International audience; This work evaluates the capabilities of Large Eddy Simulation with perfectly stirred reactor (PSR) assumption and detailed chemistry to predict unsteady, premixed, hydrogen combustion sequences. The model was benchmarked with hydrogen-air experimental tests and with numerical data of flame acceleration in an obstructed channel. Results permit to identify major shortcomings that should be addressed with this approach and to assess the uncertainties linked to the use of different sub-models. Spatial resolution was found to be critical and limits the applications of this approach due to the increase of the computational costs with the flame surface. While the influence of the detailed kinetic chemical scheme used was low, the impact of the sub-grid turbulence model used was high. Results showed that simulations provided good agreement with the experimental data when a minimum spatial resolution of 1/8 of the laminar flame thickness was imposed. This threshold permits to simulate with good results the early stages of the combustion sequence (ignition and initial flame acceleration) but limits the model applications when the flame surface increases. In-situ Adaptive Tabulation (ISAT) was an effective strategy to overcome the limitations and partially reduce the computational cost when detailed chemistry models are used together with PSR-LES.

International audience; The stability constants of Mn2+ complexes with ligands containing a trans-1,2-cyclobutanediamine spacer functionalized with picolinate and/or carboxylate functions were determined using potentiometric titrations (25 °C, 0.1 M KCl). The stability constant of the complex with a hexadentate ligand containing four acetate groups (L14−, log KMnL = 10.26) is improved upon replacing one (L24−, log KMnL = 14.71) or two (L34−, log KMnL = 15.81) carboxylate groups with picolinates. The [Mn(L1)]2− complex contains a water molecule coordinated to the metal ion in aqueous solutions, as evidenced by 1H NMRD studies and 17O chemical shifts and transverse relaxation rates. The 1H relaxivities determined at 60 MHz (3.3 and 2.4 mM−1 s−1 at 25 and 37 °C, respectively) are comparable to those of monohydrated complexes such as [Mn(edta)]2−. The exchange rate of the inner-sphere water molecule (k298ex = 248 × 106 s−1) is slightly lower than that of the edta4− analogue. DFT calculations (M11/def2-TZVP) suggest that the water exchange reaction follows a dissociatively activated mechanism, providing activation parameters in reasonably good agreement with the experimental data. DFT calculations also show that the 17O hyperfine coupling constant A/ℏ is affected slightly by changes in the Mn–Owater distance and the orientation of the water molecule with respect to the Mn–O vector.

International audience; This paper explores multi-instrument space-borne observations in order to validate physical concepts of Lithosphere-Atmosphere-Ionosphere Coupling (LAIC) in relation to a selection of major seismic events. In this study we apply some validated techniques to observations in order to identify atmospheric and ionospheric precursors associated with some of recent most destructive earthquakes: M8.6 of March 28, 2005 and M8.5 of Sept. 12, 2007 in Sumatra, and M7.9 of May 12, 2008 in Wenchuan, China. New investigations are also presented concerning these three earthquakes and for the M7.2 of March 2008 in the Xinjiang-Xizang border region, China (the Yutian earthquake). It concerns the ionospheric density, the Global Ionospheric Maps (GIM) of the Total Electron Content (TEC), the Thermal Infra-Red (TIR) anomalies, and the Outgoing Longwave Radiation (OLR) data. It is shown that all these anomalies are identified as short-term precursors, which can be explained by the LAIC concept proposed in [S. Pulinets, D. Ouzounov, J. Asian Earth Sci. 41, 371 (2011)].

Full list of authors: Baldi, R. D.; Williams, D. R. A.; McHardy, I. M.; Beswick, R. J.; Brinks, E.; Dullo, B. T.; Knapen, J. H.; Argo, M. K.; Aalto, S.; Alberdi, A.; Baan, W. A.; Bendo, G. J.; Corbel, S.; Fenech, D. M.; Gallagher, J. S.; Green, D. A.; Kennicutt, R. C.; Klöckner, H. -R.; Körding, E.; Maccarone, T. J.; Muxlow, T. W. B.; Mundell, C. G.; Panessa, F.; Peck, A. B.; Pérez-Torres, M. A.; Romero-Cañizales, C.; Saikia, P.; Shankar, F.; Spencer, R. E.; Stevens, I. R.; Varenius, E.; Ward, M. J.; Yates, J.; Uttley, P., We present the second data release of high-resolution (≤0.2 arcsec) 1.5-GHz radio images of 177 nearby galaxies from the Palomar sample, observed with the e-MERLIN array, as part of the Legacy e-MERLIN Multi-band Imaging of Nearby Galaxies Sample (LeMMINGs) survey. Together with the 103 targets of the first LeMMINGs data release, this represents a complete sample of 280 local active (LINER and Seyfert) and inactive galaxies (H ii galaxies and absorption line galaxies, ALG). This large program is the deepest radio survey of the local Universe, ≳1017.6 W Hz-1, regardless of the host and nuclear type: we detect radio emission ≳0.25 mJy beam-1 for 125/280 galaxies (44.6 per cent) with sizes of typically ≲100 pc. Of those 125, 106 targets show a core which coincides within 1.2 arcsec with the optical nucleus. Although we observed mostly cores, around one third of the detected galaxies features jetted morphologies. The detected radio core luminosities of the sample range between ∼1034 and 1040 erg s-1. LINERs and Seyferts are the most luminous sources, whereas H ii galaxies are the least. LINERs show FR I-like core-brightened radio structures while Seyferts reveal the highest fraction of symmetric morphologies. The majority of H ii galaxies have single radio core or complex extended structures, which probably conceal a nuclear starburst and/or a weak active nucleus (seven of them show clear jets). ALGs, which are typically found in evolved ellipticals, although the least numerous, exhibit on average the most luminous radio structures, similar to LINERs. © 2020 The Author(s). Published by Oxford University Press on behalf of Royal Astronomical Society., The authors thank the anonymous referee for his/her helpful comments to improve the manuscript. AA and MAPT acknowledge support from the Spanish MCIU through grant PGC2018-098915-B-C21 and from the State Agency for Research of the Spanish MCIU through the 'Center of Excellence Severo Ochoa' award for the Instituto de Astrof ' isica de Andalucia (SEV-2017-0709). BTD acknowledges support from a Spanish postdoctoral fellowship 'Ayudas 1265 para la atraccion del talento investigador. Modalidad 2: jovenes investigadores.' funded by Comunidad de Madrid under grant number 2016-T2/TIC-2039. BTD also acknowledges support from grant 'Ayudas para la realizaci on de proyectos de I + D para jovenes doctores 2019.' funded by Comunidad de Madrid and Universidad Complutense de Madrid under grant number PR65/19-22417. JHK acknowledges financial support from the European Union's Horizon 2020 research and innovation programme under Marie Sklodowska-Curie grant agreement No. 721463 to the SUNDIAL ITN network, from the State Research Agency (AEI-MCINN) of the Spanish Ministry of Science and Innovation under the grant 'The structure and evolution of galaxies and their central regions' with reference PID2019-105602GB-I00/10.13039/501100011033, and from IAC project P/300724, financed by the Ministry of Science and Innovation, through the State Budget and by the Canary Islands Department of Economy, Knowledge and Employment, through the Regional Budget of the Autonomous Community. JSG thanks the University of Wisconsin-Madison and its Foundation for support of this research through his Rupple Bascom Professorship. FS acknowledges partial support from a Leverhulme Trust Research fellowship. CGM acknowledges support from the University of Bath and Jim and Hiroko Sherwin. e-MERLIN is a National Facility operated by the University of Manchester at Jodrell Bank Observatory on behalf of STFC, part of UK Research and Innovation.

We present HI absorption spectra of the black hole candidate X-ray binary (XRB) MAXI J1348-630 using the Australian Square Kilometre Array Pathfinder (ASKAP) and MeerKAT. The ASKAP HI spectrum shows a maximum negative radial velocity (with respect to the local standard of rest) of $-31\pm4$ km s$^{-1}$ for MAXI J1348-630, as compared to $-50\pm4$ km s$^{-1}$ for a stacked spectrum of several nearby extragalactic sources. This implies a most probable distance of $2.2^{+0.5}_{-0.6}$ kpc for MAXI J1348-630, and a strong upper limit of the tangent point distance at $5.3\pm0.1$ kpc. Our preferred distance implies that MAXI J1348-630 reached $17\pm10$ % of the Eddington luminosity at the peak of its outburst, and that the source transited from the soft to the hard X-ray spectral state at $2.5\pm1.5$ % of the Eddington luminosity. The MeerKAT HI spectrum of MAXI J1348-630 (obtained from the older, low-resolution 4k mode) is consistent with the re-binned ASKAP spectrum, highlighting the potential of the eventual capabilities of MeerKAT for XRB spectral line studies., Comment: Accepted for publication in MNRAS Letters

International audience; We report herein an investigation on the use of eucalyptol as new solvent for organic transformations applied to the Migita-Kosugi-Stille palladium-catalyzed cross-coupling reaction. Heterocycles containing oxygen, sulfur and nitrogen were chosen as starting materials. Eucalyptol turned out to be a viable sustainable alternative to common solvents for this reaction.

International audience

This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (NanoMOFdeli), ERC-2016-COG 726380, Innovate UK (104384) and EPSRC IAA (IAA/RG85685). N.R. acknowledges the support of the Cambridge International Scholarship and the TrinityHenry Barlow Scholarship (Honorary). O.K.F. and R.Q.S. acknowledge funding from the U.S. Department of Energy (DE-FG02-08ER15967). R.S.F. and D.B. acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (SCoTMOF), ERC-2015-StG 677289. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA-0003525. The authors gratefully acknowledge funding from the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, through the Hydrogen Storage Materials Advanced Research Consortium (HyMARC). This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. J.D.E. acknowledges the support of the Alexander von Humboldt Foundation and the Center for Information Services and High Performance Computing (ZIH) at TU Dresden. S.K.G. and S.M. acknowledge SERB (Project No. CRG/2019/000906), India for financial support. K.K. and R.K. acknowledge Active Co. Research Grant for funding. S.K. acknowledges funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (COSMOS), ERC-2017-StG 756489. N.L. and J.G.M acknowledge funding from the European Commission through the H2020-MSCA-RISE-2019 program (ZEOBIOCHEM -872102) and the Spanish MICINN and AEI/FEDER (RTI2018-099504-B-C21). N.L. thanks the University of Alicante for funding (UATALENTO17-05). ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV-2017-0706) S.M.J.R. and A.L. wish to thank the Fund for Scientific Research Flanders (FWO), under grant nos. 12T3519N and 11D2220N. L.S. was supported by the EPSRC Cambridge NanoDTC EP/L015978/1. C.T.Y. and T.S.N. acknowledges funds from the National Research Foundation of Korea, NRF-2017M3A7B4042140 and NRF-2017M3A7B4042235. P.F. and H. Y. acknowledge US Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under Award No. DE-SC0010596 (P.F.). R.O. would like to acknowledge funding support during his Ph.D. study from Indonesian Endowment Fund for Education-LPDP with the contract No. 202002220216006. Daniel Siderius: Official contribution of the National Institute of Standards and Technology (NIST), not subject to copyright in the United States of America. Daniel Siderius: Certain commercially available items may be identified in this paper. This identification does not imply recommendation by NIST, nor does it imply that it is the best available for the purposes described. B.V.L, S.T.E and A.M.P acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Program (Grant agreement no. 639233, COFLeaf)., Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of microand mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This roundrobin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible., European Research Council (ERC) ERC-2016-COG 726380 ERC-2015-StG 677289 ERC-2017-StG 756489 639233, UK Research & Innovation (UKRI) Innovate UK 104384 UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) IAA/RG85685, Cambridge International Scholarship TrinityHenry Barlow Scholarship, United States Department of Energy (DOE) DE-FG02-08ER15967, National Nuclear Security Administration DE-NA-0003525, United States Department of Energy (DOE), Alexander von Humboldt Foundation, Center for Information Services and High Performance Computing (ZIH) at TU Dresden, Department of Science & Technology (India), Science Engineering Research Board (SERB), India CRG/2019/000906, Active Co. Research Grant, European Commission through the H2020-MSCA-RISE-2019 program ZEOBIOCHEM -872102, Spanish MICINN and AEI/FEDER RTI2018-099504-B-C21, University of Alicante UATALENTO17-05, Spanish Government SEV-2017-0706 FWO 12T3519N 11D2220N, UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) EP/L015978/1, National Research Foundation of Korea NRF-2017M3A7B4042140 NRF-2017M3A7B4042235, United States Department of Energy (DOE) DE-SC0010596, Indonesian Endowment Fund for Education-LPDP 202002220216006

International audience; Introduction The tomato plant, Solanum lycopersicum L. (Solanaceae), is one of the most widely consumed vegetables in the world and plays an important role in human diet. Tomato cultivars are hosts for diverse types of pests, implying diverse chemical defence strategies. Glycoalkaloids are the main specialised metabolites produced by tomato leaves and fruits to protect against pests. However, the roots have received little attention, leading to limited knowledge about their phytochemical content.Objective The main goal of the current study was the development of an untargeted ultra-high-performance liquid chromatography high-resolution mass spectrometry (UHPLC-HRMS) based metabolomic approach to study phytochemical variations in tomato roots at two different development stages (i.e. 34th and 62nd day after sowing).Methods UHPLC-HRMS was used to establish the fingerprint of 24 batches of tomato roots. Statistical analyses were performed to highlight the compounds that discriminated between young and mature tomato roots. A dereplication strategy using molecular networking and HRMS/MS data was set up to identify the metabolites regulated during early root development.Key findings The main biomarkers were guanidine and adenosine derivatives associated with tryptophan. Secondary metabolites such as glycoalkaloids and steroidal alkaloids were also characterised. Most of the metabolites were up-regulated in young tomato roots (34 days old) while tryptophan was up-regulated in the older roots (62 days old).Conclusion The metabolic changes observed in this work contribute to a deeper understanding of early-stage root development and may help our understanding of the complex processes involved in the tomato root defence arsenal.

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International audience; This paper reports the results of a recent geological and archaeological survey conducted in the Sarab district (Sabalan area) in Northwestern Iran. This survey aimed to identify potential obsidian outcrops in the region and to investigate archaeological sites in the vicinity to assess their obsidian exploitation patterns. We located a new obsidian source, Ideloo, and surveyed the previously known archaeological sites of Tepe Qalehjoogh, Kultepe Asbfrooshan, Tepe Emam Chay and Qaleh Tepe Abarghan. Here, we describe the methods and results of our surveys, along with the geochemical characterisation, using portable XRF and LA‐ICP‐MS, of both the new outcrop and the obsidian artefacts found on the sites. Our analyses have revealed the consumption of Ideloo obsidian on three of the four sites surveyed, confirming its exploitation by local communities. While validating previous assumptions regarding the existence of potential obsidian sources in Northwestern Iran, our study also highlights the consumption of raw materials originating from the Caucasus or Eastern Anatolia in complement to local resources. However, the diffusion of the Ideloo obsidian seems so far restricted to a small area, which suggests more complex consumption and trade patterns than previously expected.

We prove that, given a constant $K> 2$ and a bounded linear operator $T$ from a JB$^*$-triple $E$ into a complex Hilbert space $H$, there exists a norm-one functional $\psi\in E^*$ satisfying $$\|T(x)\| \leq K \, \|T\| \, \|x\|_{\psi},$$ for all $x\in E$. Applying this result we show that, given $G > 8 (1+2\sqrt{3})$ and a bounded bilinear form $V$ on the Cartesian product of two JB$^*$-triples $E$ and $B$, there exist norm-one functionals $\varphi\in E^{*}$ and $\psi\in B^{*}$ satisfying $$|V(x,y)| \leq G \ \|V\| \, \|x\|_{\varphi} \, \|y\|_{\psi}$$ for all $(x,y)\in E \times B$. These results prove a conjecture pursued during almost twenty years., Comment: 23 pages. We corrected a misprint, added some comments and precised one reference

International audience; The photophysical properties of Eu3+ and Tb3+ complexes of DOTAGA and DO3A-monoamide conjugates of the Pittsburgh compound B (PiB) chromophore, prepared using linkers of different lengths and flexibilities, and which form stable negatively charged (LnL1), and uncharged (LnL2) complexes, respectively, were studied as potential probes for optical detection of amyloid aggregates. The phenylbenzothiazole (PiB) moiety absorbs light at wavelengths longer than 330 nm with a high molar absorption coefficient in both probes, and acts as an antenna in these systems. The presence of the luminescent Ln3+ ion quenches the excited states of PiB through an energy transfer process from the triplet state of PiB to the metal centre, and structured emission is seen from Eu3+ and Tb3+. The luminescence study indicates the presence of a 5D4 → T1 back transfer process in the Tb3+ complexes. It also provides insights on structural properties of the Eu3+ complexes, such as the high symmetry environment of the Eu3+ ion in a single macrocyclic conformation and the presence of one water molecule in its inner coordination sphere. The overall quantum yield of luminescence of EuL1 is higher than for EuL2. However, their low values reflect the low overall sensitization efficiency of the energy transfer process, which is a consequence of the large distances between the metal center and the antenna, especially in the EuL2 complex. DFT calculations confirmed that the most stable conformation of the Eu3+ complexes involves a combination of a square antiprismatic (SAP) geometry of the chelate and an extended conformation of the linker. The large calculated average distances between the metal center and the antenna point to the predominance of the Förster energy transfer mechanism, especially for EuL2. This study provides insights into the behavior of amyloid-targeted Ln3+ complexes as optical probes, and contributes towards their rational design.

We consider the elliptic quasilinear equation - Δ m ⁢ u = u p ⁢ | ∇ ⁡ u | q {-\Delta_{m}u=u^{p}\lvert\nabla u\rvert^{q}} in ℝ N {\mathbb{R}^{N}} , q ≥ m {q\geq m} and p > 0 {p>0} , 1 < m < N {1 . Our main result is a Liouville-type property, namely, all the positive C 1 {C^{1}} solutions in ℝ N {\mathbb{R}^{N}} are constant. We also give their asymptotic behaviour; all the solutions in an exterior domain ℝ N ∖ B r 0 {\mathbb{R}^{N}\setminus B_{r_{0}}} are bounded. The solutions in B r 0 ∖ { 0 } {B_{r_{0}}\setminus\{0\}} can be extended as continuous functions in B r 0 {B_{r_{0}}} . The solutions in ℝ N ∖ { 0 } {\mathbb{R}^{N}\setminus\{0\}} has a finite limit l ≥ 0 {l\geq 0} as | x | → ∞ {\lvert x\rvert\to\infty} . Our main argument is a Bernstein estimate of the gradient of a power of the solution, combined with a precise Osserman-type estimate for the equation satisfied by the gradient.

International audience; The synthesis of fused bicyclic oxazolidin-2-one (OZO) iminosugars was achieved through a tandem Staudinger reduction/retro-Michael/intramolecular Michael addition from the corresponding OZO azidosugars. Those precursors, based on both aldopentofuranoses and ketofuranohexoses backbones, were obtained following alkylation and oxidation of the related oxazolidine-2-thione (OZT) azidosugars. Eight OZO based iminosugars were isolated in good yields and evaluated for their potency as glycosidases inhibitors, thus extending the family of known 1-Deoxynojirimycin (DNJ) bicyclic analogues.

We present results from six epochs of quasi-simultaneous radio, (sub-)millimetre, infrared, optical, and X-ray observations of the black hole X-ray binary MAXI~J1535$-$571. These observations show that as the source transitioned through the hard-intermediate X-ray state towards the soft intermediate X-ray state, the jet underwent dramatic and rapid changes. We observed the frequency of the jet spectral break, which corresponds to the most compact region in the jet where particle acceleration begins (higher frequencies indicate closer to the black hole), evolve from the IR band into the radio band (decreasing by $\approx$3 orders of magnitude) in less than a day. During one observational epoch, we found evidence of the jet spectral break evolving in frequency through the radio band. Estimating the magnetic field and size of the particle acceleration region shows that the rapid fading of the high-energy jet emission was not consistent with radiative cooling; instead the particle acceleration region seems to be moving away from the black hole on approximately dynamical timescales. This result suggests that the compact jet quenching is not caused by local changes to the particle acceleration, rather we are observing the acceleration region of the jet travelling away from the black hole with the jet flow. Spectral analysis of the X-ray emission show a gradual softening in the few days before the dramatic jet changes, followed by a more rapid softening $\sim$1--2\,days after the onset of the jet quenching., 17 pages, 6 figures, data provided in the appendices. Accepted for publication in MNRAS

CeNbO4+δ, a family of oxygen hyperstoichiometry materials with varying oxygen content (CeNbO4, CeNbO4.08, CeNbO4.25, CeNbO4.33) that shows mixed electronic and oxide ionic conduction, has been known for four decades. However, the oxide ionic transport mechanism has remained unclear due to the unknown atomic structures of CeNbO4.08 and CeNbO4.33. Here, we report the complex (3 + 1)D incommensurately modulated structure of CeNbO4.08, and the supercell structure of CeNbO4.33 from single nanocrystals by using a three-dimensional electron diffraction technique. Two oxide ion migration events are identified in CeNbO4.08 and CeNbO4.25 by molecular dynamics simulations, which was a synergic-cooperation knock-on mechanism involving continuous breaking and reformation of Nb2O9 units. However, the excess oxygen in CeNbO4.33 hardly migrates because of the high concentration and the ordered distribution of the excess oxide ions. The relationship between the structure and oxide ion migration for the whole series of CeNbO4+δ compounds elucidated here provides a direction for the performance optimization of these compounds.

International audience; The purpose of this study is to better understand the system of Quaternary loess-palaeosol sequences (LPS) of the Matmata region in southern Tunisia. Results from a combination of predominantly classical methods (grain size and mineral analysis, CaCO3- content estimation, environmental magnetism) indicate strong soil formation phases during which the conditions of sedimentation changed drastically. The heavy mineral analysis underlines northwest, west and southwest provenances of the loessic material. Furthermore, we discuss the process of soil formation in LPS and explain why these soils are very sandy in comparison to the loess units. During phases of soil formation, the northwestern sediment transport path was blocked while sandy material was blown dominantly from the southwestern Grand Erg. Therefore, we present a conceptual model including a provenance analysis of the loessic material that support and improve earlier results of Coudé-Gaussen and collaborators.; Dans cette étude, nous présentons un modèle conceptuel pour une meilleure compréhension du système de séquences de loess paléosol (LPS) dans la région de Matmata située dans le sud de la Tunisie. Les résultats d'une combinaison de méthodes principalement classiques (analyse granulométrique, analyse minéralogique, détermination de la teneur en CaCO3, magnétisme environnemental) indiquent des phases de formation importante de sols au cours desquelles les conditions de sédimentation ont fondamentalement changé. L'analyse des minéraux lourds met en évidence une origine nord-ouest, ouest et sud-ouest du matériel loessique. En outre, nous discutons la nature de la formation des sols et expliquons pourquoi ces sols sont si sableux par rapport aux unités de loess. Pendant les phases de formation des sols, le trajet des sédiments en provenance du nord-ouest a été bloqué alors que les matériaux sableux pouvaient encore être soufflés à partir du Grand Erg au sud-ouest. Notre modèle conceptuel de la provenance du lœss à Matmata soutient et précise les conclusions de Coudé-Gaussen et collaborateurs.