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We study alternating automata with qualitative semantics over infinite binary trees: Alternation means that two opposing players construct a decoration of the input tree called a run, and the qualitative semantics says that a run of the automaton is accepting if almost all branches of the run are accepting. In this article, we prove a positive and a negative result for the emptiness problem of alternating automata with qualitative semantics. The positive result is the decidability of the emptiness problem for the case of Büchi acceptance condition. An interesting aspect of our approach is that we do not extend the classical solution for solving the emptiness problem of alternating automata, which first constructs an equivalent non-deterministic automaton. Instead, we directly construct an emptiness game making use of imperfect information. The negative result is the undecidability of the emptiness problem for the case of co-Büchi acceptance condition. This result has two direct consequences: the undecidability of monadic second-order logic extended with the qualitative path-measure quantifier and the undecidability of the emptiness problem for alternating tree automata with non-zero semantics, a recently introduced probabilistic model of alternating tree automata.

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

The class of Divergence-free symmetric tensors is ubiquitous in Continuum Mechanics. We show its invariance under projective transformations of the independent variables. This action, which preserves the positiveness, extends Sophus Lie's group analysis of Newtonian dynamics. When applied to models of gas dynamics --~such as Euler system or Boltzmann equation,~-- in combination with Compensated Integrability, this yields new dispersive estimates. The most accurate one is obtained for mono-atomic gases. Then the space-time integral of $t\rho^\frac1d p$ is bounded in terms of the total mass and moment of inertia alone.

We prove unexpected decay of the L2-distance from the solution u(t) of a hyperbolic scalar conservation law, to some convex, flow-invariant target sets.

The aim of this note is to give a formula expressing the trace form associated with the 27 lines of a cubic surface.

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This paper studies a large class of two-player perfect-information turn-based parity games on infinite graphs, namely those generated by collapsible pushdown automata. The main motivation for studying these games comes from the connections from collapsible pushdown automata and higher-order recursion schemes, both models being equi-expressive for generating infinite trees. Our main result is to establish the decidability of such games and to provide an effective representation of the winning region as well as of a winning strategy. Thus, the results obtained here provide all necessary tools for an in-depth study of logical properties of trees generated by collapsible pushdown automata/recursion schemes., Comment: 51 pages

The ~3.22 Ga Moodies Group, Barberton Greenstone Belt (BGB), South Africa, provides a unique window into Archaean sedimentary, magmatic and ecological processes. In the central BGB, a regional mafic complex, consisting of a genetically related major mafic sill, a peperitic dyke stockwork, and extensive basaltic lava flows affected thick quartzose sandstones of the Moodies Group. We argue that epithermal hydrothermalism associated with this magmatic event occurred, at least in part, syndepositionally and in places destroyed, in other places preserved the abundant benthic microbial mats in terrestrial- and coastal-facies sandstone of this unit. We differentiate four principal types of hydrothermal alteration: (1) Sericitization resulted from ubiquitous feldspar breakdown; (2) iron-oxide alteration replaced the original matrix by fine-grained iron oxide; (3) silicification replaced matrix and most non-silica grains by microcrystalline silica and locally preserved kerogenous microbial mats; and (4) hydraulic fracturing at shallow depth brecciated consolidated Moodies Group sandstone and created closely spaced, randomly oriented fractures and quartz-filled veins. Because stockwork intrusion locally interacted with unconsolidated water-saturated sediment and because the dykes connect the sill with the mafic lava but also follow zones of structural weakness, we suggest that hydrothermalism associated with this magmatic event occurred syndepositionally but was also – within the resolution of radiometric age data – contemporaneous with tight regional folding. We conclude that microbial organisms in Paleoarchaean coastal (tidal, estuarine) environments may have been formerly widespread, possibly even abundant, but are nearly nowhere preserved because they were easily degradable. Preservation of Early Archaean microbial mats in a thermal aureole in the central BGB was controlled by the “just right” degree of heating and very early hydrothermal silicification.

We consider the motion of a finite though large number N of hard spheres in the whole space $${\mathbb R}^n$$ . Particles move freely until they experience elastic collisions. We use our recent theory of Compensated Integrability in order to estimate how much the particles are deviated by collisions. Our result, which is expressed in terms of hodographs, tells us that only $$O(N^2)$$ collisions are significant.

Side-chain-constrained amino acids are useful tools to modulate the biological properties of peptides. In this study, we applied side-chain constraints to apelin-13 (Ape13) by substituting the Pro12 and Phe13 positions, affecting the binding affinity and signaling profile on the apelin receptor (APJ). The residues 1Nal, Trp, and Aia were found to be beneficial substitutions for Pro12, and the resulting analogues displayed high affinity for APJ (Ki 0.08-0.18 nM vs Ape13 Ki 0.7 nM). Besides, constrained (d-Tic) or α,α-disubstituted residues (Dbzg; d-α-Me-Tyr(OBn)) were favorable for the Phe13 position. Compounds 47 (Pro12-Phe13 replaced by Aia-Phe, Ki 0.08 nM) and 53 (Pro12-Phe13 replaced by 1Nal-Dbzg, Ki 0.08 nM) are the most potent Ape13 analogues activating the Gα12 pathways (53, EC50 Gα12 2.8 nM vs Ape13, EC50 43 nM) known to date, displaying high affinity, resistance to ACE2 cleavage as well as improved pharmacokinetics in vitro (t1/2 5.8-7.3 h in rat plasma) and in vivo.

Metal–organic frameworks (MOFs)/graphene oxide (GO) composites are of growing interest due to their properties which can exceed those of the pure components, including post-combustion CO2 capture. Series of composites suitable for CO2 capture under flue gas conditions based on the microporous water stable MIL-91(Ti) have been prepared with different GO contents, following two routes, in situ and post-synthetic. It was observed that the 5 wt% GO in situ composite exhibits a semi-conducting behavior, while the post-synthetic materials are insulating, even with high (20 wt%) GO content. As a consequence, this composite absorbs microwave radiation more efficiently compared to the pure MOF and post-synthetic materials. Finally, we report that CO2 desorption is much faster under microwave irradiation compared to direct electric heating on MOF/GO in situ materials, paving the way for future energy-saving microwave swing adsorption processes.

Biocompatible nanoscale iron carboxylate metal-organic frameworks (nanoMOFs) have already demonstrated their ability to efficiently deliver various therapeutic molecules. The versatility of the synthesis methods and functionalization strategies could further improve their drug carrier potential. However, in oncology, preclinical evaluation still suffers from the lack of relevant models able to mimic the heterogeneity and the microenvironment of human tumors. This may impact the significance of the preclinical data, hindering the clinical translation and drug development process. Motivated by this hurdle, a 3D lung tumor model is herein developed to investigate nanoMOFs, as bare nanoparticles or coated with polyethylene glycol. Loading with doxorubicin, as a model drug, enables the investigation of their penetration capacity and efficacy in the 3D tumor nodule. NanoMOFs carry a large cargo, can diffuse efficiently within the tumor and are capable of significant intracellular penetration. Nevertheless, they prove to be therapeutically ineffective because the loaded drug is sequestrated in the lysosomal compartment and does not reach the nucleus, the doxorubicin sub-cellular target. These results question the in vivo evaluation of these nanoMOFs and call for further optimization to achieve successful drug delivery.

—A study of the morphology, composition, and age (by the CHIME and LA–ICP–MS methods) of monazite from the Ichet’yu occurrence, located in Middle Timan, revealed some principal differences in the typomorphic features and genesis of its two varieties. The common yellow monazite from this occurrence is monazite-(Ce), in which the content of La is higher than that of Nd. The time of its crystallization (recrystallization) is estimated by the CHIME method as 518 ± 40 Ma. Kularite (a grayish-brown globular variety of monazite, in which Nd is higher than La) was dated at 978 ± 31 Ma. The age of some kularite grains is 520 ± 27 Ma, which may be interpreted as the date of a hydrothermal event that resulted in the simultaneous recrystallization of both monazite and kularite. However, these two monazite varieties were formed in two completely different sources and were combined in the mineral parasteresis of the Ichet’yu occurrence. The CHIME age of monazite from the Ichet’yu occurrence that belongs to two intervals (500–600 and 960–1000 Ma) is consistent with the age determined in the same monazite grains using the LA–ICP–MS technique.

In recent years, groundwater pumping has increased for domestic, industrial, and irrigation use in the Modjo River catchment. Understanding changes in groundwater levels is crucial for the sustainable use and management of aquifer. This study investigates the groundwater flow system and aquifer response to increased groundwater pumping and reduced recharge using the calibrated steady-state groundwater level and budget as a baseline. The groundwater flow corresponds to the direction of the Modjo River flow, following the topographic gradient. The simulated groundwater budget indicates that recharge from precipitation and surface water (crater lakes and river) are the main inflow to the aquifer, while the outflow from the aquifer is due to groundwater pumping, natural subsurface flow to downstream area, and base flow. Analysis of the different scenarios reveals that both an increase in well pumping and a decline in recharge resulted in a decrease of the base flow to Bishoftu crater lakes and Mojo River, and to the downstream subsurface flow. In conclusion, increasing human demand for groundwater and variability in recharge will affect groundwater contribution to surface water and ultimately will be a source of concern in the future for both environmental flows and groundwater management.

ObjectiveTo examine whether late-life exposure to PM2.5 (particulate matter with aerodynamic diameters MethodsAD pattern similarity (AD-PS) scores, developed by supervised machine learning and validated with MRI data from the Alzheimer’s Disease Neuroimaging Initiative, were used to capture high-dimensional gray matter atrophy in brain areas vulnerable to AD (e.g., amygdala, hippocampus, parahippocampal gyrus, thalamus, inferior temporal lobe areas, and midbrain). Using participants' addresses and air monitoring data, we implemented a spatiotemporal model to estimate 3-year average exposure to PM2.5 preceding MRI-1. General linear models were used to examine the association between PM2.5 and AD-PS scores (baseline and 5-year standardized change), accounting for potential confounders and white matter lesion volumes.ResultsFor 1,365 women 77.9 ± 3.7 years of age in 2005 to 2006, there was no association between PM2.5 and baseline AD-PS score in cross-sectional analyses (β = −0.004; 95% confidence interval [CI] −0.019 to 0.011). Longitudinally, each interquartile range increase of PM2.5 (2.82 µg/m3) was associated with increased AD-PS scores during the follow-up, equivalent to a 24% (hazard ratio 1.24, 95% CI 1.14–1.34) increase in AD risk over 5 years (n = 712, age 77.4 ± 3.5 years). This association remained after adjustment for sociodemographics, intracranial volume, lifestyle, clinical characteristics, and white matter lesions and was present with levels below US regulatory standards (3).ConclusionsLate-life exposure to PM2.5 is associated with increased neuroanatomic risk of AD, which may not be explained by available indicators of cerebrovascular damage.

Since their discovery a few decades ago, metal–organic frameworks (MOFs) have suffered from poor hydrolytic stability. Since then, significant effort has been devoted to design robust MOFs, including their utilization for water-related applications to overcome relevant societal challenges. This short review provides guidelines on the key parameters that drive the assembly of hydrothermally stable MOFs together with the most relevant physicochemical features needed in their water-related applications. It also highlights some of the recent advances in MOF-water applications (based on water sorption or mediation and separation in the presence of water) as well as the most critical challenges to overcome.

Exposure to wildfire smoke causes adverse health outcomes, suggesting the importance of accurately estimating smoke concentrations. Geostatistical methods can combine observed, modeled, and satellite-derived concentrations to produce accurate estimates. Here, we estimate daily average ground-level PM2.5 concentrations at a 1 km resolution during the October 2017 California wildfires, using the Constant Air Quality Model Performance (CAMP) and Bayesian Maximum Entropy (BME) methods to bias-correct and fuse three concentration datasets: permanent and temporary monitoring stations, a chemical transport model (CTM), and satellite-derived estimates. Four BME space/time kriging and data fusion methods were evaluated. All BME methods produce more accurate estimates than the standalone CTM and satellite products. Adding temporary station data increases the R2 by 36%. The data fusion of observations with the CAMP-corrected CTM and satellite-derived concentrations provides the best estimate (R2 = 0.713) in fire-impacted regions, emphasizing the importance of combining multiple datasets. We estimate that approximately 65,000 people were exposed to very unhealthy air (daily average PM2.5 ≥ 150.5 μg/m3).

We have shown in a recent collaboration that the Cauchy problem for the multi-dimensional Burgers equation is well-posed when the initial data u(0) is taken in the Lebesgue space L 1 (R n), and more generally in L p (R n). We investigate here the situation where u(0) is a bounded measure instead, focusing on the case n = 2. This is motivated by the description of the asymptotic behaviour of solutions with integrable data, as t $\rightarrow$ +$\infty$. MSC2010: 35F55, 35L65. Notations. We denote $\times$ p the norm in Lebesgue L p (R n). The space of bounded measure over R m is M (R m) and its norm is denoted $\times$ M. The Dirac mass at X $\in$ R n is $\delta$ X or $\delta$ x=X. If $\nu$ $\in$ M (R m) and $\mu$ $\in$ M (R q), then $\nu$ $\otimes$ $\mu$ is the measure over R m+q uniquely defined by $\nu$ $\otimes$ $\mu$, $\psi$ = $\nu$, f $\mu$, g whenever $\psi$(x, y) $\not\equiv$ f (x)g(y). The closed halves of the real line are denoted R + and R --. * U.M.P.A., UMR CNRS-ENSL \# 5669. 46 all{\'e}e d'Italie

Sr-Nd-Hf-Pb isotopes and major/trace element data are presented for amphibole megacrysts from two separate instances of lamprophyric intraplate magmatism in Zealandia (Cretaceous Westland Dike Swar...

International audience; Here we propose an innovative strategy to synthesize single-crystal nanowires (NWs) of the Al 3+ dicarboxylate MIL-69(Al) MOF by using graphene oxide nanoscrolls as structure directing agents. MIL-69(Al) NWs with an average diameter of 70 ± 20 nm and lengths up to 2 m were found to preferentially grow along the [001] crystallographic direction. Advanced characterization tools (electron diffraction, TEM, STEM-HAADF, SEM, XPS) and molecular modelling revealed the mechanism of formation of MIL-69(Al) NWs involving size-confinement and templating effects. The formation of MIL-69(Al) seeds and the self-scroll of GO sheets followed by the anisotropic growth of MIL-69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures.

Ebola virus (EBOV) disease outbreaks, as well as the ability of EBOV to persist in the environment under certain conditions, highlight the need to develop effective decontamination techniques against the virus. We evaluated the efficacy of hydrogen peroxide vapor (HPV) to inactivate MS2 and Phi6 bacteriophages, the latter a recommended surrogate for EBOV. The phages were inoculated onto six material types with and without the presence of whole human blood. The inoculated materials were then exposed to either a high or low concentration of HPV for various elapsed times. The phages were also recovered from positive controls at these same elapsed times, to assess environmental persistence and decontamination efficacy. Low concentration hydrogen peroxide vapor (LCHP; 25 ppm) was effective against both phages on all materials without the presence of blood at 2 h. LCHP was ineffective against the phages in the presence of blood, on all materials, even with a 3-day contact time. Higher concentrations of HPV (>400 ppm) with contact times of 24–32 h achieved approximately 2–6 log reduction of the phages in the presence of blood. [Image: see text]

The successful development of modern gas sensing technologies requires high sensitivity and selectivity coupled to cost effectiveness, which implies the necessity to miniaturize devices while reducing the amount of sensing material. The appealing alternative of integrating nanoparticles of a porous metal–organic framework (MOF) onto capacitive sensors based on interdigitated electrode (IDE) chips is presented. We report the deposition of MIL-96(Al) MOF thin films via the Langmuir–Blodgett (LB) method on the IDE chips, which allowed the study of their gas/vapor sensing properties. First, sorption studies of several organic vapors like methanol, toluene, chloroform, etc. were conducted on bulk MOF. The sorption data revealed that MIL-96(Al) presents high affinity toward water and methanol. Later on, ordered LB monolayer films of MIL-96(Al) particles of ∼200 nm were successfully deposited onto IDE chips with homogeneous coverage of the surface in comparison to conventional thin film fabrication techniques such as drop-casting. The sensing tests showed that MOF LB films were selective for water and methanol, and short response/recovery times were achieved. Finally, chemical vapor deposition (CVD) of a porous thin film of Parylene C (thickness ∼250–300 nm) was performed on top of the MOF LB films to fabricate a thin selective layer. The sensing results showed an increase in the water selectivity and sensitivity, while those of methanol showed a huge decrease. These results prove the feasibility of the LB technique for the fabrication of ordered MOF thin films onto IDE chips using very small MOF quantities., The research leading to these results has received funding from Spanish MINECO and FEDER (projects MAT2016-78257-R and MAT2017-86826-R), the Aragon Government (DGA) and FEDER (research group E31_17R). M.A.A. acknowledges the support of Ministerio de Educación from the Spanish Government under an FPU grant (Formación de Profesorado Universitario, FPU14/05367), a short-term mobility FPU grant (EST18/00291), and of the King Abdullah University of Science and Technology and Advanced Membranes and Porous Materials Center under the Visiting Student Program.

Assessment of groundwater quality is vital for the sustainable use of the resources for domestic and agricultural purposes. In this study spatial variation of physicochemical parameters were analyzed for Northeast Adama Town. Water Quality Index (WQI) and irrigation indices were used to determine the suitability of groundwater for drinking and irrigation purposes, respectively. Further, the physical-chemical results were compared with the Ethiopian standards and the World Health Organization (WHO) standards for drinking and public health. Using GIS interpolation methods in Arc GIS 10.3.1, spatial distribution maps of pH, TDS, EC, Cl−, HCO32−, SO42−, Ca2+, Mg2+, Na+ and K+, RSC, SAR, Na% were prepared. Results indicated that except ASTU well 2, all samples are below the desirable limits of WHO. The WQI results indicated that 85% of samples and 15% of samples were in good and poor categories, respectively. Irrigation indices show that the most groundwater samples have excellent water classes, indicating that they are suitable for irrigation purposes.

International audience; Climate change has an ever-increasing impact on island territories. Whether it is due to rising sea levels or the increase in recurrence and intensity of extreme events, island territories are increasingly vulnerable. These impacts are expected to affect marine and terrestrial biodiversity, human occupation (infrastructure) and other activities such as agriculture and tourism, the two economic pillars of French Polynesia. While the current and future impacts of climate change on island territories are generally accepted, data acquisition, modeling, and projections of climate change are more complex to obtain and limitedly cover the island territories of the Pacific region. This article aims to develop methodologies for the acquisition and exploitation of data on current and future climate risks and their impacts in French Polynesia. This work of acquisition and valorization is part of a research project for the development of an observatory of resilience to climate risks in the perspective of building a spatial decision support system.

In the present work we investigate for the first time the 2D fluid transport of the plasma in WEST during an entire discharge from the start-up to the ramp-down (shot #54487). The evolution of density profile, electron and ion temperatures together with the experimental magnetic equilibrium, total current and gas-puff rate is investigated. Comparisons with the interferometry diagnostic show a remarkable overall qualitative agreement during the discharge that can be quantitative at some locations in the plasma core. If at the onset of the X-points during the ramp-up the electron heat flux is dominant at the target, present results show that the ion heat flux becomes dominant during the stationary phase of the discharge. Using a simple model for erosion, present results assess the tungsten sputtering due to deuterium ions during the start-up and ramp-up phases of the discharge and confirm the need to consider full discharge simulation to accurately treat the W source of contamination. This work also demonstrates the interest of developing magnetic equilibrium free solver including efficient time integration to step toward predictive capabilities in the future for fusion operation.

Transport processes around the magnetic X-point of tokamaks, such as turbulence and mean-field drifts, are scarcely understood. The assessment of the capability of turbulence codes to quantitatively reproduce these dynamics has been hampered by limitations in computational power and available experimental data. In this paper, we present a rigorous validation of full-scale simulations of a newly developed X-point scenario in the basic toroidal plasma device TORPEX, performed with the four state-of-the-art codes FELTOR, GBS, GRILLIX, and STORM. High-resolution Langmuir probe array measurements of various time-averaged and fluctuating quantities and across the entire cross section of TORPEX show that this X-point scenario features the key ingredients of X-point dynamics, such as small-scale fluctuations and background drifts. The codes are able to qualitatively reproduce some characteristics of the time-averaged fields, such as the ion saturation current profiles at mid-height, the plasma up-down asymmetry, and the blob trajectories. A quantitative agreement is found for the background E × B velocity pattern, while the fluctuation levels are generally underestimated typically by factors of 2 or more, and thus, background fluxes are found to dominate over turbulent ones in simulations. The sensitivity of the simulation results on the plasma collisionality and on the position of the sources is tested in GBS, showing a mild effect on the overall quantitative agreement with the experiment. Overall, this validation reveals the challenges to reproduce the plasma dynamics near an X-point and provides a clear path to a quantitative and computationally relatively inexpensive assessment of future developments in turbulence codes.

International audience; Metal-organic frameworks (MOFs) are one of the most prominent families of porous materials. With their great chemical and structural versatility, MOFs have shown to be suitable for a great number of applications related to energy, environment, or medical fields. Nevertheless, in order to expand their potential into wider horizons, some limitations must be overcome. MOFs with higher stability (robust MOFs) and greener more efficient synthetic routes are among the main targets that must be achieved in order to promote their use in industry. In the last years, these two aspects have been broadly studied. This chapter presents, firstly, a discussion of some of the most relevant strategies that can be employed to improve chemical, thermal and/or mechanical stabilities of MOFs. Approaches to strengthen/preserve the coordination bond, as well as some other structural factors that can enhance the stability of MOFs are discussed throughout some relevant examples. Finally, some environmentally friendly synthetic pathways for MOFs production are presented.

International audience; This paper addresses simulation of heat dominated compressible flows in a closed cavity using a pressure-based lattice Boltzmann (LB) method, in which thermal effects are modeled by applying a pressure-featured zero-order moment of distribution functions. A focus is made on the conservation of mass at boundary nodes, which is a challenging issue that significantly complicated by the density-decoupled zero-order moment here. The mass leakage at boundary nodes is mathematically quantified, which enables an efficient local mass correction scheme. The performance of this solver is assessed by simulating buoyancy-driven flows in a closed deferentially heated cavity with large temperature differences (non-Boussinesq) at Rayleigh numbers ranging from 103 to 107. Simulations show that mass leakage at solid walls in such configurations is a critical issue to obtain reliable solutions, and it eventually leads to simulations overflow when the cavity is inclined. The proposed mass correction scheme is, however, shown to be effective to control the mass leakage and get accurate solutions. Thus, associated with the proposed mass conservation scheme, the pressure-based LB method becomes reliable to study natural convection dominated flows at large temperature differences in closed geometries with mesh aligned boundaries or not

International audience; This contribution presents the recent effort at CEA and French federation for Fusion to simulate edge plasma transport with the new code SOLEDGE3X. The latter can be used both as a 2D transport code or as a 3D turbulence code. It makes possible simulating edge plasma up to the first wall including the complex wall geometry. It also includes neutral recycling and impurity sputtering, seeding and transport. In order to improve turbulence description in transport simulation, a reduced model for turbulence intensity prediction has been derived and implemented, based on "kepsilon" like models from the neutral fluid community. Applications to a JET L-mode detached plasma and to a WEST plasma are used as illustration of the code abilities

International audience; A two-equation model to self-consistently determine cross-field fluxes in the edge and scrape-off layer region of diverted plasma is used to complete 2D mean-field edge transport description of plasma wall interaction. Inspired by the Reynolds Average Navier-Stokes simulations for neutral fluids, this model is based on the local evolution of the turbulent kinetic energy κ and its dissipation rate ε. These two equations are algebraically derived for RANS modeling and are very slightly modified and adapted to describe self-consistent plasma turbulent transport. The general features of the model are discussed and bridged to the well-known predatorprey and quasilinear models commonly used to investigate plasma transport. Specific closures are proposed based on the interchange turbulence. Results of the 1D model are confronted to experimental evidence by analyzing the computed SOL width and comparing the results to the existing scaling law for L-mode plasmas. Introducing a dependence on the shear of large scale flows, typically the zonal flows, 1D simulations can exhibit an H-mode like transition when increasing the input power, generating an increased stored energy thanks to an interface barrier located at the separatrix. Further 2D plasma-wall interaction simulations for WEST are analyzed that show a good match with the experimental profiles, as well as a ballooned transport driving turbulent transport in the divertor SOL and nearly no transport in the private flux region. The SOL width of WEST is also recovered. These results show the remarkable capability of the κ-ε model to capture key aspects of the physics of turbulent transport throughout the plasma knowing that a unique scalar free parameter is available to tune cross field transport in the whole 2D cross section of the plasma.

Hundreds of cytotoxic natural or synthetic lipidic compounds contain chiral alkynylcarbinol motifs, but the mechanism of action of those potential therapeutic agents remains unknown. Using a genetic screen in haploid human cells, we discovered that the enantiospecific cytotoxicity of numerous terminal alkynylcarbinols, including the highly cytotoxic dialkynylcarbinols, involves a bioactivation by HSD17B11, a short-chain dehydrogenase/reductase (SDR) known to oxidize the C-17 carbinol center of androstan-3-alpha,17-beta-diol to the corresponding ketone. A similar oxidation of dialkynylcarbinols generates dialkynylketones, that we characterize as highly protein-reactive electrophiles. We established that, once bioactivated in cells, the dialkynylcarbinols covalently modify several proteins involved in protein-quality control mechanisms, resulting in their lipoxidation on cysteines and lysines through Michael addition. For some proteins, this triggers their association to cellular membranes and results in endoplasmic reticulum stress, unfolded protein response activation, ubiquitin-proteasome system inhibition and cell death by apoptosis. Finally, as a proof-of-concept, we show that generic lipidic alkynylcarbinols can be devised to be bioactivated by other SDRs, including human RDH11 and HPGD/15-PGDH. Given that the SDR superfamily is one of the largest and most ubiquitous, this unique cytotoxic mechanism-of-action could be widely exploited to treat diseases, in particular cancer, through the design of tailored prodrugs. Graphical abstract

International audience; The WEST experiment is currently operating with tungsten plasma-facing components and testing ITER-like divertor monoblocks. In order to support WEST experiments interpretation, numerical analyses were carried out. Starting from WEST experimental data, realistic background plasma conditions were reproduced through SolEdge-EIRENE and used as input for ERO2.0 simulations to investigate tungsten migration. Tungsten contamination due to the different plasma-facing components was modelled under different plasma conditions, highlighting a non-negligible contribution of tungsten coming from the tokamak main chamber. Tungsten penetration factor was computed and used as an indication for tungsten screening by the background plasma at the different tokamak plasma-facing components. Simulations showed the main chamber components to be very weakly screened. Light impurities charge was showed to influence not only tungsten sputtering, but also its probability to enter the confined plasma. Simulations results indicated that even when the tungsten source is not heavily influenced by self-sputtering, contamination of the confined plasma can be strongly impacted by it in low density background plasma conditions. Finally, a one-to-one comparison between tungsten visible spectroscopy at the lower divertor from experimental data and from synthetic diagnostics was performed, showing that it is possible to reproduce a realistic lower divertor signal following experimental evidence on light impurities asymmetry between the targets.

The present deployment of photovoltaic (PV) panels on the rooftop has been far below its potential. Stakeholders often see the PV as a strong design constraint, isolated from the built environment and not adapted to their requirements. Here, we propose a new design that combines the PV panels with a metal-organic framework basedsorptive thermal battery, which serves as a multi-functional building element and is more actively involved in the indoor environment regulation. The open-loop thermal battery can stock moisture from air with 105 times its volume so that the built environment with high humidity at night is dried to a comfortable and healthy level. The moisture is removed at daytime with unpleasant solar heat, thereby cools the PV panels simultaneously,improving electricity generation by 5%. The benefits of this design can be translated into economic added value to facilitate investment decisions of building-integrated PV projects.

International audience; Progressing towards more reliable numerical solutions in the simulation of plasma for magnetic confinement fusion has become a critical issue for the success of the ITER operation. This requires developing rigorous and efficient methods of verification of the numerical simulations in any relevant flow regimes of the operation. The paper introduces a new formulation of the PoPe 1 method, namely the independent Projection on Proper elements method (iPoPe) to quantify the numerical error by performing a data-driven identification of the mathematical model from the simulation outputs. Based on a statistical postprocessing of the outputs database, the method provides a measure of the error by estimating the distance between the (numerical) effective and (analytical) theoretical weights of each operator implemented in the mathematical model. The efficiency of the present method is illustrated on turbulent edge plasma simulations based on a drift-reduced Braginskii fluid model in realistic magnetic geometries. Results show the effective order of the numerical method in these multiscale flow regimes as well as the values of the plasma parameters which can be safely simulated with respect to a given discretization. In this sense, the method goes one step further than the Method of Manufactured Solution (MMS 2-4), recently introduced in fusion, and provides an efficient verification procedure of the numerical simulations in any regimes, including turbulent ones that could be generalized to other scientific domains.

Li-air batteries possess higher specific energies than the current Li-ion batteries. Major drawbacks of the air cathode include the sluggish kinetics of the oxygen reduction (OER), high overpotentials and pore clogging during discharge processes. Metal–Organic Frameworks (MOFs) appear as promising materials because of their high surface areas, tailorable pore sizes and catalytic centers. In this work, we propose to use, for the first time, aluminum terephthalate (well known as MIL-53) as a flexible air cathode for Li-O2 batteries. This compound was synthetized through hydrothermal and microwave-assisted routes, leading to different particle sizes with different aspect ratios. The electrochemical properties of both materials seem to be equivalent. Several behaviors are observed depending on the initial value of the first discharge capacity. When the first discharge capacity is higher, no OER occurs, leading to a fast decrease in the capacity during cycling. The nature and the morphology of the discharge products are investigated using ex situ analysis (XRD, SEM and XPS). For both MIL-53 materials, lithium peroxide Li2O2 is found as the main discharge product. A morphological evolution of the Li2O2 particles occurs upon cycling (stacked thin plates, toroids or pseudo-spheres).

International audience; Organic waste (OW) reuse in agriculture is a common practice fostered by benefits in terms of waste recycling and crop production. However, OW amendments potentially affect the fate of pesticide spread on fields to protect the crops from pests and weeds. The influence of OW on the sorption, degradation, and leaching of pesticides is generally studied for each mechanism separately under artificial laboratory conditions. Our study aims at evaluating the balance of these mechanisms under more realistic conditions to clarify the influence of three common OW amendments on the fate, in soil, of the widely used herbicide S-Metolachlor. We performed leaching experiments in large undisturbed soil cores amended with raw sewage sludge, composted sludge, and digested pig slurry (digestate), respectively. We monitored S-Metolachlor and its two main metabolites MET-OA and MET-ESA in the leachates during a succession of 10 rainfall events over 126 days. We also quantified the remaining S-Metolachlor and metabolites in the soil at the end of the experiments. S-Metolachlor leaching didn't exceed 0.1% of the applied dose with or without OW amendment. Despite a soil organic carbon increase of 3 to 32%, OW amendments did not significantly affect the amount of S-Metolachlor that leached through the soil (0.01 to 0.1%) nor its transformation rate (6.0 to 8.6%). However, it affected the degradation pathways with an increase of MET-OA relative to MET-ESA formed after OW amendment (28 to 54%) compared to the controls (8%). Concentration of S- Metolachlor and metabolites in the leachates of all treatments greatly exceeded the regulatory limit for groundwater intended for human consumption in Europe. These high concentrations were probably the consequence of preferential macropore flow. Colloids had comparable levels in the leachates after S-Metolachlor application. Dissolved organic carbon was also comparable in the controls, digestate, and sludge treatments but was 65% higher in the compost-amended cores. These results, along with a great variability among replicates inherent to experiments performed under realistic conditions, partly explain the limited impact of OW on the transport of S-Metolachlor.

International audience; The potential of safe and low-cost batch production processes for Metal-Organic Frameworks (MOFs) at an industrial scale has been evaluated based on the prototypical MOF MIL-160(Al), a bio-derived material of high practical interest that can be made with a high space-time yield using green ambient pressure conditions. A simple method to calculate the production cost of this material has been determined based on a simulated process constructed with the data collected from laboratory pilot largescale tests taking into account for the first time in MOF cost evaluation all the process parameters such as the scale, the cost of the raw materials, recirculation, and washing. The investment for a production plant established the ground for the estimation of the complete cost. The expected cost ranged from ca. 55 $ per kg at 100 tons per year down to 29.5 $ per kg for 1 kton per year production with longer term perspectives of reaching costs below 10 $ per kg once the bio-derived ligand is considered for the large-scale production of bioplastics.

Consistent time series rainfall datasets are important in performing climate trend analyses and agro-hydrological modeling. However, temporally consistent ground-based and long-term observed rainfall data are usually lacking for such analyses, especially in mountainous and developing countries. In the absence of such data, satellite-derived rainfall products, such as the Climate Hazard Infrared Precipitations with Stations (CHIRPS) and Global Precipitation Measurement Integrated Multi-SatellitE Retrieval (GPM-IMERG) can be used. However, as their performance varies from region to region, it is of interest to evaluate the accuracy of satellite-derived rainfall products at the basin scale using ground-based observations. In this study, we evaluated and demonstrated the performance of the three-run GPM-IMERG (early, late, and final) and CHIRPS rainfall datasets against the ground-based observations over the Ziway Lake Basin in Ethiopia. We performed the analysis at monthly and seasonal time scales from 2000 to 2014, using multiple statistical evaluation criteria and graphical methods. While both GPM-IMERG and CHIRPS showed good agreement with ground-observed rainfall data at monthly and seasonal time scales, the CHIRPS products slightly outperformed the GPM-IMERG products. The study thus concluded that CHIRPS or GPM-IMERG rainfall data can be used as a surrogate in the absence of ground-based observed rainfall data for monthly or seasonal agro-hydrological studies.

Coastal ecosystems are increasingly threatened by eutrophication and dystrophy. In this context, the full pattern of a bloom dominated by the dinoflagellate, Lepidodinium chlorophorum, was investigated by a high frequency monitoring buoy equipped with sensors allowing nutrients and photosynthesis measurements. An increase of the N/P ratio affected phytoplankton physiology leading to bloom collapse with a slight oxygen depletion. In parallel, enrichment experiments were performed on the natural bloom population. After 5 days of incubation the community structure, using flow cytometry and several physiological parameters were analysed. The data reveal a potential N and P co-limitation and a decoupling between primary production and productivity in fully enriched conditions. Under unbalanced N/P inputs, high level of alkaline phosphatase activity and transparent exopolymeric particle production, which favour phytoplankton sedimentation, were observed. Nutrient inputs and their stoichiometry control phytoplankton growth, the community structure, physiological regulations, the fate of the bloom and consequences.

Among crop fruit trees, the apricot (Prunus armeniaca) provides an excellent model to study divergence and adaptation processes. Here, we obtain nearly 600 Armeniaca apricot genomes and four high-quality assemblies anchored on genetic maps. Chinese and European apricots form two differentiated gene pools with high genetic diversity, resulting from independent domestication events from distinct wild Central Asian populations, and with subsequent gene flow. A relatively low proportion of the genome is affected by selection. Different genomic regions show footprints of selection in European and Chinese cultivated apricots, despite convergent phenotypic traits, with predicted functions in both groups involved in the perennial life cycle, fruit quality and disease resistance. Selection footprints appear more abundant in European apricots, with a hotspot on chromosome 4, while admixture is more pervasive in Chinese cultivated apricots. Our study provides clues to the biology of selected traits and targets for fruit tree research and breeding., The evolutionary and domestication history of apricots is poorly understood. Here, the authors provide four apricot high-quality genome assemblies, the genomes of 578 accessions from natural and cultivated populations, and show that Chinese and European apricots constitute two different gene pools, resulting from independent domestication events.

The impact of triangularity on edge plasma transport and turbulence is addressed from full 3D turbulence simulations performed with TOKAM3X. Flux driven fluid simulations are run on analytical magnetic equilibria generated with positive and negative triangularity δ in a bottom limiter configuration. The conservation of the energy is assured by the increase of the bottom limiter radial position from δ > 0 to δ 0 . Changing the triangularity impacts both the plasma equilibrium and the turbulence. In particular, negative triangularity leads to a reduction of the density and electron temperature decay lengths in agreement with the literature. Concerning the turbulence, in all the simulations, it remains ballooned with an enhanced level of fluctuations at low field side in comparison to the high field one. Moreover, no clear trend is visible on the relative level of fluctuations of both density and electron temperature in the CFR whereas an enhancement (resp. reduction) is visible in the scrape-off layer at the low field side midplane for the negative (resp. positive) triangularity simulations. This behaviour differs from TCV and DIII-D measurements which show the benefit of negative triangularity in terms of turbulence reduction and increased confinement. However, no conclusion is drawn from our preliminary study concerning the impact of triangularity on the turbulent transport. Change in triangularity impacts many simulation control parameters, as in the experiments, and that the analysis of its impact alone on the dynamics of the plasma is not obvious in this configuration.

Microperoxidases 8 (MP8) and 11 (MP11) are heme-containing peptides obtained by the proteolytic digestion of Cytochrome c. They act as mini-enzymes that combine both peroxidase-like and Cytochrome P450-like activities that may be useful in the synthesis of fine chemicals or in the degradation of environmental pollutants. However, their use is limited by their instability in solution due to (i) the bleaching of the heme in the presence of an excess of H2O2, (ii) the decoordination of the distal histidine ligand of the iron under acidic conditions and, (iii) their tendency to aggregate in aqueous alkaline solutions, even at low concentrations. Additionally, both MP8 and MP11 show relatively low selectivity, due to the lack of control of the substrates by a specific catalytic pocket on the distal face of the heme. Both stability and selectivity issues can be effectively addressed by immobilization of microperoxidases in solid matrices, which can also lead to their possible recycling from the reaction medium. Considering their relatively small size, the pore inclusion of MPs into Metal-Organic Frameworks appeared to be more adequate compared to other immobilization methods that have been widely investigated for decades. The present minireview describes the catalytic activities of MP8 and MP11, their limitations, and various results describing their immobilization into MOFs which led to MP11- or MP8@MOF hybrid materials that display good activity in the oxidation of dyes and phenol derivatives, with remarkable recyclability due to the stabilization of the MPs inside the MOF cavities. An example of selective oxidation of dyes according to their charge by MP8@MOF hybrid materials is also highlighted.

With the purpose of improving the production of methyl lactate (ML) from sugars (glucose and sucrose), a new metal‐organic framework (MOF) denoted as UZAR‐S10, containing Sn ions and ligand 2‐aminobenzene‐1,4‐dicarboxylate was synthesized. The SEM and PXRD characterization revealed that UZAR‐S10 was highly crystalline. The empirical formula of UZAR‐S10 is [(NH2‐BDC)Sn]·(NH2‐BDC)0.5, i.e., per Sn atom, with one structural ligand molecule and half ligand molecule trapped in the MOF structure. The removal of the trapped ligand by either solvent extraction or thermal treatment damaged the structure of UZAR‐S10, not enabling its activation. The performance of UZAR‐S10 in the production of ML was compared to those achieved with different types of carboxylate MOFs, especially with that of Sn partially substituted Ti tetracarboxylate MOF denoted MIP‐177‐LT (MIP‐177‐LT(Ti/Sn)). The highest ML yields achieved from sucrose were 29.5 % and 42.0 % for UZAR‐S10 and MIP‐177‐LT(Ti/Sn), respectively. For comparison, other carboxylate type MOFs (MIL‐53(Al), NH2‐MIL‐53(Al), UiO‐66, MIL‐101(Cr) and HKUST‐1) were tested at the same conditions with worse performance than the two Tin‐containing MOFs., Financial support from the Spanish Ministry of Economy and Competitiveness (MAT2016–77290‐R) and the European Social Fund (ESF) through the Aragón Government (T43–17R) is gratefully acknowledged.

Porous carbons have been considered very important for a long time because of various possible applications. In this review, we summarize the current progress in the field of porous carbons, especially N-enriched carbons, obtained from the carbonization of MOFs with or without additional N-containing compounds. Moreover, metal- or metal oxide-loaded N-doped carbons are also dealt with. Not only the preparation but also the applications in adsorption and catalysis are summarized. More importantly, research ideas or trends will be suggested for further development of these fields. Finally, this study summarizes a number of methods for the preparation of N-enriched carbons (with or without metal or metal oxide) and their efficiencies in various potential applications, including adsorption (liquid-/gas-phase) and organo-/photo-/electro-catalyses, based on their physicochemical properties.

A reduced model for radial anomalous transport of plasma in tokamaks, inspired by the Reynolds-Averaged Navier–Stokes (RANS) approach, is presented assuming diffusion as governing mechanism. In order to self-consistently calculate transport coefficients, an empirical equation is built for the turbulent kinetic energy and the system is closed via the scaling law of global confinement. In such way the SOL width appears to recover experimental dependencies with respect to machine parameters and interestingly, when the model is implemented in a 2D transport code for a realistic study-case, mean fields retrieve some features already observed in 1st-principle turbulent codes.

The long-term effect of non-point source pollution on groundwater from agricultural practices is a major concern globally. Non-point source pollutants such as nitrate that occurs through fertilizers and animal waste eventually make their way into the aquifer by infiltrating soil. The goal of this study is to develop an approach for characterization of nitrate concentrations at potential source locations under conditions of geologic uncertainty. A Bayesian framework using the Markov Chain Monte Carlo (MCMC) approach is developed to estimate posterior probability distributions of non-point sources by incorporating nitrate concentration data as well as geologic uncertainties. The proposed approach is tested using hypothetical contamination scenarios and then validated using an application case study in North Carolina. Uncertainty existing in geologic formation (i.e., heterogeneous hydraulic conductivity field) is treated as prior and used in evaluating the likelihood function that measures the match between observed and simulated concentrations. The likelihood function computation involves a numerical model that simulates nitrate transport in groundwater from non-point agricultural sources and predicts nitrate concentrations at observation wells. Effectiveness of the MCMC approach is evaluated through a convergence analysis. Comparison among different sampling algorithms is carried out with respect to MCMC convergence diagnostics and making inference. The Bayesian inference analysis methodology developed in this research will help decision makers and water managers to identify potential areas for source containment and decide if further sampling is required.

We have developed a new statistical approach (M3Fusion) for combining surface ozone observations from thousands of monitoring sites around the world with the output from multiple atmospheric chemistry models to produce a global surface ozone distribution with greater accuracy than can be provided by any individual model. The ozone observations from 4766 monitoring sites were provided by the Tropospheric Ozone Assessment Report (TOAR) surface ozone database, which contains the world's largest collection of surface ozone metrics. Output from six models was provided by the participants of the Chemistry-Climate Model Initiative (CCMI) and NASA's Global Modeling and Assimilation Office (GMAO). We analyze the 6-month maximum of the maximum daily 8 h average ozone value (DMA8) for relevance to ozone health impacts. We interpolate the irregularly spaced observations onto a fine-resolution grid by using integrated nested Laplace approximations and compare the ozone field to each model in each world region. This method allows us to produce a global surface ozone field based on TOAR observations, which we then use to select the combination of global models with the greatest skill in each of eight world regions; models with greater skill in a particular region are given higher weight. This blended model product is bias corrected within 2∘ of observation locations to produce the final fused surface ozone product. We show that our fused product has an improved mean squared error compared to the simple multi-model ensemble mean, which is biased high in most regions of the world.

This work reports on the fabrication, optimization and characterization of ultrathin films containing submicrometer particles (sMPs) of the hydrophilic and water stable UiO-66-COOH(Zr) metal organic framework (MOF). MOF particles of ≈200 nm have been synthesized and assembled at the air–water interface by the Langmuir–Blodgett technique. The use of different solvents, mixtures of solvents and surfactants has been investigated in order to improve the stability of MOF dispersions and reduce particle aggregation. The compact MOF/surfactant films containing 10 wt % octadecylphoshonic acid (ODP) have been deposited on substrates of different nature by Langmuir–Blodgett (LB) and Langmuir–Schaefer (LS) methods, showing that the presence of even only one MOF/ODP monolayer can increase the water contact angle of highly hydrophilic substrates such as mica or glass up to 120°. These films were characterized by scanning electron microscopy, grazing incidence X-ray diffraction, Fourier transform infrared spectroscopy and atomic force microscopy, revealing the formation of a continuous film where ODP molecules adopt an almost vertical position and cover MOF particles. Moreover, the presence of MOF particles significantly enhances the surface roughness and allows ultrathin, hydrophobic coverage to be obtained. Finally, it has been shown that the crystallinity and the porosity of the MOF remains almost unaltered in MOF/ODP films., The research leading to these results has received funding from the European Union Seventh Framework Programme (FP7/2007-2013) under grant agreement number 608490, project M4CO2, and also financial support from Spanish MINECO and FEDER (projects MAT2016-78257-R and MAT2017-86826-R), the Aragon Government (DGA) and the ESF (research groups E31_17R). Miguel A. Andrés wants to acknowledge the support of Ministerio de Educación from the Spanish Government under a FPU grant (Formación de Profesorado Universitario).

International audience; The so-called Graftfast reaction in water and at room temperature (RT) was applied to graft polyethylene glycol (PEG) at the surface of the microporous zeolitic imidazolate framework ZIF-8 nanoparticles (NPs) using acrylPEG of different chain lengths (480 Da and 5 kDa). In comparison to non-modified ZIF-8 NPs, both chemical and colloidal stabilities of PEGylated ZIF-8 NPs are significantly enhanced in water. A series of colloidal complex fluids by mixing PEG grafted ZIF-8 (i. e. PEG-g-ZIF-8) NPs with different amounts of polyvinylalcohol (PVA) was prepared and characterized by advanced characterization tools such as dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) thereby showing their long-term colloidal stability. Finally, dense and supported mixed matrix membranes were cast from PEG-g-ZIF-8/PVA solutions and have shown high performance in isopropanol (IPA) dehydration by pervaporation. The permeation flux of the supported MMM (i. e. 0.091 kg/(m$^2$h) is eleven times higher than that of the pure PVA membrane and these MMMs present a high separation factor (i. e. 7326). These transport properties are presumably due to the molecular sieving effects induced by ZIF-8 and the good interfacial properties of the membrane. The computational exploration of the ZIF-8/PVA and PEG/PVA interfaces provides a microscopic scale explanation for the enhanced compatibility of PVA with the PEGylated MOF when compared to that for the composite based on the bare ZIF-8 as a filler.

As evidenced by the number of publications and patents published in the last years, the radiosynthesis of 6-[ 18 F]fluoro-3,4-dihydroxy-L-phenylalanine ([ 18 F]FDOPA) using nucleophilic [ 18 F]F-process remains currently a challenge for the radiochemists scientific community even if promising methods for the radiofluorination of electron-rich aromatic structures were recently developed from arylboronate, arylstannane or iodoniums salts precursors. In such context, based on the use of an iodonium triflate salt precursor, we optimized a fast and efficient radiofluorination route fully automated and free from any base, cryptand or metal catalyst for the radiosynthesis of [ 18 F]FDOPA. Using this method, this clinically relevant radiotracer was produced in 64 min, 27-38% RCY d.c. (n = 5), >99% RCP, >99% e.e., and high molar activity 170-230 GBq/µmol. In addition, this optimisation study clearly highlighted the important role of a triflate-hydrogen carbonate counterion exchange during the radiolabelling process to achieve high fluorine-18 incorporation yields.