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The reaction of the Schiff base 2-[1-(pyridin-2-yl)ethylideneamino]ethanol (HL), which is formed by reaction of 2-aminoethanol and 2-acetylpyridine with CuBr2 in ethanol results in the isolation of the new polymeric complex poly[hexa-μ-bromido-bis{2-[1-(pyridin-2-yl)ethylideneamino]ethanolato}tetracopper(II)], [Cu4Br6(C9H11N2O)2]n or [Cu4Br6L2]n. The asymmetric unit of the crystal structure of the polymeric [Cu4Br6L2]n complex is composed by four copper (II) cations, two monodeprotonated molecules of the ligand, and six bromide anions, which act as bridges. The ligand molecules act in a tridentate fashion through their azomethine nitrogen atoms, their pyridine nitrogen atoms, and their alcoholate O atoms. The crystal structure shows two types of geometries in the coordination polyhedrons around Cu2+ ions. Two copper cations are situated in a square-based pyramidal environment, while the two other copper cations adopt a tetrahedral geometry. Bromides anions acting as bridges between two metal ions connect the units, resulting in a tetranuclear polymer compound.

Since 2018 an unexpected number of earthquakes have been occurring offshore Mayotte, in the Mozambique Channel. They are linked to the eruption of the Fani Maoré submarine volcano. Using a recently-developed comprehensive automatic catalog, we explore two years of volcano-tectonic (VT) seismicity between March 2019 and March 2021 and analyse in detail the active structures of the magmatic plumbing system using ~33,000 events. The VT earthquakes highlight three magma storage zones and two aseismic conduits that had never been observed before. The temporal evolution of the seismicity reveals a probable regime change in March 2020. While before, the plumbing system reacted to the drainage of magma from a deep reservoir and to the migration of magma towards the seafloor, it is now responding to new migrations of fluids and to the redistribution of the stress-load across the system's pre-existing faults. This analysis is key to better understand long-term volcanism worldwide.

Recently, benchtop nuclear magnetic resonance (NMR) spectrometers utilizing permanent magnets have emerged as versatile tools with applications across various fields, including food and pharmaceuticals. Their efficacy is further enhanced when coupled with chemometric methods. This study presents an innovative approach to leveraging a compact benchtop NMR spectrometer coupled with chemometrics for screening honey-based food supplements adulterated with active pharmaceutical ingredients. Initially, fifty samples seized by French customs were analyzed using a 60 MHz benchtop spectrometer. The investigation unveiled the presence of tadalafil in 37 samples, sildenafil in 5 samples, and a combination of flibanserin with tadalafil in 1 sample. After conducting comprehensive qualitative and quantitative characterization of the samples, we propose a chemometric workflow to provide an efficient screening of honey samples using the NMR dataset. This pipeline, utilizing partial least squares discriminant analysis (PLS-DA) models, enables the classification of samples as either adulterated or non-adulterated, as well as the identification of the presence of tadalafil or sildenafil. Additionally, PLS regression models are employed to predict the quantitative content of these adulterants. Through blind analysis, this workflow allows for the detection and quantification of adulterants in these honey supplements.

As a result of screening a panel of marine organisms to identify lead molecules for the stimulation of endochondral bone formation, the calcareous sponge Pericharax heteroraphis was identified to exhibit significant activity during endochondral differentiation. On further molecular networking analysis, dereplication and chemical fractionation yielded the known clathridine A-related metabolites 3–6 and the homodimeric complex (clathridine A)2 Zn2+ (9), together with the new unstable heterodimeric complex (clathridine A–clathridimine)Zn2+ (10). With the presence of the zinc complexes annotated through the LC-MS analysis of the crude extract changing due to the instability of some metabolites and complexes constituting the mixture, we combined the isolation of the predicted molecules with their synthesis in order to confirm their structure and to understand their reactivity. Interestingly, we also found a large quantity of the contaminant benzotriazoles BTZ (7) and its semi-dimer (BTZ)2CH2 (8), which are known to form complexes with transition metals and are used for preventing corrosion in water. All isolated 2-aminoimidazole derivatives and complexes were synthesized not only for structural confirmation and chemical understanding but to further study their bioactivity during endochondral differentiation, particularly the positively screened imidazolone derivatives. Compounds leucettamine B, clathridine A and clathridimine were found to increase type X collagen transcription and stimulate endochondral ossification in the ATDC5 micromass model.

ExoY virulence factors are members of a family of bacterial nucleotidyl cyclases (NCs) that are activated by specific eukaryotic cofactors and overproduce cyclic purine and pyrimidine nucleotides in host cells. ExoYs act as actin-activated NC toxins. Here, we explore the Vibrio nigripulchritudo Multifunctional-Autoprocessing Repeats-in-ToXin (MARTX) ExoY effector domain (Vn-ExoY) as a model for ExoY-type members that interact with monomeric (G-actin) instead of filamentous (F-actin) actin. Vn-ExoY exhibits moderate binding affinity to free or profilin-bound G-actin but can capture the G-actin:profilin complex, preventing its spontaneous or VASP- or formin-mediated assembly at F-actin barbed ends in vitro. This mechanism may prolong the activated cofactor-bound state of Vn-ExoY at sites of active actin cytoskeleton remodelling. We present a series of high-resolution crystal structures of nucleotide-free, 3'-deoxy-ATP- or 3'-deoxy-CTP-bound Vn-ExoY, activated by free or profilin-bound G-actin-ATP/-ADP, revealing that the cofactor only partially stabilises the nucleotide-binding pocket (NBP) of NC toxins. Substrate binding induces a large, previously-unidentified, closure of their NBP, confining catalytically important residues and metal cofactors around the substrate, and facilitating the recruitment of two metal ions to tightly coordinate the triphosphate moiety of purine or pyrimidine nucleotide substrates. We validate critical residues for both the purinyl and pyrimidinyl cyclase activity of NC toxins in Vn-ExoY and its distantly-related ExoY from Pseudomonas aeruginosa, which specifically interacts with F-actin. The data conclusively demonstrate that NC toxins employ a similar two-metal-ion mechanism for catalysing the cyclisation of nucleotides of different sizes. These structural insights into the dynamics of the actin-binding interface of actin-activated ExoYs and the multi-step activation of all NC toxins offer new perspectives for the specific inhibition of class II bacterial NC enzymes.

In 2019, a new underwater volcano was discovered at 3500 m below sea level (b.s.l.), 50 km east of Mayotte Island in the northern part of the Mozambique Channel. In January 2021, the submarine eruption was still going on and the volcanic activity, along with the intense seismicity that accompanies this crisis, was monitored by the recently created REVOSIMA (MAyotte VOlcano and Seismic Monitoring) network. In this framework, four hydrophones were moored in the SOFAR channel in October 2020. Surrounding the volcano, they monitor sounds generated by the volcanic activity and the lava flows. The first year of hydroacoustic data evidenced many earthquakes, underwater landslides, large marine mammal calls, along with anthropogenic noise. Of particular interest are impulsive signals that we relate to steam bursts during lava flow emplacement. A preliminary analysis of these impulsive signals (ten days in a year, and only one day in full detail) reveals that lava emplacement was active when our monitoring started, but faded out during the first year of the experiment. A systematic and robust detection of these specific signals would hence contribute to monitor active submarine eruptions in the absence of seafloor deep-tow imaging or swath-bathymetry surveys of the active area.

The protection of ITER in-vessel components and the plasma-wall interaction studies will be based on a large network of infrared (IR) cameras covering 70% of the tokamak. The surface temperature measurement from IR images remains challenging due to the presence of metallic targets, with changes in surface thermo-radiative properties (emissivity) and the presence of multiple reflections. The paper provides an overview of major progress to improve the interpretation of IR image and to get more reliable surface temperature from IR synthetic diagnostics. The paper presents the latest development of (1) the forward model to include the modelling of the edge localised modes and a new advanced camera that is better adapted to experimental data (2) the inverse model to retrieve the emissivity of the targets and the surface temperature from a neural network trained exclusively from synthetic IR images. Promising results have been obtained both from simulated test images with an estimated emissivity better than 0.05 and a surface temperature better than 10%, and from WEST experimental images of ITER-like wide-angle to filter reflection patterns.

Botulinum neurotoxin A (BoNT/A) is a potent neurotoxin that silences cholinergic neurotransmission through the cleavage of the synaptic protein SNAP-25. Previous studies have shown that, in addition to its paralytic effects, BoNT/A can inhibit sensory nerve activity. The aim of this study was to identify how BoNT/A inhibits afferent signalling from the bladder. To investigate the role of SNAP-25 cleavage in the previously reported BoNT/A-dependent inhibition of sensory signalling, we developed a recombinant form of BoNT/A with an inactive light chain, rBoNT/A (0), unable to paralyse muscle. We also developed recombinant light chain (LC)-domain-only proteins to better understand the entry mechanisms, as the heavy chain (HC) of the protein is responsible for the internalisation of the light chain. We found that, despite a lack of catalytic activity, rBoNT/A (0) potently inhibited the afferent responses to bladder distension to a greater degree than catalytically active rBoNT/A. This was also clear from the testing of the LC-only proteins, as the inactive rLC/A (0) protein inhibited afferent responses significantly more than the active rLC/A protein. Immunohistochemistry for cleaved SNAP-25 was negative, and purinergic and nitrergic antagonists partially and totally reversed the sensory inhibition, respectively. These data suggest that the BoNT/A inhibition of sensory nerve activity in this assay is not due to the classical well-characterised ‘double-receptor’ mechanism of BoNT/A, is independent of SNAP25 cleavage and involves nitrergic and purinergic signalling mechanisms.

The seismic crisis that began in May, 2018 off the coast of Mayotte announced the onset of a volcanic eruption that started two months later 50 km southeast of the island. This seismicity has since been taken as an indicator of the volcanic and tectonic activity in the area. In response to this activity, a network of stations was deployed on Mayotte over the past three years. We used the machine learning-based method PhaseNet to re-analyze the seismicity recorded on land since March 2019. We detect 50,512 events compared to around 6508 manually picked events between March 2019 and March 2021. We locate them with NonLinLoc and a locally developed 1-D velocity model. While eruptions are often monitored through the analysis of Volcano-Tectonic (VT) seismicity (2–40 Hz), we focus on the lower frequency, Long Period (LP) earthquakes (0.5–5 Hz), which are thought to be more directly related to fluid movement at depth. In Mayotte, the VT events are spread between two clusters, whereas the LP events are all located in a single cluster in the bigger proximal VT cluster, at depths ranging from 25 to 40 km. Moreover, while the VT earthquakes of the proximal cluster occur continuously with no apparent pattern, LP events occur in swarms that last for tens of minutes. We show that during the swarms, LP events generally migrate downward at a speed of 5 m/s. While these events do not appear directly linked to upward fluid migration, their waveform signature could result from propagation through a fluid-rich medium. They occur at a different location than VT earthquakes, also suggesting a different origin which could be linked to the Very Long Period events (VLP) observed above the LP earthquakes in Mayotte.

Changes in the number of synaptic AMPA receptors underlie many forms of synaptic plasticity. These variations are controlled by an interplay between their intracellular transport (IT), export to the plasma membrane (PM), stabilization at synapses, and recycling. The cytosolic C-terminal domain of the AMPAR GluA1 subunit is specifically associated with 4.1 N and SAP97. We analyze how interactions between GluA1 and 4.1N or SAP97 regulate IT and exocytosis in basal conditions and after cLTP induction. The down-regulation of 4.1N or SAP97 decreases GluA1 IT properties and export to the PM. The total deletion of its C-terminal fully suppresses its IT. Our results demonstrate that during basal transmission, the binding of 4.1N to GluA1 allows their exocytosis whereas the interaction with SAP97 is essential for GluA1 IT. During cLTP, the interaction of 4.1N with GluA1 allows its IT and exocytosis. Our results identify the differential roles of 4.1N and SAP97 in the control of various phases of GluA1 IT.

A strategy to access fluorinated spiroindolenines has been developed, involving a selective functionalization of indoles with fluorinated moieties and subsequent catalytic dearomatization. Trifluomethylthio (SCF3), diethyl phosphono(difluoromethyl)thio (SCF2P(O)(OEt)2) and (phenylsulfonyl)difluoromethyl (CF2SO2Ph) groups were embedded at the C2 position of indole derivatives substituted with alkynes, allenes, and allyl carbonate moieties at the C3 position. A gold‐catalyzed cycloisomerization gave access to five spiroindolenines, and an enantioselective palladium catalyzed cyclization provided 10 fluorinated spirocyclic products with up to 77% ee. [ABSTRACT FROM AUTHOR]

This article reports the synthesis, along with structural and photophysical characterization of 2‐(2'‐hydroxyphenyl)benzazole derivatives functionalized with various azaheterocycles (pyridine, pyrimidine, terpyridine). These compounds show dual‐state emission properties, that is intense fluorescence both in solution and in the solid‐state with a range of fluorescent color going from blue to orange. Moreover, the nature of their excited state can be tuned by the presence of external stimuli such as protons or metal cations. In the absence of stimuli, these dyes show emission stemming from anionic species obtained after deprotonation (D* transition), whereas upon protonation or metal chelation, ESIPT process occurs leading to a stabilized and highly emissive K* transition. With the help of extensive ab initio calculations, we confirm that external stimuli can switch the nature of the transitions, making this series of dyes attractive candidates for the development of stimuli‐responsive fluorescent ratiometric probes. [ABSTRACT FROM AUTHOR]

Background and purpose: Late onset Pompe disease (LOPD) is a rare neuromuscular disorder caused by a deficit in acid alpha‐glucosidase. Macroglossia and swallowing disorders have already been reported, but no study has focused yet on its frequency and functional impact on patients' daily life. Methods: We reviewed 100 adult LOPD patients followed in 17 hospitals in France included in the French national Pompe disease registry. The Swallowing Quality of Life Questionnaire and the Sydney Swallow Questionnaire were completed by patients, and a specialist carried out a medical examination focused on swallowing and assigned a Salassa score to each patient. Respiratory and motor functions were also recorded. Subgroup analysis compared patients with and without swallowing difficulties based on Salassa score. Results: Thirty‐two percent of patients presented with swallowing difficulties, often mild but sometimes severe enough to require percutaneous endoscopic gastrostomy (1%). Daily dysphagia was reported for 20% of our patients and aspirations for 18%; 9.5% were unable to eat away from home. Macroglossia was described in 18% of our patients, and 11% had lingual atrophy. Only 15% of patients presenting with swallowing disorders were followed by a speech therapist. Swallowing difficulties were significantly associated with macroglossia (p = 0.015), longer duration of illness (p = 0.032), and a lower body mass index (p = 0.047). Conclusions: Swallowing difficulties in LOPD are common and have significant functional impact. Increased awareness by physicians of these symptoms with systematic examination of the tongue and questions about swallowing can lead to appropriate multidisciplinary care with a speech therapist and dietitian if needed. [ABSTRACT FROM AUTHOR]

Molecular photoswitches provide interesting tools to reversibly control various biological functions with light. Thanks to its small size and easy introduction into the biomolecules, azobenzene derivatives have been widely employed in the field of photopharmacology. All visible‐light switchable azobenzenes with controllable thermostability are highly demanded. Based on the reported tetra‐o‐chloroazobenzenes, we synthesized push‐pull systems, by introducing dialkyl amine and nitro groups as strong electron‐donating and electron‐withdrawing groups on the para‐positions, and then transformed to push‐push systems by a simple reduction step. The developed push‐pull and push‐push tetra‐o‐chloroazobenzene derivatives displayed excellent photoswitching properties, as previously reported. The half‐life of the Z‐isomers can be tuned from milliseconds for the push‐pull system to several hours for the push‐push system. The n‐π* and π‐π* transitions have better resolution in the push‐push molecules, and excitation at different wavelengths can tune the E/Z ratio at the photostationary state. For one push‐pull molecule, structure and absorption spectra obtained from theoretical calculations are compared with experimental data, along with data on the push‐push counterpart. [ABSTRACT FROM AUTHOR]

The radical Truce–Smiles rearrangement is a straightforward strategy for incorporating aryl groups into organic molecules for which asymmetric processes remains rare. By employing a readily available and non‐expensive chiral auxiliary, we developed a highly efficient asymmetric photocatalytic acyl and alkyl radical Truce–Smiles rearrangement of α‐substituted acrylamides using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom–transfer photocatalyst, along with aldehydes or C−H containing precursors. The rearranged products exhibited excellent diastereoselectivities (7 : 1 to >98 : 2 d.r.) and chiral auxiliary was easily removed. Mechanistic studies allowed understanding the transformation in which density functional theory (DFT) calculations provided insights into the stereochemistry‐determining step. [ABSTRACT FROM AUTHOR]

Valvometry techniques used to monitor bivalve gaping activity have elucidated numerous relationships with environmental fluctuations, along with biological rhythms ranging from sub-daily to seasonal. Thus, a precise understanding of the natural activity of bivalves (i.e., not exposed to stressful environmental variations) is necessary as a baseline for detecting abnormal behaviors (deviations). This knowledge is also needed to reliably interpret observations of bivalve gaping behavior and associated biological processes (e.g., respiration, nutrition) acquired over time-limited periods. With this in mind, we investigated the natural daily gaping activity of the great scallop (Pecten maximus) by continuously monitoring 35 individuals in several individual tanks and in situ (Bay of Saint-Brieuc, Brittany, France) using fully autonomous Hall effect sensors. Our results revealed a circadian cycle (τ = 24.0h) in scallop gaping activity. Despite significant inter-individual variability in mean opening and cycle amplitude, almost all individuals (87.5%) exhibited nocturnal activity, with valves more open at night than during the day. A shift in light regime in the tanks triggered an instantaneous change in opening pattern, indicating that light levels strongly determine scallop activity. Based on the opening status of scallops, we also identified several gaping behaviors deviating from the regular daily pattern (lack of rhythmicity, high daytime opening), potentially reflecting physiological weakness. While further long-term studies are required to fully understand the natural activity of scallops, these findings pave the way for studies focused on the scallop response to external factors and introduce further research into the detection of abnormal behaviors. Coupling observations of diel valve gaping cycles with other daily variations in organismal and environmental parameters could help explain mechanisms driving the growth patterns of scallops observed in their shell striations. From a technical perspective, our field-based monitoring demonstrates the suitability of autonomous valvometry sensors for studying mobile subtidal bivalve activity in remote offshore environments.

Visualisation of TARP localisation is hindered by existing imaging tools. Here the authors report a labelling and imaging platform using genetic code expansion and non-canonical amino acids; they use this to fluorescently label live neurons and localise TARP proteins using super resolution microscopy.

The majority of Earth volcanism takes place in the deep ocean. Deep-sea volcanoes are particularly complicated to study due to their remoteness. Very different methods can be used and their combination can lead to crucial information about submarine volcanoes behavior. In Mayotte, Comoros archipelago, efforts have been made to study and monitor the deep volcanic activity (∼3000 m) currently occurring east of Mayotte through various methods and campaigns on land and at sea. In October 2020, a line of 10 Ocean Bottom Seismometers was deployed during 10 days, leading to a hand-picked catalog of more than a thousand of hydro-acoustic signals, which have been associated with reactions between hot lava and deep cold ocean waters. During the same period, repeated swath bathymetry surveys were performed over an active lava flow field. We compare the time evolution of the hydro-acoustic events locations and bathymetry differences observed between each survey. While bathymetric information gives absolute location of new lava flows, hydro-acoustic events give detailed relative time variations leading to short-term spatial evolution. Bathymetric information thus provides snapshots of the eruptive area evolution at specific times, when hydro-acoustic signals show its continuous evolution. By combining both complementary analyses we are able to clearly define the detailed evolution of the lava flows pattern in the short time period of 10 days. Applied to the data already acquired on Mayotte since 2019, this method could allow us to estimate more precisely the volcano effusion rate and its evolution, giving further insights on the feeding system.

The United Nations (UN) Sendai Framework for Disaster Risk Reduction 2015–2030 aims to mitigate natural disasters, specifically in developing regions. It promotes the adoption of people-centered disaster risk reduction approaches. Hence, citizen science represents an interesting tool to engage populations in the mitigation of disaster risk, through data collection and analysis, and in the dissemination of scientific and safety information. Herein, we evaluate the potential and feasibility of a citizen science project on the island of Mayotte (in the Mozambique Channel). Mayotte has been experiencing an unexpected volcano-seismic crisis since 2018, which has generated strong anxiety in the population. To address this, we have developed a citizen seismology program to engage Mayotte’s inhabitants in seismic data processing. First, we conducted an initial test of our protocol to identify seismic events with a set of university students. We then conducted 15 interviews with members of local administrations and associations to assess the potential for engaging the general population in this project. The results show that we are able to collect reliable data from citizens with non-professional backgrounds using the protocol designed in the project. We also show a strong demand for scientific information from Mayotte’s inhabitants, associated with a robust trust in science and scientists, despite the circulation of alternative explanations for the seismicity among the population. Based on these results, our citizen science project could be positively received by Mayotte’s inhabitants, if advertised adequately. Finally, we discuss the value of these results for disaster risk reduction in vulnerable territories.

The title molecular structure, namely, diaquatris(μ3-1,3-bis{[1-(2-oxidophenyl)ethylidene]amino}propan-2-olato)-μ3-hydroxido-dinitratohexacopper(II) ethanol trisolvate, [Cu6(C19H19N2O3)3(NO3)2(OH)(H2O)2]·3C2H5OH, corresponds to a non-symmetric hexanuclear copper complex. The complex exhibits one core in which three CuII metal centres are mutually interconnected, two by two, via three phenolato oxygen anions acting in a μ2-mode. These three copper cations are interconnected in a μ3-mode by one hydroxyl group. An open-cube structure is generated in which each of the CuII cations of the three CuO4N units is connected by two μ2-O anions from phenolate groups and one μ3-O atom from a hydroxy anion. Each of the three pentacoordinated CuII cations situated in the open-cube unit has a distorted NO4 square-pyramidal environment. Each of these three CuII centres is interconnected with another CuII cation via one enolate O atom in μ2-mode, yielding one CuNO4 unit and two CuNO3 units. The pentacoordinated CuII atom has a distorted square-pyramidal environment while the two tetracoordinated copper(II) cations are situated in a square-planar environment. A series of intramolecular O—H...O hydrogen bonds are observed. In the crystal, the units are connected two by two by intermolecular C—H...O and O—H...O hydrogen bonds, thus forming sheets parallel to the ac plane.

The synthesis and crystallization of 2,3,5-tri-O-benzyl-d-xylofuranose permitted us to isolate the alpha anomer with a small contamination of the beta form (ca 10%), whose first crystallographic structure obtained in the P212121 space group was determined at 100 K up to a resolution of sin θmax/λ = 0.71 Å−1 and refined to an R1 value of 0.0171 with a Hirshfeld atom refinement (HAR) approach.