Search

Nonhost resistance is the outcome of most plant/pathogen interactions, but it has rarely been described in Rosaceous fruit species. Apple (Malus x domesticaBorkh.) have a nonhost resistance toVenturia pyrina, the scab species attacking European pear (Pyrus communisL.). Reciprocally,P. communishave a nonhost resistance toVenturia inaequalis, the scab species attacking apple. The major objective of our study was to compare the scab nonhost resistance in apple and in European pear, at the phenotypic and transcriptomic levels. Macro- and microscopic observations after reciprocal scab inoculations indicated that, after a similar germination step, nonhost apple/V. pyrinainteraction remained nearly symptomless, whereas more hypersensitive reactions were observed during nonhost pear/V. inaequalisinteraction. Comparative transcriptomic analyses of apple and pear nonhost interactions withV. pyrinaandV. inaequalis, respectively, revealed differences. Very few differentially expressed genes were detected during apple/V. pyrinainteraction, preventing the inferring of underlying molecular mechanisms. On the contrary, numerous genes were differentially expressed during pear/V. inaequalisinteraction, allowing a deep deciphering. Pre-invasive defense, such as stomatal closure, could be inferred, as well as several post-invasive defense mechanisms (apoplastic reactive oxygen species accumulation, phytoalexin production and alterations of the epidermis composition). In addition, a comparative analysis between pear scab host and nonhost interactions indicated that, although specificities were observed, two major defense lines seems to be shared in these resistances: cell wall and cuticle potential modifications and phenylpropanoid pathway induction. This first deciphering of the molecular mechanisms underlying a nonhost scab resistance in pear offers new possibilities for the genetic engineering of sustainable scab resistance in this species. Concerning nonhost scab resistance in apple, further analyses must be considered with the aid of tools adapted to this resistance with very few cells engaged.

International audience; Nowadays, Thermally Activated Delayed Fluorescence (TADF) compounds have proven to be attractive for highly efficient optoelectronic devices as they can exploit both singlet and triplet excited states generated by charge recombinations that occur in such devices. However, quenching of excited states limits such benefits at high current densities. We have studied the quenching in the case of cationic copper(I) complexes coordinated by both N-heterolytic carbene (NHC) and 2,2′-dipyridylamine (dpa) ligands. Defects are created in their crystals by a strong laser irradiation. Then we have investigated, by analysing their fluorescence decay as a function of temperature, the quenching mechanism and the exciton mobility. Using a time-resolved version of the Perrin’s quenching model, we show that the quenching volume depends on temperature according to the singlet/triplet equilibrium. At room temperature, the singlet states are responsible for 75% of the quenching although they contribute for 2% to the excited states population. From the analysis of the decay curves, we show that the excitons are not mobile in the crystals and are quenched through Förster Resonant Energy Transfer (FRET).

We report a visible-light-induced iron-catalyzed α-alkylation of ketones. The photocatalytic system is based on the single diaminocyclopentadienone iron tricarbonyl complex. Two catalytic intermediates of this complex are able to harvest light, allowing the synthesis of substituted aromatic and aliphatic ketones at room temperature using the borrowing hydrogen strategy in the presence of various substituted primary alcohols as alkylating reagents. Preliminary mechanistic studies unveil the role of light for both the dehydrogenation and reduction step.

International audience; The development of highly efficient plastic scintillators for neutron/gamma pulse shape discrimination is a matter of current interest. This is generally achieved using two fluorophores, with one of them being added to the polymer formulation at a concentration higher than typically 15 weight percent (wt%). Here, we report our results concerning the development of highly performant poly(vinyltoluene)-based (PVT) plastic scintillators for efficient fast neutron/gamma pulse shape discrimination, using 1-phenyl-3-(mesityl)-2-pyrazoline (1) as the only guest fluorophore. On our route during this study, the synthesis of the compound 1 has been revisited. Analysis and evaluation of the radioluminescence properties of these novel PVT-based plastic scintillators containing compound 1 are also described. In particular their light output and neutron/gamma discrimination ability were characterized. The sample doped with 15 wt% of compound 1 has a light output of 0.65 relative to EJ-200 and a neutron/gamma discrimination figure of merit of 0.84 in the range 450–500 keVee.

The cryptophyte Teleaulax amphioxeia is a source of plastids for the ciliate Mesodinium rubrum and both organisms are members of the trophic chain of several species of Dinophysis. It is important to better understand the ecology of organisms at the first trophic levels before assessing the impact of principal factors of global change on Dinophysis spp. Therefore, combined effects of temperature, irradiance, and pH on growth rate, photosynthetic activity, and pigment content of a temperate strain of T. amphioxeia were studied using a full factorial design (central composite design 23 *) in 17 individually controlled bioreactors. The derived model predicted an optimal growth rate of T. amphioxeia at a light intensity of 400 μmol photons · m-2 · s-1 , more acidic pH (7.6) than the current average and a temperature of 17.6°C. An interaction between temperature and irradiance on growth was also found, while pH did not have any significant effect. Subsequently, to investigate potential impacts of prey quality and quantity on the physiology of the predator, M. rubrum was fed two separate prey: predator ratios with cultures of T. amphioxeia previously acclimated at two different light intensities (100 and 400 μmol photons · m-2 s-1 ). M. rubrum growth appeared to be significantly dependent on prey quantity while effect of prey quality was not observed. This multi-parametric study indicated a high potential for a significant increase of T. amphioxeia in future climate conditions but to what extent this would lead to increased occurrences of Mesodinium spp. and Dinophysis spp. should be further investigated.

ObjectivesMedical compression therapy is used for non-invasive treatment of venous and lymphatic diseases. Medical compression therapy-associated adverse events and contraindications have been reported, although some contraindications are theoretically based. This consensus statement provides recommendations on medical compression therapy risks and contraindications.MethodsA systematic literature search of medical compression therapy publications reporting adverse events up until November 2017 was performed. A consensus panel comprising 15 international experts critically reviewed the publications and formulated the recommendations.ResultsSixty-two publications reporting medical compression therapy adverse events were identified. The consensus panel issued 21 recommendations on medical compression therapy contraindications and adverse event risk mitigation, in addition to reviewing medical compression therapy use in borderline indications. The most frequently reported non-severe medical compression therapy-associated adverse events included skin irritation, discomfort and pain. Very rare but severe adverse events, including soft tissue and nerve injury, were also identified.ConclusionThis consensus statement summarises published medical compression therapy-associated adverse events and contraindications, and provides guidance on medical compression therapy. Severe medical compression therapy-associated adverse events are very rarely encountered if compression is used correctly and contraindications are considered.

The reductive amination process under hydrogen at high pressure catalyzed by iron complexes is of great synthetic interest. In this work, we report Density Functional Theory (DFT) studies on the reductive amination catalyzed by a Knölker-type iron complex. Different modifications of the catalyst are explored to improve the efficiency and guide experiments towards milder conditions. DFT calculations in conjunction with analysis of the chemical structure in terms of geometry, fragment partial charges, Effective Oxidation States (EOS) and aromaticity, allows to conclude that the presence of electron-withdrawing substituents on the cyclopentadienone ring induces a decrease of the activation barriers of most relevant steps, leading to a more efficient catalysis. The present work is a clear example that predictive catalysis can have a fundamental role in sustainable catalytic transformations S.G., N.J., and J.-L.R. gratefully acknowledge financial support from the “Ministere de la Recherche et des Nouvelles ̀ Technologies”, Normandie Université, CNRS, and the LABEX SynOrg (ANR-11-LABX-0029). N.J. acknowledges the Graduate School of Research XL-Chem (ANR-18-EURE0020 XL-Chem) for the PhD fellowship. A.P., P.S., and M.S. thank the Ministerio de Economía y Competitividad (MINECO) of Spain for projects PGC2018-097722-B-I00, PGC2018-098212-B-C22, and PID2020-13711GB-I00 and Generalitat de Catalunya for projects 2017SGR39 and ICREA Academia prize 2019. A.P. is a Serra Hunter fellow. ́ M.G. thanks the Generalitat de Catalunya and Fons Social Europeu for the predoctoral fellowship (2018 FI_B01120). S.E. thanks Universitat de Girona and Donostia International Physics Center (DIPC) for an IFUdG2019 predoctoral fellowship Open Access funding provided thanks to the CRUE-CSIC agreement with ACS

BackgroundScab is the most important fungal disease of apple and pear. Apple (Malus x domesticaBorkh.) and European pear (Pyrus communisL.) are genetically related but they are hosts of two different fungal species:Venturia inaequalisfor apple andV. pyrinafor European pear. The apple/V. inaequalispathosystem is quite well known, whereas knowledge about the pear/V. pyrinapathosystem is still limited. The aim of our study was to analyse the mode of action of a major resistance gene of apple (Rvi6) in transgenic apple and pear plants interacting with the two scab species (V. inaequalisandV. pyrina), in order to determine the degree of functional transferability between the two pathosystems.ResultsTransgenic pear clones constitutively expressing theRvi6gene from apple were compared to a scab transgenic apple clone carrying the same construct. After inoculation in greenhouse withV. pyrina, strong defense reactions and very limited sporulation were observed on all transgenic pear clones tested. Microscopic observations revealed frequent aborted conidiophores in theRvi6transgenic pear /V. pyrinainteraction. The macro- and microscopic observations were very comparable to theRvi6apple /V. inaequalisinteraction. However, this resistance in pear proved variable according to the strain ofV. pyrina, and one of the strains tested overcame the resistance of most of the transgenic pear clones. Comparative transcriptomic analyses of apple and pear resistant interactions withV. inaequalisandV. pyrina, respectively, revealed different cascades of molecular mechanisms downstream of the pathogen recognition byRvi6in the two species. Signal transduction was triggered in both species with calcium (and G-proteins in pear) and interconnected hormonal signaling (jasmonic acid in pear, auxins in apple and brassinosteroids in both species), without involvement of salicylic acid. This led to the induction of defense responses such as a remodeling of primary and secondary cell wall, lipids biosynthesis (galactolipids in apple and cutin and cuticular waxes in pear), systemic acquired resistance signal generation (in apple) or perception in distal tissues (in pear), and the biosynthesis of phenylpropanoids (flavonoids in apple but also lignin in pear).ConclusionThis study is the first example of a successful intergeneric transfer of a resistance gene amongRosaceae, with a resistance gene functioning towards another species of pathogen.

Purpose This paper aims to describe coupon tests performed at elevated temperatures on S355 to S500 steel grades and comparison of test results with previous research studies and current EN 1993-1-2 material laws. The objective is to state if these steel grades satisfy to the current material laws and if the scope of application of these laws could be extended to S500 grades. Design/methodology/approach Two experimental programmes were launched to investigate the behaviour of S460M and S500M steel grades developed for hot-rolled sections. The first research programme was focussed on a comparison between S355 and S460 grades, where the second experimental programme was focussed on the recently developed S500M steel grade. The latter one comprised steady-state tests, transient-state tests and two large-scale beam tests. Findings Results of steady-state and transient-state tests correlate well with the reduction factors defined in EN 1993-1-2, currently limited to S460 grade. On the basis of this study, the scope of EN 1993-1-2 applies to S500 grades. For steady-state tests, the testing procedure (with and without acceleration after Rp0,2) led to noticeable differences. Transient-state tests, which are not standardised up to now, have been performed considering 5 K/min and 10 K/min constant heating rates. The slowest rate leads to lower strengths as creep effects are more significant. However, all the results are in line with EN 1993-1-2 material law. Importance should be given to the reference yield strength of steel at ambient temperature. Originality/value The revision of EN 1993-1-2 is on-going and this piece of work provides a contribution for extending the scope of application of material law of steel under fire conditions.

We report herein the biological activities of several imidazolium aurate(I) salts. The cytotoxicity on three cell-lines (i. e. Hela, H460 and 3T3), enzyme inhibition on a panel of five enzymes (i. e. prolyl endopeptidase, butyrylcholinesterase, tyrosinase, dipeptidyl peptidase and carbonic anhydrase), iron chelation and in vitro Leishmanicidal assay for promastigotes are described. A comparison with other data found in the literature using similar standards to our control experiment is also discussed. Finally, all these data lead us to establish some structure-activity correlations and to determine the potential importance of the gold moiety in these salts.

International audience; A transition-metal frustrated Lewis pair approach has been envisaged to enhance the catalytic activity of tricarbonyl phosphine-free iron complexes in reduction of amines. A new cyclopentadienyl iron(II) tricarbonyl complex has been isolated, fully characterized, and applied in hydrogenation. This phosphine-free iron complex is the first Earth-abundant metal complex that is able to catalyze chemoselective reductive alkylation of various functionalized amines with functionalized aldehydes. Such selectivity and functionality tolerance (alkenes, esters, ketones, acetals, unprotected hydroxyl groups, and phosphines) have been demonstrated also for the first time at room temperature with an Earth-abundant metal complex. This alkylation reaction was also performed without any preliminary condensation and generated only water as a byproduct. The resulting amines provided rapid access to potential building blocks, metal ligands, or drugs. Density functional theory calculations highlighted first that the formation of the 16 electron species, via the activation of the tricarbonyl complex Fe3, was facilitated and, second, that the hydrogen cleavage did not follow the same pathway as bond breaking, usually described with the known cyclopentadienone iron tricarbonyl complexes (Fe1 and Fe4). These calculations highlighted that the new complex Fe3 does not behave as a bifunctional catalyst, in contrast to its former congeners.

International audience; The borrowing hydrogen strategy has been applied in the synthesis of α-branched methylated ketones via a tandem three-component reaction catalyzed by a diaminocyclopentadienone iron tricarbonyl complex. Various alkyl and aromatic methyl ketones underwent dialkylation with various primary alcohols and methanol as alkylating agents in mild reaction conditions and good yields. Deuterium labeling experiments suggested that the benzylic alcohol was the hydrogen source in this tandem process.

International audience; The synthesis of a broad variety of hetero- and carbocyclic scaffolds via a Pd-catalyzed domino Heck/SO¬2 insertion reaction is reported. This reaction utilizes DABSO, a safe and easy-to-handle alternative to SO2 gas. The reaction pro-ceeds through a sulfinate intermediate, which can act as a lynchpin for the in-situ generation of sulfones, sulfona-mides, and sulfonyl fluorides. Good yields and scalability are demonstrated

Herein we report a diaminocyclopentadienone iron tricarbonyl complex catalyzed synthesis of substituted cyclopentane, cyclohexane and cycloheptane compounds using the borrowing hydrogen strategy in the presence of various substituted primary and secondary 1,n diols as alkylating reagents. Deuterium labeling experiments confirm that the diols were the hydride source in this cascade process.

International audience; Herein we report a diaminocyclopentadienone iron tricarbonyl complex catalyzed synthesis of substituted cyclopentane, cyclohexane and cycloheptane compounds using the borrowing hydrogen strategy in the presence of various substituted primary and secondary 1,n diols as alkylating reagents. Deuterium labeling experiments confirm that the diols were the hydride source in this cascade process

The use of ball-mills enabled the straightforward synthesis of a variety of silver(I) complexes featuring challenging NHC ligands. Sterically hindered including electron-poor or with very low solubility imidazolium salts were grinded with silver(I) oxide to furnish heteroleptic or homoleptic complexes in high yield and short reaction times. The synthesis of heteroleptic bis-NHC silver(I) complexes was also performed for the first time in a ball-mill. The efficiency and rapidity of the mechanochemical approach enabled the generation of a library of unprecedented NHC silver complexes, which cytotoxicity on HCT116 colorectal cancer cell line was evaluated providing a rare example of medicinal mechanochemistry. The cationic silver complexes were found more potent than the neutral analogues, with IC50 values down to 21 nM, 256 times more potent than cisplatin.; The use of ball-mills enabled the straightforward synthesis of a variety of silver(I) complexes featuring challenging NHC ligands. Sterically hindered including electron-poor or with very low solubility imidazolium salts were grinded with silver(I) oxide to furnish heteroleptic or homoleptic complexes in high yield and short reaction times. The synthesis of heteroleptic bis-NHC silver(I) complexes was also performed for the first time in a ball-mill. The efficiency and rapidity of the mechanochemical approach enabled the generation of a library of unprecedented NHC silver complexes, which cytotoxicity on HCT116 colorectal cancer cell line was evaluated providing a rare example of medicinal mechanochemistry. The cationic silver complexes were found more potent than the neutral analogues, with IC50 values down to 21 nM, 256 times more potent than cisplatin.

Dinoflagellates of the genus Dinophysis are the most prominent producers of Diarrhetic Shellfish Poisoning (DSP) toxins which have an impact on public health and on marine aquaculture worldwide. In particular, Dinophysis acuminata has been reported as the major DSP agent in Western Europe. Still, its contribution to DSP events in the regions of the English Channel and the Atlantic coast of France, and the role of the others species of the Dinophysis community in these areas are not as clear. In addition, species identification within the D. acuminata complex has proven difficult due to their highly similar morphological features. In the present study, 30 clonal strains of the dominant Dinophysis species have been isolated from French coasts including the English Channel (3 sites), the Atlantic Ocean (11 sites) and the Mediterranean Sea (6 sites). Morphologically, strains were identified as three species: D. acuta, D. caudata, D. tripos, as well as the D. acuminata-complex. Sequences of the ITS and LSU rDNA regions confirmed these identifications and revealed no genetic difference within the D. acuminata-complex. Using the mitochondrial gene cox1, two groups of strains differing by only one substitution were found in the D. acuminata-complex, but SEM analysis of various strains showed a large range of morphological variations. Based on geographical origin and morphology, strains of the subclade A were ascribed to ‘D. acuminata’ while those of the subclade B were ascribed to ‘D. sacculus’. Nevertheless, the distinction into two separate species remains questionable and was not supported by our genetic data. The considerable variations observed in cultured strains suggest that physiological factors might influence cell contour and bias identification. Analyses of Dinophysis cultures from French coastal waters using liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) revealed species-conserved toxin profiles for D. acuta (dinophysistoxin 2 (DTX2), okadaic acid (OA), pectenotoxin 2 (PTX2)), D. caudata (PTX2) and D. tripos (PTX2), irrespective of geographical origin (Atlantic Ocean or Mediterranean Sea). Within the D. acuminata-complex, two different toxin profiles were observed: the strains of ‘D. acuminata’ (subclade A) from the English Channel and the Atlantic Ocean contained only OA while strains of ‘D. sacculus’ (subclade B) from Mediterranean Sea/Atlantic Ocean contained PTX2 as the dominant toxin, with OA and C9-esters also being present, albeit in lower proportions. The same difference in toxin profiles between ‘D. sacculus’ and ‘D. acuminata’ was reported in several studies from Galicia (NW- Spain). This difference in toxin profiles has consequences in terms of public health, and consequently for monitoring programs. While toxin profile could appear as a reliable feature separating ‘D. acuminata’ from ‘D. sacculus’ on both French and Spanish coasts, this does not seem consistent with observations on a broader geographical scale for the D. acuminata complex, possibly due to the frequent lack of genetic characterization.

The first aminomethylation of oxabenzonorbornadienes using dual photoredox/nickel catalysis has been disclosed. This cascade reaction allowed the preparation of the cis-aminomethyl dihydronaphthale...

An iron-catalyzed borrowing hydrogen strategy has been applied in the synthesis of β-branched carbonyl compounds. Various secondary benzylic and aliphatic alcohols have been used as alkylating reagents under mild reaction conditions. The ketones have been isolated in good to excellent yield. Deuterium labeling experiments provide evidence that the alcohol is the hydride source in this reaction and that no reversible step or hydrogen/deuterium scrambling takes place during the process.

The development of efficient and low-cost catalytic systems is important for the replacement of the robust noble metal complexes. A highly efficient, stable, phosphine-free, and easy-to-synthesize ...

International audience; We report a new artificial hydrogenase made by covalent anchoring of the iron Knölker's complex to a xylanase S212C variant. This artificial metalloenzyme was found to be able to catalyze efficiently the transfer hydrogenation of the benchmark substrate trifluoroacetophenone by sodium formate in water, yielding the corresponding secondary alcohol as a racemic. The reaction proceeded more than threefold faster with the XlnS212CK biohybrid than with the Knölker's complex alone. In addition, efficient conversion of trifluoroacetophenone to its corresponding alcohol was reached within 60 H with XlnS212CK, whereas a 2.5-fold lower conversion was observed with Knölker's complex alone as catalyst. Moreover, the data were rationalized with a computational strategy suggesting the key factors of the selectivity. These results suggested that the Knölker's complex was most likely flexible and could experience free rotational reorientation within the active-site pocket of Xln A, allowing it to access the subsite pocket populated by trifluoroacetophenone.

International audience; The development of efficient and low-cost catalytic systems is important for the replacementof robust noble metal complexes. The synthesis and application of a stable, phosphine-free,water-soluble cyclopentadienone iron tricarbonyl complex in the reduction of polarized doublebonds in pure water is reported. In the presence of cationic bifunctional iron complexes, a variety ofalcohols and amines were prepared in good yields under mild reaction conditions.

This review focuses on the state‐of‐the‐art of solid‐state lighting devices (SSLDs)—that is, organic light‐emitting diodes (OLEDs) and light‐emitting electrochemical cells (LECs)—prepared with transition metal complexes featuring thermally activated delayed fluorescence (TADF) mechanism. First, the TADF mechanism is briefly introduced, as well as the experimental and theoretical methods applied to study TADF in transition metal complexes. Second, the review presents an exhaustive overview of OLED and LEC devices incorporating organometallic TADF emitters. For each type of device, the description of TADF is organized by respective elements focusing on each emission color, that is, blue, green/yellow, orange/red and, if existing, white. Finally, insights and future potential development of organometallic TADF emitters for lighting devices are comprehensively discussed. Overall, this review complements recent ones focused on TADF small molecules applied to the SSLD field., This work was supported by the “Ministère de la Recherche et des Nouvelles Technologies,” CNRS (Centre National de la Recherche Scientifique), and the LABEX SynOrg (ANR‐11‐LABX‐0029). The authors thank Normandie University (G.U.M.) for funding. R.D.C. acknowledges the program “Ayudas para la atracción de talento investigador – Modalidad 1 of the Consejería de Educación, Juventud y Deporte—Comunidad de Madrid with the reference number 2016‐T1/IND‐1463.” R.D.C. acknowledges Spanish MINECO for the Ramón y Cajal program (RYC‐2016‐20891), the Europa Excelencia program (ERC2019‐092825), the 2018 Leonardo Grant for Researchers and Cultural Creators from BBVA Foundation, and FOTOART‐CM project funded by Madrid region under programme P2018/NMT‐4367. J.F.‐C. acknowledges the Marie Skłodowska‐Curie Individual Fellowships (H2020‐MSCA‐IF‐2017).

The cryptophyte Teleaulax amphioxeia is a source of plastids for the ciliate Mesodinium rubrum and both organisms are members of the trophic chain of several species of Dinophysis. It is important to better understand the ecology of organisms at the first trophic levels before assessing the impact of principal factors of global change on Dinophysis spp. Therefore, combined effects of temperature, irradiance, and pH on growth rate, photosynthetic activity, and pigment content of a temperate strain of T. amphioxeia were studied using a full factorial design (central composite design 2

Objective Medical compression stockings are a standard, non-invasive treatment option for all venous and lymphatic diseases. The aim of this consensus document is to provide up-to-date recommendations and evidence grading on the indications for treatment, based on evidence accumulated during the past decade, under the auspices of the International Compression Club. Methods A systematic literature review was conducted and, using PRISMA guidelines, 51 relevant publications were selected for an evidence-based analysis of an initial 2407 unrefined results. Key search terms included: ‘acute', CEAP', ‘chronic', ‘compression stockings', ‘compression therapy', ‘lymph', ‘lymphatic disease', ‘vein' and ‘venous disease'. Evidence extracted from the publications was graded initially by the panel members individually and then refined at the consensus meeting. Results Based on the current evidence, 25 recommendations for chronic and acute venous disorders were made. Of these, 24 recommendations were graded as: Grade 1A (n = 4), 1B (n = 13), 1C (n = 2), 2B (n = 4) and 2C (n = 1). The panel members found moderately robust evidence for medical compression stockings in patients with venous symptoms and prevention and treatment of venous oedema. Robust evidence was found for prevention and treatment of venous leg ulcers. Recommendations for stocking-use after great saphenous vein interventions were limited to the first post-interventional week. No randomised clinical trials are available that document a prophylactic effect of medical compression stockings on the progression of chronic venous disease (CVD). In acute deep vein thrombosis, immediate compression is recommended to reduce pain and swelling. Despite conflicting results from a recent study to prevent post-thrombotic syndrome, medical compression stockings are still recommended. In thromboprophylaxis, the role of stockings in addition to anticoagulation is limited. For the maintenance phase of lymphoedema management, compression stockings are the most important intervention. Conclusion The beneficial value of applying compression stockings in the treatment of venous and lymphatic disease is supported by this document, with 19/25 recommendations rated as Grade 1 evidence. For recommendations rated with Grade 2 level of evidence, further studies are needed.

International audience; Dinophysis is the main dinoflagellate genus responsible for diarrheic shellfish poisoning (DSP) in human consumers of filter feeding bivalves contaminated with lipophilic diarrheic toxins. Species of this genus have a worldwide distribution driven by environmental conditions (temperature, irradiance, salinity, nutrients etc.), and these factors are sensitive to climate change. The D. acuminata-complex may contain several species, including D. sacculus. The latter has been found in estuaries and semi-enclosed areas, water bodies subjected to quick salinity variations and its natural repartition suggests some tolerance to salinity changes. However, the response of strains of D. acuminata-complex (D. cf. sacculus) subjected to salinity stress and the underlying mechanisms have never been studied in the laboratory. Here, a 24 h hypoosmotic (25) and hyperosmotic (42) stress was performed in vitro in a metabolomic study carried out with three cultivated strains of D. cf. sacculus isolated from the French Atlantic and Mediterranean coasts. Growth rate, biovolume and osmolyte (proline, glycine betaine and dimethylsulfoniopropionate (DMSP)) and toxin contents were measured. Osmolyte contents were higher at the highest salinity, but only a significant increase in glycine betaine was observed between the control (35) and the hyperosmotic treatment. Metabolomics revealed significant and strain-dependent differences in metabolite profiles for different salinities. These results, as well as the absence of effects on growth rate, biovolume, okadaic acid (OA) and pectenotoxin (PTXs) cellular contents, suggest that the D. cf. sacculus strains studied are highly tolerant to salinity variations.

A Diaminocyclopentadienone iron tricarbonyl complex has been applied in chemoselective hydrogen transfer reductions. This bifunctional iron complex demonstrated a broad applicability in mild conditions in various reactions, such as reduction of aldehydes over ketones, reductive alkylation of various functionalized amines with functionalized aldehydes and reduction of α,β-unsaturated ketones into the corresponding saturated ketones. A broad range of functionalized substrates has been isolated in excellent yields with this practical procedure.

International audience; β-Branched alkylated alcohols have been prepared in good yields using a double-hydrogen autotransfer strategy in the presence of our diaminocyclopentadienone iron tricarbonyl complex Fe1. The alkylation of some 2-arylethanol derivatives was successfully addressed with benzylic alcohols and methanol as alkylating reagents under mild conditions. Deuterium labeling experiments suggested that both alcohols (2-arylethanol and either methanol or benzyl alcohol) served as hydrogen donors in this cascade process.

International audience; Cytotoxicity of cationic (NHC)Cu(I) complexes bearing 2,2′-dipyridylamine (dpa) type ligands has been evaluated toward 4 cancer cell lines, and compared to the one of neutral (NHC)Cu(I) complexes. The high cytotoxicity of these novel cationic (NHC)Cu(I) complexes, combined with the straightforward synthesis, and versatility of dpa type ligands may offer new prospects in cancer research, toward the development of novel carrier linked prodrugs.

International audience; The hydrogenation of carbon dioxide into formic acid (FA) with Earth-abundant metals is a vibrant research area because FA is an attractive molecule for hydrogen storage. We report a cyclopentadienyl iron tricarbonyl complex that provides up to 3000 turnover number for carbon dioxide hydrogenation when combined with a catalytic amount of the chromium dicarboxylate MOF MIL-53(Cr). To date, this is the highest turnover number reported in the presence of a phosphine-free iron complex.

International audience; 2,2'-Dipyridylamine (dpa) and related compounds belong to the family of polydentate nitrogen ligands. More than a century has passed since its first report but new complexes and applications have been emerging in the recent years owing to the versatility of dpa-based architectures. This review aims to present and highlight the main achievements attained with dpa-containing metal complexes in the domains of homogeneous catalysis and luminescent materials.

International audience; Cyclopentadienone iron carbonyl complexes have been applied in alkylation of indoles with various benzylic alcohols, aliphatic alcohols (butanol, ethanol, methanol and 2‐methylpentanol) via the hydrogen autotransfer strategy in mild reaction conditions. Experimental works highlight the role of the bifunctional iron complexes and the base. These iron complexes demonstrated a broad applicability in mild conditions and extended the scope of substrates in iron catalyzed C−C bond formation.

Complexes with non-noble metals are becoming more and more important in organometallic and organic chemistry. This mini-review covers the recent progress in cobalt- and iron-catalyzed consecutive reactions involving at least one hydrogenation step. 1 Introduction 2 Synthesis of the Iron and Cobalt Complexes 2.1 Synthesis of the Iron Complexes 2.2 Synthesis of the Cobalt Complexes 3 Hydrogenation of Carboxylic and Carbonic Compounds 3.1 Hydrogenation of Esters and Amides 3.2 Hydrogenation of Nitriles 3.3 Hydrogenation of Carbon Dioxide and Carbonates 3.3.1 Hydrogenation of Carbon Dioxide 3.3.2 Hydrogenation of Carbonate and Bicarbonate 4 Processes Involving a Hydrogenation Step 4.1 Reductive Amination 4.2 Alkylation of Amines 4.3 Alkylation of Ketones 4.4 Alkylation of Allylic Alcohols 5 Conclusion

We report on the synthesis of biotinylated (cyclopentadienone)iron tricarbonyl complexes, the in situ generation of the corresponding streptavidin conjugates and their application in asymmetric hydrogenation of imines and ketones.

International audience; Harmful algal blooms (HABs) of toxic species of the dinoflagellate genus Dinophysis are a threat to human health as they are mainly responsible for diarrheic shellfish poisoning (DSP) in the consumers of contaminated shellfish. Such contamination leads to shellfish farm closures causing major economic and social issues. The direct effects of numerous HAB species have been demonstrated on adult bivalves, whereas the effects on critical early life stages remain relatively unexplored. The present study aimed to determine the in vitro effects of either cultivated strains of D. sacculus and D. acuminata isolated from France or their associated toxins (i.e. okadaic acid (OA) and pectenotoxin 2 (PTX2)) on the quality of the gametes of the Pacific oyster Crassostrea gigas. This was performed by assessing the ROS production and viability of the gametes using flow cytometry, and fertilization success using microscopic counts. Oocytes were more affected than spermatozoa and their mortality and ROS production increased in the presence of D. sacculus and PTX2, respectively. A decrease in fertilization success was observed at concentrations as low as 0.5 cell mL-1 of Dinophysis spp. and 5 nM of PTX2, whereas no effect of OA could be observed. The effect on fertilization success was higher when both gamete types were concomitantly exposed compared to separate exposures, suggesting a synergistic effect. Our results also suggest that the effects could be due to cell-to-cell contact. These results highlight a potential effect of Dinophysis spp. and PTX2 on reproduction and recruitment of the Pacific oyster.

International audience; An iron(0) complex bearing a cyclopentadienone ligand catalyzed N-methylation and N-ethylation of aryl and aliphatic amines with methanol or ethanol in mild and basic conditions through a hydrogen autotransfer borrowing process is reported. A broad range of aromatic and aliphatic amines underwent mono- or dimethylation in high yields. DFT calculations suggest molecular hydrogen acts not only as a reducing agent but also as an additive to displace thermodynamic equilibria.

International audience; Recently, the use of a new family of electroluminescent copper(I) complexes—i.e., the archetypal [Cu(IPr)(3‐Medpa)][PF6] complex; IPr: 1,3‐bis‐(2,6‐di‐iso‐propylphenyl)imidazole‐2‐ylidene; 3‐Medpa: 2,2′‐bis‐(3‐methylpyridyl)amine—has led to blue light‐emitting electrochemical cells (LECs) featuring luminances of 20 cd m−2, stabilities of 4 mJ, and efficiencies of 0.17 cd A−1. Herein, this study rationalizes how to enhance these figures‐of‐merit optimizing both device fabrication and design. On one hand, a comprehensive spectroscopic and electrochemical study reveals the degradation of this novel emitter in common solvents used for LEC fabrication, as well as the impact on the photoluminescence features of thin‐films. On the other hand, spectro‐electrochemical and electrochemical impedance spectroscopy assays suggest that the device performance is strongly limited by the irreversible formation of oxidized species that mainly act as carrier trappers and luminance quenchers. Based on all of the aforementioned, device optimization was realized using ionic additives and a hole transporter either as a host–guest or as a multilayered architecture approach to decouple hole/electron injection. The latter significantly enhances the LEC performance, reaching luminances of 160 cd m−2, stabilities of 32.7 mJ, and efficiencies of 1.2 cd A−1. Overall, this work highlights the need of optimizing both device fabrication and design toward highly efficient and stable LECs based on cationic copper(I) complexes.

International audience; An iron‐catalyzed chemo‐ and diastereoselective reduction of α,β‐unsaturated ketones into the corresponding saturated ketones in mild reaction conditions is reported herein. DFT calculations and experimental work underline that transfer hydride reduction is a more facile process than hydrogenation, unveiling the fundamental role of the base.

International audience; In this minireview, a state of the art of the NHC transition metal complexes applied in two different modern technologies for lightening applications, namely Organic Light Emitting Diodes (OLEDs) and Light-Emitting Electrochemical Cells (LECs), is presented. In each technology, the different transition metal centres studied are described and the advantages brought by the NHC ligands in terms of electronic and steric properties is discussed. Devices obtained with these complexes are also presented and the stability and their efficiencies are also highlighted.