Phosphaalkenes, phospholyls and phosphinines : New tools in coordination chemistry and catalysis

55 pages ReviewThis review covers recent achievements in the area of low coordinate phosphorus ligands featuring P=C double bonds such as phosphaalkenes, phospholide-based complexes and phosphinines. The most significant developments are presented and discussed for each class of ligands. Particular attention has been paid to the use of these new systems as ligands in homogeneous catalysis

The CO/PC analogy in coordination chemistry and catalysis

9 pagesThis short account summarizes recent results obtained in the coordination chemistry of phosphinines and emphasizes their analogy with CO ligands. Reduced complexes can be easily assembled through the reaction of reduced 2,2'-biphosphinine dianions with transition metal fragments. Theoretical calculations were performed to establish the oxidation state of the metal in these complexes. Though many reduced complexes are available, phosphinines proved to be too sensitive toward nucleophiles to be used as efficient ligands in most catalytic processes. However, the high electrophilicity of the phosphorus atom can be exploited to synthesize phosphacylohexadienyl anions which exhibit a surprising coordination chemistry. When phosphino sulfide groups are incorporated as ancillary tridentate anionic SPS ligands can be easily produced. These ligands can bind different transition metal fragments such as M-X (M = group 10 metal, X = halogen), Rh-L (L = 2 electron donor ligand), Cu-X and Au-X (X = halogen). Palladium(II) complexes proved to be active catalyst in the Miyaura cross-coupling reaction. Bidentate anionic PS ligands were also synthesized following a similar approach. Their Pd(II) (allyl) derivatives showed a very good activity in the Suzuki catalyzed cross-coupling process that allows the synthesis of biphenyl derivatives through the reaction of phenylboronic acid with bromoarenes

Recent developments of marine ingredients for food and nutraceutical applications: a review.

Remerciements à l'éditeur pour son accord de diffusion. L'article original est aussi accessible sur le site de l'éditeur à l'adresse : http://www.halieutique.org/23201b.htmlInternational audienceIn a global context of marine biological resource overexploitation, a better upgrading of fish and shellfish biomass is a challenge for the 21st century. One of the main and promising issues will be the production of marine bio-ingredients using enzymatic hydrolysis. This paper presents the key steps in the production of enzymatic hydrolysates, such as (i) enzymatic treatment for the bioconversion of solid discards, and more particularly, use of proteases, (ii) quantification of the proteolysis extend and procedures of quality-control and (iii) identification of biological activity, using in vitro and in vivo methods. In the last part, examples of marine, commercially available functional foods or nutraceutical ingredients carrying bioactive properties are presented in order to demonstrate the interest of biotechnological exploitation of marine resources

La pêche artisanale dans l'Economie comorienne

L'étude socio-économique de la pêche artisanale aux Comores avait pour objectif la proposition d'un cadre de politique de développement du système Pêche, Les deux axes prioritaires de ce travail portent sur les conditions de rentabilité des flottilles et sur les circuits de commercialisation. Dans un document de synthèse, des recommandations sur la définition des facteurs potentiels de croissance du secteur halieutique ont été proposées. Dans la partie spécifique des conditions de rentabilité, nous avons évalué la contribution des unités de pêche artisanale comorienne à la richesse nationale afin d'aider à définir les cadres d'une politique de développement. Pour cela, il nous a fallu établir des comptes d'exploitation pour chaque type d'embarcation et par île afin d'observer la significativité des postes de coûts et de recettes dans la rentabilité des embarcations. Dans une première partie, nous définirons les charactéristiques de la pêche artisanale aux Comores en tenant compte des zones de pêche, des espèces exploitées et de l'engin utilisé. Ceci sera complété par une typologie globale des coûts et recettes des embarcations. Dans une seconde section, nous présenterons les résultats de l'analyse de données (Analyse des Correspondances Multiples) établie à partir des principales variables liées aux aspects techniques et économiques des flottilles. Enfin, sur la base des comptes d'exploitation, nous tenterons d'évaluer le poids des consommations intermédiaires de la pêche artisanale comorienne. Nous serons alors en mesure de situer le secteur halieutique au sein de l'économie domestique. La valeur globale réalisée par l'ensemble des embarcations permettra d'apprécier leur contribution au PIB total.Keywords: Costs and revenues, Artisanal Fishing, Fleet profitabilityKeywords: Costs and revenues, Artisanal Fishing, Fleet profitabilit

Iminophosphorane-based [P₂N₂] rhodium complexes: synthesis, reactivity, and application in catalysed transfer hydrogenation of polar bonds

International audience[Rh(P2N2)X] complexes (2-X, X = Cl, BF4) featuring a tetradentate iminophosphorane phosphine ligand were synthesised and characterised. X-Ray analysis provides evidence for a square planar geometry without coordination of the chloride anion. These complexes proved to be air-sensitive, and their oxidation to Rh(III) complexes 3-X was observed in air. The controlled reaction of 2-BF4 with one equivalent of hexachloroethane yielded [Rh(P2N2)Cl2(BF4)] (3-BF4). Direct synthesis of 3-Cl can also be achieved by coordination of the [P2N2] ligand to [RhCl(THT)3] (THT = tetrahydrothiophene). The reactivity of Rh(I) complexes 2 was further investigated, and no reaction was observed with silanes, aryl halides, or pinacolborane, although decomposition was observed under 1 atm of H2 upon prolonged heating. Interestingly, reduction of complex 3-Cl was observed by NMR upon treatment with silanes or sodium isopropoxide. Therefore, complex 3-Cl was used for catalytic transfer hydrogenation of polar bonds. The reduction of aromatic and aliphatic ketones can be carried out using 1% catalyst and 10% sodium isopropoxide, while imines are partially reduced under these conditions

Extracorporeal Membrane Oxygenation for Severe Acute Respiratory Distress Syndrome associated with COVID-19: An Emulated Target Trial Analysis.

RATIONALE: Whether COVID patients may benefit from extracorporeal membrane oxygenation (ECMO) compared with conventional invasive mechanical ventilation (IMV) remains unknown. OBJECTIVES: To estimate the effect of ECMO on 90-Day mortality vs IMV only Methods: Among 4,244 critically ill adult patients with COVID-19 included in a multicenter cohort study, we emulated a target trial comparing the treatment strategies of initiating ECMO vs. no ECMO within 7 days of IMV in patients with severe acute respiratory distress syndrome (PaO2/FiO2 <80 or PaCO2 ≥60 mmHg). We controlled for confounding using a multivariable Cox model based on predefined variables. MAIN RESULTS: 1,235 patients met the full eligibility criteria for the emulated trial, among whom 164 patients initiated ECMO. The ECMO strategy had a higher survival probability at Day-7 from the onset of eligibility criteria (87% vs 83%, risk difference: 4%, 95% CI 0;9%) which decreased during follow-up (survival at Day-90: 63% vs 65%, risk difference: -2%, 95% CI -10;5%). However, ECMO was associated with higher survival when performed in high-volume ECMO centers or in regions where a specific ECMO network organization was set up to handle high demand, and when initiated within the first 4 days of MV and in profoundly hypoxemic patients. CONCLUSIONS: In an emulated trial based on a nationwide COVID-19 cohort, we found differential survival over time of an ECMO compared with a no-ECMO strategy. However, ECMO was consistently associated with better outcomes when performed in high-volume centers and in regions with ECMO capacities specifically organized to handle high demand. This article is open access and distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives License 4.0 (http://creativecommons.org/licenses/by-nc-nd/4.0/)

Time to Switch to Second-line Antiretroviral Therapy in Children With Human Immunodeficiency Virus in Europe and Thailand.

Background: Data on durability of first-line antiretroviral therapy (ART) in children with human immunodeficiency virus (HIV) are limited. We assessed time to switch to second-line therapy in 16 European countries and Thailand. Methods: Children aged <18 years initiating combination ART (≥2 nucleoside reverse transcriptase inhibitors [NRTIs] plus nonnucleoside reverse transcriptase inhibitor [NNRTI] or boosted protease inhibitor [PI]) were included. Switch to second-line was defined as (i) change across drug class (PI to NNRTI or vice versa) or within PI class plus change of ≥1 NRTI; (ii) change from single to dual PI; or (iii) addition of a new drug class. Cumulative incidence of switch was calculated with death and loss to follow-up as competing risks. Results: Of 3668 children included, median age at ART initiation was 6.1 (interquartile range (IQR), 1.7-10.5) years. Initial regimens were 32% PI based, 34% nevirapine (NVP) based, and 33% efavirenz based. Median duration of follow-up was 5.4 (IQR, 2.9-8.3) years. Cumulative incidence of switch at 5 years was 21% (95% confidence interval, 20%-23%), with significant regional variations. Median time to switch was 30 (IQR, 16-58) months; two-thirds of switches were related to treatment failure. In multivariable analysis, older age, severe immunosuppression and higher viral load (VL) at ART start, and NVP-based initial regimens were associated with increased risk of switch. Conclusions: One in 5 children switched to a second-line regimen by 5 years of ART, with two-thirds failure related. Advanced HIV, older age, and NVP-based regimens were associated with increased risk of switch

China-France Workshop on molecular Catalysits and Catalysis.

18-21 Juillet 2006 Université de Renne