Hauri (Germany)

Le titre V de la loi pour la reconquête de la biodiversité promulguée le 08 août 2016 vise à transposer en droit interne le protocole de Nagoya et le règlement n°511/2014 du Parlement Européen et du Conseil du 16 avril 2014. Plutôt que de s’appuyer sur la notion de communauté autochtone et locale voire de prendre en considération le caractère autonome de la notion de communauté locale, le législateur a fait le choix d’user de la notion de communauté d’habitants. La notion de communauté locale, propre au droit de l’environnement, est pourtant susceptible de satisfaire aux exigences de la jurisprudence constitutionnelle puisqu’elle ne consiste pas en une communauté d’origine, de culture, de langue ou de croyance. Au delà de la logique inhérente à la loi du 08 août 2016, la reconnaissance de communautés locales au cœur du dispositif d’accès et de partage des avantages doit permettre d’en corriger les multiples insuffisances tant en matière d’accès aux ressources génétiques et aux connaissances traditionnelles qu’en ce qui concerne le partages des avantages résultant de leur utilisation.

A copper catalyzed efficient synthetic method has been developed to access bis(N-arylbenzamide) selenides from 2-halo-N-arylbenzamide substrates and disodium selenide in HMPA at 110 °C. The developed protocol tolerates substituents in both N-aryl and benzamide rings of the 2-halobenzamide substrates and provides an array of bis(N-arylbenzamide) selenides in practical yields. The resulting selenides were transformed into hypervalent spirodiazaselenuranes by oxidation using aqueous hydrogen peroxide. (N-(1-Naphthyl)) spirodiazaselenurane is also structurally characterized by a single crystal X-ray study. Hydroxy-substituted spiroselenuranes have been prepared by careful demethylation of methoxy-substituted selenides followed by oxidation by hydrogen peroxide. Antioxidant properties for the decomposition of hydrogen peroxide and for the deactivation of radicals of hydroxy-substituted spiroselenuranes have been studied by the thiol assay and 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. Both hydroxy-substituted spiroselenuranes exhibit dual mimic functions of glutathione peroxidase (GPx) selenoenzyme and α-tocopherol for decomposition of hydrogen peroxide and deactivation of radicals, respectively.

The first example of a pentacoordinate CoII single-ion magnet based on a P-donor ligand with vacant octahedral coordination geometry is reported here. Thorough magnetic measurements reveal the presence of field induced slow relaxation behavior with an easy-plane magnetic anisotropy. The combined theoretical and experimental studies disclose that direct and quantum tunneling processes become dominant at low temperature to relax the magnetization; however, from the thermal dependence of relaxation time it can be observed that the optical or acoustic Raman processes become important to the overall relaxation process.

Inner cavities in cast ingots have to be closed by means of open-die forging to guarantee the integrity of the forged components during usage. In the paper a differentiation is made between the macroscopic and the microscopic closing of natural inner cavities. Special attention is paid to the dendritic structure of the surfaces of inner cavities and their impact on the microscopic closing behavior. Additionally, investigation showed that a closing on the microscopic scale is only possible if the cavities do not come in contact to the atmosphere during hot forming. For the analysis of the cavity closing, ingots of a heat-treatable, hot-working and a cold-working steel were used. The ingots were cast, forged and the surface of the inner voids was analyzed with the help of light-microscopy, SEM and EDS for the microstructure and by using tensile tests on macroscopic scale. Also, numerical investigations were a part of the work, whereby the parameters void size, void shape and anvil-shape were varied. As a result of the numerical investigation, a so called closing function was formed. This function enables the user to calculate the necessary height-reduction for closing of inner cavities of the regarded ingot format.

Desilylative C(sp2)-C(sp2) cross-coupling reactions of arylsilanes with aryldiazonium salts under Au(i)/photoredox catalysis have been reported. The addition of Cu-salts as catalysts was found to be crucial for the success of this transformation.

Host-guest complexation of mono and dicationic quinine with cucurbit[7]uril (CB7), a water-soluble macrocyclic host molecule, has been investigated. Job's plot, time-resolved anisotropy as well as concentration dependent NMR titration confirm the binding of two CB7 macrocycles with one quinine molecule. The binding affinity of dicationic quinine with CB7 is one order of magnitude higher than the binding constant of mono-cationic quinine. Such preferential binding results in one unit pKa shift in the ground-state of the quinoline ring. However, using fluorescence spectroscopy we have obtained two acid-dissociation constants, one for quinoline ring nitrogen and the other for the nitrogen of the quinuclidine moiety. In the excited state, CB7 complexation causes one unit pKa shift for the quinoline ring and 1.9 unit shift for the quinuclidine moiety. Interestingly, a large enhancement of fluorescence lifetime and anisotropy of quinine at pH 2.7 and pH 9.0 upon CB7 complexation was observed due to the restriction of conformational flexibility. Moreover, at pH 3.0, a large fluorescence enhancement of quinine due to CB7 complexation was observed and it was quite significant as compared to that of quinine in 0.1 (M) HCl without CB7. We believe that this study of quinine complexation with CB7 will reduce phototoxicity, increase bioavailability and offer an alternative standard for quantum yield measurements in an amiable condition.

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