Valence change of europium in the Eu(Ir1−x Pd x )2Si2 silicides

Eu(Ir_1–x Pd _x )₂Si₂ solid solutions which exist only for 0x0.125 and 0.75x1 crystallize in the tetragonal ThCr₂Si₂-type structure. X-ray diffraction data, magnetic susceptibility and¹⁵¹Eu Mössbauer measurements suggest that these compounds can be characterized as homogeneous mixed valence systems. At room temperature and for 0x0.125, the europium valence decreases asx increases. For 0.75x1, a sharp continuous valence transition from Eu²⁺ to Eu³⁺ occurs near 48 K, 54 K and 78 K forx=0.75, 0.81 and 0.94 respectively. These valence changes are discussed in relation with the Eu–(Ir, Pd) interatomic distance.     

Homolytic Cyclizations of N-Chloroalkenylamines

Many N-chloroalkylamines with double bond(s) dissociate homolytically to give chlorine atoms and aminyl radicals which undergo intramolecular cyclization reactions. Here, the nature of the aminyl radicals (neutral, protonated, or complexed to metal salts) appears to be important. The reactivity varies strongly from one species to another, and their selectivities can be different towards addition, substitution, abstraction, or dimerization reactions. A good synthetic tool appears to be the “complexed radical”, which is generated under mild conditions. A variety of β-functionalized, substituted, fused, or bridged azaheterocycles with alkaloid part structures thus become easily accessible in high yields, in a regio- and, possibly, stereoselective manner. Many examples are discussed illustrating the synthetic possibilities, limitations, and mechanistic features of this cyclization process.     

On estimating a density using Hellinger distance and some other strange facts

Résumé On s'intéresse ici aux possibles vitesses d'estimation d'une densité à support compact dans ^m sous des hypothèses de régularité, lorsque la perte est mesurée par le carré de la distance de Hellinger (on regardera aussi le cas connu des normes pour 1q2) et le risque est le risque minimax sur la famille. On donne une méthode générale permettant de traiter les problèmes dans le cadre de la théorie de l'approximation sous des conditions concernant l'entropie métrique et l' -capacité des familles à estimer. Les rapports entre régularité et entropie métrique étant bien connus, nous pourrons aussi traiter les cas classiques et d'autres qui le sont moins. Sous des conditions de bornes inférieures les vitesses sont celles observées pour la norme mais elles diffèrent dans le cas général. On montre aussi que les restrictions sur la compacité du support ou la régularité sont indispensables et que leur absence mène à l'impossibilité d'obtenir une estimation raisonnable en ce sens que n'importe quelle suite d'estimateurs sera arbitrairement mauvaise en un point au moins. Un résultat analogue est vrai sous des conditions de régularité.

---

---

This work was carried out during a visit of the author at the Mathematical Sciences Research Institute at Berkeley     

Phase transfer of metal cations by induced dynamic carrier agents: biphasic extraction based on dynamic covalent chemistry

In contrast to the classical method where a single molecule is designed to extract metal cations under specific conditions, dynamic covalent chemistry provides an approach based on the implementation of an adaptive dynamic covalent library for inducing the generation of the extractant species. This approach has been applied to the liquid–liquid extraction of copper(ii) nitrate based on a dynamic library of acylhydrazones constituents that self-build and distribute through the interface of a biphasic system. The addition of copper(ii) cations to this library triggers a modification of its composition and the up-regulation of the ligand molecules driven by coordination to the metal cations. Among these, one species has proven to be sufficiently lipophilic to play the role of carrier agent and its formation by component exchange enables the partial extraction of the copper(ii). The study of different pathways to generate the dynamic covalent library demonstrates the complete reversibility and the adaptability of the system. The detailed analytical investigation of the system provides a means to assess the mechanism of the dynamic extraction process.

Phase transfer of Cu(ii) cations is achieved by component exchange in a dynamic covalent library of acylhydrazone ligands. B1/B2 component exchange leads to the generation of a lipophilic carrier agent that extracts Cu(ii) into chloroform.     

Grafting of phosphonate groups on the silica surface for the elaboration of ion-sensitive field-effect transistors

Ion-sensitive field-effect transistors (ISFETs) sensitive to Ca(2+) ions could be elaborated by means of a new grafting process of the phosphonate group at the surface of the silica gate of FETs. A grafting process involving only one chemical reaction step at the surface afforded a significant improvement of the ISFET properties. The sensitivity of the ISFET towards Ca(2+) ions at pH 10 was quasi-linear in the concentration range from 10(-1) to 10(-3) M, and the slope was 10 mV pCa(-1). The site-binding model works well in predicting the experimental data, giving the complexation constant of 10(2.7) and a low value of the grafting density. The origin of the poor response of ISFETs sensitized by means of a multistep grafting process was investigated on silica powders of high specific area: the cleavage of the organic grafts at the SiOSi bonds occurring at each step could be disclosed by means of elemental analyses, infrared, and cross-polarization and magic angle spinning nuclear magnetic resonance of the grafts.     

Capto-dative Substituent Effects in Syntheses with Radicals and Radicophiles [New synthetic methods (32)]

The 100 yers old Wurster's salts have long been recognized as compounds with redical cations. Their unusual stabilization derives partly form capto-dative (cd) substitution. This principle is now discussed as one factor of radical stabilization and it is applied to simple methine derivatives. cd-Substitution has synthetically useful applications: cd-substituents on a carbon atom allow its selective dehydrodimerization. Olefines with geminal and thus cross-conjugated cd-substituents are “radicophilic” and permit twofold carbon radical addition. cd-Substituted olefines are useful antioxidants, polymerization inhibitors and are promising agents in the control of biological radical reactions. Generally, many reactions of cd-substituted molecules appear to involve radicals.     

Cyphostemmins A-B, two new antifungal oligostilbenes from Cyphostemma crotalarioides (Vitaceae)

Two new antifungal resveratrol dimers, cyphostemmins A-B (1–2), have isolated from the roots of Cyphostemma crotalarioides planch (Vitaceae) together with resveratrol 3 and previously known reseveratrol dimers (4–7). Structures of these new compounds have been established on the basis of their MS and ¹H and ¹³C NMR spectroscopic data.