High Spin and Anisotropic Molecules Based on Polycyanometalate Chemistry

 This paper points out some recent achievements in the chemistry and physics of high spin and anisotropic molecules based on polycyanometalate complexes. Following a step by step synthetic strategy and using a localized electron orbital model, isotropic high spin molecules were obtained with ground spin states ranging from S = 9/2 to 27/2. In the same way, anisotropic molecules with various nuclearities (bi, tri, tetra, hexa, and hepta-nuclear complexes) have been synthesized. Mixing these two approaches, it has been possible to obtained anisotropic high spin molecules that behave as single molecule magnets. The paper reviews some of the steps that lead to these findings and some of the prospects opened in the field of single molecule magnets. Corresponding author. E-mail: marvaud@ccr.jussieu.fr Received July 19, 2002; accepted July 23, 2002     

A relaxation method for two-phase flow models with hydrodynamic closure law

Summary. This paper is devoted to the numerical approximation of the solutions of a system of conservation laws arising in the modeling of two-phase flows in pipelines. The PDEs are closed by two highly nonlinear algebraic relations, namely, a pressure law and a hydrodynamic one. The severe nonlinearities encoded in these laws make the classical approximate Riemann solvers virtually intractable at a reasonable cost of evaluation. We propose a strategy for relaxing solely these two nonlinearities. The relaxation system we introduce is of course hyperbolic but all associated eigenfields are linearly degenerate. Such a property not only makes it trivial to solve the Riemann problem but also enables us to enforce some further stability requirements, in addition to those coming from a Chapman-Enskog analysis. The new method turns out to be fairly simple and robust while achieving desirable positivity properties on the density and the mass fractions. Extensive numerical evidences are provided.Mathematics Subject Classification (1991): 76T10, 76N15, 35L65, 65M06     

Déformations formelles de revêtements: un principe local-global

LetC be a generically smooth, locally complete intersection curve defined over an algebraically closed fieldk of characteristicp≥0. LetG⊃ Aut _k C be a finite group of automorphisms ofC. We develop a theory ofG-equivariant deformations of the Galois coverC→C/G. We give a thorough study of the local obstructions, those localized at singular or widely ramified points, to deform equivariantly a cover. As an application, we discuss the case ofG-equivariant deformations of semistable curves.      

Capabilities and Disadvantages of Combined Matrix-Assisted Laser-Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) and High-Performance Thin-Layer Chromatography (HPTLC): Analysis of Egg Yolk Lipids

JPC – Journal of Planar Chromatography – Modern TLC - Lipids are important natural products and essential in nutrition, cosmetic formulations, pharmaceuticals, etc. Lipids and,...     

Problem of formation of quotients and base change

Let X/S be a semistable curve equipped with the action of a finite group G and let H be a normal subgroup of G. The main result of this paper is the following. If the action of G is free on an open dense set on any geometric fiber, then for any base change TS, (X/G)×_ST is isomorphic to (X×_ST)/G. As an application, this allows us to define induction and restriction morphisms between the G-equivariant deformation functor of X and the G/H-equivariant (resp. H-equivariant) deformation functor of X/H (resp. X).

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Résumé. Soit X/S une courbe semi-stable munie de laction dun groupe fini G. Soit H un sous-groupe normal de G. Nous proposons une nouvelle condition sous laquelle (X/G)×_ST est isomorphe à (X×_ST)/G quel que soit le changement de base TS : il suffit que sur toutes les fibres géométriques, laction de G soit libre sur un ouvert dense. Comme application de ce résultat nous définissons des morphismes dinduction et de restriction entre le foncteur de déformations G-équivariantes de X et le foncteur de déformations G/H-équivariantes (resp. H-équivariantes) de X/H (resp. X).

     

Hexacyanometalate molecular chemistry: heptanuclear heterobimetallic complexes; control of the ground spin state

Following a bottom-up approach to nanomaterials, we present a rational synthetic route from hexacyanometalates [M(CN)(6)](3-) (M=Cr(III), Co(III)) cores to well-defined heptanuclear complexes. By changing the nature of the metallic cations and using a localised orbital model it is possible to control and to tune the ground state spin value. Thus, with M=Cr(III), d(3), S=3/2, three heptanuclear species were built and characterised by mass spectrometry in solution, by single-crystal X-ray diffraction and by powder magnetic susceptibility measurements, [Cr(III)(CNbondM'L(n))(6)](9+) (M'=Cu(II), Ni(II), Mn(II), L(n)=polydentate ligand), showing spin ground states S(G)=9/2 [Cu(II)], with ferromagnetic interactions J(Cr,Cu)=+45 cm(-1), S(G)=15/2 [Ni(II)] and J(Cr,Ni)=+17.3 cm(-1), S(G)=27/2 [Mn(II)], with an antiferromagnetic interaction J(Cr,Mn)=-9 cm(-1), (interaction Hamiltonian H=-J(Cr,M) [S(Cr)Sigma(i)S(M)(i)], i=1-6). With M=Co(III), d(6), S=0, the heptanuclear analogues [Co(III)(CN-M'L(n))(6)](9+) (M'=Cu(II), Ni(II), Mn(II)) were similarly synthesised and studied. They present a singlet ground state and allow us to evaluate the weak antiferromagnetic coupling constant between two next-nearest neighbours M'-Co-M'.     

Molecular tectonics. Dendritic construction of porous hydrogen-bonded networks

Molecules that associate to form porous networks can be made by attaching multiple hydrogen-bonding sites to suitable cores. Pentaerythrityl tetraphenyl ether, a four-armed core, is the progenitor of dendritic derivatives with more arms, including dipentaerythrityl hexaphenyl ether 7. An advantage of such dendritic derivatives is that the resulting networks are held together by larger numbers of intermolecular hydrogen bonds. [structure: see text]     

Carbon nanotube thin films modified with a mixture of Prussian blue and ruthenium purple: combining materials and properties

Thin films of iron-filled carbon nanotubes prepared through the liquid/liquid interfacial method were modified with a mixture of hexacyanometallates (HCMs) Prussian blue and ruthenium purple. Two different approaches were used in order to obtain both materials in the composites, based on a direct reaction starting from a mixture of both precursors or a step-by-step deposition of each compound. The modified films were characterized by cyclic voltammetry, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, and UV-Vis spectroscopy, confirming the formation of a mixture of HCMs in both methods of synthesis. Stability studies were evaluated in different supporting electrolytes, and composites presented good performances due to carbon nanotube stabilization. Electrochromic properties were also evaluated for selected composites, showing high electrochromic efficiency and stability.

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Imidazol-2-and-4-ylidene by decarboxylation. Studies on the cross-conjugated mesomeric betaine-alkaloid norzooanemonine and its pseudo-cross-conjugated isomer

1,3-Dimethylimidazolium-2-carboxylate and -4-carboxylate (norzooanemonine), which belong to two distinct classes of heterocyclic mesomeric betaines, undergo thermal decarboxylations to the N-heterocyclic carbenes imidazol-2-ylidene and imidazol-4-ylidene, respectively. These carbenes can be detected by ESI mass spectrometry and can be trapped by isocyanates to imidazolium-amidates, the structure of which was proved by independent syntheses. We performed calculations to characterize the different types of conjugation in the imidazolium-carboxylates.     

Magnetic Control of Macromolecular Conformations in Supramolecular Anionic Polysaccharide–Iron Complexes

The anionic iota carrageenan polysaccharide is enriched with Fe^II and Fe^III by ion exchange against FeSO₄ and FeCl₃. With divalent iron, portions of polymer chains undergo a secondary structure transition from random coils to single helices. The single‐chain macromolecular conformations can be manipulated by an external magnetic field: upon exposure to 1.1 T, the helical portions exhibit 1.5‐fold stiffening and 1.1‐fold stretching, whereas the coil conformations respond much less as a result of lower contents of condensed iron ions. Along with the coil–helix transition, the trivalent iron triggers the formation of superstructures. The applicability of iron‐enriched iota carrageenan as functional ingredient for food fortification is tested by free Fe²⁺ and Fe³⁺ contents, respectively, with the most promising iota‐Fe^III yielding 53 % of bound iron, which is due to the superstructures, where the ferric ions are chelated by the supramolecularly self‐assembled polymer host.