Lavoisier and meat stock

Antoine-Laurent de Lavoisier published his results on ‘meat stock’ preparation in 1783. Measuring density, he stated that ‘food principles’ were better extracted using a large quantity of water. This result was checked. To cite this article: H. This et al., C. R. Chimie 9 (2006).     

Solid-state synthesis of boron subnitride, B6N: myth or reality?

Solid-state synthesis of boron subnitride, B₆N, as a result of chemical interaction between boron and boron nitride at 7.5 GPa and 1700 °C has been previously reported by Hubert et al. However, a critical analysis of the results has shown that the evidence for the formation of boron subnitride with B₆O-like structure is inconclusive. We have studied in situ the interaction between boron and BN at the same p–T conditions using X-ray diffraction with synchrotron radiation. At 7.4 GPa and 1700 °C the formation of a new phase has not been observed. At the same time, HP–HT treatment has resulted in strong and unpredictable preferred orientation of boron crystallites. This leads to the rise of some weak boron reflections that might be erroneously attributed to the appearance of a new phase. To cite this article: V.L. Solozhenko et al., C. R. Chimie 9 (2006).     

Modeling of reactive systems in twin-screw extrusion: challenges and applications

Reactive extrusion processes involve the difficulties of mastering classical polymer processes, such as twin-screw extrusion for example, and the problems of controlling a chemical reaction in very specific conditions (high-viscosity medium, high temperatures, short residence times). Therefore, it is often very difficult to intuitively understand all the aspects of the process and to clarify the complex interactions between the numerous variables, and then to properly design and optimize the industrial process. Numerical modeling can be a very efficient tool to overcome these difficulties. However, it remains a real challenge, as it necessitates to couple flow simulation in complex geometry, reaction kinetics and evolutionary rheological behavior. Moreover, the information needed is sometimes difficult to obtain with the required accuracy. After a general presentation of the principles of the different reactive extrusion modeling methodologies, we will focus on the models we developed, based on continuum mechanics. Different examples of applications are presented for illustrating the interest of this method. To cite this article: B. Vergnes et al., C. R. Chimie 9 (2006).     

Benzo[f]isoindole derivatives from cycloaddition reaction of 2,4-dimethylpyrimido[2,1-a]isoindole and maleimides

In contrast to the previously reported results in the reaction of maleimides with pyrido[2,1-a]isoindole and 1,2-bis substituted isoindoles, the reaction between 2,4-dimethylpyrimido[2,1-a]isoindole and maleimides leads to the formation of unusual products. Their structure is assessed by NMR and mass spectrometry. An original reaction pathway is proposed. The high quantum yields observed in fluorescence opens the route to applications as biological probes. To cite this article: Z.V. Voitenko et al., C. R. Chimie 9 (2006).     

Biodegradable materials by reactive extrusion: from catalyzed polymerization to functionalization and blend compatibilization

This contribution aims at reviewing how reactive extrusion (REx) technique can participate in the design and development of biodegradable polymeric materials more particularly based on aliphatic polyesters issued from both renewable (agrochemical) and fossil (petrochemical) resources. On one side, REx will be approached for producing in a continuous way biodegradable aliphatic polyesters by ring-opening polymerization of lactones. Tin and aluminum-based catalysts will be considered for quantitatively converting the cyclic monomer in high molecular weight polyester chains within residence time of a few minutes only. On the other hand, such polyesters will undergo various chemical modifications again performed by REx. Self-branching reactions will be investigated in order to compensate the characteristic molecular weight reduction of the polyester chains as triggered by hydrolysis and/or transesterification side-reactions. Controlled functionalization reactions by maleic anhydride treatment will be studied as well. Finally biodegradable composite materials will be produced by REx and will rely upon the interface compatibilization between the polyester matrix and natural fillers such as starch granules or talc microparticles. To cite this article: J.-M. Raquez, et al., C. R. Chimie 9 (2006).     

New rheological developments for reactive processing of poly(ε-caprolactone)

This short review aims to show how an integrated activity on reactive processing have been developed these last years in our laboratory. We can say that the originality of this approach is based on combining developments in chemistry, in line instrumentation, and rheology aspects. Our rheological works can be divided into four important contributions: rheo-physics, rheo-chemistry, rheo-mixing and rheo-processing. These different parts are illustrated from the ε-caprolactone polymerisation in bulk and dispersed media. Rheo-physics studies allowed us to calculate the molecular weight distribution and chain structures of in situ polymerised poly(ε-caprolactone) samples. From rheo-chemistry works, we are now able to predict the variation of the complex shear modulus versus the extent of the polymerisation. The developments of new rheological tools such as rheo-mixer enable us to investigate complex mixing situations encountered in reactive polymer blends and formulations. Lastly, a rheo-processing approach based on the in-line measurement of the viscosity in a slit rheometer at the die exit of the extruder allows us to envisage its application to the experimental control of the reactive processing in extruder. To cite this article: P. Cassagnau et al., C. R. Chimie 9 (2006).     

Synthesis and properties of copper quinonoid complexes for optical recording application

We describe the synthesis of novel quinonemonimines Cu(II) coordination complexes, of the type:

Full-size image (1K)

which, in addition to their intrinsic interest, have potential application in optical recording. The following key parameters have been highlighted: (i) the presence of coordinating arms on the quinonoid core of the ligand leads to octahedral complexes with increased solubility, (ii) the presence of Cu(II) as a metal centre leads to a favourable exothermic decomposition, (iii) the presence of quinonoid moieties results in the optical absorption to be in the desired wavelength range. To cite this article: P. Braunstein et al., C. R. Chimie 9 (2006).     

Synthesis and reactivity of new heterodinuclear iron/rhenium Cx complexes of the formula (η-C5Me5)Re(NO)(PPh3)(CC)n(η-dppe)Fe(η-C5Me5) (n = 3, 4): Redox properties and a dicobalt hexacarbonyl adduct

We report in this communication the synthesis and characterization of two Fe/Re heterodinuclear complexes 3_n of formula (η⁵-C₅Me₅)Re(NO)(PPh₃)(CC)_n(η²-dppe)Fe(η⁵-C₅Me₅) (n = 3, 4) as well as the hexacarbonyl dicobalt adduct (4) of the hexatriynediyl complex 3₃. We show by cyclic voltammetry that the “electronic communication” between the organometallic endgroups and thereby the thermodynamic stability of the corresponding mixed-valent (MV) parent 3_n⁺ is strongly influenced by bridge extension or by complexation of the [Co₂(CO)₆] fragment. In the case of the hexatriynediyl complex, the MV complex 3₃⁺ or 4 can be isolated by performing the chemical oxidation of 3₃ at low temperature. Spectroscopic studies of this compound and of other stable oxidized redox congeners should now help us to unravel how bridge extension modifies the electronic communication between the different redox-active endgroups in this family of unsymmetrically-substituted polyynediyl compounds.     

Viscoelastic behaviour of butyl acrylate/styrene/2-hydroxyethyl methacrylate/acrylic acid latices thickened with associative thickeners

The rheological behaviour of butyl acrylate/styrene/acrylic acid latices thickened with a hydrophobically modified ethoxylated polyurethane (HEUR) or hydrophobically modified alkali-soluble polyacrylate emulsion (HASE) was investigated. While the pseudoplastic character of frequency dependence of complex viscosity was similar for both thickeners, viscoelastic behaviour, expressed as the ratio of loss and storage moduli, significantly differed, indicating that the HEUR molecules, unlike swollen HASE particles, create a viscoelastic space structure. The increase in hydrophilicity of the particle surface, achieved by incorporation of 2-hydroxyethyl methacrylate (HEMA) monomer into the latex copolymer reduced the viscoelasticity of latices thickened with HEUR, but not of those thickened with HASE. This confirms that adsorption of hydrophobic end-groups on particle surface is important for thickening of latices with HEUR and that a physical network of latex particles interconnected by the thickener macromolecules is formed. To cite this article: O. Quadrat et al., C. R. Chimie 6 (2003).     

Enantiopure aryl-[1,2,5,6-tetrahydro-pyridinyl] methanols and their use for heterogeneous hydrogenation of ethyl pyruvate

Both enantiomers of two new chiral modifiers (naphthyl- and anthryl-[1,2,5,6-tetrahydro-pyridinyl] methanols, 4H and 5H) are obtained for the first time from inexpensive d-mannitol in 10 easy steps. Until now erythro-4H is the only synthetic chiral modifier available under both enantiomeric forms, which provide enantioselectivities almost as high as those obtained with natural cinchonidine, for which only one enantiomer is available. It is shown that the anthryl group may be less efficient than the naphthyl (the e.e.% drops from 75% with erythro-4H to 46% with erythro-5H) and that N-methyl substitution (trisubstituted nitrogen as in cinchonidine) leads also to a drop in the e.e.% (from 75% with 4H to 39% with 4Me).     

Technetium transmutation and production of artificial stable ruthenium

The recent Russian results on technetium transmutation into ruthenium are summarized, including the first isolation of artificial stable ruthenium from irradiated technetium targets. To cite this article: V. Peretroukhine et al., C. R. Chimie 7 (2004).

Résumé

Transmutation du technétium et production du ruthénium artificiel. Les résultats obtenus en Russie sur la transmutation du technétium en ruthénium artificiel et son isolement des cibles irradiées sont présentés. Pour citer cet article : V. Peretroukhine et al., C. R. Chimie 7 (2004).     

Synthesis and structure of the unsymmetrical β-diimine precursor: The β-iminoamine

The reaction of benzoylacetone with ortho-substituted aniline derivatives gives the unsymmetrical β-iminoamine ligands (5–8) with high yields. A convenient synthesis is described. These compounds have been characterized by NMR and IR spectroscopies. The structure of the β-iminoamine 5, 3-N-(2,6-diisopropylphenylamino)-1-phenyl-1N-(2,6-diisopropylphenylimino)but-2-ene, was solved by X-ray diffraction methods.     

The synergistic effect of cobalt-dicarbollide anions on the extraction of M lanthanide cations by Calix[4]arenes: a molecular dynamics study at the water–‘oil’ interface

We report molecular dynamics studies on the effect of CCD^– (chlorinated cobalt-dicarbollide) anions on the Eu³⁺ lanthanide cation extraction by a calix[4]arene-CMPO ligand L, focusing on the water–‘oil’ interface, where ‘oil’ is modelled by chloroform. The free L ligand and its EuL³⁺ complex are found to adsorb and to concentrate at the interface, but are too hydrophilic to be extracted. Addition of CCD^– anions in diluted conditions (either covalent linked to L or as separated CCD^– H₃O⁺ ions) also leads to adsorption of these species at the interface. However, at high concentrations, CCD^– anions saturate the interface and promote the extraction of EuL³⁺ to the oil phase. Another important feature concerns the uncomplexed Eu(CCD)₃ salt: accumulation of CCD^– anions at the interface creates a negative potential which attracts the hydrated Eu³⁺ ions, therefore facilitating their complexation by interfacial ligands. These features allow us to better understand the synergistic effect of lipophilic anions in the assisted liquid-liquid extraction of trivalent M³⁺ lanthanide or actinide cations. To cite this article: B. Coupez, G. Wipf, C. R. Chimie 7 (2004).

Résumé

Synergie due aux anions dicarbollides lors de l’extraction d’ions lanthanides M³⁺ par des calix[4]arènes : simulations de dynamique moléculaire à l’interface eau–« huile ». Nous étudions par simulations de dynamique moléculaire l’effet de synergie dû aux anions CCD^– (cobalt-dicarbollides) lors de l’extraction de Eu³⁺ par un calix [4]arène L, en se focalisant sur l’interface eau–« huile », l’huile étant modélisée par du chloroforme. On montre que le ligand L et son complexe EuL³⁺ s’adsorbent à l’interface, mais sont trop hydrophiles pour être extraits. L’addition d’anions CCD^– (qu’ils soient sous la forme d’ions CCD^– H₃O⁺ séparés ou greffés de façon covalente au calixarène) conduit aussi à l’adsorption de ces espèces à l’interface. Cependant, aux plus fortes concentrations, les anions CCD^– saturent l’interface et induisent l’extraction du complexe EuL³⁺ vers l’huile. Un autre résultat remarquable concerne les sels Eu(CCD)₃ : l’accumulation des anions CCD^– à l’interface y crée un potentiel négatif, ce qui attire les cations Eu³⁺ et facilite ainsi leur complexation par des ligands à l’interface. Ces résultats permettent de mieux comprendre l’effet de synergie dû aux anions CCD^– lors de l’extraction d’ions lanthanides ou actinides M³⁺ et, d’une manière générale, ce qui se passe à l’interface entre l’eau et des liquides non miscibles. Pour citer cet article : B. Coupez, G. Wipf, C. R. Chimie 7 (2004).     

Dinuclear vanadium and tetranuclear iron complexes obtained with the open Wells–Dawson [Si2W18O66] tungstosilicate

Reaction of two transition metal cations M (M = V^V, Fe^III) on the open Wells–Dawson anion α-[{K(H₂O)₂}Si₂W₁₈O₆₆]^15– leads to dinuclear and tetranuclear complexes, respectively. The molecular anions [{KV₂O₃(H₂O)₂}(Si₂W₁₈O₆₆)]^11– and [{Fe₄(OH)₆}(Si₂W₁₈O₆₆)]^10– have been structurally characterized by single crystal X-ray diffraction. The oxo/hydroxometallic clusters [KV₂O₃(H₂O)₂]⁵⁺ and [Fe₄(OH)₆]⁶⁺ are included in the pocket between the two subunits of [Si₂W₁₈O₆₆]^16–. The Fe^III atoms of the iron complex can be reduced to Fe^II by a single four-electron step. To cite this article: N. Leclerc-Laronze et al., C. R. Chimie 9 (2006).     

Reversible adsorption of spherical particles from binary mixtures: long-time behaviour

Formation of monolayers of spherical particles in processes with reversible adsorption from mixtures of large and small particles was simulated in computer experiments. Computer program was based on an algorithm that took into account random sequential adsorption, desorption and lateral diffusion of adsorbed particles (RSA–DLD model). Computer experiments were performed for systems with rate constants of particle adsorption at least 10³ times higher than rate constants of desorption. In processes with very fast adsorption and slow desorption, formation of monolayer can be divided into two stages. During the first stage, the total surface coverage (the coverage with particles of both types) increases very fast and becomes very close to that at equilibrium. During the second stage, the total coverage changes very slowly and the system approaches equilibrium mainly by the replacement of large particles with the small ones. A simple kinetic model for evolution of the monolayer composition during the second stage has been proposed. Kinetic equations related to this model allow the determination of large particles’ desorption rate constants on the basis of changes in the surface concentrations of adsorbed large and small microspheres. The validity of the model has been tested comparing large particles’ desorption rate constants values that had been used for simulations with values of the corresponding rate constants determined using analytical equations, with a view to analysing the simulation results. To cite this article: S. Slomkowski et al., C. R. Chimie 6 (2003).     

Cosurfactant effects on the microemulsion polymerization of styrene

The polymerization of styrene in o/w microemulsions stabilized with dodecyltrimethylammonium bromide (DTAB) with or without cosurfactant (n-butanol, n-hexanol or n-octanol) is examined here. The addition of a cosurfactant enhances the one-phase region in the order: n-butanol > n-hexanol > n-octanol. The kinetics of polymerization slows down in the presence of the alcohol. With the alcohol, the molar masses increase, but no particular trend was noticed on particle size of the lattices. However, by changing the surfactant counter-ion to chloride, alcohol effects on the kinetics almost vanish. Possible explanations to these results are given here. To cite this article: J.E. Puig et al., C. R. Chimie 6 (2003).     

Particle size distribution in mini-emulsion polymerization

The particle size distribution polydispersities of a number of macro- and mini-emulsion latexes are reported. In cases where the macro-emulsion and mini-emulsions were produced under very nearly identical conditions, the mini-emulsion will have a polydispersity equal to, or only very slightly greater than, the equivalent macro-emulsion. To cite this article: K. Landfester et al., C. R. Chimie 6 (2003).     

The effect of first-stage polymer Tg on the morphology and thermomechanical properties of structured polymer latex particles

A series of heterogeneous latexes having stage ratios of 40:60 between the first and second stage polymers were prepared by emulsion polymerization. The first-stage polymers were non-polar S-BuA with T_gs ranging from + 100 °C to + 20 °C and the second stage polymer was polar MMA–BuA–MAA having a T_g of 20 °C. The latex particle morphologies were studied using TEM and the thermomechanical properties of the resulting latex films were studied with DSC and DMA. Calculated diffusion rates for propagating species during the reactions were correlated to the observed morphologies and to the amount of interphase in the latex particles. To cite this article: O.J. Karlsson et al., C. R. Chimie 6 (2003).     

Research and application of inorganic selective sorbents at Mayak PA

This work has been performed in order to identify selective inorganic sorbents for caesium and strontium. Thin-layer sorbents with nickel ferrocyanide embedded in an inert matrix were found to be the best for caesium. Sorbents including non-stoichiometric manganese dioxide were selected for strontium. Bench tests have been carried out on the purification of desalted water of SNF storage-pool from ¹³⁷Cs, and on the purification of contaminated natural water from ⁹⁰Sr. The facility for synthesizing the ferrocyanide sorbent with the registered mark ‘Seleks-CFN’ has been brought into operation. The sorbent ISM-S seems promising for ⁹⁰Sr decontamination. To cite this article: M.V. Logunov et al., C. R. Chimie 7 (2004).

Résumé

Recherches et applications sur l’utilisation de sorbants spécifiques à Mayak. Des sorbants sélectifs du césium et du strontium ont été identifiés. Pour le césium, le meilleur s’avère être le ferrocyanure de nickel, s’il est utilisé sous forme de couche mince. Pour le strontium, on a sélectionné des composés non stœchiométriques de dioxyde de manganèse. On a mené des tests visant à épurer en césium l’eau des piscines d’entreposage des combustibles nucléaires usagés, et en strontium des eaux contaminées. Une installation industrielle permettant de préparer le sorbant à base de ferrocyanure de marque « Seleks-CFN » a été réalisée. Le sorbant ISM-S semble prometteur pour la décontamination en strontium. Pour citer cet article : M.V. Logunov et al., C. R. Chimie 7 (2004).     

Reversible photomagnetic properties of the molecular compound [{Cu(bipy)2}2{Mo(CN)8}]·9H2O·CH3OH

The optical and photomagnetic properties of [{Cu^II(bipy)₂}₂{Mo^IV(CN)₈}]·9H₂O·CH₃OH (1) have been reinvestigated. A comparison between spectra in solution and in the solid state revealed the presence of an intervalence band (or Metal–Metal Charge Transfer, hereafter noted MMCT) at 570 nm. The photomagnetic properties have been performed in a Superconducting QUantum Interference Device at 10 K with irradiation in the range of the MMCT: 488 nm, 520 nm and 647 nm at 10 K. An important increase of the magnetic signal has been measured after 1 h of irradiation at 488 nm, whereas a weaker increase has been obtained for the irradiation at 520 nm in the same conditions. Moreover, after an excitation at 488 nm, an irradiation at 647 nm has induced a decrease of the magnetic moment, which corresponds to a partial deexcitation. The complete characterization of the photoproduct has been realised after an irradiation of 4 h at 488 nm. The photomagnetic properties have shown an increase of the paramagnetism of 1 at low temperature. After a thermal heating at 300 K, the material goes back to its initial state before irradiation. It is the first time that a fully reversible photomagnetic behaviour for the compound [{Cu^II(bipy)₂}₂{Mo^IV(CN)₈}]·9H₂O·CH₃OH has been described. The observed properties have been discussed in terms of an electron transfer mechanism Mo → Cu.