Comparative reactivity of glycols in PET glycolysis

The kinetics of poly(ethylene terephthalate) (PET) glycolysis by diethylene glycol (DEG), dipropylene glycol (DPG), glycerol (Gly) and mixtures of these glycols have been studied with two experimental procedures: uncatalysed at 220 °C and catalysed at 190 °C. An experimental device was set up allowing the isothermal kinetics to be monitored. A precise initial reaction time was obtained by separately warming the glycol and the polyester at the temperature of reaction before mixing them.The reactivity order of different glycols varies according to the conditions of temperature and catalysis. Schematically, the global reactivity does depend not only on the chemical reactivity of the glycol but also on its physico-chemical properties: ability to solvate the solid polyesters and polarity of the reaction mixture. Attempts to find synergic effects failed for almost all mixtures, except the mixture DPG + Gly in which the PET is digested more quickly than in pure DPG or Gly.     

Ca(2.5)Sr(0.5)GaMn2O8: diamagnetic Ga in control of the structural and electronic properties of a bilayered manganate

The temperature dependence of the crystal structure and electronic properties of brownmillerite-like Ca(2.5)Sr(0.5)GaMn(2)O(8) has been studied by neutron powder diffraction and muSR spectroscopy. The results show that short-range 2D magnetic order begins to develop within the perovskite-like bilayers of MnO(6) octahedra approximately 50 K above the 3D Néel temperature of approximately 150 K. The bilayers show a structural response to the onset of magnetism throughout this temperature range whereas the GaO(4) layers that separate the bilayers only respond below the 3D ordering temperature. XANES spectroscopy shows that the sample contains Mn(3+) and Mn(4+) cations in a 1:1 ratio, and the behavior in the region of the Néel transition is interpreted as a local charge ordering. Electron diffraction and high-resolution electron microscopy have been used to show that the local microstructure is more complex than the average structure revealed by neutron diffraction, and that microdomains exist in which the GaO(4) tetrahedra show different orientations. It is argued that the bonding requirements of diamagnetic gallium control the electronic behavior within the perovskite-like bilayers.     

MIL-50, an open-framework GaPO with a periodic pattern of small water ponds and dry rubidium atoms: a combined XRD,NMR, and computational study

A new fluorinated gallium phosphate, MIL-50, has been synthesized under mild hydrothermal conditions using 1,6-diaminohexane. The chemical formula of MIL-50 is Rb(2)Ga(9)(PO(4))(8)(HPO(4))(OH)F(6).2N(2)C(6)H(18).7H(2)O. The structure is a network of hexameric units of Ga(3)(PO(4))(3)F(2) and Ga(3)(PO(4))(2)(HPO(4))F(3) via corner sharing. It creates a three-dimensional open-framework delimiting 6- and 18-ring channels running along the c axis. The diprotonated 1,6-diaminohexane and water molecules are trapped within the 18-ring pores, whereas the rubidium cations reside in the 6-ring ones. A double quantum (31)P NMR experiment and partial charge calculations indicate that water molecules are present under the form of periodic small clusters, lowering the multiplicity of one phosphorus site, P3. Though water hops within the clusters, the motion leaves the water pattern periodic. Rubidium is so tightly embedded into the framework that water moving in the large 18-ring channels does not reach it, leaving it therefore dry. The crystal framework may be ascribed to the orthorhombic space group Cmc2(1) (n degrees 36), a = 32.1510(2), b = 17.2290(3), c = 10.2120(1) A. The periodic water pattern has a different symmetry than that of the framework. A method has been devised to superpose the two sublattices that coexist in the same unit cell in order to have full occupancy of each site and to perform Madelung summations. This original method is of general interest for most zeolitic materials exhibiting a different symmetry for the framework and the template sublattices.     

The future of laboratory automation urgency, technology and strategy

The commercial application of laboratory robotics is entering its eight year. Developments in general purpose computer and software technology combined with developments in laboratory robotics have contributed to significant improvements in performance, reliability, and ease-of-use. The need for high quality laboratory automation continues to increase. Competitive pressure for higher quality and lower cost products and the shrinking supply of qualified technical people demands more effective use of our people resources. This presentation will develop the need for a new role and broader contribution from automation to the laboratory of the future. Specifically, I will discuss the critical decrease in the number of young people embarking on careers in chemistry and science and how automation can help make these career opportunities more challenging and exciting. The second part of the presentation will discuss the evolution of laboratory robotics technology and project some of the trends ahead.     

Substrate-reagent complexation ability in enantioselective 1,4 addition reactions

Hydrogen-aarbonyl chelation and magnesium-arene π coordination are proposed to aooount for enhanced enantioselectivïty in 1,4-addition reactions of chiral cuprates.     

Arbres,espaces ultramétriques et bases de structure uniforme

Résumé On décrit une bijection canonique qui associe à un bon espace ultramétrique, localement compact, non compact, un arbre pointé par un bout: cet espace s'identifie à l'ensemble des autres bouts.

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We describe a canonical bijection, which associates a tree with a chosen end to a nice ultrametric, locally compact, non-compact space: this space is identified with the set of other ends.

     

Detecting proximities between quadrupolar nuclei by double-quantum NMR

A robust, easy to optimize, and efficient homonuclear correlation NMR experiment for half-integer quadrupolar nuclei in solids is described and has been experimentally tested on anhydrous Na2HPO4-(23Na, S= 3/2 nucleus) and as-synthesized AlPO4-14 (27Al, S= 5/2 nucleus), an aluminophosphate molecular sieve.     

The relative susceptibility to racemization of L- and D-residues in peptide synthesis

An activated D-residue of a protected dipeptide when coupled racemizes twice as much as an activated L-residue, which is contrary to the case for couplings of acylamino acids.     

Supramolecular porphyrin-fullerene via 'two-point' binding strategy: axial-coordination and cation-crown ether complexation

A highly stable porphyrin-fullerene conjugate with defined distance and orientation, was formed using a newly developed 'two-point' binding strategy involving axial-coordination and cation-crown ether complexation; photochemical studies performed in benzonitrile revealed efficient charge separation and slow charge-recombination in the supramolecular complex.