Triacetic acid lactone as a bioprivileged molecule in organic synthesis

1. Download high-res image (148KB)
2. Download full-size image

     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Phase state stabilization of ammonium nitrate for creating an oxidizing agent for smokeless gas-generating formulations yielding no toxic combustion products

Methods for phase stabilization of ammonium nitrate were sought for in order to considerably expand the application area of this oxidizing agent in various-purpose self-combustible formulations, including that in a new generation of gas-generating formulations for automobile air bags. New methods for stabilization of ammonium nitrate were studied and, in particular, a search was made for organic compounds that can stabilize ammonium nitrate even at their low content. The mechanism of phase state stabilization of ammonium nitrate by compounds of this kind was examined.     

Effect of phonon scattering from neutral and charged impurity centers on the lattice heat conductivity of PbTe:(Tl, Na)

Experimental data on the effect of thallium and sodium impurities on the lattice heat conductivity of PbTe at room temperature are reported. Because the lattice of lead chalcogenides is strongly polarized near charged impurities, the effect of impurities on the lattice heat conductivity depends substantially on their charge state. This property of the material has been used to determine the charge state of the thallium impurity in PbTe. The results obtained argue for a model of quasi-local thallium-impurity states which assumes low electron-correlation energy at an impurity center. Fiz. Tverd. Tela (St. Petersburg) 40, 1206–1208 (July 1998)     

Laser spectroscopy of the 1s HFS of H-like ions at a bunched beam in the storage ring ESR

The investigation of the 1s HFS provides a good possibility for testing QED effects in a combination of a strong electric and magnetic field. Here, we report about the laserspectroscopic measurements of the ground state hyperfine splitting in ²⁰⁷Pb⁸¹⁺. To handle this M1-transition in the infrared optical regime with its long lifetime, we developed a new detection technique using a bunched ion beam. For the observation of fluorescence light, a new mirror system is adapted to the emission characteristics from an ion beam at relativistic velocities. This revised version was published online in July 2006 with corrections to the Cover Date.     

Efficient Collocation Schemes for Singular Boundary Value Problems

We discuss an error estimation procedure for the global error of collocation schemes applied to solve singular boundary value problems with a singularity of the first kind. This a posteriori estimate of the global error was proposed by Stetter in 1978 and is based on the idea of Defect Correction, originally due to Zadunaisky. Here, we present a new, carefully designed modification of this error estimate which not only results in less computational work but also appears to perform satisfactorily for singular problems. We give a full analytical justification for the asymptotical correctness of the error estimate when it is applied to a general nonlinear regular problem. For the singular case, we are presently only able to provide computational evidence for the full convergence order, the related analysis is still work in progress. This global estimate is the basis for a grid selection routine in which the grid is modified with the aim to equidistribute the global error. This procedure yields meshes suitable for an efficient numerical solution. Most importantly, we observe that the grid is refined in a way reflecting only the behavior of the solution and remains unaffected by the unsmooth direction field close to the singular point.     

Characters of irreducibleG-modules and cohomology ofG/P for the lie supergroupG=Q(N)

We prove a character formula for any finite-dimensional irreducible representationV of the “queer” Lie superalgebra g=q(n). It expresses chV in terms of the multiplicities of the irreducible g-subquotients of the cohomology groups of certain dominant g-bundles on the Π-symmetric projective spaces (i.e., on the homogeneous superspacesG/P whose reduced space is a projective space, whereG=Q(n)). We also establish recurrent relations for the above multiplicities, and this enables us to compute explicitly chV for any givenV. This provides a complete solution to the Kac character problem for the Lie superalgebraq(n). Finally, we consider the particular cases ofq(2), q(3), andq(4) in which we compare the new character formula with the generic character formula of [12]. Translated from Itogi Nauki i Tekhniki, Seriya Sovremennaya Matematika i Ee Prilozheniya. Tematicheskie Obzory. Vol. 41, Algebraic Geometry-7, 1997.