Precipitation of inorganic salts inside hollow micrometer-sized polyelectrolyte shells

Hollow polymer shells formed by layer-by-layer adsorption of oppositely charged polyelectrolytes onto micrometer-sized colloidal particles with subsequent decomposition of the colloidal core were employed as a model system for the study of inorganic crystallization reactions in restricted volumes. The size-selective permeability of shells is used for spatially controlling the precipitation of inorganic salts CaCO3 and BaCO3 into the shell interior. Outside the shells the precipitation was suppressed by the polymers, which are unable to penetrate the shell wall. The precipitates were studied by scanning electron microscopy and atomic force microscopy. The fundamental and applied aspects of research on spatially confined synthesis of inorganic particles are under discussion.     

Unique charge-separated pyridinium-barbituric acid zwitterions

A synthetic procedure for the preparation of the unusual charge-separated pyridinium barbiturate zwitterion 2 from 1,3-dimethylbarbituric acid and 2-pyridinecarbaldehyde in methanol was developed. The structure of the compound was confirmed with X-ray analysis to demonstrate the strong charge separation throughout the molecule. One would expect that this charge separation would increase its reactivity; however, contrary to this expectation, the compound is very stable in acidic media, and in the presence of a base, decarbonylation occurs on one barbituric acid while the zwitterionic moiety of the molecule stays intact.     

Synthesis of nopol over MCM-41 catalysts

MCM-41 was found to be an active heterogeneous catalyst for the synthesis of nopol by the Prins condensation of beta-pinene and paraformaldehyde, but Sn-MCM-41 in which Sn has been grafted on MCM-41 by chemical vapor deposition is far more active and combines high efficiency and recyclability.     

The structure of the uncharged-molecule complex between a dinaphthopyridino-18-crown-6 host and acetonitrile (1 : 2)

Single crystal X-ray analysis of a 1 : 2 complex between the dinaphthopyridino-l8-crown-6 host (1) and acetonitrile is reported. Crystals of the complex are monoclinic,P2₁/c witha = 12.178(5),b = 8.186(1),c = 30.873(1) Å, = 96.86(1)°, andD _c = 1.25 g cm^–3 forZ = 4. The host molecule reveals an approximate mirror symmetry and exists in a so-called dentist's chair conformation. One of the acetonitrile guest molecules is involved in possible weak interactions to two oxygen atoms of the host macroring, while the other fills free lattice space only.     

Molecular Ions of Transient Species: Vinylamine-Cation

Vinylamine 1 was prepared by thermolysis of cyclobutylamine and its photoelectron spectrum was measured. I = 8.20 eV and I = 8.65 eV were found, the dominant vibrational progression (? = 725 cm^?1) indicating that in the course of 1(X)→1 ⁺( X? ) flattening around the N-atom occurs. The Franck-Condon profile of this band, however, suggests that a skeletal mode of ? ≈ 1400 cm^?1 (observed also in the iso-π-electronic systems vinyl-alcohol-cation and allyl radical) may also be excited. Comparison with the data for the isomer acetaldehyde-imine 2 and its cation s ⁺ shows that the isomer couple 1/2 constitutes a further notable example for a relative thermochemical stability inversion on going from the neutrals to the cations.     

Kinetische Untersuchungen über die Silicium—Aryl-Spaltung mit Bromwasserstoff

Rate constants of the cleavage reaction of silicon aryl linkages with HBr were estimated for various aryl derivatives by means of NMR. A row of substituents was obtained, dependent on the cleavage rates. Correlation with theHammett function shows the electrophilic character of the reaction. The different cleavage rates give the possibility for specific cleavages of aryl groups from silanes.