The Keto-Enol Equilibrium of Pentane-2,4-dione Studied by ab initio Methods

 The mechanism of the keto-enol interconversion of pentane-2,4-dione (trivial name: acetylacetone, acac) was examined at the restricted Hartree-Fock (HF) level and the DFT correlation functional BLYP method using the 6-311G^** basis, both included in the program GAUSSIAN 98. Two initial enol forms are considered: the omega and sickle forms, related by a rotation of 180° around the OC*CC bond. The study is restricted to the through-space transfer of the hydroxyl proton to C(2). The two geometry-optimized enol forms are planar; the geometry optimization of the diketone forms leads to the same non-planar structure, regardless of the starting enol geometry. The transition state of the through-space omega-enol→diketone conversion has also a non-planar structure, indicating that the hydroxyl proton moves outside of the CCC plane. The BLYP-calculated energy barrier of the forward (omega-enol→diketone) conversion is 245 kJ·mol⁻¹, that of the reverse (diketone→omega-enol) conversion 222 kJ·mol⁻¹; thus, an almost symmetric barrier, which is not thermally accessible, is defined. The energy barrier for the sickle-enol→diketone conversion is considerably lower (187 kJ·mol⁻¹), to access the sickle form from the more stable omega form, a rotation is needed (energy barrier: 88 kJ·mol⁻¹). The HF-calculated barriers are 1.3–1.4 times higher than those obtained with the BLYP method.     

Surface Chemistry Study of the Interactions of Sesame Oil with Meibomian Films

A possible approach for the treatment of meibomian gland disease (MGD) can be the supplementation of meibomian gland secretion (MGS) with nonpolar lipids (NPL) rich plant oils. Sesame oil (SO), approximately equal in monounsaturated fat (oleic acid, 40% of total) and polyunsaturated fat (linoleic acid, 42% of total), has shown multiple health benefits due to its anti-inflammatory and antioxidant effects. Thus, the interactions between SO and MGS in surface layers deserve further study. Therefore, pseudobinary films were formed with controlled MGS/SO molar ratios (0%, 10%, 30%, 50%, and 100% SO) at the air/water surface of the Langmuir trough over phosphate buffered saline (pH 7.4) subphase. Surface pressure (π)-area (A) isotherms and Brewster angle microscopy observations showed nonideal interactions where SO aggregates with MGS and complements the NPL stratum of the meibomian layers. The analysis of stress relaxation transients with Kohlrausch–Williams–Watts equation revealed that the supplementation of fixed amount of MGS with excess lipids via SO altered the dilatational elasticity of the films as reflected by the increase of the exponent β. Thus, SO with its unique combination of high oxidative stability and abundance of long polyunsaturated acyl chains might be a useful supplement to MGS layers.     

On the origin of the (1216)-orientation in epitaxial AIN layers on R-plane sapphire

Epitaxial AIN grown by MOCVD on (011 2)Al₂O₃ substrates usually is (12 10)-oriented. Here for the first time (12 16)AIN was found in MOCVD layers. This AIN orientation is known from other growth techniques, its origin is generally not understood. An explanation is given based on twinning in the early growth stages which is also applicable to the growth of (12 16)ZnO on (011 2)Al₂O₃.     

Invariants of the length spectrum and spectral invariants of planar convex domains

This paper is concerned with a conjecture of Guillemin and Melrose that the length spectrum of a strictly convex bounded domain together with the spectra of the linear Poincaré maps corresponding to the periodic broken geodesics in determine uniquely the billiard ball map up to a symplectic conjugation. We consider continuous deformations of bounded domains _s ,s[0, 1], with smooth boundaries and suppose that ₀ is strictly convex and that the length spectrum does not change along the deformation. We prove that ₀ is strictly convex for anys along the deformation and that for different values of the parameters the corresponding billiard ball maps are symplectically equivalent to each other on the union of the invariant KAM circles. We prove as well that the KAM circles and the restriction of the billiard ball map on them are spectral invariants of the Laplacian with Dirichlet (Neumann) boundary conditions for suitable deformations of strictly convex domains.Supported by Alexander von Humboldt foundation     

Über Herstellung und Thermostabilität der Chalkogenate von Antimon und Wismut, 4. Mitt.: Herstellung und Untersuchung der Thermostabilität von Wismutselenat

A method of obtaining bismuth(III) selenate Bi₂(SeO₄)₃ will be described. The thermal dissociation in air was studied by means of thermal, thermogravimetric, X-ray and chemical analysis. The probable scheme of the thermal dissociation of the compound will be discussed.

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The cluster Ir4 and its interaction with a hydrogen impurity. A density functional study

To contribute to the understanding of how iridium particles act as catalysts for hydrogenation and dehydrogenation of hydrocarbons, we have determined structures and binding energies of various isomers of Ir(4) as well as HIr(4) on the basis of relativistic density functional theory. The most stable isomer of Ir(4) showed a square planar structure with eight unpaired electrons. The tetrahedral structure, experimentally suggested for supported species, was calculated 49 kJ mol(-1) less stable. Hydrogen coordinates preferentially to a single Ir center of the planar cluster with a binding energy of up to 88 kJ mol(-1) with respect to the atom in the H(2) molecule. Terminal interaction of hydrogen with an Ir(4) tetrahedron causes the cluster to open to a butterfly structure. We calculated terminal binding of hydrogen at different Ir(4) isomers to be more stable than bridge coordination, at variance with earlier studies.