Fluordiazadiphosphetidine, 11. Mitt.: Eine neue Methode zur Herstellung der doppelt zwitterionischen Verbindung (CH3N)6P4F8

A new synthetic route for the preparation of the betain-like compound (CH₃N)₆P₄F₈ from (CH₃NPF₃)₂,N-methyl-hexamethyldisilazane andN,N-dimethyl-urea has been found. The steps of this multi-stage reaction could be rationalized to a far extent.

10. Mitteilung:Kubjacek M., Utvary K., Mh. Chem.112, 305 (1981).     

Isomerization ofn-hexane overplatinum loaded zeolites

The effect of the calcination temperature of bifunctional Pt/zeolites on the isomerization ofn-hexane has been investigated. The catalyst calcined at 350°C showed the highest metal dispersity and the best activity. The higher selectivity of dimethylbutanes over Pt/H- than over Pt/H-MOR might be attributed to the combined effect of acidity, channel structure and pore size of zeolites.     

Calculation of harmonic force constants,vibrational frequencies and integrated intensities of some organic molecules using the MINDO—Forces method

The harmonic force constants, vibrational frequencies and integrated intensity ratios of CH₂, H₂O, CH₂O, C₂H₂, CO₂, HCN, CH₃, CH₄, and C₂H₄ have been calculated using the MINDO—FORCES program and the Pulay method for the calculation of the molecular force constants. The results obtained are in general quite satisfactory when compared with available literature values. The results are, however, not as satisfactory in case of molecules containing heteroatoms, due to the neglect of some dipolar repulsion integrals for the heteroatoms by the MINDO/3 method. Calculated integrated intensities for CH₃ and C₂H₄ agree well with experimental results. The calculated integrated intensities for other molecules are obtained for the first time and no comparison with published data is therefore possible.Part of the M.Sc. Thesis of K. H. A. 1978.     

Zur Bildung von Xylol-tricarbonylchrom (Dimethylbenchrotrenen) aus Di-n-butylether und Hexacarbonylchrom

The reaction of fluorenone ethyleneketal (9), diphenic anhydride as well as of biphenyls such as4 with Cr(CO)₆ in refluxing di-n-butylether (BE) gives dimethylbenchrotrenes [xylene-Cr(CO)₃,7] which are also formed by refluxing pureBE with Cr(CO)₆—although with much lower yields. Similarily, from di-n-pentylether and Cr(CO)₆ isobutyl- and 1-methyl-3-propyl-benchrotrene (13 and14) were obtained, whilst from di-n-propyl- and-hexylether, resp., and Cr(CO)₆ no benchrotrenes could be isolated.Tentative assumptions on the catalytic action of certain functional groups were confirmed by the reaction ofBE and Cr(CO)₆ in the presence of carbonamides, such as acetamide, urea and pyrrolidone, where 1,4-dimethylbenchrotrene (7 c) was formed with appreciable yields.Studies using dideuteratedBE showed that—at least for the reaction of9 with Cr(CO)₆ (giving a much lower yield of7 than with undeuteratedBE)—a simple bimolecular mechanism can be excluded.

     

Superoxes,high temperature universal phases in (GC)2

Most of the common classes of organic compounds chromatograph normally on Superoxes. There is no tailing or adverse effect from excessively different activity different activity coefficients. Superoxes are therefore universal phases for gas chromatography. This is also expressed by a wide useful temperature range from ～50° to ～300°. High MW Superox-4 has a MAOT about 20° higher than the lower MW Superox-0.1. Several applications illustrating the versatility of Superox phases in (GC)² are presented.     

A new general-purpose isothermal microcalorimeter for use at temperatures up to 200 °C

The design and some properties of a new general-purpose isothermal microcalorimeter are reported. The instrument is a twin thermopile heat conduction calorimeter, which is designed for use up to 200 °C. The calorimetric units and surrounding heat sink are suspended inside a hollow aluminium construction, which is thermostated. Above that unit a second thermostated block is positioned and the whole assembly is suspended inside a Dewar vessel. When the instrument is used at room temperature and below, the thermostated units are cooled by use of an insertion Peltier effect cooler. The instrument can be used with a wide range of different reaction vessels (diameter 14 mm). Baseline experiments have been conducted in the temperature range 15-200 °C. Typical values obtained during 10 h periods at 200 °C are ±3 and ±10 nW for the baseline drift and baseline fluctuations, respectively. The heat detection limit, determined by release of electrical energy, is about 2 μJ. Preliminary stability measurements have been conducted at 100 °C on samples of stabilised and non-stabilised polyamide film.     

On invexity-type nonlinear programming problems

In this paper, we propose a new class of nonlinear programing, called SFJ-invex programming. The optimality characterization shows that a problem is SFJ-invex if and only if a Fritz John point together with its multiplier, is a Fritz John saddle point of the problem. Under any constraint qualification assumption, a problem is SFJ-invex if and only if a Kuhn-Tucker point together with its multiplier is a Kuhn-Tucker saddle point of the problem. Furthermore, a generalization of the SFJ-invex, class is developed; the applications to (h, )-convex programming, particularly geometric programming, and to generalized fractional programming provide a relaxation in constraint qualification for differentiable problems to get saddle-point type optimality criteria.The author wishes to thank the referee for helpful comments.     

On input/output stabilization of singular integrodifferential systems

In this paper we consider a class of systems described by singular integrodifferential equations. This type of systems appear, for example, in the modeling of certain aeroelastic control problems. We study these systems in frequency domain framework and show the existence of finite-dimensional stabilizing controllers. An algorithmic procedure is outlined for the construction of such controllers. In order to illustrate the numerical aspects of this algorithm, we present an example involving the classical Theodorsen model of an airfoil, which fits in the class of systems considered here.This work was supported in part by the National Science Foundation under Grants DMS-8907019 and MSS-9203418.     

Standard pseudo-Hermitian structure on manifolds and seifert fibration

A strictly pseudoconvex pseudo-Hermitian manifoldM admits a canonical Lorentz metric as well as a canonical Riemannian metric. Using these metrics, we can define a curvaturelike function onM. AsM supports a contact form, there exists a characteristic vector field dual to the contact structure. If induces a local one-parameter group ofCR transformations, then a strictly pseudoconvex pseudo-Hermitian manifoldM is said to be a standard pseudo-Hermitian manifold. We study topological and geometric properties of standard pseudo-Hermitian manifolds of positive curvature or of nonpositive curvature . By the definition, standard pseudo-Hermitian manifolds are calledK-contact manifolds by Sasaki. In particular, standard pseudo-Hermitian manifolds of constant curvature turn out to be Sasakian space forms. It is well known that a conformally flat manifold contains a class of Riemannian manifolds of constant curvature. A sphericalCR manifold is aCR manifold whose Chern-Moser curvature form vanishes (equivalently, Weyl pseudo-conformal curvature tensor vanishes). In contrast, it is emphasized that a sphericalCR manifold contains a class of standard pseudo-Hermitian manifolds of constant curvature (i.e., Sasakian space forms). We shall classify those compact Sasakian space forms. When 0, standard pseudo-Hermitian closed aspherical manifolds are shown to be Seifert fiber spaces. We consider a deformation of standard pseudo-Hermitian structure preserving a sphericalCR structure.Dedicated to Professor Sasao Seiya for his sixtieth birthday     

Spectroscopic properties of the photoproducts of pyridoxal-5′-P irradiation: Catalytic site recognition of ribonuclease A

Photoproducts of pyridoxal-5-P, i.e., 4-pyridoxic-5-P and bis-pyridoxal-5-P, have been studied by spectroscopic methods. The spectroscopic properties of bis-pyridoxal-5-P (bis-PLP) resemble those of pyridoxal-5-P (PLP) under similar experimental conditions. The coupling of methylen hydrogens to the phosphorus atom has been shown by NMR spectroscopy. The singlet in the³¹P-NMR spectra and the triplet in¹H-undecoupled experiments confirm the presence of the phosphate group in the 5 position of the structure of the vitamin. The effect of pH and solvent composition on the relative distribution of species of bis-pyridoxine-5-P (bis-PNP) has been investigated by absorption and fluorescence spectroscopy. The acid-base dissociation of the phosphate group is easily detected by emission spectroscopy. Bis-PNP and bis-PLP bind to the enzyme RNase A and they behave as competitive inhibitors with respect to the substrate cytidine-2-3-cyclic phosphate. The natural forms of vitamin B₆, pyridoxine, and pyridoxine-5-P have no effect on the catalytic activity of the protein. Experimental evidence derived from fluorescence and inhibition experiments is consistent with the hypothesis that bis-PNP recognizes the catalytic site of RNase A.