Identification of cis/trans isomers of methyl ester and oxazoline derivatives of unsaturated fatty acids using GC–FTIR–MS

Identification of cis/trans isomers of unsaturated fatty acids cannot usually be achieved by GC-MS (gas chromatography-mass spectrometry) without reference substances. In this study a GC-FTIR-MS system (gas chromatography-Fourier transform-mass spectrometry) was used to identify fatty acid methyl esters (FAMEs) and differentiate between the cis/trans isomers. Besides methyl esters, 2-alkenyl-4,4-dimethyloxazoline derivatives (DMOX), which have been used to locate double bond positions of unsaturated fatty acids, were examined with respect to their suitability for cis/trans differentiation. A combined GC-FTIR-MS system with a wide band (4000–550 cm^?1) mercury cadmium telluride (MCT) detector was used in series and parallel to identify 31 reference unsaturated fatty acids, including 7 pairs of cis/trans isomers. Serum samples of healthy persons and commercially available fish oil were analyzed as examples of complex mixtures. Using splitless injection the detection limit for the less sensitive IR detector was 25 ng/μl in case of the weak cis and trans bands. In the FTIR spectra cis/trans isomers were identified by analysis of bands arising from C? H out-of-plane (oop) bending: for both the FAME and DMOX derivatives cis-1,2-disubstituted double bonds give a strong band near 720 cm^?1 and the corresponding trans isomers near 967 cm^?1. cis Isomers could be identified further by a band at 3012 cm^?1. With the combined data of the GC-FTIR-MS system it is now possible to identify polyunsaturated fatty acids with regard to the discrimination of cis/trans isomers.     

XVI. (2,5-C4Bu2RHN)MCl3 (M = Ti, Zr, Hf; R = H, SiMe3)—Azacyclopentadienyl-Komplexe der Gruppe 4-Metalle

The azacyclopentadienyl compounds (2,5-C₄^tBu₂RHN)MCl₃ (M = Ti, Zr, Hf; R = H, SiMe₃) have been prepared as stable solids from the lithiated pyrroles and MCl₄. The π-coordination of the azacyclopentadienyl ligands, as suggested from ¹³ C NMR data, has been confirmed for (2,5-C₄^tBu₂H₂N)TiCl₃ by an X-ray diffraction study.     

First synthesis of a beta(2)-homoamino acid by enantioselective catalysis

The enantioselective conjugate addition of diethylzinc to the activated nitroolefin methyl 3-nitropropenoate is efficiently catalyzed by copper(I) complexes with BINOL-based enantiopure phosphoramidite ligands. The nitroolefin moiety acts as the predominant Michael acceptor, giving rise to the unambiguous formation of 2-alkyl-3-nitro-propanoates. Moderate to excellent enantioselectivities and high chemical yields are obtained. The product can easily be transformed into a beta(2)-homoamino acid. [reaction--see text]     

Über die endliche Lösbarkeit des Plateau-Problems in Riemannschen Mannigfaltigkeiten

We prove finiteness results of Plateau's problem for boundary curves in a normal chart of radius R < /2 in an analytic Riemannian manifold. It is shown that for analytic there exist only finitely many minimal surfaces of the type of the disc bounded by , which represent an absolute minimum of area, and if boundary branch points are excluded, there exist only finitely many relative minima in the normal chart. If lies on the boundary of a strict convex manifold, there cannot exist any boundary branch points.

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Die vorliegende Arbeit entstand als Dissertation am Mathematischen] Institut der Universität Saarbrücken.

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Herrn Prof. Dr. F. Tomi möchte ich für die Bereitstellung des Themas und für seine Betreuung sehr herzlich danken.     

State-transition structures in physics and in computation

In order to establish close connections between physical and computational processes, it is assumed that the concepts of state and of transition are acceptable both to physicists and to computer scientists, at least in an informal way. The aim of this paper is to propose formal definitions of state and transition elements on the basis of very low level physical concepts in such a way that (1) all physically possible computations can be described as embedded in physical processes; (2) the computational aspects of physical processes can be described on a well-defined level of abstraction; (3) the gulf between the continuous models of physics and the discrete models of computer science can be bridged by simple mathematical constructs which may be given a physical interpretation; (4) a combinatorial, nonstatistical definition of information can be given on low levels of abstraction which may serve as a basis to derive higher-level concepts of information, e.g., by a statistical or probabilistic approach. Conceivable practical consequences are discussed.     

Different modes of aggregation in organoaluminium and -gallium hydroxylamides

The organoaluminium and -gallium hydroxylamides (Me2GaONMe2)2, (tBu2AlONMe2)2, (tBu2GaONMe2)2 and (Me2AlONiPr2)2 have been prepared by the reaction of the hydroxylamines Me2NOH and iPr2NOH with the trialkylmetal compounds trimethylgallium, tri-tbutylaluminium and tri-tbutylgallium, respectively. All compounds have been characterised by NMR spectroscopy (1H, 13C, 15N, 17O and 27Al), by mass spectrometry and elemental analyses. The crystal structures of the four compounds have been determined, showing that they all form dimers but with different modes of aggregation: (Me2GaONMe2)2 has a Ga2O2N2 six-membered ring, (tBu2AlONMe2)2 and (Me2AlONiPr2)2 have Al2O2 four-membered rings, (tBu2GaONMe2)2 forms a Ga2O2N five-membered ring.     

2‐Iminoimidazoline — starke Stickstoffbasen als Koordinationspartner in der Anorganischen Chemie

2‐Iminoimidazolines — Strong Nitrogen Bases als Ligands in Inorganic Chemistry Due to the tendency of the 5‐membered cyclic fragment to accept a positive charge which yields an ylide type bonding situation, 2‐iminoimidazolines are strong nitrogen bases. They can serve as neutral ligands being 2+2 electron donors. Deprotonation leads to the anions which are potential 2+4 electron donors. We describe first the synthesis and characterization of the title compound 2‐imino‐1, 3‐dimethylimidazoline (ImNH, 8 ) and its anion 9 . Next we demonstrate their properties as ligands in complexes of main group elements and transition metals. In a third chapter we describe attempts to functionalize iminoimidazolines with the goal to create neutral ligands that coordinate in a semistable fashion. On this way we want to make a contribution to the chemistry of complex compounds directed towards catalysis.     

A sufficient condition for a graph to be hamiltonian

Those non-hamiltonian graphsG withn vertices are characterized, which satisfy the Ore-type degree-conditiond(x)+d(y)n–2 for each pairx,yM of different nonadjacent vertices whereM consists of two vertices ofG. As an application a theorem on hamiltonian connectivity of graphs is given. Furthermore, a condition is presented which is sufficient for the existence of a covering of a graph by two disjoint paths with prescribed set of startpoints and prescribed set of endpoints. A class of graphs is described which have no covering of this kind.     

Symmetries and correlation inequalities for classicaln-vector models

We describe a new class of single spin measures on then-dimensional sphereS _r ⁿ of radiusr (n 4) for which Lebowitz-type [J. Lebowitz,J. Stat. Phys. 16:463 (1977)] inequalities hold. This is achieved by an appropriate parametrization ofS _r ⁿ . The above class includes the uniform measures onxs Rⁿ ¦x¦ r for any 0 p r. The second topic of this paper is an abstract formulation of the first Griffiths inequality [R. B. Griffiths,J. Math. Phys. 8:478 (1967)] and the underlying symmetry property.     

Synthesis and characterization of the open-framework barium bisphosphonate [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O

Following the strategy of using polyfunctional phosphonic acids for the synthesis of open-framework metal phosphonates, the phosphonocarboxylic acid (H2O3PCH2)2NCH2C6H4COOH was used in the hydrothermal synthesis of new Ba phosphonates. Its decomposition led to the first open-framework barium phosphonate [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O. The synthesis was also successfully performed using iminobis(methylphosphonic acid), (H2O3PCH2)2NH, as a starting material, and the synthesis was optimized to obtain as a pure material. The reaction setup as well as the pH are the dominant parameters, and only a diffusion-controlled reaction led to the desired compound. The crystal structure was solved from single-crystal data: monoclinic; C2/c; a=2328.7(2), b=1359.95(7), and c=718.62(6) pm; beta=98.732(10) degrees ; V=2249.5(3)x10(6) pm3; Z=4; R1=0.036; and wR2=0.072 (all data). The structure of [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O is built up from BaO8 and BaO10 polyhedra forming BaO chains and layers, respectively. These are connected to a three-dimensional metal-oxygen-metal framework with the iminobis(methylphosphonic acid) formally coating the inner walls of the pores. The one-dimensional pores (3.6x4 A) are filled with H2O molecules that can be thermally removed. Thermogravimetric investigations and temperature-dependent X-ray powder diffraction demonstrate the stability of the crystal structure up to 240 degrees C. The uptake of N,N-dimethylformamide and H2O by dehydrated samples is demonstrated. Furthermore, IR, Raman, and 31P magic-angle-spinning NMR data are also presented.