Ga8Ir4B – ein Gallium-Iridiumborid mit isolierten,annähernd quadratisch planaren Ir4B-Gruppen in einer vom CaF2-Typ abgeleiteten Struktur

Ga₈Ir₄B – a Gallium Iridium Boride with isolated, nearly square planar Ir₄B Groups in a Structure derived from the CaF₂ Type The new compound Ga₈Ir₄B (tetragonal, I4₁/acd, a = 853.69(2) pm, c = 2 105.69(6) pm, Z = 8, 614 reflections, 31 parameters, R = 0.034) was prepared by reaction of the elements at 1 100°C. The structure is derived from the CaF₂ type. It contains isolated Ir₄B groups with boron in an unusual, nearly square planar coordination.     

Chiral [2H]-Labelled Methylene Groups in Trienoic- and Dienoic Fatty Acids: A Facile Approach via Asymmetric Epoxidation of [2H] Allyl Alcohols

Chiral [²H] -labelled methylene groups flanked by two double bonds within (poly)unsaturated fatty acids are readily available from trans-2,3-epoxy[2,3-²H₂] alk-4-yn-l-ols, obtained in their turn by asymmetric epoxidation of the corresponding (E)-[2,3-²H₂] alk-2-en-4-yn-l-ols (see Scheme 3). The procedure is exemplified for (8S,3Z,6Z,9Z)-[7,8-²H₂] trideca-3,6,9-trienoic acid ((8S)- 11 ) and (8R)- 11 (Scheme 4) as well as for (5S,3Z,6Z)-[4,5^?2H₂]deca-3,6-dienoic acid ((5S)- 13 ) and (5R)- 13 (Scheme 5).     

Sterospecific Syntheses and Spectroscopic Properties of Isomeric 2,4,6,8-Undecatetraenes. New Hydrocarbons from the Marine Brown Alga Giffordia mitchellae. Part IV.

Giffordene (=(2Z,4Z,6E,8Z)-2,4,6,8-undecatetraene; 9f ) and five steroisomers are new C₁₁H₁₆ hydrocarbons from the marine brown alga Giffordia mitchellae. Their synthesis is based on non-stereoselective Wittig reactions of (E)-2-alkenals with appropriate acetylenic phosphoranes and subsequent chromatographic separation of the resulting (E/Z)-pairs. The uniform enynes (>98% purity) are then stereospecifically reduced to (Z)-alkenes with Zn(Cu/Ag) in aq. MeOH at r.t. ¹³C- and ¹ H-NMR data of the new tetraenes are presented. Biosynthetically, giffordene ( 9f ) originates from dodeca-3,6,9-trienoic acid via an unstable (3Z,5Z,8Z)-1,3,5,8,-undecatetraene followed by a thermally allowed antarafacial 1,7-sigmatropic hydrogen shift to the (2Z,4Z,6E,8Z)-isomer 9f .     

Bestimmung des Enantiomerenüberschusses von chiralen Ammonium-Ionen mit Hilfe von Flüssigmembranelektroden

Determination of the Enantiomeric Excess of Chiral Ammonium long Using Liquid Membrane Electrodes A cell assembly with two membranes each containing one enantiomer of a chiral ionophore is described. It is suitable for the direct potentiometric determination of the enantiomeric excess of ions. The method is used to determine the enantiomeric excess of ephedronium ions in aqueous solutions.     

Preparation of Neutral Ionophores for Alkali and Alkaline Earth Metal Cations and their application in ion selective membrane electrodes

The preparation of a series of non-cyclic, uncharged ligands able to selectively complex alkali and alkaline earth metal cations is described. These molecules are designed to be used as carriers for cations through membranes. Some of the compounds show high Ca²⁺ and Na⁺ selectivity, respectively, in liquid membrane electrodes.     

EFFECTS OF QUENCHING AGENTS ON THE PHOTODYNAMICALLY-INDUCED CHEMOTACTIC RESPONSE OF THE COLORLESS FLAGELLATE Polytomella magna

Abstract In the presence of the photosensitizer riboflavin at high fluence rates a photoproduct, most probably H₂O₂, is formed which causes negative phototaxis in the colorless flagellate Polytomella magna . The aim of this study was to find out whether H₂O₂ is produced in a type I or II reaction. As has been shown, ¹O₂ quenchers either do not influence the photodynamic action of riboflavin (furfuryl ethanol, DPBF, l -histidine, crocetin) or show slight quenching effects only at very high concentrations ≧ 10⁻² M (DABCO, DMF, imidazole). D₂O is toxic to P. magna even in 1:1 and 1:2 mixtures with H₂O. On the other hand, the quenching effect of 1,4-benzoquinone, highly indicative for the type I pathway, is more than two orders of magnitude stronger than the one of the above mentioned ¹O₂ quenchers. The results suggest that H₂O₂ is produced in a type I reaction. Superoxide does not seem to be involved since superoxide dismutase does not diminish the photodynamic effect of riboflavin.     

Use of Dimethylsilyl Ethers for Characterizing Primary Aliphatic Alcohols: A comparison of mass spectrometric fragmentation of di- and trimethylsilyl derivatives

Mass spectral fragmentation patterns of dimethylsilyl (DMS) ethers of primary unbranched, branched, and secondary unbranched aliphatic alcohols in the C₅ to C₁₀ range are compared with those of the corresponding trimethylsilyl (TMS) derivatives. Unlike their TMS analogues, DMS ethers of primary alcohols exhibit pronounced rupture of the C? C bond adjacent to the oxygen atom within the alkyl moiety (loss of an alkyl radical R) in marked preference to cleavage within the silyl substituent (loss of CH₃). Within this class of compounds, complementary preparation of DMS derivatives can therefore be used to establish or to confirm the site, and thus the primary nature of the hydroxyl group, whereas preparation of TMS ethers may be of advantage in deducing molecular size. For the derivatives of secondary alcohols this diagnostically useful difference in fragmentation behaviour is not observed.     

Non-linear autonomous systems of differential equations and Carleman linearization procedure

The non-linear autonomous of differential equations

$\text{x}\text{?}{}_{\mathrm{i}}\text{=}\text{∑}\text{j}\text{a}{}_{\mathrm{ij}}\text{x}{}_{\mathrm{j}}\text{+}\text{∑}\text{j,k}\text{b}{}_{\mathrm{ijk}}\text{x}{}_{\mathrm{j}}\text{x}{}_{\mathrm{k}}\text{(}\text{x}\text{?}{}_{\mathrm{i}}\text{=dx}{}_{\mathrm{i}}\text{/dt, i, j, k= 1,2,…n)}$

which plays an important role in chemical kinetics and other fields of physics (turbulence and plasma physics) is investigated using the Carleman linearization procedure.     

Numerical application of Euler's series transformation and its generalizations

Summary A nonlinear generalizationÊ _z of Euler's series transformation is compared with the (linear) Euler-Knopp transformationE _z and a twoparametric methodE . It is shown how to applyE orE _, to compute the valuef(z_o) of a functionf from the power series at 0 iff is holomorphic in a half plane or in the cut plane. BothE andE _, are superior toÊ _z . A compact recursive algorithm is given for computingE andE _,.     

Synthesis and Crystal Structure of Bis(tetraethylammonium) Octabromo‐triselenate(II)‐{dibromodiselenate(I)}, [NEt4]2[Se3Br8(Se2Br2)], the Salt of a Mixed‐valence Bromoselenate(II,I) Anion

The brown crystals of [NEt₄]₂[Se₃Br₈(Se₂Br₂)] ( 1 ) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of tetraethylammonium bromide. The crystal structure of 1 has been determined by the X‐ray methods and refined to R = 0.0308 for 10433 reflections. The crystals are monoclinic, space group P2₁ with Z = 2 and a = 12.0393(3) Å, b = 11.8746(3) Å, c = 13.1946(3) Å, β = 96.561(1)° (123 K). In the solid state structure the anion of 1 is built up of Se₃Br₈ unit which consists of a triangular arrangement of three planar SeBr₄ units sharing a common edge through two μ₃‐bridging Br atoms, and one Se₂Br₂ molecule which is linked to one of μ₃‐bridging Br atoms. The three Se^II atoms form a triangle which is almost perpendicular to the planes given by three SeBr₄ moieties. The contact between the μ₃Br and the Se^I atom of the Se₂Br₂ molecule is 3.1711(8) Å and can be interpreted as a bond of the donor‐acceptor type with the μ₃Br as donor and the Se₂Br₂ molecule as acceptor. The terminal Se^II‐Br and μ₃Br‐Se^II bond lengths are in the ranges 2.3537(7)–2.4737(7) Å and 2.7628(7)–3.1701(7) Å, respectively. The bond lengths in coordinated Se₂Br₂ molecule are: Se^I‐Se^I = 2.2636(9) Å, Se^I‐Br = 2.3387(11) and 2.3936(8) Å.