Austauscher mit cyclischen Polyethern als Ankergruppen—II: Anwendungen

Exchangers with cyclic polyethers as anchor groups have a large range of applications such as separations of cations with a common anion, of anions with a common cation, and of neutral organic compounds, and the determination of water by elution chromatography. Some crown ether monomers, especially 4- and 4,4′-alkyl-substituted benzo-derivatives are suitable for extractions and their adducts with heteropoly acids are used as liquid ion-exchangers. The exchangers are also applied in thin-layer chromatography and thin-layer electrophoresis. Furthermore the exchangers are successfully used in preparative chemistry, e.g., in salt conversions in order to isolate salts which are difficult to prepare by other means, in isolation and purification of organic compounds, and for anion activation in organic reactions.     

One-step synthesis of N-[(methylthio)methyl]imidazole and related heterocyclic derivatives via a fummerer rearrangement

N-[(Methylthio)methyl]imidazole may be prepared from dimethylsulfoxide and N-(trimethylsilyl)imidazole or N-(t-butyldimethylsilyl)imidazole at elevated temperatures via a Purnmerer rearrangement. The product was characterized by elemental analysis, mass spectrometry and proton and carbon nmr. Preliminary experiments show that corresponding derivatives of 2-methylimidazole, pyrazole, triazole and benzimidazole may also be prepared in an analogous manner.     

Spin trapping chemistry of sodium 2-sulfonatophenyl t-butyl nitrone . a negatively charged water-soluble spin trap

A new water-soluble negatively charged spin trap, sodium 2-sulfonatophenyl $\text{t}$-butyl nitrone is described.     

O-(2-Hydroxy-5-methyl-phenylazo)benzoes?ure als Reagens zur polarographischen, inversvoltammetrischen und photometrischen Be(II)-Bestimmung

Zusammenfassung o-(2-Hydroxy-5-methyl-phenylazo)-benzoesäure bildet mit Be(II) einen Chelatkomplex, der zu polarographischen, inversvoltammetrischen und photometrischen Bestimmungen verwendet werden kann. In Gegenwart von Al(III), Fe(III), Co(II), Ni(II) und Cu(II) erfolgt die Komplexbildung bevorzugt mit Be(II), wenn die Selektivität des Komplexbildners durch Zugabe von Methanol oder Acetonitril erhöht wird. Für die Polarographie lassen sich die störenden Kationen mit Solochromviolett RS maskieren. So können z. B. bis 10^–9 Mol/ml Be(II) mit einem 3000fachen Al(III)-Überschuß bei einem relativen Fehler von ± 4% simultan bestimmt werden.

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O-(2-Hydroxy-5-methyl-phenylazo)-benzoic acid as reagent for the polarographic, inverse-voltammetric and photometric determination of beryllium(II)

o-(2-Hydroxy-5-methyl-phenylazo)-benzoic acid forms a chelate complex with Be(II) which can be used for polarographic, invers-voltammetric and photometric determinations. In the presence of Al(III), Fe(III), Co(II), Ni(II), and Cu(II) the formation of the Be(II)-complex is selective if methanol or acetonitrile is added. In the polarographic technique interfering cations can be masked with Solochrome Violet RS. 10^–9 mol/ml of Be(II) can be determined simultaneously with a 3000-fold excess of Al(III) with an error ± 4%.

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Zum Teil vorgetragen auf der GDCh-Tagung in Karlsruhe, 13.–18. 9. 1971.     

Mode selective directional couplers for overmoded waveguide systems

Two types of directional couplers for transverse electric (TE) modes are described: short and multihole couplers, respectively. They selectively pick one mode out of a mode mixture in an overmoded circular waveguide system. Unwanted modes are either statistically kept at low level or are suppressed by destructive interference in the coupling waveguide. Mode selectivity and directivity in multihole couplers oscillate up and down with an increasing number of holes, finally reaching a minimum of approximately 20 dB, unless there are competing modes with rational fractions of the beat wavelength. A multihole coupler for the TE₀₂ mode (28 GHz, 63.4 mm waveguide diameter, 41 holes) and a length of 1.6 m shows a calculated directivity of 68 dB and suppresses the unwanted modes TE₀₁ with 34 dB (24 dB), TE₂₂ with 37 dB (45 dB), and further modes TE_m (<5, m<6) with 17 dB to 34 dB in forward direction (figures in parentheses are for unwanted modes propagating in backward direction).A short directional coupler for the TE₀₁ mode (28 GHz, 63.4 mm waveguide diameter) with 16 holes and a length of 230 mm shows a directivity of 55 to 100 dB between 27.9 and 28.1 GHz, suppressing the TE₀₂ mode with 35 to 80 dB, the TE₀₃ mode with 30 to 65 dB, and the TE₂₂ mode with 30 to 70 dB.     

Packings and stationary phases for biopolymer separations by HPLC

Summary Packings and stationary phases applied to high resolution separations of proteins, enzymes, and nucleic acids must satisfy a series of distinct criteria that are different from those usually required by HPLC of low molecular weight non-biologically active analytes. These requirements have been met through substantial improvements in classical gel media together with novel developments in silica supports, and have led to a family of products with tailor-made and reproducible properties. Supports consisting of cross-linked organic gels, and inorganic materials (mostly silicas) are now available with graduated particle sizes, pore sizes, porosities and surface areas as well as non-porous beads. A whole range of stationary phases, such as reversed phase, hydrophobic interaction, ion exchanger and affinity packings, were designed for application as chemical sensors for biopolymer recognition in adsorptive chromatography. The phase systems are operated in the gradient mode, giving high resolution and high peak capacities. In addition, aqueous liquid-liquid partitioning systems have been developed for the fractionation of proteins and nucleic acids. Size exclusion media complete the set of HPLC variants enabling a discrimination of proteins according to their size and shape in an isocratic elution mode. Basically, protein purification and isolation is a multistage process where-by the HPLC variants are combined in a logistic sequence, utilizing the different selectivities of the phase systems and thus maximising resolution, speed and throughput.     

Synthese und EPR-spektroskopie dicyclopentadienylanaloger der schlenkschen und tschitschibabinschen kohlenwasserstoffe

The synthesis of several hydrocarbon biradicals consisting of two tetraphenylcyclopentadienyl moieties with different bridge fragments is described. The ESR powder spectra show that there is an intramolecular coupling of two unpaired electron spins to a triplet spin state. The magnitude of the zero field splitting (zfs) is used to discriminate between different molecular conformations. More detailed structural informations are obtained from the observed zfs by quantummechanical calculations of the zfs-parameter D as a function of various torsional angles and cis- or trans-orientations of molecular fragments. The behaviour of the four highest occupied MO's with respect to structural changes in the biradicals is discussed.