Synthesis of regiospecifically meta-substituted poly(phenylacetylene)s and some of their electrical properties

The syntheses, characterizations, and electrical properties of four regiospecifically substituted poly(phenylacetylene)s are described. Tungsten(VI) chloride/tetra-n-butyltin (WCl₆/n-Bu₄Sn) catalyst system (Higashimura–Masuda, H.–M. catalyst) was used to polymerize 3-bromo-, 3-chloro-, 3-trimethylsilyl-, and 3-trimethylstannylphenylacetylenes in order to obtain high-molecular-weight and soluble materials. Characterizations of these polymers were done by IR and UV spectroscopic methods, GPC, DSC, and elemental analysis. The electrical conductivities of the polymers were measured on the surface of pressed pellets by a four-point probe.     

Wärmeleitung beim Erstarren geometrisch einfacher Körper

Zusammenfassung Die Erstarrung vor einer ebenen Platte sowie an der Innen- und Außenseite eines Zylinders und einer Kugel wurde numerisch berechnet und in Diagrammen systematisch zusammengestellt. Aus diesen kann man die Erstarrungszeiten für Kühlung bei endlichem Wärmeübergang, konstanter Temperatur oder konstantem Wärmestrom bestimmen. Ein Vergleich mit bekannten Näherungslösungen zeigt, daß diese nur in bestimmten Bereichen der maßgebenden Kennzahlen zu brauchbaren Ergebnissen führen.

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Heat conduction in solidification of geometrically simple bodies

The solidification on a flat plate as well as on the inside and outside of a cylindrical and a spherical container was numerically calculated and is presented systematically in diagrams. The diagrams show the solidification times for finite heat transfer between the solidified layer and the coolant, constant wall temperature, and constant heat transfer rates. A comparison with known approximations proves, that these yield useful results only in limited ranges of the relevant dimensionless parameters.

     

Study of transient and quasi-steady ablation of polytetrafluoroethylene layers

A study of the transient one-dimensional ablation of a PTFE-layer heated by a constant heat flux at the surface and cooled by finite heat transfer at the back is performed using a previously presented analytical model. The influences of various parameters upon the course of ablation are investigated and some limiting cases are discussed. The numerical solution for the quasi-steady ablation is presented by graphs, which are also approximated by correlations for the computation of the coupled boundary layer and PTFE-ablator.

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Instationäre und quasi-stationäre Ablation von PTFE-Schichten

Zusammenfassung Die instationäre, eindimensionale Ablation einer PTFE-Schicht wird untersucht, der ein konstanter Wärmestrom an der Oberfläche zugeführt und ein Kühlstrom durch endlichen Wärmeübergang an der Rückseite abgeführt wird. Dabei wird ein analytisches Modell zugrundegelegt, über das kürzlich berichtet wurde, und verschiedene Einflüsse auf den Ablationsverlauf betrachtet sowie Grenzfälle diskutiert. Die numerische Lösung für quasistationäre Ablation kann Diagrammen entnommen werden. Außerdem werden hierfür Korrelationen angegeben für die simultane Berechnung des PTFE-Ablators mit einer Grenzschicht.

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Nomenclature a thermal diffusivity - c polymer mass fraction: density ratio of the decomposing and the undecomposed material - k coefficient of heat transmission - m ablation rate (ablating mass flux) - q heat flux to the surface - Q dimensionless heat flux - t time - T temperature - x coordinate - x_O initial layer thickness - y₁ (x-)/(-), transformed coordinate - y₂ (x-)/(-), transformed coordinate - penetration bond - phase interface - thermal conductivity of crystalline PTFE at the melting point - layer thickness Indices k coolant - at the phase interface (melting point) - at the surface     

A nickel hydride complex in the active site of methyl-coenzyme m reductase: implications for the catalytic cycle

Methanogenic archaea utilize a specific pathway in their metabolism, converting C1 substrates (i.e., CO2) or acetate to methane and thereby providing energy for the cell. Methyl-coenzyme M reductase (MCR) catalyzes the key step in the process, namely methyl-coenzyme M (CH3-S-CoM) plus coenzyme B (HS-CoB) to methane and CoM-S-S-CoB. The active site of MCR contains the nickel porphinoid F430. We report here on the coordinated ligands of the two paramagnetic MCR red2 states, induced when HS-CoM (a reversible competitive inhibitor) and the second substrate HS-CoB or its analogue CH3-S-CoB are added to the enzyme in the active MCR red1 state (Ni(I)F430). Continuous wave and pulse EPR spectroscopy are used to show that the MCR red2a state exhibits a very large proton hyperfine interaction with principal values A((1)H) = [-43,-42,-5] MHz and thus represents formally a Ni(III)F430 hydride complex formed by oxidative addition to Ni(I). In view of the known ability of nickel hydrides to activate methane, and the growing body of evidence for the involvement of MCR in "reverse" methanogenesis (anaerobic oxidation of methane), we believe that the nickel hydride complex reported here could play a key role in helping to understand both the mechanism of "reverse" and "forward" methanogenesis.     

On the Edge of the Known: Extremely Electron-Rich (Di)Carboranyl Phosphines

The syntheses of the first B9-connected carboranylphosphines (B9-Phos) featuring two carboranyl moieties as well as access to B9-Phos ligands with bulky electron-donating substituents, previously deemed unattainable, is reported. The electrochemical properties of the B9-Phos ligands were investigated, revealing the ability of the mesityl derivatives to form stabilized phosphoniumyl radical cations. The B9-Phos ligands display an extremely electron-releasing character surpassing that of alkyl phosphines and commonly used N-heterocyclic carbenes. This is demonstrated by their very small Tolman electronic parameters (TEPs) as well as extremely low P−Se coupling constants. Cone angles and buried volumes attest to the high steric demand exerted by the (di)carboranyl phosphines. The dicarboranyl phosphine Au^I complexes show superior catalytic performance in the hydroamination of alkynes compared to the monocarboranyl phosphine analogs.     

Enantioselective separation of all-E-astaxanthin and its determination in microbial sources

A method for the enantioselective separation of all-E-astaxanthin (3,3'-dihydroxy-beta,beta-carotene-4,4'-dione), an important colorant in the feed industry, was developed. Different chiral stationary phases (CSPs) such as Pirkle phases (R,R Ulmo and l-leucine), modified polysaccharides and a beta-cyclodextrin have been investigated on their separation performance of astaxanthin enantiomers. Direct resolution was only achieved employing the Chiralcel OD-RH (cellulose-tris-3,5-dimethylphenyl-carbamate) under reversed phase conditions. The chiral separation of the enantiomeric forms of astaxanthin produced in microalgae and yeasts was reported. The yeast Xanthophyllomyces sp. produces astaxanthin predominantly in the R,R configuration, whereas in the green microalgae Scenedesmus sp. astaxanthin is built primarily in the S,S form. The separation method for the identification of astaxanthin enantiomers is of great interest since astaxanthin is used as functional food additive in human nutrition. Moreover the method may be used as a food chain indicator in farmed salmon.     

Wärme- und Stofftransport in Teflon-Schichten bei der Ablationskühlung

For the transient, one-dimensional ablation of a teflon ablation layer an analytical model has been developed. It takes into account the crystalline-amorphous phase transition, the thermal expansion, the depolymerization and the formation of higher-molecular products at the surface. The results of the numerical computation are compared with ablation measurements in arc jet facilities for transient ablation and the limiting case of quasisteady ablation. The course of the ablation process in principle is illustrated, and different influences and limiting cases are investigated.

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Wärme- und Stofftransport in Teflon-Schichten bei der Ablationskühlung

Zusammenfassung Für die instationäre, eindimensionale Ablation einer Teflon-Ablationsschicht wurde ein analytisches Modell entwickelt. Es berücksichtigt den kristallin-amorphen Phasenübergang innerhalb der TeflonSchicht, die thermische Ausdehnung, die Depolymerisation und die Bildung höhermolekularer Produkte and der Oberflache. Die Ergebnisse der numerischen Rechnung werden für instationären Ablation und den Grenzfall quasistationärer Ablation mit Meßwerten aus Ablationsversuchen im Plasmakanal verglichen. Nach der Erläuterung des grundsätzlichen Ablauts werden verschiedene Einflüsse und Grenzfälle untersucht.

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Vorgetragen auf der DGLR-Fachausschußsitzung FA 3.1 Wärmeübergang und Ablation am 15.5.1975 in Köln-Porz (DLR-Mih. 75-20)     

Quantum Chemical Microsolvation by Automated Water Placement

We developed a quantitative approach to quantum chemical microsolvation. Key in our methodology is the automatic placement of individual solvent molecules based on the free energy solvation thermodynamics derived from molecular dynamics (MD) simulations and grid inhomogeneous solvation theory (GIST). This protocol enabled us to rigorously define the number, position, and orientation of individual solvent molecules and to determine their interaction with the solute based on physical quantities. The generated solute–solvent clusters served as an input for subsequent quantum chemical investigations. We showcased the applicability, scope, and limitations of this computational approach for a number of small molecules, including urea, 2-aminobenzothiazole, (+)-syn-benzotriborneol, benzoic acid, and helicene. Our results show excellent agreement with the available ab initio molecular dynamics data and experimental results.     

Coumarins give misleading absorbance with Ellman's reagent suggestive of thiol conjugates

In the course of a screening for phytochelatins in cadmium-exposed bryophytes in the terrestrial mosses Polytrichum formosum and Atrichum undulatum we detected compounds with absorption properties and retention times similar to phytochelatins when applying the commonly used standard method RP-HPLC and post-column derivatization with thiol-specific DTNB (Ellman) reagent. Moreover, as with phytochelatins known in other plants, the concentrations of these compounds increased slightly after Cd stress. The concentration of the precursor glutathione (gamma-ECG), however, increased in the presence of Cd. In order to verify the identity of these putative phytochelatins we performed LC-ESI-MS analyses as well as 1H NMR on extracts from P. formosum and A. undulatum. Spectroscopic investigations indicated that the detected compounds were neither phytochelatins nor other thiol compounds. From the results of HPLC-1H NMR and mass spectrometry we concluded that at least one of these substances was a coumarin, probably a 5,8-dihydroxy-7-methoxycoumarin-5-beta-glucopyranoside, which has already been described for A. undulatum and P. formosum. The results of our investigations prove that under the basic pH conditions essential for the Ellman test for thiol compounds, coumarins show comparable UV/VIS absorption properties. Therefore, a positive post-column Ellman reaction cannot unambiguously prove the presence of thiol-containing compounds in plants.