Untersuchungen zur 3-Phononenabsorption in partiell kristallinen Polymeren

Zusammenfassung In dieser Arbeit wird die Dreiphononenabsorption in Polymeren, die den Hauptanteil an den dielektrischen Verlusten im Millimeterwellengebiet stellt, theoretisch und experimentell untersucht. Aus der Störungsrechnung bis zur 2. Ordnung wird die Temperaturabhängigkeit der Absorption abgeschätzt. Damit ist eine befriedigende Deutung des gesamten Temperaturverlaufs der dielektrischen Verlust-Kurven möglich. Im Hochtemperaturbereich läßt sich die Mehrphononenabsorption eindeutig gegenüber restlichen Relaxationsprozessen abgrenzen. Im Tieftemperaturgebiet konnte erstmals auch für das Millimeterwellengebiet ein temperaturunabhängiger Bestandteil fehlordnungsinduzierter Einphononenabsorption nachgewiesen werden. Im Übergangsbereich durchlaufen die Absorptionskurven einen Wendepunkt bei einer charakteristischen TemperaturT ₀, die dem Schwerpunkt der am Absorptionsprozeß beteiligten Phononenfrequenzen entspricht. Daraus konnten in Übereinstimmung mit dem Experiment die Frequenzen der niedrigsten optisch aktiven Phononen für die verschiedenen Polymeren abgeschätzt werden.

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Summary The 3-phonon absorption in polymers, which gives the main contribution to their dielectric loss in the microwave region, is theoretically and experimentally investigated. Perturbation theory up to the second order is used for the evaluation of its temperature dependence. The theoretical results allow an interpretation of the total absorption-temperature-curves: In the high temperature region 3-phonon absorption can be distinguished from residual relaxation losses (above the glass temperature). In the low temperature region the existence of a low frequency tail of temperature independent disorderinduced one-phonon absorption became evident. At intermediate temperatures (50–150°K) the curves show an inflexion point or plateau at a characteristic temperatureT ₀, which according toT ₀= ⁰, corresponds to the frequencies of those phonons, that mainly contribute to the multiphonon absorption. The plateau gives, in good agreement with the experiment, the frequencies of the lowest optically active phonons in the various polymers.

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Mit 6 Abbildungen in 8 Einzeldarstellungen

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Vorgetragen auf der Arbeitssitzung des Fachausschusses Physik der Hochpolymeren in der Frühjahrstagung 1970 des Regionalverbandes Hessen-Mittelrhein-Saar der Deutschen Physikalischen Gesellschaft in Darmstadt, 10.–13. März 1970.     

Über die adrenale Steroid-Biosynthese in vitro. III. Selektive Hemmung der Nebennierenrinden-Funktion

The possibility is discussed of inhibiting the adrenocortical functions either selectively or preferentially by blocking the hydroxylations in positions 11β, 17α, 18 and 19 of the steroid nucleus or in 20α, 21 and 22 of the side chain, which are necessary for the formation of the individual corticosteroids from cholesterol. Many compounds with or without other biological activities, such as o,p′-DDD, Amphenone B, various blockers of cholesterol biosynthesis, heparinoids and various heterocyclic compounds, are shown to be devoid of a specific blocking activity on the adrenal cortex in vitro. However, amongst a large group of glutaric imides a few compounds proved to be active, mainly by blocking the 20α-hydroxylation of cholesterol, the most active being a cyclic hydrazide; the secretion in vivo of corticosteroids greatly decreased in response to 3–20 mg/kg. A new class of compounds active in vitro was found among simple imidazole derivatives, which block 17α, 18 and 19-hydroxylation.     

Optical rotatory dispersion studies—CIV Low-temperature circular dichroism behavior of various chromophoric derivatives of alcohols and amines

The low-temperature circular dichroism behavior of various cyclic and alicyclic systems containing the methyl xanthato-, N,N-diethyl-N′-acylthioureyl-, N-phthalimido-, nitrito- and dithio-carbalkoxy- chromophores is discussed. Rotational strength (R₀^T) values are reported where possible and changes in this parameter upon variation of the temperature are interpreted, where relevant, in terms of the degree of steric inhibition to free rotation about the various bonds connected to the asymmetric center bearing (or nearest to) the chromophore moiety.     

The electron-impact induced fragmentation of substituted 4-styrylquinolines

The fragmentation of 4-styrylquinoline (I), 4-(p-nitrostyryl)-quinoline (II), 4-(p-chlorostyryl)-quinoline (III), 4-(p-hydroxystyryl)-quinoline (IV), 4-(p-methoxystyryl)-quinoline (V), 4-(p-dimethylaminostyryl)-quinoline (VI) and 4-(p-cyanostyryl)-quinoline (VII) under electron-impact in the mass spectrometer is reported. The role and the influence of substituents on the fragmentation scheme is discussed. The loss of the substituents from the molecular ion is correlated with LCAOMO quantities.     

Time spectroscopy in theA 1∑ u + state of Li2

We have determined effective cross-sections for resonant transfer of excitation energy from state-selected Li₂ molecules to ground state Li atoms $$Li_2 A\left( {\upsilon ',J'} \right) + Li2S \to Li_2 X\left( {\upsilon '',J''} \right) + Li2P$$ with two different experimental techniques. Absolute cross-sections were derived from lifetime measurements of 114 rotational levels of theA-state subject to resonant collisions which belong to vibrational statesv′=4, 5, 6, 7 and 11 of⁶Li₂ and⁷Li₂. Cross-sections amount to several thousand Ų dropping off sharply with a resonance half-width of about 16 cm^?1. The resonance behaviour of the collision cross-section inferred from lifetime data could be confirmed by a double resonance technique probing the number of excited atoms with a second laser while the first laser was scanned over the Li₂ X?A absorption band. Due to their high reliability our data prove a good basis for the test of theoretical models. In contrast to earlier investigations significant deviations were found to exist between the measured cross-sections and those predicted by the first-order dipole-dipole scattering theory.     

Bis(1,2-bis(diphenylphosphino)ethane)tungsten(0) Complexes Containing Electron-Saturated Metal Centers and Singly-Coordinated Bridging Ligands

Reaction of 1,4-diisocyanobenzene or 4-isocyanobenzonitrile with trans-W(N(2))(2)(DPPE)(2) (DPPE = 1,2-bis(diphenylphosphino)ethane) produced cis-WL(2)(DPPE)(2), where L = 1,4-diisocyanobenzene or 4-isocyanobenzonitrile. cis-(CNC(6)H(4)NC)(2)W(DPPE)(2) crystallizes in the triclinic space group P&onemacr;, with a = 12.848(3) ?, b = 13.596(3) ?, c = 19.072(3) ?, alpha = 78.99(2) degrees, beta = 70.66(2) degrees, gamma = 65.26(2) degrees, V = 2849.8(11) ?(3), and Z = 2. cis-(NCC(6)H(4)NC)(2)W(DPPE)(2) crystallizes in the triclinic space group P&onemacr;, with a = 12.712(3) ?, b = 13.700(3) ?, c = 19.109(3) ?, alpha = 77.91(2) degrees, beta = 70.63(2) degrees, gamma = 64.76(2) degrees, V = 2830.7(13) ?(3), and Z = 2. Both compounds possess a distorted octahedral geometry about the metal center, with the two isocyanide ligands cis to one another. The isocyanide ligands are substantially bent along the CNC axis of the isocyanide group coordinated to tungsten. For the complex containing the symmetric ligand, CNC(6)H(4)NC, the mean CNC angle for the coordinated end of the isocyanide is 139.1(11) degrees, the average W-C bond length is 1.86(1) ?, and the C&tbd1;N bond lengths have a mean value of 1.30(2) ?. These data indicate substantial back-donation from an electron-saturated tungsten atom. This is supported spectroscopically, with substantial shifts to lower wavenumbers for the C-N stretching frequencies of the coordinated isocyanide groups. Similar trends are observed in cis-(NCC(6)H(4)NC)(2)W(DPPE)(2). Both compounds contain electron-rich metals surrounded by large ligands which apparently protect the metals from atmospheric oxidation. The isocyanide ligands in both complexes contain a second coordinating group pointing away from the metal into the environment surrounding the molecules, providing the potential for polymetallic complexes containing metals in a variety of oxidation states.     

Classical theory of vibration energy transfer in collinear collisions

Classical theory of collisions is cast in a form which also includes the uncertainty principle. This theory is used for analyzing the vibration energy transfer in the collinear collision which approximates the He-H₂ system. The results are compared with the quantum calculations and several classical and semiclassical approaches. Very good agreement with quantum theory is found, for all the parameters investigated.     

Long-path photometry in clinical analysis : I. The determination of chromium using diphenylcarbazide

The diphenylcarbazide method for determining chromium in biological material was reinvestigated and scaled down to require only 0.2 ml (or 0.2 g) of sample. The samples are digested at 300 °C within 1 hr by a mixture of concentrated sulfuric, nitric, and perchloric acids in a volume ratio 75:15:10. Chromium is oxidized to dichromate with permanganate and the excess of the latter is destroyed by azide. The color reagent is added and the absorbance is measured in a 20-cm long-path microcell requiring less than 0.3 ml of solution. Results on serum pools shown a standard deviation of about ±1.1 ng of Cr/ml of serum for contents in the range of 25 ng/ml. The results compare very favorable with those obtained by flameless atomic absorption. The determinations can be made by using a simple, dedicated photometer consisting of the long-path cell with a green LED attached to one window and a phototransistor to the other and needing only very simple circuits and low battery power.