Raman spectroscopic investigations of the structure and phase transitions of liquid crystalline lead(II) alkanoates

Lead(II) alkanoates with even chain lengths from octanoate to octadecanoate have been investigated by Raman spectroscopy. In the low frequency region, transverse and longitudinal acoustical modes (TAM, LAM) have been assigned. It was shown that LAM-1 is the vibration of the double chain with the node of the vibration in the Pb²⁺ layer. A fully extended conformation of the chains in the low temperature phase was confirmed. The frequencies and intensities of the LAMs as compared with those of the alkanes and the fatty acids led to an estimate of the force constant and polarizability of the Pb²⁺ -COO^- bond relative to the C-C bond. The defects at the chain ends were investigated in the ρ(CH₃) and v(CC) region. For the intermediate (CM) phase, both the Pb²⁺ layer distance reduction and the chain length independent enthalpy contributions can be attributed mainly to defects at the chain ends.     

Analyse der Rückstoßprodukte in neutronenbestrahlten Phenylarsenverbindungen, 3. Mitteilung: Über die Bestimmung der Ausbeute an Diphenylarsen-Rückstoßprodukten

Für das in der 1. Mitteilung [1] beschriebene Trennverfahren zur Anfarbeitung bestrahlter Mono-, Di- und Triphenylarsenverbindungen sollte die Effektivität der chromatographischen Trennung an dem Kationenaustauscher KPS (6% DVB) mit Hilfe einer unabhängigen Methode überprüft werden. Außerdem sollten Hinweise über Art und Anzahl der nichtidentifizierten ?unbckanntcn Produkte“ erhalten werden, die gemeinsam mit den Diphenylarsen-Rüekstoßprodukten im NaOH-Eluat auftreten. Zu diesem Zweck wurde die von Siuda [2] vorgeschlagene papierelektrophoretische Trennung benutzt.     

Constructing Self-Dual Strings

We present an ADHMN-like construction which generates self-dual string solutions to the effective M5-brane worldvolume theory from solutions to the Basu-Harvey equation. Our construction finds a natural interpretation in terms of gerbes, which we develop in some detail. We also comment on a possible extension to stacks of multiple M5-branes.     

2. Mitteilung: Tetraphenylarsoniumverbindungen und Pentaphenylarsen

Es wurde ein Trennverfahren ausgeabeitet, das es gestattet, die Aktivitätsausbeuten für Mono-, Di- und Triphenylarsenverbindungen, für Tetraphenylarsoniumverbindungen und für Pentaphenylarsen sowie für nicht organisch gebundenes Arsen in neutronenbestrahlten Tetraphenylarsoniumver erbindungen und in Pentaphenylarsen zu bestimmen. Als Trennmethoden werden Extraktion, Ionenaustauwsch und Al₂O₃-Chromatographic benutzt. Zur Reinigung und Ausbeutebestimmung von Di- und Triphenylarsenprodukten sowie von Tetraphenylarsonimverbindungen finden Kristallisations- bzw. Fällungsreaktionen Anwendung unter Ausnutzung des Prinzips der Isotopenverdünnungsanalyse.     

Strahlungschemie von Kohlenwasserstoffen. 16. Mitteilung. Benzol-Brombenzol

The decrease of the concentration of bromobenzene and the formation of biphenyl and bromobiphenyl have been studied in the system benzene-bromobenzene under the influence of γ-rays. Bromobenzene is in competition with its own products for the reactive state of benzene or it can transfer its energy to its products. The rate of this transfer to decomposition is 74 l/Mol. With the help of additives it has been shown that they can act in two ways: firstly they compete with bromobenzene for an activated state of benzene in a reaction that does not depend on temperature. The nature of this activated state has not been determined. Secondly they scavenge phenyl radicals that have been formed in about 70% of the decomposed bromobenzene molecules. This yield depends slightly on temperature. The relative reactivities compared to bromobenzene for the first case and to benzene in the second have been determined as follows: naphthalene (0.6; 23); anthracene (5.8; 800); benzophenone (0.5; 17); cyclohexene (-; 20); N₂O (0.018; -); NO (1.7; 250); O₂ (-; 3400). Naphthacene in benzene is strongly decomposed in the presence of bromobenzene, but it also enhances the decomposition of the latter.     

New perthiophosphonic acid anhydrides and the direct indication of the dimer-monomer equilibrium. NMR and X-Ray Studies

New perthiophosphonic acid anhydrides (R-PS₂)_n with R = 2,4,6-tri-iso-propylphenyl and 2,4-di-tert-butyl-6-methylphenyl have been prepared. For the latter case, the isolation of the monomer (n = 1), the 2,4-di-tertbutyl-6-methylphenyl-dithioxophosphorane, and both dimers (n = 2), cis- and trans-2,4-bis(2,4-di-tertbutyl-6-methylphenyl)-2, 4-dithioxo-1, 3, 2, 4-dithiadiphosphetane, has been determined. The new cis and trans dithiadiphosphetanes and dithioxophosphoranes as well as the known compounds (2,4,6-trimethylphenyl-PS₂)₂ and 2,4,6-tri-tert-butylphenyl-PS₂ are characterized by solution and high resolution solid-state ³¹P and ¹³C NMR spectroscopy. The existence of a dimer-monomer equilibrium is directly proved by 2D exchange ³¹P NMR spectroscopy. It is shown that the reaction of the monomer with methanol is faster than the reaction of the dimer with methanol.     

CrIII-Phthalocyaninate: Darstellung,Eigenschaften und Kristallstruktur von l-Bis(triphenylphosphin)iminium-trans-di(nitrito(O))phthalocyaninato(2–)-chromat(III)

Cr^III Phthalocyaninates: Synthesis, Properties, and Crystal Structure of l-Bis(triphenylphosphine)iminium trans-Di(nitrito(O))phthalocyaninato(2–)chromate(III) [Cr(H₂O)₂Pc^2?]I_x reacts with excess (PNP)NO₂ in dimethylformamide to yield less soluble greenblack l-bis(triphenylphosphine)iminium trans-di(nitrito(O))phthalocyaninato(2–)chromate(III), ^l(PNP)^trans[Cr(ONO)₂Pc^2?], which crystallizes in the triclinic space group P1 (No. 2) with Z = 2. The Cr atom is in the center of the Pc^2? ligand and the two nitrite ions are monodentate O-coordinated in a mutually trans arrangement to the Cr atom. The Cr? O and Cr? N_iso bond distances are 1.9898(14) und 1.981(2) Å, respectively. The geometric data of the coordinated nitrite ion are: d(N? O) = 1.307(2) Å; d(N? O) = 1.205(2) Å; ?(O? N? O) = 113.7(2)°; ?(Cr? O? N) = 116.85(12)°. The non-bonding O atoms are trans to the Cr atom. The Pc^2? ligand is slightly saddled. Three weak spin-allowed trip-quartet(TQ) transitions (in 10³ cm^?1): TQ1 (8.20) < TQ2 (11.3) < TQ3 (20.33) and the characteristic π-π* transitions of the Pc^2? ligand: B (14.68) < Q₁ (27.1) < Q₂ (29.0) < N (35.4) are observed in the UV-VIS-NIR spectrum. Prominent luminescence spectra are obtained by excitation within the TQ1 region, in which the spin-forbidden trip-sextet transition at 7376 cm^?1 dominates at low temperatures (T < 50 K). The vibrational spectra are discussed. In coincidence of the excitation lines with TQ3, v_s(Cr? O) at 378 cm^?1 is selectively resonance Raman (RR) enhanced. v_as(Cr? O) is observed in the FIR spectrum at 391 cm^?1. The following internal vibrations (in cm^?1) of the nitrito ligand are in the MIR spectrum: v_as(N? O)/1447 > v_as(N? O)/1018/1029 > δ(O? N? O)/828 and in the RR-spectrum: v_s(N? O)/1410 > v_s(N? O)/952, the last followed by three overtones.     

Eine Tüpfelreaktion für den Nitritnachweis

Zusammenfassung Durch Tüpfeln auf Chromatographiepapier, das mit Brucin, Benzidin und Phosphorsäure imprägniert wurde, läßt sich Nitrit empfindlieh und spezifisch nachweisen. 20 ng Nitrit können neben Nitrat und anderen Anionen festgestellt werden.

---

Summary Nitrite can be detected sensitively and specifically by spotting on Chromatograph paper impregnated with brucine, benzidine and phosphoric acid. It is possible to detect 20g nitrite in the presence of nitrate and other anions.

---

Résumé On peut rechercher les nitrites d'une manière sensible et spécifique sur les taches du papier chromatographique et qui a été imprégné de brucine, de benzidine et d'acide phosphorique. On peut déceler 20g de nitrite en présence de nitrates et d'autres ions A-.

     

Eine Tüpfelreaktion zur Unterscheidung oxydierender Anionen

Zusammenfassung Die Herstellung eines Reagenspapiers wird beschrieben, mit dessen Hilfe die Identifizierung oxydierender Anionen [Nitrit, Hypochlorit, Chromat, Bromat, Hexacyanoferrat(III), Peroxydisulfat, Jodat, Chlorat und Nitrat ] durch einen einfachen Tüpfeltest möglich ist.

---

Summary The preparation of a reagent is described with whose aid it is possible to identify oxidant anions through a simple spot test. The anions are: nitrite, hypochlorite, chromate, bromate, hexacyanoferrate (III), peroxodisulfate, iodate, chlorate, nitrate.

---

Résumé On décrit la préparation d'un papier-réactif permettant l'identification des anions oxydants (nitrite, hypochlorite, chromate, bromate, ferricyanure, peroxydisulfurique, iodate, chlorate et nitrate) par une réaction à la touche simple.