On the relationship between fluorescence and molecular geometry. Formation of a luminescent intramolecular anthracene-ethylene exciplex by electronic excitation of lepidopterene

Electronic excitation of the bridged benzenoid hydrocarbon lepidoptene (L) in the crystalline state and in solution gives rise to an anomalous luminescence which is attributed to the radiative deactivation of an intramolecular anthraceneethylene exciplex E*. The formation of E* and the regeneration of L are discussed in terms of a geometry-dependent reversible [4 + 2] cycloaddition. Relevant quantum yield data are presented in an energy level diagram.     

Darstellung SiH-haltiger Silylphosphine und Untersuchung ihrer PMR-Spektren

The preparation of SiH-containing silylphosphines from SiH-containing chlorosilanes is successful by using an excess of chlorosilans. Chemical shift data and coupling constants of the compounds H_xSi[P(C₂H₅)₂]_4?x and (CH₃)_xSi[P(C₂H₅)₂]_4?x are communicated and compared with those of H_xSiX_4?x and (CH₃)_xSiX_4?x (X = halogen or H).     

A CNDO-MO calculation of VCl4

The electronic structure of the tetrahedral molecule VCL₄ is investigated within the CNDO-MO approximations. The metal and ligand valence orbitals, 3d, 4s, 4p; and 3s, 3p; respectively, have been systematically varied in an attempt to minimize the total energy; “optimum” V 4s(χ₄ = 1.10) and 4p(d ³ p ²) orbitals have been established, but V 3d(d ⁿ ) and Cl(-δ) valence orbitals are only seen to favor lower energy for expanded orbitals. Since determining the one-electron molecular orbital level which is occupied by the vanadium lone electron is a major aspect of this investigation, all calculations have been performed in triplicate: calculations assuming the unpaired electron occupies the 3a ₁, 2 _e and 4t ₂ molecular orbital (ground state electronic configurations² A ₁,² E, and² T ₂, respectively). The Hartree-Fock equations have been solved by Roothaan's SCF method for open shells, but off-diagonal multipliers between filled and partly filled molecular orbitals of the same symmetry have been neglected. As a qualitative estimate of the error introduced by this simplification, the pertinent overlap integrals between the eigenfunctions from calculations for the three possible configurations,² A ₁,² E, and² T ₂, are investigated as functions of the component 3d(d ⁿ ) and Cl(-δ) valence orbitals. The overlap integrals from the relevant² A ₁ and² T ₂ calculations are reasonably small, but the neglect of off-diagonal multipliers in calculations on the² E state is found to be a poor approximation. An ordering of the non-filled molecular orbitals in VCl₄ of 4t ₂ < 3a ₁ < 2e < 5t ₂ seems most consistent with the numerous calculations. This suggested ground state electronic configuration of² T ₂ introduces new aspects to the consideration of a (dynamic) Jahn-Teller effect in VCl₄. Experimental data pertinent to the electronic structure of VCl₄ has been briefly summarized, but unfortunately it is inadequate to confirm or deny the present calculations.     

Wirkung von Actinomycin D auf die RNS-Synthese und die synchrone Mitosetätigkeit in Physarum polycephalum

Zusammenfassung Actinomycin D (250 /ml) hemmt in Suspensionskulturen vonPhysarum polycephalum spezifisch die RNS-Synthese, während die DNS- und Proteinsynthese innerhalb der ersten drei Stunden nur wenig beeinträchtigt werden. Die Auslösung einer synchronen Kernteilung in Makroplasmodien kann durch 250 /ml Actinomycin D verhindert oder stark verzögert werden, sofern der Hemmstoff spätestens zu Beginn des letzten Drittels der Interphase ( 2 Stdn. vor Prophase) dem Medium zugesetzt wird. Die Mitosehemmung ist durch Auswaschen des Hemmstoffes reversibel. Die Ergebnisse sprechen dafür, daß zur Vorbereitung einer Mitose während des größten Teiles der Interphase DNS-abhängige RNS neu gebildet werden muß, die möglicherweise als Informationsüberträger die Synthese mitosespezifischer Proteine kontrolliert. Es wird eine Arbeitshypothese diskutiert, nach der die Mitose als ein durch Genregulation gesteuerter Vorgang aufzufassen wäre.

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Actinomycin D (250 /ml) specifically inhibits RNA synthesis in suspension cultures ofPhysarum polycephalum whereas DNA and protein synthesis are less affected within the first three hours. Onset of synchronous mitoses in macroplasmodia is prohibited or largely delayed by 250 /ml actinomycin D if the inhibitor is added to the medium at or prior to the beginning of the last third of interphase ( 2 hrs. prior to prophase). Removal of the inhibitor from the medium reverses the inhibitory effect on mitosis. The results indicate that preparation of mitosis requires synthesis of DNA dependent RNA during the major part of interphase. These RNA molecules possibly carry information for the synthesis of proteins specifically involved with mitosis. A working hypothesis is discussed suggesting that mitotic activities may by controlled by gene regulation.

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Mit 4 Abbildungen

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Herrn Prof. Dr.Hermann Bretschneider zum 60. Geburtstag gewidmet.     

Acyl- und Alkylidenphosphane. XVIII. Monoacetyl- und Diacetylphosphan

Acyl- and Alkylidenephosphines. XVIII. Monoacetyl- and Diacetylphosphine When triacetylphosphine 3a is treated with methanol 4 or benzyl alcohol 6 P? C(O) bonds are cleaved and a mixture of diacetyl- 2a and monoacetylphosphine 1a is formed. The thermally labile phosphine 1a decomposes completely within a few hours at +20°C; but 2a also reacts slowly within days to give triacetylphosphine 3a and further unknown compounds. As it is found by nmr-spectroscopic studies the acidic hydrogen atoms of monoacetylphosphine 1a are both bound to phosphorus. In liquid diacetylphosphine 2a or in solutions of this compound, However, there exists an equilibrium between the keto tautomer K- 2a with a PH and the enol tautomer E- 2a with an O? H? O group; compared with pentane-2,4-dione 8a the keto tautomerpredo minates in 2a . As in 1,3-diketones a low temperature and a small dielectric constant of the solvent increase the amount of enol tautomer E- 2a present. The ¹H-nmr resonance of the enolic hydrogen atom is observed at very low field (δ = 18,3 ppm).     

INVESTIGATION INTO THE SPECTROSCOPY AND PHOTOISOMERIZATION OF A SERIES OF POLY (ETHYLENE GLYCOL) PEPTIDE SCHIFF BASES OF 11-cis RETINAL

Abstract— The 11-cis and all-trans isomers of a series of poly(ethylene glycol)-oligopeptide - Schiff bases as models for rhodopsin were synthesized and studied. Absorption data for certain of the PEG-peptide Schiff bases demonstrated that no intramolecular hydrogen-bonding (or protonation) occurs between the Schiff base and an acidic amino acid residue, as was previously thought. Photoisomerization of the 11-cis protonated and unprotonated Schiff bases were examined using both steady state and laser flash techniques. Also with 355 nm excitation (and additionally 532 nm in one case), an approximate 40% increase in quantum yield of isomerization (φ) occurred for all protonated PEG-peptide Schiff bases compared to the H⁺-n-butylamine counterparts (in methanol). In one case, a > 100% increase in φ was found in dichloromethane. These data show that PEG-oligopeptide Schiff bases are still further improved models for rhodopsin compared to their n-butylamine analogs.     

Emissionsspektrometrische Analyse von Roheisen

Zusammenfassung Die spektrometrische Analyse von weiß erstarrtem Roheisen (auf C, Si, Mn, P, S, Cu) ist mit der gleichen Anregung und in der gleichen Funkzeit wie diejenige von Stahl möglich. Eine spezielle Kalibriertechnik mit Stahlproben garantiert ein ausreichend reproduzierbares und richtiges Resultat in relativ kurzer Zeit (20 sec).

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Emission-spectrometrical analysis of pig iron

The conditions of pig iron analysis by using a direct reading spectrometer for routine determination of C, Si, Mn, P, S and Cu, the influence of sampling and a new calibration technique of the instrument are described. The whole time needed for complete spectrometrical analysis is about 20 sec.

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Wir sind Herrn T. Nientiedt für zahlreiche Anregungen und Diskussionen zu Dank verpflichtet.     

Molekulargewicht

Ohne Zusammenfassung