The Radical Anions of N,N′-Dicyanoquinone Diimines,a New Class of Electron Acceptors

The radical anions of 12 N,N′-dicyanoquinone diimines, a new class of electron acceptors, hace been characterized by their hyperfine data with the use of ESR and ENDOR spectroscopy. The largest coupling constant (0.30–0.45 mT), due to the two ¹⁴N nuclei in the exocyclic positions, gives rise to a conspicuous broadening of the peripheral ESR lines by an incomplete averaging of the hyperfine anisotropy. The most plausible interpretation of the experimental results for the radical anions of N,N′-dicyano- 1,4-benzoquinone diimine ( 1 ) and N,N′-Dicyano-9,10-anthraquinone diimine ( 9 ) is in terms of both ‘syn’- and ‘anti’-configurations contributing to the ESR and ENDOR spectra and having equal proton- and ¹⁴N-coupling constants. The π-spin distribution in the radical anions of N,N′-dicyanoquinone diimines is compared with those in the analogous ions of tetracyanoquinodimethanes and quinones.     

Tetrahydrofurane und Lactone,I. Synthese und Reaktionen chiraler 2,5-überbrückter Tetrahydrofurane – ein neuer Weg zu optisch aktiven γ-Lactonen und γ-Bislactonen

Tetrahydrofurans and Lactones, I. - Synthesis and Reactions of Chiral 2,5-Bridged Tetrahydrofurans - A New Approach to Optically Active γ-Lactones and γ-Bislactones Diels-Alder reaction of 3,4-hexamethylenefuran with acrylic acid gives the carboxylic acid 1a with high endo selectivity. 1a was separated into the enantiomers via the α-phenylethylammonium salts. Comparison of the CD spectra of (−)- 1a and (−)- 3 and the X-ray structural analysis of the camphanoyl derivative (−)- 4b lead to the 1R,2S,4S configuration of (−)- 1a as well. The 2,5-bridged tetrahydrofuran (−)- 5 with all-cis and RSS configuration is obtained by ozonolysis of the ester (−)- 1b . (−)- 5 can be oxidized to the γ-lactone (2R,3S)-(−)- 6 with sodium metaperiodate/potassium permanganate in 22% yield. Hydride reduction of (−)- 6 under various conditions leads to the γ-bislactones (−)- 8 and (−)- 9 or to the bislactol (−)- 10 . (−)- 8 has the same absolute configuration as the naturally occuring (−)-canadensolide.     

The possible discovery of neutron activation in 1910

One-hundred-two years ago, on 21 April 1910, the Austrian chemist Carl Auer von Welsbach published a short comment on a fundamental discovery he had made in the field of nuclear sciences. He reported that “jonium” (²³⁰Th) was able to induce radioactivity in other materials if stored in contact with the ionium sample. He was well aware that this observation was “not quite in agreement with current theories”, because, as a basic principle, a radioactive substance cannot activate an inactive substance. Since he could not remove any superficial contamination, he concluded that the previously inactive materials had become radioactive themselves. Auer von Welsbach predicted that this observation “might be of importance for the mysterious field of radioactivity research”. In fact, we believe that in this experiment he incidentally discovered neutron activation and the production of artificial radionuclides (24 years before I. Curie and F. Joliot) or even induced nuclear fission. The neutron source in his experiments is yet unknown and shall be identified in this project. The neutrons could have been produced from nuclear reactions with impurities of beryllium in the sample. Auer von Welsbach may even have observed nuclear fission 29 years before O. Hahn, F. Straßmann, L. Meitner and O. R. Frisch. In any case, he may have noticed the effects of neutron radiation—22 years before its discovery by J. Chadwick. The main aim of this interdisciplinary project (of which preliminary results are presented herein) is to repeat the 1910-experiment and to identify the source of the neutrons. It will be equally important to investigate the historical reasons and circumstances why Auer’s report remained mostly uncommented in the scientific community. The hypothetical consequences are worth discussion: Auer’s publication could have started the “nuclear age” much earlier than it finally began, with all the consequences for mankind.     

Electron deficiency in tetrahedral transition-metal clusters: electronic structure and magnetic properties of [Ru4(eta6-C6H6)4(mu3-H)4](2+)

Analysis of the electronic structure of the electron-deficient cluster cation [Ru4(eta6-C6H6)4H4](2+) (1(2+)) by density functional theory calculations shows a very small energy gap (0.06 eV) between the diamagnetic singlet state and the paramagnetic triplet state, as a consequence of the absence of a significant Jahn-Teller distortion in the molecular structure of 1(2+). Magnetic measurements of [1]Cl2, [1][BF4]2, and [1][PF6]2 show 1(2+) to be diamagnetic in the fundamental state, with some weak temperature-independent paramagnetism, depending upon the nature of the counterion.     

The surface charge of regenerated cellulose fibres

In this paper the influence of charged species on the sheet strength of viscose fibres was investigated. Four samples of chemical modified viscose fibres, as well as a reference fibre were studied. The swelling of these viscose fibres and the breaking length of hand sheets have been determined. Comparing the results, the influence of both, swelling and surface charge on the bonding force, is evident. The allocation of the charges, induced by cationic starch and Carboxmethylcellulose, has been analyzed by Titration, attenuated total reflection spectroscopy (ATR) and X-ray photoelectron spectroscopy (XPS). Titration was used to make a first estimation of the charge distribution within the fibre. Using ATR and XPS, more detailed information about the surface charge has been achieved. All measurement methods showed a significant amount of charge on the fibre surface.     

Feasibility study for production of 99mTc by neutron irradiation of MoO3 in a 250 kW TRIGA Mark II reactor

The subject of this paper is to explore the possibility to obtain ^99mTc from activation of ⁹⁸Mo, using the TRIGA Mark II low flux research reactor (Vienna, Austria). Irradiation of both natural and enriched in ⁹⁸Mo molybdenum oxides was compared. Aims of this work included the determination of neutron fluxes and ⁹⁸Mo(n, γ)⁹⁹Mo reaction effective cross section in the TRIGA Mark II reactor irradiation channels, calculation of ⁹⁹Mo specific activities, determination of optimal irradiation conditions for the subsequent ^99mTc separation from MoO₃ targets using concentrating technologies.     

Integrated biological–chemical approach for the isolation and selection of polyaromatic mutagens in surface waters

Many environmental mutagens, including polyaromatic compounds are present in surface waters, often in complex mixtures and at low concentrations. The present study provides and applies a novel, integrated approach to isolate polyaromatic mutagens in river water using a sample from the River Elbe. The sample was taken downstream of industrial discharges using blue rayon (BR) as a passive sampler that selectively adsorbs polyaromatic compounds and was subjected to effect-directed fractionation in order to characterise the compounds causing the detected effect(s). The procedure relies on three complementary fractionation steps, the Ames fluctuation assay with strains TA98, YG1024 and YG1041 with and without S9 activation and analytical screening. Several mutagenic fractions were isolated by combining mutagenicity testing with fractionation. The enhanced mutagenicity in the nitroreductase and/or O-acetyltransferase overexpressing strains YG1024 and YG1041 strains suggested amino- and/or nitro-compounds causing mutagenicity in several fractions. Analytical screening of mutagenic fractions with LC-HRMS/MS provided a list of molecular formulas typically containing one to ten nitrogen and at least two oxygen atoms supporting the presence of amino and nitro-compounds in the mutagenic fractions.

Control of Excited‐State Conformations in B,N‐Acenes

We present a new concept to control the conformations of molecules in the excited state through harvesting negative hyperconjugation. The strategy was realized with the 2,3,1,4‐benzodiazadiborinane scaffold, which was prepared by a new synthetic procedure. Photochemical studies identified dual light emission, which was assigned to well‐defined conformers. The emission at longer wavelength can be switched off by restricting the rotational degrees of freedom in the solid state as well as by controlling the energy levels of the excited states through adjusting the solvent polarity.