Consequences of the ‘Pedersen papers’ on crown type chemistry at Würzburg and Bonn Universities: From heteroaromatic crowns and podands to large molecular and crystalline cavities including multisite receptors,cascade molecules,chromoionophores, siderophores,surfactant-type,and extreme ligands

We thank the editors of this issue for the opportunity to present the historic development of crown chemistry at the Universities of Wurzburg and Bonn in memory of C. J. Pedersen, the originator of the crown ethers. His legacy of science has tremendously stimulated research at both universities.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Thioacetylacetone: structural and vibrational assignments.

Thioacetylacetone and its variously deuterated isotopomers have been investigated using electronic and vibrational spectroscopy combined with quantum chemical calculations. Thioacetylacetone is known for its photochromic properties, but the structures of the initial and final forms have been the subject of a long debate. Analysis of the IR spectra recorded in low-temperature argon and xenon matrices, room-temperature solutions, and in the gas phase has allowed us to establish the nature of the photochromic species and of its precursor. Similar to the case of another beta-thioxoketone, monothiodibenzoylmethane, the photo-product has been assigned to the nonchelated SH exo-rotamer of the (Z)-enethiol tautomeric form, whereas the dominant ground-state species corresponds to the chelated (Z)-enol tautomeric form. Detailed vibrational assignments have been proposed for both forms based on quantum chemical calculations and polarization experiments. In the case of the chelated (Z)-enol species prevailing in the ground state, a second-order perturbative anharmonic analysis at the B3LYP/cc-pVTZ level indicated strong anharmonic effects associated with the intramolecular hydrogen bond, leading to a shift of more than 600 cm-1 of the wavenumber of the OH-stretching vibration. A small fraction of the SH endo-rotameric chelated (Z)-enethiol form was also detected under unperturbed conditions. The (Z)-enethiol form can be converted into the (Z)-enol form by irradiation at 290 nm.     

Separation and determination of aluminium by single-column ion-chromatography

A quick, reliable method for the determination of Al(III) in the presence of other metal ions is presented. A Chromatographic system consisting of a low-capacity cation-exchange column, an eluent of diprotonated p-phenylenediamine, and a conductivity detector was used to measure the retention times for various cations. During the course of this work, it was found that Al(III) was eluted later than most bivalent metal ions but earlier than other tervalent metal ions. Therefore the concentration of eluent was adjusted so that an early sharp peak was obtained for Al(III) and the bivalent metal ions were eluted as a group. Through analysis of an NBS standard, as well as of solutions containing Al(III) and other metal ions, the method was shown to be precise, accurate and rapid for determination of Al(III) without interference from common bivalent metal ions.     

Application of the photoionization detector for the determination of ethanol in aqueous solutions and human breath

A determination of ethanol is described, which is based on a purging system in conjunction with a photoionization detector. With that system a fast and reliable determination of ethanol in aqueous solutions is possible. The system has been used for the analysis of wine. The 3-detection limit has been 0.005% ethanol, the relative standard deviation 4.8 to 6.0% and the time constant of the entire analytical system 20 s. The photoionization detector has been also applied to the analysis of artificial and genuine human breath. A comparison with gas-chromatography and non-dispersive IR-detection has been proven the reliability of results.     

Bildung Siliciumorganischer Verbindungen. LV. Die Konformeren des 1,3,5,7-Tetrasila-bicyclo[3,3,1]nonans und 2,4,6,8,9-Pentasila-bicyclo[3,3,1]nonans

Formation of Organosilicon Compounds. LV. Conformeres of the 1,3,5,7-Tetrasilabicyclo [3,3,1] nonane and 2,4,6,8,9-Pentasila-bicyclo [3,3,1] nonane Two types of carbosilanes with a bicyclo [3,3,1] nonane structure are reported, derivatives of 1,3,5,7-Tetrasila-bicyclo-[3,3,1] nonane (a) and of 2,4,6,8,9-Pentasila-bicyclo [3,3,1] nonane (b) with an inverse structure in respect to the Si- and C-atoms. By means of NMR-investigations the structure can be determined. Derivatives of (a) are present in the Si₄C₁₁H₂₈ with fully methylated Si-atoms, the 1,5 dichloro-1,3,5,7-tetrasila-bicyclo [3,3,1] nonane and Si₄Cl₆C₅H₁₀ with fully chlorinated Si-atoms with twofold boat conformation. In the derivatives of type (b) as Si₅H₁₀C₄H₆ with hydrogenated Si-atoms as well as in 9,9-dichloro-2,4,6,8,9-pentasila-bicyclo [3,3,1] nonane a change in conformation is observed, whereas a rigid chair conformation is found for both rings in the Si-chlorimated derivative Si₅Cl₁₀C₄H₁₀. A comparison of atom-resp. H? H distances in cyclohexane and 1,3,5-Trisilacyclohexane gives evidence that the boat conformation is more preferable for the 1,3,5-Trisilacyclohexane than for cyclohexane due to larger H? H-distances (caused by Si? C-distances).     

The Gas-Solid Interface the adsorption of nitrogen,argon, neopentane,sulfur dioxide,carbon dioxide and sulfur hexafluoride on rhombic sulfur

Physical adsorption of the title compounds on rhombic sulfur of 0.4 to 0.5 m²/g is reported. The isotherms are of type II for N₂, Ar and C₅H₁₂, of type III for SO₂ and CO₂, and linear for SF₆. There is no hysteresis. The method of Ross & Olivier shows that the surface is relatively heterogenous (γ 17). Isosteric heats of adsorption and c values of the B.E.T. equation are also reported.     

ANTIVIRAL ACTIVITY OF MEROCYANINE 540

Abstract Simultaneous exposure to the lipophilic dye merocyanine 540 (MC 540) and white light inactivates several enveloped viruses. The same treatment appears to have little or no effect on pluripotent hematopoietic stem cells, mature red cells, and mature leukocytes. At least some components of the clotting system are spared, too. The molecular basis of the virucidal effect of MC 540 and light is not yet completely understood. Based on what is known about the interactions of MC 540 with cells and artificial membranes, it seems likely that MC 540 binds to and damages the viral envelope. MC 540-mediated photosensitization may have implications for the sterilization of bone marrow and blood products, the preparation of vaccines, and selected areas of antiviral therapy.     

Stereochemistry of Polynuclear Cadmium(II)thioglycolates: Crystal Structure of [ICd8(SCH2CH2OH)12]3+ · 3I− · H2O

Crystals of the title compound are triclinic, a = 27.87 Å, b = 10.77 Å, c = 12.94 Å, α 73.1°, β 116.1°, γ 120.0°, space group P1 . The structure consists of octanuclear ions: Eight Cd(II) ions are found at the corners of a distorted cube, the center of the cube is occupied by an iodide, the twelve thioglycolate sulfur atoms bridge the twelve edges of the cube thereby forming a distorted icosahedron. Cadmium ions are either five or seven coordinate. The phase problem for this structure was solved using a combination of very high and very low E-values.     

Colorimetric uranium determination with arsenazo

A rapid and sensitive method is described for the quantitative colorimetric determination of uranium(Vl). Masking agents such as EDTA, tartaric acid or thioglycerol make possible the determination of uranium in the presence of many foreign metal ions. If thorium is present, a preliminary extraction of uranium as the diethyldithiocarbamate is required.     

Phosphorothioate Analogues of Nucleotides—Tools for the Investigation of Biochemical Processes

Nucleoside phosphorothioates are analogues of nucleotides with a wide range of applications. Thus, on the one hand, in many but not all cases they are more stable against hydrolysis than the unmodified nucleotides—a property which they share with other nucleotide analogues. On the other hand, however, they are good substrates for many, but not all reactions where the nucleotide or the phosphorothioate group is transferred to an acceptor other than H₂O. As a consequence, once incorporated into a system such as DNA, phosphorothioates cannot be easily removed. What makes these compounds unique to a certain extent is the chirality at the phosphorus center if two nonequivalent residues are linked to the phosphorothioate group. This opens the way for the use of these compounds to investigate stereochemical aspects of enzymatic reactions. In addition to these properties, there are those expected from exchange of an oxygen for a sulfur atom in a phosphate group, e.g. the increased affinity towards mercury derivatives and the large chemical shift of the ³¹P-NMR sinals. If one considers how many biologically interesting compounds contain phosphate groups, the considerable interest in these nucleotide analogues is not surprising.