Canonical quantization without conjugate momenta

In the traditional form of canonical quantization, certain field components (not having conjugate momenta) must be regarded as noncanonical. This long-known distinction enters modern gauge theories, when they are canonically quantized as by Kugo and Ojima. We avoid that peculiarity by not using any conjugate momenta at all. In our formulation, canonical quantization can be related to Feynman's path integral.     

Synthesis and characterization of new oligosilane derivatives of iron and molybdenum

By use of salt elimination, the transition metal substituted oligosilanes (η⁵-C₅Me₄Et)Fe(CO)₂SiMe₂SiMe₂Cl 1, (η⁵-C₅Me₄Et)Mo(CO)₃SiMe₂SiMe₂Br 2, (η⁵-C₅Me₄Et)Fe(CO)₂(SiMe₂)₆(CO)₂Fe(η⁵-C₅Me₄Et) 3 and (η⁵-C₅Me₄Et)Fe(CO)₂(SiMe₂)₆Br 4 were prepared and characterized. Compound 1 is well crystallized from pentane and its structure has been determined by X-ray diffraction analysis.     

Ab initio investigation of the potential energy surfaces of C2H2F2 and C2H2F2+

Ab initio MO calculations have been performed for neutral and cationic C₂H₂F₂ structures. Olefinic and carbene structures are investigated for the neutral isomers, while olefinic, carbene, and fluoronium-type cations are found. Stability orders and rotational barriers are discussed in terms of orbital and Coulomb interaction. Contrary to previous studies, the higher stability of the geminal isomers is interpreted to be caused by Coulomb attraction.     

Formation of Zn(1-x)MnxS nanowires within mesoporous silica of different pore sizes

Arrays of highly ordered Zn(1-x)MnxS quantum wires with x ranging from 0.01 to 0.3 and with lateral dimensions of 3, 6, and 9 nm were synthesized within mesoporous SiO2 host structures of the MCM-41 and SBA-15 type. The hexagonal symmetry of these arrays (space group p6m) and the high degree of order was confirmed by X-ray diffraction and transmission electron microscopy (TEM) studies. Physisorption measurements show the progressive filling of the pores of the SiO2 host structures, while TEM and Raman studies reveal the wire-like character of the incorporated Zn(1-x)MnxS nanostructures. X-ray absorption near-edge structure, extended X-ray absorption fine structure, photoluminescence excitation (PLE), and electron paramagnetic resonance studies confirm the good crystalline quality of the incorporated Zn(1-x)MnxS guest species and, in particular, that the Mn2+ ions are randomly distributed and are situated on tetrahedrally coordinated cation sites of the Zn(1-x)MnxS wires for all x up to 0.3. The amount of Mn2+ ions loosely bound to the surface of the Zn(1-x)MnxS nanowires is less than 4% of the total Mn content even for the 3 nm nanostructures up to the highest Mn content of x = 0.3. The effects of the reduction of the lateral dimensions on electronic properties of the diluted magnetic semiconductor were studied by PLE spectroscopy. Due to the quantum confinement of the excitons in the wires an increase of the direct band gap with decreasing particle size is observed.     

A novel technique to specifically analyze the secretome of cells and tissues

The secretome of cells and tissues may reflect a broad variety of pathological conditions and thus represents a rich source of biomarkers. The identity of secreted proteins, usually isolated from cell supernatants or body fluids, is hardly accessible by direct proteome analysis, because these proteins are often masked by high amounts of proteins actually not secreted by the investigated cells. Here, we present a novel method for the specific detection of proteins secreted by human tissue specimen as well as cultured cells and chose liver as a model. The method is based on the metabolic labelling of proteins synthesized during a limited incubation period. Then, the cell supernatant is filtered, precipitated, and subjected to two-dimensional gel electrophoresis. Whereas fluorography detected a large number of proteins derived from residual plasma and dead cells, the autoradiographs selectively displayed genuinely secreted proteins. We demonstrate the feasibility of this approach by means of the secretomes of the hepatocellular carcinoma-derived cell line HepG2 and human liver slices. The selective identification of cell- and tissue-specific protein secretion profiles may help to identify novel sets of biomarkers for wide clinical applications.     

Forward and backward pericyclic photochemical reactions have intermediates in common, yet cyclobutenes break the rules.

Photochemical pericyclic reactions are believed to proceed via a so-called pericyclic minimum on the lowest excited potential surface (S(1)), which is common to both the forward and backward reactions. Such a common intermediate has never been directly detected. The photointerconversion of 1,3-butadiene and cyclobutene is the prevailing prototype for such reactions, yet only diene ring closure proceeds with the stereospecificity that the Woodward-Hoffmann rules predict. This contrast seems to exclude a common intermediate. Using ultrafast spectroscopy, we show that the excited states of two cyclobutene/diene isomeric pairs are linked by not one, but by two common minima, p* and ct*. Starting from the diene side (cyclohepta-1,3-diene and cycloocta-1,3-diene), electrocyclic ring closure passes via the pericyclic minimum p*, whereas ct* is mainly responsible for cis-trans isomerization. Starting from the corresponding cyclobutenes (bicyclo[3.2.0]heptene-6 and bicyclo[4.2.0]octene-7), the forbidden isomer is formed from ct*. The path branches at the first (S(2)/S(1)) conical intersection towards p* and ct*. The fact that the energetically unfavorable ct* path can compete is ascribed to a dynamic effect: the momentum in C=C twist direction, acquired--such as in other olefins--in the Franck-Condon region of the cyclobutenes.     

[O9,24] [2.1.2.1] metacyclophane-9-ene,a “twin cyclophane”, and its dehydrogenation products - synthesis structure determination and 1H-NMR-spectroscopy

The synthesis of [O⁹,24] [2.1.2.1]metacyclophane-9-ene and of its dehydrogenation products^the new pyrenocyclophanes $\text{8}$, $\text{10}$, $\text{11}$, and $\text{12}$, is described; their structures are discussed in connection with their ¹H-NMR-spectra.     

Quninone chemistry. Synthesis of 3-dialkylsulfoximido- and 2-dialkyl-sulfimido-3-carbomethoxy-1,4-benzo- and naphthoquinone derivatives

3-Methoxy[2, 1]benzisoxazole-4, 7-quinones 1 and naphth[2,3-c]isoxazole-4,9-quinone 4 react with dimethyl sulfoxides to give sulfoximidoquinones 2 and 5 , sulfimidoquinones 8 and 11 respectively as major products.     

Radon as a tracer to determine the mean residence times of groundwater in decontamination reactors

The groundwater at a former gasoline production site in Germany is heavily contaminated with aromatic hydrocarbons (mostly benzene) and is currently being treated in bioreactors under anaerobic conditions. To determine the reaction kinetics it is essential to know the mean residence time of the groundwater in these reactors. Most of the commonly used tracers (dyes and salts) did not give reliable results because of their interaction with the mineral matrix in the reactors. In this study radon (²²²Rn) dissolved in the groundwater is used as the tracer. The flow rate of groundwater through the reactors is 1 l/h. Over a period of 8 hours the radon-spiked groundwater was injected into the natural groundwater which has a very low radon concentration. The radon concentration of the discharged water is measured online at the reactor outlet. An increasing radon concentration at the reactor exit indicates the shortest residence time of the water. The time-dependent progress of the radon concentration provides detailed information about the flow behavior and residence times of water in the reactor.