Über die Darstellung einero-Aminothiophenol-sulfosäure

Ohne Zusammenfassung Vorliegende Untersuchung war bereits vor l?ngerer Zeit (1921) abgeschlossen und kommt lediglich aus ?u?eren Gründen erst jetzt zur Ver?ffentlichung.     

Oxidative degradation of nitrogen-containing organic compounds: vaccum-ultraviolet (VUV) photolysis of aqueous solutions of 3-amino 5-methylisoxazole

The oxidative degradation of 3-amino 5-methyl isoxazole initiated by the VUV photolysis of water at 172 nm has been studied. Mineralization of CO₂, H₂O, NO ₃ ^– and NH ₄ ⁺ is more efficient when reductive conditions (argon saturated solutions) are favoured. Formation of compounds which cannot be completely oxidised to CO₂ is observed. Experiments performed under strictly oxidative conditions show higher yields of these inert compounds and, hence, incomplete mineralization. Cyanide was formed in concentrations lower than 5×10^–5 mol/l. In alkaline aqueous solutions, cyanide is completely transformed into CO ₃ ^2– , NH ₄ ⁺ and NO ₃ ^– during the irradiation time needed to mineralize the isoxazole. Therefore, cyanide does not present a potential risk for the use of the VUV photolysis for isoxazole degradation. Similarly, organic nitrogen is converted into both, NO ₃ ^– and NH ₄ ⁺ . The relative concentrations of the two ions depend on total irradiation time, oxygen saturation and reactor geometry. A sequence of reactions is proposed and discussed.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Asymptotics of heavy atoms in high magnetic fields: I. Lowest landau band regions

The ground state energy of an atom of nuclear charge Ze in a magnetic field B is evaluated exactly to leading order as Z → ∞. In this and a companion work (see [28]) we show that there are five regions as Z → ∞: B < Z^4/3, B ～ Z^4/3, Z^4/3 < B < Z³, B ～ Z³, B > Z³. Regions 1, 2, 3, and 4 (and conceivably 5) are relevant for neutron stars. Different regions have different physics and different asymptotic theories. Regions 1, 2, and 3 are described by a simple density functional theory of the semiclassical Thomas-Fermi form. Here we concentrate mainly on regions 4 and 5 which cannot be so described, although 3, 4, and 5 have the common feature (as shown here) that essentially all electrons are in the lowest Landau band. Region 5 does have, however, a simple non-classical density functional theory (which can be solved exactly). Region 4 does not, but, surprisingly, it can be described by a novel density matrix functional theory. © 1994 John Wiley & Sons, Inc.     

Partially Commutative Moment Problems

Partially commutative tensor algebras occur naturally in the algebraic formulation of Wightman field theory. A state on an algebra of this type leads via GNS-construction to a partially commutative family of hermitean operators on Hilbert space. We discuss the question when these operators can be extended to self adjoint operators preserving the commutation properties and state a necessary and sufficient condition for the existence of such an extension in terms of a positivity property of the state.     

Bose-Einstein condensate coupled to a nanomechanical resonator on an atom chip

We theoretically study the coupling of Bose-Einstein condensed atoms to the mechanical oscillations of a nanoscale cantilever with a magnetic tip. This is an experimentally viable hybrid quantum system which allows one to explore the interface of quantum optics and condensed matter physics. We propose an experiment where easily detectable atomic spin flips are induced by the cantilever motion. This can be used to probe thermal oscillations of the cantilever with the atoms. At low cantilever temperatures, as realized in recent experiments, the backaction of the atoms onto the cantilever is significant and the system represents a mechanical analog of cavity quantum electrodynamics. With high but realistic cantilever quality factors, the strong coupling regime can be reached, either with single atoms or collectively with Bose-Einstein condensates. We discuss an implementation on an atom chip.     

Material Discrimination in Nanoparticle Hetero-Aggregates by Analysis of Scanning Transmission Electron Microscopy Images

Hetero-contacts are interfaces between different materials at the nanoscale leading to novel functional properties. In hetero-aggregates, primary particles of at least two different materials are mixed at primary particle or cluster level. Double flame spray pyrolysis (DFSP) is a versatile technique for the controlled synthesis of such materials. Characterization of hetero-aggregates by scanning transmission electron microscopy (STEM) requires acquisition and evaluation of many aggregate images in order to derive statistically significant results. Usually, STEM energy dispersive X-ray spectroscopy (EDXS) is used to acquire elemental maps providing the material distribution of the primary particles within hetero-aggregates. However, the acquisition of a single EDXS map takes up to several minutes. For this reason, determination of material types of primary particles from the intensity in high-angle annular dark field STEM images alone is desirable. These images can be acquired within a couple of seconds. In the present work, a method is suggested which allows for achieving this objective. It can be applied to distinguish materials with a significant difference in their atomic number and hence sufficient material contrast in the STEM images.     

Dynamics of Fluorescent Dyes Attached to G‐Quadruplex DNA and their Effect on FRET Experiments

FRET spectroscopy is a promising approach for investigating the dynamics of G‐quadruplex DNA folds and improving the targeting of G‐quadruplexes by potential anticancer compounds. To better interpret such experiments, classical and replica‐exchange molecular dynamics simulations and fluorescence‐lifetime measurements are used to understand the behavior of a range of Cy3‐based dyes attached to the 3′ end of G‐quadruplex DNA. The simulations revealed that the dyes interact extensively with the G‐quadruplex. Identification of preferred dye positions relative to the G‐quadruplex in the simulations allows the impact of dye–DNA interactions on FRET results to be determined. All the dyes show significant deviations from the common approximation of being freely rotating and not interacting with the host, but one of the Cy3 dye analogues is slightly closer to this case.     

CH Oxidation of Ingenanes Enables Potent and Selective Protein Kinase C Isoform Activation

Ingenol derivatives with varying degrees of oxidation were prepared by two‐phase terpene synthesis. This strategy has allowed access to analogues that cannot be prepared by semisynthesis from natural ingenol. Complex ingenanes resulting from divergent C? H oxidation of a common intermediate were found to interact with protein kinase C in a manner that correlates well with the oxidation state of the ingenane core. Even though previous work on ingenanes has suggested a strong correlation between potential to activate PKCδ and induction of neutrophil oxidative burst, the current study shows that the potential to activate PKCβII is of key importance while interaction with PKCδ is dispensable. Thus, key modifications of the ingenane core allowed PKC isoform selectivity wherein PKCδ‐driven activation of keratinocytes is strongly reduced or even absent while PKCβII‐driven activation of neutrophils is retained.     

Photo‐Wolff Rearrangement of 2‐Diazo‐1,2‐naphthoquinone: Stern–Volmer Analysis of the Stepwise Reaction Pathway

2‐Diazo‐1,2‐naphthoquinone (1) and its derivatives are the photoactive components in Novolak photoresists. A femtosecond infrared study has established that the photoreaction of 1 proceeds largely by a concerted Wolff rearrangement yielding the ketene 1H‐inden‐1‐ylidene‐methanone (3) within 300 fs after excitation, but earlier trapping studies gave evidence for a minor reaction path via a carbene intermediate 1‐oxo‐2(1H)‐naphthalenylidene (2) with a lifetime of about 10 ps. Here, we provide a quantitative assessment of the stepwise pathway by Stern–Volmer analysis of the trapping of 2 by methanol to yield 2‐methoxy‐1‐naphthol (4). We conclude that the lifetime of the carbene 2 is at least 200 ps. Moreover, [3 + 2]cycloaddition of 2 and acetonitrile yielding 2‐methylnaphth[2,1‐d]oxazole (5) was observed. A comparison of the yields of 5 formed upon photolysis and upon thermolysis of 1 in acetonitrile provides evidence that a substantial part of the hot nascent carbene 2 formed photolytically rearranges to the ketene 3 during its vibrational relaxation (hot ground‐state reaction).     

Ruthenium‐Catalyzed C?C Bond Cleavage in Lignin Model Substrates

Ruthenium–triphos complexes exhibited unprecedented catalytic activity and selectivity in the redox‐neutral C C bond cleavage of the β‐O‐4 lignin linkage of 1,3‐dilignol model compounds. A mechanistic pathway involving a dehydrogenation‐initiated retro‐aldol reaction for the C C bond cleavage was proposed in line with experimental data and DFT calculations.