1,3-Dioxolium-, 1,3-dithiolium- und 1,3-diselenolium-ionen - aromatische strukturen oder durch heteroatome stabilisierte carbeniumionen?

Protonation of the bases 6, 7 and 8 with trifluoroacetic acid was investigated on the basis of ^1–3C-nmr measurements. Two models for the generated ions 1–3 are discussed. A decision is possible in favour of carbenium ions, which are stabilized by adjacent heteroatoms.     

A bi-symmetric square wave Zeeman modulator for nuclear quadrupole resonance.

A simple circuit has been designed to generate a bi-symmetric square wave Zeeman modulation for the detection of nuclear quadrupole resonance. The square waveform not only provides an optimum result among bi-symmetric modulation waveforms, but also allows the observation of the Zeeman perturbed NQR powder pattern without the need for an extra external magnetic field.     

Conformal gauge fixing in Minkowski space

Conformal gauge fixing on simply connected parts of world sheets in Minkowski space is examined in detail. It is proved that conformal gauge fixing can be imposed, including the usual boundary conditions.     

Direct coupling of a flow–flow electromembrane extraction probe to LC-MS

A fully integrated and automated electromembrane extraction LC-MS (EME-LC-MS) system has been developed and characterized. Hyphenation of a flow–flow EME probe to LC-MS was accomplished by using an in-built 10-port switching valve of the LC-MS system. The 10-port switching valve decoupled the high pressure of the UHPLC-system from the low pressure required for operation of the EME-probe by automated switching between a sample extraction/analysis and a sample load position. In the sample load position the extracted analytes were loaded into a HPLC sample loop. By switching the valve to the sample extraction/analysis position the setup allowed simultaneous analysis of previously loaded analytes while extracting a new sample. Performance of the system was characterized with respect to precision and linearity (RSD < 2.5%, R²: 0.998) and the setup was applied for studying the in-vitro metabolism of methadone by rat liver microsomes. As the metabolic reaction proceeded, methadone and its metabolites were extracted and analyzed in parallel by LC-MS using either isocratic or gradient elution. Compared to a conventional in-vitro metabolism analysis based on protein precipitation followed by LC-MS analysis the fully automated EME-LC-MS system offers a significant time saving and in addition demonstrates increased sensitivity as the analytes were automatically enriched during the extraction process. The experiment revealed 6 to 16 times higher S/N ratios of the EME-LC-MS method compared to protein precipitation followed by LC-MS and thus concomitantly lower LOD and LOQ. The setup integrates a complete analytical workflow of rapid extraction, enrichment, separation and detection of analytes in a fully automated manner. These attributes make the developed system a powerful alternative approach for a wide range of analytical applications.     

Charge-transfer-type fluorescence of 4-(1H-pyrrol-1-yl)benzonitrile (PBN) and N-phenylpyrrole (PP) in cryogenic matrixes: evidence for direct excitation of the CT band

The fluorescence spectrum of PBN in a neat argon matrix is excitation-wavelength-dependent: at short excitation wavelengths, it consists of dual emission assigned to a charge-transfer (CT) state and a much weaker band assigned to the locally excited (LE) state. The CT emission is broad and almost completely devoid of vibrational structure, whereas the LE band is characterized by vibrationally resolved emission. At long excitation wavelengths, only CT emission is observed, indicating that the CT state is populated directly by light absorption and not via the LE state. Comparison with jet-cooled spectra of the bare molecule allows the unambiguous assignment of the LE spectrum and the location of the 0,0 band. The matrix LE emission spectrum is blue-shifted with respect to that of the gas phase, showing that the dipole moment of the LE state is smaller than that of the ground state. The fluorescence spectrum of PBN in an argon matrix does not change appreciably when acetonitrile (AN) is added to the matrix, in contrast to the case of N-phenylpyrrol (PP) (Schweke, D.; Haas, Y. J. Phys. Chem. A 2003, 107, 9554), for which addition of AN results in the appearance of two well separated emission bands. The different photophysical behaviors of PP and PBN in an argon matrix (and in supersonic jets) are analyzed by a simple model that considers the restriction of large-amplitude motions in the matrix. The implications of these low-temperature studies for understanding the properties of these systems in liquid solution are discussed.     

High resolution photoabsorption spectroscopy at the carbonK-Edge

Using plane grating, ellipsoidal mirror, grazing incidence monochromators at the storage ring BESSY, a resolution of 150meV was achieved for a photon energy of 285 eV. This high energy resolution considerably extends the range of possible studies using core level Spectroscopy. Some of the new opportunities are illustrated at the CK edge by resolving the vibrational fine structure of condensed C₂H₄ multilayers in the (1s^–1, ^*) state by means of photoabsorption spectroscopy. For the sake of comparison with other high resolution instruments, the vibrational fine structure of condensed N₂ multilayers at the NK edge ( 400eV) was also measured, yielding a resolving power of 3000.