Optical and redox properties of a series of 3,4-ethylenedioxythiophene oligomers

The optical and redox properties of a series of 3,4-ethylenedioxythiophene oligomers (EDOTn, n=1-4) and their beta,beta'-unsubstituted analogues (Tn, n=1-4) are described. Both series are end capped with phenyl groups to prevent irreversible alpha-coupling reactions during oxidative doping. Absorption and fluorescence spectra of both series reveal a significantly higher degree of intrachain conformational order in the EDOTn oligomers. Oxidation potentials (E(PA1) and E(PA2)) determined by cyclic voltammetry reveal that those of EDOTn are significantly lower than the corresponding Tn oligomers as a consequence of the electron-donating 3,4-ethylenedioxy substitution. Linear fits of E(PA1) and E(PA2) versus the reciprocal number of double bonds reveal significantly steeper slopes for the EDOTn than for the Tn oligomers. This could indicate a more effective conjugation for the EDOTn series, confirmed by the fact that coalescence of E(PA1) and E(PA2) is reached already at relatively short chain lengths ( approximately 5 EDOT units) in contrast to the Tn series (>10 thiophene units). The stepwise chemical oxidation of the EDOTn and Tn oligomers in solution was carried out to obtain radical cations and dications. The energies of the optical transitions of the radical cations and dications as determined by UV/Vis/NIR spectroscopy were similar for the two series. These spectroscopic observations are consistent with quantum-chemical calculations performed on the singly charged molecules. Cooling solutions containing T2.+, T3.+, EDOT2.+, and EDOT3.+ revealed the reversible formation of dimers, albeit with a somewhat different tendency, expressed in the values for the dimerization enthalpy.     

Real-space measurement of the potential distribution inside organic semiconductors

We demonstrate that the soft nature of organic semiconductors can be exploited to directly measure the potential distribution inside such an organic layer by scanning-tunneling microscope (STM) based spectroscopy. Keeping the STM feedback system active while reducing the tip-sample bias forces the tip to penetrate the organic layer. From an analysis of the injection and bulk transport processes it follows that the tip height versus bias trace obtained in this way directly reflects the potential distribution in the organic layer.     

Onsager-Zerlegung und Entropieproduktion für einen Defektspin in der linearen Spinkette mitX-Y-Kopplung

The autocorrelation function of an impurity spin in an infinite chain of spins withX-Y-coupling in thermal equilibrium is shown to be an example of “Onsager separation”. This separability ensures that the statistical entropy production associated with the impurity spin relaxation contains a phenomenological part which proves to be always positive.     

Mass spectrometry-gas chromatographic determination of mecloqualone metabolites from urine extracts

Summary The separation and identification of metabolites of mecloqualone in human urine samples by GLC-MS analysis are described. Four hydroxylated mecloqualone derivates have been identified.

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Zusammenfassung Die Trennung und Identifizierung von Metaboliten des Mecloqualons in Menschenharn durch Gas-Flüssigchromatographie und Massenspektrometrie wurde beschrieben. Vier Hydroxylderivate des Mecloqualons wurden identifiziert.

     

Die Struktur endlicher schwach abgeschlossener Jordanalgebren Teil I. Stetige Jordanalgebren

On the basis of the authors previous paper [6] the properties of the lattice of idempotents in a finite weakly closed Jordan algebra A are examined. The results then yield a unique direct decomposition A=A_d⊕A_c where A_d is a discrete and A_c is a continuous Jordan algebra. An application of Jacobsons coordinatization theorem shows A_c=H(D), D associative, since there exist sufficiently many strongly connected idempotents. Then we prove that D is a uniquely determined continuous real W^* -algebra with finite normal faithful trace.     

Fluktuationen von Besetzungszahlen

Kinetic equations for the fluctuations and the fluctuation spectrum of the occupation numbers in a nonequilibrium stationary state are derived within a stochastic theory. The probability of changes of the distribution in infinitesimal time intervals is given by the “Stoßzahlansatz”. It is assumed for the decoupling of the higher correlations, that the occupation numbers are macroscopic variables.     

Low energy Auger and loss electron spectra from magnesium and its oxide

Data have been obtained from Auger and energy loss processes in clean metallic Mg, Mg during stages of oxidation, and UHV cleaved MgO(100) surfaces. Particular attention has been paid to twenty features below 200 eV in the Auger spectra from these surfaces. A comparison of spectra from the metal, oxidised metal surface, and single crystal MgO has enabled estimates to be made of surface charging effects, and the MgO steady state surface potential is found to be near + 10 V above ground. All the Auger features are given assignments, two of which are interfacial processes involving ionic initial states and metallic final states. Several features in the low energy Auger spectrum are attributed to diffraction of true secondary electrons.     

Implementing solenoid microcoils for wide-line solid-state NMR

Solid-state nuclear magnetic resonance (NMR) probeheads using solenoid microcoils with an inner diameter of 300-400 microm are developed for the study of mass-limited solid samples. Some attention is paid to the mechanical ruggedness of the probes allowing sample changing. The performance, in terms of sensitivity and RF-characteristics, of these probeheads is studied for (1)H, (31)P, and (27)Al in different model compounds in view of the feasibility of specific applications. The results show that the sensitivity is high enough to detect approximately 10(14) spins/sqrt Hz with a signal-to-noise ratio of 1 in a single scan. A specific advantage of microcoils for solid-state NMR applications is that they can generate extremely high RF-fields if implemented in appropriate circuits. Using RF-powers in the hundreds of Watts range, RF-fields well in excess of 1MHz can be made. This allows the excitation of spectra of nuclei whose resonance lines are dispersed of several megahertz. This is particularly useful for quadrupolar nuclei experiencing large quadrupolar interactions as is demonstrated for (27)Al in single crystal and powdered minerals.     

Improvement of the hydrothermal stability of SAPO-34

Hydrothermal stability of SAPO-34 is greatly improved by the treatment of the acidic form of the SAPO-34 with NH3.