Adiabatic approximation in nonperturbative time-dependent density-functional theory

We construct the exact exchange-correlation potential of time-dependent density-functional theory and the approximation to it that is adiabatic but exact otherwise. For the strong-field double ionization of the Helium atom these two potentials are virtually identical. Thus, memory effects play a negligible role in this paradigm process of nonlinear, nonperturbative electron dynamics. We identify the regime of high-frequency excitations where the adiabatic approximation breaks down and explicitly calculate the nonadiabatic contribution to the exchange-correlation potential.     

Die Doppelbrechung von Seifensolen

Zusammenfassung Zusammengefaßt hat sich ergeben: Seifensole zeigen eine Vorzeichenumkehr der Strömungsdoppelbrechung. Diese Umkehr ist reversibel. Das Vorzeichen der Doppelbrechung beim Strömen hängt ab von der Konzentration der Wasserstoffionen im Dispersionsmittel. Durch H-Ionen wird die Dissoziation der COOH-Gruppe der Fettsäuren zurückgedrängt, dagegen durch OH-Ionen gefördert. Bei starker Dissoziation und hoher Ladung der COOH-Gruppe überwiegt die heteropolare Ionenbindung — die Seifenmoleküle ordnen sich hintereinander an (Stäbchen). Bei geringer Dissoziation der COOH Gruppe überwiegt die homöopolare Nebenvalenzbindung der Paraffinketten — und die Fettsäuremoleküle ordnen sich nebeneinander an (Plättchen).Die verschiedenartigen Mizellen haben ein verschiedenes optisches Verhalten. Im Inversionspunkt ist das Sol isotrop. Dieser Punkt ist wahrscheinlich der Neutralpunkt der Seifen. Die Inversion ist eine Zeitreaktion.Die Änderung des mizellaren Aufbaus der Seife wie auch von Palmitat und Stearat gibt sich gleichzeitig in einer Änderung der Viskosität, der Trübung, der Spinnbarkeit, der Häutchenbildung, der Gelbildung und dem Schaumvermögen zu erkennen.     

Generation of Nanopores Down to 10 nm for Use in Deep‐Nulling Interferometry

Scanning electron microscope images show that it is easy to generate nanopores on polycarbonate membranes with well‐defined pore diameters by ion‐track perforation and subsequent magnetron sputtering with metal. The size reduction of the nanopores during sputtering with gold is a linear function of time. Images of different angles and from the bottom side of the membrane show that the channels are the smallest very close to the surface of the metal layer, have a conelike shape, and reach about half as much into the polymer membranes as the metal‐layer thickness. This topographical pore shape is ideal for use as optically coherent near‐field sources in deep‐nulling microscopy. We present the first results of significantly improved nulling stabilization in the presence (<2 nm optical pathway difference) and the absence (<0.6 nm optical pathway difference) of the nanoapertures in the focal region of a deep‐nulling microscope.     

Use of an electrochemically synthesised metabolite of a selective androgen receptor modulator for mass spectrometry-based sports drug testing

The elucidation of the metabolism of new therapeutics is a major task for pharmaceutical companies and of great interest for drug testing laboratories. The latter in particular need to determine the presence or absence of drugs or their metabolic products in urine to test for a misuse of these compounds. Commonly, in vitro or animal models are used to mimic the human metabolism and produce potential targets in amounts allowing for method development. An alternative route based on electrochemical reactions of drugs was reported to allow for the generation of selected metabolites. The utility of this approach for doping control purposes was demonstrated with a novel class of anabolic agents termed selective androgen receptor modulators (SARMs). An arylpropionamide- derived drug candidate was subjected to electrochemical "metabolism" and a major phase-I- metabolite, resulting from the elimination of a substituted phenol residue as identified in in vitro experiments, was generated and characterised using liquid chromatography/nuclear magnetic resonance spectroscopy and high resolution/high accuracy mass spectrometry. The metabolite was included in routine doping control procedures based on liquid chromatography/tandem mass spectrometry and has served as a reference compound for 5000 doping control specimens.     

Mechanism of enzymatic Birch reduction: stereochemical course and exchange reactions of benzoyl-CoA reductase

Dearomatizing benzoyl-coenzyme A reductases (BCR) from facultatively anaerobic bacteria are key enzymes in the anaerobic degradation of aromatic compounds. They catalyze the ATP-dependent reduction of benzoyl-CoA (BCoA) to cyclohexa-1,5-diene-1-carboxyl-CoA (dienoyl-CoA). A Birch reduction mechanism involving alternate electron transfer and protonation steps has been proposed for BCR. In this work we reacted BCoA in H2O and D2O, and d5-BCoA in H2O with BCR and the second enzyme of the pathway, dienoyl-CoA hydratase (DCH). The 1,4 hydration product formed from the dienoyl-CoA, 6-hydroxycyclohex-1-ene-1-carbonyl-CoA, was analyzed by several NMR techniques. The results obtained indicate that BCR stereoselectively forms the trans-dienoyl-CoA product, and DCH stereoselectively catalyzes a trans-1,4 water addition. Moreover, unexpected proton exchanges at C-2 and C-6 were observed. They indicate that a free radical intermediate with an unusual low pKa is formed during BCR catalysis. This finding provides evidence for the proposed Birch reduction mechanism of BCR and is in agreement with the established radical mechanism of homologous alpha-hydroxyacyl-CoA dehydratases.     

Even-electron ions: a systematic study of the neutral species lost in the dissociation of quasi-molecular ions

The collision-induced dissociations of the even-electron [M + H](+) and/or [M - H](-) ions of 121 model compounds (mainly small aromatic compounds with one to three functional groups) ionized by electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) have been studied using an ion trap instrument, and the results are compared with the literature data. While some functional groups (such as COOH, COOCH(3), SO(3)H in the negative ion mode, or NO(2) in both the positive and negative ion modes) generally promote the loss of neutrals that are characteristic as well as specific, other functional groups (such as COOH in the positive ion mode) give rise to the loss of neutrals that are characteristic, but not specific. Finally, functional groups such as OH and NH(2) in aromatic compounds do not lead to the loss of a neutral that reflects the presence of these substituents. In general, the dissociation of [M + H](+) and [M - H](-) ions generated from aliphatic compounds or compounds containing an aliphatic moiety obeys the even-electron rule (loss of a molecule), but deviations from this rule (loss of a radical) are sometimes observed for aromatic compounds, in particular for nitroaromatic compounds. Thermochemical data and ab initio calculations at the CBS-QB3 level of theory provide an explanation for these exceptions. When comparing the dissociation behaviour of the even-electron [M + H](+) and/or [M - H](-) ions (generated by ESI or APCI) with that of the corresponding odd-electron [M](+) ions (generated by electron ionization, EI), three cases may be distinguished: (1) the dissociation of the two ionic species differs completely; (2) the dissociation involves the loss of a common neutral, yielding product ions differing in mass by one Da, or (3) the dissociations lead to a common product ion.     

Time Domain Impedance Boundary Conditions for a Slip Mean FlowBoundary

In modeling the physical condition of an impedance boundary, the assumption of either particle displacement continuity (PDC) or particle normal velocity continuity (PVC) at the interface between the acoustic treatment and the adjacent fluid needs to be used. Although it is well accepted that the impedance boundary condition derived from the PDC is the appropriate impedance boundary condition when there is a slip mean flow at the liner surface, the time domain impedance boundary condition is however unstable due to the Kelvin‐Helmholtz instability associated with the ”vortex sheet.” In this paper, an effective time domain impedance boundary condition for a slip mean flow boundary is proposed and validated. Several relevant issues related to the PDC and PVC are discussed. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)