Structural investigation of asymmetrical dimer radical cation system (H2O-H2S)+: proton-transferred or hemi-bonded?

Ab initio molecular orbital and hybrid density functional methods have been employed to characterize the structure and bonding of (H2O-H2S)+, an asymmetrical dimer radical cation system. A comparison has been made between the two-center three-electron (2c-3e) hemi-bonded system and the proton-transferred hydrogen-bonded systems of (H2O-H2S)+. Geometry optimization of these systems was carried out using unrestricted Hartree Fock (HF), density functional theory with different functionals, and second-order M?ller-Plesset perturbation (MP2) methods with 6-311++G(d,p) basis set. Hessian calculations have been done at the same level to check the nature of the equilibrium geometry. Energy data were further improved by calculating basis set superposition error for the structures optimized through MP2/6-311++G(d,p) calculations. The calculated results show that the dimer radical cation structure with H2O as proton acceptor is more stable than those structures in which H2O acts as a proton donor or the 2c-3e hemi-bonded (H2O thereforeSH2)+ system. This stability trend has been further confirmed by more accurate G3, G3B3, and CCSD(T) methods. On the basis of the present calculated results, the structure of H4OS+ can best be described as a hydrogen-bonded complex of H3O+ and SH with H2O as a proton acceptor. It is in contrast to the structure of neutral (H2O...H2S) dimer where H2O acts as a proton donor. The present work has been able to resolve the ambiguity in the nature of bonding between H2O and H2S in (H2O-H2S)+ asymmetrical dimer radical cation.     

Stroboscopic XMCD-PEEM imaging of standing and propagating spinwave modes in permalloy thin-film structures

Using synchrotron-based stroboscopic photoemission electron microscopy with X-ray circular dichroism as contrast method, we have investigated the high-frequency response of permalloy thin-film structures. Standing precessional modes have been studied in rectangular elements (16 × 32 μm², 10 nm thick) with a high time resolution of about 15 ps in the low-α mode of BESSY. With increasing amplitude of the applied magnetic AC field the particle is driven from an initial symmetric Landau flux-closure state into an asymmetric state and finally into a single-domain state magnetized perpendicular to the applied field H_AC. The electromagnetic microwave field thus can induces a net magnetization in a small particle. This behaviour is a result of the constant throughput of energy (open system) that allows for an increase of local order, contrary to the usual increase on entropy in closed systems. A propagating spinwave in an ultrathin elliptical particle (semi axes 6 × 12 μm², 3 nm thick) was observed in a snapshot series with 25 ps time increment. The phase front of the spinwave with large precessional angle (bright contrast) propagates with a velocity of 8100 m/s, i.e. much faster than typical domain wall velocities in permalloy.     

Determination of enalapril and enalaprilat in small human serum quantities for pediatric trials by HPLC-tandem mass spectrometry

The angiotensin converting enzyme‐inhibitor enalapril is the prodrug of enalaprilat and used in the treatment pediatric hypertension and chronic heart failure. Pharmacokinetic data are lacking to provide adequate dosing and for pediatric pharmacotherapeutical trials it is imperative to minimize sample volume. Therefore an HPLC‐tandem mass spectrometry (MS) method for the determination of enalapril and enalaprilat in 100 μL of human serum was developed and validated with benazepril as internal standard (IS). After solid‐phase extraction, chromatography was performed on a Luna^® RP‐C₁₈(2) column with methanol–water–formic acid (65:35:1, v/v/v) as mobile phase and a flow rate of 0.4 mL/min. The MS was set to positive‐mode electrospray ionization and multiple reaction monitoring, analyzing the m/z transitions channels 377.3 → 234.2, 349.3 → 206.1 and 425.3 → 351.2 for enalapril, enalaprilat and IS. Calibration curves were linear in the range of 1.61–206 ng/mL (enalapril) and 1.84–236 ng/mL (enalaprilat) with coefficients of determination >0.99. Relative standard deviations of intra‐ and inter‐run precisions were below 7% and relative errors were below 6 ± 7% for both analytes. Also stabilities were acceptable for both analytes. As an application example, concentrations of enalapril and enalaprilat in serum after oral administration of 20 mg enalapril maleat in a healthy volunteer were determined. Copyright © 2011 John Wiley & Sons, Ltd.     

Design and Synthesis of Nucleoproline Amino Acids for the Straightforward Preparation of Chiral and Conformationally Constrained Nucleopeptides

A straightforward synthesis of orthogonally protected nucleoproline (Nup) amino acids and their coupling to oligomers are described. A key step is the attachment of alkynylated nucleobases to Fmoc‐protected 4‐azidoproline (Fmoc‐Azp‐OH) by a Cu‐catalyzed 1,3‐dipolar cycloaddition (‘click reaction’). The developed protocol allows preparation of the nucleoprolines in scales of >30 g. Solid‐phase peptide synthesis proved to be straightforward with these Nup amino acids. The resulting oligonucleoproline peptides adopt defined helices, are very well H₂O soluble, and show comparable cell‐penetrating properties as recently reported α‐nucleoalanine peptides.     

Resonant invisibility with finite range interacting fermions

We study the eigenstates of two opposite spin fermions on a one-dimensional lattice with finite range interaction. The eigenstates are projected onto the set of Fock eigenstates of the noninteracting case. We find antiresonances for symmetric eigenstates, which eliminate the interaction between two symmetric Fock states when satisfying a corresponding selection rule.     

Theoretical analysis of dilepton spectra in heavy ion collisions at GSI-FAIR energies

This paper addresses the theoretical analysis of dilepton spectra in C+C collisions at GSI-SIS energies. Theoretical predictions for the recent data of the HADES Collaboration at SIS energies are made with the help of a hadron-string transport model, the Ultra-relativistic Quantum Molecular Dynamics (UrQMD) model. A mass shift of the ρ meson due to kinematical effects is discussed.