Interactions between glycine and amorphous solid water nanoscale films

The interactions of glycine (Gly) with amorphous solid water (ASW) nanolayers (≤ 100 ML), vapor-deposited on single crystalline AlO_x surfaces at 100 K, have been investigated by near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K-edge, temperature-programmed thermal desorption (TPD), X-ray photoelectron spectroscopy (XPS), and temperature-dependent work function measurements. Gly-on-ASW, ASW-on-Gly, and Gly on top of ASW-on-Gly ultrathin films have been fabricated. In contrast to the uniform ASW films grown directly on the hydrophilic AlO_x, water molecules adsorb on the hydrophobic Gly films in the form of 3D ASW clusters. This leads to significant differences in the NEXAFS and work function data obtained from ASW-on-AlO_x and ASW-on-Gly films, respectively. Furthermore, these structural differences influence the chemical state of Gly molecules (neutral vs. zwitterionic) adsorbed on top of ASW films. N1s XPS measurements revealed an increased amount of neutral Gly molecules in the film top-deposited on the ASW-on-Gly structure in comparison to the neutral Gly in the films directly condensed on AlO_x or grown on the ASW substrate. H₂O TPD spectra demonstrate that the crystallization and desorption processes of ASW are affected in a different way by the Gly layers, top-deposited on to ASW-on-AlO_x and ASW-on-Gly films. At the same time, Gly adlayers sink into the ASW film during crystallization/desorption of the latter and land softly on the alumina surface in the form of zwitterionic clusters.     

Studies on the chiral recognition of peptide enantiomers by neutral and sulfated beta-cyclodextrin and heptakis-(2,3-di-O-acetyl)-beta-cyclodextrin using capillary electrophoresis and nuclear magnetic resonance

The separation of dipeptide and tripeptide enantiomers using a neutral single isomer cyclodextrin (CD) derivative, heptakis-(2,3-di-O-acetyl)-beta-CD (DIAC-beta-CD), was investigated with respect to the amino acid sequence applying standard separation conditions. With only one exception the DD-enantiomers migrated faster than the LL-stereoisomers. Separations obtained for the same set of peptides using beta-CD and the sulfated single isomer derivatives heptakis-(2,3-di-O-acetyl-6-sulfo)-beta-CD (HDAS-beta-CD) and heptakis-6-sulfo-beta-CD (HS-beta-CD) revealed identical enantiomer migration order in the presence of the 2,3-disubstituted derivatives DIAC-beta-CD and HDAS-beta-CD. In contrast, reversed migration sequence was found for beta-CD and HS-beta-CD compared to DIAC-beta CD and HDAS-beta-CD indicating the importance of the substitution pattern on the wider rim of the CD cavity on the chiral recognition of the peptide enantiomers by the CDs. Nuclear magnetic resonance (NMR) experiments indicated different complexation modes between the enantiomers and the CDs depending on the presence of acetyl substituents on the wider rim of the CD torus. Thus, the CD-induced chemical shifts observed in samples containing Ala-Phe or Ala-Tyr and beta-CD or HS-beta-CD were consistent with an inclusion of the aromatic moiety into the CD cavity. Although the CD-induced chemical shifts in the presence of DIAC-beta-CD and HDAS-beta-CD did not allow direct conclusions on the complexation mode they substantially differed from those observed in the presence of 2,3-unsubstituted CDs indicating different structures of the peptide-CD complexes.     

Implementation Strategies for Accurate and Efficient Control Volume-Based Two-Phase Hydrothermal Flow Solutions

Numerical models of magmatic hydrothermal systems have become powerful tools for linking surface and seafloor observations to chemical and fluid-dynamic processes at depth. This task requires resolving multi-phase flow over large distances of several kilometers, a wide range of pressure (p) and temperature (T) conditions, and over timescales of several thousands of years. The key numerical challenge is that realistic simulations have to consider the high nonlinearity and strong coupling of the governing conservation equations for mass and energy, while also being numerically efficient so that the required spatial and temporal scales can be resolved. Here we outline possible solutions to this problem by evaluating different implementation strategies and presenting a numerical scheme for fully coupled accurate and efficient flow solutions. The general scheme, based on the Newton–Raphson (NR) method, is presented for the simplified case of 2-D pure water convection and uses a control volume discretization on unstructured meshes. We find that the presented techniques significantly reduce the computational effort with respect to sequential/decoupled schemes. Key to this is a theta-time-differencing method for better accuracy, stability and convergence behavior of the NR-iterations, as well as improvements regarding upwinding. These features make the presented methods useful for coupled simulations of magmatic hydrothermal systems and a potential basis for future 3-D multi-phase codes.     

Über eine Verallgemeinerung des Hasseschen Normensatzes

Ohne ZusammenfassungHelmut Hasse zum Gedenken gewidmet     

Template‐Free Galvanic Nanostructuring of Gold Electrodes for Sensitive Electrochemical Biosensors

Gold nanostructuring of smooth gold disk‐electrodes has been performed by electrodeposition. FE‐SEM images indicate a strongly enlarged electrochemically active surface of the modified electrodes. This could be approved by the gold oxide reduction peak in cyclic voltammetry. The electrodes were also applied for sequence‐specific DNA detection. For this, complementary single stranded capture probes were immobilized on the electrodes and consecutively hybridized with complementary and noncomplementary [OsO₄(bipy)]‐labeled DNA targets. We found that intermediate dehybridization steps did not decrease the sensitivity for the specific target. Moreover, the surface modification increased the voltammetric signal by an approx. factor of 9. Further, an enhanced linear calibration range was observed. The presented simple nanostructuring process holds great promise for many electrochemical sensor applications.     

Atomic engineering of oxide nanostructure superlattices

Low-dimensional nanoscale oxide-metal hybrid structures have been fabricated by decoration of a vicinal noble metal surface, Pd(1,1,17), by 1-D and 2-D Mn-oxide nanowires and nanostripes. STM and LEED demonstrate that highly ordered superlattices of Mn-oxide nanostructures can be obtained. The coupling of the oxide nanophases to the metal steps and terraces leads to a mesoscopic stabilization of the step–terrace morphology thus creating nearly perfect nanopatterned oxide systems.