Methyltrimethoxysilane (MTMS)-based silica-iron oxide superhydrophobic nanocomposites.

We report a facile synthesis of superhydrophobic silica-iron oxide nanocomposites via a co-precursor sol-gel process. The choice of the silica precursor (Methyltrimethoxysilane, MTMS) in combination with iron nitrate altered the pore structure dramatically. The influence of iron oxide doping on the structural properties of pristine MTMS aerogel is discussed.

Nanostructure characterization by a combined x-ray absorption/scanning force microscopy system.

A combined x-ray transmission and scanning force microscope setup (NanoXAS) recently installed at a dedicated beamline of the Swiss Light Source combines complementary experimental techniques to access chemical and physical sample properties with nanometer scale resolution. While scanning force microscopy probes physical properties such as sample topography, local mechanical properties, adhesion, electric and magnetic properties on lateral scales even down to atomic resolution, scanning transmission x-ray microscopy offers direct access to the local chemical composition, electronic structure and magnetization. Here we present three studies which underline the advantages of complementary access to nanoscale properties in prototype thin film samples.

Homochiral conglomerates and racemic crystals in two dimensions: tartaric acid on Cu(110).

Two-dimensional lattice structures formed by racemic tartaric acid on a single crystalline Cu(110) surface have been studied and compared with the enantiopure lattices. At low coverage, the doubly deprotonated bitartrate species is separated into two-dimensional conglomerates showing opposite enantiomorphism. At higher coverage, however, a singly deprotonated monotartrate species forms a heterochiral, racemic crystal lattice. While the enantioseparated bitartrate system undergoes decomposition at the same temperature as the enantiopure system, the racemic monotartrate lattice has a lower thermal stability than the enantiopure lattice of identical periodicity and surface density. At monolayer saturation coverage, the pure enantiomers form a denser lattice than the racemate. This is in contrast to the three-dimensional tartaric acid crystals, where the racemate crystallizes in a lattice of higher density, which is also more thermally stable than the enantiopure tartaric acid crystals.

Induction of homochirality in achiral enantiomorphous monolayers.

We report the induction of homochirality in enantiomorphous layers of achiral succinic acid on a Cu(110) surface after doping with tartaric acid (TA) enantiomers. Succinic acid becomes chiral upon adsorption due to symmetry-breaking interactions with the Cu(110) surface. The doubly deprotonated bisuccinate forms mirror domains on the surface, which leads to a superposition of (11,-90) and (90,-11) patterns observed by low-energy electron diffraction (LEED). On average, however, the surface layer is racemic. An amount of 2 mol % of (R,R)- or (S,S)-tartaric acid in the monolayer, corresponding to an absolute coverage of 0.001 tartaric acid molecule per surface copper atom, is sufficient to make the LEED spots of one enantiomorphous lattice disappear. After thermally induced desorption of TA, the succinic acid lattice turns racemic again. In analogy to the "sergeants-and-soldiers" principle described for helical polymers, this effect is explained by a lateral cooperative interaction within the two-dimensional lattice.

Chiral recognition in surface explosion.

The vast majority of chiral compounds crystallize into racemic crystals. It has been predicted and was experimentally established as a rule that chiral molecules on surfaces are more easily separated into homochiral domains due to confinement into a plane and lower entropic contributions. We investigated the formation and stability of two-dimensional tartrate crystals on a Cu(110) surface for the racemic mixture for the first time by means of temperature-programmed desorption (TPD), low-energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). At low coverage, a bitartrate species becomes separated into homochiral domains, while at high coverage a monotartrate species forms a racemic mixture. At the same coverage and lateral arrangement, the thermally induced autocatalytic decomposition reaction occurs for the monotartrate racemate at a lower temperature than for the pure enantiomers. The stereochemistry in this so-called "surface explosion" reaction is explained by a higher stability of the enantiopure lattice due to lateral hydrogen-bond formation. The higher stability of the enantiopure two-dimensional lattice is in contrast to the higher stability of racemic three-dimensional tartaric acid crystals but is consistent with the observation that homochirality is preferred in hydrogen-bonded self-assembled biomolecular structures.

Diffusing-Wave Spectroscopy of Concentrated Alumina Suspensions during Gelation.

Using diffusing-wave spectroscopy, we followed the aggregation and gelation of concentrated (30 vol%) alumina suspensions. The suspensions were destabilized by either shifting the pH to the isoelectric point or by increasing the ionic strength. Both effects can be achieved continuously and homogeneously by using an enzyme-catalyzed internal chemical reaction. Based on the light-scattering data, we could derive quantitative information about the sol-gel transition and the viscoelastic properties of the gels, as well as a characterization of changes in the microstructure. The elastic moduli determined from light scattering are found to be in good agreement with rheological measurements. Copyright 2001 Academic Press.