The monitoring of water and water vapour diffusion into clay by impedance spectroscopy

The diffusion of water vapour into Bayard montmorillonite and the diffusion/flow of liquid water into Friedland clay were examined with impedance spectroscopy as a first step towards the development of an impedance based sensor system for the in situ monitoring of clay-based barriers for waste containment. By impedance measurements the diffusion of water vapour into clay and the leaching of liquid water through clay barriers can be monitored time-dependently and parameters can be derived from the data that can be used to predict the speed of diffusion/flow through the barrier. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Inclusion of thiamine diphosphate and S-adenosylmethionine at their chemically active sites

[structure: see text] Molecular clips functionalized by phosphonate or phosphate groups bind thiamine diphosphate (TPP) and S-adenosylmethionine (SAM) with high affinity in water; both sulfur-based cofactors transfer organic groups to biomolecules. For TPP, various analytical tools point toward a simultaneous insertion of both heterocyclic rings into the electron-rich clip cavity. Similarly, SAM is also embedded with its sulfonium moiety inside the receptor cavity. This paves the way for enzyme models and direct interference with enzymatic processes.     

Zipping up 'the crushed fullerene' C60H30:C60 by fifteen-fold,consecutive intramolecular H2 losses

MALDI TOF-MS of tribenzo[l:1':1"]benzo[1,2-e:3,4-e':5,6-e"]triacephenanthrylene (1a, C60H30) gives C60.+ by multiple intramolecular cyclodehydrogenation reactions.     

Experimental observation of structural crossover in binary mixtures of colloidal hard spheres

Using confocal microscopy, we investigate the structure of binary mixtures of colloidal hard spheres with size ratio q=0.61. As a function of the packing fraction of the two particle species, we observe a marked change of the dominant wavelength in the pair-correlation function. This behavior is in excellent agreement with a recently predicted structural crossover in such mixtures. In addition, the repercussions of structural crossover on the real-space structure of a binary fluid are analyzed. We suggest a relation between crossover and the lateral extension of networks containing only equally-sized particles that are connected by nearest-neighbor bonds. This is supported by Monte Carlo simulations which are performed at different packing fractions and size ratios.     

Charge transport parameters of the pentathienoacene crystal

Pentathienoacene, the thiophene equivalent of pentacene, is one of the latest additions to the family of organic crystal semiconductors with a great potential for use in thin film transistors. By using density functional theory and gas-phase ultraviolet photoelectron spectroscopy, we investigate the microscopic charge transport parameters of the pentathienoacene crystal. We find that the valence band exhibits a stronger dispersion than those in the pentacene and rubrene single crystals with marked uniaxial characteristics within the molecular layer due to the presence of one-dimensional pi-stacks; a small hole effective mass is also found along the direction perpendicular to the molecular layers. In the conduction band, strong intermolecular sulfur-sulfur interactions give rise to a significant interstack electronic coupling whereas the intrastack dispersion is greatly reduced. The intramolecular vibronic coupling (reorganization energy) is stronger than that in pentacene but comparable to that in sexithiophene; it is larger for holes than for electrons, as a result of low-frequency modes induced by the sulfur atoms. The polarization energy is large, but its effect on the vibronic coupling remains small. Charge transport is discussed in the framework of both band and hopping models.     

Preparation and characterization of structured hydrogel microparticles based on cross-linked hyperbranched polyglycerol

The aim of this work was to obtain well-defined HyPG-MA (methacrylated hyperbranched polyglycerol) microparticles with uniform sizes. Therefore, three different preparation methods were evaluated. First, we assessed a micromolding technique using rigid SU-8 (a photoresist based on epoxies) grids. Independent of the surface treatment of the SU-8 grid or the type of polymer used, approximately 50% of the microgels remained attached to the SU-8 grid or broke into smaller particles during the release process in which drying of the gels was followed by a sonication process. Although 90% methacrylate conversion could be obtained, this method has some additional drawbacks as the obtained dried microgels did not rehydrate completely after the drying step. Second, a soft micromolding technique was evaluated using elastomeric PDMS (poly(dimethyl siloxane)) grids. The use of these flexible grids resulted in a high yield (80-90% yield; >90% methacrylate conversion) of microgels with a well-defined size and shape (squares 100 microm x 100 microm x 50 microm or hexagons with ? 30 microm and a thickness of 20 microm) without the occurrence of water evaporation. However, a number of particles showed a less-defined shape as not all grids could be filled well. The microgels showed restricted swelling, implying that these gels are dimensionally stable. Third, an alternative method referred to as photolithography was evaluated. This method was suitable to tailor accurately the size and shape of HyPG-MA microgels and additionally gained 100% yield. Well-defined HyPG-MA microgels in the size range of 200-1400 microm (thickness of 6, 20, or 50 microm), with a methacrylate conversion of >90%, could easily be prepared by adding an inhibitor (e.g., 1% (w/v) of vitamin C) to the polymer solution to inhibit dark polymerization. Microgels in the size range of 30-100 microm (>90% conversion) could only be obtained when applying the photomask in direct contact with the polymer solution and using a higher (i.e., 2% (w/v)) concentration of vitamin C. Additionally, the microgels showed limited swelling, indicating that rather dimensionally stable particles were obtained. In conclusion, this paper shows that photolithography and soft micromolding, as compared to rigid micromolding, are the most appropriate techniques to fabricate structured HyPG-MA microgels with a tailorable and well-defined size and shape. These microgels have great potential in tissue engineering and drug delivery applications.     

Rapid prototyping of microfluidic devices with a wax printer

We demonstrate a rapid and inexpensive approach for the fabrication of high resolution poly(dimethylsiloxane) (PDMS)-based microfluidic devices. The complete process of fabrication could be performed in several hours (or less) without any specialized equipment other than a consumer-grade wax printer. The channels produced by this method are of high enough quality that we are able to demonstrate the sizing and separation of DNA fragments using capillary electrophoresis (CE) with no apparent loss of resolution over that found with glass chips fabricated by conventional photolithographic methods. We believe that this method will greatly improve the accessibility of rapid prototyping methods.     

Supercooled dynamics of grain boundary particles in two-dimensional colloidal crystals

We experimentally investigate the dynamics of particles constituting grain boundaries in a two-dimensional colloidal crystal, using video-microscopy. A clear plateau in the mean square displacement of the grain boundary particles is found, followed by an upswing indicative of cage breaking. The van Hove correlation functions and the non-Gaussian parameter show that grain boundary particle dynamics are highly heterogeneous. Furthermore, we identified clusters of cooperatively moving particles and analyzed the time-dependence of the weight-averaged mean cluster size. We find good correlation between the behavior of the mean square displacement, and the time dependence of the non-Gaussian parameter and the cluster size, as also reported for various supercooled systems. Our results therefore provide experimental support for the similarity between particle dynamics in grain boundaries and in supercooled liquids as suggested by recent computer simulations.