On-column polymer-imbedded graphite inlet electrode for capillary electrophoresis coupled on-line with flow injection analysis in a poly(dimethylsiloxane) interface

A method for coupling an electrophoretic driven separation to a liquid flow, using conventional fused-silica capillaries and a soft polymeric interface is presented. A novel design of the electrode providing high voltage to the electrophoretic separation was also developed. The electrode consisted of a conductive polyimide/graphite imbedded coating immobilized onto the capillary electrophoresis (CE) column inlet. This integrated electrode gave the same separation performance as a commonly used platinum electrode. The on-column electrode also showed good electrochemical stability in chronoamperometric experiments. In addition, with this electrode design, the electrode position relative to the inlet end of the CE column will always be constant and well defined. The on-line flow injection analysis (FIA)-CE system was used with electrospray ionization (ESI)-time of flight (TOF)-mass spectrometry detection. The preparation of the PDMS (poly(dimethylsiloxane)) interface for FIA-CE is described in detail and used for initial tests of the on-column polymer-imbedded graphite inlet electrode. In this interface, a pressure-driven liquid flow, a make up CE electrolyte and a CE column inlet meet in a two-level cross (95 microm ID) in the PDMS structure, enabling independent flow characterization.     

Endohedral Mixed Aggregates: Sodium Alkoxide Cages with Organic or Inorganic Central Anions and Variable Hull

Alkali metal alkoxides are widely used in chemistry due to their Brønsted basic and nucleophilic properties. Potassium alkoxides assist alkyllithium in the metalation of hydrocarbons in Lochmann-Schlosser-bases. Both compounds form mixed aggregates, which enhance the thermal stability, solubility, and the basic reactivity of these mixtures. A very unusual spherical mixed alkoxy aggregate was discovered by Grützmacher et al., where a central dihydrogen phosphide anion is surrounded by a highly dynamic shell of thirteen sodium atoms and a hull of twelve tert-butoxide groups. This structural motif can be reproduced by a reaction of trimethylsilyl compounds of methane, halogens, or pseudo-halogens with excess sodium tert-butoxide. A nucleophilic substitution releases the corresponding anion, which is then encapsulated by the sodium alkoxide units. The compounds are soluble in hydrocarbon solvents, enabling studies of solutions by high-resolution NMR spectroscopy and IR/Raman studies of the crystalline materials.     

Precipitation of dissolved alkali salts and fullerenes on surfaces of doped porous matter

Standard porcelain samples burnt at different temperatures were doped with LiCl, organo-Li solutions, or with fullerene solution and then dried. The depth profiles of both Li and fullerene were determined. The distributions of the incorporated dopants strongly depend on the samples' porosity. Additional ultrasonic treatment during the diffusion process has a fatal influence on the porcelain structure, resulting in enhanced dopant uptake of the remaining sample. The surface-near shape of the depth profiles is interpreted by solvation, i.e., by precipitation of the dissolved salts or fullerenes in the surface-near zone during the drying process. It is shown that the solvation effect is important only in the case of media with high porosity.     

Conductivity of aged non-overlapping and overlapping tracks in ion irradiated polyimide

Non-overlapping as well as overlapping tracks of energetic ions have been introduced into polyimide foils. After aging their conductivity was measured. This — to our knowledge — first systematic study shows that conductivity does not only result from multiple track overlapping, but can be found already in single ion tracks. This conductivity is shown to be primarily a consequence of electronic energy transfer. The conductivity of single ion tracks is higher than that of typical insulators, but still orders of magnitude lower than that of typical semiconductors. The conductivity is independent of the applied electric field strength until at excessive voltages the electric current increases nonlinearly up to complete breakthrough. The total conductivity of an irradiated polyimide foil increases proportionally with ion fluence for large ion track spacings, and approaches saturation when the electronically active track regimes begin to overlap. Above some thousand times track overlapping however, new chemical and structural changes in the irradiated material lead to another strong increase in conductivity.     

Corrosion effects of nuclear tracks in polymers

Usually ion tracks are studies ex-situ, i.e. after removal of the ion-irradiated sample from the evacuated irradiation vessel. The exposure to ambient air leads to degradation effects which are frequently neglected and consequently have been studied rarely. They have never been explained consistently. In this work we compile and discuss them in the frame of today's general understanding of ion tracks in polymers. It appears that some pristine polymers such as polyethylene are covered by a surface layer which is badly permeable for gaseous contaminants. Ion irradiation leads to destruction of this protective layer so that oxygen and moisture from the ambient air can easily penetrate through the ion tracks, and eventually even into the surrounding pristine material. Moisture absorption along the tracks gives rise to some faint conductivity. Oxygen uptake adds new trapping centers to the existing ones along the tracks, so that on one hand an increased dopant uptake capability is recorded, and on the other hand oxygen-sensitive mobile dopants are immobilized along the ion tracks. Photooxidation processes contribute to the fading of the optical blackening of irradiated polymers.