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In miniaturized separation techniques, such as capillary electrophoresis (CE) or capillary liquid chromatography (LC), conventional on-line radioactivity detection of labeled compounds is restricted, because of insufficient sensitivity. It will be shown that a microplate scintillation counter for 96-well plates (TopCount) can be used as a sensitive and easy-to-handle radioactivity detector for capillary LC and CE. The attractive combination of capillary LC, eluent fractionation, and subsequent off-line counting is described. The new method is applied for rapid and sensitive separation and detection of (super 3)H-labeled parent drug and its metabolites at levels between 25 and 700 cpm in rat urine. The advantages of capillary LC coupled to the TopCount, and combined with LC-MS data, can be of benefit in many analytical areas, including the characterization of metabolites at low concentration within complex biological fluids. With the same setup, the fractionation with subsequent off-line counting is equally applicable to CE. This is demonstrated with electrophoretically separated (super 14)C-labeled impurities, nicely resolved from a negatively charged main compound, at low levels.

A novel refractive index detector suitable for capillary separations is presented and demonstrated in the capillary electrophoretic separation of metal cations in 10-micrometer-i.d. tubes. The principle of the detector is interferometric; it features a laser diode and, as the main optical element, a holographic optical element which performs several optical functions allowing the use of capillaries with inner diameters as small as 5 micrometers. In contrast to the 'off-axis' method, the use of holographic plates permits probing of the capillary through its center, where the optical path is larger and diffraction effects are smaller. With an i.d. = 10 micrometers capillary the detector resolves 2 microns RIU and covers a linear dynamic range of three to four decades. Joule heat effects preclude the detector to operate at its maximum sensitivity which is delivered in the absence of electrical fields. For this reason, the use of smaller inner diameter capillaries and buffers having low conductivities is recommended. Under field-amplified sample injection conditions, the detection limits for the studied cations are in the low nanomolar range. The performance of this detector is compared with indirect UV-absorption detection, which also helps to elucidate the mechanisms leading to refractive index changes in ionic solutions.

The ability of polymeric nanoparticles to promote glass bead and pentlandite (Pn, nickel sulfide mineral) attachment to air bubbles in flotation was measured as a function of the nanoparticle glass transition temperature using six types of nanoparticles based on styrene/N-butylacrylate copolymers. Nanoparticle size, surface charge density, and hydrophobicity were approximately constant over the series. The ability of the nanoparticles to promote air bubble attachment and perform as flotation collectors was significantly greater for softer nanoparticles. We propose that softer nanoparticles were more firmly attached to the glass beads or mineral surface because the softer particles had a greater glass/polymer contact areas and thus stronger overall adhesion. The diameters of the contact areas between polymeric nanoparticles and glass surfaces were estimated with the Young-Laplace equation for soft, liquidlike particles, whereas JKR adhesion theory was applied to the harder polystyrene particles. The diameters of the contact areas were estimated to be more than an order of magnitude greater for the soft particles compared to harder polystyrene particles.