Microcylinder electrodes as sensitive detectors for high-efficiency, high-speed liquid chromatography

A carbon fiber microcylinder electrode (r = 3.5 microns) is used as a detector for high-efficiency and high-speed liquid chromatography. The microcylinder has a detection volume of a few picoliters, and can be placed directly at the outlet frit of the column. With proper positioning equipment, the electrode can be placed at the region of the outlet frit where the separation efficiency is highest. Such selective sampling results in greatly increased measured efficiency over a conventional electrochemical detector when short (4 cm) columns of conventional diameter (3.2 mm) are used. The microcylinder detector is sensitive and subpicomole detection limits are obtained in less than 30 s for norepinephrine. The need for expensive positioning equipment is eliminated by mounting the electrode into a fitting which can be mated directly with the column.     

Faradaic electrochemistry at microcylinder,band, and tubular band electrodes

Current-time relationships of faradaic processes at microcylinder, band, and tubular band electrodes have been evaluated. Microcylinder electrodes were fabricated from platinum wires (5 μm radius) sealed in glass capillaries. Band and tubular electrodes were constructed with platinum sheets (～ 20 μm width) or thin pieces of graphite (～ 5 μm width) sealed between insulating mateials. The temporal response of the current at a microcylinder electrode for the reduction of ferricyanide in aqueous potassium chloride solutions is in excellent agreement with that predicted by equations derived for heat flux to a cylinder. An estimation of the magnitude and temporal properties of the measured current at a band electrode can be obtained when a hemicylinder geometry is assumed. The current respone is identical at band and tubular band electrodes even for the smallest tubular radius investigated, 0.54 mm. Cyclic voltammograms at electrodes of all three geometries show significant contributions from radial diffusion at slow scan rates (< 20 mV s^?1). The current at a graphite tubular band electrode was found to be independent of flow of solution through the electrode at flow rates up to 3 ml min^?1.     

Manganese oxides: parallels between abiotic and biotic structures

A large number of microorganisms are responsible for the oxidation of Mn(2+)((aq)) to insoluble Mn(3+/4+) oxides (MnO(x)()) in natural aquatic systems. This paper reports the structure of the biogenic MnO(x)(), including a quantitative analysis of cation vacancies, formed by the freshwater bacterium Leptothrix discophora SP6 (SP6-MnO(x)()). The structure and the morphology of SP6-MnO(x)() were characterized by transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS), including full multiple-scattering analysis, and powder X-ray diffraction (XRD). The biogenic precipitate consists of nanoparticles that are approximately 10 nm by 100 nm in dimension with a fibrillar morphology that resembles twisted sheets. The results dem-onstrate that this biogenic MnO(x)() is composed of sheets of edge-sharing of Mn(4+)O(6) octahedra that form layers. The detailed analysis of the EXAFS spectra indicate that 12 +/- 4% of the Mn(4+) layer cation sites in SP6-MnO(x)() are vacant, whereas the analysis of the XANES suggests that the average oxidation state of Mn is 3.8 +/- 0.3. Therefore, the average chemical formula of SP6-MnO(x)() is M(n)()(+)(y)()Mn(3+)(0.12)[ square(0.12)Mn(4+)(0.88)]O(2).zH(2)O, where M(n)()(+)(y)() represents hydrated interlayer cations, square(0.12) represents Mn(4+) cation vacancies within the layer, and Mn(3+)(0.12) represents hydrated cations that occupy sites above/below these cation vacancies.     

Conical tungsten tips as substrates for the preparation of ultramicroelectrodes

Here we describe a simple method to prepare voltammetric microelectrodes using tungsten wires as a substrate. Tungsten wires have a high tensile modulus and enable the fabrication of electrodes that have small dimensions overall while retaining rigidity. In this work, 125 microm tungsten wires with a conical tip were employed. For the preparation of gold or platinum ultramicroelectrodes, commercial tungsten microelectrodes, completely insulated except at the tip, were used as substrates. Following removal of oxides from the exposed tungsten, platinum or gold was electroplated, yielding surfaces with an electroactive area of between 1 x 10-6 and 2 x 10-6 cm2. Carbon surfaces on the etched tip of tungsten microwires were prepared by coating with photoresist followed by pyrolysis. The entire electrode was then insulated with Epoxylite except the tip, yielding an exposed carbon surface with an area of around 4 x 10-6 to 6 x 10-6 cm2. All three types of ultramicroelectrodes fabricated on the tungsten wire had similar electrochemical behavior to electrodes fabricated from wires or fibers insulated with glass tubes.     

Segmental durations in the vicinity of prosodic phrase boundaries.

Numerous studies have indicated that prosodic phrase boundaries may be marked by a variety of acoustic phenomena including segmental lengthening. It has not been established, however, whether this lengthening is restricted to the immediate vicinity of the boundary, or if it extends over some larger region. In this study, segmental lengthening in the vicinity of prosodic boundaries is examined and found to be restricted to the rhyme of the syllable preceding the boundary. By using a normalized measure of segmental lengthening, and by compensating for differences in speaking rate, it is also shown that at least four distinct types of boundaries can be distinguished on the basis of this lengthening.     

The effect of pH on some outer-sphere electrode reactions at carbon electrodes

The apparent heterogeneous rate constant, k°_app, for three couples known to undergo outer-sphere electron transfer reactions has been investigated at carbon, gold, and platinum electrodes as a function of solution pH. The rates are found to be pH dependent at two different types of glassy carbon and at carbon paste but not at metallic electrodes. The rate is found to decrease with increasing pH for Fe(CN)^{$\text{3?}\text{4?}$}₆ and IrCl^{$\text{2?}\text{3?}$}₆, and the opposite effect is observed for the Ru(NH₃)^{$\text{3+}\text{2+}$}₆ couple. For the three compounds examined, the magnitude of the pH dependent rate changes can be associated with a change in the magnitude of the potential of the reaction layer induced by a change in surface charge of ～ 2 × 10^?7 C cm^?2. The pH dependence of the observed rate constant at glassy carbon can be attenuated by heat treatment, chemical reduction, or esterification of the surface. This behaviour is consistent with the theory that the pH dependence of k°_app arises from the presence of functional groups on the carbon surface.     

Informational masking of speech in children: effects of ipsilateral and contralateral distracters

Using a closed-set speech recognition paradigm thought to be heavily influenced by informational masking, auditory selective attention was measured in 38 children (ages 4-16 years) and 8 adults (ages 20-30 years). The task required attention to a monaural target speech message that was presented with a time-synchronized distracter message in the same ear. In some conditions a second distracter message or a speech-shaped noise was presented to the other ear. Compared to adults, children required higher target/distracter ratios to reach comparable performance levels, reflecting more informational masking in these listeners. Informational masking in most conditions was confirmed by the fact that a large proportion of the errors made by the listeners were contained in the distracter message(s). There was a monotonic age effect, such that even the children in the oldest age group (13.6-16 years) demonstrated poorer performance than adults. For both children and adults, presentation of an additional distracter in the contralateral ear significantly reduced performance, even when the distracter messages were produced by a talker of different sex than the target talker. The results are consistent with earlier reports from pure-tone masking studies that informational masking effects are much larger in children than in adults.