The principle cause for lower plate numbers in capillary zone electrophoresis with most organic solvents.

With longitudinal diffusion as an unavoidable source of peak broadening, the peak efficiency (expressed by the plate number, N) in capillary zone electrophoresis depends on the ratio of electrophoretic mobility, mu, and tracer- or self-diffusion coefficient, D. Both parameters are functions of the ionic strength of the electrolyte solution. According to theory, the mobility is decreased with increasing ionic strength by the relaxation effect (depending on the relative permittivity) and the electrophoretic effect (depending on the relative permittivity and the viscosity of the solvent), whereas the diffusion coefficient is decreased only by the relaxation effect. This allows the theoretical predictions that the plate number, which is proportional to the ratio mu/D, decreases with increasing ionic strength and that the magnitude of this reduction depends on the solvent. Taking the values for relative permittivity and viscosity allows forecasting that, in general, water as a solvent exhibits the smallest lowering of the plate number, as compared to organic solvents. The theoretical predictions are confirmed by the data for the ratio calculated from measured mobilities and diffusion coefficients for iodide as the analyte ion in water, methanol, and acetonitrile with ionic strength of the background electrolyte varying between 0.005 and 0.080 mol L(-1). Whereas the experimentally observed plate number per volt is reduced from its "ultimate value" of about 20 (analyte charge number z = 1, zero ionic strength) in water by only 10%, the decrease at the same ionic strength in methanol and acetonitrile reaches 25 to 30%. Thus, the maximum plate number should read Nmax approximately equals 13 zU (with U being the effective voltage) for these solvents with ionic strengths normally applied in capillary electrophoresis. This reduction is not stemming from inappropriate experimental conditions, but has fundamental physicochemical causes.     

Efficient computation of optical disk readout by use of the chirp z transform

Computation of the readout signal of an optical disk involves Fourier transforms from the objective lens pupil to the disk and, after interaction with the disk, from the disk to the objective pupil. Traditionally, the complex two-dimensional Fourier transform is numerically evaluated as a two-dimensional fast Fourier transform. To obtain sufficient resolution in the involved planes, one must choose sampling grid sizes of typically 1,024 x 1,024 or higher, resulting in a substantial computation time if the calculation is to be repeated many times. Discussed is an alternative method for evaluating the Fourier transform, based on the chirp z transform, by which a considerable improvement in efficiency can be obtained without loss of accuracy.     

Simultaneous measurement of foveal spectral reflectance and cone-photoreceptor directionality

An instrument for simultaneous measurement of foveal spectral reflectance and cone-photoreceptor directionality is described. The key element is an imaging spectrograph (spectral range of 420-790 nm) with its entrance slit conjugate to the pupil plane of a human eye. A 1.9-deg spot on the retina is sampled in 1 s. Video observation of the retina and the pupil facilitates proper alignment. Measurements were performed on 21 healthy subjects. Model analysis of the spectra provided densities of photostable ocular absorbers. As an example, macular pigment and melanin are discussed in more detail. Spatial profiles exhibited the optical Stiles-Crawford effect, reflecting cone-photoreceptor directionality.     

Energy Scales in the Local Magnetic Excitation Spectrum of YBa2Cu3O6+y

The wave-vector integrated dynamical spin susceptibility _2D() of YBa ₂ Cu ₃ O _6+y cuprates is considered. _2D is calculated in the superconducting state from a renormalized mean-field theory of the t–t–J-model, based on the slave-boson formulation. Besides the well-known 41 meV resonance a second, much broader peak ('hump') appears in Im _2D. It is caused by particle-hole excitations across the maximum gap ⁰ . In contrast to the resonance, which moves to lower energies when the hole filling is reduced from optimal doping, the position of this 'hump' at 2 ⁰ stays almost unchanged. The results are in reasonable agreement with inelastic neutronscattering experiments.     

Fly ash reactivity: Extension and application of a shrinking core model and thermodynamic approach

In the present paper a theoretical study is presented on the dissolution (reaction) of pulverised powder coal fly ash. A shrinking core model is derived for hollow spheres that contain two regions (outer hull and inner region). The resulting analytical equations are applied to the dissolution experiments by Pietersen (Mat.Res.Soc.Symp.Proc., Vol. 178, Materials Research Society, 1990, p. 139; Ph.D. Thesis, Delft University of Technology, The Netherlands, 1993), yielding reaction rates at various temperatures and pH for two class F fly ashes. It is revealed that the available amount of reactive fly ash is proportional to the glass content of the fly ash, and that the reaction rate is proportional to this glass content as well. Moreover, it is concluded that the outer region is less reactive than the inner region, and that these reactivities are proportional to a power of the hydroxyl concentration. Subsequently, experimental data and model are used to assess the magnitude of inner and outer region. It seems that the outer hull of solid spheres and cenospheres are having the same thickness, about 2 m. Based on the observed trends a reaction mechanism is proposed which accounts for the glass content and composition of the fly ash (and that is applicable to slags as well). Finally, using the reaction product, thermodynamic properties of the studied fly ashes are derived: the free energy, enthalpy and entropy of reaction.     

Comparison of semi-automatic and automatic data acquisition methods for studying three-dimensional distributions of large neuronal populations and axonal plexuses

Neuroanatomy is in need of high throughput methods for reliably recording the distribution of tissue elements across large brain regions. We compared two methods for recording the spatial distribution of identified neuronal elements such as tracer labelled cell bodies or axonal plexuses. The methods compared were computerized image-combining microscopy (semi-automatic method), which is a user controlled method providing feedback during digitization, and digital camera technology with image analysis software (automatic method). Both methods were applied to biotinylated dextran amine labelled axonal plexuses and FluoroRuby labelled neuronal cell bodies, in the pontine nuclei of the rat. Coordinates were assigned to the labelled elements using both methods. The ensuing distribution patterns were compared, section by section, and in three-dimensional reconstruction. The experienced investigator, using the semi-automatic method, could detect individual axons, fragments of axons, weakly labelled elements, and overlapping cell bodies, better than the automatic system. Nevertheless, both methods detected the overall distribution of the labelled axons and cells investigated. Automatic methods provide opportunities for efficient large-scale data acquisition of labelled neuronal elements.     

The influence of contact zone configuration on the flow structure in a dissolved air flotation pilot plant

The dissolved air flotation process is used in water and wastewater treatment. Among many parameters the fluid dynamics determine the capacity of the process. The contact zone is assumed to be important for the removal function, as it is believed to be the location for the aggregation of bubbles and flocs. This paper presents an experimental study on the flow structure in a contact zone of a DAF pilot tank and the influence of contact zone configuration. The flow structure in the contact zone was examined for different horizontal lengths of the zone and for different heights and inclinations of the shaft wall. The hydraulic surface loading was 11 m/h over the total tank surface area and the recycle rate was constant at 10% of the main flow. The examined hydraulic surface loading over the contact zone ranged from 40 to 98 m/h. Water velocities in the longitudinal, central section of the tank were measured with an acoustical Doppler velocimeter in a grid net for the different contact zone configurations, giving an insight into the flow structure. The result showed that the flow structure in the contact zone was characterised by a turbulent lower region and a plug-flow higher region. The hydraulic surface loading, a function of the length of the contact zone, seemingly determined the extension of the turbulent region. A higher hydraulic surface loading decreased the turbulent region while the lower loading increased it. A hydraulic surface loading of 65 m/h was suggested for design. It was not possible to determine the turbulent intensity quantitatively due to the measurement method. The height and inclination of the shaft wall did not seem to have a significant influence on the turbulent region. However, an increased height of the contact zone enhanced the higher, plug flow region and a recommended height of 0.81 m or higher for the recommended hydraulic surface loading was suggested when both mixing and plug-flow are desired. The separation zone was characterised by a stratified flow structure, mainly influenced by the cross-flow velocity that is a function of the distance between the shaft wall top and the water surface. A cross-flow velocity of 37m/h or higher resulted in a clearly defined stratification, believed to be crucial for an efficient separation of flocs. Finally, the extension of the lower, denser plug-flow region in the separation zone increased when the shaft wall height increased.     

Optimisation of sulphate reduction in a methanol-fed thermophilic bioreactor

Several methods were tested to optimise sulphate reduction and minimise methane formation in thermophilic (65 degrees) expanded granular sludge bed reactors fed with a medium containing sulphate and methanol. Lowering the pH from 7.5 to 6.75 resulted in a rapid decrease of methane formation and a concomitant increase in sulphate reduction. The inhibition of methane formation was irreversible on the short-term. Lowering the COD/SO4(2-) ratio (COD: chemical oxygen demand) from 6 to 0.34 (g/g) rapidly favoured sulphate reduction over methanogenesis. Continuous addition of 2 g L(-1) 2-bromoethanesulphonate was ineffective as complete inhibition of methanogenesis was obtained only for two days. Inhibition of methanogens by sulphide at pH 7.5 was only effective when the total sulphide concentration was above 1200 mg S L(-1). For practical applications, a relatively short exposure to a slightly acidic pH in combination with operating the reactor at a volumetric methanol-COD loading rate close to the maximum volumetric sulphide-COD formation rate.