New technique for capillary electrophoresis directly coupled with end-column electrochemiluminescence detection

capillary electrophoresis (CE) is characterized. A 300 mum diameter Pt working electrode was used to directly couple with a 75 mum inner diameter separation capillary without an electric field decoupler. The hydrodynamic cyclic voltammogram (CV) of Ru(bpy)(3)(2+) showed that electrophoretic current did not affect the ECL reaction. The presence of high-voltage (HV) field only resulted in the shift of the ECL detection potential. The distance of capillary to electrode was an important parameter for optimizing detection performance as it determined the characteristics of mass transport toward the electrode and the actual concentration of Ru(bpy)(3)(2+) in the detection region. The optimum distance of capillary to electrode was decided by the inner diameter of the capillary, too. For a 75 mum capillary, the working electrode should be placed away from the capillary outlet at a distance within the range of 20-260 mum. The effects of pH value of ECL solution and molecular structure of analytes on peak height and theoretical plate numbers were discussed. Using the 75 mum capillary, under the optimum conditions, the method provided a linear range for tripropylamine (TPA) between 1 x 10(-10) and 1 X 10(-5) mol/L with correlation coefficient of 0.998. The detection limit (signal-to-noise ratio S/N = 3) was 5.0 x 10(-11) mol/L. The relative standard deviation in peak height for eight consecutive injections was 5.6%. By this new technique lidocaine spiked in a urine sample was determined. The method exhibited the linear range for lidocaine from 5.0 x 10(-8) to 1.0 X 10(-5) mol/L with correlation efficient of 0.998. The limit of detection (S/N = 3) was 2.0 x 10(-1) mol/L.

A study of tetraethylammonium ion transfer across a micro liquid/liquid interface

Tetraethylammonium (TEA(+)) ion transfer across micro-liquid/liquid interface has been studied with cyclic voltammetric measurements. The results showed that voltammetric responses of the currents obtained were peak and steady-state for TEA(+) transfer from inside and outside of the micropipette when the radius was bigger than 3 mum. However, the currents were pseudo-steady-state when the micropipette diameters were less than 3 mum. The values of i(p) decreased with decreasing concentration of TEA(+). Peak current was proportional to the square root of the scan rate and it obeyed a Randles-Sevcik type relationship. The mechanism of mass transport across a liquid/ liquid microinterface for TEA(+) system was aslo discussed.

Study on diffusion of electroactive species in polyelectrolyte polyethylene glycol lithium perchlorate by chronoamperometry at a microdisk electrode

The mass transport dynamics of Ferrocene in polyelectrolyte polyethylene glycol lithium perchlorate (PEG . LiClO4) was studied by using chronoamperometry at a microdisk electrode. Chronoamperometry is a powerful method for the study of mass transport in polyelectrolyte, it has many advantages over the conventional methods at a microelectrode and the steady-state method at an ultramicroelectrode. By using this method the apparent diffusion coefficient D-app and concentration C-a of the electroactive species, can be estimated from a single experiment without previous knowledge of either one. We have estimated D-app and C-a of ferrocene in PEG . LiClO4 polyelectrolyte from 25 degrees C to 75 degrees C. The dependence on the concentration of electroactive species was observed. The diffusion coefficients decrease with increasing ferrocene concentration and decreasing temperature. The mass transport mechanism is explained, by using a free volume model.

SOLID-STATE VOLTAMMETRY OF ELECTROACTIVE SOLUTES IN POLYMER SOLVENTS (PEO) AT ULTRAMICROELECTRODES

This paper describes the electrochemical oxidation and reduction of electroactive solutes which are dissolved in and diffusing through the polymer electrolyte solvent, poly(ethylene oxide) (PEO). The characteristics of electrochemical reactions in polymeric solutions are discussed, including how rigid solvent environments affect mass transport rates, and the transport phenomenon of electroactive species in PEO with bathing gases is explained by using the voltammetric theory of ultramicroelectrodes. The possibility that the microelectrode coated with PEO film can be used as a gas sensor has been discussed.

Numerical modeling of water wave interaction with a soft mud bed

A vertical 2-D numerical model is presented for simulating the interaction between water waves and a soft mud bed. Taking into account nonlinear rheology, a semi-empirical rheological model is applied to this water-mud model, reflecting the combined visco-elasto-plastic properties of soft mud under such oscillatory external forces as water waves. In order to increase the resolution of the flow in the neighborhood of both sides of the inter-surface, a logarithmic grid in the vertical direction is employed for numerical treatment. Model verifications are given through comparisons between the calculated and the measured mud mass transport velocities as well as wave height changes.

Evolution of freshwater plumes and salinity fronts in the northern Bay of Bengal

[1] The evolution of freshwater plumes and the associated salinity fronts in the northern Bay of Bengal ( henceforth the bay) is studied using rotated empirical orthogonal function (REOF) analysis and extended associate pattern analysis (EAPA). The results show that sea surface salinity distribution is featured by eastern-bay and western-bay plumes in the northern bay during different seasons. The western-bay plume begins in early July, peaks in late August, and then turns into a bay-shaped plume with the two plumes in either side of the bay, which peaks in late October. The southward extension of the western-bay plume can be explained by the southwestward geostrophic flow associated with the cyclonic gyre in the northern bay, which counters the northeastward Ekman drift driven by wind stress. The offshore expansion of the western-bay plume is induced by the offshore Ekman drift which also produces a salinity front near the east coast of India. The bay-shaped plume appears when the cyclonic gyre shifts westward and a weak anticyclonic gyre occupies the northeastern bay. As the season advances, the western part of the bay-shaped plume decays while the eastern part persists until the following June, which is believed to be associated with the anticyclonic gyre in the northern bay. The evolution of the plumes except the eastern part of the bay-shaped plume in fall can be partly explained by the seasonal variation of mass transport associated with the Sverdrup balance. The fact that the western-bay (eastern-bay) plume appears when surface freshwater flux in the northeastern bay increases ( decreases) dramatically suggests that the plumes are not produced directly by surface freshwater flux. River discharge seems to be the freshwater source for the plumes and has little to do with the evolution of the plumes.

Late Pliocene-Pleistocene changes in mass accumulation rates of eolian deposits on the central Chinese Loess Plateau

IEECAS SKLLQG

Reconstructing The Vertical Distribution Of The Aeolian Saltation Mass Flux Based On The Probability Distribution Of Lift-Off Velocity

The probability distribution of lift-off velocity of the saltating grains is a bridge to linking microscopic and macroscopic research of aeolian sand transport. The lift-off parameters of saltating grains (i.e., the horizontal and vertical lift-off velocities, resultant lift-off velocity, and lift-off angle) in a wind tunnel are measured by using a Phase Doppler Particle Analyzer (PDPA). The experimental results show that the probability distribution of horizontal lift-off velocity of saltating particles on a bed surface is a normal function, and that of vertical lift-off velocity is an exponential function. The probability distribution of resultant lift-off velocity of saltating grains can be expressed as a log-normal function, and that of lift-off angle complies with an exponential function. A numerical model for the vertical distribution of aeolian mass flux based on the probability distribution of lift-off velocity is established. The simulation gives a sand mass flux distribution which is consistent with the field data of Namikas (Namikas, S.L., 2003. Field measurement and numerical modelling of acolian mass flux distributions on a sandy beach, Sedimentology 50, 303-326). Therefore, these findings are helpful to further understand the probability characteristics of lift-off grains in aeolian sand transport. (c) 2007 Elsevier B.V. All rights reserved.

Investigation of native defects and property of bulk ZnO single crystal grown by a closed chemical vapor transport method

Hall effect, Raman scattering, photoluminescence spectroscopy (PL), optical absorption (OA), mass spectroscopy, and X-ray diffraction have been used to study bulk ZnO single crystal grown by a closed chemical vapor transport method. The results indicate that shallow donor impurities (Ga and Al) are the dominant native defects responsible for n-type conduction of the ZnO single crystal. PL and OA results suggest that the as-grown and annealed ZnO samples with poor lattice perfection exhibit strong deep level green photoluminescence and weak ultraviolet luminescence. The deep level defect in as-grown ZnO is identified to be oxygen vacancy. After high-temperature annealing, the deep level photoluminescence is suppressed in ZnO crystal with good lattice perfection. In contrast, the photoluminescence is nearly unchanged or even enhanced in ZnO crystal with grain boundary or mosaic structure. This result indicates that a trapping effect of the defect exists at the grain boundary in ZnO single crystal. (C) 2007 Elsevier B.V. All rights reserved.

Electronic transport through self-assembled quantum disks

In this paper we study a single electron tunneling through a vertically stacked self-assembled quantum disks structure using a transfer matrix technique in the framework of effective mass approximation. In the disks, the electron is confined both laterally and vertically; we separate the motion in the vertical and lateral directions within the adiabatic approximation and treat the energy levels of the latter as an effective confining potential. The influence of a constant applied electric field is taken into account using an exact Airy-function formalism and the current density is calculated at zero temperature. By increasing the widths of the barriers, we find the peaks of the current density shift toward lower voltage region; meanwhile, they can become even sharper. (C) 2004 Elsevier Ltd. All rights reserved.

Magneto-transport characteristics of two-dimensional electron gas for Si delta-doped InAlAs/InGaAs single quantum well

Magneto-transport measurements have been carried out on a Si heavily delta-doped In0.52Al0.48As/In(0.53)G(0.47)As single quantum well in the temperature range between 1.5 and 60 K under magnetic field up to 10 T. We studied the Shubnikov-de Haas(SdH) effect and the Hall effect for the In0.52Al0.48As/In(0.53)G(0.47)As single quantum well occupied by two subbands, and have obtained the electron concentration, mobility, effective mass and energy levels respectively. The electron concentrations of the two subbands derived from mobility spectrum combined with multi-carrier fitting analysis are well consistent with the result from the SdH oscillation. From fast Fourier transform analysis for d(2)rho/dB(2)-1/B, it is observed that there is a frequency of f(1)-f(2) insensitive to the temperature, besides the frequencies f(1), f(2) for the two subbands and the frequency doubling 2f(1), both dependent on the temperature. This is because That the electrons occupying the two different subbands almost have the same effective mass in the quantum well and the magneto-intersubband scattering between the two subbands is strong.

Electronic structure and transport properties of quantum rings in a magnetic field

The electronic structure of quantum rings is studied in the framework of the effective-mass theory and the two dimensional hard wall approximation. In cases of both the absence and presence of a magnetic field the electron momenta of confined states and the Coulomb energies of two electrons are given as functions of the angular momentum, inner radius, and magnetic-field strength. By comparing with experiments it is found that the width of the real confinement potential is 14 nm, much smaller than the phenomenal width. The Coulomb energy of two electrons is calculated as 11.1 meV. The quantum waveguide transport properties of Aharonov-Bohm (AB) rings are studied complementarily, and it is found that the correspondence of the positions of resonant peaks in AB rings and the momentum of confined states in closed rings is good for thin rings, representing a type of resonant tunneling.

The effects of sediment transport on grain-size distributions

Changes in statistics (mean, sorting, and skewness) describing grain-size distributions have long been used to speculate on the direction of sediment transport. We present a simple model whereby the distributions of sediment in transport are related to their source by a sediment transfer function which defines the relative probability that a grain within each particular class interval will be eroded and transported. A variety of empirically derived transfer functions exhibit negatively skewed distributions (on a phi scale). Thus, when a sediment is being eroded, the probability of any grain going into transport increases with diminishing grain size throughout more than half of its size range. This causes the sediment in transport to be finer and more negatively skewed than its source, whereas the remaining sediment (a lag) must become relatively coarser and more positively skewed. Flume experiments show that the distributions of transfer functions change from having a highly negative skewness to being nearly symmetrical (although still negatively skewed) as the energy of the transporting process increases. We call the two extremes low-energy and high-energy transfer functions , respectively. In an expanded sediment-transport model, successive deposits in the direction of transport are related by a combination of two transfer functions. If energy is decreasing and the transfer functions have low-energy distributions, successive deposits will become finer and more negatively skewed. If, however, energy is decreasing, but the initial transfer function has a high-energy distribution, successive deposits will become coarser and more positively skewed. The variance of the distributions of lags, sediment in transport, and successive deposits in the down-current direction must eventually decrease (i.e., the sediments will become better sorted). We demonstrate that it is possible for variance first to increase, but suggest that, in reality, an increasing variance in the direction of transport will seldom be observed, particularly when grain-size distributions are described in phi units. This model describing changes in sediment distributions was tested in a variety of environments where the transport direction was known. The results indicate that the model has real-world validity and can provide a method to predict the directions of sediment transport

Determination of mercury in biological samples using organic compounds as matrix modifiers by inductively coupled plasma mass spectrometry

A method was developed for the determination of total mercury in biological samples. The effects of aqueous ammonia, ethylenediamine and triethanolamine on Hg signal intensity by inductively coupled plasma mass spectrometry has been evaluated and the possible mechanisms discussed. It has been proved that the signal intensity of Hg significantly increases with adding, in the presence of small amounts of aqueous ammonia, ethylenediamine or triethanolamine. The normalized intensity (the signal intensity ratio with amine and without amine) of Hg increases as the concentration of aqueous ammonia, ethylenediamine or triethanolamine increases, but the degree of enhancement of aqueous ammonia was smaller than that of ethylenediamine and triethanolamine. The normalized intensity of Hg with aqueous ammonia, ethylenediamine and triethanolamine decreases as the nebulizer flow rate increases, but decreasing degree of aqueous ammonia was smaller than that of ethylenediamine and triethanolamine. The higher the RF powers the higher the normalized intensity of Hg at the same nebulizer flow rate. The addition of aqueous ammonia, ethylenediamine and triethanolamine into analytical solutions significantly improved the transport efficiency of Hg. The detection limit of Hg is improved about ten times by the addition of ethylenediamine or triethanolamine under the optimum experimental parameters. The method has been used to determine mercury in biological standard reference materials (SRM). The analytical results are very close to the certified values and the determined values for similar samples.