Abnormal phenomenon of the dependence of the retention factors for uncharged species on applied voltage in capillary electrochromatography

Polymethacrylate-based monolithic columns were prepared for capillary electrochromatography (CEC) by in situ copolymerization of butyl methacrylate (BMA), 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), and ethylene dimethacrylate (EDMA) in the presence of a porogen in fused-silica capillaries of 100 mum I.D. The abnormal phenomenon that retention factors for neutral species decreases with applied voltage in CEC was observed. Capillary electrophoresis (CE) instruments usually require a period of time to increase voltage from 0 kV to desired value, which is called as ramp time. Such ramp time and any error in the determination of dead time should be taken into account during the accurate calculation of retention factors. After the correction of the retention factors, the plots of the corrected factors for alkylbenzene versus applied voltage were made, the absolute value of the plot slopes are less than 1.8 X 10(-4), Which indicates that the corrected retention times for neutral species do not show any dependence on applied voltage. Further, the plots of the corrected retention times for acidic and basic compounds versus the reciprocal of applied voltage were drawn, where the target compounds were eluted in neutral form. The very nice linearity of the plots was obtained. The linear correlation coefficients are over 0.999. Here, the slopes of the plots represent

Retention behavior of hydrophobic organic chemicals as a function of temperature in soil leaching column chromatography

To study the transport mechanism of hydrophobic organic chemicals (HOCs) and the energy change in soil/solvent system, a soil leaching column chromatographic (SLCC) experiment at an environmental temperature range of 20-40 degreesC was carried out, which utilized a reference soil (SP 14696) packed column and a methanol-water (1:4 by volume ratio) eluent. The transport process quickens with the increase of column temperature. The ratio of retention factors at 30 and 40 degreesC (k'(30)/k'(40)) ranged from 1.08 to 1.36. The lower enthalpy change of the solute transfer in SLCC (from eluent to soil) than in conventional reversed-phase liquid chromatography (e.g., from eluent to C-18) is consistent with the hypothesis that HOCs were dominantly and physically partitioned between solvent and soil. The results were also verified by the linear solvation energy relationships analysis. The chief factor controlling the retention was found to be the solute solvophobic partition, and the second important factor was the solute hydrogen-bond basicity, while the least important factors were the solute polarizability-dipolarity and hydrogen-bond acidity. With the increase of temperature, the contributions of the solute solvophobic partition and hydrogen-bond basicity gradually decrease, and the latter decreases faster than the former. (C) 2002 Elsevier Science Ltd. All rights reserved.

Modeling and optimization for separation of ionic solutes in pressurized flow capillary electrochromatography

By manipulation of applied pressure or voltage, pressurized flow capillary electrochromatography (P-CEC) permits unique control of selectivity for ionic solutes. A simple mathematical model has been developed to describe the quantitative relationship between the electrochromatographic retention factor (k(*)) of charged solutes and the applied voltage and pressure. The validity of the model was verified experimentally with hydrophilic interaction mode CEC (HI-CEC). On the basis of the model developed, it was found that the value of k(*) could be predicted accurately using only a limited number of data points from the initial experiments at different voltages or pressures. Correlation between the experimentally measured and calculated k(*) was excellent, with a correlation coefficient greater than 0.999. Optimization for the separation of peptides by P-CEC was also performed successfully on the basis of the proposed model.

Characteristics of elution profile in radial chromatography under linear conditions

Based on the mass balance equations of solute transfer in the radial chromatographic column, the theoretical expression to describe the column efficiency and shape of elution profile is obtained under linear isotherm case. Moreover, the tendency for the variation of column efficiency and symmetry of peak profile is systematically discussed. The results showed that in radial chromatography the relationship between the column efficiency and volumetric flow rate is similar with that relationship in axial chromatography; relatively high column efficiency still can be obtained under high flow rate in radial chromatography. Accompanying the increase of retention factor of solutes and injection time, the column efficiency decreases monotonously. The effect of column diameter and column length on the column efficiency interfere with each other. It is more advantageous to increase the column efficiency by applying columns with larger column diameter and shorter column length. According to the discussion of the effect of diffusion on the column efficiency, radial chromatography is proved to be suitable for the separation of samples with relatively high diffusion coefficient, which predicts its obvious advantage in the preparative separation of samples such as proteins and DNA.

Influence of methanol on retention of hydrophobic organic chemicals in soil leaching column chromatography

The influence of methanol in methanol-water mixed eluents on the capacity factor (P), an important parameter which could depict leaching potential of hydrophobic organic chemicals (HOCs) in soil leaching column chromatography (SLCC), was investigated. Two reference soils, GSE 17201 obtained from Bayer Landwirtschaftszentrum, Monheim, Germany and SP 14696 from LUFA, Spencer, Germany, were used as packing materials in soil columns, and isocratic elution with methanol-water mixtures at different volume fractions of methanol (phi) were tested. Shortterm exposure of the column (packed with the GSE 17201 soil) to the eluents increased solute retention by a certain (23% log-unit) degree evaluated through a correlation with the retention on the same soil column but unpreconditioned by methanol-containing eluents. Long-term exposure of soil columns to the eluents did not influence the solute retention. A log-linear equation, log k' = log k'(w) - Sphi, could well and generally describe the retention of HOCs in SLCC. For the compounds of homologous series, logk'(w), had good linear relationship with S, indicating the hydrophobic partition mechanism existing in the retention process. (C) 2002 Elsevier Science Ltd. All rights reserved.

Linear solvation energy relationships regarding sorption and retention properties of hydrophobic organic compounds in soil leaching column chromatography

The capacity factors of a series of hydrophobic organic compounds (HOCs) were measured in soil leaching column chromatography (SLCC) on a soil column, and in reversed-phase liquid chromatography on a C-18 column with different volumetric fractions (phi) of methanol in methanol-water mixtures. A general equation of linear solvation energy relationships, log(XYZ) = XYZ(0) + mV(1)/100 + spi* + bbeta(m) + aalpha(m), was applied to analyze capacity factors (k'), soil organic partition coefficients (K-oc) and octanol-water partition coefficients (P). The analyses exhibited high accuracy. The chief solute factors that control log K-oc, log P, and log k' (on soil and on C-18) are the solute size (V-1/100) and hydrogen-bond basicity (beta(m)). Less important solute factors are the dipolarity/polarizability (pi*) and hydrogen-bond acidity (alpha(m)). Log k' on soil and log K-oc have similar signs in four fitting coefficients (m, s, b and a) and similar ratios (m:s:b:a), while log k' on C-18 and log P have similar signs in coefficients (m, s, b and a) and similar ratios (m:s:b:a). Consequently, log k' values on C-18 have good correlations with log P (r > 0.97), while log k' values on soil have good correlations with log K-oc (r > 0.98). Two K-oc estimation methods were developed, one through solute solvatochromic parameters, and the other through correlations with k' on soil. For HOCs, a linear relationship between logarithmic capacity factor and methanol composition in methanol-water mixtures could also be derived in SLCC. (C) 2002 Elsevier Science Ltd. All rights reserved.

Dynamic stress intensity factor of a functionally graded material under antiplane shear loading

The dynamic response of a finite crack in an unbounded Functionally Graded Material (FGM) subjected to an antiplane shear loading is studied in this paper. The variation of the shear modulus of the functionally graded material is modeled by a quadratic increase along the direction perpendicular to the crack surface. The dynamic stress intensity factor is extracted from the asymptotic expansion of the stresses around the crack tip in the Laplace transform plane and obtained in the time domain by a numerical Laplace inversion technique. The influence of graded material property on the dynamic intensity factor is investigated. It is observed that the magnitude of dynamic stress intensity factor for a finite crack in such a functionally graded material is less than in the homogeneous material with a property identical to that of the FGM crack plane.

Stress intensity factor histories of a steadily propagating crack under 3-D combined mode traction

Elastodynamic stress intensity factor histories of an unbounded solid containing a semi-infinite plane crack that propagates at a constant velocity under 3-D time-independent combined mode loading are considered. The fundamental solution, which is the response of point loading, is obtained. Then, stress intensity factor histories of a general loading system are written out in terms of superposition integrals. The methods used here are the Laplace transform methods in conjunction with the Wiener-Hopf technique.

Elastodynamic stress intensity factor history for a semi-infinite crack under three-dimensional transient loading

The dynamic stress intensity factor history for a semi-infinite crack in an otherwise unbounded elastic body is analyzed. The crack is subjected to a pair of suddenly-applied point loadings on its faces at a distance L away from the crack tip. The exact expression for the mode I stress intensity factor as a function of time is obtained. The method of solution is based on the direct application of integral transforms, the Wiener-Hopf technique and the Cagniard-de Hoop method. Due to the existence of the characteristic length in loading this problem was long believed a knotty problem. Some features of the solutions are discussed and graphical result for numerical computation is presented.

Fusion energy-production from a deuterium-tritium plasma in the jet tokamak

Describes a series of experiments in the Joint European Torus (JET), culminating in the first tokamak discharges in deuterium-tritium fuelled mixture. The experiments were undertaken within limits imposed by restrictions on vessel activation and tritium usage. The objectives were: (i) to produce more than one megawatt of fusion power in a controlled way; (ii) to validate transport codes and provide a basis for accurately predicting the performance of deuterium-tritium plasmas from measurements made in deuterium plasmas; (iii) to determine tritium retention in the torus systems and to establish the effectiveness of discharge cleaning techniques for tritium removal; (iv) to demonstrate the technology related to tritium usage; and (v) to establish safe procedures for handling tritium in compliance with the regulatory requirements. A single-null X-point magnetic configuration, diverted onto the upper carbon target, with reversed toroidal magnetic field was chosen. Deuterium plasmas were heated by high power, long duration deuterium neutral beams from fourteen sources and fuelled also by up to two neutral beam sources injecting tritium. The results from three of these high performance hot ion H-mode discharges are described: a high performance pure deuterium discharge; a deuterium-tritium discharge with a 1% mixture of tritium fed to one neutral beam source; and a deuterium-tritium discharge with 100% tritium fed to two neutral beam sources. The TRANSP code was used to check the internal consistency of the measured data and to determine the origin of the measured neutron fluxes. In the best deuterium-tritium discharge, the tritium concentration was about 11% at the time of peak performance, when the total neutron emission rate was 6.0 × 10¹⁷ neutrons/s. The integrated total neutron yield over the high power phase, which lasted about 2 s, was 7.2 × 10¹⁷ neutrons, with an accuracy of ±7%. The actual fusion amplification factor, Q_DT was about 0.15

A new method of measuring the waveguide dispersion factor and the thermo-optic coefficient of long-period fiber gratings

Based on the Mach-Zehnder effect between the core mode and the cladding modes, the interference fringes are formed by a pair of cascaded long-period fiber gratings (CLPFGs). Theoretical analyses show that the spectral spacing and the wavelength of these fringes are functions of the waveguide dispersion factor gamma, which is a characterizing parameter to LPFG and with theoretical and applicational significance. By measuring the characteristics of the transmission spectra of CLPFGs, the absolute value of gamma can be obtained. At the same time, the thermo-optic coefficient of effective refractive index difference between core and cladding modes, p, can also be obtained by measured the temperature sensitivity of these fringes. In the experiments, \gamma\ and mu were measured by this method to be 0.874 and 4.08 x 10(-5) degreesC(-1), respectively, for LPFGs with period of 450 mum and with a HE14 resonant peak at 1554 nm. (C) 2004 Elsevier B.V. All rights reserved.

Anomalous scattering factor determined by semicircle fitting near the K-absorption edge of Ge

It is shown that the locus of the f' + if '' plot in the complex plane, f' being determined from measured f '' by using the dispersion relation, looks like a semicircle very near the absorption edge of Ge. The semicircular locus is derived from a quantum theory of X-ray resonant scattering when there is a sharp isolated peak in f '' just above the K-absorption edge. Using the semicircular behavior, an approach is proposed to determine the anomalous scattering factors in a crystal by fitting known calculated values based on an isolated-atom model to a semicircular focus. The determined anomalous scattering factors f' show excellent agreement with the measured values just below the absorption edge. In addition, the phase determination of a crystal structure factor has been considered by using the semicircular behavior.