DETERMINATION OF CYSTEINE AND REDUCED GLUTATHIONE IN HUMAN PLASMA BY LIQUID-CHROMATOGRAPHY WITH PULSED AMPEROMETRIC ELECTROCHEMICAL DETECTION USING A PLATINUM-PARTICLES MODIFIED GLASSY-CARBON ELECTRODE

An assay procedure utilizing pulsed amperometric detection at a platinum-particles modified electrode has been developed for the determination of cysteine and glutathione in blood samples following preliminary separation by reversed-phase liquid chromatography. A chemically modified electrode (CME) constructed by unique electroreduction from a platinum-salt solution to produce dispersed Pt particles on a glassy carbon surface was demonstrated to catalyze the electo-oxidation of sulfhydryl-containing compounds: DL-cysteine (CYS), reduced glutathione (GSH). When used as the sensing electrode in flow-system pulsed-amperometric detection (PAD), electrode fouling could be avoided using a waveform in which the cathodic reactivation process occurred at a potential of - 1.0 V vs. Ag/AgCl to achieve a cathodic desorption of atomic sulfur. A superior detection limit for these free thiols was obtained at a Pt particle-based GC electrode compared with other methods; this novel dispersed Pt particles CME exhibited high electrocatalytic stability and activity when it was employed as an electrochemical detector in FIA and HPLC for the determination of those organo-sulfur compounds.

PLASMA-INDUCED GRAFTING OF STYRENE ONTO NASCENT POLYETHYLENE POWDER

In this paper, the graft copolymers of styrene to nascent linear polyethylene reactor powders were prepared through plasma graft polymerization. The grafting reaction was initiated by the alkyl radicals formed on the surface of nascent polyethylene with plasma treatment as indicated by electron spin resonance spectra. In graft copolymerization by alkyl radicals, the grafting yield increased with either the plasma power or the plasma treatment lime. Compared with ordinary polyethylene powders, nascent polyethylene reactor powders were found to be more easily plasma-grafted. This has been attributed to the greater sensitivity to irradiation in producing reactive centres under the same conditions. High density polyethylene showed almost the same grafting yield as linear low density polyethylene at 50 degrees C. The surface morphology of nascent polyethylene observed by scanning electron microscope before and after the grafting showed that the silk-like fibrils were not destroyed by plasma treatment.

A DIFFERENTIAL SCANNING CALORIMETRY STUDY OF PLASMA IRRADIATION GRAFTING OF NASCENT POLYETHYLENE REACTOR POWDER

The melting behavior of poly(methyl methacrylate)-grafted nascent polyethylene reactor powder by plasma irradiation was studied by differential scanning calorimetry (DSC). The grafting yield ranged hom 11 to 190%. Grafting was found to lower both melting point and heat of fusion during the first run of DSC determination. The heat of fusion was used to calculate the apparent grafting yield of the samples. There was little strain induced by plasma-irradiated grafting on the surface of the polyethylene crystals. A method to determine the covalent grafting yield in the graft copolymer systems was developed. (C) 1995 John Wiley & Sons, Inc.

ELECTROCHEMICAL MECHANISM FOR FULLERENE FORMATION IN PLASMA ARCS

During the synthesis of fullerenes by dc plasma arcs, it has been found that the anodic graphite rod consistently burns up, while the cathodic graphite rod grows slag at its end. Further investigations revealed that the anodic and cathodic graphite rods p

IMPROVEMENT OF OXYGEN NITROGEN PERMSELECTIVITY OF POLY[1-(TRIMETHYLSILYL)-1-PROPYNE] MEMBRANE BY PLASMA POLYMERIZATION

The oxygen permselectivity of a poly[1-(trimethylsilyl)-1-propyne) (PTMSP) membrane was drastically improved by plasma polymerization of fluorine-containing monomers. The effects of such plasma polymerization conditions as deposition time, plasma power an

RESOLUTION OF CLOSELY SPACED LINES WITH KALMAN FILTERING IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

Effects of some factors on the performance of our Kalman filter in discrimination of closely spaced overlapping signals were investigated. The resolution power of the filter for overlapping lines can be strengthened by reduction of the step size in scans. The minimum peak separation of two lines which the Kalman filter can effectively handle generally equals two to three times the step size in scans. Significant difference between the profiles of the analysis and interfering lines and multiple lines from matrix in the spectral window of the analysis line are very helpful for the Kalman filter to discern closely spaced analysis and interfering signals correctly, which allow the filter well to resolve the line pair with very small peak distance or even the entirely coincident lines.

ON THE SIGNIFICANCE OF WAVELENGTH POSITIONING ACCURACY IN MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper reports some definite evidence for the significance of wavelength positioning accuracy in multicomponent analysis techniques for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). Using scanning spectrometers commercially available today, a large relative error, DELTA(A) may occur in the estimated analyte concentration, owing to wavelength positioning errors, unless a procedure for data processing can eliminate the problem of optical instability. The emphasis is on the effect of the positioning error (deltalambda) in a model scan, which is evaluated theoretically and determined experimentally. A quantitative relation between DELTA(A) and deltalambda, the peak distance, and the effective widths of the analysis and interfering lines is established under the assumption of Gaussian line profiles. The agreement between calculated and experimental DELTA(A) is also illustrated. The DELTA(A) originating from deltalambda is independent of the net analyte/interferent signal ratio; this contrasts with the situation for the positioning error (dlambda) in a sample scan, where DELTA(A) decreases with an increase in the ratio. Compared with dlambda, the effect of deltalambda is generally less significant.

WAVELENGTH POSITIONING ERRORS AND TRUE DETECTION LIMIT IN RELATION TO MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper deals with the evaluation of the relative error (DELTA(A)) in estimated analyte concentrations originating from the wavelength positioning error in a sample scan when multicomponent analysis (MCA) techniques are used for correcting line interferences in inductively coupled plasma atomic emission spectrometry. In the theoretical part, a quantitative relation of DELTA(A) with the extent of line overlap, bandwidth and the magnitude of the positioning error is developed under the assumption of Gaussian line profiles. The measurements of eleven samples covering various typical line interferences showed that the calculated DELTA(A) generally agrees well with the experimental one. An expression of the true detection limit associated with MCA techniques was thus formulated. With MCA techniques, the determination of the analyte and interferent concentrations depend on each other while with conventional correction techniques, such as the three-point method, the estimate of interfering signals is independent of the analyte signals. Therefore. a given positioning error results in a larger DELTA(A) and hence a higher true detection limit in the case of MCA techniques than that in the case of conventional correction methods. although the latter could be a reasonable approximation of the former when the peak distance expressed in the effective width of the interfering line is larger than 0.4. In the light of the effect of wavelength positioning errors, MCA techniques have no advantages over conventional correction methods unless the former can bring an essential reduction ot the positioning error.

APPLICATION OF FACTOR-ANALYSIS TO CORRECTION OF SPECTRAL OVERLAP INTERFERENCE IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

Correction of spectral overlap interference in inductively coupled plasma atomic emission spectrometry by factor analysis is attempted. For the spectral overlap of two known lines, a data matrix can be composed from one or two pure spectra and a spectrum of the mixture. The data matrix is decomposed into a spectra matrix and a concentration matrix by target transformation factor analysis. The component concentration of interest in a binary mixture is obtained from the concentration matrix and interference from the other component is eliminated. This method is applied to correcting spectral interference of yttrium on the determination of copper and aluminium: satisfactory results are obtained. This method may also be applied to correcting spectral overlap interference for more than two lines. Like other methods of correcting spectral interferences, factor analysis can only be used for additive spectral overlap. Results obtained from measurements on copper/yttrium mixtures with different white noise added show that random errors in measurement data do not significantly affect the results of the correction method.

GAS PERMEABILITIES OF POLY(TRIMETHYLSILYLPROPYNE) MEMBRANES SURFACE MODIFIED WITH CF4 PLASMA

Surface fluorination of poly (trimethylsilylpropyne) (PTMSP) membranes by CF4 plasma was studied. The surface fluorination of the membranes was carried out in an atmosphere of CF4 in a capacitively coupled discharge apparatus with external electrodes. Dramatic increase in selectivity (P(O2)/P(N2)) was observed. The effect of fluorination conditions such as duration of treatment and discharge power on the permeabilities of the membranes was studied. X-ray photoelectron spectrometric data of modified PTMSP membranes showed a drastic alternation in the surface layer. The P(O2) and P(O2)/P(N2) of the membranes were observed to be dependent on the F/C atomic ratio. At F/C > 1, the P(O2/P(N2) value of the membranes could be more than four.

KALMAN FILTERING FOR RESOLUTION OF OVERLAPPING LINES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

A Kalman filter was developed for resolving overlapping lines in inductively coupled plasma atomic emission spectrometry (ICP-AES) and evaluated experimentally with the determination of La in the presence of Ho, and Cu in the presence of Pr. The whiteness of the innovation sequence for an optimal filter was explored to be the criterion for the correction of the wavelength positioning errors which may occur in spectral scans. Under the conditions of the medium-resolution spectrometer and 1.5 pm step size in scans, the filter effectively resolved the Cu/Pr line pair having a small peak separation of 4.8 pm. For the La/Ho line pair with a peak distance of 9.8 pm, an unbiased estimate for La concentration was still obtained even when the signal-to-background ratio was down to 0.048. Favourable detection limits for real samples were achieved. Unstructured backgrounds were modeled theoretically and all spectral scans therefore did not require the correction for solvent.

EVALUATION OF THE RELIABILITY OF KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This paper deals with the evaluation of the reliability of the analytical results obtained by Kalman filtering. Two criteria for evaluation were compared: one is based on the autocorrelation analysis of the innovation sequence, the so-called NAC criterion; the other is the innovations number, which actually is the autocorrelation coefficient of the innovation sequence at the initial wavelength. Both criteria allow compensation for the wavelength positioning errors in spectral scans, but there exists a difference in the way they work. The NAC criterion can provide information about the reliability of an individual result, which is very useful for the indication of unmodelled emissions, while the innovations number should be incorporated with the normalization of the innovations or seek the help of the sequence itself for the same purpose. The major limitation of the NAC criterion is that it does not allow the theoretical modelling of continuous backgrounds, which, however, is convenient in practical analysis and can be taken with the innovations number criterion.

PLASMA POLYMERIZATION OF OCTAFLUOROCYCLOBUTANE AND HYDROPHOBIC MICROPOROUS COMPOSITE MEMBRANES FOR MEMBRANE DISTILLATION

In this paper, hydrophilic microporous cellulose nitrate membranes have been surface-modified by plasma polymerization of octafluorocyclobutane (OFCB). The microporous composite membranes with a hydrophilic layer sandwiched between two hydrophobic layers have been obtained. The obtained composite membranes have been used in a membrane distillation (MD) process and have exhibited good performance. The effects of polymerization conditions, such as glow-discharge power and deposition time, on the structures and MD performances of the obtained composite membranes have been investigated by SEM, X-ray microscopical analysis, and XPS. The polymerization conditions should be as mild as possible in order to prepare the hydrophobic composite membrane with good MD performance. The typical MD behaviors of the obtained hydrophobic composite membranes are in agreement with that of hydrophobic membranes directly prepared from hydrophobic polymeric materials, like PVDF, PTFE, or PP.

LEAST-SQUARES POLYNOMIAL SMOOTHING FOR INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTRA

The use of least-squres polynomial smoothing in ICP-AES is discussed and a method of points insertion into spectral scanning intervals is proposed in the present paper. Optimal FWHM/SR ratio can be obtained, and distortion of smoothed spectra can be avoided by use of the recommended method.

EVALUATION OF THE EFFECT OF WAVELENGTH POSITIONING ERRORS ON KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This work evaluates the effect of wavelength positioning errors in spectral scans on analytical results when the Kalman filtering technique is used for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a positioning accuracy of 0.1 pm is required in order to obtain accurate and precise estimates for analyte concentrations. The positioning error in sample scans is more crucial than that in model scans. The relative bias in measured analyte concentration originating from a positioning error in a sample scan increases linearly with an increase in the magnitude of the error and the peak distance of the overlapping lines, but is inversely proportional to the signal-to-background ratio. By the use of an optimization procedure for the positions of scans with the innovations number as the criterion, the wavelength positioning error can be reduced and, correspondingly, the accuracy and precision of analytical results improved.