You-Zhao He

Mechanism of porous core electroosmotic pump flow injection system and its application to determination of chromium(VI) in waste-water

An electroosmotic pump flow injection system is introduced in this paper. According to electroosmotic theory, the pumps properties were described. A large flow range (mul min(-1)-ml min(-1)), moderate carrier pressure (>0.15 MPa), reduced performance voltage (<500 V) and stable flow rate (RSD<3.0% in 4 h) are the main properties of the pump. NH(4)OH (0.35 mM) was used as carrier for improving the pumps flow stability. The electroosmotic efficiency of the pumps medium, porous core, can be recovered and regenerated. A sandwich zone was used for sample and reagent introduction in order to adapt to the pump performance. Flow injection-spectrophotometry was employed for the determination of Cr(VI) in waste-water, based on the formation of the complex with 1,5-diphenylcarbazide and absorbance measurement at 540 nm. Within the calibration range of 0-7.0 mg l(-1) of Cr(VI), the RSD was 0.4% (n=5). The recovery of 0.70 mg l(-1) Cr(VI) added to the waste-water sample was 94.5+/-2.0% (n=5).

Determination of kanamycin A, amikacin and tobramycin residues in milk by capillary zone electrophoresis with post-column derivatization and laser-induced fluorescence detection.

An analytical method for kanamycin A, amikacin and tobramycin of aminoglycoside (AG) antibiotics in milk samples was proposed using capillary zone electrophoresis (CZE) with post-column derivatization and laser-induced fluorescence detection. A simple and convenient homemade coaxial-gap reactor was adopted in the post-column derivatization of the AGs with 1.0 mmol/L naphthalene-2,3-dicarboxaldehyde and 8.0 mmol/L 2-mercaptoethanol in 35 mmol/L sodium tetraborate buffer (pH 10.0) of 30% (v/v) methanol. 50 mmol/L sodium acetate (pH 5.0) containing 0.5 mmol/L cetyltrimethyl ammonium bromide was used as the separation buffer. The linear calibration concentrations and detection limits were from 2.1 x 10(-5) to 5.0 x 10(-2)g/L and in the range of 7 x 10(-6) to 2 x 10(-5)g/L, respectively. The recoveries of the AGs in milk samples were from 81.6 to 93.1% (n=3).

On-line pretreatment and determination of parabens in cosmetic products by combination of flow injection analysis, solid-phase extraction and micellar electrokinetic chromatography

A convenient and automated method for on-line pretreatment and determination of three parabens (i.e. methyl, ethyl and propyl p-hydroxybenzoate) in cosmetic products is proposed by using flow injection analysis (FIA), solid-phase extraction (SPE) and micellar electrokinetic chromatography (MEKC). An improved split-flow interface is used to couple SPE on C(8)-bonded silica with MEKC separation, which can avoid running buffer contamination and reduce buffer consumption, especially, containing expensive reagents. The analytes are loaded onto a C(8) column at 0.6 mL/min for 60s and eluted with a mixed eluent of 40% (v/v) 10 mmol/L sodium tetraborate buffer (pH 9.3) and 60% (v/v) ethanol at 0.75 mL/min. The MEKC separation is accomplished with a running buffer of 20 mmol/L sodium tetraborate (pH 9.3) containing 100 mmol/L sodium dodecyl sulfate (SDS) at 15 kV. For butyl p-hydroxybenzoate did not be detected in the cosmetic products, it was used as an internal standard (IS) added into the real samples. This FIA-SPE-MEKC method using IS allows the sample separation within 12 min and the sample throughput of five samples per hour with the relative standard deviation (R.S.D.) less than 2.3% (n=5). The limits of detection (LOD) are in the range from 0.07 to 0.1 microg/mL (S/N=3 and n=11). The proposed method has been used to determine three parabens in real cosmetic products satisfactorily.

Determination of benzoic acid and sorbic acid in food products using electrokinetic flow analysis–ion pair solid phase extraction–capillary zone electrophoresis

An electrokinetic flow analysis system (EFA), consisting of one electroosmotic pump, five solenoid valves and one on-line homemade solid phase extraction (SPE) unit, combined with capillary zone electrophoresis (CZE) was proposed to determine benzoic acid and sorbic acid in food products. Tetrabutylammonium bromide (TBAB) was adopted as an ion pair reagent to improve the retention of the preservatives on C(8)-bonded silica sorbent, which was also used to remove sample matrices. By using the SPE unit, the EFA-SPE-CZE system was able to perform the SPE operation and CZE separation simultaneously. With a modified interface of EFA and CZE, the buffer consumption was reduced to 130 microL for each running. The preservatives were separated and determined under optimized conditions with p-hydroxybenzoic acid as an internal standard. The relative standard deviation (R.S.D.) of peak area for each analyte was less than 3.1% (n=5) and the limits of detection (LODs) ranged from 10 to 20 ngmL(-1) (K=3, n=11).

Direct determination of dissolved selenium (vi) and selenium (vi) in sea-water by continuous flow hydride generation atomic fluorescence spectrometry

Highly sensitive and simple methods were developed for the direct determination of trace amounts of selenite and selenate in sea-water. For SeIV determination, sea-water samples and reagent blank in 1.5 mol l–1 HCl containing 2.0% m/v KH2PO4, as an interference eliminating reagent, are merged with 1.5% m/v NaBH4 in 0.5% m/v NaOH using flow rates of 22 and 2.0 ml min–1, respectively. The selenium hydride produced is passed through a gas–liquid separator and a dryer tube using an argon carrier flow of 0.45 l min–1, and Se is determined with a mini-hydrogen diffusion flame by a non-dispersive atomic fluorescence spectrometer equipped with a Se boosted discharge hollow cathode lamp. For total Se determination, samples are acidified (1.5 mol l–1) and treated with NaBr (4.0% m/v) by heating at 70 °C for 60 min to reduce selenate. The determination of total Se by atomic fluorescence is then carried out as described above. SeVI is calculated as the difference between total Se and SeIV. The detection limits (3σ of blank) of the methods were reached with 0.96–1.3 ng l–1 of Se. The calibration graph was rectilinear up to 80 ng l–1. The recoveries of 20 ng l–1 SeIV added into sea-water were 99.3–100 (s±8.4) %, and those of SeVI were 98.9–104 (s±4.0) %. The method is suitable for the direct analysis of natural samples and the results obtained for a certified reference material were in good agreement with the reported value.

On-column liquid–liquid–liquid microextraction coupled with base stacking as a dual preconcentration method for capillary zone electrophoresis

A simple and efficient dual preconcentration method of on-column liquid-liquid-liquid microextraction (LLLME) coupled with base stacking was developed for capillary zone electrophoresis (CZE) in this paper. Four N-methyl carbamates were used as target compounds to evaluate the enrichment means. The carbamates in sample solutions (donor phase) were extracted into a dodecanol phase immobilized on a porous hollow fiber, hydrolyzed and back extracted into 0.20 microL running buffer (acceptor phase) of 30 mmol/L methylamine hydrochloride (pH 11.6) containing 0.5 mmol/L tetradecyltrimethylammonium bromide inside the hollow fiber, stacked further with 0.5 mol/L NaOH injected at -10 kV for 60s, and separated by CZE. Analytical parameters affecting the LLLME, base stacking and CZE were investigated, including sample solution volume, pH and temperature, extraction time, stirring rate, buffer component, buffer pH, NaOH concentration, stacking time, etc. The enrichment factors of the carbamates were higher than 1100. The relative standard deviation (RSD) of peak height and limits of detection (LODs) were 4.5-5.5% (n=6) and 2-4 ng/mL (S/N=3) for standard solutions, respectively. The proposed method was applied to the analysis of vegetable and fruit samples with the RSD less than 6.0% (n=3) and LODs of 6-10 ng/g (S/N=3). The calibration solutions were prepared by diluting the stock solutions with blank sample solutions, and the calibration concentrations ranged from 0.012 to 1.0 microg/mL (r>0.9951). The analytical results demonstrated that the LLLME coupled with base stacking was a simple, convenient and reliable on-column sample pretreatment method for the analysis of anionic analytes in CZE.

Determination of preservatives by integrative coupling method of headspace liquid-phase microextraction and capillary zone electrophoresis

An integrative coupling method of headspace liquid-phase microextraction (HS-LPME) and capillary zone electrophoresis (CZE) was proposed in this paper. In the method, a separation capillary was used to create a microextraction droplet of the running buffer solution of CZE, hold the droplet at the capillary inlet, extract analytes of sample solutions in the headspace of a sample vial, inject concentrated analytes into the capillary and separate the analytes by CZE. The proposed method was applied to determine the preservatives of benzoic acid and sorbic acid in soy sauce and soft drink samples, in which the running buffer solution of 50 mmol/L tetraborate (pH 9.2) was directly used to form the acceptor droplet at the capillary inlet by pressure, and the preservatives in a 6-mL sample solution containing 0.25 g/mL NaCl were extracted at 90°C for 30 min in the headspace of a 14-mL sample vial. Then the concentrated preservatives were injected into the capillary at 10 cm height difference for 20 s and separated by CZE. The enrichment factors of benzoic acid and sorbic acid achieved 266 and 404, and the limits of detection (LODs) were 0.03 and 0.01 μg/mL (S/N=3), respectively. The recoveries were in the range of 88.7-105%. The integrative coupling method of HS-LPME and CZE was simple, convenient, reliable and suitable for concentrating volatile and semi-volatile organic acids and eliminating matrix interferences of real samples.

Improving separation efficiency of capillary zone electrophoresis of tryptophan and phenylalanine with the transient moving chemical reaction boundary method.

A simple and convenient mode--moving chemical reaction boundary method-capillary zone electrophoresis (MCRBM-CZE)--was designed for the enhancement of separating efficiency of CZE. In this mode, the transient MCRBM is used for the on-line pre-treatment of sample. By analyses of tryptophan (Trp) and phenylalanine (Phe) as an example, the experiments by MCRBM-CZE were carried out and further compared with those by normal CZE without the transient MCRBM. The results reveal that by carefully selected appropriate electrolytes, a strong condensation effect can be achieved by using MCRBM-CZE; this effect can greatly improve the separation efficiency, resolution and peak height of Trp and Phe in CZE as compared with those of normal CZE of Trp and Phe. Even if the sample comprises high concentrations of salt, such as 80 mM NaCl (concentration of sodium ion up to 145.6 mM), the same condensation effect can also been observed; this implies obvious significance for biological samples like urine and serum. However, if the electrolytes was chosen inappropriately only a poor compression effect of sample was observed in the MCRBM-CZE runs.

Determination of polyphenol components in herbal medicines by micellar electrokinetic capillary chromatography with Tween 20

A simple and convenient method of micellar electrokinetic capillary chromatography (MEKC) using polyoxyethylene sorbitan monolaurate (Tween 20) to form single micelle and methanol as a buffer additive was introduced for the simultaneous determination of five polyphenols, including scopoletin, rutin, esculetin, chlorogenic acid and caffeic acid. A running buffer solution of pH 9.3, 20 mmol/L sodium tetraborate containing 64 mmol/L Tween 20 and 9% (v/v) methanol was adopted in the separation. Because rutin and esculetin were difficult to be separated by capillary zone electrophoresis (CZE) and SDS-based MEKC, Tween 20-based MEKC was adopted and the polyphenols were separated satisfactorily. The proposed method was used to determine the polyphenol components in the herbal medicine of Cortex fraxini. The separation mechanism of Tween 20-based MEKC for the polyphenols was discussed preliminarily.

Determination of chromium(VI) and lead(II) in drinking water by electrokinetic flow analysis system and graphite furnace atomic absorption spectrometry

An electrokinetic flow analysis system (EKFA) using an electroosmotic pump (Peo) and a bi-directional electrostacking (BDES) unit is introduced in this paper. Large flow range, moderate carrier pressure, low performance voltage and stable flow rate, especially in mulmin(-1) level, are the main specialties of the Peo. Diethanolamine, 0.5 mM, is selected as its carrier to improve the pump efficiency and stability further. Moreover, BDES, a feasibility investigation for the simultaneous separation and pre-concentration of cations and anions, and graphite furnace atomic absorption spectrometry (GFAAS) determination are presented. The calibration series for both of Cr(VI) and Pb(II) are from 0.2 to 40 mugl(-1) with 10 mul pipette volume and GFAAS determination directly. The detection limit of Cr(VI) and Pb(II) with 10 min BDES is 10 and 13 ngl(-1)(3sigma of blank, n=11), respectively. The recovery of Cr(VI) and Pb(II) is (103-105)+/-1% and (95.9-96.9)+/-1.0% with three independent determinations, respectively. The investigated method is also suitable for the simultaneous separation and pre-concentration of trace cations and anions in low conductivity sample solutions with different detection instruments.