Simultaneous determination of flumequine and oxolinic acid in chicken tissues by solid phase extraction and capillary electrophoresis

This paper describes capillary electrophoresis (CE) methodology for simultaneous determination of oxolinic acid (OXO) and flumequine (FLU) in spiked chicken tissue using norfloxacin (NOR) as internal standard (IS), with diode array detection. The analytes were extracted using dichlorometane and NaOH and pre-concentrated by solid phase extraction (SPE).The recoveries obtained were 94 and 84% for oxolinic acid and flumequine , respectively. The detection and quantification limits achieved were 15 and 48 μg kg⁻¹ for oxolinic acid, respectively, and 10 and 30 μg kg⁻¹ for flumequine. The sensitivity of the method proposed allows the determination of these drugs at a residue level far below their maximum residue limit (MRL) established by the European Union (EU).     

Rapid determination of catecholamines in urine samples by nonaqueous microchip electrophoresis with LIF detection

A method was developed for the rapid separation of catecholamines by nonaqueous microchip electrophoresis (NAMCE) with LIF detection, A homemade pump‐free negative pressure sampling device was used for rapid bias‐free sampling in NAMCE, the injection time was 0.5 s and the electrophoresis separation conditions were optimized. Under the optimized conditions, the samples were separated completely in <1 min. The average migration times of the epinephrine (E), dopamine (DA), and norepinephrine (NE) were 34.26, 43.81, and 50.07 s, with an RSD of 1.05, 1.26, and 0.89% (n = 7), respectively. The linearity of the method ranged from 0.0125 to 2.0 mg/L for E and 0.025～4.0 mg/L for DA and NE, with correlation coefficients ranging between 0.9978 and 0.9986. The detection limits of E, DA, and NE were 2.5, 5.0, and 5.0 μg/L, respectively. The recoveries of E, DA, and NE in spiked urine samples were between 86 and 103%, with RSDs of 4.5～6.8% (n = 5). The proposed NAMCE with LIF detection combined with a pump‐free negative pressure sampling device is a simple, inexpensive, energy efficient, miniaturized system that can be successfully applied for the determination of catecholamines in urine samples.     

Simultaneous analysis of Cu and Pb as ABEDTA complexes in Rhizoma coptidis by capillary electrophoresis coupled with solid phase extraction

A novel capillary electrophoresis method for simultaneous determination of Cu and Pb has been developed in this paper.Cu（Ⅱ） and Pb（Ⅱ） ions were reacted with ABEDTA to form complex to achieve an ideal sensitivity of heavy metal complexes.The digestion solution of Rhizoma coptidis drug sample was purified by neutral Al₂O₃ column chromatography and the chromatographic behavior of metal-L complexes was investigated.The calibration curve was linear in the range of 5-60μg/mL for Cu²⁺ and 5-25μg/mL for Pb²⁺ with the correlation coefficients 0.9970 and 0.9972 for each（n = 5）.The average recoveries were 86.2%for Pb and 90.1%for Cu,while the relative standard deviations were 5.1%and 3.6%respectively.The method was successfully applied to determine Cu and Pb in R.coptidis drug samples.     

Ionic liquids used in and analyzed by capillary and microchip electrophoresis

This review, covering reports published from 2001 to December 2008, shows how ionic liquids (ILs) have made significant contributions in the improvement of capillary and microchip electrophoresis (CE and μCE) for the separation and detection of analytes such as phenols and aromatic acids, metal ions, medicines, enantiomers, biological materials, etc. Furthermore, CE methods applied in the sensitive and accurate determination of physico-chemical properties of ILs have been summarized. Accordingly, research vacancies and future development trends in these areas are discussed.     

Determination of five priority haloacetic acids by capillary electrophoresis with contactless conductivity detection and solid phase extraction preconcentration

A sensitive capillary electrophoretic separation method with contactless conductivity detection (C4D) for analysis of five priority haloacetic acids (HAA5) is presented. The analytes were baseline separated in an electrolyte composed of 20 mM 2-(N-Morpholino) ethanesulfonic acid (MES), 20 mM L-histidine (HIS), and 30 μM cetyltrimethylammonium bromide (CTAB) at pH 6.0 in less than 4 min. A simplified solid-phase extraction (SPE) preconcentration procedure on highly cross-linked polystyrene-divinylbenzene (PS-DVB) type sorbent was developed and optimized with respect to short preconcentration time. HAA5 from a 25-mL sample aliquot of tap and swimming pool water could be preconcentrated in less than 5 min using an in-house made SPE column with recoveries ranging from 23 to 98%. Combining the SPE preconcentration procedure with capillary electrophoretic analysis, the attained limits of detection were between 6.1 and 12.2 μg/L with total analysis time of less than 10 min.     

Micro-porous membrane liquid-liquid extraction as an enrichment step prior to nonaqueous capillary electrophoresis determination of sulfonylurea herbicides

A method based on micro-porous membrane liquid-liquid extraction (MMLLE) enrichment and nonaqueous capillary electrophoresis (CE) separation, was established for the analysis of sulfonylurea herbicides in water samples. After MMLLE, the analyte trapped in the chloroform was treated mildly with nitrogen flow to dryness and then dissolved in 200 μl of 4 mM Tris methanol solution for CE analysis. Five sulfonylurea herbicides were separated by nonaqueous CE with Tris/acetate of methanol solution as the run buffer. MMLLE related parameters such as organic solvent used as acceptor, sample flow rate, sample pH, enrichment time, and salt effect were investigated with tribenuron methyl (TBM) as a model compound. Results showed that with a sample flow rate of 3.0 ml min⁻¹ and an enrichment time of 20 min, the proposed method has good linear relationship over the scope of 1-15 ng ml⁻¹ with related coefficient of R²=0.9911, and a detection limit of 0.4 ng ml⁻¹. This method was applied to determine TBM in realworld water samples with recoveries over the range of 89-97%.     

Magnetic solid phase extraction based on phenyl silica adsorbent for the determination of tetracyclines in milk samples by capillary electrophoresis

A magnetic solid phase extraction method coupled to capillary electrophoresis is proposed for the determination of tetracycline, oxytetracycline, chlortetracycline and doxycycline in milk samples. Five different magnetic phenyl silica adsorbents covered with magnetite were synthesized by varying the molar ratio of phenyltrimethylsilane and tetramethylorthosilicate; these adsorbents were evaluated in terms of their pH and degree of hydrophobicity for tetracycline retention. The optimal, selected combination of conditions was a pH of 10.0 and a magnetic sorbent ratio of 4:1; under these conditions, the retention capacity ranged from 99.7% to 101.2% for the four tetracyclines analyzed. The elution conditions and initial sample volume of the proposed extraction method were also optimized, and the best results were obtained with 1×10(-3) M acetic acid in methanol as eluent and a 200 ml of sample volume. Under optimal conditions, average recoveries ranged from 94.2% to 99.8% and the limits of detection ranged from 2 to 9 μg l(-1) for the four tetracyclines. After the proposed method was optimized and validated, 25 milk samples of different brands were analyzed, oxytetracycline residues were detected in five samples, in concentrations ranging from 98 to 213 μg l(-1). Subsequent analysis of positive samples by SPE-CE and magnetic solid phase extraction-HPLC revealed than no significant differences were found from results obtained by the proposed methodology. Thus, the developed magnetic extraction is a robust pre-concentration technique that can be coupled to other analytical methods for the quantitative determination of tetracyclines.     

Integrated electrokinetically driven microfluidic devices with pH‐mediated solid‐phase extraction coupled to microchip electrophoresis for preterm birth biomarkers

Integration in microfluidics is important for achieving automation. Sample preconcentration integrated with separation in a microfluidic setup can have a substantial impact on rapid analysis of low‐abundance disease biomarkers. Here, we have developed a microfluidic device that uses pH‐mediated solid‐phase extraction (SPE) for the enrichment and elution of preterm birth (PTB) biomarkers. Furthermore, this SPE module was integrated with microchip electrophoresis for combined enrichment and separation of multiple analytes, including a PTB peptide biomarker (P1). A reversed‐phase octyl methacrylate monolith was polymerized as the SPE medium in polyethylene glycol diacrylate modified cyclic olefin copolymer microfluidic channels. Eluent for pH‐mediated SPE of PTB biomarkers on the monolith was optimized using different pH values and ionic concentrations. Nearly 50‐fold enrichment was observed in single channel SPE devices for a low nanomolar solution of P1, with great elution time reproducibility (<7% RSD). The monolith binding capacity was determined to be 400 pg (0.2 pmol). A mixture of a model peptide (FA) and a PTB biomarker (P1) was extracted, eluted, injected, and then separated by microchip electrophoresis in our integrated device with ∼15‐fold enrichment. This device shows important progress towards an integrated electrokinetically operated platform for preconcentration and separation of biomarkers.     

Effective sorbents for solid-phase extraction in the analysis of quinolones in animal tissues by capillary electrophoresis

In this work, several commercial sorbents (Zorbax C18, Bond Elut C18, Isolute ENV+, Oasis HLB, Oasis MAX, SDB-RPS, and MPC-SD) were compared for the solid-phase extraction of the series of quinolones regulated by the European Community in chicken tissues in order to establish a method for the determination of this series of quinolones by capillary electrophoresis and diode array detection. Sorbents were chosen in order to achieve maximum recoveries and optimal clean-up efficiency. Better results were obtained using SDB-RPS and Oasis MAX which would provide suitable limits of detection, below of the maximum residue limits (MRLs) regulated.     

Automated capillary electrophoresis with on-line preconcentration by solid phase extraction using a sequential injection manifold and contactless conductivity detection

An extension of a capillary electrophoresis instrument coupled to a sequential injection analysis manifold was developed for automated measurements with on-line solid-phase extraction preconcentration. An in-house built capacitively coupled contactless conductivity detector was employed for sensitive detection with narrow capillaries of 25 μm internal diameter. The system was assembled into standardized 19 in. frames and racks for easy transport and mobile deployment. The system can be left running unattendedly without manual intervention with good operation stability. To demonstrate the application of the system, a method for the determination of four drugs, namely ibuprofen, diclofenac, naproxen and bezafibrate, was developed with enrichment factors of up to several hundreds. Detection of the drug residues down to the nM-scale was found possible and the method was found suitable for the detection of ibuprofen in the waste water of a hospital in Hanoi.     

Analysis of urinary neurotransmitters by capillary electrophoresis: sensitivity enhancement using field-amplified sample injection and molecular imprinted polymer solid phase extraction

Capillary electrophoresis (CE) has been investigated for the analysis of some neurotransmitters, dopamine (DA), 3-methoxytyramine (3-MT) and serotonin (5-hydroxytryptamine, 5-HT) at nanomolar concentrations in urine. Field-amplified sample injection (FASI) has been used to improve the sensitivity through the online pre-concentration samples. The cationic analytes were stacked at the capillary inlet between a zone of low conductivity - sample and pre-injection plug - and a zone of high conductivity - running buffer. Several FASI parameters have been optimized (ionic strength of the running buffer, concentration of the sample protonation agent, composition of the sample solvent and nature of the pre-injection plug). Best results were obtained using H₃PO₄–LiOH (pH 4, ionic strength of 80 mmol L⁻¹) as running buffer, 100 μmol L⁻¹ of H₃PO₄ in methanol–water 90/10 (v/v) as sample solvent and 100 μmol L⁻¹ of H₃PO₄ in water for the pre-injection plug.In these conditions, the linearity was verified in the 50–300 nmol L⁻¹ concentration range for DA, 3-MT and 5-HT with a determination coefficient (r²) higher than 0.99. The limits of quantification (10 nmol L⁻¹ for DA and 3-MT, 5.9 nmol L⁻¹ for 5-HT) were 500 times lower than those obtained with hydrodynamic injection. However, if this method is applied to the analysis of neurotransmitters in urine, the presence of salts in the matrix greatly reduces the sensitivity of the FASI/CE–UV method.Therefore, a solid phase extraction (SPE) on a dedicated imprinted polymer (MIP) was developed to extract specific neurotransmitters, catecholamines, metanephrines and indolamines, from urine. Matrix salts were thus discarded after sample extraction on AFFINIMIP™ Catecholamine & Metanephrine (100 mg) cartridge.Therefore, lower limits of quantification were determined in artificial urine (46 nmol L⁻¹ for DA, 11 nmol L⁻¹ for 3-MT and 6 nmol L⁻¹ for 5-HT).The application of this protocol MIP-SPE/FASI–CE–UV analysis of neurotransmitters in human urine gave rise to electropherograms with a very good base line and signal to noise ratios above 15.     

Ultrasonic solvent extraction and nonaqueous CE for the determination of herbicide residues in potatoes

In the present work we address the development of a simple and effective method for the determination of triazine herbicide residues in horticultural products by CE in nonaqueous media (NACE). Potato samples were selected as a representative matrix of such foods with a nonfatty content. Isolation of the analytes from the sample matrix was accomplished by extraction with organic solvents, assisted by ultrasound; a clean‐up step of the organic extracts was carried out with SPE, using an Oasis MCX® sorbent to retain the analytes directly from the organic medium. The detection limits achieved in spiked potatoes (1.7–4.0 μg/kg) were lower than the default value of maximum residue level (MRL) established by current EU legislation for pesticide residues in foodstuffs. The results obtained were compared with HPLC in order to evaluate the performance of the NACE procedure.     

Microchip-based capillary electrophoresis for determination of lactate dehydrogenase isoenzymes

This article describes a novel microchip-based capillary electrophoresis and oncolumn enzymatic reaction analysis protocol for lactate dehydrogenase (LDH) isoenzymes with a home-made xenon lamp-induced fluorescence detection system. A microchip integrated with a temperature-control unit is designed and fabricated for low-temperature electrophoretic separation of LDH isoenzymes, optimal enzyme reaction temperature control, and product detection. A four-step operation and temperature control are employed for the determination of LDH activity by on-chip monitoring of the amount of incubation product of NADH during the fixed incubation period and at a fixed temperature. Experiments on the determination of LDH standard sample and serum LDH isoenzymes from a healthy adult donor are carried out. The results are comparable with those obtained by conventional CE. Shorter analysis times and a more stable and lower background baseline can be achieved. The efficient separation of different LDH forms indicates the potential of microfluidic devices for isoenzyme assay.     

Ultraviolet absorbance detection of colchicine and related alkaloids on a capillary electrophoresis microchip

The separation and UV absorbance detection of four toxic alkaloids, colchicine, thiocolchicine, colchicoside, and thiocolchicoside, on a microchip-based capillary electrophoresis device are reported. To increase the sensitivity of UV absorbance detection, optical cells with extended path lengths were integrated into the separation channel during the microfabrication process. The absorbance values realized on the microchip using these optical cells were proportional to the increase in average depths according to the Beer-Lambert Law, resulting in sensitivity enhancements by as much as five times. Linearity of response was observed from 5.0 to 500 mg L⁻¹ of colchicine, with detection limits ranging from 2 to 6 mg L⁻¹ depending upon the specific alkaloid and the dimension of the optical cell. The extraction of colchicine from spiked milk samples was performed and an average recovery rate of 83% with a relative standard deviation of 3.8% was determined using the optimized conditions on the microchip.     

Comprehensive two-dimensional separations based on capillary high-performance liquid chromatography and microchip electrophoresis

A novel comprehensive two-dimensional (2-D) separation system coupling capillary high-performance liquid chromatography (cHPLC) with microchip electrophoresis (chip CE) is demonstrated. Reversed-phase cHPLC was used as the first dimension, and chip CE acted as the second dimension to perform fast sample transfers and separations. A valve-free gating interface was devised simply by inserting the outlet-end of LC column into the cross-channel on a specially designed chip. A home-made confocal laser-induced fluorescence detector was used to perform on-chip high-sensitive detection. The cHPLC effluents were continuously delivered to the chip and pinched injections of the effluents every 20 seconds were employed for chip CE separation. Gradient elution of cHPLC was carried out to obtain the high-efficiency separation. Free-zone electrophoresis was performed with triethylamine buffer to achieve high-speed separation and prevent sample adsorption. Such a simple-made comprehensive system was proved to be effective. The relative standard deviations for migration time and peak height of rhodamine B in 150 sample transfers were 3.2% and 9.8%, respectively. Peptides of the fluorescein isothiocyanate (FITC)-labeled tryptic digests of bovine serum albumin were fairly resolved and detected with this comprehensive 2-D system.     

Qualitative and quantitative analysis of active flavonoids in Flos Lonicerae by capillary zone electrophoresis coupled with solid-phase extraction

Flavonoids are an important bioactive group in the commonly used herbal medicine Flos Lonicerae. A new method of capillary zone electrophoresis (CZE) coupled with solid-phase extraction (SPE) was developed for simultaneous assay of flavonoid aglycones and glycosides in Flos Lonicerae. Optimum CZE separation was achieved with a background electrolyte (BGE) solution consisting of 80 mM boric acid and 20 mM phosphate acid, adjusted to pH 8.1, with 15% acetonitrile (v/v) added, and applying a separation voltage of 28 kV. The SPE method was used for pretreating the complex matrix of botanical materials and good reproducibility was obtained when avicularin was used as internal standard. Linearity of the method was excellent with correlation coefficients (r2) in the range of 0.9995-0.9999 and detection limits were lower than 0.6 microg/mL for the four flavonoids. The obtained recoveries varied between 93 to 104% while the relative standard deviations (RSDs) were below 4.4% (n=3). The developed CZE method was successfully used for the separation of eight flavonoids and the quantification of the four flavonoids in five species of Flos Lonicerae.     

毛细管电泳在火炸药研究中的应用

近年来,毛细管电泳以其高效、快速、微量的特点,在火炸药分析领域被广泛应用并迅速发展。本文从毛细管区带电泳、胶束电动毛细管色谱、毛细管电色谱、芯片毛细管电泳、微乳毛细管电动色谱这五种毛细管电泳的模式出发,结合本实验室的最新研究进展,综述毛细管电泳在火炸药研究中的应用。     

Monitoring environmental pollutants by microchip capillary electrophoresis with electrochemical detection

During the past decade, significant progress in the development of miniaturized microfluidic systems has occurred due to the numerous advantages of microchip analysis. This review focuses on recent advances and the key strategies in microchip capillary electrophoresis (CE) with electrochemical detection (ECD) for separating and detecting a variety of environmental pollutants. The subjects covered include the fabrication of microfluidic chips, ECD, typical applications of microchip CE with ECD in environmental analysis, and future prospects. It is expected that microchip CE-ECD will become a powerful tool in the environmental field and will lead to the creation of truly portable devices.     

Separation of open-cage fullerenes using nonaqueous capillary electrophoresis

In this study, nonaqueous capillary electrophoresis (NACE) was used to separate three open-cage fullerenes. Trifluoroacetic acid (TFA) was used as the nonaqueous background electrolyte to change the analytes’ mobilities. The selectivity and separation efficiency were critically affected by the nature of the buffer system, the choice of organic solvent, and the concentrations of TFA and sodium acetate (NaOAc) in the background electrolyte. The optimized separation occurred using 200 mM TFA/20 mM NaOAc in MeOH/acetonitrile (10:90, v/v), providing highly efficient baseline separation of the open-cage fullerenes within 5 min. The migration time repeatability for the three analytes was less than 1% (relative standard deviation). Thus, NACE is a rapid, useful alternative to high-performance liquid chromatography for the separation of open-cage fullerenes.     

Novel nonaqueous capillary electrophoresis separation and determination of bioactive flavone derivatives in Chinese herbs

Nonaqueous CE (NACE) coupled to UV detection is described for the separation and determination of bioactive flavone derivatives in Chinese herbs extraction. After optimization of electrophoresis parameters, including the electrolyte nature and the organic solvent composition, a reliable separation of the analytes in an ACN/methanol (60:40, v/v) mixture containing 80 mM Tris and 10 mM sodium cholate was performed. The detection was performed at 254 nm. Method performances, including migration time and peak area reproducibility, linearity, sensitivity, and accuracy, were evaluated. The method was applied to determine bioactive flavone derivatives in seven Chinese herbs.