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1.
《Analytical letters》2012,45(13):1991-2000
A graphene-based solid phase extraction (SPE) technique was developed for the extraction of parabens (methylparaben, ethylparaben, propylparaben, and butylparaben) in cosmetic samples, followed by determination by capillary electrophoresis (CE). The SPE extraction parameters such as eluent reagent and eluent volume, washing solution, sample pH, and flow-rate of sample loading, were investigated for satisfied recoveries. The running buffer, consisting of 25 mM borate solution (pH 10.0), was used for the separation of four parabens with the CE method within 10 min. The limits of detection were 0.14 mg/L, 0.13 mg/L, 0.15 mg/L, and 0.10 mg/L for methylparaben, ethylparaben, propylparaben, and butylparaben, respectively, and the mean recoveries obtained were between 62.6% and 100.4%. The developed method was used for the determination of parabens in real cosmetic products.  相似文献   

2.
Proteins were concentrated and separated in 0.6% poly(ethylene oxide) (PEO) solution using a capillary filled with Tris-borate (TB) buffer prior to analysis and detected by laser-induced native fluorescence using a pulsed Nd:YAG laser. During the concentration and separation, PEO solution entered the capillary by electroosmotic flow. When proteins dissolved in high salts (phosphate-buffered saline) were separated using 0.6% PEO solution prepared in 200 mM TB buffer, pH 9.0, the limits of detection (LODs) at signal-to noise ratios=3 for carbonic anhydrase (CA) and alpha-lactalbumin (alpha-lac) were on the levels of sub microM and microM, respectively. The LOD values compared to those obtained in 38 mM TB buffer were relatively high, which is likely due to salt quenching, Joule heating and poor stacking. To improve sensitivity for analysis of proteins in high-conductivity media, two on-line concentration approaches without desalting were developed. When using a capillary filled with 1.5 M TB buffer, pH 10.0, and PEO solution prepared in 800 mM TB buffer, pH 9.0, the LOD values for CA and alpha-lac were 13.8 nM and 126.0 nM, respectively, which were about 4.7 and 11.2-fold sensitivity enhancements compared to those obtained by a conventional hydrodynamic injection (30 cm height for 10 s), respectively. The sensitivity was further improved by injecting a short plug of low pH buffer after protein injection using a capillary filled with 1.5 M TB buffer, pH 10.0, and PEO solution prepared in 400 mM TB buffer, pH 9.0. A linear relationship between the peak height and the injection volume up to 0.81 microl was obtained and the LOD values for CA and alpha-lac were down to 4.7 and 37.8 nM.  相似文献   

3.
A new approach for the analysis of large-volume naphthalene-2,3-dicarboxaldehyde (NDA) derivatives of amino acids by micellar electrokinetic chromatography (MEKC) in conjunction with a purple light-emitting diode-induced fluorescence detection is described. In order to optimize resolution, speed, and stacking efficiency, a discontinuous condition is essential for the analysis of NDA-amino acid derivatives. The optimum conditions use 2.0M TB (pH 10.0) buffer containing 40mM sodium dodecyl sulfate (SDS) to fill the capillary, deionized water to dilute samples, and 200mM TB (pH 9.0) containing 10mM SDS to prepare 0.6% poly(ethylene oxide) (PEO). Once high voltage is applied, PEO solution enters the capillary via electroosmotic flow and SDS micelles interact and thus sweep the NDA-amino acid derivatives having smaller electrophoretic mobilities than that of SDS micelles in the sample zone. When the aggregates between SDS micelles and NDA amino acid derivatives enter PEO zone, they are stacked due to decrease in electric field and increases in viscosity. Under the optimum conditions, the concentration and separation of 0.53-microL 13 NDA-amino acid derivatives that are negatively charged has been demonstrated by using a 60-cm capillary, with the efficiencies 0.3-9.0x10(5) theoretical plates and the LODs at signal-to-noise ratio 3 ranging from 0.30 to 2.76nM. When compared to standard injection (30-cm height for 10s), the approach allows the sensitivity enhancements over the range of 50-800 folds for the derivatives. The new approach has been applied to the analysis of a red wine sample, with great linearity of fluorescent intensity against concentrations (R(2)>0.98) and the RSD (three repetitive runs in one day) values of the migration times for the ten identified amino acids less than 2.8%.  相似文献   

4.
We describe simultaneous analysis of naphthalene-2,3-dicarboxaldehyde (NDA)-amino acid and NDA-biogenic amine derivatives by CE in conjunction with light-emitting diode-induced fluorescence detection using poly(ethylene oxide) (PEO) solutions containing sodium dodecyl sulfate (SDS). After sample injection, via EOF 0.1% PEO prepared in 100 mM TB solution (pH 9.0) containing 30 mM SDS entered a capillary filled with 0.5 M TB solution (pH 10.2) containing 40 mM SDS. Under this condition, 14 NDA-amino acid and NDA-amine derivatives were separated within 16 min, with high efficiency ((1.0–3.2) × 105 theoretical plates) and sensitivity (LODs at S/N = 3 ranging from 2.06 to 19.17 nM). In the presence of SDS and PEO, analytes adsorption on the capillary wall was suppressed, leading to high efficiency and reproducibility. The intraday analysis RSD values (n = 3) of the mobilities for the analytes are less than 0.52%. We have validated the practicality of this approach by quantitative determination of 9 amino acids in breast cancer cells (MCF-7) and 10 amino acids in normal epithelial cells (H184B5F5/M10). The concentrations of Tau and Gln in the MCF-7 cells were different than those in the H184B5F5/M10 cells, respectively. Our results show the potential of this approach for cancer study.  相似文献   

5.
In this study, separation and determination of nine preservatives ranging from hydrophilic to hydrophobic properties, which are commonly used as additives in various pharmaceutical and cosmetic products, by micellar electrokinetic chromatograpy (MEKC) and microemulsion electrokinetic chromatography (MEEKC) were compared. The effect of temperature, buffer pH, and concentration of surfactant on separation were examined. In MEKC, the separation resolution of preservatives improved markedly by changing the sodium dodecyl sulfate concentration. Temperature and pH of running buffers were used mainly to shorten the magnitude of separation time. However, in order to detect all preservatives in a single run in a MEEKC system, a microemulsion of higher pH was needed. The separation resolution was improved dramatically by changing temperature, and a higher concentration of SDS was necessary for maintaining a stable microemulsion solution, therefore the separation of the nine preservatives in MEEKC took longer than in MEKC. An optimum MEKC method for separation of the nine preservatives was obtained within 9.0 min with a running buffer of pH 9.0 containing 20 mM SDS at 25 degrees C. A separation with baseline resolution was also obtained within 16 min using a microemulsion of pH 9.5 which composed of SDS, 1-butanol, and octane, and a shorter capillary column at 34 degrees C. Finally, the developed MEKC and MEEKC methods determined successfully preservatives in various cosmetic and pharmaceutical products.  相似文献   

6.
A CD‐modified CE method was established for quantitative determination of seven hydroxy acids in cosmetic products. This method involved chemometric experimental design aspects, including fractional factorial design and central composite design. Chemometric experimental design was used to enhance the method's separation capability and to explore the interactions between parameters. Compared to the traditional investigation that uses multiple parameters, the method that used chemometric experimental design was less time‐consuming and lower in cost. In this study, the influences of three experimental variables (phosphate concentration, surfactant concentration, and methanol percentage) on the experimental response were investigated by applying a chromatographic resolution statistic function. The optimized conditions were as follows: a running buffer of 150 mM phosphate solution (pH 7) containing 0.5 mM CTAB, 3 mM γ‐CD, and 25% methanol; 20 s sample injection at 0.5 psi; a separation voltage of ?15 kV; temperature was set at 25°C; and UV detection at 200 nm. The seven hydroxy acids were well separated in less than 10 min. The LOD (S/N = 3) was 625 nM for both salicylic acid and mandelic acid. The correlation coefficient of the regression curve was greater than 0.998. The RSD and relative error values were all less than 9.21%. After optimization and validation, this simple and rapid analysis method was considered to be established and was successfully applied to several commercial cosmetic products.  相似文献   

7.
Several strategies, namely, large volume sample stacking (LVSS), field‐amplified sample injection (FASI), sweeping, and in‐line SPE‐CE, were investigated for the simultaneous separation and preconcentration of a group of parabens. A BGE consisting of 20 mM sodium dihydrogenphosphate (pH 2.28) and 150 mM SDS with 15% ACN was used for the separation and preconcentration of the compounds by sweeping, and a BGE consisting of 30 mM sodium borate (pH 9.5) was used for the separation and preconcentration of the compounds by LVSS, FASI, and in‐line SPE‐CE. Several factors affecting the preconcentration process were investigated in order to obtain the maximum enhancement of sensitivity. The LODs obtained for parabens were in the range of 18–27, 3–4, 2, and 0.01–0.02 ng/mL, and the sensitivity evaluated in terms of LODs was improved up to 29‐, 77‐, 120‐, and 18 400‐fold for sweeping, LVSS, FASI, and in‐line SPE‐CE, respectively. These preconcentration techniques showed potential as good strategies for focusing parabens. The four methods were validated with standard samples to show the potential of these techniques for future applications in real samples, such as biological and environmental samples.  相似文献   

8.
We report the separation of polycyclic aromatic hydrocarbons (PAHs) using 0.1% poly(ethylene oxide) (PEO) in micellar electrokinetic chromatography (MEKC). In the presence of PEO, adsorption of PAHs on the capillary wall was reduced, leading to better resolution and reproducibility. Effects of tetrapentylammonium iodide (TPAI), dextran sulfate (DS), methanol, and sodium lauryl sulfate (SDS) on the separation of PAHs were elucidated. In terms of resolution and speed, DS, compared to TPAI, is a better additive for separation of PAHs. When using 0.1% PEO solution containing 45% methanol, 50 mM SDS, and 0.02% DS, separation of 10 PAHs containing 2 to 5 benzene rings was accomplished in less than 12 min at 15 kV in a commercial CE system. The method has also been tested for separating seven PAHs with high quantum yields when excited at 325 nm using a He-Cd laser. Unfortunately, separation of the seven PAHs was not achieved and sensitivity diminished under the same conditions. To optimize sensitivity, resolution and speed, a stepwise technique in MEKC has been proposed. The seven PAHs were resolved in 35 min at 15 kV when separation was performed in 0.1% PEO solution containing 35 mM SDS, 40% methanol and 0.02% DS for 2 min, and subsequently in 0.1% PEO solution containing 20 mM SDS, 50% methanol, and 0.02% DS.  相似文献   

9.
We describe the stacking and separation of d- and l-aspartic acid (Asp) by capillary electrophoresis (CE) with light-emitting diode-induced fluorescence detection (LEDIF). In the presence of cyanide, d- and l-Asp were derivatized with naphthalene-2,3-dicarboxaldehyde (NDA) to form fluorescent derivatives prior to CE-LEDIF. The separation of NDA-derivatized d- and l-Asp was accomplished using a discontinuous system - buffer vials contained a solution of 0.6% poly(ethylene oxide) (PEO), 150 mM sodium dodecyl sulfate (SDS), and 60 mM hydroxypropyl-β-cyclodextrin (Hp-β-CD), while a capillary was filled with a solution of 150 mM SDS and 60 mM Hp-β-CD. The role of PEO, Hp-β-CD, and SDS is to act as a concentrating media, as a chiral selector, and as a pseudostationary phase, respectively. This discontinuous system could be employed for the stacking of 600 nL of NDA-derivatized d- and l-Asp without the loss of chiral resolution. The stacking mechanism is mainly based on the difference in viscosity between sample zone and PEO as well as SDS sweeping. The limits of detection at signal-to-noise of 3 for d- and l-Asp were down to 2.4 and 2.5 × 10−10 M, respectively. Compared to normal sample injection volume (25 nL), this stacking approach provided a 100- and 110-fold improvement in the sensitivity of d- and l-Asp, respectively. This method was further applied for determining d- and l-Asp in cerebrospinal fluid, soymilk, and beer.  相似文献   

10.
Huang CC  Hsieh MM  Chiu TC  Lin YC  Chang HT 《Electrophoresis》2001,22(20):4328-4332
We report concentration and separation of DNA in the presence of electroosmotic flow (EOF) using poly(ethylene oxide) (PEO) solution. DNA fragments migrating against EOF stacked between the sample zone and PEO solution. To maximize the injection volume, several factors, such as concentrations of Tris-borate (TB) buffer and PEO solution, capillary size, and matrix, were carefully evaluated. The use of 25 mM TB buffers, pH 10.0, containing suitable amounts (less than 10 mM) of salts, such as sodium chloride, sodium phosphate, and sodium acetate, to prepare DNA is essential for the concentration of large-volume samples. In the presence of salts, the peaks also became sharper and the fluorescence intensity of DNA complexes increased. Using 2.5% PEO and a 150 microm capillary filled with 400 mM TB buffer, pH 10.0, up to 5 microL DNA samples (phiX 174 RF DNA-HaeIII digest or the mixture of pBR 322/HaeIII, pBR 328/Bg/I, and pBR 328/HinfI digests) have been analyzed, resulting in more than 400-fold improvements in the sensitivity compared to that by conventional injections (ca. 36 nL). Moreover, this method allows the analysis of 3.5 microL PCR products amplified after 17 cycles without any sample pretreatment.  相似文献   

11.
Although polyethylene oxide (PEO) offers several advantages as a sieving polymer in SDS capillary polymer electrophoresis (SDS-CPE), solution properties of PEO cause deterioration in the electrophoresis because PEO in solution aggregates itself, degrades into smaller pieces, and forms polymer-micelle complexes with SDS. We examined protein separation on SDS-CPE with PEO as a sieving matrix in four individual buffer solutions: Tris-CHES, Tris-Gly, Tris-Tricine, and Tris-HCl buffers. The solution properties of PEO as a sieving matrix in those buffers were examined by dynamic light scattering (DLS) and by surface tension. Preferential SDS adsorption onto PEO disturbed protein-SDS complexation and impaired the protein separation efficiency. Substantial adsorption of SDS to PEO was particularly observed in Tris-Gly buffer. The Tris-CHES buffer prevented SDS from adsorbing onto the PEO. Only Tris-CHES buffer achieved separation of six proteins. This study demonstrated efficient protein separation on SDS-CPE with PEO.  相似文献   

12.
De Rossi A  Desiderio C 《Electrophoresis》2002,23(19):3410-3417
A fast capillary electrochromatographic method was developed for the analysis of paraben preservatives in drugs and cosmetics in the presence of their main metabolite and/or impurity, 4-hydroxybenzoic acid. The separation was optimized in a 75 num ID capillary, fully packed with 5 num C18 stationary phase, studying the effects of mobile phase pH and composition (buffer type and organic solvent content). The mobile phase 5 mM ammonium formate, pH 3.0, containing 65% acetonitrile allowed us to obtain the baseline separation of methyl-, ethyl-, propyl-, butyl-, and benzylparabens from a mixture in less than 2.5 min with repeatability and linearity using the short-end injection method (8 cm separation capillary effective length). Under the optimum experimental conditions, the method provided high separation efficiency for parabens, in the range of 129 312-140 325 number of theoretical plates per meter, and analyte quantitation limits (LOQs) in the range of 1.25-2.50 nug/mL. The method was successfully applied to the quantitative analysis of paraben preservatives in pharmaceutical and cosmetic industrial samples with direct injection or after reduced sample pretreatment.  相似文献   

13.
Chiu TC  Tu WC  Chang HT 《Electrophoresis》2008,29(2):433-440
We describe the stacking and separation of proteins by CE under discontinuous conditions in conjunction with light-emitting diode induced fluorescence (LEDIF) detection using a violet LED at 405 nm. The proteins were derivatized with naphthalene-2,3-dicarboxaldehyde (NDA) to form NDA-protein derivatives prior to CE-LEDIF analysis. During the separation, poly(ethylene oxide) (PEO) solution containing CTAB enters from the cathodic inlet to the capillary via electroosomotic flow (EOF). The optimum conditions are: the capillary was filled with 50 mM glycine buffer (pH 9.0) containing 1.0 mM CTAB, NDA-protein derivatives were prepared in deionized water containing 1.0 mM CTAB, and 0.6% PEO was prepared in 50 mM glycine (pH 9.0) containing 2.0 mM CTAB. The analysis of four NDA-protein derivatives is fast (<3 min), with RSD <1.5% in terms of migration time. In order to improve the sensitivity of NDA-protein derivatives, a stacking approach based on increases in viscosity and electric field, as well as sieving was applied. The efficient stacking approach provides LODs (S/N = 3) of 2.41, 0.59, 0.61, and 4.22 nM for trypsin inhibitor, HSA, beta-lactoglobulin, and lysozyme, respectively. In addition, we also applied the stacking approach to determination of the concentration of HSA in one urine sample, which was determined to be 0.31 +/- 0.05 microM (n = 3).  相似文献   

14.
以十二烷基硫酸钠(SDS)胶束为准固定相,考察了头孢哌酮、头孢哌酮S-异构体、头孢哌酮杂质A及其他未知杂质在胶束电动毛细管色谱(MECC)分离模式下的分离行为。研究了运行缓冲液的pH值、磷酸盐浓度、SDS浓度、甲醇体积分数、分离电压、分离温度等因素对头孢哌酮、S-异构体、头孢哌酮杂质A及其他杂质的迁移时间、分离度以及可分离出的杂质个数的影响。结果发现,这些因素对头孢哌酮与诸杂质间的分离及检测有显著的影响,尤以pH值为最。它不仅影响它们的迁移时间和分离效率,还直接影响头孢哌酮及其杂质峰的检测。优化后的分离条件:运行缓冲液为70 mmol/L磷酸盐-100 mmol/L SDS (pH 6.5),分离电压为15 kV,分离温度为25 ℃。在此条件下,用非涂渍石英毛细管51.0 cm×75 μm(有效长度42.5 cm),压力进样5 kPa×5 s,在254 nm波长下进行检测,可分离出28个杂质,诸杂质彼此间及与头孢哌酮间可得到有效分离。并将该方法成功地用于测定注射用头孢哌酮钠的含量和有关物质,结果令人满意。  相似文献   

15.
Summary Four parabens (esters of 4-hydroxybenzoic acid), effective preservatives against the growth of bacteria, yeast, and mold in numerous industrial products, have been used in this work as model compounds to demonstrate the resolving power of capillary electrophoresis (CE). The simultaneous determination of methyl-(MP), ethyl-(EP), propyl-(PP), and butylparaben (BP) was achieved by capillary zone electrophoresis (CZE) with UV diode-array detection at 294 nm. When run voltage, temperature, and electrolyte concentration and pH were optimized the most effective separation was achieved within 7 min by use of 50 cm (effective length) fused silica capillary tubing and operation at 25kV and 20°C. Background electrolyte comprising 35 mM tetraborate buffer adjusted to pH 10.0 gave the best results. The limits of detection of the optimized method ranged from 0.65 μg mL−1 for BP to 0.81 μg mL−1 for MP; the relative standard deviation was between 0.35 and 0.50%. These results showed that the method enables the determination of the four parabens in commerially available cosmetic and pharmaceutical preparations containing some of the parabens and in an unidentified canned berry fruit juice.  相似文献   

16.
The main constituents of artichoke extract were separated by micellar electrokinetic chromatography (MEKC), using a buffer consisting of 100 mM sodium dodecyl sulfate (SDS) in 20 mM sodium dihydrogen phosphate, 20 mM disodium tetraborate (pH 8.6) as background electrolyte. Optimum separation voltage of 28 kV (positive polarity) and a capillary temperature of 25 degrees C gave the best analysis. The UV detection was performed at 200 nm. The method was successfully used to analyze plant and drug samples as well as for the study of artichoke antioxidant activity. The quantitative MEKC results were in good agreement to those obtained previously by reversed-phase high-performance liquid chromatography (RP-HPLC).  相似文献   

17.
The operating parameters that affect the performance of the online preconcentration technique “analyte focusing by micelle collapse‐MEKC (AFMC‐MEKC)” were examined using a multivariate approach involving experimental design to determine the sunscreen agents in cosmetics. Compared to the single‐variable approach, the advantage of the multivariate approach was that many factors could be investigated simultaneously to obtain the best separation condition. A fractional factorial design was used to identify the fewest significant factors in the central composite design (cCD). The cCD was adopted for evaluating the location of the minimum or maximum response in this study. The influences of the experimental variables on the response were investigated by applying a chromatographic exponential function. The optimized condition and the relationship between the experimental variables were acquired using the JMP software. The ANOVA analysis indicated that the Tris pH value, SDS concentration, and ethanol percentage influenced the separation quality and significantly contributed to the model. The optimized condition of the running buffer was 10 mM Tris buffer (pH 9.5) containing 60 mM SDS, 7 mM γ‐CD, and 20% v/v ethanol. The sample was prepared in 100 mM Tris buffer (pH 9.0) containing 7.5 mM SDS and 20% v/v ethanol. The SDS concentration in the sample matrix was slightly greater than the CMC value that makes the micelle be easily collapsed and the analytes be accumulated in the capillary. In addition, sunscreen agents in cosmetics after 1000‐fold dilution were successfully determined by AFMC‐MEKC.  相似文献   

18.
In this work, a PVP‐stabilized graphene was used in MEKC for the separation of tanshinones. Seven structurally similar tanshinones were studied, that is, tanshinone IIB, dihydrotanshinone I, tanshinone I, cryptotanshinone, 1,2‐dihydrotanshinone I, miltirone, and tanshinone IIA. To achieve optimal conditions, graphene concentration, sample solvent composition, SDS concentration, 2‐propanolconcentration, and buffer pH were investigated. At a separation voltage of 30 kV and a 41.5 cm effective length fused‐silica capillary, good resolution within 12 min was performed using 10 mM borate buffer (pH 9.3) containing 30 mM SDS, 10% v/v 2‐propanol and 6 μg/mL graphene. The method was validated in terms of linearity (r2 > 0.9970), intra‐ and inter‐day precision were less than 3.56 and 4.83%, respectively. The proposed method was then successfully applied to Danshentong capsule, an herbal preparation from Salvia miltiorrhiza. Our results indicated the high separation efficiency of PVP‐stabilized graphene provided new opportunities for the analysis of complex samples.  相似文献   

19.
We describe a segmental filling method for the analysis of SYPRO Red labeled sodium dodecyl sulfate (SDS)-proteins (SRSPs) by capillary electrophoresis-laser induced fluorescence (CE-LIF) with electroosmotic counterflow of poly(ethylene oxide) (PEO). It is shown that SDS and salt play a crucial role in determining the fluorescence intensity of the SRSP. Although the fluorimetric measurements reveal that the SRSPs fluoresce strongly in Tris-borate (TB) buffer containing 0.1% SDS and high concentrations of NaCl (100 mM), these conditions are not appropriate to CE in view of Joule heating. To overcome that impediment, we applied a plug of 0.1% SDS (1/5 to 1/3 of the injection volume) prior to injection of samples (0.64 microL) prepared in TB buffer containing 50 mM NaCl and SYPRO Red. When using a background electrolyte of 0.6% PEO in TB buffer containing NaCl, electroosmotic counterflow of the analytes allows one to concentrate large sample volumes (up to 1/3 of effective capillary length) in 21 min, with detection of 0.35 and 0.10 nM for bovine serum albumin and casein, respectively. With a linear dynamic range from 10 nM to 5 microM, this method provides the capability of determining the concentration of casein in cow's milk as 0.45 +/- 0.03 mM (n = 5).  相似文献   

20.
Capillary electrophoresis was used for determining Belofors, which are used as optical bleaching agents for improving the whiteness of writing paper. Sodium dodecyl sulfate (SDS) was used as a modifier of capillary walls in the separation of water-soluble Belofors. An optimum buffer electrolyte for separating and determining Belofors was as follows: 0.5 mM sodium hydrogen phosphate, 12.2 mM sodium tetraborate, and 30 mM SDS; pH 9.1. Bleaching agents in 39 samples of paper manufactured in Russia, Finland, Sweden, France, the Czech Republic, and Austria were determined and characterized. Common features for classifying paper types in accordance with brands and manufacturers were found.  相似文献   

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