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1.
The aim of the current study was to optimise and validate the methodology for determination of γ‐hydroxybutyric acid (GHB) in saliva by CE combined with a contactless conductivity detector (C4D) and indirect UV absorbance detection (λABS = 210 nm). The optimized BGE, consisting of 8.5 mM maleic acid, 17 mM arginine, 255 μM cetyltrimethylammonium bromide (CTAB), and 15% acetonitrile, was evaluated for the separation of GHB in saliva within 6 min. The performance characteristics of the CE‐C4D‐indirect UV methodology was validated. The instrument detection and quantification limits were 0.49 and 1.6 mg/L for C4D, and 5.1 mg/L and 17.0 mg/L for indirect UV, respectively. The linearity was obtained over the range from 2.5 to 400 mg/L for C4D and from 12.5 to 400 mg/L for indirect UV. The interday precisions were within 2.3–5.7% and intraday precisions were within 1.6–9.0% for C4D as well as 2.1–9.3%, 5.6–10.1% for indirect UV in spiked saliva, respectively. The recoveries were within 87.2–104.4%. The matrix effects were +53.2% for small concentrations up to 25 mg/L for C4D and +23.6% for concentrations up to 75 for mg/L for indirect UV detection. No matrix effects were observed for higher concentration levels. In conclusion, CE‐C4D‐indirect UV can offer a rapid, accurate, sensitive, and definitive method for the determination of GHB abuse in saliva samples as a forensic screening tool.  相似文献   

2.
Electrochemically co‐deposited sol–gel/Cu nanocomposites have been introduced as a novel, simple and single‐step technique for preparation of solid‐phase microextraction (SPME) coating to extract methadone (MDN) (a synthetic opioid) in urine samples. The porous surface structure of the sol–gel/Cu nanocomposite coating was revealed by scanning electron microscopy. Direct immersion SPME followed by HPLC‐UV determination was employed. The factors influencing the SPME procedure, such as the salt content, desorption solvent type, pH and equilibration time, were optimized. The best conditions were obtained with no salt content, acetonitrile as desorption solvent type, pH 9 and 10 min equilibration time. The calibration graphs for urine samples showed good linearity. The detection limit was about 0.2 ng mL−1. Also, the novel method for preparation of nanocomposite fiber was compared with previously reported techniques for MDN determination. The results show that the novel nanocomposite fiber has relatively high extraction efficiency.  相似文献   

3.
Trace levels analysisbenzalkonium chlorides (BAKs) in river water and wastewater treatment plants (WWTP) effluents were determined by capillary electrophoresis (CE) following solid‐phase extraction (SPE) and salting‐out extraction. Salting‐out extraction using an appropriate ratio of sodium chloride (NaCl) and acetonitrile (ACN) mixed with concentrated SPE elutant was capable of providing more than 500‐fold enhancement in detection sensitivity. The ratios of ACN and NaCl for salting‐out extraction were investigated and optimized. Matrix interference was eliminated by salting‐out extraction. Limits of quantitation of BAK homologues were achieved at 0.1 μg/L in 250 mL water samples. Recoveries of BAKs in various spiked water samples ranged from 70% to 84% with relative standard deviation (RSD) less than 9%. Trace amounts of total BAKs were detected in river water and WWTP effluent samples ranging from 27 to 145 μg/L at the first time by CE.  相似文献   

4.
Wall W  Chan K  El Rassi Z 《Electrophoresis》2001,22(11):2320-2326
In this report, we describe a surfactant-mediated electrokinetic capillary chromatography (SM-EKC) system for the separation of 9-fluoroenylmethyl chloroformate (FMOC)-derivatized anilines by capillary electrophoresis (CE). The SM-EKC system consisted of dioctyl sulfosuccinate (DOSS)/acetonitrile mixtures and was suited for the CE separation of the relatively hydrophobic FMOC-aniline analytes and other neutral compounds, e.g. alkylphenyl ketones. While the organic modifier acetonitrile (ACN) allowed the solubilization of the hydrophobic solutes and maintained the DOSS surfactant in its monomeric form by inhibiting micellization, the DOSS surfactant associated with the FMOC anilines to a varying degree thus leading to their differential migration and separation. Under these conditions, the FMOC-anilines were readily detected at the 10(-6) M level by UV at 214 nm and at the 10(-8) M level by laser-induced fluorescence (LIF) using a solid-state UV laser operating at 266 nm line as the excitation wavelength. The FMOC precolumn derivatization was also readily performed in lake water spiked with anilines at near the limit of detection (LOD) level. The lake water matrix showed no significant effects on the extent of derivatization at the LOD level as well as on the detection of the analytes due to the selectivity of the FMOC derivatization. The derivatization and detection of spiked lake water necessitated only the removal of microparticles by microfiltration prior to derivatization and detection.  相似文献   

5.
To pursue optimum condition in liquid‐liquid‐liquid microextraction (LLLME), extraction parameters dominating extraction efficiency were investigated by theoretical considerations. The theoretical considerations discussed equilibrium model for equilibrium LLLME and non‐equilibrium model for dynamic LLLME. A method described here is a dynamic LLLME technique combined with high‐performance liquid‐chromatography ultraviolet absorbance detection (HPLC/UV) to determine traces of nitrophenols in water. Analytical parameters such as organic phase, acceptor phase volume, sample agitation, extraction time, acceptor phase NaOH concentration, donor phase HCl concentration, salt addition, and absorption wavelength were identified as variable settings. Relative standard deviation (RSD, 1.8‐4.4%), coefficient of estimation (R2, 0.9994‐0.9999), and detection limit (0.032‐0.065 ng mL?1) were achieved under the variable settings. The proposed method was successfully applied to the analysis of a lake water sample, and the relative recoveries of nitrophenols from spiked water sample were up to 92.5%. The variable settings of LLLME close to optimization was responsible for an acceptable extraction efficiency.  相似文献   

6.
In this study, we investigated the performance of several commercial sorbents (Sep‐pack® C18, tC18, C8 and tC2, Oasis® HLB, Isolute® ENV+, Strata?‐X and Oasis® MCX) for the determination of opioid peptides by solid‐phase extraction coupled on‐line to capillary electrophoresis (SPE‐CE). First, standard solutions were analyzed in order to achieve the lowest LOD and the best electrophoretic separations using UV detection. The best results were obtained using C18, C8 and tC2 sorbents, which were examined for the analysis of spiked human plasma samples. A double‐step sample clean‐up pretreatment, which consisted of precipitation with acetonitrile and filtration, was needed to prevent saturation of the on‐line SPE microcartridge. The filtration step was critical to obtain optimum analyte recovery and to clean up the sample matrix. A range of centrifugal filters and filtration conditions were tested and the recoveries of the sample pretreatment were evaluated by CE‐ESI‐MS. The LODs attained through SPE‐CE‐UV were approximately ten‐fold better with C18 than with C8 and tC2. The 0.1 μg/mL LODs achieved by C18‐SPE‐CE‐UV were further improved until we could detect 1 ng/mL concentrations of opioid peptides in plasma samples by C18‐SPE‐CE‐ESI‐MS, due to the outstanding selectivity of the MS detection.  相似文献   

7.
This study describes a comparison between LC‐UV and LC–MS method for the simultaneous analyses of a few disease‐modifying agents of multiple sclerosis. Quantitative determination of fampridine (FAM), teriflunomide (TFM) and dimethyl fumarate (DMF) was performed in human plasma with the recovery values in the range of 85–115%. A reversed‐phase high‐performance liquid chromatography (HPLC) with UV as well as MS detection is used. The method utilizes an XBridge C18 silica column and a gradient elution with mobile phase consisting of ammonium formate and acetonitrile at a flow rate of 0.5 mL min?1. The method adequately resolves FAM, TFM and DMF within a run time of 15 min. Owing to low molecular weights, the estimation of DMF and FAM is more versatile in UV than MS detection. With LC‐UV, the detection limits of FAM, TFM and DMF were 0.1, 0.05, 0.05 μg and the quantification limit for all the analytes was 1 μg. With LC–MS, the detection and quantification limits for all of the analytes were 1 and 5 ng, respectively. The two techniques were completely validated and shown to be reproducible and sensitive. They were applied to a pharmacokinetic study in rats by a single oral dose. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

8.
Jiankuan Duan  Bin Hu  Man He 《Electrophoresis》2012,33(19-20):2953-2960
In this paper, a new method of nanometer‐sized alumina packed microcolumn SPE combined with field‐amplified sample stacking (FASS)–CE‐UV detection was developed for the speciation analysis of inorganic selenium in environmental water samples. Self‐synthesized nanometer‐sized alumina was packed in a microcolumn as the SPE adsorbent to retain Se(IV) and Se(VI) simultaneously at pH 6 and the retained inorganic selenium was eluted by concentrated ammonia. The eluent was used for FASS–CE–UV analysis after NH3 evaporation. The factors affecting the preconcentration of both Se(IV) and Se(VI) by SPE and FASS were studied and the optimal CE separation conditions for Se(IV) and Se(VI) were obtained. Under the optimal conditions, the LODs of 57 ng L?1 (Se(IV)) and 71 ng L?1 (Se(VI)) were obtained, respectively. The developed method was validated by the analysis of a certified reference material of GBW(E)080395 environmental water and the determined value was in a good agreement with the certified value. It was also successfully applied to the speciation analysis of inorganic selenium in environmental water samples, including Yangtze River water, spring water, and tap water.  相似文献   

9.
Alberti  Agnes  Blazics  Balazs  Kery  Agnes 《Chromatographia》2008,67(1):107-111

A reversed-phase high-performance liquid chromatography method with UV detection was developed for determination of [(N-morpholine)methylene]daunorubicin hydrochloride (DD-M) during studies of its stability. In this LC method the following were used: an RP-column, the mobile phase—acetonitrile:methanol:solution A (9:1:10 v/v/v) [solution A contains 2.88 g of sodium laurilsulfate and 1.6 mL of phosphoric acid(V)] with a flow rate of 1.4 mol L−1 and quinine hydrochloride as an internal standard. The detection wavelength was 254 nm. The method was validated with regard to linearity, limit of detection, limit of quantitation, selectivity and precision. Hydrolysis of the DD-M catalyzed by hydrogen ions in hydrochloric acid and a spontaneous reaction of the DD-M degradation under the influence of the water in sodium hydroxide took place. The thermodynamic parameters of these reactions—energy, enthalpy and entropy of activation—were calculated. It was observed that a positive salt effect occurred in hydrochloric acid.

  相似文献   

10.
The present work describes the development and optimization of a capillary (zone) electrophoresis/mass spectrometric (CE/MS) analysis method for polar hydrophilic aromatic sulfonates (ASs). The compounds were detected by negative ion electrospray ionization (NIESI) and selected ion monitoring (SIM). In comparison with CE/UV, for CE/MS a lower-concentration volatile ammonium acetate buffer (5 mM) without organic modifier and a higher separation voltage were better suited for separation. Sensitivity of CE/MS was slightly better than for CF/UV, with the limit of detection (LOD) ranging between 0.1 and 0.4 mg l(-1). For verification of the CE/MS results, ASs were also analysed by ion-pair liquid chromatography/diode array UV detection coupled in series with electrospray mass spectrometry (IPC/DAD/ESI-MS). Real water samples of different waste water treatment plants (WWTPs) in Catalonia (NE Spain) were extracted by solid-phase extraction (SPE) with LiChrolut EN and analysed with CE/MS and LC/MS. ASs were found in influent and effluent water samples of the WWTPs in the microg l(-1) concentration range. LC/MS offered a higher separation efficiency and sensitivity than CE/MS. Therefore with LC/MS more compounds could be identified in the WWTPs. The persistency of the ASs was distinct: some compounds were well degraded during the water treatment process, while others were quite persistent.  相似文献   

11.
Here, we describe an easy field-amplified sample injection capillary electrophoresis method with UV detection for the separation and detection of free plasma arginine and dimethylated arginines. The analytes were baseline-separated within 22?min by using 50?mmol/L Tris phosphate pH 2.3 as running buffer. The plasma samples were treated with acetonitrile/ammonia for protein elimination, the supernatants were dried, re-swollen in water and directly injected in the capillary without complex cleanup by solid phase extraction and/or tedious sample derivatization procedures. Due to the stacking effects of the electrokinetic injection, it was possible to operate a consistent on-line pre-concentration of the analytes before running the electrophoresis. This procedure allowed to reach a detection limit in the real sample of 10?nmol/L for dimethylated arginines and 20?nmol/L for arginine, thus improving about threefold our previous method, that required a more complicated pre-analytical procedure to concentrate samples. The recovery of plasma ADMA was 99-104% and inter-day CV was less than 3%. The assay performance was evaluated measuring the levels of arginine and its dimethyl derivatives in 50 subjects. The statistical tests for the methods comparison suggest that the data obtained by our new method and by our previous CE assay are similar.  相似文献   

12.
A simple, rapid, and sensitive method based on dispersive liquid–liquid microextraction combined with HPLC‐UV detection applied for the quantification of chlordiazepoxide in some real samples. The effect of different extraction conditions on the extraction efficiency of the chlordiazepoxide drug was investigated and optimized using central composite design as a conventional efficient tool. Optimum extraction condition values of variables were set as 210 μL chloroform, 1.8 mL methanol, 1.0 min extraction time, 5.0 min centrifugation at 5000 rpm min?1, neutral pH, 7.0% w/v NaCl. The separation was reached in less than 8.0 min using a C18 column using isocratic binary mobile phase (acetonitrile/water (60:40, v/v)) with flow rate of 1.0 mL min?1. The linear response (r2 > 0.998) was achieved in the range of 0.005–10 μg mL?1 with detection limit 0.0005 μg mL?1. The applicability of this method for simultaneous extraction and determination of chlordiazepoxide in four different matrices (water, urine, plasma, and chlordiazepoxide tablet) were investigated using standard addition method. Average recoveries at two spiking levels were over the range of 91.3–102.5% with RSD < 5.0% (n = 3). The obtained results show that dispersive liquid–liquid microextraction combined with HPLC‐UV is a fast and simple method for the determination of chlordiazepoxide in real samples.  相似文献   

13.
Rapid and direct online preconcentration followed by CE with capacitively coupled contactless conductivity detection (CE‐C4D) is evaluated as a new approach for the determination of glyphosate, glufosinate (GLUF), and aminophosphonic acid (AMPA) in drinking water. Two online preconcentration techniques, namely large volume sample stacking without polarity switching and field‐enhanced sample injection, coupled with CE‐C4D were successfully developed and optimized. Under optimized conditions, LODs in the range of 0.01–0.1 μM (1.7–11.1 μg/L) and sensitivity enhancements of 48‐ to 53‐fold were achieved with the large volume sample stacking‐CE‐C4D method. By performing the field‐enhanced sample injection‐CE‐C4D procedure, excellent LODs down to 0.0005–0.02 μM (0.1–2.2 μg/L) as well as sensitivity enhancements of up to 245‐ to 1002‐fold were obtained. Both techniques showed satisfactory reproducibility with RSDs of peak height of better than 10%. The newly established approaches were successfully applied to the analysis of glyphosate, glufosinate, and aminophosphonic acid in spiked tap drinking water.  相似文献   

14.
A simple and rapid method has been developed for the analysis of anthracycline antibiotics doxorubicin (DOX) and daunorubicin (DAU) in human serum using mirochip-based capillary electrophoresis (CE) with laser-induced fluorescence (LIF) detection. In this study, method development included studies of the effect of buffer pH, buffer concentration, organic solvents and separation voltage on sensitivity and separation efficiencies for the CE separation of DOX and DAU. Acetonitrile was found to have significantly improved the sensitivity and separation efficiency. The method was validated with regard to reproducibilities, linearity and limit of detection (LOD). The optimum electrophoretic separation conditions were 10 mM sodium tetraborate buffer at pH 9.5 with 40% acetonitrile (V/V) and a separation voltage of 2.1 kV. DOX and DAU were separated in 60 s under the optimum separation conditions. Linear relationships were obtained between the concentration and peak area (or peak height) in the 1–75 µg mL− 1 range and with the detection limits of 0.3 and 0.2 μg mL− 1 for DOX and DAU, respectively. The stability of both migration time and peak height of the analytes showed relative standard deviations of less than 5% (n = 9). The potential of this method was verified by spiking a human serum sample with the two drugs and analyzing the recovery ratios.  相似文献   

15.
The lipophillic ammonium salt of 1‐pyrrolidine dicarbodithioic acid (PCDT) (I) was introduced as a new selective ionophore for an iron selective electrode. In addition, the effect of immobilization of 18‐crown‐6 (18CE6) (membrane type‐II), on the electrode performance was discussed. The slope of the PCDT‐based (I) electrode was (20 mV/decade). The linear concentration range was (10?5–10?1 M) after one day doping. The detection limit for electrode type‐(II) was (1.3×10?6 M). For membrane with only 18CE6 (type‐III) the linear range and the detection limit were improved (10?5–10?1 M and 3.2×10?6 M, respectively). The pH‐range was between 5–11 for type‐II, and III electrodes, while it was 7–11 for type‐I electrode. Most of the common cations were tested for the evaluation of the electrode selectivity with correlation to the ionic radii of the tested cations. Among them only Ag+ and Pb2+ were the real interference for type‐III electrode. Application of using the electrode for the determination of iron in lubrication oil samples was performed with RSD (1.77–2.7%) and (1.01–2.3%) for type‐II and III electrodes, respectively. The corresponding recovery ranges were (93.0–99.9%) and (96.3–100%). The obtained results were compared to those of an atomic absorption spectrophotometric method.  相似文献   

16.
In this work, a novel and simple analytical method using capillary electrophoresis (CE) with capacitively coupled contactless conductivity detection (C4D) is proposed for the determination of the polyols erythritol, maltitol, xylitol, and sorbitol in sugar‐free chocolate. CE separation of the polyols was achieved in less than 6 min, and it was mediated by the interaction between the polyols and the borate ions in the background electrolyte, forming negatively charged borate esters. The extraction of the polyols from the samples was simply obtained using ultra‐pure water and ultrasonic energy. Linearity was assessed by calibration curves that showed R2 varying from 0.9920 to 0.9976. The LOQs were 12.4, 15.9, 9.0, and 9.0 μg/g for erythritol, maltitol, xylitol, and sorbitol, respectively. The accuracy of the method was evaluated by recovery tests, and the obtained recoveries varied from 70 to 116% with standard deviations ranging from 0.2 to 19%. The CE‐C4D method was successfully applied for the determination of the studied polyols in commercial samples of sugar‐free chocolate.  相似文献   

17.
Paralytic shellfish toxins (PSTs) are produced by marine and freshwater microalgae and accumulate in shellfish including mussels, oysters, and scallops, causing possible fatalities when inadvertently consumed. Monitoring of PST content of shellfish is therefore important for food safety, with currently approved methods based on HPLC, using pre‐ or postcolumn oxidation for fluorescence detection (HPLC‐FLD). CE is an attractive alternative for screening and detection of PSTs as it is compatible with miniaturization and could be implemented in portable instrumentation for on‐site monitoring. In this study, CE methods were developed for C4D, FLD, UV absorption detection, and MS—making this first report of C4D and FLD for PSTs detection. Because most oxidized toxins are neutral, MEKC was used in combination with FLD. The developed CZE‐UV and CZE‐C4D methods provide better resolution, selectivity, and separation efficiency compared to CZE‐MS and MEKC‐FLD. The sensitivity of the CZE‐C4D and MEKC‐FLD methods was superior to UV and MS, with LOD values ranging from 140 to 715 ng/mL for CZE‐C4D and 60.9 to 104 ng/mL for MEKC‐FLD. With the regulatory limit for shellfish samples of 800 ng/mL, the CZE‐C4D and MEKC‐FLD methods were evaluated for the screening and detection of PSTs in shellfish samples. While the CZE‐C4D method suffered from significant interferences from the shellfish matrix, MEKC‐FLD was successfully used for PST screening of a periodate‐oxidized mussel sample, with results confirmed by HPLC‐FLD. This confirms the potential of MEKC‐FLD for screening of PSTs in shellfish samples.  相似文献   

18.
Electromembrane extraction (EME) and CE with capacitively coupled contactless conductivity detection (CE‐C4D) was applied to rapid and sensitive determination of perchlorate in drinking water and environmental samples. Porous polypropylene hollow fiber impregnated with 1‐heptanol acted as a supported liquid membrane (SLM) and perchlorate was transported and preconcentrated in the fiber lumen on application of electric field. High selectivity of perchlorate determination and its baseline separation from major inorganic anions was achieved in CE‐C4D using background electrolyte solution consisting of 7.5 mM L ‐histidine and 40 mM acetic acid at pH 4.1. The analytical method showed excellent parameters in terms of reproducibility; RSD values for migration times and peak areas at a spiked concentration of 15 μg/L of perchlorate (US EPA recommended limit for drinking water) were below 0.2 and 8.7%, respectively, in all examined water samples. Linear calibration curves were obtained for perchlorate in the concentration range 1–100 μg/L (r2≥0.999) with limits of detection at 1 μg/L for tap water and at 0.25–0.35 μg/L for environmental and bottled potable water samples. Recoveries at 15 μg/L of perchlorate were between 95.9 and 106.7% with minimum and maximum recovery values for snow and bottled potable water samples, respectively.  相似文献   

19.
A sensitive capillary electrophoresis (CE) method with chemiluminescence (CL) detection was developed for the determination of homocysteine (HCys) in human plasma. In this work, N‐(4‐aminobutyl)‐N‐ethylisoluminol was used as tagging reagent to label the analyte for achieving high assay sensitivity. N‐(4‐Aminobutyl)‐N‐ethylisoluminol‐tagged HCys after CE separation reacted with hydrogen peroxide in the presence of horseradish peroxidase, producing CL emission. Experimental conditions for labeling analyte, CE separation, and CL detection were studied. The CL intensity was proportional to the concentration of HCys in the range of 2.5×10?8 to 5.0×10?6 M. Detection limit (S/N=3) was 7.6×10?9 M. Human plasma samples from healthy donors were analyzed by the presented method. HCys levels were found to be in the range of 9.50–15.3 μM.  相似文献   

20.
HPLC and CE methods were employed to determine the quaternary benzo[c]phenanthridine alkaloid sanguinarine in biological matrices (rat hepatocytes, human gingival fibroblasts, feed, porcine faeces, body fluids and tissues). HPLC was carried out on a C18 column using gradient elution and ion pairing techniques with 1‐heptanesulfonic acid as ion pairing agent under acidic conditions. The detection limit for fluorimetric detection at λex = 327 nm and λem = 577 nm was 3 nM sanguinarine. CE analyses were performed in 50 mM phosphate‐Na buffer pH 2.5, with 150 mM SDS used for pre‐concentration by the sweeping effect. This experimental configuration allows injecting the total capillary length with sanguinarine sample. The detection limit for UV detection at 285 nm was 12 nM. Both methods are suitable for analysing submicromolar quantities of sanguinarine in biological materials. The HPLC method is more sensitive than CE because it uses fluorescence detection.  相似文献   

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