Three-phase Hollow Fiber Liquid-phase Microextraction Research Articles

The usability of green deep eutectic solvents in hollow fiber Liquid-Phase microextraction for the simultaneous extraction of analytes of different Natures: A comprehensive study

In the current study, a wide range of deep eutectic solvents (DESs) with different properties (hydrophilic, hydrophobic, ionic, and nonionic) were prepared in the initial phase. Subsequently, an assessment was conducted to evaluate some characteristics of the produced DESs, including their stability at room temperature and their capacity to extract three distinct types of analytes (anionic, cationic, and non-ionic) simultaneously through hollow fiber-liquid phase microextraction (HF-LPME) technique. To carry out the extraction procedure, the prepared DESs were inserted into the pores (as supported liquid membrane (SLM)) and lumen of hollow fiber membrane (HF) to apply two-phase and three-phase HF-LPME techniques. After a thorough evaluation, the three-phase HF-LPME technique (HF(3)-LPME) was chosen by using a mixture of menthol/TBAB-based hydrophobic DES (DES-35) as SLM and the mixture of malic acid/citric acid/water-based hydrophilic DES (DES-2) as an extraction solvent in the lumen of HF. All factors affecting the extraction recovery (including pH, extraction time, extraction temperature, stirring speed, and salt effect) were optimized utilizing the one-variable-at-a-time (OVAT) methodology. After applying the extraction procedure, all extracted samples were analyzed using the UV–Vis spectrometer and results were recorded at different wavelengths including 655 nm for Methylene blue, 550 nm for Amaranth, and 375 nm for Quercetin. The calibration graphs showed linearity in the range of 20.0–1500 µg/L, with a limit of detection of 6.2–15.1 µg/L and correlation coefficients higher than 0.9913 for the studied analytes. Moreover, the intra-day RSD, inter-day RSD, preconcentration factor (PF), enrichment factors (EF), and extraction recoveries (ER%) were obtained in the range of 3.1–4.8, 3.8–6.7, 125, 102.9–111.4, and 82.3–89.1 %, respectively. The use of the selected DES in the HF-LPME methodology resulted in an ecologically friendly strategy, as evidenced by the use of green metrics from the SPMS tool. The proposed strategy is also considered environmentally friendly due to its use of minimal solvents, waste reduction, and low energy consumption. The proposed technique effectively and simultaneously extractedmethylene blue, amaranth, and quercetin analytes in different real samples.

Deep eutectic solvent as the acceptor phase in three-phase hollow fiber liquid-phase microextraction for the determination of pyrethroid insecticides from environmental water samples prior to HPLC.

In this study, a deep eutectic solvent as the acceptor phase was applied in three-phase hollow fiber liquid-phase microextraction for the microextraction of two pyrethroids (permethrin as well as deltamethrin) from environmental water samples prior to HPLC-UV. A deep eutectic solvent was synthesized of tetrabutylammonium bromide-decanoic acid (in a ratio of 1:2) as an acceptor phase and 1-decanol was applied as a supported liquid membrane. Some main variables affecting the extraction recoveries, comprising the types/contents of extraction solvent and acceptor phase, stirring speed, sample phase pH and extraction time, were checked and optimized. Under optimal conditions, the detection limits and limits of quantitation determined were 0.09-0.12 and 0.29-0.39 μgl-1 for deltamethrin and permethrin, respectively. The enrichment factors were 627 and 613, while the relative standard deviations (n= 5) were 4.8 and 5.7%, for deltamethrin and permethrin, respectively. The created technique was assessed as satisfactory to ascertain the two pyrethroid poisons (permethrin and deltamethrin) in environmental water samples.

Three-phase hollow fiber liquid-phase microextraction combined with HPLC for determination of three trace acidic plant growth regulators in Anoectochilus roxburghii (Wall.) Lindl.

The analysis of plant growth regulators presents a challenge due to their trace quantities and complex matrices. A novel, simple, and effective analytical method for the determination of three trace acidic plant growth regulators in Anoectochilus roxburghii (Wall.) Lindl was developed to address this issue. Three-phase hollow fiber liquid-phase microextraction combined with high-performance liquid chromatography was applied for the enrichment, purification, and determination of three acidic plant growth regulators, namely, indole-3-acetic-acid, indole-3-butyric-acid, and (+)-abscisic acid. The factors affecting extraction performance, including extractant species, pH of donor and acceptor phases, salt addition dosage, extraction time, temperature, and stirring rate, were investigated and optimized. Under optimum conditions, the proposed method provided good linearity (R2 , 0.9994-0.9999), low limit of detection (0.038-0.12ng/mL), and acceptable relative recoveries (56.7-117.6%). The enrichment factors were between 153 and 328. The developed method was successfully applied to the enrichment and determination of plant growth regulators in Anoectochilus roxburghii (Wall.) Lindl and exhibited increased purification capacity, higher sensitivity, and decreased organic solvent consumption compared with conventional sample preparation methods. This method may provide atesting platform for the monitoring of plant growth regulator residues, ensuring the safe and effective use of traditional Chinese medicine.

Reverse Micelle Hollow Fiber Liquid-Phase Microextraction Coupled with HPLC for the Determination of Q-Markers of Anthraquinones in Rhubarb and Their Plasma Protein Binding Rates

A three-phase hollow fiber liquid-phase microextraction based on reversed micellar supramolecule was developed and employed for the determination of quality markers of three anthraquinones in Rhubarb and their plasma protein binding rates. Moreover, the extraction mechanism of reversed micellar supramolecule and determination mechanism of plasma protein binding rate by the proposed method are both explored. In this procedure, n-nonanol was impregnated in the wall pores and reverse micelle of tetrabutylammonium chloride/n-nonanol filled in lumen of hollow fibers, which were covered with a thin salt film and used for the microextraction of target compounds prior to HPLC analysis. Important extraction parameters including extraction solvent type, reversed micellar supramolecule type and concentration, sample phase pH, salt concentration, stirring rate, extraction time, and binding time between active compound and plasma protein were investigated. Under the optimized conditions, limits of detection were 0.1–0.4 ng/mL with enrichment factors in the range of 54.2–100.7. The linearities were 0.5–500 ng/mL with r2 ≥ 0.9838. Satisfactory accuracies (relative recoveries 95.7–98.3%) were also obtained. The average plasma protein binding rates of rhein, chrysophenol, and physcion were 96.7%, 41.8%, and 46.7%, respectively. The results showed that the proposed procedure can not only extract and concentrate anthraquinones in Rhubarb, but also determine their plasma protein binding rates.

Hollow fiber liquid phase microextraction combined with total reflection X-ray fluorescence spectrometry for the determination of trace level inorganic arsenic species in waters

In the present study, we investigated the possibilities and drawbacks of hollow fiber liquid phase microextraction (HF-LPME) combined with total reflection X-ray fluorescence (TXRF) spectrometry for the determination of low amounts of inorganic arsenic (As) species in water samples. The obtained results showed that a three-phase HF-LPME system was more suitable to be used in combination with TXRF than the two phase configuration, since lower detection limit and better precision for As determination can be attained. Relevant experimental parameters affecting As extraction (i.e. types of extractant, organic solvent, agitation speed, pH and extraction time) and TXRF analysis (deposition volume and drying mode) were systematically evaluated. It was found that As(III) was more efficiently extracted at pH 13, whereas, optimum pH for As(V) extraction was at pH 8.5. Limits of detection (LOD) achieved using the best analytical conditions meet the requirements of current legislation and allow the determination of inorganic As(V) and As(III) in water. The proposed method was also applied to different spiked environmental water samples for the preconcentration and subsequent determination of trace inorganic As species.

Three-phase hollow-fiber liquid-phase microextraction based on deep eutectic solvent as acceptor phase for extraction and preconcentration of main active compounds in a traditional Chinese medicinal formula.

A three-phase hollow-fiber liquid-phase microextraction based on deep eutectic solvent as acceptor phase was developed and coupled with high-performance capillary electrophoresis for the simultaneous extraction, enrichment, and determination of main active compounds (hesperidin, honokiol, shikonin, magnolol, emodin, and β,β'-dimethylacrylshikonin) in a traditional Chinese medicinal formula. In this procedure, two hollow fibers, impregnated with n-heptanol/n-nonanol (7:3, v/v) mixture in wall pores as the extraction phase and a combination (9:1, v/v) of methyltrioctylammonium chloride/glycerol (1:3, n/n) and methanol in lumen as the acceptor phase, were immersed in the aqueous sample phase. The target analytes in the sample solution were first extracted through the organic phase, and further back-extracted to the acceptor phase during the stirring process. Important extraction parameters such as types and composition of extraction solvent and deep eutectic solvent, sample phase pH, stirring rate, and extraction time were investigated and optimized. Under the optimal conditions, detection limits were 0.3-0.8ng/mL with enrichment factors of 6-114 for the analytes and linearities of 0.001-13μg/mL (r2 ≥ 0.9901). The developed method was successfully applied to the simultaneous extraction and concentration of the main active compounds in a formula of Zi-Cao-Cheng-Qi decoction with the major advantages of convenience, effectiveness, and environmentally friendliness.

Extraction and determination of trace amounts of three anticancer pharmaceuticals in urine by three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents followed by high-performance liquid chromatography.

An automated three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents followed by high-performance liquid chromatography with UV-Vis detection method was applied for the extraction and determination of exemestane, letrozole, and paclitaxel in water and urine samples. n-Dodecane was selected as the supported liquid membrane and its polarity was justified by trioctylphosphine oxide. Acetonitrile was used as an organic acceptor phase with desirable immiscibility having n-dodecane. All the effective parameters of the microextraction procedure such as type of the organic acceptor phase, the supported liquid membrane composition, extraction time, pH of the donor phase, hollow fiber length, stirring rate, and ionic strength were evaluated and optimized separately by a one variable at-a-time method. Under the optimal conditions, the linear dynamic ranges were 1.8-200 (R2 =0.9991), 0.9-200 (R2 =0.9987) and 1.2-200μg/L (R2 =0.9983), and the limits of detection were 0.6, 0.3, and 0.4μg/L for exemestane, letrozole, and paclitaxel, respectively. To evaluate the capability of the proposed method in the analysis of biological samples, three different urinary samples were analyzed under the optimal conditions. The relative recoveries of the three pharmaceuticals were in the range of 91-107.3% for these three analytes.

Evaluation of a Hollow-Fiber Liquid-Phase Microextraction Technique for the Simultaneous Determination of PPI Drugs in Human Plasma by LC-DAD.

This study involved the development, validation and application of a three-phase hollow-fiber liquid-phase microextraction (HF-LPME) and liquid chromatography with diode array detection (LC-DAD) method for the simultaneous determination of the proton pump inhibitor (PPI) drugs omeprazole, pantoprazole and lansoprazole in human plasma. The evaluation of the HF-LPME parameters was crucial for the determination of the drugs and the conditions selected were: 1-octanol as solvent; phosphate buffer at pH 5 as donor phase; borate buffer at pH 10 as acceptor phase; extraction time of 15 min; stirring at 750 rpm and NaCl was added at 5% (w/v). Validation of the method according to US-FDA recommendations showed a good linear range (0.2-2.0 μg/mL) for all analytes, with a determination coefficient >0.9910. Precision was evaluated using intra- and inter-day assays, which showed relative standard deviations (RSD), <15% for all concentrations, with a limit of quantification (LOQ) of 0.2 μg/mL. Accuracy was also assessed at these concentration levels and was in the range from 80 to 130%. Finally, the sensitive, selective and reproducible HF-LPME/LC-DAD developed method was successfully applied to human plasma samples from patients undergoing therapy with the PPI drugs.

In situ derivatization and hollow-fiber liquid-phase microextraction to determine sulfonamides in water using UHPLC with fluorescence detection.

A sensitive method for determining sulfonamides in water was developed and validated through in situ derivatization and hollow-fiber liquid-phase microextraction with ultra-high performance liquid chromatography and fluorescence detection. The target sulfonamides were sulfadiazine, sulfacetamide, sulfamerazine, sulfamethazine, sulfamethoxypyridazine, sulfachloropyridazine, sulfamethoxazole, and sulfisoxazole. Following in situ derivatization with fluorescamine, three-phase hollow-fiber liquid-phase microextraction with an S 6/2 polypropylene hollow-fiber membrane was applied automatically using a multipurpose autosampler. Experimental parameters including derivatization time, choice of organic phase, pH of donor and acceptor phase, stirring rate, extraction temperature and time were optimized. Under optimized conditions, the target sulfonamides achieved excellent linearity with correlation coefficients of 0.9924-0.9994 within the concentration range of 0.05-5μg/L. The limits of detection of the eight sulfonamides were 3.1-11.2ng/L, and the limits of quantification were 10.3-37.3ng/L. Enrichment factors of 0.1 and 5μg/L sulfonamides spiked in lake water were 14-60, and recoveries were 56-113% with relative standard derivations of 3-19%. Applied with the developed method, sulfamerazine and sulfamethoxazole were measurable in both influent and effluent water of the three sewage treatment plants in Guangzhou, China. The developed method was sensitive and provided an alternative method for simultaneously enriching and quantifying multiple sulfonamides in environmental water.

Estimation of the toxicity of sulfadiazine to Daphnia magna using negligible depletion hollow-fiber liquid-phase microextraction independent of ambient pH

The toxicity of ionizable organic compounds to organisms depends on the pH, which therefore affects risk assessments of these compounds. However, there is not a direct chemical method to predict the toxicity of ionizable organic compounds. To determine whether hollow-fiber liquid-phase microextraction (HF-LPME) is applicable for this purpose, a three-phase HF-LPME was used to measure sulfadiazine and estimate its toxicity to Daphnia magna in solutions of different pH. The result indicated that the sulfadiazine concentrations measured by HF-LPME decreased with increasing pH, which is consistent with the decreased toxicity. The concentration immobilize 50% of the daphnids (EC50) in 48 h calculated from nominal concentrations increased from 11.93 to 273.5 mg L−1 as the pH increased from 6.0 to 8.5, and the coefficient of variation (CV) of the EC50 values reached 104.6%. When calculated from the concentrations measured by HF-LPME (pH 12 acceptor phase), the EC50 ranged from 223.4 to 394.6 mg L−1, and the CV decreased to 27.60%, suggesting that the concentrations measured by HF-LPME can be used to estimate the toxicity of sulfadiazine irrespective of the solution pH.

Automated hollow-fiber liquid-phase microextraction followed by liquid chromatography with mass spectrometry for the determination of benzodiazepine drugs in biological samples.

In this study, two-phase hollow-fiber liquid-phase microextraction and three-phase hollow-fiber liquid-phase microextraction based on two immiscible organic solvents were compared for extraction of oxazepam and Lorazepam. Separations were performed on a liquid chromatography with mass spectrometry instrument. Under optimal conditions, three-phase hollow-fiber liquid-phase microextraction based on two immiscible organic solvents has a better extraction efficiency. In a urine sample, for three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents, the calibration curves were found to be linear in the range of 0.6-200 and 0.9-200 μg L(-1) and the limits of detection were 0.2 and 0.3 μg L(-1) for oxazepam and lorazepam, respectively. For two-phase hollow fiber liquid-phase microextraction, the calibration curves were found to be linear in the range of 1-200 and 1.5-200 μg L(-1) and the limits of detection were 0.3 and 0.5 μg L(-1) for oxazepam and lorazepam, respectively. In a urine sample, for three-phase hollow-fiber-based liquid-phase microextraction based on two immiscible organic solvents, relative standard deviations in the range of 4.2-4.5% and preconcentration factors in the range of 70-180 were obtained for oxazepam and lorazepam, respectively. Also for the two-phase hollow-fiber liquid-phase microextraction, preconcentration factors in the range of 101-257 were obtained for oxazepam and lorazepam, respectively.

Three-phase hollow-fiber microextraction combined with ion-pair high-performance liquid chromatography for the simultaneous determination of five components of compound α-ketoacid tablets in human urine.

The determination of α-ketoacid concentration is demanded to evaluate the absorption and metabolic behavior of compound α-ketoacid tablets taken by chronic kidney disease patients. To eliminate the interference of endogenous substance of urine and enrich the analytes, a three-phase hollow-fiber liquid-phase microextraction combined with ion-pair high-performance liquid chromatography method was established for the determination of d,l-α-hydroxymethionine calcium, d,l-α-ketoisoleucine calcium, α-ketovaline calcium, α-ketoleucine calcium, and α-ketophenylalanine calcium of compound α-ketoacid tablets in human urine samples. The extraction parameters, such as organic solvent, pH of donor phase and acceptor phase, stirring rate, and extraction time were optimized. Under the optimal conditions, the obtained enrichment factors were up to 11-, 110-, 198-, 202-, and 50-fold, respectively. The calibration curves for these analytes were linear over the range of 0.1-10 mg/L for α-ketovaline calcium, d,l-α-ketoisoleucine calcium, and α-ketoleucine calcium, 0.5-10 mg/L for d,l-α-hydroxymethionine calcium, and α-ketophenylalanine calcium with r > 0.99. The relative standard deviations (n = 5) were less than 6.27% and the LODs were 100.7, 10.0, 5.8, 7.8, and 8.6 μg/L (based on S/N = 3), respectively. Good recoveries from spiked urine samples (92-118%) were obtained. The proposed method demonstrated excellent sample clean-up and analytes enrichment to determine the five components in human urine.

On-line extraction and determination of two herbicides: comparison between two modes of three-phase hollow fiber microextraction.

Two different modes of three-phase hollow fiber liquid-phase microextraction were studied for the extraction of two herbicides, bensulfuron-methyl and linuron. In these two modes, the acceptor phases in the lumen of the hollow fiber were aqueous and organic solvents. The extraction and determination were performed using an automated hollow fiber microextraction instrument followed by high-performance liquid chromatography. For both three-phase hollow fiber liquid-phase microextraction modes, the effect of the main parameters on the extraction efficiency were investigated and optimized by central composite design. Under optimal conditions, both modes showed good linearity and repeatability, but the three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents has a better extraction efficiency and figures of merit. The calibration curves for three-phase hollow fiber liquid-phase microextraction with an organic acceptor phase were linear in the range of 0.3-200 and 0.1-150 μg/L and the limits of detection were 0.1 and 0.06μg/L for bensulfuron-methyl and linuron, respectively. For the conventional three-phase hollow fiber liquid-phase microextraction, the calibration curves were linear in the range of 3.0-250 and 15-400 μg/L and LODs were 1.0 and 5.0 μg/L for bensulfuron-methyl and linuron, respectively. The real sample analysis was carried out by three-phase hollow fiber liquid phase microextraction based on two immiscible organic solvents because of its more favorable characteristics.

Hollow-fiber micro-extraction combined with HPLC for the determination of sitagliptin in urine samples

This study successfully developed a three-phase hollow-fiber liquid phase micro extraction coupled with high performance liquid chromatography for determination of trace levels of an anti-diabetic drug, sitagliptin (STG), in urine samples. Sitagliptin was extracted from 15 mL of the basic sample solution with a pH of 8.5 into an organic extracting solvent (n-octanol) impregnated in the pores of a hollow fiber and then back extracted into an acidified aqueous solution in the lumen of the hollow fiber with a pH of 3. After extraction, 20 ?L of the acceptor phase was injected into HPLC. In order to obtain high extraction efficiency, the parameters affecting the HF-LPME including pH of the source and receiving phases, type of organic phase, ionic strength, stirring rate, extraction time, the volume ratio of donor phase to acceptor phase and temperature were studied and optimized. Under the optimized conditions, enrichment factors up to 88 were achieved and the relative standard deviation of the method was in the range of 3 % to 6%. The results indicated that HF-LPME method has an excellent clean-up capacity and a high preconcentration factor and can serve as a simple and sensitive method for monitoring the drug in the urine samples.

Ionic liquid-based hollow fiber liquid-phase microextraction for the determination of trace lead (II) in environmental water and tea drinks samples by graphite furnace atomic absorption spectrometry

A three-phase hollow fiber liquid-phase microextraction (HF-LPME) was used to determine the trace amounts of Lead (II) in environmental water and tea drinks. In this approach, green solvent ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM]PF6) was used as membrane carrier that dissolved in hollow fiber pores. 1-(2-Pyridylazo)-2-naphthol (PAN) was placed in aqueous solution to form hydrophobic complex with Pb(II). Ethylene diamine tetraacetic acid (EDTA) was used as stripping agent that it can form water-soluble complex with Pb(II). After extraction, the acceptor solution was directly injected into the graphite furnace atomic absorption spectrometry (GF-AAS) for analysis. Some important parameters that influence the extraction efficiency were investigated, such as PAN concentration, pH, EDTA concentration, stirring rate, extraction time, and interfering metal ions. Under the optimized conditions, an enrichment factor (EF) of 210 and a limit of detection (LOD) of 0.004 ng mL−1 were obtained. The calibration curve was linear in the range of 0.05–0.5 ng mL−1 (R = 0.999). The relative standard deviation (RSD) at the 0.12 ng mL−1 Pb(II) level is 4.5 % (n = 6). The proposed method was successfully applied to determination of Pb(II) in environmental water and tea drinks samples with satisfactory recoveries in the range of 94–105 %.

Three-phase hollow-fiber liquid-phase microextraction combined with HPLC-UV for the determination of isothiazolinone biocides in adhesives used for food packaging materials

The present study deals with the development of a liquid microextraction procedure for enhancing the sensitivity of the determination of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one in adhesives. The procedure involves a three-phase hollow-fiber liquid-phase microextraction using a semipermeable polypropylene membrane, which contained 1-octanol as the organic phase in the pores of the membrane. The donor and acceptor phases are aqueous acidic and alkaline media, respectively, and the final liquid phase (acceptor) is analyzed by HPLC coupled with diode array detection. The most appropriate conditions were extraction time 20 min, stirring speed 1400 rpm, extraction temperature 50°C. The quantification limits of the method were 0.123 and 0.490 μg/g for 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, respectively. Three different adhesive samples were successfully analyzed. The procedure was compared to direct analysis using ultra high pressure liquid chromatography coupled with TOF-MS, where the identification of the compounds and the quantification values were confirmed.

Vortex-Assisted Hollow-Fiber Liquid-Phase Microextraction Coupled with High Performance Liquid Chromatography for the Determination of Three Synthetic Endocrine Disrupting Compounds in Milk

In this study, a vortex-assisted three-phase hollow fiber liquid-phase microextraction (VA-HF-LPME) coupling with high performance liquid chromatography (HPLC) method was developed for determination of three synthetic endocrine disrupting compounds[EDCs, bisphenol-A (BPA), bisphenol-AF (BPAF) and tetrabromobisphenol-A (TBBPA)] in milk samples. Vortex provided effective and mild mixing of the sample solution and increased the contact between analytes and boundary layers of the hollow fibre, thereby enhancing mass transfer rate and leading to high extraction efficiency of the target analytes. The influencing parameters of VA-HF-LPME sample preparation method, such as organic solvents (acceptor phase), pH of sample solution (donor phase), sample volume, concentration of NaOH, extraction time, and ionic strength were systematically optimized. The instrumental calibration curves of BPA, BPAF and TBBPA show good linear relations (R2 > 0.9988) in the concentration range of 0.5-200, 0.5-200 and 1.0-250 µg L-1, respectively. The relative standard deviations (RSD, n = 5) were 1.3-3.7%. The limits of detection (LOD, S/N = 3) were in the range of 0.16-0.35 µg L-1 and the limits of quantification (LOQ, S/N = 10) were in the range of 0.51-1.12 µg L-1. The proposed method was successfully applied to the extraction of EDCs in milk samples.

Simultaneous determination of three purines in Alysicarpus vaginalis (L.) DC. by hollow fiber‐based liquid‐phase microextraction combined with high‐performance liquid chromatography

In this paper, a three-phase hollow fiber liquid-phase microextraction (HF-LPME) method combined with high-performance liquid chromatography (HPLC) was developed for the determination of hypoxanthine (HX), xanthine (Xan) and adenine (A) and then for the first time successfully applied to the analysis of HX, Xan and A in Alysicarpus vaginalis (L.) DC. medicinal materials. Different factors affecting the HF-LPME procedure were investigated and optimized. Under optimal extraction conditions (1-octanol as organic solvent, pH of the donor and acceptor phase 10.0 and 3.5, respectively, extraction time 40 min, stirring rate 800 rpm and salt addition 10%, w/v), HX, Xan and A could be determined within the test ranges with a good correlation coefficient (r(2) > 0.9992). The limit of detection for HX, Xan and A was 153, 173 and 97 ng/mL, respectively, and the intra- and inter-day relative standard deviations were no more than 9.8%. The content of HX, Xan and A in Alysicarpus vaginalis (L.) DC. medicinal materials was 120.40, 18.37 and 62.75 µg/g, respectively. This procedure afforded a convenient, sensitive, accurate and inexpensive method with a high extraction efficiency for determination of HX, Xan and A.

Hollow‐fiber liquid‐phase microextraction combined with capillary HPLC for the selective determination of six sulfonylurea herbicides in environmental waters

A three-phase hollow-fiber liquid-phase microextraction combined with a capillary LC method using diode array detection was proposed for the determination of six sulfonylurea herbicides, triasulfuron, metsulfuron-methyl, chlorsulfuron, flazasulfuron, chlorimuron-ethyl, and primisulfuron-methyl, in environmental water samples. Different factors that can affect the extraction process such as extraction solvent, acidity of the donor phase, composition and pH of the acceptor phase, salt addition, stirring speed, and extraction time were optimized. Under the optimum conditions, detection and quantitation limits between 0.1-1.7 and 0.3-5.7 μg/L, respectively, and enrichment factors ranging from 71 to 548 were obtained. The calibration curves were linear within the range of 0.3-40 μg/L. Intra- and interday RSDs were <6.3 and 8.4%, respectively. The relative recoveries of the spiked ground and river water samples were in the range of 69.4-119.2 and 77.4-111.7%, respectively. The results of the study revealed that the developed methodology involves an efficient sample pretreatment allowing the preconcentration of analytes, combined with the use of a miniaturized separation technique, suitable for the accurate determination of sulfonylurea herbicides in water.

Determination of Trace Bisphenol A in Water Using Three-phase Hollow Fiber Liquid-phase Microextraction Coupled with High Performance Liquid Chromatography

Abstract A method for the determination of trace bisphenol A (BPA) in water was developed by high performance liquid chromatography (HPLC) using three-phase hollow fiber liquid-phase microextraction (HF-LPME) as sample preparation technique. The system of three-phase hollow fiber liquid-phase microextraction was designed. The optimized microextraction conditions were as follows: n -octanol was used as the extraction solvent, 0.09 M NaOH solution was used as acceptor phase, the pH value of sample solutions was 4.0, 30 g L −1 NaCl was solved in sample solutions, the stirring rate was 900 rpm and the extraction time was 60 min. The analysis of BPA was finished with injecting 20 μL acceptor phase by HPLC. Under the optimal microextraction conditions, the linear range for BPA was 0.5–200 μg L −1 ( r > 0.999), the detection limit ( S/N = 3) of BPA was 0.2 μg L −1 , the enrichment factor was 241, and the relative standard deviations (RSD) were lower than 3.2%. This method was applied to the determination of the BPA in environmental water samples. The average spiked recoveries were within the range of 92.8%–101.9% ( n = 3). The developed method was simple and environmentally friendly for the determination of BPA in water.