Surfactant-assisted dispersive liquid–liquid micro-extraction combined with magnetic solid-phase extraction for analysis of polyphenols in tobacco samples

A novel and simple two-step micro-extraction technique combining surfactant-assisted dispersive liquid–liquid micro-extraction and magnetic solid-phase extraction prior to high-performance liquid chromatography was established for analysis of polyphenols including chlorogenic acid, caffeic acid, and scopoletin in tobacco samples. In the developed system, Fe₃O₄ nanoparticles were synthesized by a one-step chemical co-precipitation method and used to remove hydrophobic substances in tobacco samples by physical adsorption. Low-density solvent (1-heptanol) and cationic surfactant cethyltrimethyl ammonium bromide were employed as extraction solvent and disperser agent, respectively. Under the optimized experimental conditions, a good linearity of the method was obtained over the concentration range from 0.1 to 1000 ng mL^?1 for target analytes. The limits of detection (S/N?=?3) were 0.05 ng mL^?1 for CGA, 0.10 ng mL^?1 for CFA, and 0.12 ng mL^?1 for SP, respectively. Finally, the applicability of the developed method was evaluated by extraction and determination of these three phenolic compounds in tobacco samples and satisfactory average recoveries of spiked samples were between 96.6 and 102.7%.     

SBA-15/Metformin as a novel sorbent combined with surfactant-assisted dispersive liquid–liquid microextraction (SA-DLLME) for highly sensitive determination of Pb,Cd and Ni in food and environmental samples

This paper established a new, rapid and sensitive method for the ultra-trace determination of lead, cadmium and nickel in food and environmental samples preconcentrated by dispersive solid-phase extraction (DSPE) combined with surfactant-assisted dispersive liquid–liquid microextraction (SA-DLLME) prior to graphite furnace atomic absorption spectrometry. SBA-15/Met was synthesized and used as a new efficient sorbent for the extraction of metal ions in DSPE. It was characterized by TEM and TGA techniques. After DSPE step, stripped metal elements were complexed with dithizone, and then, the complexes were extracted into carbon tetrachloride by using SA-DLLME. A conventional nonionic surfactant, triton X-100 was used as a disperser agent. Under the optimized conditions, the limit of quantifications was found to be 2.5 ng L^?1 for Pb²⁺, Cd²⁺ and 5.0 ng L^?1 for Ni²⁺. The limits of detection were 1.5 ng L^?1 for Ni²⁺ and 0.75 ng L^?1 for Pb²⁺ and Cd²⁺, with enrichment factor of 1650. The optimized method exhibited a good precision level with relative standard deviations (RSDs%) values of 4.9, 5.2 and 5.0% for 1 μg L^?1 Pb²⁺, Cd²⁺ and Ni²⁺, respectively (n = 7). Application of the proposed method to the analysis of fish-certified reference material produced results that were in good agreement with the certified values.     

Determination of Herbicides in Soil by Dispersive Solid-Phase Extraction,Dispersive Liquid–Liquid Microextraction,and High-Performance Liquid Chromatography

A method for determination of five herbicides (i.e., quinclorac, metsulfuron-methyl, bensulfuron-methyl, atrazine, prometryn) in soil was developed by dispersive solid-phase extraction combined with dispersive liquid–liquid microextraction and high-performance liquid chromatography. The analytes were removed from the soil by liquid partitioning with acetonitrile/5% acetic acid, purified using a octadecylsilane sorbent, and subsequently extracted before chromatographic analysis. Under the optimized conditions, the linear dynamic range was from 10.0 to 300 ng g^?1 with correlation coefficients (r) between 0.9971 and 0.9985. The limits of detection were between 1.5 and 3.1 ng g^?1, with relative standard deviations from 3.8% to 6.7% (n = 5). The recovery of the herbicides from soil at fortification levels of 20.0 and 100.0 ng g^?1 were between 71.5% and 94.3%. The method was successfully applied to the determination of the analytes in soil.     

Determination of Two Pesticides in Soils by Dispersive Liquid–Liquid Microextraction Combined with LC-Fluorescence Detection

In the present work, a simple, rapid and sensitive sample pre-treatment technique, dispersive liquid–liquid microextraction (DLLME) coupled with liquid chromatography-fluorescence detection (LC-FLD), has been developed to determine carbamate (carbaryl) and organophosphorus (triazophos) pesticide residues in soil samples. Methanol was first used as extraction solvent for the extraction of pesticides from the soil samples and then as dispersive solvent in the DLLME procedure. Under the optimum extraction conditions, the linearity was obtained in the concentration range of 0.1–1,000 ng g^?1 for carbaryl and 1–5,000 ng g^?1 for triazophos, respectively. Correlation coefficients varied from 0.9997 to 0.9999. The limits of detection (LODs), based on signal-to-noise ratio (S/N) of 3, ranged from 14 to 110 pg g^?1. The relative standard deviation (RSDs, for 20.0 ng g^?1 of each pesticide) varied from 1.96 to 4.24% (n = 6). The relative recoveries of two pesticides from soil A1, A2 and A3 at spiking levels of 10.0, 20.0 and 50.0 ng g^?1 were in the range of 88.2–108.8%, 80.8–110.7% and 81.0–111.1%, respectively. The results demonstrated that DLLME was a sensitive and accurate method to determine the target pesticides, at trace levels, in soils.     

Simultaneous preconcentration and determination of malachite green and fuchsine dyes in seafood and environmental water samples using nano-alumina-based molecular imprinted polymer solid-phase extraction

Molecular imprinted polymer for determination of malachite green (MG) and fuchsine basic (FU) dyes by spectrophotometry has been used, to develop a novel simultaneous extraction and preconcentration method. Molecularly imprinted layer-coated nano-alumina (MIP@Nano-Al₂O₃) as adsorbent was prepared by surface molecular imprinting technique, and characterised by FTIR spectroscopy, scanning electron microscopy, energy dispersive X-ray analysis (EDAX) and thermogravimetric analysis (TGA). The method is based on simultaneous extraction of MG and FU dyes from aqueous solution by using molecularly imprinted polymer and measuring the absorbance at 617 and 546 nm for MG and FU, respectively. Parameters which affect the extraction efficiency such as pH, volume of eluent and amount of adsorbent were investigated and optimised. Linear calibration curves were obtained in the range of 2–750 ng mL^?1 for MG and 1–240 ng mL^?1 for FU under optimum conditions. Detection limit based on three times the standard deviation of the blank (3S_b) was 0.655 and 0.245 ng mL^?1 (n = 10) for MG and FU, respectively. The relative standard deviation (RSD) for 100 ng mL^?1 of MG and FU was 2.35 and 3.06% (n = 7), respectively. The method was applied to the simultaneous determination of the dyes in different seafood and environmental water samples.     

Determination of ultra traces of lead in water samples after combined solid-phase extraction–dispersive liquid–liquid microextraction by graphite furnace atomic absorption spectrometry

A solid-phase extraction coupled with dispersive liquid–liquid microextraction (DLLME) method followed by graphite furnace atomic absorption spectrometry (GFAAS) was developed for the extraction, preconcentration, and determination of ultra trace amounts of lead in water samples. Variables affecting the performance of both steps were thoroughly investigated. Under optimized conditions, 100 mL of lead solution were first concentrated using a solid phase sorbent. The extracts were collected in 1.50 mL of THF and 18 μL of carbon tetrachloride was dissolved in the collecting solvent. Then 5.0 mL pure water was injected rapidly into the mixture of THF and carbon tetrachloride for DLLME, followed by GFAAS determination of lead. The analytical figures of merit of method developed were determined. With an enrichment factor of 1,800, a linear calibration of 3–60 ng L^?1 and a limit of detection of 1.0 ng L^?1 were obtained. The relative standard deviation for seven replicate measurements of 30 ng L^?1 of lead was 5.2 %. The relative recoveries of lead in mineral, tap, well, and river water samples at spiking level of 10 and 20 ng L^?1 are in the range 94–106 %.     

An Effective High-Performance Liquid Chromatographic–Mass Spectrometric Assay for Catecholamines, as the N(O,S)-Ethoxycarbonyl Ethyl Esters, in Human Urine

The purpose of this study was to develop a simple and accurate analytical method for determination of norepinephrine, epinephrine, and dopamine in urine. The method involves liquid–liquid extraction then liquid chromatography–mass spectrometry (LC–MS). Alkyl chloroformate derivatives were prepared, as the N(O,S)-alkoxycarbonyl alkyl esters of the analytes, in the aqueous samples. The optimum derivatizing reagent for preparation of the N(O,S)-alkoxycarbonyl alkyl esters was chosen by comparing the efficiency of LC of the derivatized analytes after liquid–liquid extraction. The optimum conditions for liquid–liquid extraction from the aqueous matrix were pH 3.0, no salt, and diethyl ether as extraction solvent. Limits of detection (LOD) were 0.5 ng mL^?1 for dopamine and epinephrine and 0.1 ng mL^?1 for norepinephrine. Limits of quantification (LOQ) for urine samples were 1.0 ng mL^?1 for all three compounds. The precision of intra- and inter-day assays was 1.65–581 and 7.17–9.73% (relative standard deviation, RSD), respectively. The range of inaccuracy for intra- and inter-day assays was ?6.47 to 11.9% and ?7.5 to 7.76% (bias) at concentrations of 5 and 50 ng mL^?1, respectively.     

Magnetic Nanoparticle-Based Micro-Solid Phase Extraction and GC�CMS Determination of Oxadiargyl in Aqueous Samples

A new facile, rapid, inexpensive, and sensitive method based on magnetic micro-solid phase extraction (M-??-SPE) coupled to gas chromatography?Cmass spectrometry (GC?CMS) was developed for determination of the herbicide oxadiargyl in environmental water samples. The feasibility of employing non-modified magnetic nanoparticles (MNPs) as sorbent was examined and applied to perform the extraction process. Influential parameters affecting the extraction efficiency along with desorption conditions were investigated and optimized. The limit of detection (LOD, S/N = 3) and limit of quantification (LOQ, S/N = 10) of the method under optimized conditions were 0.005 and 0.030 ng mL^?1, respectively. The relative standard deviations (RSD) (n = 3) at a concentration of 0.10 ng mL^?1 was 11%. The calibration curve of oxadiargyl showed linearity in the range of 0.050?C0.50 ng mL^?1. The developed method was successfully applied to the extraction of oxadiargyl from spiked tap water and Zayande-Rood River water samples and the relative recoveries of 98 and 94% were obtained, respectively.     

Determination of Estrone and 17β-Estradiol in Water Samples Using Dispersive Liquid–Liquid Microextraction Followed by LC

A new method, termed dispersive liquid–liquid microextraction (DLLME), was developed for the extraction and pre-concentration of estrone (E1) and 17β-estradiol (E2) in water samples. The samples were extracted by 0.50 mL methanol (disperser solvent) containing 25.0 μL tetrachloroethane (extraction solvent). Important factors such as the volume and type of extraction and disperser solvent, extraction time and salt effect were studied. Under optimum conditions, the enrichment factors and the limits of detection were 347 and 0.2 ng mL^?1 for E1, and 203 and 0.1 ng mL^?1 for E2, respectively. The linear range was 0.5–5,000 ng mL^?1. Compared to other methods, DLLME–LC–VWD has advantages for E1 and E2 analysis in water: high enrichment factor, low cost, simplicity, quick and easy operation.     

Ultrasound-assisted temperature-controlled ionic-liquid dispersive liquid-phase microextraction method for simultaneous determination of anethole,estragole, and para-anisaldehyde in different plant extracts and human urine: a comparative study

In this study, the performances of four ionic-liquid-based microextraction methods, ionic-liquid-based dispersive liquid–liquid microextraction (IL-DLLME), ionic-liquid-based ultrasound-assisted emulsification microextraction (IL-USA-ME), temperature-controlled ionic-liquid dispersive liquid-phase microextraction (TC-IL-DLME), and ultrasound-assisted temperature-controlled ionic-liquid dispersive liquid-phase microextraction (USA-TC-IL-DLME), were investigated for extraction of three bioactive compounds (anethole, estragole, and anisaldehyde) from different plant extracts and human urine. Anethole and estragole were chosen because they can alter cellular processes positively or negatively, and an efficient method is needed for their extraction and sensitive determination in the samples mentioned. Because there is no previous report on the separation of anethole and estragole (structural isomers), first, simultaneous gradient elution and flow programming were used. The microextraction methods were then applied and compared for analysis of these compounds in plant extracts and human urine by use of high-performance liquid chromatography (HPLC). The effect of conditions on extraction efficiency was studied and under the optimum conditions, the best enrichment factors (58–64), limits of detection (14–18 ng mL^?1), limits of quantification (47–60 ng mL^?1), and recovery (94.4–101.7 %) were obtained by use of USA-TC-IL-DLME. The optimized conditions were used to determine anethole, estragole, and para-anisaldehyde in fennel, anise, and tarragon extracts and in human urine.     

Sensitive quantification of uranium using cloud point extraction coupled with inductively coupled plasma-optical emission spectrometry

This article reports the utilization of cloud point extraction as a preconcentration strategy prior to U(VI) determination by inductively coupled plasma-optical emission spectrometry. Complexes of U(VI) with Cyanex-301 were preconcentrated into mixed-micellar medium using Triton X-100 and Cetylpyridinium bromide at ambient temperature. Optimal values of parameters impacting the extraction efficiency were determined. The proposed technique has linearity range of 5–200 ng mL^?1 with r = 0.99 and detection and quantification limits of 0.57 and 0.85 ng mL^?1, respectively. The method has good selectivity for U(VI) over various cations and was successfully applied to U(VI) determination in water samples with satisfactory results.     

A Pretreatment Method for GC–MS Determination of Endocrine Disrupting Chemicals in Mollusk Tissues

Automatic soxhlet extraction followed by silica gel cartridge cleanup process was developed as a pretreatment method for GC–MS determination of seven endocrine disrupting chemicals in mollusk tissues. Operation parameters including extraction time, adsorption flow rate and elution flow rate were optimized as 140 min, 2 mL min^?1 and 2 mL min^?1, respectively. Thirty percent dichloromethane in n-hexane and 70% dichloromethane in n-hexane were used as elution solvents in turn. Recovery rates were 93.7, 91.7, 84.5, 83.3, 88.4, 81.2, and 79.7% for nonylphenols (NPs), bisphenol A (BPA), 17α-ethynylestradiol (EE2), estrone (E1), 17α-estradiol (17α-E2), 17β-estradiol (E2), and estriol (E3), respectively. Acceptable relative standard derivations ranged from 8.5 to 12.1%. Method detection limits ranged from 0.27 to 0.68 ng g^?1 dry weight (dw), and quantitative detection limits ranged from 0.62 to 1.26 ng g^?1 dw. The method was successfully applied to five mollusk species in Dapeng Bay of China to verify its practicability, and NPs, BPA, EE2, E1 and 17α-E2 were detected in the range from 1.6 to 131.5 ng g^?1 dw.     

Simultaneous Determination of Ebastine and Its Active Metabolite (Carebastine) in Human Plasma Using LC–MS–MS

A sensitive and rapid LC–MS–MS method was developed for the simultaneous determination of ebastine and carebastine in human plasma. Solid-phase extraction was used to isolate the compounds from the biological matrix followed by separation on a Symmetry C18 column under isocratic conditions. The mobile phase was 10 mM ammonium formate in water/acetonitrile (40:60, v/v). Detection was carried out using a triple-quadrupole mass spectrometer in positive electrospray ionization and multiple reaction monitoring mode. The method was fully validated over the concentration range of 0.1–10 ng mL^?1 for ebastine and 0.2–200 ng mL^?1 for carebastine in human plasma, respectively. The lower limit of quantification (LLOQ) was 0.1 ng mL^?1 for ebastine and 0.2 ng mL^?1 for carebastine. For ebastine and carebastine inter- and intra-day precision (CV%) and accuracy values were all within ±15% and 85–115%, respectively. The extraction recovery was on average 60.0% for ebastine and 60.3% for carebastine.     

Sulfur modified with 2-mercaptobenzoxazole as a new sorbent for preconcentration of silver prior to determination by flame atomic absorption spectrometry

A solid-phase extraction method for preconcentration of silver and consequent determination by atomic absorption spectrometry is described. The method is based on the retention of silver on sulfur modified with 2-mercaptobenzoxazole. The retained silver is eluted from the column with a thiourea solution and determined by flame atomic absorption spectrometry. The preconcentration conditions such as pH, amount of reagent loaded on sorbent, type of eluent and its volume, flow rate and interfering ions were investigated. The calibration graph was linear in the range of 3–200 ng mL^?1 of Ag⁺ in the initial solution with r = 0.9985. The limit of detection based on 3S_b was 1.0 ng mL^?1. The relative standard deviation for ten replicate measurements of 50 and 150 ng mL^?1 of Ag⁺ was 4.1 and 1.4 %, respectively. The method was applied to the determination of silver in radiology film and water samples.     

Dissolved carbon dioxide flotation-assisted in-syringe dispersive liquid–liquid microextraction coupled with microsampling flame atomic absorption spectrometry for selective determination of palladium in water samples

Dissolved carbon dioxide flotation-assisted in-syringe dispersive liquid–liquid microextraction (DCF-IS-DLLME) followed by microsampling flame atomic absorption spectrometry was developed as a simple, inexpensive and fast method for extraction and determination of Pd(II). In the proposed approach, N,N′-bis (naphthylideneimino) diethylenetriamine (NAPdien) was utilized as a selective complexing reagent for Pd(II) ion. Several influential factors on the extraction efficiency including types and volumes of extraction and disperser solvents, pH of the sample solution, concentration of NAPdien and interfering ions were studied. By applying the optimal conditions, a preconcentration factor of 28.7 and limit of detection of 2.5 ng mL^?1 were provided by the proposed method. Linearity was in the range of 10–400 ng mL^?1 with a correlation coefficient (R ²) of 0.9968. Intra-day RSD% values for five repetitive measurements of the spiked solutions at the concentrations of 20 and 100 ng mL^?1 were 5.2 and 2.4%, respectively, whereas it was obtained within the range of 3.6–18.6% for the real samples. Inter-day RSD% values of the spiked solutions were found to be 9.6 and 8.7%, respectively. The results demonstrated that except for Fe²⁺ and Fe³⁺, no remarkable interfering effect was created by the other studied ions for determination of Pd(II) so that the tolerance limits (W _Ion/W _Pd(II)) of the major cations and anions were in the range of 1000–10,000. Finally, DCF-IS-DLLME was successfully applied for determination of Pd(II) in different water samples and the obtained relative recoveries in the range of 94.5–105% illustrated favorable accuracies for the proposed method.     

A highly sensitive procedure for determination of ultra trace amounts of molybdenum by graphite furnace atomic absorption spectrometry after dispersive liquid-liquid microextraction

A simple, rapid and sensitive method is developed for selective determination of ultra trace amounts of molybdenum(V?) from different water samples. The method is based on highly efficient separation and pre-concentration of molybdenum(V?) by dispersive liquid-liquid microextraction followed by its determination with graphite furnace atomic absorption spectrometry. Ultra traces of the target ion were extracted and pre-concentrated from acidic water samples by using sodium diethyldithiocarbamate as a suitable chelating agent, and carbon tetrachloride and acetone as extraction and disperser solvents, respectively. After optimizing different parameters, including type and volume of extraction and disperser solvents, pH of test solution, extraction time, volume and concentration of the chelating agent and sample volume, an enrichment factor of 362 was obtained. The linear concentration range, limit of detection and relative standard deviation of the method were evaluated as 0.04–0.8 ng mL^?1, 0.007 ng mL^?1 and 4.5%, respectively. This method was applied successfully to the determination of molybdenum in tap water and wastewater samples.     

Determination of phthalate esters in edible oils by use of QuEChERS coupled with ionic-liquid-based dispersive liquid–liquid microextraction before high-performance liquid chromatography

A selective and low organic-solvent-consuming method of sample preparation combined with high-performance liquid chromatography with diode-array detection is introduced for analysis of phthalic acid esters in edible oils. Sample treatment involves initial liquid–liquid partitioning with acetonitrile, then QuEChERS cleanup by dispersive solid-phase extraction with primary secondary amine as sorbent. Preconcentration of the analytes is performed by ionic-liquid-based dispersive liquid–liquid microextraction, with the cleaned-up extract as disperser solvent and 1-hexyl-3-methylimidazolium hexafluorophosphate as extraction solvent. Under the optimized conditions, correlation coefficients (r) were 0.998–0.999 and standard errors (S _y/x ) were 2.67–3.37?×?10³ for calibration curves in the range 50–1000 ng g^?1. Detection limits, at a signal-to-noise ratio of 3, ranged from 6 to 9 ng g^?1. Intra-day and inter-day repeatability, expressed as relative standard deviation, were in the ranges 1.0–6.9 % and 2.4–9.4 %, respectively. Recovery varied between 84 % and 106 %. The developed method was successfully used for analysis of the analytes in 28 edible oils. The dibutyl phthalate content of four of the 28 samples (14 %) exceeded the specific migration limit established by domestic and international regulations.

Simultaneous Determination of Pethidine and Atropine in Rabbit Plasma by LC�CMS�CMS and Its Application to a Pharmacokinetic Study after Intramuscular Administration

A sensitive and selective liquid chromatography?Ctandem mass spectrometry method for the determination of pethidine and atropine in rabbit plasma was developed and validated. The analytes and internal standard (IS) are extracted from plasma by liquid?Cliquid extraction using ethyl acetate, and separated on a Zorbax SB-Aq column (2.1 × 150 mm, 3.5 ??m) using acetonitrile?C0.1% formic acid as mobile phase with gradient elution. Electrospray ionization source was applied and operated in positive ion mode, and multiple reaction monitoring mode was used for quantification using target fragment ions m/z 247.8 ?? 219.7 for pethidine, m/z 289.9 ?? 123.8 for atropine and m/z 295.0 ?? 266.8 for IS, respectively. The assay is linear over the range of 5?C1,000 ng mL^?1 for pethidine and atropine, with a lower limit of quantification of 3 ng mL^?1 for pethidine and 5 ng mL^?1 for atropine. Intra-day and inter-day precision are less than 11% and the accuracy are in the range of 90.4?C106.3%. Furthermore, the newly developed method is successfully used for the determination of pethidine and atropine in rabbit plasma for pharmacokinetic study.     

Determination of Biogenic Amines in Cheese Using Simultaneous Derivatization and Microextraction Method Followed by Gas Chromatography–Mass Spectrometry

Microwave-assisted extraction and dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry as a sensitive and efficient method was applied to extract and determine four biogenic amines (BAs) in Iranian Lighvan cheese samples. Carrez solutions were used for the sedimentation of proteins. Effective factors on the performance of microextraction were studied and optimized. The proposed method showed good linear ranges from 5 to 500 ng mL^?1, with the coefficients of determination higher than 0.9929. Average recoveries were between 97 and 103%. Limits of detection for all analyzed BAs ranged from 5.9 to 14.0 ng g^?1, and limits of quantitation ranged between 19.7 and 46.2 ng g^?1. Compared with previous methods, the proposed method is simple, fast, accurate, and precise and gives low detection limits for investigating trace amounts of BAs in Iranian Lighvan cheese samples. The levels of four BAs were determined in five Lighvan cheese samples. Cadaverine was found as prevailing amine in the cheese samples. Putrescine, tyramine, and histamine were present at the second, third, and fourth highest levels, respectively.     

A new treatment by dispersive liquid–liquid microextraction for the determination of parabens in human serum samples

Alkyl esters of p-hydroxybenzoic acid (parabens) are a family of compounds that have been in use since the 1920s as preservatives in cosmetic formulations, with one of the lowest rates of skin problems reported in dermatological patients. However, in the last few years, many scientific publications have demonstrated that parabens are weak endocrine disruptors, meaning that they can interfere with the function of endogenous hormones, increasing the risk of breast cancer. In the present work, a new sample treatment method is introduced based on dispersive liquid–liquid microextraction for the extraction of the most commonly used parabens (methyl-, ethyl-, propyl-, and butylparaben) from human serum samples followed by separation and quantification using ultrahigh performance liquid chromatography–tandem mass spectrometry. The method involves an enzymatic treatment to quantify the total content of parabens. The extraction parameters (solvent and disperser solvent, extractant and dispersant volume, pH of the sample, salt addition, and extraction time) were accurately optimized using multivariate optimization strategies. Ethylparaben ring ¹³C₆-labeled was used as surrogate. Limits of quantification ranging from 0.2 to 0.7 ng mL^?1 and an interday variability (evaluated as relative standard deviations) from 3.8 to 11.9 % were obtained. The method was validated using matrix-matched calibration standard and a spike recovery assay. Recovery rates for spiked samples ranged from 96 to 106 %, and a good linearity up to concentrations of 100 ng mL^?1 was obtained. The method was satisfactorily applied for the determination of target compounds in human serum samples.