Application of the molecularly imprinted solid-phase extraction to the organophosphate residues determination in strawberries

This study describe an analytical method employing gas chromatography (GC) using flame photometric detection that has been developed for the simultaneous determination of organophosphate pesticides (diazinon, disulfoton, parathion, chlorpyrifos and malathion) in strawberry samples. For this purpose, molecularly imprinted solid-phase extraction was applied as a sample preparation technique. The method was linear in the ranges from 0.10 to 1.00?μg?g^?1, for diazinon, disulfoton, parathion and chlorpyrifos, and 0.10 to 2.00?μg?g^?1 for malathion with r?>?0.99. The detection limits (LD) ranged from 0.02 to 0.05?μg?g^?1. Recovery studies yielded average recoveries in the range of 65.25 to 87.70?%. These results showed the potential of this technique for organophosphate residue monitoring in strawberry samples.     

Polyaniline/graphene oxide nanocomposite as a sorbent for extraction and determination of nicotine using headspace solid-phase microextraction and gas chromatography–flame ionization detector

A solid-phase microextraction fiber was prepared by polyaniline/graphene oxide nanocomposite as sorbent on the surface of a platinized stainless steel wire using electrospinning technique. The nanocomposite structure was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The polyaniline/graphene oxide nanocomposite fiber was used for the determination of nicotine from tobacco samples using headspace solid-phase microextraction method and gas chromatography–flame ionization detection. Influential experimental variables on the extraction efficiency of nicotine, such as extraction time and temperature, humidity and desorption conditions, were evaluated and optimized. Under the optimal experimental conditions? the limit of detection, linear dynamic range, intraday and inter-days precisions were found to be 0.01 μg g^?1, 0.05–700 µg g^?1 (R²?=?0.996), 6.9 and 8.1%, respectively. Comparison of the polyaniline/graphene oxide nanocomposite sorbent with polyaniline and commercial fibers shows longer durability, larger capacity and higher extraction efficiency. The polyaniline/graphene oxide nanocomposite fiber was successfully applied for the determination of nicotine in tobacco samples.     

Improved Homogeneous Liquid–Liquid Extraction Combined with GC–ECD for the Determination of Organochlorinated Pesticides in Water

In this study, improved homogeneous liquid–liquid extraction (HLLE), equipped with GC–ECD has been developed for the extraction and determination of organochlorinated pesticides (OCPs) in water. The phase separation phenomenon occurred by temperature in a ternary solvent (water/methanol/chloroform) system. Several factors influencing the extraction efficiency were investigated and optimized with orthogonal array design. Furthermore, in this study, for the first time, before immiscible organic phase formation, different volumes of deionized water were subjected to homogeneous solution to investigate the effect of this factor on the extraction performance of HLLE. Optimal results were as follows: volume of the extracting solvent (chloroform), 50?μL; volume of the consolute solvent (methanol), 1.2?mL; volume of the sample, 2.5?mL; volume of the deionized water, 0.5?mL; time of centrifuge, 7?min. Under the optimum conditions, repeatability was obtained by spiking OCPs at concentration level of 20?μg?L^?1, the RSDs varied between 4.8 and 10.7% (n?=?4). The limits of detection of 0.02–0.12?μg?L^?1 were obtained for the OCPs. Enrichment factors and the extraction percent of the studied compounds were in the range of 240–300 and 69.2–84.0%, respectively. Finally, the results of the proposed HLLE method were compared with the same HLLE method without addition of deionized water. The results indicated that the proposed method has higher enrichment factors and lower detection limits.     

Analysis of trace amounts of chlorobenzenes in water samples: An approach towards the automation of dynamic hollow fiber liquid-phase microextraction

We have combined dynamic hollow fiber liquid-phase microextraction with GC and electron capture detection for the quantitative determination of five chlorobenzenes in water samples. Extraction is based on an automated dynamic extraction device called TT-tube extractor which consists of a polypropylene hollow fiber mounted inside a stainless steel tube. Toluene is used as the extraction solvent that fills the lumen and pores of the hydrophobic fiber and flows through the lumen of the fiber using a programmable syringe pump. The type of organic solvent, ionic strength, diameter of the TT-tube, sample volume, and the times for extraction and dwelling were optimized. Under optimum conditions, the method gives limits of detection as low as 10–100?ng?L^?1, a linear dynamic range of 0.05–100?μg?L^?1, and relative standard deviations of <7% (n?=?6). The preconcentration factor can be as large as 562–973. In an example for a practical application, the chlorobenzenes were successfully determined in environmental aqueous samples. The hollow fiber membrane can be used at least 20 times without any carry-over or loss in extraction efficiency. The system is inexpensive and convenient, and requires minimal manual handling.

Analysis of eight pyrethroids in water samples by liquid–liquid microextraction based on solidification of floating organic droplet combined with gas chromatography

A novel method was developed for the determination of eight pyrethroids in water samples by liquid–liquid microextraction based on solidification of floating organic droplets followed by gas chromatography with electron capture detection. The type and volume of the extraction solvents, extraction time, sample solution temperature, stirring rate and ionic strength were studied and optimized. Under the optimum conditions, enrichment factors ranged from 824 to 1,432, and the limit of detection range from 2.0 to 50 ng?L^?1. The calibration graph is linear from 0.15 to 80 μg?L^?1 for cyfluthrin, fenvalerate, fluvalinate and deltamethrin, 0.09 to 80 μg?L^?1 for fenpropathrin, 0.006 to 80 μg?L^?1 for lambda-cyhalothrin, 0.026 to 80 μg?L^?1 for permethrin, 0.01 to 80 μg?L^?1 for cypermethrin. The correlation coefficients (r) varied from 0.9961 to 0.9988. The method was successfully applied to the determination of pyrethroid pesticide residues in tap water, well water, reservoir water, and river water. Recoveries ranged from 79.0% to 113.6%, and relative standard deviations are between 4.1% and 8.7%.     

Selenium analysis in water samples by dispersive liquid-liquid microextraction based on piazselenol formation and GC–ECD

The application of the recently introduced dispersive liquid–liquid microextraction (DLLME) for the separation and determination of an inorganic selenite [Se(IV)] derivative by means of a gas chromatography–electron-capture detection system has been studied. The selenium derivative was extracted with the DLLME technique using a mixture of ethanol (disperser solvent) and chlorobenzene (extraction solvent). The influences of the various analytical parameters on the derivatization reaction and microextraction procedure have been evaluated and optimized. Under the optimum conditions, an enrichment factor of 122 was obtained for only 5.00 mL of the water sample. The calibration graph was linear in the range of 0.015–10 μg L^?1 with a detection limit of 0.005 μg L^?1. The relative standard deviation for ten replicate measurements of 2 μg L^?1 of selenium was 4.1%. The method was applied to the determination of selenium in environmental surface water samples with satisfactory recovery.     

Optimization of modified dispersive liquid–liquid microextraction coupled with high‐performance liquid chromatography for the simultaneous preconcentration and determination of nitrazepam and midazolam drugs: An experimental design

A simple, sensitive, and rapid microextraction method, namely, ultrasound‐assisted surfactant‐enhanced emulsification microextraction based on the solidification of floating organic droplet method coupled with high‐performance liquid chromatography was developed for the simultaneous preconcentration and determination of nitrazepam and midazolam. The significant parameters affecting the extraction efficiency were considered using Plackett–Burman design as a screening method. To obtain the optimum conditions with consideration of the selected significant variables, a Box–Behnken design was used. The microextraction procedure was performed using 29.1 μL of 1‐undecanol, 1.36% (w/v) of NaCl, 10.0 μL of sodium dodecyl sulfate (25.0 μg mL^?1), and 1.0 μL of Tween80 (25.0 μg mL^?1) as an emulsifier in an extraction time of 20.0 min at pH 7.88. In order to investigate the validation of the developed method, some validation parameters including the linear dynamic range, repeatability, limit of detection, and recoveries were studied under the optimum conditions. The detection limits of the method were 0.017 and 0.086 ng mL^?1 for nitrazepam and midazolam, respectively. The extraction recovery percentages for the drugs studied were above 91.0 with acceptable relative standard deviation. The proposed methodology was successfully applied for the determination of these drugs in a number of human serum samples.     

Hollow fiber supported liquid membrane microextraction of Cu2+ followed by flame atomic absorption spectroscopy determination

Hollow fiber supported liquid membrane microextraction, a relatively new sample preparation technique, has attracted much interest in the field of environmental analysis. In the current study, a novel method based on hollow-fiber liquid-phase microextraction and flame atomic absorption spectrometry (FAAS) for the measurement of copper ion in aqueous samples is described. Hollow-fiber liquid-phase microextraction conditions such as the type of extraction solvent, pH, the stirring rate, and the amounts of chelating agents, sample volume, and the extraction time were investigated. Under the optimized conditions, the linear range was found to be 0.01–15 μg ml^?1 for copper ion, and the limit of detection to be 0.004 μg ml^?1. Tap water and surface water samples collected from Mashhad, Iran and Dorongar river; Khorasan, Iran, respectively, were successfully analyzed using the proposed method. The recoveries from the spiked water samples were 72.4% and 105%, respectively; and the relative standard deviation (RSD) at the 2 μg ml^?1 level was 6%.     

Homogeneous liquid-liquid microextraction via flotation assistance coupled with gas chromatography-mass spectrometry for determination of myclobutanil in cucumber,tomato, grape,and strawberry using genetic algorithm

Facile and potent homogeneous liquid–liquid microextraction via flotation assistance method (HLLME-FA) combined with gas chromatography-mass spectrometry was proposed for determination of trace amounts of myclobutanil in fruit and vegetable samples. The paramount parameters, such as extraction and homogeneous solvent types and volumes, ionic strength and extraction time were studied. Under optimum conditions, the detection limit of 0.005 ng g^?1, the linear range of 0.05–100 ng g^?1, and the precision of 3.8% were acquired. A three-layer arti?cial neural network (ANN) model was used with 10 neurons and tan-sigmoid function at hidden layer and a linear transfer function at output layer were developed to predict the process. The results indicated that the proposed ANN model could perfectly predict the process with the mean square error of 0.89%. Then genetic algorithm was utilised to optimise the parameters. The proposed procedure showed satisfactory results for analysis of cucumber, tomato, grape, and strawberry.     

Preconcentration and spectrophotometric determination of trace amount of formaldehyde using hollow fiber liquid-phase microextraction based on derivatization by Hantzsch reaction

Formaldehyde is known as a highly toxic compound to humans and identified as a carcinogenic substance. In this study, Hantzsch reaction was utilized for the derivatization of trace amounts of formaldehyde in aqueous samples with acetylacetone in the presence of ammonia to form an extractable colored product named 3,5-diacetyl 1,4-dihydrolutidine (DDL) and its further extraction using two-phase hollow fiber liquid-phase microextraction. The main experimental variables affecting the extraction performance were investigated and optimized. Under the optimum conditions (sample volume 12 mL; reaction temperature 70 °C; ammonium acetate buffer solution 4 mL 0.1 mol L^?1; acetylacetone 5 mL 0.15 mol L^?1; solvent octanol, salt concentration 20% (w/v) NaCl; pH of donor phase 7.0; stirring speed 400 rpm and extraction time 30 min), the linear dynamic range, limit of detection (LOD as 3S _b/m) and relative standard deviation (RSD %) of the proposed method were obtained as 5–250 μg L^?1 (r ² = 0.9979), 3.6 μg L^?1 and 2.5%, respectively. Finally, the applicability of the proposed method was examined, and very good results were obtained. The results confirmed the applicability of the proposed method as a versatile, low-cost and sensitive preconcentration method for determination of low concentrations of formaldehyde in aqueous solutions.     

A greener microwave-assisted extraction method for rapid spectroscopic determination of selected metals in river and freshwater sediment certified reference materials

The current study describes development of novel, cost-effective, rapid and greener microwave-assisted extraction (MW-AE) method using diluted hydrogen peroxide (H₂O₂) and 400 µL of concentrated aqua-regia for the extraction of 10 selected metals (Ba, Cr, Cu, Co Fe, Mn, Ni, Pb, V and Zn) in sediment certified reference materials (CRMs), prior to inductively coupled plasma-optical emission spectroscopic analysis. The optimum extraction conditions were achieved when 0.2 g of sediment was extracted with 1 mol L^?1 of H₂O₂ (12.00 mL) and 400 µL of concentrated aqua-regia, at 180°C microwave extraction temperature for 30 min. Accuracy of the proposed MW-AE method was evaluated by using river (LGC6187) and freshwater (CRM015-050) sediment CRMs. Quantitative extraction recoveries of 80–120% in LGC6187 and 74–124% in CRM0150-050 were obtained with acceptable precision (0.4–1.0%). The proposed extraction method has a clear advantage over classical approaches as 1 mol L^?1 H₂O₂ was used instead of notorious acidic mixture (Hydrochloric acid/ nitric acid/ hydrofluoric). The method detection limits (MDLs) of 0.03–0.9 μg g^?1 were obtained for all the investigated metals and were fairly comparable with the MDLs of the published literature reports. Therefore, the proposed MW-AE method can be routinely used for monitoring of metal ions in various river and fresh water sediments.     

Ultrasonic-Assisted Nebulization Extraction Coupled with SPE and HPLC for the Determination of Triterpenoids in Root of Euphorbia pekinensis Rupr.

In this work, a novel method based on ultrasonic-assisted nebulization extraction coupled with solid phase extraction (UANE-SPE) and determined by high performance liquid chromatography was developed for the determination of triterpenoids in root of Euphorbia pekinensis Rupr. The experimental conditions for the UANE-SPE, such as type of extraction solvent, sample amount, type and amount of sorbent, extraction time and volume of the elution solvent, were examined and optimized. The method was successfully applied to determine euphol and tirucallol in the dried root of E. pekinensis Rupr. The recoveries of the analytes were in the range of 89.1–102.0 %. The limits of detection were 12 μg g^?1 for tirucallol and 10 μg g^?1 for euphol. The extraction yields obtained by the proposed method are higher than those obtained by the conventional extraction methods, such as reflux and ultrasonic-assisted extraction. Compared with the traditional methods, the proposed method can reduce the consumption of the labor, shorten the sample preparation time and increase the efficiencies in the extraction of active constituents from plant materials.     

A fluorescent sandwich assay for thrombin using aptamer modified magnetic beads and quantum dots

We report on a simple, rapid and efficient extraction procedure, referred to as ultrasound-assisted cold-induced aggregation (USA-CIAME), for the extraction of phenol from aqueous samples. In this method, very small amounts of the ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate (the extractant) are dissolved in a sample solution containing phenol and ultrasonicated for 1?min. The solution is cooled in an ice bath upon which a cloudy solution forms. Following centrifugation, the extractant phase settles at the bottom of a conical-bottom centrifuge tube. Phenol is photometrically determined after its chromogenic reaction with 4-aminoantipyrine in the presences of hexacyanoferrate at pH 10.0. Compared to the conventional cold-induced aggregation microextraction (CIAME) and dispersive liquid liquid microextraction (DLLME), the optimized approach displays the highest extraction efficiency at room temperature, and the shortest extraction time (5?min). Key parameters affecting the performance were evaluated and optimized. Under optimum conditions, the limit of detection of phenol is 0.86?μg?L^?1, and the enrichment factor is 75. The calibration graph as linear over the range from 3 to 150?μg?L^?1, and the relative standard deviation is 2.65% (n?=?5). The method was successfully applied to the determination of phenol in water samples.

A novel reusable ionic liquid chemically bonded fused-silica fiber for headspace solid-phase microextraction/gas chromatography-flame ionization detection of methyl tert-butyl ether in a gasoline sample

A novel ionic liquid (IL) bonded fused-sil-ica fiber for headspace solid-phase microextraction (HS-SPME)/gas chromatography-flame ionization detection (GC-FID) of methyl tert-butyl ether (MTBE) in a gasoline sample was prepared and used. The new proposed chemically bonded fiber has better thermal stability and durability than its corresponding physically coated fiber. Another advantage is that no spacer was used for the purpose of bonding the IL to the surface of the fused-silica. The latter advantage makes the preparation of these fibers easier with lower cost than those prepared using sol–gel method. The ionic liquid 1-methyl-3-(3-trimethoxysilyl propyl) imidazolium bis(trifluoromethylsulfonyl) imide was synthesized and cross linked to the surface of the fused-silica fiber. Then, the chemically IL-modified fibers were applied to the headspace extraction of MTBE. The chemically IL-modified fibers showed improved thermal stability at temperatures up to 220 °C relative to the physically IL-modified fibers (180 °C). The chemically bonded IL film on the surface of the fused-silica fiber was durable over 16 headspace extractions without any significant loss of the IL film. The calibration graph was linear in a concentration range of 2–240 μg L⁻¹ (R² = 0.996) with the detection limit of 0.1 μg L⁻¹ level. The reproducibility (RSD %, n = 6) of the new IL bonded fused-silica fiber (8.9%) was better than the physically coated fiber (12%) suggesting that the proposed chemically IL-modified fiber is more robust than the physically IL-modified fiber. The optimum extraction conditions were the followings: 40 °C extraction temperature, 12 min extraction time, 30 s desorption time and sample agitation at 200 rpm.     

Simultaneous determination of fluoroquinolone and tetracycline antibacterials in sewage sludge using ultrasonic-assisted extraction and HPLC-MS/MS

A reliable method was proposed for the simultaneous determination of five fluoroquinolones (FQs) and two tetracyclines (TCs) in sewage sludge using ultrasonic-assisted extraction (USE) followed by SPE cleanup and high-performance liquid chromatography-mass spectrometry (HPLC-MS)/MS analysis with electrospray ionisation (ESI) in a positive mode. The USE conditions (e.g. extraction solvent, pH, and extraction cycles) and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) parameters were optimised. Quantification was performed by internal standard calibration in multiple reaction monitoring mode. Recoveries of the antibacterials ranged from 41 to 123%, with relative standard deviations within 17%. The sample-based limits of quantification were 10–63?ng?g^?1 dry weight (dw) for FQs (ciprofloxacin, enrofloxacin, lomefloxacin, norfloxacin, and ofloxacin) and 250–500?ng?g^?1 dw for TCs (tetracycline and oxytetracycline). The method was applied to determine the antibacterials in sewage sludge and sediment samples were collected from the Pearl River Delta, China. Ciprofloxacin, norfloxacin, and ofloxacin were frequently detected, ranging from 1052 to 17740?ng?g^?1 dw in dewatered sludge samples, 585–3545?ng?g^?1 dw in untreated solids, and 98–258?ng?g^?1 dw in an urban stream sediment sample, respectively. Lomefloxacin and enrofloxacin were also occasionally detected.     

Chemical modification of alumina surface by immobilization of 1-((5-nitrofuran-2-yl)methylene)thiosemicarbazide for extractive concentration of silver ions

A column, solid phase extraction (SPE), preconcentration method was developed for determination of silver by using alumina coated with 1-((5-nitrofuran-2-yl)methylene)thiosemicarbazide and determination by flame atomic absorption spectrometry. The separation/preconcentration conditions for the quantitative recovery were investigated. At pH 2, the maximum sorption capacity of Ag⁺ was 7.5?mg?g^?1. The linearity was maintained in the concentration range of 0.02–11.0?µg?mL^?1 in the final solution or 0.14–1.10?×?10^4?ng?mL^?1 in the original solution for silver. The preconcentration factor of 140 and relative standard deviation of ±1.4% was obtained, under optimum conditions. The limit of detection (LOD) was calculated as 0.112?ng?mL^?1, based on 3σ_bl/m (n?=?8) in the original solutions. The proposed method was successfully applied to the determination trace amounts of silver in the environmental samples such as tea, rice and wheat flour, mint, and real water samples.     

Electromembrane extraction (EME)—an easy, novel and rapid extraction procedure for the HPLC determination of fluoroquinolones in wastewater samples

For the first time, an electromembrane extraction combined with a HPLC procedure using diode array and fluorescence detection has been developed for the determination of seven widely used fluoroquinolones (FQs): marbofloxacin, norfloxacin, ciprofloxacin, danofloxacin, enrofloxacin, gatifloxacin and grepafloxacin. The drugs were extracted from acid aqueous sample solutions (pH 5), through a supported liquid membrane consisting of 1-octanol impregnated in the walls of a S6/2 Accurel® polypropylene hollow fiber, to an acid (pH 2) aqueous acceptor solution inside the lumen of the hollow fiber. The main operational parameters were optimized, and extractions were carried out in 15 min using a potential of 50 V. Enrichment factors of 40–85 have been obtained using only 15 min of extraction time versus 330 min used in a previously proposed hollow-fiber liquid-phase microextraction procedure. The procedure allows low detection and quantitation limits of 0.005–0.07 and 0.007–0.15 μg?L^?1, respectively. The proposed method was successfully applied to the FQs analysis in urban wastewaters.

Extraction of neurotransmitters from rat brain using graphene as a solid-phase sorbent, and their fluorescent detection by HPLC

A simple, cost-effective and efficient method was developed for the determination of glycine, gamma-aminobutyrate and taurine in rat brain using graphene as a sorbent for solid-phase extraction. The analytes were eluted from a graphene-packed solid-phase extraction cartridge with methanol, derivatized at their amino groups with the fluorescent label 4-carboxy-2,6-dimethylquinoline N-hydroxysuccinimide ester, and then separated and fluorescently detected by HPLC. The type and volume of eluent, sample pH, extraction time and sample volume were optimized with respect to sensitivity and precision. Under optimal conditions, linear response is obtained in the concentration range from 0.1 to 50?μg?g?1, with correlation coefficients of >0.990. The limits of detection are 23.4?ng?g^?1 (gamma-aminobutyrate), 45.3?ng?g^?1 (glycine) and 67.5?ng?g^?1 (taurine) (S/N?=?3). The results reveal the potential of graphene as a sorbent in the analysis of biological samples.

Process development for isolation of dietary eugenol from leaves of basil (Ocimum sanctum) in combination of optimization of process variables and modeling by artificial neural network

Dietary eugenol helps prevent free radical-induced and lifestyle-related chronic illnesses such as cancer, autoimmune disorders, cardiovascular disease, and aging. A technique for extracting eugenol from green basil (Ocimum sanctum) leaves is created using a combination of extraction variable optimization and the organization of an artificial neural network (ANN) model. For thermally degradable bioactive eugenol, solvent extraction is the recommended separation method. With the following optimum variables: polarity of the solvent of 0.009, the solid-solvent ratio of 1.0 ?g/20 ?mL, stirring speed of 200 ?rpm, extraction temperature of 40 ?°C, and extraction duration of 40 ?min, a yield of 5.39 × ?10^?3 ?kg eugenol per kilogram dried leaves of basil was found. At 10 ?min of batch extraction, the highest throughput of eugenol was found to be 5.4 ?× ?10^?3 ?kg ?m^?3 ?s^?1. Additionally, experimental data are used to construct the yield prediction model. The statistical parameters that are obtained in model evaluation encourage the use of the predicted model for the commercialization of eugenol isolation.     

Ultrasound-assisted emulsification microextraction using low density solvent for analysis of toxic nitrophenols in natural waters

An ultrasound-assisted emulsification microextraction (USAEME) based on low-density solvents was successfully applied for the extraction and pre-concentration of four toxic nitrophenols in water samples. The extracted analytes were analyzed by high-performance liquid chromatography-UV detection. The important parameters influencing the extraction efficiency were studied and optimized utilizing two different optimization methods: one variable at a time (OVAT) and central composite design (CCD). The results showed that the emulsification process can be completed in a few seconds using low-density solvents, but almost 10–20?min is necessary for high-density solvents. Under the optimum conditions (extraction solvent, 1-octanol; extraction solvent volume, 40?µL; sample pH, 3.0; salt concentration, 20% (w/v) NaCl; extraction temperature, 40 (±3)°C), limits of detection of the method were in the range of 0.25 to 1?µg?L^?1 and the repeatability and reproducibility of the proposed method, expressed as relative deviation, varied in the range of 2.2–4.2% and 4.7–6.9%, respectively. Linearity was found to be in the range of 1 to 200?µg?L^?1 and the preconcentration factors (PFs) were between 77 and 175. The relative recoveries of the four nitrophenols from water samples at spiking level of 10.0?µg?L^?1 were in the range of 92.0 to 115.0%.