Rapid screening of oxytetracycline residue in catfish muscle by dispersive liquid-liquid microextraction and europium-sensitized luminescence

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Oxytetracycline (OTC) residue in catfish muscle was screened by dispersive liquid-liquid microextraction (DLLME) and europium-sensitized luminescence (ESL). After extraction in EDTA, HCl, and acetonitrile, cleanup was carried out by DLLME, and ESL was measured at microgram = 385 nm and wavelength = ...

Ionic-liquid-based dispersive liquid-liquid microextraction combined with magnetic solid-phase extraction for the determination of aflatoxins B1 , B2 , G1 , and G2 in animal feeds by high-performance liquid chromatography with fluorescence detection.

Science.gov (United States)

Zhao, Jiao; Zhu, Yan; Jiao, Yang; Ning, Jinyan; Yang, Yaling

2016-10-01

A novel two-step extraction technique combining ionic-liquid-based dispersive liquid-liquid microextraction with magnetic solid-phase extraction was developed for the preconcentration and separation of aflatoxins in animal feedstuffs before high-performance liquid chromatography coupled with fluorescence detection. In this work, ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate was used as the extractant in dispersive liquid-liquid microextraction, and hydrophobic pelargonic acid modified Fe 3 O 4 magnetic nanoparticles as an efficient adsorbent were applied to retrieve the aflatoxins-containing ionic liquid. Notably, the target of magnetic nanoparticles was the ionic liquid rather than the aflatoxins. Because of the rapid mass transfer associated with the dispersive liquid-liquid microextraction and magnetic solid phase steps, fast extraction could be achieved. The main parameters affecting the extraction recoveries of aflatoxins were investigated and optimized. Under the optimum conditions, vortexing at 2500 rpm for 1 min in the dispersive liquid-liquid microextraction and magnetic solid-phase extraction and then desorption by sonication for 2 min with acetonitrile as eluent. The recoveries were 90.3-103.7% with relative standard deviations of 3.2-6.4%. Good linearity was observed with correlation coefficients ranged from 0.9986 to 0.9995. The detection limits were 0.632, 0.087, 0.422 and 0.146 ng/mL for aflatoxins B 1 , B2, G1, and G2, respectively. The results were also compared with the pretreatment method carried out by conventional immunoaffinity columns. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Binary Solvents Dispersive Liquid-Liquid Microextraction (BS-DLLME) Method for Determination of Tramadol in Urine Using High-Performance Liquid Chromatography.

Science.gov (United States)

Kiarostami, Vahid; Rouini, Mohamad-Reza; Mohammadian, Razieh; Lavasani, Hoda; Ghazaghi, Mehri

2014-02-03

Tramadol is an opioid, synthetic analog of codeine and has been used for the treatment of acute or chronic pain may be abused. In this work, a developed Dispersive liquid liquid microextraction (DLLME) as binary solvents-based dispersive liquid-liquid microextraction (BS-DLLME) combined with high performance liquid chromatography (HPLC) with fluorescence detection (FD) was employed for determination of tramadol in the urine samples. This procedure involves the use of an appropriate mixture of binary extraction solvents (70 μL CHCl3 and 30 μL ethyl acetate) and disperser solvent (600 μL acetone) for the formation of cloudy solution in 5 ml urine sample comprising tramadol and NaCl (7.5%, w/v). After centrifuging, the small droplets of extraction solvents were precipitated. In the final step, the HPLC with fluorescence detection was used for determination of tramadol in the precipitated phase. Various factors on the efficiency of the proposed procedure were investigated and optimized. The detection limit (S/N = 3) and quantification limit (S/N = 10) were found 0.2 and 0.9 μg/L, respectively. The relative standard deviations (RSD) for the extraction of 30 μg L of tramadol was found 4.1% (n = 6). The relative recoveries of tramadol from urine samples at spiking levels of 10, 30 and 60 μg/L were in the range of 95.6 - 99.6%. Compared with other methods, this method provides good figures of merit such as good repeatability, high extraction efficiency, short analysis time, simple procedure and can be used as microextraction technique for routine analysis in clinical laboratories.

Rapid determination of octanol-water partition coefficient using vortex-assisted liquid-liquid microextraction.

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Román, Iván P; Mastromichali, Anna; Tyrovola, Konstantina; Canals, Antonio; Psillakis, Elefteria

2014-02-21

Vortex-assisted liquid-liquid microextraction (VALLME) coupled with high-performance liquid chromatography (HPLC) is proposed here for the rapid determination of octanol-water partitioning coefficients (Kow). VALLME uses vortex agitation, a mild emulsification procedure, to disperse microvolumes of octanol in the aqueous phase thus increasing the interfacial contact area and ensuring faster partitioning rates. With VALLME, 2min were enough to achieve equilibrium conditions between the octanolic and aqueous phases. Upon equilibration, separation was achieved using centrifugation and the octanolic microdrop was collected and analyzed in a HPLC system. Six model compounds with logKow values ranging between ∼0.5 and 3.5 were used during the present investigations. The proposed method produced logKow values that were consistent with previously published values and the recorded uncertainty was well within the acceptable log unit range. Overall, the key features of the proposed Kow determination procedure comprised speed, reliability, simplicity, low cost and minimal solvent consumption. Copyright © 2014 Elsevier B.V. All rights reserved.

In-syringe dispersive liquid-liquid microextraction with liquid chromatographic determination of synthetic pyrethroids in surface water

Directory of Open Access Journals (Sweden)

Saeed S. Albaseer

2012-03-01

Full Text Available An indigenously fabricated in laboratory glass syringe was used for in-syringe dispersive liquid-liquid microextraction (is-DLLME and preconcentration of synthetic pyrethroids (SPs from surface waters suitable for their determination by high performance liquid chromatography. In contrast to classical DLLME, is-DLLME allows the use of lighter-than-water organic solvents and the analysis of environmental contaminants’ samples without prior filtration, which is of great importance due to the high affinity of pyrethroids to adsorb to solid particulates present in environmental samples. The effects of various parameters on the extraction efficiency were evaluated and optimized systemically using one-factor-at-a-time method (OFAT and statistically using full factorial design (24. Three SPs (viz.; cypermethrin, resmethrin and permethrin were analyzed. The method showed good accuracy with RSD% in the range of of 4.8–6.9%. The method detection limits of the three pesticides ranged from 0.14 to 0.16 ng mL-1. The proposed method was applied for the determination of synthetic pyrethroids in lake water

Rapid determination of some beta-blockers in complicated matrices by tandem dispersive liquid-liquid microextraction followed by high performance liquid chromatography.

Science.gov (United States)

Hemmati, Maryam; Asghari, Alireza; Bazregar, Mohammad; Rajabi, Maryam

2016-11-01

In this research work, an efficient tandem dispersive liquid-liquid microextraction (TDLLME) procedure coupled with high performance liquid chromatography-ultraviolet detection (HPLC-UV) was successfully applied for the determination of beta-blockers in human plasma and pharmaceutical wastewater samples. High clean-up and preconcentration factor are easily and rapidly feasible via this novel, cheap, and safe microextraction method, leading to high quality experimental data. It consists of two sequential dispersive liquid-liquid microextraction methods, accomplished via air/ultrasonic agitation and air agitation, respectively. In order to enrich the optimal values for the mentioned procedures, the Box-Behnken design (BBD) combined with the desirability function (DF) was used. The optimum values were found to be 11.0 % (w/v) of the salt amount, an initial pH value of 12.0, 103 μL of organic extractant phase, and 45 μL of aqueous extractant phase with pH value of 2.0, resulted in reasonable recovery percentages with a logical desirability. Under optimal experimental conditions, good linear ranges (3-2000 ng mL -1 for metoprolol and 2.5-2500 ng mL -1 for propranolol with the correlation of determinations (R 2 s) higher than 0.99) and low limits of detection (0.8 and 1.0 ng mL -1 for propranolol and metoprolol, respectively) were obtainable. Also, TDLLME-HPLC-UV provided good proper repeatabilities (relative standard deviations (RSDs) below 5.7 %, n = 3) and high enrichment factors (EFs) of 75-100. Graphical abstract TDLLME of beta-blockers from complicated matrices.

Ionic liquid ultrasound assisted dispersive liquid-liquid microextraction method for preconcentration of trace amounts of rhodium prior to flame atomic absorption spectrometry determination

Energy Technology Data Exchange (ETDEWEB)

Molaakbari, Elaheh [Chemistry Department, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Young Research Society, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Mostafavi, Ali, E-mail: mostafavi.ali@gmail.com [Chemistry Department, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Afzali, Daryoush [Environment and Nanochemistry Department, Research Institute of Environmental Science, International Center for Science, High Technology and Environmental Science, Kerman (Iran, Islamic Republic of); Mineral Industries Research Center, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of)

2011-01-30

In this article, we consider ionic liquid based ultrasound-assisted dispersive liquid-liquid microextraction of trace amounts of rhodium from aqueous samples and show that this is a fast and reliable sample pre-treatment for the determination of rhodium ions by flame atomic absorption spectrometry. The Rh(III) was transferred into its complex with 2-(5-bromo-2-pyridylazo)-5-diethylamino phenol as a chelating agent, and an ultrasonic bath with the ionic liquid, 1-octyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide at room temperature was used to extract the analyte. The centrifuged rhodium complex was then enriched in the form of ionic liquid droplets and prior to its analysis by flame atomic absorption spectrometry, 300 {mu}L ethanol was added to the ionic liquid-rich phase. Finally, the influence of various parameters on the recovery of Rh(III) was optimized. Under optimum conditions, the calibration graph was linear in the range of 4.0-500.0 ng mL{sup -1}, the detection limit was 0.37 ng mL{sup -1} (3S{sub b}/m, n = 7) and the relative standard deviation was {+-}1.63% (n = 7, C = 200 ng mL{sup -1}). The results show that ionic liquid based ultrasound assisted dispersive liquid-liquid microextraction, combined with flame atomic absorption spectrometry, is a rapid, simple, sensitive and efficient analytical method for the separation and determination of trace amounts of Rh(III) ions with minimum organic solvent consumption.

Pesticide extraction from table grapes and plums using ionic liquid based dispersive liquid-liquid microextraction.

Science.gov (United States)

Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Herrera-Herrera, Antonio V; Rodríguez-Delgado, Miguel Angel

2009-12-01

Room temperature ionic liquids (RTILs) have been used as extraction solvents in dispersive liquid-liquid microextraction (DLLME) for the determination of eight multi-class pesticides (i.e. thiophanate-methyl, carbofuran, carbaryl, tebuconazole, iprodione, oxyfluorfen, hexythiazox, and fenazaquin) in table grapes and plums. The developed method involves the combination of DLLME and high-performance liquid chromatography with diode array detection. Samples were first homogenized and extracted with acetonitrile. After evaporation and reconstitution of the extract in water containing sodium chloride, a quick DLLME procedure that used the ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM][PF(6)]) and methanol was developed. The RTIL dissolved in a very small volume of acetonitrile was directed injected in the chromatographic system. The comparison between the calibration curves obtained from standards and from spiked sample extracts (matrix-matched calibration) showed the existence of a strong matrix effect for most of the analyzed pesticides. A recovery study was also developed with five consecutive extractions of the two types of fruits spiked at three concentration levels. Mean recovery values were in the range of 72-100% for table grapes and 66-105% for plum samples (except for thiophanate-methyl and carbofuran, which were 64-75% and 58-66%, respectively). Limits of detection (LODs) were in the range 0.651-5.44 microg/kg for table grapes and 0.902-6.33 microg/kg for plums, representing LODs below the maximum residue limits (MRLs) established by the European Union in these fruits. The potential of the method was demonstrated by analyzing 12 commercial fruit samples (six of each type).

Development of a robust ionic liquid-based dispersive liquid-liquid microextraction against high concentration of salt for preconcentration of trace metals in saline aqueous samples: Application to the determination of Pb and Cd

International Nuclear Information System (INIS)

Yousefi, Seyed Reza; Shemirani, Farzaneh

2010-01-01

A new ionic liquid-based dispersive liquid-liquid microextraction method was developed for preconcentration and determination of compounds in aqueous samples containing very high salt concentrations. This method can solve the problems associated with the limited application of the conventional IL-based DLLME in these samples. This is believed to arise from dissolving of the ionic liquids in aqueous samples with high salt content. In this method, the robustness of microextraction system against high salt concentration (up to 40%, w/v) is increased by introducing a common ion of the ionic liquid into the sample solution. The proposed method was applied satisfactorily to the preconcentration of lead and cadmium in saline samples. After preconcentration, the settled IL-phase was dissolved in 100 μL ethanol and aspirated into the flame atomic absorption spectrometer (FAAS) using a home-made microsample introduction system. Several variables affecting the microextraction efficiency were investigated and optimized. Under the optimized conditions and preconcentration of only 10 mL of sample, the enhancement factors of 273 and 311 and the detection limits of 0.6 μg L -1 and 0.03 μg L -1 were obtained for lead and cadmium, respectively. Validation of the method was performed by both an analysis of a certified reference material (CRM) and comparison of results with those obtained by ISO standard method.

Rapid determination of some psychotropic drugs in complex matrices by tandem dispersive liquid-liquid microextraction followed by high performance liquid chromatography.

Science.gov (United States)

Asghari, Alireza; Fahimi, Ebrahim; Bazregar, Mohammad; Rajabi, Maryam; Boutorabi, Leila

2017-05-01

Simple and rapid determinations of some psychotropic drugs in some pharmaceutical wastewater and human plasma samples were successfully accomplished via the tandem dispersive liquid-liquid microextraction combined with high performance liquid chromatography-ultraviolet detection (TDLLME-HPLC-UV). TDLLME of the three psychotropic drugs clozapine, chlorpromazine, and thioridazine was easily performed through two consecutive dispersive liquid-liquid microextractions. By performing this convenient method, proper sample preconcentrations and clean-ups were achieved in just about 7min. In order to achieve the best extraction efficiency, the effective parameters involved were optimized. The optimal experimental conditions consisted of 100μL of CCl 4 (as the extraction organic solvent), and the pH values of 13 and 2 for the donor and acceptor phases, respectively. Under these optimum experimental conditions, the proposed TDLLME-HPLC-UV technique provided a good linearity in the range of 5-3000ngmL -1 for the three psychotropic drugs with the correlation of determinations (R 2 s) higher than 0.996. The limits of quantification (LOQs) and limits of detection (LODs) obtained were 5.0ngmL -1 and 1.0-1.5ngmL -1 , respectively. Also the proper enrichment factors (EFs) of 96, 99, and 88 for clozapine, chlorpromazine, and thioridazine, respectively, and good extraction repeatabilities (relative standard deviations below 9.3%, n=5) were obtained. Copyright © 2017 Elsevier B.V. All rights reserved.

Simultaneous determination of several phytohormones in natural coconut juice by hollow fiber-based liquid-liquid-liquid microextraction-high performance liquid chromatography.

Science.gov (United States)

Wu, Yunli; Hu, Bin

2009-11-06

A simple, selective, sensitive and inexpensive method of hollow fiber-based liquid-liquid-liquid microextraction (HF-LLLME) combined with high performance liquid chromatography (HPLC)-ultraviolet (UV) detection was developed for the determination of four acidic phytohormones (salicylic acid (SA), indole-3-acetic acid (IAA), (+/-) abscisic acid (ABA) and (+/-) jasmonic acid (JA)) in natural coconut juice. To the best of our knowledge, this is the first report on the use of liquid phase microextraction (LPME) as a sample pretreatment technique for the simultaneous analysis of several phytohormones. Using phenetole to fill the pores of hollow fiber as the organic phase, 0.1molL(-1) NaOH solution in the lumen of hollow fiber as the acceptor phase and 1molL(-1) HCl as the donor phase, a simultaneous preconcentration of four target phytohormones was realized. The acceptor phase was finally withdrawn into the microsyringe and directly injected into HPLC for the separation and quantification of the target phytohormones. The factors affecting the extraction efficiency of four phytohormones by HF-LLLME were optimized with orthogonal design experiment, and the data was analyzed by Statistical Product and Service Solutions (SPSS) software. Under the optimized conditions, the enrichment factors for SA, IAA, ABA and JA were 243, 215, 52 and 48, with the detection limits (S/N=3) of 4.6, 1.3, 0.9ngmL(-1) and 8.8 microg mL(-1), respectively. The relative standard deviations (RSDs, n=7) were 7.9, 4.9, 6.8% at 50ngmL(-1) level for SA, IAA, ABA and 8.4% at 500 microg mL(-1) for JA, respectively. To evaluate the accuracy of the method, the developed method was applied for the simultaneous analysis of several phytohormones in five natural coconut juice samples, and the recoveries for the spiked samples were in the range of 88.3-119.1%.

Extensible automated dispersive liquid–liquid microextraction

Energy Technology Data Exchange (ETDEWEB)

Li, Songqing; Hu, Lu; Chen, Ketao; Gao, Haixiang, E-mail: hxgao@cau.edu.cn

2015-05-04

Highlights: • An extensible automated dispersive liquid–liquid microextraction was developed. • A fully automatic SPE workstation with a modified operation program was used. • Ionic liquid-based in situ DLLME was used as model method. • SPE columns packed with nonwoven polypropylene fiber was used for phase separation. • The approach was applied to the determination of benzoylurea insecticides in water. - Abstract: In this study, a convenient and extensible automated ionic liquid-based in situ dispersive liquid–liquid microextraction (automated IL-based in situ DLLME) was developed. 1-Octyl-3-methylimidazolium bis[(trifluoromethane)sulfonyl]imide ([C{sub 8}MIM]NTf{sub 2}) is formed through the reaction between [C{sub 8}MIM]Cl and lithium bis[(trifluoromethane)sulfonyl]imide (LiNTf{sub 2}) to extract the analytes. Using a fully automatic SPE workstation, special SPE columns packed with nonwoven polypropylene (NWPP) fiber, and a modified operation program, the procedures of the IL-based in situ DLLME, including the collection of a water sample, injection of an ion exchange solvent, phase separation of the emulsified solution, elution of the retained extraction phase, and collection of the eluent into vials, can be performed automatically. The developed approach, coupled with high-performance liquid chromatography–diode array detection (HPLC–DAD), was successfully applied to the detection and concentration determination of benzoylurea (BU) insecticides in water samples. Parameters affecting the extraction performance were investigated and optimized. Under the optimized conditions, the proposed method achieved extraction recoveries of 80% to 89% for water samples. The limits of detection (LODs) of the method were in the range of 0.16–0.45 ng mL{sup −1}. The intra-column and inter-column relative standard deviations (RSDs) were <8.6%. Good linearity (r > 0.9986) was obtained over the calibration range from 2 to 500 ng mL{sup −1}. The proposed

Extensible automated dispersive liquid–liquid microextraction

International Nuclear Information System (INIS)

Li, Songqing; Hu, Lu; Chen, Ketao; Gao, Haixiang

2015-01-01

Highlights: • An extensible automated dispersive liquid–liquid microextraction was developed. • A fully automatic SPE workstation with a modified operation program was used. • Ionic liquid-based in situ DLLME was used as model method. • SPE columns packed with nonwoven polypropylene fiber was used for phase separation. • The approach was applied to the determination of benzoylurea insecticides in water. - Abstract: In this study, a convenient and extensible automated ionic liquid-based in situ dispersive liquid–liquid microextraction (automated IL-based in situ DLLME) was developed. 1-Octyl-3-methylimidazolium bis[(trifluoromethane)sulfonyl]imide ([C 8 MIM]NTf 2 ) is formed through the reaction between [C 8 MIM]Cl and lithium bis[(trifluoromethane)sulfonyl]imide (LiNTf 2 ) to extract the analytes. Using a fully automatic SPE workstation, special SPE columns packed with nonwoven polypropylene (NWPP) fiber, and a modified operation program, the procedures of the IL-based in situ DLLME, including the collection of a water sample, injection of an ion exchange solvent, phase separation of the emulsified solution, elution of the retained extraction phase, and collection of the eluent into vials, can be performed automatically. The developed approach, coupled with high-performance liquid chromatography–diode array detection (HPLC–DAD), was successfully applied to the detection and concentration determination of benzoylurea (BU) insecticides in water samples. Parameters affecting the extraction performance were investigated and optimized. Under the optimized conditions, the proposed method achieved extraction recoveries of 80% to 89% for water samples. The limits of detection (LODs) of the method were in the range of 0.16–0.45 ng mL −1 . The intra-column and inter-column relative standard deviations (RSDs) were <8.6%. Good linearity (r > 0.9986) was obtained over the calibration range from 2 to 500 ng mL −1 . The proposed method opens a new avenue

Determination of ten pyrethroids in various fruit juices: comparison of dispersive liquid-liquid microextraction sample preparation and QuEChERS method combined with dispersive liquid-liquid microextraction.

Science.gov (United States)

Zhang, Yaohai; Zhang, Xuelian; Jiao, Bining

2014-09-15

Dispersive liquid-liquid microextraction (DLLME) sample preparation and the quick, easy, cheap, effective, rugged and safe (QuEChERS) method combined with DLLME were developed and compared for the analysis of ten pyrethroids in various fruit juices using gas chromatography-electron capture detection (GC-ECD). QuEChERS-DLLME method has found its widespread applications to all the fruit juices including those samples with more complex matrices (orange, lemon, kiwi and mango) while DLLME was confined to the fruit juices with simpler matrices (apple, pear, grape and peach). The two methods provided acceptable recoveries and repeatability. In addition, the applicabilities of two methods were demonstrated with the real samples and further confirmed by gas chromatography-mass spectrometry (GC-MS). Copyright © 2014. Published by Elsevier Ltd.

Pre-concentration of uranium from water samples by dispersive liquid-liquid micro-extraction

Energy Technology Data Exchange (ETDEWEB)

Khajeh, Mostafa; Nemch, Tabandeh Karimi [Zabol Univ. (Iran, Islamic Republic of). Dept. of Chemistry

2014-07-01

In this study, a simple and rapid dispersive liquid-liquid microextraction (DLLME) was developed for the determination of uranium in water samples prior to high performance liquid chromatography with diode array detection. 1-(2-pyridylazo)-2-naphthol (PAN) was used as complexing agent. The effect of various parameters on the extraction step including type and volume of extraction and dispersive solvents, pH of solution, concentration of PAN, extraction time, sample volume and ionic strength were studied and optimized. Under the optimum conditions, the limit of detection (LOD) and preconcentration factor were 0.3 μg L{sup -1} and 194, respectively. Furthermore, the relative standard deviation of the ten replicate was <2.6%. The developed procedure was then applied to the extraction and determination of uranium in the water samples.

Pre-concentration of uranium from water samples by dispersive liquid-liquid micro-extraction

International Nuclear Information System (INIS)

Khajeh, Mostafa; Nemch, Tabandeh Karimi

2014-01-01

In this study, a simple and rapid dispersive liquid-liquid microextraction (DLLME) was developed for the determination of uranium in water samples prior to high performance liquid chromatography with diode array detection. 1-(2-pyridylazo)-2-naphthol (PAN) was used as complexing agent. The effect of various parameters on the extraction step including type and volume of extraction and dispersive solvents, pH of solution, concentration of PAN, extraction time, sample volume and ionic strength were studied and optimized. Under the optimum conditions, the limit of detection (LOD) and preconcentration factor were 0.3 μg L -1 and 194, respectively. Furthermore, the relative standard deviation of the ten replicate was <2.6%. The developed procedure was then applied to the extraction and determination of uranium in the water samples.

Preconcentration and determination of ceftazidime in real samples using dispersive liquid-liquid microextraction and high-performance liquid chromatography with the aid of experimental design.

Science.gov (United States)

Razmi, Rasoul; Shahpari, Behrouz; Pourbasheer, Eslam; Boustanifar, Mohammad Hasan; Azari, Zhila; Ebadi, Amin

2016-11-01

A rapid and simple method for the extraction and preconcentration of ceftazidime in aqueous samples has been developed using dispersive liquid-liquid microextraction followed by high-performance liquid chromatography analysis. The extraction parameters, such as the volume of extraction solvent and disperser solvent, salt effect, sample volume, centrifuge rate, centrifuge time, extraction time, and temperature in the dispersive liquid-liquid microextraction process, were studied and optimized with the experimental design methods. Firstly, for the preliminary screening of the parameters the taguchi design was used and then, the fractional factorial design was used for significant factors optimization. At the optimum conditions, the calibration curves for ceftazidime indicated good linearity over the range of 0.001-10 μg/mL with correlation coefficients higher than the 0.98, and the limits of detection were 0.13 and 0.17 ng/mL, for water and urine samples, respectively. The proposed method successfully employed to determine ceftazidime in water and urine samples and good agreement between the experimental data and predictive values has been achieved. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fully-automated in-syringe dispersive liquid-liquid microextraction for the determination of caffeine in coffee beverages.

Science.gov (United States)

Frizzarin, Rejane M; Maya, Fernando; Estela, José M; Cerdà, Víctor

2016-12-01

A novel fully-automated magnetic stirring-assisted lab-in-syringe analytical procedure has been developed for the fast and efficient dispersive liquid-liquid microextraction (DLLME) of caffeine in coffee beverages. The procedure is based on the microextraction of caffeine with a minute amount of dichloromethane, isolating caffeine from the sample matrix with no further sample pretreatment. Selection of the relevant extraction parameters such as the dispersive solvent, proportion of aqueous/organic phase, pH and flow rates have been carefully evaluated. Caffeine quantification was linear from 2 to 75mgL(-1), with detection and quantification limits of 0.46mgL(-1) and 1.54mgL(-1), respectively. A coefficient of variation (n=8; 5mgL(-1)) of a 2.1% and a sampling rate of 16h(-1), were obtained. The procedure was satisfactorily applied to the determination of caffeine in brewed, instant and decaf coffee samples, being the results for the sample analysis validated using high-performance liquid chromatography. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dispersive liquid-liquid microextraction combined with graphite furnace atomic absorption spectrometry

International Nuclear Information System (INIS)

Zeini Jahromi, Elham; Bidari, Araz; Assadi, Yaghoub; Milani Hosseini, Mohammad Reza; Jamali, Mohammad Reza

2007-01-01

Dispersive liquid-liquid microextraction (DLLME) technique was successfully used as a sample preparation method for graphite furnace atomic absorption spectrometry (GF AAS). In this extraction method, 500 μL methanol (disperser solvent) containing 34 μL carbon tetrachloride (extraction solvent) and 0.00010 g ammonium pyrrolidine dithiocarbamate (chelating agent) was rapidly injected by syringe into the water sample containing cadmium ions (interest analyte). Thereby, a cloudy solution formed. The cloudy state resulted from the formation of fine droplets of carbon tetrachloride, which have been dispersed, in bulk aqueous sample. At this stage, cadmium reacts with ammonium pyrrolidine dithiocarbamate, and therefore, hydrophobic complex forms which is extracted into the fine droplets of carbon tetrachloride. After centrifugation (2 min at 5000 rpm), these droplets were sedimented at the bottom of the conical test tube (25 ± 1 μL). Then a 20 μL of sedimented phase containing enriched analyte was determined by GF AAS. Some effective parameters on extraction and complex formation, such as extraction and disperser solvent type and their volume, extraction time, salt effect, pH and concentration of the chelating agent have been optimized. Under the optimum conditions, the enrichment factor 125 was obtained from only 5.00 mL of water sample. The calibration graph was linear in the rage of 2-20 ng L -1 with detection limit of 0.6 ng L -1 . The relative standard deviation (R.S.D.s) for ten replicate measurements of 20 ng L -1 of cadmium was 3.5%. The relative recoveries of cadmium in tap, sea and rivers water samples at spiking level of 5 and 10 ng L -1 are 108, 95, 87 and 98%, respectively. The characteristics of the proposed method have been compared with cloud point extraction (CPE), on-line liquid-liquid extraction, single drop microextraction (SDME), on-line solid phase extraction (SPE) and co-precipitation based on bibliographic data. Therefore, DLLME combined with

In-situ ionic liquid dispersive liquid-liquid microextraction using a new anion-exchange reagent combined Fe3O4 magnetic nanoparticles for determination of pyrethroid pesticides in water samples.

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Fan, Chen; Liang, You; Dong, Hongqiang; Ding, Guanglong; Zhang, Wenbing; Tang, Gang; Yang, Jiale; Kong, Dandan; Wang, Deng; Cao, Yongsong

2017-07-04

In this work, in-situ ionic liquid dispersive liquid-liquid microextraction combined ultrasmall Fe 3 O 4 magnetic nanoparticles was developed as a kind of pretreatment method to detect pyrethroid pesticides in water samples. New anion-exchange reagents including Na[DDTC] and Na[N(CN) 2 ] were optimized for in-situ extraction pyrethroids, which showed enhanced microextraction performance. Pyrethroids were enriched by hydrophilic ionic liquid [P 4448 ][Br] (aqueous solution, 200 μL, 0.2 mmol mL -1 ) reaction in-situ with anion-exchange reagent Na[N(CN) 2 ] (aqueous solution, 300 μL, 0.2 mmol mL -1 ) forming hydrophobic ionic liquid as extraction agent in water sample (10 mL). Ultrasmall superparamagnetic iron oxide nanoparticles (30 mg) were used to collect the mixture of ionic liquid and pyrethroids followed by elution with acetonitrile. The extraction of ionic liquid strategies was unique and efficiently fulfilled with high enrichment factors (176-213) and good recoveries (80.20-117.31%). The method was successively applied to the determination of pyrethroid pesticides in different kinds of water samples with the limits of detection ranged from 0.16 to 0.21 μg L -1 . The proposed method is actually nanometer-level microextraction (average size 80 nm) with the advantages of simplicity, rapidity, and sensitivity. Copyright © 2017 Elsevier B.V. All rights reserved.

Optimisation of ultrasound-assisted reverse micelles dispersive liquid-liquid micro-extraction by Box-Behnken design for determination of acetoin in butter followed by high performance liquid chromatography.

Science.gov (United States)

Roosta, Mostafa; Ghaedi, Mehrorang; Daneshfar, Ali

2014-10-15

A novel approach, ultrasound-assisted reverse micelles dispersive liquid-liquid microextraction (USA-RM-DLLME) followed by high performance liquid chromatography (HPLC) was developed for selective determination of acetoin in butter. The melted butter sample was diluted and homogenised by n-hexane and Triton X-100, respectively. Subsequently, 400μL of distilled water was added and the microextraction was accelerated by 4min sonication. After 8.5min of centrifugation, sedimented phase (surfactant-rich phase) was withdrawn by microsyringe and injected into the HPLC system for analysis. The influence of effective variables was optimised using Box-Behnken design (BBD) combined with desirability function (DF). Under optimised experimental conditions, the calibration graph was linear over the range of 0.6-200mgL(-1). The detection limit of method was 0.2mgL(-1) and coefficient of determination was 0.9992. The relative standard deviations (RSDs) were less than 5% (n=5) while the recoveries were in the range of 93.9-107.8%. Copyright © 2014. Published by Elsevier Ltd.

Detection of Organophosphorus Pesticides in Wheat by Ionic Liquid-Based Dispersive Liquid-Liquid Microextraction Combined with HPLC

Directory of Open Access Journals (Sweden)

Wei Liu

2018-01-01

Full Text Available Food safety issues closely related to human health have always received widespread attention from the world society. As a basic food source, wheat is the fundamental support of human survival; therefore, the detection of pesticide residues in wheat is very necessary. In this work, the ultrasonic-assisted ionic liquid-dispersive liquid-liquid microextraction (DLLME method was firstly proposed, and the extraction and analysis of three organophosphorus pesticides were carried out by combining high-performance liquid chromatography (HPLC. The extraction efficiencies of three ionic liquids with bis(trifluoromethylsulfonylimide (Tf2N anion were compared by extracting organophosphorus in wheat samples. It was found that the use of 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonylimide ([OMIM][Tf2N] had both high enrichment efficiency and appropriate extraction recovery. Finally, the method was used for the determination of three wheat samples, and the recoveries of them were 74.8–112.5%, 71.8–104.5%, and 83.8–115.5%, respectively. The results show that the method proposed is simple, fast, and efficient, which can be applied to the extraction of organic matters in wheat samples.

Liquid phase microextraction for the analysis of trace elements and their speciation

International Nuclear Information System (INIS)

Hu, Bin; He, Man; Chen, Beibei; Xia, Linbo

2013-01-01

Trace/ultra-trace elements and their speciation analysis in complex matrices usually require sample preparation procedures to achieve sample clean-up and analyte preconcentration. Sample preparation is often the bottleneck in trace elements and their speciation analysis which has a direct impact on accuracy, precision and limits of detection and is often the rate-determining step of the analytical process. Recent trends in sample preparation include miniaturization, automation, high-throughput performance and reduction in solvent/sample consumption and operation time. Liquid-phase microextraction (LPME) technique as a novel and promising alternative in sample preparation can meet these requirements and has become a very efficient sample preparation technique. This review updates the state of art of LPME for trace elements and their speciation analysis and discusses its promising prospects. The major thrust of the article highlights the applications of LPME including single-drop microextraction (SDME), hollow fiber-liquid phase microextraction (HF-LPME), dispersive liquid liquid microextraction (DLLME) and solidified floating organic drop microextraction (SFODME) to the fields of elemental and their speciation analysis by atomic spectrometry-based methods, especially inductively coupled plasma mass spectrometry. General and specific concepts, different extraction formats and characteristics of LPME are described and compared, along with examples of recent innovations and applications presented to demonstrate its potential for trace elements and their speciation analysis in biological and environmental fields. Moreover, the application potential and an outlook on the combination of LPME and atomic spectrometry-based techniques for inorganic analysis are commentated. - Highlights: • The state of art of LPME for trace elements and their speciation analysis is updated. • Different extraction formats of LPME are described. • The application potential and future

Simultaneous determination of six synthetic phenolic antioxidants in edible oils using dispersive liquid-liquid microextraction followed by high-performance liquid chromatography with diode array detection.

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Xu, Shuangjiao; Liu, Liangliang; Wang, Yanqin; Zhou, Dayun; Kuang, Meng; Fang, Dan; Yang, Weihua; Wei, Shoujun; Xiao, Aiping; Ma, Lei

2016-08-01

A simple, rapid, organic-solvent- and sample-saving pretreatment technique, called dispersive liquid-liquid microextraction, was developed for the determination of six synthetic phenolic antioxidants from edible oils before high-performance liquid chromatography with diode array detection. The entire procedure was composed of a two-step microextraction and a centrifugal process and could be finished in about 5 min, only consuming only 25 mg of sample and 1 mL of the organic solvent for each extraction. The influences of several important parameters on the microextraction efficiency were thoroughly investigated. Recovery assays for oil samples were spiked at three concentration levels, 50, 100 and 200 mg/kg, and provided recoveries in the 86.3-102.5% range with a relative standard deviation below 3.5%. The intra-day and inter-day precisions for the analysis were less than 3.8%. The proposed method was successfully applied for the determination of synthetic phenolic antioxidants in different oil samples, and satisfactory results were obtained. Thus, the developed method represents a viable alternative for the quality control of synthetic phenolic antioxidant concentrations in edible oils. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vortex-assisted magnetic β-cyclodextrin/attapulgite-linked ionic liquid dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the fast determination of four fungicides in water samples.

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Yang, Miyi; Xi, Xuefei; Wu, Xiaoling; Lu, Runhua; Zhou, Wenfeng; Zhang, Sanbing; Gao, Haixiang

2015-02-13

A novel microextraction technique combining magnetic solid-phase microextraction (MSPME) with ionic liquid dispersive liquid-liquid microextraction (IL-DLLME) to determine four fungicides is presented in this work for the first time. The main factors affecting the extraction efficiency were optimized by the one-factor-at-a-time approach and the impacts of these factors were studied by an orthogonal design. Without tedious clean-up procedure, analytes were extracted from the sample to the adsorbent and organic solvent and then desorbed in acetonitrile prior to chromatographic analysis. Under the optimum conditions, good linearity and high enrichment factors were obtained for all analytes, with correlation coefficients ranging from 0.9998 to 1.0000 and enrichment factors ranging 135 and 159 folds. The recoveries for proposed approach were between 98% and 115%, the limits of detection were between 0.02 and 0.04 μg L(-1) and the RSDs changed from 2.96 to 4.16. The method was successfully applied in the analysis of four fungicides (azoxystrobin, chlorothalonil, cyprodinil and trifloxystrobin) in environmental water samples. The recoveries for the real water samples ranged between 81% and 109%. The procedure proved to be a time-saving, environmentally friendly, and efficient analytical technique. Copyright © 2015 Elsevier B.V. All rights reserved.

Ionic liquid based dispersive liquid-liquid microextraction for the extraction of pesticides from bananas.

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Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Asensio-Ramos, María; Rodríguez-Delgado, Miguel Angel

2009-10-23

This paper describes a dispersive liquid-liquid microextraction (DLLME) procedure using room temperature ionic liquids (RTILs) coupled to high-performance liquid chromatography with diode array detection capable of quantifying trace amounts of eight pesticides (i.e. thiophanate-methyl, carbofuran, carbaryl, tebuconazole, iprodione, oxyfluorfen, hexythiazox and fenazaquin) in bananas. Fruit samples were first homogenized and extracted (1g) with acetonitrile and after suitable evaporation and reconstitution of the extract in 10 mL of water, a DLLME procedure using 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM][PF(6)]) as extraction solvent was used. Experimental conditions affecting the DLLME procedure (sample pH, sodium chloride percentage, ionic liquid amount and volume of disperser solvent) were optimized by means of an experimental design. In order to determine the presence of a matrix effect, calibration curves for standards and fortified banana extracts (matrix matched calibration) were studied. Mean recovery values of the extraction of the pesticides from banana samples were in the range of 69-97% (except for thiophanate-methyl and carbofuran, which were 53-63%) with a relative standard deviation lower than 8.7% in all cases. Limits of detection achieved (0.320-4.66 microg/kg) were below the harmonized maximum residue limits established by the European Union (EU). The proposed method, was also applied to the analysis of this group of pesticides in nine banana samples taken from the local markets of the Canary Islands (Spain). To the best of our knowledge, this is the first application of RTILs as extraction solvents for DLLME of pesticides from samples different than water.

Liquid-phase microextraction approaches combined with atomic detection: A critical review

International Nuclear Information System (INIS)

Pena-Pereira, Francisco; Lavilla, Isela; Bendicho, Carlos

2010-01-01

Liquid-phase microextraction (LPME) displays unique characteristics such as excellent preconcentration capability, simplicity, low cost, sample cleanup and integration of steps. Even though LPME approaches have the potential to be combined with almost every analytical technique, their use in combination with atomic detection techniques has not been exploited until recently. A comprehensive review dealing with the applications of liquid-phase microextraction combined with atomic detection techniques is presented. Theoretical features, possible strategies for these combinations as well as the effect of key experimental parameters influencing method development are addressed. Finally, a critical comparison of the different LPME approaches in terms of enrichment factors achieved, extraction efficiency, precision, selectivity and simplicity of operation is provided.

Ionic liquid-based air-assisted liquid-liquid microextraction followed by high performance liquid chromatography for the determination of five fungicides in juice samples.

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You, Xiangwei; Chen, Xiaochu; Liu, Fengmao; Hou, Fan; Li, Yiqiang

2018-01-15

A novel and simple ionic liquid-based air-assisted liquid-liquid microextraction technique combined with high performance liquid chromatography was developed to analyze five fungicides in juice samples. In this method, ionic liquid was used instead of a volatile organic solvent as the extraction solvent. The emulsion was formed by pulling in and pushing out the mixture of aqueous sample solution and extraction solvent repeatedly using a 10mL glass syringe. No organic dispersive solvent was required. Under the optimized conditions, the limits of detection (LODs) were 0.4-1.8μgL -1 at a signal-to-noise ratio of 3. The limits of quantification (LOQs) set as the lowest spiking levels with acceptable recovery in juices were 10μgL -1 , except for fludioxonil whose LOQ was 20μgL -1 . The proposed method was applied to determine the target fungicides in juice samples, and acceptable recoveries ranging from 74.9% to 115.4% were achieved. Copyright © 2017. Published by Elsevier Ltd.

Determination of atenolol in human plasma using ionic-liquid-based ultrasound-assisted in situ solvent formation microextraction followed by high-performance liquid chromatography.

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Zeeb, Mohsen; Farahani, Hadi; Papan, Mohammad Kazem

2016-06-01

An efficient analytical method called ionic-liquid-based ultrasound-assisted in situ solvent formation microextraction followed by high-performance liquid chromatography was developed for the determination of atenolol in human plasma. A hydrophobic ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) was formed by the addition of a hydrophilic ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) to a sample solution containing an ion-pairing agent during microextraction. The analyte was extracted into the ionic liquid phase while the microextraction solvent was dispersed throughout the sample by utilizing ultrasound. The sample was then centrifuged, and the extracting phase retracted into the microsyringe and injected to liquid chromatography. After optimization, the calibration curve showed linearity in the range of 2-750 ng/mL with the regression coefficient corresponding to 0.998. The limits of detection (S/N = 3) and quantification (S/N = 10) were 0.5 and 2 ng/mL, respectively. A reasonable relative recovery range of 90-96.7% and satisfactory intra-assay (4.8-5.1%, n = 6) and interassay (5.0-5.6%, n = 9) precision along with a substantial sample clean-up demonstrated good performance of the procedure. It was applied for the determination of atenolol in human plasma after oral administration and some pharmacokinetic data were obtained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alternative solvent-based methyl benzoate vortex-assisted dispersive liquid-liquid microextraction for the high-performance liquid chromatographic determination of benzimidazole fungicides in environmental water samples.

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Santaladchaiyakit, Yanawath; Srijaranai, Supalax

2014-11-01

Vortex-assisted dispersive liquid-liquid microextraction using methyl benzoate as an alternative extraction solvent for extracting and preconcentrating three benzimidazole fungicides (i.e., carbendazim, thiabendazole, and fluberidazole) in environmental water samples before high-performance liquid chromatographic analysis has been developed. The selected microextraction conditions were 250 μL of methyl benzoate containing 300 μL of ethanol, 1.0% w/v sodium acetate, and vortex agitation speed of 2100 rpm for 30 s. Under optimum conditions, preconcentration factors were 14.5-39.0 for the target fungicides. Limits of detection were obtained in the range of 0.01-0.05 μg/L. The proposed method was then applied to surface water samples and the recovery evaluations at three spiked concentration levels of 5, 30, and 50 μg/L were obtained in the range of 77.4-110.9% with the relative standard deviation water samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitation of tetrabromobisphenol-A from dust sampled on consumer electronics by dispersed liquid-liquid microextraction

International Nuclear Information System (INIS)

Di Napoli-Davis, Gina; Owens, Janel E.

2013-01-01

Tetrabromobisphenol-A (TBBPA) is a brominated flame retardant used worldwide. Despite its widespread use, there are few data concerning environmental concentrations of TBBPA. Thus, the objective of this work was to optimize an ultrasound-assisted dispersed liquid-liquid microextraction (DLLME) method to analyze swabbed surfaces of consumer electronics to determine TBBPA concentrations. Upon sample preparation with DLLME, TBBPA was derivatized with acetic anhydride and then analyzed by gas chromatography–mass spectrometry (GC/MS). Using a 13 C 12 -TBBPA internal standard to improve precision and quantitation, a recovery study was performed. At concentrations of 250–1000 ng/mL, recoveries were 104–106%. Sample preparation with solid phase extraction had comparable recoveries, although overall, improved analyte recovery and precision were achieved with DLLME. In a small survey study, TBBPA concentrations in dust collected from 100 cm 2 areas on electronic surfaces (monitor, microwave, refrigerator, and TV) were determined to range from less than the LOQ to 523 ng/mL. -- Highlights: •Tetrabromobisphenol-A (TBBPA) concentrations in dust samples were determined. •Dust samples were collected from surfaces of consumer electronics. •Dispersed liquid-liquid microextraction was used to prepare samples for GC/MS. •A 13 C 12 -labeled internal standard was used to improve precision and quantitation. •TBBPA was found in dust samples at levels below LOQ to 523 ng/mL. -- This work describes the analysis of the brominated flame retardant, tetrabromobisphenol-A (TBBPA), from dust sampled on surfaces of consumer electronics

Simultaneous determination of atorvastatin and valsartan in human plasma by solid-based disperser liquid-liquid microextraction followed by high-performance liquid chromatography-diode array detection.

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Farajzadeh, Mir Ali; Khorram, Parisa; Pazhohan, Azar

2016-04-01

A simple, sensitive, and efficient method has been developed for simultaneous estimation of valsartan and atorvastatin in human plasma by combination of solid-based dispersive liquid-liquid microextraction and high performance liquid chromatography-diode array detection. In the proposed method, 1,2-dibromoethane (extraction solvent) is added on a sugar cube (as a solid disperser) and it is introduced into plasma sample containing the analytes. After manual shaking and centrifugation, the resultant sedimented phase is subjected to back extraction into a small volume of sodium hydrogen carbonate solution using air-assisted liquid-liquid microextraction. Then the cloudy solution is centrifuged and the obtained aqueous phase is transferred into a microtube and analyzed by the separation system. Under the optimal conditions, extraction recoveries are obtained in the range of 81-90%. Calibration curves plotted in drug-free plasma sample are linear in the ranges of 5-5000μgL(-1) for valsartan and 10-5000μgL(-1) for atorvastatin with the coefficients of determination higher than 0.997. Limits of detection and quantification of the studied analytes in plasma sample are 0.30-2.6 and 1.0-8.2μgL(-1), respectively. Intra-day (n=6) and inter-days (n=4) precisions of the method are satisfactory with relative standard deviations less than 7.4% (at three levels of 10, 500, and 2000μgL(-1), each analyte). These data suggest that the method can be successfully applied to determine trace amounts of valsartan and atorvastatin in human plasma samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Modified ionic liquid cold-induced aggregation dispersive liquid-liquid microextraction followed by atomic absorption spectrometry for trace determination of zinc in water and food samples

International Nuclear Information System (INIS)

Zeeb, M.; Sadeghi, M.

2011-01-01

We report on a new method for the microextraction and determination of zinc (II). The ion is accumulated via ionic-liquid cold-induced aggregation dispersive liquid-liquid microextraction (IL-CIA-DLLME) followed by flame atomic absorption spectrometry (FAAS). The ionic liquid (IL) 1-hexyl-3-methylimidazolium hexafluorophosphate is dispersed into a heated sample solution containing sodium hexafluorophosphate as a common ion source. The solution is then placed in an ice-water bath upon which a cloudy solution forms due to the decrease of the solubility of the IL. Zinc is complexed with 8-hydroxyquinoline and extracted into the IL. The enriched phase is dissolved in a diluting agent and introduced to the FAAS. The method is not influenced by variations in the ionic strength of the sample solution. Factors affecting the performance were evaluated and optimized. At optimum conditions, the limit of detection is 0.18 μg L -1 , and the relative standard deviation is 3.0% (at n=5). The method was validated by recovery experiments and by analyzing a certified reference material and successfully applied to the determination of Zn (II) in water and food samples. (author)

Magnetomotive room temperature dicationic ionic liquid: a new concept toward centrifuge-less dispersive liquid-liquid microextraction.

Science.gov (United States)

Beiraghi, Asadollah; Shokri, Masood; Seidi, Shahram; Godajdar, Bijan Mombani

2015-01-09

A new centrifuge-less dispersive liquid-liquid microextraction technique based on application of magnetomotive room temperature dicationic ionic liquid followed by electrothermal atomic absorption spectrometry (ETAAS) was developed for preconcentration and determination of trace amount of gold and silver in water and ore samples, for the first time. Magnetic ionic liquids not only have the excellent properties of ionic liquids but also exhibit strong response to an external magnetic field. These properties provide more advantages and potential application prospects for magnetic ionic liquids than conventional ones in the fields of extraction processes. In this work, thio-Michler's ketone (TMK) was used as chelating agent to form Ag/Au-TMK complexes. Several important factors affecting extraction efficiency including extraction time, rate of vortex agitator, pH of sample solution, concentration of the chelating agent, volume of ionic liquid as well as effects of interfering species were investigated and optimized. Under the optimal conditions, the limits of detection (LOD) were 3.2 and 7.3ngL(-1) with the preconcentration factors of 245 and 240 for Au and Ag, respectively. The precision values (RSD%, n=7) were 5.3% and 5.8% at the concentration level of 0.05μgL(-1) for Au and Ag, respectively. The relative recoveries for the spiked samples were in the acceptable range of 96-104.5%. The results demonstrated that except Hg(2+), no remarkable interferences are created by other various ions in the determination of Au and Ag, so that the tolerance limits (WIon/WAu or Ag) of major cations and anions were in the range of 250-1000. The validated method was successfully applied for the analysis of Au and Ag in some water and ore samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Trace determination of volatile polycyclic aromatic hydrocarbons in natural waters by magnetic ionic liquid-based stir bar dispersive liquid microextraction.

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Benedé, Juan L; Anderson, Jared L; Chisvert, Alberto

2018-01-01

In this work, a novel hybrid approach called stir bar dispersive liquid microextraction (SBDLME) that combines the advantages of stir bar sorptive extraction (SBSE) and dispersive liquid-liquid microextraction (DLLME) has been employed for the accurate and sensitive determination of ten polycyclic aromatic hydrocarbons (PAHs) in natural water samples. The extraction is carried out using a neodymium stir bar magnetically coated with a magnetic ionic liquid (MIL) as extraction device, in such a way that the MIL is dispersed into the solution at high stirring rates. Once the stirring is ceased, the MIL is magnetically retrieved onto the stir bar, and subsequently subjected to thermal desorption (TD) coupled to a gas chromatography-mass spectrometry (GC-MS) system. The main parameters involved in TD, as well as in the extraction step affecting the extraction efficiency (i.e., MIL amount, extraction time and ionic strength) were evaluated. Under the optimized conditions, the method was successfully validated showing good linearity, limits of detection and quantification in the low ng L -1 level, good intra- and inter-day repeatability (RSD < 13%) and good enrichment factors (18 - 717). This sensitive analytical method was applied to the determination of trace amounts of PAHs in three natural water samples (river, tap and rainwater) with satisfactory relative recovery values (84-115%), highlighting that the matrices under consideration do not affect the extraction process. Copyright © 2017 Elsevier B.V. All rights reserved.

Analysis of aromatic amines in water samples by liquid-liquid-liquid microextraction with hollow fibers and high-performance liquid chromatography.

Science.gov (United States)

Zhao, Limian; Zhu, Lingyan; Lee, Hian Kee

2002-07-19

Liquid-liquid-liquid microextraction (LLLME) with hollow fibers in high-performance liquid chromatography (HPLC) has been applied as a rapid and sensitive quantitative method for the detection of four aromatic amines (3-nitroaniline, 4-chloroaniline, 4-bromoaniline and 3,4-dichloroaniline) in environmental water samples. The preconcentration procedure was induced by the pH difference inside and outside the hollow fiber. The target compounds were extracted from 4-ml aqueous sample (donor solution, pH approximately 13) through a microfilm of organic solvent (di-n-hexyl ether), immobilized in the pores of a hollow fiber (1.5 cm length x 0.6 mm I.D.), and finally into 4 microl of acid acceptor solution inside the fiber. After a prescribed period of time, the acceptor solution inside the fiber was withdrawn into the microsyringe and directly injected into the HPLC system for analysis. Factors relevant to the extraction procedure were studied. Up to 500-fold enrichment of analytes could be obtained under the optimized conditions (donor solution: 0.1 M sodium hydroxide solution with 20% sodium chloride and 2% acetone; organic phase: di-n-hexyl ether; acceptor solution: 0.5 M hydrochloric acid and 500 mM 18-crown-6 ether; extraction time of 30 min; stirring at 1,000 rev./min). The procedure also served as a sample clean-up step. The influence of humic acid on the extraction efficiency was also investigated, and more than 85% relative recoveries of the analytes at two different concentrations (20 and 100 microg/l) were achieved at various concentration of humic acid. This technique is a low cost, simple and fast approach to the analysis of polar compounds in aqueous samples.

Kinetic aspects of hollow fiber liquid-phase microextraction and electromembrane extraction

DEFF Research Database (Denmark)

Gjelstad, Astrid; Jensen, Henrik; Rasmussen, Knut Einar

2012-01-01

In this paper, extraction kinetics was investigated experimentally and theoretically in hollow fiber liquid-phase microextraction (HF-LPME) and electromembrane extraction (EME) with the basic drugs droperidol, haloperidol, nortriptyline, clomipramine, and clemastine as model analytes. In HF...

Microwave-assisted liquid-liquid microextraction based on solidification of ionic liquid for the determination of sulfonamides in environmental water samples.

Science.gov (United States)

Song, Ying; Wu, Lijie; Lu, Chunmei; Li, Na; Hu, Mingzhu; Wang, Ziming

2014-12-01

An easy, quick, and green method, microwave-assisted liquid-liquid microextraction based on solidification of ionic liquid, was first developed and applied to the extraction of sulfonamides in environmental water samples. 1-Ethy-3-methylimidazolium hexafluorophosphate, which is a solid-state ionic liquid at room temperature, was used as extraction solvent in the present method. After microwave irradiation for 90 s, the solid-state ionic liquid was melted into liquid phase and used to finish the extraction of the analytes. The ionic liquid and sample matrix can be separated by freezing and centrifuging. Several experimental parameters, including amount of extraction solvent, microwave power and irradiation time, pH of sample solution, and ionic strength, were investigated and optimized. Under the optimum experimental conditions, good linearity was observed in the range of 2.00-400.00 μg/L with the correlation coefficients ranging from 0.9995 to 0.9999. The limits of detection for sulfathiazole, sulfachlorpyridazine, sulfamethoxazole, and sulfaphenazole were 0.39, 0.33, 0.62, and 0.85 μg/L, respectively. When the present method was applied to the analysis of environmental water samples, the recoveries of the analytes ranged from 75.09 to 115.78% and relative standard deviations were lower than 11.89%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Binary Solvents Dispersive Liquid—Liquid Microextraction (BS-DLLME) Method for Determination of Tramadol in Urine Using High-Performance Liquid Chromatography

Science.gov (United States)

2014-01-01

Background Tramadol is an opioid, synthetic analog of codeine and has been used for the treatment of acute or chronic pain may be abused. In this work, a developed Dispersive liquid liquid microextraction (DLLME) as binary solvents-based dispersive liquid-liquid microextraction (BS-DLLME) combined with high performance liquid chromatography (HPLC) with fluorescence detection (FD) was employed for determination of tramadol in the urine samples. This procedure involves the use of an appropriate mixture of binary extraction solvents (70 μL CHCl3 and 30 μL ethyl acetate) and disperser solvent (600 μL acetone) for the formation of cloudy solution in 5 ml urine sample comprising tramadol and NaCl (7.5%, w/v). After centrifuging, the small droplets of extraction solvents were precipitated. In the final step, the HPLC with fluorescence detection was used for determination of tramadol in the precipitated phase. Results Various factors on the efficiency of the proposed procedure were investigated and optimized. The detection limit (S/N = 3) and quantification limit (S/N = 10) were found 0.2 and 0.9 μg/L, respectively. The relative standard deviations (RSD) for the extraction of 30 μg L of tramadol was found 4.1% (n = 6). The relative recoveries of tramadol from urine samples at spiking levels of 10, 30 and 60 μg/L were in the range of 95.6 – 99.6%. Conclusions Compared with other methods, this method provides good figures of merit such as good repeatability, high extraction efficiency, short analysis time, simple procedure and can be used as microextraction technique for routine analysis in clinical laboratories. PMID:24495475

2-Naphthalenthiol derivatization followed by dispersive liquid-liquid microextraction as an efficient and sensitive method for determination of acrylamide in bread and biscuit samples using high-performance liquid chromatography.

Science.gov (United States)

Faraji, Mohammad; Hamdamali, Mohammadrezza; Aryanasab, Fezzeh; Shabanian, Meisam

2018-07-13

In this research, an ultrasonic-assisted extraction followed by 2-naphthalenthiol derivatization and dispersive liquid-liquid microextraction of acrylamide (AA) was developed as simple and sensitive sample preparation method for AA in bread and biscuit samples using high performance liquid chromatography. Influence of derivatization and microextraction parameters were evaluated and optimized. Results showed that the derivatization of AA leads to improve its hydrophobicity and chromatographic behavior. Under optimum conditions of derivatization and microextraction, the method yielded a linear calibration curve ranging from 10 to 1000 μg L -1 with a determination coefficient (R 2 ) of 0.9987. Limit of detection (LOD) and limit of quantification (LOQ) were 3.0 and 9.0 μg L -1 , respectively. Intra-day (n = 6) and inter-day (n = 3) precisions based on relative standard deviation percent (RSD%) for extraction and determination of AA at 50 and 500 μg L -1 levels were less than 9.0%. Finally, the performance of proposed method was investigated for determination of AA in some bread and biscuit samples, and satisfactory results were obtained (relative recovery ≥ 90%). Copyright © 2018. Published by Elsevier B.V.

Quantitative Analysis of Piroxicam Using Temperature-Controlled Ionic Liquid Dispersive Liquid Phase Microextraction Followed By Stopped-Flow Injection Spectrofluorimetry

Directory of Open Access Journals (Sweden)

Mohammad Reza Ganjali

2013-07-01

Full Text Available Background:Piroxicam (PXM belongs to the wide class of non-steroidal anti-inflammatory drugs (NSAIDs. PXM has been widely applied in the treatment of rheumatoid arthritis, gonarthrosis, osteoarthritis, backaches, neuralgia, mialgia. In the presented work, a green and benign sample pretreatment method called temperature-controlled ionic liquid dispersive liquid phase microextraction (TCIL-DLPME was followed with stopped-flow injection spectrofluorimetry (SFIS for quantitation of PXM in pharmaceutical formulations and biological samples.Methods:Temperature-controlled ionic liquid dispersive liquid phase microextraction (TCIL-DLPME was applied as an environmentally friendly sample enrichment method to extract and isolate PXM prior to quantitation. Dispersion of 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim][PF6] ionic liquid (IL through the sample aqueous solution was performed by applying a relatively high temperature. PXM was extracted into the extractor, and after phase separation, PXM in the final solution was determined by stopped-flow injection spectrofluorimetry (SFIS.Results and Major Conclusion:Different factors affecting the designed method such as IL amount, diluting agent, pH and temperature were investigated in details and optimized. The method provided a linear dynamic range of 0.2-150 μg l-1, a limit of detection (LOD of 0.046 μg l-1 and a relative standard deviation (RSD of 3.1%. Furthermore, in order to demonstrate the analytical applicability of the recommended method, it was applied for quantitation of PXM in real samples.

Sensitive determination of melamine in milk and powdered infant formula samples by high-performance liquid chromatography using dabsyl chloride derivatization followed by dispersive liquid-liquid microextraction.

Science.gov (United States)

Faraji, M; Adeli, M

2017-04-15

A new and sensitive pre-column derivatization with dabsyl chloride followed by dispersive liquid-liquid microextraction was developed for the analysis of melamine (MEL) in raw milk and powdered infant formula samples by high performance liquid chromatography (HPLC) with visible detection. Derivatization with dabsyl chloride leads to improving sensitivity and hydrophobicity of MEL. Under optimum conditions of derivatization and microextraction steps, the method yielded a linear calibration curve ranging from 1.0 to 500μgL -1 with a determination coefficient (R 2 ) of 0.9995. Limit of detection and limit of quantification were 0.1 and 0.3μgL -1 , respectively. The relative standard deviation (RSD%) for intra-day (repeatability) and inter-day (reproducibility) at 25 and 100μgL -1 levels of MEL was less than 7.0% (n=6). Finally, the proposed method was successfully applied for the preconcentration and determination of MEL in different raw milk and powdered infant formula, and satisfactory results were obtained (relative recovery ⩾94%). Copyright © 2016 Elsevier Ltd. All rights reserved.

Ligandless-dispersive liquid-liquid microextraction of trace amount of copper ions

International Nuclear Information System (INIS)

Mohammadi, Sayed Zia; Afzali, Daryoush; Baghelani, Yar Mohammad

2009-01-01

In the present work, a new ligandless-dispersive liquid-liquid microextraction (LL-DLLME) method has been developed for preconcentration trace amounts of copper as a prior step to its determination by flame atomic absorption spectrometry. In the proposed approach 1,2-dicholorobenzene and ethanol were used as extraction and dispersive solvents, respectively. Some factors influencing on the extraction efficiency of copper and its subsequent determination were studied and optimized, such as the extraction and dispersive solvent type and volume, pH of sample solution, extraction time and salting out effect. Under the optimal conditions, the calibration curve was linear in the range of 1.0 ng mL -1 -0.6 μg mL -1 of copper with R 2 = 0.9985. Detection limit was 0.5 ng mL -1 in original solution (3S b /m) and the relative standard deviation for seven replicate determination of 0.2 μg mL -1 copper was ±1.4%. The proposed method has been applied for determination of copper in standard and water samples with satisfactory results.

Low Density Solvent-Based Dispersive Liquid-Liquid Microextraction for the Determination of Synthetic Antioxidants in Beverages by High-Performance Liquid Chromatography

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Çabuk, Hasan; Köktürk, Mustafa

2013-01-01

A simple and efficient method was established for the determination of synthetic antioxidants in beverages by using dispersive liquid-liquid microextraction combined with high-performance liquid chromatography with ultraviolet detection. Butylated hydroxy toluene, butylated hydroxy anisole, and tert-butylhydroquinone were the antioxidants evaluated. Experimental parameters including extraction solvent, dispersive solvent, pH of sample solution, salt concentration, and extraction time were optimized. Under optimal conditions, the extraction recoveries ranged from 53 to 96%. Good linearity was observed by the square of correlation coefficients ranging from 0.9975 to 0.9997. The relative standard deviations ranged from 1.0 to 5.2% for all of the analytes. Limits of detection ranged from 0.85 to 2.73 ng mL−1. The method was successfully applied for determination of synthetic antioxidants in undiluted beverage samples with satisfactory recoveries. PMID:23853535

Low Density Solvent-Based Dispersive Liquid-Liquid Microextraction for the Determination of Synthetic Antioxidants in Beverages by High-Performance Liquid Chromatography

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Hasan Çabuk

2013-01-01

Full Text Available A simple and efficient method was established for the determination of synthetic antioxidants in beverages by using dispersive liquid-liquid microextraction combined with high-performance liquid chromatography with ultraviolet detection. Butylated hydroxy toluene, butylated hydroxy anisole, and tert-butylhydroquinone were the antioxidants evaluated. Experimental parameters including extraction solvent, dispersive solvent, pH of sample solution, salt concentration, and extraction time were optimized. Under optimal conditions, the extraction recoveries ranged from 53 to 96%. Good linearity was observed by the square of correlation coefficients ranging from 0.9975 to 0.9997. The relative standard deviations ranged from 1.0 to 5.2% for all of the analytes. Limits of detection ranged from 0.85 to 2.73 ng mL−1. The method was successfully applied for determination of synthetic antioxidants in undiluted beverage samples with satisfactory recoveries.

Ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction and derivatization of sulfonamides in river water, honey, milk, and animal plasma.

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Xu, Xu; Su, Rui; Zhao, Xin; Liu, Zhuang; Zhang, Yupu; Li, Dan; Li, Xueyuan; Zhang, Hanqi; Wang, Ziming

2011-11-30

The ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction (IL-based MADLLME) and derivatization was applied for the pretreatment of six sulfonamides (SAs) prior to the determination by high-performance liquid chromatography (HPLC). By adding methanol (disperser), fluorescamine solution (derivatization reagent) and ionic liquid (extraction solvent) into sample, extraction, derivatization, and preconcentration were continuously performed. Several experimental parameters, such as the type and volume of extraction solvent, the type and volume of disperser, amount of derivatization reagent, microwave power, microwave irradiation time, pH of sample solution, and ionic strength were investigated and optimized. When the microwave power was 240 W, the analytes could be derivatized and extracted simultaneously within 90 s. The proposed method was applied to the analysis of river water, honey, milk, and pig plasma samples, and the recoveries of analytes obtained were in the range of 95.0-110.8, 95.4-106.3, 95.0-108.3, and 95.7-107.7, respectively. The relative standard deviations varied between 1.5% and 7.3% (n=5). The results showed that the proposed method was a rapid, convenient and feasible method for the determination of SAs in liquid samples. Copyright © 2011 Elsevier B.V. All rights reserved.

Microwave-assisted ionic liquid homogeneous liquid-liquid microextraction coupled with high performance liquid chromatography for the determination of anthraquinones in Rheum palmatum L.

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Wang, Zhibing; Hu, Jianxue; Du, Hongxia; He, Shuang; Li, Qing; Zhang, Hanqi

2016-06-05

The microwave-assisted ionic liquid homogeneous liquid-liquid microextraction (MA-IL-HLLME) coupled with high performance liquid chromatography with diode array detection (HPLC-DAD) was developed for the determination of anthraquinones, including aloe-emodin, emodin, chrysophanol and physcion in root of Rheum palmatum L. Several experimental parameters influencing the extraction efficiency, including amount of sample, type and volume of ionic liquid, volume and pH value of extraction medium, microwave power and extraction time, concentration of NH4PF6 as well as centrifugal condition were optimized. When 140μL of ionic liquid ([C8MIM][BF4]) was used as an extraction solvent, target analytes can be extracted from sample matrix in one minute with the help of microwave irradiation. The MA-IL-HLLME is simple and quick. The calibration curves exhibited good linear relationship (r>0.9984). The limits of detection and quantification were in the range of 0.015-0.026 and 0.051-0.088μgmL(-1), respectively. The spiked recovery for each analyte was in the range of 81.13-93.07% with relative standard deviations lower than 6.89%. The present method is free of volatile organic solvents, and represents lower expenditures of sample, extraction time and solvent, compared with ultrasonic and heat reflux extraction. The results indicated that the present method can be successfully applied to the determination of anthraquinones in medicinal plant. Copyright © 2016 Elsevier B.V. All rights reserved.

Development of a dispersive liquid-liquid microextraction method for the determination of polychlorinated biphenyls in water

International Nuclear Information System (INIS)

Rezaei, Fatemeh; Bidari, Araz; Birjandi, Afsoon Pajand; Milani Hosseini, Mohammad Reza; Assadi, Yaghoub

2008-01-01

A very simple and powerful microextraction procedure, the dispersive liquid-liquid microextraction (DLLME), was used for the determination of the content of 10 polychlorinated biphenyls (PCBs) in water samples, using gas chromatography coupled with electron-capture detection (GC-ECD). The appropriate amount of acetone (disperser solvent) and chlorobenzene (extraction solvent) at the microlevel volume was used for this procedure. The conditions for the microextraction performance were investigated and optimized. The optimized method exhibited a good linearity (R 2 > 0.996) over the studied range (0.005-2 μg L -1 ), illustrating a satisfactory precision level with R.S.D. values between 4.1% and 11.0%. The values of the detection limit (S/N = 3) were found to be lower than 0.002 μg L -1 . Furthermore, a large enrichment factor for the analytes (up to a 540-fold) was achieved in a very short time for only a 5.00-mL water sample. The effectiveness of the method towards real samples was tested by analyzing well, river and seawater samples. The relative recoveries of the well, river and seawater samples, which had been spiked with different levels of PCBs were equal to 92.0-114.0%, 97.0-102.0% and 96.0-103.0%, respectively. The attained results demonstrated that DLLME combined with GC-ECD was a fast and inexpensive technique for the PCBs determination in water samples

The recent developments in dispersive liquid–liquid microextraction for preconcentration and determination of inorganic analytes

Directory of Open Access Journals (Sweden)

H.M. Al-Saidi

2014-12-01

Full Text Available Recently, increasing interest on the use of dispersive liquid–liquid microextraction (DLLME developed in 2006 by Rezaee has been found in the field of separation science. DLLME is miniaturized format of liquid–liquid extraction in which acceptor-to-donor phase ratio is greatly reduced compared with other methods. In the present review, the combination of DLLME with different analytical techniques such as atomic absorption spectrometry (AAS, inductively coupled plasma-optical emission spectrometry (ICP-OES, gas chromatography (GC, and high-performance liquid chromatography (HPLC for preconcentration and determination of inorganic analytes in different types of samples will be discussed. Recent developments in DLLME, e.g., displacement-DLLME, the use of an auxiliary solvent for adjustment of density of extraction mixture, and the application of ionic liquid-based DLLME in determination of inorganic species even in the presence of high content of salts are presented in the present review. Finally, comparison of DLLME with the other liquid-phase microextraction approaches and limitations of this technique are provided.

An on-line push/pull perfusion-based hollow-fiber liquid-phase microextraction system for high-performance liquid chromatographic determination of alkylphenols in water samples.

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Chao, Yu-Ying; Jian, Zhi-Xuan; Tu, Yi-Ming; Wang, Hsaio-Wen; Huang, Yeou-Lih

2013-06-07

In this study, we employed a novel on-line method, push/pull perfusion hollow-fiber liquid-phase microextraction (PPP-HF-LPME), to extract 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-n-nonylphenol, and 4-n-octylphenol from river and tap water samples; we then separated and quantified the extracted analytes through high-performance liquid chromatography (HPLC). Using this approach, we overcame the problem of fluid loss across the porous HF membrane to the donor phase, permitting on-line coupling of HF-LPME to HPLC. In our PPP-HF-LPME system, we used a push/pull syringe pump as the driving source to perfuse the acceptor phase, while employing a heating mantle and an ultrasonic probe to accelerate mass transfer. We optimized the experimental conditions such as the nature of the HF supported intermediary phase and the acceptor phase, the composition of the donor and acceptor phases, the sample temperature, and the sonication conditions. Our proposed method provided relative standard deviations of 3.1-6.2%, coefficients of determination (r(2)) of 0.9989-0.9998, and limits of detection of 0.03-0.2 ng mL(-1) for the analytes under the optimized conditions. When we applied this method to analyses of river and tap water samples, our results confirmed that this microextraction technique allows reliable monitoring of alkylphenols in water samples.

Application and optimization of microwave-assisted extraction and dispersive liquid-liquid microextraction followed by high-performance liquid chromatography for sensitive determination of polyamines in turkey breast meat samples.

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Bashiry, Moein; Mohammadi, Abdorreza; Hosseini, Hedayat; Kamankesh, Marzieh; Aeenehvand, Saeed; Mohammadi, Zaniar

2016-01-01

A novel method based on microwave-assisted extraction and dispersive liquid-liquid microextraction (MAE-DLLME) followed by high-performance liquid chromatography (HPLC) was developed for the determination of three polyamines from turkey breast meat samples. Response surface methodology (RSM) based on central composite design (CCD) was used to optimize the effective factors in DLLME process. The optimum microextraction efficiency was obtained under optimized conditions. The calibration graphs of the proposed method were linear in the range of 20-200 ng g(-1), with the coefficient determination (R(2)) higher than 0.9914. The relative standard deviations were 6.72-7.30% (n = 7). The limits of detection were in the range of 0.8-1.4 ng g(-1). The recoveries of these compounds in spiked turkey breast meat samples were from 95% to 105%. The increased sensitivity in using the MAE-DLLME-HPLC-UV has been demonstrated. Compared with previous methods, the proposed method is an accurate, rapid and reliable sample-pretreatment method. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ligandless-dispersive liquid-liquid microextraction of trace amount of copper ions

Energy Technology Data Exchange (ETDEWEB)

Mohammadi, Sayed Zia, E-mail: szmohammadi@yahoo.com [Department of Chemistry, Payame Noor University (PNU), Kerman (Iran, Islamic Republic of); Afzali, Daryoush [Environment Department, Institute Research of Environmental Sciences, International Center for Science, High Technology and Environmental Sciences, Kerman (Iran, Islamic Republic of); Baghelani, Yar Mohammad [Department of Chemistry, Payame Noor University (PNU), Kerman (Iran, Islamic Republic of)

2009-10-27

In the present work, a new ligandless-dispersive liquid-liquid microextraction (LL-DLLME) method has been developed for preconcentration trace amounts of copper as a prior step to its determination by flame atomic absorption spectrometry. In the proposed approach 1,2-dicholorobenzene and ethanol were used as extraction and dispersive solvents, respectively. Some factors influencing on the extraction efficiency of copper and its subsequent determination were studied and optimized, such as the extraction and dispersive solvent type and volume, pH of sample solution, extraction time and salting out effect. Under the optimal conditions, the calibration curve was linear in the range of 1.0 ng mL{sup -1}-0.6 {mu}g mL{sup -1} of copper with R{sup 2} = 0.9985. Detection limit was 0.5 ng mL{sup -1} in original solution (3S{sub b}/m) and the relative standard deviation for seven replicate determination of 0.2 {mu}g mL{sup -1} copper was {+-}1.4%. The proposed method has been applied for determination of copper in standard and water samples with satisfactory results.

Simultaneous Determination of Food-Related Biogenic Amines and Precursor Amino Acids Using in Situ Derivatization Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction by Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry.

Science.gov (United States)

He, Yongrui; Zhao, Xian-En; Wang, Renjun; Wei, Na; Sun, Jing; Dang, Jun; Chen, Guang; Liu, Zhiqiang; Zhu, Shuyun; You, Jinmao

2016-11-02

A simple, rapid, sensitive, selective, and environmentally friendly method, based on in situ derivatization ultrasound-assisted dispersive liquid-liquid microextraction (in situ DUADLLME) coupled with ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) using multiple reaction monitoring (MRM) mode has been developed for the simultaneous determination of food-related biogenic amines and amino acids. A new mass-spectrometry-sensitive derivatization reagent 4'-carbonyl chloride rosamine (CCR) was designed, synthesized, and first reported. Parameters and conditions of in situ DUADLLME and UHPLC-MS/MS were optimized in detail. Under the optimized conditions, the in situ DUADLLME was completed speedily (within 1 min) with high derivatization efficiencies (≥98.5%). With the cleanup and concentration of microextraction step, good analytical performance was obtained for the analytes. The results showed that this method was accurate and practical for quantification of biogenic amines and amino acids in common food samples (red wine, beer, wine, cheese, sausage, and fish).

Ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction combined with graphite furnace atomic absorption spectrometric for selenium speciation in foods and beverages.

Science.gov (United States)

Tuzen, Mustafa; Pekiner, Ozlem Zeynep

2015-12-01

A rapid and environmentally friendly ultrasound assisted ionic liquid dispersive liquid liquid microextraction (USA-IL-DLLME) was developed for the speciation of inorganic selenium in beverages and total selenium in food samples by using graphite furnace atomic absorption spectrometry. Some analytical parameters including pH, amount of complexing agent, extraction time, volume of ionic liquid, sample volume, etc. were optimized. Matrix effects were also investigated. Enhancement factor (EF) and limit of detection (LOD) for Se(IV) were found to be 150 and 12 ng L(-1), respectively. The relative standard deviation (RSD) was found 4.2%. The accuracy of the method was confirmed with analysis of LGC 6010 Hard drinking water and NIST SRM 1573a Tomato leaves standard reference materials. Optimized method was applied to ice tea, soda and mineral water for the speciation of Se(IV) and Se(VI) and some food samples including beer, cow's milk, red wine, mixed fruit juice, date, apple, orange, grapefruit, egg and honey for the determination of total selenium. Copyright © 2015 Elsevier Ltd. All rights reserved.

Overcoming the challenges of conventional dispersive liquid-liquid microextraction: analysis of THMs in chlorinated swimming pools.

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Faraji, Hakim; Helalizadeh, Masoumeh; Kordi, Mohammad Reza

2018-01-01

A rapid, simple, and sensitive approach to the analysis of trihalomethanes (THMs) in swimming pool water samples has been developed. The main goal of this study was to overcome or to improve the shortcomings of conventional dispersive liquid-liquid microextraction (DLLME) and to maximize the realization of green analytical chemistry principles. The method involves a simple vortex-assisted microextraction step, in the absence of the dispersive solvent, followed by salting-out effect for the elimination of the centrifugation step. A bell-shaped device and a solidifiable solvent were used to simplify the extraction solvent collection after phase separation. Optimization of the independent variables was performed by using chemometric methods in three steps. The method was statistically validated based on authentic guidance documents. The completion time for extraction was less than 8 min, and the limits of detection were in the range between 4 and 72 ng L -1 . Using this method, good linearity and precision were achieved. The results of THMs determination in different real samples showed that in some cases the concentration of total THMs was more than threshold values of THMs determined by accredited healthcare organizations. This method indicated satisfactory analytical figures of merit. Graphical Abstract A novel green microextraction technique for overcoming the challenges of conventional DLLME. The proposed procedure complies with the principles of green/sustainable analytical chemistry, comprising decreasing the sample size, making easy automation of the process, reducing organic waste, diminishing energy consumption, replacing toxic reagents with safer reagents, and enhancing operator safety.

Determination of organochlorine pesticides in water using dynamic hook-type liquid-phase microextraction

Energy Technology Data Exchange (ETDEWEB)

Chen, Pai-Shan; Huang, Shih-Pin [Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan (China); Fuh, Ming-Ren, E-mail: msfuh@mail.scu.edu.tw [Department of Chemistry, Soochow University, Taipei, Taiwan (China); Huang, Shang-Da, E-mail: sdhuang@mx.nthu.edu.tw [Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan (China)

2009-08-11

We developed a simple and efficient headspace liquid-phase microextraction (LPME) technique named dynamic hook-type liquid-phase microextraction (DHT-LPME) and used it in combination with gas chromatography-mass spectrometry (GC-MS) and an electron capture detector (ECD). Aqueous specimens of organochlorine pesticides (OCPs) were used as model compounds to demonstrate the effectiveness of the technique. In the present study, the calibration curves were linear over at least 2 orders of magnitude with R{sup 2} values of 0.997. The method detection limits (MDLs) varied from 2 to 44.0 ng L{sup -1}. The precision of DHT-LPME ranged from 6.5 to 14.4%. The relative recoveries of OCPs in rainwater were more than 84.2%. Enrichment factors (EF) in the range 275-1127 were obtained using DHT-LPME.

Determination of organochlorine pesticides in water using dynamic hook-type liquid-phase microextraction

International Nuclear Information System (INIS)

Chen, Pai-Shan; Huang, Shih-Pin; Fuh, Ming-Ren; Huang, Shang-Da

2009-01-01

We developed a simple and efficient headspace liquid-phase microextraction (LPME) technique named dynamic hook-type liquid-phase microextraction (DHT-LPME) and used it in combination with gas chromatography-mass spectrometry (GC-MS) and an electron capture detector (ECD). Aqueous specimens of organochlorine pesticides (OCPs) were used as model compounds to demonstrate the effectiveness of the technique. In the present study, the calibration curves were linear over at least 2 orders of magnitude with R 2 values of 0.997. The method detection limits (MDLs) varied from 2 to 44.0 ng L -1 . The precision of DHT-LPME ranged from 6.5 to 14.4%. The relative recoveries of OCPs in rainwater were more than 84.2%. Enrichment factors (EF) in the range 275-1127 were obtained using DHT-LPME.

Extraction and preconcentration of trace Al and Cr from vegetable samples by vortex-assisted ionic liquid-based dispersive liquid-liquid microextraction prior to atomic absorption spectrometric determination.

Science.gov (United States)

Altunay, Nail; Yıldırım, Emre; Gürkan, Ramazan

2018-04-15

In the study, a simple, and efficient microextraction approach, which is termed as vortex-assisted ionic liquid-based dispersive liquid-liquid microextraction (VA-IL-DLLME), was developed for flame atomic absorption spectrometric analysis of aluminum (Al) and chromium (Cr) in vegetables. The method is based on the formation of anionic chelate complexes of Al(III) and Cr(VI) with o-hydroxy azo dye, at pH 6.5, and then extraction of the hydrophobic ternary complexes formed in presence of cetyltrimethylammonium bromide (CTAB) into a 125 μL volume of 1-butyl-3-methylimidazolium bis(trifluorosulfonyl)imide [C 4 mim][Tf 2 N]) as extraction solvent. Under optimum conditions, the detection limits were 0.02 µg L -1 in linear working range of 0.07-100 µg L -1 for Al(III), and 0.05 µg L -1 in linear working range of 0.2-80 µg L -1 for Cr(VI). After the validation by analysis of a certified reference material (CRM), the method was successfully applied to the determination of Al and Cr in vegetables using standard addition method. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evaluation and application of microwave-assisted extraction and dispersive liquid-liquid microextraction followed by high-performance liquid chromatography for the determination of polar heterocyclic aromatic amines in hamburger patties.

Science.gov (United States)

Aeenehvand, Saeed; Toudehrousta, Zahra; Kamankesh, Marzieh; Mashayekh, Morteza; Tavakoli, Hamid Reza; Mohammadi, Abdorreza

2016-01-01

This study developed an analytical method based on microwave-assisted extraction and dispersive liquid-liquid microextraction followed by high-performance liquid chromatography for the determination of three polar heterocyclic aromatic amines from hamburger patties. Effective parameters controlling the performance of the microextraction process, such as the type and volume of extraction and disperser solvents, microwave time, nature of alkaline aqueous solution, pH and salt amount, were optimized. The calibration graphs were linear in the range of 1-200 ng g(-1), with a coefficient of determination (R(2)) better than 0.9993. The relative standard deviations (RSD) for seven analyses were between 3.2% and 6.5%. The recoveries of those compounds in hamburger patties were from 90% to 105%. Detection limits were between 0.06 and 0.21 ng g(-1). A comparison of the proposed method with the existing literature demonstrates that it is a simple, rapid, highly selective and sensitive, and it gives good enrichment factors and detection limits for determining HAAs in real hamburger patties samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

Determination of five antiarrhythmic drugs in human plasma by dispersive liquid-liquid microextraction and high-performance liquid chromatography.

Science.gov (United States)

Jouyban, Abolghasem; Sorouraddin, Mohammad Hossein; Farajzadeh, Mir Ali; Somi, Mohammad Hossein; Fazeli-Bakhtiyari, Rana

2015-03-01

A fast and sensitive high-performance liquid chromatography (HPLC) method with ultraviolet (UV) detection was developed and validated for the simultaneous quantitation of five antiarrhythmic drugs (metoprolol, propranolol, carvedilol, diltiazem, and verapamil) in human plasma samples. It involves dispersive liquid-liquid microextraction (DLLME) of the desired drugs from 660 µL plasma and separation using isocratic elution with UV detection at 200 nm. The complete separation of all analytes was achieved within 7 min. Acetonitrile (as disperser solvent) resulting from the protein precipitation procedure was mixed with 100 µL dichloromethane (as an extraction solvent) and rapidly injected into 5 mL aqueous solution (pH 11.5) containing 1% (w/v), NaCl. After centrifugation, the sedimented phase containing enriched analytes was collected and evaporated to dryness. The residue was re-dissolved in 50 µL de-ionized water (acidified to pH 3) and injected into the HPLC system for analysis. Under the optimal conditions, the enrichment factors and extraction recoveries ranged between 4.4-10.8 and 33-82%, respectively. The suggested method was linear (r(2) ≥0.997) over a dynamic range of 0.02-0.80 µg mL(-1) in plasma. The intra- and inter-days relative standard deviation (RSD%) and relative error (RE%) values of the method were below 20%, which shows good precision and accuracy. Finally, this method was applied to the analysis of real plasma samples obtained from the patients treated with these drugs. Copyright © 2014 Elsevier B.V. All rights reserved.

Combination of solvent extractants for dispersive liquid-liquid microextraction of fungicides from water and fruit samples by liquid chromatography with tandem mass spectrometry.

Science.gov (United States)

Pastor-Belda, Marta; Garrido, Isabel; Campillo, Natalia; Viñas, Pilar; Hellín, Pilar; Flores, Pilar; Fenoll, José

2017-10-15

A multiresidue method was developed to determine twenty-five fungicides belonging to three different chemical families, oxazoles, strobilurins and triazoles, in water and fruit samples, using dispersive liquid-liquid microextraction (DLLME) and liquid chromatography/tandem mass spectrometry (LC-MS 2 ). Solid-liquid extraction with acetonitrile was used for the analysis in fruits, the extract being used as dispersant solvent in DLLME. Since some of the analytes showed high affinity for chloroform and the others were more efficiently extracted with undecanol, a mixture of both solvents was used as extractant in DLLME. After evaporation of CHCl 3 , the enriched phase was analyzed. Enrichment factors in the 23-119 and 12-60 ranges were obtained for waters and fruits, respectively. The approach was most sensitive for metominostrobin with limits of quantification of 1ngL -1 and 5ngkg -1 in waters and fruits, respectively, while a similar sensitivity was attained for tebuconazole in fruits. Recoveries of the fungicides varied between 86 and 116%. Copyright © 2017 Elsevier Ltd. All rights reserved.

Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction for the determination of sulfonamides in animal tissues using high-performance liquid chromatography.

Science.gov (United States)

Wang, Zhibing; He, Mengyu; Jiang, Chunzhu; Zhang, Fengqing; Du, Shanshan; Feng, Wennan; Zhang, Hanqi

2015-12-01

Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction was developed and applied to the extraction of some sulfonamides, including sulfamerazine, sulfamethazine, sulfathiazole, sulfachloropyridazine, sulfadoxine, sulfisoxazole, and sulfaphenazole, in animal tissues. High-performance liquid chromatography was applied to the separation and determination of the target analytes. The solid sample was directly treated by matrix solid-phase dispersion and the eluate obtained was treated by homogeneous ionic liquid microextraction. The ionic liquid was used as the extraction solvent in this method, which may result in the improvement of the recoveries of the target analytes. To avoid using organic solvent and reduce environmental pollution, water was used as the elution solvent of matrix solid-phase dispersion. The effects of the experimental parameters on recoveries, including the type and volume of ionic liquid, type of dispersant, ratio of sample to dispersant, pH value of elution solvent, volume of elution solvent, amount of salt in eluate, amount of ion-pairing agent (NH4 PF6 ), and centrifuging time, were evaluated. When the present method was applied to the analysis of animal tissues, the recoveries of the analytes ranged from 85.4 to 118.0%, and the relative standard deviations were lower than 9.30%. The detection limits for the analytes were 4.3-13.4 μg/kg. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of Dispersive Liquid-Liquid Microextraction and UV-Vis Spectrophotometry for the Determination of Cadmium in Water Samples

Directory of Open Access Journals (Sweden)

J. Pérez-Outeiral

2014-01-01

Full Text Available A simple and inexpensive method for cadmium determination in water using dispersive liquid-liquid microextraction and ultraviolet-visible spectrophotometry was developed. In order to obtain the best experimental conditions, experimental design was applied. Calibration was made in the range of 10–100 μg/L, obtaining good linearity (R2 = 0.9947. The obtained limit of detection based on calibration curve was 8.5 μg/L. Intra- and interday repeatability were checked at two levels, obtaining relative standard deviation values from 9.0 to 13.3%. The enrichment factor had a value of 73. Metal interferences were also checked and tolerable limits were evaluated. Finally, the method was applied to cadmium determination in real spiked water samples. Therefore, the method showed potential applicability for cadmium determination in highly contaminated liquid samples.

Comparison of micellar extraction combined with ionic liquid based vortex-assisted liquid-liquid microextraction and modified quick, easy, cheap, effective, rugged, and safe method for the determination of difenoconazole in cowpea.

Science.gov (United States)

Chen, Xiaochu; Bian, Yanli; Liu, Fengmao; Teng, Peipei; Sun, Pan

2017-10-06

Two simple sample pretreatment for the determination of difenoconazole in cowpea was developed including micellar extraction combined with ionic liquid based vortex-assisted liquid-liquid microextraction (ME-IL-VALLME) prior to high performance liquid chromatography (HPLC), and modified quick, easy, cheap, effective, rugged, and safe method (QuEChERS) coupled with HPLC-MS/MS. In ME-IL-VALLME method, the target analyte was extracted by surfactant Tween 20 micellar solution, then the supernatant was diluted with 3mL water to decrease the solubility of micellar solution. Subsequently, the vortex-assisted liquid-liquid microextraction (VALLME) procedure was performed in the diluted extraction solution by using the ionic liquid of 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM]PF 6 ) as the extraction solvent and Tween 20 as an emulsifier to enhance the dispersion of the water-immiscible ionic liquid into the aqueous phase. Parameters that affect the extraction have been investigated in both methods Under the optimum conditions, the limits of quantitation were 0.10 and 0.05mgkg -1 , respectively. And good linearity was achieved with the correlation coefficient higher than 0.9941. The relative recoveries ranged from 78.6 to 94.8% and 92.0 to 118.0% with the relative standard deviations (RSD) of 7.9-9.6% and 1.2-3.2%, respectively. Both methods were quick, simple and inexpensive. However, the ME-IL-VALLME method provides higher enrichment factor compared with conventional QuEChERS method. The ME-IL-VALLME method has a strong potential for the determination of difenoconazole in complex vegetable matrices with HPLC. Copyright © 2017 Elsevier B.V. All rights reserved.

Ceria nanocubic-ultrasonication assisted dispersive liquid-liquid microextraction coupled with matrix assisted laser desorption/ionization mass spectrometry for pathogenic bacteria analysis.

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Abdelhamid, Hani Nasser; Bhaisare, Mukesh L; Wu, Hui-Fen

2014-03-01

A new ceria (CeO2) nanocubic modified surfactant is used as the basis of a novel nano-based microextraction technique for highly sensitive detection of pathogenic bacteria (Pseudomonas aeruginosa and Staphylococcus aureus). The technique uses ultrasound enhanced surfactant-assisted dispersive liquid-liquid microextraction (UESA-DLLME) with and without ceria (CeO2) followed by matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS). In order to achieve high separation efficiency, we investigated the influential parameters, including extraction time of ultrasonication, type and volume of the extraction solvent and surfactant. Among various surfactants, the cationic surfactants can selectively offer better extraction efficiency on bacteria analysis than that of the anionic surfactants due to the negative charges of bacteria cell membranes. Extractions of the bacteria lysate from aqueous samples via UESA-DLLME-MALDI-MS were successfully achieved by using cetyltrimethyl ammonium bromide (CTAB, 10.0 µL, 1.0×10(-3) M) as surfactants in chlorobenzene (10.0 µL) and chloroform (10.0 µL) as the optimal extracting solvent for P. aeruginosa and S. aureus, respectively. Ceria nanocubic was synthesized, and functionalized with CTAB (CeO2@CTAB) and then characterized using transmission electron microscopy (TEM) and optical spectroscopy (UV and FTIR). CeO2@CTAB demonstrates high extraction efficiency, improve peaks ionization, and enhance resolution. The prime reasons for these improvements are due to the large surface area of nanoparticles, and its absorption that coincides with the wavelength of MALDI laser (337 nm, N2 laser). CeO2@CTAB-based microextraction offers lowest detectable concentrations tenfold lower than that of without nanoceria. The present approach has been successfully applied to detect pathogenic bacteria at low concentrations of 10(4)-10(5) cfu/mL (without ceria) and at 10(3)-10(4) cfu/mL (with ceria) from bacteria suspensions. Finally, the

A new chiral residue analysis method for triazole fungicides in water using dispersive liquid-liquid microextraction (DLLME).

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Luo, Mai; Liu, Donghui; Zhou, Zhiqiang; Wang, Peng

2013-09-01

A rapid, simple, reliable, and environment-friendly method for the residue analysis of the enantiomers of four chiral fungicides including hexaconazole, triadimefon, tebuconazole, and penconazole in water samples was developed by dispersive liquid-liquid microextraction (DLLME) pretreatment followed by chiral high-performance liquid chromatography (HPLC)-DAD detection. The enantiomers were separated on a Chiralpak IC column by HPLC applying n-hexane or petroleum ether as mobile phase and ethanol or isopropanol as modifier. The influences of mobile phase composition and temperature on the resolution were investigated and most of the enantiomers could be completely separated in 20 min under optimized conditions. The thermodynamic parameters indicated that the separation was enthalpy-driven. The elution orders were detected by both circular dichroism detector (CD) and optical rotatory dispersion detector (ORD). Parameters affecting the DLLME performance for pretreatment of the chiral fungicides residue in water samples, such as the extraction and dispersive solvents and their volume, were studied and optimized. Under the optimum microextraction condition the enrichment factors were over 121 and the linearities were 30-1500 µg L(-1) with the correlation coefficients (R(2)) over 0.9988 and the recoveries were between 88.7% and 103.7% at the spiking levels of 0.5, 0.25, and 0.05 mg L(-1) (for each enantiomer) with relative standard deviations varying from 1.38% to 6.70% (n = 6) The limits of detection (LODs) ranged from 8.5 to 29.0 µg L(-1) (S/N = 3). © 2013 Wiley Periodicals, Inc.

Combination of dispersive liquid-liquid microextraction with flame atomic absorption spectrometry using microsample introduction for determination of lead in water samples.

Science.gov (United States)

Naseri, Mohammad Taghi; Hemmatkhah, Payam; Hosseini, Mohammad Reza Milani; Assadi, Yaghoub

2008-03-03

The dispersive liquid-liquid microextraction (DLLME) was combined with the flame atomic absorption spectrometry (FAAS) for determination of lead in the water samples. Diethyldithiophosphoric acid (DDTP), carbon tetrachloride and methanol were used as chelating agent, extraction solvent and disperser solvent, respectively. A new FAAS sample introduction system was employed for the microvolume nebulization of the non-flammable chlorinated organic extracts. Injection of 20 microL volumes of the organic extract into an air-acetylene flame provided very sensitive spike-like and reproducible signals. Some effective parameters on the microextraction and the complex formation were selected and optimized. These parameters include extraction and disperser solvent type as well as their volume, extraction time, salt effect, pH and amount of the chelating agent. Under the optimized conditions, the enrichment factor of 450 was obtained from a sample volume of 25.0 mL. The enhancement factor, calculated as the ratio of the slopes of the calibration graphs with and without preconcentration, which was about 1000. The calibration graph was linear in the range of 1-70 microgL(-1) with a detection limit of 0.5 microgL(-1). The relative standard deviation (R.S.D.) for seven replicate measurements of 5.0 and 50 microgL(-1) of lead were 3.8 and 2.0%, respectively. The relative recoveries of lead in tap, well, river and seawater samples at the spiking level of 20 microgL(-1) ranged from 93.8 to 106.2%. The characteristics of the proposed method were compared with those of the liquid-liquid extraction (LLE), cloud point extraction (CPE), on-line and off-line solid-phase extraction (SPE) as well as co-precipitation, based on bibliographic data. Operation simplicity, rapidity, low cost, high enrichment factor, good repeatability, and low consumption of the extraction solvent at a microliter level are the main advantages of the proposed method.

Selective determination of inorganic cobalt in nutritional supplements by ultrasound-assisted temperature-controlled ionic liquid dispersive liquid phase microextraction and electrothermal atomic absorption spectrometry

International Nuclear Information System (INIS)

Berton, Paula; Martinis, Estefanía M.; Martinez, Luis D.; Wuilloud, Rodolfo G.

2012-01-01

Highlights: ► Synergy of ultrasound energy and TILDLME technique for improved metal extraction. ► Highly selective determination of inorganic Co species at trace levels. ► Speciation analysis of Co in several nutritional supplements with highly complex matrices. ► Development of an environmentally friendly microextraction technique with minimal waste production and sample consumption. - Abstract: In the present work, a simple and rapid analytical method based on application of ionic liquids (ILs) for inorganic Co(II) species (iCo) microextraction in a variety of nutrient supplements was developed. Inorganic Co was initially chelated with 1-nitroso-2-naphtol (1N2N) reagent followed by a modern technique named ultrasound-assisted temperature-controlled ionic liquid dispersive liquid phase microextraction (USA-TILDLME). The extraction was performed with 1-hexyl-3-methylimidazolium hexafluorophosphate [C 6 mim][PF 6 ] with the aid of ultrasound to improve iCo recovery. Finally, the iCo-enriched IL phase was solubilized in methanol and directly injected into an electrothermal atomic absorption spectrometer (ETAAS). Several parameters that could influence iCo microextraction and detection were carefully studied. Since the main difficulty in these samples is caused by high concentrations of potential interfering ions, different approaches were evaluated to eliminate interferences. The limit of detection (LOD) was 5.4 ng L −1 , while the relative standard deviation (RSD) was 4.7% (at 0.5 μg L −1 Co level and n = 10), calculated from the peak height of absorbance signals. Selective microextraction of iCo species was achieved only by controlling the pH value during the procedure. The method was thus successfully applied for determination of iCo species in nutritional supplements.

Selective determination of inorganic cobalt in nutritional supplements by ultrasound-assisted temperature-controlled ionic liquid dispersive liquid phase microextraction and electrothermal atomic absorption spectrometry

Energy Technology Data Exchange (ETDEWEB)

Berton, Paula; Martinis, Estefania M. [Analytical Chemistry Research and Development Group (QUIANID), (LISAMEN-CCT-CONICET-Mendoza), Av. Ruiz Leal S/N Parque General San Martin, M 5502 IRA Mendoza (Argentina); Martinez, Luis D. [INQUISAL-CONICET, Departamento de Quimica Analitica, Facultad de Quimica, Bioquimica y Farmacia, Universidad Nacional de San Luis, San Luis (Argentina); Wuilloud, Rodolfo G., E-mail: rwuilloud@mendoza-conicet.gob.ar [Analytical Chemistry Research and Development Group (QUIANID), (LISAMEN-CCT-CONICET-Mendoza), Av. Ruiz Leal S/N Parque General San Martin, M 5502 IRA Mendoza (Argentina); Instituto de Ciencias Basicas, Universidad Nacional de Cuyo, Mendoza (Argentina)

2012-02-03

Highlights: Black-Right-Pointing-Pointer Synergy of ultrasound energy and TILDLME technique for improved metal extraction. Black-Right-Pointing-Pointer Highly selective determination of inorganic Co species at trace levels. Black-Right-Pointing-Pointer Speciation analysis of Co in several nutritional supplements with highly complex matrices. Black-Right-Pointing-Pointer Development of an environmentally friendly microextraction technique with minimal waste production and sample consumption. - Abstract: In the present work, a simple and rapid analytical method based on application of ionic liquids (ILs) for inorganic Co(II) species (iCo) microextraction in a variety of nutrient supplements was developed. Inorganic Co was initially chelated with 1-nitroso-2-naphtol (1N2N) reagent followed by a modern technique named ultrasound-assisted temperature-controlled ionic liquid dispersive liquid phase microextraction (USA-TILDLME). The extraction was performed with 1-hexyl-3-methylimidazolium hexafluorophosphate [C{sub 6}mim][PF{sub 6}] with the aid of ultrasound to improve iCo recovery. Finally, the iCo-enriched IL phase was solubilized in methanol and directly injected into an electrothermal atomic absorption spectrometer (ETAAS). Several parameters that could influence iCo microextraction and detection were carefully studied. Since the main difficulty in these samples is caused by high concentrations of potential interfering ions, different approaches were evaluated to eliminate interferences. The limit of detection (LOD) was 5.4 ng L{sup -1}, while the relative standard deviation (RSD) was 4.7% (at 0.5 {mu}g L{sup -1} Co level and n = 10), calculated from the peak height of absorbance signals. Selective microextraction of iCo species was achieved only by controlling the pH value during the procedure. The method was thus successfully applied for determination of iCo species in nutritional supplements.

Multimycotoxin LC-MS/MS Analysis in Tea Beverages after Dispersive Liquid-Liquid Microextraction (DLLME).

Science.gov (United States)

Pallarés, Noelia; Font, Guillermina; Mañes, Jordi; Ferrer, Emilia

2017-11-29

The aim of the present study was to develop a multimycotoxin liquid chromatography tandem mass spectrometry (LC-MS/MS) method with a dispersive liquid-liquid microextraction procedure (DLLME) for the analysis of AFs, 3aDON, 15aDON, NIV, HT-2, T-2, ZEA, OTA, ENNs, and BEA in tea beverages and to evaluate their mycotoxin contents. The proposed method was characterized in terms of linearity, limits of detection (LODs), limits of quantification (LOQs), recoveries, repeatability (intraday precision), reproducibility (interday precision), and matrix effects to check suitability. The results show LODs in the range of 0.05-10 μg/L, LOQs in the range of 0.2-33 μg/L, and recoveries in the range of 65-127% (RSD tea, red tea, green tea, and green mint tea. The results show that, of the analyzed mycotoxins, AFB2, AFG2, 15aDON, AFG1, and ENB were detected in the samples. AFB2 (14.4-32.2 μg/L) and 15aDON (60.5-61 μg/L) presented the highest levels. Green mint tea contained the highest concentration of mycotoxins. The risk assessment study shows that the population is not much exposed to mycotoxins through the consumption of tea beverages.

One-step displacement dispersive liquid-liquid microextraction coupled with graphite furnace atomic absorption spectrometry for the selective determination of methylmercury in environmental samples.

Science.gov (United States)

Liang, Pei; Kang, Caiyan; Mo, Yajun

2016-01-01

A novel method for the selective determination of methylmercury (MeHg) was developed by one-step displacement dispersive liquid-liquid microextraction (D-DLLME) coupled with graphite furnace atomic absorption spectrometry. In the proposed method, Cu(II) reacted with diethyldithiocarbamate (DDTC) to form Cu-DDTC complex, which was used as the chelating agent instead of DDTC for the dispersive liquid-liquid microextraction (DLLME) of MeHg. Because the stability of MeHg-DDTC is higher than that of Cu-DDTC, MeHg can displace Cu from the Cu-DDTC complex and be preconcentrated in a single DLLME procedure. MeHg could be extracted into the extraction solvent phase at pH 6 while Hg(II) remained in the sample solution. Potential interference from co-existing metal ions with lower DDTC complex stability was largely eliminated without the need of any masking reagent. Under the optimal conditions, the limit of detection of this method was 13.6ngL(-1) (as Hg), and an enhancement factor of 81 was achieved with a sample volume of 5.0mL. The proposed method was successfully applied for the determination of trace MeHg in some environmental samples with satisfactory results. Copyright © 2015 Elsevier B.V. All rights reserved.

Rapid and sensitive analysis of polychlorinated biphenyls and acrylamide in food samples using ionic liquid-based in situ dispersive liquid-liquid microextraction coupled to headspace gas chromatography.

Science.gov (United States)

Zhang, Cheng; Cagliero, Cecilia; Pierson, Stephen A; Anderson, Jared L

2017-01-20

A simple and rapid ionic liquid (IL)-based in situ dispersive liquid-liquid microextraction (DLLME) method was developed and coupled to headspace gas chromatography (HS-GC) employing electron capture (ECD) and mass spectrometry (MS) detection for the analysis of polychlorinated biphenyls (PCBs) and acrylamide at trace levels from milk and coffee samples. The chemical structures of the halide-based ILs were tailored by introducing various functional groups to the cations to evaluate the effect of different structural features on the extraction efficiency of the target analytes. Extraction parameters including the molar ratio of IL to metathesis reagent and IL mass were optimized. The effects of HS oven temperature and the HS sample vial volume on the analyte response were also evaluated. The optimized in situ DLLME method exhibited good analytical precision, good linearity, and provided detection limits down to the low ppt level for PCBs and the low ppb level for acrylamide in aqueous samples. The matrix-compatibility of the developed method was also established by quantifying acrylamide in brewed coffee samples. This method is much simpler and faster compared to previously reported GC-MS methods using solid-phase microextraction (SPME) for the extraction/preconcentration of PCBs and acrylamide from complex food samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction combined with electrothermal atomic absorption spectrometry for a sensitive determination of cadmium in water samples

International Nuclear Information System (INIS)

Li Shengqing; Cai Shun; Hu Wei; Chen Hao; Liu Hanlan

2009-01-01

A new method was developed for the determination of cadmium in water samples using ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction (IL-based USA-DLLME) followed by electrothermal atomic absorption spectrometry (ETAAS). The IL-based USA-DLLME procedure is free of volatile organic solvents, and there is no need for a dispersive solvent, in contrast to conventional DLLME. The ionic liquid, 1-hexyl-3-methylimidazolium hexafluorophosphate (HMIMPF 6 ), was quickly disrupted by an ultrasonic probe for 1 min and dispersed in water samples like a cloud. At this stage, a hydrophobic cadmium-DDTC complex was formed and extracted into the fine droplets of HMIMPF 6 . After centrifugation, the concentration of the enriched cadmium in the sedimented phase was determined by ETAAS. Some effective parameters of the complex formation and microextraction, such as the concentration of the chelating agent, the pH, the volume of the extraction solvent, the extraction time, and the salt effect, have been optimized. Under optimal conditions, a high extraction efficiency and selectivity were reached for the extraction of 1.0 ng of cadmium in 10.0 mL of water solution employing 73 μL of HMIMPF 6 as the extraction solvent. The enrichment factor of the method is 67. The detection limit was 7.4 ng L - 1 , and the characteristic mass (m 0 , 0.0044 absorbance) of the proposed method was 0.02 pg for cadmium (Cd). The relative standard deviation (RSD) for 11 replicates of 50 ng L - 1 Cd was 3.3%. The method was applied to the analysis of tap, well, river, and lake water samples and the Environmental Water Reference Material GSBZ 50009-88 (200921). The recoveries of spiked samples were in the range of 87.2-106%.

Dispersive liquid-liquid microextraction for metals enrichment: a useful strategy for improving sensitivity of laser-induced breakdown spectroscopy in liquid samples analysis.

Science.gov (United States)

Aguirre, M A; Selva, E J; Hidalgo, M; Canals, A

2015-01-01

A rapid and efficient Dispersive Liquid-Liquid Microextraction (DLLME) followed by Laser-Induced Breakdown Spectroscopy detection (LIBS) was evaluated for simultaneous determination of Cr, Cu, Mn, Ni and Zn in water samples. Metals in the samples were extracted with tetrachloromethane as pyrrolidinedithiocarbamate (APDC) complexes, using vortex agitation to achieve dispersion of the extractant solvent. Several DLLME experimental factors affecting extraction efficiency were optimized with a multivariate approach. Under optimum DLLME conditions, DLLME-LIBS method was found to be of about 4.0-5.5 times more sensitive than LIBS, achieving limits of detection of about 3.7-5.6 times lower. To assess accuracy of the proposed DLLME-LIBS procedure, a certified reference material of estuarine water was analyzed. Copyright © 2014 Elsevier B.V. All rights reserved.

Speciation of mercury in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Jia Xiaoyu; Han Yi; Liu Xinli; Duan Taicheng; Chen Hangting

2011-01-01

The dispersive liquid-liquid microextraction (DLLME) combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry for the speciation of mercury in water samples was described. Firstly methylmercury (MeHg + ) and mercury (Hg 2+ ) were complexed with sodium diethyldithiocarbamate, and then the complexes were extracted into carbon tetrachloride by using DLLME. Under the optimized conditions, the enrichment factors of 138 and 350 for MeHg + and Hg 2+ were obtained from only 5.00 mL sample solution. The detection limits of the analytes (as Hg) were 0.0076 ng mL -1 for MeHg + and 0.0014 ng mL -1 for Hg 2+ , respectively. The relative standard deviations for ten replicate measurements of 0.5 ng mL -1 MeHg + and Hg 2+ were 6.9% and 4.4%, respectively. Standard reference material of seawater (GBW(E)080042) was analyzed to verify the accuracy of the method and the results were in good agreement with the certified values. Finally, the developed method was successfully applied for the speciation of mercury in three environmental water samples.

Dispersive liquid-liquid microextraction (DLLME combined with graphite furnace atomic absorption spectrometry (GFAAS for determination of trace Cu and Zn in water Samples

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Ghorbani A.

2014-07-01

Full Text Available Dispersive liquid-liquid microextraction (DLLME combined with graphite furnace atomic absorption spectrometry (GFAAS was proposed for the determination of trace amounts of Copper and Zinc ions using 8-hydroxyquinoline (8-HQ as chelating agent. Several factors influencing the microextraction efficiency of Cu and Zn and their subsequent determinations, such as pH, extraction and disperser solvent type and their volume, concentration of the chelating agent and extraction time were studied, and the optimized experimental conditions were established. After extraction, the enrichment factors were 25 and 26 for Cu and Zn, respectively. The detection limits of the method were 0.025 and 0.0033 μg/L for Cu and Zn, and the relative standard deviations (R.S.D for five determinations of 1 ng/ml Cu and Zn were 8.51% and 7.41%, respectively.

A new dispersive liquid-liquid microextraction using ionic liquid based microemulsion coupled with cloud point extraction for determination of copper in serum and water samples.

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Arain, Salma Aslam; Kazi, Tasneem Gul; Afridi, Hassan Imran; Arain, Mariam Shahzadi; Panhwar, Abdul Haleem; Khan, Naeemullah; Baig, Jameel Ahmed; Shah, Faheem

2016-04-01

A simple and rapid dispersive liquid-liquid microextraction procedure based on ionic liquid assisted microemulsion (IL-µE-DLLME) combined with cloud point extraction has been developed for preconcentration copper (Cu(2+)) in drinking water and serum samples of adolescent female hepatitits C (HCV) patients. In this method a ternary system was developed to form microemulsion (µE) by phase inversion method (PIM), using ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) and nonionic surfactant, TX-100 (as a stabilizer in aqueous media). The Ionic liquid microemulsion (IL-µE) was evaluated through visual assessment, optical light microscope and spectrophotometrically. The Cu(2+) in real water and aqueous acid digested serum samples were complexed with 8-hydroxyquinoline (oxine) and extracted into IL-µE medium. The phase separation of stable IL-µE was carried out by the micellar cloud point extraction approach. The influence of of different parameters such as pH, oxine concentration, centrifugation time and rate were investigated. At optimized experimental conditions, the limit of detection and enhancement factor were found to be 0.132 µg/L and 70 respectively, with relative standard deviation <5%. In order to validate the developed method, certified reference materials (SLRS-4 Riverine water) and human serum (Sero-M10181) were analyzed. The resulting data indicated a non-significant difference in obtained and certified values of Cu(2+). The developed procedure was successfully applied for the preconcentration and determination of trace levels of Cu(2+) in environmental and biological samples. Copyright © 2015 Elsevier Inc. All rights reserved.

Use of dispersive liquid-liquid microextraction for simultaneous preconcentration of samarium, europium, gadolinium and dysprosium

International Nuclear Information System (INIS)

Mallah, M.H.; Atomic Energy Organization of Iran, Tehran; Shemirani, F.; Ghannadi Maragheh, M.

2008-01-01

A new preconcentration method of dispersive liquid-liquid microextraction (DLLME) was developed for simultaneous preconcentration of samarium, europium, gadolinium and dysprosium. DLLME technique was successfully used as a sample preparation method. In this preconcentration method, an appropriate mixture of extraction solvent, disperser solvent was injected rapidly into an aqueous solution containing Sm, Eu, Gd and Dy after complex formation using chelating reagent of the 1-(2-pyridylazo)-2-naphthol (PAN). After phase separation, 0.5 mL of the settled phase containing enriched analytes was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The main factors affected the preconcentration of Sm, Eu, Gd and Dy were extraction and dispersive solvent type and their volume, extraction time, volume of chelating agent (PAN), centrifuge speed and drying temperature of the samples. Under the best operating condition simultaneous preconcentration factors of 80, 100, 103 and 78 were obtained for Sm, Eu, Gd and Dy, respectively. (author)

Facile and sensitive determination of N-nitrosamines in food samples by high-performance liquid chromatography via combining fluorescent labeling with dispersive liquid-liquid microextraction.

Science.gov (United States)

Lu, Shuaimin; Wu, Di; Li, Guoliang; Lv, Zhengxian; Gong, Peiwei; Xia, Lian; Sun, Zhiwei; Chen, Guang; Chen, Xuefeng; You, Jinmao; Wu, Yongning

2017-11-01

The intake of N-nitrosamines (NAs) from foodstuffs is considered to be an important influence factor for several cancers. But the rapid and sensitive screening of NAs remains a challenge in the field of food safety. Inspired by that, a sensitive and rapid method was demonstrated for determination of five NAs (Nitrosopyrrolidine, Nitrosodimethylamine, Nitrosodiethylamine, Nitrosodipropylamine and Nitrosodibutylamine) using dispersive liquid-liquid microextraction (DLLME) followed by high-performance liquid chromatography with fluorescence detection (HPLC-FLD). The NAs were firstly denitrosated and labeled by 2-(11H-benzo[a]carbazol-11-yl) ethyl carbonochloridate (BCEC-Cl) and finally enriched by DLLME. Furthermore, the main DLLME conditions were optimized systematically. Under the optimal conditions, satisfactory limits of detection (LODs) were obtained with a range of 0.01-0.07ngg -1 , which were significantly lower than the reported methods. The developed method showed many merits including rapidity, simplicity, high sensitivity and excellent selectivity, which shows a broad prospect in food safety analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

An evaporation-assisted dispersive liquid-liquid microextraction technique as a simple tool for high performance liquid chromatography tandem-mass spectrometry determination of insecticides in wine.

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Timofeeva, Irina; Kanashina, Daria; Moskvin, Leonid; Bulatov, Andrey

2017-08-25

A sample pre-treatment technique based on evaporation-assisted dispersive liquid-liquid microextraction (EVA-DLLME), followed by HPLC-MS/MS has been developed for the determination of organophosphate insecticides (malathion, diazinon, phosalone) in wine samples. The procedure includes the addition of mixture of organic solvents (with density higher than water), consisting of the extraction (low density) and volatile (high density) solvents, to aqueous sample followed by heating of the mixture obtained, what promotes the volatile solvent evaporation and moving extraction solvent droplets from down to top of the aqueous sample and, as a consequence, microextraction of target analytes. To initiate the evaporation process an initiator is required. It was established that hexanol (extraction solvent) and dichloromethane (volatile solvent) mixture (1:1, v/v) provides effective microextraction of the insecticides from wine samples with recovery from 92 to 103%. The conditions of insecticides' microextraction such as selection of extraction solvent, ratio of hexanol/dichloromethane and hexanol/sample, type and concentration of initiator, and effect of ethanol as one of the main components of wine have been studied. Under optimal experimental conditions the linear detection ranges were found to be 10 -7 -10 -3 gL -1 for malathion, 10 -9 -10 -4 gL -1 for diazinon, and 10 -6 -10 -2 gL -1 for phosalone. The LODs, calculated from a blank test, based on 3σ, found to be 3×10 -8 gL -1 for malathion, 3×10 -10 gL -1 for diazinon and 3×10 -7 gL -1 for phosalone. The advantages of EVA-DLLME are the rapidity, simplicity, high sample throughput and low cost. As an outcome, the analytical results agreed fairly well with the results obtained by a reference GC-MS method. Copyright © 2017 Elsevier B.V. All rights reserved.

Solid-phase extraction in combination with dispersive liquid-liquid microextraction and ultra-high performance liquid chromatography-tandem mass spectrometry analysis: the ultra-trace determination of 10 antibiotics in water samples.

Science.gov (United States)

Liang, Ning; Huang, Peiting; Hou, Xiaohong; Li, Zhen; Tao, Lei; Zhao, Longshan

2016-02-01

A novel method, solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME), was developed for ultra-preconcentration of 10 antibiotics in different environmental water samples prior to ultra-high performance liquid chromatography-tandem mass spectrometry detection. The optimized results were obtained as follows: after being adjusted to pH 4.0, the water sample was firstly passed through PEP-2 column at 10 mL min(-1), and then methanol was used to elute the target analytes for the following steps. Dichloromethane was selected as extraction solvent, and methanol/acetonitrile (1:1, v/v) as dispersive solvent. Under optimal conditions, the calibration curves were linear in the range of 1-1000 ng mL(-1) (sulfamethoxazole, cefuroxime axetil), 5-1000 ng mL(-1) (tinidazole), 10-1000 ng mL(-1) (chloramphenicol), 2-1000 ng mL(-1) (levofloxacin oxytetracycline, doxycycline, tetracycline, and ciprofloxacin) and 1-400 ng mL(-1) (sulfadiazine) with a good precision. The LOD and LOQ of the method were at very low levels, below 1.67 and 5.57 ng mL(-1), respectively. The relative recoveries of the target analytes were in the range from 64.16% to 99.80% with relative standard deviations between 0.7 and 8.4%. The matrix effect of this method showed a great decrease compared with solid-phase extraction and a significant value of enrichment factor (EF) compared with dispersive liquid-liquid microextraction. The developed method was successfully applied to the extraction and analysis of antibiotics in different water samples with satisfactory results.

Application of dispersive liquid-liquid microextraction for the preconcentration of eight parabens in real samples and their determination by high-performance liquid chromatography.

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Shen, Xiong; Liang, Jian; Zheng, Luxia; Lv, Qianzhou; Wang, Hong

2017-11-01

A simple and sensitive method for the simultaneous determination of eight parabens in human plasma and urine samples was developed. The samples were preconcentrated using dispersive liquid-liquid microextraction based on the solidification of floating organic drops and determined by high-performance liquid chromatography with ultraviolet detection. The influence of variables affecting the extraction efficiency was investigated and optimized using Placket-Burman design and Box-Behnken design. The optimized values were: 58 μL of 1-decanol (as extraction solvent), 0.65 mL methanol (as disperser solvent), 1.5% w/v NaCl in 5.0 mL of sample solution, pH 10.6, and 4.0 min centrifugation at 4000 rpm. The extract was injected into the high-performance liquid chromatography system for analysis. Under the optimum conditions, the linear ranges for eight parabens in plasma and urine were 1.0-1000 ng/mL, with correlation coefficients above 0.994. The limit of detection was 0.2-0.4 and 0.1-0.4 ng/mL for plasma and urine samples, respectively. Relative recoveries were between 80.3 and 110.7%, while relative standard deviations were less than 5.4%. Finally, the method was applied to analyze the parabens in 98 patients of primary breast cancer. Results showed that parabens existed widely, at least one paraben detected in 96.9% (95/98) of plasma samples and 98.0% (96/98) of urine samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectrophotometric determination of mercury in water samples after preconcentration using dispersive liquid-liquid microextraction.

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Lemos, Valfredo Azevedo; dos Santos, Liz Oliveira; Silva, Eldevan dos Santos; Vieira, Emanuel Vitor dos Santos

2012-01-01

A simple method for the determination of mercury in water samples after preconcentration using dispersive liquid-liquid microextraction is described. The procedure is based on the extraction of mercury in the form of a complex and its subsequent determination by spectrophotometry. The complex is formed between Hg(II) and 2-(2-benzothiazolylazo)-p-cresol. The detection at 650 nm is performed directly in the metal-rich phase, which is spread on a triacetylcellulose membrane. The method eliminates the need to use a cuvet or large quantities of samples and reagents. The parameters that influence the preconcentration were studied, and the analytical characteristics were determined. The enrichment factor and the consumptive index for this method were 64 and 0.16 mL, respectively. The LOD (3.3 microg/L) and LOQ (11.1 microg/L) were also determined. The accuracy of the method was tested by the determination of mercury in certified reference materials BCR 397 (Human Hair) and SRM 2781 (Domestic Sludge). The method was applied to the determination of mercury in samples of drinking water, sea water, and river water.

Ionic liquid based vortex assisted liquid-liquid microextraction combined with liquid chromatography mass spectrometry for the determination of bisphenols in thermal papers with the aid of response surface methodology.

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Asati, Ankita; Satyanarayana, G N V; Panchal, Smita; Thakur, Ravindra Singh; Ansari, Nasreen G; Patel, Devendra K

2017-08-04

A sensitive, rapid and efficient ionic liquid-based vortex assisted liquid-liquid microextraction (IL-VALLME) with Liquid Chromatography Mass spectrometry (LC-MS/MS) method is proposed for the determination of bisphenols in thermal paper. Extraction factors were systematically optimized by response surface methodology. Experimental factors showing significant effects on the analytical responses were evaluated using design of experiment. The limit of detection for Bisphenol-A (BPA) and Bisphenol-S (BPS) in thermal paper were 1.25 and 0.93μgkg -1 respectively. The dynamic linearity range for BPA was between 4 and 100μgkg -1 and the determination of coefficient (R 2 ) was 0.996. The values of the same parameters were 3-100μgkg -1 and 0.998 for BPS. The extraction recoveries of BPA and BPS in thermal paper were 101% and 99%. Percent relative standard deviation (% RSD) for matrix effect and matrix match effects were not more than 10%, for both bisphenols. The proposed method uses a statistical approach for the analysis of bisphenols in environmental samples, and is easy, rapid, requires minimum organic solvents and efficient. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of antimony and tin in beverages using inductively coupled plasma-optical emission spectrometry after ultrasound-assisted ionic liquid dispersive liquid-liquid phase microextraction.

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Biata, N Raphael; Nyaba, Luthando; Ramontja, James; Mketo, Nomvano; Nomngongo, Philiswa N

2017-12-15

The aim of this study was to develop a simple and fast ultrasound-assisted ionic liquid dispersive liquid-liquid phase microextraction (UA-IL-DLLME) method for preconcetration of trace antimony and tin in beverage samples. The novelty of this study was based on the application of ligandless UA-IL-DLLME using low-density ionic liquid and organic solvents for preconcentration of Sb and Sn. The concentration of Sb and Sn were quantified using ICP-OES. Under the optimum conditions, the calibration graph was found to be LOQ-250µgL -1 (r 2 =0.9987) for Sb and LOQ-350µgL -1 for Sn. The LOD and LOQ of Sb and Sn ranged from 1.2to 2.5ngL -1 and 4.0 to 8.3ngL -1 , respectively, with high preconcentration factors. The precisions (%RSD) of the proposed method ranged from 2.1% to 2.5% and 3.9% to 4.7% for Sb and Sn, respectively. The proposed method was successfully applied for determination of Sb and Sn in beverages. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of three estrogens and bisphenol A by functional ionic liquid dispersive liquid-phase microextraction coupled with ultra-high performance liquid chromatography and ultraviolet detection.

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Jiang, Yuehuang; Tang, Tingting; Cao, Zhen; Shi, Guoyue; Zhou, Tianshu

2015-06-01

A hydroxyl-functionalized ionic liquid, 1-hydroxyethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, was employed in an improved dispersive liquid-phase microextraction method coupled with ultra high performance liquid chromatography for the enrichment and determination of three estrogens and bisphenol A in environmental water samples. The introduced hydroxyl group acted as the H-bond acceptor that dispersed the ionic liquid effectively in the aqueous phase without dispersive solvent or external force. Fourier transform infrared spectroscopy indicated that the hydroxyl group of the cation of the ionic liquid enhanced the combination of extractant and analytes through the formation of hydrogen bonds. The improvement of the extraction efficiency compared with that with the use of alkyl ionic liquid was proved by a comparison study. The main parameters including volume of extractant, temperature, pH, and extraction time were investigated. The calibration curves were linear in the range of 5.0-1000 μg/L for estrone, estradiol, and bisphenol A, and 10.0-1000 μg/L for estriol. The detection limits were in the range of 1.7-3.4 μg/L. The extraction efficiency was evaluated by enrichment factor that were between 85 and 129. The proposed method was proved to be simple, low cost, and environmentally friendly for the determination of the four endocrine disruptors in environmental water samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction and derivatization of sulfonamides in river water, honey, milk, and animal plasma

Energy Technology Data Exchange (ETDEWEB)

Xu Xu; Su Rui; Zhao Xin; Liu Zhuang; Zhang Yupu; Li Dan; Li Xueyuan; Zhang Hanqi [College of Chemistry, Jilin University, Changchun 130012 (China); Wang Ziming, E-mail: analchem@jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130012 (China)

2011-11-30

Graphical abstract: The extraction and derivatization efficiency of SAs is dependent on type and volume of extraction solvent, type and volume of disperser, microwave power and irradiation time, volume of derivatization reagent, pH of sample solution as well as ionic strength. Highlights: Black-Right-Pointing-Pointer A new, rapid and sensitive method for determining sulfonamides (SAs) was proposed. Black-Right-Pointing-Pointer Derivatization, extraction and preconcentration of SAs were performed in one step. Black-Right-Pointing-Pointer IL-based MADLLME and derivatization were first applied for the determination of SAs. Black-Right-Pointing-Pointer Trace SAs in river water, honey, milk, and pig plasma were determined. - Abstract: The ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction (IL-based MADLLME) and derivatization was applied for the pretreatment of six sulfonamides (SAs) prior to the determination by high-performance liquid chromatography (HPLC). By adding methanol (disperser), fluorescamine solution (derivatization reagent) and ionic liquid (extraction solvent) into sample, extraction, derivatization, and preconcentration were continuously performed. Several experimental parameters, such as the type and volume of extraction solvent, the type and volume of disperser, amount of derivatization reagent, microwave power, microwave irradiation time, pH of sample solution, and ionic strength were investigated and optimized. When the microwave power was 240 W, the analytes could be derivatized and extracted simultaneously within 90 s. The proposed method was applied to the analysis of river water, honey, milk, and pig plasma samples, and the recoveries of analytes obtained were in the range of 95.0-110.8, 95.4-106.3, 95.0-108.3, and 95.7-107.7, respectively. The relative standard deviations varied between 1.5% and 7.3% (n = 5). The results showed that the proposed method was a rapid, convenient and feasible method for the determination

Selective extraction of emerging contaminants from water samples by dispersive liquid-liquid microextraction using functionalized ionic liquids.

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Yao, Cong; Li, Tianhao; Twu, Pamela; Pitner, William R; Anderson, Jared L

2011-03-25

Functionalized ionic liquids containing the tris(pentafluoroethyl)trifluorophosphate (FAP) anion were used as extraction solvents in dispersive liquid-liquid microextraction (DLLME) for the extraction of 14 emerging contaminants from water samples. The extraction efficiencies and selectivities were compared to those of an in situ IL DLLME method which uses an in situ metathesis reaction to exchange 1-butyl-3-methylimidazolium chloride (BMIM-Cl) to 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMIM-NTf(2)). Compounds containing tertiary amine functionality were extracted with high selectivity and sensitivity by the 1-(6-amino-hexyl)-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (HNH(2)MPL-FAP) IL compared to other FAP-based ILs and the BMIM-NTf(2) IL. On the other hand, polar or acidic compounds without amine groups exhibited higher enrichment factors using the BMIM-NTf(2) IL. The detection limits for the studied analytes varied from 0.1 to 55.1 μg/L using the traditional IL DLLME method with the HNH(2)MPL-FAP IL as extraction solvent, and from 0.1 to 55.8 μg/L using in situ IL DLLME method with BMIM-Cl+LiNTf(2) as extraction solvent. A 93-fold decrease in the detection limit of caffeine was observed when using the HNH(2)MPL-FAP IL compared to that obtained using in situ IL DLLME method. Real water samples including tap water and creek water were analyzed with both IL DLLME methods and yielded recoveries ranging from 91% to 110%. Copyright © 2011 Elsevier B.V. All rights reserved.

Determination of statin drugs in hospital effluent with dispersive liquid-liquid microextraction and quantification by liquid chromatography.

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Martins, Ayrton F; Frank, Carla da S; Altissimo, Joseline; de Oliveira, Júlia A; da Silva, Daiane S; Reichert, Jaqueline F; Souza, Darliana M

2017-08-24

Statins are classified as being amongst the most prescribed agents for treating hypercholesterolaemia and preventing vascular diseases. In this study, a rapid and effective liquid chromatography method, assisted by diode array detection, was designed and validated for the simultaneous quantification of atorvastatin (ATO) and simvastatin (SIM) in hospital effluent samples. The solid phase extraction (SPE) of the analytes was optimized regarding sorbent material and pH, and the dispersive liquid-liquid microextraction (DLLME), in terms of pH, ionic strength, type and volume of extractor/dispersor solvents. The performance of both extraction procedures was evaluated in terms of linearity, quantification limits, accuracy (recovery %), precision and matrix effects for each analyte. The methods proved to be linear in the concentration range considered; the quantification limits were 0.45 µg L -1 for ATO and 0.75 µg L -1 for SIM; the matrix effect was almost absent in both methods and the average recoveries remained between 81.5-90.0%; and the RSD values were <20%. The validated methods were applied to the quantification of the statins in real samples of hospital effluent; the concentrations ranged from 18.8 µg L -1 to 35.3 µg L -1 for ATO, and from 30.3 µg L -1 to 38.5 µg L -1 for SIM. Since the calculated risk quotient was ≤192, the occurrence of ATO and SIM in hospital effluent poses a potential serious risk to human health and the aquatic ecosystem.

Combination of dispersive liquid-liquid microextraction with flame atomic absorption spectrometry using microsample introduction for determination of lead in water samples

International Nuclear Information System (INIS)

Naseri, Mohammad Taghi; Hemmatkhah, Payam; Hosseini, Mohammad Reza Milani; Assadi, Yaghoub

2008-01-01

The dispersive liquid-liquid microextraction (DLLME) was combined with the flame atomic absorption spectrometry (FAAS) for determination of lead in the water samples. Diethyldithiophosphoric acid (DDTP), carbon tetrachloride and methanol were used as chelating agent, extraction solvent and disperser solvent, respectively. A new FAAS sample introduction system was employed for the microvolume nebulization of the non-flammable chlorinated organic extracts. Injection of 20 μL volumes of the organic extract into an air-acetylene flame provided very sensitive spike-like and reproducible signals. Some effective parameters on the microextraction and the complex formation were selected and optimized. These parameters include extraction and disperser solvent type as well as their volume, extraction time, salt effect, pH and amount of the chelating agent. Under the optimized conditions, the enrichment factor of 450 was obtained from a sample volume of 25.0 mL. The enhancement factor, calculated as the ratio of the slopes of the calibration graphs with and without preconcentration, which was about 1000. The calibration graph was linear in the range of 1-70 μg L -1 with a detection limit of 0.5 μg L -1 . The relative standard deviation (R.S.D.) for seven replicate measurements of 5.0 and 50 μg L -1 of lead were 3.8 and 2.0%, respectively. The relative recoveries of lead in tap, well, river and seawater samples at the spiking level of 20 μg L -1 ranged from 93.8 to 106.2%. The characteristics of the proposed method were compared with those of the liquid-liquid extraction (LLE), cloud point extraction (CPE), on-line and off-line solid-phase extraction (SPE) as well as co-precipitation, based on bibliographic data. Operation simplicity, rapidity, low cost, high enrichment factor, good repeatability, and low consumption of the extraction solvent at a microliter level are the main advantages of the proposed method

Ionic liquid ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of the aqueous phase for preconcentration of heavy metals ions prior to determination by LC-UV.

Science.gov (United States)

Werner, Justyna

2018-05-15

Ionic liquid ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of the aqueous phase was used for preconcentration of Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ , Pb 2+ in natural water samples prior to liquid chromatography with UV detection. In the proposed method, the ammonium pyrrolidinedithiocarbamate was used as a complexing agent and the phosphonium ionic liquid trihexyl(tetradecyl)phosphonium bis[(2,4,4-trimethyl)pentyl]phosphinate (Cyphos IL 104) was used as an extractant. Ultrasound energy was used to disperse the extractant in the aqueous phase. After microextraction, the ionic liquid and aqueous phases were separated by centrifugation. Then the aqueous phase was frozen and the lighter than water ionic liquid phase containing metal ions complexes with pyrrolidinedithiocarbamate was separated and dissolved in a small volume of methanol prior to injection into the liquid chromatograph. Several parameters including the volume of extractant, the pH of the sample, the concentration of complexing agent, the time of ultrasound energy treatment, the time and speed of centrifugation and the effect of ionic strength were optimized. Under the optimized conditions (10 µL of Cyphos IL 104, pH = 5, 0.3% w/v ammonium pyrrolidinedithiocarbamate, 60 s of ultrasound use, 5 min/5000 rpm (2516×g) of centrifugation, 2.0 mg of NaCl), preconcentration factors were 211, 210, 209, 207 and 211 for Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ and Pb 2+ respectively. Linearity was observed in the ranges 0.2-75.0 µg L -1 for Pb 2+ , Cd 2+ , Co 2+ and 0.5-100.0 µg L -1 for Cu 2+ , Ni 2+ . The limits of detection were 0.03 µg L -1 for Ni 2+ , 0.03 µg L -1 for Co 2+ , 0.03 µg L -1 for Cd 2+ , 0.02 µg L -1 for Cu 2+ , 0.02 µg L -1 for Pb 2+ , respectively. The accuracy of this method was evaluated by preconcentration and determination of Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ , Pb 2+ in certified reference materials (TMRAIN-04 and NIST 1643e

Determination of Trichloroethylene in Water by Liquid–Liquid Microextraction Assisted Solid Phase Microextraction

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Mengliang Zhang

2015-02-01

Full Text Available A method for the determination of trichloroethylene (TCE in water using portable gas chromatography/mass spectrometry (GC/MS was developed. A novel sample preparation method, liquid–liquid microextraction assisted solid phase microextraction (LLME–SPME, is introduced. In this method, 20 µL of hexane was added to 10 mL of TCE contaminated aqueous samples to assist headspace SPME. The extraction efficiency of SPME was significantly improved with the addition of minute amounts of organic solvents (i.e., 20 µL hexane. The absolute recoveries of TCE at different concentrations were increased from 11%–17% for the samples extracted by SPME to 29%–41% for the samples extracted by LLME–SPME. The method was demonstrated to be linear from 10 to 1000 ng mL−1 for TCE in water. The improvements on extraction efficiencies were also observed for toluene and 1, 2, 4-trichlorobenzene in water by using LLME–SPME method. The LLME–SPME method was optimized by using response surface modeling (RSM.

Comparison of two novel in-syringe dispersive liquid-liquid microextraction techniques for the determination of iodide in water samples using spectrophotometry.

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Kaykhaii, Massoud; Sargazi, Mona

2014-01-01

Two new, rapid methodologies have been developed and applied successfully for the determination of trace levels of iodide in real water samples. Both techniques are based on a combination of in-syringe dispersive liquid-liquid microextraction (IS-DLLME) and micro-volume UV-Vis spectrophotometry. In the first technique, iodide is oxidized with nitrous acid to the colorless anion of ICl2(-) at high concentration of hydrochloric acid. Rhodamine B is added and by means of one step IS-DLLME, the ion-pair formed was extracted into toluene and measured spectrophotometrically. Acetone is used as dispersive solvent. The second method is based on the IS-DLLME microextraction of iodide as iodide/1, 10-phenanthroline-iron((II)) chelate cation ion-pair (colored) into nitrobenzene. Methanol was selected as dispersive solvent. Optimal conditions for iodide extraction were determined for both approaches. Methods are compared in terms of analytical parameters such as precision, accuracy, speed and limit of detection. Both methods were successfully applied to determining iodide in tap and river water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Determination of spirocyclic tetronic/tetramic acid derivatives and neonicotinoid insecticides in fruits and vegetables by liquid chromatography and mass spectrometry after dispersive liquid-liquid microextraction.

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Pastor-Belda, Marta; Garrido, Isabel; Campillo, Natalia; Viñas, Pilar; Hellín, Pilar; Flores, Pilar; Fenoll, José

2016-07-01

Dispersive liquid-liquid microextraction was used to preconcentrate three spirocyclic tetronic/tetramic acid derivatives (spirotetramat, spiromesifen and spirodiclofen) and five neonicotinoid (thiamethoxam, chlotianidin, imidacloprid, acetamiprid and thiacloprid) insecticides previously extracted from fruit and vegetable matrices with acetonitrile. The organic enriched phase was evaporated, reconstituted in 25μL acetonitrile and analyzed by reversed-phase liquid chromatography with tandem mass spectrometry using a triple quadrupole in selected reaction monitoring mode. Enrichment factors in the 15-100 range were obtained. A matrix effect was observed, the detection limits varying between 0.025 and 0.5ngg(-1), depending on the compound and the sample matrix. The developed method was applied to the analysis of 25 samples corresponding to five different fruit and vegetable matrices. Only thiamethoxam was detected in a lemon sample at a concentration close to the quantification limit, and spiromesifen and spirotetramat at concentrations between 11.6 and 54.5ngg(-1). Copyright © 2016 Elsevier Ltd. All rights reserved.

Ionic Liquid Dispersive Liquid-Liquid Microextraction Method for the Determination of Irinotecan, an Anticancer Drug, in Water and Urine Samples Using UV-Vis Spectrophotometry.

Science.gov (United States)

Uysal, Deniz; Karadaş, Cennet; Kara, Derya

2017-05-01

A new, simple, efficient, and environmentally friendly ionic liquid dispersive liquid-liquid microextraction method was developed for the determination of irinotecan, an anticancer drug, in water and urine samples using UV-Vis spectrophotometry. The ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate was used as the extraction solvent, and ethanol was used as the disperser solvent. The main parameters affecting the extraction efficiency, including sample pH, volume of the ionic liquid, choice of the dispersive solvent and its volume, concentration of NaCl, and extraction and centrifugation times, were investigated and optimized. The effect of interfering species on the recovery of irinotecan was also examined. Under optimal conditions, the LOD (3σ) was 48.7 μg/L without any preconcentration. Because the urine sample was diluted 10-fold, the LOD for urine would be 487 μg/L. However, this could be improved 16-fold if preconcentration using a 40 mL aliquot of the sample is used. The proposed method was successfully applied to the determination of irinotecan in tap water, river water, and urine samples spiked with 10.20 mg/L for the water samples and 8.32 mg/L for the urine sample. The average recovery values of irinotecan determined were 99.1% for tap water, 109.4% for river water, and 96.1% for urine.

Liquid-phase microextraction for simultaneous chromatographic analysis of three antidepressant drugs in plasma

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Carlos Eduardo Dobrovolskni Porto

2012-01-01

Full Text Available A method using Liquid Phase Microextraction for simultaneous detection of citalopram (CIT, paroxetine (PAR and fluoxetine (FLU, using venlafaxine as internal standard, in plasma by high performance liquid chromatography with fluorescence detection was developed. The linearity was evaluated between 5.0 and 500 ng mL-1 (r > 0.99 and the limit of quantification was 2.0, 3.0 and 5.0 ng mL-1 for CIT, PAR and FLU, respectively. Therefore, it can be applied to therapeutic drug monitoring, pharmacokinetics or bioavailability studies and its advantages are that it necessary relatively inexpensive equipment and sample preparation techniques.

Development of a novel 96-well format for liquid-liquid microextraction and its application in the HPLC analysis of biological samples.

Science.gov (United States)

Borijihan, Guirong; Li, Youxin; Gao, Jianguo; Bao, James J

2014-05-01

A novel 96-well liquid-liquid microextraction system combined with modern HPLC was developed and used for the simultaneous analysis of 96 biological samples. The system made use of hollow fibers, a 96-well plate, and a plastic base with a center hole and a side hole. One end of the hollow fiber was sealed, while the other end was attached to one of the holes positioned at the center for the plastic base. The needle was inserted into the liquid from inside or outside of the hollow fiber through the center or the side holes, respectively. The system was tested with plasma samples containing three compounds, acidic indomethacin, neutral dexamethasone, and basic propafenone. Some parameters, such as the kind and dimension of hollow fiber, pH and salt concentration of the donor phase, the selection of organic solvent for the acceptor phase, and the extraction time were investigated. Under the optimization conditions, the Log D and drug concentration of indomethacin, dexamethasone, and propafenone in plasma and urine samples were analyzed. Then, the methodology was validated. The results demonstrated that ng/mL levels could be exactly and rapidly analyzed by our system, which was equipped with an auto-injection sampler, making sample analysis more convenient. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In-syringe magnetic-stirring-assisted liquid-liquid microextraction for the spectrophotometric determination of Cr(VI) in waters.

Science.gov (United States)

Henríquez, Camelia; Horstkotte, Burkhard; Solich, Petr; Cerdà, Víctor

2013-08-01

A fully automated method for the determination of chromate is described. It is based on the selective reaction of Cr(VI) with diphenylcarbazide in acidic media to form a colored complex of Cr(III) with the oxidation product diphenylcarbazone. The reaction was performed within the syringe of an automatic burette containing a magnetic stirrer for homogenization of the sample and the required reagents. In-syringe stirring was made possible using a specially designed driving device placed around the syringe barrel to achieve a rotating magnetic field in the syringe, forcing the stirrer to spin. In a second step, the reaction mixture in the syringe was neutralized to allow in-syringe magnetic-stirring-assisted dispersive liquid-liquid microextraction of the complex into 125 μL of n-hexanol. After phase separation by droplet flotation over 30 s, the organic phase was propelled into a coupled spectrophotometric detection cell. The entire multistep procedure including in-system standard preparation was done within 270 s. The method was used for the analysis of natural waters, achieving average analyte recovery of 103%, a limit of detection of 0.26 μg L(-1), and a repeatability of less than 4% relative standard deviation.

Speciation of mercury in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Jia Xiaoyu; Han Yi; Liu Xinli [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Duan Taicheng, E-mail: tcduan@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022 (China); Chen Hangting, E-mail: htchen@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022 (China)

2011-01-15

The dispersive liquid-liquid microextraction (DLLME) combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry for the speciation of mercury in water samples was described. Firstly methylmercury (MeHg{sup +}) and mercury (Hg{sup 2+}) were complexed with sodium diethyldithiocarbamate, and then the complexes were extracted into carbon tetrachloride by using DLLME. Under the optimized conditions, the enrichment factors of 138 and 350 for MeHg{sup +} and Hg{sup 2+} were obtained from only 5.00 mL sample solution. The detection limits of the analytes (as Hg) were 0.0076 ng mL{sup -1} for MeHg{sup +} and 0.0014 ng mL{sup -1} for Hg{sup 2+}, respectively. The relative standard deviations for ten replicate measurements of 0.5 ng mL{sup -1} MeHg{sup +} and Hg{sup 2+} were 6.9% and 4.4%, respectively. Standard reference material of seawater (GBW(E)080042) was analyzed to verify the accuracy of the method and the results were in good agreement with the certified values. Finally, the developed method was successfully applied for the speciation of mercury in three environmental water samples.

Determination of desipramine in biological samples using liquid-liquid-liquid microextraction combined with in-syringe derivatization, gas chromatography, and nitrogen/phosphorus detection.

Science.gov (United States)

Saraji, Mohammad; Mehrafza, Narges; Bidgoli, Ali Akbar Hajialiakbari; Jafari, Mohammad Taghi

2012-10-01

A method was established for the determination of desipramine in biological samples using liquid-liquid-liquid microextraction followed by in-syringe derivatization and gas chromatography-nitrogen phosphorus detection. The extraction method was based on the use of two immiscible organic solvents. n-Dodecane was impregnated in the pores of the hollow fiber and methanol was placed inside the lumen of the fiber as the acceptor phase. Acetic anhydride was used as the reagent for the derivatization of the analyte inside the syringe barrel. Parameters that affect the extraction efficiency (composition of donor and acceptor phase, ionic strength, sample temperature, and extraction time) as well as derivatization efficiency (amount of acetic anhydride and reaction time and temperature) were investigated. The limit of detection was 0.02 μg/L with intra and interday RSDs of 2.6 and 7.7%, respectively. The linearity of the method was in the range of 0.2-20 μg/L (r(2) = 0.9986). The method was successfully applied to determine desipramine in human plasma and urine. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hollow fiber-based liquid-liquid-liquid micro-extraction with osmosis: II. Application to quantification of endogenous gibberellins in rice plant.

Science.gov (United States)

Wu, Qian; Wu, Dapeng; Duan, Chunfeng; Shen, Zheng; Guan, Yafeng

2012-11-23

The phenomenon and benefits of osmosis in hollow fiber-based liquid-liquid-liquid micro-extraction (HF-LLLME) were theoretically discussed in part I of this study. In this work, HF-LLLME with osmosis was coupled with high performance liquid chromatography-triple quadrupole mass spectrometry (HPLC-triple quadrupole MS/MS) to analyze eight gibberellins (gibberellin A(1), gibberellin A(3), gibberellin A(4), gibberellin A(7), gibberellin A(8), gibberellin A(9), gibberellin A(19) and gibberellin A(20)) in rice plant samples. According to the theory of HF-LLLME with osmosis, single factor experiments, orthogonal design experiments and mass transfer simulation of extraction process were carried out to select the optimal conditions. Cyclohexanol - n-octanol (1:3, v/v) was selected as organic membrane. Donor phase of 12 mL was adjusted to pH 2 and 20% NaCl (w/v) was added. Acceptor phase with an initial volume of 20 μL was the solution of 0.12 mol L(-1) Na(2)CO(3)-NaHCO(3) buffer (pH 9). Temperature was chosen to be 30 °C and extraction time was selected to be 90 min. Under optimized conditions, this method provided good linearity (r, 0.99552-0.99991) and low limits of detection (0.0016-0.061 ng mL(-1)). Finally, this method was applied to the analysis of endogenous gibberellins from plant extract which was obtained with traditional solvent extraction of rice plant tissues, and the relative recoveries were from 62% to 166%. Copyright © 2012 Elsevier B.V. All rights reserved.

Automated dispersive liquid-liquid microextraction coupled to high performance liquid chromatography - cold vapour atomic fluorescence spectroscopy for the determination of mercury species in natural water samples.

Science.gov (United States)

Liu, Yao-Min; Zhang, Feng-Ping; Jiao, Bao-Yu; Rao, Jin-Yu; Leng, Geng

2017-04-14

An automated, home-constructed, and low cost dispersive liquid-liquid microextraction (DLLME) device that directly coupled to a high performance liquid chromatography (HPLC) - cold vapour atomic fluorescence spectroscopy (CVAFS) system was designed and developed for the determination of trace concentrations of methylmercury (MeHg + ), ethylmercury (EtHg + ) and inorganic mercury (Hg 2+ ) in natural waters. With a simple, miniaturized and efficient automated DLLME system, nanogram amounts of these mercury species were extracted from natural water samples and injected into a hyphenated HPLC-CVAFS for quantification. The complete analytical procedure, including chelation, extraction, phase separation, collection and injection of the extracts, as well as HPLC-CVAFS quantification, was automated. Key parameters, such as the type and volume of the chelation, extraction and dispersive solvent, aspiration speed, sample pH, salt effect and matrix effect, were thoroughly investigated. Under the optimum conditions, linear range was 10-1200ngL -1 for EtHg + and 5-450ngL -1 for MeHg + and Hg 2+ . Limits of detection were 3.0ngL -1 for EtHg + and 1.5ngL -1 for MeHg + and Hg 2+ . Reproducibility and recoveries were assessed by spiking three natural water samples with different Hg concentrations, giving recoveries from 88.4-96.1%, and relative standard deviations <5.1%. Copyright © 2017 Elsevier B.V. All rights reserved.

Ionic Liquid-Assisted Liquid-Liquid Microextraction based on the Solidification of Floating Organic Droplet in Sample Preparation for Simultaneous Determination of Herbicide Residues in Fruits.

Science.gov (United States)

Vichapong, Jitlada; Santaladchaiyakit, Yanawath; Burakham, Rodjana; Srijaranai, Supalax

2017-09-01

An ionic liquid-assisted liquid-liquid microextraction based on the solidification of floating organic droplet (ILSFODLLME) was investigated for analysis of four herbicide residues (i.e. simazine, atrazine, propazine, and linuron) by high performance liquid chromatography. For ILSFOD-LLME, the optimal extraction conditions were 5% w/v Na2SO4, 30 μL [C4MIM][PF6]RTIL, 100 μL of 1-octanol, ultrasonication time 30 s and centrifugation at 5000 rpm for 5 min. Under the optimal conditions, linearity was obtained within the range of 0.1-1000 μg kg-1, with the correlation coefficients greater than 0.999. The high enrichment factors of the target analytes were in the range of 64.5-139.9 and low limit of detection could be obtained. A modified QuEChERS was applied for fruit sample preparation before analysis. Matrix effects were also investigated using matrix matched standards for construction of the calibration graph. The proposed method has been successfully applied for extraction and preconcentration of herbicide residues in fruit samples, and good recoveries in the range of 87.32% to 99.93% were obtained.

Dispersive Liquid-Liquid Microextraction Combined with Ultrahigh Performance Liquid Chromatography/Tandem Mass Spectrometry for Determination of Organophosphate Esters in Aqueous Samples

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Haiying Luo

2014-01-01

Full Text Available A new technique was established to identify eight organophosphate esters (OPEs in this work. It utilised dispersive liquid-liquid microextraction in combination with ultrahigh performance liquid chromatography/tandem mass spectrometry. The type and volume of extraction solvents, dispersion agent, and amount of NaCl were optimized. The target analytes were detected in the range of 1.0–200 µg/L with correlation coefficients ranging from 0.9982 to 0.9998, and the detection limits of the analytes were ranged from 0.02 to 0.07 µg/L (S/N=3. The feasibility of this method was demonstrated by identifying OPEs in aqueous samples that exhibited spiked recoveries, which ranged between 48.7% and 58.3% for triethyl phosphate (TEP as well as between 85.9% and 113% for the other OPEs. The precision was ranged from 3.2% to 9.3% (n=6, and the interprecision was ranged from 2.6% to 12.3% (n=5. Only 2 of the 12 selected samples were tested to be positive for OPEs, and the total concentrations of OPEs in them were 1.1 and 1.6 µg/L, respectively. This method was confirmed to be simple, fast, and accurate for identifying OPEs in aqueous samples.

Simultaneous determination of organophosphorus pesticides and phthalates in baby food samples by ultrasound-vortex-assisted liquid-liquid microextraction and GC-IT/MS.

Science.gov (United States)

Notardonato, Ivan; Salimei, Elisabetta; Russo, Mario Vincenzo; Avino, Pasquale

2018-05-01

Baby foods are either a soft, liquid paste or an easily chewed food since babies lack developed muscles and teeth to chew effectively. Babies typically move to consuming baby food once nursing or formula is not sufficient for the child's appetite. Some commercial baby foods have been criticized for their contents. This article focuses on the simultaneous determination of organophosphorus pesticides and phthalates by means of a method based on ultrasound-vortex-assisted liquid-liquid microextraction coupled with gas chromatography-ion trap mass spectrometry (GC-IT/MS). The protocol developed allowed the determination of six phthalates [dimethyl phthalate, diethyl phthalate, dibutyl phthalate, isobutyl cyclohexyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate] and 19 organophosphorus pesticides. Freeze-dried product samples (0.1-0.2 g) were dissolved in 10 mL of warm distilled water along with 5 μL of an internal standard (anthracene at 10 mg mL -1 in acetone): the choice of extraction solvent was studied, with the most suitable being n-heptane, which is used for phthalate determination in similar matrices. The solution, held for 5 min in a vortex mixer and for 6 min in a 100-W ultrasonic bath to favor solvent dispersion and consequently analyte extraction, was centrifuged at 4000 rpm for 30 min. Then 1 μL was injected into the GC-IT/MS system (SE-54 capillary column; length 30 m, inner diameter 250 μm, film thickness 0.25 μm). All analytical parameters investigated are discussed in depth. The method was applied to real commercial freeze-dried samples: significant contaminant concentrations were not found. Graphical abstract Simultaneous and sensitive determination of organophosphorus pesticides and phthalates in baby foods by the ultrasound-vortex-assisted liquid-liquid microextraction ֪gas chromatography-ion trap mass spectrometry procedure. 1 methacrifos, 2 pirofos, 3 phorate, 4 seraphos, 5 diazinon, 6 etrimphos, 7 dichlofenthion, 8

Determination of carbohydrates in tobacco by pressurized liquid extraction combined with a novel ultrasound-assisted dispersive liquid-liquid microextraction method.

Science.gov (United States)

Cai, Kai; Hu, Deyu; Lei, Bo; Zhao, Huina; Pan, Wenjie; Song, Baoan

2015-07-02

A novel derivatization-ultrasonic assisted-dispersive liquid-liquid microextraction (UA-DLLME) method for the simultaneous determination of 11 main carbohydrates in tobacco has been developed. The combined method involves pressurized liquid extraction (PLE), derivatization, and UA-DLLME, followed by the analysis of the main carbohydrates with a gas chromatography-flame ionization detector (GC-FID). First, the PLE conditions were optimized using a univariate approach. Then, the derivatization methods were properly compared and optimized. The aldononitrile acetate method combined with the O-methoxyoxime-trimethylsilyl method was used for derivatization. Finally, the critical variables affecting the UA-DLLME extraction efficiency were searched using fractional factorial design (FFD) and further optimized using Doehlert design (DD) of the response surface methodology. The optimum conditions were found to be 44 μL for CHCl3, 2.3 mL for H2O, 11% w/v for NaCl, 5 min for the extraction time and 5 min for the centrifugation time. Under the optimized experimental conditions, the detection limit of the method (LODs) and linear correlation coefficient were found to be in the range of 0.06-0.90 μg mL(-1) and 0.9987-0.9999. The proposed method was successfully employed to analyze three flue-cured tobacco cultivars, among which the main carbohydrate concentrations were found to be very different. Copyright © 2015 Elsevier B.V. All rights reserved.

Ultrasound-air-assisted demulsified liquid-liquid microextraction by solidification of a floating organic droplet for determination of three antifungal drugs in water and biological samples.

Science.gov (United States)

Ezoddin, Maryam; Shojaie, Mehran; Abdi, Khosrou; Karimi, Mohammad Ali

2017-03-01

A novel ultrasound-air-assisted demulsified liquid-liquid microextraction by solidification of a floating organic droplet (UAAD-LLM-SFO) followed by HPLC-UV detection was developed for the analysis of three antifungal drugs in water and biological samples. In this method, 1-dodecanol was used as the extraction solvent. The emulsion was rapidly formed by pulling in and pushing out the mixture of sample solution and extraction solvent for 5 times repeatedly using a 10-mL glass syringe while sonication was performed. Therefore, an organic dispersive solvent required in common microextraction methods was not used in the proposed method. After dispersing, an aliquot of acetonitrile was introduced as a demulsifier solvent into the sample solution to separate two phases. Therefore, some additional steps, such as the centrifugation, ultrasonication, or agitation of the sample solution, are not needed. Parameters influencing the extraction recovery were investigated. The proposed method showed a good linearity for the three antifungal drugs studied with the correlation coefficients (R 2  > 0.9995). The limits of detection (LODs) and the limits of the quantification (LOQs) were between 0.01-0.03 μg L -1 and 0.03-0.08 μg L -1 , respectively. The preconcentration factors (PFs) were in the range of 107-116, respectively. The precisions, as the relative standard deviations (RSDs) (n = 5), for inter-day and intra-day analysis were in the range of 2.1-4.5% and 6.5-8.5%, respectively. This method was successfully applied to determine the three antifungal drugs in tap water and biological samples. The recoveries of antifungal drugs in these samples were 92.4-98.5%. Graphical abstract Ultrasound-air-assisted demulsified liquid-liquid microextraction by solidification of a floating organic droplet for the analysis of three antifungal drugs prior HPLC-UV.

Determination of parabens using two microextraction methods coupled with capillary liquid chromatography-UV detection.

Science.gov (United States)

Chen, Chen-Wen; Hsu, Wen-Chan; Lu, Ya-Chen; Weng, Jing-Ru; Feng, Chia-Hsien

2018-02-15

Parabens are common preservatives and environmental hormones. As such, possible detrimental health effects could be amplified through their widespread use in foods, cosmetics, and pharmaceutical products. Thus, the determination of parabens in such products is of particular importance. This study explored vortex-assisted dispersive liquid-liquid microextraction techniques based on the solidification of a floating organic drop (VA-DLLME-SFO) and salt-assisted cloud point extraction (SA-CPE) for paraben extraction. Microanalysis was performed using a capillary liquid chromatography-ultraviolet detection system. These techniques were modified successfully to determine four parabens in 19 commercial products. The regression equations of these parabens exhibited good linearity (r 2 =0.998, 0.1-10μg/mL), good precision (RSD<5%) and accuracy (RE<5%), reduced reagent consumption and reaction times (<6min), and excellent sample versatility. VA-DLLME-SFO was also particularly convenient due to the use of a solidified extract. Thus, the VA-DLLME-SFO technique was better suited to the extraction of parabens from complex matrices. Copyright © 2017 Elsevier Ltd. All rights reserved.

Air-assisted dispersive liquid-liquid microextraction based on a new hydrophobic deep eutectic solvent for the preconcentration of benzophenone-type UV filters from aqueous samples.

Science.gov (United States)

Ge, Dandan; Zhang, Yi; Dai, Yixiu; Yang, Shumin

2018-04-01

Deep eutectic solvents are considered as new and green solvents that can be widely used in analytical chemistry such as microextraction. In the present work, a new dl-menthol-based hydrophobic deep eutectic solvent was synthesized and used as extraction solvents in an air-assisted dispersive liquid-liquid microextraction method for preconcentration and extraction of benzophenone-type UV filters from aqueous samples followed by high-performance liquid chromatography with diode array detection. In an experiment, the deep eutectic solvent formed by dl-menthol and decanoic acid was added to an aqueous solution containing the UV filters, and then the mixture was sucked up and injected five times by using a glass syringe, and a cloudy state was achieved. After extraction, the solution was centrifuged and the upper phase was subjected to high-performance liquid chromatography for analysis. Various parameters such as the type and volume of the deep eutectic solvent, number of pulling, and pushing cycles, solution pH and salt concentration were investigated and optimized. Under the optimum conditions, the developed method exhibited low limits of detection and limits of quantitation, good linearity, and precision. Finally, the proposed method was successfully applied to determine the benzophenone-type filters in environmental water samples with relative recoveries of 88.8-105.9%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessment of strobilurin fungicides' content in soya-based drinks by liquid micro-extraction and liquid chromatography with tandem mass spectrometry.

Science.gov (United States)

Campillo, Natalia; Iniesta, María Jesús; Viñas, Pilar; Hernández-Córdoba, Manuel

2015-01-01

Seven strobilurin fungicides were pre-concentrated from soya-based drinks using dispersive liquid-liquid micro-extraction (DLLME) with a prior protein precipitation step in acid medium. The enriched phase was analysed by liquid chromatography (LC) with dual detection, using diode array detection (DAD) and electrospray-ion trap tandem mass spectrometry (ESI-IT-MS/MS). After selecting 1-undecanol and methanol as the extractant and disperser solvents, respectively, for DLLME, the Taguchi experimental method, an orthogonal array design, was applied to select the optimal solvent volumes and salt concentration in the aqueous phase. The matrix effect was evaluated and quantification was carried out using external aqueous calibration for DAD and matrix-matched calibration method for MS/MS. Detection limits in the 4-130 and 0.8-4.5 ng g(-1) ranges were obtained for DAD and MS/MS, respectively. The DLLME-LC-DAD-MS method was applied to the analysis of 10 different samples, none of which was found to contain residues of the studied fungicides.

Rapid determination of 226Ra in drinking water samples using dispersive liquid-liquid microextraction coupled with liquid scintillation counting

International Nuclear Information System (INIS)

Sadi, B.K.; Chunsheng Li; Kramer, G.H.; Johnson, C.L.; Queenie Ko; Lai, E.P.C.

2011-01-01

A new radioanalytical method was developed for rapid determination of 226 Ra in drinking water samples. The method is based on extraction and preconcentration of 226 Ra from a water sample to an organic solvent using a dispersive liquid-liquid microextraction (DLLME) technique followed by radiometric measurement using liquid scintillation counting. In DLLME for 226 Ra, a mixture of an organic extractant (toluene doped with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone) and a disperser solvent (acetonitrile) is rapidly injected into the water sample resulting in the formation of an emulsion. Within the emulsion, 226 Ra reacts with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone and partitions into the fine droplets of toluene. The water/toluene phases were separated by addition of acetonitrile as a de-emulsifier solvent. The toluene phase containing 226 Ra was then measured by liquid scintillation counting. Several parameters were studied to optimize the extraction efficiency of 226 Ra, including water immiscible organic solvent, disperser and de-emulsifier solvent type and their volume, chelating ligands for 226 Ra and their concentrations, inorganic salt additive and its concentration, and equilibrium pH. With the optimized DLLME conditions, the accuracy (expressed as relative bias, B r ) and method repeatability (expressed as relative precision, S B ) were determined by spiking 226 Ra at the maximum acceptable concentration level (0.5 Bq L -1 ) according to the Guidelines for Canadian Drinking Water Quality. Accuracy and repeatability were found to be less than -5% (B r ) and less than 6% (S B ), respectively, for both tap water and bottled natural spring water samples. The minimum detectable activity and sample turnaround time for determination of 226 Ra was 33 mBq L -1 and less than 3 h, respectively. The DLLME technique is selective for extraction of 226 Ra from its decay progenies. (author)

Optimization of two different dispersive liquid-liquid microextraction methods followed by gas chromatography-mass spectrometry determination for polycyclic aromatic hydrocarbons (PAHs) analysis in water.

Science.gov (United States)

Tseng, Wan-Chi; Chen, Pai-Shan; Huang, Shang-Da

2014-03-01

Novel sample preparation methods termed "up-and-down shaker-assisted dispersive liquid-liquid microextraction (UDSA-DLLME)" and "water with low concentration of surfactant in dispersed solvent-assisted emulsion dispersive liquid-liquid microextraction (WLSEME)" coupled with gas chromatography-mass spectrometry (GC-MS) have been developed for the analysis of 11 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. For UDSA-DLLME, an up-and-down shaker-assisted emulsification was employed. Extraction was complete in 3min. Only 14 μL of 1-heptanol was required, without a dispersive solvent. Under the optimum conditions, the linear range was 0.08-100 µg L(-1), and the LODs were in the range 0.022-0.060 µg L(-1). The enrichment factors (EFs) ranged from 392 to 766. Relative recoveries were between 84% and 113% for river, lake, and field water. In WLSEME, 9 μL of 1-nonanol as extraction solvent and 240 μL of 1 mg L(-1) Triton X-100 as surfactant were mixed in a microsyringe to form a cloudy emulsified solution, which was then injected into the samples. Compared with other surfactant-assisted emulsion methods, WLSEME uses much less surfactant. The linear range was 0.08-100 µg L(-1), and the LODs were 0.022-0.13 µg L(-1). The EFs ranged from 388 to 649. The relative recoveries were 86-114% for all three water specimens. Copyright © 2013 Elsevier B.V. All rights reserved.

Development of an ionic-liquid-based dispersive liquid-liquid microextraction method for the determination of antichagasic drugs in human breast milk: Optimization by central composite design.

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Padró, Juan M; Pellegrino Vidal, Rocío B; Echevarria, Romina N; Califano, Alicia N; Reta, Mario R

2015-05-01

Chagas disease constitutes a major public health problem in Latin America. Human breast milk is a biological sample of great importance for the analysis of therapeutic drugs, as unwanted exposure through breast milk could result in pharmacological effects in the nursing infant. Thus, the goal of breast milk drug analysis is to inquire to which extent a neonate may be exposed to a drug during lactation. In this work, we developed an analytical technique to quantify benznidazole and nifurtimox (the two antichagasic drugs currently available for medical treatment) in human breast milk, with a simple sample pretreatment followed by an ionic-liquid-based dispersive liquid-liquid microextraction combined with high-performance liquid chromatography and UV detection. For this technique, the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate has been used as the "extraction solvent." A central composite design was used to find the optimum values for the significant variables affecting the extraction process: volume of ionic liquid, volume of dispersant solvent, ionic strength, and pH. At the optimum working conditions, the average recoveries were 77.5 and 89.7%, the limits of detection were 0.06 and 0.09 μg/mL and the interday reproducibilities were 6.25 and 5.77% for benznidazole and nifurtimox, respectively. The proposed methodology can be considered sensitive, simple, robust, accurate, and green. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Miniaturized preconcentration methods based on liquid-liquid extraction and their application in inorganic ultratrace analysis and speciation: A review

International Nuclear Information System (INIS)

Pena-Pereira, Francisco; Lavilla, Isela; Bendicho, Carlos

2009-01-01

Liquid-liquid extraction (LLE) is widely used as a pre-treatment technique for separation and preconcentration of both organic and inorganic analytes from aqueous samples. Nevertheless, it has several drawbacks, such as emulsion formation or the use of large volumes of solvents, which makes LLE expensive and labour intensive. Therefore, miniaturization of conventional liquid-liquid extraction is needed. The search for alternatives to the conventional LLE using negligible volumes of extractant and the minimum number of steps has driven the development of three new miniaturized methodologies, i.e. single-drop microextraction (SDME), hollow fibre liquid-phase microextraction (HF-LPME) and dispersive liquid-liquid microextraction (DLLME). The aim of this paper is to provide an overview of these novel preconcentration approaches and their potential use in analytical labs involved in inorganic (ultra)trace analysis and speciation. Relevant applications to the determination of metal ions, metalloids, organometals and non-metals are included

Modified dispersive liquid-liquid microextraction for pre-concentration of benzene, toluene, ethylbenzene and xylenes prior to their determination by GC

International Nuclear Information System (INIS)

Faraji, Hakim; Feizbakhsh, Alireza; Helalizadeh, Masoumeh

2013-01-01

We have developed a modified method for the extraction and preconcentration of benzene, toluene, ethylbenzene and xylenes (BTEX) in aqueous samples. It based on dispersive liquid-liquid microextraction along with solidification of floating organic microdrops. The dispersion of microvolumes of an extracting solvent into the aqueous occurs without dispersive solvent. Various parameters have been optimized. BTEX were quantified via GC with FID detection. Under optimized conditions, the preconcentration factors range from 301 to 514, extraction efficiencies from 60 to 103 %, repeatabilities from 2.2 to 4.1 %, and intermediate precisions from 3.5 to 7.0 %. The relative recovery for each analyte in water samples at three spiking levels is >85.6 %, with a relative standard deviation of <7.4 %. (author)

Speciation of chromium by dispersive liquid–liquid microextraction followed by laser-induced breakdown spectrometry detection (DLLME–LIBS)

OpenAIRE

Gaubeur, Ivanise; Aguirre Pastor, Miguel Ángel; Kovachev, Nikolay; Hidalgo Núñez, Montserrat; Canals Hernández, Antonio

2015-01-01

In this study, an analytical methodology based on a combination of dispersive liquid–liquid microextraction with laser-induced breakdown spectrometry was evaluated for simultaneous pre-concentration, speciation and detection of Cr. The microextraction procedure was based on the injection of appropriated quantities of 1-undecanol and ethanol into a sample solution containing the complexes formed between Cr(VI) and diethyldithiocarbamate (DDTC). The main experimental factors affecting the compl...

Simple and Rapid Dual-Dispersive Liquid-Liquid Microextraction as an Innovative Extraction Method for Uranium in Real Water Samples Prior to the Determination of Uranium by a Spectrophotometric Technique.

Science.gov (United States)

Khan, Naeemullah; Tuzen, Mustafa; Kazi, Tasneem Gul

2017-11-01

An innovative, rapid, and simple dual-dispersive liquid-liquid microextraction (DDLL-ME) approach was used to extract uranium from real samples for the first time. The main objective of this study was to disperse extraction solvent by using an air-agitated syringe system to overcome matrix effects and avoid dispersion of hazardous dispersive organic solvents by using heat. The DDLL-ME method consisted of two dispersive liquid-liquid extraction steps with chloroform as the extracting solvent. Uranium formed complexes with 4-(2-thiazolylazo) resorcinol in the aqueous phase and was extracted in extracting solvent (chloroform) after the first dispersive liquid-liquid process. Uranium was then back-extracted in the acidic aqueous phase in a second dispersive liquid-liquid process. Finally, uranium was determined by a spectrophotometric detection technique. The variables that played a key role in the proposed method were studied and optimized. The LOD and sensitivity enhancement factor for uranium were found to be 0.60 µg/L and 45, respectively, under optimized conditions. Calibration graphs were found to be linear in the range of 5.0-600 µg/L. The RSD was 2.5%. Reliability of the proposed method was verified by analyzing certified reference material TM-28.3.

Dispersive liquid-liquid microextraction followed by high-performance liquid chromatography-ultraviolet detection to determination of opium alkaloids in human plasma.

Science.gov (United States)

Ahmadi-Jouibari, Toraj; Fattahi, Nazir; Shamsipur, Mojtaba; Pirsaheb, Meghdad

2013-11-01

A novel, simple, rapid and sensitive dispersive liquid-liquid microextraction method based on the solidification of floating organic drop (DLLME-SFO) combined with high-performance liquid chromatography-ultraviolet detection (HPLC-UV) was used to determine opium alkaloids in human plasma. During the extraction procedure, plasma protein was precipitated by using a mixture of zinc sulfate solution and acetonitrile. Some effective parameters on extraction were studied and optimized. Under the optimum conditions (extraction solvent: 30.0 μl 1-undecanol; disperser solvent: 470 μl acetone; pH: 9; salt addition: 1%(w/v) NaCl and extraction time: 0.5 min), calibration curves are linear in the range of 1.5-1000 μgl(-1) and limit of detections (LODs) are in the range of 0.5-5 μgl(-1). The relative standard deviations (RSDs) for 100 μgl(-1) of morphine and codeine, 10.0 μgl(-1) of papaverine and 20.0 μgl(-1) of noscapine in diluted human plasma are in the range of 4.3-7.4% (n=5). Finally, the method was successfully applied in the determination of opium alkaloids in the actual human plasma samples. The relative recoveries of plasma samples spiked with alkaloids are 88-110.5%. The obtained results show that DLLME-SFO combined with HPLC-UV is a fast and simple method for the determination of opium alkaloids in human plasma. Copyright © 2013 Elsevier B.V. All rights reserved.

Elemental analysis by surface-enhanced Laser-Induced Breakdown Spectroscopy combined with liquid–liquid microextraction

International Nuclear Information System (INIS)

Aguirre, M.A.; Legnaioli, S.; Almodóvar, F.; Hidalgo, M.; Palleschi, V.; Canals, A.

2013-01-01

In this work, the possibility of using Laser-Induced Breakdown Spectrometry (LIBS) combined with liquid–liquid microextraction techniques is evaluated as a simple and fast method for trace elemental analysis. Two different strategies for LIBS analysis of manganese contained in microdroplets of extraction solvent (Triton X-114) are studied: (i) analysis by direct laser irradiation of microdroplets; and (ii) analysis by laser irradiation of microdroplets dried on metallic substrates (surface-enhanced LIBS — SENLIBS). Experiments were carried out using synthetic samples with different concentrations of manganese in a 10% w/w Triton X-114 matrix. The analysis by direct laser irradiation of microdroplets showed low precision, sensitivity and poor linearity across the concentration range evaluated (R 2 −1 of Mn. - Highlights: ► LIBS combined with microextraction procedures for trace analysis is proposed. ► The proposed combination depends on LIBS ability to analyze sample microvolumes. ► A surface-enhanced LIBS methodology for microdroplet analysis was evaluated. ► Results indicate this combination to be promising for trace analysis in liquids

Analysis of drugs of abuse in human plasma by dispersive liquid-liquid microextraction and high-performance liquid chromatography.

Science.gov (United States)

Fernández, P; Regenjo, M; Bermejo, A M; Fernández, A M; Lorenzo, R A; Carro, A M

2015-04-01

Opioids and cocaine are widely used at present, both for recreational purposes and as drugs of abuse. This raises the need to develop new analytical methods specifically designed for the simultaneous detection of several drugs of abuse in biological samples. In this work, dispersive liquid-liquid microextraction (DLLME) was assessed as a new sample treatment for the simultaneous extraction of morphine (MOR), 6-acetylmorphine (6AM), cocaine (COC), benzoylecgonine (BZE) and methadone (MET) from human plasma. Preliminary assays were done before developing an experimental design based on a Uniform Network Doehlert which allowed the optimum extraction conditions to be identified, namely: a volume of extractant solvent (chloroform) and dispersant solvent (acetonitrile) of 220 µl and 3.2 ml, respectively; 0.2 g of NaCl as a salting-out additive; pH 10.6 and ultrasound stirring for 3.5 min. The resulting extracts were analyzed by high-performance liquid chromatography with photodiode array detection (HPLC-PDA), using an XBridge® RP18 column (250 × 4.6 mm i.d., 5 µm particle size). Calibration graphs were linear over the concentration range 0.1-10 µg ml⁻¹, and detection limits ranged from 13.9 to 28.5 ng ml⁻¹. Precision calculated at three different concentration levels in plasma was included in the range 0.1-6.8% RSD. Recoveries of the five drugs were all higher than 84% on average. Finally the proposed method was successfully applied to 22 plasma samples from heroin, cocaine and/or methadone users, and the most frequently detected drug was benzoylecgonine, followed by methadone, cocaine and morphine. Copyright © 2014 John Wiley & Sons, Ltd.

Iron species determination by task-specific ionic liquid-based in situ solvent formation dispersive liquid-liquid microextraction combined with flame atomic absorption spectrometry.

Science.gov (United States)

Sadeghi, Susan; Ashoori, Vahid

2017-10-01

The task-specific ionic liquid (TSIL) of 1-ethyl-3-methylimidazolium bromide functionalized with 8-hydroxyquinoline was used as a chelating agent and extracting solvent for dispersive liquid-liquid microextraction and subsequent determination of Fe(III) by flame atomic absorption spectrometry. The in situ solvent formation of TSIL using KPF 6 provided the desired water-immiscible ionic liquid. The total Fe concentration could be determined after pre-oxidation of Fe(II) to Fe(III). Various factors affecting the proposed extraction procedure were optimized. The proposed analytical conditions were: sample pH 5, TSIL amount 0.3% (w/v), KPF 6 amount 0.15% (w/v), anti-sticking 0.1% (w/v) and salt concentration 5% (w/v). Under optimal conditions, the linear dynamic ranges for Fe(III) and total Fe were 20-80 and 20-110 ng mL -1 , respectively, with a detection limit of 6.9 ng mL -1 for Fe(III) and relative standard deviation of 2.2%. The proposed method was successfully applied to the determination of trace Fe(III) in water (underground, tap, refined water and artificial sea water) and beverage (apple, tomato, and tea) samples. The developed method offers advantages such as simplicity, ease of operation, and extraction of Fe(III) from aqueous solutions without the use of organic solvent. It was successfully applied for iron speciation in different real samples. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Sensitive determination of three aconitum alkaloids and their metabolites in human plasma by matrix solid-phase dispersion with vortex-assisted dispersive liquid-liquid microextraction and HPLC with diode array detection.

Science.gov (United States)

Wang, Xiaozhong; Li, Xuwen; Li, Lanjie; Li, Min; Liu, Ying; Wu, Qian; Li, Peng; Jin, Yongri

2016-05-01

A simple and sensitive method for determination of three aconitum alkaloids and their metabolites in human plasma was developed using matrix solid-phase dispersion combined with vortex-assisted dispersive liquid-liquid microextraction and high-performance liquid chromatography with diode array detection. The plasma sample was directly purified by matrix solid-phase dispersion and the eluate obtained was concentrated and further clarified by vortex-assisted dispersive liquid-liquid microextraction. Some important parameters affecting the extraction efficiency, such as type and amount of dispersing sorbent, type and volume of elution solvent, type and volume of extraction solvent, salt concentration as well as sample solution pH, were investigated in detail. Under optimal conditions, the proposed method has good repeatability and reproducibility with intraday and interday relative standard deviations lower than 5.44 and 5.75%, respectively. The recoveries of the aconitum alkaloids ranged from 73.81 to 101.82%, and the detection limits were achieved within the range of 1.6-2.1 ng/mL. The proposed method offered the advantages of good applicability, sensitivity, simplicity, and feasibility, which makes it suitable for the determination of trace amounts of aconitum alkaloids in human plasma samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hollow fiber liquid-phase microextraction of cadmium(II) using an ionic liquid as the extractant

International Nuclear Information System (INIS)

Chen, Hui; Wang, Yun; Hu, Yutao; Ni, Liang; Liu, Yingying; Kang, Wenbing; Liu, Yan; Han, Juan

2014-01-01

A method is presented for hollow fiber liquid-phase microextraction (HF-LPME) of cadmium(II), which is chelated with 1-(2-pyridylazo)-2-naphthol (PAN) to obtain a hydrophobic complex which then is extracted into a polypropylene hollow fiber containing an ionic liquid in its pores which acts as the membrane phase. EDTA is then injected into the lumen of the membrane as an acceptor phase to trap the analyte. The extraction time (20 min), agitation (400 rpm at 25 °C), pH value (10.0), and the concentrations of PAN (2.5 ng mL −1 ) and EDTA (250 ng mL −1 ) were optimized. With a sample volume of 50 mL and a stripping volume of 15 μL, the enrichment factor is 162. Cadmium(II) was then quantified by graphite furnace AAS. The limit of detection is 0.12 pg mL −1 , the relative standard deviation is 5.2 %, and the linear working range extends from 4 to 45 pg mL −1 . The method was successfully applied to the determination of Cd(II) in environmental and food samples. (author)

Ion-pair vortex assisted liquid-liquid microextraction with back extraction coupled with high performance liquid chromatography-UV for the determination of metformin in plasma.

Science.gov (United States)

Alshishani, Anas; Makahleh, Ahmad; Yap, Hui Fang; Gubartallah, Elbaleeq Adam; Salhimi, Salizawati Muhamad; Saad, Bahruddin

2016-12-01

A new sample preparation method, ion-pair vortex assisted liquid-liquid microextraction (VALLME-BE), for the determination of a highly polar anti-diabetic drug (metformin) in plasma sample was developed. The VALLME-BE was performed by diluting the plasma in borate buffer and extracted to 150µL 1-octanol containing 0.2M di-(2-ethylhexyl)phosphoric acid as intermediate phase. The drug was next back-extracted into 20µL of 0.075M HCl solution. The effects of pH, ion-pair concentration, type of organic solvent, volume of extraction phases, ionic strength, vortexing and centrifugation times on the extraction efficiency were investigated. The optimum conditions were at pH 9.3, 60s vortexing and 2min centrifugation. The microextract, contained metformin and buformin (internal standard), was directly injected into a HPLC unit using C1 column (250mm×4.6mm×10µm) and detected at 235nm. The method was validated and calibration curve was linear with r 2 >0.99 over the range of 20-2000µgL -1 . The limits of detection and quantitation were 1.4 and 4.1µgL -1 , respectively. The accuracy was within 94.8-108% of the nominal concentration. The relative standard deviation for inter- and intra-day precision was less than 10.8%. The method was conveniently applied for the determination of metformin in plasma samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Liquid-phase microextraction combined with graphite furnace atomic absorption spectrometry: A review.

Science.gov (United States)

de la Calle, Inmaculada; Pena-Pereira, Francisco; Lavilla, Isela; Bendicho, Carlos

2016-09-14

An overview of the combination of liquid-phase microextraction (LPME) techniques with graphite furnace atomic absorption spectrometry (GFAAS) is reported herein. The high sensitivity of GFAAS is significantly enhanced by its association with a variety of miniaturized solvent extraction approaches. LPME-GFAAS thus represents a powerful combination for determination of metals, metalloids and organometallic compounds at (ultra)trace level. Different LPME modes used with GFAAS are briefly described, and the experimental parameters that show an impact in those microextraction processes are discussed. Special attention is paid to those parameters affecting GFAAS analysis. Main issues found when coupling LPME and GFAAS, as well as those strategies reported in the literature to solve them, are summarized. Relevant applications published on the topic so far are included. Copyright © 2016 Elsevier B.V. All rights reserved.

A dispersive liquid--liquid microextraction methodology for copper (II) in environmental samples prior to determination using microsample injection flame atomic absorption spectrometry.

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Alothman, Zeid A; Habila, Mohamed; Yilmaz, Erkan; Soylak, Mustafa

2013-01-01

A simple, environmentally friendly, and efficient dispersive liquid-liquid microextraction method combined with microsample injection flame atomic absorption spectrometry was developed for the separation and preconcentration of Cu(II). 2-(5-Bromo-2-pyridylazo)-5-(diethylamino)phenol (5-Br-PADAP) was used to form a hydrophobic complex of Cu(II) ions in the aqueous phase before extraction. To extract the Cu(II)-5-Br-PADAP complex from the aqueous phase to the organic phase, 2.0 mL of acetone as a disperser solvent and 200 microL of chloroform as an extraction solvent were used. The influences of important analytical parameters, such as the pH, types and volumes of the extraction and disperser solvents, amount of chelating agent, sample volume, and matrix effects, on the microextraction procedure were evaluated and optimized. Using the optimal conditions, the LOD, LOQ, preconcentration factor, and RSD were determined to be 1.4 microg/L, 4.7 microg/L, 120, and 6.5%, respectively. The accuracy of the proposed method was investigated using standard addition/recovery tests. The analysis of certified reference materials produced satisfactory analytical results. The developed method was applied for the determination of Cu in real samples.

Simultaneous extraction and quantification of albendazole and triclabendazole using vortex-assisted hollow-fiber liquid-phase microextraction combined with high-performance liquid chromatography.

Science.gov (United States)

Asadi, Mohammad; Haji Shabani, Ali Mohammad; Dadfarnia, Shayessteh

2016-06-01

A novel, simple, and rapid vortex-assisted hollow-fiber liquid-phase microextraction method was developed for the simultaneous extraction of albendazole and triclabendazole from various matrices before their determination by high-performance liquid chromatography with fluorescence detection. Several factors influencing the microextraction efficiency including sample pH, nature and volume of extraction solvent, ionic strength, vortex time, and sample volume were investigated and optimized. Under the optimal conditions, the limits of detection were 0.08 and 0.12 μg/L for albendazole and triclabendazole, respectively. The calibration curves were linear in the concentration ranges of 0.3-50.0 and 0.4-50.0 μg/L with the coefficients of determination of 0.9999 and 0.9995 for albendazole and triclabendazole, respectively. The interday and intraday relative standard deviations for albendazole and triclabendazole at three concentration levels (1.0, 10.0, and 30.0 μg/L) were in the range of 6.0-11.0 and 5.0-7.9%, respectively. The developed method was successfully applied to determine albendazole and triclabendazole in water, milk, honey, and urine samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Glyoxal and methylglyoxal as urinary markers of diabetes. Determination using a dispersive liquid-liquid microextraction procedure combined with gas chromatography-mass spectrometry.

Science.gov (United States)

Pastor-Belda, M; Fernández-García, A J; Campillo, N; Pérez-Cárceles, M D; Motas, M; Hernández-Córdoba, M; Viñas, P

2017-08-04

Glyoxal (GO) and methylglyoxal (MGO) are α-oxoaldehydes that can be used as urinary diabetes markers. In this study, their levels were measured using a sample preparation procedure based on salting-out assisted liquid-liquid extraction (SALLE) and dispersive liquid-liquid microextraction (DLLME) combined with gas chromatography-mass spectrometry (GC-MS). The effect of the derivatization reaction with 2,3-diaminonaphthalene, the addition of acetonitrile and sodium chloride to urine, and the DLLME step using the acetonitrile extract as dispersant solvent and carbon tetrachloride as extractant solvent were carefully optimized. Quantification was performed by the internal standard method, using 5-bromo-2-chloroanisole. The intraday and interday precisions were lower than 6%. Limits of detection were 0.12 and 0.06ngmL -1 , and enrichment factors 140 and 130 for GO and MGO, respectively. The concentrations of these α-oxoaldehydes in urine were between 0.9 and 35.8ngg -1 levels (creatinine adjusted). A statistical comparison of the analyte contents of urine samples from non-diabetic and diabetic patients pointed to significant differences (P=0.046, 24 subjects investigated), particularly regarding MGO, which was higher in diabetic patients. The novelty of this study compared with previous procedures lies in the treatment of the urine sample by SALLE based on the addition of acetonitrile and sodium chloride to the urine. The DLLME procedure is performed with a sedimented drop of the extractant solvent, without a surfactant reagent, and using acetonitrile as dispersant solvent. Separation of the analytes was performed using GC-MS detection, being the analytes unequivocal identified. The proposed procedure is the first microextraction method applied to the analysis of urine samples from diabetic and non-diabetic patients that allows a clear differentiation between both groups using a simple analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Trace determination of five triazole fungicide residues in traditional Chinese medicine samples by dispersive solid-phase extraction combined with ultrasound-assisted dispersive liquid-liquid microextraction and UHPLC-MS/MS.

Science.gov (United States)

Ma, Shuping; Yuan, Xucan; Zhao, Pengfei; Sun, Hong; Ye, Xiu; Liang, Ning; Zhao, Longshan

2017-08-01

A novel and reliable method for determination of five triazole fungicide residues (triadimenol, tebuconazole, diniconazole, flutriafol, and hexaconazol) in traditional Chinese medicine samples was developed using dispersive solid-phase extraction combined with ultrasound-assisted dispersive liquid-liquid microextraction before ultra-high performance liquid chromatography with tandem mass spectrometry. The clean up of the extract was conducted using dispersive solid-phase extraction by directly adding sorbents into the extraction solution, followed by shaking and centrifugation. After that, a mixture of 400 μL trichloromethane (extraction solvent) and 0.5 mL of the above supernatant was injected rapidly into water for the dispersive liquid-liquid microextraction procedure. The factors affecting the extraction efficiency were optimized. Under the optimum conditions, the calibration curves showed good linearity in the range of 2.0-400 (tebuconazole, diniconazole, and hexaconazole) and 4.0-800 ng/g (triadimenol and flutriafol) with the regression coefficients higher than 0.9958. The limit of detection and limit of quantification for the present method were 0.5-1.1 and 1.8-4.0 ng/g, respectively. The recoveries of the target analytes ranged from 80.2 to 103.2%. The proposed method has been successfully applied to the analysis of five triazole fungicides in traditional Chinese medicine samples, and satisfactory results were obtained. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic solvent-free air-assisted liquid-liquid microextraction for optimized extraction of illegal azo-based dyes and their main metabolite from spices, cosmetics and human bio-fluid samples in one step.

Science.gov (United States)

Barfi, Behruz; Asghari, Alireza; Rajabi, Maryam; Sabzalian, Sedigheh

2015-08-15

Air-assisted liquid-liquid microextraction (AALLME) has unique capabilities to develop as an organic solvent-free and one-step microextraction method, applying ionic-liquids as extraction solvent and avoiding centrifugation step. Herein, a novel and simple eco-friendly method, termed one-step air-assisted liquid-liquid microextraction (OS-AALLME), was developed to extract some illegal azo-based dyes (including Sudan I to IV, and Orange G) from food and cosmetic products. A series of experiments were investigated to achieve the most favorable conditions (including extraction solvent: 77μL of 1-Hexyl-3-methylimidazolium hexafluorophosphate; sample pH 6.3, without salt addition; and extraction cycles: 25 during 100s of sonication) using a central composite design strategy. Under these conditions, limits of detection, linear dynamic ranges, enrichment factors and consumptive indices were in the range of 3.9-84.8ngmL(-1), 0.013-3.1μgmL(-1), 33-39, and 0.13-0.15, respectively. The results showed that -as well as its simplicity, fastness, and use of no hazardous disperser and extraction solvents- OS-AALLME is an enough sensitive and efficient method for the extraction of these dyes from complex matrices. After optimization and validation, OS-AALLME was applied to estimate the concentration of 1-amino-2-naphthol in human bio-fluids as a main reductive metabolite of selected dyes. Levels of 1-amino-2-naphthol in plasma and urinary excretion suggested that this compound may be used as a new potential biomarker of these dyes in human body. Copyright © 2015 Elsevier B.V. All rights reserved.

Dispersive liquid-liquid microextraction with solidification of floating organic droplets for simultaneous extraction of pesticides, pharmaceuticals and personal care products

International Nuclear Information System (INIS)

Marube, Liziane Cardoso; Caldas, Sergiane Souza; Soares, Karina Lotz; Primel, Ednei Gilberto

2015-01-01

Dispersive liquid-liquid microextraction based on solidification of floating organic droplets (DLLME-SFO) has been applied to the extraction of pharmaceutical and personal care products (PPCPs) and pesticides from water samples. The PPCPs included bisphenol A, sodium diclofenac, gemfibrozil, furosemide, glibenclamide, nifedipine, nimesulide, propylparaben and triclocarban. The pesticides included 2,4-D, atrazine, azoxystrobin, cyproconazole, clomazone, dichloran, difenoconazole, diuron, epoxiconazole, fenoxaprop-p-ethyl, fipronil, iprodione, irgarol, propanil, propiconazole, tebuconazole, and trifloxystrobin. The type and volume of extraction solvent, type and volume of disperser solvent, ionic strength and pH were optimized. All species were then quantified by liquid chromatography tandem mass spectrometry (LC-MS/MS). The limits of quantification (LOQs) ranged from 50 to 500 ng L −1 , and the linearity ranged from the LOQ of each compound up to 10,000 ng L −1 . Recoveries ranged from 63 to 120 %, with relative standard deviations lower than 14 %. It is making use of a low-toxicity and affordable extraction solvent (1-dodecanol) and was successfully applied to the analysis of surface water samples. (author)

Comparison of solidification of floating drop and homogenous liquid-liquid microextractions for the extraction of two plasticizers from the water kept in PET-bottles.

Science.gov (United States)

Yamini, Yadollah; Ghambarian, Mahnaz; Khalili-Zanjani, Mohammad Reza; Faraji, Mohammad; Shariati, Shahab

2009-09-01

Two approaches based on solidification of floating drop microextraction (SFDME) and homogenous liquid-liquid microextraction (HLLE) were compared for the extraction and preconcentration of di-(2-ethylhexyl) phthalate (DEHP) and di-(2-ethylhexyl) adipate (DEHA) from the mineral water samples. In SFDME, a floated drop of the mixture of acetophenone/1-undecanol (1:8) was exposed on the surface of the aqueous solution and extraction was permitted to occur. In HLLE, a homogenous ternary solvent system was used by water/methanol/chloroform and the phase separation phenomenon occurred by salt addition. Under the optimal conditions, the LODs for the two target plasticizers (DEHA and DEHP), obtained by SFDME-GC-FID and HLLE-GC-FID, were ranged from 0.03 to 0.01 microg/L and 0.02 to 0.01 microg/L, respectively. HLLE provided higher preconcentration factors (472.5- and 551.2-fold) within the shorter extraction time as well as better RSDs (4.5-6.9%). While, in SFDME, high preconcentration factors in the range of 162-198 and good RSDs in the range of 5.2-9.6% were obtained. Both methods were applied for the analysis of two plasticizers in different water samples and two target plasticizers were found in the bottled mineral water after the expiring time and the boiling water was exposed to a polyethylene vial.

Combination of flame atomic absorption spectrometry with ligandless-dispersive liquid- liquid microextraction for preconcentration and determination of trace amount of lead in water samples

Directory of Open Access Journals (Sweden)

Y.M. Baghelani

2013-05-01

Full Text Available A new ligandless-dispersive liquid–liquid microextraction method has been developed for the separation and flame atomic absorption spectrometry determination of trace amount of lead(II ion. In the proposed approach 1,2-dicholorobenzene and ethanol were used as extraction and dispersive solvents. Factors influencing the extraction efficiency of lead, including the extraction and dispersive solvent type and volume, pH of sample solution, concentration of chloride and extraction time were studied. Under the optimal conditions, the calibration curve was linear in the range of 7.0–6000 ng mL−1 of lead with R2 = 0.9992 (n = 10 and detection limit based on three times the standard deviation of the blank (3Sb was 0.5 ng mL−1 in original solution. The relative standard deviation for eight replicate determinations of 1.0 mg mL-1 lead was ±1.6%. The high efficiency of dispersive liquid-liquid microextraction to carry out the determination of trace amounts of lead in complex matrices was demonstrated. The proposed method has been applied for determination of trace amounts of lead in water samples and satisfactory results were obtained. The accuracy was checked by analyzing a certified reference material from the National Institute of Standard and Technology, Trace elements in water (NIST CRM 1643e.

Synthesis and application of magnetic deep eutectic solvents: Novel solvents for ultrasound assisted liquid-liquid microextraction of thiophene.

Science.gov (United States)

Khezeli, Tahere; Daneshfar, Ali

2017-09-01

Two novel magnetic deep eutectic solvents (MDESs), comprised of cheap and simple components named [choline chloride/phenol] [FeCl 4 ] and [choline chloride/ethylene glycol] [FeCl 4 ] were prepared and characterized by CHN elemental analysis, proton nuclear magnetic resonance ( 1 H NMR), vibrating sample magnetometery (VSM), Raman, Fourier transform-infrared (FT-IR) and UV-Vis spectrometery. The extraction efficiency of the prepared MDESs has been investigated in ultrasound assisted liquid-liquid microextraction based MDES (UALLME-MDES). Briefly, MDESs were added to n-heptan containing thiophene. Then, MDESs were dispersed in n-heptane by sonication. After that, microdroplets of MDESs were collected by a magnet and the remained concentration of thiophene in n-heptane phase was analyzed by GC-FID. The results indicated that [choline chloride/phenol] [FeCl 4 ] has higher extraction efficiency than [choline chloride/ethylene glycol] [FeCl 4 ]. This work opens a new way to the application of MDESs. Copyright © 2016 Elsevier B.V. All rights reserved.

Air-assisted liquid-liquid microextraction integrated with QuEChERS for determining endocrine-disrupting compounds in fish by high-performance liquid chromatography-tandem mass spectrometry.

Science.gov (United States)

Luo, Zhoufei; Lu, Jing; Li, Haipu; Tu, Yi; Wan, Yuehao; Yang, Zhaoguang

2018-09-15

A new, sensitive, and rapid method based on the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) approach and air-assisted liquid-liquid microextraction (AALLME) technology was developed for the determination of 20 endocrine-disrupting compounds (EDCs) in fish by high-performance liquid chromatography-tandem mass spectrometry. The method first integrates AALLME into QuEChERS to achieve clean-up and enrichment of the EDCs in one step. A self-made glass tube was enfolded with plasticine to withstand the high centrifugal force. The established method was developed by optimization of the parameters. High linearities (R 2  > 0.9924) and recoveries (78.2-118.6%) at three spiked levels (5, 10, and 20 ng g -1 ), and low relative standard deviation values (1.1-14.5%) and limits of detection (0.03-0.80 ng g -1 ) were obtained. The method comparison shows that the proposed method is superior as it involves less organic solvent usage, simple operation and high efficiency. This method was successfully applied to different fishes for analyzing EDCs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Simultaneous determination of pyrethroids and pyrethrins by dispersive liquid-liquid microextraction and liquid chromatography triple quadrupole mass spectrometry in environmental samples.

Science.gov (United States)

Ccanccapa-Cartagena, Alexander; Masiá, Ana; Picó, Yolanda

2017-08-01

A simple and environmentally friendly dispersive liquid-liquid microextraction (DLLME) method coupled with electrospray ionization liquid chromatography triple quadrupole mass spectrometry (LC-QqQ-MS/MS) was developed for the simultaneous determination of 17 synthetic and natural pyrethroids. A comparison of solid-phase extraction (SPE) versus DLLME for water samples and only "dilute and shoot" versus the additional extract cleanup by DLLME for sediment samples is reported. Chloroform was the extracting solvent in the DLLME technique for both water and sediment samples. Ultrasonic energy was applied to fully extract the analytes into fine droplets, providing high recoveries in short times. Method detection limits (MDLs) ranged from 0.12 to 0.62 ng L -1 and recoveries from 70 to 119% with RSD values 2-15% (n = 5) for water samples. In sediment samples, MDLs ranged from 0.50 to 2.50 ng g -1 and recoveries from 71 to 112% with RSDs 2-16% (n = 5). The proposed method showed a good linearity within the range of 10-500 ng mL -1 , with coefficients of determination (R 2 ) higher than 0.99. Matrix effects were observed for most compounds in water and sediment (ME% Albufera wetland and Turia River. Acrinathrin (48 ng g -1 ) and etofenprox (16 ng g -1 ) were detected in sediment samples. Graphical abstract Pyrethrins and pyrethroid determination in water and sediments by DLLME and LC-MS/MS.

Highly selective ionic liquid-based microextraction method for sensitive trace cobalt determination in environmental and biological samples

International Nuclear Information System (INIS)

Berton, Paula; Wuilloud, Rodolfo G.

2010-01-01

A simple and rapid dispersive liquid-liquid microextraction procedure based on an ionic liquid (IL-DLLME) was developed for selective determination of cobalt (Co) with electrothermal atomic absorption spectrometry (ETAAS) detection. Cobalt was initially complexed with 1-nitroso-2-naphtol (1N2N) reagent at pH 4.0. The IL-DLLME procedure was then performed by using a few microliters of the room temperature ionic liquid (RTIL) 1-hexyl-3-methylimidazolium hexafluorophosphate [C 6 mim][PF 6 ] as extractant while methanol was the dispersant solvent. After microextraction procedure, the Co-enriched RTIL phase was solubilized in methanol and directly injected into the graphite furnace. The effect of several variables on Co-1N2N complex formation, extraction with the dispersed RTIL phase, and analyte detection with ETAAS, was carefully studied in this work. An enrichment factor of 120 was obtained with only 6 mL of sample solution and under optimal experimental conditions. The resultant limit of detection (LOD) was 3.8 ng L -1 , while the relative standard deviation (RSD) was 3.4% (at 1 μg L -1 Co level and n = 10), calculated from the peak height of absorbance signals. The accuracy of the proposed methodology was tested by analysis of a certified reference material. The method was successfully applied for the determination of Co in environmental and biological samples.

Microextraction Techniques Coupled to Liquid Chromatography with Mass Spectrometry for the Determination of Organic Micropollutants in Environmental Water Samples

Directory of Open Access Journals (Sweden)

Mª Esther Torres Padrón

2014-07-01

Full Text Available Until recently, sample preparation was carried out using traditional techniques, such as liquid–liquid extraction (LLE, that use large volumes of organic solvents. Solid-phase extraction (SPE uses much less solvent than LLE, although the volume can still be significant. These preparation methods are expensive, time-consuming and environmentally unfriendly. Recently, a great effort has been made to develop new analytical methodologies able to perform direct analyses using miniaturised equipment, thereby achieving high enrichment factors, minimising solvent consumption and reducing waste. These microextraction techniques improve the performance during sample preparation, particularly in complex water environmental samples, such as wastewaters, surface and ground waters, tap waters, sea and river waters. Liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS and time-of-flight mass spectrometric (TOF/MS techniques can be used when analysing a broad range of organic micropollutants. Before separating and detecting these compounds in environmental samples, the target analytes must be extracted and pre-concentrated to make them detectable. In this work, we review the most recent applications of microextraction preparation techniques in different water environmental matrices to determine organic micropollutants: solid-phase microextraction SPME, in-tube solid-phase microextraction (IT-SPME, stir bar sorptive extraction (SBSE and liquid-phase microextraction (LPME. Several groups of compounds are considered organic micropollutants because these are being released continuously into the environment. Many of these compounds are considered emerging contaminants. These analytes are generally compounds that are not covered by the existing regulations and are now detected more frequently in different environmental compartments. Pharmaceuticals, surfactants, personal care products and other chemicals are considered micropollutants. These

Salt-assisted liquid-liquid microextraction of Cr(VI) ion using an ionic liquid for preconcentration prior to its determination by flame atomic absorption spectrometry

International Nuclear Information System (INIS)

Majidi, B.; Shemirani, F.

2012-01-01

We report on the salt-assisted liquid-liquid microextraction of cationic complexes of Cr(VI) ion using the hydrophilic ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoraborate and potassium hydrogen phosphate. This is a novel, simple, non-toxic and effective technique for sample pretreatment technique that displays large extraction efficiency and represents a new platform where Cr(VI) is complexed with 1,5-diphenylcarbazide (DPC) in sulfuric acid medium. It was applied to the extraction of Cr(VI) in the form of the Cr(VI)-DPC complex prior to its determination by flame atomic absorption spectrometry. Cr(III) ion also can be determined by this procedure after oxidation to Cr(VI). Extraction is mainly affected by the amount of water-soluble IL, the kind and quantity of inorganic salts, by pH and the concentration of DPC. Calibration plots are linear in the range from 3 to 150 μg L -1 of Cr(VI), and the limit of detection is 1. 25 μg L -1 . The method was successfully applied to the speciation and determination of trace levels of Cr(III) and Cr(VI) in environmental water samples containing high levels of dissolved salts or food grade salts. (author)

Combination of saponification and dispersive liquid-liquid microextraction for the determination of tocopherols and tocotrienols in cereals by reversed-phase high-performance liquid chromatography.

Science.gov (United States)

Shammugasamy, Balakrishnan; Ramakrishnan, Yogeshini; Ghazali, Hasanah M; Muhammad, Kharidah

2013-07-26

A simple sample preparation technique coupled with reversed-phase high-performance liquid chromatography was developed for the determination of tocopherols and tocotrienols in cereals. The sample preparation procedure involved a small-scale hydrolysis of 0.5g cereal sample by saponification, followed by the extraction and concentration of tocopherols and tocotrienols from saponified extract using dispersive liquid-liquid microextraction (DLLME). Parameters affecting the DLLME performance were optimized to achieve the highest extraction efficiency and the performance of the developed DLLME method was evaluated. Good linearity was observed over the range assayed (0.031-4.0μg/mL) with regression coefficients greater than 0.9989 for all tocopherols and tocotrienols. Limits of detection and enrichment factors ranged from 0.01 to 0.11μg/mL and 50 to 73, respectively. Intra- and inter-day precision were lower than 8.9% and the recoveries were around 85.5-116.6% for all tocopherols and tocotrienols. The developed DLLME method was successfully applied to cereals: rice, barley, oat, wheat, corn and millet. This new sample preparation approach represents an inexpensive, rapid, simple and precise sample cleanup and concentration method for the determination of tocopherols and tocotrienols in cereals. Copyright © 2013 Elsevier B.V. All rights reserved.

Preconcentration procedure using vortex-assisted liquid-liquid microextraction for the fast determination of trace levels of thorium in water samples

International Nuclear Information System (INIS)

Ehsan Zolfonoun; Maryam Salahinejad

2013-01-01

A new simple and rapid vortex-assisted liquid-liquid microextraction method was applied for the determination of thorium in water samples. In this method, chloroform used as extraction solvent was directly injected into the water sample solution. The extraction solvent was dispersed into the aqueous phase under vigorously shaking with the vortex. After centrifuging, the fine droplets of extractant phase were settled to the bottom of the conical-bottom centrifuge tube. The effect of different experimental parameters on the performance of the method were studied and discussed. Under the optimum conditions, the detection limit for Th(IV) was 7.5 ng mL -1 . The precision of the method, evaluated as the relative standard deviation obtained by analyzing of 10 replicates, was 2.8 %. The practical applicability of the developed method was examined using natural water and monazite sand samples. (author)

Determination of lead in environmental waters with dispersive liquid-liquid microextraction prior to atomic fluorescence spectrometry

International Nuclear Information System (INIS)

Zhou, Qingxiang; Zhao, Na; Xie, Guohong

2011-01-01

This paper established a new, rapid and sensitive method for the determination of lead in water samples preconcentrated by dispersive liquid-liquid microextraction (DLLME) prior to atomic fluorescence spectrometry. Dithizone was used as the chelating agent. In the DLLME procedure, lead formed lead-dithizone complex and migrated into the carbon tetrachloride micro-droplets. Important factors that would affect the extraction efficiency had been investigated including the kind and volume of extraction solvent and dispersive solvent, sample pH, the amount of chelating agent, extraction time and centrifugation time. The results showed that the coexisting ions containing in water samples had no obvious negative effect on the determination of lead. The experimental results indicated that the proposed method had a good linear range of 0.01-100 ng mL -1 (r 2 = 0.9990). The precision was 2.12% (RSD, n = 7) and the detection limit was 0.95 ng L -1 . Proposed method was validated with four real environmental samples and the results indicated that the proposed method was excellent for the future use and satisfied spiked recoveries were in the range of 92.9-97.4%.

Dispersive liquid-liquid microextraction of copper ions as neocuproine complex in environmental aqueous samples.

Science.gov (United States)

Shariati, Shahab; Golshekan, Mostafa

2011-06-01

In the present study, a simple and efficient extraction method based on dispersive liquid-liquid microextraction prior to UV-Vis spectrophotometry was developed for the preconcentration and determination of copper ions in environmental samples. Briefly, cupric ions (Cu II) were reduced to cuprous (Cu I) with addition of hydroxyl amine hydrochloride and formed hydrophobic chelates with neocuproine. Then, a proper mixture of acetonitrile (as dispersive solvent) and choloroform (as extraction solvent) was rapidly injected into the solution and a cloudy solution was formed. After centrifuging, choloroform was sedimented at the bottom of a conical tube and diluted with 100 µL of methanol for further UV-Vis spectrophotometry measurement. An orthogonal array design (OAD) was employed to study the effects of different parameters on the extraction efficiency. Under the optimum experimental conditions, a preconcentration factor up to 63.6 was achieved for extraction from 5.0 mL of sample solution. The limit of detection (LOD) based on S/N = 3 was 0.33 µg L-1 and the calibration curve was linear in the range of 1-200 µg L-1 with reasonable linearity (r2 > 0.997). Finally, the accuracy of the proposed method was successfully evaluated by determination of trace amounts of copper ions in different water samples and satisfactory results were obtained.

Combination of solid phase extraction and dispersive liquid-liquid microextraction for separation/preconcentration of ultra trace amounts of uranium prior to its fiber optic-linear array spectrophotometry determination.

Science.gov (United States)

Dadfarnia, Shayessteh; Shabani, Ali Mohammad Haji; Shakerian, Farid; Shiralian Esfahani, Golnaz

2013-12-15

A simple and sensitive method for the separation and preconcentration of the ultra trace amounts of uranium and its determination by spectrophotometry was developed. The method is based on the combination of solid phase extraction and dispersive liquid-liquid microextraction. Thus, by passing the sample through the basic alumina column, the uranyl ion and some cations are separated from the sample matrix. The retained uranyl ion along with the cations are eluted with 5 mL of nitric acid (2 mol L(-1)) and after neutralization of the eluent, the extracted uranyl ion is converted to its anionic benzoate complex and is separated from other cations by extraction of its ion pair with malachite green into small volume of chloroform using dispersive liquid-liquid microextraction. The amount of uranium is then determined by the absorption measurement of the extracted ion pair at 621 nm using flow injection spectrophotometry. Under the optimum conditions, with 500 mL of the sample, a preconcentration factor of 1980, a detection limit of 40 ng L(-1), and a relative standard deviation of 4.1% (n=6) at 400 ng L(-1) were obtained. The method was successfully applied to the determination of uranium in mineral water, river water, well water, spring water and sea water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Ionic liquid-based dispersive microextraction of nitro toluenes in water samples

International Nuclear Information System (INIS)

Berton, Paula; Regmi, Bishnu P.; Spivak, David A.; Warner, Isiah M.

2014-01-01

We describe a method for dispersive liquid-liquid microextraction of nitrotoluene-based compounds. This method is based on use of the room temperature ionic liquid (RTIL) 1-hexyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide as the accepting phase, and is shown to work well for extraction of 4-nitrotoluene, 2,4-dinitrotoluene, and 2,4,6-trinitrotoluene. Separation and subsequent detection of analytes were accomplished via HPLC with UV detection. Several parameters that influence the efficiency of the extraction were optimized using experimental design. In this regard, a Plackett–Burman design was used for initial screening, followed by a central composite design to further optimize the influencing variables. For a 5-mL water sample, the optimized IL-DLLME procedure requires 26 mg of the RTIL as extraction solvent and 680 μL of methanol as the dispersant. Under optimum conditions, limits of detection (LODs) are lower than 1.05 μg L −1 . Relative standard deviations for 6 replicate determinations at a 4 μg L −1 analyte level are <4.3 % (calculated using peak areas). Correlation coefficients of >0.998 were achieved. This method was successfully applied to extraction and determination of nitrotoluene-based compounds in spiked tap and lake water samples. (author)

Maghemite nanoparticle-decorated hollow fiber electromembrane extraction combined with dispersive liquid-liquid microextraction for the determination of thymol from Carum copticum

DEFF Research Database (Denmark)

Khajeh, Mostafa; Pedersen-Bjergaard, Stig; Bohlooli, Mousa

2017-01-01

BACKGROUND A novel technique using maghemite nanoparticle-decorated hollow fibers to assist electromembrane extraction is proposed. Electromembrane extraction combined with dispersive liquid–liquid microextraction (EME-DLLME) was applied for the extraction of thymol from Carum copticum, followed...... by gas chromatography with flame ionization detection (GC-FID). RESULTS The use of maghemite nanoparticle-decorated hollow fibers was found to improve the extraction efficiency of thymol significantly. Important operational parameters, including pH of acceptor phase, extraction time, voltage...

A novel microextraction technique based on 1-hexylpyridinium hexafluorophosphate ionic liquid for the preconcentration of zinc in water and milk samples

International Nuclear Information System (INIS)

Abdolmohammad-Zadeh, H.; Sadeghi, G.H.

2009-01-01

A simple dispersive liquid-liquid microextraction methodology based on the application of 1-hexylpyridinium hexafluorophosphate [HPy][PF 6 ] ionic liquid (IL) as an extractant solvent was proposed for the preconcentration of trace levels of zinc as a prior step to determination by flame atomic absorption spectrometry (FAAS). Zinc was complexed with 8-hydroxyquinoline (oxine) and extracted into ionic liquid. Some effective factors that influence the microextraction efficiency such as pH, oxine concentration, amount of IL, ionic strength, temperature and centrifugation time were investigated and optimized. In the optimum experimental conditions, the limit of detection (3 s) and the enhancement factor were 0.22 μg L -1 and 71, respectively. The relative standard deviation (RSD) for six replicate determinations of 13 μg L -1 Zn was 1.92%. In order to validate the developed method, a certified reference material (NIST SRM 1549) was analyzed and the determined values were in good agreement with the certified values. The proposed method was successfully applied to the trace determination of zinc in water and milk samples.

In-syringe-stirring: A novel approach for magnetic stirring-assisted dispersive liquid–liquid microextraction

International Nuclear Information System (INIS)

Horstkotte, Burkhard; Suárez, Ruth; Solich, Petr; Cerdà, Víctor

2013-01-01

Graphical abstract: -- Highlights: •We propose a new automatic magnetic stirring assisted dispersive liquid–liquid microextraction. •It allows the extraction of aluminum from seawater and freshwater samples within less than 4 min. •The method was applicable to the natural samples. -- Abstract: For the first time, the use of a magnetic stirrer within the syringe of an automated syringe pump and the resulting possible analytical applications are described. A simple instrumentation following roughly the one from sequential injection analyzer systems is used in combination with an adaptor, which is placed onto the barrel of a glass syringe. Swirling around the longitudinal axis of the syringe and holding two strong neodymium magnets, it causes a rotating magnetic field and serves as driver for a magnetic stirring bar placed inside of the syringe. In a first study it was shown that this approach leads to a sealed but also automatically adaptable reaction vessel, the syringe, in which rapid and homogeneous mixing of sample with the required reagents within short time can be carried out. In a second study in-a-syringe magnetic stirring-assisted dispersive liquid–liquid microextraction (MSA-DLLME) was demonstrated by the application of the analyzer system to fluorimetric determination of aluminum in seawater samples using lumogallion. A linear working range up to 1.1 μmol L −1 and a limit of detection of 6.1 nmol L −1 were found. An average recovery of 106.0% was achieved for coastal seawaters with a reproducibility of 4.4%. The procedure lasted 210 s including syringe cleaning and only 150 μL of hexanol and 4.1 mL of sample were required

Combination of electromembrane extraction and liquid-phase microextraction in a single step: Simultaneous group separation of acidic and basic drugs

DEFF Research Database (Denmark)

Huang, Chuixiu; Seip, Knut Fredrik; Gjelstad, Astrid

2015-01-01

at high concentration. This approach was further investigated from human plasma. Extraction recoveries were strongly dependent on dilution of plasma with buffer and on extraction time. Finally, this simultaneous EME/LPME approach was evaluated in combination with liquid chromatography (LC......Electromembrane extraction (EME) and liquid-phase microextraction (LPME) were combined in a single step for the first time to realize simultaneous and clear group separation of basic and acidic drugs. Using 2-nitrophenyl octyl ether as the supported liquid membrane (SLM) for EME and dihexyl ether...

An Ion-pair Dispersive Liquid-Liquid Microextraction for Simultaneous Determination of Synthetic Dyes in Ice Cream Samples by HPLC

Directory of Open Access Journals (Sweden)

Mohammad Faraji

2017-05-01

Full Text Available An efficient, sensitive and fast method was developed based on an ultrasound-assisted extraction followed by an ion-pair dispersive liquid-liquid microextraction (USAE-IP-DLLME for the simultaneous determination of five commonly used synthetic sulfonate dyes (tartarazine, quinoline yellow, sunset yellow, azorubine, and brilliant blue in ice cream samples using high performance liquid chromatography. First, important parameters on USAE and samples clean-up were investigated and optimized. Then, some effective parameters on DLLME were studied and optimized. Under the optimum conditions, good linearity (0.5–1000 µg L-1, > r2=0.99 were obtained for the dyes. Limits of detection and limits of quantization were in the range of 0.01–0.05 µg L-1 and 0.03–0.15 µg L-1, respectively. The recoveries of the five synthetic colorants ranged from 90.3 to 109.7%. Intra (1.4–6.4% and inter-day precision (3.9–9.7% expressed as relative standard deviation (RSD at 10 and 100 µg L-1 levels less than 10% were also achieved. Finally, this method has been applied successfully in the determination of the colorants in the ice cream samples.

Guanidinium ionic liquid-based surfactants as low cytotoxic extractants: Analytical performance in an in-situ dispersive liquid-liquid microextraction method for determining personal care products.

Science.gov (United States)

Pacheco-Fernández, Idaira; Pino, Verónica; Ayala, Juan H; Afonso, Ana M

2017-05-01

The IL-based surfactant octylguanidinium chloride (C 8 Gu-Cl) was designed and synthetized with the purpose of obtaining a less harmful surfactant: containing guanidinium as core cation and a relatively short alkyl chain. Its interfacial and aggregation behavior was evaluated through conductivity and fluorescence measurements, presenting a critical micelle concentration value of 42.5 and 44.6mmolL -1 , respectively. Cytotoxicity studies were carried out with C 8 Gu-Cl and other IL-based and conventional surfactants, specifically the analogue 1-octyl-3-methylimidazolium chloride (C 8 MIm-Cl), and other imidazolium- (C 16 MIm-Br) and pyridinium- (C 16 Py-Cl) based surfactants, together with the conventional cationic CTAB and the conventional anionic SDS. From these studies, C 8 Gu-Cl was the only one to achieve the classification of low cytotoxicity. An in situ dispersive liquid-liquid microextraction (DLLME) method based on transforming the water-soluble C 8 Gu-Cl IL-based surfactant into a water-insoluble IL microdroplet via a simple metathesis reaction was then selected as the extraction/preconcentration method for a group of 6 personal care products (PCPs) present in cosmetic samples. The method was carried out in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The method was properly optimized, requiring the use of only 30μL of C 8 Gu-Cl for 10mL of aqueous sample with a NaCl content of 8% (w/v) to adjust the ionic strength and pH value of 5. The metathesis reaction required the addition of the anion exchange reagent (bis[(trifluoromethyl)sulfonyl]imide - 1:1 molar ratio), followed by vortex and centrifugation, and dilution of the final microdroplet up to 60μL with acetonitrile before the injection in the HPLC-DAD system. The optimum in situ DLLME-HPLC-DAD method takes ∼10min for the extraction step and ∼22min for the chromatographic separation, with analytical features of low detection limits: down to 0.4�

Centrifugeless dispersive liquid-liquid microextraction based on salting-out phenomenon followed by high performance liquid chromatography for determination of Sudan dyes in different species.

Science.gov (United States)

Bazregar, Mohammad; Rajabi, Maryam; Yamini, Yadollah; Arghavani-Beydokhti, Somayeh; Asghari, Alireza

2018-04-01

In this work, a novel method, namely centrifugeless dispersive liquid-liquid microextraction, is introduced for the efficient extraction of banned Sudan dyes from foodstuff and water samples. In this method, which is based upon the salting-out phenomenon, in order to accelerate the extraction process, the extraction solvent (1-undecanol, 75 μL) is dispersed into the sample solution. Then the mixture is passed through a small column filled with 5 g sodium chloride, used as a separating reagent. In this condition, fine droplets of the extraction solvent are floated on the mixture, and the phase separation is simply achieved. This method is environmentally friendly, simple, and very fast, so that the overall extraction time is only 7 min. Under the optimal experimental conditions, the preconcentration factors in the range of 90-121 were obtained for the analytes. Also good linearities were obtained in the range of 2.5-1200 ng mL -1 (r 2  ≥ 0.993). Copyright © 2017 Elsevier Ltd. All rights reserved.

Dispersive solid-phase extraction followed by vortex-assisted dispersive liquid-liquid microextraction based on the solidification of a floating organic droplet for the determination of benzoylurea insecticides in soil and sewage sludge.

Science.gov (United States)

Peng, Guilong; He, Qiang; Mmereki, Daniel; Lu, Ying; Zhong, Zhihui; Liu, Hanyang; Pan, Weiliang; Zhou, Guangming; Chen, Junhua

2016-04-01

A novel dispersive solid-phase extraction combined with vortex-assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet was developed for the determination of eight benzoylurea insecticides in soil and sewage sludge samples before high-performance liquid chromatography with ultraviolet detection. The analytes were first extracted from the soil and sludge samples into acetone under optimized pretreatment conditions. Clean-up of the extract was conducted by dispersive solid-phase extraction using activated carbon as the sorbent. The vortex-assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet procedure was performed by using 1-undecanol with lower density than water as the extraction solvent, and the acetone contained in the solution also acted as dispersive solvent. Under the optimum conditions, the linearity of the method was in the range 2-500 ng/g with correlation coefficients (r) of 0.9993-0.9999. The limits of detection were in the range of 0.08-0.56 ng/g. The relative standard deviations varied from 2.16 to 6.26% (n = 5). The enrichment factors ranged from 104 to 118. The extraction recoveries ranged from 81.05 to 97.82% for all of the analytes. The good performance has demonstrated that the proposed methodology has a strong potential for application in the multiresidue analysis of complex matrices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of Bisphenol A and Bisphenol AF in Vinegar samples by two-component mixed ionic liquid dispersive liquid-phase microextraction coupled with high performance liquid chromatography

International Nuclear Information System (INIS)

Tai, Z.; Liu, M.; Hu, X.; Yang, Y.

2014-01-01

This paper describes a sensitive and simple method for the determination of bisphenol A (BPA) and bisphenol AF (BPAF) in vinegar samples using two-component mixed ionic liquid dispersive liquid-phase microextraction coupled with high performance liquid chromatography. In this work, BPA and BPAF were selected as the model analytes, and two-component mixed ionic liquid included 1-butyl-3-methylimidazolium hexafluorophosphate ((C4Mim)PF6) and 1-hexyl-3-methyl-imidazolium hexafluorophosphate ((C6Mim)PF6) was used as the extraction solvent for the first time here. Parameters that affect the extraction efficiency were investigated. Under the optimum conditions, good linear relationships were discovered in the range of 1.0-100 micro g/L for BPA and 2.0-150 micro g/L for BPAF, respectively. Detection limits of proposed method based on the signal-to-noise ratio (S/N=3) were in the range of 0.15-0.38 micro g/L. The efficiencies of proposed method have also been demonstrated with spiked real vinegar samples. The result show this method/ procedure to be a more efficient approach for the determination of BPA and BPAF in real vinegar, presenting average recovery rate of 89.3-112 % and precision values of 0.9-13.5% (RSDs, n = 6). In comparison with traditional solid phase extraction procedures this method results in lower solvent consumption, low pollution levels, and faster sample preparation. (author)

Direct solid-phase microextraction combined with gas and liquid chromatography for the determination of lidocaine in human urine

NARCIS (Netherlands)

Koster, E.H M; Hofman, N.S K; de Jong, G.J.

Solid-phase microextraction (SPME) has been combined with gas chromatography (GC) and liquid chromatography (LC) for the determination of lidocaine in human urine. A polydimethylsiloxane (PDMS) coated fibre was directly immersed into buffered urine. Extraction conditions such as time, pH, ionic

On-line liquid phase micro-extraction based on drop-in-plug sequential injection lab-at-valve platform for metal determination

Energy Technology Data Exchange (ETDEWEB)

Mitani, Constantina [Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, Thessaloniki 54124 (Greece); Anthemidis, Aristidis N., E-mail: anthemid@chem.auth.gr [Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, Thessaloniki 54124 (Greece)

2013-04-10

Highlights: ► Drop-in-plug micro-extraction based on SI-LAV platform for metal preconcentration. ► Automatic liquid phase micro-extraction coupled with FAAS. ► Organic solvents with density higher than water are used. ► Lead determination in environmental water and urine samples. -- Abstract: A novel automatic on-line liquid phase micro-extraction method based on drop-in-plug sequential injection lab-at-valve (LAV) platform was proposed for metal preconcentration and determination. A flow-through micro-extraction chamber mounted at the selection valve was adopted without the need of sophisticated lab-on-valve components. Coupled to flame atomic absorption spectrometry (FAAS), the potential of this lab-at-valve scheme is demonstrated for trace lead determination in environmental and biological water samples. A hydrophobic complex of lead with ammonium pyrrolidine dithiocarbamate (APDC) was formed on-line and subsequently extracted into an 80 μL plug of chloroform. The extraction procedure was performed by forming micro-droplets of aqueous phase into the plug of the extractant. All critical parameters that affect the efficiency of the system were studied and optimized. The proposed method offered good performance characteristics and high preconcentration ratios. For 10 mL sample consumption an enhancement factor of 125 was obtained. The detection limit was 1.8 μg L{sup −1} and the precision expressed as relative standard deviation (RSD) at 50.0 μg L{sup −1} of lead was 2.9%. The proposed method was evaluated by analyzing certified reference materials and applied for lead determination in natural waters and urine samples.

A new combined method of stable isotope-labeling derivatization-ultrasound-assisted dispersive liquid-liquid microextraction for the determination of neurotransmitters in rat brain microdialysates by ultra high performance liquid chromatography tandem mass spectrometry.

Science.gov (United States)

Zheng, Longfang; Zhao, Xian-En; Zhu, Shuyun; Tao, Yanduo; Ji, Wenhua; Geng, Yanling; Wang, Xiao; Chen, Guang; You, Jinmao

2017-06-01

In this work, for the first time, a new hyphenated technique of stable isotope-labeling derivatization-ultrasound-assisted dispersive liquid-liquid microextraction has been developed for the simultaneous determination of monoamine neurotransmitters (MANTs) and their biosynthesis precursors and metabolites. The developed method was based on ultra high performance liquid chromatography tandem mass spectrometry detection using multiple-reaction monitoring mode. A pair of mass spectrometry sensitizing reagents, d 0 -10-methyl-acridone-2-sulfonyl chloride and d 3 -10-methyl-acridone-2-sulfonyl chloride, as stable isotope probes was utilized to facilely label neurotransmitters, respectively. The heavy labeled MANTs standards were prepared and used as internal standards for quantification to minimize the matrix effects in mass spectrometry analysis. Low toxic bromobenzene (extractant) and acetonitrile (dispersant) were utilized in microextraction procedure. Under the optimized conditions, good linearity was observed with the limits of detection (S/N>3) and limits of quantification (S/N>10) in the range of 0.002-0.010 and 0.015-0.040nmol/L, respectively. Meanwhile, it also brought acceptable precision (4.2-8.8%, peak area RSDs %) and accuracy (recovery, 96.9-104.1%) results. This method was successfully applied to the simultaneous determination of monoamine neurotransmitters and their biosynthesis precursors and metabolites in rat brain microdialysates of Parkinson's disease and normal rats. This provided a new method for the neurotransmitters related studies in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

Dispersive liquid-liquid microextraction coupled with magnetic nanoparticles for extraction of zearalenone in wheat samples

Directory of Open Access Journals (Sweden)

Mitra Amoli-Diva

2017-01-01

Full Text Available A new, sensitive and fast dispersive liquid-liquid microextraction (DLLME coupled with micro-solid phase extraction (μ-SPE was developed for determination of zearalenone (ZEN in wheat samples. The DLLME was performed using acetonitrile/water (80:20 v/v as the disperser solvent and 1-octanol as the extracting solvent.  The acetonitrile/water (80:20 v/v solvent was also used to extract ZEN from solid wheat matrix, and was directly applied as the disperser solvent for DLLME process. Additionally, hydrophobic oleic-acid-modified magnetic nanoparticles were used in μ-SPE approach to retrieve the analyte from the DLLME step. So, the method uses high surface area and strong magnetism properties of these nanoparticles to avoid time-consuming column-passing processes in traditional SPE. Main parameters affecting the extraction efficiency and signal enhancement were investigated and optimized. Under the optimum conditions, the calibration curve showed a good linearity in the range of 0.1-500 μg kg−1 (R2=0.9996 with low detection limit of 83 ng g−1. The intra-day and inter-day precisions (as RSD % in the range of 2.6-4.3 % and high recoveries ranging from 91.6 to 99.1 % were obtained. The pre-concentration factor was 3. The method is simple, inexpensive, accurate and remarkably free from interference effects.

Rapid and sensitive determination of phytosterols in functional foods and medicinal herbs by using UHPLC-MS/MS with microwave-assisted derivatization combined with dual ultrasound-assisted dispersive liquid-liquid microextraction.

Science.gov (United States)

Sun, Jing; Zhao, Xian-En; Dang, Jun; Sun, Xiaoyan; Zheng, Longfang; You, Jinmao; Wang, Xiao

2017-02-01

In this work, a hyphenated technique of dual ultrasound-assisted dispersive liquid-liquid microextraction combined with microwave-assisted derivatization followed by ultra high performance liquid chromatography tandem mass spectrometry has been developed for the determination of phytosterols in functional foods and medicinal herbs. Multiple reaction monitoring mode was used for the tandem mass spectrometry detection. A mass spectrometry sensitive reagent, 4'-carboxy-substituted rosamine, has been used as the derivatization reagent for five phytosterols, and internal standard diosgenin was used for the first time. Parameters for the dual microextraction, microwave-assisted derivatization, and ultra high performance liquid chromatography tandem mass spectrometry were all optimized in detail. Satisfactory linearity, recovery, repeatability, accuracy and precision, absence of matrix effect, extremely low limits of detection (0.005-0.015 ng/mL) and limits of quantification (0.030-0.10 ng/mL) were achieved. The proposed method was compared with previously reported methods. It showed better sensitivity, selectivity, and accuracy. The matrix effect was also significantly reduced. The proposed method was successfully applied to the determination of five phytosterols in vegetable oil (sunflower oil, olive oil, corn oil, peanut oil), milk and orange juice (soymilk, peanut milk, orange juice), and medicinal herbs (Ginseng, Ganoderma lucidum, Cordyceps, Polygonum multiflorum) for the quality control of functional foods and medicinal herbs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Facile Vortex-Assisted Dispersive Liquid-Liquid Microextraction Method for the Determination of Uranyl Ion at Low Levels by Spectrophotometry.

Science.gov (United States)

Corazza, Marcela Zanetti; Pires, Igor Matheus Ruiz; Diniz, Kristiany Moreira; Segatelli, Mariana Gava; Tarley, César Ricardo Teixeira

2015-08-01

A facile and reliable UV-Vis spectrophotometric method associated with vortex-assisted dispersive liquid-liquid microextraction has been developed and applied to the determination of U(VI) at low levels in water samples. It was based on preconcentration of 24.0 mL sample at pH 8.0 in the presence of 7.4 µmol L(-1) 1-(2-pyridylazo)-2-naphthol, 1.0 mL of methanol as disperser solvent and 1.0 mL of chloroform as extraction solvent. A high preconcentration factor was achieved (396 times), thus providing a wide analytical curve from 6.9 up to 75.9 µg L(-1) (r=0.9982) and limits of detection and quantification of 0.40 and 1.30 µg L(-1), respectively. When necessary, EDTA or KCN can be used to remove interferences of foreign ions. The method was applied to the analysis of real water samples, such as tap, mineral and lake waters with good recovery values.

Air-assisted liquid-liquid microextraction using floating organic droplet solidification for simultaneous extraction and spectrophotometric determination of some drugs in biological samples through chemometrics methods

Science.gov (United States)

Farahmand, Farnaz; Ghasemzadeh, Bahar; Naseri, Abdolhossein

2018-01-01

An air assisted liquid-liquid microextraction by applying the solidification of a floating organic droplet method (AALLME-SFOD) coupled with a multivariate calibration method, namely partial least squares (PLS), was introduced for the fast and easy determination of Atenolol (ATE), Propanolol (PRO) and Carvedilol (CAR) in biological samples via a spectrophotometric approach. The analytes would be extracted from neutral aqueous solution into 1-dodecanol as an organic solvent, using AALLME. In this approach a low-density solvent with a melting point close to room temperature was applied as the extraction solvent. The emulsion was immediately formed by repeatedly pulling in and pushing out the aqueous sample solution and extraction solvent mixture via a 10-mL glass syringe for ten times. After centrifugation, the extractant droplet could be simply collected from the aqueous samples by solidifying the emulsion at a lower than the melting point temperature. In the next step, analytes were back extracted simultaneously into the acidic aqueous solution. Derringer and Suich multi-response optimization were utilized for simultaneous optimizing the parameters of three analytes. This method incorporates the benefits of AALLME and dispersive liquid-liquid microextraction considering the solidification of floating organic droplets (DLLME-SFOD). Calibration graphs under optimized conditions were linear in the range of 0.30-6.00, 0.32-2.00 and 0.30-1.40 μg mL- 1 for ATE, CAR and PRO, respectively. Other analytical parameters were obtained as follows: enrichment factors (EFs) were found to be 11.24, 16.55 and 14.90, and limits of detection (LODs) were determined to be 0.09, 0.10 and 0.08 μg mL- 1 for ATE, CAR and PRO, respectively. The proposed method will require neither a highly toxic chlorinated solvent for extraction nor an organic dispersive solvent in the application process; hence, it is more environmentally friendly.

Trace determination of organophosphate esters in white wine, red wine, and beer samples using dispersive liquid-liquid microextraction combined with ultra-high-performance liquid chromatography-tandem mass spectrometry.

Science.gov (United States)

Pang, Long; Yang, Huiqiang; Yang, Peijie; Zhang, Hongzhong; Zhao, Jihong

2017-08-15

In this study, dispersive liquid-liquid microextraction coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry was developed for the analysis of five representative organophosphate esters (OPEs) in wine samples. Under optimized conditions, the proposed method resulted in good linearity (R 2 >0.9933) over the range of 0.1-100μgL -1 , with limits of detection (LODs, S/N =3) and quantification (LOQs, S/N =10) in the ranges of 0.48-18.8ngL -1 and 1.58-62.5ngL -1 , respectively. Inter- and intra-assay precisions of RSD% ranged from 3.21% to 6.13% and from 1.69% to 7.63%, respectively. The spiked recoveries of target OPEs from white wine, red wine, and beer samples were in the ranges of 80-122%, 76-120%, and 76-110%, respectively, at two different concentration levels. The total concentrations of five OPEs found in white wine, red wine, and beer samples were in the ranges of 0.29-0.85μgL -1 , 1.00-3.05μgL -1 , and 0.86-1.47μgL -1 , respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

A novel extraction technique based on carbon nanotubes reinforced hollow fiber solid/liquid microextraction for the measurement of piroxicam and diclofenac combined with high performance liquid chromatography.

Science.gov (United States)

Song, Xin-Yue; Shi, Yan-Ping; Chen, Juan

2012-10-15

A novel design of carbon nanotubes reinforced hollow fiber solid/liquid phase microextraction (CNTs-HF-SLPME) was developed to determine piroxicam and diclofenac in different real water samples. Functionalized multi-walled carbon nanotubes (MWCNTs) were held in the pores of hollow fiber with sol-gel technology. The pores and lumen of carbon nanotubes reinforced hollow fiber were subsequently filled with a μL volume of organic solvent (1-octanol), and then the whole assembly was used for the extraction of the target analytes in direct immersion sampling mode. The target analytes were extracted from the sample by two extractants, one of which is organic solvent placed inside the pores and lumen of hollow fiber and the other one is CNTs held in the pores of hollow fiber. After extraction, the analytes were desorbed in acetonitrile and analyzed using high performance liquid chromatography. This novel extraction mode showed more excellent extraction performance in comparison with conventional hollow fiber liquid microextraction (without adding CNTs) and carbon nanotubes reinforced hollow fiber solid microextraction (CNTs held in the pores of hollow fiber, but no organic solvents placed inside the lumen of hollow fiber) under the respective optimum conditions. This method provided 47- and 184-fold enrichment factors for piroxicam and diclofenac, respectively, good inter-fiber repeatability and batch-to-batch reproducibility. Linearity was observed in the range of 20-960 μg L(-1) for piroxicam, and 10-2560 μg L(-1) for diclofenac, with correlation coefficients of 0.9985 and 0.9989, respectively. The limits of detection were 4.58 μg L(-1) for piroxicam and 0.40 μg L(-1) for diclofenac. Copyright © 2012 Elsevier B.V. All rights reserved.

Determination of some organophosphorus pesticides in water and watermelon samples by microextraction prior to high-performance liquid chromatography.

Science.gov (United States)

Wang, Chun; Wu, Qiuhua; Wu, Chunxia; Wang, Zhi

2011-11-01

A novel method based on simultaneous liquid-liquid microextraction and carbon nanotube reinforced hollow fiber microporous membrane solid-liquid phase microextraction has been developed for the determination of six organophosphorus pesticides, i.e. isocarbophos, phosmet, parathion-methyl, triazophos, fonofos and phoxim, in water and watermelon samples prior to high-performance liquid chromatography (HPLC). Under the optimum conditions, the method shows a good linearity within a range of 1-200 ng/mL for water samples and 5-200 ng/g for watermelon samples, with the correlation coefficients (r) varying from 0.9990 to 0.9997 and 0.9986 to 0.9995, respectively. The limits of detection (LODs) were in the range between 0.1 and 0.3 ng/mL for water samples and between 1.0 and 1.5 ng/g for watermelon samples. The recoveries of the method at spiking levels of 5.0 and 50.0 ng/mL for water samples were between 85.4 and 100.8%, and at spiking levels of 5.0 and 50.0 ng/g for watermelon samples, they were between 82.6 and 92.4%, with the relative standard deviations (RSDs) varying from 4.5-6.9% and 5.2-7.4%, respectively. The results suggested that the developed method represents a simple, low-cost, high analytes preconcentration and excellent sample cleanup procedure for the determination of organophosphorus pesticides in water and watermelon samples. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Parallel artificial liquid membrane extraction

DEFF Research Database (Denmark)

Gjelstad, Astrid; Rasmussen, Knut Einar; Parmer, Marthe Petrine

2013-01-01

This paper reports development of a new approach towards analytical liquid-liquid-liquid membrane extraction termed parallel artificial liquid membrane extraction. A donor plate and acceptor plate create a sandwich, in which each sample (human plasma) and acceptor solution is separated by an arti......This paper reports development of a new approach towards analytical liquid-liquid-liquid membrane extraction termed parallel artificial liquid membrane extraction. A donor plate and acceptor plate create a sandwich, in which each sample (human plasma) and acceptor solution is separated...... by an artificial liquid membrane. Parallel artificial liquid membrane extraction is a modification of hollow-fiber liquid-phase microextraction, where the hollow fibers are replaced by flat membranes in a 96-well plate format....

Simultaneous determination of furfural and its degradation products, furoic acid and maleic acid, in transformer oil by the reversed-phase vortex-assisted liquid-liquid microextraction followed by high-performance liquid chromatography.

Science.gov (United States)

Wang, Yifan; Li, Haiyan; Yang, Zhen; Zhang, Weijie; Hua, Jia

2017-12-01

To explore why the use of furfural as a transformer oil-paper insulation aging characteristic is problematic in real world application, we developed a method for the simultaneous determination of furfural, furoic acid, and maleic acid in transformer oil by reversed-phase vortex-assisted liquid-liquid microextraction combined with high-performance liquid chromatography. The conditions for the proposed method were optimized, and the obtained extract can be directly analyzed by high-performance liquid chromatography. The detection limits (signal-to-noise ratio = 3) of the method ranged from 1.0 to 4.6 μg/L, the enrichment factors for furfural, furoic acid, maleic acid, and fumaric acid were 4.6, 25.1, 15.6, and 17.5, respectively, and the recovery rates for three analytes (fumaric acid was undetected) range from 82.1 to 106.2%. The contents of furfural, furoic acid, and maleic acid resulted from accelerated aging of transformer insulation oil-paper were measured using the present method for the first time, and the aging samples were analyzed by liquid chromatography with mass spectrometry for the identification of furoic acid and maleic acid in the aging transformer oil samples. Using the optimal method, the target products of samples at different aging time were tracked and measured. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-step extraction of polar drugs from plasma by Parallel Artificial Liquid Membrane Extraction

DEFF Research Database (Denmark)

Pilařová, Veronika; Sultani, Mumtaz; Ask, Kristine Skoglund

2017-01-01

in the pores of a thin polymeric membrane, a well-known extraction principle also used in hollow fiber liquid-phase microextraction (HF-LPME). However, the new PALME technique offers a more user-friendly setup in which the supported liquid membrane is incorporated in a 96 well plate system. Thus, high......The new microextraction technique named parallel artificial liquid membrane extraction (PALME) was introduced as an alternative approach to liquid-liquid extraction of charged analytes from aqueous samples. The concept is based on extraction of analytes across a supported liquid membrane sustained...... for extraction of polar basic drugs was developed in the present work. The basic drugs hydralazine, ephedrine, metaraminol, salbutamol, and cimetidine were used as model analytes, and were extracted from alkalized human plasma into an aqueous solution via the supported liquid membrane. The extraction...

Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography.

Science.gov (United States)

Yu, Honglian; Merib, Josias; Anderson, Jared L

2016-03-18

Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

Simple and fast method for iron determination in white and red wines using dispersive liquid-liquid microextraction and ultraviolet-visible spectrophotometry.

Science.gov (United States)

Maciel, Juliana V; Soares, Bruno M; Mandlate, Jaime S; Picoloto, Rochele S; Bizzi, Cezar A; Flores, Erico M M; Duarte, Fabio A

2014-08-20

This work reports the development of a method for Fe extraction in white and red wines using dispersive liquid-liquid microextraction (DLLME) and determination by ultraviolet-visible spectrophotometry. For optimization of the DLLME method, the following parameters were evaluated: type and volume of dispersive (1300 μL of acetonitrile) and extraction (80 μL of C(2)Cl(4)) solvents, pH (3.0), concentration of ammonium pyrrolidinedithiocarbamate (APDC, 500 μL of 1% m/v APDC solution), NaCl concentration (not added), and extraction time. The calibration curve was performed using the analyte addition method, and the limit of detection and relative standard deviation were 0.2 mg L(-1) and below 7%, respectively. The accuracy was evaluated by comparison of results obtained after Fe determination by graphite furnace atomic absorption spectrometry, with agreement ranging from 94 to 105%. The proposed method was applied for Fe determination in white and red wines with concentrations ranging from 1.3 to 4.7 mg L(-1).

Surfactant-enhanced liquid-liquid microextraction coupled to micro-solid phase extraction onto highly hydrophobic magnetic nanoparticles

International Nuclear Information System (INIS)

Giannoulis, Kiriakos M.; Giokas, Dimosthenis L.; Tsogas, George Z.; Vlessidis, Athanasios G.; Zhu, Qing; Pan, Qinmin

2013-01-01

We are presenting a simplified alternative method for dispersive liquid-liquid microextraction (DLLME) by resorting to the use of surfactants as emulsifiers and micro solid-phase extraction (μ-SPE). In this combined procedure, DLLME of hydrophobic components is initially accomplished in a mixed micellar/microemulsion extractant phase that is prepared by rapidly mixing a non-ionic surfactant and 1-octanol in aqueous medium. Then, and in contrast to classic DLLME, the extractant phase is collected by highly hydrophobic polysiloxane-coated core-shell Fe 2 O 3 (at)C magnetic nanoparticles. Hence, the sample components are the target analyte in the DLLME which, in turn, becomes the target analyte of the μ-SPE step. This 2-step approach represents a new and simple DLLME procedure that lacks tedious steps such as centrifugation, thawing, or delicate collection of the extractant phase. As a result, the analytical process is accelerated and the volume of the collected phase does not depend on the volume of the extraction solvent. The method was applied to extract cadmium in the form of its pyrrolidine dithiocarbamate chelate from spiked water samples prior to its determination by FAAS. Detection limits were brought down to the low μg L −1 levels by preconcentrating 10 mL samples with satisfactory recoveries (96.0–108.0 %). (author)

A green deep eutectic solvent dispersive liquid-liquid micro-extraction (DES-DLLME) for the UHPLC-PDA determination of oxyprenylated phenylpropanoids in olive, soy, peanuts, corn, and sunflower oil.

Science.gov (United States)

Ferrone, Vincenzo; Genovese, Salvatore; Carlucci, Maura; Tiecco, Matteo; Germani, Raimondo; Preziuso, Francesca; Epifano, Francesco; Carlucci, Giuseppe; Taddeo, Vito Alessandro

2018-04-15

A green dispersive liquid-liquid microextraction (DLLME) using deep eutectic solvent (DES) as the extracting solvent has been developed and applied for the simultaneous quantification of ferulic acid, umbelliferone, boropinic acid, 7-isopentenyloxycoumarin, 4'-geranyloxyferulic acid (GOFA), and auraptene in some vegetable oils using ultra high performance liquid chromatography (UHPLC) with photodiode array detection (PDA). All parameters in the extraction step, including selection and loading of both extracting and dispersing solvents, amount of both extractant and disperser solvent were investigated and optimized. PhAA/TMG DES achieved higher recovery and enrichment factor compared to other DESs. The validated method showed good linearity with correlation coefficients, r 2 >0.9990 for all the analytes. Furthermore, this is the first time that eco-friendly solvents are used for the extraction of oxyprenylated phenylpropanoids and the corresponding extract analyzed with ultra high performance liquid chromatography with photodiode array detection. Copyright © 2017 Elsevier Ltd. All rights reserved.

Headspace solid-phase microextraction (HS-SPME) and liquid-liquid extraction (LLE): comparison of the performance in classification of ecstasy tablets. Part 2.

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Bonadio, Federica; Margot, Pierre; Delémont, Olivier; Esseiva, Pierre

2008-11-20

Headspace solid-phase microextraction (HS-SPME) is assessed as an alternative to liquid-liquid extraction (LLE) currently used for 3,4-methylenedioxymethampethamine (MDMA) profiling. Both methods were compared evaluating their performance in discriminating and classifying samples. For this purpose 62 different seizures were analysed using both extraction techniques followed by gas chromatography-mass spectroscopy (GC-MS). A previously validated method provided data for HS-SPME, whereas LLE data were collected applying a harmonized methodology developed and used in the European project CHAMP. After suitable pre-treatment, similarities between sample pairs were studied using the Pearson correlation. Both methods enable to distinguish between samples coming from the same pre-tabletting batches and samples coming from different pre-tabletting batches. This finding emphasizes the use of HS-SPME as an effective alternative to LLE, with additional advantages such as sample preparation and a solvent-free process.

Hollow fiber based liquid-phase microextraction for the determination of mercury traces in water samples by electrothermal atomic absorption spectrometry

Energy Technology Data Exchange (ETDEWEB)

Lopez-Garcia, Ignacio; Rivas, Ricardo E. [Department of Analytical Chemistry, Faculty of Chemistry, Regional Campus of International Excellence ' Campus Mare Nostrum' , University of Murcia, E-30071 Murcia (Spain); Hernandez-Cordoba, Manuel, E-mail: hcordoba@um.es [Department of Analytical Chemistry, Faculty of Chemistry, Regional Campus of International Excellence ' Campus Mare Nostrum' , University of Murcia, E-30071 Murcia (Spain)

2012-09-19

Highlight: Black-Right-Pointing-Pointer Hg (II) traces are preconcentrated by means of a three-phase liquid microextraction system. Black-Right-Pointing-Pointer PAN and ammonium iodide are used in the donor and acceptor phase, respectively. Black-Right-Pointing-Pointer Hollow-fiber pores are continuously fed with toluene placed in the lumen. Black-Right-Pointing-Pointer Mercuric ions can be measured in waters below the {mu}g L{sup -1} level. - Abstract: A three-phase liquid microextraction procedure for the determination of mercury at low concentrations is discussed. To the aqueous sample placed at pH 7 by means of a phosphate buffer, 0.002% (m/v) 1-(2-pyridylazo)-2-naphthol (PAN) is incorporated, and the mixture submitted to microextraction with a hollow-fiber impregnated with toluene and whose lumen contains a 0.05 mol L{sup -1} ammonium iodide solution. The final measurement of the extract is carried out by electrothermal atomic absorption spectrometry (300 Degree-Sign C and 1100 Degree-Sign C for the calcination and atomization temperatures, respectively). The pyrolytic graphite atomizer is coated electrolytically with palladium. An enrichment factor of 270, which results in a 0.06 {mu}g L{sup -1} mercury for the detection limit is obtained. The relative standard deviation at the 1 {mu}g L{sup -1} mercury level is 3.2% (n = 5). The reliability of the procedure is verified by analyzing waters as well as six certified reference materials.

Liquid-phase microextraction combined with graphite furnace atomic absorption spectrometry: A review

Energy Technology Data Exchange (ETDEWEB)

Calle, Inmaculada de la; Pena-Pereira, Francisco; Lavilla, Isela; Bendicho, Carlos, E-mail: bendicho@uvigo.es

2016-09-14

An overview of the combination of liquid-phase microextraction (LPME) techniques with graphite furnace atomic absorption spectrometry (GFAAS) is reported herein. The high sensitivity of GFAAS is significantly enhanced by its association with a variety of miniaturized solvent extraction approaches. LPME-GFAAS thus represents a powerful combination for determination of metals, metalloids and organometallic compounds at (ultra)trace level. Different LPME modes used with GFAAS are briefly described, and the experimental parameters that show an impact in those microextraction processes are discussed. Special attention is paid to those parameters affecting GFAAS analysis. Main issues found when coupling LPME and GFAAS, as well as those strategies reported in the literature to solve them, are summarized. Relevant applications published on the topic so far are included. - Highlights: • We review the LPME-GFAAS combination in a comprehensive way. • A brief description of main LPME modes is included. • Effect of experimental parameters in the performance of LPME-GFAAS is discussed. • Main applications for trace element analysis and speciation are reviewed.

Liquid-phase microextraction combined with graphite furnace atomic absorption spectrometry: A review

International Nuclear Information System (INIS)

Calle, Inmaculada de la; Pena-Pereira, Francisco; Lavilla, Isela; Bendicho, Carlos

2016-01-01

An overview of the combination of liquid-phase microextraction (LPME) techniques with graphite furnace atomic absorption spectrometry (GFAAS) is reported herein. The high sensitivity of GFAAS is significantly enhanced by its association with a variety of miniaturized solvent extraction approaches. LPME-GFAAS thus represents a powerful combination for determination of metals, metalloids and organometallic compounds at (ultra)trace level. Different LPME modes used with GFAAS are briefly described, and the experimental parameters that show an impact in those microextraction processes are discussed. Special attention is paid to those parameters affecting GFAAS analysis. Main issues found when coupling LPME and GFAAS, as well as those strategies reported in the literature to solve them, are summarized. Relevant applications published on the topic so far are included. - Highlights: • We review the LPME-GFAAS combination in a comprehensive way. • A brief description of main LPME modes is included. • Effect of experimental parameters in the performance of LPME-GFAAS is discussed. • Main applications for trace element analysis and speciation are reviewed.

Salting-out-enhanced ionic liquid microextraction with a dual-role solvent for simultaneous determination of trace pollutants with a wide polarity range in aqueous samples.

Science.gov (United States)

Gao, Man; Qu, Jingang; Chen, Kai; Jin, Lide; Dahlgren, Randy Alan; Wang, Huili; Tan, Chengxia; Wang, Xuedong

2017-11-01

In real aquatic environments, many occupational pollutants with a wide range of polarities coexist at nanogram to milligram per liter levels. Most reported microextraction methods focus on extracting compounds with similar properties (e.g., polarity or specific functional groups). Herein, we developed a salting-out-enhanced ionic liquid microextraction based on a dual-role solvent (SILM-DS) for simultaneous detection of tetracycline, doxycycline, bisphenol A, triclosan, and methyltriclosan, with log K ow ranging from -1.32 to 5.40 in complex milk and environmental water matrices. The disperser in the ionic-liquid-based dispersive liquid-liquid microextraction was converted to the extraction solvent in the subsequent salting-out-assisted microextraction procedures, and thus a single solvent performed a dual role as both extractant and disperser in the SILM-DS process. Acetonitrile was selected as the dual-role solvent because of its strong affinity for both ionic liquids and water, as well as the extractant in the salting-out step. Optimized experimental conditions were 115 μL [C 8 MIM][PF 6 ] as extractor, 1200 μL acetonitrile as dual-role solvent, pH 2.0, 5.0 min ultrasound extraction time, 3.0 g Na 2 SO 4 , and 3.0 min vortex extraction time. Under optimized conditions, the recoveries of the five pollutants ranged from 74.5 to 106.9%, and their LODs were 0.12-0.75 μg kg -1 in milk samples and 0.11-0.79 μg L -1 in environmental waters. Experimental precision based on relative standard deviation was 1.4-6.4% for intraday and 2.3-6.5% for interday analyses. Compared with previous methods, the prominent advantages of the newly developed method are simultaneous determination of pollutants with a wide range of polarities and a substantially reduced workload for ordinary environmental monitoring and food tests. Therefore, the new method has great application potential for simultaneous determination of trace pollutants with strongly contrasting polarities in several

Dispersive liquid-liquid microextraction for simultaneous determination of cadmium, cobalt, lead and nickel in water samples by inductively coupled plasma optical emission spectrometry

International Nuclear Information System (INIS)

Dos Santos Silva, E.; Correia, L.O.; Dos Santos, L.O.; Dos Santos Vieira, E.V.; Lemos, V.A.

2012-01-01

We report on a new method for the dispersive liquid-liquid microextraction of Cd(II), Co(II), Pb(II) and Ni (II) from water samples prior to their simultaneous determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The procedure is based on the injection of a ternary solvent system composed of appropriate quantities of extraction solvent (trichloroethylene), dispersive solvent (ethanol), and the chelating reagent 2-(2'-benzothiazolylazo)-p-cresol into the sample solution. The solution turns turbid immediately after injection, and the analytes are extracted into the droplets of the organic phase which was dried and dissolved in a mixture of Triton X-114, nitric acid, and ethanol. The metal ions in this mixture were quantified by ICP-OES. The detection limits under optimized conditions are 0.2, 0.3, 0.2 and 0.7 μg L -1 for Cd(II), Co(II), Pb(II) and Ni(II), respectively. The enrichment factors were also calculated for Cd (13), Co (11), Pb (11) and Ni (8). The procedure was applied to the determination of cadmium, cobalt, lead and nickel in certified reference material (waterway sediment) and water samples. (author)

Preconcentration of valsartan by dispersive liquid-liquid microextraction based on solidification of floating organic drop and its determination in urine sample: Central composite design.

Science.gov (United States)

Pebdani, Arezou Amiri; Shabani, Ali Mohammad Haji; Dadfarnia, Shayesteh; Talebianpoor, Mohammad Sharif; Khodadoust, Saeid

2016-05-01

In this work, a fast, easy, and efficient dispersive liquid-liquid microextraction method based on solidification of floating organic drop followed by high-performance liquid chromatography with UV detection was developed for the separation/preconcentration and determination of the drug valsartan. Experimental design was applied for the optimization of the effective variables (such as volume of extracting and dispersing solvents, ionic strength, and pH) on the extraction efficiency of valsartan from urine samples. The optimized values were 250.0 μL ethanol, 65.0 μL 1-dodecanol, 4.0% w/v NaCl, pH 3.8, 1.0 min extraction time, and 4.0 min centrifugation at 4000 rpm min(-1) . The linear response (r(2) = 0.997) was obtained in the range of 0.013-10.0 μg mL(-1) with a limit of detection of 4.0 ng mL(-1) and relative standard deviations of less than 5.0 % (n = 6). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dispersive liquid-liquid microextraction coupled with digital image colorimetric analysis for detection of total iron in water and food samples.

Science.gov (United States)

Peng, Bo; Chen, Guorong; Li, Kai; Zhou, Min; Zhang, Ji; Zhao, Shengguo

2017-09-01

A simple and low cost assay for total iron in various samples based on dispersive liquid-liquid microextraction (DLLME) coupled with digital scanning image analysis was proposed. Orthogonal experiment design was utilized to optimize the amount of extraction solvent and disperser solvent, O-phenanthroline concentration and buffer pH. Under the optimum conditions, the calibration curve was linear over the range of 0.047-1.0μgmL -1 (R 2 >0.99) of iron. The limit of detection (LOD) for iron was 14.1μgL -1 and limit of quantification (LOQ) was 46.5μgL -1 . The relative standard deviations for seven replicate determinations of 0.5μgmL -1 of iron was 3.75%. The method was successfully applied for analysis of total iron in water and food samples without using any spectral instrument and it could have a potential industrial impact in developing fast and portable devices to analyze the iron content in water and certain foods. Copyright © 2017 Elsevier Ltd. All rights reserved.

Separation/preconcentration and determination of vanadium with dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) and electrothermal atomic absorption spectrometry.

Science.gov (United States)

Asadollahi, Tahereh; Dadfarnia, Shayessteh; Shabani, Ali Mohammad Haji

2010-06-30

A novel dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) for separation/preconcentration of ultra trace amount of vanadium and its determination with the electrothermal atomic absorption spectrometry (ETAAS) was developed. The DLLME-SFO behavior of vanadium (V) using N-benzoyl-N-phenylhydroxylamine (BPHA) as complexing agent was systematically investigated. The factors influencing the complex formation and extraction by DLLME-SFO method were optimized. Under the optimized conditions: 100 microL, 200 microL and 25 mL of extraction solvent (1-undecanol), disperser solvent (acetone) and sample volume, respectively, an enrichment factor of 184, a detection limit (based on 3S(b)/m) of 7 ng L(-1) and a relative standard deviation of 4.6% (at 500 ng L(-1)) were obtained. The calibration graph using the preconcentration system for vanadium was linear from 20 to 1000 ng L(-1) with a correlation coefficient of 0.9996. The method was successfully applied for the determination of vanadium in water and parsley. Copyright 2010 Elsevier B.V. All rights reserved.

Liquid phase micro-extraction: Towards the green methodology for ultratrace metals determination in aquatic ecosystems

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López-López J. A.

2013-04-01

Full Text Available Heavy metals are normally found, in natural waters, in very low concentrations. Some of them are essential for life in low level; however, in higher level they are toxic. Therefore, analyzing their bio-available fraction is of main interest. Standard methodology is based in the collection of a number of samples from a water body. Collected samples must be stored, pre-treated and then analyzed. Pre-treatment usually involves pre-concentrating the metal, with the corresponding risk of contamination or loss of analyte. This way, punctual information is obtained from every sampling campaign. As an alternative, passive sampling techniques allow the continuous and coupled sampling-pre-treatment for heavy metals analysis, giving a better approach in the characterization of the studied water body. Liquid phase micro-extraction (LPME is a green analytical alternative for liquid-liquid extraction that promotes a reduction of sample volume, solvent needed and waste generation. Using these systems, polypropylene hollow fibers (HF with pores in their walls can be used. A few micro-liters of organic solvent are supported in the pores. The sample is placed in the outer part of the fiber and a receiving phase is placed in its inner part, allowing continuous liquid extraction of the metal from the sample. Several fibers with different physical features have been employed to analyzed total concentration and bio-availability of some heavy metals (Ag, Ni, Cu in natural water samples. Thanks to fibers configuration, devices for passive sampling based in HF-LPME could be designed. Advantages of this methodology over existing ones are supported because the receiving phase is liquid. As a consequence, retained metals do not need to be eluted from the acceptor prior to instrumental analysis.

Dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous separation/preconcentration of nickel, cobalt and copper prior to determination by electrothermal atomic absorption spectrometry

Directory of Open Access Journals (Sweden)

Mooud Amirkavei

2013-01-01

Full Text Available A dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous extraction of trace amounts of nickel, cobalt and copper followed by their determination with electrothermal atomic absorption spectrometry was developed. 300 µL of acetone and 1-undecanol was injected into an aqueous sample containing diethyldithiocarbamate complexes of metal ions. For a sample volume of 10 mL, enrichment factors of 277, 270 and 300 and detection limits of 1.2, 1.1 and 1 ng L-1 for nickel, cobalt and copper were obtained, respectively. The method was applied to the extraction and determination of these metals in different water samples.

Determination of thiobencarb in water samples by gas chromatography using a homogeneous liquid-liquid microextraction via flotation assistance procedure

Directory of Open Access Journals (Sweden)

H.A. Mashayekhi

2013-09-01

Full Text Available Homogeneous liquid-liquid microextraction via flotation assistance (HLLME-FA coupled with gas chromatography-flame ionization detection (GC-FID was applied for the extraction and determination of thiobencarb in water samples. In this study, a special extraction cell was designed to facilitate collection of the low-density solvent extraction. No centrifugation was required in this procedure. The water sample solution was added into the extraction cell which contained an appropriate mixture of toluene (as an extraction solvent and acetone (as a homogeneous solvent. By using air flotation, the organic solvent was collected at the conical part of the designed cell. The effect of the different parameters on the efficiency of extraction such as type and volume of extraction and homogeneous solvents, ionic strength and extraction time were studied and optimized. Under the optimal conditions, linearity of the method was in the range of 1.0-200 µg L-1. The relative standard deviations in the real samples varied from 7.8-11.7 % (n = 3. The proposed method was successfully applied to analysis of thiobencarb in the water samples and satisfactory results were obtained.DOI: http://dx.doi.org/10.4314/bcse.v27i3.4

Application of dispersive liquid-liquid microextraction and dispersive micro-solid-phase extraction for the determination of quinolones in swine muscle by high-performance liquid chromatography with diode-array detection

International Nuclear Information System (INIS)

Tsai, Wen-Hsien; Chuang, Hung-Yi; Chen, Ho-Hsien; Huang, Joh-Jong; Chen, Hwi-Chang; Cheng, Shou-Hsun; Huang, Tzou-Chi

2009-01-01

Dispersive liquid-liquid microextraction (DLLME) and dispersive micro-solid-phase extraction (DMSPE) are two simple and low-cost sample preparation methods for liquid samples. In this work, these two methods were applied to solid tissue sample for the determination of seven quinolones by high-performance liquid chromatography with diode-array detection (HPLC-DAD). After the homogenization of the swine muscle with acetonitrile and salt-promoted partitioning, small amounts of the extract were used for the DLLME and DMSPE methods. In the DLLME approach, the target analytes in the extraction solvent were rapidly extracted into a small volume of dichloromethane for drying and the residue was reconstituted for HPLC-DAD analysis. In the DMSPE approach, the target analytes in the extraction solvent were trapped by dispersive silica-based PSA (primary and secondary amine) sorbents and desorbed into a small amount of desorption solution for HPLC-DAD analysis. Under the optimal conditions, relative recoveries were determined for swine muscle spiked 50-200 μg kg -1 and quantification was achieved by matrix-matched calibration. The calibration curves of seven quinolones showed linearity with a correlation coefficient value above 0.998 for both approaches. Relative recoveries ranged from 93.0 to 104.7% and from 95.5 to 111.0% for DLLME and DMSPE, respectively. Limits of detection (LODs) ranged from 5.6 to 23.8 μg kg -1 and from 7.5 to 26.3 μg kg -1 for DLLME and DMSPE, respectively.

Determination of phthalate esters in distillates by ultrasound-vortex-assisted dispersive liquid-liquid micro-extraction (USVADLLME) coupled with gas chromatography/mass spectrometry.

Science.gov (United States)

Montevecchi, Giuseppe; Masino, Francesca; Zanasi, Luca; Antonelli, Andrea

2017-04-15

A method for the extraction of phthalate esters (PAEs) by Ultrasound-Vortex-Assisted Dispersive Liquid-Liquid Micro-Extraction (USVADLLME) approach was optimised and applied for the first time to a historical series of brandies. These contaminants are widely spread in the environment as a consequence of about half century of use in different fields of applications. The concern about these substances and the recent legal restrictions of China in distillates import need a quick and sensitive method for their quantification. The proposed method, moreover, is environmentally oriented due to the disposal of micro-quantities of solvent required. In fact, sub-ppm-limits of detection were achieved with a solvent volume as low as 160μL. The analysed samples were within the legal limits, except for some very ancient brandies whose contamination was probably due to a PAEs concentration effect as a consequence of long ageing and for the use of plastic pipelines no more operative. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ionic liquid-based microwave-assisted dispersive liquid–liquid microextraction and derivatization of sulfonamides in river water, honey, milk, and animal plasma

International Nuclear Information System (INIS)

Xu Xu; Su Rui; Zhao Xin; Liu Zhuang; Zhang Yupu; Li Dan; Li Xueyuan; Zhang Hanqi; Wang Ziming

2011-01-01

Graphical abstract: The extraction and derivatization efficiency of SAs is dependent on type and volume of extraction solvent, type and volume of disperser, microwave power and irradiation time, volume of derivatization reagent, pH of sample solution as well as ionic strength. Highlights: ► A new, rapid and sensitive method for determining sulfonamides (SAs) was proposed. ► Derivatization, extraction and preconcentration of SAs were performed in one step. ► IL-based MADLLME and derivatization were first applied for the determination of SAs. ► Trace SAs in river water, honey, milk, and pig plasma were determined. - Abstract: The ionic liquid-based microwave-assisted dispersive liquid–liquid microextraction (IL-based MADLLME) and derivatization was applied for the pretreatment of six sulfonamides (SAs) prior to the determination by high-performance liquid chromatography (HPLC). By adding methanol (disperser), fluorescamine solution (derivatization reagent) and ionic liquid (extraction solvent) into sample, extraction, derivatization, and preconcentration were continuously performed. Several experimental parameters, such as the type and volume of extraction solvent, the type and volume of disperser, amount of derivatization reagent, microwave power, microwave irradiation time, pH of sample solution, and ionic strength were investigated and optimized. When the microwave power was 240 W, the analytes could be derivatized and extracted simultaneously within 90 s. The proposed method was applied to the analysis of river water, honey, milk, and pig plasma samples, and the recoveries of analytes obtained were in the range of 95.0–110.8, 95.4–106.3, 95.0–108.3, and 95.7–107.7, respectively. The relative standard deviations varied between 1.5% and 7.3% (n = 5). The results showed that the proposed method was a rapid, convenient and feasible method for the determination of SAs in liquid samples.

Headspace liquid-phase microextraction of methamphetamine and amphetamine in urine by an aqueous drop

International Nuclear Information System (INIS)

He Yi; Vargas, Angelica; Kang, Youn-Jung

2007-01-01

This study developed a headspace liquid-phase microextraction (LPME) method by using a single aqueous drop in combination with high performance liquid chromatography (HPLC)-UV detection for the determination of methamphetamine (MAP) and amphetamine (AP) in urine samples. The analytes, volatile and basic, were released from sample matrix into the headspace first, and then protonated and dissolved in an aqueous H 3 PO 4 drop hanging in the headspace by a HPLC syringe. After extraction, this drop was directly injected into HPLC. Parameters affecting extraction efficiency were investigated and optimized. This method showed good linearity in the investigated concentration range of 1.0-1500 μg L -1 , repeatability of the extraction (R.S.D. -1 for both analytes). Enrichment factors of about 400-fold and 220-fold were achieved for MAP and AP, respectively, at optimum conditions. The feasibility of the method was demonstrated by analyzing human urine samples

Feasibility of corona discharge ion mobility spectrometry for direct analysis of samples extracted by dispersive liquid-liquid microextraction.

Science.gov (United States)

Jafari, Mohammad T; Riahi, Farhad

2014-05-23

The capability of corona discharge ionization ion mobility spectrometry (CD-IMS) for direct analysis of the samples extracted by dispersive liquid-liquid microextraction (DLLME) was investigated and evaluated, for the first time. To that end, an appropriate new injection port was designed and constructed, resulting in possibility of direct injection of the known sample volume, without tedious sample preparation steps (e.g. derivatization, solvent evaporation, and re-solving in another solvent…). Malathion as a test compound was extracted from different matrices by a rapid and convenient DLLME method. The positive ion mobility spectra of the extracted malathion were obtained after direct injection of carbon tetrachloride or methanol solutions. The analyte responses were compared and the statistical results revealed the feasibility of direct analysis of the extracted samples in carbon tetrachloride, resulting in a convenient methodology. The coupled method of DLLME-CD-IMS was exhaustively validated in terms of sensitivity, dynamic range, recovery, and enrichment factor. Finally, various real samples of apple, river and underground water were analyzed, all verifying the feasibility and success of the proposed method for the easy extraction of the analyte using DLLME separation before the direct analysis by CD-IMS. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of free formaldehyde in cosmetics containing formaldehyde-releasing preservatives by reversed-phase dispersive liquid-liquid microextraction and liquid chromatography with post-column derivatization.

Science.gov (United States)

Miralles, Pablo; Chisvert, Alberto; Alonso, M José; Hernandorena, Sandra; Salvador, Amparo

2018-03-30

An analytical method for the determination of traces of formaldehyde in cosmetic products containing formaldehyde-releasing preservatives has been developed. The method is based on reversed-phase dispersive liquid-liquid microextraction (RP-DLLME), that allows the extraction of highly polar compounds, followed by liquid chromatography-ultraviolet/visible (LC-UV/vis) determination with post-column derivatization. The variables involved in the RP-DLLME process were studied to provide the best enrichment factors. Under the selected conditions, a mixture of 500 μL of acetonitrile (disperser solvent) and 50 μL of water (extraction solvent) was rapidly injected into 5 mL of toluene sample solution. The extracts were injected into the LC-UV/vis system using phosphate buffer 6 mmol L -1 at pH 2 as mobile phase. After chromatographic separation, the eluate merged with a flow stream of pentane-2,4-dione in ammonium acetate solution as derivatizing reagent and passed throughout a post-column reactor at 85 °C in order to derivatize formaldehyde into 3,5-diacetyl-1,4-dihydrolutidine, according to Hantzsch reaction, which was finally measured spectrophotometrically at 407 nm. The method was successfully validated showing good linearity, an enrichment factor of 86 ± 2, limits of detection and quantification of 0.7 and 2.3 ng mL -1 , respectively, and good repeatability (RSD < 9.2%). Finally, the proposed analytical method was applied to the determination of formaldehyde in different commercial cosmetic samples containing formaldehyde-releasing preservatives, such as bronopol, diazolidinyl urea, imidazolidinyl urea, and DMDM hydantoin, with good relative recovery values (91-113%) thus showing that matrix effects were negligible. The good analytical features of the proposed method besides of its simplicity and affordability, make it useful to carry out the quality control of cosmetic products containing formaldehyde-releasing preservatives. Copyright �

Determination of Levetiracetam in Human Plasma by Dispersive Liquid-Liquid Microextraction Followed by Gas Chromatography-Mass Spectrometry

Science.gov (United States)

2016-01-01

Levetiracetam (LEV) is an antiepileptic drug that is clinically effective in generalized and partial epilepsy syndromes. The use of this drug has been increasing in clinical practice and intra- or -interindividual variability has been exhibited for special population. For this reason, bioanalytical methods are required for drug monitoring in biological matrices. So this work presents a dispersive liquid-liquid microextraction method followed by gas chromatography-mass spectrometry (DLLME-GC-MS) for LEV quantification in human plasma. However, due to the matrix complexity a previous purification step is required. Unlike other pretreatment techniques presented in the literature, for the first time, a procedure employing ultrafiltration tubes Amicon® (10 kDa porous size) without organic solvent consumption was developed. GC-MS analyses were carried out using a linear temperature program, capillary fused silica column, and helium as the carrier gas. DLLME optimized parameters were type and volume of extraction and dispersing solvents, salt addition, and vortex agitation time. Under chosen parameters (extraction solvent: chloroform, 130 μL; dispersing solvent: isopropyl alcohol, 400 μL; no salt addition and no vortex agitation time), the method was completely validated and all parameters were in agreement with the literature recommendations. LEV was quantified in patient's plasma sample using less than 550 μL of organic solvent. PMID:27830105

Determination of Levetiracetam in Human Plasma by Dispersive Liquid-Liquid Microextraction Followed by Gas Chromatography-Mass Spectrometry

Directory of Open Access Journals (Sweden)

Greyce Kelly Steinhorst Alcantara

2016-01-01

Full Text Available Levetiracetam (LEV is an antiepileptic drug that is clinically effective in generalized and partial epilepsy syndromes. The use of this drug has been increasing in clinical practice and intra- or -interindividual variability has been exhibited for special population. For this reason, bioanalytical methods are required for drug monitoring in biological matrices. So this work presents a dispersive liquid-liquid microextraction method followed by gas chromatography-mass spectrometry (DLLME-GC-MS for LEV quantification in human plasma. However, due to the matrix complexity a previous purification step is required. Unlike other pretreatment techniques presented in the literature, for the first time, a procedure employing ultrafiltration tubes Amicon® (10 kDa porous size without organic solvent consumption was developed. GC-MS analyses were carried out using a linear temperature program, capillary fused silica column, and helium as the carrier gas. DLLME optimized parameters were type and volume of extraction and dispersing solvents, salt addition, and vortex agitation time. Under chosen parameters (extraction solvent: chloroform, 130 μL; dispersing solvent: isopropyl alcohol, 400 μL; no salt addition and no vortex agitation time, the method was completely validated and all parameters were in agreement with the literature recommendations. LEV was quantified in patient’s plasma sample using less than 550 μL of organic solvent.

Determination of lead at trace levels in mussel and sea water samples using vortex assisted dispersive liquid-liquid microextraction-slotted quartz tube-flame atomic absorption spectrometry.

Science.gov (United States)

Erarpat, Sezin; Özzeybek, Gözde; Chormey, Dotse Selali; Bakırdere, Sezgin

2017-12-01

In this study, dispersive liquid-liquid microextraction (DLLME) and slotted quartz tube (SQT) were coupled to flame atomic absorption spectrometry (FAAS) to increase the sensitivity of lead. Conditions such as the formation of the lead-dithizone complex, efficiency of the DLLME method and the output of the SQT were systematically optimized to improve the detection limit for the analyte. The conventional FAAS system was improved upon by about 3.0 times with SQT-FAAS, 32 times with DLLME-FAAS and 142 times with DLLME-SQT-FAAS. The method was applicable over a wide linear range (10-500 μg L -1 ). The limit of detection (LOD) determined by DLLME-SQT-FAAS for seawater and mussel were 2.7 μg L -1 and 270 μg kg -1 , respectively. The percent recoveries obtained for mussel and seawater samples (spiked at 20 and 50 μg L -1 ) were 95-96% and 98-110%, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Magnetic stirrer induced dispersive ionic-liquid microextraction for the determination of vanadium in water and food samples prior to graphite furnace atomic absorption spectrometry.

Science.gov (United States)

Naeemullah; Kazi, Tasneem Gul; Tuzen, Mustafa

2015-04-01

A new dispersive liquid-liquid microextraction, magnetic stirrer induced dispersive ionic-liquid microextraction (MS-IL-DLLME) was developed to quantify the trace level of vanadium in real water and food samples by graphite furnace atomic absorption spectrometry (GFAAS). In this extraction method magnetic stirrer was applied to obtained a dispersive medium of 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6] in aqueous solution of (real water samples and digested food samples) to increase phase transfer ratio, which significantly enhance the recovery of vanadium - 4-(2-pyridylazo) resorcinol (PAR) chelate. Variables having vital role on desired microextraction methods were optimised to obtain the maximum recovery of study analyte. Under the optimised experimental variables, enhancement factor (EF) and limit of detection (LOD) were achieved to be 125 and 18 ng L(-1), respectively. Validity and accuracy of the desired method was checked by analysis of certified reference materials (SLRS-4 Riverine water and NIST SRM 1515 Apple leaves). The relative standard deviation (RSD) for 10 replicate determinations at 0.5 μg L(-1) of vanadium level was found to be <5.0%. This method was successfully applied to real water and acid digested food samples. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sensitive Detection of Organophosphorus Pesticides in Medicinal Plants Using Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction Combined with Sweeping Micellar Electrokinetic Chromatography.

Science.gov (United States)

Wei, Jin-Chao; Hu, Ji; Cao, Ji-Liang; Wan, Jian-Bo; He, Cheng-Wei; Hu, Yuan-Jia; Hu, Hao; Li, Peng

2016-02-03

A simple, rapid, and sensitive method using ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) combined with sweeping micellar electrokinetic chromatography (sweeping-MEKC) has been developed for the determination of nine organophosphorus pesticides (chlorfenvinphos, parathion, quinalphos, fenitrothion, azinphos-ethyl, parathion-methyl, fensulfothion, methidathion, and paraoxon). The important parameters that affect the UA-DLLME and sweeping efficiency were investigated. Under the optimized conditions, the proposed method provided 779.0-6203.5-fold enrichment of the nine pesticides compared to the normal MEKC method. The limits of detection ranged from 0.002 to 0.008 mg kg(-1). The relative standard deviations of the peak area ranged from 1.2 to 6.5%, indicating the good repeatability of the method. Finally, the developed UA-DLLME-sweeping-MEKC method has been successfully applied to the analysis of the investigated pesticides in several medicinal plants, including Lycium chinense, Dioscorea opposite, Codonopsis pilosula, and Panax ginseng, indicating that this method is suitable for the determination of trace pesticide residues in real samples with complex matrices.

[Determination of four phenolic endocrine disruptors in environmental water samples by high performance liquid chromatography-fluorescence detection using dispersive liquid-liquid microextraction coupled with derivatization].

Science.gov (United States)

Wang, Xiaoyan; Qi, Weimei; Zhao, Xian'en; Lü, Tao; Wang, Xiya; Zheng, Longfang; Yan, Yehao; You, Jinmao

2014-06-01

To achieve accurate, fast and sensitive detection of phenolic endocrine disruptors in small volume of environmental water samples, a method of dispersive liquid-liquid microextraction (DLLME) coupled with fluorescent derivatization was developed for the determination of bisphenol A, nonylphenol, octylphenol and 4-tert-octylphenol in environmental water samples by high performance liquid chromatography-fluorescence detection (HPLC-FLD). The DLLME and derivatization conditions were investigated, and the optimized DLLME conditions for small volume of environmental water samples (pH 4.0) at room temperature were as follows: 70 microL chloroform as extraction solvent, 400 microL acetonitrile as dispersing solvent, vortex mixing for 3 min, and then high-speed centrifugation for 2 min. Using 2-[2-(7H-dibenzo [a, g] carbazol-7-yl)-ethoxy] ethyl chloroformate (DBCEC-Cl) as precolumn derivatization reagent, the stable derivatives of the four phenolic endocrine disruptors were obtained in pH 10.5 Na2CO3-NaHCO3 buffer/acetonitrile at 50 degrees C for 3 min, and then separated within 10 min by HPLC-FLD. The limits of detection (LODs) were in the range of 0.9-1.6 ng/L, and the limits of quantification (LOQs) were in the range of 3.8-7.1 ng/L. This method had perfect linearity, precision and recovery results, and showed obvious advantages and practicality comparing to the previously reported methods. It is a convenient and validated method for the routine analysis of phenolic endocrine disruptors in waste water of paper mill, lake water, domestic wastewater, tap water, etc.

Deep eutectic solvent-based ultrasound-assisted dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the determination of ultraviolet filters in water samples.

Science.gov (United States)

Wang, Huazi; Hu, Lu; Liu, Xinya; Yin, Shujun; Lu, Runhua; Zhang, Sanbing; Zhou, Wenfeng; Gao, Haixiang

2017-09-22

In the present study, a simple and rapid sample preparation method designated ultrasound-assisted dispersive liquid-liquid microextraction based on a deep eutectic solvent (DES) followed by high-performance liquid chromatography with ultraviolet (UV) detection (HPLC-UVD) was developed for the extraction and determination of UV filters from water samples. The model analytes were 2,4-dihydroxybenzophenone (BP-1), benzophenone (BP) and 2-hydroxy-4-methoxybenzophenone (BP-3). The hydrophobic DES was prepared by mixing trioctylmethylammonium chloride (TAC) and decanoic acid (DecA). Various influencing factors (selection of the extractant, amount of DES, ultrasound duration, salt addition, sample volume, sample pH, centrifuge rate and duration) on UV filter recovery were systematically investigated. Under optimal conditions, the proposed method provided good recoveries in the range of 90.2-103.5% and relative standard deviations (inter-day and intra-day precision, n=5) below 5.9%. The enrichment factors for the analytes ranged from 67 to 76. The limits of detection varied from 0.15 to 0.30ngmL -1 , depending on the analytes. The linearities were between 0.5 and 500ngmL -1 for BP-1 and BP and between 1 and 500ngmL -1 for BP-3, with coefficients of determination greater than 0.99. Finally, the proposed method was applied to the determination of UV filters in swimming pool and river water samples, and acceptable relative recoveries ranging from 82.1 to 106.5% were obtained. Copyright © 2017. Published by Elsevier B.V.

Determination of benzimidazoles in meat samples by capillary zone electrophoresis tandem mass spectrometry following dispersive liquid-liquid microextraction.

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Tejada-Casado, Carmen; Moreno-González, David; Lara, Francisco J; García-Campaña, Ana M; Del Olmo-Iruela, Monsalud

2017-03-24

A novel method based on capillary zone electrophoresis-tandem mass spectrometry has been proposed and validated for the identification and simultaneous quantification of twelve benzimidazoles in meat samples. Electrophoretic separation was carried out using 500mM formic acid (pH 2.2) as background electrolyte and applying a voltage of 25kV at 25°C. In order to improve the sensitivity, stacking mode injection was applied, using as injection solvent a mixture of 30:70 acetonitrile/water at 50mbar for 75s. Sensitivity enhancement factors from 74 to 317 were obtained under these conditions. Detection using an ion trap as analyzer, operating in multiple reactions monitoring mode was employed. The main MS/MS parameters as well as the composition of the sheath liquid and other electrospray variables were optimized in order to obtain the highest sensitivity and precision in conjunction with an unequivocal identification. The method was applied to poultry and pork muscle samples. The deproteinization of samples and extraction of benzimidazoles was carried out with acetonitrile. MgSO 4 and NaCl were added as salting-out agents. Subsequently, dispersive liquid-liquid microextraction was applied as clean up procedure. The organic layer (acetonitrile, used as dispersant) containing the benzimidazoles was mixed with the extractant (chloroform) and both were injected in water, producing a cloudy solution. Recoveries for fortified samples were higher than 70%, with relative standard deviations lower than 16% were obtained in all cases. The limits of detection were below 3μgkg -1 , demonstrating the applicability of this fast, simple, and environmentally friendly method. Copyright © 2017 Elsevier B.V. All rights reserved.

Ionic liquid solvent bar micro-extraction of CdCln(n-2)- species for ultra-trace Cd determination in seawater.

Science.gov (United States)

Herce-Sesa, Belén; López-López, José A; Moreno, Carlos

2018-02-01

Water analysis of trace metals has been benefited by recent studies on sample preparation by liquid micro-extraction. However, there are still limitations for its application to seawater, such as the need of additives to preserve the sample or the availability of chemical extractants for the selective extraction from highly saline samples. In this work, a three phase solvent bar micro-extraction (3SBME) system containing the ionic liquid trioctylmethylammonium chloride (Aliquat ® 336) has been used for isolation and pre-concentration of Cd from seawater samples, due to its ability for ionic exchange of CdCl n (n-2)- . The system was optimized to work at the natural pH of seawater, and conditions for application to real samples were 0.18 M Aliquat ® 336 dissolved in kerosene with 0.25 M dodecan-1-ol as organic solution, 1.5 M HNO 3 as acceptor solution, 60 min extraction time, and 800 rpm stirring speed in the sample. Loss of organic solution into the sample during extraction was evaluated and revealed its dependence on stirring rate and extraction time. Under optimum conditions samples containing Cd 0.09-0.90 nM were pre-concentrated 65 times. GF-AAS was used for metal quantification with a limit of detection of 0.04 nM. Accuracy was successfully evaluated measuring Cd in a seawater certified reference material BCR-403. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solid-phase extraction assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet to determine sildenafil and its analogues in dietary supplements.

Science.gov (United States)

Li, Jing; Roh, Si Hun; Shaodong, Jia; Hong, Ji Yeon; Lee, Dong-Kyu; Shin, Byong-Kyu; Park, Jeong Hill; Lee, Jeongmi; Kwon, Sung Won

2017-08-01

A novel analytical method for the simultaneous determination of the concentration of sildenafil and its five analogues in dietary supplements using solid-phase extraction assisted reversed-phase dispersive liquid-liquid microextraction based on solidification of floating organic droplet combined with ion-pairing liquid chromatography with an ultraviolet detector was developed. Parameters that affect extraction efficiency were systematically investigated, including the type of solid-phase extraction cartridge, pH of the extraction environment, and the type and volume of extraction and dispersive solvent. The method linearity was in the range of 5.0-100 ng/mL for sildenafil, homosildenafil, udenafil, benzylsildenafil, and thiosildenafil and 10-100 ng/mL for acetildenafil. The coefficients of determination were ≥0.996 for all regression curves. The sensitivity values expressed as limit of detection were between 2.5 and 7.5 ng/mL. Furthermore, intraday and interday precisions expressed as relative standard deviations were less than 5.7 and 9.9%, respectively. The proposed method was successfully applied to the analysis of sildenafil and its five analogues in complex dietary supplements. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

Rosero-Moreano, Milton; Canellas, Elena; Nerín, Cristina

2014-02-01

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. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Headspace liquid-phase microextraction of methamphetamine and amphetamine in urine by an aqueous drop

Energy Technology Data Exchange (ETDEWEB)

He Yi [Department of Sciences, John Jay College of Criminal Justice, City University of New York, 445 W 59th Street, New York, NY 10019 (United States)]. E-mail: yhe@jjay.cuny.edu; Vargas, Angelica [Department of Sciences, John Jay College of Criminal Justice, City University of New York, 445 W 59th Street, New York, NY 10019 (United States); Kang, Youn-Jung [Department of Sciences, John Jay College of Criminal Justice, City University of New York, 445 W 59th Street, New York, NY 10019 (United States)

2007-04-25

This study developed a headspace liquid-phase microextraction (LPME) method by using a single aqueous drop in combination with high performance liquid chromatography (HPLC)-UV detection for the determination of methamphetamine (MAP) and amphetamine (AP) in urine samples. The analytes, volatile and basic, were released from sample matrix into the headspace first, and then protonated and dissolved in an aqueous H{sub 3}PO{sub 4} drop hanging in the headspace by a HPLC syringe. After extraction, this drop was directly injected into HPLC. Parameters affecting extraction efficiency were investigated and optimized. This method showed good linearity in the investigated concentration range of 1.0-1500 {mu}g L{sup -1}, repeatability of the extraction (R.S.D. < 5%, n = 6), and low detection limits (0.3 {mu}g L{sup -1} for both analytes). Enrichment factors of about 400-fold and 220-fold were achieved for MAP and AP, respectively, at optimum conditions. The feasibility of the method was demonstrated by analyzing human urine samples.

Separation and determination of copper in bottled water samples by combination of dispersive liquid--liquid microextraction and microsample introduction flame atomic absorption spectrometry.

Science.gov (United States)

Citak, Demirhan; Tuzen, Mustafa

2013-01-01

A new and simple method for the determination of trace amounts of Cu(II) was developed by combination of dispersive liquid-liquid microextraction (DLLME) preconcentration and microsample introduction flame atomic absorption spectrometry. In this method, ethanol and chloroform were chosen as disperser and extraction solvents, respectively, and 1-nitroso-2-naphthol was used as the complexing agent. The factors affecting the extraction efficiency and determination of Cu(II), including extraction and disperser solvent nature and volume, concentration of the complexing agent, pH of the solution, extraction time, and matrix ions, were investigated. Under optimal conditions, the LOD for Cu(II) was 0.95 microg/L with a preconcentration factor of 70. The RSD was 1.9%. The accuracy of the developed DLLME method was verified by determination of Cu(II) in a certified reference material (NRCC-SLRS-4 river water). The relative error was -3.31%. The developed preconcentration procedure was successfully applied to the analysis of bottled drinking water samples.

Ionic Liquid-Bonded Fused Silica as a New Solid-Phase Microextraction Fiber for the Liquid Chromatographic Determination of Bisphenol A as an Endocrine Disruptor.

Science.gov (United States)

Mohammadnezhad, Nasim; Matin, Amir Abbas; Samadi, Naser; Shomali, Ashkan; Valizadeh, Hassan

2017-01-01

Linear ionic liquid bonded to fused silica and its application as a solid-phase microextraction fiber for the extraction of bisphenol A (BPA) from water samples were studied. After optimization of microextraction conditions (15 mL sample volume, extraction time of 40 min, extraction temperature of 30 ± 1°C, 300 μL acetonitrile as the desorption solvent, and desorption time of 7 min), the fiber was used to extract BPA from packed mineral water, followed by HPLC-UV on an XDB-C18 column (150 × 4.6 mm id, 3.5 μm particle) with a mobile phase of acetonitrile-water (45 + 55%, v/v) and flow rate of 1 mL . min-1). A low LOD (0.20 μg . L-1) and good linearity (0.9977) in the calibration graph indicated that the proposed method was suitable for the determination of BPA.

Determination of valproic acid in human plasma using dispersive liquid-liquid microextraction followed by gas chromatography-flame ionization detection

Science.gov (United States)

Fazeli-Bakhtiyari, Rana; Panahi-Azar, Vahid; Sorouraddin, Mohammad Hossein; Jouyban, Abolghasem

2015-01-01

Objective(s): Dispersive liquid-liquid microextraction coupled with gas chromatography (GC)-flame ionization detector was developed for the determination of valproic acid (VPA) in human plasma. Materials and Methods: Using a syringe, a mixture of suitable extraction solvent (40 µl chloroform) and disperser (1 ml acetone) was quickly added to 10 ml of diluted plasma sample containing VPA (pH, 1.0; concentration of NaCl, 4% (w/v)), resulting in a cloudy solution. After centrifugation (6000 rpm for 6 min), an aliquot (1 µl) of the sedimented organic phase was removed using a 1-µl GC microsyringe and injected into the GC system for analysis. One variable at a time optimization method was used to study various parameters affecting the extraction efficiency of target analyte. Then, the developed method was fully validated for its accuracy, precision, recovery, stability, and robustness. Results: Under the optimum extraction conditions, good linearity range was obtained for the calibration graph, with correlation coefficient higher than 0.998. Limit of detection and lower limit of quantitation were 3.2 and 6 μg/ml, respectively. The relative standard deviations of intra and inter-day analysis of examined compound were less than 11.5%. The relative recoveries were found in the range of 97 to 107.5%. Finally, the validated method was successfully applied to the analysis of VPA in patient sample. Conclusion: The presented method has acceptable levels of precision, accuracy and relative recovery and could be used for therapeutic drug monitoring of VPA in human plasma. PMID:26730332

Dual ultrasonic-assisted dispersive liquid-liquid microextraction coupled with microwave-assisted derivatization for simultaneous determination of 20(S)-protopanaxadiol and 20(S)-protopanaxatriol by ultra high performance liquid chromatography-tandem mass spectrometry.

Science.gov (United States)

Zhao, Xian-En; Lv, Tao; Zhu, Shuyun; Qu, Fei; Chen, Guang; He, Yongrui; Wei, Na; Li, Guoliang; Xia, Lian; Sun, Zhiwei; Zhang, Shijuan; You, Jinmao; Liu, Shu; Liu, Zhiqiang; Sun, Jing; Liu, Shuying

2016-03-11

This paper, for the first time, reported a speedy hyphenated technique of low toxic dual ultrasonic-assisted dispersive liquid-liquid microextraction (dual-UADLLME) coupled with microwave-assisted derivatization (MAD) for the simultaneous determination of 20(S)-protopanaxadiol (PPD) and 20(S)-protopanaxatriol (PPT). The developed method was based on ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) detection using multiple-reaction monitoring (MRM) mode. A mass spectrometry sensitizing reagent, 4'-carboxy-substituted rosamine (CSR) with high reaction activity and ionization efficiency was synthesized and firstly used as derivatization reagent. Parameters of dual-UADLLME, MAD and UHPLC-MS/MS conditions were all optimized in detail. Low toxic brominated solvents were used as extractant instead of traditional chlorinated solvents. Satisfactory linearity, recovery, repeatability, accuracy and precision, absence of matrix effect and extremely low limits of detection (LODs, 0.010 and 0.015ng/mL for PPD and PPT, respectively) were achieved. The main advantages were rapid, sensitive and environmentally friendly, and exhibited high selectivity, accuracy and good matrix effect results. The proposed method was successfully applied to pharmacokinetics of PPD and PPT in rat plasma. Copyright © 2016 Elsevier B.V. All rights reserved.

Magnetic silica nanomaterials for solid-phase extraction combined with dispersive liquid-liquid microextraction of ultra-trace quantities of plasticizers

International Nuclear Information System (INIS)

Yamini, Yadollah; Faraji, Mohammad; Adeli, Mahnaz

2015-01-01

We are presenting surface modified magnetic silica nanoparticles (m-Si-NPs) for use in solid-phase extraction combined with dispersive liquid-liquid microextraction (DLLME). The m-Si-NPs were surface-functionalized with octadecyl groups to give a material for the extraction of the plasticizers dibutyl phthalate, di(2-ethylhexyl) adipate and di(2-ethylhexyl) phthalate from water samples. The functionalized m-Si-NPs were characterized by scanning electron microscopy, FTIR spectroscopy, thermal gravimetric analysis, and vibrating sample magnetometry. The results showed that the m-Si-NPs were well functionalized with octadecyl groups. The effects of various experimental variables on the extraction efficiencies were investigated. The analytes were quantified by GC/FID. Under optimal conditions, the calibration plots are linear in the range from 0.01 to 100 μg∙L -1 , and very high enrichment factors (mean value ∼20,000) were obtained. As a result of the high enrichment factors, the detection limits are as low as 2–3 ng∙L -1 . The method was successfully employed to the extraction of the plasticizers from (spiked) water samples, and recoveries are in the order of 93.9 to 106.7 %. The method is low cost, fast, and very sensitive (author)

In-vial liquid-liquid microextraction-capillary electrophoresis method for the determination of phenolic acids in vegetable oils.

Science.gov (United States)

Abu Bakar, Nur Bahiyah; Makahleh, Ahmad; Saad, Bahruddin

2012-09-12

An in-vial liquid-liquid microextraction method was developed for the selective extraction of the phenolic acids (caffeic, gallic, cinnamic, ferulic, chlorogenic, syringic, vanillic, benzoic, p-hydroxybenzoic, 2,4-dihydroxybenzoic, o-coumaric, m-coumaric and p-coumaric) in vegetable oil samples. The optimised extraction conditions for 20 g sample were: volume of diluent (n-hexane), 2 mL; extractant, methanol: 5 mM sodium hydroxide (60:40; v/v); volume of extractant, 300 μL (twice); vortex, 1 min; centrifugation, 5 min. Recoveries for the studied phenolic acids were 80.1-119.5%. The simultaneous determination of the phenolic acid extracts was investigated by capillary electrophoresis (CE). Separations were carried out on a bare fused-silica capillary (50 μm i.d.× 40 cm length) involving 25 mM sodium tetraborate (pH 9.15) and 5% methanol as CE background electrolyte in the normal polarity mode, voltage of 30 kV, temperature of 25°C, injection time of 4s (50 mbar) and electropherograms were recorded at 200 nm. The phenolic acids were successfully separated in less than 10 min. The validated in-vial LLME-CE method was applied to the determination of phenolic acids in vegetable oil samples (extra virgin olive oil, virgin olive oil, pure olive oil, walnut oil and grapeseed oil). The developed method shows significant advantages over the current methods as lengthy evaporation step is not required. Copyright © 2012 Elsevier B.V. All rights reserved.

Magnetic matrix solid phase dispersion assisted dispersive liquid liquid microextraction of ultra trace polychlorinated biphenyls in water prior to GC-ECD determination

International Nuclear Information System (INIS)

Diao, Chunpeng; Li, Cong; Yang, Xiao; Sun, Ailing; Liu, Renmin

2016-01-01

Magnetic matrix solid phase dispersion (MMSPD) assisted dispersive liquid liquid microextraction (DLLME) was applied to extract ultra traces of polychlorinated biphenyls (PCBs) from water samples prior to gas chromatography with electron capture detection. PCBs in water were adsorbed by micro particles of magnetic bamboo charcoal and then transferred into the elution solvent. PCBs in the elution solvent of the MMSPD were further concentrated into trace volume extraction solvent of the DLLME procedure. Under optimized conditions, good linearity in the range of 0.2–100 ng L"−"1 was obtained with regression coefficients (r) higher than 0.9987. Based on a signal-noise ratio of 3, the limits of detection (LODs) range from 0.05–0.1 ng L"−"1. These LODs are much lower than those of MMSPD or DLLME alone. Relative standard deviations are between 4.9–8.2 %. The method was successfully applied to the determination of PCBs in lake and river water. Relative recoveries were 85.5–117.4 % for the spiked environmental water samples. (author)

Determination of chlorophenols in landfill leachate using headspace sampling with ionic liquid-coated solid-phase microextraction fibers combined with gas chromatography–mass spectrometry

International Nuclear Information System (INIS)

Ho, Tse-Tsung; Chen, Chung-Yu; Li Zuguang; Yang, Thomas Ching-Cherng; Lee, Maw-Rong

2012-01-01

Highlights: ► Ionic liquid (IL), ([C 4 MIM][PF 6 ]), was rapid synthesized by microwave radiation. ► Trace chlorophenols in landfill leachate were extract by SPME coated IL. ► The IL-coated SPME-GC/MS method is low-cost, solvent-free and sensitive. - Abstract: A new microextraction technique based on ionic liquid solid-phase microextraction (IL-SPME) was developed for determination of trace chlorophenols (CPs) in landfill leachate. The synthesized ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C 4 MIM][PF 6 ]), was coated onto the spent fiber of SPME for extraction of trace CPs. After extraction, the absorbed analytes were desorbed and quantified using gas chromatography–mass spectrometry (GC/MS). The term of the proposed method is as ionic liquid-coated of solid-phase microextraction combined with gas chromatography–mass spectrometry (IL-SPME-GC/MS). No carryover effect was found, and every laboratory-made ionic liquids-coated-fiber could be used for extraction at least eighty times without degradation of efficiency. The chlorophenols studied were 2,4-dichlorophenol (2,4-DP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP), and pentachlorophenol (PCP). The best results of chlorophenols analysis were obtained with landfill leachate at pH 2, headspace extraction for 4 min, and thermal desorption with the gas chromatograph injector at 240 °C for 4 min. Linearity was observed from 0.1 to 1000 μg L −1 with relative standard deviations (RSD) less than 7% and recoveries were over 87%. The limit of detection (LOD) for pentachlorophenol was 0.008 μg L −1 . The proposed method was tested by analyzing landfill leachate from a sewage farm. The concentrations of chlorophenols were detected to range from 1.1 to 1.4 μg L −1 . The results demonstrate that the IL-SPME-GC/MS method is highly effective in analyzing trace chlorophenols in landfill leachate.

Determination of chlorophenols in landfill leachate using headspace sampling with ionic liquid-coated solid-phase microextraction fibers combined with gas chromatography-mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Ho, Tse-Tsung; Chen, Chung-Yu [Department of Chemistry, National Chung Hsing University, Taichung 40227, Taiwan (China); Li Zuguang [Department of Chemistry, National Chung Hsing University, Taichung 40227, Taiwan (China); College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, Zhejiang (China); Yang, Thomas Ching-Cherng [Department of Chemistry, National Kaohsiung Normal University, Kaohsiung 82444, Taiwan (China); Lee, Maw-Rong, E-mail: mrlee@dragon.nchu.edu.tw [Department of Chemistry, National Chung Hsing University, Taichung 40227, Taiwan (China)

2012-01-27

Highlights: Black-Right-Pointing-Pointer Ionic liquid (IL), ([C{sub 4}MIM][PF{sub 6}]), was rapid synthesized by microwave radiation. Black-Right-Pointing-Pointer Trace chlorophenols in landfill leachate were extract by SPME coated IL. Black-Right-Pointing-Pointer The IL-coated SPME-GC/MS method is low-cost, solvent-free and sensitive. - Abstract: A new microextraction technique based on ionic liquid solid-phase microextraction (IL-SPME) was developed for determination of trace chlorophenols (CPs) in landfill leachate. The synthesized ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C{sub 4}MIM][PF{sub 6}]), was coated onto the spent fiber of SPME for extraction of trace CPs. After extraction, the absorbed analytes were desorbed and quantified using gas chromatography-mass spectrometry (GC/MS). The term of the proposed method is as ionic liquid-coated of solid-phase microextraction combined with gas chromatography-mass spectrometry (IL-SPME-GC/MS). No carryover effect was found, and every laboratory-made ionic liquids-coated-fiber could be used for extraction at least eighty times without degradation of efficiency. The chlorophenols studied were 2,4-dichlorophenol (2,4-DP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP), and pentachlorophenol (PCP). The best results of chlorophenols analysis were obtained with landfill leachate at pH 2, headspace extraction for 4 min, and thermal desorption with the gas chromatograph injector at 240 Degree-Sign C for 4 min. Linearity was observed from 0.1 to 1000 {mu}g L{sup -1} with relative standard deviations (RSD) less than 7% and recoveries were over 87%. The limit of detection (LOD) for pentachlorophenol was 0.008 {mu}g L{sup -1}. The proposed method was tested by analyzing landfill leachate from a sewage farm. The concentrations of chlorophenols were detected to range from 1.1 to 1.4 {mu}g L{sup -1}. The results demonstrate that the IL-SPME-GC/MS method is highly effective in

Bio-dispersive liquid liquid microextraction based on nano rhaminolipid aggregates combined with magnetic solid phase extraction using Fe3O4@PPy magnetic nanoparticles for the determination of methamphetamine in human urine.

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Haeri, Seyed Ammar; Abbasi, Shahryar; Sajjadifar, Sami

2017-09-15

In the present investigation, extraction and preconcentration of methamphetamine in human urine samples was carried out using a novel bio-dispersive liquid liquid microextraction (Bio-DLLME) technique coupled with magnetic solid phase extraction (MSPE). Bio-DLLME is a kind of microextraction technique based nano-materials which have potential capabilities in many application fields. Bio-DLLME is based on the use of a binary part system consisting of methanol and nano rhaminolipid biosurfactant. Use of this binary mixture is ecologically accepted due to their specificity, biocompatibility and biodegradable nature. The potential of nano rhaminolipid biosurfactant as a biological agent in the extraction of organic compounds has been investigated in recent years. They are able to partition at the oil/water interfaces and reduce the interfacial tension in order to increase solubility of hydrocarbons. The properties of the prepared Fe 3 O 4 @PPy magnetic nanoparticles were characterized using Fourier transform infrared spectroscopy and X-ray diffraction methods The influences of the experimental parameters on the quantitative recovery of analyte were investigated. Under optimized conditions, the enrichment factor was 310, the calibration graph was linear in the methamphetamine concentration range from 1 to 60μgL -1 , with a correlation coefficient of 0.9998. The relative standard deviations for six replicate measurements was 5.2%. Copyright © 2017 Elsevier B.V. All rights reserved.

Plasma-liquid system with rotational gliding discharge with liquid electrode

International Nuclear Information System (INIS)

Nedybaliuk, O.A.; Solomenko, O.V; Martysh, E.V.; Fedirchuk, I.I.

2014-01-01

Plasma-liquid system based on rotational gliding discharge with one liquid electrode was developed. Emission spectra of plasma of rotational gliding discharge with one liquid electrode were investigated. Discovered effective mechanism of controlling non-isothermal level of plasma in dynamic plasma-liquid systems. Major mechanism of expulsion of metal anode material from plasma-liquid systems with rotational discharges was shown.

Method for the determination of carboxylic acids in industrial effluents using dispersive liquid-liquid microextraction with injection port derivatization gas chromatography-mass spectrometry.

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Makoś, Patrycja; Fernandes, Andre; Boczkaj, Grzegorz

2017-09-29

The paper presents a new method for the determination of 15 carboxylic acids in samples of postoxidative effluents from the production of petroleum bitumens using ion-pair dispersive liquid-liquid microextraction and gas chromatography coupled to mass spectrometry with injection port derivatization. Several parameters related to the extraction and derivatization efficiency were optimized. Under optimized experimental conditions, the obtained limit of detection and quantification ranged from 0.0069 to 1.12μg/mL and 0.014 to 2.24μg/mL, respectively. The precision (RSD ranged 1.29-6.42%) and recovery (69.43-125.79%) were satisfactory. Nine carboxylic acids at concentrations ranging from 0.10μg/mL to 15.06μg/mL were determined in the raw wastewater and in samples of effluents treated by various oxidation methods. The studies revealed a substantial increase of concentration of benzoic acids, in samples of wastewater after treatment, which confirms the need of carboxylic acids monitoring during industrial effluent treatment processes. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of salt and pH-induced solidified floating organic droplets homogeneous liquid-liquid microextraction for extraction of ten pyrethroid insecticides in fresh fruits and fruit juices followed by gas chromatography-mass spectrometry.

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Torbati, Mohammadali; Farajzadeh, Mir Ali; Torbati, Mostafa; Nabil, Ali Akbar Alizadeh; Mohebbi, Ali; Afshar Mogaddam, Mohammad Reza

2018-01-01

A new microextraction method named salt and pH-induced homogeneous liquid-liquid microextraction has been developed in a home-made extraction device for the extraction and preconcentration of some pyrethroid insecticides from different fruit juice samples prior to gas chromatography-mass spectrometry. In the present work, an extraction device made from two parallel glass tubes with different lengths and diameters was used in the microextraction procedure. In this method, a homogeneous solution of a sample solution and an extraction solvent (pivalic acid) was broken by performing an acid-base reaction and the extraction solvent was produced in whole of the solution. The produced droplets of the extraction solvent went up through the solution and solidified using an ice-bath. They were collected without centrifugation step. Under the optimum conditions, limits of detection and quantification were obtained in the ranges of 0.006-0.038, and 0.023-0.134ngmL -1 , respectively. The enrichment factors and extraction recoveries of the selected analytes ranged from 365-460 to 73-92%, respectively. The relative standard deviations were lower than 9% for intra- (n = 6) and inter-day (n = 4) precisions at a concentration of 1ngmL -1 of each analyte. Finally, some fruit juice samples were effectively analyzed by the proposed method. Copyright © 2017 Elsevier B.V. All rights reserved.

Multi-residue method for determination of 58 pesticides, pharmaceuticals and personal care products in water using solvent demulsification dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry.

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Caldas, Sergiane Souza; Rombaldi, Caroline; Arias, Jean Lucas de Oliveira; Marube, Liziane Cardoso; Primel, Ednei Gilberto

2016-01-01

A rapid and efficient sample pretreatment using solvent-based de-emulsification dispersive liquid-liquid microextraction (SD-DLLME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was studied for the extraction of 58 pharmaceuticals and personal care products (PPCPs) and pesticides from water samples. Type and volume of extraction and disperser solvents, pH, salt addition, amount of salt and type of demulsification solvent were evaluated. Limits of quantification (LOQ) in the range from 0.0125 to 1.25 µg L(-1) were reached, and linearity was in the range from the LOQ of each compound to 25 μg L(-1). Recoveries ranged from 60% to 120% for 84% of the compounds, with relative standard deviations lower than 29%. The proposed method demonstrated, for the first time, that sample preparation by SD-DLLME with determination by LC-MS/MS can be successfully used for the simultaneous extraction of 32 pesticides and 26 PPCPs from water samples. The entire procedure, including the extraction of 58 organic compounds from the aqueous sample solution and the breaking up of the emulsion after extraction with water, rather than with an organic solvent, was environmentally friendly. In addition, this technique was less expensive and faster than traditional techniques. Finally, the analytical method under study was successfully applied to the analysis of all 58 pesticides and PPCPs in surface water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Poly(ionic liquids)-coated stainless-steel wires packed into a polyether ether ketone tube for in-tube solid-phase microextraction.

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Feng, Juanjuan; Wang, Xiuqin; Tian, Yu; Luo, Chuannan; Sun, Min

2017-12-01

An in-tube solid-phase microextraction device was developed by packing poly(ionic liquids)-coated stainless-steel wires into a polyether ether ketone tube. An anion-exchange process was performed to enhance the extraction performance. Surface properties of poly(ionic liquids)-coated stainless-steel wires were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. The extraction device was connected to high-performance liquid chromatography equipment to build an online enrichment and analysis system. Ten polycyclic aromatic hydrocarbons were used as model analytes, and important conditions including extraction time and desorption time were optimized. The enrichment factors from 268 to 2497, linear range of 0.03-20 μg/L, detection limits of 0.010-0.020 μg/L, extraction and preparation repeatability with relative standard deviation less than 1.8 and 19%, respectively were given by the established online analysis method. It has been used to detect polycyclic aromatic hydrocarbons in environmental samples, with the relative recovery (5, 10 μg/L) in the range of 85.1-118.9%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dispersive liquid-liquid microextraction and gas chromatography accurate mass spectrometry for extraction and non-targeted profiling of volatile and semi-volatile compounds in grape marc distillates.

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Fontana, Ariel; Rodríguez, Isaac; Cela, Rafael

2018-04-20

The suitability of dispersive liquid-liquid microextraction (DLLME) and gas chromatography accurate mass spectrometry (GC-MS), based on a time-of-flight (TOF) MS analyzer and using electron ionization (EI), for the characterization of volatile and semi-volatile profiles of grape marc distillates (grappa) are evaluated. DLLME conditions are optimized with a selection of compounds, from different chemical families, present in the distillate spirit. Under final working conditions, 2.5 mL of sample and 0.5 mL of organic solvents are consumed in the sample preparation process. The absolute extraction efficiencies ranged from 30 to 100%, depending on the compound. For the same sample volume, DLLME provided higher responses than solid-phase microextraction (SPME) for most of the model compounds. The GC-EI-TOF-MS records of grappa samples were processed using a data mining non-targeted search algorithm. In this way, chromatographic peaks and accurate EI-MS spectra of sample components were linked. The identities of more than 140 of these components are proposed from comparison of their accurate spectra with those in a low resolution EI-MS database, accurate masses of most intense fragment ions of known structure, and available chromatographic retention index. The use of chromatographic and spectral data, associated to the set of components mined from different grappa samples, for multivariate analysis purposes is also illustrated in the study. Copyright © 2018 Elsevier B.V. All rights reserved.

Analysis of amino acid and monoamine neurotransmitters and their metabolites in rat urine of Alzheimer's disease using in situ ultrasound-assisted derivatization dispersive liquid-liquid microextraction with UHPLC-MS/MS.

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Zhao, Xian-En; He, Yongrui; Li, Meng; Chen, Guang; Wei, Na; Wang, Xiao; Sun, Jing; Zhu, Shuyun; You, Jinmao

2017-02-20

Neurotransmitters (NTs) may play an important role in neurodegenerative disorders such as Alzheimer's disease (AD). In order to investigate the potential links, a new simple, fast, accurate and sensitive analytical method, based on in situ ultrasound-assisted derivatization dispersive liquid-liquid microextraction (in situ UA-DDLLME) coupled with ultra high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS), has been developed and validated. The quantitation of amino acid neurotransmitters (AANTs) and monoamine neurotransmitters (MANTs) in urine of AD rats were performed in this work. The in situ UA-DDLLME procedure involved the rapid injection of the mixture of low toxic 4-bromoanisole (extractant) and acetonitrile (dispersant), which containing the new designed and synthesized 4'-carbonyl chloride rosamine (CCR) as derivatization reagent, into the aqueous phase of real sample and buffer. Under the selected conditions, the derivatization and microextraction of analytes were simultaneously completed within 1min. Good linearity for each analyte (R>0.992) was observed with low limit of detections (LODs, S/N>3). Moreover, the proposed method was compared with direct detection or other reported methods, and the results showed that low matrix effects and good recoveries results were obtained in this work. Taken together, in situ UA-DDLLME coupled with UHPLC-MS/MS analysis was demonstrated to be a good method for sensitive, accurate and simultaneous monitoring of AANTs and MANTs. This method would be expected to be highly useful in AD diseases' clinical diagnostics and may have potential value in monitoring the efficacy of treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Centrifuge-less dispersive liquid-liquid microextraction base on the solidification of switchable solvent for rapid on-site extraction of four pyrethroid insecticides in water samples.

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Hu, Lu; Wang, Huazi; Qian, Heng; Liu, Chaoran; Lu, Runhua; Zhang, Sanbing; Zhou, Wenfeng; Gao, Haixiang; Xu, Donghui

2016-11-11

An on-site dispersive liquid liquid microextraction base on the solidification of switchable solvent has been developed as a simple, rapid and eco-friendly sample extraction method for the fast determination of pyrethroid insecticides in aqueous samples using high-performance liquid chromatography with ultraviolet detection. In this extraction method, medium-chain saturated fatty acids (n≥10), which can rapidly solidify at low temperatures (centrifugation. The microextraction process was performed in a 10mL syringe and the pretreatment process could thus be finished in 5min. No external energy resources were required in this method, which makes it a potential method for on-site extraction. The optimal experimental parameters were as follows: 350μL of decanoic acid (1mol/L) was used as the extraction solvent, 150μL of sulfuric acid (2mol/L) was used to decrease the pH of the samples, no salt was added, and the temperature of the samples was in the range of 20-40°C. Finally, the sample was cooled in an ice bath for three minutes. Under these optimal conditions, good responses for four pyrethroid insecticides were obtained in the concentration ranges of 1-500μg/L, with coefficients of determination greater than 0.9993. The recoveries of the four pyrethroid insecticides ranged from 84.7 to 95.3%, with relative standard deviations ranging from 1.6 to 4.6%. The limits of detection based on a signal-to-noise ratio of 3 were in the range of 0.24-0.68μg/L, and the enrichment factors were in the range of 121-136. The results demonstrate that this method was successfully applied to determine pyrethroid insecticides in real water samples. No centrifugation or any special apparatus are required, make this a promising method for rapid field-sampling procedures. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of push/pull perfusion and ultrasonication on the extraction efficiencies of phthalate esters in sports drink samples using on-line hollow-fiber liquid-phase microextraction.

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Chao, Yu-Ying; Lee, Chien-Hung; Chien, Tzu-Yang; Shih, Yu-Hsuan; Lu, Yin-An; Kuo, Ting-Hsuan; Huang, Yeou-Lih

2013-08-28

In previous studies, we developed a process, on-line ultrasound-assisted push/pull perfusion hollow-fiber liquid-phase microextraction (UA-PPP-HF-LPME), combining the techniques of push/pull perfusion (PPP) and ultrasonication with hollow-fiber liquid-phase microextraction (HF-LPME), to achieve rapid extraction of acidic phenols from water samples. In this present study, we further evaluated three more-advanced and novel effects of PPP and ultrasonication on the extraction efficiencies of neutral high-molecular-weight phthalate esters (HPAEs) in sports drinks. First, we found that inner-fiber fluid leakage occurs only in push-only perfusion-based and pull-only perfusion-based HF-LPME, but not in the PPP mode. Second, we identified a significant negative interaction between ultrasonication and temperature. Third, we found that the extraction time of the newly proposed system could be shortened by more than 93%. From an investigation of the factors affecting UA-PPP-HF-LPME, we established optimal extraction conditions and achieved acceptable on-line enrichment factors of 92-146 for HPAEs with a sampling time of just 2 min.

Determination of trace bisphenol A in environmental water by high-performance liquid chromatography using magnetic reduced graphene oxide based solid-phase extraction coupled with dispersive liquid-liquid microextraction.

Science.gov (United States)

Li, Danping; Ma, Xiaoguo; Wang, Rui; Yu, Yumian

2017-02-01

Bisphenol A (BPA), an endocrine-disrupting chemical, has received much attention from researchers and the general public. In this paper, a novel method of determining BPA at trace levels was developed, using magnetic reduced graphene oxide (rGO-Fe 3 O 4 )-based solid-phase extraction coupled with dispersive liquid-liquid microextraction (DLLME), followed by high-performance liquid chromatographic determination. The rGO-Fe 3 O 4 was prepared and then characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, and vibrating sample magnetometry. The greatest saturation magnetization of rGO-Fe 3 O 4 was up to 43.8 emu g -1 , which allowed rapid isolation of the rGO-Fe 3 O 4 from solutions upon applying an appropriate magnetic field. The effects of solution pH, adsorbent amount, type and volume of eluent and extraction solvent, extraction time, and salt concentration on the extraction efficiency of BPA were examined and optimized. Under the optimum conditions, an enrichment factor of 5217 and an LOD of 0.01 μg L -1 for BPA were obtained. The reusability of rGO-Fe 3 O 4 for at least 12 repeated cycles without any significant decrease in the extraction recovery of BPA was demonstrated. The proposed method was applied to the determination of BPA in different real water samples, with relative recoveries of 84.8-104.9 % and RSDs of 0.8-8.3 % in the spiked concentration range 1-10 μg L -1 .

A novel task specific magnetic polymeric ionic liquid for selective preconcentration of potassium in oil samples using centrifuge-less dispersive liquid-liquid microextraction technique and its determination by flame atomic emission spectroscopy.

Science.gov (United States)

Beiraghi, Asadollah; Shokri, Masood

2018-02-01

In the present study a new centrifuge-less dispersive liquid-liquid microextraction technique based on application of a new task specific magnetic polymeric ionic liquid (TSMPIL) as a chelating and extraction solvent for selective preconcentration of trace amounts of potassium from oil samples is developed, for the first time. After extraction, the fine droplets of TSMPIL were transferred into an eppendorf tube and diluted to 500µL using distilled water. Then, the enriched analyte was determined by flame atomic emission spectroscopy (FAES). Several important factors affecting both the complexation and extraction efficiency including extraction time, rate of vortex agitator, amount of carbonyl iron powder, pH of sample solution, volume of ionic liquid as well as effects of interfering species were investigated and optimized. Under the optimal conditions, the limits of detection (LOD) and quantification (LOQ) were 0.5 and 1.6µgL -1 respectively with the preconcentration factor of 128. The precision (RSD %) for seven replicate determinations at 10µgL -1 of potassium was better than 3.9%. The relative recoveries for the spiked samples were in the acceptable range of 95-104%. The results demonstrated that no remarkable interferences are created by other various ions in the determination of potassium, so that the tolerance limits (W Ion /W K ) of major cations and anions were in the range of 2500-10,000. The purposed method was successfully applied for the analysis of potassium in some oil samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Liquid-Liquid Extraction in Systems Containing Butanol and Ionic Liquids – A Review

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Kubiczek Artur

2017-03-01

Full Text Available Room-temperature ionic liquids (RTILs are a moderately new class of liquid substances that are characterized by a great variety of possible anion-cation combinations giving each of them different properties. For this reason, they have been termed as designer solvents and, as such, they are particularly promising for liquid-liquid extraction, which has been quite intensely studied over the last decade. This paper concentrates on the recent liquid-liquid extraction studies involving ionic liquids, yet focusing strictly on the separation of n-butanol from model aqueous solutions. Such research is undertaken mainly with the intention of facilitating biological butanol production, which is usually carried out through the ABE fermentation process. So far, various sorts of RTILs have been tested for this purpose while mostly ternary liquid-liquid systems have been investigated. The industrial design of liquid-liquid extraction requires prior knowledge of the state of thermodynamic equilibrium and its relation to the process parameters. Such knowledge can be obtained by performing a series of extraction experiments and employing a certain mathematical model to approximate the equilibrium. There are at least a few models available but this paper concentrates primarily on the NRTL equation, which has proven to be one of the most accurate tools for correlating experimental equilibrium data. Thus, all the presented studies have been selected based on the accepted modeling method. The reader is also shown how the NRTL equation can be used to model liquid-liquid systems containing more than three components as it has been the authors’ recent area of expertise.

Simultaneous extraction and determination of albendazole and triclabendazole by a novel syringe to syringe dispersive liquid phase microextraction-solidified floating organic drop combined with high performance liquid chromatography.

Science.gov (United States)

Asadi, Mohammad; Dadfarnia, Shayessteh; Haji Shabani, Ali Mohammad

2016-08-17

A syringe to syringe dispersive liquid phase microextraction-solidified floating organic drop was introduced and used for the simultaneous extraction of trace amounts of albendazole and triclabendazole from different matrices. The extracted analytes were determined by high performance liquid chromatography along with fluorescence detection. The analytical parameters affecting the microextraction efficiency including the nature and volume of the extraction solvent, sample volume, sample pH, ionic strength and the cycles of extraction were optimized. The calibration curves were linear in the range of 0.1-30.0 μg L(-1) and 0.2-30.0 μg L(-1) with determination coefficients of 0.9999 and 0.9998 for albendazole and triclabendazole respectively. The detection limits defined as three folds of the signal to noise ratio were found to be 0.02 μg L(-1) for albendazole and 0.06 μg L(-1) for triclabendazole. The inter-day and intra-day precision (RSD%) for both analytes at three concentration levels (0.5, 2.0 and 10.0 μg L(-1)) were in the range of 6.3-10.1% and 5.0-7.5% respectively. The developed method was successfully applied to determine albendazole and triclabendazole in water, cow milk, honey, and urine samples. Copyright © 2016. Published by Elsevier B.V.

ANALYSIS OF BASIC PSYCHOTROPIC DRUGS IN BIOLOGICAL FLUIDS AND TISSUES BY REVERSED-PHASE HIGH PERFORMANCE LIQUID CHROMATOGRAPHY.

Science.gov (United States)

Petruczynik, Anna; Waksmundzka-Hajnos, Monika

2017-03-01

The review of the RP HPLC analysis of basic psychotropic drugs is presented. It contains sample preparation methods with centrifugation, protein precipitation, liquid-liquid extraction (LLE), dispersive liquid-liquid microextraction (DLLME), solid-phase extraction (SPE), solid-phase microextraction (SPME), microwave-assisted extraction (MAE) and RP-HPLC analysis. Chromatographic behavior of basic drugs in aqueous media - eluents used in reversed phase systems is discussed. Methods of blocking of residue surface silanols' interaction are mentioned. Analytical methods used for the analysis are divided into parts according with the above methods: the use of low-pH eluents, the use of high-pH eluents, the use of silanol blockers, special stationary phases for basic analytes. Literature connected with the sample preparation methods and analytical systems for the drug analysis are cited in details and presented also in Table 1.

Liquid-phase microextraction and fibre-optics-based cuvetteless CCD-array micro-spectrophotometry for trace analysis

International Nuclear Information System (INIS)

Sharma, Nisha; Pillai, Aradhana K.K.V.; Pathak, Neeraj; Jain, Archana; Verma, Krishna K.

2009-01-01

Liquid-phase microextraction (LPME) has been investigated for trace analysis in the present work in conjunction with fibre-optic-based micro-spectrophotometry which accommodates sample volume of 1 μL placed between the two ends of optical fibres. Methods have been evolved for the determination of (i) 1-100 μM and 0.5-20 μM of thiols by single drop microextraction (SDME) and LPME in 25 μL of the organic solvent, respectively, involving their reaction with the Ellman reagent and ion pair microextraction of thiolate ion formed; (ii) 70 μg to 7 mg L -1 of chlorine/chlorine dioxide by headspace in-drop reaction with alternative reagents, viz., mixed phenylhydrazine-4-sulphonic acid and N-(1-naphthyl)ethylenediamine dihydrochloride, o-dianisidine, o-tolidine, and N,N-diethyl-p-phenylenediamine; (iii) 0.2-4 mg L -1 of ammonia by reaction with 2,4-dinitro-1-fluorobenzene to give 2,4-dinitroaniline which was diazotized and coupled with 1-naphthylamine, the resulting dye was subjected to preconcentration by solid-phase extraction and LPME; and (iv) 25-750 μg L -1 of iodide/total iodine by oxidation of iodide by 2-iodosobenzoate, microextraction of iodine in organic solvent, and re-extraction into aqueous starch-iodide reagent drop held in the organic phase. LPME using 25-30 μL of organic solvent was found to produce more sensitive results than SDME. The cuvetteless spectrophotometry as used in combination with sample handling techniques produced limits of detection of analytes which were better than obtained by previously reported spectrophotometry.

Solid-phase extraction followed by dispersive liquid-liquid microextraction for the sensitive determination of ecstasy compounds and amphetamines in biological samples

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H. A. Mashayekhi

2014-09-01

Full Text Available A novel approach for the determination of ecstasy and amphetamines (3,4-methylenedioxymethylamphetamine (MDMA, Ecstasy, 3,4-methylenedioxyamphetamine (MDA, 3,4-methylenedioxyethylamphetamine (MDEA and 3,4-methylenedioxypropylamphetamine (MDPA in biological samples is presented. The analytes were extracted from the matrix and transferred to a small volume of a high density, water insoluble solvent using solid-phase extraction (SPE followed by dispersive liquid-liquid microextraction (DLLME. This combination not only resulted in a high enrichment factor, but also it could be used in complex matrices (biological samples. Some important extraction parameters, such as sample solution flow rate, sample pH, type and volume of extraction and disperser solvents as well as the salt addition, were studied and optimized. Under the optimized conditions, the calibration graphs were linear in the range of 0.5-500 µg L-1 and 1.0-500 µg L-1 with detection limits in the range of 0.1-0.3 µg L-1 and 0.2-0.7 µg L-1 in urine and plasma samples, respectively. The results showed that SPE-DLLME is a suitable method for the determination of ecstasy components and amphetamines in biological and water samples. DOI: http://dx.doi.org/10.4314/bcse.v28i3.3

RAPID AND SENSITIVE DETERMINATION OF PALLADIUM USING HOMOGENEOUS LIQUID-LIQUID MICROEXTRACTION VIA FLOTATION ASSISTANCE FOLLOWED BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY

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Mohammad Rezaee

2015-05-01

Full Text Available A method for the determination of trace amounts of palladium was developed using homogeneous liquid-liquid microextraction via flotation assistance (HLLME-FA followed by graphite furnace atomic absorption spectrometry (GFAAS. Ammonium pyrrolidine dithiocarbamate (APDC was used as a complexing agent. This was applied to determine palladium in three types of water samples. In this study, a special extraction cell was designed to facilitate collection of the low-density solvent extraction. No centrifugation was required in this procedure. The water sample solution was added to the extraction cell which contained an appropriate mixture of extraction and homogeneous solvents. By using air flotation, the organic solvent was collected at the conical part of the designed cell. Parameters affecting extraction efficiency were investigated and optimized. Under the optimum conditions, the calibration graph was linear in the range of 1.0-200 µg L-1 with a limit of detection of 0.3 µg L-1. The performance of the method was evaluated for the extraction and determination of palladium in water samples and satisfactory results were obtained. In order to verify the accuracy of the approach, the standard addition method was applied for the determination of palladium in spiked synthetic samples and satisfactory results were obtained.

A fully automated effervescence assisted dispersive liquid–liquid microextraction based on a stepwise injection system. Determination of antipyrine in saliva samples

Energy Technology Data Exchange (ETDEWEB)

Medinskaia, Kseniia; Vakh, Christina; Aseeva, Darina [Department of Analytical Chemistry, Institute of Chemistry, Saint Petersburg State University, RU-198504 Saint Petersburg (Russian Federation); Andruch, Vasil, E-mail: vasil.andruch@upjs.sk [Department of Analytical Chemistry, University of P.J. Šafárik, SK-04154 Košice (Slovakia); Moskvin, Leonid [Department of Analytical Chemistry, Institute of Chemistry, Saint Petersburg State University, RU-198504 Saint Petersburg (Russian Federation); Bulatov, Andrey, E-mail: bulatov_andrey@mail.ru [Department of Analytical Chemistry, Institute of Chemistry, Saint Petersburg State University, RU-198504 Saint Petersburg (Russian Federation)

2016-01-01

A first attempt to automate the effervescence assisted dispersive liquid–liquid microextraction (EA-DLLME) has been reported. The method is based on the aspiration of a sample and all required aqueous reagents into the stepwise injection analysis (SWIA) manifold, followed by simultaneous counterflow injection of the extraction solvent (dichloromethane), the mixture of the effervescence agent (0.5 mol L{sup −1} Na{sub 2}CO{sub 3}) and the proton donor solution (1 mol L{sup −1} CH{sub 3}COOH). Formation of carbon dioxide microbubbles generated in situ leads to the dispersion of the extraction solvent in the whole aqueous sample and extraction of the analyte into organic phase. Unlike the conventional DLLME, in the case of EA-DLLME, the addition of dispersive solvent, as well as, time consuming centrifugation step for disruption of the cloudy state is avoided. The phase separation was achieved by gentle bubbling of nitrogen stream (2 mL min{sup −1} during 2 min). The performance of the suggested approach is demonstrated by determination of antipyrine in saliva samples. The procedure is based on the derivatization of antipyrine by nitrite-ion followed by EA-DLLME of 4-nitrosoantipyrine and subsequent UV–Vis detection using SWIA manifold. The absorbance of the yellow-colored extract at the wavelength of 345 nm obeys Beer's law in the range of 1.5–100 µmol L{sup −1} of antipyrine in saliva. The LOD, calculated from a blank test based on 3σ, was 0.5 µmol L{sup −1}. - Highlights: • First attempt to automate the effervescence assisted dispersive liquid–liquid microextraction. • Automation based on Stepwise injection analysis manifold in flow batch system. • Counterflow injection of extraction solvent and the effervescence agent. • Phase separation performed by gentle bubbling of nitrogen. • Application for the determination of antipyrine in saliva samples.

A fully automated effervescence assisted dispersive liquid–liquid microextraction based on a stepwise injection system. Determination of antipyrine in saliva samples

International Nuclear Information System (INIS)

Medinskaia, Kseniia; Vakh, Christina; Aseeva, Darina; Andruch, Vasil; Moskvin, Leonid; Bulatov, Andrey

2016-01-01

A first attempt to automate the effervescence assisted dispersive liquid–liquid microextraction (EA-DLLME) has been reported. The method is based on the aspiration of a sample and all required aqueous reagents into the stepwise injection analysis (SWIA) manifold, followed by simultaneous counterflow injection of the extraction solvent (dichloromethane), the mixture of the effervescence agent (0.5 mol L"−"1 Na_2CO_3) and the proton donor solution (1 mol L"−"1 CH_3COOH). Formation of carbon dioxide microbubbles generated in situ leads to the dispersion of the extraction solvent in the whole aqueous sample and extraction of the analyte into organic phase. Unlike the conventional DLLME, in the case of EA-DLLME, the addition of dispersive solvent, as well as, time consuming centrifugation step for disruption of the cloudy state is avoided. The phase separation was achieved by gentle bubbling of nitrogen stream (2 mL min"−"1 during 2 min). The performance of the suggested approach is demonstrated by determination of antipyrine in saliva samples. The procedure is based on the derivatization of antipyrine by nitrite-ion followed by EA-DLLME of 4-nitrosoantipyrine and subsequent UV–Vis detection using SWIA manifold. The absorbance of the yellow-colored extract at the wavelength of 345 nm obeys Beer's law in the range of 1.5–100 µmol L"−"1 of antipyrine in saliva. The LOD, calculated from a blank test based on 3σ, was 0.5 µmol L"−"1. - Highlights: • First attempt to automate the effervescence assisted dispersive liquid–liquid microextraction. • Automation based on Stepwise injection analysis manifold in flow batch system. • Counterflow injection of extraction solvent and the effervescence agent. • Phase separation performed by gentle bubbling of nitrogen. • Application for the determination of antipyrine in saliva samples.

Comparison of two microextraction methods based on solidification of floating organic droplet for the determination of multiclass analytes in river water samples by liquid chromatography tandem mass spectrometry using Central Composite Design.

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Asati, Ankita; Satyanarayana, G N V; Patel, Devendra K

2017-09-01

Two low density organic solvents based liquid-liquid microextraction methods, namely Vortex assisted liquid-liquid microextraction based on solidification of floating organic droplet (VALLME-SFO) and Dispersive liquid-liquid microextraction based on solidification of floating organic droplet(DLLME-SFO) have been compared for the determination of multiclass analytes (pesticides, plasticizers, pharmaceuticals and personal care products) in river water samples by using liquid chromatography tandem mass spectrometry (LC-MS/MS). The effect of various experimental parameters on the efficiency of the two methods and their optimum values were studied with the aid of Central Composite Design (CCD) and Response Surface Methodology(RSM). Under optimal conditions, VALLME-SFO was validated in terms of limit of detection, limit of quantification, dynamic linearity range, determination of coefficient, enrichment factor and extraction recovery for which the respective values were (0.011-0.219ngmL -1 ), (0.035-0.723ngmL -1 ), (0.050-0.500ngmL -1 ), (R 2 =0.992-0.999), (40-56), (80-106%). However, when the DLLME-SFO method was validated under optimal conditions, the range of values of limit of detection, limit of quantification, dynamic linearity range, determination of coefficient, enrichment factor and extraction recovery were (0.025-0.377ngmL -1 ), (0.083-1.256ngmL -1 ), (0.100-1.000ngmL -1 ), (R 2 =0.990-0.999), (35-49), (69-98%) respectively. Interday and intraday precisions were calculated as percent relative standard deviation (%RSD) and the values were ≤15% for VALLME-SFO and DLLME-SFO methods. Both methods were successfully applied for determining multiclass analytes in river water samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Development and Validation of a Sensitive Method for Trace Nickel Determination by Slotted Quartz Tube Flame Atomic Absorption Spectrometry After Dispersive Liquid-Liquid Microextraction.

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Yolcu, Şükran Melda; Fırat, Merve; Chormey, Dotse Selali; Büyükpınar, Çağdaş; Turak, Fatma; Bakırdere, Sezgin

2018-05-01

In this study, dispersive liquid-liquid microextraction was systematically optimized for the preconcentration of nickel after forming a complex with diphenylcarbazone. The measurement output of the flame atomic absorption spectrometer was further enhanced by fitting a custom-cut slotted quartz tube to the flame burner head. The extraction method increased the amount of nickel reaching the flame and the slotted quartz tube increased the residence time of nickel atoms in the flame to record higher absorbance. Two methods combined to give about 90 fold enhancement in sensitivity over the conventional flame atomic absorption spectrometry. The optimized method was applicable over a wide linear concentration range, and it gave a detection limit of 2.1 µg L -1 . Low relative standard deviations at the lowest concentration in the linear calibration plot indicated high precision for both extraction process and instrumental measurements. A coal fly ash standard reference material (SRM 1633c) was used to determine the accuracy of the method, and experimented results were compatible with the certified value. Spiked recovery tests were also used to validate the applicability of the method.

Trace analysis of three antihistamines in human urine by on-line single drop liquid-liquid-liquid microextraction coupled to sweeping micellar electrokinetic chromatography and its application to pharmacokinetic study.

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Gao, Wenhua; Chen, Yunsheng; Chen, Gaopan; Xi, Jing; Chen, Yaowen; Yang, Jianying; Xu, Ning

2012-09-01

A rapid and efficient dual preconcentration method of on-line single drop liquid-liquid-liquid microextraction (SD-LLLME) coupled to sweeping micellar electrokinetic chromatography (MEKC) was developed for trace analysis of three antihistamines (mizolastine, chlorpheniramine and pheniramine) in human urine. Three analytes were firstly extracted from donor phase (4 mL urine sample) adjusted to alkaline condition (0.5 M NaOH). The unionized analytes were subsequently extracted into a drop of n-octanol layered over the urine sample, and then into a microdrop of acceptor phase (100 mM H(3)PO(4)) suspended from a capillary inlet. The enriched acceptor phase was on-line injected into capillary with a height difference and then analyzed directly by sweeping MEKC. Good linear relationships were obtained for all analytes in a range of 6.25 × 10(-6) to 2.5 × 10(-4)g/L with correlation coefficients (r) higher than 0.987. The proposed method achieved limits of detections (LOD) varied from 1.2 × 10(-7) to 9.5 × 10(-7)g/L based on a signal-to-noise of 3 (S/N=3) with 751- to 1372-fold increases in detection sensitivity for analytes, and it was successfully applied to the pharmacokinetic study of three antihistamines in human urine after an oral administration. The results demonstrated that this method was a promising combination for the rapid trace analysis of antihistamines in human urine with the advantages of operation simplicity, high enrichment factor and little solvent consumption. Copyright © 2012 Elsevier B.V. All rights reserved.

Determination of phthalic acid esters in Chinese white spirit using dispersive liquid-liquid microextraction coupled with sweeping β-cyclodextrin-modified micellar electrokinetic chromatography.

Science.gov (United States)

Sun, Jianzhi; He, Hui; Liu, Shuhui

2014-07-01

A simple method that consumes low organic solvent is proposed for the analysis of phthalic acid esters in Chinese white spirit using dispersive liquid-liquid microextraction coupled with sweeping-micellar electrokinetic chromatography. Tetrachloromethane and white-spirit-containing ethanol were used as the extraction and dispersing solvents, respectively. The electrophoresis separation buffer was composed of 5 mM β-cyclodextrin, 50 mM sodium dodecyl sulfate and 25 mM borate buffer (pH 9.2) with 9% acetonitrile, enabling the baseline resolution of the analytes within 13 min. Under the optimum conditions, satisfactory linearities (5-1000 ng/mL, r ≥ 0.9909), good reproducibility (RSD ≤ 6.7% for peak area, and RSD ≤ 2.8% for migration time), low detection limits (0.4-0.8 ng/mL) and acceptable recovery rates (89.6-105.7%) were obtained. The proposed method was successfully applied to 22 Chinese white spirits, and the content of dibutyl phthalate in 55% of the samples exceeded the Specific Migration Limit of 0.3 mg/kg established by the domestic and international regulations. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microextração em fase líquida (LPME: fundamentos da técnica e aplicações na análise de fármacos em fluidos biológicos Liquid-phase microextraction (LPME: fundamentals and applications to the analysis of drugs in biological samples

Directory of Open Access Journals (Sweden)

Anderson Rodrigo Moraes de Oliveira

2008-01-01

Full Text Available The analysis of drugs and metabolites in biological fluids usually requires extraction procedures to achieve sample clean-up and analyte preconcentration. Commonly, extraction procedures are performed using liquid-liquid extraction or solid-phase extraction. Nevertheless, these extraction techniques are considered to be time-consuming and require a large amount of organic solvents. On this basis, microextraction techniques have been developed. Among them, liquid-phase microextraction has been standing out. This review describes the liquid-phase microextraction technique based on hollow fibers as a novel and promising alternative in sample preparation prior to chromatographic or electrophoretic analysis. The basic concepts related to this technique and its applicability in extraction of drugs are discussed.

Ultrasound assisted dispersive liquid-liquid microextraction coupled with high performance liquid chromatography designated for bioavailability studies of felodipine combinations in rat plasma.

Science.gov (United States)

Ahmed, Sameh; Atia, Noha N; Bakr Ali, Marwa Fathy

2017-03-01

Felodipine (FLD), a calcium channel antagonist, is commonly prescribed for the treatment of hypertension either with Metoprolol (MET) or Ramipril (RAM) in two different drug combinations. FLD has high plasma protein binding ability affecting its extraction recoveries from plasma samples. Hence, a specific ultrasound assisted dispersive liquid-liquid microextraction (UA-DLLME) method coupled with HPLC using photodiode array detector was developed and validated for the simultaneous determination of FLD, MET and RAM in rat plasma after oral administration of these combinations. The factors affecting UA-DLLME were carefully optimized. In this study, UA-DLLME method could provide simple and efficient plasma extraction procedures with superior recovery results. Under optimum condition, all target drugs were separated within 13min. The validation procedures was carried out in agreement with US-FDA guidelines and shown to be suitable for anticipated purposes. Linear calibration ranges were obtained in the range 0.05-2.0μgmL -1 for FLD and MET and 0.1-2.0μgmL -1 for RAM with detection limits of 0.013-0.031μgmL -1 for all the studied drug combinations. The%RSD for inter-day and intra-day precisions was in range of 0.63-3.85% and the accuracy results were in the range of 92.13-100.5%. The validated UA-DLLME-HPLC method was successfully applied for the bioavailability studies of FLD, MET and RAM. The pharmacokinetic parameters were calculated for all the investigated drugs in rats after single-dose administrations of two different drug combinations. Although FLD was bioequivalent in the two formulations, a small increase in plasma levels of MET and RAM was found in the presence of FLD. Copyright © 2017 Elsevier B.V. All rights reserved.

A novel separation/preconcentration technique based on ultrasonic dispersion liquid-liquid microextraction for determination of trace cobalt by flame atomic absorption spectrometry

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Jingci Li

2012-12-01

Full Text Available An improved method for the determination of trace cobalt in water samples has been developed using ultrasonic dispersion liquid-liquid microextraction (US-DLLME prior to flame atomic absorption spectrometry (FAAS analysis. In this method, cobalt was extracted into the fine droplets of carbon tetrachloride after chelate formation with the water soluble ligand, ammonium pyrrolidine dithiocarbamate (APDC. The fine droplets of carbon tetrachloride were formed and dispersed in the aqueous sample with the help of ultrasonic waves which accelerated the formation of the fine cloudy solution without using disperser solvents. Under optimum conditions, the calibration curve was linear in the range of 2.5-500 μg L-1, with a detection limit of 0.8 μg L-1. The relative standard deviation (RSD for ten replicate measurements of 20 and 500 μg L-1 of cobalt were 3.3 and 2.2%. This proposed method was successfully applied to tap water, river water, and sea water, and accuracy was assessed through the analysis of certified reference water or recovery experiments. Operation simplicity, low cost, high enrichment factor, and low consumption of the extraction solvent are the main advantages of the proposed method.DOI: http://dx.doi.org/10.4314/bcse.v26i1.2

Development of a new extraction method based on counter current salting-out homogenous liquid-liquid extraction followed by dispersive liquid-liquid microextraction: Application for the extraction and preconcentration of widely used pesticides from fruit juices.

Science.gov (United States)

Farajzadeh, Mir Ali; Feriduni, Behruz; Mogaddam, Mohammad Reza Afshar

2016-01-01

In this paper, a new extraction method based on counter current salting-out homogenous liquid-liquid extraction (CCSHLLE) followed by dispersive liquid-liquid microextraction (DLLME) has been developed for the extraction and preconcentration of widely used pesticides in fruit juice samples prior to their analysis by gas chromatography-flame ionization detection (GC-FID). In this method, initially, sodium chloride as a separation reagent is filled into a small column and a mixture of water (or fruit juice) and acetonitrile is passed through the column. By passing the mixture sodium chloride is dissolved and the fine droplets of acetonitrile are formed due to salting-out effect. The produced droplets go up through the remained mixture and collect as a separated layer. Then, the collected organic phase (acetonitrile) is removed with a syringe and mixed with 1,1,2,2-tetrachloroethane (extraction solvent at µL level). In the second step, for further enrichment of the analytes the above mixture is injected into 5 mL de-ionized water placed in a test tube with conical bottom in order to dissolve acetonitrile into water and to achieve a sedimented phase at µL-level volume containing the enriched analytes. Under the optimal extraction conditions (extraction solvent, 1.5 mL acetonitrile; pH, 7; flow rate, 0.5 mL min(-1); preconcentration solvent, 20 µL 1,1,2,2-tetrachloroethane; NaCl concentration; 5%, w/w; and centrifugation rate and time, 5000 rpm and 5 min, respectively), the extraction recoveries and enrichment factors ranged from 87% to 96% and 544 to 600, respectively. Repeatability of the proposed method, expressed as relative standard deviations, ranged from 2% to 6% for intra-day (n=6, C=250 or 500 µg L(-1)) and inter-days (n=4, C=250 or 500 µg L(-1)) precisions. Limits of detection are obtained between 2 and 12 µg L(-1). Finally, the proposed method is applied for the determination of the target pesticide residues in the juice samples. Copyright © 2015

Hydrophilic interaction chromatography combined with dispersive liquid-liquid microextraction as a preconcentration tool for the simultaneous determination of the panel of underivatized neurotransmitters in human urine samples.

Science.gov (United States)

Konieczna, Lucyna; Roszkowska, Anna; Niedźwiecki, Maciej; Bączek, Tomasz

2016-01-29

A simple and sensitive method using dispersive liquid-liquid microextraction (DLLME) followed by liquid chromatography coupled to mass spectrometry (LC-MS) with a hydrophilic interaction chromatography (HILIC) column was developed for the simultaneous determination of 13 compounds of different polarities, comprising monoamine neurotransmitters (dopamine, norepinephrine, epinephrine and serotonin) along with their respective precursors and metabolites, in human urine samples. The microextraction procedure was based on the fast injection of a mixture of ethanol (disperser solvent) and dichloromethane (extraction solvent) into a human urine sample, forming a cloudy solution in the Eppendorf tube. After centrifugation, the sedimented phase was collected and subsequently analyzed by LC-HILIC-MS in about 12min without a derivatization step. The separation was performed on an XBridge Amide™ BEH column 3.0×100mm, 3.5mm and the mobile phase consisted of phase A: 10mM ammonium formate buffer in water pH 3.0 and phase B: 10 mM ammonium formate buffer in acetonitrile, under gradient program elution. Tyrosine, tryptophan, 5-hydroxytryptophan, dopamine, epinephrine, norepinephrine, serotonin, 3-methoxytyramine, 5-hydroxyindole-3-acetic acid, 3,4-dihydroxy-l-phenylalanine and norvaline (internal standard) were detected in the positive ionization mode. While vanillylmandelic acid, homovanillic acid, 3,4-dihydroxyphenylacetic acid and 3,4-dihydroxybenzylamine (internal standard) were detected in the negative ionization mode. Parameters influencing DLLME and LC-HILIC-MS were investigated. Under the optimum conditions, the proposed method exhibited a low detection limit (5-10ngmL(-1)), and good linearity with R between 0.9991 and 0.9998. The recoveries in human urine samples were 99.0%±3.6%. for the 13 studied biogenic amines with intra- and inter-day RSDs of 0.24-9.55% and 0.31-10.0%, respectively. The developed DLLME-LC-MS method could be successfully applied for the

Novel amphiphilic polymeric ionic liquid-solid phase micro-extraction membrane for the preconcentration of aniline as degradation product of azo dye Orange G under sonication by liquid chromatography-tandem mass spectrometry.

Science.gov (United States)

Cai, Mei-Qiang; Wei, Xiao-Qing; Du, Chun-Hui; Ma, Xu-Ming; Jin, Mi-Cong

2014-07-04

A novel amphiphilic polymeric ionic liquid membrane containing a hydrophilic bromide anion and a hydrophobic carbonyl group was synthesized in dimethylformamide (DMF) systems using the ionic liquid 1-butyl-3-vinylimidazolium bromide (BVImBr) and the methylmethacrylate (MMA) as monomers. The prepared amphiphilic ploy-methylmethacrylate-1-butyl-3-vinylimidazolium bromide (MMA-BVImBr) was characterized by a scanning electron microscope and an infrared spectrum instrument. The results of solid-phase micro-extraction membrane (SPMM) experiments showed that the adsorption capacity of membrane was about 0.76μgμg(-1) for aniline. Based on this, a sensitive method for the determination of trace aniline, as a degradation product of azo dye Orange G under sonication, was developed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The calibration curve showed a good linearity ranging from 0.5 to 10.0μgL(-1) with a correlation coefficient value of 0.9998. The limit of quantification was 0.5μgL(-1). The recoveries ranged from 90.6% to 96.1%. The intra- and inter-day relative standard deviations were less than 8.3% and 10.9%. The developed SPMM-LC-MS/MS method was used successfully for preconcentration of trace aniline produced during the sonication of Orange G solution. Copyright © 2014 Elsevier B.V. All rights reserved.

Room temperature ionic liquids enhanced the speciation of Cr(VI) and Cr(III) by hollow fiber liquid phase microextraction combined with flame atomic absorption spectrometry

Energy Technology Data Exchange (ETDEWEB)

Zeng, Chujie, E-mail: cjzeng@126.com [Department of Chemistry and Material, Yulin Normal College, Yulin, Guangxi 537000 (China); Lin, Yao; Zhou, Neng; Zheng, Jiaoting; Zhang, Wei [Department of Chemistry and Material, Yulin Normal College, Yulin, Guangxi 537000 (China)

2012-10-30

Highlights: Black-Right-Pointing-Pointer First reported enhancement effect of RTILs in HF-LPME for the speciation of chromium. Black-Right-Pointing-Pointer The addition of RTILs led to 3.5 times improvement of the sensitivity of Cr(VI). Black-Right-Pointing-Pointer The proposed method is a simplicity, sensitivity, low cost, green method. - Abstract: A new method for the speciation of Cr(VI) and Cr(III) based on enhancement effect of room temperature ionic liquids (RTILs) for hollow fiber liquid phase microextraction (HF-LPME) combined with flame atomic absorption spectrometry (FAAS) was developed. Room temperature ionic liquids (RTILs) and diethyldithiocarbamate (DDTC) were used enhancement reagents and chelating reagent, respectively. The addition of room temperature ionic liquids led to 3.5 times improvement in the determination of Cr(VI). In this method, Cr(VI) reacts with DDTC yielding a hydrophobic complex, which is subsequently extracted into the lumen of hollow fiber, whereas Cr(III) is remained in aqueous solutions. The extraction organic phase was injected into FAAS for the determination of Cr(VI). Total Cr concentration was determined after oxidizing Cr(III) to Cr(VI) in the presence of KMnO{sub 4} and using the extraction procedure mentioned above. Cr(III) was calculated by subtracting of Cr(VI) from the total Cr. Under optimized conditions, a detection limit of 0.7 ng mL{sup -1} and an enrichment factor of 175 were achieved. The relative standard deviation (RSD) was 4.9% for Cr(VI) (40 ng mL{sup -1}, n = 5). The proposed method was successfully applied to the speciation of chromium in natural water samples with satisfactory results.

Room temperature ionic liquids enhanced the speciation of Cr(VI) and Cr(III) by hollow fiber liquid phase microextraction combined with flame atomic absorption spectrometry

International Nuclear Information System (INIS)

Zeng, Chujie; Lin, Yao; Zhou, Neng; Zheng, Jiaoting; Zhang, Wei

2012-01-01

Highlights: ► First reported enhancement effect of RTILs in HF-LPME for the speciation of chromium. ► The addition of RTILs led to 3.5 times improvement of the sensitivity of Cr(VI). ► The proposed method is a simplicity, sensitivity, low cost, green method. - Abstract: A new method for the speciation of Cr(VI) and Cr(III) based on enhancement effect of room temperature ionic liquids (RTILs) for hollow fiber liquid phase microextraction (HF-LPME) combined with flame atomic absorption spectrometry (FAAS) was developed. Room temperature ionic liquids (RTILs) and diethyldithiocarbamate (DDTC) were used enhancement reagents and chelating reagent, respectively. The addition of room temperature ionic liquids led to 3.5 times improvement in the determination of Cr(VI). In this method, Cr(VI) reacts with DDTC yielding a hydrophobic complex, which is subsequently extracted into the lumen of hollow fiber, whereas Cr(III) is remained in aqueous solutions. The extraction organic phase was injected into FAAS for the determination of Cr(VI). Total Cr concentration was determined after oxidizing Cr(III) to Cr(VI) in the presence of KMnO 4 and using the extraction procedure mentioned above. Cr(III) was calculated by subtracting of Cr(VI) from the total Cr. Under optimized conditions, a detection limit of 0.7 ng mL −1 and an enrichment factor of 175 were achieved. The relative standard deviation (RSD) was 4.9% for Cr(VI) (40 ng mL −1 , n = 5). The proposed method was successfully applied to the speciation of chromium in natural water samples with satisfactory results.

Method for the simultaneous determination of monoaromatic and polycyclic aromatic hydrocarbons in industrial effluents using dispersive liquid-liquid microextraction with gas chromatography-mass spectrometry.

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Makoś, Patrycja; Fernandes, André; Boczkaj, Grzegorz

2018-02-23

We present a new method for simultaneous determination of 22 monoaromatic and polycyclic aromatic hydrocarbons in postoxidative effluents from the production of petroleum bitumen using dispersive liquid-liquid microextraction coupled to gas chromatography and mass spectrometry. The eight extraction parameters including the type and volume of extraction and disperser solvent, pH, salting out effect, extraction, and centrifugation time were optimized. The low detection limit ranging from 0.36 to 28 μg/L, limit of quantitation (1.1-84 μg/L), good reproducibility, and wide linear ranges, as well as the recoveries ranging from 71.74 to 114.67% revealed that the new method allows the determination of aromatic hydrocarbons at low concentration levels in industrial effluents having a very complex composition. The developed method was applied to the determination of content of mono- and polycyclic aromatic hydrocarbons in samples of raw postoxidative effluents in which 15 compounds were identified at concentrations ranging from 1.21 to 1017.0 μg/L as well as in effluents after chemical treatment. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dispersive liquid-liquid microextraction combined with gas chromatography-electron capture detection for the determination of polychlorinated biphenyls in soils

International Nuclear Information System (INIS)

Hu Jia; Fu Lingyan; Zhao Xinna; Liu Xiujuan; Wang Huili; Wang Xuedong; Dai Liyan

2009-01-01

In this article, dispersive liquid-liquid microextraction (DLLME) and gas chromatography-electron capture detection (GC-ECD) were presented for the extraction and determination of five polychlorinated biphenyls (PCBs) in soil samples. Acetone was used as extraction solvent for the extraction of PCBs from soil samples. In DLLME, the target analytes in the extraction solvent were rapidly transferred from the acetone extract to chlorobenzene when the extraction process began. The main advantages of this method are quick speed, high enrichment factor, high recovery and good repeatability. Under the optimum conditions, the method yields a linear calibration curve in the concentration range from 2 to 2000 μg kg -1 for PCB 52, and 0.4 to 400 μg kg -1 for other target analytes. Coefficients of correlation (r 2 ) ranged from 0.9993 to 0.9999. The repeatability was tested by spiking soil samples at a concentration level of 10 μg kg -1 for PCBs. The relative standard deviations (RSDs, n = 11) varied between 2.2% and 6.4%. The limits of detection (LODs), based on signal-to-noise (S/N) of 3, were between 0.20 and 0.50 μg kg -1 . The relative recoveries of the five PCBs from soil S1, S2 and S3 at spiking levels of 10, 20 and 50 μg kg -1 were in the range of 88.70-103.8%, 82.50-106.3% and 82.30-113.6%, respectively. Therefore, DLLME combined with GC-ECD can be successfully applied for the determination of trace PCB residues in real soil samples.

Rapid determination of triclosan in personal care products using new in-tube based ultrasound-assisted salt-induced liquid-liquid microextraction coupled with high performance liquid chromatography-ultraviolet detection.

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Chen, Ming-Jen; Liu, Ya-Ting; Lin, Chiao-Wen; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

2013-03-12

This paper describes the development of a novel, simple and efficient in-tube based ultrasound-assisted salt-induced liquid-liquid microextraction (IT-USA-SI-LLME) technique for the rapid determination of triclosan (TCS) in personal care products by high performance liquid chromatography-ultraviolet (HPLC-UV) detection. IT-USA-SI-LLME method is based on the rapid phase separation of water-miscible organic solvent from the aqueous phase in the presence of high concentration of salt (salting-out phenomena) under ultrasonication. In the present work, an indigenously fabricated home-made glass extraction device (8-mL glass tube inbuilt with a self-scaled capillary tip) was utilized as the phase separation device for USA-SI-LLME. After the extraction, the upper extractant layer was narrowed into the self-scaled capillary tip by pushing the plunger plug; thus, the collection and measurement of the upper organic solvent layer was simple and convenient. The effects of various parameters on the extraction efficiency were thoroughly evaluated and optimized. Under optimal conditions, detection was linear in the concentration range of 0.4-100ngmL(-1) with correlation coefficient of 0.9968. The limit of detection was 0.09ngmL(-1) and the relative standard deviations ranged between 0.8 and 5.3% (n=5). The applicability of the developed method was demonstrated for the analysis of TCS in different commercial personal care products and the relative recoveries ranged from 90.4 to 98.5%. The present method was proven to be a simple, sensitive, less organic solvent consuming, inexpensive and rapid procedure for analysis of TCS in a variety of commercially available personal care products or cosmetic preparations. Copyright © 2013 Elsevier B.V. All rights reserved.

Optimization of dispersive liquid-phase microextraction based on solidified floating organic drop combined with high-performance liquid chromatography for the analysis of glucocorticoid residues in food.

Science.gov (United States)

Huang, Yuan; Zheng, Zhiqun; Huang, Liying; Yao, Hong; Wu, Xiao Shan; Li, Shaoguang; Lin, Dandan

2017-05-10

A rapid, simple, cost-effective dispersive liquid-phase microextraction based on solidified floating organic drop (SFOD-LPME) was developed in this study. Along with high-performance liquid chromatography, we used the developed approach to determine and enrich trace amounts of four glucocorticoids, namely, prednisone, betamethasone, dexamethasone, and cortisone acetate, in animal-derived food. We also investigated and optimized several important parameters that influenced the extraction efficiency of SFOD-LPME. These parameters include the extractant species, volumes of extraction and dispersant solvents, sodium chloride addition, sample pH, extraction time and temperature, and stirring rate. Under optimum experimental conditions, the calibration graph exhibited linearity over the range of 1.2-200.0ng/ml for the four analytes, with a reasonable linearity(r 2 : 0.9990-0.9999). The enrichment factor was 142-276, and the detection limits was 0.39-0.46ng/ml (0.078-0.23μg/kg). This method was successfully applied to analyze actual food samples, and good spiked recoveries of over 81.5%-114.3% were obtained. Copyright © 2017. Published by Elsevier B.V.

Liquid Phase Micro-Extraction of Linear Alkylbenzene Sulfonate Anionic Surfactants in Aqueous Samples

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Jan Åke Jönsson

2011-10-01

Full Text Available Hollow fiber liquid phase micro-extraction (LPME of linear alkylbenzene sulfonates (LAS from aqueous samples was studied. Ion pair extraction of C10, C11, C12 and C13 homologues was facilitated with trihexylamine as ion-pairing agent, using di-n-hexylether as solvent for the supported liquid membrane (SLM. Effects of extraction time, acceptor buffer concentration, stirring speed, sample volume, NaCl and humic acids were studied. At 10–50 µg L−1 linear R2-coefficients were 0.99 for C10 and C11 and 0.96 for C12. RSD was typically ~15%. Three observations were especially made. Firstly, LPME for these analytes was unusually slow with maximum enrichment observed after 15–24 h (depending on sample volume. Secondly, the enrichment depended on LAS sample concentration with 35–150 times enrichment below ~150 µg L−1 and 1850–4400 times enrichment at 1 mg L−1. Thirdly, lower homologues were enriched more than higher homologues at low sample concentrations, with reversed conditions at higher concentrations. These observations may be due to the fact that LAS and the amine counter ion themselves influence the mass transfer at the water-SLM interface. The observations on LPME of LAS may aid in LPME application to other compounds with surfactant properties or in surfactant enhanced membrane extraction of other compounds.

Simultaneous determination of 12 pharmaceuticals in water samples by ultrasound-assisted dispersive liquid-liquid microextraction coupled with ultra-high performance liquid chromatography with tandem mass spectrometry.

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Guan, Jin; Zhang, Chi; Wang, Yang; Guo, Yiguang; Huang, Peiting; Zhao, Longshan

2016-11-01

A new analytical method was developed for simultaneous determination of 12 pharmaceuticals using ultrasound-assisted dispersive liquid-liquid microextraction (DLLME) followed by ultra-high performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS). Six nonsteroidal anti-inflammatory drugs (NSAIDs, ketoprofen, mefenamic acid, tolfenamic acid, naproxen, sulindac, and piroxicam) and six antibiotics (tinidazole, cefuroxime axetil, ciprofloxacin, sulfamethoxazole, sulfadiazine, and chloramphenicol) were extracted by ultrasound-assisted DLLME using dichloromethane (800 μL) and methanol/acetonitrile (1:1, v/v, 1200 μL) as the extraction and dispersive solvents, respectively. The factors affecting the extraction efficiency, such as the type and volume of extraction and dispersive solvent, vortex and ultrasonic time, sample pH, and ionic strength, were optimized. The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution by using a small volume of dispersive solvent, which increased the extraction efficiency and reduced the equilibrium time. Under the optimal conditions, the calibration curves showed good linearity in the range of 0.04-20 ng mL -1 (ciprofloxacin and sulfadiazine), 0.2-100 ng mL -1 (ketoprofen, tinidazole, cefuroxime axetil, naproxen, sulfamethoxazole, and sulindac), and 1-200 ng mL -1 (mefenamic acid, tolfenamic acid, piroxicam, and chloramphenicol). The LODs and LOQs of the method were in the range of 0.006-0.091 and 0.018-0.281 ng mL -1 , respectively. The relative recoveries of the target analytes were in the range from 76.77 to 99.97 % with RSDs between 1.6 and 8.8 %. The developed method was successfully applied to the extraction and analysis of 12 pharmaceuticals in five kinds of water samples (drinking water, running water, river water, influent and effluent wastewater) with satisfactory results. Graphical Abstract Twelve pharmaceuticals in water samples analyted by UHPLC

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

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Liu, Hongjiao; Lei, Ming; Liang, Xiao; Jiang, Zhen; Guo, Xingjie

2014-02-01

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. Copyright © 2013 John Wiley & Sons, Ltd.

Development of a new microextraction method based on elevated temperature dispersive liquid-liquid microextraction for determination of triazole pesticides residues in honey by gas chromatography-nitrogen phosphorus detection.

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Farajzadeh, Mir Ali; Mogaddam, Mohammad Reza Afshar; Ghorbanpour, Houshang

2014-06-20

In the present study, a rapid, highly efficient, and reliable sample preparation method named "elevated temperature dispersive liquid-liquid microextraction" followed by gas chromatography-nitrogen-phosphorus detection was developed for the extraction, preconcentration, and determination of five triazole pesticides (penconazole, hexaconazole, diniconazole, tebuconazole, and difenoconazole) in honey samples. In this method the temperature of high-volume aqueous phase was adjusted at an elevated temperature and then a disperser solvent containing an extraction solvent was rapidly injected into the aqueous phase. After cooling to room temperature, the phase separation was accelerated by centrifugation. Various parameters affecting the extraction efficiency such as type and volume of the extraction and disperser solvents, temperature, salt addition, and pH were evaluated. Under the optimum extraction conditions, the method resulted in low limits of detection and quantification within the range 0.05-0.21ngg(-1) in honey (15-70ngL(-1) in solution) and 0.15-1.1ngg(-1) in honey (45-210ngL(-1) in solution), respectively. Enrichment factors and extraction recoveries were in the ranges of 1943-1994 and 97-100%, respectively. The method precision was evaluated at 1.5ngg(-1) of each analyte, and the relative standard deviations were found to be less than 4% for intra-day (n=6) and less than 6% for inter-days. The method was successfully applied to the analysis of honey samples and difenoconazole was determined at ngg(-1) levels. Copyright © 2014 Elsevier B.V. All rights reserved.

Urea functionalized surface-bonded sol-gel coating for on-line hyphenation of capillary microextraction with high-performance liquid chromatography.

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Jillani, Shehzada Muhammad Sajid; Alhooshani, Khalid

2018-03-30

Sol-gel urea functionalized-[bis(hydroxyethyl)amine] terminated polydimethylsiloxane coating was developed for capillary microextraction-high performance liquid chromatographic analysis from aqueous samples. A fused silica capillary is coated from the inside with surface bonded coating material and is created through in-situ sol-gel reaction. The urea-functionalized coating was immobilized to the inner surface of the capillary by the condensation reaction of silanol groups of capillary and sol-solution. The characterization of the coating material was successfully done by using X-ray photoelectron spectroscopy, thermogravimetric analysis, field emission scanning electron microscope, and energy dispersive X-ray spectrometer. To make a setup of online capillary microextraction-high performance liquid chromatography, the urea functionalized capillary was installed in the HPLC manual injection port. The analytes of interest were pre-concentrated in the coated sampling loop, desorbed by the mobile phase, chromatographically separated on C-18 column, and analyzed by UV detector. Sol-gel coated capillaries were used for online extraction and high-performance liquid chromatographic analysis of phenols, ketones, aldehydes, and polyaromatic hydrocarbons. This newly developed coating showed excellent extraction for a variety of analytes ranging from highly polar to non-polar in nature. The analysis using sol-gel coating showed excellent overall sensitivity in terms of lower detection limits (S/N = 3) for the analytes (0.10 ng mL -1 -14.29 ng mL -1 ) with acceptable reproducibility that is less than 12.0%RSD (n = 3). Moreover, the capillary to capillary reproducibility of the analysis was also tested by changing the capillary of the same size. This provided excellent%RSD of less than 10.0% (n = 3). Copyright © 2018 Elsevier B.V. All rights reserved.

Thermal properties of ionic systems near the liquid-liquid critical point.

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Méndez-Castro, Pablo; Troncoso, Jacobo; Pérez-Sánchez, Germán; Peleteiro, José; Romaní, Luis

2011-12-07

Isobaric heat capacity per unit volume, C(p), and excess molar enthalpy, h(E), were determined in the vicinity of the critical point for a set of binary systems formed by an ionic liquid and a molecular solvent. Moreover, and, since critical composition had to be accurately determined, liquid-liquid equilibrium curves were also obtained using a calorimetric method. The systems were selected with a view on representing, near room temperature, examples from clearly solvophobic to clearly coulombic behavior, which traditionally was related with the electric permittivity of the solvent. The chosen molecular compounds are: ethanol, 1-butanol, 1-hexanol, 1,3-dichloropropane, and diethylcarbonate, whereas ionic liquids are formed by imidazolium-based cations and tetrafluoroborate or bis-(trifluromethylsulfonyl)amide anions. The results reveal that solvophobic critical behavior-systems with molecular solvents of high dielectric permittivity-is very similar to that found for molecular binary systems. However, coulombic systems-those with low permittivity molecular solvents-show strong deviations from the results usually found for these magnitudes near the liquid-liquid phase transition. They present an extremely small critical anomaly in C(p)-several orders of magnitude lower than those typically obtained for binary mixtures-and extremely low h(E)-for one system even negative, fact not observed, up to date, for any liquid-liquid transition in the nearness of an upper critical solution temperature. © 2011 American Institute of Physics

Hollow fiber liquid phase microextraction combined with graphite furnace atomic absorption spectrometry for the determination of methylmercury in human hair and sludge samples

Energy Technology Data Exchange (ETDEWEB)

Jiang Hongmei [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Hu Bin [Department of Chemistry, Wuhan University, Wuhan 430072 (China)], E-mail: binhu@whu.edu.cn; Chen Beibei; Zu Wanqing [Department of Chemistry, Wuhan University, Wuhan 430072 (China)

2008-07-15

Two methods, based on hollow fiber liquid-liquid-liquid (three phase) microextraction (HF-LLLME) and hollow fiber liquid phase (two phase) microextraction (HF-LPME), have been developed and critically compared for the determination of methylmercury content in human hair and sludge by graphite furnace atomic absorption spectrometry (GFAAS). In HF-LPME, methylmercury was extracted into the organic phase (toluene) prior to its determination by GFAAS, while inorganic mercury remained as a free species in the sample solution. In HF-LLLME, methylmercury was first extracted into the organic phase (toluene) and then into the acceptor phase (4% thiourea in 1 mol L{sup -1} HCl) prior to its determination by GFAAS, while inorganic mercury remained in the sample solution. The total mercury was determined by inductively coupled plasma-mass spectrometry (ICP-MS), and the levels of inorganic mercury in both HF-LLLME and HF-LPME were obtained by subtracting methylmercury from total mercury. The factors affecting the microextraction of methylmercury, including organic solvent, extraction time, stirring rate and ionic strength, were investigated and the optimal extraction conditions were established for both HF-LLLPME and HF-LPME. With a consumption of 3.0 mL of the sample solution, the enrichment factors were 204 and 55 for HF-LLLPME and HF-LPME, respectively. The limits of detection (LODs) for methylmercury were 0.1 {mu}g L{sup -1} and 0.4 {mu}g L{sup -1} (as Hg) with precisions (RSDs (%), c = 5 {mu}g L{sup -1} (as Hg), n = 5) of 13% and 11% for HF-LLLPME-GFAAS and HF-LPME-GFAAS, respectively. For ICP-MS determination of total mercury, a limit of detection of 39 ng L{sup -} {sup 1} was obtained. Finally, HF-LLLME-GFAAS was applied to the determination of methylmercury content in human hair and sludge, and the recoveries for the spiked samples were in the range of 99-113%. In order to validate the method, HF-LLLME-GFAAS was also applied to the analysis of a certified reference

Simultaneous Pre-Concentration of Cadmium and Lead in Environmental Water Samples with Dispersive Liquid-Liquid Microextraction and Determination by Inductively Coupled Plasma-Atomic Emission Spectrometry

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M. Salahinejad

2013-06-01

Full Text Available The dispersive liquid–liquid microextraction (DLLME method for determination of Pb+2 and Cd+2 ions in the environmental water samples was combined with inductively coupled plasma-atomic emission spectrometry (ICP-AES. Ammonium pyrrolidine dithiocarbamate (APDC, chloroform and ethanol were used as chelating agent, extraction solvent and disperser solvent, respectively. Some effective parameters on the microextraction and the complex formation were selected and optimized. These parameters included extraction and disperser solvent type as well as their volume, extraction time, salt effect, pH, sample volume and amount of the chelating agent.   Under the optimum conditions, the enrichment factor of 75 and 105 for Cd+2 and Pb+2 ions respectively was obtained from only 5.00mL of water sample. The detection limit (S/N=3 was 12 and 0.8ngmL−1 for Pb and Cd respectively. The relative standard deviation (RSDs for five replicate measurements of 0.50 mgL−1 of lead and cadmium was 6.5 and 4.4 % respectively. Mineral, tap, river, sea, dam and spiked water samples were analyzed for Cd and Pb amount.

Development of Hollow-Fiber Liquid-Phase Microextraction Method for Determination of Urinary -Muconic Acid as a Biomarker of Benzene Exposure

Directory of Open Access Journals (Sweden)

Farhad Ghamari

2016-01-01

Full Text Available For the first time, hollow-fiber liquid-phase microextraction combined with high-performance liquid chromatography-ultraviolet was used to extract trans, trans -muconic acid, in urine samples of workers who had been exposed to benzene. The parameters affecting the metabolite extraction were optimized as follows: the volume of sample solution was 11 mL with pH 2, liquid membrane containing dihexyl ether as the supporter, 15% (w/v of trioctylphosphine oxide as the carrier, the time of extraction was 120 minutes, and stirring rate was 500 rpm. Organic phase impregnated in the pores of a hollow fiber was extracted into 24 μL solution of 0.05 mol L −1 Na 2 CO 3 located inside the lumen of the fiber. Under optimized conditions, a high enrichment factor of 153-182 folds, relative recovery of 83%-92%, and detection limit of 0.001 μg mL −1 were obtained. The method was successfully applied to the analysis of ttMA in real urine samples.

In-line carbon nanofiber reinforced hollow fiber-mediated liquid phase microextraction using a 3D printed extraction platform as a front end to liquid chromatography for automatic sample preparation and analysis: A proof of concept study.

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Worawit, Chanatda; Cocovi-Solberg, David J; Varanusupakul, Pakorn; Miró, Manuel

2018-08-01

A novel concept for automation of nanostructured hollow-fiber supported microextraction, combining the principles of liquid-phase microextraction (LPME) and sorbent microextraction synergically, using mesofluidic platforms is proposed herein for the first time, and demonstrated with the determination of acidic drugs (namely, ketoprofen, ibuprofen, diclofenac and naproxen) in urine as a proof-of-concept applicability. Dispersed carbon nanofibers (CNF) are immobilized in the pores of a single-stranded polypropylene hollow fiber (CNF@HF) membrane, which is thereafter accommodated in a stereolithographic 3D-printed extraction chamber without glued components for ease of assembly. The analytical method involves continuous-flow extraction of the acidic drugs from a flowing stream donor (pH 1.7) into an alkaline stagnant acceptor (20 mmol L -1 NaOH) containing 10% MeOH (v/v) across a dihexyl ether impregnated CNF@HF membrane. The flow setup features entire automation of the microextraction process including regeneration of the organic film and on-line injection of the analyte-laden acceptor phase after downstream neutralization into a liquid chromatograph (LC) for reversed-phase core-shell column-based separation. Using a 12-cm long CNF@HF and a sample volume of 6.4 mL, linear dynamic ranges of ketoprofen, naproxen, diclofenac and ibuprofen, taken as models of non-steroidal anti-inflammatory drugs, spanned from ca. 5-15 µg L -1 to 500 µg L -1 with enhancement factors of 43-97 (against a direct injection of 10 µL standards into LC), and limits of detection from 1.6 to 4.3 µg L -1 . Relative recoveries in real urine samples ranged from 97% to 105%, thus demonstrating the reliability of the automatic CNF@HF-LPME method for in-line matrix clean-up and determination of drugs in urine at therapeutically relevant concentrations. Copyright © 2018 Elsevier B.V. All rights reserved.

Effervescence-assisted dispersive liquid-liquid microextraction using a solid effervescent agent as a novel dispersion technique for the analysis of fungicides in apple juice.

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Jiang, Wenqing; Chen, Xiaochu; Liu, Fengmao; You, Xiangwei; Xue, Jiaying

2014-11-01

A novel effervescence-assisted dispersive liquid-liquid microextraction method has been developed for the determination of four fungicides in apple juice samples. In this method, a solid effervescent agent is added into samples to assist the dispersion of extraction solvent. The effervescent agent is environmentally friendly and only produces an increase in the ionic strength and a negligible variation in the pH value of the aqueous sample, which does not interfere with the extraction of the analytes. The parameters affecting the extraction efficiency were investigated including the composition of effervescent agent, effervescent agent amount, formulation of effervescent agent, adding mode of effervescent agent, type and volume of extraction solvent, and pH. Under optimized conditions, the method showed a good linearity within the range of 0.05-2 mg/L for pyrimethanil, fludioxonil, and cyprodinil, and 0.1-4 mg/L for kresoxim-methyl, with the correlation coefficients >0.998. The limits of detection for the method ranged between 0.005 and 0.01 mg/L. The recoveries of the target fungicides in apple juice samples were in the range of 72.4-110.8% with the relative standard deviations ranging from 1.2 to 6.8%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combination of solid-phase extraction with dispersive liquid-liquid microextraction followed by GC-MS for determination of pesticide residues from water, milk, honey and fruit juice.

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Shamsipur, Mojtaba; Yazdanfar, Najmeh; Ghambarian, Mahnaz

2016-08-01

In this work, an effective preconcentration method for the extraction and determination of traces of multi-residue pesticides was developed using solid-phase extraction (SPE) coupled with dispersive liquid-liquid microextraction and gas chromatography-mass spectrometry (GC-MS). Variables affecting the performance of both extraction steps such as type and volume of elution and extraction solvents, breakthrough volume, salt addition, extraction time were thoroughly investigated. The proposed method resulted in good linearities (R(2)>0.9915) over the ranges of 1-10,000ngkg(-1), limits of detection (LODs) in the range of 0.5-1.0ngkg(-1) at S/N=3, and precision of RSD% of ⩽11.8. Under optimal conditions, the preconcentration factors were obtained in the range of 2362-10,593 for 100mL sample solutions. Comparison of the proposed method with other ones demonstrated that SPE-DLLME method provides higher extraction efficiency and larger preconcentration factor for determination of pesticides residues. Further, it is simple, inexpensive, highly sensitive, and can be successfully applied to separation, preconcentration and determination of the pesticides (and other noxious materials) in different real food samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enhanced spectrophotometric detection of Hg in water samples by surface plasmon resonance of Au nanoparticles after preconcentration with vortex-assisted liquid-liquid microextraction

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Martinis, Estefanía M.; Wuilloud, Rodolfo G.

2016-10-01

This article presents an efficient, simple, and cost-effective method for the determination of trace amounts of Hg by vortex-assisted liquid-liquid microextraction (VALLME) coupled to microvolume UV-Vis spectrophotometry. This method correlates changes in the intensity of localized surface plasmon resonance (LSPR) of tetraoctylammonium bromide (TOABr) coated Au nanoparticles (NPs) after interaction with Hg2+ ion. Spectroscopic measurements of the TOABr-coated Au NPs phase with particular absorption properties (strong and well-defined absorption bands) after analyte extraction by VALLME, provide an accurate and sensitive determination of Hg in water samples, comparable with measurements obtained by atomic absorption spectrometry (AAS). Different variables including sample volume, extraction time, and TOABr-coated Au NPs dispersion volume were carefully studied; final experimental conditions were 5 mL, 120 μL and 5 min respectively. The limit of detection (LOD) was 0.8 ng mL- 1. The calibration curve was linear at concentrations between the limit of quantification (LOQ) (4.9 ng mL- 1) and up to at least 120 ng mL- 1 of Hg. The relative standard deviation for six replicate determinations of 20 ng mL- 1 of Hg was 4.7%. This method exhibited an excellent analytical performance in terms of selectivity and sensitivity and it was finally applied for Hg determination in spiked tap and mineral water samples.

A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air-assisted liquid-liquid microextraction from human urine and plasma samples followed by gas chromatography-nitrogen phosphorous detection.

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Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza; Alizadeh Nabil, Ali Akbar

2015-12-01

In present study, a simultaneous derivatization and air-assisted liquid-liquid microextraction method combined with gas chromatography-nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1-flouro-2,4-dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05-0.34 ng mL(-1) are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd.

Dispersive liquid-liquid microextraction for the determination of vitamins D and K in foods by liquid chromatography with diode-array and atmospheric pressure chemical ionization-mass spectrometry detection.

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Viñas, Pilar; Bravo-Bravo, María; López-García, Ignacio; Hernández-Córdoba, Manuel

2013-10-15

A simple and rapid method was developed using reversed-phase liquid chromatography (LC) with both diode array (DAD) and atmospheric pressure chemical ionization mass spectrometric (APCI-MS) detection, for the simultaneous analysis of the vitamins ergocalciferol (D2), cholecalciferol (D3), phylloquinone (K1), menaquinone-4 (K2) and a synthetic form of vitamin K, menadione (K3). The Taguchi experimental method, an orthogonal array design (OAD), was used to optimize an efficient and clean preconcentration step based on dispersive liquid-liquid microextraction (DLLME). A factorial design was applied with six factors and three levels for each factor, namely, carbon tetrachloride volume, methanol volume, aqueous sample volume, pH of sample, sodium chloride concentration and time of the centrifugation step. The DLLME optimized procedure consisted of rapidly injecting 3 mL of acetonitrile (disperser solvent) containing 150 µL carbon tetrachloride (extraction solvent) into the aqueous sample, thereby forming a cloudy solution. Phase separation was performed by centrifugation, and the sedimented phase was evaporated with nitrogen, reconstituted with 50 µL of acetonitrile, and injected. The LC analyses were carried out using a mobile phase composed of acetonitrile, 2-propanol and water, under gradient elution. Quantification was carried out by the standard additions method. The APCI-MS spectra, in combination with UV spectra, permitted the correct identification of compounds in the food samples. The method was validated according to international guidelines and using a certified reference material. The validated method was applied for the analysis of vitamins D and K in infant foods and several green vegetables. There was little variability in the forms of vitamin K present in vegetables, with the most abundant vitamer in all the samples being phylloquinone, while menadione could not be detected. Conversely, cholecalciferol, which is present in food of animal origin, was

Dispersive liquid-liquid microextraction followed by flow injection-inductively coupled plasma mass spectrometry (FI-ICPMS) determination of 14 lanthanides from ground water

International Nuclear Information System (INIS)

Chandrasekaran, K.; Karunasagar, D.; Arunachalam, J.

2011-01-01

The aim of the present work was to develop a dispersive liquid-liquid microextraction (DLLME) method for the sensitive determination of REEs at a few parts per billion in groundwater by flow injection-inductively coupled plasma mass spectrometry (FI-ICPMS). In the developed method, methanol (500 μl) and chloroform (200μl) were used as the disperser and extractant respectively. The REEs were complexed with 4-(2-pyridylazo resorcinol) (PAR) at a pH of 7. Acetate ion was added as an auxiliary ligand for neutralization of the charge on the lanthanide-PAR complex. The disperser (MeOH) - extraction solvent (CHCl 3 ) mixture was rapidly injected using a disposable syringe, thereby forming a cloudy solution. The lanthanide-PAR complex was extracted into the fine droplets of the chloroform dispersed in the aqueous phase. The solution was centrifuged and the aqueous layer at the top was discarded. The REEs were back extracted from the chloroform layer with nitric acid for determination by ICPMS. Important parameters for complex formation and extraction, such as volume of extraction/disperser solvent, extraction time, pH and concentration of the chelating agent and the auxiliary ligand are being optimized using ICP-MS. The optimization is being carried out at 5 μg L -1 concentration level of REE in the initial water sample. Preliminary studies have shown an extraction recovery of 80-85% for all the 14 lanthanide elements and these will be presented

Liquid waste treatment system. Final report

International Nuclear Information System (INIS)

Baker, M.N.; Houston, H.M.

1999-01-01

Pretreatment of high-level liquid radioactive waste (HLW) at the West Valley Demonstration Project (WVDP) involved three distinct processing operations: decontamination of liquid HLW in the Supernatant Treatment System (STS); volume reduction of decontaminated liquid in the Liquid Waste Treatment System (LWTS); and encapsulation of resulting concentrates into an approved cement waste form in the Cement Solidification System (CSS). Together, these systems and operations made up the Integrated Radwaste Treatment System (IRTS)

Bis(trifluoromethylsulfonyl)imide-based frozen ionic liquid for the hollow-fiber solid-phase microextraction of dichlorodiphenyltrichloroethane and its main metabolites.

Science.gov (United States)

Pang, Long; Yang, Peijie; Pang, Rong; Li, Shunyi

2017-08-01

1-Hexadecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide is a solid-phase ionic organic material under ambient temperature and is considered as a kind of "frozen" ionic liquid. Because of their solid-state and ultra-hydrophobicity, "frozen" ionic liquids are able to be confined in the pores of hollow fiber, based on which a simple method was developed for the hollow-fiber solid-phase microextraction of dichlorodiphenyltrichloroethane and its main metabolites. Under optimized conditions, the proposed method results in good linearity (R 2 > 0.9965) over the range of 0.5-50 μg/L, with low limits of detection and quantification in the range of 0.33-0.38 and 1.00-1.25 μg/L, respectively. Intra- and interday precisions evaluated by relative standard deviation were 3-6 and 1-6%, respectively. The spiked recoveries of dichlorodiphenyltrichloroethane and its main metabolites from real water samples were in the range of 64-113 and 79-112%, respectively, at two different concentration levels. The results suggest that "frozen" ionic liquids are promising for use as a class of novel sorbents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid–liquid microextraction in a multicommuted flow system for direct spectrophotometric determination of iodine value in biodiesel

Energy Technology Data Exchange (ETDEWEB)

Pereira, Andréia C.; Rocha, Fábio R.P., E-mail: frprocha@cena.usp.br

2014-06-01

Highlights: • First flow-based procedure for iodine value determination in biodiesel. • Simple, fast and reliable procedure. • Detection without sample pretreatment or phase separation. • Liquid–liquid microextraction with low sample and reagent volumes. • Avoid toxic reagents and organic solvent used in the reference procedure. Abstract: A flow-based procedure was developed for the direct spectrophotometric determination of the iodine value (IV) in biodiesel. The procedure was based on the microextraction/reaction of unsaturated compounds with triiodide ions in an aqueous medium by inserting the reagent solution between the aliquots of biodiesel without any pretreatment. The interaction occurred through the biodiesel film formed on the inner walls of the hydrophobic tube used as the reactor and at the aqueous/biodiesel interfaces. The spectrophotometric detection was based on the discoloration of the I₃⁻ reagent in the aqueous phase by using a glass tube coupled to a fiber-optic spectrophotometer as the detection cell. Reference solutions were prepared by dilution of biodiesel samples with previously determined IV in hexane. The analytical response was linear for IV from 13 to 135 g I₂/100 g with a detection limit of 5 g I₂/100 g. A coefficient of variation of 1.7% (n = 10) and a sampling rate of 108 determinations per hour were achieved by consuming 224 μL of the sample and 200 μg of I₂ per determination. The slopes of analytical curves obtained with three different biodiesel samples were in agreement (variations in slopes lower than 3.1%), thus indicating an absence of any matrix effects. Results for biodiesel samples from different sources agreed with the volumetric official procedure at the 95% confidence level. The proposed procedure is therefore a simple, fast, and reliable alternative for estimating the iodine value of biodiesel.

Liquid–liquid microextraction in a multicommuted flow system for direct spectrophotometric determination of iodine value in biodiesel

International Nuclear Information System (INIS)

Pereira, Andréia C.; Rocha, Fábio R.P.

2014-01-01

Highlights: • First flow-based procedure for iodine value determination in biodiesel. • Simple, fast and reliable procedure. • Detection without sample pretreatment or phase separation. • Liquid–liquid microextraction with low sample and reagent volumes. • Avoid toxic reagents and organic solvent used in the reference procedure. - Abstract: A flow-based procedure was developed for the direct spectrophotometric determination of the iodine value (IV) in biodiesel. The procedure was based on the microextraction/reaction of unsaturated compounds with triiodide ions in an aqueous medium by inserting the reagent solution between the aliquots of biodiesel without any pretreatment. The interaction occurred through the biodiesel film formed on the inner walls of the hydrophobic tube used as the reactor and at the aqueous/biodiesel interfaces. The spectrophotometric detection was based on the discoloration of the I 3 − reagent in the aqueous phase by using a glass tube coupled to a fiber-optic spectrophotometer as the detection cell. Reference solutions were prepared by dilution of biodiesel samples with previously determined IV in hexane. The analytical response was linear for IV from 13 to 135 g I 2 /100 g with a detection limit of 5 g I 2 /100 g. A coefficient of variation of 1.7% (n = 10) and a sampling rate of 108 determinations per hour were achieved by consuming 224 μL of the sample and 200 μg of I 2 per determination. The slopes of analytical curves obtained with three different biodiesel samples were in agreement (variations in slopes lower than 3.1%), thus indicating an absence of any matrix effects. Results for biodiesel samples from different sources agreed with the volumetric official procedure at the 95% confidence level. The proposed procedure is therefore a simple, fast, and reliable alternative for estimating the iodine value of biodiesel

Nanofluid of zinc oxide nanoparticles in ionic liquid for single drop liquid microextraction of fungicides in environmental waters prior to high performance liquid chromatographic analysis.

Science.gov (United States)

Amde, Meseret; Tan, Zhi-Qiang; Liu, Rui; Liu, Jing-Fu

2015-05-22

Using a nanofluid obtained by dispersing ZnO nanoparticles (ZnO NPs) in 1-hexyl-3-methylimidazolium hexafluorophosphate, new single drop microextraction method was developed for simultaneous extraction of three fungicides (chlorothalonil, kresoxim-methyl and famoxadone) in water samples prior to their analysis by high performance liquid chromatography (HPLC-VWD). The parameters affecting the extraction efficiency such as amount of ZnO NPs in the nanofluid, solvent volume, extraction time, stirring rate, pH and ionic strength of the sample solution were optimized. Under the optimized conditions, the limits of detection were in the range of 0.13-0.19ng/mL, the precision of the method assessed with intra-day and inter-day relative standard deviations were water samples including lake water, river water, as well as effluent and influent of wastewater treatment plant, with recoveries in the range of 74.94-96.11% at 5ng/mL spiking level. Besides to being environmental friendly, the high enrichment factor and the data quality obtained with the proposed method demonstrated its potential for application in multi residue analysis of fungicides in actual water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Simultaneous derivatisation and preconcentration of parabens in food and other matrices by isobutyl chloroformate and dispersive liquid-liquid microextraction followed by gas chromatographic analysis.

Science.gov (United States)

Jain, Rajeev; Mudiam, Mohana Krishna Reddy; Chauhan, Abhishek; Ch, Ratnasekhar; Murthy, R C; Khan, Haider A

2013-11-01

A simple, rapid and economical method has been proposed for the quantitative determination of parabens (methyl, ethyl, propyl and butyl paraben) in different samples (food, cosmetics and water) based on isobutyl chloroformate (IBCF) derivatisation and preconcentration using dispersive liquid-liquid microextraction in single step. Under optimum conditions, solid samples were extracted with ethanol (disperser solvent) and 200 μL of this extract along with 50 μL of chloroform (extraction solvent) and 10 μL of IBCF was rapidly injected into 2 mL of ultra-pure water containing 150 μL of pyridine to induce formation of a cloudy state. After centrifugation, 1 μL of the sedimented phase was analysed using gas chromatograph-flame ionisation detector (GC-FID) and the peaks were confirmed using gas chromatograph-positive chemical ionisation-mass spectrometer (GC-PCI-MS). Method was found to be linear over the range of 0.1-10 μg mL(-1) with square of correlation coefficient (R(2)) in the range of 0.9913-0.9992. Limit of detection (LOD) and limit of quantification (LOQ) were found to be 0.029-0.102 μg mL(-1) and 0.095-0.336 μg mL(-1) with a signal to noise ratio of 3:1 and 10:1, respectively. Copyright © 2013 Elsevier Ltd. All rights reserved.

A simple and sensitive vortex-assisted ionic liquid-dispersive microextraction and spectrophotometric determination of selenium in food samples.

Science.gov (United States)

Bağda, Esra; Tüzen, Mustafa

2017-10-01

In the present study, a novel and eco-friendly vortex-assisted ionic liquid-based microextraction method was developed for the determination of selenium in food. The microextraction method is based on the liberation of iodine in the presence of selenium; the liberated iodine reacts with I - to form I 3 - . Anionic I 3 - reacts with cationic crystal violet dye, and the product is extracted into 1-hexyl-3-methylimidazolium hexafluorophosphate phase in the presence of Triton X-114. The proposed method is linear in the range of 2.0-70µgL -1 and has a detection limit of 9.8×10 -2 µgL -1 . Relative standard deviations were 3.67% and 2.89% for the five replicate measurements of 14 and 35µgL -1 Se(IV), respectively. The proposed method was successfully applied to different food samples (NIST SRM 2976 mussel tissue, pepper, ginger, wheat flour, red lentil, traditional soup, cornflour, cornstarch, and garlic) after microwave digestion. Copyright © 2017 Elsevier Ltd. All rights reserved.

Binary liquid-liquid equilibria of aniline-paraffin and furfural-paraffin systems

Energy Technology Data Exchange (ETDEWEB)

Sen, S.C.; Maity, S.; Ganguli, K.; Ray, P. (Calcutta Univ., (India))

1991-12-01

Liquid-liquid-equilibria (L-L-E) of hydrocarbon containing systems are of considerable commercial importance to refineries. But prediction of L-L-E of such systems is extremely difficult owing to the complex nature of the petroleum fluids. For treating such complex mixtures, a continuous component method is appropriate and for representing such liquids, a group contribution model like the UNIFAC is extremely convenient. It is, however, necessary to determine the appropriate group interaction parameters, and also to test the applicability of the UNIFAC method to these cases. Binary liquid-liquid-equilibria data for several aniline-paraffin and furfural-paraffin systems have been taken. These data along with data for other aniline-hydrocarbon and furfural-hydrocarbon systems from literature have been correlated using the UNIFAC model. The UNIFAC group interaction parameters have been found to have a linear temperature dependence. The CH{sub 2} groups in cyclo and non-cyclo paraffins require different interaction parameters. It was also found that a scaling of the combinatorial term is necessary for higher molecular weight hydrocarbons. 13 refs., 12 figs., 5 tabs.

Kinetics of glycoalkaloid hydrolysis and solanidine extraction in liquid-liquid systems

Directory of Open Access Journals (Sweden)

Stanković Mihajlo Z.

2002-01-01

Full Text Available The kinetics of glycoalkaloid hydrolysis and solanidine extraction in Analyzed in this study. obtained from dried and milled potato haulm to to which hydrochlotic acid was added is the first liquid phase, while chloroform trichloroethylene or carbon tetrachlondeisthe second organic, liquid phase. The purpose of this paper was to combine the processes of glycoalkaloid hydrolysis to solanidine and solanidine extraction into one step, and to find the optimal liquid-liquid system for such a process.

Solid-phase extraction combined with dispersive liquid-liquid microextraction and chiral liquid chromatography-tandem mass spectrometry for the simultaneous enantioselective determination of representative proton-pump inhibitors in water samples.

Science.gov (United States)

Zhao, Pengfei; Deng, Miaoduo; Huang, Peiting; Yu, Jia; Guo, Xingjie; Zhao, Longshan

2016-09-01

This report describes, for the first time, the simultaneous enantioselective determination of proton-pump inhibitors (PPIs-omeprazole, lansoprazole, pantoprazole, and rabeprazole) in environmental water matrices based on solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME) and chiral liquid chromatography-tandem mass spectrometry. The optimized results of SPE-DLLME were obtained with PEP-2 column using methanol-acetonitrile (1/1, v/v) as elution solvent, dichloroethane, and acetonitrile as extractant and disperser solvent, respectively. The separation and determination were performed using reversed-phase chromatography on a cellulose chiral stationary phase, a Chiralpak IC (250 mm × 4.6 mm, 5 μm) column, under isocratic conditions at 0.6 mL min(-1) flow rate. The analytes were detected in multiple reaction monitoring (MRM) mode by triple quadrupole mass spectrometry. Isotopically labeled internal standards were used to compensate matrix interferences. The method provided enrichment factors of around 500. Under optimal conditions, the mean recoveries for all eight enantiomers from the water samples were 89.3-107.3 % with 0.9-10.3 % intra-day RSD and 2.3-8.1 % inter-day RSD at 20 and 100 ng L(-1) levels. Correlation coefficients (r (2)) ≥ 0.999 were achieved for all enantiomers within the range of 2-500 μg L(-1). The method detection and quantification limits were at very low levels, within the range of 0.67-2.29 ng L(-1) and 2.54-8.68 ng L(-1), respectively. This method was successfully applied to the determination of the concentrations and enantiomeric fractions of the targeted analytes in wastewater and river water, making it applicable to the assessment of the enantiomeric fate of PPIs in the environment. Graphical Abstract Simultaneous enantioselective determination of representative proton-pump inhibitors in water samples.

Ionic liquid-based single-drop microextraction followed by liquid chromatography-ultraviolet spectrophotometry detection to determine typical UV filters in surface water samples.

Science.gov (United States)

Vidal, Lorena; Chisvert, Alberto; Canals, Antonio; Salvador, Amparo

2010-04-15

A user-friendly and inexpensive ionic liquid-based single-drop microextraction (IL-SDME) procedure has been developed to preconcentrate trace amounts of six typical UV filters extensively used in cosmetic products (i.e., 2-hydroxy-4-methoxybenzophenone, isoamyl 4-methoxycinnamate, 3-(4'-methylbenzylidene)camphor, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-methoxycinnamate) from surface water samples prior to analysis by liquid chromatography-ultraviolet spectrophotometry detection (LC-UV). A two-stage multivariate optimization approach was developed by means of a Plackett-Burman design for screening and selecting the significant variables involved in the SDME procedure, which were later optimized by means of a circumscribed central composite design. The studied variables were drop volume, sample volume, agitation speed, ionic strength, extraction time and ethanol quantity. Owing to particularities, ionic liquid type and pH of the sample were optimized separately. Under optimized experimental conditions (i.e., 10 microL of 1-hexyl-3-methylimidazolium hexafluorophosphate, 20 mL of sample containing 1% (v/v) ethanol and NaCl free adjusted to pH 2, 37 min extraction time and 1300 rpm agitation speed) enrichment factors up to ca. 100-fold were obtained depending on the target analyte. The method gave good levels of repeatability with relative standard deviations varying between 2.8 and 8.8% (n=6). Limits of detection were found in the low microg L(-1) range, varying between 0.06 and 3.0 microg L(-1) depending on the target analyte. Recovery studies from different types of surface water samples collected during the winter period, which were analysed and confirmed free of all target analytes, ranged between 92 and 115%, showing that the matrix had a negligible effect upon extraction. Finally, the proposed method was applied to the analysis of different water samples (taken from two beaches, two swimming pools and a

PEP liquid level system

International Nuclear Information System (INIS)

Lauritzen, T.; Sah, R.C.

1981-03-01

A liquid level system has been installed in the accelerator housing of the PEP storage ring. This instrument spans the entire 2.2 km circumference of the PEP project, and over one hundred readouts provide reference elevations which are used for the accurate alignment of accelerator components. The liquid level has proven to be extremely precise (+-0.10 mm) and quick to use, and it has contributed to the accurate alignment of PEP before beam turn-on. Since the liquid level readouts are rigidly attached to the accelerator housing, the liquid level has been a convenient means to monitor the settling of the accelerator housing

Dual liquid and gas chromatograph system

Science.gov (United States)

Gay, D.D.

A chromatographic system is described that utilizes one detection system for gas chromatographic and micro-liquid chromatographic determinations. The detection system is a direct-current, atmospheric-pressure, helium plasma emission spectrometer. The detector utilizes a nontransparent plasma source unit which contains the plasma region and two side-arms which receive effluents from the micro-liquid chromatograph and the gas chromatograph. The dual nature of this chromatographic system offers: (1) extreme flexibility in the samples to be examined; (2) extreme low sensitivity; (3) element selectivity; (4) long-term stability; (5) direct correlation of data from the liquid and gas samples; (6) simpler operation than with individual liquid and gas chromatographs, each with different detection systems; and (7) cheaper than a commercial liquid chromatograph and a gas chromatograph.

Liquid-liquid phase transition and glass transition in a monoatomic model system.

Science.gov (United States)

Xu, Limei; Buldyrev, Sergey V; Giovambattista, Nicolas; Stanley, H Eugene

2010-01-01

We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses.

Liquid-Liquid Phase Transition and Glass Transition in a Monoatomic Model System

Directory of Open Access Journals (Sweden)

Nicolas Giovambattista

2010-12-01

Full Text Available We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses.

Development of dispersive liquid-liquid microextraction technique using ternary solvents mixture followed by heating for the rapid and sensitive analysis of phthalate esters and di(2-ethylhexyl) adipate.

Science.gov (United States)

Farajzadeh, Mir Ali; Khoshmaram, Leila

2015-01-30

In this study, for the first time, a dispersive liquid-liquid microextraction technique using a ternary solvent mixture is reported. In order to extract five phthalate esters and di(2-ethylhexyl) adipate with different polarities from aqueous samples, a simplex centroid experimental design method was used to select an optimal mixture of ternary solvents prior to gas chromatographyflame ionization detection. In this work, dimethyl formamide as a disperser solvent containing dichloromethane, chloroform, and carbon tetrachloride as a ternary extraction solvent mixture is injected into sample solution and a cloudy solution is formed. After centrifuging, 250μL of the obtained sedimented phase was transferred into another tube and 5μL DMF was added to it. Then, the tube was heated in a water bath at 75°C for 5min in order to evaporate the main portion of the extraction solvents. Finally, 2μL of the remained phase is injected into the separation system. Under the optimum extraction conditions, the method shows wide linear ranges and low limits of detection and quantification between 0.03-0.15 and 0.09-0.55μgL(-1), respectively. Enrichment factors and extraction recoveries are in the ranges of 980-4500 and 20-90%, respectively. The method is successfully applied in the determination of the target analytes in mineral water, soda, lemon juice, vinegar, dough, and yogurt packed in plastic packages. Copyright © 2014 Elsevier B.V. All rights reserved.

Ultrasound assisted extraction combined with dispersive liquid-liquid microextraction (US-DLLME)-a fast new approach to measure phthalate metabolites in nails.

Science.gov (United States)

Alves, Andreia; Vanermen, Guido; Covaci, Adrian; Voorspoels, Stefan

2016-09-01

A new, fast, and environmentally friendly method based on ultrasound assisted extraction combined with dispersive liquid-liquid microextraction (US-DLLME) was developed and optimized for assessing the levels of seven phthalate metabolites (including the mono(ethyl hexyl) phthalate (MEHP), mono(2-ethyl-5-hydroxyhexyl) phthalate (5-OH-MEHP), mono(2-ethyl-5-oxohexyl) phthalate (5-oxo-MEHP), mono-n-butyl phthalate (MnBP), mono-isobutyl phthalate (MiBP), monoethyl phthalate (MEP), and mono-benzyl phthalate (MBzP)) in human nails by UPLC-MS/MS. The optimization of the US-DLLME method was performed using a Taguchi combinatorial design (L9 array). Several parameters such as extraction solvent, solvent volume, extraction time, acid, acid concentration, and vortex time were studied. The optimal extraction conditions achieved were 180 μL of trichloroethylene (extraction solvent), 2 mL trifluoroacetic acid in methanol (2 M), 2 h extraction and 3 min vortex time. The optimized method had a good precision (6-17 %). The accuracy ranged from 79 to 108 % and the limit of method quantification (LOQm) was below 14 ng/g for all compounds. The developed US-DLLME method was applied to determine the target metabolites in 10 Belgian individuals. Levels of the analytes measured in nails ranged between <12 and 7982 ng/g. The MEHP, MBP isomers, and MEP were the major metabolites and detected in every sample. Miniaturization (low volumes of organic solvents used), low costs, speed, and simplicity are the main advantages of this US-DLLME based method. Graphical Abstract Extraction and phase separation of the US-DLLME procedure.

Novel proton-type ionic liquid doped polyaniline for the headspace solid-phase microextraction of amines

Energy Technology Data Exchange (ETDEWEB)

Ai, Youhong [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials & Key Laboratory for the Synthesis and Application of Organic Functional Molecules (Ministry of Education), College of Chemistry & Chemical Engineering, Hubei University, Wuhan 430062 (China); Zhao, Faqiong [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Zeng, Baizhao, E-mail: bzzeng@whu.edu.cn [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China)

2015-06-23

Graphical abstract: The novel proton-type ionic liquid (1-sulfobutyl-3-methylimidazolium hydrosulfate) doped polyaniline coating showed granular porous nanostructure and it had high self-EF values and extraction efficiency for amines. - Highlights: • A proton-type ionic liquid-doped polyaniline was fabricated by electrodeposition. • It showed porous granular nanostructure and had large specific surface. • It had high extraction capacity to aromatic amines. • A reasonable self-enrichment factor of SPME fiber has been proposed. - Abstract: A novel proton-type ionic liquid doped polyaniline (HIL-doped PANI) coating was presented, which was prepared on a stainless steel wire by electrodeposition in an aqueous solution containing aniline and 1-sulfobutyl-3-methylimidazolium hydrosulfate. The HIL-doped PANI coating showed granular nanostructure and had large specific surface. When it was applied to the headspace solid-phase microextraction of several amines (i.e., aniline, N-methylaniline, 3-methylaniline, 2-chloroaniline and 3-chloroaniline), it showed high extraction efficiency. The enrichment factors were 191.8–343.9 for different amines, much higher than those of common PANI and commercial polydimethylsiloxane/divinylbenzene coatings. Coupled with gas chromatographic analysis, the linear ranges were 0.097–100 μg/L with correlation coefficients above 0.9942, and the detection limits were 0.012–0.048 μg/L (S/N = 3) for different amines. The relative standard deviations (RSD) were smaller than 8.1% for five successive measurements with single fiber and the fiber-to-fiber RSDs were 8.6–13.8% (n = 5) for these amines. The proposed method was successfully applied to the extraction and determination of amines in organic waste water samples, and the recoveries were 78.3–112.8% for different analytes.

Novel proton-type ionic liquid doped polyaniline for the headspace solid-phase microextraction of amines

International Nuclear Information System (INIS)

Ai, Youhong; Zhao, Faqiong; Zeng, Baizhao

2015-01-01

Graphical abstract: The novel proton-type ionic liquid (1-sulfobutyl-3-methylimidazolium hydrosulfate) doped polyaniline coating showed granular porous nanostructure and it had high self-EF values and extraction efficiency for amines. - Highlights: • A proton-type ionic liquid-doped polyaniline was fabricated by electrodeposition. • It showed porous granular nanostructure and had large specific surface. • It had high extraction capacity to aromatic amines. • A reasonable self-enrichment factor of SPME fiber has been proposed. - Abstract: A novel proton-type ionic liquid doped polyaniline (HIL-doped PANI) coating was presented, which was prepared on a stainless steel wire by electrodeposition in an aqueous solution containing aniline and 1-sulfobutyl-3-methylimidazolium hydrosulfate. The HIL-doped PANI coating showed granular nanostructure and had large specific surface. When it was applied to the headspace solid-phase microextraction of several amines (i.e., aniline, N-methylaniline, 3-methylaniline, 2-chloroaniline and 3-chloroaniline), it showed high extraction efficiency. The enrichment factors were 191.8–343.9 for different amines, much higher than those of common PANI and commercial polydimethylsiloxane/divinylbenzene coatings. Coupled with gas chromatographic analysis, the linear ranges were 0.097–100 μg/L with correlation coefficients above 0.9942, and the detection limits were 0.012–0.048 μg/L (S/N = 3) for different amines. The relative standard deviations (RSD) were smaller than 8.1% for five successive measurements with single fiber and the fiber-to-fiber RSDs were 8.6–13.8% (n = 5) for these amines. The proposed method was successfully applied to the extraction and determination of amines in organic waste water samples, and the recoveries were 78.3–112.8% for different analytes

46 CFR 128.450 - Liquid-mud systems.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Liquid-mud systems. 128.450 Section 128.450 Shipping...: EQUIPMENT AND SYSTEMS Design Requirements for Specific Systems § 128.450 Liquid-mud systems. (a) Liquid-mud... this chapter. (b) Tanks for oil-based liquid mud must be fitted with tank vents equipped with flame...

Ionic liquid-based single-drop microextraction/gas chromatographic/mass spectrometric determination of benzene, toluene, ethylbenzene and xylene isomers in waters.

Science.gov (United States)

Aguilera-Herrador, Eva; Lucena, Rafael; Cárdenas, Soledad; Valcárcel, Miguel

2008-08-01

The direct coupling between ionic liquid-based single-drop microextraction and gas chromatography/mass spectrometry is proposed for the rapid and simple determination of benzene, toluene, ethylbenzene and xylenes isomers (BTEX) in water samples. The extraction procedure exploits not only the high affinity of the selected ionic liquid (1-methyl-3-octyl-imidazolium hexaflourophosphate) to these aromatic compounds but also its special properties like viscosity, low vapour pressure and immiscibility with water. All the variables involved in the extraction process have been studied in depth. The developed method allows the determination of these single-ring compounds in water under the reference concentration level fixed by the international legislation. In this case, limits of detection were in the range 20 ng L(-1) (obtained for benzene) and 91 ng L(-1) (for o-xylene). The repeatability of the proposed method, expressed as RSD (n=5), varied between 3.0% (o-xylene) and 5.2% (toluene).

Detection based on rainbow refractometry of droplet sphericity in liquid-liquid systems.

Science.gov (United States)

Lohner, H; Lehmann, P; Bauckhage, K

1999-03-01

The shape of droplets in liquid-liquid systems influences their mass and momentum transfer processes. The deviation from sphericity of rising droplets in liquid-liquid systems was investigated for different droplet sizes. Rainbow refractometry permits one to test, in this case, whether the use of laser-optical particle sizing will be correct or faulty. Since the assumption of spherical particle geometry is a general basis of laser-optical particle-sizing techniques such as rainbow refractometry or phase Doppler anemometry, deviation from the spherical shape results in a measuring error. A sphericity check based on rainbow refractometry is introduced.

Solid-Liquid and Liquid-Liquid Equilibrium in the Formamide-Acetophenone System.

Czech Academy of Sciences Publication Activity Database

Malijevská, I.; Sedláková, Zuzana; Řehák, K.; Vrbka, P.

2006-01-01

Roč. 71, 9 (2006) , s. 1350-1358 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40720504 Keywords : solid-liquid equilibria * liquid-liquid equilibria * metastable Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.881, year: 2006

Liquid-Liquid Extraction in Systems Containing Butanol and Ionic Liquids – A Review

OpenAIRE

Kubiczek Artur; Kamiński Władysław

2017-01-01

Room-temperature ionic liquids (RTILs) are a moderately new class of liquid substances that are characterized by a great variety of possible anion-cation combinations giving each of them different properties. For this reason, they have been termed as designer solvents and, as such, they are particularly promising for liquid-liquid extraction, which has been quite intensely studied over the last decade. This paper concentrates on the recent liquid-liquid extraction studies involving ionic liqu...

A highly selective dispersive liquid-liquid microextraction approach based on the unique fluorous affinity for the extraction and detection of per- and polyfluoroalkyl substances coupled with high performance liquid chromatography tandem-mass spectrometry.

Science.gov (United States)

Wang, Juan; Shi, Yali; Cai, Yaqi

2018-04-06

In the present study, a highly selective fluorous affinity-based dispersive liquid-liquid microextraction (DLLME) technique was developed for the extraction and analysis of per- and polyfluoroalkyl substances (PFASs) followed by high performance liquid chromatography tandem-mass spectrometry. Perfluoro-tert-butanol with multiple C-F bonds was chosen as the extraction solvent, which was injected into the aqueous samples with a dispersive solvent (acetonitrile) in a 120:800 (μL, v/v) mixture for PFASs enrichment. The fluorous affinity-based extraction mechanism was confirmed by the significantly higher extraction recoveries for PFASs containing multiple fluorine atoms than those for compounds with fewer or no fluorine atoms. The extraction recoveries of medium and long-chain PFASs (CF 2  > 5) exceeded 70%, except perfluoroheptanoic acid, while those of short-chain PFASs were lower than 50%, implying that the proposed DLLME may not be suitable for their extraction due to weak fluorous affinity. This highly fluoroselective DLLME technique can greatly decrease the matrix effect that occurs in mass spectrometry detection when applied to the analysis of urine samples. Under the optimum conditions, the relative recoveries of PFASs with CF 2  > 5 ranged from 80.6-121.4% for tap water, river water and urine samples spiked with concentrations of 10, 50 and 100 ng/L. The method limits of quantification for PFASs in water and urine samples were in the range of 0.6-8.7 ng/L. Furthermore, comparable concentrations of PFASs were obtained via DLLME and solid-phase extraction, confirming that the developed DLLME technique is a promising method for the extraction of PFASs in real samples. Copyright © 2018 Elsevier B.V. All rights reserved.

In situ derivatization-ultrasound-assisted dispersive liquid-liquid microextraction for the determination of neurotransmitters in Parkinson's rat brain microdialysates by ultra high performance liquid chromatography-tandem mass spectrometry.

Science.gov (United States)

He, Yongrui; Zhao, Xian-En; Zhu, Shuyun; Wei, Na; Sun, Jing; Zhou, Yubi; Liu, Shu; Liu, Zhiqiang; Chen, Guang; Suo, Yourui; You, Jinmao

2016-08-05

Simultaneous monitoring of several neurotransmitters (NTs) linked to Parkinson's disease (PD) has important scientific significance for PD related pathology, pharmacology and drug screening. A new simple, fast and sensitive analytical method, based on in situ derivatization-ultrasound-assisted dispersive liquid-liquid microextraction (in situ DUADLLME) in a single step, has been proposed for the quantitative determination of catecholamines and their biosynthesis precursors and metabolites in rat brain microdialysates. The method involved the rapid injection of the mixture of low toxic bromobenzene (extractant) and acetonitrile (dispersant), which containing commercial Lissamine rhodamine B sulfonyl chloride (LRSC) as derivatization reagent, into the aqueous phase of sample and buffer, and the following in situ DUADLLME procedure. After centrifugation, 50μL of the sedimented phase (bromobenzene) was directly injected for ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) detection in multiple reaction monitoring (MRM) mode. This interesting combination brought the advantages of speediness, simpleness, low matrix effects and high sensitivity in an effective way. Parameters of in situ DUADLLME and UHPLC-MS/MS conditions were all optimized in detail. The optimum conditions of in situ DUADLLME were found to be 30μL of microdialysates, 150μL of acetonitrile containing LRSC, 50μL of bromobenzene and 800μL of NaHCO3-Na2CO3 buffer (pH 10.5) for 3.0min at 37°C. Under the optimized conditions, good linearity was observed with LODs (S/N>3) and LOQs (S/N>10) of LRSC derivatized-NTs in the range of 0.002-0.004 and 0.007-0.015 nmol/L, respectively. It also brought good precision (3.2-12.8%, peak area CVs%), accuracy (94.2-108.6%), recovery (94.5-105.5%) and stability (3.8-8.1%, peak area CVs%) results. Moreover, LRSC derivatization significantly improved chromatographic resolution and MS detection sensitivity of NTs when compared with the

Systemic Liquidity Shocks and Banking Sector Liquidity Characteristics on the Eve of Liquidity Coverage Ratio Application - The Case of the Czech Republic1

Directory of Open Access Journals (Sweden)

Brůna Karel

2016-01-01

Full Text Available The paper contains an analysis of the economic and regulatory concept of bank liquidity in the context of systemic liquidity shock. A formal model analysis shows that the application of liquidity coverage ratio (LCR based on Basel III will lead to a significant adaptation of banks liquidity management. LCR causes a change in bank’s liquidity allocation and funding to be less effective and more costly and restrictive for providing credits comparing with economic determinants. It is demonstrated that the application of LCR underestimates actual liquidity position of a bank and leads to allocation ineffectiveness. The empirical part contains simulation of impacts of systemic liquidity shock on the banking sector’s ability to withstand the unfavourable credit shock while solvency is maintained. The results confirm the robustness of the Czech banking system ensuing from the systemic surplus of liquidity, high volume of bank capital and its high profitability. The estimations of the VAR model show that the relations between liquidity characteristics of banks, sources of aggregate liquidity shock, interbank market illiquidity and the credit facilities of the Czech National Bank are relatively weak, supporting the conclusion that the banks face liquidity shocks of non-persistent character.

Novel capsule phase microextraction in combination with liquid chromatography-tandem mass spectrometry for determining personal care products in environmental water.

Science.gov (United States)

Lakade, Sameer S; Borrull, Francesc; Furton, Kenneth G; Kabir, Abuzar; Marcé, Rosa Maria; Fontanals, Núria

2018-05-01

A novel sample preparation technique named capsule phase microextraction (CPME) is presented here. The technique utilizes a miniaturized microextraction capsule (MEC) as the extraction medium. The MEC consists of two conjoined porous tubular polypropylene membranes, one of which encapsulates the sorbent through sol-gel technology, while the other encapsulates a magnetic metal rod. As such, MEC integrates both the extraction and stirring mechanisms into a single device. The aim of this article is to demonstrate the application potential of CPME as sample preparation technique for the extraction of a group of personal care products (PCPs) from water matrices. Among the different sol-gel sorbent materials (UCON ® , poly(caprolactone-dimethylsiloxane-caprolactone) (PCAP-DMS-CAP) and Carbowax 20M (CW-20M)) evaluated, CW-20M MEC demonstrated the best extraction performance for the selected PCPs. The extraction conditions for sol-gel CW-20M MEC were optimized, including sample pH, stirring speed, addition of salt, extraction time, sample volume, liquid desorption solvent, and time. Under the optimal conditions, sol-gel CW-20M MEC provided recoveries, ranging between 47 and 90% for all analytes, except for ethylparaben, which showed a recovery of 26%. The method based on CPME with sol-gel CW-20M followed by liquid chromatography-tandem mass spectrometry was developed and validated for the extraction of PCPs from river water and effluent wastewater samples. When analyzing different environmental samples, some analytes such as 2,4-dihydroxybenzophenone, 2,2-dihydroxy-4-4 methoxybenzophenone and 3-benzophenone were found at low ng L -1 .

(Liquid + liquid), (solid + liquid), and (solid + liquid + liquid) equilibria of systems containing cyclic ether (tetrahydrofuran or 1,3-dioxolane), water, and a biological buffer MOPS

International Nuclear Information System (INIS)

Altway, Saidah; Taha, Mohamed; Lee, Ming-Jer

2015-01-01

Graphical abstract: - Highlights: • MOPS buffer induced liquid phase splitting for mixtures of water with THF or 1,3-dioxolane. • Phase boundaries of LLE, SLE, and SLLE were determined experimentally. • Tie-lines at LLE and at SLLE were also measured. • Phase diagrams of MOPS + water + THF or 1,3-dioxolane are prepared. • LLE tie-line data are correlated satisfactorily with the NRTL model. - Abstract: Two liquid phases were formed as the addition of a certain amount of biological buffer 3-(N-morpholino)propane sulfonic acid (MOPS) in the aqueous solutions of tetrahydrofuran (THF) or 1,3-dioxolane. To evaluate the feasibility of recovering the cyclic ethers from their aqueous solutions with the aid of MOPS, we determined experimentally the phase diagrams of the ternary systems of {cyclic ether (THF or 1,3-dioxolane) + water + MOPS} at T = 298.15 K under atmospheric pressure. In this study, the solubility data of MOPS in water and in the mixed solvents of water/cyclic ethers were obtained from the results of a series of density measurements, while the (liquid + liquid) and the (solid + liquid + liquid) phase boundaries were determined by visually inspection. Additionally, the tie-line results for (liquid + liquid) equilibrium (LLE) and for (solid + liquid + liquid) equilibrium (SLLE) were measured using an analytical method. The reliability of the experimental LLE tie-line results data was validated by using the Othmer–Tobias correlation. These LLE tie-line values were correlated well with the NRTL model. The phase diagrams obtained from this study reveal that MOPS is a feasible green auxiliary agent to recover the cyclic ethers from their aqueous solutions, especially for 1,3-dioxolane

Polyol-enhanced dispersive liquid-liquid microextraction coupled with gas chromatography and nitrogen phosphorous detection for the determination of organophosphorus pesticides from aqueous samples, fruit juices, and vegetables.

Science.gov (United States)

Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza; Alizadeh Nabil, Ali Akbar

2015-12-01

Polyol-enhanced dispersive liquid-liquid microextraction has been proposed for the extraction and preconcentration of some organophosphorus pesticides from different samples. In the present study, a high volume of an aqueous phase containing a polyol (sorbitol) is prepared and then a disperser solvent along with an extraction solvent is rapidly injected into it. Sorbitol showed the best results and it was more effective on the extraction recoveries of the analytes than inorganic salts such as sodium chloride, potassium chloride, and sodium sulfate. Under the optimum extraction conditions, the method showed low limits of detection and quantification within the ranges of 12-56 and 44-162 pg/mL, respectively. Enrichment factors and extraction recoveries were in the ranges of 2799-3033 and 84-92%, respectively. The method precision was evaluated at a concentration of 10 ng/mL of each analyte, and relative standard deviations were found to be less than 5.9% for intraday (n = 6) and less than 7.8% for interday (n = 4). Finally, some aqueous samples were successfully analyzed using the proposed method and four analytes (diazinon, dimethoate, chlorpyrifos, and phosalone) were determined, some of them at ng/mL level. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of an in situ solvent formation microextraction and preconcentration method based on ionic liquids for the determination of trace cobalt (II in water samples by flame atomic absorption spectrometry

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Mohammad Reza Jamali

2017-02-01

Full Text Available A simple in situ solvent formation microextraction (ISFME methodology based on the application of ionic liquid (IL as an extractant solvent and sodium hexafluorophosphate (NaPF6 as an ion-pairing agent was proposed for the preconcentration of the trace levels of cobalt ions. In this method cobalt was complexed with 2-(5-bromo-2-pyridylazo-5-diethylaminophenol (5-Br-PADAP and extracted into an ionic liquid phase. After phase separation, the enriched analyte in the final solution is determined by flame atomic absorption spectrometry (FAAS. Some effective factors that influence the microextraction efficiency were investigated and optimized. Under the optimum experimental conditions, the limit of detection and the enrichment factor were 0.97 μg L−1 and 50, respectively. The relative standard deviation (R.S.D. was obtained as 2.4%. The proposed method was assessed through the analysis of certified reference water and recovery experiments.

Determination of multi-class herbicides in soil by liquid-solid extraction coupled with headspace solid phase microextraction method

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Đurović-Pejčev Rada

2016-01-01

Full Text Available A method is described for simultaneous determination of five herbicides (metribuzin, acetochlor, clomazone, oxyfluorfen and dimethenamid belonging to different pesticides groups in soil samples. Developed headspace solid phase microextraction method (HS-SPME in combination with liquid-solid sample preparation (LS was optimized and applied in the analysis of some agricultural samples. Optimization of microextraction conditions, such as temperature, extraction time and sodium chloride (NaCl content was perfor-med using 100 μm polydimethyl-siloxane (PDMS fiber. The extraction effi-ciencies of methanol, methanol:acetone=1:1 and methanol:acetone:hexane= =2:2:1 and the optimum number of extraction steps during the sample prepa-ration, were tested, as well. Gas chromatography-mass spectrometry (GC-MS was used for detection and quantification, obtaining relative standard deviation (RSD below 13%, and recovery values higher than 83% for multiple analyses of soil samples fortified at 30 μg kg-1 of each herbicide. Limits of detection (LOD were less than 1.2 μg kg-1 for all the studied herbicides. [Projekat Ministarstva nauke Republike Srbije, br. TR31043 i br. III43005

Ternary (liquid + liquid) equilibria of {trifluorotris(perfluoroethyl)phosphate based ionic liquids + thiophene + heptane}

International Nuclear Information System (INIS)

Marciniak, Andrzej; Królikowski, Marek

2012-01-01

Highlights: ► Ternary (liquid + liquid) equilibria for 3 ionic liquid + thiophene + heptane systems. ► The influence of ionic liquid structure on phase diagrams is discussed. ► High selectivity for separation of heptane/thiophene is observed. - Abstract: Ternary (liquid + liquid) equilibria for three systems containing ionic liquids {(4-(2-methoxyethyl)-4-methylmorpholinium trifluorotris(perfluoroethyl)phosphate, 1-(2-methoxyethyl)-1-methylpiperidinium trifluorotris(perfluoroethyl)phosphate, 1-(2-methoxyethyl)-1-methylpyrrolidinium trifluorotris(perfluoroethyl)phosphate) + thiophene + heptane} have been determined at T = 298.15 K. All systems showed high solubility of thiophene in the ionic liquid and low solubility of heptane. The solute distribution coefficient and the selectivity were calculated for all systems. High values of selectivity were obtained. The experimental results have been correlated using NRTL model. The influence of ionic liquid structure on phase equilibria is discussed.

Sensitive and simple determination of zwitterionic morphine in human urine based on liquid-liquid micro-extraction coupled with surface-enhanced Raman spectroscopy.

Science.gov (United States)

Yu, Borong; Cao, Chentai; Li, Pan; Mao, Mei; Xie, Qiwen; Yang, Liangbao

2018-08-15

Morphine, a kind of illicit drugs, is also one of the main heroin metabolites. In consideration of a noninvasive way to monitor and identify drug abuse during forensic cases, the urine samples are usually detected. Here, colloidal gold nanorods (Au NRs) were introduced to act as active substrate, because of the strong optical extinction and spectral tunability of the longitudinal surface plasmon resonance (SPR). Thus, well surface-enhanced Raman spectra of morphine even at low concentrations could be obtained by portable Raman spectrometer. For the complex matrix environment of urine, liquid-liquid micro-extraction (LLME), a simple and inexpensive pretreatment, was employed to avoid the interferences. And then, the coupled surface-enhanced Raman spectroscopy (SERS) can give full play to the advantages of high sensitivity and unique spectroscopic fingerprint. According to the zwitterionic structure and physicochemical parameters of morphine molecules, the pH value of urine sample was adjusted to about 9 by buffer solution (KOH/NaB 4 O 7 ) and the mixture of chloroform and isopropyl alcohol (V/V=9:1) was chosen as extractant. Moreover, such pretreatment was proved to be appropriate for separation and concentration of morphine from urine. The developed LLME-SERS method could provide a detection limit less than 1 ppm in the human urine environment and the whole process of detection just needed take 5-6 min. What's more, the results of urine samples from heroin users exhibited application value of the proposed technique. The excellent performance makes it promising to become a rapid, reliable, and on-spot analyzer, especially for public safety and healthcare. Copyright © 2018 Elsevier B.V. All rights reserved.

A novel polythiophene – ionic liquid modified clay composite solid phase microextraction fiber: Preparation, characterization and application to pesticide analysis

International Nuclear Information System (INIS)

Pelit, Füsun Okçu; Pelit, Levent; Dizdaş, Tuğberk Nail; Aftafa, Can; Ertaş, Hasan; Yalçınkaya, E.E.; Türkmen, Hayati; Ertaş, F.N.

2015-01-01

Highlights: • A novel polythiophene – ionic liquid modified clay surface has been prepared. • Polymerization was performed electrochemically on a stainless steel wire. • This material was used as a SPME fiber in head space mode. • This new SPME fiber was applied for analysis of pesticides in juice samples. • Fiber adsorption properties were improved by modification of ionic liquids. - Abstract: This report comprises the novel usage of polythiophene – ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett–Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box–Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002–0.667 ng mL −1 . Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues

A novel polythiophene – ionic liquid modified clay composite solid phase microextraction fiber: Preparation, characterization and application to pesticide analysis

Energy Technology Data Exchange (ETDEWEB)

Pelit, Füsun Okçu, E-mail: fusun.okcu@ege.edu.tr; Pelit, Levent; Dizdaş, Tuğberk Nail; Aftafa, Can; Ertaş, Hasan; Yalçınkaya, E.E.; Türkmen, Hayati; Ertaş, F.N.

2015-02-15

Highlights: • A novel polythiophene – ionic liquid modified clay surface has been prepared. • Polymerization was performed electrochemically on a stainless steel wire. • This material was used as a SPME fiber in head space mode. • This new SPME fiber was applied for analysis of pesticides in juice samples. • Fiber adsorption properties were improved by modification of ionic liquids. - Abstract: This report comprises the novel usage of polythiophene – ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett–Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box–Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002–0.667 ng mL{sup −1}. Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues.

Polymeric ionic liquid-based portable tip microextraction device for on-site sample preparation of water samples.

Science.gov (United States)

Chen, Lei; Pei, Junxian; Huang, Xiaojia; Lu, Min

2018-06-05

On-site sample preparation is highly desired because it avoids the transportation of large-volume samples and ensures the accuracy of the analytical results. In this work, a portable prototype of tip microextraction device (TMD) was designed and developed for on-site sample pretreatment. The assembly procedure of TMD is quite simple. Firstly, polymeric ionic liquid (PIL)-based adsorbent was in-situ prepared in a pipette tip. After that, the tip was connected with a syringe which was driven by a bidirectional motor. The flow rates in adsorption and desorption steps were controlled accurately by the motor. To evaluate the practicability of the developed device, the TMD was used to on-site sample preparation of waters and combined with high-performance liquid chromatography with diode array detection to measure trace estrogens in water samples. Under the most favorable conditions, the limits of detection (LODs, S/N = 3) for the target analytes were in the range of 4.9-22 ng/L, with good coefficients of determination. Confirmatory study well evidences that the extraction performance of TMD is comparable to that of the traditional laboratory solid-phase extraction process, but the proposed TMD is more simple and convenient. At the same time, the TMD avoids complicated sampling and transferring steps of large-volume water samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Ultrasonic-energy enhance the ionic liquid-based dual microextraction to preconcentrate the lead in ground and stored rain water samples as compared to conventional shaking method.

Science.gov (United States)

Nizamani, Sooraj; Kazi, Tasneem G; Afridi, Hassan I

2018-01-01

An efficient preconcentration technique based on ultrasonic-assisted ionic liquid-based dual microextraction (UA-ILDµE) method has been developed to preconcentrate the lead (Pb +2 ) in ground and stored rain water. In the current proposed method, Pb +2 was complexed with a chelating agent (dithizone), whereas an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) was used for extraction purpose. The ultrasonic irradiation and electrical shaking system were applied to enhance the dispersion and extraction of Pb +2 complex in aqueous samples. For second phase, dual microextraction (DµE phase), the enriched Pb +2 complex in ionic liquid, extracted back into the acidic aqueous solution and finally determined by flame atomic absorption spectrometry. Some major analytical parameters that influenced the extraction efficiency of developed method, such as pH, concentration of ligand, volume of ionic liquid and samples, time of shaking in thermostatic electrical shaker and ultrasonic bath, effect of back extracting HNO 3 volume, matrix effect, centrifugation time and rate were optimized. At the sample volume of 25mL, the calculated preconcentration factor was 62.2. The limit of detection of proposed procedure for Pb +2 ions was found to be 0.54μgL -1 . The validation of developed method was performed by the analysis of certified sample of water SRM 1643e and standard addition method in a real water sample. The extraction recovery of Pb +2 was enhanced≥2% with shaking time of 80s in ultrasonic bath as compared to used thermostatic electrical shaker, where for optimum recovery up to 10min was required. The developed procedure was successfully used for the enrichment of Pb +2 in ground and stored rain water (surface water) samples of an endemic region of Pakistan. The resulted data indicated that the ground water samples were highly contaminated with Pb +2 , while some of the surface water samples were also have higher values of Pb +2 than permissible limit of

Experimental measurement and prediction of (liquid + liquid + liquid) equilibrium for the system (n-hexadecane + water + triacetin)

International Nuclear Information System (INIS)

Revellame, Emmanuel D.; Holmes, William E.; Hernandez, Rafael; French, W. Todd; Forks, Allison; Ashe, Taylor; Estévez, L. Antonio

2016-01-01

Highlights: • Phase diagram for the system n-hexadecane + water + triacetin was established at T = 296.15 K and atmospheric pressure (0.1 MPa). • Both NRTL and UNIQUAC activity coefficient model adequately predicts the LLLE of the ternary system. • The phase equilibrium of the system is predominantly dictated by enthalpic contributions to the activity coefficient. - Abstract: The phase diagram for the ternary system containing (n-hexadecane + water + triacetin) was obtained experimentally at T = 296.15 K and ambient pressure. Results show that this system is of Type 3 according to the Treybal classification of ternary system. NRTL and UNIQUAC interaction parameters were calculated from binary phase equilibrium values and were used to predict the (liquid + liquid + liquid) equilibrium (LLLE) region. Results indicated that both NRTL and UNIQUAC could predict the LLLE region of the system with similar precision as indicated by the comparable standard deviations. This indicates that the enthalpic contribution to the activity coefficient is predominant and entropic contributions can be neglected.

Dispersive solid phase micro-extraction of mercury(II from environmental water and vegetable samples with ionic liquid modified graphene oxide nanoparticles

Directory of Open Access Journals (Sweden)

Nasrollahpour Atefeh

2017-01-01

Full Text Available A new dispersive solid phase micro-extraction (dispersive-SPME method for separation and preconcentration of mercury(II using ionic liquid modified magnetic reduced graphene oxide (IL-MrGO nanoparticles, prior to the measurement by cold vapour atomic absorption spectrometry (CV-AAS has been developed. The IL-MrGO composite was characterized by Brunauer– Emmett–Teller method (BET for adsorption-desorption measurement, thermogravimetric analysis (TGA, powder X-ray diffraction (XRD and X-ray photoelectron spectroscopy (XPS. The method is based on the sorption of mercury( II on IL-MrGO nanoparticles due to electrostatic interaction and complex formation of ionic liquid part of IL-MrGO with mercury(II. The effect of experimental parameters for preconcentration of mercury(II, such as solution type, concentration and volume of the eluent, pH, time of the sorption and desorption, amount of the sorbent and coexisting ion concentration have been optimized. Under the optimized conditions, a linear response was obtained in the concentration range of 0.08–10 ng mL-1 with a determination coefficient of 0.9995. The limit of detection (LOD of the method at a signal to noise ratio of 3 was 0.01 ng mL-1. Intra-day and inter-day precisions were obtained equal to 3.4 and 4.5 %, respectively. The dispersive solid phase micro-extraction of mercury(II on IL-MrGO nanoparticles coupled with cold vapour atomic absorption spectrometry was successfully used for extraction and determination of mercury(II in water and vegetable samples.

Combination of in situ metathesis reaction with a novel "magnetic effervescent tablet-assisted ionic liquid dispersive microextraction" for the determination of endogenous steroids in human fluids.

Science.gov (United States)

Wu, Jia; Xu, Zilin; Pan, Yixuan; Shi, Yi; Bao, Xiujie; Li, Jun; Tong, Yu; Tang, Han; Ma, Shuyan; Wang, Xuedong; Lyu, Jianxin

2018-05-01

Herein, a novel magnetic effervescence tablet-assisted microextraction coupled to in situ metathesis reaction of ionic liquid (IS-META-ILDM) is presented for the determination of four endogenous steroids in human urine, pregnant women's blood, and fetal umbilical cord blood. The magnetic effervescent tablets, which were composed of Fe 3 O 4 nanoparticles, sodium carbonate (alkaline source), and tartaric acid (acidic source), were used to disperse the extractant and for convenient magnetic separation. After the effervescent reaction, in situ reaction between NH 4 PF 6 and [C 6 MIM]BF 4 was adopted to change hydrophilic ionic liquid to hydrophobic liquid, which could be separated from the aqueous phase. The newly developed method has three obvious advantages: (1) combination of effervescent dispersion and magnetic nanoparticles' retrieval is cost-effective and the dispersion and collection of the extractant can be completed almost simultaneously; (2) as compared to temperature-controlled ionic liquid dispersive microextraction and cold-induced solidified microextraction, this method avoids a heating and cooling process which significantly reduces the extraction time and energy cost; and (3) the combination of adsorption by magnetic nanoparticles with extraction by in situ metathesis reaction easily produces high recoveries for target analytes. The optimized composition of effervescent tablet and experimental parameters are as follows: 0.64 g mixture of sodium carbonate and tartaric acid, 7 mg of Fe 3 O 4 (20 nm) as magnetic sorbents, 40 μL of [C 6 MIM]BF 4 as the extraction solvent, 0.15 g NH 4 PF 6 , and 300 μL of elution solvent. Under the optimized conditions, the newly developed method provided high extraction recoveries (90.0-118.5%) and low LODs (0.14-0.17 μg L -1 ) in urine and blood samples. In total, this IS-META-ILDM method provided high extraction efficiency, fast and convenient separation, and underutilization of any organic solvent, and thus

In situ emulsification microextraction using a dicationic ionic liquid followed by magnetic assisted physisorption for determination of lead prior to micro-sampling flame atomic absorption spectrometry

International Nuclear Information System (INIS)

Shokri, Masood; Beiraghi, Asadollah; Seidi, Shahram

2015-01-01

For the first time, a simple and efficient in situ emulsification microextraction method using a dicationic ionic liquid followed by magnetic assisted physisorption was presented to determine trace amounts of lead. In this method, 400 μL of 1.0 mol L −1 lithium bis (trifluoromethylsulfonyl) imide aqueous solution, Li[NTf 2 ], was added into the sample solution containing 100 μL of 1.0 mol L −1 1,3-(propyl-1,3-diyl) bis (3-methylimidazolium) chloride, [pbmim]Cl 2 , to form a water immiscible ionic liquid, [pbmim][NTf 2 ] 2 . This new in situ formed dicationic ionic liquid was applied as the acceptor phase to extract the lead-ammonium pyrrolidinedithiocarbamate (Pb-APDC) complexes from the sample solution. Subsequently, 30 mg of Fe 3 O 4 magnetic nanoparticles (MNPs) were added into the sample solution to collect the fine droplets of [pbmim][NTf 2 ] 2 , physisorptively. Finally, MNPs were eluted by acetonitrile, separated by an external magnetic field and the obtained eluent was subjected to micro-sampling flame atomic absorption spectrometry (FAAS) for further analysis. Comparing with other microextraction methods, no special devices and centrifugation step are required. Parameters influencing the extraction efficiency such as extraction time, pH, concentration of chelating agent, amount of MNPs and coexisting interferences were studied. Under the optimized conditions, this method showed high extraction recovery of 93% with low LOD of 0.7 μg L −1 . Good linearity was obtained in the range of 2.5–150 μg L −1 with determination coefficient (r 2 ) of 0.9921. Relative standard deviation (RSD%) for seven repeated measurements at the concentration of 10 μg L −1 was 4.1%. Finally, this method was successfully applied for determination of lead in some water and plant samples. - Highlights: • A dicationic ionic liquid was used as the extraction solvent, for the first time. • A simple and efficient in situ emulsification microextraction

A novel, donor-active solvent-assisted liquid-phase microextraction procedure for spectrometric determination of zinc

Energy Technology Data Exchange (ETDEWEB)

Kocurova, Livia; Fatlova, Martina; Bazel, Yaroslav; Serbin, Rastislav; Andruch, Vasil, E-mail: liviamonika.kocurova@gmail.com [Department of Analytical Chemistry, University of P. J. Safarik, Kosice (Slovakia); Balogh, Ioseph S. [Department of Chemistry, College of Nyiregyhaza (Hungary); Simon, Andras [Department of General and Analytical Chemistry, Budapest University of Technology and Economics, Budapest (Hungary); Badida, Miroslav; Rusnak, Radoslav [Department of Environmentalistics, Faculty of Mechanical Engineering, Technical University of Kosice (Slovakia)

2014-02-15

Based on the reaction of Zn(II), thiocyanate and 2-[2-(5-dimethylamino-thiophen-2-yl)-vinyl]- 1,3,3-trimethyl-3H-indolium bromide (DTVTI), a donor-active solvent-assisted liquid-phase microextraction procedure followed by spectrophotometric determination of zinc at 570 nm was developed. The optimum experimental conditions were investigated and found to be as follows: concentration of NH{sub 4}SCN 0.02 mol L{sup -1} concentration of DTVTI 4 x 10{sup -5} mol L{sup -1}. Various extraction solvents were studied alone as well as in mixtures with different improvers, and a mixture of toluene as the extraction solvent and tributylphosphate as the donor-active solvent in a 4:1 v/v ratio was selected. The calibration plot was linear up to 2.62 mg L{sup 1} of zinc with limit of detection 0.09 mg L{sup -1}. The developed procedure was applied for zinc determination in dietary supplements. (author)

Ternary (liquid + liquid) equilibria of {bis(trifluoromethylsulfonyl)-amide based ionic liquids + butan-1-ol + water}

International Nuclear Information System (INIS)

Marciniak, Andrzej; Wlazło, Michał; Gawkowska, Joanna

2016-01-01

Highlights: • Ternary (liquid + liquid) equilibria for 3 ionic liquid + butanol + water systems. • The influence of ionic liquid structure on phase diagrams is discussed. • Influence of IL structure on S and β for butanol/water separation is discussed. - Abstract: Ternary (liquid + liquid) phase equilibria for 3 systems containing bis(trifluoromethylsulfonyl)-amide ionic liquids (1-buthyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)-amide, 1-(2-methoxyethyl)-1-methylpiperidinium bis(trifluoromethylsulfonyl)-amide, {1-(2-methoxyethyl)-1-methylpyrrolidinium bis(trifluorylsulfonyl)-amide) + butan-1-ol + water} have been determined at T = 298.15 K. The selectivity and solute distribution ratio were calculated for investigated systems and compared with literature data for other systems containing ionic liquids. In each system total solubility of butan-1-ol and low solubility of water in the ionic liquid is observed. The experimental results have been correlated using NRTL model. The influence of the structure of ionic liquid on phase equilibria, selectivity and solute distribution ratio is shortly discussed.

Expanding the Applicability of Poly(Ionic Liquids in Solid Phase Microextraction: Pyrrolidinium Coatings

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David J. S. Patinha

2017-09-01

Full Text Available Crosslinked pyrrolidinium-based poly(ionic liquids (Pyrr-PILs were synthesized through a fast, simple, and solventless photopolymerization scheme, and tested as solid phase microextraction (SPME sorbents. A series of Pyrr-PILs bearing three different alkyl side chain lengths with two, eight, and fourteen carbons was prepared, characterized, and homogeneously coated on a steel wire by using a very simple procedure. The resulting coatings showed a high thermal stability, with decomposition temperatures above 350 °C, excellent film stability, and lifetime of over 100 injections. The performance of these PIL-based SPME fibers was evaluated using a mixture of eleven organic compounds with different molar volumes and chemical functionalities (alcohols, ketones, and monoterpenes. The Pyrr-PIL fibers were obtained as dense film coatings, with 67 μm thickness, with an overall sorption increase of 90% and 55% as compared to commercial fibers of Polyacrylate (85 μm (PA85 and Polydimethylsiloxane (7 μm (PDMS7 coatings, respectively. A urine sample doped with the sample mixture was used to study the matrix effect and establish relative recoveries, which ranged from 60.2% to 104.1%.

Ion-pair hollow-fiber liquid-phase microextraction of the quaternary ammonium surfactant dicocodimethylammonium chloride.

Science.gov (United States)

Hultgren, Sofie; Larsson, Niklas; Nilsson, Bo F; Jönsson, Jan Ake

2009-02-01

A two-phase hollow-fiber (HF) liquid-phase microextraction (LPME) method was developed for determination of a quaternary ammonium compound surfactant, dicocodimethylammonium chloride, in aqueous samples. The porous HF was fixed on a metal rod support and was impregnated with approximately 6.6 microL of organic extractant, which was immobilized in the HF pores. Surfactant extraction was facilitated by addition of carboxylic acid to the sample forming neutral ion pairs with the quaternary ammonium compound. After extraction, the analyte was transferred from the organic extractant in the fiber pores by dissolving the 1-octanol into 100 microL methanol. The methanol extract was analyzed by liquid chromatography-mass spectrometry. The method was optimized (with optimized parameters in brackets) with regard to type of organic extractant (1-octanol), fiber length (2 cm), choice and concentration of anionic carrier (600 microg L(-1) octanoate), procedure of transfer to methanol (15-min sonication), sample volume (250 mL), extraction time (17 h), pH (10), and ionic strength (50 mM carbonate). Aspects influencing repeatability in LPME of (quaternary ammonium) surfactants are discussed. The enrichment factor achieved in 250-mL carbonate buffer was around 400. Due to matrix effects, the enrichment factors achieved when industrial process water was analyzed were 120 or about 30% of that in carbonate buffer. Detection limits of 0.3 microg L(-1) in carbonate buffer and 0.9 microg L(-1) in industrial process water were obtained. If the studied compound is seen as a model substance representing quaternary dialkylated dimethylated ammonium surfactants in general, the developed method may be applied to other quaternary ammonium surfactants.

Rapid determination of 9 aromatic amines in mainstream cigarette smoke by modified dispersive liquid liquid microextraction and ultraperformance convergence chromatography tandem mass spectrometry.

Science.gov (United States)

Deng, Huimin; Yang, Fei; Li, Zhonghao; Bian, Zhaoyang; Fan, Ziyan; Wang, Ying; Liu, Shanshan; Tang, Gangling

2017-07-21

Aromatic amines in mainstream cigarette smoke have long been monitored due to their carcinogenic toxicity. In this work, a reliable and rapid method was developed for the simultaneous determination of 9 aromatic amines in mainstream cigarette smoke by modified dispersive liquid liquid microextraction (DLLME) and ultraperformance convergence chromatography tandem mass spectrometry (UPC 2 -MS/MS). Briefly, the particulate phase of the cigarette smoke was captured by a Cambridge filter pad, and diluted hydrogen chloride aqueous solution is employed to extract the aromatic amines under mechanical shaking. After alkalization with sodium hydroxide solution, small amount of toluene was introduced to further extract and enrich aromatic amines by modified DLLME under vortexing. After centrifugation, toluene phase was purified by a universal QuEChERS cleanup kit and was finally analyzed by UPC 2 -MS/MS. Attributing to the superior performance of UPC 2 -MS/MS, this novel approach allowed the separation and determination of 9 aromatic amines within 5.0min with satisfactory resolution and sensitivity. The proposed method was finally validated using Kentucky reference cigarette 3R4F, and emission levels of targeted aromatic amines determined were comparable to previously reported methods At three different spiked levels, the recoveries of most analytes were ranged from 74.01% to 120.50% with relative standard deviation (RSD) less than 12%, except that the recovery of p-toluidine at low spiked level and 3-aminobiphenyl at medium spiked level was 62.77% and 69.37% respectively. Thus, this work provides a novel alternative method for the simultaneous analysis of 9 aromatic amines in mainstream cigarette smoke. Copyright © 2017 Elsevier B.V. All rights reserved.

Application of derivative and derivative ratio spectrophotometry to simultaneous trace determination of rhodamine B and rhodamine 6G after dispersive liquid-liquid microextraction.

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Xiao, Ni; Deng, Jian; Huang, Kaihui; Ju, Saiqin; Hu, Canhui; Liang, Jun

2014-07-15

Two novel methods, first derivative spectrophotometric method ((1)D) and first derivative ratio spectrophotometric method ((1)DR), have been developed for the simultaneous trace determination of rhodamine B (RhB) and rhodamine 6G (Rh6G) in food samples after dispersive liquid-liquid microextraction (DLLME). The combination of derivative spectrophotometric techniques and DLLME procedure endows the presented methods with enhanced sensitivity and selectivity. Under optimum conditions, the linear calibration curves ranged from 5 to 450 ng mL(-1), with the correlation coefficients (r) of 0.9997 for RhB and 0.9977 for Rh6G by (1)D method, and 0.9987 for RhB and 0.9958 for Rh6G by (1)DR method, respectively. The calculated limits of detection (LODs) based on the variability of the blank solutions (S/N = 3 criterion) for 11 measurements were in the range of 0.48-1.93 ng mL(-1). The recoveries ranged from 88.1% to 111.6% (with RSD less than 4.4%) and 91.5-110.5% (with RSD less than 4.7%) for (1)D and (1)DR method, respectively. The influence of interfering substances such as foreign ions and food colorants which might be present in the food samples on the signals of RhB and Rh6G was examined. The developed methods have been successfully applied to the determination of RhB and Rh6G in black tea, red wine and chilli powder samples with the characteristics of simplicity, cost-effectiveness, environmental friendliness, and could be valuable for routine analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of 2-Octanone in Biological Samples Using Liquid–Liquid Microextractions Followed by Gas Chromatography–Flame Ionization Detectio

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Abolghasem Jouyban, Maryam Abbaspour, Mir Ali Farajzadeh, Maryam Khoubnasabjafari

2017-06-01

Full Text Available Background: Analysis of chemicals in biological fluids is required in many areas of medical sciences. Rapid, highly efficient, and reliable dispersive and air assisted liquid–liquid microextraction methods followed by gas chromatography-flame ionization detection were developed for the extraction, preconcentration, and determination of 2-octanone in human plasma and urine samples. Methods: Proteins of plasma samples are precipitated by adding methanol and urine sample is diluted with water prior to performing the microextraction procedure. Fine organic solvent droplets are formed by repeated suction and injection of the mixture of sample solution and extraction solvent into a test tube with a glass syringe. After extraction, phase separation is performed by centrifuging and the enriched analyte in the sedimented organic phase is determined by the separation system. The main factors influencing the extraction efficiency including extraction solvent type and volume, salt addition, pH, and extraction times are investigated. Results: Under the optimized conditions, the proposed method showed good precision (relative standard deviation less than 7%. Limit of detection and lower limit of quantification for 2-octanone were obtained in the range of 0.1–0.5 µg mL−1. The linear ranges were 0.5-500 and 0.5-200 µg mL−1 in plasma and urine, respectively (r2 ≥ 0.9995. Enrichment factors were in the range of 13-37. Good recoveries (55–86% were obtained for the spiked samples. Conclusion: Preconcentration methods coupled with GC analysis were developed and could be used to monitor 2-octanone in biological samples.

Rapid determination of hydrophilic phenols in olive oil by vortex-assisted reversed-phase dispersive liquid-liquid microextraction and screen-printed carbon electrodes.

Science.gov (United States)

Fernández, Elena; Vidal, Lorena; Canals, Antonio

2018-05-01

A novel approach is presented to determine hydrophilic phenols in olive oil samples, employing vortex-assisted reversed-phase dispersive liquid-liquid microextraction (RP-DLLME) for sample preparation and screen-printed carbon electrodes for voltammetric analysis. The oxidation of oleuropein, hydroxytyrosol, caffeic acid, ferulic acid and tyrosol was investigated, being caffeic acid and tyrosol selected for quantification. A matrix-matching calibration using sunflower oil as analyte-free sample diluted with hexane was employed to compensate matrix effects. Samples were analyzed under optimized RP-DLLME conditions, i.e., extractant phase, 1M HCl; extractant volume, 100µL; extraction time, 2min; centrifugation time, 10min; centrifugation speed, 4000rpm. The working range showed a good linearity between 0.075 and 2.5mgL -1 (r = 0.998, N = 7) for caffeic acid, and between 0.075 and 3mgL -1 (r = 0.999, N = 8) for tyrosol. The methodological limit of detection was empirically established at 0.022mgL -1 for both analytes, which is significantly lower than average contents found in olive oil samples. The repeatability was evaluated at two different spiking levels (i.e., 0.5mgL -1 and 2mgL -1 ) and coefficients of variation ranged from 8% to 11% (n = 5). The applicability of the proposed method was tested in olive oil samples of different quality (i.e., refined olive oil, virgin olive oil and extra virgin olive oil). Relative recoveries varied between 83% and 108% showing negligible matrix effects. Finally, fifteen samples were analyzed by the proposed method and a high correlation with the traditional Folin-Ciocalteu spectrophotometric method was obtained. Thereafter, the concentrations of the fifteen oil samples were employed as input variables in linear discriminant analysis in order to distinguish between olive oils of different quality. Copyright © 2017 Elsevier B.V. All rights reserved.

Microwave-assisted of dispersive liquid-liquid microextraction and spectrophotometric determination of uranium after optimization based on Box-Behnken design and chemometrics methods

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Niazi, Ali; Khorshidi, Neda; Ghaemmaghami, Pegah

2015-01-01

In this study an analytical procedure based on microwave-assisted dispersive liquid-liquid microextraction (MA-DLLME) and spectrophotometric coupled with chemometrics methods is proposed to determine uranium. In the proposed method, 4-(2-pyridylazo) resorcinol (PAR) is used as a chelating agent, and chloroform and ethanol are selected as extraction and dispersive solvent. The optimization strategy is carried out by using two level full factorial designs. Results of the two level full factorial design (24) based on an analysis of variance demonstrated that the pH, concentration of PAR, amount of dispersive and extraction solvents are statistically significant. Optimal condition for three variables: pH, concentration of PAR, amount of dispersive and extraction solvents are obtained by using Box-Behnken design. Under the optimum conditions, the calibration graphs are linear in the range of 20.0-350.0 ng mL-1 with detection limit of 6.7 ng mL-1 (3δB/slope) and the enrichment factor of this method for uranium reached at 135. The relative standard deviation (R.S.D.) is 1.64% (n = 7, c = 50 ng mL-1). The partial least squares (PLS) modeling was used for multivariate calibration of the spectrophotometric data. The orthogonal signal correction (OSC) was used for preprocessing of data matrices and the prediction results of model, with and without using OSC, were statistically compared. MA-DLLME-OSC-PLS method was presented for the first time in this study. The root mean squares error of prediction (RMSEP) for uranium determination using PLS and OSC-PLS models were 4.63 and 0.98, respectively. This procedure allows the determination of uranium synthesis and real samples such as waste water with good reliability of the determination.

Microwave-assisted of dispersive liquid-liquid microextraction and spectrophotometric determination of uranium after optimization based on Box-Behnken design and chemometrics methods.

Science.gov (United States)

Niazi, Ali; Khorshidi, Neda; Ghaemmaghami, Pegah

2015-01-25

In this study an analytical procedure based on microwave-assisted dispersive liquid-liquid microextraction (MA-DLLME) and spectrophotometric coupled with chemometrics methods is proposed to determine uranium. In the proposed method, 4-(2-pyridylazo) resorcinol (PAR) is used as a chelating agent, and chloroform and ethanol are selected as extraction and dispersive solvent. The optimization strategy is carried out by using two level full factorial designs. Results of the two level full factorial design (2(4)) based on an analysis of variance demonstrated that the pH, concentration of PAR, amount of dispersive and extraction solvents are statistically significant. Optimal condition for three variables: pH, concentration of PAR, amount of dispersive and extraction solvents are obtained by using Box-Behnken design. Under the optimum conditions, the calibration graphs are linear in the range of 20.0-350.0 ng mL(-1) with detection limit of 6.7 ng mL(-1) (3δB/slope) and the enrichment factor of this method for uranium reached at 135. The relative standard deviation (R.S.D.) is 1.64% (n=7, c=50 ng mL(-1)). The partial least squares (PLS) modeling was used for multivariate calibration of the spectrophotometric data. The orthogonal signal correction (OSC) was used for preprocessing of data matrices and the prediction results of model, with and without using OSC, were statistically compared. MA-DLLME-OSC-PLS method was presented for the first time in this study. The root mean squares error of prediction (RMSEP) for uranium determination using PLS and OSC-PLS models were 4.63 and 0.98, respectively. This procedure allows the determination of uranium synthesis and real samples such as waste water with good reliability of the determination. Copyright © 2014. Published by Elsevier B.V.

Liquid over-feeding air conditioning system and method

Science.gov (United States)

Mei, Viung C.; Chen, Fang C.

1993-01-01

A refrigeration air conditioning system utilizing a liquid over-feeding operation is described. A liquid refrigerant accumulator-heat exchanger is placed in the system to provide a heat exchange relationship between hot liquid refrigerant discharged from condenser and a relatively cool mixture of liquid and vaporous refrigerant discharged from the evaporator. This heat exchange relationship substantially sub-cools the hot liquid refrigerant which undergoes little or no evaporation across the expansion device and provides a liquid over-feeding operation through the evaporator for effectively using 100 percent of evaporator for cooling purposes and for providing the aforementioned mixture of liquid and vaporous refrigerant.

Air-assisted Liquid Liquid Microextraction Combined with Graphite Furnace Atomic Absorption Spectrometry for Preconcentration and Determination of Trace Amount of Co(II and Ni(II Ions in Water Samples

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Saeed Mohammad Sorouraddin

2017-12-01

Full Text Available A simple, rapid and efficient method has been developed for the extraction, preconcentration and determination of cobalt (II and nickel (II ions in water samples by air-assisted liquid-liquid microextraction (AALLME coupled with graphite furnace atomic absorption spectrometry (GFAAS. In the proposed method, much less volume of an organic solvent was used as the extraction solvent in the absence of disperser solvent. Fine organic droplets were formed by sucking and injecting of the mixture of aqueous sample solution and extraction solvent with a syringe for several times in a conical test tube. After extraction, phase separation was performed by centrifugation and the enriched analytes in the sedimented phase were determined by GFAAS. Several variables that could affect the extraction efficiency were investigated and optimized. Calibration graphs were linear in the range of 6.5-100 ng L-1. Detection limits for Co and Ni were 2.3 ng L-1 and 3 ng L-1, respectively. The accuracy of the developed procedure was checked by analyzing NRCC-SLRS4 Riverine water as a certified reference material. Finally, the proposed method has been successfully applied for the determination of cobalt (II and nickel (II ions in tap, surface and river water samples.

PREFACE: Functionalized Liquid Liquid Interfaces

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Girault, Hubert; Kornyshev, Alexei A.; Monroe, Charles W.; Urbakh, Michael

2007-09-01

Most natural processes take place at interfaces. For this reason, surface science has been a focal point of modern research. At solid-liquid interfaces one can induce various species to adsorb or react, and thus may study interactions between the substrate and adsorbates, kinetic processes, optical properties, etc. Liquid-liquid interfaces, formed by immiscible liquids such as water and oil, have a number of distinctive features. Both sides of the interface are amenable to detailed physical and chemical analysis. By chemical or electrochemical means, metal or semiconductor nanoparticles can be formed or localised at the interface. Surfactants can be used to tailor surface properties, and also to place organic molecular or supermolecular constructions at the boundary between the liquids. Electric fields can be used to drive ions from one fluid to another, or even change the shape of the interface itself. In many cases, both liquids are optically transparent, making functionalized liquid-liquid interfaces promising for various optical applications based on the transmission or reflection of light. An advantage common to most of these systems is self-assembly; because a liquid-liquid interface is not mechanically constrained like a solid-liquid interface, it can easily access its most stable state, even after it has been driven far from equilibrium. This special issue focuses on four modes of liquid-liquid interfacial functionalization: the controlled adsorption of molecules or nanoparticles, the formation of adlayers or films, electrowetting, and ion transfer or interface-localized reactions. Interfacial adsorption can be driven electrically, chemically, or mechanically. The liquid-liquid interface can be used to study how anisotropic particles orient at a surface under the influence of a field, how surfactants interact with other adsorbates, and how nanoparticles aggregate; the transparency of the interface also makes the chirality of organic adsorbates amenable to

Liquid over-feeding air conditioning system and method

Science.gov (United States)

Mei, V.C.; Chen, F.C.

1993-09-21

A refrigeration air conditioning system utilizing a liquid over-feeding operation is described. A liquid refrigerant accumulator-heat exchanger is placed in the system to provide a heat exchange relationship between hot liquid refrigerant discharged from condenser and a relatively cool mixture of liquid and vaporous refrigerant discharged from the evaporator. This heat exchange relationship substantially sub-cools the hot liquid refrigerant which undergoes little or no evaporation across the expansion device and provides a liquid over-feeding operation through the evaporator for effectively using 100 percent of evaporator for cooling purposes and for providing the aforementioned mixture of liquid and vaporous refrigerant. 1 figure.

Liquid Level Sensing System

Science.gov (United States)

Korman, Valentin (Inventor); Wiley, John T. (Inventor); Duffell, Amanda G. (Inventor)

2014-01-01

A liquid level sensing system includes waveguides disposed in a liquid and distributed along a path with a gap between adjacent waveguides. A source introduces electromagnetic energy into the waveguides at a first end of the path. A portion of the electromagnetic energy exits the waveguides at a second end of the path. A detector measures the portion of the electromagnetic energy exiting the second end of the path.

Comparison between dispersive solid-phase and dispersive liquid-liquid microextraction combined with spectrophotometric determination of malachite green in water samples based on ultrasound-assisted and preconcentration under multi-variable experimental design optimization.

Science.gov (United States)

Alipanahpour Dil, Ebrahim; Ghaedi, Mehrorang; Asfaram, Arash; Zare, Fahimeh; Mehrabi, Fatemeh; Sadeghfar, Fardin

2017-11-01

The ultrasound-assisted dispersive solid-phase microextraction (USA-DSPME) and the ultrasound-assisted dispersive liquid-liquid microextraction (USA-DLLME) developed for as an ultra preconcentration and/or technique for the determination of malachite green (MG) in water samples. Central composite design based on analysis of variance and desirability function guide finding best operational conditions and represent dependency of response to variables viz. volume of extraction, eluent and disperser solvent, pH, adsorbent mass and ultrasonication time has significant influence on methods efficiency. Optimum conditions was set for USA-DSPME as: 1mg CNTs/Zn:ZnO@Ni 2 P-NCs; 4min sonication time and 130μL eluent at pH 6.0. Meanwhile optimum point for USA-DLLME conditions were fixed at pH 6.0; 4min sonication time and 130, 650μL and 10mL of extraction solvent (CHCl 3 ), disperser solvent (ethanol) and sample volume, respectively. Under the above specified best operational conditions, the enrichment factors for the USA-DSPME and USA-DLLME were 88.89 and 147.30, respectively. The methods has linear response in the range of 20.0 to 4000.0ngmL -1 with the correlation coefficients (r) between 0.9980 to 0.9995, while its reasonable detection limits viz. 1.386 to 2.348ngmL -1 and good relative standard deviations varied from 1.1% to 2.8% (n=10) candidate this method for successful monitoring of analyte from various media. The relative recoveries of the MG dye from water samples at spiking level of 500ngmL -1 were in the range between 94.50% and 98.86%. The proposed methods has been successfully applied to the analysis of the MG dye in water samples, and a satisfactory result was obtained. Copyright © 2017. Published by Elsevier B.V.

Ultra-trace determination of gold nanoparticles in environmental water by surfactant assisted dispersive liquid liquid microextraction coupled with electrothermal vaporization-inductively coupled plasma-mass spectrometry

Science.gov (United States)

Liu, Ying; He, Man; Chen, Beibei; Hu, Bin

2016-08-01

A new method by coupling surfactant assisted dispersive liquid liquid microextraction (SA-DLLME) with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) was proposed for the analysis of gold nanoparticles (AuNPs) in environmental water samples. Effective separation of AuNPs from ionic gold species was achieved by using sodium thiosulphate as a complexing agent. Various experimental parameters affecting SA-DLLME of AuNPs, such as the organic solvent, organic solvent volume, pH of the sample, the kind of surfactant, surfactant concentration, vortex time, speed of centrifugation, centrifugation time, and different coating as well as sizes of AuNPs were investigated carefully. Furthermore, the interference of coexisting ions, dissolved organic matter (DOM) and other metal nanoparticles (NPs) were studied. Under the optimal conditions, a detection limit of 2.2 ng L- 1 and an enrichment factor of 152-fold was achieved for AuNPs, and the original morphology of the AuNPs could be maintained during the extraction process. The developed method was successfully applied for the analysis of AuNPs in environmental water samples, including tap water, the East Lake water, and the Yangtze River water, with recoveries in the range of 89.6-102%. Compared with the established methods for metal NPs analysis, the proposed method has the merits of simple and fast operation, low detection limit, high selectivity, good tolerance to the sample matrix and no digestion or dilution required. It provides an efficient quantification methodology for monitoring AuNPs' pollution in the environmental water and evaluating its toxicity.

Ultrasound-assisted leaching-dispersive solid-phase extraction followed by liquid-liquid microextraction for the determination of polybrominated diphenyl ethers in sediment samples by gas chromatography-tandem mass spectrometry.

Science.gov (United States)

Fontana, Ariel R; Lana, Nerina B; Martinez, Luis D; Altamirano, Jorgelina C

2010-06-30

Ultrasound-assisted leaching-dispersive solid-phase extraction followed by dispersive liquid-liquid microextraction (USAL-DSPE-DLLME) technique has been developed as a new analytical approach for extracting, cleaning up and preconcentrating polybrominated diphenyl ethers (PBDEs) from sediment samples prior gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis. In the first place, PBDEs were leached from sediment samples by using acetone. This extract was cleaned-up by DSPE using activated silica gel as sorbent material. After clean-up, PBDEs were preconcentrated by using DLLME technique. Thus, 1 mL acetone extract (disperser solvent) and 60 microL carbon tetrachloride (extraction solvent) were added to 5 mL ultrapure water and a DLLME technique was applied. Several variables that govern the proposed technique were studied and optimized. Under optimum conditions, the method detection limits (MDLs) of PBDEs calculated as three times the signal-to-noise ratio (S/N) were within the range 0.02-0.06 ng g(-1). The relative standard deviations (RSDs) for five replicates were or =0.9991. Validation of the methodology was carried out by standard addition method at two concentration levels (0.25 and 1 ng g(-1)) and by comparing with a reference Soxhlet technique. Recovery values were > or =80%, which showed a satisfactory robustness of the analytical methodology for determination of low PBDEs concentration in sediment samples. Copyright 2010 Elsevier B.V. All rights reserved.

Liquid level control system for vapour generator

International Nuclear Information System (INIS)

Singh, G.

1984-01-01

A system for regulating the liquid level in a vapor generator, in which the incoming flow of feed liquid is regulated in response to the difference between the measured liquid level and a reference level, the difference between the exiting vapor mass flow rate and the incoming liquid mass flow rate, and a function of the measured incoming liquid temperature. The temperature function produces a gain value, which increases in response to decreasing incoming liquid temperature. The purpose of the temperature function is to stabilize the level control under transient conditions (e.g. sudden lose of load). (author)

Water-saving liquid-gas conditioning system

Science.gov (United States)

Martin, Christopher; Zhuang, Ye

2014-01-14

A method for treating a process gas with a liquid comprises contacting a process gas with a hygroscopic working fluid in order to remove a constituent from the process gas. A system for treating a process gas with a liquid comprises a hygroscopic working fluid comprising a component adapted to absorb or react with a constituent of a process gas, and a liquid-gas contactor for contacting the working fluid and the process gas, wherein the constituent is removed from the process gas within the liquid-gas contactor.

Hollow fibre-based liquid phase microextraction combined with high-performance liquid chromatography for the analysis of flavonoids in Echinophora platyloba DC. and Mentha piperita.

Science.gov (United States)

Hadjmohammadi, Mohammadreza; Karimiyan, Hanieh; Sharifi, Vahid

2013-11-15

A simple, inexpensive and efficient three phase hollow fibre liquid phase microextraction (HF-LPME) technique combined with HPLC was used for the simultaneous determination of flavonoids in Echinophora platyloba DC. and Mentha piperita. Different factors affecting the HF-LPME procedure were investigated and optimised. The optimised extraction conditions were as follows: 1-octanol as an organic solvent, pHdonor=2, pHacceptor=9.75, stirring rate of 1000rpm, extraction time of 80min, without addition of salt. Under these conditions, the enrichment factors ranged between 146 and 311. The values of intra and inter-day relative standard deviations (RSD) were in the range of 3.18-6.00% and 7.25-11.00%, respectively. The limits of detection (LODs) ranged between 0.5 and 7.0ngmL(-1). Among the investigated flavonoids quercetin was found in E. platyloba DC. and luteolin was found in M. piperita. Concentration of quercetin and luteolin was 0.015 and 0.025mgg(-1) respectively. Copyright © 2013 Elsevier Ltd. All rights reserved.

(Vapour + liquid) equilibria of ternary systems with ionic liquids using headspace gas chromatography

International Nuclear Information System (INIS)

Mokhtarani, Babak; Gmehling, Juergen

2010-01-01

(Vapour + liquid) equilibrium (VLE) data for the ternary systems (hexane + benzene), (hexane + cyclohexane), (benzene + cyclohexane), and (ethanol + water) with an ionic liquid as entrainer for extractive distillation were measured by headspace gas chromatography. As ionic liquids, 1-hexyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [HMIM][BTI], 1-octyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [OMIM][BTI], 1-octyl-3-methyl-imidazolium trifluoro-methanesulfonate [OMIM][OTF], and 1-butyl-3-methyl-imidazolium trifluoro-methanesulfonate [BMIM][OTF] were used. The experimental data show that the ionic liquids investigated have a great influence on the separation factors of the systems (hexane + benzene), (hexane + cyclohexane), and (benzene + cyclohexane). The experimental data were compared with the predicted results using mod. UNIFAC (Do). The predicted results are in good agreement with the experimental data.

(Vapour + liquid) equilibria of ternary systems with ionic liquids using headspace gas chromatography

Energy Technology Data Exchange (ETDEWEB)

Mokhtarani, Babak [Chemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186, Tehran (Iran, Islamic Republic of); Gmehling, Juergen, E-mail: gmehling@tech.chem.uni-oldenburg.d [Carl von Ossietzky Universitaet Oldenburg, Technische Chemie, D-26111 Oldenburg (Germany)

2010-08-15

(Vapour + liquid) equilibrium (VLE) data for the ternary systems (hexane + benzene), (hexane + cyclohexane), (benzene + cyclohexane), and (ethanol + water) with an ionic liquid as entrainer for extractive distillation were measured by headspace gas chromatography. As ionic liquids, 1-hexyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [HMIM][BTI], 1-octyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [OMIM][BTI], 1-octyl-3-methyl-imidazolium trifluoro-methanesulfonate [OMIM][OTF], and 1-butyl-3-methyl-imidazolium trifluoro-methanesulfonate [BMIM][OTF] were used. The experimental data show that the ionic liquids investigated have a great influence on the separation factors of the systems (hexane + benzene), (hexane + cyclohexane), and (benzene + cyclohexane). The experimental data were compared with the predicted results using mod. UNIFAC (Do). The predicted results are in good agreement with the experimental data.

Cryogenic system for liquid hydrogen polarimeter

International Nuclear Information System (INIS)

Kitami, T.; Chiba, M.; Hirabayashi, H.; Ishii, T.; Kato, S.

1979-01-01

A cryogenic system has been constructed for a liquid hydrogen polarimeter in order to measure polarization of high energy proton at the 1.3 GeV electron synchrotron of Institute for Nuclear Study, University of Tokyo. The system principally consists of a cryogenerator with a cryogenic transfer line, a liquid hydrogen cryostat, and a 14.5 l target container of thin aluminum alloy where liquid hydrogen is served for the experiment. The refrigeration capacity is about 54 W at 20.4 K without a target container. (author)

Experimental (solid + liquid) or (liquid + liquid) phase equilibria of (amine + nitrile) binary mixtures

International Nuclear Information System (INIS)

Domanska, Urszula; Marciniak, Malgorzata

2007-01-01

(Solid + liquid) phase diagrams have been determined for (hexylamine, or octylamine, or 1,3-diaminopropane + acetonitrile) mixtures. Simple eutectic systems have been observed in these mixtures. (Liquid + liquid) phase diagrams have been determined for (octylamine, or decylamine + propanenitrile, or + butanenitrile) mixtures. Mixtures with propanenitrile and butanenitrile show immiscibility in the liquid phase with an upper critical solution temperature, UCST. (Solid + liquid) phase diagrams have been correlated using NRTL, NRTL 1, Wilson and UNIQUAC equations. (Liquid + liquid) phase diagrams have been correlated using NRTL equation

Development of Dispersive Liquid-Liquid Microextraction Based on Solidification of Floating Organic Drop for the Sensitive Determination of Trace Copper in Water and Beverage Samples by Flame Atomic Absorption Spectrometry

International Nuclear Information System (INIS)

Wu, Chunxia; Zhao, Bin; Li, Yingli; Wu, Qiuhua; Wang, Chun; Wang, Zhi

2011-01-01

A dispersive liquid-liquid microextraction based on solidification of floating organic droplet (DLLME-SFO) has been developed as a new approach for the extraction of trace copper in water and beverage samples followed by the determination with flame atomic absorption spectrometry. In the DLLME-SFO, 8-hydroxy quinoline, 1-dodecanol, and methanol were used as chelating agent, extraction solvent and dispersive solvent, respectively. The experimental parameters related to the DLLME-SFO such as the type and volume of the extraction and dispersive solvent, extraction time, sample volume, the concentration of chelating agent and salt addition were investigated and optimized. Under the optimum conditions, the enrichment factor for copper was 122. The method was linear in the range from 0.5 to 300 ng mL -1 of copper in the samples with a correlation coefficient (r) of 0.9996 and a limit of detection of 0.1 ng mL -1 . The method was applied to the determination of copper in water and beverage samples. The recoveries for the spiked water and beverage samples at the copper concentration levels of 5.0 and 10.0 ng mL -1 were in the range between 92.0% and 108.0%. The relative standard deviations (RSD) varied from 3.0% to 5.6%

Hollow fiber-based liquid phase microextraction combined with high-performance liquid chromatography for extraction and determination of some antidepressant drugs in biological fluids.

Science.gov (United States)

Esrafili, Ali; Yamini, Yadollah; Shariati, Shahab

2007-12-05

The applicability of hollow fiber-based liquid phase microextraction (HF-LPME) was evaluated for the extraction and preconcentration of three antidepressant drugs (amitriptyline, imipramine and sertraline) prior to their determination by HPLC-UV. The target drugs were extracted from 11.0 mL of aqueous solution with pH 12.0 (source phase) into an organic extracting solvent (n-dodecane) impregnated in the pores of a hollow fiber and finally back extracted into 24 microL of aqueous solution located inside the lumen of the hollow fiber and adjusted to pH 2.1 using 0.1M of H3PO4 (receiving phase). The extraction was performed due to pH gradient between the inside and outside of the hollow fiber membrane. In order to obtain high extraction efficiency, the parameters affecting the HF-LPME including pH of the source and receiving phases, the type of organic phase, ionic strength and volume of the source phase, stirring rate and extraction time were studied and optimized. Under the optimized conditions, enrichment factors up to 300 were achieved and the relative standard deviation (R.S.D.%) of the method was in the range of 2-12%. The calibration curves were obtained in the range of 5-500 microg L(-1) with reasonable linearity (R2>0.998) and the limits of detection (LODs) ranged between 0.5 and 0.7 microg L(-1) (based on S/N=3). Finally, the applicability of the proposed method was evaluated by extraction and determination of the drugs in urine, plasma and tap water samples. The results indicated that hollow fiber microextraction method has excellent clean-up and high-preconcentration factor and can be served as a simple and sensitive method for monitoring of antidepressant drugs in the biological samples.

Systems and methods for analyzing liquids under vacuum

Science.gov (United States)

Yu, Xiao-Ying; Yang, Li; Cowin, James P.; Iedema, Martin J.; Zhu, Zihua

2013-10-15

Systems and methods for supporting a liquid against a vacuum pressure in a chamber can enable analysis of the liquid surface using vacuum-based chemical analysis instruments. No electrical or fluid connections are required to pass through the chamber walls. The systems can include a reservoir, a pump, and a liquid flow path. The reservoir contains a liquid-phase sample. The pump drives flow of the sample from the reservoir, through the liquid flow path, and back to the reservoir. The flow of the sample is not substantially driven by a differential between pressures inside and outside of the liquid flow path. An aperture in the liquid flow path exposes a stable portion of the liquid-phase sample to the vacuum pressure within the chamber. The radius, or size, of the aperture is less than or equal to a critical value required to support a meniscus of the liquid-phase sample by surface tension.

Study of the factors affecting the performance of microextraction by packed sorbent (MEPS) using liquid scintillation counter and liquid chromatography-tandem mass spectrometry

International Nuclear Information System (INIS)

Altun, Zeki; Abdel-Rehim, Mohamed

2008-01-01

Microextraction by packed sorbent (MEPS) is a new technique for sample preparation that can be connected on-line with LC or GC. In MEPS, approximately 1-2 mg of the solid packing material is inserted into a syringe (100-250 μL) as a plug. Sample preparation takes place on the packed bed. The bed can be packed or coated to provide selective and suitable sampling conditions. The new method is very promising for extraction of drugs and metabolites from biological samples. In this paper, some factors affecting the performance of MEPS such as recovery, carry-over, leakage, washing volume and elution volume were studied using C18 and hydroxylated polystyrene-divinylbenzene copolymer (ENV+) as sorbents. Radioactively labelled bupivacaine in plasma samples was used as test analyte. For the extraction of this drug, using methanol/water 95:5 (v/v) (0.25% ammonium hydroxide) was used as elution solvent. The analyte response increased with increasing the elution volume and it was linear upp up to 100 μL utilizing liquid scintillation counter. Further, for concentrating the sample, we found that MEPS may be used such that the sample can be drawn through the needle, up and down, several times. The analyte leakage increases as the volume washing increases, though higher washing volumes may also result in cleaner extracts. To eliminate analyte carry-over, the sorbents were washed first with 3 x 250 μL elution solution and then with 3 x 250 μL washing solution. In addition, the reproducibility measurements show relatively good relative standard deviation (RSD) % values concerning analyte recovery and analyte leakage. The present study provides an understanding of basic aspects when optimizing methods for MEPS. In this study, MEPS was used off-line with liquid scintillation counter and on-line with LC-MS/MS

Study of the factors affecting the performance of microextraction by packed sorbent (MEPS) using liquid scintillation counter and liquid chromatography-tandem mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Altun, Zeki [Karlstad University, Faculty of Technology and Science, SE-651 88 Karlstad (Sweden); Abdel-Rehim, Mohamed [Karlstad University, Faculty of Technology and Science, SE-651 88 Karlstad (Sweden); Clinical Pharmacology and DMPK, AstraZeneca R and D Soedertaelje, SE-151 85 Soedertaelje (Sweden)], E-mail: Mohamed.Abdel-Rehim@Astrazeneca.com

2008-12-23

Microextraction by packed sorbent (MEPS) is a new technique for sample preparation that can be connected on-line with LC or GC. In MEPS, approximately 1-2 mg of the solid packing material is inserted into a syringe (100-250 {mu}L) as a plug. Sample preparation takes place on the packed bed. The bed can be packed or coated to provide selective and suitable sampling conditions. The new method is very promising for extraction of drugs and metabolites from biological samples. In this paper, some factors affecting the performance of MEPS such as recovery, carry-over, leakage, washing volume and elution volume were studied using C18 and hydroxylated polystyrene-divinylbenzene copolymer (ENV+) as sorbents. Radioactively labelled bupivacaine in plasma samples was used as test analyte. For the extraction of this drug, using methanol/water 95:5 (v/v) (0.25% ammonium hydroxide) was used as elution solvent. The analyte response increased with increasing the elution volume and it was linear upp up to 100 {mu}L utilizing liquid scintillation counter. Further, for concentrating the sample, we found that MEPS may be used such that the sample can be drawn through the needle, up and down, several times. The analyte leakage increases as the volume washing increases, though higher washing volumes may also result in cleaner extracts. To eliminate analyte carry-over, the sorbents were washed first with 3 x 250 {mu}L elution solution and then with 3 x 250 {mu}L washing solution. In addition, the reproducibility measurements show relatively good relative standard deviation (RSD) % values concerning analyte recovery and analyte leakage. The present study provides an understanding of basic aspects when optimizing methods for MEPS. In this study, MEPS was used off-line with liquid scintillation counter and on-line with LC-MS/MS.

Prediction of (liquid + liquid) equilibrium for binary and ternary systems containing ionic liquids with the bis[(trifluoromethyl)sulfonyl]imide anion using the ASOG method

International Nuclear Information System (INIS)

Robles, Pedro A.; Cisternas, Luis A.

2015-01-01

Highlights: • ASOG model was used to predict LLE data for ionic liquid systems. • Twenty five binary and seven ternary systems that include the NTf 2 anion were used. • New group interaction parameters were determined. • The results are satisfactory, with rms deviations of about 3%. - Abstract: Ionic liquids are neoteric, environmentally friendly solvents (as they do not produce emissions) composed of large organic cations and relatively small inorganic anions. They have favorable physical properties, such as negligible volatility and a wide range of liquid existence. (Liquid + liquid) equilibrium (LLE) data for systems including ionic liquids, although essential for the design, optimization and operation of separation processes, remain scarce. However, some recent studies have presented ternary LLE data involving several ionic liquids and organic compounds such as alkanes, alkenes, alkanols, ethers and aromatics, as well as water. In this work, the ASOG model for the activity coefficient is used to predict LLE data for 25 binary and 07 ternary systems at 101.3 kPa and several temperatures; all the systems are formed by ionic liquids including the bis[(trifluoromethyl)sulfonyl]imide (NTf 2 ) anion plus alkanes, alkenes, cycloalkanes, alkanols, water, thiophene and aromatics. New group interaction parameters were determined using a modified Simplex method, minimizing a composition-based objective function of experimental data obtained from the literature. The results are satisfactory, with rms deviations of approximately 3%

Design and implementation of an automated liquid-phase microextraction-chip system coupled on-line with high performance liquid chromatography

DEFF Research Database (Denmark)

Li, Bin; Petersen, Nickolaj J.; Payán, María D Ramos

2014-01-01

. The composition of the supported liquid membrane (SLM) and carrier was optimized in order to achieve reasonable extraction performance of all the five alkaloids. With 1-octanol as SLM solvent and with 25mM sodium octanoate as anionic carrier, extraction recoveries for the different opium alkaloids ranged between...

Hollow fibre liquid phase micro-extraction by facilitated anionic exchange for the determination of flavonoids in faba beans (Vicia faba L.).

Science.gov (United States)

Chaieb, Nadia; López-Mesas, Montserrat; Luis González, Johannes; Mars, Messaoud; Valiente, Manuel

2015-01-01

Flavonoids are polyphenolic compounds found ubiquitously in foods of plant origin. They are commonly extracted from plant materials with ethanol, methanol, water, their combination or even with acidified extracting solutions. The disadvantages of these methods are the use of high quantity of organic solvent, the possible loss of analytes in the different steps and the laborious process of the techniques. In addition, the complexity of the phenolic mixtures present in plant materials requires a preliminary clean-up and fractionation of the crude extracts. To develop a hollow fibre liquid phase micro-extraction (HF-LPME) method for a one step clean-up and pre-concentration of flavonoids. Two flavonoids (catechin and rutin) has been extracted by HF-LPME and analysed by HPLC. The related driving force for the liquid membrane has been studied by means of facilitated and non-facilitated transport. Different ionic and non-ionic water insoluble compounds [trioctylamine (TOA), tributyl phosphate (TBP), trioctylphosphine oxide (TOPO) and methyltrioctylammonium chloride (aliquat 336)] were used as carriers. The liquid membrane was constituted by a solution of n-decanol in the presence or absence of carriers. Maximum enrichment factors were obtained with n-decanol/aliquat 336 (20%) as organic liquid membrane, sodium hydroxide (NaOH) (0.1 M) as donor solution, sodium chloride (NaCl) (2 M) as acceptor solution and 3 h as extraction time. Under these conditions, good results for validation parameters were obtained [for linearity, limit of detection (LOD), limit of quantitation (LOQ) and repeatability]. The developed method is simple, effective and has been successfully applied to determine catechin and rutin in ethanolic extracts of faba beans. Copyright © 2015 John Wiley & Sons, Ltd.

Liquid Effluent Monitoring Information System (LEMIS) System Construction

International Nuclear Information System (INIS)

Adams, R.T.

1994-01-01

The liquid effluent sampling program is part of the effort to minimize adverse environmental impact during the cleanup operation at the Hanford Site. Of the 33 Phase I and Phase II liquid effluents, all streams actively discharged to the soil column will be sampled. The Liquid Effluent Monitoring Information System (LEMIS) is being developed as the organized information repository facility in support of the liquid effluent monitoring requirements of the Tri-Party Agreement. It is necessary to provide an automated repository into which the results from liquid effluent sampling will be placed. This repository must provide for effective retention, review, and retrieval of selected sample data by authorized persons and organizations. This System Construction document is the aggregation of the DMR P+ methodology project management deliverables. Together they represent a description of the project and its plan through four Releases, corresponding to the definition and prioritization of requirements defined by the user

Thermophysical properties of biodiesel and related systems: (Liquid + liquid) equilibrium data for castor oil biodiesel

International Nuclear Information System (INIS)

Mazutti, Marcio A.; Voll, Fernando A.P.; Cardozo-Filho, Lúcio; Corazza, Marcos L.; Lanza, Marcelo; Priamo, Wagner L.; Oliveira, J. Vladimir

2013-01-01

Highlights: ► (Liquid + liquid) equilibrium data for multicomponent castor oil FAME and FAEE castor oil. ► Tie-lines and solubility curves (binodal) by cloud-point method for FAME and FAEE systems. ► Experimental data correlated using the UNIQUAC model. -- Abstract: This work reports new liquid–liquid solubility values (binodal curves) as well as (liquid + liquid) equilibrium data for, ternary and quaternary systems containing fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE) from castor oil, water, glycerol, methanol and anhydrous ethanol at T = (303.15, 318.15, and 333.15) K. Solubility curves (binodal) were also obtained by the cloud-point method for binary systems containing FAME, FAEE, water, or glycerol. All results obtained can be considered of good quality. The experimental values were correlated using the UNIQUAC model, whose results presented good performance and satisfactory fitting of equilibrium values

[Detecting Thallium in Water Samples using Dispersive Liquid Phase Microextraction-Graphite Furnace Atomic Absorption Spectroscopy].

Science.gov (United States)

Zhu, Jing; Li, Yan; Zheng, Bo; Tang, Wei; Chen, Xiao; Zou, Xiao-li

2015-11-01

To develope a method of solvent demulsification dispersive liquid phase microextraction (SD-DLPME) based on ion association reaction coupled with graphite furnace atomic absorption spectroscopy (GFAAS) for detecting thallium in water samples. Methods Thallium ion in water samples was oxidized to Tl(III) with bromine water, which reacted with Cl- to form TlCl4-. The ionic associated compound with trioctylamine was obtained and extracted. DLPME was completed with ethanol as dispersive solvent. The separation of aqueous and organic phase was achieved by injecting into demulsification solvent without centrifugation. The extractant was collected and injected into GFAAS for analysis. With palladium colloid as matrix modifier, a two step drying and ashing temperature programming process was applied for high precision and sensitivity. The linear range was 0.05-2.0 microg/L, with a detection limit of 0.011 microg/L. The relative standard derivation (RSD) for detecting Tl in spiked water sample was 9.9%. The spiked recoveries of water samples ranged from 94.0% to 103.0%. The method is simple, sensitive and suitable for batch analysis of Tl in water samples.

Determination of monoamine neurotransmitters in human urine by carrier-mediated liquid-phase microextraction based on solidification of stripping phase.

Science.gov (United States)

Jiang, Liwei; Chen, Yibang; Chen, Yejun; Ma, Ming; Tan, Yueming; Tang, Hao; Chen, Bo

2015-11-01

A novel method was developed for the analysis of monoamine neurotransmitters (MNTs) in human urine by carrier-mediated liquid-phase microextraction based on solidification of stripping phase method (CM-LPME-SSP) coupled with high performance liquid chromatography-electrochemical detector (HPLC-ECD). By adding an appropriate carrier in organic phase, simultaneous extraction of hydrophilic analytes, MNTs, with high enrichment factors (22.6-36.1 folds) and excellent sample cleanup was achieved. A new strategy, solidifying the aqueous stripping phase in the back-extraction process, was developed to facilitate the collection of the stripping phase as small as a few microliters. Combined with HPLC-ECD analysis, the linear ranges of the established method were 0.015-2.0 μg/mL for NE, E, DA, and 0.020-2.0 μg/mL for 5-HT. The limits of detection and quantification were in the range of 5.5-10.8 ng/mL and 15-20 ng/mL, respectively. The relative recoveries were in the range of 87-108%, with intraday and interday relative standard deviations lower than 13%. This method was successfully applied to analysis of MNTs in real urine. Copyright © 2015 Elsevier B.V. All rights reserved.

Simultaneous derivatization and lighter-than-water air-assisted liquid-liquid microextraction using a homemade device for the extraction and preconcentration of some parabens in different samples.

Science.gov (United States)

Farajzadeh, Mir Ali; Aghdam, Mehri Bakhshizadeh; Mogaddam, Mohammad Reza Afshar; Nabil, Ali Akbar Alizadeh

2018-06-06

Simultaneous derivatization and air-assisted liquid-liquid microextraction using an organic solvent lighter than water has been developed for the extraction of some parabens in different samples with the aid of a newly designed device for collecting the extractant. For this purpose, the sample solution is transferred into a glass test tube and a few microliters of acetic anhydride (as a derivatization agent) and p-xylene (as an extraction solvent) are added to the solution. After performing the procedure, the homemade device consists of an inverse funnel with a capillary tube placed into the tube. In this step, the collected extraction solvent and a part of the aqueous solution are transferred into the device and the organic phase indwells in the capillary tube of the device. Under the optimal conditions, limits of detection and quantification for the analytes were obtained in the ranges of 0.90-2.7 and 3.0-6.1 ng mL -1 , respectively. The enrichment and enhancement factors were in the ranges of 370-430 and 489-660, respectively. The method precision, expressed as the relative standard deviation, was within the ranges of 4-6% (n = 6) and 4-9% (n = 4) for intra- and inter-day precisions, respectively. The proposed method was successfully used for the determination of methyl-, ethyl-, and propyl parabens in cosmetic, hygiene, and food samples, and personal care products. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Experimental study on desulfurization efficiency and gas-liquid mass transfer in a new liquid-screen desulfurization system

International Nuclear Information System (INIS)

Sun, Zhongwei; Wang, Shengwei; Zhou, Qulan; Hui, Shi'en

2010-01-01

This paper presents a new liquid-screen gas-liquid two-phase flow pattern with discarded carbide slag as the liquid sorbent of sulfur dioxide (SO 2 ) in a wet flue gas desulfurization (WFGD) system. On the basis of experimental data, the correlations of the desulfurization efficiency with flue gas flow rate, slurry flow rate, pH value of slurry and liquid-gas ratio were investigated. A non-dimensional empirical model was developed which correlates the mass transfer coefficient with the liquid Reynolds number, gas Reynolds number and liquid-gas ratio (L/G) based on the available experimental data. The kinetic reaction between the SO 2 and the carbide slag depends on the pressure distribution in this desulfurizing tower, gas liquid flow field, flue gas component, pH value of slurry and liquid-gas ratio mainly. The transient gas-liquid mass transfer involving with chemical reaction was quantified by measuring the inlet and outlet SO 2 concentrations of flue gas as well as the characteristics of the liquid-screen two-phase flow. The mass transfer model provides a necessary quantitative understanding of the hydration kinetics of sulfur dioxide in the liquid-screen flue gas desulfurization system using discarded carbide slag which is essential for the practical application. (author)

Thermophysical properties of biodiesel and related systems: (Liquid + liquid) equilibrium data for soybean biodiesel

International Nuclear Information System (INIS)

Mazutti, Marcio A.; Voll, Fernando A.P.; Cardozo-Filho, Lúcio; Corazza, Marcos L.; Lanza, Marcelo; Priamo, Wagner L.; Oliveira, J. Vladimir

2013-01-01

Highlights: ► (Liquid + liquid) equilibrium data for the systems of biodiesel production. ► LLE data for multicomponent FAME and FAEE from (303.15 to 333.15) K. ► Experimental data correlated using the UNIQUAC model. -- Abstract: This work reports (liquid + liquid) equilibrium (LLE) data for the systems of interest in soybean biodiesel production. Numerical data for LLE were obtained for binary, ternary and quaternary systems comprising fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE) from soybean oil, water, glycerol, methanol, and ethanol at temperatures of (303.15, 318.15, and 333.15) K. Quantification of compounds in equilibrium in both phases was determined by analytical methods whereas solubility curves (binodal) were obtained by the cloud-point method. For all systems investigated, good alignments were obtained between phase compositions and the initial as well as overall compositions hence indicating low deviations from the mass balance. Experimental results were correlated using the UNIQUAC model with satisfactory agreement between experiment and theory

Two-step microextraction combined with high performance liquid chromatographic analysis of pyrethroids in water and vegetable samples.

Science.gov (United States)

Mukdasai, Siriboon; Thomas, Chunpen; Srijaranai, Supalax

2014-03-01

Dispersive liquid microextraction (DLME) combined with dispersive µ-solid phase extraction (D-µ-SPE) has been developed as a new approach for the extraction of four pyrethroids (tetramethrin, fenpropathrin, deltamethrin and permethrin) prior to the analysis by high performance liquid chromatography (HPLC) with UV detection. 1-Octanol was used as the extraction solvent in DLME. Magnetic nanoparticles (Fe3O4) functionalized with 3-aminopropyl triethoxysilane (APTS) were used as the dispersive in DLME and as the adsorbent in D-µ-SPE. The extracted pyrethroids were separated within 30 min using isocratic elution with acetonitrile:water (72:28). The factors affecting the extraction efficiency were investigated. Under the optimum conditions, the enrichment factors were in the range of 51-108. Linearity was obtained in the range 0.5-400 ng mL(-1) (tetramethrin) and 5-400 ng mL(-1) (fenpropathrin, deltamethrin and permethrin) with the correlation coefficients (R(2)) greater than 0.995. Detection limits were 0.05-2 ng mL(-1) (water samples) and 0.02-2.0 ng g(-1) (vegetable samples). The relative standard deviations of peak area varied from 1.8 to 2.5% (n=10). The extraction recoveries of the four pyrethroids in field water and vegetable samples were 91.7-104.5%. The proposed method has high potential for use as a sensitive method for determination of pyrethroid residues in water and vegetable samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Air assisted dispersive liquid-liquid microextraction with solidification of the floating organic droplets (AA-DLLME-SFO) and UHPLC-PDA method: Application to antibiotics analysis in human plasma of hospital acquired pneumonia patients.

Science.gov (United States)

Ferrone, Vincenzo; Cotellese, Roberto; Carlucci, Maura; Di Marco, Lorenzo; Carlucci, Giuseppe

2018-03-20

An ultra high-performance liquid chromatographic (UHPLC) method with PDA detection was developed and validated for the simultaneous quantification of metronidazole, meropenem, ciprofloxacin, linezolid and piperacillin in human plasma and applied to patients suffering from hospital acquired pneumonia (HAP). The method uses an air assisted dispersive liquid-liquid microextraction for sample preparation. All parameters in the extraction step, including selection of extractant, amount of extractant, ionic strength, pH, and extraction cycles, were investigated and optimized. Chromatography was carried out using a Poroshell 120 SB C 18 (50 × 2.1 mm I.D. 2.6 μm particle size) column and a gradient mobile phase consisting of ammonium acetate buffer (10 mM, pH 4.0) (eluent A); and a mixture of acetonitrile-methanol in a ratio (80/20)(eluent B). Ulifloxacin was used as internal standard. The method demonstrated good linearity with correlation coefficients, r 2  > 0.9995 for the drugs, as well as high precision (RSD% ≤ 9.87%), accuracy ranged from -8.14% to +8.98. The enrichment factor (EF) obtained ranged within 87 and 121. During the validation, the concentrations of the analytes were found to be stable after 3 freeze-thaw cycles and for at least 24 h after extraction. Subsequently, this method was used to quantify the drugs in patients with HAP in order to establish if the dosage regimen given was sufficient to eradicate the infection at the target site. Copyright © 2017. Published by Elsevier B.V.

A dispersive liquid-liquid microextraction based on solidification of floating organic droplet followed by injector port silylation coupled with gas chromatography-tandem mass spectrometry for the determination of nine bisphenols in bottled carbonated beverages.

Science.gov (United States)

Mandrah, Kapil; Satyanarayana, G N V; Roy, Somendu Kumar

2017-12-15

In the present study, a method has been efficiently developed for the first time to determine nine bisphenol analogues [bisphenol A (BPA), bisphenol C (BPC), bisphenol AF (BPAF), bisphenol E (BPE), bisphenol F (BPF), bisphenol G (BPG), bisphenol M (BPM), bisphenol S (BPS), and bisphenol Z (BPZ)] together in bottled carbonated beverages (collected from the local market of Lucknow, India) using dispersive liquid-liquid microextraction process. This is based on solidification of floating organic droplet (DLLME-SFO) followed by injector port silylation coupled with gas chromatography-tandem mass spectrometry. The process investigated parameters of DLLME-SFO (including the type of extraction and disperser solvents with their volumes, effect of pH, ionic strength, and the sample volume), factors influencing to injection port derivatization like, collision energy, injector port temperature, derivatizing reagent with sample injection volume, and type of organic solvent. BPA, BPF, BPZ, and BPS were detected in each sample; whereas, other bisphenols were also detected in some carbonated beverage samples. After optimizing the required conditions, good linearity of analytes was achieved in the range of 0.097-100ngmL -1 with coefficients of determination (R 2 )≥0.995. Intra-day and inter day precision of the method was good, with relative standard deviation (% RSD)≤10.95%. The limits of detection (LOD) and limits of quantification (LOQ) values of all bisphenols were ranged from 0.021 to 0.104ngmL -1 and 0.070 to 0.343ngmL -1 , respectively. The recovery of extraction was good (73.15-95.08%) in carbonated beverage samples and good enrichment factors (96.36-117.33) were found. Thus, the developed method of microextraction was highly precise, fast, and reproducible to determine the level of contaminants in bottled carbonated beverages. Copyright © 2017 Elsevier B.V. All rights reserved.

Accurate determination of 3-alkyl-2-methoxypyrazines in wines by gas chromatography quadrupole time-of-flight tandem mass spectrometry following solid-phase extraction and dispersive liquid-liquid microextraction.

Science.gov (United States)

Fontana, Ariel; Rodríguez, Isaac; Cela, Rafael

2017-09-15

A new reliable method for the determination 3-alkyl-2-methoxypyrazines (MPs) in wine samples based on the sequential combination of solid-phase extraction (SPE), dispersive liquid-liquid microextraction (DLLME) and gas chromatography (GC) quadrupole time-of-flight accurate tandem mass spectrometry (QTOF-MS/MS) is presented. Primary extraction of target analytes was carried out by using a reversed-phase Oasis HLB (200mg) SPE cartridge combined with acetonitrile as elution solvent. Afterwards, the SPE extract was submitted to DLLME concentration using 0.06mL carbon tetrachloride (CCl 4 ) as extractant. Under final working conditions, sample concentration factors above 379 times and limits of quantification (LOQs) between 0.3 and 2.1ngL -1 were achieved. Moreover, the overall extraction efficiency of the method was unaffected by the particular characteristics of each wine; thus, accurate results (relative recoveries from 84 to 108% for samples spiked at concentrations from 5 to 25ngL -1 ) were obtained using matrix-matched standards, without using standard additions over every sample. Highly selective chromatographic records were achieved considering a mass window of 5mDa, centered in the quantification product ion corresponding to each compound. Twelve commercial wines, elaborated with grapes from different varieties and geographical origins, were processed with the optimized method. The 2-isobutyl-3-methoxypyrazine (IBMP) was determined at levels above the LOQs of the method in half of the samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Liquidity in Retirement Savings Systems: An International Comparison

OpenAIRE

Beshears, John Leonard; Choi, James J.; Hurwitz, Joshua Bayard; Laibson, David I.; Madrian, Brigitte

2015-01-01

What is the socially optimal level of liquidity in a retirement savings system? Liquid retirement savings are desirable because liquidity enables agents to flexibly respond to pre-retirement events that raise the marginal utility of consumption. On the other hand, pre-retirement liquidity is undesirable when it leads to under-saving arising from, for example, planning mistakes or self-control problems. This paper compares the liquidity that six developed economies have built into their employ...

Radioactive liquid waste processing system

International Nuclear Information System (INIS)

Noda, Tetsuya; Kuramitsu, Kiminori; Ishii, Tomoharu.

1997-01-01

The present invention provides a system for processing radioactive liquid wastes containing laundry liquid wastes, shower drains or radioactive liquid wastes containing chemical oxygen demand (COD) ingredients and oil content generated from a nuclear power plant. Namely, a collecting tank collects radioactive liquid wastes. A filtering device is connected to the exit of the collective tank. A sump tank is connected to the exit of the filtering device. A powdery active carbon supplying device is connected to the collecting tank. A chemical fluid tank is connected to the collecting tank and the filtering device by way of chemical fluid injection lines. Backwarding pipelines connect a filtered water flowing exit of the filtering device and the collecting tank. The chemical solution is stored in the chemical solution tank. Then, radioactive materials in radioactive liquid wastes generated from a nuclear power plant are removed by the filtering device. The water quality standard specified in environmental influence reports can be satisfied. In the filtering device, when the filtering flow rate is reduced, the chemical fluid is supplied from the chemical fluid tank to the filtering device to recover the filtering flow rate. (I.S.)

Development of prototype liquid scintillator system for monitoring liquid radioactive waste

International Nuclear Information System (INIS)

Nam, Uk Won; Seon, Kwang Il; Kong, Kyoung Nam; Kim, Chang Kyu; Lee, Dong Myung; Lee, Sang Kook

2003-01-01

A prototype liquid scillatillator system for measurement of multiple beta-labeled mixtures was developed and its characteristic was investigated. The signal processing system consists of two photomultiplier tubes and the coincident count circuit. The characteristic of the system was analyzed using 4 beta-labeled samples ( 3 H, 14 C, 36 Cl and 90 Sr). Beta spectra from the samples were obtained without radiation shielding, and the detection limits for each nuclides were estimated based on the spectra. The estimated detection limits were compared to the legal regulation values. It is found that the liquid radioactive nuclides are detectable well below the legal regulation values

Application of dispersive Liquid-Liquid microextraction based on solidification of floating organic droplet multi-residue method for the simultaneous determination of polychlorinated biphenyls, organochlorine, and pyrethroid pesticides in aqueous sample

International Nuclear Information System (INIS)

Zuo, Mei; Li, Man-Liang; Cheng, Jing; Matsadiq, Guzalnur; Liu, Lu; Zhang, Miao

2012-01-01

Dispersive liquid-liquid microextraction based on solidification of floating organic droplet (DLLME-SFO) technique was successfully applied for simultaneous assay of eight polychlorinated biphenyls, two organochlorine, and four pyrethroid pesticides multi-residue in aqueous samples by using GC-electron capture detection. The effects of various parameters such as kind of extractant and dispersant and volume of them, extraction time, effect of salt addition, and pH were optimized. As a result, 5.0 μL 1-dodecanol was chosen as extraction solvent, 600 μL methanol were used as dispersive solvent without salt addition, pH was adjusted to 7. Under the optimized conditions, the limits of detection (LOD) were ranged from 1.4 to 8.3 ng L -1 . Satisfactory linear range was observed from 5.0 to 2000 ng L -1 with correlation coefficient better than 0.9909. Good precisions were also acquired with RSD better than 13.6% for all target analytes. The enrichment factors of the method were ranged from 786 to 1427. The method can be successfully applied to simultaneous separation and determination of three class residues in real water samples and good recoveries were obtained ranging from 76 to 130, 73 to 129, and 78 to 130% for tap water, lake water, and industrial waste water, respectively. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Determination of twelve herbicides in tobacco by a combination of solid–liquid–solid dispersive extraction using multi-walled carbon nanotubes, dispersive liquid-liquid micro-extraction, and detection by GC with triple quadrupole mass spectrometry

International Nuclear Information System (INIS)

Liao, Qie Gen; Zhou, Yao Min; Luo, Lin Guang; Wang, Li Bing; Feng, Xiao Hu

2014-01-01

We report on a method for the determination of twelve herbicides using solid–liquid–solid dispersive extraction (SLSDE), followed by dispersive liquid-liquid micro-extraction (DLLME) and quantitation by gas chromatography with triple quadrupole mass spectrometric detection. SLSDE was applied to the extraction of herbicides from tobacco samples using multi-walled carbon nanotubes (MWCNTs) as clean-up adsorbents. The effect of the quantity of MWCNTs on SLSDE, and of type and volume of extraction and disperser solvents and of salt effect on DLLME were optimized. Good linearity is obtained in the 5.0 - 500 μg kg −1 concentration range, with regression coefficients of >0.99. Intra-day and inter-day repeatability, expressed as relative standard deviations, are between 3 and 9 %. The recoveries in case of herbicide-spiked tobacco at concentration levels of 20.0, 50.0 and 100.0 g kg −1 ranged from 79 to 105 %, and LODs are between 1.5 and 6.1 μg kg −1 . All the tobacco samples were found to contain butralin and pendimethalin at levels ranging from 15.8 to 500.0 μg kg −1 . (author)

Ferrofluids in liquid crystalline systems

International Nuclear Information System (INIS)

Figueiredo Neto, A.M.; Liebert, L.

1989-08-01

It is a well-known fact that intermediate or mesomorphic phase may exist between the crystalline and the isotropic liquid phases. The symmetry properties of these mesophases are intermediate between those of a crystal and a liquid. In this paper, some aspects of the use of ferrofluids in thermotropic and lyotropic systems are studied both the experimental difficulties as well as the fundamental phypical phenomena involved. (A.C.A.S.) [pt

Development of a polymeric ionic liquid coating for direct-immersion solid-phase microextraction using polyhedral oligomeric silsesquioxane as cross-linker.

Science.gov (United States)

Chen, Chunyan; Liang, Xiaotong; Wang, Jianping; Zou, Ying; Hu, Huiping; Cai, Qingyun; Yao, Shouzhuo

2014-06-27

A novel solid-phase microextraction (SPME) fiber was developed by chemical binding of a crosslinked polymeric ionic liquid (PIL) on the surface of an anodized Ti wire, and was applied in direct-immersion mode for the extraction of perfluorinated compounds (PFCs) from water samples coupled with high performance liquid chromatography-tandem mass spectrometry analysis. The PIL coatings were synthesized by using 1-vinyl-3-hexylimidazolium hexafluorophosphate as monomer and methylacryloyl-substituted polyhedral oligomeric silsesquioxane (POSS) as cross-linker via free radical reaction. The proposed fiber coating exhibited high mechanical stability due to the chemical bonding between the coating and the Ti wire surface. The integration of POSS reagent enhanced the organic solvent resistance of the coating. The parameters affecting the extraction performance of the fiber coating including extraction time, pH of solution, ionic strength and desorption conditions were optimized. The developed PIL-POSS fiber showed good linearity (R<0.998) between 0.1 and 50ngmL(-1) with method detection limits ranging from 0.005 to 0.08ngmL(-1) depending on the analyte, and with relative standard deviation for single-fiber repeatability and fiber-to-fiber reproducibility less than 8.6% and 9.5%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

Ultra-preconcentration and determination of selected pharmaceutical and personal care products in different water matrices by solid-phase extraction combined with dispersive liquid-liquid microextraction prior to ultra high pressure liquid chromatography tandem mass spectrometry analysis.

Science.gov (United States)

Celano, Rita; Piccinelli, Anna Lisa; Campone, Luca; Rastrelli, Luca

2014-08-15

Pharmaceutical and personal care products (PPCPs) are one of the most important classes of emerging contaminants. The potential of ecological and environmental impacts associated with PPCPs are of particular concern because they continually penetrate the aquatic environment. This work describes a novel ultra-preconcentration technique for the rapid and highly sensitive analysis of selected PPCPs in environmental water matrices at ppt levels. Selected PPCPs were rapidly extracted and concentrated from large volumes of aqueous solutions (500 and 250mL) by solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME) and then analyzed using UHPLC-MS/MS. Experimental parameters were carefully investigated and optimized to achieve the best SPE-DLLME efficiency and higher enrichment factors. The best results were obtained using the ternary mixture acetonitrile/methanol/dichloromethane 3:3:4, v/v/v, both as SPE eluent and DLLME extractant/dispersive mixture. DLLME aqueous solution (5% NaCl, 10mgL(-1) TBAB) was also modified to improve the extraction efficiency of more hydrophilic PPCPs. Under the optimal conditions, an exhaustive extraction for most of the investigated analytes (recoveries >70%), with a precision (RSD drinking, sea, river and wastewater). Method detection and quantification limits were at very low ppt levels and below 1 and 3ngL(-1), respectively, for 15 of selected PPCPs. The proposed analytical procedure offers numerous advantages such as the simplicity of operation, rapidity, a high enrichment factor and sensitivity. So it is suitable for monitoring and studies of occurrence of PPCPs in different environmental compartments. Copyright © 2014 Elsevier B.V. All rights reserved.

Air-assisted liquid–liquid microextraction by solidifying the floating organic droplets for the rapid determination of seven fungicide residues in juice samples

Energy Technology Data Exchange (ETDEWEB)

You, Xiangwei [Tobacco Research Institute, Chinese Academy of Agricultural Sciences, Qingdao 266101 (China); College of Science, China Agricultural University, Beijing 100193 (China); Xing, Zhuokan [College of Science, China Agricultural University, Beijing 100193 (China); Liu, Fengmao, E-mail: liufengmao@cau.edu.cn [College of Science, China Agricultural University, Beijing 100193 (China); Zhang, Xu [College of Science, China Agricultural University, Beijing 100193 (China)

2015-05-22

Highlights: • A novel AALLME-SFO method was firstly reported for pesticide residue analysis. • Solvent with low density and proper melting point was used as extraction solvent. • The formation of “cloudy solvent” with a syringe only. • The new method avoided the use of organic dispersive solvent. - Abstract: A novel air assisted liquid–liquid microextraction using the solidification of a floating organic droplet method (AALLME-SFO) was developed for the rapid and simple determination of seven fungicide residues in juice samples, using the gas chromatography with electron capture detector (GC-ECD). This method combines the advantages of AALLME and dispersive liquid–liquid microextraction based on the solidification of floating organic droplets (DLLME-SFO) for the first time. In this method, a low-density solvent with a melting point near room temperature was used as the extraction solvent, and the emulsion was rapidly formed by pulling in and pushing out the mixture of aqueous sample solution and extraction solvent for ten times repeatedly using a 10-mL glass syringe. After centrifugation, the extractant droplet could be easily collected from the top of the aqueous samples by solidifying it at a temperature lower than the melting point. Under the optimized conditions, good linearities with the correlation coefficients (γ) higher than 0.9959 were obtained and the limits of detection (LOD) varied between 0.02 and 0.25 μg L{sup −1}. The proposed method was applied to determine the target fungicides in juice samples and acceptable recoveries ranged from 72.6% to 114.0% with the relative standard deviations (RSDs) of 2.3–13.0% were achieved. Compared with the conventional DLLME method, the newly proposed method will neither require a highly toxic chlorinated solvent for extraction nor an organic dispersive solvent in the application process; hence, it is more environmentally friendly.

Air-assisted liquid–liquid microextraction by solidifying the floating organic droplets for the rapid determination of seven fungicide residues in juice samples

International Nuclear Information System (INIS)

You, Xiangwei; Xing, Zhuokan; Liu, Fengmao; Zhang, Xu

2015-01-01

Highlights: • A novel AALLME-SFO method was firstly reported for pesticide residue analysis. • Solvent with low density and proper melting point was used as extraction solvent. • The formation of “cloudy solvent” with a syringe only. • The new method avoided the use of organic dispersive solvent. - Abstract: A novel air assisted liquid–liquid microextraction using the solidification of a floating organic droplet method (AALLME-SFO) was developed for the rapid and simple determination of seven fungicide residues in juice samples, using the gas chromatography with electron capture detector (GC-ECD). This method combines the advantages of AALLME and dispersive liquid–liquid microextraction based on the solidification of floating organic droplets (DLLME-SFO) for the first time. In this method, a low-density solvent with a melting point near room temperature was used as the extraction solvent, and the emulsion was rapidly formed by pulling in and pushing out the mixture of aqueous sample solution and extraction solvent for ten times repeatedly using a 10-mL glass syringe. After centrifugation, the extractant droplet could be easily collected from the top of the aqueous samples by solidifying it at a temperature lower than the melting point. Under the optimized conditions, good linearities with the correlation coefficients (γ) higher than 0.9959 were obtained and the limits of detection (LOD) varied between 0.02 and 0.25 μg L −1 . The proposed method was applied to determine the target fungicides in juice samples and acceptable recoveries ranged from 72.6% to 114.0% with the relative standard deviations (RSDs) of 2.3–13.0% were achieved. Compared with the conventional DLLME method, the newly proposed method will neither require a highly toxic chlorinated solvent for extraction nor an organic dispersive solvent in the application process; hence, it is more environmentally friendly

Ultra-fast liquid chromatography with tandem mass spectrometry determination of ochratoxin A in traditional Chinese medicines based on vortex-assisted solid-liquid microextraction and aptamer-affinity column clean-up.

Science.gov (United States)

Yang, Xihui; Hu, Yichen; Kong, Weijun; Chu, Xianfeng; Yang, Meihua; Zhao, Ming; Ouyang, Zhen

2014-11-01

A rapid, selective, and sensitive ultra-fast liquid chromatography with tandem mass spectrometry method was developed for the determination of ochratoxin A in traditional Chinese medicines based on vortex-assisted solid-liquid microextraction and aptamer-affinity column clean-up. Through optimizing the sample pretreatment procedures and chromatographic conditions, good linearity (r(2) ≥ 0.9993), low limit of detection (0.5-0.8 μg/kg), and satisfactory recovery (83.54-94.44%) expressed the good reliability and applicability of the established method in various traditional Chinese medicines. Moreover, the aptamer-affinity column, prepared in-house, showed an excellent feasibility owing to its specific identification of ochratoxin A in various kinds of selected traditional Chinese medicines. The maximum adsorption amount and applicability value were 188.96 ± 10.56 ng and 72.3%, respectively. The matrix effects were effectively eliminated, especially for m/z 404.2→358.0 of ochratoxin A. The application of the developed method for screening the natural contamination levels of ochratoxin A in 25 random traditional Chinese medicines on the market in China indicated that only eight samples were contaminated with low levels below the legal limit (5.0 μg/kg) set by the European Union. This study provided a preferred choice for the rapid and accurate monitoring of ochratoxin A in complex matrices. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of ammonium in aqueous samples using new headspace dynamic in-syringe liquid-phase microextraction with in situ derivitazation coupled with liquid chromatography-fluorescence detection.

Science.gov (United States)

Muniraj, Sarangapani; Yan, Cheing-Tong; Shih, Hou-Kung; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

2012-11-19

A new simultaneous derivatization and extraction method for the preconcentration of ammonia using new one-step headspace dynamic in-syringe liquid-phase microextraction with in situ derivatization was developed for the trace determination of ammonium in aqueous samples by liquid chromatography with fluorescence detection (LC-FLD). The acceptor phase (as derivatization reagent) containing o-phthaldehyde and sodium sulfite was held within a syringe barrel and immersed in the headspace of sample container. The gaseous ammonia from the alkalized aqueous sample formed a stable isoindole derivative with the acceptor phase inside the syringe barrel through the reciprocated movements of plunger. After derivatization-cum-extraction, the acceptor phase was directly injected into LC-FLD for analysis. Parameters affecting the ammonia evolution and the extraction/derivatization efficiency such as sample matrix, pH, temperature, sampling time, and the composition of derivatization reagent, reaction temperature, and frequency of reciprocated plunger, were studied thoroughly. Results indicated that the maximum extraction efficiency was obtained by using 100μL derivatization reagent in a 1-mL gastight syringe under 8 reciprocated movements of plunger per min to extract ammonia evolved from a 20mL alkalized aqueous solution at 70°C (preheated 4min) with 380rpm stirring for 8min. The detection was linear in the concentration range of 0.625-10μM with the correlation coefficient of 0.9967 and detection limit of 0.33μM (5.6ng mL(-1)) based on SN(-1)=3. The method was applied successfully to determine ammonium in real water samples without any prior cleanup of the samples, and has been proved to be a simple, sensitive, efficient and cost-effective procedure for trace ammonium determination in aqueous samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Thermophysical properties of biodiesel and related systems: (Liquid + liquid) equilibrium data for Jatropha curcas biodiesel

International Nuclear Information System (INIS)

Silva, Juliana R.F.; Mazutti, Marcio A.; Voll, Fernando A.P.; Cardozo-Filho, Lúcio; Corazza, Marcos L.; Lanza, Marcelo; Priamo, Wagner L.; Vladimir Oliveira, J.

2013-01-01

Highlights: ► (Liquid + liquid) equilibrium data for multicomponent Jatropha curcas FAME and FAEE. ► Tie-lines, solubility curves (binodal curves) with low deviations from mass balance. ► Experimental data correlated with the UNIQUAC model. -- Abstract: Reported in this study are (liquid + liquid) equilibrium data for binary, ternary, and quaternary systems formed by fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE) of Jatropha curcas oil, water, glycerol, methanol, and ethanol at temperatures of (303.15, 318.15, and 333.15) K. In general, all the systems investigated resulted in good agreement between phase compositions of crunodes of tie-lines, solubility curves (binodal curves) and overall compositions, hence indicating low deviations from mass balance. Experimental results were correlated with the UNIQUAC model, showing low deviations among experimental and calculated values

A smartphone controlled handheld microfluidic liquid handling system.

Science.gov (United States)

Li, Baichen; Li, Lin; Guan, Allan; Dong, Quan; Ruan, Kangcheng; Hu, Ronggui; Li, Zhenyu

2014-10-21

Microfluidics and lab-on-a-chip technologies have made it possible to manipulate small volume liquids with unprecedented resolution, automation and integration. However, most current microfluidic systems still rely on bulky off-chip infrastructures such as compressed pressure sources, syringe pumps and computers to achieve complex liquid manipulation functions. Here, we present a handheld automated microfluidic liquid handling system controlled by a smartphone, which is enabled by combining elastomeric on-chip valves and a compact pneumatic system. As a demonstration, we show that the system can automatically perform all the liquid handling steps of a bead-based HIV1 p24 sandwich immunoassay on a multi-layer PDMS chip without any human intervention. The footprint of the system is 6 × 10.5 × 16.5 cm, and the total weight is 829 g including battery. Powered by a 12.8 V 1500 mAh Li battery, the system consumed 2.2 W on average during the immunoassay and lasted for 8.7 h. This handheld microfluidic liquid handling platform is generally applicable to many biochemical and cell-based assays requiring complex liquid manipulation and sample preparation steps such as FISH, PCR, flow cytometry and nucleic acid sequencing. In particular, the integration of this technology with read-out biosensors may help enable the realization of the long-sought Tricorder-like handheld in vitro diagnostic (IVD) systems.

Sensitive trace enrichment of environmental andiandrogen vinclozolin from natural waters and sediment samples using hollow-fiber liquid-phase microextraction.

Science.gov (United States)

Lambropoulou, Dimitra A; Albanis, Triantafyllos A

2004-12-17

The presence of vinclozolin in the environment as far as the endocrine disruption effects in biota are concerned has raised interest in the environmental fate of this compound. In this respect, the present study attempts to investigate the feasibility of applying a novel quantitative method, liquid-phase microextraction (LPME), so as to determine this environmental andiandrogen in environmental samples such as water and sediment samples. The technique involved the use of a small amount (3 microL) of organic solvent impregnated in a hollow fiber membrane, which was attached to the needle of a conventional GC syringe. The extracted samples were analyzed by gas chromatography coupled with electron-capture detection. Experimental LPME conditions such as extraction solvent, stirring rate, content of NaCl and pH were tested. Once LPME was optimized, the performance of the proposed technique was evaluated for the determination of vinclozolin in different types of natural water samples. The recovery of spiked water samples was from 80 to 99%. The procedure was adequate for quantification of vinclozolin in waters at levels of 0.010 to 50 microg/L (r> 0.994) with a detection limit of 0.001 microg/L (S/N= 3). Natural sediment samples from the Aliakmonas River area (Macedonia, Greece) spiked with the target andiandrogen compound were liquid-liquid extracted and analyzed by the methodology developed in this work. No significant interferences from the samples matrix were noticed, indicating that the reported methodology is an innovative tactic for sample preparation in sediment analysis, with a considerable improvement in the achieved detection limits. The results demonstrated that apart from analyte enrichment, the proposed LPME procedure also serves as clean-up method and could be successfully performed to determine trace amounts of vinclozolin in water and sediment samples.

The Bevatron liquid nitrogen circulation system

International Nuclear Information System (INIS)

Hunt, D.; Stover, G.

1987-03-01

A nitrogen liquefier and computer controlled valving system have been added to the Bevatron cryoliner vacuum system to cut operating costs by reducing liquid nitrogen consumption. The computer and interface electronic systems, which control the temperatures of twenty-eight liquid nitrogen circuits, have been chosen and designed to operate in the Bevatron's pulsating magnetic field. The nitrogen exhaust is routed back to a liquefier, of about five kilowatt capacity, liquefied, and rerouted through the cooling circuits. A description of the system and operating results are presented

Lyotropic liquid crystalline phase behaviour in amphiphile-protic ionic liquid systems.

Science.gov (United States)

Chen, Zhengfei; Greaves, Tamar L; Fong, Celesta; Caruso, Rachel A; Drummond, Calum J

2012-03-21

Approximate partial phase diagrams for nine amphiphile-protic ionic liquid (PIL) systems have been determined by synchrotron source small angle X-ray scattering, differential scanning calorimetry and cross polarised optical microscopy. The binary phase diagrams of some common cationic (hexadecyltrimethyl ammonium chloride, CTAC, and hexadecylpyridinium bromide, HDPB) and nonionic (polyoxyethylene (10) oleyl ether, Brij 97, and Pluronic block copolymer, P123) amphiphiles with the PILs, ethylammonium nitrate (EAN), ethanolammonium nitrate (EOAN) and diethanolammonium formate (DEOAF), have been studied. The phase diagrams were constructed for concentrations from 10 wt% to 80 wt% amphiphile, in the temperature range 25 °C to >100 °C. Lyotropic liquid crystalline phases (hexagonal, cubic and lamellar) were formed at high surfactant concentrations (typically >50 wt%), whereas at thermal stability of the phases formed by these surfactants persisted to temperatures above 100 °C. The phase behaviour of amphiphile-PIL systems was interpreted by considering the PIL cohesive energy, liquid nanoscale order, polarity and ionicity. For comparison the phase behaviour of the four amphiphiles was also studied in water.

Boiling water reactor liquid radioactive waste processing system

International Nuclear Information System (INIS)

Anon.

1977-01-01

The standard sets forth minimum design, construction and performance requirements with due consideration for operation of the liquid radioactive waste processing system for boiling water reactor plants for routine operation including design basis fuel leakage and design basis occurrences. For the purpose of this standard, the liquid radioactive waste processing system begins at the interfaces with the reactor coolant pressure boundary, at the interface valve(s) in lines from other systems and at those sumps and floor drains provided for liquid waste with the potential of containing radioactive material. The system terminates at the point of controlled discharge to the environment, at the point of interface with the waste solidification system and at the point of recycle back to storage for reuse. The standard does not include the reactor coolant clean-up system, fuel pool clean-up system, sanitary waste system, any nonaqueous liquid system or controlled area storm drains

Development of a new green non-dispersive ionic liquid microextraction method in a narrow glass column for determination of cadmium prior to couple with graphite furnace atomic absorption spectrometry

Energy Technology Data Exchange (ETDEWEB)

Naeemullah, E-mail: naeemullah433@yahoo.com [Gaziosmanpaşa University, Faculty of Science and Arts, Chemistry Department, 60250 Tokat (Turkey); National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080 (Pakistan); Kazi, Tasneem Gul [National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080 (Pakistan); Tuzen, Mustafa [Gaziosmanpaşa University, Faculty of Science and Arts, Chemistry Department, 60250 Tokat (Turkey); Shah, Faheem; Afridi, Hassan Imran [National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080 (Pakistan); Citak, Demirhan [Gaziosmanpaşa University, Faculty of Science and Arts, Chemistry Department, 60250 Tokat (Turkey)

2014-02-17

Graphical abstract: -- Highlights: •A novel and rapid non-dispersive ionic liquid based microextractions. •We used a long narrow glass column to provide more contact area between two media (aqueous and extractive). •APDC using as complexing agent and analyzed by GFAAS. •Introduced a novel approach that reduced solvent consumption, effort, time. •It was applied for determination of understudy analytes in real water sample. -- Abstract: Easy and innovative non-dispersive ionic liquid based microextraction (NDILME) has been developed for preconcentration of trace level of cadmium (Cd) in aqueous real surface water samples prior to couple with graphite furnace atomic absorption spectrometry (GFAAS). A 200 cm long narrow glass column containing aqueous solution of standard/sample was used to increase phase transfer ratio by providing more contact area between two medium (aqueous and extractive), which drastically improve the recoveries of labile hydrophobic chelate of Cd ammonium pyrrolidinedithiocarbamate (APDC), into ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [C{sub 4}mim][PF{sub 6}]. Different aspect of the desire method have been investigated and optimized. Under the optimized key experimental variables, limit of detection (LOD) and enhancement factor (EF) were achieved to be 0.5 ng L{sup −1} and 150, respectively. Reliability of the model method was checked by relative standard deviation (%RSD), which was found to be < 5%. Validity and accuracy of the developed method was checked by analysis of certified reference water samples (SLRS-4 Riverine water) using standard addition method. Application of the model method was productively performed by analysis of Cd in real surface water samples (tap and sea)

LIQUID-LIQUID EXTRACTION COLUMNS

Science.gov (United States)

Thornton, J.D.

1957-12-31

This patent relates to liquid-liquid extraction columns having a means for pulsing the liquid in the column to give it an oscillatory up and down movement, and consists of a packed column, an inlet pipe for the dispersed liquid phase and an outlet pipe for the continuous liquid phase located in the direct communication with the liquid in the lower part of said column, an inlet pipe for the continuous liquid phase and an outlet pipe for the dispersed liquid phase located in direct communication with the liquid in the upper part of said column, a tube having one end communicating with liquid in the lower part of said column and having its upper end located above the level of said outlet pipe for the dispersed phase, and a piston and cylinder connected to the upper end of said tube for applying a pulsating pneumatic pressure to the surface of the liquid in said tube so that said surface rises and falls in said tube.

Rapid analysis of Fructus forsythiae essential oil by ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction followed by gas chromatography–mass spectrometry

International Nuclear Information System (INIS)

Jiao, Jiao; Ma, Dan-Hui; Gai, Qing-Yan; Wang, Wei; Luo, Meng; Fu, Yu-Jie; Ma, Wei

2013-01-01

Graphical abstract: -- Highlights: •A new ILAMD-HS-SDME method is developed for the microextraction of essential oil. •ILs used as destruction agent of plant cell walls and microwave absorption medium. •Parameters affecting the extraction efficiency are optimized by Box–Behnken design. •Procedure benefits: similar constituents, shorter duration and smaller sample amount. •ILAMD-HS-SDME followed by GC–MS is a promising technique in analytical fields. -- Abstract: A rapid, green and effective miniaturized sample preparation and analytical technique, i.e. ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction (ILAMD-HS-SDME) followed by gas chromatography–mass spectrometry (GC–MS) was developed for the analysis of essential oil (EO) in Fructus forsythiae. In this work, ionic liquids (ILs) were not only used as the absorption medium of microwave irradiation but also as the destruction agent of plant cell walls. 1-Ethyl-3-methylimidazolium acetate ([C 2 mim]OAc) was chosen as the optimal ILs. Moreover, n-heptadecane (2.0 μL) was selected as the appropriate suspended solvent for the extraction and concentration of EO. Extraction conditions of the proposed method were optimized using the relative peak area of EO constituents as the index, and the optimal operational parameters were obtained as follows: irradiation power (300 W), sample mass (0.7 g), mass ratio of ILs to sample (2.4), temperature (78 °C) and time (3.4 min). In comparison to previous reports, the proposed method was faster and required smaller sample amount but could equally monitor all EO constituents with no significant differences

Rapid analysis of Fructus forsythiae essential oil by ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction followed by gas chromatography–mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Jiao, Jiao [State Key Laboratory of Tree Genetics and Breeding, Northeast Forestry University, Harbin 150040 (China); Ma, Dan-Hui [College of Life Sciences, Northeast Forestry University, Harbin 150040 (China); Gai, Qing-Yan; Wang, Wei; Luo, Meng [State Engineering Laboratory of Bio-Resource Eco-Utilization, Northeast Forestry University, Harbin 150040 (China); Fu, Yu-Jie, E-mail: yujie_fu2002@yahoo.com [State Engineering Laboratory of Bio-Resource Eco-Utilization, Northeast Forestry University, Harbin 150040 (China); Ma, Wei, E-mail: mawei@hljucm.net [State Key Laboratory of Tree Genetics and Breeding, Northeast Forestry University, Harbin 150040 (China); School of Pharmaceutical, Heilongjiang University of Chinese Medicine, Harbin 150040 (China)

2013-12-04

Graphical abstract: -- Highlights: •A new ILAMD-HS-SDME method is developed for the microextraction of essential oil. •ILs used as destruction agent of plant cell walls and microwave absorption medium. •Parameters affecting the extraction efficiency are optimized by Box–Behnken design. •Procedure benefits: similar constituents, shorter duration and smaller sample amount. •ILAMD-HS-SDME followed by GC–MS is a promising technique in analytical fields. -- Abstract: A rapid, green and effective miniaturized sample preparation and analytical technique, i.e. ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction (ILAMD-HS-SDME) followed by gas chromatography–mass spectrometry (GC–MS) was developed for the analysis of essential oil (EO) in Fructus forsythiae. In this work, ionic liquids (ILs) were not only used as the absorption medium of microwave irradiation but also as the destruction agent of plant cell walls. 1-Ethyl-3-methylimidazolium acetate ([C{sub 2}mim]OAc) was chosen as the optimal ILs. Moreover, n-heptadecane (2.0 μL) was selected as the appropriate suspended solvent for the extraction and concentration of EO. Extraction conditions of the proposed method were optimized using the relative peak area of EO constituents as the index, and the optimal operational parameters were obtained as follows: irradiation power (300 W), sample mass (0.7 g), mass ratio of ILs to sample (2.4), temperature (78 °C) and time (3.4 min). In comparison to previous reports, the proposed method was faster and required smaller sample amount but could equally monitor all EO constituents with no significant differences.

Use of micro-emulsions in liquid-liquid extraction

International Nuclear Information System (INIS)

Komornicki, Jacques

1982-01-01

As liquid-liquid extraction of metallic cations is an important method of separation and concentration of metals present in diluted aqueous solutions, and as the extraction rate is limited by one or several steps of matter transfer at the liquid-liquid interface, the extraction kinetics can be improved by creating a wide surface interface and by allowing an increased reactivity between species. In this research thesis, the author aims at determining to which extent systems of interface with a wide surface obtained by using for example amphiphile molecules to create micro-emulsions, can be used as reaction media for physical-chemical processes of liquid-liquid extraction. He also aims at identifying their applicability limitations and problems which might arise with their application. The author notably focuses of the liquid-liquid extraction of metallic cations exhibiting particularly slow extraction kinetics

Liquids and liquid mixtures

CERN Document Server

Rowlinson, J S; Baldwin, J E; Buckingham, A D; Danishefsky, S

2013-01-01

Liquids and Liquid Mixtures, Third Edition explores the equilibrium properties of liquids and liquid mixtures and relates them to the properties of the constituent molecules using the methods of statistical thermodynamics. Topics covered include the critical state, fluid mixtures at high pressures, and the statistical thermodynamics of fluids and mixtures. This book consists of eight chapters and begins with an overview of the liquid state and the thermodynamic properties of liquids and liquid mixtures, including vapor pressure and heat capacities. The discussion then turns to the thermodynami

Ionic Liquid-Liquid Chromatography: A New General Purpose Separation Methodology.

Science.gov (United States)

Brown, Leslie; Earle, Martyn J; Gîlea, Manuela A; Plechkova, Natalia V; Seddon, Kenneth R

2017-08-10

Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid-liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous character of ionic liquid-based solvent systems to be used in a wide variety of separations (including transition metal salts, arenes, alkenes, alkanes, bio-oils and sugars).

Salicylic acid determination in estuarine and riverine waters using hollow fiber liquid-phase microextraction and capillary zone electrophoresis.

Science.gov (United States)

da Silva, Gilmar Silvério; Lima, Diana L D; Esteves, Valdemar Inocêncio

2017-06-01

A low-cost methodology using hollow fiber liquid-phase microextraction (HF-LPME) and capillary zone electrophoresis (CZE) with UV-Vis detector was developed to analyze the salicylic acid (SA) in estuarine and riverine waters. The technique is easy-to-use and rapid, and demands little volume of organic solvent. The extraction was carried out using a polypropylene membrane supporting into octan-1-ol. HF-LPME under optimized conditions (donor solution sample pH 2, acceptor solution pH 14, sample volume 25 mL, fiber length 10 cm, acceptor volume 25 μL, extraction time 3 h and stirring speed 350 rpm) presented high enrichment factor (407 times) and good recovery in real water samples (from 88 to 110%). A limit of detection of 2.6 μg L -1 was achieved using CZE with UV-Vis detector as quantification method. The method was applied to direct quantification of SA in environmental complex estuarine and riverine water matrices.

A multiple hollow fibre liquid-phase microextraction method for the determination of halogenated solvent residues in olive oil.

Science.gov (United States)

Manso, J; García-Barrera, T; Gómez-Ariza, J L; González, A G

2014-02-01

The present paper describes a method based on the extraction of analytes by multiple hollow fibre liquid-phase microextraction and detection by ion-trap mass spectrometry and electron capture detectors after gas chromatographic separation. The limits of detection are in the range of 0.13-0.67 μg kg(-1), five orders of magnitude lower than those reached with the European Commission Official method of analysis, with three orders of magnitude of linear range (from the quantification limits to 400 μg kg(-1) for all the analytes) and recoveries in fortified olive oils in the range of 78-104 %. The main advantages of the analytical method are the absence of sample carryover (due to the disposable nature of the membranes), high enrichment factors in the range of 79-488, high throughput and low cost. The repeatability of the analytical method ranged from 8 to 15 % for all the analytes, showing a good performance.

Efficient energy storage in liquid desiccant cooling systems

Energy Technology Data Exchange (ETDEWEB)

Hublitz, Astrid

2008-07-18

Liquid Desiccant Cooling Systems (LDCS) are open loop sorption systems for air conditioning that use a liquid desiccant such as a concentrated salt solution to dehumidify the outside air and cool it by evaporative cooling. Thermochemical energy storage in the concentrated liquid desiccant can bridge power mismatches between demand and supply. Low-flow LDCS provide high energy storage capacities but are not a state-of-the-art technology yet. The key challenge remains the uniform distribution of the liquid desiccant on the heat and mass transfer surfaces. The present research analyzes the factors of influence on the energy storage capacity by simulation of the heat and mass transfer processes and specifies performance goals for the distribution of the process media. Consequently, a distribution device for the liquid desiccant is developed that reliably meets the performance goals. (orig.)

Liquid-liquid displacement in slippery liquid-infused membranes (SLIMs)

OpenAIRE

Bazyar, Hanieh; Lv, Pengyu; Wood, Jeffery A.; Porada, Slawomir; Lohse, Detlef; Lammertink, Rob G. H.

2018-01-01

Liquid-infused membranes inspired by slippery liquid-infused porous surfaces (SLIPS) have been recently introduced to membrane technology. The gating mechanism of these membranes is expected to give rise to anti-fouling properties and multi-phase transport capabilities. However, the long-term retention of the infusion liquid has not yet been explored. To address this issue, we investigate the retention of the infusion liquid in slippery liquid-infused membranes (SLIMs) via liquid-liquid displ...

Quaternary isobaric (vapor + liquid + liquid) equilibrium and (vapor + liquid) equilibrium for the system (water + ethanol + cyclohexane + heptane) at 101.3 kPa

International Nuclear Information System (INIS)

Pequenin, Ana; Asensi, Juan Carlos; Gomis, Vicente

2011-01-01

Highlights: → Water-ethanol-cyclohexane-heptane and water-cyclohexane-heptane isobaric VLLE. → Isobaric experimental data were determined at 101.3 kPa. → A dynamic recirculating still with an ultrasonic homogenizer was used. → The quaternary system does not present quaternary azeotropes. - Abstract: Experimental isobaric (vapor + liquid + liquid) and (vapor + liquid) equilibrium data for the ternary system {water (1) + cyclohexane (2) + heptane (3)} and the quaternary system {water (1) + ethanol (2) + cyclohexane (3) + heptane (4)} were measured at 101.3 kPa. An all-glass, dynamic recirculating still equipped with an ultrasonic homogenizer was used to determine the VLLE. The results obtained show that the system does not present quaternary azeotropes. The point-by-point method by Wisniak for testing the thermodynamic consistency of isobaric measurements was used to test the equilibrium data.

Experimental performance of indirect air–liquid membrane contactors for liquid desiccant cooling systems

International Nuclear Information System (INIS)

Das, Rajat Subhra; Jain, Sanjeev

2013-01-01

Owing to the stringent indoor air quality (IAQ) requirements and high cost of desiccants, one of the major concerns in liquid desiccant technology has been the carryover, which can be eliminated through indirect contact between desiccant and air. Membrane contactors using microporous semipermeable hydrophobic membranes have a great potential in this regard. This communication investigates the performance of semipermeable membrane based indirect contactors as dehumidifiers in liquid desiccant cooling applications. Experiments on different types of membrane contactors are carried out using lithium chloride (LiCl) solution as desiccant. The membrane contactors consist of alternate channels of air and liquid desiccant flowing in cross-flow direction. Hydrophobic membranes form a liquid tight, vapor permeable porous barrier between hygroscopic solution and moist air, thus eliminating carryover of desiccant droplets. In order to provide maximum contact area for air–desiccant interaction, a wicking material is sandwiched between two membranes in the liquid channel. It is observed that vapor flux upto 1300 g/m 2 h can be achieved in a membrane contactor with polypropylene (PP) membranes, although the dehumidification effectiveness remains low. The effect of key parameters on the transmembrane vapor transport is presented in the paper. - Highlights: • Indirect membrane contactors developed to avoid carryover in liquid desiccant system. • Dehumidification effectiveness and vapor flux reported under varying conditions. • Vapor flux upto 1295 g/m 2 h in polypropylene contactor with high area density. • Dehumidification effectiveness with LiCl solution varies within 23% to 45%

A system extinguishing a fire by insulating a liquid fuel

International Nuclear Information System (INIS)

Colome, Jacques; Duchene, Alain; Regnier, Jean.

1975-01-01

The invention refers to a system for quickly extinguishing a liquid fuel body on fire by insulating it completely from the ambient air. It applies particularly to the case of a high temperature liquid sodium sheet flowing accidentally from a circuit belonging to a fast neutron reactor. The system in question includes a lower receptacle for collecting the liquid fuel and a top cover shutting off the receptacle. This cover has inclined channels to take the liquid fuel flow and openings to allow this liquid through at the bottom end of the channels. These openings are closed by retractable shutters moving away under the pressure of the liquid in the channels and closing automatically after the liquid has flowed into the receptacle [fr

Liquidity policies and systemic risk

OpenAIRE

Adrian, Tobias; Boyarchenko, Nina

2013-01-01

The growth of wholesale-funded credit intermediation has motivated liquidity regulations. We analyze a dynamic stochastic general equilibrium model in which liquidity and capital regulations interact with the supply of risk-free assets. In the model, the endogenously time-varying tightness of liquidity and capital constraints generates intermediaries’ leverage cycle, influencing the pricing of risk and the level of risk in the economy. Our analysis focuses on liquidity policies’ implications ...

Ionic Liquid-Liquid Chromatography: A New General Purpose Separation Methodology

OpenAIRE

Brown, Leslie; Earle, Martyn J; Gilea, Manuela; Plechkova, Natalia V; Seddon, Kenneth R

2017-01-01

Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid-liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous char...

(Liquid + liquid) equilibria of four alcohol–water systems containing 1,8-cineole at T = 298.15 K

International Nuclear Information System (INIS)

Li, Hengde; Feng, Zhangni; Wan, Li; Huang, Cheng; Zhang, Tianfei; Fang, Yanxiong

2016-01-01

Graphical abstract: (Liquid + liquid) equilibria of C_1–C_4 alcohol–water systems containing 1,8-cineole are presented. Distribution ratios of alcohol in the mixtures are examined. The immiscible region of the LLE systems is evaluated and discussed. - Highlights: • Ternary (liquid + liquid) equilibria containing 1,8-cineole are presented. • Distribution ratios of C_1–C_4 alcohol in the mixtures are examined. • The LLE values were correlated using the NRTL and UNIQUAC models. - Abstract: As an eco-friendly compound from essential oils, 1,8-cineole (cineole, eucalyptol) has the potential to replace the ozone depleting industrial solvents. This paper presents experimental (liquid + liquid) equilibrium (LLE) data for four alcohol–water systems containing 1,8-cineole. To evaluate the phase equilibrium properties of 1,8-cineole in aqueous alcohol mixtures, LLE values for the ternary systems (water + methanol or ethanol or 1-propanol or 1-butanol + 1,8-cineole) were determined with a tie-line method at T = 298.15 K under atmospheric pressure. The well-known Hand, Bachman and Othmer–Tobias equations were used to test the reliability of the experimental results. The binodal curves and distribution ratios of alcohol in the mixtures are shown and discussed. The experimental LLE values were satisfactorily correlated by the NRTL and UNIQUAC models.

Application of salting-out effect equation to modelling of liquid-liquid distribution systems

International Nuclear Information System (INIS)

Pitsch, H.K.

1986-03-01

Physicochemical interpretation of salting-out is reviewed and effects of the medium on liquid-liquid distribution equilibria are described by two non-specific parameters of salting-out agents: total concentration of species in the aqueous phase and water activity. Thus extraction of a given constituent in various media can be forecasted with few data. Different uranyl and technetium (VII) extraction systems are analyzed to show the potentiality of the method. Coextraction of nitric acid and uranyl nitrate by tributyl phosphate is used to show the possibility of modelling complex distribution systems in industrial conditions [fr

CASH AND LIQUIDITY/LIQUIDITY AND LIQUIDITY RATIO

Directory of Open Access Journals (Sweden)

BEATRIX LIGHEZAN BREUER

2012-12-01

Full Text Available The present paper aims to present the correlation as well as the differences between liquidity/cash and liquidity ratio in terms of economic entities. Researches on this topic are based on the opinions of some specialists in accounting and in the economic-financial analysis, as well as on the national legal stipulations and the ones set out in the International Accounting Standards, the Financial report, respectively. The object of this paper is represented by the correlation between liquidity/cash and liquidity ratios representing the liquidity as current assets, assets implied in the determination of liquidity ratios. The end of the paper consists of the conclusions drawn from the issues presented in the paper but also our views on this research topic.

Recent Microextraction Techniques for Determination and Chemical Speciation of Selenium

Directory of Open Access Journals (Sweden)

Ibrahim Ahmed S. A.

2017-05-01

Full Text Available Research designed to improve extraction has led to the development of microextraction techniques (ME, which involve simple, low cost, and effective preconcentrationof analytes in various matrices. This review is concerned with the principles and theoretical background of ME, as well as the development of applications for selenium analysis during the period from 2008 to 2016. Among all ME, dispersive liquid-liquid microextraction was found to be most favorable for selenium. On the other hand, atomic absorption spectrometry was the most frequently used instrumentation. Selenium ME have rarely been coupled to spectrophotometry and X-ray spectrophotometry methods, and there is no published application of ME with electrochemical techniques. We strongly support the idea of using a double preconcentration process, which consists of microextraction prior to preconcentration, followed by selenium determination using cathodic stripping voltammetry (ME-CSV. More attention should focus on the development of accurate, precise, and green methods for selenium analysis.

Mobile liquid VR system: a cost effective alternative

International Nuclear Information System (INIS)

Soto, R.; Harkins, R.; HPD, Inc., Naperville, IL)

1985-01-01

The need for cost effective alternatives to treat large volumes of liquid radwaste has never been more evident. As part of a continuing effort to introduce such alternatives, HPD, Inc., and Chem-Nuclear Systems, Inc., have integrated two proven state-of-the-art technologies to offer a mobile liquid volume reduction system that satisfies nuclear industry requirements, with respect to liquid radwaste handling. This system optimizes proven technology by employing a crystallizer unit to concentrate the waste liquids to 50 weight percent solids, thereby reducing the volume to be solidified by factors of 40, while using only 20 percent of the energy required by conventional evaporative systems. In addition, the system employs a field proven cement solidification process which has been accepted in a Topical Report by the US NRC and which offers the highest waste to container volume ratios for stable waste forms in the industry. This volume reduction-solidification system is able to reduce over 7000 gallons of liquid waste per day to less than 30 cubic feet of 10CFR61 certified stable solidified waste for ultimate disposal or on-site storage. This document describes the GEODE System; its applicability; economics; volume reduction; scope of responsibility and experience. Major benefits include higher VR factors; assurance of continual regulatory compliance; and no capital investment

(Liquid + liquid) equilibria of perfluorocarbons with fluorinated ionic liquids

International Nuclear Information System (INIS)

Martinho, S.; Araújo, J.M.M.; Rebelo, L.P.N.; Pereiro, A.B.; Marrucho, I.M.

2013-01-01

Highlights: • (Liquid + liquid) equilibria perfluorocarbons and fluorinated ionic liquids. • Non-Random Two Liquid model was successfully applied. • Thermodynamic functions that describe the solvation process were calculated. -- Abstract: In order to evaluate the feasibility of partially replace perfluorocarbons (PFCs) with fluorinated ionic liquids (FILs) in PFCs-in-water emulsions, usually used for biomedical purposes, herein the (liquid + liquid) phase equilibria of FILs containing fluorinated chains longer than four carbons with PFCs were carried out in a wide range of temperatures. With this goal in mind, two PFCs (perfluorooctane and perfluorodecalin) were selected and the (liquid + liquid) equilibria of the binary mixtures of these PFCs and FILs were studied at atmospheric pressure in a temperature range from T (293.15 to 343.15) K. For these studies, FILs containing ammonium, pyridinium and imidazolium cations and different anions with fluorocarbon alkyl chains between 4 and 8 were included. Additionally, Non-Random Two Liquid (NRTL) thermodynamic model was successfully applied to correlate the behaviour of the PFCs + FILs binary mixtures. Moreover, thermodynamic functions that describe the solvation process were calculated from the experimental data

Spontaneous Marangoni Mixing of Miscible Liquids at a Liquid-Liquid-Air Contact Line.

Science.gov (United States)

Kim, Hyoungsoo; Lee, Jeongsu; Kim, Tae-Hong; Kim, Ho-Young

2015-08-11

We investigate the flow patterns created when a liquid drop contacts a reservoir liquid, which has implications on various physicochemical and biochemical reactions including mixing in microfluidic systems. The localized vortical flow spontaneously triggered by the difference of surface tension between the two liquids is studied, which is thus termed the Marangoni vortex. To quantitatively investigate the strength of vortices, we performed particle image velocimetry (PIV) experiments by varying the surface tension difference, the gap of the flow cell, the density and viscosity of the reservoir liquid, and the size of the drop. A scaling law that balances the interfacial energy of the system with the kinetic energy of the vortical flows allows us to understand the functional dependence of the Marangoni vortex strength on various experimental parameters.

Study of Baffle Boundary and System Parameters on Liquid-Solid Coupling Vibration of Rectangular Liquid-Storage Structure

Directory of Open Access Journals (Sweden)

Wei Jing

2016-01-01

Full Text Available In order to study the vibration problem of liquid-solid coupling of rectangular liquid-storage structure with horizontal elastic baffle, ignoring the influence of surface gravity wave, two different velocity potential functions corresponding to the liquid above and below the elastic baffle are assumed; based on the theory of mathematical equation and energy method, the formulas of basic frequency of liquid-solid coupling vibration system are derived, the baffle joined to the tank wall with 3 kinds of boundary conditions, namely, four edges simply supported, two opposite edges clamped and two opposite edges simply supported, and four edges clamped; the influence rules of baffle length-width ratio, the ratio of baffle height to liquid level, baffle elastic modulus, baffle density, baffle thickness, and liquid density on the coupling vibration performance are studied. The results show that the frequency of the clamped boundary is minimum; the influences of baffle length-width ratio and relative height on the basic frequency are much greater than that of the other system parameters; the relation between baffle length-width ratio and the frequency is exponential, while baffle relative height has a parabola relation with the frequency; the larger the baffle length-width ratio, the closer the baffle to the liquid level; the coupling frequency will be reduced more obviously.

Liquid helium target

International Nuclear Information System (INIS)

Fujii, Y.; Kitami, T.; Torikoshi, M.

1984-12-01

A liquid helium target system has been built and used for the experiment on the reaction 4 He(γ, p). The target system has worked satisfactorily; the consumption rate of liquid helium is 360 ml/h and the cryogenic system retains liquid helium for about ten hours. The structure, operation and performance of the target system are reported. (author)

Dispersive liquid-phase microextraction with solidification of floating organic droplet coupled with high-performance liquid chromatography for the determination of Sudan dyes in foodstuffs and water samples.

Science.gov (United States)

Chen, Bo; Huang, Yuming

2014-06-25

Dispersive liquid-phase microextraction with solidification of floating organic drop (SFO-DLPME) is one of the most interesting sample preparation techniques developed in recent years. In this paper, a new, rapid, and efficient SFO-DLPME coupled with high-performance liquid chromatography (HPLC) was established for the extraction and sensitive detection of banned Sudan dyes, namely, Sudan I, Sudan II, Sudan III, and Sudan IV, in foodstuff and water samples. Various factors, such as the type and volume of extractants and dispersants, pH and volume of sample solution, extraction time and temperature, ion strength, and humic acid concentration, were investigated and optimized to achieve optimal extraction of Sudan dyes in one single step. After optimization of extraction conditions using 1-dodecanol as an extractant and ethanol as a dispersant, the developed procedure was applied for extraction of the target Sudan dyes from 2 g of food samples and 10 mL of the spiked water samples. Under the optimized conditions, all Sudan dyes could be easily extracted by the proposed SFO-DLPME method. Limits of detection of the four Sudan dyes obtained were 0.10-0.20 ng g(-1) and 0.03 μg L(-1) when 2 g of foodstuff samples and 10 mL of water samples were adopted, respectively. The inter- and intraday reproducibilities were below 4.8% for analysis of Sudan dyes in foodstuffs. The method was satisfactorily used for the detection of Sudan dyes, and the recoveries of the target for the spiked foodstuff and water samples ranged from 92.6 to 106.6% and from 91.1 to 108.6%, respectively. These results indicated that the proposed method is simple, rapid, sensitive, and suitable for the pre-concentration and detection of the target dyes in foodstuff samples.

Carrier mediated hollow fiber liquid phase microextraction combined with HPLC-UV for preconcentration and determination of some tetracycline antibiotics.

Science.gov (United States)

Shariati, Shahab; Yamini, Yadollah; Esrafili, Ali

2009-02-01

In the present study, a simple and efficient preconcentration method was developed using carrier mediated three phase liquid phase microextraction prior to HPLC-UV for simultaneous extraction and determination of trace amounts of highly hydrophilic tetracycline antibiotics including tetracycline (TCN), oxytetracycline (OTCN) and doxycycline (DCN) in bovine milk, human plasma and water samples. For extraction, 11.0 mL of the aqueous sample containing TCNs and 0.05 M Na(2)HPO(4) (9.10.995). Finally, applicability of the proposed method was successfully confirmed by extraction and determination of the drugs in water and plasma samples as well as in bovine milk samples with low and high fat contents. Comparing to the traditional methods, the proposed method exhibits high sensitivity and high preconcentration factors as well as good precision. The extraction setup is simple and due to active transport of analytes, high cleanup effect and good selectivity are obtained in extraction process.

Flow transition criteria of a liquid jet into a liquid pool

Energy Technology Data Exchange (ETDEWEB)

Saito, Shimpei, E-mail: s1630195@u.tsukuba.ac.jp [Graduate School of Systems and Information Engineering, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573 (Japan); Abe, Yutaka [Faculty of Engineering, Information and Systems, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573 (Japan); Koyama, Kazuya [Reactor Core and Safety Design Department, Mitsubishi FBR Systems, Inc., 2-34-17 Jingumae, Shibuya, Tokyo 150-0001 (Japan)

2017-04-15

Highlights: • Jet breakup and droplet formation in immiscible liquid-liquid systems was studied experimentally. • The observed jet breakup behavior was classified into characteristic regimes. • The droplet size distribution was analyzed using image processing. • The variation of droplet size was compared with available melt-jet experiments. • Extrapolation to the expected SFR conditions implied that most of the hydrodynamic conditions would be the atomization regime. - Abstract: To better understand the fundamental interactions between melt jet and coolant during a core-disruptive accident at a sodium-cooled fast reactor, the jet breakup and droplet formation in immiscible liquid-liquid systems were studied experimentally. Experiments using two different pairs of test fluids were carried out at isothermal conditions. The observed jet breakup behavior was classified into characteristic regimes based on the classical Ohnesorge classification in liquid-gas systems. The variation in breakup length obtained in the present liquid-liquid system was similar to that in a liquid-gas system. The droplet size distribution in each breakup regime was analyzed using image processing and droplet formation via pinch-off, satellite formation, and entrainment was observed. The measured droplet size was compared with those available from melt jet experiments. Based on the observation and analysis results, the breakup regimes were organized on a dimensionless operating diagram, with the derived correlations representing the criteria for regime boundaries of a liquid-liquid system. Finally, the experimental data were extrapolated to the expected conditions of a sodium-cooled fast reactor. From this, it was implied that most of the hydrodynamic conditions during an accident would be close to the atomization regime, in which entrainment is the dominant process for droplet formation.

Systems and methods for monitoring a solid-liquid interface

Science.gov (United States)

Stoddard, Nathan G; Lewis, Monte A.; Clark, Roger F

2013-06-11

Systems and methods are provided for monitoring a solid-liquid interface during a casting process. The systems and methods enable determination of the location of a solid-liquid interface during the casting process.

Systemic Liquidity Crisis with Dynamic Haircuts

OpenAIRE

Sever, Can

2014-01-01

In this paper, using network tools, I analyse systemic impacts of liquidity shocks in interbank market in case of endogenous haircuts. Gai, Haldane and Kapadia (2011) introduce a benchmark for liquidity crisis following haircut shocks, and Gorton and Metrick (2010) reveal the evidence from 2007-09 crisis for increasing haircuts with banking panic. In the benchmark model, I endogenize and update haircuts dynamically during the period of stress. The results significantly differ from...

Recent developments in biocatalysis in multiphasic ionic liquid reaction systems.

Science.gov (United States)

Meyer, Lars-Erik; von Langermann, Jan; Kragl, Udo

2018-06-01

Ionic liquids are well known and frequently used 'designer solvents' for biocatalytic reactions. This review highlights recent achievements in the field of multiphasic ionic liquid-based reaction concepts. It covers classical biphasic systems including supported ionic liquid phases, thermo-regulated multi-component solvent systems (TMS) and polymerized ionic liquids. These powerful concepts combine unique reaction conditions with a high potential for future applications on a laboratory and industrial scale. The presence of a multiphasic system simplifies downstream processing due to the distribution of the catalyst and reactants in different phases.

Novel materials and methods for solid-phase extraction and liquid chromatography

Energy Technology Data Exchange (ETDEWEB)

Ambrose, Diana [Iowa State Univ., Ames, IA (United States)

1997-06-24

This report contains a general introduction which discusses solid-phase extraction and solid-phase micro-extraction as sample preparation techniques for high-performance liquid chromatography, which is also evaluated in the study. This report also contains the Conclusions section. Four sections have been removed and processed separately: silicalite as a sorbent for solid-phase extraction; a new, high-capacity carboxylic acid functionalized resin for solid-phase extraction; semi-micro solid-phase extraction of organic compounds from aqueous and biological samples; and the high-performance liquid chromatographic determination of drugs and metabolites in human serum and urine using direct injection and a unique molecular sieve.

Quantification of free and total bisphenol A and bisphenol B in human urine by dispersive liquid-liquid microextraction (DLLME) and heart-cutting multidimensional gas chromatography-mass spectrometry (MD-GC/MS).

Science.gov (United States)

Cunha, S C; Fernandes, J O

2010-11-15

A novel method combining dispersive liquid-liquid microextraction (DLLME) and heart-cutting multidimensional gas chromatography coupled to mass spectrometry was developed for the determination of free and total bisphenol A (BPA) and bisphenol B (BPB) in human urine samples. The DLLME procedure combines extraction, derivatization and concentration of the analytes into one step. Several important variables influencing the extraction efficiency and selectivity such as nature and volume of extractive and dispersive solvents as well as the amount of acetylating reagent were investigated. The temperature and time to hydrolyze BPA and BPB conjugates with a β-glucuronidase and sulfatase enzyme preparation were also studied. Under the optimized conditions good efficiency extraction (71-93%) and acceptable total DLLME yields (56-77%) were obtained for both analytes. Matrix-matched calibration curves were linear with correlation coefficients higher than 0.996 in the range level 0.1-5 μg/l, and the relative standard deviations (%RSD) were lower than 20% (n=6). The limits of detection were 0.03 and 0.05 μg/l for BPA and BPB, respectively. The applicability of the proposed method for determining urinary free and total BPA and BPB was assessed by analyzing the human urine of a group of 20 volunteers. Free BPA was detected in 45% of the sample whereas total BPA was detected in 85% of the samples at concentrations ranging between 0.39 and 4.99 μg/l. BPB was detected in conjugated form in two samples. Copyright © 2010 Elsevier B.V. All rights reserved.

A review of solid-fluid selection options for optical-based measurements in single-phase liquid, two-phase liquid-liquid and multiphase solid-liquid flows

Science.gov (United States)

Wright, Stuart F.; Zadrazil, Ivan; Markides, Christos N.

2017-09-01

Experimental techniques based on optical measurement principles have experienced significant growth in recent decades. They are able to provide detailed information with high-spatiotemporal resolution on important scalar (e.g., temperature, concentration, and phase) and vector (e.g., velocity) fields in single-phase or multiphase flows, as well as interfacial characteristics in the latter, which has been instrumental to step-changes in our fundamental understanding of these flows, and the development and validation of advanced models with ever-improving predictive accuracy and reliability. Relevant techniques rely upon well-established optical methods such as direct photography, laser-induced fluorescence, laser Doppler velocimetry/phase Doppler anemometry, particle image/tracking velocimetry, and variants thereof. The accuracy of the resulting data depends on numerous factors including, importantly, the refractive indices of the solids and liquids used. The best results are obtained when the observational materials have closely matched refractive indices, including test-section walls, liquid phases, and any suspended particles. This paper reviews solid-liquid and solid-liquid-liquid refractive-index-matched systems employed in different fields, e.g., multiphase flows, turbomachinery, bio-fluid flows, with an emphasis on liquid-liquid systems. The refractive indices of various aqueous and organic phases found in the literature span the range 1.330-1.620 and 1.251-1.637, respectively, allowing the identification of appropriate combinations to match selected transparent or translucent plastics/polymers, glasses, or custom materials in single-phase liquid or multiphase liquid-liquid flow systems. In addition, the refractive indices of fluids can be further tuned with the use of additives, which also allows for the matching of important flow similarity parameters such as density and viscosity.

Liquid-liquid extraction in flow analysis: A critical review

Energy Technology Data Exchange (ETDEWEB)

Silvestre, Cristina I.C.; Santos, Joao L.M. [REQUIMTE, Servico de Quimica-Fisica, Faculdade de Farmacia, Universidade do Porto, R. Anibal Cunha, 164, 4099-030 Porto (Portugal); Lima, Jose L.F.C., E-mail: limajlfc@ff.up.pt [REQUIMTE, Servico de Quimica-Fisica, Faculdade de Farmacia, Universidade do Porto, R. Anibal Cunha, 164, 4099-030 Porto (Portugal); Zagatto, Elias A.G. [Centro de Energia Nuclear na Agricultura, Universidade de Sao Paulo, P.O. Box 96, Piracicaba 13400-970 (Brazil)

2009-10-12

Liquid-liquid extractions (LLE) are a common sample pre-treatment in many analytical applications. This review aims at providing a critical overview of the distinct automated continuous flow-based approaches that were developed for liquid-liquid extraction with the purpose of pre-concentration and/or separation of multiple analytes, such as ultra-trace metal and metalloid species, phenolic compounds, surfactants, pharmaceuticals, etc., hyphenated with many detection technique such as UV/vis spectrophotometry, atomic spectrometric detection systems and luminescent detectors, including distinct extraction strategies and applications like single and multiple extraction schemes, wetting film extraction, supported liquid membrane extraction, back extraction, closed-loop systems and the utilisation of zone sampling, chromatomembranes and iterative reversal techniques. The analytical performance of the developed flow-based LLE methods and the influence of flow manifold components such as the segmenter, extraction coil and phase separator, is emphasised and object of discussion. An overall presentation of each system components, selectivity, advantages and shortcomings is carried out and exemplified with selected applications.

Rational approach to solvent system selection for liquid-liquid extraction-assisted sample pretreatment in counter-current chromatography.

Science.gov (United States)

Wang, Jiajia; Gu, Dongyu; Wang, Miao; Guo, Xinfeng; Li, Haoquan; Dong, Yue; Guo, Hong; Wang, Yi; Fan, Mengqi; Yang, Yi

2017-05-15

A rational liquid-liquid extraction approach was established to pre-treat samples for high-speed counter-current chromatography (HSCCC). n-Hexane-ethyl acetate-methanol-water (4:5:4:5, v/v) and (1:5:1:5, v/v) were selected as solvent systems for liquid-liquid extraction by systematically screening K of target compounds to remove low- and high-polarity impurities in the sample, respectively. After liquid-liquid extraction was performed, 1.4g of crude sample II was obtained from 18.5g of crude sample I which was extracted from the flowers of Robinia pseudoacacia L., and then separated with HSCCC by using a solvent system composed of n-hexane-ethyl acetate-methanol-water (1:2:1:2, v/v). As a result, 31mg of robinin and 37mg of kaempferol 7-O-α-l-rhamnopyranoside were isolated from 200mg of crude sample II in a single run of HSCCC. A scale-up separation was also performed, and 160mg of robinin with 95% purity and 188mg of kaempferol 7-O-α-l-rhamnopyranoside with 97% purity were produced from 1.2g of crude sample II. Copyright © 2017 Elsevier B.V. All rights reserved.

(Liquid + liquid) phase behavior for systems containing (aromatic + TBA + methylcyclohexane)

International Nuclear Information System (INIS)

Ghanadzadeh, H.; Ghanadzadeh, A.

2004-01-01

The determination region of solubility of TBA (tert-butanol) with representative compounds of the gasoline was investigated experimentally at temperature of 298.2 K. Type 1 (liquid + liquid) phase diagrams were obtained for (methylcyclohexane + TBA + aromatic compounds). These results were correlated simultaneously by the UNIQUAC model. The values of the interaction parameters between each pair of components in the systems were obtained for the UNIQUAC model using the experimental result. The root mean square deviation (RMSD) between the observed and calculated mole percents was 1.88 for (methylcyclohexane + TBA + benzene), 2.45 for (methylcyclohexane + TBA + toluene) and 2.86 for (methylcyclohexane + TBA + ethylbenzene). The mutual solubility of methylcyclohexane and aromatic compounds (e.g., benzene toluene and ethylbenzene (BTE)) was also investigated by the addition of TBA at temperature of 298.2 K

A novel poly(3,4-ethylenedioxythiophene)-ionic liquid composite coating for the headspace solid-phase microextraction and gas chromatography determination of several alcohols in soft drinks.

Science.gov (United States)

Wu, Mian; Zhang, Haibo; Zhao, Faqiong; Zeng, Baizhao

2014-11-19

A novel poly(3,4-ethylenedioxythiophene)-ionic liquid (i.e., 1-hydroxyethyl-3-methyl imidazolium-bis[(trifluoromethyl)sulfonyl]imide) composite film was electrodeposited on a Pt wire for headspace solid-phase microextraction. The film showed nodular structure and had large specific surface. In addition, it displayed high thermal stability (up to 300°C) and durable property (could be used for more than 200 times). Coupled with gas chromatography-flame ionization detection, the resulting fiber was applied to the headspace solid-phase microextraction and determination of several alcohols (i.e., linalool, nonanol, terpineol, geraniol, decanol and dodecanol). It presented higher extraction capability in comparison with the poly(3,4-ethylenedioxythiophene) and commercial polydimethylsiloxane/divinylbenzene fiber. Under the optimized conditions, the linear ranges exceeded three magnitudes with correlation coefficients above 0.9952 and the low limits of detection were 34.2-81.3ng L(-1). For different alcohols the repeatabilities (defined as RSD) were alcohols in real samples with acceptable recoveries from 81.1% to 106.6%. Copyright © 2014 Elsevier B.V. All rights reserved.

Liquidity Risk and its Management in Lithuanian Banking System

Directory of Open Access Journals (Sweden)

Erika Bareikaitė

2014-04-01

Full Text Available Banks are the main part of financial sector in each economy and strength of banking system becomes vital for ensuringfavourable economic stability and growth. Recent failure of two commercial banks in Lithuania showed that managershaven’t evaluated liquidity risk or haven’t dealt with it properly. The tasks of the paper are to investigate Lithuanian banksposition towards liquidity risk, analyse what kind of management tools banks use for ensuring favourable position towardsliquidity and to explore the liquidity influence to profitability in Lithuanian banking sector. The article examines liquidity andits management processes in Lithuanian banking sector. Description of liquidity importance is presented. Liquidity risk and itsmeasurement as well as the ways of managing the above mentioned risk is analysed in the article. In order to analyse the relationshipbetween liquidity risk and profitability of banks, analysis of scientific literature, research synthesis and generalizationshave been made.

Evaluation of a contact device type ejector system for liquid-liquid extraction

International Nuclear Information System (INIS)

Schwamback, Niomedes

2002-04-01

The objective of the present work was to evaluate an ejector system, operated simultaneously with two immiscible liquid phases and a gas phase, as a contact device for liquid-liquid extraction processes. The ejector, made of perspex, has a variable geometry, although this feature was not explored in the thesis. Motivated by recent uses of liquid-liquid extraction processes for the removal of traces of heavy metal from waste waters, it was decided to carry out tests with synthetic effluents. This strategy, typical of experimental work under evaluation of technical feasibility, greatly simplifies experiments, since the nature of the chemical species involved and their feed concentrations are known exactly and do not fluctuate. The extractant used was DEHPA (diethyl hexyl phosphoric acid). The metal chosen for tests was iron with oxidation number +3, because of its high extraction coefficient towards DEHPA and also for its chemical behavior similar to americium and other heavy metals. In addition to that, iron forms soluble coloured complexes adequate to spectrophotometric determination analysis, a simple, quick and very reliable analytical technique. The effects of electrolytes of interest, namely NaCl, FeSO 4 and Al(NO 3 ) 3 , upon the extraction process were investigated. The effects resulting from the introduction of a gas phase, actually air (bubbles), in the ejector upon the extraction efficiency were studied. By coupling advanced digital photographic technique and image analysis with microcomputer, the bubble mean size was measured. It was then correlated with equipment's geometrical (characteristic diameters) and operational variables (phases' flow rates and gas hold-ups). To enable scale-up procedures, data were preferably correlated by means of dimensionless groups. For the systems and conditions investigated in this thesis and under the same operational conditions, the introduction of air bubbles by means of an ejector has greatly improved the process

Thermodynamic modeling of ternary and quaternary (liquid + liquid) systems containing water, FeCl3, HCl and diisopropyl ether

International Nuclear Information System (INIS)

Milosevic, Miran; Hendriks, Ilse; Smits, Ralph E.R.; Schuur, Boelo; Haan, André B. de

2013-01-01

Highlights: • Literature data from various sources was validated experimentally. • Ternary and quaternary (liquid + liquid) systems were successfully described with the NRTL model. • Some deflection at higher HCl concentrations between model and data. • Additional data verification proved correctness of the literature data. -- Abstract: Liquid–liquid extraction using ethers as solvents is a potentially energy saving alternative for the concentration of aqueous ferric chloride solutions. Adequate thermodynamic models that describe the behavior of the resulting quaternary systems (FeCl 3 , ether, acid and water) are not available in the literature. In this paper, the development of an equilibrium description applying the NRTL-model is presented, including experimental validation and fitting of the NRTL-parameters on the validated data. Equilibrium experiments were performed for the ternary systems (water + HCl + DiPE) and (water + FeCl 3 + DiPE) and the obtained data is in good agreement with the results from Maljkovic et al.[37] and Cambell et al.[39]. Experimental data of the quaternary system is taken from Maljkovic et al.[37]. The obtained binary interaction parameters to describe the (liquid + liquid) quaternary system (water + FeCl 3 + HCl + DiPE) and the constituting ternaries by the NRTL model are presented. Model predictions are in good agreement with the experimental data

Volatile liquid storage system

International Nuclear Information System (INIS)

Laverman, R.J.; Winters, P.J.; Rinehart, J.K.

1992-01-01

This patent describes a method of collecting and abating emission from a volatile liquid in an above ground storage tank. It comprises the liquid storage tank having a bottom, a vertical cylindrical circular wall having a lower edge portion joined to the bottom, and an external fixed roof, the tank having an internal floating roof floating on a volatile liquid stored in the tank, and air vent means in the tank in communication with a vapor space in the tank constituting at least the space above the floating roof when the floating roof floats on a predetermined maximum volume of volatile liquid in the tank; permitting ambient air; pumping emission laden air from the tank vapor space above the floating roof; and by means of the emissions abatement apparatus eliminating most of the emission from the emissions laden air with formation of a gaseous effluent and then discharging the resulting gaseous effluent to the atmosphere

A new high-speed hollow fiber based liquid phase microextraction method using volatile organic solvent for determination of aromatic amines in environmental water samples prior to high-performance liquid chromatography.

Science.gov (United States)

Sarafraz-Yazdi, A; Mofazzeli, F; Es'haghi, Z

2009-07-15

A new and fast hollow fiber based liquid phase microextraction (HF-LPME) method using volatile organic solvents coupled with high-performance liquid chromatography (HPLC) was developed for determination of aromatic amines in the environmental water samples. Analytes including 3-nitroaniline, 3-chloroaniline and 4-bromoaniline were extracted from 6 mL basic aqueous sample solution (donor phase, NaOH 1 mol L(-1)) into the thin film of organic solvent that surrounded and impregnated the pores of the polypropylene hollow fiber wall (toluene, 20 microL), then back-extracted into the 6 mL acidified aqueous solution (acceptor phase, HCl 0.5 mol L(-1)) in the lumen of the two-end sealed hollow fiber. After the extraction, 5 microL of the acceptor phase was withdrawn into the syringe and injected directly into the HPLC system for the analysis. The parameters influencing the extraction efficiency including the kind of organic solvent and its volume, composition of donor and acceptor phases and the volume ratio between them, extraction time, stirring rate, salt addition and the effect of the analyte complexation with 18-crown-6 ether were investigated and optimized. Under the optimal conditions (donor phase: 6 mL of 1 mol L(-1) NaOH with 10% NaCl; organic phase: 20 microL of toluene; acceptor phase: 6 microL of 0.5 mol L(-1) HCl and 600 mmol L(-1) 18-crown-6 ether; pre-extraction and back-extraction times: 75 s and 10 min, respectively; stirring rate: 800 rpm), the obtained EFs were between 259 and 674, dynamic linear ranges were 0.1-1000 microg L(-1) (R>0.9991), and also the limits of detection were in the range of 0.01-0.1 micro gL(-1). The proposed procedure worked very well for real environmental water samples with microgram per liter level of the analytes, and good relative recoveries (91-102%) were obtained for the spiked sample solutions.

Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode

Energy Technology Data Exchange (ETDEWEB)

Meyer, C.; Hager, V.; Geburtig, D.; Kohr, C.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer Chemische Reaktionstechnik; Haumann, M. [Chemical Reaction Engineering, FAU Busan Campus, Korea (Korea, Republic of)

2011-07-01

Highly acidic ionic liquid (IL) catalysts offer the opportunity to convert n-alkanes at very low reaction temperatures. The results of IL catalyzed isomerization and cracking reactions of pure n-octane are presented. Influence of IL composition, [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / H{sub 2}SO{sub 4} and [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / 1-chlorooctane, on catalyst activity and selectivities to branched alkanes was investigated. Acidic chloroaluminate IL catalysts form liquid-liquid biphasic systems with unpolar organic product mixtures. Thus, recycling of the acidic IL is enabled by simple phase separation in the liquid-liquid biphasic reaction mode or the IL can be immobilized on an inorganic support with a large specific surface area. These supported ionic liquid phase (SILP) catalysts offer the advantage to get a macroscopically heterogeneous system while still preserving all benefits of the homogeneous catalyst which can be used for the slurry-phase n-alkane isomerization. The interaction of the solid support and acidic IL influences strongly the catalytic activity. (orig.)

Solid-state chemiluminescence assay for ultrasensitive detection of antimony using on-vial immobilization of CdSe quantum dots combined with liquid–liquid–liquid microextraction

Energy Technology Data Exchange (ETDEWEB)

Costas-Mora, Isabel; Romero, Vanesa; Lavilla, Isela; Bendicho, Carlos, E-mail: bendicho@uvigo.es

2013-07-25

Graphical abstract: -- Highlights: •Solid-state chemiluminescence based on CdSe QDs was developed. •QDs immobilization in a vial was achieved in a simple and fast way. •Antimony detection was achieved by inhibition of the CdSe QDs/H{sub 2}O{sub 2} CL reaction. •LLLME allowed improving the selectivity and sensitivity of the CL assay. •The capping ligand played a critical role in the selectivity of the CL system. -- Abstract: On-vial immobilized CdSe quantum dots (QDs) are applied for the first time as chemiluminescent probes for the detection of trace metal ions. Among 17 metal ions tested, inhibition of the chemiluminescence when CdSe QDs are oxidized by H{sub 2}O{sub 2} was observed for Sb, Se and Cu. Liquid–liquid–liquid microextraction was implemented in order to improve the selectivity and sensitivity of the chemiluminescent assay. Factors influencing both the CdSe QDs/H{sub 2}O{sub 2} chemiluminescent system and microextraction process were optimized for ultrasensitive detection of Sb(III) and total Sb. In order to investigate the mechanism by which Sb ions inhibit the chemiluminescence of the CdSe QDs/H{sub 2}O{sub 2} system, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), UV–vis absorption and fluorescence measurements were performed. The selection of the appropriate CdSe QDs capping ligand was found to be a critical issue. Immobilization of QDs caused the chemiluminescence signal to be enhanced by a factor of 100 as compared to experiments carried out with QDs dispersed in the bulk aqueous phase. Under optimized conditions, the detection limit was 6 ng L{sup −1} Sb and the repeatability expressed as relative standard deviation (N = 7) was about 1.3%. An enrichment factor of 95 was achieved within only 3 min of microextraction. Several water samples including drinking, spring, and river waters were analyzed. The proposed method was validated against CRM NWTM-27.2 fortified lake water, and a recovery study was

Microsystems for liquid-liquid extraction of radionuclides in the analytical protocols

International Nuclear Information System (INIS)

Helle, Gwendolyne

2014-01-01

Radiochemical analyses are necessary to numerous steps for nuclear wastes management and for the control of the environment. An analytical protocol generally includes different steps of chemical separations which are lengthy, manual and complicated to implement because of their confinement in glove boxes and because of the hostile chemical and radiochemical media. Thus there is a huge importance to propose innovative and robust solutions to automate these steps but also to reduce the volumes of the radioactive and chemical wastes at the end of the analytical cycle. One solution consists in the miniaturization of the analyses through the use of lab-on-chip. The objective of this thesis work was to propose a rational approach to the conception of separative microsystems for the liquid-liquid extraction of radionuclides. To achieve this, the hydrodynamic behavior as well as the extraction performances have been investigated in one chip for three different chemical systems: Eu(III)-HNO 3 /DMDBTDMA, Eu(III)-AcO(H,Na)-HNO 3 /HDEHP and U(VI)-HCl/Aliquat336. A methodology has been developed for the implementation of the liquid-liquid extraction in micro-system for each chemical system. The influence of various geometric parameters such as channel length or specific interfacial area has been studied and the comparison of the liquid-liquid extraction performances has led to highlight the influence of the phases viscosities ratio on the flows. Thanks to the modeling of both hydrodynamics and mass transfer in micro-system, the criteria related to physical and kinetic properties of the chemical systems have been distinguished to propose a rational conception of tailor-made chips. Finally, several examples of the liquid-liquid extraction implementation in micro-system have been described for analytical applications in the nuclear field: U/Co separation by Aliquat336, Eu/Sm separation by DMDBTDMA or even the coupling between a liquid-liquid extraction chip and the system of

Liquid / liquid biphasic electrochemistry in ultra-turrax dispersed acetonitrile / aqueous electrolyte systems

International Nuclear Information System (INIS)

Watkins, John D.; Amemiya, Fumihiro; Atobe, Mahito; Bulman-Page, Philip C.; Marken, Frank

2010-01-01

Unstable acetonitrile | aqueous emulsions generated in situ with ultra-turrax agitation are investigated for applications in dual-phase electrochemistry. Three modes of operation for liquid / liquid aqueous-organic electrochemical processes are demonstrated with no intentionally added electrolyte in the organic phase based on (i) the formation of a water-soluble product in the aqueous phase in the presence of the organic phase, (ii) the formation of a product and ion transfer at the liquid / liquid-electrode triple phase boundary, and (iii) the formation of a water-insoluble product in the aqueous phase which then transfers into the organic phase. A three-electrode electrolysis cell with ultra-turrax agitator is employed and characterised for acetonitrile / aqueous 2 M NaCl two phase electrolyte. Three redox systems are employed in order to quantify the electrolysis cell performance. The one-electron reduction of Ru(NH 3 ) 6 3+ in the aqueous phase is employed to determine the rate of mass transport towards the electrode surface and the effect of the presence of the acetonitrile phase. The one-electron oxidation of n-butylferrocene in acetonitrile is employed to study triple phase boundary processes. Finally, the one-electron reduction of cobalticenium cations in the aqueous phase is employed to demonstrate the product transfer from the electrode surface into the organic phase. Potential applications in biphasic electrosynthesis are discussed.

(Liquid + liquid) equilibrium for binary systems of N-formylmorpholine with alkanes

International Nuclear Information System (INIS)

Wang Zhengrong; Xia Shuqian; Ma Peisheng; Liu Tao; Han Kewei

2012-01-01

Highlights: ► The LLE data of four binary systems containing N-formylmorpholine were measured. ► Both NRTL and UNIQUAC models can fit the experimental data well. ► The new group interaction parameters of UNIFAC (Do) were regressed from the LLE data. ► The estimated result shows that the group interaction parameters and methods are reliable. - Abstract: (Liquid + liquid) equilibrium (LLE) data were determined for four binary systems containing N-formylmorpholine (NFM) and alkanes (3-methylpentane, heptane, nonane, and 2,2,4-trimethylpentane) over the temperature range from around 300 K to near 420 K using a set of newly designed equilibrium equipment. The compositions of both light and heavy phases were analyzed by gas chromatography. The mutual solubility increased as the temperature increased for all these systems. The binary (liquid + liquid) equilibrium data were correlated by the NRTL and UNIQUAC equations with temperature-dependent parameters. Both models correlate the experimental results well. Furthermore, the UNIFAC (Do) group contribution model was used to correlate and estimate the LLE data for NFM containing systems. Two methods of group division for NFM were used. NFM is treated as a single group: NFM group (method I) or divided into two groups: CHO and C 4 H 8 NO (method II), respectively. The group interaction parameters for CH 2 –NFM, or CH 2 –CHO and CH 2 –C 4 H 8 NO were fitted from the experimental LLE data. The UNIFAC (Do) model correlates the experimental data well. In addition, in order to develop UNIFAC (Do) group contribution model to estimate the LLE data of (NFM + cycloalkane) systems, some literature LLE data were used. The group interaction parameters for c-CH 2 –NFM, c-CH 2 –CHO and c-CH 2 –C 4 H 8 NO were correlated. Then these group interaction parameters were used to estimate the phase equilibrium data of binary systems in the literature by the UNIFAC (Do) model. The results showed that the estimated values are in

Phase stability analysis of liquid-liquid equilibrium with stochastic methods

Directory of Open Access Journals (Sweden)

G. Nagatani

2008-09-01

Full Text Available Minimization of Gibbs free energy using activity coefficient models and nonlinear equation solution techniques is commonly applied to phase stability problems. However, when conventional techniques, such as the Newton-Raphson method, are employed, serious convergence problems may arise. Due to the existence of multiple solutions, several problems can be found in modeling liquid-liquid equilibrium of multicomponent systems, which are highly dependent on the initial guess. In this work phase stability analysis of liquid-liquid equilibrium is investigated using the NRTL model. For this purpose, two distinct stochastic numerical algorithms are employed to minimize the tangent plane distance of Gibbs free energy: a subdivision algorithm that can find all roots of nonlinear equations for liquid-liquid stability analysis and the Simulated Annealing method. Results obtained in this work for the two stochastic algorithms are compared with those of the Interval Newton method from the literature. Several different binary and multicomponent systems from the literature were successfully investigated.

21 CFR 862.2250 - Gas liquid chromatography system for clinical use.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Gas liquid chromatography system for clinical use... Instruments § 862.2250 Gas liquid chromatography system for clinical use. (a) Identification. A gas liquid chromatography system for clinical use is a device intended to separate one or more drugs or compounds from a...

Active liquid/liquid interfaces: contributions of non linear optics and tensiometry

International Nuclear Information System (INIS)

Gassin, P.M.

2013-01-01

Liquid-liquid extraction processes are widely used in the industrial fields of selective separation. Despite its numerous applications, the microscopic mechanisms which occur during a liquid-liquid extraction processes are really unknown specially at the liquid/liquid interface. Thus, this work deals on the understanding of the phenomena which drive the mass transfer across a liquid/liquid interface. Two experimental techniques were used in this work: dynamic interfacial tension measurement and non-linear optical experiments. Along with the use of this experimental approach, a numerical model describing the mass transfer dynamic has been developed. This model works under the assumption that both diffusion and a chemical step describing adsorption and desorption processes contribute to the global transfer kinetics. Model systems of surfactant molecules, chromophore molecules and complexing molecule were investigated at liquid/liquid and air/liquid interface. Interfacial phenomena like adsorption, surface aggregation and ion complexing were studied. Finally, the methodology developed in this work was applied to studied an extractant molecule with potential industrial application. (author) [fr

(Liquid + liquid) equilibrium of {water + phenol + (1-butanol, or 2-butanol, or tert-butanol)} systems

International Nuclear Information System (INIS)

Hadlich de Oliveira, Leonardo; Aznar, Martin

2010-01-01

(Liquid + liquid) equilibrium (LLE) and binodal curve data were determined for the systems (water + phenol + tert-butanol) at T = 298.15 K, (water + phenol + 2-butanol) and (water + phenol + 1-butanol) at T = 298.15 K and T = 313.15 K by the combined techniques of densimetry and refractometry. Type I curve (for tert-butanol) and Type II curves (for 1- and 2-butanol) were found. The data were correlated with the NRTL model and the parameters estimated present root mean square deviations below 2% for the system with tert-butanol and lower than 0.8% for the other systems.

SISAK liquid-liquid extraction experiments with preseparated {sup 257}Rf

Energy Technology Data Exchange (ETDEWEB)

Omtvedt, Jon Petter; Alstad, J.; Breivik, H. [University of Oslo, Department of Chemistry, Oslo (NO)] (and others)

2002-06-01

The SISAK liquid-liquid extraction system was used to extract 4.0-s {sup 257}Rf. The {sup 257}Rf was produced in the reaction {sup 208}Pb({sup 50}Ti, 1n){sup 257}Rf with 237-MeV beam energy on target, separated in the Berkeley Gas-filled Separator (BGS) and transferred to a gas jet using the Recoil Transfer Chamber (RTC). The activity delivered by the gas jet was dissolved in 6-M HNO{sub 3} and Rf was extracted into 0.25-M dibutyl-phosphoric acid in toluene. This was the first time a transactinide, i.e., an element with Z{>=}104, was extracted and unequivocally identified by the SISAK system. Thus, this pilot experiment demonstrates that the fast liquid-liquid extraction system SISAK, in combination with liquid-scintillation detectors, can be used for investigating the chemical properties of the transactinides. The extraction result is in accordance with the behaviour shown by the Rf group IV homologues Zr and Hf. (author)

Explosion hazard in liquid nitrogen cooled fusion systems

International Nuclear Information System (INIS)

Brereton, S.J.

1988-01-01

The explosion hazard associated with the use of liquid nitrogen in a radiation environment in fusion facilities has been investigated. The principal product of irradiating liquid nitrogen is thought to be ozone, resulting from the action of radiation on oxygen impurity. Ozone is a very unstable material, and explosions may occur as it rapidly decomposes to oxygen. Occurrences of this problem in irradiated liquid nitrogen systems are reviewed. An empirical expression, from early experiments, for the yield of ozone in liquid nitrogen-oxygen mixtures exposed to gamma radiation is employed to assess the degree of ozone explosion hazard expected at fusion facilities. The problem is investigated for the Compact Ignition Tokamak (CIT) as a particular example. 16 refs., 5 figs., 1 tab