Microextraction In Packed Syringe Research Articles

Determination of mercury cation using modified graphene oxide with specific mercury aptamer as adsorbent for microextraction in packed syringe (MEPS)

Determination of mercury cation using modified graphene oxide with specific mercury aptamer as adsorbent for microextraction in packed syringe (MEPS)

Bisphenol A in canned soft drinks, plastic-bottled water, and household water tank from Punjab, India

The aim of this study was the quantification of Bisphenol A (BPA) in canned soft drinks, plastic-bottled water and household water tanks from Punjab, India. Samples of five brands of canned soft drinks and plastic-bottled water purchased from local markets. Fifteen samples each of household plastic water tanks and concrete water tank were selected from three different cities (5 from each city) of Punjab, India. Samples were selected randomly. The plastic household water tank samples were collected in the months of December and June to check the effect of temperature on release of BPA in a plastic water tanks. The analysis method consists of microextraction in packed syringe (MEPS) followed by gas chromatography with mass spectrometric (GC-MS) detection. The detection limits and quantitation for BPA were 0.46 pg/mL and 1.52 pg/mL, respectively. Traces of BPA were detected in all canned soft drinks samples. Canned soft drinks and plastic-bottled water samples of five brands were having the BPA concentrations 8.2-14.01 pg/mL and 60-90 pg/mL, respectively. The BPA concentrations in the plastic water tanks were nondetected-12 pg/mL and nondetected-10 pg/mL in concrete water tank.

Gelatin/sodium triphosphate hydrogel electrospun nanofiber mat as a novel nanosorbent for microextraction in packed syringe of La3+ and Tb3+ ions prior to their determination by ICP-OES

In the present study, the novel gelatin/sodium triphosphate hydrogel nanofiber mat (GT/STP HNFM) was fabricated using the electrospinning strategy. Owing to the formation of ionic complex between STP and GT, the water stability of synthesized nanofiber increased, thereafter, the synthesized water-insoluble nanofiber was applied as a novel nanosorbent in microextraction in packed syringe (MEPS) method, using for the preconcentration of La3+ and Tb3+ in environmental and industrial water samples to the detection of them by an inductively coupled plasma optical emission spectroscopy (ICP-OES). The characterization of nanosorbent was performed and the effect of main parameters on adsorption performance were investigated. Under the optimum condition, the method showed a good linearity ranging from 1 to 500 ng mL−1 with a correlation coefficient superior to 0.998. Additionally, the low detection limits (0.1–0.2 ng mL−1) revealed good sensitivity of the proposed method. Finally, the MESP-ICP-OES method was applied for the determination of La3+ and Tb3+ in environmental and industrial water samples with relative recoveries (RRs) ranging from 85 to 102% and relative standard deviations (RSDs) lower than 2.7%. The outcome of this study revealed an effective method for the extraction and recovery of La3+ and Tb3+ from aqueous solutions using a non-toxic, inexpensive, and efficient nanosorbent.

Application of metal-organic framework MIL-101(Cr) to microextraction in packed syringe for determination of triazine herbicides in corn samples by liquid chromatography-tandem mass spectrometry

In this work, a metal-organic framework material MIL-101(Cr) was prepared and used as the sorbent for a laboratory-made semi-automated microextraction in packed syringe (MEPS). Six triazine herbicides, including desmetryn, prometon, ametryn, prometryn, atraton, and dipropetryn, that are commonly found in corn samples, were extracted and determined by the MEPS method and high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Key parameters affecting the extraction efficiencies, including type of extraction solvent, type and amount of sorbent, time of ultrasonic extraction and adsorption, and type, volume and flow rate of elution solvent, were investigated. The limits of detection (LODs, S/N = 3) and quantification (LOQs, S/N = 10) for all analytes obtained by the proposed method were in the ranges of 0.01–0.12 ng g−1 and 0.04–0.35 ng g−1, respectively, which were far lower than that of reported methods. The findings indicated that the proposed semi-automated MEPS method was easy and efficient for the extraction of triazine herbicides in corn samples.

Microextraction in packed syringe by using a three-dimensional carbon nanotube/carbon nanofiber–graphene nanostructure coupled to dispersive liquid-liquid microextraction for the determination of phthalate esters in water samples

Microextraction in packed syringe (MEPS) was combined with dispersive liquid-liquid microextraction (DLLME) for the extraction of phthalate esters (PEs) from water samples prior to their determination by GC with flame ionization detection. A three-dimensional nanomaterial composed of carbon nanotubes, carbon nanofibers and graphene was prepared by chemical vapor deposition (CVD) and employed as a sorbent for MEPS. The porous structure of the sorbent has been revealed by scanning electron microscopy, transmission electron microscopy, and Brunauer-Emmett-Teller adsorption. The effects of various experimental variables on the extraction efficiencies of the following PEs were studied: Dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, and di-2-ethylhexyl phthalate. After extraction, the GC assay gives a linear calibration plot that covers the 0.02 to 200 ng mL−1 PE concentration ranges. The method displays detection limits (at an S/N ratio of 3) in the range from 1 to 10 ng mL−1. Relative standard deviations for intra-day and inter-day precision are between 5.7 and 8.9%, and between 7.6 and 10.1%, respectively. The feasibility of the method was demonstrated by extracting and determining PEs in (spiked) real water samples, whereby recoveries in the range of 90.3–98.8% and RSD% lower than 10.3% were attained.

An imprinted interpenetrating polymer network for microextraction in packed syringe of carbamazepine

An imprinted interpenetrating polymer network (IPN) was synthesized and used as a medium for isolation of carbamazepine from urine samples. The polymer network consisted of a homogeneous polystyrene–sol gel hybrid constructed by in–situ radical polymerization method. In this process, within the sol–gel reaction duration, styrene monomer could penetrate into the reaction mixture and after the polymerization initiation, a monolithic IPN structure was prepared. The scanning electron microscopy (SEM) image and energy dispersive spectroscopy (EDX) are indications of the polystyrene dispersion at nano- to micro-meter level in the sol gel matrix. Eventually, the synthesized IPN was used as a sorbent in microextraction in packed syringe (MEPS) combined with high performance liquid chromatography (HPLC) for isolation of carbamazepine, naproxen and dexamethasone from urine samples. The molecularly imprinted IPN showed some degree of selectivity towards carbamazepine. To assess the important parameters influencing the extraction and desorption processes, an experimental design strategy was used. By the current method, low limits of detection (1.3–1.5μgL−1) and quantification (4.2–5μgL−1) were achieved (hydrocortisone as the internal standard). The intra- and inter-day precision data at 50 and 300μgL−1 were 1.3–7.4%, while the working linear dynamic range was from 4.2 to 500μgL−1.

Synthesis of nano-hydroxyapatite sorbent for microextraction in packed syringe of phthalate esters in water samples

An easy alkoxide–based sol–gel method using Ca(NO3)2·4H2O and tri–ethyl phosphate (PO(OC2H5)3; TEP) precursors employed to synthesize nano-hydroxyapatite (HAP). The structural characterization of samples was studied using XRD, TEM and elemental analysis of SEM. Scherrer and Williamson–Hall equations were applied to measurement of the crystallite size distributions and micro–strain of the synthesized HAP powder. The synthesized HAP nanoparticles were applied as an efficient sorbent for the microextraction in packed syringe (MEPS) of phthalate esters (PAEs) from water samples. Separation and determination of the PAEs were performed by gas chromatography–flame ionization detection (GC–FID). Several variables affecting the extraction efficiency of the analytes i.e., desorption solvent, volume of desorption solvent and number of extraction cycles were investigated and optimized. Under optimized conditions, the calibration curves were linear (R > 0.9916) in the concentration range of 0.05–100 ng mL−1. The method displays detection limits (at an S/N ration of 3) in the range from 0.02 to 0.1 ng mL−1, and the limits of quantification (at an S/N ratio of 10) are between 0.07 and 0.25 ng mL−1. Relative standard deviations (RSDs) for intra- and inter-day precision are 4.8–8.3%, and 6.1–8.5%, respectively. The applicability of the developed method was examined by analyzing different water samples (river water, bottled mineral water and tap water) and the relative recovery values for the spiked water samples were found to be in the range of 85.5–99.2%.

Analytical approach to determining human biogenic amines and their metabolites using eVol microextraction in packed syringe coupled to liquid chromatography mass spectrometry method with hydrophilic interaction chromatography column

Analysis of biogenic amines (BAs) in different human samples provides insight into the mechanisms of various biological processes, including pathological conditions, and thus may be very important in diagnosing and monitoring several neurological disorders and cancerous tumors. In this work, we developed a simple and fast procedure using a digitally controlled microextraction in packed syringe (MEPS) coupled to liquid chromatography mass spectrometry (LC–MS) method for simultaneous determination of biogenic amines, their precursors and metabolites in human plasma and urine samples. The separation of 12 low molecular weight and hydrophilic molecules with a wide range of polarities was achieved with hydrophilic interaction chromatography (HILIC) column without derivatization step in 12min. MEPS was implemented using the APS sorbent in semi-automated analytical syringe (eVol®) and small volume of urine and plasma samples, 50µL and 100μL, respectively. We evaluated important parameters influencing MEPS efficiency, including stationary phase selection, sample pH and volume, number of extraction cycles, and washing and elution volumes. In optimized MEPS conditions, the analytes were eluted by 3×50μL of methanol with 0.1% formic acid. The chromatographic separation of analytes was performed on XBridge Amide™ BEH analytical column (3.0mm×100mm, 3.5µm) using gradient elution with mobile phase consisting of phase A: 10mM ammonium formate buffer in water pH 3.0 and phase B: 10mM ammonium formate buffer in acetonitrile pH 3.0. The LC–HILIC–MS method was validated and, in optimum conditions, presented good linearity in concentration range within 10–2000ng/mL for all the analytes with a determination coefficient (r2) higher than 0.999 for plasma and urine samples. Method recovery ranged within 87.6–104.3% for plasma samples and 84.2–98.6% for urine samples. The developed method utilizing polar APS sorbent along with polar HILIC column was applied for simultaneous bioanalysis of trace amounts of polar endogenous biogenic amines in real human urine and plasma samples.

Microextraction of antidepressant drugs into syringes packed with a nanocomposite consisting of polydopamine, silver nanoparticles and polypyrrole

We describe a nanocomposite prepared from polydopamine, silver nanoparticles, and polypyrrole (PDA-Ag-PPy) that can be used for the microextraction in packed syringe (MEPS) of tricyclic antidepressants from urine samples. The PDA-Ag-PPy composite was prepared in-situ by the reduction of silver ion - doped PPy during oxidative polymerization of dopamine. The PDA-Ag coatings on the nanoribbon – shaped PPy represent a highly porous, inorganic–organic hybrid nanomaterial that has a wide range of applications. The nanocomposite was characterized by FTIR and scanning electron microscopy. It is shown to be an efficient sorbent for the MEPS of the tricyclic antidepressants amitriptyline, imipramine and citalopram from urine samples. After extraction, the antidepressants were desorbed with acetonitrile and analyzed by GC-MS. Parameters influencing the extraction and desorption processes were optimized. The method has an analytical range that extends from 0.03 to 100 μg L−1. Limits of detection (S/N = 3) and limits of quantification (for S/N = 10) are in the range from 0.03 - 0.05 μg L−1 and 0.1 - 0.2 μg L−1, respectively. The relative standard deviations (for n = 4) are in the 5–9 % range. If applied to the analysis of spiked urine samples, the relative recoveries are between 88 and 104 %.

ChemInform Abstract: Microextraction in Packed Syringe: Solvent‐Minimized Sample Preparation Technique

AbstractReview: 69 refs.

Microextraction in packed syringe: solvent-minimized sample preparation technique

In recent years, great effort has been made to develop new analytical methods, such as microextraction techniques, that greatly reduce the limitations of conventional methods. Microextraction in packed syringe (MEPS) is a novel miniaturized solid-phase extraction (SPE) technique that works online with gas and liquid chromatography. MEPS is designed in the syringe format, wherein a small amount of the sorbent is packed between the barrel and the needle as a cartridge or inside a syringe as a plug. MEPS is a green sample preparation technique because of the small amount of sorbent used and the small volumes of solvent required. This article gives an overview of the successful approaches proposed concerning MEPS and provides the state of the art for biological, environmental, and food analyses. Selection of factors affecting MEPS performance is discussed. A comparison between MEPS and other techniques such as SPE, solid phase microextraction, and protein precipitation is provided.

Silver Nanoparticles–Polyaniline Nanocomposite for Microextraction in Packed Syringe

A rapid, convenient and reliable method for microextraction in packed syringe (MEPS) of the loop diuretic furosemide (FUR) in urine along with high-performance liquid chromatography (HPLC) was developed. A nanocomposite based on silver nanoparticles/polyaniline (Ag-NPs/PANI) was synthesized and used as the MEPS packing material. This nanocomposite was prepared conveniently using interfacial polymerization without the need for any templates or functional dopants. The feasibility of the synthesized nanocomposites was examined by isolation of FUR from diluted urine samples. After extraction, the analyte was desorbed by 200 μL of methanol. It was then dried and the residue was dissolved in 30 μL of methanol and an aliquot of 25 μL was, finally, injected into the HPLC system. Important parameters influencing the extraction and desorption processes were optimized and 25 cycles of draw–eject gave maximum peak area, when desorption was performed. The linearity was studied by preconcentration of 5 mL of diluted urine sample spiked with a standard solution of FUR in the concentration range of 15–750 μg L−1. The coefficient of determination was satisfactory (r2 > 0.99) and the relative standard deviation (RSD %) value under the optimized condition was 8.8 %. The limit of detection and limit of quantification were 7 and 15 μg L−1, respectively.

A new approach for antibiotic drugs determination in human plasma by liquid chromatography–mass spectrometry

Sensitive and selective analytical procedures based on high performance liquid chromatography with mass spectrometric detection were developed for the determination of linezolid (LIN) and amoxicillin (AMOX) in human plasma samples. Samples were prepared by applying protein precipitation (PP), solid phase extraction (SPE), and microextraction in packed syringe (MEPS). The analytical separation was carried out using reversed phase liquid chromatography in isocratic mode. All analytes were monitored by mass spectrometry (MS) detection in the product ion mode and the method was validated covering the corresponding therapeutic range of 1–30μg/mL and 1–50μg/mL for LIN and AMOX respectively. The assay was linear over AMOX and LIN concentration ranges. The method provided good validation data: accuracy (102.9% (LIN), 100.9% (AMOX)), limit of detection (0.1407ng/mL (LIN); 0.1341ng/mL (AMOX); quantification (0.3814ng/mL (LIN), 0.4249ng/mL (AMOX)) and acceptable stability within 24h in the auto-sampler. Three different methods were compared as regards precision, accuracy, recovery and matrix effects. The proposed methods offer a fast and simple way to determine selected antibiotic drugs in human plasma that could be applied in pharmacokinetic studies.

Analytical approach to determine biogenic amines in urine using microextraction in packed syringe and liquid chromatography coupled to electrochemical detection

The goal of this work was to develop and validate an analytical method for the detection and quantification of the biogenic amines serotonin (5-HT), dopamine (DA) and norepinephrine (NE), using microextraction in packed syringe (MEPS) and liquid chromatography coupled to electrochemical detection (HPLC-ED) in urine. The method was validated according to internationally accepted guidelines from the Food and Drug Administration. Linearity was established between 50 and 1000 ng/mL for 5-HT and between 5 and 1000 ng/mL for DA and NE, with determination coefficients (R(2)) >0.99 for all compounds. The limits of quantification and detection were respectively 50 and 20 ng/mL for 5-HT, and 5 and 2 ng/mL for DA and NE. Within- and between-run precision ranged from 0.84 to 9.41%, while accuracy ranged from 0.79 to 12.76% for all compounds. The intermediate precision and accuracy were 1.50-8.36 and 0.54-13.51%, respectively. The method was found suitable for clinical routine analysis of the studied compounds, using a sample volume of 0.5 mL. This is the first study employing a commercially available MEPS column for the simultaneous detection and quantification of 5-HT, DA and NE in urine by coulometric detection.

Multiresidue determination of pesticides from aquatic media using polyaniline nanowires network as highly efficient sorbent for microextraction in packed syringe

A simple, rapid and sensitive method based on microextraction in packed syringe (MEPS), in combination with gas chromatography–mass spectrometry (GC–MS) was developed. Polyaniline (PANI) nanowires network was synthesized and used as sorbent of MEPS for the multiresidue determination of selected analytes from triazine, organochlrorine and organophosphorous pesticides in aqueous samples. The PANI nanowires network was prepared using soft template technique and its characterization was studied by scanning electron microscopy (SEM). The presence of micelles in this methodology showed to be an important parameter in shaping the growing polymer. Hexadecyltrimethylammonium bromide (HTAB) was used as structure directing agent in PANI preparation procedure and this was led to the formation of nanowires with diameters ranging from 35nm to 45nm. The synthesized PANI nanowires network showed higher extraction capability in comparison with the bulk PANI. Important parameters influencing the extraction and desorption processes including desorption solvent, elution volume, draw–eject cycles of sample, draw–eject mode, pH effect and amount of sorbent were optimized. Limits of detection were in the range of 0.07–0.3ngmL−1 using time scheduled selected ion monitoring (SIM) mode. The linearity of method was in the range from 0.5–200ngmL−1 to 0.2–1000ngmL−1. The method precision (RSD %) with three replicates were in the range of 5.3–18.4% at the concentration level of 5ngmL−1. The developed method was successfully applied to the Zayandeh-rood river water samples and the matrix factor obtained for the spiked real water samples were in the range of 0.79–0.94.

Negative electrospray ionization ion mobility spectrometry combined with microextraction in packed syringe for direct analysis of phenoxyacid herbicides in environmental waters

A novel method based on microextraction in packed syringe (MEPS) coupled with negative electrospray ionization-ion mobility spectrometry (ESI-IMS) was developed for simultaneous and direct determination of phenoxyacid herbicides in water samples. The effects of various parameters such as pH of the sample solution, sample loading rate, the nature of elution solvent and its volume, and the number of extraction cycles were investigated. The method was exhaustively validated in terms of sensitivity, recovery, reproducibility, and enrichment factor. The detection limits of the method for 2,4-D, silvex, and haloxyfop were found to be 60, 70, and 90ngL−1, respectively. The recovery of the analyzed herbicides was in the range 73–102%, and the relative standard deviation (RSD) was lower than 10% for all the experiments. Various real samples were analyzed with the proposed method, and the obtained results revealed the efficient extraction of the analytes using MEPS extraction before the analysis by negative ESI-IMS.

Reinforced polydiphenylamine nanocomposite for microextraction in packed syringe of various pesticides

Reinforced polydiphenylamine (PDPA) nanocomposite was synthesized by oxidation of diphenylamine in 4 mol L −1 sulfuric acid solution containing a fixed amount of carbon nanotubes (CNTs) in the presence of cetyltrimethylammonium bromide (CTAB). The surface characteristic of PDPA and PDPA/CNT nanocomposites was investigated using scanning electron microscopy (SEM). The prepared PDPA/CNT nanocomposite was used as an extraction medium for microextraction in packed syringe (MEPS) of selected pesticides from aquatic environment. The effect of CNT doping level and the presence of surfactant on the extraction capability of nanocomposite was investigated and it was revealed that when 4% (w/w) of CNT in the presence of CTAB is being used, the highest extraction recovery could be achieved. Eventually, the developed MEPS technique in off-line combination with gas chromatography–mass spectrometry (GC–MS) was applied to the analysis of some pesticides including triazine, organophosphorous, organochlorine and aryloxyphenoxy propionic acid pesticides. Important parameters influencing the extraction and desorption processes were optimized and a 25 cycles of draw-eject gave maximum peak area, when desorption was performed using 200 μL of n-hexane. Limits of detection (LODs) were in the range of 0.01–0.1 ng mL −1 and 0.02–0.1 ng mL −1 for distilled water and river water respectively, using time scheduled selected ion monitoring (SIM) mode. The method precision (RSD %) with four replicates was in the range of 1.6–14.6% for distilled water and 1.5–16.2% for river water at the concentration level of 5 ng mL −1 while the linearity of method was in the range of 0.15–100 and 0.5–500 ng mL −1. The developed method was successfully applied to different river water samples and the matrix factor for the spiked river water samples were found to be in the range of 0.74–1.09.

Polypyrrole/polyamide electrospun‐based sorbent for microextraction in packed syringe of organophosphorous pesticides from aquatic samples

A novel method based on microextraction in packed syringe (MEPS) as sample preparation technique coupled off-line with gas chromatography-mass spectrometry was developed using electrospun nanofibers as sorbent. For electrospinning of polypyrrole/polyamide-based nanofiber, a homogeneous solution containing nylon 6, ferric chloride and pyrrole monomer was prepared and then was drawn into a 2.5-mL syringe. By applying a voltage of 13 kV between the needle of the syringe and an aluminum-foil collector, the nanofibers could be formed on the surface of the collector. The prepared sheet was used as the sorbent for MEPS to analyze some selected organophosphorous pesticides. Important parameters influencing the extraction and desorption processes were optimized. Limits of detection were in the range of 0.04-0.1 ng/mL using time scheduled selected ion monitoring mode, and the relative standard deviation (RSD %) values with four replicates were in the range of 3.7-11.8% at a concentration level of 5 ng/mL. The linearity of the method was in the range of 0.5-500 ng/mL for diazinon and fenithrothion and 0.5-200 ng/mL for the rest of the analytes. The developed method was successfully applied to Zayandeh-roud river water samples, whereas the matrix factors were in the range of 0.87-0.98.

Determination of remifentanil in human plasma by liquid chromatography–tandem mass spectrometry utilizing micro extraction in packed syringe (MEPS) as sample preparation

Remifentanil is a synthetic short-acting opioid with a short half-life that is being used during anaesthesia of small children. In this work an LC–MS/MS method for remifentanil quantification in 20 μL volume of human plasma was developed and validated in connection with a clinical study on neonatal children. Sample preparation was performed with micro extraction in packed syringe (MEPS), which is a miniaturization of solid phase extraction. For this method a mixed phase sorbent M1 (C8, cation exchange), and a protocol for basic compound extraction was followed. Remifentanil- 13C 6 was used as internal standard. For chromatographic separation, a C18 analytical column with gradient elution was used with mobile phase consisting of aqueous 0.1% formic acid and methanol. The total analysis time was 5.0 min and the measuring range was between 0.05 and 50 ng/mL. Precision and accuracy were with acceptance criteria of ±15%. Plasma samples were stable for 5 weeks at −20 °C and for 4 h at room temperature while 50% was lost after 24 h. This method was successfully applied for remifentanil determination in clinical samples and results agreed with a reference method. With this method using MEPS, a low limit of quantification and much reduced sample volume was obtained as compared with previous methods.

Polypyrrole nanowires network for convenient and highly efficient microextraction in packed syringe

A novel method based on microextraction in packed syringe (MEPS), as a sample preparation technique in combination with gas chromatography-mass spectrometry (GC-MS) was developed using a polypyrrole (PPy) nanowires network as the extracting medium. The PPy nanowires network was prepared using a soft template technique and its characterization was studied by scanning electron microscopy (SEM). The use of micelles in this methodology has an important role in the shape of the growing polymer. The pyrrole monomer was introduced into cetyltrimethylammonium bromide (CTAB) micelles and this has led to the formation of nanowires with diameters ranging from 30 to 60 nm. The bulk PPy prepared without CTAB were all spherical particles with diameters of 100–400 nm. The PPy nanowires network was shown to have a 7–28 times higher extraction capability in comparision with bulk PPy. The developed method was applied to the analysis of some important triazine herbicides. Important parameters influencing the extraction and desorption processes were optimized and a 25 cycles of draw–eject of sample with a speed of 10 rpm gave a maximum peak area, when 2 mg of PPy nanowires network was packed in the syringe. After entrapment of the selected analytes, the desorption was performed using 150 μL of acetonitrile. Limits of detection (LODs) were in the range of 0.02 to 0.05 ng mL−1 using the time scheduled selected ion monitoring (SIM) mode. Intraday precision (RSD %) values for four replicates ranged from 7 to 10% and interday precision values obtained for three replicates measured on different days were in the range of 10–12% at a concentration level of 5 ng mL−1. The linearity of the method was in the range of 0.5–500 ng mL−1. The developed method was successfully applied to the analysis of water samples obtained from the Zayandeh-roud river and the matrix factor for the spiked real water samples was found to be in the range of 0.72–0.92.