Application of solid‐phase microextraction in current biomedical research

Extraction of endogenous compounds and drugs and their corresponding metabolites from complex matrices, such as biofluids and solid tissues, requires adequate analytical approach facilitating qualitative and quantitative analysis. To this end, solid‐phase microextraction has been introduced as modern technology that is capable of efficient and high‐throughput extraction of compounds due to its ability to amalgamate sampling, extraction, and pre‐concentration steps, while requiring minimal use of organic solvents. The ability of solid‐phase microextraction to enable analyses on small‐volume biological samples and growing availability of biocompatible solid‐phase microextraction coatings make it a highly useful technology for variety of applications. For example, solid‐phase microextraction is particularly useful for identifying biomarkers in metabolomics studies, and it can be successfully applied in pharmaceutical and toxicological studies requiring the fast and sensitive determination of drug levels, especially those that are present at low levels in biological matrices such as plasma, urine, saliva, and hair. Moreover, solid‐phase microextraction can be directly applied in in vivo studies because this extraction technique is non‐exhaustive and its biocompatible probes offer minimal invasiveness to the analyzed system. In this article, we review recent progress in well‐established solid‐phase microextraction technique for in vitro and in vivo analyses of various metabolites and drugs in clinical, pharmaceutical, and toxicological applications.     

Simultaneous analysis of multiple urinary biomarkers for the evaluation of oxidative stress by automated online in‐tube solid‐phase microextraction coupled with negative/positive ion‐switching mode liquid chromatography–tandem mass spectrometry

This study described an automated online method for the simultaneous determination of 8‐isoprostane, 8‐hydroxy‐2′‐deoxyguanosine, and 3‐nitro‐l ‐tyrosine in human urine. The method involves in‐tube solid‐phase microextraction using a Carboxen 1006 PLOT capillary column as an extraction device, followed by liquid chromatography with tandem mass spectrometry using a CX column and detection in the negative/positive switching ion‐mode by multiple reaction monitoring. Using their stable isotope‐labeled internal standards, each of these oxidative stress biomarkers showed good linearity from 0.02 to 2.0 ng/mL. Their detection limits (S/N = 3) were 3.4–21.5 pg/mL, and their intra‐ and inter‐day precisions (relative standard deviations) were >3.9 and 6.5% (n = 5), respectively. This method was applied successfully to the analysis of urine samples, without any other pretreatment and interference peaks.     

Zeolitic imidazolate framework‐8 reinforced hollow‐fiber liquid‐phase microextraction of free urinary biomarkers of whole grain intake followed by CE analysis

The whole grain intake is closely associated with human health. In this work, three‐phase dynamic hollow‐fiber liquid‐phase microextraction reinforced with 0.10 mg/mL 30 nm zeolitic imidazolate framework‐8 nanoparticles was introduced for purification and enrichment of free urinary metabolite biomarkers of whole grain intake. Eight milliliters of HCl (pH 3.00) and 8 μL of 300 mM NaOH solutions were used as the donor and acceptor phases, respectively. The temperature and stirring rate were kept at 25℃ and 500 rpm, and the extraction time was 40 min. The extraction process required no further desorption, and the resultant extract was directly used for electrophoretic analysis without derivatization. Based on the synergistic effect of hollow‐fiber liquid‐phase microextraction and the electrophoretic stacking, the enrichment factors of 3,5‐dihydroxybenzoic acid and 3‐(3,5‐dihydroxyphenyl)‐1‐propionic acid reached 1018–1034 times, and their limits of detection achieved 0.33–0.67 ng/mL (S/N = 3) in urine matrix. The developed method has been successfully used for urine analysis, and the sample recovery data were in the range of 97.0–103.5%. This developed method provided an attractive alternative for the determination of urinary metabolite biomarkers of whole grain intake due to its sensitive, fast, low‐cost, and environmental‐friendly features.     

Enantioselective analysis of mirtazapine,demethylmirtazapine and 8‐hydroxy mirtazapine in human urine after solid‐phase microextraction

A selective and reproducible off‐line solid‐phase microextraction procedure was developed for the simultaneous enantioselective determination of mirtazapine (MRT), demethylmirtazapine and 8‐hydroxymirtazapine in human urine. CE was used for optimization of the extraction procedure whereas LC‐MS was used for method validation and application. The influence of important factors in the solid‐phase microextraction efficiency is discussed, such as the fiber coatings, extraction time, pH, ionic strength, temperature and desorption time. Before extraction, human urine samples were submitted to enzymatic hydrolysis at 37°C for 16 h. Then, the enzyme was precipitated with trichloroacetic acid and the pH was adjusted to 8 with 1 mol/L pH 11 phosphate buffer solution. In the extraction, the analytes were transferred from the aqueous solution to the polydimethylsiloxane‐divinylbenzene fiber coating and then desorbed in methanol. The mean recoveries were 5.4, 1.7 and 1.0% for MRT, demethylmirtazapine and 8‐hydroxymirtazapine enantiomers, respectively. The method was linear over the concentration range of 62–1250 ng/mL. The within‐day and between‐day assay precision and accuracy were lower than 15%. The method was successfully employed in a preliminary cumulative urinary excretion study after administration of racemic MRT to a healthy volunteer.     

Determination of urinary 8‐hydroxy‐2′‐deoxyguanosine by a combination of on‐line molecularly imprinted monolithic solid phase microextraction with high performance liquid chromatography–ultraviolet detection

8‐Hydroxy‐2′‐deoxyguanosine (8‐OHdG) is a sensitive biomarker for DNA oxidative damage. However, its determination in human urine is confounded by trace level and complex matrix. In this study, a new configuration of on‐line solid phase microextraction coupled to high performance liquid chromatography‐ultraviolet detection was established with molecularly imprinted monolithic column as extraction sorbent. The tailor made monolith exhibited high extraction efficiency with the enrichment factor 101.84 for 8‐OHdG owing to its special porous structure and inherent selectivity. Under optimal condition, appreciable sensitivity had been achieved for this incorporation with limit of detection 2.04 nmol/L (S/N = 3) and limit of quantification 7.12 nmol/L (S/N = 10), respectively. Precise determination with wide range linearity (0.007–5.00 μmol/L) afforded a practical alternative in urinary 8‐OHdG analysis and 107 different subjects had been successfully analyzed. This newly developed method embodied useful prospect for the investigation of DNA oxidative damage with less expense, convenient maintenance and ease of operation     

Determination of free formaldehyde in vaccines and biological samples using solid‐phase microextraction coupled to GC–MS

A headspace solid‐phase microextraction method coupled to GC–MS was successfully developed for the trace determination of formaldehyde in veterinary bacterial and human vaccines, and diphtheria–tetanus antigen. The formaldehyde was derivatized by means of the Hantzsch reaction prior to extraction and subsequent determination. Three different types of solid‐phase microextraction fibers, polar, and nonpolar poly(dimethylsiloxane) and polyethylene glycol were prepared by using a sol–gel technique. The effects of different parameters such as type of fiber coating, extraction time and temperature, desorption conditions, agitation rate, and salt effect were investigated. Under the optimized conditions, the detection limit of the method was 979 ng/L using the selected ion‐monitoring mode. The interday and intraday precisions of the developed method under the optimized conditions were below 13%, and the method shows linearity in the range of 1.75–800 μg/L with a correlation coefficient of 0.9963. The optimized method was applied to the determination of formaldehyde from some biological products. The results were satisfactory compared to the standard method.     

Paper‐based solid‐phase microextraction for analysis of 8‐hydroxy‐2’‐deoxyguanosine in urine sample by CE‐LIF

An easy‐to‐do paper‐based solid‐phase microextraction (p‐SPME) was developed for determination of 8‐hydroxy‐2’‐deoxyguanosine (8‐OHdG) in urine sample by CE‐LIF. Small piece of filter paper was used as a solid phase to extract 8‐OHdG from urine sample. Its primary mechanism is based on the hydrogen‐bonding interaction between 8‐OHdG and cellulose molecules. The effects of the pH of the sample solution, extraction time, and temperature on the peak area of the analyte were investigated in order to obtain the optimal p‐SPME conditions. Comparing with the untreated sample, the p‐SPME can significantly reduce the interference to the separation of 8‐OHdG by CE‐LIF. Meanwhile, the p‐SPEM can provide more than three times concentrated effect. The developed method was evaluated according to an FDA guideline for biological analysis. The precisions (RSD%, n = 5) of the peak area and migration time of the analyte at three different concentrations were within 3.02–5.82% and 0.92–1.58%, respectively. The limit of identification of the method is about 5 nM according to the significant difference between two sets of the samples with and without spiking the standard (Student's t ‐test, p < 0.05). Good linearity was obtained in the range of 10–1000 nM (R ²>0.99) based on the standard addition. The recoveries at three different concentrations were within 99.8–103.5%. The results of the real sample analysis are consistent with those reported in our previous paper (Electrophoresis 2014, 35, 1873–1879).     

Electromembrane‐surrounded solid‐phase microextraction coupled to ion mobility spectrometry for the determination of nonsteroidal anti‐inflammatory drugs: A rapid screening method in complicated matrices

A new robust method of electromembrane‐surrounded solid‐phase microextraction coupled to ion mobility mass spectrometry was applied for nonsteroidal anti‐inflammatory drugs determination in complex matrices. This is the first time that a graphene/polyaniline composite coating is applied in electromembrane‐surrounded solid‐phase microextraction method. The homemade graphene/polyaniline composite is characterized by a high electrical conductivity and thermal stability. The variables affecting electromembrane‐surrounded solid‐phase microextraction, including extraction time; applied voltage and pH were optimized through chemometric methods, central composite design, and response surface methodology. Under the optimized conditions, limits of detection of 0.04 and 0.05 ng/mL were obtained for mefenamic acid and ibuprofen, respectively. The feasibility of electromembrane‐surrounded solid‐phase microextraction followed by ion mobility mass spectrometry was successfully confirmed by the extraction and determination of low levels of ibuprofen and mefenamic acid in human urine and plasma samples and satisfactory results were obtained.     

Discrimination Between 8‐Oxo‐2′‐Deoxyguanosine and 2′‐Deoxyguanosine in DNA by the Single Nucleotide Primer Extension Reaction with Adap Triphosphate

The adenosine derivative of 2‐oxo‐1,3‐diazaphenoxazine (Adap) exhibits a superb ability to recognize and form base pairs with 8‐oxo‐2′‐deoxyguanosine (8‐oxo‐dG) in duplex DNA. In this study, the triphosphate of Adap (dAdapTP) was synthesized and tested for single nucleotide incorporation into primer strands using the Klenow Fragment. The efficiency of dAdapTP incorporation into 8‐oxo‐dG‐containing templates was more than 36‐fold higher than with dG‐containing templates, and provides better discrimination than does the incorporation of natural 2′‐deoxyadenosine triphosphate (dATP). The selective incorporation of dAdapTP into 8‐oxo‐dG templates was therefore applied to the detection of 8‐oxo‐dG in human telomeric DNA sequences extracted from H₂O₂‐treated HeLa cells. The enzymatic incorporation of dAdapTP into 8‐oxo‐dG‐containing templates may provide a novel basis for sequencing oxidative DNA damage in the genome.     

Effect of sample matrix on sensitivity of mercury and methylmercury quantitation in human urine,saliva, and serum using GC‐MS

A rapid and sensitive method has been developed for the simultaneous determination of monomethylmercury (MMHg) and inorganic mercury (iHg) in human body fluids. The procedure is based on in situ derivatization of MMHg and iHg with sodium tetraethylborate (NaBEt₄) directly in aqueous solutions followed by headspace solid phase microextraction (HS‐SPME). The extracted species from spiked human urine, saliva, and serum are separated by capillary gas chromatography and detected by quadrupole MS (GC‐MS). The optimization of the HS‐SPME conditions like temperature, sample volume, extraction duration, and amount of alkylation agent, was performed in urinary solutions and aqueous solutions similarly buffered. The gas chromatographic conditions like injection temperature, helium flow rate, temperature program, and pressure conditions were also optimized. The recovery was ranged between 85 and 96% for MMHg and 88 and 98% for iHg. The LODs achieved were 10 and 15 ng/L for iHg and MMHg in urine, respectively, 54 and 60 ng/L for iHg and MMHg in saliva, respectively, and 61 and 81 ng/L for iHg and MMHg in serum, respectively. The RSD was ranged between 6.2 and 9.2% for MMHg and 5.0 and 8.2% for iHg.     

Simultaneous determination of 8‐oxo‐2′‐deoxyguanosine and 8‐oxo‐2′‐deoxyadenosine in DNA using online column‐switching liquid chromatography/tandem mass spectrometry

Sensitive and reliable methods are required for the assessment of oxidative DNA damage, which can result from reactive oxygen species that are generated endogenously from cellular metabolism and inflammatory responses, or by exposure to exogenous agents. The development of a liquid chromatography/tandem mass spectrometry (LC/MS/MS) selected reaction monitoring (SRM) method is described, that utilises online column‐switching valve technology for the simultaneous determination of two DNA adduct biomarkers of oxidative stress, 8‐oxo‐7,8‐dihydro‐2′‐deoxyguanosine (8‐oxodG) and 8‐oxo‐7,8‐dihydro‐2′‐deoxyadenosine (8‐oxodA). To allow for the accurate quantitation of both adducts the corresponding [¹⁵N₅]‐labelled stable isotope internal standards were synthesised and added prior to enzymatic hydrolysis of the DNA samples to 2′‐deoxynucleosides. The method required between 10 and 40 µg of hydrolysed DNA on‐column for the analysis and the limit of detection for both 8‐oxodG and 8‐oxodA was 5 fmol. The analysis of calf thymus DNA treated in vitro with methylene blue (ranging from 5 to 200 µM) plus light showed a dose‐dependent increase in the levels of both 8‐oxodG and 8‐oxodA. The level of 8‐oxodG was on average 29.4‐fold higher than that of 8‐oxodA and an excellent linear correlation (r = 0.999) was observed between the two adducts. The influence of different DNA extraction procedures for 8‐oxodG and 8‐oxodA levels was assessed in DNA extracted from rat livers following dosing with carbon tetrachloride. The levels of 8‐oxodG and 8‐oxodA were on average 2.9 (p = 0.018) and 1.4 (p = 0.018) times higher, respectively, in DNA samples extracted using an anion‐exchange column procedure than in samples extracted using a chaotropic procedure, implying artefactual generation of the two adducts. In conclusion, the online column‐switching LC/MS/MS SRM method provides the advantages of increased sample throughput with reduced matrix effects and concomitant ionisation suppression, making the method ideally suited when used in conjunction with chaotropic DNA extraction for the determination of oxidative DNA damage. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and selective recognition of a novel solid‐phase microextraction fiber combined with molecularly imprinted polymers for the extraction of parabens in soy sample

A prepared molecularly imprinted polymer with ethyl p‐hydroxybenzoate as template molecule was applied for the first time to a homemade solid‐phase microextraction fiber. The molecularly imprinted polymer‐coated solid‐phase microextraction fiber was characterized by scanning electron microscopy and thermogravimetric analysis. Various parameters were investigated, including extraction temperature, extraction time, and desorption time. Under the optimum extraction conditions, the molecularly imprinted polymer‐coated solid‐phase microextraction fiber exhibited higher selectivity with greater extraction capacity toward parabens compared with the nonimprinted polymer‐coated solid‐phase microextraction fiber and commercial fibers. The molecularly imprinted polymer‐coated solid‐phase microextraction fiber was tested using gas chromatography to determine parabens, including methyl p‐hydroxybenzoate, ethyl p‐hydroxybenzoate, and propyl p‐hydroxybenzoate. The linear ranges were 0.01–10 μg/mL with a correlation coefficient above 0.9943. The detection limits (under signal‐to‐noise ratio of 3) were below 0.30 μg/L. The fiber was successfully applied to the simultaneous analysis of three parabens in spiked soy samples with satisfactory recoveries of 95.48, 97.86, and 92.17%, respectively. The relative standard deviations (n=6) were within 2.83–3.91%. The proposed molecularly imprinted polymer‐coated solid‐phase microextraction method is suitable for selective extraction and determination of trace parabens in food samples.     

Multiple monolithic fiber solid‐phase microextraction based on a polymeric ionic liquid with high‐performance liquid chromatography for the determination of steroid sex hormones in water and urine

The development of a simple and sensitive analytical approach that combines multiple monolithic fiber solid‐phase microextraction with liquid desorption followed by high‐performance liquid chromatography with diode array detection is proposed for the determination of trace levels of seven steroid sex hormones (estriol, 17β‐estradiol, testosterone, ethinylestradiol, estrone, progesterone and mestranol) in water and urine matrices. To extract the target analytes effectively, multiple monolithic fiber solid‐phase microextraction based on a polymeric ionic liquid was used to concentrate hormones. Several key extraction parameters including desorption solvent, extraction and desorption time, pH value and ionic strength in sample matrix were investigated in detail. Under the optimal experimental conditions, the limits of detection were found to be in the range of 0.027–0.12 μg/L. The linear range was 0.10–200 μg/L for 17β‐estradiol, 0.25–200 μg/L estriol, ethinylestradiol and estrone, and 0.50–200 μg/L for the other hormones. Satisfactory linearities were achieved for analytes with the correlation coefficients above 0.99. Acceptable method reproducibility was achieved by evaluating the repeatability and intermediate precision with relative standard deviations of both less than 8%. The enrichment factors ranged from 54‐ to 74‐fold. Finally, the proposed method was successfully applied to the analysis of steroid sex hormones in environmental water samples and human urines with spiking recoveries ranged from 75.6 to 116%.     

Inhibiting sorbent stripping by designing a sorbent‐packed porous probe for headspace solid‐phase microextraction

To prevent the stripping of coating sorbents in headspace solid‐phase microextraction, a porous extraction probe with packed sorbent was introduced by using a porous stainless steel needle tube and homemade sol–gel sorbents. The traditional stainless‐steel needle tube was punched by a laser to obtain two rows of holes, which supply a passageway for analyte vapor during extraction and desorption. The sorbent was prepared by a traditional sol–gel method with both poly(ethylene glycol) and hydroxy‐terminated silicone oil as coating ingredients. Eight polycyclic aromatic hydrocarbons and six benzene series compounds were used as illustrative semi‐volatile and volatile organic compounds in sequence to verify the extraction performance of this porous headspace solid‐phase microextraction probe. It was found that the analysis method combining a headspace solid‐phase microextraction probe and gas chromatography with mass spectrometry yielded determination coefficients of no less than 0.985 and relative standard deviations of 4.3–12.4%. The porous headspace solid‐phase microextraction probe showed no decrease of extraction ability after 200 uses. These results demonstrate that the packed extraction probe with porous structure can be used for headspace solid‐phase microextraction. This novel design may overcome both the stripping and breakage problems of the conventional coating fiber.     

A rapid MCM‐41 dispersive micro‐solid phase extraction coupled with LC/MS/MS for quantification of ketoconazole and voriconazole in biological fluids

A rapid dispersive micro‐solid phase extraction (D‐μ‐SPE) combined with LC/MS/MS method was developed and validated for the determination of ketoconazole and voriconazole in human urine and plasma samples. Synthesized mesoporous silica MCM‐41 was used as sorbent in d ‐μ‐SPE of the azole compounds from biological fluids. Important D‐μ‐SPE parameters, namely type desorption solvent, extraction time, sample pH, salt addition, desorption time, amount of sorbent and sample volume were optimized. Liquid chromatographic separations were carried out on a Zorbax SB‐C₁₈ column (2.1 × 100 mm, 3.5 μm), using a mobile phase of acetonitrile–0.05% formic acid in 5 mm ammonium acetate buffer (70:30, v /v). A triple quadrupole mass spectrometer with positive ionization mode was used for the determination of target analytes. Under the optimized conditions, the calibration curves showed good linearity in the range of 0.1–10,000 μg/L with satisfactory limit of detection (≤0.06 μg/L) and limit of quantitation (≤0.3 μg/L). The proposed method also showed acceptable intra‐ and inter‐day precisions for ketoconazole and voriconazole from urine and human plasma with RSD ≤16.5% and good relative recoveries in the range 84.3–114.8%. The MCM‐41‐D‐μ‐SPE method proved to be rapid and simple and requires a small volume of organic solvent (200 μL); thus it is advantageous for routine drug analysis.     

Preparation and application of a polythiophene solid‐phase microextraction fiber for the determination of endocrine‐disruptor pesticides in well waters

A robust solid‐phase microextraction fiber was fabricated by electropolymerization of thiophene on a stainless steel wire. This fiber was applied for the determination of endocrine‐disruptor pesticides, namely, chlorpyrifos, penconazole, procymidone, bromopropylate, and λ‐cyhalothrin in well waters by a headspace solid‐phase microextraction procedure. Operational parameters, namely, pH, sample volume, adsorption temperature and time, desorption temperature, stirring rate, and salt amount were optimized as 7.0, 8 mL, 70°C and 20 min, 250°C, 600 rpm, and 0.3 g/mL, respectively. The separation power of GC was coupled with the excellent sensitivity of the developed fiber enabling us to determine pesticide mixtures simultaneously in a ng/mL range. The LOD was in the range of 0.02–0.64 ng/mL. The method was successfully applied for the selective and sensitive determination of target pesticides in well water samples with acceptable recovery values (92–110%). The polythiophene fiber gives satisfactory results compared with commercial fibers. Commonly used pesticides with different polarities were chosen as representative compounds to search the applicability of the fiber for well water analysis collected from vineyards.     

Solid‐phase microextraction of methadone in urine samples by electrochemically co‐deposited sol–gel/Cu nanocomposite fiber

Electrochemically co‐deposited sol–gel/Cu nanocomposites have been introduced as a novel, simple and single‐step technique for preparation of solid‐phase microextraction (SPME) coating to extract methadone (MDN) (a synthetic opioid) in urine samples. The porous surface structure of the sol–gel/Cu nanocomposite coating was revealed by scanning electron microscopy. Direct immersion SPME followed by HPLC‐UV determination was employed. The factors influencing the SPME procedure, such as the salt content, desorption solvent type, pH and equilibration time, were optimized. The best conditions were obtained with no salt content, acetonitrile as desorption solvent type, pH 9 and 10 min equilibration time. The calibration graphs for urine samples showed good linearity. The detection limit was about 0.2 ng mL⁻¹. Also, the novel method for preparation of nanocomposite fiber was compared with previously reported techniques for MDN determination. The results show that the novel nanocomposite fiber has relatively high extraction efficiency.     

Solid‐phase microextraction of ultra‐trace amounts of tramadol from human urine by using a carbon nanotube/flower‐shaped zinc oxide hollow fiber

A new method is successfully developed for the separation and determination of a very low amount of tramadol in urine using functionalized multiwalled carbon nanotubes/flower‐shaped zinc oxide before solid‐phase microextraction combined with gas chromatography. Under ultrasonic agitation, a sol of multiwalled carbon nanotubes and flower‐shaped zinc oxide were forced into and trapped within the pore structure of the polypropylene and the sol solution immobilized into the hollow fiber. Flower‐shaped zinc oxide was synthesized and characterized by Fourier transform infrared spectroscopy. The morphology of the fabricated solid‐phase microextraction surface was investigated by scanning electron microscopy and X‐ray diffraction. The parameters affecting the extraction efficiencies were investigated and optimized. Under the optimized conditions, the method shows linearity in a wide range of 0.12–7680 ng/mL, and a low detection limit (S/N = 3) of 0.03 ng/mL. The precision of the method was determined and a relative standard deviation of 3.87% was obtained. This method was successfully applied for the separation and determination of tramadol in urine samples. The relative recovery percentage obtained for the spiked urine sample at 1000 ng/mL was 94.2%.     

Electro‐assisted solid‐phase microextraction based on poly(3,4‐ethylenedioxythiophen) combined with GC for the quantification of tricyclic antidepressants

In this study, a platinum wire coated with poly(3,4‐ethylenedioxythiophen) was used as an electro‐assisted solid‐phase microextraction fiber for the quantification of tricyclic antidepressant drugs in biological samples by coupling to GC employing a flame ionization detector. In this study, an electric field increased the extraction rate and recovery. The fiber used as a solid phase was synthesized by the electropolymerization of 3,4‐ethylenedioxythiophen monomers onto a platinum wire. The ability of this fiber to extract imipramine, desipramine, and clomipramine by using the electro‐assisted solid‐phase microextraction technique was evaluated. The effect of various parameters that influence the extraction efficiency, which include solution temperature, extraction time, stirring rate, ionic strength, time and temperature of desorption, and thickness of the fiber, was optimized. Under optimized conditions, the linear ranges and regression coefficients of calibration curves were in the range of 0.5–250 and 0.990–0.998 ng/mL, respectively. Detection limits were in the range of 0.15–0.45 ng/mL. Finally, this method was applied to the determination of drugs in urine and wastewater samples and recoveries were 4.8–108.9%.     

Application of ionic‐liquid‐supported magnetic dispersive solid‐phase microextraction for the determination of acaricides in fruit juice samples

In this study, ionic liquid (IL) supported magnetic dispersive solid‐phase microextraction was developed and a systematic investigation was conducted on imidazolium ILs for their extraction performance. This nano‐based pretreatment procedure was then applied for the determination of acaricides in fruit juice samples for the first time. A feature of this technique is that the commonly laborious chemical modification of magnetic nanoparticles (MNPs) was skillfully circumvented. Because of the combination of ILs, dispersive liquid–liquid microextraction, and dispersive MNP solid‐phase microextraction, the extraction efficiency can be significantly improved using commercial MNPs. Parameters of the extraction method were investigated by one‐factor‐at‐a‐time approach. The optimal experimental conditions were as follows: emulsification for 2 min by sonication with the addition of 50 μL [C₆MIM][NTf₂] in the dispersive liquid–liquid microextraction step and vortexing for 90 s after adding 40 mg spherical barium ferrite nanoparticles (20 nm). The desorption time was 2 min. Good linearity (0.5–500 ng/mL) and detection limits within the range of 0.05–0.53 ng/mL were achieved. The application of the proposed method was demonstrated by the analysis of real fruit juice samples, in which recoveries between 85.1 and 99.6% were obtained.