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1.
The molecularly imprinted SPE directly coupled to RP LC‐MS/MS method has been developed and successfully validated for the determination of six hormones in water and sediment samples. The method is based on the use the home‐made column filled with a molecularly imprinted sorbent (imprinted against estrogens) that was used under nonaqueous conditions. Thus, its high selectivity could be utilized resulting in low matrix components’ coextraction. The method showed excellent recovery (92–105%) and satisfactory sensitivity (LOQs water: 1.9–4.0 ng/L; LOQs sediment: 0.2–0.5 ng/g). The intra‐ and interprecision for water and sediment was in the range of 4.0–6.0% and 4.4–7.6%, respectively. Finally, 20 water and sediment samples collected from the Svratka river were analyzed. Only estrone was quantified in eight water samples (4.4–7.1 ng/L); no analytes were found in sediment samples.  相似文献   

2.
In this work, a novel magnetic nanomaterial functionalized with a molecularly imprinted polymer was prepared for the extraction of protoberberine alkaloids. Molecularly imprinted polymers were made on the surface of Fe3O4 nanoparticles by using berberine as template, acetonitrile/water as porogen, acrylamide as functional monomer and ethylene glycol dimethacrylate as cross‐linker. The optimized molar ratio of template/functional monomer was 1:7. The polymeric magnetic nanoparticles were characterized by transmission electron microscopy and Fourier transform infrared spectroscopy. The stability and adsorption capacity of the molecularly imprinted polymers were investigated. The molecularly imprinted polymers were used as a selective sorbent for the magnetic molecularly imprinted solid‐phase extraction and determination of jatrorrhizine, palmatine, and berberine. Extraction parameters were studied including loading pH, sample volume, stirring speed, and extraction time. Finally, a magnetic molecularly imprinted solid‐phase extraction coupled to high‐performance liquid chromatography method was developed. Under the optimized conditions, the method showed good linear range of 0.1–150 ng/mL for berberine and 0.1–100 ng/mL for jatrorrhizine and palmatine. The limit of detection was 0.01 ng/mL for berberine and 0.02 ng/mL for jatrorrhizine and palmatine. The proposed method has been applied to determine protoberberine alkaloids in Cortex phellodendri and rat plasma samples. The recoveries ranged from 87.33–102.43%, with relative standard deviation less than 4.54% in Cortex phellodendri and from 102.22–111.15% with relative standard deviation less than 4.59% in plasma.  相似文献   

3.
The computer‐assisted design and synthesis of molecularly imprinted polymers for the simultaneous capture of six carbamate pesticides from environmental water are reported in this work. The quantum mechanical computational approach was employed to design the molecularly imprinted polymers with carbofuran as template. The interaction energies between the template molecule and different functional monomers in various solvents were calculated to assist in the selection of the functional monomer and porogen. The optimised molecularly imprinted polymer was subsequently used as a class‐selective sorbent in solid‐phase extraction for pre‐concentration and determination of carbamates from environmental water. The parameters influencing the extraction efficiency of the molecularly imprinted solid‐phase extraction procedure were systematically investigated to facilitate the class‐selective extraction. For the proposed method, linearity was observed over the range of 2–500 ng/mL with the correlation coefficient ranging from 0.9760 to 1.000. The limits of detection ranged from 0.2 to 1.2 ng/mL, and the limit of quantification was 4 ng/mL. These results confirm that computer‐assisted design is an effective evaluation tool for molecularly imprinted polymers synthesis, and that molecularly imprinted solid‐phase extraction can be applied to the simultaneous analysis of carbamates in environmental water.  相似文献   

4.
In this study, we developed a simple and selective spin column extraction technology utilizing hydrophilic molecularly imprinted polymers as the sorbents for extracting nitrophenol pollutants in water samples (the East Lake, the Yangtze River, and wastewater). The whole procedure was achieved by centrifugation of the spin column, and multiple samples were simultaneously processed with a low volume of solvent and without evaporation. Under the optimized condition, recoveries of nitrophenol compounds on the spin column packed with hydrophilic molecularly imprinted polymers ranged from 87.3 to 92.9% and an excellent purification effect was obtained. Compared with activated carbon, multi‐walled carbon nanotubes, LC‐C18 sorbents, hydrophilic molecularly imprinted polymers exhibited a highly selective recognition ability for nitrophenol compounds and satisfactory sample extraction efficiency. Subsequently, the spin column extraction coupled with high‐performance liquid chromatography was established, which was found to be linear in the range of 2–1000 ng/mL for 2,4‐dinitropehnol and 2‐nitrophenol, and 6–1000 ng/mL for 4‐nitrophenol with correlation coefficients greater than 0.998. The detection limits ranged from 0.3–0.5 ng/mL. It is shown that the proposed method can be used for the determination of trace nitrophenol pollutants in complex samples, which is not only beneficial for water quality analysis but also for environmental risk assessment.  相似文献   

5.
A molecularly imprinted polymer designed for the selective extraction of donepezil from serum samples was synthesized using a noncovalent molecular imprinting approach. The molecularly imprinted polymer was evaluated chromatographically and then its affinity for donepezil was confirmed by solid‐phase extraction. The optimal conditions for solid‐phase extraction were provided by cartridge conditioning using acidified water purified from a Milli‐Q system, sample loading under basic aqueous conditions, clean‐up using acetonitrile, and elution with methanol/tetrahydrofuran. Desirable molecular recognition properties of the molecularly imprinted polymer led to good donepezil recoveries (90–102%). The data indicated that the imprinted polymer has a perfect selectivity and affinity for donepezil and could be used for selective extraction and analysis of donepezil in human serum.  相似文献   

6.
Sample pretreatment is essential for the analysis of complicated real samples due to their complex matrices and low analyte concentrations. Among all sample pretreatment methods, solid‐phase extraction is arguably the most frequently used one. However, the majority of available solid‐phase extraction adsorbents suffer from limited selectivity. Molecularly imprinted polymers are a type of tailor‐made artificial antibodies and receptors with specific recognition sites for target molecules. Using molecularly imprinted polymers instead of conventional adsorbents can greatly improve the selectivity of solid‐phase extraction, and therefore molecularly imprinted polymer‐based solid‐phase extraction has been widely applied to separation, clean up and/or preconcentration of target analytes in various kinds of real samples. In this article, after a brief introduction, the recent developments and applications of molecularly imprinted polymer‐based solid‐phase extraction for determination of different analytes in complicated real samples during the 2015‐2020 are reviewed systematically, including the solid‐phase extraction modes, molecularly imprinted adsorbent types and their preparations, and the practical applications of solid‐phase extraction to various real samples (environmental, food, biological, and pharmaceutical samples). Finally, the challenges and opportunities of using molecularly imprinted polymer‐based solid‐phase extraction for real sample analysis are discussed.  相似文献   

7.
A novel and highly efficient approach to obtain magnetic molecularly imprinted polymers is described to detect avermectin in fish samples. The magnetic molecularly imprinted polymers were synthesized by surface imprinting polymerization using magnetic multiwalled carbon nanotubes as the support materials, atom transfer radical polymerization as the polymerization method, avermectin as template, acrylamide as functional monomer, and ethylene glycol dimethacrylate as crosslinker. The characteristics of the magnetic molecularly imprinted polymers were assessed by using transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, vibrating sample magnetometry, X‐ray diffraction, and thermogravimetric analysis. The binding characteristics of magnetic molecularly imprinted polymers were researched through isothermal adsorption experiment, kinetics adsorption experiment, and the selectivity experiment. Coupled with ultra high performance liquid chromatography and tandem mass spectrometry, the extraction conditions of the magnetic molecularly imprinted polymers as adsorbents for avermectin were investigated in detail. The recovery of avermectin was 84.2–97.0%, and the limit of detection was 0.075 μg/kg. Relative standard deviations of intra‐ and inter‐day precisions were in the range of 1.7–2.9% and 3.4–5.6%, respectively. The results demonstrated that the extraction method not only has high selectivity and accuracy, but also is convenient for the determination of avermectin in fish samples.  相似文献   

8.
Reaching trace amounts of mycotoxin contamination requires sensitive and selective analytical tools for their determination. Improving the selectivity of sample pretreatment steps covering new and modern extraction techniques is one way to achieve it. Molecularly imprinted polymers as selective sorbent for extraction undoubtedly meet these criteria. The presented work is focused on the hyphenation of on‐line molecularly imprinted solid‐phase extraction with a chromatography system using a column‐switching approach. Making a critical comparison with a simultaneously developed off‐line extraction procedure, evaluation of pros and cons of each method, and determining the reliability of both methods on a real sample analysis were carried out. Both high‐performance liquid chromatography methods, using off‐line extraction on molecularly imprinted polymer and an on‐line column‐switching approach, were validated, and the validation results were compared against each other. Although automation leads to significant time savings, fewer human errors, and required no handling of toxic solvents, it reached worse detection limits (15 versus 6 μg/L), worse recovery values (68.3–123.5 versus 81.2–109.9%), and worse efficiency throughout the entire clean‐up process in comparison with the off‐line extraction method. The difficulties encountered, the compromises made during the optimization of on‐line coupling and their critical evaluation are presented in detail.  相似文献   

9.
The dummy molecularly imprinted polymers were prepared by Pickering emulsion polymerization. 4,4′‐(1‐Phenylethylidene) bisphenol was selected as the dummy template to avoid the leakage of the target bisphenols. The microsphere particles were characterized by scanning electron microscopy and nitrogen adsorption–desorption measurements, demonstrating that the regular‐shaped and medium‐sized particles (40–70 μm) were obtained with a specific surface area of 355.759 m2/g and a total pore volume of 0.561 cm3/g. The molecular imprinting properties of the particles were evaluated by static adsorption and chromatographic evaluation experiments. The association constant and maximum adsorption amount of bisphenol A were 0.115 mmol/L and 3.327 μmol/g using Scatchard analysis. The microsphere particles were then used as a solid‐phase extraction sorbent for selective extraction of seven bisphenols. The method of dummy molecularly imprinted solid‐phase extraction coupled with high‐performance liquid chromatography and diode array detection was successfully established for the extraction and determination of seven bisphenols from environmental sediment samples with method detection limits of 0.6–1.1 ng/g. Good recoveries (75.5–105.2%) for sediment samples at two spiking levels (500 and 250 ng/g) and reproducibility (RSDs < 7.7%, n = 3) were obtained.  相似文献   

10.
Novel molecularly imprinted polymers of phthalate esters were prepared by atom transfer radical polymerization using methyl methacrylate as functional monomer, cyclohexanone as solvent, cuprous chloride as catalyst, 1‐chlorine‐1‐ethyl benzene as initiator and 2,2‐bipyridyl as cross‐linker in the mixture of methanol and water (1:1, v/v). The effect of reaction conditions such as monomer ratio and template on the adsorption properties was investigated. The optimum condition was obtained by an orthogonal experiment. The obtained polymers were characterized using scanning electron microscopy. The binding property was studied with both static and dynamic methods. Results showed that the polymers exhibited excellent recognition capacity and outstanding selectivity for ten phthalate esters. Factors affecting the extraction efficiency of the molecularly imprinted solid‐phase extraction were systematically investigated. An analytical method based on the molecularly imprinted coupled with gas chromatography and flame ionization detection was successfully developed for the simultaneous determination of ten phthalate esters from edible oil. The method detection limits were 0.10–0.25 μg/mL, and the recoveries of spiked samples were 82.5–101.4% with relative standard deviations of 1.24–5.37% (n = 6).  相似文献   

11.
A new LC method to detect fusaric acid (FA) in maize is reported based on a molecularly imprinted SPE clean‐up using mimic‐templated molecularly imprinted polymers. Picolinic acid was used as a toxin analog for imprinting polymers during a thermolytic synthesis. Both acidic and basic functional monomers were predicted to have favorable binding interactions by MP2 ab initio calculations. Imprinted polymers synthesized with methacrylic acid or 2‐dimethylaminoethyl methacrylate exhibited imprinting effects in SPE analysis. FA levels were determined using RP ion‐pairing chromatography with diode‐array UV detection and tetrabutylammonium hydrogen sulfate in the mobile phase. A method was developed to detect FA in maize using molecularly imprinted SPE analysis within the range of 1–100 μg/g with recoveries between 83.9 and 92.1%.  相似文献   

12.
A simple, sensitive, and selective molecularly imprinted solid‐phase extraction and spectrophotometric method has been developed for the clean‐up and preconcentration of indapamide from human urine. Molecularly imprinted polymers were prepared by a non‐covalent imprinting approach using indapamide as a template molecule, 2‐(trifluoromethyl) acrylic acid as a functional monomer, ethylene glycol dimethacrylate as a crosslinker, N,N‐azobisisobutyronitrile as a thermal initiator and acetonitrile as a porogenic solvent. A non‐imprinted polymer was also prepared in the same way, but in the absence of template. Molecularly imprinted polymer and non‐imprinted polymer sorbents were dry‐packed into solid‐phase extraction cartridges. Eluates from cartridges were analyzed using a spectrophotometer for the determination of indapamide by referring to the calibration curve in the range 0.14–1.50 μg/mL. Preconcentration factor, limit of detection, and limit of quantification were 16.30, 0.025 μg/mL, and 0.075 μg/mL, respectively. A relatively high imprinting factor (9.3) was also achieved and recovery values for the indapamide spiked into human urine were in the range of 80.1–81.2%. In addition, relatively low within‐day (0.17–0.42%) and between‐day (1.1–1.4%) precision values were obtained as well. The proposed molecularly imprinted solid‐phase extraction and spectrophotometric method was successfully applied to selective extraction, preconcentration, and determination of indapamide from human urine samples.  相似文献   

13.
Methyltriphenylphosphonium bromide/chalcone/formic acid, a green ternary deep eutectic solvent, was applied as a functional monomer and dummy template simultaneously in the synthesis of a new molecularly imprinted polymer. Ternary deep eutectic solvent based molecularly imprinted polymers are used as a solid‐phase extraction sorbent in the separation and purification of rutin and quercetin from Herba Artemisiae Scopariae combined with high‐performance liquid chromatography. Fourier transform infrared spectroscopy and field‐emission scanning electron microscopy were applied to characterize the deep eutectic solvent based molecularly imprinted polymers synthesized using different molar ratios of chalcone. The static and competitive adsorption tests were performed to examine the recognition ability of the molecularly imprinted polymers to rutin and quercetin. The ternary deep eutectic solvent consisting of formic acid/chalcone/methyltriphenylphosphonium bromide (1:0.05:0.5) had the best molecular recognition effect. After optimization of the washing solvents (methanol/water, 1:9) and eluting solvents (acetonitrile/acetic acid, 9:1), a reliable analytical method was developed for strong recognition towards rutin and quercetin in Herba Artemisiae Scopariae with satisfactory extraction recoveries (rutin: 92.48%, quercetin: 94.23%). Overall, the chalcone ternary deep eutectic solvent‐based molecularly imprinted polymer coupled with solid‐phase extraction is an effective method for the selective purification of multiple bioactive compounds in complex samples.  相似文献   

14.
A new sample preparation method based on microextraction in packed syringe was developed for preconcentration of quercetin prior to its spectrophotometric determination. Molecularly imprinted polymers as packing material was used for higher extraction efficiency. First, glass powder as support material because of low cost and available substrate was modified, and then molecularly imprinted polymers were synthesized by the sol–gel method using 3-aminopropyltriethoxysilane as a functional monomer and tetraethyl orthosilicate as cross-linker agent. The combination of a molecularly imprinted polymers and microextraction in packed syringe increased the selectivity and sensitivity. The surface morphology and functionality of the prepared molecularly imprinted polymers was characterized using Fourier-transform infrared spectroscopy, Field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and thermogravimetric analysis. Different influencing parameters on extraction efficiency such as effect of the number of sample sorption/desorption cycles, type and volume of desorption solvent, pH of the sample solution, and molecularly imprinted polymers amounts were optimized. Under the optimum condition, the proposed method displayed a linear range from 0.01 to 5 µg mL−1 and limit of detection 3.68 ng mL−1. Relative standard deviation for three replicate determination of 1 µg mL−1 quercetin was 2.1 %. The proposed method was applied successfully for the selective extraction of quercetin from tea and coffee samples.  相似文献   

15.
In this study, the use of monolithic molecularly imprinted polymers in a micropipette tip format allowing the simple and fast extraction of flavonoids from standard solutions and a black tea sample is demonstrated. The imprinted polymer employed quercetin, methacrylic acid or 4‐vinylpyridine, and ethylene glycol dimethacrylate as template, functional monomer, and cross‐linker, respectively. Surface morphologies of the quercetin‐imprinted polymers and the corresponding nonimprinted polymers were characterized by SEM. Extraction of flavonoid standards was performed to evaluate the selectivity and recovery with these imprinted and nonimprinted polymers. Flavonoid compositions in aliquots eluted from the tips were identified using fast GC with flame ionization detection. Maximum specific capacities of 0.2, 5.7, and 16.0 mg/g for catechin, morin, and quercetin, respectively, were obtained with the imprinted polymer prepared with methacrylic acid, with the corresponding recoveries of 99.8, 98.8, and 95.4%, respectively. Efficient extraction by the quercetin‐imprinted polymer of epicatechin, catechin, and quercetin from an apple‐flavored black tea sample was achieved, with GC–MS employed for compound identification for both the tea and extracted samples.  相似文献   

16.
This work demonstrates the synthesis and characterization of core‐shell magnetic molecularly imprinted polymers based on surface imprinting using methacryloyl chloride as a functional monomer for the selective extraction of imidacloprid (template) from apple fruit. The characterization analysis results ensured the successful synthesis of the magnetic molecularly imprinted polymers owing to their heterogeneous structure and good magnetic properties. An isothermal binding test was assessed with a pseudo‐second‐order kinetic model, and the kinetic results fit well to the Freundlich isothermal model. The polymers exhibited an adsorption capacity of 5.75 mg/g for the target analyte with a good selective extraction ability. In addition, the polymers can be reused several times without significant performance loss. The molecularly imprinted polymers showed good performance in the analysis of spiked apple sample with a linear range of 0.05–1.0 mg/L, a limit of detection of 0.048 mg/L and a limit of quantification of 0.146 mg/L (S/N = 3/10). The recoveries of the samples were 77.66–96.57% and their respective relative standard deviations were 3.36–0.45%. All the results indicated that the proposed method provided good selective extraction, as qualifying the analytical standards.  相似文献   

17.
A method based on molecular crowding and ionic liquids as reaction solvents has been used for the synthesis of molecularly imprinted polymers. Levofloxacin was selected as the template, polymethyl methacrylate was the molecular crowding agent, and 1‐butyl‐3‐methylimidazolium tetrafluoroborate (ionic liquid) was selected as the reaction solvent and porogen. The optimized proportion for the mixed porogen was dimethyl sulfoxide/ionic liquid/polymethyl methacrylate 1:1.6:5 in chloroform (150 mg mL?1). The morphology and chemical composition of levofloxacin imprinted polymers were assessed by scanning electron microscopy and Fourier transform infrared spectroscopy. The absorption experiments demonstrated that the levofloxacin imprinted polymers possess high selective recognition property to levofloxacin and analogs, including enrofloxacin, ciprofloxacin and gatifloxacin, which all belong to fluoroquinolones. An extraction method using levofloxacin imprinted polymers as sorbent followed by high‐performance liquid chromatography analysis was optimized for the determination of four fluoroquinolones in milk and lake water samples. Under the optimized conditions, good linearity was observed in a range of 5–1000 ng g?1 with the limit of detection between 0.3 and 0.5 ng g?1 for the four fluoroquinolones. The recoveries at three spiked levels ranged 82.4–98.3% with the relative standard deviation ≤4.9.  相似文献   

18.
A novel molecularly imprinted solid‐phase extraction with spectrofluorimetry method has been developed for the selective extraction of telmisartan from human urine. Molecularly imprinted polymers were prepared by a noncovalent imprinting approach through UV‐radical polymerization using telmisartan as a template molecule, 2‐dimethylamino ethyl methacrylate as a functional monomer, ethylene glycol dimethacrylate as a cross‐linker, N,N‐azobisisobutyronitrile as an initiator, chloroform as a porogen. Molecularly imprinted polymers and nonimprinted control polymer sorbents were dry‐packed into solid‐phase extraction cartridges, and eluates from cartridges were analyzed using a spectrofluorimeter. Limit of detection and limit of quantitation values were 11.0 and 36.0 ng/mL, respectively. A very high imprinting factor (16.1) was achieved and recovery values for the telmisartan spiked in human urine were in the range of 76.1–79.1%. In addition, relatively low within‐day (0.14–1.6%) and between‐day (0.11–1.31%) precision values were obtained. Valsartan was used to evaluate the selectivity of sorbent as well. As a result, a sensitive, selective, and simple molecularly imprinted solid‐phase extraction with spectrofluorimetry method has been developed and successfully applied to the direct determination telmisartan in human urine.  相似文献   

19.
Dexamethasone‐imprinted polymers were fabricated by reversible addition–fragmentation chain transfer polymerization on the surface of magnetic nanoparticles under mild polymerization conditions, which exhibited a narrow polydispersity and high selectivity for dexamethasone extraction. The dexamethasone‐imprinted polymers were characterized by scanning electron microscopy, transmission electron microscope, Fourier transform infrared spectroscopy, X‐ray diffraction, energy dispersive spectrometry, and vibrating sample magnetometry. The adsorption performance was evaluated by static adsorption, kinetic adsorption and selectivity tests. The results confirmed the successful construction of an imprinted polymer layer on the surface of the magnetic nanoparticles, which benefits the characteristics of high adsorption capacity, fast mass transfer, specific molecular recognition, and simple magnetic separation. Combined with high‐performance liquid chromatography, molecularly imprinted polymers as magnetic extraction sorbents were used for the rapid and selective extraction and determination of dexamethasone in skincare cosmetic samples, with the accuracies of the spiked samples ranging from 93.8 to 97.6%. The relative standard deviations were less than 2.7%. The limit of detection and limit of quantification were 0.05 and 0.20 μg/mL, respectively. The developed method was simple, fast and highly selective and could be a promising method for dexamethasone monitoring in cosmetic products.  相似文献   

20.
Estrone molecularly imprinted polymers were synthesized through the self‐polymerization of dopamine on the surface of silica gels, which had the characteristics of mild polymerization conditions, simple reaction procedure and good specific recognition ability for estrone. The estrone molecularly imprinted polymers were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis and nitrogen adsorption–desorption tests. The characterization confirmed that the imprinted polymers were successfully grafted on the surface of silica gels. Through investigating the adsorption performance, the prepared estrone molecularly imprinted polymers exhibited high adsorption capacity, fast mass transfer, as well as excellent selectivity toward estrone. The estrone molecularly imprinted polymers as the solid‐phase extraction adsorbent coupled with high‐performance liquid chromatography was developed to determine estrone from the milk samples. The developed estrone molecularly imprinted polymer solid‐phase extraction with high‐performance liquid chromatography method exhibited satisfactory specificity, precision, accuracy and good linearity relationship in the range of 0.2–20 μg/mL. The developed method is simple, fast, effective and high specificity method and it provides a new method to detect the residues of estrone in animal foods.  相似文献   

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