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1.
Different kinds of deep eutectic solvents based on choline chloride and ionic liquids based on 1‐methylimidazole were used to modify hybrid molecularly imprinted polymers with the monomer γ‐aminopropyltriethoxysilane‐methacrylic and three templates (rutin, scoparone, and quercetin). The materials were adopted as solid‐phase extraction packing agents, and were characterized by FTIR spectroscopy and field emission scanning electron microscopy. The hybrid molecularly imprinted polymers modified by deep eutectic solvents had high recoveries and a strong recognition of rutin, scoparone, and quercetin in Herba Artemisiae Scopariae than those modified by ionic liquids. In the procedure of solid‐phase extraction, deep eutectic solvents‐2‐hybrid molecularly imprinted polymers were obtained with the best recoveries with rutin (92.27%), scoparone (87.51%), and quercetin (80.02%), and the actual extraction yields of rutin (5.6 mg/g), scoparone (2.3 mg/g), and quercetin (3.4 mg/g). Overall, the proposed approach with the high affinity of hybrid molecularly imprinted polymers might offer a novel method for the purification of complex samples.  相似文献   

2.
New magnetic molecularly imprinted polymers with two templates were fabricated for the recognition of polysaccharides (fucoidan and alginic acid) from seaweed by magnetic solid‐phase extraction, and the materials were modified by seven types of deep eutectic solvents. It was found that the deep eutectic solvents magnetic molecularly imprinted polymers showed stronger recognition and higher recoveries for fucoidan and alginic acid than magnetic molecularly imprinted polymers, and the deep eutectic solvents‐4‐magnetic molecularly imprinted polymers had the best effects. The practical recovery of the two polysaccharides (fucoidan and alginic acid) purified with deep eutectic solvents‐4‐magnetic molecular imprinted polymers in seaweed under the optimal conditions were 89.87, and 92.0%, respectively, and the actual amounts extracted were 20.6 and 18.7 μg/g, respectively. To sum up, the developed method proved to be a novel and promising method for the recognition of complex polysaccharide samples from seaweed.  相似文献   

3.
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   

4.
Ternary deep eutectic solvent magnetic molecularly imprinted polymers grafted on silica were developed for the selective recognition and separation of theophylline, theobromine, (+)‐catechin hydrate, and caffeic acid from green tea through dispersive magnetic solid‐phase microextraction. A new ternary deep eutectic solvent was adopted as a functional monomer. The materials obtained were characterized by FTIR spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, NMR spectroscopy, and powder X‐ray diffraction. The practical recovery of the theophylline, theobromine, (+)‐catechin hydrate, and caffeic acid isolated with ternary deep eutectic solvent magnetic molecularly imprinted polymers in green tea were 91.82, 92.13, 89.96, and 90.73%, respectively, and the actual amounts extracted were 5.82, 4.32, 18.36, and 3.69 mg/g, respectively. The new method involving the novel material coupled with dispersive magnetic solid‐phase microextraction showed outstanding recognition, selectivity and excellent magnetism, providing a new perspective for the separation of bioactive compounds.  相似文献   

5.
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   

6.
This research highlights the application of highly efficient molecularly imprinted solid‐phase extraction for the preconcentration and analysis of melamine in aquaculture feed samples. Melamine‐imprinted polymers were synthesized employing methacrylic acid and ethylene glycol dimethacrylate as functional monomer and cross‐linker, respectively. The characteristics of obtained polymers were evaluated by scanning electron microscopy, Fourier transform infrared spectroscopy and binding experiments. The imprinted polymers showed an excellent adsorption ability for melamine and were applied as special solid‐phase extraction sorbents for the selective cleanup of melamine. An off‐line molecularly imprinted solid‐phase extraction procedure was developed for the separation and enrichment of melamine from aquaculture feed samples prior to high‐performance liquid chromatography analysis. Optimum molecularly imprinted solid‐phase extraction conditions led to recoveries of the target in spiked feed samples in the range 84.6–96.6% and the relative standard deviation less than 3.38% (n = 3). The aquaculture feed sample was determined, and there was no melamine found. The results showed that the molecularly imprinted solid‐phase extraction protocols permitted the sensitive, uncomplicated and inexpensive separation and pre‐treatment of melamine in aquaculture feed samples.  相似文献   

7.
A novel molecularly imprinted polymer based on graphene oxide was prepared as a solid‐phase extraction adsorbent for the selective adsorption and extraction of cyromazine from seawater samples. The obtained graphene oxide molecularly imprinted polymer and non‐imprinted polymer were nanoparticles and characterized by scanning electron microscopy. The imprinted polymer showed higher adsorption capacity and better selectivity than non‐imprinted polymer, and the maximum adsorption capacity was 14.5 mg/g. The optimal washing and elution solvents for molecularly imprinted solid phase extraction procedure were 2 mL of acetonitrile/water (80:20, v/v) and methanol/acetic acid (70:30, v/v), respectively. The recoveries of cyromazine in the spiked seawater samples were in the range of 90.3–104.1%, and the relative standard deviation was <5% (n = 3) under the optimal procedure and detection conditions. The limit of detection of the proposed method was 0.7 μg/L, and the limit of quantitation was 2.3 μg/L. Moreover, the imprinted polymer could keep high adsorption capacity for cyromazine after being reused six times at least. Finally, the synthesized graphene oxide molecularly imprinted polymer was successfully used as a satisfied sorbent for high selectivity separation and detection of cyromazine from seawater coupled with high‐performance liquid chromatography.  相似文献   

8.
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%.  相似文献   

9.
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.  相似文献   

10.
An efficient and sensitive analytical method based on molecularly imprinted solid‐phase extraction (MISPE) and reverse‐phase ultrasound‐assisted dispersive liquid–liquid microextraction (USA‐DLLME) coupled with LC–MS/MS detection was developed and validated for the analysis of urinary 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol (NNAL), a tobacco‐specific nitrosamine metabolite. The extraction performances of NNAL on three different solid‐phase extraction (SPE) sorbents including the hydrophilic‐lipophilic balanced sorbent HLB, the mixed mode cationic MCX sorbent and the molecularly imprinted polymers (MIP) sorbent were evaluated. Experimental results showed that the analyte was well retained with the highest extraction recovery and the optimum purification effect on MIP. Under the optimized conditions of MIP and USA‐DLLME, an enrichment factor of 23 was obtained. Good linearity relationship was obtained in the range of 5‐1200 pg/mL with a correlation coefficient of 0.9953. The limit of detection (LOD) was 0.35 pg/mL. The recoveries at three spiked levels ranged between 88.5% and 93.7%. Intra‐ and inter‐day relative standard deviations varied from 3.6% to 7.4% and from 5.4% to 9.7%, respectively. The developed method combing the advantages of MISPE and DLLME significantly improves the purification and enrichment of the analyte and can be used as an effective approach for the determination of ultra‐trace NNAL in complex biological matrices.  相似文献   

11.
A homogeneous liquid‐liquid extraction performed in narrow tube coupled to in–syringe‐dispersive liquid‐liquid microextraction based on deep eutectic solvent has been developed for the extraction of six herbicides from tea samples. In this method, sodium chloride as a separation agent is filled into the narrow tube and the tea sample is placed on top of the salt. Then a mixture of deionized water and deep eutectic solvent (water miscible) is passed through the tube. In this procedure, the deep eutectic solvent is realized as tiny droplets in contact with salt. By passing the droplets from the tea layer placed on the salt layer, the analytes are extracted into them. After collecting the solvent as separated layer, it is mixed with another deep eutectic solvent (choline chloride/butyric acid) and the mixture is dispersed into deionized water placed in a syringe. After adding acetonitrile to break up the cloudy state, the collected organic phase is injected into gas chromatography‐mass spectrometry. Under optimal conditions, limits of detection and quantification in the ranges of 2.6–8.4 and 9.7–29 ng/kg, respectively, were obtained. The extraction recoveries and enrichment factors in the ranges of 70–89% and 350–445 were obtained, respectively.  相似文献   

12.
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   

13.
In this study, novel monodisperse restricted access media‐molecularly imprinted polymers were successfully prepared by surface initiated reversible addition‐fragmentation chain transfer polymerization using monodisperse crosslinked poly (glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) microspheres as the carrier and acryloyl chloride‐modified β‐cyclodextrin as the hydrophilic functional monomer. The surface morphology, protein exclusion, and adsorption properties of the molecularly imprinted polymers were investigated. The results show that the material has excellent monodispersity and hydrophilicity, and simultaneously exhibit high adsorption capacity, fast binding kinetics, high selectivity, and significant thermal stability. The molecularly imprinted polymers as dispersive solid‐phase extraction adsorbent combined with reversed‐phase high‐performance liquid chromatography was used to selectively enrich, separate, and analyze trace 17β‐estradiol in milk samples. The recovery of 17β‐estradiol is 88–95% with relative standard deviation of <4%, and the limits of detection and quantification of this method are 2.08 and 9.29 µg/L, respectively. The novel restricted access media‐molecularly imprinted polymer adsorbents provide an effective method for the selective extraction and detection of 17β‐estradiol directly from complex samples.  相似文献   

14.
Dispersive liquid–liquid microextraction using deep eutectic solvents, as novel extraction solvents, was developed for the separation, preconcentration, and determination of chlorophenol, 2,3-dihydroxybenzoic acid, p-cresol, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol in vegetable oil. Seven deep eutectic solvents composed of choline chloride and different hydrogen bond donors (ethyl glycol, glycerol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, urea, and acetic acid) were characterized. The deep eutectic solvents formed by choline chloride-1,6-hexanediol in a 1:2 molar ratio provided the highest extraction efficiency. The sonication time, deep eutectic solvent volume, and disperser solvent were optimized. Under the optimal conditions of a sonication time of 11?min, a deep eutectic solvent volume of 90?µL, and acetone as the disperser solvent, extraction recoveries from 76.1 to 88.3% were obtained with 8.46 to 9.46 enrichment factors and the limits of detection exceeding 0.1?µg/mL with the relative standard deviations from 1.0 to 3.5%. This method using dispersive liquid–liquid microextraction with deep eutectic solvents is simple and provides high enrichment.  相似文献   

15.
A molecularly imprinted polymer has been synthesized to specifically extract adefovir, an antiviral drug, from serum and urine by dispersive solid‐phase extraction before high‐performance liquid chromatography with UV analysis. The imprinted polymers were prepared by bulk polymerization by a noncovalent imprinting method that involved the use of adefovir (template molecule) and functional monomer (methacrylic acid) complex prior to polymerization, ethylene glycol dimethacrylate as cross‐linker, and chloroform as porogen. Molecular recognition properties, binding capacity, and selectivity of the molecularly imprinted polymers were evaluated and the results show that the obtained polymers have high specific retention and enrichment for adefovir in aqueous medium. The new imprinted polymer was utilized as a molecular sorbent for the separation of adefovir from human serum and urine. The serum and urine extraction of adefovir by the molecularly imprinted polymer followed by high‐performance liquid chromatography showed a linear calibration curve in the range of 20–100 μg/L with excellent precisions (2.5 and 2.8% for 50 μg/L), respectively. The limit of detection and limit of quantization were determined in serum (7.62 and 15.1 μg/L), and urine (5.45 and 16 μg/L). The recoveries for serum and urine samples were found to be 88.2–93.5 and 84.3–90.2%, respectively.  相似文献   

16.
In this study, molecularly imprinted polymer fibers for solid‐phase microextraction have been prepared with a single bifunctional monomer, N,O‐bismethacryloyl ethanolamine using the so‐called “one monomer molecularly imprinted polymers” method, replacing the conventional combination of functional monomer and cross‐linker to form high fidelity binding sites. For comparison, imprinted fibers were prepared following the conventional approach based on ethylene glycol dimethacrylate as cross‐linker and methacrylic acid as monomer. The recognition performance of the new fibers was evaluated in the solid‐phase microextraction of parabens, and from this study it was concluded that they provided superior performance over conventionally formulated fibers. Ultimately, real‐world environmental testing on spiked solid samples was successful by the molecularly imprinted solid‐phase microextraction of samples, and the relative recoveries obtained at enrichment levels of 10 ng/g of parabens were within 78–109% for soil and 83–109% for sediments with a relative standard deviation <15% (n = 3).  相似文献   

17.
Novel molecularly imprinted chitosan microspheres were prepared on the surface of magnetic graphene oxide, with deep eutectic solvents both as a functional monomer and template. The prepared molecularly imprinted chitosan microspheres‐magnetic graphene oxide was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, Brunauer‐Emmett‐Teller surface area, thermogravimetric analysis were subsequently combined with solid‐phase micro‐extraction for simultaneous separation and enrichment of the extraction of chlorophenols from environmental water. Factors affecting the extraction efficiency of chlorophenols were optimized using response surface methodology. The actual extraction capacities under the optimal conditions (liquid to solid ratio = 3, cycles of adsorption/desorption = 5, 40°C extraction temperature, and extraction time for 35 min) were 86.90 mg/g. Compared to the traditional materials, the molecularly imprinted chitosan microspheres‐magnetic graphene oxide produced higher selectivity and extraction capacity.  相似文献   

18.
Molecularly imprinted covalent organic polymers were constructed by an imine‐linking reaction between 1,3,5‐triformylphloroglucinol and 2,6‐diaminopyridine and used for the selective solid‐phase extraction of benzoxazole fluorescent whitening agents from food samples. Binding experiments showed that imprinting sites on molecularly imprinted polymers had higher selectivity for targets compared with those of the corresponding non‐imprinted polymers. Parameters affecting the solid‐phase extraction procedure were examined. Under optimal conditions, actual samples were treated and the eluent was analyzed with high‐performance liquid chromatography with diode‐array detection. The results showed that the established method has a wide linearity, satisfactory detection limits and quantification limits, and acceptable recoveries. Thus, this developed method possesses the practical potential for the selective determination of benzoxazole fluorescent whitening agents in complex food samples.  相似文献   

19.
Five iridoid glycosides were prepared using molecularly imprinted solid‐phase extraction combined with preparative high‐performance liquid chromatography. Hydrophilic molecularly imprinted polymers were synthesized using α‐1‐allyl‐2‐N‐acetyl glucosamine, which introduced an abundance of hydrophilic groups into the polymers. Using molecularly imprinted solid‐phase extraction as the sample pretreatment procedure, five iridoid glycosides, gardenoside, geniposide, shanzhiside, geniposidic acid, and genipin‐1‐O‐gentiobioside, were selectively enriched from Gardenia fructus extracts. Preparative high‐performance liquid chromatography then provided iridoid glycosides with a purity >98%. The structures were elucidated by using nuclear magnetic resonance spectroscopy, optical rotation and melting point measurements, and mass spectrometry. The results demonstrate that molecularly imprinted solid‐phase extraction combined with preparative high‐performance liquid chromatography was an efficient, rapid, and economical method for the preparation of bioactive compounds from natural products.  相似文献   

20.
In this study, a simple and accurate sample preparation method based on dispersive solid‐phase extraction and dispersive liquid‐liquid microextraction has been developed for the determination of seven novel succinate dehydrogenase inhibitor fungicides (isopyrazam, fluopyram, pydiflumetofen, boscalid, penthiopyrad, fluxapyroxad, and thifluzamide) in watermelon. The watermelon samples were extracted with acetonitrile, cleaned up by dispersive solid‐phase extraction procedure using primary secondary amine, extracted and concentrated by the dispersive liquid‐liquid microextraction procedure with 1,1,2,2‐tetrachloroethane, and then analyzed by ultra high performance liquid chromatography with tandem mass spectrometry. The main experimental factors affecting the performance of dispersive solid‐phase extraction and dispersive liquid‐liquid microextraction procedure on extraction efficiency were investigated. The proposed method had a good linearity in the range of 0.1–100 µg/kg with correlation coefficients (r) of 0.9979–0.9999. The limit of quantification of seven fungicides was 0.1 µg/kg in the method. The fortified recoveries of seven succinate dehydrogenase inhibitor fungicides at three levels ranged from 72.0 to 111.6% with relative standard deviations of 3.4–14.1% (n = 5). The proposed method was successfully used for the rapid determination of seven succinate dehydrogenase inhibitor fungicides in watermelon.  相似文献   

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