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1.
A novel l‐ phenylalanine molecularly imprinted solid‐phase extraction sorbent was synthesized by the combination of Pickering emulsion polymerization and ion‐pair dummy template imprinting. Compared to other polymerization methods, the molecularly imprinted polymers thus prepared exhibit a high specific surface, large pore diameter, and appropriate particle size. The key parameters for solid‐phase extraction were optimized, and the result indicated that the molecularly imprinted polymer thus prepared exhibits a good recovery of 98.9% for l‐ phenylalanine. Under the optimized conditions of the procedure, an analytical method for l‐ phenylalanine was well established. By comparing the performance of the molecularly imprinted polymer and a commercial reverse‐phase silica gel, the obtained molecularly imprinted polymer as an solid‐phase extraction sorbent is more suitable, exhibiting high precision (relative standard deviation 3.2%, n = 4) and a low limit of detection (60.0 ± 1.9 nmol·L?1) for the isolation of l‐ phenylalanine. Based on these results, the combination of the Pickering emulsion polymerization and ion‐pair dummy template imprinting is effective for preparing selective solid‐phase extraction sorbents for the separation of amino acids and organic acids from complex biological samples.  相似文献   

2.
A new method for the selective extraction of p‐aminosalicylic acid from aqueous and urine samples has been developed using magnetic molecularly imprinted polymer nanoparticles before determination by high‐performance liquid chromatography. The Fe3O4 nanoparticles were first prepared through the chemical coprecipitation of Fe2+ and Fe3+ and then coated with a vinyl shell. Subsequently, a layer of molecularly imprinted polymers was grafted onto the vinyl‐modified magnetic nanoparticles by precipitation polymerization. FTIR spectroscopy, scanning electron microscopy, vibrating sample magnetometry, and thermogravimetric analysis were applied to characterize the sorbent properties. Moreover, the predominant parameters affecting the magnetic solid phase extraction such as sample pH, sorption and elution times, the amount of sorbent, and composition and volume of eluent were investigated thoroughly. The maximum sorption capacity of the imprinted polymer toward p‐aminosalicylic acid was 70.9 mg/g, which is 4.5 times higher than that of the magnetic nonimprinted polymer. The magnetic molecularly imprinted polymer nanoparticles were applied for the selective extraction of p‐aminosalicylic acid from aqueous and urine samples and satisfactory results were achieved. The results illustrate that magnetic molecularly imprinted polymer nanoparticles have a great potential in the extraction of p‐aminosalicylic acid from environmental and biological matrices.  相似文献   

3.
As signal molecules, auxins play an important role in mediating plant growth. Due to serious interfering substances in plants, it is difficult to accurately detect auxins with traditional solid‐phase extraction methods. To improve the selectivity of sample pretreatment, a novel molecularly imprinted polymer ‐coated solid‐phase microextraction fiber, which could be coupled directly to high‐performance liquid chromatography, was prepared with indole acetic acid as template molecule for the selective extraction of auxins. The factors influencing the polymer formation, such as polymerization solvent, cross‐linker, and polymerization time, were investigated in detail to enhance the performance of indole acetic acid‐molecularly imprinted polymer coating. The morphological and chemical stability of this molecularly imprinted polymer‐coated fiber was characterized by scanning electron microscopy, infrared spectrometry, and thermal analysis. The extraction capacity of the molecularly imprinted polymer‐coated solid‐phase microextraction fiber was evaluated for the selective extraction of indole acetic acid and indole‐3‐pyruvic acid followed by high‐performance liquid chromatography analysis. The linear range for indole acetic acid and indole‐3‐pyruvic acid was 1–100 µg/L and their detection limit was 0.5 µg/L. The method was applied to the simultaneous determination of two auxins in two kinds of tobacco (Nicotiana tabacum L and Nicotiana rustica L) samples, with recoveries range from 82.1 to 120.6%.  相似文献   

4.
Magnetic molecularly imprinted polymer nanoparticles for bisphenol A were prepared by coassembling magnetic nanoparticles and amphiphilic random copolymers. Under optimized conditions, bisphenol A as template molecules, magnetic molecularly imprinted polymer particles with regular morphology, small size, good monodispersity, and high content of OA‐Fe3O4 were prepared by the coassembly method using P(MMA‐co‐MAA) with monomer ratio of 9:1. These magnetic molecularly imprinted polymer particles could be rapidly collected by an external magnet within 1 min. The saturated adsorption capacity of the magnetic molecularly imprinted polymer for bisphenol A was 201.5 mg/g, and the imprinting factor was 2.5. The separation factors for bisphenol A to β‐estradiol, estriol, and diethylstilbestrol was 3.1, 2.9, and 3.7, respectively. Unlike assembling amphiphilic copolymer in the selective solvent, the coassembly process was simple and rapid. Therefore, the present work provided a facile and versatile approach to construct magnetic molecularly imprinted polymer nanoparticles under mild conditions.  相似文献   

5.
A dual responsive molecularly imprinted polymer sensitive to both photonic and magnetic stimuli was successfully prepared for the detection of four sulfonamides in aqueous media. The photoresponsive magnetic molecularly imprinted polymer was prepared by surface imprinting polymerization using superparamagnetic Fe3O4 nanoparticles functionalized with a silica layer as a support, water‐soluble 4‐[(4‐methacryloyloxy)phenylazo]benzenesulfonic acid as the functional monomer, and sulfadiazine as the template. The magnetic molecularly imprinted polymers showed specific affinity to sulfadiazine and its structural analogs in aqueous media. Upon alternate irradiation at 365 and 440 nm, the quantitative bind and release of the four sulfonamides by magnetic molecularly imprinted polymers occurred. Furthermore, the prepared magnetic molecularly imprinted polymers were used as solid‐phase extraction material selectively extracted the four sulfonamides from water samples with good recoveries. Thus, a simple, convenient, and reliable detection method for sulfonamides in the environment based on responsive magnetic molecularly imprinted polymers was successfully established.  相似文献   

6.
Monodisperse molecularly imprinted polymers for strychnine were prepared by precipitation polymerization and multistep swelling and polymerization, respectively. In precipitation polymerization, methacrylic acid and divinylbenzene were used as a functional monomer and crosslinker, respectively, while in multistep swelling and polymerization, methacrylic acid and ethylene glycol dimethacrylate were used as a functional monomer and crosslinker, respectively. The retention and molecular recognition properties of the molecularly imprinted polymers prepared by both methods for strychnine were evaluated using a mixture of sodium phosphate buffer and acetonitrile as a mobile phase by liquid chromatography. In addition to shape recognition, ionic and hydrophobic interactions could affect the retention of strychnine in low acetonitrile content. Furthermore, molecularly imprinted polymers prepared by both methods could selectively recognize strychnine among solutes tested. The retention factors and imprinting factors of strychnine on the molecularly imprinted polymer prepared by precipitation polymerization were 220 and 58, respectively, using 20 mM sodium phosphate buffer (pH 6.0)/acetonitrile (50:50, v/v) as a mobile phase, and those on the molecularly imprinted polymer prepared by multistep swelling and polymerization were 73 and 4.5. These results indicate that precipitation polymerization is suitable for the preparation of a molecularly imprinted polymer for strychnine. Furthermore, the molecularly imprinted polymer could be successfully applied for selective extraction of strychnine in nux‐vomica extract powder.  相似文献   

7.
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   

8.
This work reports the preparation of molecularly imprinted polymer particles for the selective extraction and determination of four benzophenones from aqueous media. The polymer was prepared by using 4‐vinylpridine as functional monomer, ethylene glycol dimethacrylate as cross‐linker, acetonitrile as porogenic solvent and 2,2’,4,4’‐tetrehydroxybenzophenone as template. Good specific adsorption capacity (Qmax = 27.90 μmol/g) for 2,2’,4,4’‐tetrehydroxybenzophenone was obtained in the sorption experiment and good class selectivity for 2,2’,4,4’‐tetrehydroxybenzophenone, 2,4‐dihydroxybenzophenone, 2,2’‐dihydroxy‐4‐methoxybenzophenone, 2,2’‐dehydroxy‐4,4’‐dimethoxybenzophenone was demonstrated by the chromatographic evaluation experiment. Factors affecting the extraction efficiency of the molecularly imprinted solid‐phase extraction procedure were investigated systematically. An accurate and sensitive analytical method based on the molecularly imprinted solid‐phase extraction coupled with high‐performance liquid chromatography and diode array detection has been successfully developed for the simultaneous determination of four benzophenones from tap water and river water with method detection limits of 0.25–0.72 ng/mL. The recoveries of benzophenones for water samples at two spiking levels (500 and 5000 ng/mL for each benzophenone) were in the range of 86.9–103.3% with relative standard deviations (n = 3) below 9.2%.  相似文献   

9.
A novel magnetic molecularly imprinted polymer adsorbing material was successfully synthesized to detect ribavirin in animal feedstuff. Molecularly imprinted polymer was prepared through surface polymerization by using ribavirin as template molecule, methyl methacrylate, and γ‐methacryloxypropyl trimethoxy silane functionalized magnetic mesoporous silica as bifunctional monomers, and ethylene diglycidyl ether as crosslinking agent. The prepared magnetic molecularly imprinted polymer was characterized by scanning electron microscopy and infrared spectroscopy. Static and dynamic adsorption experiments and selective adsorption analysis were performed to evaluate the adsorption and selectivity of magnetic molecularly imprinted polymer. Different experiments were conducted to optimize the magnetic solid‐phase extraction conditions. Under optimal experimental conditions, a magnetic molecularly imprinted solid‐phase extraction coupled with high‐performance liquid chromatography method was successfully developed for ribavirin detection. The established method achieved a satisfactory linear range of 0.20–50 mg/L (R> 0.99) and a low detection limit (0.081 mg/kg). An average recovery of 92–105% with relative standard deviation of <6.5% was obtained upon the application of the developed method to detect ribavirin in real feedstuff samples. Thus, established method can be used for the rapid and simple separation and detection of added ribavirin in feedstuff.  相似文献   

10.
A multitemplate molecularly imprinted polymer was synthesized using fragments similar to gonyautoxins 1 and 4 including 2,4,6-triaminopyrimidine, 4-hydroxy-2-butanone, and imidazole as dummy templates by bulk polymerization. Scanning electron microscopy and infrared spectroscopy showed a porous structure and the formation of organic groups in the imprinting process of the polymer. One millilitre of 0.1?mol?L?1 acetic acid and 1?mL of 95% methanol were the optimized washing and eluting solutions during the molecularly imprinted solid-phase extraction. The adsorption capacity of the multitemplate molecularly imprinted polymer was lower than for the monotemplate molecularly imprinted polymer prepared in a previous study in seawater in which Alexandrium tamarense and Alexandrium minutum were cultivated. This result may due to the inappropriate combination of the dummy template fragments in the synthesis resulting in the unfitness of the imprinting sites for gonyautoxins 1 and 4. In general, it is inappropriate to use fragments with the similar parts to the analyte as the dummy templates. However, this work indicated the optimal molecularly imprinted polymer for the selective extraction of gonyautoxins 1 and 4.  相似文献   

11.
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   

12.
The development and application of an imazethapyr molecularly imprinted polymer‐based solid‐phase microextraction coating were investigated. A novel molecularly imprinted polymer coating with imazethapyr as template was firstly prepared by a one‐step in situ polymerization method, and demonstrated specific selectivity to imidazolinone herbicides in complicated samples. The structural characteristics and extraction performance of the imazethapyr molecularly imprinted polymer coating were studied. The molecularly imprinted polymer coating was homogeneous, dense, and heat and solvent resistant. Adsorption capacity experiments showed that the molecularly imprinted polymer coating could selectively extract imazethapyr and its structural analogs, and the maximum adsorption capacity was 2.5 times as much as that of the nonimprinted polymer coating. A method for the determination of five imidazolinones by imazethapyr molecularly imprinted polymer solid‐phase microextraction coupled with high‐performance liquid chromatography was developed. The linear range was 0.50–50 μg/L for imazameth, imazamox, imazapyr acid, and imazethapyr, and 1.0–100 μg/L for imazaquin acid, and the detection limits were within the range of 0.070–0.29 μg/L. The method was applied to simultaneous and multiresidual determinations of trace imidazolinones in rice, peanut, and soil samples with satisfactory recoveries of 60.6–99.5, 79.1–123, and 61.3–116%, respectively, and relative standard deviations of 0.40–10%, which indicated that this method was suitable for the trace analysis of imidazolinones in complex food and environmental samples.  相似文献   

13.
Ginsenoside Rg1 is a valuable bioactive molecule but its high polarity and low concentration in complex mixtures makes it a challenge to separate Ginsenoside Rg1 from other saponins with similar structures, resulting in low extraction efficiency. The successful development of effective Rg1 molecularly imprinted polymers that exhibit high selectivity and adsorption may offer an improved method for the enrichment of active compounds. In this work, molecularly imprinted polymers were prepared with two different methods, precipitation polymerization or surface imprinted polymerization. Comparison of the adsorption abilities showed higher adsorption of the surface molecularly imprinted polymers prepared by surface imprinted polymerization, 46.80 mg/g, compared to the 27.74 mg/g observed for the molecularly imprinted polymers prepared by precipitation polymerization. Therefore, for higher adsorption of the highly polar Rg1, surface imprinted polymerization is a superior technique to make Rg1 molecularly imprinted polymers. The prepared surface molecularly imprinted polymers were tested as a solid‐phase extraction column to directionally enrich Rg1 and its analogues from ginseng tea and total ginseng extracts. The column with surface molecularly imprinted polymers showed higher enrichment efficiency and better selectivity than a C18 solid‐phase extraction column. Overall, a new, innovative method was developed to efficiently enrich high‐polarity bioactive molecules present at low concentrations in complex matrices.  相似文献   

14.
A silica‐based surface magnetic molecularly imprinted polymer for the selective recognition of parabens was prepared using a facile and general method that combined atom‐transfer radical polymerization with surface imprinting technique. The prepared magnetic molecularly imprinted polymer was characterized by transmission electron microscopy, Fourier transform infrared spectrometry and physical property measurement. The isothermal adsorption experiment and kinetics adsorption experiment investigated the adsorption property of magnetic molecularly imprinted polymer to template molecule. The four parabens including methylparaben, ethylparaben, propylparaben, and butylparaben were used to assess the rebinding selectivity. An extraction method, which used magnetic molecularly imprinted polymer as adsorbents coupled with high‐performance liquid chromatography for the determination of the four parabens in fruit juice samples was developed. Under the optimal conditions, the limits of detections of the four parabens were 0.028, 0.026, 0.021, and 0.026 mg/L, respectively. The precision expressed as relative standard deviation ranging from 2.6 to 8.9% was obtained. In all three fortified levels, recoveries of parabens were in the range of 72.5–89.4%. The proposed method has been applied to different fruit juice samples including orange juice, grape juice, apple juice and peach juice, and satisfactory results were obtained.  相似文献   

15.
Pyrrolizidine alkaloids are the most widely distributed natural toxins, and pyrrolizidine alkaloid‐containing herbal medicines are probably the most common poisonous plants affecting humans. We reported pyrrolizidine alkaloid‐molecularly imprinted polymer solid‐phase microextraction for the selective adsorption of toxic pyrrolizidine alkaloids from herbal medicine. A sulfonic compound, sodium allylsulfonate, was chosen as the functional monomer to interact with pyrrolizidine alkaloids through strong ionic interaction. To avoid template leakage and for the aim of cost saving, a relatively cheap dummy template was used for the fabrication of molecularly imprinted polymer‐solid‐phase microextraction fibers. The obtained fibers showed selective adsorption ability for four pyrrolizidine alkaloids, including europine, echimidine, lasiocarpine, and heliotrine. The extraction parameters, such as extraction time, extraction temperature, shaking speed, elution solvent and elution time, were optimized. Then ultra high performance liquid chromatography with mass spectrometry coupled with molecularly imprinted polymer‐solid‐phase microextraction method was developed for the fast and efficient analysis of four pyrrolizidine alkaloids from the model herbal plant Farfarae Flos. The established method was validated and exhibited satisfactory accuracy and precision. The present method provides an innovative and fast analytical strategy for the determination of trace toxic pyrrolizidine alkaloids in complicated samples.  相似文献   

16.
In this article, for the first time, a molecularly imprinted polymer (MIP) for the metolcarb was prepared by bulk polymerization using metolcarb as the template, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the cross‐linker. The prepared polymer was characterized by FT‐IR, static and kinetic adsorption experiments, and the results showed that it has been successfully synthesized and had good selective ability for metolcarb. The MIP was applied as a sorbent in molecularly imprinted SPE coupled with HPLC‐UV for separation and determination of trace metolcarb in three kinds of food matrices at three concentration levels. Under the optimal conditions, the LODs (S/N=3) of cabbage, cucumber and pear were 7.622, 6.455 and 13.52 μg/kg, respectively, and recoveries were in the range of 68.80–101.31% with RSD (n=3) below 3.78% in all cases. To demonstrate further the selectivity of the MIP obtained, a comparison with commercially available C18 SPE was performed. The results indicated that molecularly imprinted SPE showed better chromatography, better selectivity and higher recoveries for metolcarb than commercially available C18 SPE.  相似文献   

17.
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   

18.
Surface enrofloxacin‐imprinted magnetic nanoparticles were prepared for the selective recognition and fast separation of fluoroquinolones in human serum by surface‐initiated reversible addition fragmentation chain transfer polymerization. The surface morphology and imprinted behavior were investigated and optimized. The living/controlled nature of reversible addition‐fragmentation chain transfer polymerization reaction allowed the successful construction of well‐defined imprinted polymer layer outside the Fe3O4 core. Such molecularly imprinted polymers exhibited superparamagnetic properties and specific recognition toward fluoroquinolones. Combined with reversed‐phase high‐performance liquid chromatography, the prepared molecularly imprinted polymers were used for the selective enrichment and analysis of fluoroquinolones in human serum samples. The recoveries of four fluoroquinolones were 86.8–95.3% with relative standard deviations of 2.0–6.8% (n  = 3). Such magnetic molecularly imprinted polymers have great prospects in the separation and enrichment of trace analysts in complex biological samples.  相似文献   

19.
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   

20.
A molecularly imprinted polymer (MIP) based on free‐radical polymerization was prepared with 1‐(N,N‐biscarboxymethyl)amino‐3‐allylglycerol and N,N‐dimethylacrylamide as functional monomers, N,N‐methylene diacrylamide as the cross‐linker, copper ion‐clonazepam as the template and 2,2‐azobis(2‐methylbutyronitrile) as the initiator. The imprinted polymer was characterized by Fourier transform infrared spectroscopy, elemental analysis, thermogravimetric analysis, and SEM. The MIP of agglomerated microparticles with multipores was used for SPE. The imprinted polymer sorbent was selective for clonazepam. The optimum pH and sorption capacity were 5 and 0.18 mg/g at 20°C, respectively. The profile of the drug uptake by the sorbent reflects good accessibility of the active sites in the imprinted polymer sorbent. The MIP‐SPE was the most feasible technique for the extraction of clonazepam with a high recovery from human plasma and urine samples.  相似文献   

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