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1.
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   

2.
Aristolochic acid I is a toxic compound found in the genus of Aristolochia plants, which are commonly used as herbal cough treatment medicines. To remove the aristolochic acid I in extract efficiently and selectively, a molecularly imprinted polymer composed of ethylimidazole ionic liquid‐based zeolitic imidazolate framework‐67 was synthesized and used as the adsorbent. Under the conditions optimized by the software design expert, the sorbent showed highest adsorption amount of 34.25 mg/g in methanol/water (95:5, v/v) at 39°C for 138 min. The sorbent was then applied to solid phase extraction to isolate aristolochic acid I from the extract of the herbal plant Fibraurea Recisa Pierre. 0.043 mg/g of aristolochic acid I was obtained after the loading, washing, and elution processes. The limit of detection of 2.41 × 10?5 mg/mL and good recoveries provided evidence for the accuracy of this method.  相似文献   

3.
The aim of this work was to develop a method for the clean‐up and preconcentration of warfarin from biological sample employing a new molecularly imprinted polymer (MIP) as a selective adsorbent for solid‐phase extraction (SPE). This MIP was synthesized using warfarin as a template, pyrrole as a functional monomer and vinyl triethoxysilane as a cross‐linker. The molar ratio of 1:4:20 (template–functional monomer–cross‐linker) showed the best results. Nonimprinted polymers (NIPs) were prepared and treated with the same method, but in the absence of warfarin. The prepared polymer was characterized by Fourier transmission infrared spectrometry and scanning electron microscopy. An adsorption process (SPE) for the removal of warfarin using the fabricated MIPs and NIPs was evaluated under various conditions. Effective parameters on warfarin extraction, for example, type and volume of elution solvent, pH of sample solution, breakthrough volume and maximum loading capacity, were studied. The limits of detection were in the range of 0.0035–0.0050 µg mL?1. Linearity of the method was determined in the range of 0.0165–10.0000 µg mL?1 for plasma and 0.0115–10.0000 µg mL?1 for urine with coefficients of determination (R2) ranging from 0.9975 to 0.9985. The recoveries for plasma and urine samples were >95%. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

4.
In this work, core/shell magnetic molecularly imprinted polymer nanoparticles were synthesized for extraction and pre‐concentration of valsartan from different samples and then it was measured with high‐performance liquid chromatography. For preparation of molecularly imprinted polymer nanoparticles, Fe3O4 nanoparticles were coated with tetraethyl orthosilicate and then functionalized with 3‐(trimethoxysilyl) propyl methacrylate. In the next step, molecularly imprinted polymer nanoparticles were synthesized under reflux and distillation conditions via polymerization of methacrylic acid, valsartan (as a template), azobisisobutyronitrile and ethylene glycol dimethacrylate as cross linking. The properties of molecularly imprinted polymer nanoparticle were investigated by FTIR spectroscopy, field emission scanning electron microscopy, and X‐ray diffraction. Box‐Behnken design with the aid of desirability function was used for optimizing the effect of variables such as the amounts of molecularly imprinted polymer nanoparticles, time of sonication, pH, and volume of methanol on the extraction percentage of valsartan. According to the obtained results, the affecting variables extraction condition were set as 10 mg of adsorbent, 16 min for sonication, pH = 5.5 and 0.6 mL methanol. The obtained linear response (r2 > 0.995) was in the range of 0.005–10 µg/mL with detection limit 0.0012 µg/mLand extraction recovery was in the range of 92–95% with standard deviation less than 6% (n = 3).  相似文献   

5.
《Analytical letters》2012,45(16):2583-2596
Molecularly imprinted polymers grafted on to the surface of carboxyl-modified multiwalled carbon nanotubes were developed using methacrylic acid as a functional monomer and trihydroxymethylpropyl trimethylacrylate as a crosslinker for application to rhodamine B determination. The synthesis, characteristics, and evaluation of the molecularly imprinted polymer are described. The apparent morphology of the polymers was characterized by scanning electron microscopy. To evaluate the binding ability of the molecularly imprinted polymers, equilibrium binding experiments were conducted and revealed the maximal binding capacity to be 561.54 µg g?1. The introduction of nanomaterials into the polymer composite made important contributions to the affinity enhancement and recognition properties of the molecularly imprinted polymers. Moreover, the polymers were preliminarily applied as an adsorbent for separation and extraction of Rhodamine B from dried chili powder samples, based on solid phase extraction technology. The calibration curve was linear in the range of 0–7 µg mL?1. For all tested samples, recoveries were reliable and in the range of 101.75–109.73%. The relative standard deviation ranged from 6.43–14.32%, which demonstrated that the polymer has potential for preconcentration of Rhodamine B from chili powder samples.  相似文献   

6.
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   

7.
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   

8.
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   

9.
A novel core–shell magnetic nano‐adsorbent with surface molecularly imprinted polymer coating was fabricated and then applied to dispersive micro‐solid‐phase extraction followed by determination of rhodamine 6G using high‐performance liquid chromatography. The molecularly imprinted polymer coating was prepared by copolymerization of dopamine and m‐aminophenylboronic acid (functional monomers), in the presence of rhodamine 6G (template). The selection of the suitable functional monomers was based on the interaction between different monomers and the template using the density functional theory. The ratios of the monomers to template were further optimized by an OA9 (34) orthogonal array design. The binding performances of the adsorbent were evaluated by static, kinetic, and selective adsorption experiments. The results reveal that the adsorbent possesses remarkable affinity and binding specificity for rhodamine 6G because of the enhanced Lewis acid‐base interaction between the B(Ш) embedded in the imprinted cavities and the template. The nano‐adsorbent was successfully applied to dispersive micro‐solid‐phase extraction coupled to high‐performance liquid chromatography for the trace determination of rhodamine 6G in samples with a detection limit of 2.7 nmol/L. Spiked recoveries ranged from 93.0–99.1, 89.5–92.7, and 86.9–105% in river water, matrimony vine and paprika samples, respectively, with relative standard deviations of less than 4.3%.  相似文献   

10.
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   

11.
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   

12.
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   

13.
A molecularly imprinted polymer as a selective solid-phase extraction adsorbent for efficient preconcentration and analysis of metribuzin residues in corn fields has been synthesised and evaluated. Results showed that molecular imprinting of the polymer was highly effective and the polymer had high affinity and selectivity for metribuzin in water-containing systems. A monolithic column containing molecularly imprinted polymer was prepared and used for on-line preconcentration, separation, and detection of metribuzin residues in soil sampled during investigation of the degradation of the herbicide metribuzin in corn fields. The detection limit of the method was 8.3 × 10?4 mg kg?1, recovery was between 94.9% and 103%, and RSD in analysis of soil samples was less than 3.2%.  相似文献   

14.
Double‐templated molecularly imprinted polymers with specific recognition of three matrine‐type alkaloids were prepared using matrine and oxymatrine as the template molecules. An approach based on double‐templated molecularly imprinted solid‐phase extraction coupled with high‐performance liquid chromatography and tandem mass spectrometry was then developed to extract and purify matrine, oxymatrine, and sophocarpine from Sophora moorcroftiana in the Tibetan plateau herbs. The polymers were characterized by Fourier‐transform infrared spectroscopy and scanning electron microscopy. Their adsorption characteristics were evaluated using adsorption kinetics, isotherms, selectivity, and recycling experiments. This polymer exhibited excellent molecular recognition ability and good selectivity. The obtained polymers as adsorbent was further used for the determination of three matrine‐type alkaloids coupled to high‐performance liquid chromatography with tandem mass spectrometry, the recoveries of three matrines spiked at three concentration levels in samples were 73.25–98.42% (n = 5) with a relative standard deviation less than 6.82%. The limits of detection for the method were 9.23–15.42 μg/kg (S/N = 3). This proposed method was assessed to be an effective method for simultaneous extraction, isolation, and identification of matrine, oxymatrine, and sophocarpine from Sophora moorcroftiana.  相似文献   

15.
A new adsorbent for molecularly imprinted solid phase extraction (MISPE) of metoprolol was synthesized using methacrylic acid (MAA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross‐linking agent causing a non‐covalent, bulk, thermal radical‐polymerization. Control polymer (non‐imprinted polymer) was prepared under well defined conditions without the use of metoprolol. The synthesized polymers were characterized by IR spectroscopy, X‐ray diffraction and thermal analysis techniques. This polymer was used for the rapid extraction and preconcentration of metoprolol from real samples prior to spectrophotometric determination. Extraction efficiency and the influence of flow rates of sample and stripping solutions, pH, type of eluent for elution of metoprolol from polymer, break through volume and limit of detection were studied. The detection limit of the proposed method is 0.4 ng·mL?1. The method was applied successfully to the recovery and determination of metoprolol in tablets, human urine and plasma samples.  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.
A novel molecularly imprinted polymer that could selectively recognize tetracyclines in milk powder was synthesized using a metal–organic framework as a support material, tetracycline as template molecule, and 3‐aminophenylboronic acid as a functional monomer and a cross‐linking agent. The novel molecularly imprinted polymer was characterized by Fourier transform infrared spectrometry, transmission electron microscopy, X‐ray diffractometry, thermogravimetric analysis, and N2 adsorption/desorption measurements. The adsorption isotherms, adsorption kinetics, adsorption thermodynamics, and selective adsorption experiments of the novel molecularly imprinted polymer to tetracycline were also studied. The novel molecularly imprinted polymer was used as dispersant of matrix solid‐phase dispersion to extraction tetracyclines. After that, the tetracyclines extracted from milk powder were determined by ultra high performance liquid chromatography with tandem mass spectrometry. Under the optimal conditions, the detection limits of tetracyclines were 0.217–0.318 ng/g. The relative standard deviations of intra‐ and interday precision ranged from 3.8 to 6.9% and from 2.8 to 7.4%, respectively. In all three concentration levels (1.0, 10, 50 ng/g), the recoveries of tetracyclines ranged from 84.7 to 93.9%. The method was successfully applied to the determination of tetracyclines in milk powder.  相似文献   

18.
Molecularly imprinted polymers for strobilurin fungicides were prepared by precipitation polymerization employing azoxystrobin as template molecular together with methacrylic acid monomer and trimethylolpropane triacrylate cross‐linker. Morphological characterization showed molecularly imprinted polymers were uniform spherical particles with about 0.2 μm in diameter, while the morphologies of nonimprinted polymers were irregular bulk. The equilibrium binding and selective experiments proved that molecularly imprinted polymers possessed a higher affinity toward four fungicides compared to nonimprinted polymers and heterogeneous binding sites were found in the molecularly imprinted polymers. Molecularly imprinted solid‐phase extraction conditions, including sample loading solvents, selective washing, and elution solvents, were carefully optimized. The developed method showed good recoveries (70.0–114.0%) with relative standard deviations in range of 1.0–9.8% (n  =  3) for samples (cucumber and peach) spiked at three different levels (10, 50, and 100 μg/ kg). The detection limit (signal/noise = 3) ranged from 0.01 to 0.08 μg/kg. The results demonstrated good potential use of this convenient and highly efficient method for determining trace strobilurin fungicides in agricultural products.  相似文献   

19.
A class‐specific macrolide molecularly imprinted polymer was synthesized by precipitation polymerization using tulathromycin as the template and methacrylic acid as the functional monomer. The polymers revealed different specific adsorption and imprinting factor for macrolides with different spatial arrangement of side chains as well as lactonic ring size. And the molecularly imprinted polymer possessed maximum adsorption capacity (54.1 mg/g) and highest imprinting factor (2.4) toward 15‐membered ring azithromycin. On the basis of molecularly imprinted polymer dispersive solid‐phase extraction, a rapid, selective, and reproducible method for simultaneous determination of seven macrolide antibiotics residues in pork was established by using liquid chromatography with tandem mass spectrometry. At spiking levels of 5, 10, 25, and 100 μg/kg, average recoveries of seven macrolides ranged from 68.6 to 95.5% with intraday and interday relative standard deviations below 8%. The limits of detection and limits of quantification were 0.2–0.5 and 0.5–2.0 μg/kg, respectively.  相似文献   

20.
A molecularly imprinted polymer was synthesized and applied as a sorbent in the solid‐phase extraction device. The imprinted polymer was characterized by fourier‐transform infrared spectroscopy and scanning electron microscope. The results revealed that imprinted polymer possess sensitive selectivity and reliable adsorption properties for five NSAIDs. The imprinted polymer was successfully applied to the pre‐concentration for five NSAIDs in different water samples prior to UPLC‐MS/MS. In the early studies, several factors were investigated, including pH adjustment, the kind of elution solvent and the volume of elution solvent. Finally, we found that the pH 5 and an aliquot of 2 mL methanol were suitable for the water samples. The limits of detection and limits of quantitation of five nonsteroidal anti‐inflammatory drugs varied from 0.007 to 0.480 μg L−1 and 0.03 to 1.58 μg L−1, respectively. The spiking recoveries of the target analytes were 50.33‐127.64% at the levels of 0.2 μg L−1, 2 μg L−1 and 5 μg L−1. The precision and accuracy of this method showed a great increase compared with traditional solid‐phase extraction. The developed method was successfully applied to extraction and analysis of NSAIDs in different water samples with satisfactory results which could help us better understand their environmental fate and risk to ecological health.  相似文献   

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