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1.
In this work, we initiated to study new synthetic conditions to obtain uniformly sized molecularly imprinted polymers (MIPs) in the micrometer to nanometer range, using carbamazepine (CBZ) as a model template. The MIPs were successfully prepared by precipitation polymerization using methacrylic acid (MAA) and methyl methacrylate (MMA) as functional monomers at different mole ratios. The effect of MAA-to-MMA mole ratios on the morphology, binding, recognition, and release behaviors of the final particles were studied, and the adjusting possibility of these properties was also obtained. The produced polymers were characterized by Fourier transform infrared spectroscopy and differential scanning calorimetry, and their morphology was precisely examined by scanning electron microscopy and photon correlation spectroscopy. We obtained very uniform imprinted nanospheres and microspheres with diameter in the range of 120 nm to 1.74 μm under various conditions. Among the MIP nanospheres and microspheres prepared, the MIPs using MAA-to-MMA mole ratio of 1 : 2 showed nanospheres with the lower polydispersity index (0.004) and the highest selectivity factor (10.4), which is defined as the binding ratio of CBZ and oxcarbazepine as template analog. Results from binding experiments proved that MIPs exhibit specific affinity to CBZ in contrast to control polymers, and this performance was affected by pH and concentration of the loading solution. Moreover, release experiments showed the controlled release of CBZ in long-time period. The 50% of loaded CBZ was released from the imprinted nanospheres within the first 30 h, whereas another 50% was released in the following 160 h. The release kinetics of CBZ from the MIPs highly affected with the properties of particles. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

2.
To achieve suitable properties for specific applications, we synthesized diclofenac sodium (Ds) imprinted polymer beads with controllable size in the range of around 145 nm to 3 µm in diameter by the precipitation polymerization method using methacrylic acid as functional monomer, trimethylolpropane trimethacrylate as crosslinker and azobisisobutyronitrile as initiator. We analyzed the effect of the porogenic solvent on the morphology and recognition of particles. SEM analysis showed some dissimilarity in appearance of the imprinted polymers. The specific surface areas were 246 m2 g–1 and 260 m2 g–1 for imprinted polymers prepared in a mixture of tetrahydrofuran/acetonitrile (MIP1) and tetrahydrofuran/toluene (MIP2) respectively, which were in good agreement with the binding capacities of 150.4 mg g–1 for MIP1 and 280.4 mg g–1 for MIP2, but the imprinted nanoparticles with a specific selectivity factor of 1.5 had a better recognition property to Ds than the analog template meclofenamate sodium monohydrate (Ms) and also faster rebinding kinetics or greater accessibility of Ds. Finally the imprinted microspheres were successfully applied as a solid phase extraction sorbent for the extraction of Ds from human urine with limits of detection and quantification of 0.085 mg L–1 and 0.227 mg L–1, respectively. © 2013 Society of Chemical Industry  相似文献   

3.
Submicron core‐shell polymer particles, with molecularly imprinted shells, were prepared by a two‐stage polymerization process. Particles of this type, prepared with a cholesterol‐imprinted ethyleneglycol dimethacrylate shell and in the absence of porogen, were found to be 76 nm in diameter with a surface area of 82 m2 g−1. Cholesterol uptake from a 1 mM solution in isohexane was measured at both 10 and 30 mg mL−1, with the imprinted polymer showing considerable binding (up to 57%). Imprinted but not hydrolyzed and hydrolyzed nonimprinted polymers showed very low uptakes (≤4.5%) and a phenol‐imprinted polymer showed reduced binding (36%) under the same conditions. Imprinted shells were also prepared over superparamagnetic polymer cores and over magnetite ferrocolloid alone. The cholesterol binding to magnetic particles was very similar to that of equivalent nonmagnetic materials. Magnetic particles could be sedimented in as little as 30 s in a magnetic field. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1851–1859, 2000  相似文献   

4.
Based on double-imprinting (surfactant and lomefloxacin templates) concept and self-assembly technique, a new molecularly imprinted mesoporous silica (MIP-MS) was prepared to understand and characterize the mechanism of fast binding and selective recognition of lomefloxacin (LOM) by the adsorption isotherms model, the adsorption kinetic models, and the competitive adsorption. The MIP-MS was prepared by using LOM and surfactant micelles as the templates formed through self-hydrolyzed, self-condensed, and co-condensation of tetraethoxysilane and methyltriethoxysilane in alkaline media, and with the covalently anchored organic groups in the mesoporous silica matrix. Both the molecularly imprinted polymer (MIP) and non-imprinted mesoporous polymer (NIP) were prepared for comparison. The surface area, pore size and pore volume of the MIP-MS are 270 m2 g?1, 4.42 nm and 0.28 cm3 g?1, respectively. The kinetics studies showed that the pseudo-second-order model was consistent with the kinetic data of the MIP-MS with the fast binding templates (the 95 % uptake of LOM within 10 min). The equilibrium data, at various temperatures, were described successfully by the Langmuir and Freundlich isotherm models. The Freundlich model was found to fit the experiment data well. The thermodynamics parameters (positive values of ΔS, negative values of ΔH and ΔG) indicated that the binding system for the MIP-MS was entropy-gained, exothermic, and the spontaneous adsorptive forces were stronger on MIP-MS than on NIP and MIP. The MIP-MS showed fast binding, higher affinity, and selectivity for the template of LOM compared with the NIP and MIP.  相似文献   

5.
马红玲  苏立强 《化工时刊》2010,24(12):18-20
以烟酰胺为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,偶氮二异丁腈为引发剂,乙腈为溶剂,采用沉淀聚合法制备了烟酰胺分子印迹聚合物,通过静态平衡吸附和色谱分析对印迹聚合物进行表征,结果表明,印迹聚合物对烟酰胺分子具有很好的吸附能力和特异识别性。  相似文献   

6.
Novel molecularly imprinted polymer nanofibers (MIP‐NFs) were prepared for the adsorption of bisphenol A (BPA) in a water sample using the sol–gel process and the electrospinning technique. The effects of a number of synthesis parameters on the adsorption efficiency were investigated. The successful removal of BPA from MIP‐NFs was studied using UV–visible spectroscopy. The prepared MIP‐NFs were characterized by Fourier transform infrared, field emission SEM, TEM and energy dispersive X‐ray analysis. The results showed that the required molar ratio of 3‐aminopropyltriethoxysilane (APTES) to BPA was 15:1, which indicates a good performance in the rebinding test. Likewise, the molar ratio of APTES:acid:water was 1:2:9. The nylon 6 polymer solution, with a concentration of 12 wt%, showed a maximum adsorption capacity for BPA due to a decrease in the nanofiber diameter and an increase in the accessible sites. Furthermore, the maximum adsorption capacity of BPA was achieved at pH 7. Concerning the binding of BPA on MIP‐NFs, the experimental data matched well with the pseudo‐second‐order kinetics data and the Sips isotherm model. The saturated binding capacity for MIP‐NFs was predicted to be 115.1 mg g?1, which was more than twice as high as that for non‐imprinted polymer nanofibers (46.82 mg g?1). The results obtained in this study confirmed that the prepared MIP‐NFs showed considerable binding specificity for BPA in comparison with similar structural compounds such as phenol, naphthol and Naphthol AS, in aqueous solution. The binding capacity of MIP‐NFs remained almost constant after five cycles of reuse. The real sample analysis indicated that MIP‐NFs could be utilized as a useful sorbent material for the extraction of BPA from a water sample.  相似文献   

7.
Molecularly imprinted polymer (MIP) for selective extraction of p-hydroxybenzoic acid (p-HB) was synthesized by suspension polymerization using p-HB as template, 4-vinyl pyridine as functional monomer and ethylene glycol dimethacrylate as crosslinker. As characterized by scanning electron microscopy, the MIP particles are spherical, with size ranging from 1 to 8 μm. Compared with the non-imprinted polymer (NIP), the MIP shows higher binding capacity toward p-HB: maximum binding capacity for p-HB being 8.07 μmol g−1 over MIP and 3.88 μmol g−1 over NIP. The adsorption of p-HB on MIP follows the Freundlich model and displays pseudo-second-order kinetics. The results of selective and competitive binding experiments confirm that the molecularly imprinted sites have excellent recognition ability toward p-HB. The results reveal that the MIP is a promising adsorbent for selective extraction of p-HB from water samples. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46984.  相似文献   

8.
A monolithic molecularly imprinted polymer (monolithic MIP) for dibenzoyl-D-tartaric acid (D-DBTA) was prepared in a stainless-steel chromatographic column tube (50?mm?×?4.6?mm I.D.) as HPLC stationary phase through in situ polymerization. By optimizing polymeric and chromatographic conditions, the chiral separation of DBTA enantiomers was successfully achieved in the obtained MIP in less than 25?min with a resolution Rs?=?1.25, whereas no enantioseparation effect was found on the monolithic non-imprinted polymer (NIP). Thermodynamic data of the enantioseparation were calculated. The results revealed that two different thermodynamic processes existed within the temperature range investigated, moreover, just at the transition temperature (50?°C) of the two processes, separation factor ?? reached its maximum. Scathcard analysis indicated that only one class of binding sites existed in the obtained MIP, with its K d and Q max estimated to be 5.457?×?10?4?mol?L?1 and 229.6???mol?g?1, respectively. Nitrogen adsorption experiment proved that the prepared MIP had a large specific surface area of 105?m2?g?1. Scanning electron microscopy showed that large flow-through pores were present in the prepared monolith. As a consequence, the column backpressure was only 1.2?MPa with acetonitrile as mobile phase at a flow rate of 1.0?mL?min?1.  相似文献   

9.
A polyacrylate tetracycline (TC) selective microporous molecularly imprinted polymer was prepared in three different porogenic solvents (chloroform, acetonitrile, and methanol) via precipitation polymerization, using methacrylic acid monomer, ethylene glycol dimethacrylate crosslinker, and TC as template. In all three solvents this method produced microporous particles in the scale range (200–400 nm), simply, quickly, cleanly, and in good yield. The effect of polarity of porogenic solvents on binding capacity was investigated. The imprinted polymer prepared in chloroform gave much higher binding capacity (KD = 198.6) for TC than the polymers prepared in acetonitrile (KD = 133.2) or methanol (KD = 104.7). The selectivity of imprinted polymers was evaluated by rebinding other structurally similar compounds. The results clearly indicated that the imprinted acrylate polymer exhibits an excellent selectivity toward TC, and has better ability to control the release of TC than the non‐imprinted polymer.© 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

10.
Molecularly imprinting polymer technology is used to prepare a molecularly imprinted polymer (MIP) for the selective recognition of indole‐3‐carbinol (I3C), a chemopreventive and chemotherapeutic phytochemical associated with the anticancer activities of cruciferous vegetables. Prepolymerization study via nuclear magnetic resonance technique is done to choose the best functional monomer that establishes more interaction with the template. The prepared MIP is tested before in batch experiments and subsequently used as solid‐phase extraction sorbent for the selective detection of I3C from standard solutions. In order to verify the selectivity of the MIP, the binding of structurally related compounds, such as indole‐3‐acetonitrile, teophylline, and tryptophan, on the polymer is investigated. The experiments indicate that the MIP is highly selective for I3C with an association constant of Ka = (1.37 ± 0.07) × 103 M?1. Standard mixture solution loaded on MIP‐SPE cartridge give a recovery of 95% for I3C, while the other compounds are totally eluted during washing step. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40819.  相似文献   

11.
An experimental design (ED) approach was applied to study the weight of three factors in the synthesis of a molecularly imprinted polymer (MIP) specific for iprodione fungicide. The objective was to obtain a high specific polymer with the best performance of iprodione binding. Thirteen iprodione-imprinted polymers and 13 non-imprinted polymers (NIP) were synthesized according to ED having 3 influencing factors: the polymerization method, the crosslinker nature and the functional monomer type. For each factor, two levels were studied: bulk and precipitation polymerization for the first factor, trimethylolpropane trimethacrylate (TRIM) and ethylene glycol dimethacrylate (EGDMA) for the second factor, and methacrylamide (MAM) alone or with styrene for the third factor. The ED responses were: the imprinting factor, the site number and the apparent affinity constant. They were determined after studying the interactions between iprodione and each MIP and NIP in hydro-alcoholic medium. The best polymer of the ED was synthesized using MAM as functional monomer, EGDMA as crosslinker and precipitation polymerization. It has an imprinting factor of 2.4, a site number of 1172 and an affinity constant of 19.36. The best MIP was characterized by Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and Nitrogen sorption isotherms. The best MIP has a mesoporous structure with a high specific surface area of 407 m2·g 1. Molecularly imprinted solid phase extraction (MISPE) was successfully applied, using the best MIP, to preconcentrate iprodione from a white wine containing two competing fungicides.  相似文献   

12.
BACKGROUND: There are few reports on erythromycin molecularly imprinted polymers (MIPs) used as HPLC stationary phase and solid phase extraction matrices. These imprinted polymers are prepared by bulk polymerization, which is tedious and time‐consuming, and they are irregular and possess poor reproducibility and low binding capacity. In this study, molecularly imprinted microspheres for erythromycin were prepared by aqueous suspension polymerization for the first time. RESULTS: Imprinted microspheres for erythromycin were prepared using suspension polymerization in which 1.5% PVA‐water solution is used as continuous phase, and chloroform solution containing erythromycin, methacrylic acid and crosslinker is used as disperse phase. The composition of disperse phase is optimized, and the optimum molar ratio of erythromycin to methacrylic acid was 1:5. Selectivity analysis revealed that the imprinted microspheres can specifically recognize erythromycin from its structure analogues. The binding mechanism between erythromycin and methacrylic acid was investigated by UV‐Vis spectrophotometry. Adsorption kinetics and the adsorption isotherm of the imprinted microspheres indicate that erythromycin can be adsorbed rapidly by the imprinted microspheres and the maximum theoretical static binding capacity is 128.6110 mg g?1. The imprinted microspheres were used to extract erythromycin from a milk sample and a high recovery rate was obtained. CONCLUSION: Molecularly imprinted microspheres for erythromycin were uniform and possess high adsorption capacity and excellent selectivity. They are therefore a promising extraction and chromatographic media. Copyright © 2011 Society of Chemical Industry  相似文献   

13.
A molecularly imprinted polymer (MIP) monolith for selective recognition of 4‐aminophenol (4‐AMP) was prepared by in situ polymerization technique as high‐performance liquid chromatography (HPLC) stationary phase. For this purpose, several 4‐AMP imprinted monoliths were synthesized by using only methacrylic acid (MAA), acrylamide (AAM), or isobornyl methacrylate (IBMA) in the presence of high amount of crosslinker, ethylene glycol dimethacrylate (EDMA), and these polymeric monolith columns were connected to HPLC to evaluate their separation capabilities. By selection of appropriate functional monomer and optimization of polymerization conditions, MAA‐based monolithic MIP showed good flow through properties, high selectivity to the templated molecule, and high resolution in the separation of paracetamol and its main impurity, 4‐AMP. Besides, effective binding site density and dissociation constant of this monolith were estimated by using frontal chromatography and found as 7.95 μmol/g and 1.06 mM, respectively. Surface area of the same monolith was found as 23.48 m2/g from multipoint BET analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

14.
A computational approach was developed for screening functional monomers for rational design of molecularly imprinted polymer (MIP) membranes. It was based on a comparison of the binding energy of complexes between a template and various functional monomers. According to the results of theoretical calculations, MIP membranes with chlorogenic acid as a template were prepared with a UV irradiation polymerization method, using 4‐vinylpyridine as a functional monomer and N,N′‐methylenebisacrylamide as a crosslinker, with poly(vinylidene fluoride) microfiltration membranes as the support. Membranes covered with a thin layer of imprinted polymer selective to chlorogenic acid were then obtained and tested using the equilibrium‐adsorption method. The high affinity of these synthetic membranes to chlorogenic acid, together with their straightforward and inexpensive preparation, provides a good basis for the development of applications of imprinted polymers in separation processes such as solid‐phase extraction. Copyright © 2011 Society of Chemical Industry  相似文献   

15.
Eight molecularly imprinted polymers (MIP1–MIP8) were synthesized with different functional monomers and porogens using 3,4‐dihydroxyphenylacetic acid (DOPAC) as a template. Thermal, radical bulk polymerization was employed in the presence of ethylene glycol dimethacrylate as a cross‐linker. A computational analysis indicated that complexes with four molecules of 4‐vinylpyridine, 1‐vinylimidazole and acrylonitrile had high positive enthalpies of formation. The polymers synthesized with these monomers showed an imprinting factor below 1. Polymer MIP8 synthesized with allylamine as the functional monomer, with the highest energy of interaction with DOPAC, was characterized by the highest imprinting factor equal to 1.91. Examination of the binding ability of DOPAC and a group of structurally related compounds showed that the strong interactions between amine groups in the polymer and carboxylic groups in the analyte governed the recognition mechanism. The Langmuir adsorption model and the pseudo‐second‐order mechanism properly evaluated the MIP8 and non‐imprinted polymer 8 adsorption characteristics. Scatchard analysis revealed that MIP8 had two classes of heterogeneous binding sites with Kd(1) = 0.12 µmol L?1 and Kd(2) = 1.46 µmol L?1. Finally, the potential application of MIP8 for separation of DOPAC was demonstrated. Copyright © 2011 Society of Chemical Industry  相似文献   

16.
《分离科学与技术》2012,47(1):74-80
Oleuropein has many antimicrobial, antiviral, and anticancer features found in olive leaf. Therefore, its isolation from olive leaf is very important in such kinds of applications. In this study, a solid-phase extraction system based on the molecularly imprinted polymer (MIP) was proposed for the selective separation of oleuropein from olive leaf. First, oleuropein imprinted polymer has been prepared by the suspension polymerization using methacrylolamidoantiprine–iron (III) metal-chelate monomers. After that, the oleuropein adsorption capacity and selectivity of the prepared imprinted polymer has been determined. The maximum adsorption capacity of oleuropein has found to be 140 mg g?1. Finally, MIP has been used as a sorbent in the solid-phase extraction for the separation of oleuropein from crude extract of olive leaves. The oleuropein analyses have been realized by high performance liquid chromatography. The obtained results indicated that the prepared molecularly imprinted sorbent could be used for at least 10 times for purification of oleuropein from olive leaf. The application of the proposed system in the real sample showed that 24.2 mg pure oleuropein could be obtained from 1.0 g of crude olive leaf extract. As a result, the low cost, simple, and selective adsorbent has been developed for oleuropein adsorption. Supplemental materials are available for this article. Go to the publisher's online edition of Separation Science & Technology to view the supplemental file.  相似文献   

17.
Some of the most important life-saving medications are β-lactam antibiotics (such as Penicillin G). However, these medicines have not adequately been discharged into the environment; penicillin residues offer health risks and enhance the development of resistances. Thus, its selective separation from complex matrices is a challenge worth tackling. A novel strategy of synthesis, by photopolymerization, was applied to develop magnetic molecular imprinted polymers (mag-MIPs) aiming the recognition of penicillin G (also known as benzylpenicillin). Photopolymerization, when compared with the more common thermopolymerization, has the advantage of occurring at lower temperatures, which prevents analyte degradation. The Mag-MIP presented higher surface area than the conventional MIP and good adsorption capacity of the analyte while maintaining its selectivity. The synthesized material was characterized by X-ray diffraction, showing that the magnetite nanoparticles were formed and the MIP polymerization on their surface was performed, once the material was amorphous. Furthermore, the pore formation was evaluated by BET, indicating a high surface area (832 m2 g−1) and large pore volume (0.80 cm3 g−1) in the mag-MIP compared to the magnetic non-imprinted polymer (mag-NIP: 147 m2 g−1 and 0.33 cm3 g−1). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48496.  相似文献   

18.
A molecularly imprinted polymer (MIP) prepared with Pickering emulsion polymerization was designed by a computational approach for removal of acephate from aqueous solution. Methacrylic acid, ethylene glycol dimethacrylate, and chloroform were screened as the optimal functional monomer, crosslinker, and porogen by the Gaussian 03 package using the density functional theory method. The polymerization was carried out in an oil‐in‐water emulsion using nano‐SiO2 particles as stabilizer instead of a toxic surfactant. The characterization results indicated that the prepared MIP had a porous and hollow core, and the particle size was approximately 20 μm. The binding and recognition abilities of MIP for acephate were studied through equilibrium adsorption analysis and selectivity analysis. The results showed that the MIP had high binding capacity and excellent selectivity for acephate. The saturated binding amount could reach 6.59 × 103 μg/g. The Langmuir isotherm model gave a good fit to the experimental data. Moreover, the results of a reusability analysis and practical application suggested that the prepared MIP provides the potential for removal of acephate residues from aqueous solution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43126.  相似文献   

19.
Peipei Qi 《Polymer》2010,51(23):5417-5423
Semi-covalent imprinting with carbonyl group as sacrificial spacer was employed to synthesize molecularly imprinted polymer (MIP) for phenols. A series of semi-covalently imprinted polymers were prepared by varying the templates and porogens. The MIP with 4-chlorophenyl (4-vinyl)phenyl carbonate as template was proved to be the best one, with ethylene glycol dimethacrylate (EGDMA) as cross-linker, 2,2-azobisisobutyronitrile(AIBN), and chloroform as initiator and porogen, respectively. Under such conditions, the corresponding non-covalently imprinted polymer was fabricated with 4-chlorophenol (4-CP) as template and 4-vinylpyridine (4-VP) as functional monomer. The polymer prepared by semi-covalent imprinting displayed superior selectivity to the non-covalently imprinted polymer for phenols. The peak broadening and tailing had been largely reduced on the column packed with semi-covalently imprinted polymer. Meanwhile, the constant retention for these phenols and the good linearity for phenol and 4-CP augured that the semi-covalently imprinted polymer had the potential application as stationary phase for quantitative determination of phenols.  相似文献   

20.
In this work, 2,4-dinitrophenol (2,4-DNP), a new molecularly imprinted polymer (MIP) with excellent performance was synthesized in ethanol by the sol–gel method using 3-aminopropyltriethoxysilane as functional monomer on the surface of silica particles. The structure and morphology of MIP were characterized via scanning electron microscopy, nitrogen adsorption–desorption analysis, infrared spectra, and thermogravimetry analysis. Results demonstrated that MIP had excellent selectivity toward the template molecule (2,4-DNP) with an imprinting factor of 9.55 and a maximum static adsorption capacity of 114.7 mg g−1. Data obtained from the adsorption isotherm of 2,4-DNP were fitted well with the Freundlich isotherm model, and the adsorption process can be described by the pseudo-second-order model. The investigation of adsorption mechanism revealed that the specific recognition process of MIP toward 2,4-DNP was dominated by the hydrogen bond and molecular structure. By employing as a sorbent, the as-prepared MIP was applied to recognize and remove 2,4-DNP in poster paper, nonwoven fabric and brown curtain with recoveries in the range from 85.74 to 100.00%. However, the MIP can effectively remove 2,4-DNP after five cycles.  相似文献   

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