Investigation of ractopamine‐imprinted polymer for dispersive solid‐phase extraction of trace β‐agonists in pig tissues

Ractopamine, as an alternative β‐agonist to clenbuterol, is more and more used as leanness‐enhancing agent in the swine industry. This work presents a new molecularly imprinted polymer (MIP) using ractopamine as template for dispersive solid‐phase extraction of trace ractopamine and the structural related β‐agonists in animal tissues. The binding properties and selectivity of MIP were investigated. High selectivity in polar environment was found, since the extraction capacity of ractopamine with the MIP was 4.5‐fold as much as that with the non‐imprinted polymer in acetonitrile. Cross‐selectivity investigation indicates that the MIP preferentially binds the template and then the structural analogues according to their molecular similarity. Thermodynamic and kinetic investigation was performed to interpret the specific adsorption and molecular recognition of the MIP for ractopamine. Standard free energy, standard enthalpy, and standard entropy were determined. Related information suggested that adsorption of ractopamine onto MIP was an exothermic, spontaneous process. The MIP can be applied as dispersive solid‐phase extraction material for enrichment of ractopamine, isoxsuprine, fenoterol and clenbuterol in complex samples before HPLC analysis. The method revealed detection limits of 0.20–0.90 μg/L, recoveries of 83.8–115.2 and 85.2–110.2% for the spiked pig muscle and pig liver, respectively, with the RSD from 2.5 to 8.8%.     

Removal of endocrine‐disrupting compounds from water using macroporous molecularly imprinted cryogels in a moving‐bed reactor

Highly efficient removal of endocrine‐disrupting compounds (EDCs) such as 17β‐estradiol (E2), 4‐nonylphenol (NP) and atrazine from water was achieved using a novel macroporous adsorption medium. The medium consisted of a macroporous poly(vinyl alcohol) (PVA) cryogel with molecularly imprinted polymer (MIP) particles embedded in it. The MIP was prepared using E2, NP and atrazine as templates. The macroporous composite molecularly imprinted cryogels were formed inside the open‐ended protective shells, known as Kaldnes carriers. These adsorbents (defined as Macroporous Gel Particles, MGPs) were evaluated on the removal of E2, NP and atrazine from water using different column configurations, namely column filled with the MGPs (packed‐bed column) and in moving‐bed reactors (defined here as moving‐bed MGPs reactor). Complete binding (> 99%) of E2 from a spiked aqueous solution (1 mg/L) was achieved using E2‐MIP/MGPs in a moving‐bed MGPs reactor at the retention time in the reactor of 4 min, while only 77% was bound to the nonimprinted medium (NIP/MGPs). Similar results were also obtained for the adsorption medium imprinted with atrazine. All contaminants studied (E2, atrazine and NP) were effectively removed from water at low (environmentally relevant) concentrations by the respective adsorption medium.     

Critical comparison of the on‐line and off‐line molecularly imprinted solid‐phase extraction of patulin coupled with liquid chromatography

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

Development of a Sensitive Method for the Determination of 4‐(Methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol in Human Urine Using Solid‐phase Extraction Combined with Ultrasound‐assisted Dispersive Liquid–liquid Microextraction and LC‐MS/MS Detection

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.     

Chromatographic performance of molecularly imprinted polymers: Core‐shell microspheres by precipitation polymerization and grafted MIP films via iniferter‐modified silica beads

In this work, two different surface imprinting formats have been evaluated using thiabendazole (TBZ) as model template. The first format is a thin film of molecularly imprinted polymer (MIP) grafted from preformed silica particles using an immobilized iniferter‐type initiator (inif‐MIP). The second format is molecularly imprinted polymer microspheres with narrow particle size distribution and core‐shell morphology prepared by precipitation polymerization in a two‐step procedure. For the latter format, polymer microspheres (the core particles) were obtained by precipitation polymerization of divinylbenzene‐80 (DVB‐80) in acetonitrile. Thereafter, the core particles were used as seed particles in the synthesis of MIP shells by copolymerization of DVB‐80 and methacrylic acid in the presence of TBZ in a mixed solvent porogen (acetonitrile/toluene). The materials were characterized by elemental microanalysis, nitrogen sorption porosimetry and scanning (and transmission) electron microscopy. Thereafter, the imprinted materials were assessed as stationary phases in liquid chromatography. From this study it can be concluded that grafted MIP beads can be obtained in a simple and direct manner, consuming only a fraction of the reagents used typically to prepare imprinted particles from a monolithic imprinted polymer. Such materials can be used in the development of in‐line molecularly imprinted solid‐phase extraction methods. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1058–1066, 2010     

Selective Solid‐phase Extraction of Bisphenol A Using a Novel Stir Bar Based on Molecularly Imprinted Monolithic Material

In this paper, a novel monolithic stir bar based on molecularly imprinted polymer (MIP) was firstly developed by filling modified neodymium magnet (Nd₂Fe₁₄B) powders into a glass tube (60 × 4 mm), followed by the imprinted grafting with bisphenol A (BPA) as the template molecule by thermal polymerization. It has been successfully used for the stir bar sorptive extraction (SBSE) and its extraction performance illustrated that the MIP‐encapsulated stir bar had stronger affinity to the template molecule, compared with the stir bar based on the non‐imprinted molecularly polymer (NIP). Under the optimal extraction conditions, a simple method based on the coupling of MIP‐SBSE with high performance liquid chromatography (HPLC) was used for the selective determination of the model mixtures of BPA, 4‐phenylphenol (PP) and phenol (P) in bottled water. The recoveries of BPA, PP and P were in the range of 88.5‐96.1%, 78.2‐89.7%, 81.3‐89.5% at three spiked levels, respectively, demonstrating that higher extraction and the specific absorption occurred between the template molecule and the prepared MIP stir bar.     

Extraction of crocin from saffron (Crocus sativus) using molecularly imprinted polymer solid‐phase extraction

A new molecularly imprinted polymer for extraction of crocin from saffron stigmas was prepared using gentiobiose (a glycoside moiety in crocin structure) as a template. Crocin binding to gentiobiose imprinted polymer (Gent‐MIP) was studied in comparison with a blank nonimprinted polymer in aqueous media. Affinity of the Gent‐MIP for the crocin was more than the nonimprinted polymer at all concentrations. In Scatchard analysis, the number of binding sites in each gram of polymer (maximum binding sites) and dissociation constant of crocin to binding sites were 18.4 μmol/g polymer and 11.2 μM, respectively. The Gent‐MIP was then used as the sorbent in an SPE method for isolation and purification of crocin from methanolic extract of saffron stigmas. The recovery of crocin, safranal and picrocrocin was determined in washing and elution steps. The Gent‐MIP had significantly higher affinity for crocin than other compounds and enabled selective extraction of crocin with a high recovery (84%) from a complex mixture. The results demonstrated the possibility of using a part of a big molecule in preparing a molecularly imprinted polymer with a good selectivity for the main structure.     

A new ionic liquid surface‐imprinted polymer for selective solid‐phase‐extraction and determination of sulfonamides in environmental samples

Toward improving the selective adsorption performance of molecularly imprinted polymers in strong polar solvents, in this work, a new ionic liquid functional monomer, 1‐butyl‐3‐vinylimidazolium bromide, was used to synthesize sulfamethoxazole imprinted polymer in methanol. The resulting molecularly imprinted polymer was characterized by Fourier transform infrared spectra and scanning electron microscopy, and the rebinding mechanism of the molecularly imprinted polymer for sulfonamides was studied. A static equilibrium experiment revealed that the as‐obtained molecularly imprinted polymer had higher molecular recognition for sulfonamides (e.g., sulfamethoxazole, sulfamonomethoxine, and sulfadiazine) in methanol; however, its adsorption of interferent (e.g., diphenylamine, metronidazole, 2,4‐dichlorophenol, and m‐dihydroxybenzene) was quite low. ¹H NMR spectroscopy indicated that the excellent recognition performance of the imprinted polymer was based primarily on hydrogen bond, electrostatic and π‐π interactions. Furthermore, the molecularly imprinted polymer can be employed as a solid phase extraction sorbent to effectively extract sulfamethoxazole from a mixed solution. Combined with high‐performance liquid chromatography analysis, a valid molecularly imprinted polymer‐solid phase extraction protocol was established for extraction and detection of trace sulfamethoxazole in spiked soil and sediment samples, and with a recovery that ranged from 93–107%, and a relative standard deviation of lower than 9.7%.     

Voltammetric Determination of Urinary 1‐Hydroxypyrene Using Molecularly Imprinted Polymer‐Modified Screen‐Printed Carbon Electrodes

A two step non‐competitive affinity method for the trace determination of 1‐hydroxypyrene (1‐OHP) using a disposable molecularly imprinted polymer (MIP) modified screen‐printed carbon electrode (MIP‐SPCE) has been developed. The MIP was synthesized according to a novel strategy, which is described, and is capable of rebinding the phenolic analyte, 1‐hydroxypyrene (1‐OHP), from high pH aqueous organic media, via ionic interactions. In the first step of our method 1‐OHP was accumulated at the MIP‐SPCE from 35% aqueous methanol containing 0.014 M NaOH and 0.14 M NaCl, at open circuit. In the second step, the resulting SPCE with accumulated 1‐OHP was then transferred to fresh, clean phosphate buffered aqueous methanol, and subjected to cyclic voltammetry (CV) or differential pulse voltammetry (DPV). The latter technique proved to be more sensitive at detecting 1‐OHP, with a limit of detection of 182 nM and a linear range to 125 μM on unmodified electrodes. The possible effects of interference by related phenolic compounds in the MIP‐SPCE of 1‐OHP were investigated. Finally the method was evaluated by carrying out 1‐OHP determinations on spiked human urine samples; the recovery of 1‐OHP was 79.4% and the coefficient of variation was found to be 7.7% (n= 4) using a separate MIP‐SPCE for each determination. Therefore, the performance data suggests that the method is reliable at the concentrations examined in this study. The method was found to be superior to the direct determination of 1‐OHP in human urine by DPV alone, which was greatly affected by interference from uric acid.     

Solid‐phase Extraction of β‐Sitosterol from Oldenlandia diffusa Using Molecular Imprinting Polymer

The β‐sitosterol imprinted polymer was prepared for selective extraction and analysis of β‐sitosterol from Oldenlandia diffusa (O. diffusa) followed by HPLC with UV detection. The imprinted polymers show high affinity and selectivity to β‐sitosterol. Using this molecularly imprinted polymer (MIP) cartridge as solid‐phase extraction (SPE) material, the interferences could be quickly washed out and β‐sitosterol was selectively retained and enriched. HPLC analysis method was used to evaluate the characteristics of this MIP material. At the condition of mobile phase composed of MeOH/H₂O/H₃PO₄ (99/1/0.1, V/V/V, pH=6.0) and the flow rate of 1.0 mL·min^?1, a good linear relationship was demonstrated when the concentrations of β‐sitosterol were in the range of 0.50–100.0 µg·mL^?1. The recoveries ranged from 75.3% to 86.5% and the inter‐day and intra‐day relative standard deviations were less than 5%. This developed HPLC method was proved to be acceptable for extraction of β‐sitosterol from O. diffusa.     

Preparation of l‐phenylalanine‐imprinted solid‐phase extraction sorbent by Pickering emulsion polymerization and the selective enrichment of l‐phenylalanine from human urine

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.     

Molecularly imprinted polymer surfaces as solid-phase extraction sorbents for the extraction of 2-nitrophenol and isomers from environmental water

The novel surface molecularly imprinted polymer (MIP) with 2‐nitrophenol (2‐NP) as the template has been prepared and used as the adsorbent for the solid‐phase extraction (SPE). The selectivity of the polymer was checked toward several selected nitrophenols (NPs) such as 2‐NP, 3‐nitrophenol (3‐NP), 4‐nitrophenol (4‐NP) and 2,4,6‐trichlorophenol (2,4,6‐TCP). Under the optimized conditions, high sensitivity (detection limits: 0.07–0.12 ng/mL) and good reproducibility of analytes (2.3–4.8% for four cycles) were achieved. Then, the method was applied for the analysis of selected phenols in spiked tap, lake and river water samples. High recoveries (>83.3%) for nitrophenols (NPs) were obtained, but lower recoveries (<63.4%) were achieved for 2,4,6‐TCP. The method was found to be linear in the range of 1–300 ng/mL with correlation coefficients (R²) greater than 0.99 and repeatability relative standard deviation (RSD) below 7.2% in all cases. For analysis of 120 mL water samples, the method detection limits (LODs) ranged from 0.10 to 0.22 ng/mL and the limit of quantification (LOQs) from 0.33 to 0.72 ng/mL. These results showed the suitability of the MIP‐SPE method for the selective extraction of a group of structurally related isomeric compounds.     

Surface Plasmon Resonance‐based Inhibitive Immunoassay Coupled with Dummy Template Molecularly Imprinted Polymer Solid Phase Extraction for On‐line Analysis of Trace Clenbuterol

A new indirect inhibitive immunoassay using surface plasmon resonance (SPR) coupled with molecularly imprinted polymer (MIP) was developed and applied for the analysis of trace clenbuterol (CL). A MIP coating using phenylephrine as the dummy template was synthesized in a flexible quartz capillary (30 cm×0.25 mm i.d.) by in situ polymerization technique, which then was used as the online solid phase extraction (SPE) tube before SPR detection. The thickness of the coating was 198 nm on average, illustrated by scanning electron microscope (SEM) image. The mechanism for adsorption of CL on dummy template MIP was found to be a Freundlich isotherm and pseudo‐second‐order model. The immunoassay was conducted on BIAcore 3000 biosensor automatically without pre‐treatment. The calibration curve was generated by linear fit in the range of 0.1–10 ng L^‐1 and 10–100 ng L^‐1. The detection limit was 0.1 ng L^–1, which is super sensitive. This method was directly applied for the analysis of real‐world samples without pretreatment.     

Comparison of three cross‐linking agents for imprinting diethylstilbestrol in solid‐phase extraction

Molecularly imprinted polymer (MIP) has been heavily studied for years. However, most efforts focused on functional monomer and particular study of cross‐linking agents on imprinting effect and pore structure is rare. In this paper, diethylstilbestrol (DES) imprinted polymers cross‐linked by three types of agents and their imprinting effects in solid‐phase extraction (SPE) were discussed. Evolution of UV spectral and simulation of cross‐linking agents or monomer mixed with DES revealed that there was a particular interaction between divinylbenzene and DES. Clear imprinting effects towards DES showed for divinylbenzene made imprinted polymer (DM), with imprinting factors up to 16.02 (STD = 2.20), while the other two imprinted polymers showed limited effects with imprinting factors of 4.95 (STD = 0.45) and 1.63 (STD = 0.54). Specific surface areas, pore volumes, and pore size distributions of the particles also confirmed that DM showed distinguished structure, and the average pore size of it was just fit the size of DES and bisphenol A (BPA), while no pore was found in divinylbenzene made blank polymer. Other imprinted and non‐imprinted polymers showed no pore or big pores relatively. These results show that the cross‐linking monomer is not merely an inert component for the MIPs, it could play a positive role in promoting interactions with the template to afford molecular recognition in imprinting DES. Copyright © 2011 John Wiley & Sons, Ltd.     

Novel metal‐ion‐mediated,complex‐imprinted solid‐phase microextraction fiber for the selective recognition of thiabendazole in citrus and soil samples

A novel metal‐ion‐mediated complex‐imprinted‐polymer‐coated solid‐phase microextraction (SPME) fiber used to specifically recognize thiabendazole (TBZ) in citrus and soil samples was developed. The complex‐imprinted polymer was introduced as a novel SPME coating using a “complex template” constructed with Cu(II) ions and TBZ. The recognition and enrichment properties of the coating in water were significantly improved based on the metal ion coordination interaction rather than relying on hydrogen bonding interactions that are commonly applied for the molecularly imprinting technique. Several parameters controlling the extraction performance of the complex‐imprinted‐polymer‐coated fiber were investigated including extraction solvent, pH value, extraction time, metal ion species, etc. Furthermore, SPME coupled with HPLC was developed for detection of TBZ, and the methods resulted in good linearity in the range of 10.0–150.0 ng/mL with a detection limit of 2.4 ng/mL. The proposed method was applied to the analysis of TBZ in spiked soil, orange, and lemon with recoveries of 80.0–86.9% and RSDs of 2.0–8.1%. This research provides an example to prepare a desirable water‐compatible and specifically selective SPME coating to extract target molecules from aqueous samples by introducing metal ions as the mediator.     

Preconcentration of indapamide from human urine using molecularly imprinted solid‐phase extraction

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.     

Solid‐phase extraction based on a molecularly imprinted polymer for the selective determination of four benzophenones in tap and river water

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 (Q_max = 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%.     

Selective 17‐β‐estradiol molecular imprinting

An efficient novel method for the synthesis of a covalent molecularly imprinted polymer (MIP) highly specific to β‐estradiol have been developed. MIP prepared by both covalent and non covalent techniques, demonstrated high selectivity toward β‐estradiol. MIPs were synthesized by radical polymerization of 17‐β‐estradiol 4‐vinyl‐benzene carboxyl or sulfonyl esters used as covalent functional monomers, methacrylic acid as noncovalent functional monomer, ethylene glycol dimethacrylate as crosslinking agent, and acetonitrile as swelling and porogenic component. Almost 35% (w/w) of 17‐β‐estradiol was successfully removed from the polymer network by basic hydrolysis. The binding ability of MIP was 10.73 μg/mg MIP following removal of 17‐β‐estradiol in the 2 mg/mL β‐estradiol solution. Selective rebinding of β‐estradiol toward MIP was tested in the presence of competitive binders including estrone, 19‐nortestosterone, epiandrosterone, and cholesterol. Estrone having closest similar chemical structure to β‐estradiol exhibited only 0.6 μg/mg MIP competitive binding, being exposed to equivalent concentrations. Moreover, other competitive steroids demonstrated negligible affinity toward MIP indicating high selectivity of novel MIP system toward β‐estradiol. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5534–5542, 2009     

Synthesis of poly(2‐hydroxyethyl methacrylate)‐based molecularly imprinted polymer nanoparticles containing timolol maleate: morphological,thermal, and drug release along with cell biocompatibility studies

This work was aimed to synthesize and characterize poly(2‐hydroxyethyl methacrylate) [poly (HEMA)]‐based molecularly imprinted polymer nanoparticles (MIP NPs) containing timolol maleate (TM) via precipitation polymerization. The molecular structures of the MIP and non‐imprinted polymer (NIP) NPs were compared by means of Fourier transform infrared spectroscopy. The morphological observations by using scanning electron microscopy and transmission electron microscopy confirmed the formation of MIP NPs as small as 128 nm in average diameter with appropriate synthesis conditions. Thermal behaviors of the samples were also studied by the use of thermogravimetric analysis and differential scanning calorimetry. By considering a series of key factors such as monomer : template ratio, cross‐linker type, pH, and temperature, the sample with promising characteristics was found to be that of HEMA : TM ratio of 10:1, 40 mmol of ethylene glycol dimethacrylate as cross‐linker, and polymerization temperature of 60°C in acetonitrile as porogenic solvent. Furthermore, the ultraviolet‐visible (UV‐vis) spectrophotometry results proved a controlled release of TM from the MIP NP samples compared with NIP ones at extended periods. Moreover, the cytotoxicity of the MIP and NIP NPs samples was evaluated on mesenchymal stem cells, and the obtained observations showed that they had no adverse side effect on the living cells; especially the surface of the MIP NPs sample depicted highly cell's biocompatibility. Finally, the outcomes from designed different experiments conducted us that the HEMA‐based MIP NPs have great potential as an ocular nanocarrier for TM delivery. Copyright © 2016 John Wiley & Sons, Ltd.     

Via protoporphyrin to the synthesis of levofloxacin‐imprinted polymer

A new molecularly imprinted polymer (MIP) for levofloxacin was prepared by the combined use of methacrylic acid and protoporphyrin as functional monomers. The adsorption properties of resultant imprinted polymers were evaluated by equilibrium rebinding experiments. The highest binding capacity of levofloxacin achieved from the optimized imprinted polymer in acetonitrile was 246.26 µmol/g with an imprinting factor of 2.05. A ?uorescence quenching effect was observed when a protoporphyrin‐based imprinted polymer was incubated in the solutions of levofloxacin. The results indicated that the protoporphyrin‐based MIPs were able to create higher binding cavities for template compared with MIPs using only methacrylic acid as a functional monomer. It should be expected that the cooperative use of the protoporphyrin with supplemental different functional monomers may be an alternative to obtain MIP with the improvement of the selectivity. Copyright © 2010 John Wiley & Sons, Ltd.