Removal of cefalexin using yeast surface‐imprinted polymer prepared by atom transfer radical polymerization

The first use of yeast as a support in the molecular imprinting field combined with atom transfer radical polymerization was described. Then, the as‐prepared molecularly imprinted polymers were characterized by Fourier transmission infrared spectrometry, scanning electron microscope, thermogravimetric analysis, and elemental analysis. The obtained imprinted polymers demonstrated elliptical‐shaped particles with the thickness of imprinting layer of 0.63 μm. The batch mode experiments were adopted to investigate the adsorption equilibrium, kinetics, and selectivity. The kinetic properties of imprinted polymers were well described by the pseudo‐second‐order kinetic equation, indicating the chemical process was the rate‐limiting step for the adsorption of cefalexin (CFX). The equilibrium data were well fitted by the Freundlich isotherm, and the multimolecular layers adsorption capacity of imprinted polymers was 34.07 mg g^?1 at 298 K. The selectivity analysis suggested that the imprinted polymers exhibited excellent selective recognition for CFX in the presence of other compounds with related structure. Finally, the analytical method based on the imprinted polymers extraction coupled with high‐performance liquid chromatograph was successfully used for CFX analysis in spiked pork and water samples.     

Preparation of 17β‐estradiol surface molecularly imprinted polymers and their application to the analysis of biological samples

17β‐Estradiol (E2) surface molecularly imprinted polymers have been prepared using functionalized monodispersed poly(glycidyl methacrylate‐co‐ethylene dimethacrylate) beads as a support. The resulting polymers were found to be uniform in size (5 μm), and the surfaces of the microspheres possessed large pore‐like structures. A chromatographic experiment demonstrated that the resulting microspheres exhibited high levels of recognition and selectivity toward the target molecule. The particles were employed as a novel sorbent in a molecularly imprinted SPE protocol. A method was then developed involving the combination of the pretreatment with HPLC to determine the levels of estrogen secreted from Michigan Cancer Foundation‐7 cells. The obtained results revealed that the extraction recoveries of E2 from real samples were in the range of 73.0–97.5% with RSDs of < 7.5% (n = 3). Calibration curves were established with R values > 0.9996 for concentrations in the range of 0.50–100.00 ng/mL. The LOD of this new method was 0.14 ng/mL. Compared with traditional C₁₈ SPE agents, the particles showed high selectivity and extraction efficiency for E2 in the pretreatment process. The particles could therefore be used to determine trace estrogen in biological samples with a UV detector only.     

Fabrication and evaluation of molecularly imprinted regenerated cellulose composite membranes via atom transfer radical polymerization

A simple and effective method for surface molecularly imprinted composite membranes （MICMs） for artemisinin （Ars） based on regenerated cellulose membranes was first prepared through surface- initiated atom transfer radical polymerization （ATRP）, and the as-prepared MICMs were then evaluated as adsorbents for selective recognition and separation of Ars molecules. Batch rebinding studies were conducted to determine the specific adsorption equilibrium, kinetics and selective permeation performance. The adsorption capacity of MICMs toward Ars by the Langmuir isotherm model was 2.008 mgg-1, which was nearly 5.0 times higher than non-molecularly imprinted composite membranes （NICMs）. The kinetic property of MICMs was well-fitted by the pseudo-second-order rate equation. The selective permeation experiments were successfully investigated to prove the excellent selective permeation performance for Ars than the competitive analog （artemether）.     

Recovery and separation of erythromycin from industrial wastewater by imprinted magnetic nanoparticles that exploit β‐cyclodextrin as the functional monomer

A type of surface imprinting over magnetic Fe₃O₄ nanoparticles utilizing erythromycin‐A as a template for use in the separation and recovery of erythromycin was developed and investigated. As the intermolecular forces play a key role in the performance of imprinted materials, differential scanning calorimetry, and ¹H NMR spectroscopy was employed to evaluate the interactions between erythromycin and the functional monomer β‐cyclodextrin. To synthesize the surface imprinted polymers, magnetic Fe₃O₄ nanoparticles, the core materials, were modified with a free radical initiator to initialize polymerization in a “grafting from” manner. Then using acryloyl‐modified β‐cyclodextrin as the functional monomer and ethyleneglycol dimethacrylate as the cross‐linker, thin erythromycin‐imprinted films were fabricated by the radical‐induced graft copolymerization of monomers on the surface of the Fe₃O₄ nanoparticles. Selectivity experiments showed that the erythromycin‐A‐imprinted materials had recognition ability toward erythromycin derivatives. Finally, these magnetic molecularly imprinted particles were successfully used for the separation and enrichment of erythromycin from the mother liquor. The recovery, detected by high‐performance liquid chromatography and differential pulse voltammetry, approached 97%. The combination of the specific selectivity of the imprinted material and the magnetic separation provided a powerful tool that is simple, flexible, and selective for the separation and recovery of erythromycin.     

Kinetics of surface‐initiated atom transfer radical polymerization

Although atom transfer radical polymerization (ATRP) is often a controlled/living process, the growth rate of polymer films during surface‐initiated ATRP frequently decreases with time. This article investigates the mechanism behind the termination of film growth. Studies of methyl methacrylate and methyl acrylate polymerization with a Cu/tris[2‐(dimethylamino)ethyl]amine catalyst system show a constant but slow growth rate at low catalyst concentrations and rapid growth followed by early termination at higher catalyst concentrations. For a given polymerization time, there is, therefore, an optimum intermediate catalyst concentration for achieving maximum film thickness. Simulations of polymerization that consider activation, deactivation, and termination show trends similar to those of the experimental data, and the addition of Cu(II) to polymerization solutions results in a more constant rate of film growth by decreasing the concentration of radicals on the surface. Taken together, these studies suggest that at high concentrations of radicals, termination of polymerization by radical recombination limits film growth. Interestingly, stirring of polymerization solutions decreases film thickness in some cases, presumably because chain motion facilitates radical recombination. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 386–394, 2003     

Superparamagnetic lysozyme surface-imprinted polymer prepared by atom transfer radical polymerization and its application for protein separation

Molecular imprinting as a promising and facile separation technique has received much attention because of their high selectivity for target molecules. In this study, the superparamagnetic lysozyme surface-imprinted polymer was prepared by a novel fabricating protocol, the grafting of the imprinted polymer on magnetic particles in aqueous media was done by atom transfer radical polymerization (ATRP), and the properties of the imprinted polymer were characterized in detail. Its high selective adsorption and recognition to lysozyme demonstrated the separation ability of the magnetic imprinted material to template molecule, and it has been used for quick and direct separation of lysozyme from the mixture of standard proteins and real egg white samples under an external magnetic field. Furthermore, the elution of lysozyme from the imprinted material was achieved by PEG/sulphate aqueous two-phase system, which caused lysozyme not only desorption from the imprinted materials but also redistribution in the top and bottom phase of aqueous two-phase system. The aqueous two-phase system exhibited some of the extraction and enrichment effect to desorbed lysozyme. Our results showed that ATRP is a promising method for the protein molecularly imprinted polymer preparation.     

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     

Radical‐initiated polymerization of β‐methyl‐α‐methylene‐γ‐butyrolactone

β‐Methyl‐α‐methylene‐γ‐butyrolactone (MMBL) was synthesized and then was polymerized in an N,N‐dimethylformamide (DMF) solution with 2,2‐azobisisobutyronitrile (AIBN) initiation. The homopolymer of MMBL was soluble in DMF and acetonitrile. MMBL was homopolymerized without competing depolymerization from 50 to 70 °C. The rate of polymerization (R_p) for MMBL followed the kinetic expression R_p = [AIBN]^0.54[MMBL]^1.04. The overall activation energy was calculated to be 86.9 kJ/mol, k_p/k_t^1/2 was equal to 0.050 (where k_p is the rate constant for propagation and k_t is the rate constant for termination), and the rate of initiation was 2.17 × 10^?8 mol L^?1 s^?1. The free energy of activation, the activation enthalpy, and the activation entropy were 106.0, 84.1, and 0.0658 kJ mol^?1, respectively, for homopolymerization. The initiation efficiency was approximately 1. Styrene and MMBL were copolymerized in DMF solutions at 60 °C with AIBN as the initiator. The reactivity ratios (r₁ = 0.22 and r₂ = 0.73) for this copolymerization were calculated with the Kelen–Tudos method. The general reactivity parameter Q and the polarity parameter e for MMBL were calculated to be 1.54 and 0.55, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1759–1777, 2003     

Preparation of polymer‐grafted carbon black nanoparticles by surface‐initiated atom transfer radical polymerization

Pristine carbon black was oxidized with nitric acid to produce carboxyl group, and then the carboxyl group was consecutively treated with thionyl chloride and glycol to introduce hydroxyl group. The hydroxyl group on the carbon black surface was reacted with 2‐bromo‐2‐methylpropionyl bromide to anchor atom transfer radical polymerization (ATRP) initiator. The ATRP initiator on carbon black surface was verified by TGA, FTIR, EDS, and elemental analysis. Then, poly (methyl methacrylate) and polystyrene chains were respectively, grown from carbon black surface by surface‐initiated atom transfer radical polymerization (SI‐ATRP) using CuCl/2,2‐dipyridyl (bpy) as the catalyst/ligand combination at 110 °C in anisole. ¹H NMR, TGA, TEM, AFM, DSC, and DLS were used to systemically characterize the polymer‐grafted carbon black nanoparticles. Dispersion experiments showed that the grafted carbon black nanoparticles had good solubilities in organic solvents such as THF, chloroform, dichloromethane, DMF, etc. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3451–3459, 2007     

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%.     

Preparation of molecularly imprinted polymers via atom transfer radical “bulk” polymerization

The first application of atom transfer radical “bulk” polymerization (ATRBP) in molecular imprinting is described, which provides molecularly imprinted polymers (MIPs) with obvious imprinting effects towards the template, very fast binding kinetics, and an appreciable selectivity over structurally related compounds. In comparison with the MIP prepared via the normally used traditional “bulk” free radical polymerization (BFRP), the MIPs obtained via ATRBP showed somewhat lower binding capacities and apparent maximum numbers N_max for high‐affinity sites as well as quite similar binding association constants K_a for high‐affinity sites and high‐affinity site densities, in contrast with the previous reports (e.g., nitroxide/iniferter‐mediated “bulk” polymerization provided MIPs with improved properties). This is tentatively ascribed to the occurrence of rather fast gelation process in ATRBP, which greatly restricted the mobility of the chemical species, leading to a heavily interrupted equilibrium between dormant species and active radicals and heterogeneous polymer networks. In addition, the general applicability of ATRBP was also confirmed by preparing MIPs for different templates. This work clearly demonstrates that applying controlled radical polymerizations (CRPs) in molecular imprinting not always benefits the binding properties of the resultant MIPs, which is of significant importance for the rational use of CRPs in generating MIPs with improved properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 532–541, 2010     

Synthesis of metronidazole‐imprinted molecularly imprinted polymers by distillation precipitation polymerization and their use as a solid‐phase adsorbent and chromatographic filler

Metronidazole‐imprinted polymers with superior recognition properties were prepared by a novel strategy called distillation–precipitation polymerization. The as‐obtained polymers were characterized by Fourier‐transform infrared spectroscopy, laser particle size determination and scanning electron microscopy, and their binding performances were evaluated in detail by static, kinetic and dynamic rebinding tests, and Scatchard analysis. The results showed that when the fraction of the monomers was 5 vol% in the whole reaction system, the prepared polymers afforded good morphology, monodispersity, and high adsorption capacity and excellent selectivity to the target molecule, metronidazole. The optimal binding performance is 12.41 mg/g for metronidazole just before leakage occurred and 38.51 mg/g at saturation in dynamic rebinding tests. Metronidazole‐imprinted polymers were further applied as packing agents in solid‐phase extraction and as chromatographic filler, both of which served for the detection of metronidazole in fish tissue. The results illustrated the recoveries of spiked samples ranged from 82.97 to 87.83% by using molecularly imprinted solid‐phase extraction combined with a C₁₈ commercial column and 93.7 to 101.2% by directly using the polymer‐packed chromatographic column. The relative standard deviation of both methods was less than 6%.     

Construction of hydroxyl‐terminated poly(N‐isopropylacrylamide) brushes on silicon wafer via surface‐initiated atom transfer radical polymerization

Surface‐initiated atom transfer radical polymerization (SI‐ATRP) of N‐isopropylacrylamide (NIPAM) on silicon wafer in the presence of 2‐mercaptoethanol (ME) chain transfer agent was conducted in attempt to create controllable hydroxyl‐terminated brushes. The initiator‐immobilized substrate, was prepared by the esterification of hydroxyl groups on silicon wafer with 2‐bromopropionyl bromide (2‐BPB); followed by the ATRP of NIPAM using a catalyst system, that is, Cu(I)Br/2,2′‐bipyridine (2,2′‐bpy) and a chain transfer agent, that is, ME. The formation of homogeneous tethered poly(N‐isopropylacrylamide) (poly(NIPAM) brushes with hydroxyl end‐group, whose thickness can be tuned by chancing ME concentration, is evidenced by using the combination of grazing angle attenuated total reflectance‐Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, ellipsometry, atomic force microscopy, gel permeation chromatography, and water contact‐angle measurements. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted poly(NIPAM) films with hydroxyl end‐group on silicon wafer and allowed us to predict a ME concentration for forming a “brush” conformation for the chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3880–3887, 2010     

Kinetic studies of surface‐initiated atom transfer radical polymerization in the synthesis of magnetic fluids

We present results from kinetic studies on the surface‐initiated atom transfer radical polymerization in the preparation of polymer brush‐coated magnetic particles from a heterogeneous system. It is shown that a controlled reaction behavior and a reproducible surface functionalization with end‐tethered polymers are achieved, although the reaction advances gradually from a biphasic solid–liquid mixture to a stable colloidal dispersion of the nanoobjects. Although the initiator‐functional magnetite nanoparticles initially form a precipitate, the formation of a polymer layer on the particle surface in the course of the reaction contributes to a sterical stabilization in dispersion. We thoroughly investigated the development of the initial heterogeneous system with time and in various concentration regimes by simultaneously monitoring the monomer conversion, molar mass, the hydrodynamic diameter of the nanoobjects, and the magnetite content of the dispersions at different reaction times. The results indicate first‐order chain growth kinetics with respect to the monomer and narrow molar mass distributions, demonstrating good control on the particle architecture. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Synthesis and application of functional polyethylene graft copolymers by atom transfer radical polymerization

This investigation attempts to elucidate the copolymerization reaction ethylene and p-methylstyrene via the homogeneous metallocene catalyst, Et(Ind)₂ZrCl₂. With increasing of p-methylstyrene concentration, the poly[ethylene-co-(p-methylstyrene)] copolymer shows systematical decrease of melting temperature and crystallinity and increase of glass transition temperature. The benzylic protons of p-methylstyrene are ready for numerous chemical reactions, such as halogenation and oxidation, which can introduce functional groups at the p-methyl group position under mild reaction conditions. With the bromination reaction of poly[ethylene-co-(p-methylstyrene)], polyethylene graft copolymers, such as polyethylene-g-poly(methyl methacrylate) and polyethylene-g-polystyrene can be prepared via atomic transfer radical polymerization. The following selective bromination reaction of p-methylstyrene units in the copolymer and the subsequent radical graft-from polymerization were effective methods of producing polymeric side chains with well-defined structure. The products were characterized by nuclear magnetic resonance, gel-permeation chromatography, differential scanning calorimetry, and thermal gravimetric analysis. Additionally, the morphology of PE/PMMA and PE/PMMA/PE-g-PMMA blend are compared by using scanning electron microscope.     

Preparation and characterization of a lamotrigine imprinted polymer and its application for drug assay in human serum

A molecularly imprinted polymer (MIP) against lamotrigine (LTG) was prepared, characterized, and its recognition properties were compared with a blank nonimprinted polymer (NIP). Two classes of binding sites were found in the MIP--high affinity (K(D) = 16.2 microM) and low affinity (K(D) = 161.3 microM). Selectivity of the synthesized MIP was examined using compounds with similar structures or therapeutic uses to LTG. In compounds which had structural similarity to LTG, the presence of amine groups appeared to affect binding to the MIP, however overall shape of the molecule was also important. Under the optimal conditions developed, other anticonvulsant drugs tested did not bind the MIP. A molecularly imprinted SPE (MISPE) procedure was developed which had a recovery of 84-89%, interday variation of less than 3.4% and intraday variation of less than 2.8%. The MISPE procedure was compared with a routine liquid-liquid extraction (LLE) procedure used for the HPLC determination of LTG in serum from patients. The data indicated that the MIP synthesized showed both good selectivity and high affinity for LTG and could be used for the extraction of the drug from serum samples or as the receptor layer for an LTG selective biosensor.     

Tailor‐made hybrid nanostructure of poly(ethyl acrylate)/clay by surface‐initiated atom transfer radical polymerization

Hybrid nanoarchitecture of tailor‐made Poly(ethyl acrylate)/clay was prepared by surface‐initiated atom transfer radical polymerization (SI‐ATRP), by tethering ATRP initiator on active hydroxyl group, present in surface as well as in the organic modifier of the clay used. Extensive exfoliation was facilitated by using these initiator modified clay platelets. Poly(ethyl acrylate) chains with controlled polymerization and narrow polydispersities were forced to be grown from within the clay gallery (intergallery) as well as from the outer surface (extragallery) of the clay platelets. The polymer chains attached onto clay surfaces might have the potential to provide the composites with enhanced compatibility in blends with common polymers. Attachment of the initiator on clay platelets was confirmed by Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), elemental analysis, Wide‐angle X‐ray diffraction (WAXD), and microscopic analysis. Finally, end group analysis (by Matrix‐Assisted Laser Desorption Ionization Mass Spectrometry, and chain extension experiment) of the cleaved polymer and morphological study (by WAXD, Transmission Electron Microscopy), performed on the polymer grafted clays examined the effect of grafting on the efficiency of polymerization and the degree of dispersion of clay tactoids in polymer. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5014–5027, 2008     

Determination of donepezil in serum samples using molecularly imprinted polymer nanoparticles followed by high‐performance liquid chromatography with ultraviolet detection

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.     

Preparation of block copolymer by atom transfer radical seeded emulsion polymerization

Poly(i-butyl methacrylate)-polystyrene block copolymer was successfully prepared in an aqueous medium by two-step atom transfer radical polymerization (ATRP), mini-emulsion- and seeded-ATRP, in which ethyl 2-bromoisobutyrate/CuBr/4,4-dinonyl-2,2-dipyridyl initiator system was used. The block copolymer had narrow molecular weight distribution (Mw/Mn=1.1) and the number-average molecular weight measured by gel permeation chromatography agreed with the calculated value.Part CCXLVIII of the series Studies on Suspension and Emulsion     

Surface functionalization of multi‐walled carbon nanotubes through surface‐initiated atom transfer radical polymerization of glycidyl methacrylate

Herein, we report the fabrication of glycidyl methacrylate (GMA) polymeric conjugates of shortened multi‐walled carbon nanotubes (sMWCNT). The synthesis method involves the attachment of initiator on the surface of nanotubes followed by surface initiated atom transfer radical polymerization (SI‐ATRP) of GMA from the initiator‐bound sMWCNT surface. This is achieved by the procedure consisting of three important steps: introduction of amino groups onto the sMWCNT and attachment of polymerization initiator, 2‐bromo‐2‐methylpropinonyl bromide, and polymerization of GMA. The structure and properties of the resultant polymeric conjugates were characterized by Fourier transform infrared (FT‐IR) spectroscopy, Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM) and SEM. The FT‐IR analysis of polymeric conjugates shows infrared (IR) peaks characteristic of GMA. AFM, TEM and SEM images clearly show the formation of poly(glycidyl methacrylate)(PGMA) polymer on sMWCNT surface. Copyright © 2009 John Wiley & Sons, Ltd.