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Molecularly imprinted polymers (MIPs) have now become one of the most remarkable materials in the field of molecular recognition. Although many efforts have been made to study the process and mechanism of molecular imprinting, it has not been possible to monitor the interactions between the template and the growing polymer chains under real-time experimental conditions. The behavior of the template-monomer complex during the whole polymerization process has remained largely unknown. In this work, we introduce a fluorescence technique that allows monitoring of the template-functional monomer complex during an actual imprinting process, as well as the real-time signaling of template binding and dissociation from the imprinted polymer. For the first proof-of-principle, we select Alizarin Red S (ARS) and 4-vinylphenylboronic acid as the template and functional monomer, respectively, to synthesize MIP particles via precipitation polymerization. As the formation of the template-functional monomer complex leads to strong fluorescence emission, it allows the status of the template binding to be monitored throughout the whole reaction process in real time. Using the same fluorescence technique, the kinetics of template binding and dissociation can be studied directly without particle separation. The hydrophilic MIP particles can be used as a scavenger to remove ARS from water. In addition, the MIP particles can be used as a recyclable sensor to detect Cu ions. As the Cu ion forms a stable complex with ARS, it causes ARS to dissociate from the MIP nanoparticles, leading to effective fluorescence quenching. The non-separation analytical method based on fluorescence measurement provides a convenient means to study molecular imprinting reactions and the kinetics of molecular recognition using imprinted polymers. The recyclable nanoparticle sensor allows toxic Cu ions to be detected directly in water in the range of 0.1-100 μM with a recovery of 84-95%.

Devising a robust, efficient and cost effective hemoglobin (Hb) purification strategy is one of the key challenges in the development of Hb-based blood substitutes. The aim of this study was to use molecularly imprinted polymers (MIPs) as a novel and efficient chromatographic resin to selectively recognize and purify different Hb variants. The results showed that the Hb-MIP material developed here could selectively recognize and purify various Hb directly from either crude E. coli extracts or human body fluids, such as blood plasma and cerebrospinal fluid (CSF), in one-step. The dynamic binding capacity at 10% breakthrough was around 7.4 mg mL -1 resin for adult Hb (HbA) and fetal Hb (HbF). This chromatographic material also allowed identification of changes related to amino acid substitutions on the Hb protein surface. For instance, when an additional lysine residue was introduced, the HbA αY42K mutant eluted later in an Hb-MIP column than wildtype HbA. Additional negative charges on the protein surface, such as aspartate, mitigated the interaction between the protein and imprinted polymers, and therefore an αA19D-αA12D HbF mutant eluted earlier, at -2.7 column volumes compared to wildtype HbF., (Copyright © 2019 Elsevier B.V. All rights reserved.)

For the last decades, molecular imprinting is developing intensively, especially in the case of the application of new imprinting techniques. In this work, for the first time, a Pickering emulsion polymerization was used to synthesize the S-naproxen-imprinted polymer spheres following a noncovalent protocol. To enhance the knowledge about imprinting process using mentioned technique, thorough analysis of the synthesis process was performed. Optimization of polymerization conditions included the selection of functional monomer, cross-linking agent, type of porogen, surfactant, and the choice of appropriate amount of the template and porogen. Prepared materials were characterized using scanning electron microscopy and nitrogen adsorption. To study the binding properties, the sorption studies, including adsorption isotherms and competitive binding, were performed. Investigation of the effect of the functional monomer on the selective recognition of S-naproxen showed that the interactions between the template molecule and 4-vinylpyridine resulted in the best recognizing ability. Moreover, the synthesis with application of ethylene glycol dimethacrylae as a cross-linker, toluene as a porogen, and Tween 20 as an additional emulsion stabilizer gave the most desired result. The optimal ratio of the porogen to monomers mixture was 0.1, due to the fact that the increase of the porogen volume resulted in the significant increase of nonspecific uptake. In addition, the tenfold molar excess of functional monomer relative to the template turned out to be optimal. Subsequent binding studies demonstrated that the material synthesized using optimized polymerization conditions consists of imprinted sites that are sensitive for the S-naproxen., (Copyright © 2017 John Wiley & Sons, Ltd.)

Molecular imprinting technique is an attractive strategy to prepare materials for target recognition and rapid separation. In this work, a new type of diclofenac (DFC)-imprinted polymer beads was synthesized by Pickering emulsion polymerization using 2-(dimethylamino)ethyl methacrylate as the functional monomer. The selectivity and capacity of the molecularly imprinted polymers (MIPs) were investigated in aqueous solution. Equilibrium binding results show that the MIPs have a high selectivity to bind DFC in a wide range of pH values. Moreover, in liquid chromatography experiment, the imprinted polymer beads were packed into column to investigate the binding selectivity under nonequilibrium conditions. The retention time of DFC on the MIP column is significantly longer than its structural analogues. Also, retention of DFC on the MIP column was significantly longer than on the nonimprinted polymer column under aqueous condition. As the new MIP beads can be used to achieve direct separation of DFC from water, the synthetic method and the affinity beads developed in this work opened new possibilities for removing toxic chemicals from environmental and drinking water., (Copyright © 2017 John Wiley & Sons, Ltd.)

Janus particles, which have two or more distinct physical surfaces, provide a number of potential applications in many fields. However, it is difficult to selectively load chemical or biological components onto the Janus particles. Here, the approach utilizing molecular imprinting and Pickering emulsion technologies for the synthesis of molecularly imprinted polymer (MIP)-based Janus particles (which showed high affinity to the targets) is described stepwise. As self-propelled microengines possessing specific molecular recognition ability, Janus molecularly imprinted polymer particles show high potential for specific and well-controlled drug delivery.

Molecular imprinting is a very powerful synthetic method for preparation of robust materials with pre-designed molecular selectivity. Molecularly imprinted polymers (MIPs) are attractive substitutes for antibodies in many analytical and bioanalytical applications, e.g. for development of biosensors and for drug assays. In addition to selective molecular binding, new functions are being added to MIPs to make the synthetic materials responsive to different environmental conditions, making it possible to modulate the binding and release of different molecular targets and to simplify affinity separation. Introduction of signal-transduction functionality into MIPs also brings in new, more easily operated chemical sensors for detection and quantification of important analytical targets.

One challenging task in building (bio)chemical sensors is the efficient and stable immobilization of receptor on a suitable transducer. Herein, we report a method for covalent immobilization of molecularly imprinted core-shell nanoparticles for construction of robust chemical sensors. The imprinted nanoparticles with a core-shell structure have selective molecular binding sites in the core and multiple amino groups in the shell. The model Au transducer surface is first functionalized with a self-assembled monolayer of 11-mercaptoundecanoic acid. The 11-mercaptoundecanoic acid is activated by treatment with carbodiimide/N-hydroxysuccinimide and then reacted with the core-shell nanoparticles to form amide bonds. We have characterized the process by studying the treated surfaces after each preparation step using atomic force microscopy, scanning electron microscopy, fluorescence microscopy, contact angle measurements and X-ray photoelectron spectroscopy. The microscopy results show the successful immobilization of the imprinted nanoparticles on the surface. The photoelectron spectroscopy results further confirm the success of each functionalization step. Further, the amino groups on the MIP surface were activated by electrostatically adsorbing negatively charged Au colloids. The functionalized surface was shown to be active for surface enhanced Raman scattering detection of propranolol. The particle immobilization and surface enhanced Raman scattering approach described here has a general applicability for constructing chemical sensors in different formats., (Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.)

We report a simple and versatile method to covalently immobilize molecularly imprinted polymer (MIP) nanoparticles on a Raman active substrate (Klarite) using a disulfide-derivatized perfluorophenylazide (PFPA-disulfide). Gold-coated Klarite was functionalized with PFPA-disulfide via a gold-sulfur bond. Upon light radiation, the available azido groups were converted to highly reactive singlet perfluorophenyl nitrene that undergoes a CH insertion reaction and form covalent bonds with the MIP nanoparticles. The resulting surfaces were characterized using scanning electron microscopy and surface enhanced Raman spectroscopy to study the morphology and template affinity of the surfaces, respectively. The Raman measurements clearly show a dose-responsive signal when propranolol binds to the MIP surface. Because the MIP particles were covalently attached to the Raman active substrate, the sensing surface was stable and could be reused after regeneration in acetic acid solution. The MIP-based Raman sensor was used successfully to detect propranolol in urine samples (7.7 × 10(-4) M). Our results show that the high selectivity of MIPs and the fingerprint Raman identification can be integrated into a compact sensing unit using high-efficiency photoconjugation. Thus, the method proposed is reliable, efficient and fast for fabricating label-free chemical sensors.

Molecularly imprinted polymers (MIPs) can be used as antibody mimics to develop robust chemical sensors. One challenging problem in using MIPs for sensor development is the lack of reliable conjugation chemistry that allows MIPs to be fixed on transducer surface. In this work, we study the use of epoxy silane to immobilize MIP nanoparticles on model transducer surfaces without impairing the function of the immobilized nanoparticles. The MIP nanoparticles with a core-shell structure have selective molecular binding sites in the core and multiple amino groups in the shell. The model transducer surface is functionalized with a self-assembled monolayer of epoxy silane, which reacts with the core-shell MIP particles to enable straightforward immobilization. The whole process is characterized by studying the treated surfaces after each preparation step using atomic force microscopy, scanning electron microscopy, fluorescence microscopy, contact angle measurements and X-ray photoelectron spectroscopy. The microscopy results show that the MIP particles are immobilized uniformly on surface. The photoelectron spectroscopy results further confirm the action of each functionalization step. The molecular selectivity of the MIP-functionalized surface is verified by radioligand binding analysis. The particle immobilization approach described here has a general applicability for constructing selective chemical sensors in different formats., (Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.)

Molecularly imprinted polymers (MIPs) have a predesigned molecular recognition capability that can be used to build robust chemical sensors. MIP-based chemical sensors allow label-free detection and are particularly interesting due to their simple operation. In this work we report the use of thiol-terminated MIP microspheres to construct surfaces for detection of a model organic analyte, nicotine, by surface enhanced Raman scattering (SERS). The nicotine-imprinted microspheres are synthesized by RAFT precipitation polymerization and converted into thiol-terminated microspheres through aminolysis. The thiol groups on the MIP surface allow the microspheres to be immobilized on a gold-coated substrate. Three different strategies are investigated to achieve surface enhanced Raman scattering in the vicinity of the imprinted sites: (1) direct sputtering of gold nanoparticles, (2) immobilization of gold colloids through the MIP's thiol groups, and (3) trapping of the MIP microspheres in a patterned SERS substrate. For the first time we show that large MIP microspheres can be turned into selective SERS surfaces through the three different approaches of assembly. The MIP-based sensing surfaces are used to detect nicotine to demonstrate the proof of concept. As synthesis and surface functionalization of MIP microspheres and nanoparticles are well established, the methods reported in this work are handy and efficient for constructing label-free chemical sensors, in particular for those based on SERS detection.

This chapter introduces the basic principle and the synthetic aspects of molecular imprinting. First, the use of a molecular template to guide the location of functional groups inside molecularly imprinted cavities is explained. Three different mechanisms that ensure a molecular template associates with functional monomers or the imprinted polymers, that is, through reversible covalent, noncovalent, and sacrificial covalent bonds, are then described. The main focus is put on noncovalent molecular imprinting using free radical polymerization. The merits of using classical radical polymerization and more sophisticated, controlled radical polymerization are analyzed. After these synthetic chemistry aspects, the chapter continues to discuss the different polymerization processes that can be used to prepare well-defined polymer monoliths, microspheres, and nanoparticles. New top-down processing techniques that produce micro- and nanopatterns of imprinted polymers are also reviewed. The chapter finishes with a brief introduction to using imprinted polymers as building blocks to construct new functional materials and devices, which we consider as one important direction for further development.

In this paper, we present a simple and rapid method for monitoring bisphenol A (BPA) and its biodegradation in environmental water using a fluorescent molecularly imprinted polymer chemosensor (fMIPcs). A fluorescent molecularly imprinted polymer (fMIP) was first synthesized by precipitation polymerization method using BPA as template, dansyl methacrylate as functional monomer. Then a fMIPcs was constructed by combining the fMIP with a fluorescent microplate reader. The fMIPcs displayed selective, concentration-dependent fluorescence quenching in response to BPA in water even in the existence of interferences, thereby allowing reliable high through-put quantification of BPA via simple fluorescence measurements. The fMIPcs was able to directly quantify BPA (from 10 to 2000 μg L(-1)) in different environmental water samples (distilled water, distilled water containing heavy metals and humic acid, tap water, and river water) with high accuracy, and to monitor BPA biodegradation in real-time. Using the fMIPcs, it was possible to achieve fast analytical results with lower limit of detection for BPA (3 μg L(-1)) from smaller sample volume (250 μL), which are superior to many relevant methods reported in the literature. Moreover, BPA levels and biodegradation rates measured by fMIPcs are comparable to the instrument-based method (HPLC). The fMIPcs developed in this work offers a new solution for simple, rapid, accurate and high through-put BPA quantification, and makes it possible to monitor BPA biodegradation in real time., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

We follow template-binding induced aggregation of nanoparticles enantioselectively imprinted against (S)-propranolol, and the non-imprinted ones, using photon correlation spectroscopy (dynamic light scattering). The method requires no separation steps. We have characterized binding of (R,S)-propranolol to the imprinted polymers and determined the degree of non-specificity by comparing the specific binding with the results obtained using non-imprinted nanoparticles. Using (S)-propranolol as a template for binding to (S)-imprinted nanoparticle, and (R)-propranolol as a non-specific control, we have determined range of concentrations where chiral recognition can be observed. By studying aggregation induced by three analytes related to propranolol, atenolol, betaxolol, and 1-amino-3-(naphthalen-1-yloxy)propan-2-ol, we were able to determine which parts of the template are involved in the specific binding, discuss several details of specific adsorption, and the structure of the imprinted site., (Copyright © 2014 John Wiley & Sons, Ltd.)

The tendency of bacteria to assemble at oil-water interfaces can be utilized to create microbial recognition sites on the surface of polymer beads. In this work, two different groups of bacteria were first treated with acryloyl-functionalized chitosan and then used to stabilize an oil-in-water emulsion composed of cross-linking monomers that were dispersed in aqueous buffer. Polymerization of the oil phase followed by removal of the bacterial template resulted in well-defined polymer beads bearing bacterial imprints. Chemical passivation of chitosan and cell displacement assays indicate that the bacterial recognition on the polymer beads was dependent on the nature of the pre-polymer and the target bacteria. The functional materials for microbial recognition show great potential for constructing cell-cell communication networks, biosensors, and new platforms for testing antibiotic drugs., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this work, a new macroporous molecularly imprinted cryogel (MIP composite cryogel) was synthesized by glutaraldehyde cross-linking reaction of poly(vinyl alcohol) (PVA) particles and amino-modified molecularly imprinted core-shell nanoparticles. The MIP core-shell nanoparticles were prepared using propranolol as a template by one-pot precipitation polymerization with sequential monomer addition. The characteristics of the MIP composite cryogel were studied by scanning electron microscopy (SEM) and texture analyzer. The macroporous structure of the composite (with the pore size varying from a few micrometers to 100 μm) enabled high mass transfer of particulate-containing fluids. In a solid phase extraction (SPE) process, the efficiency and selectivity of the MIP composite cryogel were investigated, where the cryogel was used as an affinity matrix to remove propranolol from aqueous solution as well as from complex plasma sample without prior protein precipitation. The MIP composite cryogel maintained high selectivity and stability and could be used repeatedly after regeneration., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Molecularly imprinted polymers (MIP) for histamine using methacrylic acid were developed and recognition mechanisms were thoroughly characterized for the first time in this study. The binding affinity of imprinted polymer with structurally related compounds was studied in organic and aqueous media, at various conditions. In organic media, MIP was found to bind histamine two and six times more than ranitidine and fluoxetine, respectively, whereas higher selectivity was observed in the case of dimentidene or disodium cromoglycate. The specific binding sites of MIP recognized histamine over L-histidine in aqueous conditions, while higher affinity for histamine compared to ranitidine, disodium cromoglycate, putrescine and to a putrescine analogue was observed. A combination of NMR and UV spectroscopy analyses for investigation of imprinting and recognition properties revealed that strong specific interactions between the functional monomer and histamine in the prepolymerization and in the aqueous solutions were probably responsible for histamine recognition. The preparation of histamine MIPs and elucidation of imprinting and recognition mechanism may serve as useful insight for future application of MIPs.

Molecularly imprinted nanomaterials are gaining substantial importance. As a simple and efficient synthetic method, precipitation polymerization has been used to prepare uniform molecularly imprinted microspheres for numerous template compounds. Despite of its general applicability, the difficulty of obtaining uniform particles for some difficult templates by precipitation polymerization has been reported. In this work, we attempted to produce uniform atrazine-imprinted nanoparticles using propranolol as an auxiliary template under standard precipitation polymerization condition. When propranolol was added in the prepolymerization mixture for atrazine imprinting, it displayed a significant effect on particle size and size distribution of atrazine-imprinted polymers. The molecular binding characteristics of the molecularly imprinted polymer (MIP) nanoparticles were found to be dependent on the relative ratios of the two templates. Under an optimal template propranolol-atrazine ratio of 1:3 mol/mol, very uniform imprinted nanoparticles (d(H)  = 106 nm) with a polydispersity index of 0.07 were obtained. The loading of the auxiliary template (propranolol) could be reduced to as low as 5% without sacrificing the uniformity of the MIP nanoparticles. The uniform MIP nanoparticles could be easily encapsulated into polyethylene terephthalate nanofibers using a simple electrospinning technique. The composite nanofibers containing the MIP nanoparticles maintained specific molecular binding capability for both atrazine and propranolol., (Copyright © 2012 John Wiley & Sons, Ltd.)

Molecular imprinting technology allows synthesis of polymers with specific recognition ability towards target pollutants, which show potential to selectively remove Highly Toxic Organic Pollutants (HTOPs) in the presence of common organic matrices that are thousands of times more abundant than the targets. This feature article summarizes the current development of molecular imprinting for removing HTOPs from polluted water, with a special emphasis on the application of molecularly imprinted polymers to improve the efficiency of photocatalytic and biological degradation of HTOPs in wastewater., (This journal is © The Royal Society of Chemistry 2012)

Molecularly imprinted polymer microspheres were synthesized by Pickering emulsion polymerization. Fluorescence spectroscopic investigations provided insights into the template recognition in water., (This journal is © The Royal Society of Chemistry 2011)

Molecular imprinting is a powerful synthetic technique for generating template-defined binding sites in cross-linked polymers. One scientific challenge in molecular imprinting research is to understand the intermolecular interactions leading to molecular complexation and the process of binding site formation during polymerization. In this work, we present a novel method for studying the molecular imprinting process in precipitation polymerization systems. This method employs solution (1) H NMR and dynamic light scattering (DLS) to investigate the association of template molecules with colloidal particles and the dynamic process of particle growth. Under precipitation polymerization conditions, the colloidal particles formed did not interfere with NMR signals from the soluble components, allowing unreacted monomers and free template to be easily quantified. To examine the process of particle nucleation and growth, DLS was used to measure the hydrodynamic particle size at different reaction times. To corroborate the interpretation of the NMR and DLS results, imprinted nanoparticles were collected at different reaction times and their binding characteristics were evaluated using radioligand-binding analysis. Our experimental results provide new insights into the molecular imprinting process that will be useful in the development of new imprinted nanoparticles., (Copyright © 2010 John Wiley & Sons, Ltd.)

Simultaneous imprinting on two length scales (nanometer and ångström) delivers highly specific molecular recognition sites in polymer patterns.

Due to the difficulty of monitoring trace levels of cyproheptadine (CYP) residues in complicated biological matrices, specific adsorption materials for the preconcentration and clean-up of CYP are indispensable. In this work, CYP was extracted from urine using dummy molecularly imprinted SPE (DMISPE) to avoid leakage of the imprinting molecules during the desorption phase. For synthesis of DMISPE, azatadine (AZA) was employed as the dummy template, methacrylic acid (MAA) as the monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, 2,2'-azobis(2-methylpropionitrile) (AIBN) as the initiator, and dichloromethane as the porogen solvent. An LC-MS/MS method was used to analyze CYP. Two MRM (multiple reaction monitoring) transitions for each analyte were monitored using diphenylpyraline hydrochloride (DPP.HCl), which was used as an internal standard. The advantages of DMISPE include obtaining less complex chromatograms and reducing ion suppression in ESI. The process efficiencies for DMISPE and SPE were 80% and 12%, respectively. In addition, the demonstrated reusability of the DMISPE cartridges is an advantage compared with single-use SPE cartridges or immunoaffinity materials.

A single bi-functional monomer, N,O-bismethacryloyl ethanolamine (NOBE), was used in precipitation polymerization system to synthesize molecularly imprinted polymer (MIP) microspheres. Highly specific binding sites were obtained for N-terminal protected neuropeptides, Boc-Leu-enkephalin and Pyr-Leu-enkephalin. The use of NOBE allowed binding sites to be formed in polymer microspheres that are able to recognize target peptides through the consensus C-terminal sequence. The interesting molecular binding results suggest a new approach for peptide analysis combining in situ chemical modification with MIP recognition under non-aqueous conditions.

Molecular imprinting is one of the most efficient methods for preparing synthetic receptors that possess user defined recognition properties. Despite general success of non-covalent imprinting for a large variety of templates, some groups of compounds remain difficult to tackle due to their structural complexity. In this study we investigate preparation of molecularly imprinted polymers that can bind sulfonamide compounds, which represent important drug candidates. Compared to the biological system that utilizes metal coordinated interaction, the imprinted polymer provided pronounced selectivity when hydrogen bond interaction was employed in an organic solvent. Computer simulation of the interaction between the sulfonamide template and functional monomers pointed out that although methacrylic acid had strong interaction energy with the template, it also possessed high non-specific interaction with the solvent molecules of tetrahydrofuran as well as being prone to self-complexation. On the other hand, 1-vinyl-imidazole was suitable for imprinting sulfonamides as it did not cross-react with the solvent molecules or engage in self-complexation structures.

A simple electrospinning method is developed to introduce signal transduction ability into molecularly imprinted nanofibers.

The objective of this work was to use monomers from cashew ( Anacardium occidentale L.) nut shells to develop molecularly imprinted polymers. Cashew nut shell liquid (CNSL) is a cheap and renewable agro byproduct consisting of versatile monomers. Solvent-extracted CNSL contains over 80% anacardic acid (AnAc) with more than 90% degree of unsaturation in its C 15 side chain. From AnAc monomer, anacardanyl acrylate (AnAcr) and anacardanyl methacrylate (AnMcr) monomers were synthesized and their chemical structures were characterized by Fourier transform IR and NMR. Different imprinted bulk polymers based on AnAc, AnAcr, and AnMcr functional monomers have been prepared. In the present study, each functional monomer was separately copolymerized in toluene with ethylene glycol dimethacrylate and divinylbenzene as cross-linkers, using racemic propranolol as a model template. While the AnAc based polymer revealed a meager rebinding ability, the imprinted polymers made from AnAcr and AnMcr displayed highly specific propranolol binding. At a polymer concentration of 2 mg/mL, AnAcr and AnMcr based imprinted polymers were able to bind over 50% of trace propranolol (initial concentration 1.2 nM). Under the same condition propranolol uptake by the two nonimprinted control polymers was less than 20%. Chiral recognition properties of these polymers were further confirmed using tritium-labeled (S)-propranolol as a tracer in displacement experiments, suggesting that the apparent affinity of the imprinted chiral sites for the correct enantiomer is at least 10 times that of the mismatched (R)-propranolol. Moreover, cross reactivity studies of these polymers showed that the (S)-imprinted sites have higher cross-reactivity toward (R, S)-metoprolol than (R)-propranolol and (R)-timolol.

Combining straightforward molecular imprinting with orthogonal click chemistry and accessible fluorescent dyes, a modular approach has been developed to assemble turn-on optical sensors based on fluorescence resonance energy transfer in molecularly imprinted nanoparticles. [ABSTRACT FROM AUTHOR]

The tendency of bacteria to assemble at oil-water interfaces can be utilized to create microbial recognition sites on the surface of polymer beads. In this work, two different groups of bacteria were first treated with acryloyl-functionalized chitosan and then used to stabilize an oil-in-water emulsion composed of cross-linking monomers that were dispersed in aqueous buffer. Polymerization of the oil phase followed by removal of the bacterial template resulted in well-defined polymer beads bearing bacterial imprints. Chemical passivation of chitosan and cell displacement assays indicate that the bacterial recognition on the polymer beads was dependent on the nature of the pre-polymer and the target bacteria. The functional materials for microbial recognition show great potential for constructing cell-cell communication networks, biosensors, and new platforms for testing antibiotic drugs. [ABSTRACT FROM AUTHOR]

Uniform molecularly imprinted polymer beads were synthesized by precipitation polymerization for separation of triazine herbicides. A series of imprinted polymers were prepared using ametryn as template and divinylbenzene as crosslinking monomer, in combination with three different functional monomers under different solvent conditions. Under optimized reaction conditions, we obtained uniform molecularly imprinted polymer microspheres that display favorable molecular binding selectivity for triazine herbicides. The imprinted polymer beads synthesized using methacrylic acid as functional monomer in a mixture of methyl ethyl ketone and heptane showed the best results in terms of particle size distribution and molecular selectivity. Compared with nonimprinted polymer microspheres, the imprinted microspheres displayed significantly higher binding for a group of triazine herbicides including atrazine, simazine, propazine, ametryn, prometryn, and terbutryn. For the first time, precipitation polymerization has been used to produce highly uniform imprinted microspheres suitable for affinity separation of triazine herbicides. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 [ABSTRACT FROM AUTHOR]

Nanoimprint lithography (NIL) can generate well defined nanostructures with high efficiency and at very low cost. Molecular imprinting (MIP) is a 'bottom-up' technique creating a polymer layer exhibiting structures with a molecular selectivity. Such polymer structures may be employed as molecular recognition sites for sensing applications. In this work, the authors combine NIL with MIP and they are able to obtain micro- and nanopatterns of polymer with features down to 100 nm that show high molecular selectivity. [ABSTRACT FROM AUTHOR]

Abstract: Molecularly imprinted nanoparticles were encapsulated into polymer nanofibers with a simple electrospinning method. The composite nanofibers form non-woven mats that can be used as affinity membrane to greatly simplify solid phase extraction of drug residues in analytical samples. Upward 100% of propranolol-imprinted nanoparticles can be easily encapsulated into poly(ethylene terephthalate) nanofibers, ensuring the composite materials to have a high specific binding capacity. As confirmed by radioligand binding analysis, the specific binding sites in the composite materials remain easily accessible and are chiral-selective. Using the new composite nanofiber mats as solid phase extraction materials, trace amount of propranolol (1ngmL−1) in tap water can be easily detected after a simple sample preparation. As validated in this study, there is no problem of template leakage from the composite nanofibers. Without the solid phase extraction, the existence of propranolol residues in water cannot be confirmed with even tandem HPLC–MS/MS analysis. [Copyright &y& Elsevier]

Glycoproteins represent a group of important biomarkers for cancer and other life-threatening diseases. Selective detection of specific glycoproteins is an important step for early diagnosis. Traditional glycoprotein assays are mostly based on lectins, antibodies, and enzymes, biochemical reagents that are costly and require special cold chain storage and distribution. To address the shortcomings of the existing glycoprotein assays, we propose a new approach using protein-imprinted nanoparticles to replace the traditional lectins and antibodies. Protein-imprinted binding sites were created on the surface of silica nanoparticles by copolymerization of dopamine and aminophenylboronic acid. The imprinted nanoparticles were systematically characterized by dynamic light scattering, scanning and transmission electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and elemental analysis. A boronic acid-modified fluorescent probe was used to detect the target glycoprotein captured by the imprinted nanoparticles. Using horseradish peroxidase as a model glycoprotein, we demonstrated that the proposed method can be applied to detect target protein containing multiple glycosylation sites. Because of their outstanding stability and low cost, imprinted nanoparticles and synthetic probes are attractive replacements of traditional biochemical reagents to develop simpler, faster, and more cost-effective analytical methods for glycoproteins. [ABSTRACT FROM AUTHOR]

Because of their predetermined selectivity, molecularlyimprintedpolymers (MIPs) have been extensively investigated to offer efficientseparation of organic pollutants for water analysis and purification.In this review, we first describe the current development of water-compatibleMIPs, and the physical encapsulation and chemical immobilization ofMIP particles for practical applications related to water analysisand purification. We summarize the challenges in understanding themechanisms in molecular imprinting, with a special emphasis on theuse of nuclear magnetic resonance (NMR), dynamic light scattering(DLS), and synchronous fluorescence spectroscopy to gain theoreticalinsights into the molecular imprinting process. The highlighted syntheticmethods and the mechanistic investigations discussed in this reviewshould facilitate the identification of the most crucial factors affectingthe applications of MIPs for clean water. [ABSTRACT FROM AUTHOR]

In traditional molecular imprinting reactions, the initial radicals generated by thermo- or photo-decomposition are randomly distributed in the reaction mixture. Because a noticeable portion of the initial radicals is able to cause self-polymerization of the crosslinking monomer, a significant part of the polymer product does not contain successfully imprinted molecular recognition sites. To solve this problem, we designed a molecular imprinting method using functionalized radical initiator to replace the conventional combination of initiator and functional monomer. Since the active radicals in the reaction mixture carry a template-binding moiety, the actual radical polymerization becomes more likely to take place nearby the molecular template. As a result, the efficiency of molecular imprinting can be improved. In this work, we report the use of amidine-functionalized initiator to synthesize molecularly imprinted polymers (MIPs) for selective recognition of methotrexate, a cytostatic drug used for cancer therapy. As glutamic acid represents a substructure of methotrexate, we select to use N -terminal protected glutamic acid as template to synthesize the MIPs. An initiator, 2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH) is used to provide strong interaction with the molecular template. Two MIPs synthesized using glutamic acid derivatives as templates display specific binding to the fluorescent amino acid derivative Fmoc-Glu. When the molecular binding is tested against methotrexate, the MIP particles also exhibit specific binding for the cytostatic drug. Using cationic functional initiator to target carboxyl epitope of molecular target, this work provides an additional example of molecular imprinting based on functionalized radical initiators. [Display omitted] • Synthesis of molecularly imprinted polymers using amidine-functionalized initiator. • Carboxylic acid-imprinted polymers exhibit specific binding to targeted cancer drug. • Use of functional initiator simplifies reaction systems for molecular imprinting. [ABSTRACT FROM AUTHOR]

In order to improve the selectivity in photocatalytic process, molecularly imprinted photocatalysts containing a low loading of TiO 2 (from 6.6 to 16.6% of total mass) were prepared for photocatalytic degradation of an organic pollutant, diclofenac (DIC). The photocatalytic component TiO 2 (P25), with and without being doped with Cu 2 O, was embedded in diclofenac-imprinted polymers. The molecularly imprinted polymers (MIPs) and the composite photocatalysts exhibited a superior specific target recognition for selective degradation of DIC over non-target reference molecules, fluoxetine (FLU) and paracetamol (PARA). In contrast to the non-selective commercial sample of TiO 2 , the average value of selectivity of the imprinted catalysts for photocatalytic degradation of DIC was estimated to be 2.8, which suggests that the specific binding sites created by the molecular imprinting are essential for gaining high catalytic selectivity and efficiency. After 6 cycles of testing under UV-light, the imprinted catalysts maintained almost the same efficiency for photo degradation of DIC. In addition, the morphology and the structure of the imprinted catalysts remained after repeated uses. The results suggest that it is feasible to use MIPs to control the selectivity of photocatalytic degradation of organic pollutants. [ABSTRACT FROM AUTHOR]

Purification of haemoglobin (Hb) has been studied for many years due to its ability to act as an oxygen carrier and its possible use in urgent clinical treatment. In this study, different types of chromatography columns were developed for Hb purification. Two of them showed satisfactory results as affinity chromatography columns and were thus studied more extensively. The affinity adsorbents were prepared by molecular imprinting techniques. In the first case, Pickering emulsion polymerization was used to prepare affinity adsorbents based on molecular imprinting technology. The imprinted particles were immobilized via covalent bonds on the surface of cryogel, a macroporous hydrogel produced by free radical polymerization under sub-zero temperature. In the second case, the affinity sites for Hb were formed directly on an acrylamide cryogel by protein imprinting during the cryogelation. The dynamic binding capacity of the composite cryogel with the immobilized particles and the directly imprinted acrylamide cryogel was found to be 5.2 mg/g and 3.6 mg/g, respectively. The affinity columns showed high selectivity towards Hb in spite of the presence of serum albumin as well as other interfering substances in non-clarified cell homogenates. The maximum capacity in batch mode, the fluid flow and other physical and chemical properties of these columns were investigated. [ABSTRACT FROM AUTHOR]

Manipulation of specific binding and recycling of materials are two important aspects for practical applications of molecularly imprinted polymers. In this work, we developed a new approach to control the dynamic assembly of molecularly imprinted nanoparticles by surface functionalization. Molecularly imprinted polymer nanoparticles with a well-controlled core-shell structure were synthesized using precipitation polymerization. The specific binding sites were created in the core during the first step imprinting reaction. In the second polymerization step, epoxide groups were introduced into the particle shell to act as an intermediate linker to immobilize phenylboronic acids, as well as to introduce cis -diol structures on surface. The imprinted polymer nanoparticles modified with boronic acid and cis -diol structures maintained high molecular binding specificity, and the nanoparticles could be induced to form dynamic particle aggregation that responded to pH variation and chemical stimuli. The possibility of modulating molecular binding and nanoparticle assembly in a mutually independent fashion can be exploited in a number of applications where repeated use of precious nanoparticles is needed. [ABSTRACT FROM AUTHOR]

Highlights: [•] Fast photoconjugation of nanoparticles on surface. [•] Non-destructive feature guarantees intact function of nanoparticles. [•] Direct contact between nano-objects allows efficient photon and electron transfer. [•] Possibility of generating patterned nanoparticle assemblies on surface. [•] Open new opportunities for assembling chemical sensors. [Copyright &y& Elsevier]

Abstract: Molecularly imprinted polymers (MIPs) are being increasingly used as selective adsorbents in different analytical applications. To satisfy the different application purposes, MIPs with well controlled physical forms in different size ranges are highly desirable. For examples, MIP nanoparticles are very suitable to be used to develop binding assays and for microfluidic separations, whereas MIP beads with diameter of 1.5–3μm can be more appropriate to use in new analytical liquid chromatography systems. Previous studies have demonstrated that imprinted microspheres and nanoparticles can be synthesized using a simple precipitation polymerization method. Despite that the synthetic method is straightforward, the final particle size obtained has been difficult to adjust for a given template. In this work, we initiated to study new synthetic conditions to obtain MIP beads with controllable size in the nano- to micro-meter range, using racemic propranolol as a model template. Varying the composition of the cross-linking monomer allowed the particle size of the MIP beads to be altered in the range of 130nm to 2.4μm, whereas the favorable binding property of the imprinted beads remained intact. The chiral recognition sites were further characterized with equilibrium binding analysis using tritium-labeled (S)-propranolol as a tracer. In general, the imprinted sites displayed a high chiral selectivity: the apparent affinity of the (S)-imprinted sites for (S)-propranolol was 20 times that of for (R)-propranolol. Compared to previously reported irregular particles, the chiral selectivity of competitive radioligand binding assays developed from the present imprinted beads has been increased by six to seven folds in an optimized aqueous solvent. [Copyright &y& Elsevier]

Abstract: The use of molecularly imprinted polymers (MIPs) in chemical and bioanalytical applications has been gaining in interest in recent years. Compared to their biological receptor counterparts, MIPs are easy to prepare, have long shelf stability and can be used under a variety of harsh conditions. The majority of MIPs currently used are produced by traditional free radical polymerization. One drawback with the use of standard free radical initiators is that little control can be exerted over the chemical processes that form the final imprinted cavities. In this study we set out to investigate the application of controlled (living) free radical polymerization to the preparation of MIPs. This was exemplified by the synthesis of cholesterol-imprinted bulk polymers by nitroxide-mediated polymerization (NMP). A sacrificial covalent bond was employed to maintain imprinting fidelity at elevated temperature. Selective uptake of cholesterol from solutions in hexane was studied with imprinted polymers prepared under different conditions. The imprinted hydrolyzed MIP prepared by NMP displayed higher selective cholesterol binding than that prepared by a traditional radical polymerization. [Copyright &y& Elsevier]

Abstract: The present work aims to study preparation of thin MIP films on a gold-coated QCM resonator in a well-controlled and reproducible manner. A surface-bound photo-radical initiator was used to furnish an imprinting polymerization in a dilute solution of template, functional monomer and crosslinker. Prior to polymerization, the photo-initiator was covalently coupled to a self-assembled monolayer of carboxyl terminated alkanethiol on a gold surface. With this approach we were able to control the thickness of the MIP film to be below 50nm, where the selective recognition of target analytes can be easily detected by the underlying quartz crystal resonator. When used in a flow injection analysis system, the assembled QCM sensor generated a large frequency change (>30Hz) upon encountering a small amount of analyte (0.19mM). The sensor had a very short response time (<1min), and displayed certain chiral selectivity towards the original template, (S)-propranolol at a concentration higher than 0.38mM in aqueous solution. [Copyright &y& Elsevier]