Special Issue "Biomimicry through Molecular Imprinting: From Polymer Design to Devices"

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (31 January 2019).

Special Issue Editors

Prof. Dr. Mohamed M. Chehimi
Website1 Website2
Guest Editor
Institut de Chimie et des Matériaux Paris-Est (ICMPE), CNRS, Thiais, France
Interests: surface chemical modification; polymer grafts; polymer composites; sensors; adsorbents; surface analysis; XPS
Special Issues and Collections in MDPI journals
Prof. Dr. Lei Ye
Website
Guest Editor
Division of Pure and Applied Biochemistry, Lund University Box 124, 22100 Lund (Sweden)
Interests: molecular recognition; molecular imprinting; controlled radical polymerization; functional polymers; protein-polymer conjugates

Special Issue Information

Dear Colleagues,

Molecular imprinting is a well-established technique for producing highly-selective biomimetic materials (sensors, adsorbents), so-called molecularly imprinted polymers (MIPs), based on cross-linked organic or inorganic sol-gel polymers. The materials are prepared by triggering polymerization in the presence of template molecules, (bio)macromolecules, metal ions, metal ion-ligand complexes, nanoparticles and micro-organisms. Attractive emerging trends include multi-template, dummy and surface imprinting strategies. The removal of the templates creates artificial receptor sites within the (crosslinked) polymer matrix for the rebinding of the templates or structurally analogous analytes.

In the course of synthesis, the molecular level of interactions between the monomers and the templates play a vital role and can be controlled in order to tailor the properties of the final biomimetic material. Yet, the road to successful MIP is long and winding due to numerous trials and errors needed to design highly selective MIPs. For this reason, the recent years have witnessed the rise of computational chemistry methods to assist the polymer chemists in the design of high performance MIPs in a limited number of steps.

MIPs can be produced by a range of chemical, electrochemical and radiation-induced techniques in either bulk materials, ultrathin films, nanocomposites or inverse opals. In addition, embedding of nanostructures (e.g. gold nanoparticles, graphene, carbon nanotubes) within the MIP matrices results in remarkable improvements of the sensing performances with unprecedented low detection limits.

The robustness of MIPs over antibodies and enzymes under harsh conditions and their reusability have made these mimics of antibodies exceptionally attractive for analytical, polymer and materials scientists. MIPs have also been applied to achieve efficient catalysis, controlling stereo selectivity in synthesis, controlled drug delivery, protein crystallization and bio-mineralization.

The EUPOC 2018 Special Issue of Polymers is dedicated to peer-reviewed papers of the highest quality on biomimicry by molecular imprinting for the design of tailored molecularly imprinted materials. As science and technology of MIPs go hand in hand, contributions on implementation of MIPs in electronic and other devices are extremely encouraged.

The Special Issue welcomes papers on (but not limited to):

  • Methods of MIP synthesis
  • MIP thin films
  • MIP sensors and adsorbents
  • Nanostructured MIP materials
  • Colloidal crystals and imprinted inverse opals
  • Magnetic MIPs
  • Photo-switchable MIPs
  • Multifunctional MIPs
  • Biomedical, food and environmental applications
  • Microfluidics, lab-on-chip, lab-on-paper
  • MIP-based devices.

We anticipate this Special Issue will provide current innovative biomimicry issues in polymer science and technology; and of interest to experts, engineers, students and new comers in the field.

Dr. Mohamed M. Chehimi
Prof. Lei Ye
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • surface chemical modification
  • diazonium coupling agents
  • polymer grafts
  • composites
  • sensors
  • adsorbents
  • surface analysis

Published Papers (10 papers)

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Research

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Open AccessArticle
Adsorption and Electrochemical Detection of Bovine Serum Albumin Imprinted Calcium Alginate Hydrogel Membrane
Polymers 2019, 11(4), 622; https://doi.org/10.3390/polym11040622 - 04 Apr 2019
Cited by 9
Abstract
In this paper, bovine serum albumin (BSA)-imprinted calcium alginate (CaAlg) hydrogel membrane was prepared using BSA as a template, sodium alginate (NaAlg) as a functional monomer, and CaCl2 as a cross-linker. The thickness of the CaAlg membrane was controlled by a glass [...] Read more.
In this paper, bovine serum albumin (BSA)-imprinted calcium alginate (CaAlg) hydrogel membrane was prepared using BSA as a template, sodium alginate (NaAlg) as a functional monomer, and CaCl2 as a cross-linker. The thickness of the CaAlg membrane was controlled by a glass rod enlaced with brass wires (the diameter was 0.1, 0.2, 0.3, 0.4, and 0.5 mm). The swelling properties of the CaAlg membranes prepared with different contents of NaAlg were researched. Circular dichroism indicated that the conformation of BSA did not change during the preparing and eluting process. The thinner the CaAlg hydrogel membrane was, the larger the adsorption capacity and the higher the imprinting efficiency of the CaAlg. The maximum adsorption capacity of molecularly imprinted polymer (MIP) and non-imprinted CaAlg hydrogel membrane (NIP) was 38.6 mg·g−1 and 9.2 mg·g−1, respectively, with an imprinting efficiency of 4.2. The MIP was loaded on the electrode to monitor the selective adsorption of BSA by voltammetry curve. Full article
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Open AccessArticle
Molecularly Imprinted Polymers for Gossypol via Sol–Gel, Bulk, and Surface Layer Imprinting—A Comparative Study
Polymers 2019, 11(4), 602; https://doi.org/10.3390/polym11040602 - 02 Apr 2019
Cited by 4
Abstract
Three gossypol molecularly imprinted polymers (MIPs) were prepared by bulk polymerization (MIP1), surface layer imprinting using silica gel as the support (MIP2), and the sol-gel process (MIP3). The as-prepared MIPs were characterized by SEM and nitrogen adsorption−desorption techniques to study the morphology structure. [...] Read more.
Three gossypol molecularly imprinted polymers (MIPs) were prepared by bulk polymerization (MIP1), surface layer imprinting using silica gel as the support (MIP2), and the sol-gel process (MIP3). The as-prepared MIPs were characterized by SEM and nitrogen adsorption−desorption techniques to study the morphology structure. The adsorption experiments exhibited that MIP1 had adsorption capacity as high as 564 mg·g−1. The MIP2 showed faster adsorption kinetics than MIP1 and MIP3. The adsorption equilibrium could be reached for gossypol in 40 min. A selectivity study showed that the adsorption capacity of MIPs for gossypol was about 1.9 times higher than that of the structurally-similar analogs ellagic acid and 6.6 times higher than that of the quercetin. It was found that the pseudo-second-order kinetic model and the Freundlich isotherm model were more applicable for the adsorption kinetics and adsorption isotherm of gossypol binding onto the MIP1 and MIP2, respectively. Results suggested that among those three, the MIP2 was a desirable sorbent for rapid adsorption and MIP1 was suitable for selective recognition of gossypol. Full article
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Open AccessArticle
Covalently Crosslinked Nanogels: An NMR Study of the Effect of Monomer Reactivity on Composition and Structure
Polymers 2019, 11(2), 353; https://doi.org/10.3390/polym11020353 - 18 Feb 2019
Cited by 3
Abstract
Covalently crosslinked nanogels are widely explored as drug delivery systems and sensors. Radical polymerization provides a simple, inexpensive, and broadly applicable approach for their preparation, although the random nature of the reaction requires careful study of the final chemical composition. We demonstrate how [...] Read more.
Covalently crosslinked nanogels are widely explored as drug delivery systems and sensors. Radical polymerization provides a simple, inexpensive, and broadly applicable approach for their preparation, although the random nature of the reaction requires careful study of the final chemical composition. We demonstrate how the different reactivities of the monomers influence the total degree of incorporation into the polymer matrix and the role played by the experimental parameters in maximizing polymerization efficiency. Nanogels based on N-isopropylacrylamide, N-n-propylacrylamide, and acrylamide crosslinked with N,N’-methylenebisacrylamide were included in this study, in combination with functional monomers N-acryloyl-l-proline, 2-acrylamido-2-methyl-1-propanesulfonic acid, and 4-vinyl-1H-imidazole. Total monomer concentration and initiator quantities are determining parameters for maximizing monomer conversions and chemical yields. The results show that the introduction of functional monomers, changes in the chemical structure of the polymerizable unit, and the addition of templating molecules can all have an effect on the polymerization kinetics. This can significantly impact the final composition of the matrices and their chemical structure, which in turn influence the morphology and properties of the nanogels. Full article
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Open AccessArticle
Highly Selective Copper Ion Imprinted Clay/Polymer Nanocomposites Prepared by Visible Light Initiated Radical Photopolymerization
Polymers 2019, 11(2), 286; https://doi.org/10.3390/polym11020286 - 08 Feb 2019
Cited by 5
Abstract
There is an urgent demand worldwide for the development of highly selective adsorbents and sensors of heavy metal ions and other organic pollutants. Within these environmental and public health frameworks, we are combining the salient features of clays and chelatant polymers to design [...] Read more.
There is an urgent demand worldwide for the development of highly selective adsorbents and sensors of heavy metal ions and other organic pollutants. Within these environmental and public health frameworks, we are combining the salient features of clays and chelatant polymers to design selective metal ion adsorbents. Towards this end, the ion imprinting approach has been used to develop a novel nanohybrid material for the selective separation of Cu2+ ions in an aqueous solution. The Cu2+-imprinted polymer/montmorillonite (IIP/Mt) and non-imprinted polymer/montmorillonite (NIP/Mt) nanocomposites were prepared by a radical photopolymerization process in visible light. The ion imprinting step was indeed important as the recognition of copper ions by IIP/Mt was significantly superior to that of NIP/Mt, i.e., the reference nanocomposite synthesized in the same way but in the absence of Cu2+ ions. The adsorption process as batch study was investigated under the experimental condition affecting same parameters such as contact time, concentration of metal ions, and pH. The adsorption capacity of Cu2+ ions is maximized at pH 5. Removal of Cu2+ ion achieved equilibrium within 15 min; the results obtained were found to be fitted by the pseudo-second-order kinetics model. The equilibrium process was well described by the Langmuir isothermal model and the maximum adsorption capacity was found to be 23.6 mg/g. This is the first report on the design of imprinted polymer nanocomposites using Type II radical initiators under visible light in the presence of clay intercalated with hydrogen donor diazonium. The method is original, simple and efficient; it opens up new horizons in the general domain of clay/polymer nanocomposites. Full article
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Open AccessCommunication
Towards Detection of Glycoproteins Using Molecularly Imprinted Nanoparticles and Boronic Acid-Modified Fluorescent Probe
Polymers 2019, 11(1), 173; https://doi.org/10.3390/polym11010173 - 18 Jan 2019
Cited by 7
Abstract
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 [...] Read more.
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. Full article
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Open AccessArticle
Computer-Aided Design of Molecularly Imprinted Polymers for Simultaneous Detection of Clenbuterol and Its Metabolites
Polymers 2019, 11(1), 17; https://doi.org/10.3390/polym11010017 - 23 Dec 2018
Cited by 8
Abstract
Molecular imprinting technology (MIT) offers an effective technique for efficient separation and enrichment of specific analytes from complicated matrices and has been used for illicit veterinary drug detectionin recent years due to its high selectivity, good chemical stability, and simple preparation. The development [...] Read more.
Molecular imprinting technology (MIT) offers an effective technique for efficient separation and enrichment of specific analytes from complicated matrices and has been used for illicit veterinary drug detectionin recent years due to its high selectivity, good chemical stability, and simple preparation. The development of in silico-based approaches has enabled the simulation of molecularly imprinted polymers (MIPs) to facilitate the selection of imprinting conditions such as template, functional monomer, and the best suitable solvent. In this work, using density functional theory (DFT), the molecularly imprinted polymers of clenbuterol and its metabolites were designed by computer-aided at B3LYP/6-31 + G (d, p) level. Screening molecular imprinting components such as functional monomers, cross-linkers, and solvents has been achieved in the computational simulation considerations. The simulation results showed that methacrylic acid (MAA) is the best functional monomer; the optimal imprinting ratio for both clenbuterol (CLB) and its dummy template molecule of phenylephrine (PE) to functional monomer is 1:3, while the optimal imprinting ratio for the two dummy template molecules of CLB’s metabolites is 1:5. Choosin gethyleneglycol dimethacrylate (EDGMA) as a crosslinker and aprotic solvents could increase the selectivity of the molecularly imprinted system. Atoms in Molecules (AIM) topology analysis was applied to investigate the template-monomer complexes bonding situation and helped to explain the nature of the reaction in the imprinting process. These theoretical predictions were also verified by the experimental results and found to be in good agreement with the computational results. The computer-simulated imprinting process compensates for the lack of clarity in the mechanism of the molecular imprinting process, and provides an important reference and direction for developing better recognition pattern towards CLB and its metabolite analytes in swine urine samples at the same time. Full article
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Open AccessArticle
Synthesis and Characterization of a Molecularly Imprinted Polymer of Spermidine and the Exploration of Its Molecular Recognition Properties
Polymers 2018, 10(12), 1389; https://doi.org/10.3390/polym10121389 - 14 Dec 2018
Cited by 5
Abstract
Spermidine is a functional ingredient that can extend the lifespan of many foods and indicate meat safety. However, its synthesis and enrichment is expensive and complex. To develop an effective separation material that can offer highly selective recognition of spermidine, we first applied [...] Read more.
Spermidine is a functional ingredient that can extend the lifespan of many foods and indicate meat safety. However, its synthesis and enrichment is expensive and complex. To develop an effective separation material that can offer highly selective recognition of spermidine, we first applied non-covalent molecular imprinting technology using methacrylic acid as a functional monomer, azobisisobutyronitrile as an initiator, and ethylene glycol dimethacrylate as a cross-linker. The adsorption properties of the polymers were analyzed using the Scatchard equation, the Lagergren kinetic equation, and the static distribution coefficient. The optimal polymerization molar ratio of the template molecule spermidine to the functional monomer was 1:4, the maximum adsorption amount was 97.75 μmol/g, and the adsorption equilibrium time was 300 min. The selective experiment showed that the interfering substances tyramine and histamine had selectivity factor α values of 2.01 and 1.78, respectively, indicating that the prepared polymer had good spermidine recognition ability. The density function theory calculations showed that the hydrogen bond strength, steric effect, and product energy caused adsorption and separation differences among the different imprinted polymer complexes. Full article
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Open AccessArticle
Effects of Electron Beam Irradiation on the Mechanical, Thermal, and Surface Properties of Some EPDM/Butyl Rubber Composites
Polymers 2018, 10(11), 1206; https://doi.org/10.3390/polym10111206 - 30 Oct 2018
Cited by 7
Abstract
The effects of electron beam irradiation on the properties of ethylene propylene diene monomer (EPDM)/butyl rubber composites in presence of a polyfunctional monomer were investigated by means of differential scanning calorimetry (DSC), thermal analysis, scanning electron microscopy (SEM), attenuated total reflection absorption infrared [...] Read more.
The effects of electron beam irradiation on the properties of ethylene propylene diene monomer (EPDM)/butyl rubber composites in presence of a polyfunctional monomer were investigated by means of differential scanning calorimetry (DSC), thermal analysis, scanning electron microscopy (SEM), attenuated total reflection absorption infrared spectroscopy (ATR-IR), and mechanical and surface energy measurements. The samples were exposed over a wide range of irradiation doses (20–150 kGy). The EPDM matrix was modified with butyl rubber, chlorobutyl rubber, and bromobutyl rubber. The gel content and crosslink density were found to increase with the electron beam irradiation dose. The values of the hardness and modulus increased gradually with the irradiation dose, while the tensile strength and elongation at break decreased with increasing irradiation dose. The EPDM/butyl rubber composites presented a higher thermal stability compared to the initial EPDM sample. The incorporation of butyl rubbers into the EPDM matrix led to an increase in material hydrophobicity. A similar trend was observed when the irradiation dose increased. The greatest change in the surface free energy and the contact angles occurs at an irradiation dose of 20 kGy. The Charlesby–Pinner plots prove the tendency to crosslinking as the irradiation dose increases. Full article
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Open AccessCommunication
Selective Polymer Distributed Bragg Reflector Vapor Sensors
Polymers 2018, 10(10), 1161; https://doi.org/10.3390/polym10101161 - 17 Oct 2018
Cited by 18
Abstract
We report on Flory–Huggins photonic sensors for the selective detection of volatile organic compounds without the use of any chemical functionalization. For this purpose, we employed periodic multilayers made of inert cellulose acetate alternated to active polystyrene films whose free volume was modified [...] Read more.
We report on Flory–Huggins photonic sensors for the selective detection of volatile organic compounds without the use of any chemical functionalization. For this purpose, we employed periodic multilayers made of inert cellulose acetate alternated to active polystyrene films whose free volume was modified with silanized ZnO nanoparticles. The simple UV-visible (UV-vis) dynamic optical response of such polymer distributed Bragg reflectors during exposure to vapors of benzene, toluene, o-dichlorobenzene, and carbon tetrachloride allows their detection and recognition based on different chemico–physical affinity with the active polymer medium. Full article
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Review

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Open AccessReview
Synthesis and Applications of Molecularly Imprinted Polymers Modified TiO2 Nanomaterials: A Review
Polymers 2018, 10(11), 1248; https://doi.org/10.3390/polym10111248 - 11 Nov 2018
Cited by 6
Abstract
Titanium dioxide (TiO2) nanomaterials have caused a widespread concern in the past several decades for their bulk characteristics and potential applications in many different areas. Lately, the combination between molecularly imprinted polymers (MIPs) and TiO2 nanomaterials have been proven to [...] Read more.
Titanium dioxide (TiO2) nanomaterials have caused a widespread concern in the past several decades for their bulk characteristics and potential applications in many different areas. Lately, the combination between molecularly imprinted polymers (MIPs) and TiO2 nanomaterials have been proven to improve the relative adsorption capacity, selectivity and accelerate the rate of mass transfer of analyte which is not possible using TiO2 alone. Considering the unique performance of the MIPs modified TiO2 nanomaterials, this review intends to give an overview of the recent progresses in the development of MIPs modified TiO2 nanomaterials, the potential applications of their tailor-made characteristics. The limitations and challenges in this practically promising nanomaterials have also been raised and summarized. By means of the points raised in this article, we would like to provide some assistance for further development of preparation methodologies and the expansion of some potential applications in the field of MIPs modified TiO2 nanomaterials. Full article
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