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Biomimicry through Molecular Imprinting: From Polymer Design to Devices

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

Deadline for manuscript submissions: closed (31 January 2019) | Viewed by 49117

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Special Issue Editors

Prof. Dr. Mohamed M. Chehimi

E-Mail Website1 Website2
Guest Editor

ITODYS Laboratory, Université Paris Cité & CNRS (UMR 7086), F-75013 Paris, France
Interests: surface chemical modification; biochar; composites; biomass conversion; surface analysis; XPS
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Lei Ye

E-Mail 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

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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 semimonthly 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 2700 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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11 pages, 2111 KiB

Open AccessEditor’s ChoiceArticle

Adsorption and Electrochemical Detection of Bovine Serum Albumin Imprinted Calcium Alginate Hydrogel Membrane

by Meng Qi, Kongyin Zhao, Qiwen Bao, Peng Pan, Yuwei Zhao, Zhengchun Yang, Huiquan Wang and Junfu Wei

Polymers 2019, 11(4), 622; https://0-doi-org.brum.beds.ac.uk/10.3390/polym11040622 - 04 Apr 2019

Cited by 33 | Viewed by 4926

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 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

(This article belongs to the Special Issue Biomimicry through Molecular Imprinting: From Polymer Design to Devices)

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18 pages, 4218 KiB

Open AccessArticle

Molecularly Imprinted Polymers for Gossypol via Sol–Gel, Bulk, and Surface Layer Imprinting—A Comparative Study

by Lulu Wang, Keke Zhi, Yagang Zhang, Yanxia Liu, Letao Zhang, Akram Yasin and Qifeng Lin

Polymers 2019, 11(4), 602; https://0-doi-org.brum.beds.ac.uk/10.3390/polym11040602 - 02 Apr 2019

Cited by 26 | Viewed by 4582

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. 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

(This article belongs to the Special Issue Biomimicry through Molecular Imprinting: From Polymer Design to Devices)

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14 pages, 2873 KiB

Open AccessArticle

Covalently Crosslinked Nanogels: An NMR Study of the Effect of Monomer Reactivity on Composition and Structure

by Pengfei Liu, Charles M. Pearce, Rozalia-Maria Anastasiadi, Marina Resmini and Ana M. Castilla

Polymers 2019, 11(2), 353; https://0-doi-org.brum.beds.ac.uk/10.3390/polym11020353 - 18 Feb 2019

Cited by 17 | Viewed by 5448

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 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

(This article belongs to the Special Issue Biomimicry through Molecular Imprinting: From Polymer Design to Devices)

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19 pages, 3556 KiB

Open AccessArticle

Highly Selective Copper Ion Imprinted Clay/Polymer Nanocomposites Prepared by Visible Light Initiated Radical Photopolymerization

by Radhia Msaadi, Gorkem Yilmaz, Andrit Allushi, Sena Hamadi, Salah Ammar, Mohamed M. Chehimi and Yusuf Yagci

Polymers 2019, 11(2), 286; https://0-doi-org.brum.beds.ac.uk/10.3390/polym11020286 - 08 Feb 2019

Cited by 21 | Viewed by 4112

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 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

(This article belongs to the Special Issue Biomimicry through Molecular Imprinting: From Polymer Design to Devices)

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10 pages, 3123 KiB

Open AccessCommunication

Towards Detection of Glycoproteins Using Molecularly Imprinted Nanoparticles and Boronic Acid-Modified Fluorescent Probe

by Lingdong Jiang, Rui Lu and Lei Ye

Polymers 2019, 11(1), 173; https://0-doi-org.brum.beds.ac.uk/10.3390/polym11010173 - 18 Jan 2019

Cited by 19 | Viewed by 4658

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 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

(This article belongs to the Special Issue Biomimicry through Molecular Imprinting: From Polymer Design to Devices)

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21 pages, 3553 KiB

Open AccessArticle

Computer-Aided Design of Molecularly Imprinted Polymers for Simultaneous Detection of Clenbuterol and Its Metabolites

by Bingcheng Zhang, Xin Fan and Dayun Zhao

Polymers 2019, 11(1), 17; https://0-doi-org.brum.beds.ac.uk/10.3390/polym11010017 - 23 Dec 2018

Cited by 45 | Viewed by 4898

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 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

(This article belongs to the Special Issue Biomimicry through Molecular Imprinting: From Polymer Design to Devices)

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17 pages, 2195 KiB

Open AccessArticle

Synthesis and Characterization of a Molecularly Imprinted Polymer of Spermidine and the Exploration of Its Molecular Recognition Properties

by Yu-Jie Huang, Rui Chang and Qiu-Jin Zhu

Polymers 2018, 10(12), 1389; https://0-doi-org.brum.beds.ac.uk/10.3390/polym10121389 - 14 Dec 2018

Cited by 19 | Viewed by 4542

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 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

(This article belongs to the Special Issue Biomimicry through Molecular Imprinting: From Polymer Design to Devices)

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21 pages, 8827 KiB

Open AccessArticle

Effects of Electron Beam Irradiation on the Mechanical, Thermal, and Surface Properties of Some EPDM/Butyl Rubber Composites

by Maria Daniela Stelescu, Anton Airinei, Elena Manaila, Gabriela Craciun, Nicusor Fifere, Cristian Varganici, Daniela Pamfil and Florica Doroftei

Polymers 2018, 10(11), 1206; https://0-doi-org.brum.beds.ac.uk/10.3390/polym10111206 - 30 Oct 2018

Cited by 36 | Viewed by 4926

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 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

(This article belongs to the Special Issue Biomimicry through Molecular Imprinting: From Polymer Design to Devices)

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9 pages, 1167 KiB

Open AccessCommunication

Selective Polymer Distributed Bragg Reflector Vapor Sensors

by Paola Lova

Polymers 2018, 10(10), 1161; https://0-doi-org.brum.beds.ac.uk/10.3390/polym10101161 - 17 Oct 2018

Cited by 28 | Viewed by 4395

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 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

(This article belongs to the Special Issue Biomimicry through Molecular Imprinting: From Polymer Design to Devices)

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Review

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26 pages, 4206 KiB

Open AccessReview

Synthesis and Applications of Molecularly Imprinted Polymers Modified TiO₂ Nanomaterials: A Review

by Lingna Sun, Jie Guan, Qin Xu, Xiaoyu Yang, Juan Wang and Xiaoya Hu

Polymers 2018, 10(11), 1248; https://0-doi-org.brum.beds.ac.uk/10.3390/polym10111248 - 11 Nov 2018

Cited by 41 | Viewed by 5632

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 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

(This article belongs to the Special Issue Biomimicry through Molecular Imprinting: From Polymer Design to Devices)

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