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Molecularly Imprinted Polymers: Design, Characterization and Application

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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Smart and Functional Polymers".

Deadline for manuscript submissions: closed (31 March 2024) | Viewed by 16324

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Dr. Vilma Ratautaite

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Center for Physical Sciences and Technology (FTMC), Vilnius, Lithuania
Interests: molecularly imprinted polymers; conducting polymers; electrochemical sensors; electrochemical deposition
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Prof. Dr. Arunas Ramanavicius

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NanoTechnas—Center of Nanotechnology and Materials Science, Faculty of Chemistry and Geosciences, Vilnius University, Naugarduko Str. 24, LT-03225 Vilnius, Lithuania
Interests: electrochemistry; bioelectrochemistry; molecularly imprinted polymers; conducting polymers; electrochemical sensors; electrochemical deposition
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Dear Colleagues,

We invite the submission of research articles and reviews to a Special Issue in Polymers. For this Special Issue, we aim to present the most recent developments in the design, characterization, and application of molecularly imprinted polymers (MIP). The different methods of MIP production, the characterization of dominant features of the surface, and the characterization of interactions between the polymer and the target molecule are within the scope of this Special Issue. Next, various types of additives (gold, silver, or platinum nanoparticles; multiwalled carbon nanotubes; MXenes; quantum dots; etc.) are used in the design of MIP. Therefore, characterizing the impact of these additives on the interaction of the MIP with the target molecule is encouraged. Subsequently, extracting the imprinted molecule from the polymer after the polymerization is critical to the final performance of the MIP. Finally, various applications of MIPs in electrochemical sensors, wearable sensors, and many other fields also are within the scope of this Special Issue.

Dr. Vilma Ratautaitė
Prof. Dr. Arunas Ramanavicius
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

molecularly imprinted polymers (MIPs)
molecular imprinting technology
conducting polymers
conjugated polymer
electrochemical deposition
electrochemical sensors
synthetic receptors

Related Special Issue

Molecularly Imprinted Polymers: Design, Characterization and Application, 2nd Edition in Polymers

Published Papers (10 papers)

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Research

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19 pages, 3983 KiB

Open AccessArticle

A Screen-Printed Voltammetric Sensor Modified with Electropolymerized Molecularly Imprinted Polymer (eMIP) to Determine Gallic Acid in Non-Alcoholic and Alcoholic Beverages

by Camilla Zanoni, Lucrezia Virginia Dallù, Clementina Costa, Alessandra Cutaia and Giancarla Alberti

Polymers 2024, 16(8), 1076; https://doi.org/10.3390/polym16081076 - 12 Apr 2024

Viewed by 301

Abstract

This paper presents a low-cost disposable sensor for gallic acid (GA) detection in non-alcoholic and alcoholic beverages using a screen-printed cell (SPC) whose working electrode (in graphite) is modified with electrosynthesized molecularly imprinted polypyrrole (eMIP). Our preliminary characterization of the electrochemical process shows that gallic acid (GA) undergoes irreversible oxidation at potentials of about +0.3 V. The peak potential is not affected by the presence of the eMIP film and alcohol percentages (ethanol) up to 20%. The GA determination is based on a differential pulse voltammetry (DPV) analysis leveraging its oxidation peak. The calibration data and the figures of merit of the analytical method (LOD, LOQ, and linear range) are calculated. To validate the feasibility of the sensor’s application for the dosing of GA in real matrices, some non-alcoholic and alcoholic beverages are analyzed. The results are then compared with those reported in the literature and with the total polyphenol content determined by the Folin–Ciocalteu method. In all cases, the concentrations of GA align with those previously found in the literature for the beverages examined. Notably, the values are consistently lower than the total polyphenol content, demonstrating the sensor’s selectivity in discriminating the target molecule from other polyphenols present. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Design, Characterization and Application)

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11 pages, 1864 KiB

Open AccessArticle

The Amount of Cross-Linker Influences Affinity and Selectivity of NanoMIPs Prepared by Solid-Phase Polymerization Synthesis

by Valentina Testa, Laura Anfossi, Simone Cavalera, Fabio Di Nardo, Thea Serra and Claudio Baggiani

Polymers 2024, 16(4), 532; https://doi.org/10.3390/polym16040532 - 16 Feb 2024

Viewed by 474

Abstract

The cross-linker methylene-bis-acrylamide is usually present in nanoMIPs obtained by solid-phase polymerization synthesis at 2 mol% concentration, with very few exceptions. Here, we studied the influence of variable amounts of methylene-bis-acrylamide in the range between 0 (no cross-linker) and 50 mol% concentration on the binding properties of rabbit IgG nanoMIPs. The binding parameters were determined by equilibrium binding experiments and the results show that the degree of cross-linking defines three distinct types of nanoMIPs: (i) those with a low degree of cross-linking, including nanoMIPs without cross-linker (0–05 mol%), showing a low binding affinity, high density of binding sites, and low selectivity; (ii) nanoMIPs with a medium degree of cross-linking (1–18 mol%), showing higher binding affinity, low density of binding sites, and high selectivity; (iii) nanoMIPs with a high degree of cross-linking (32–50 mol%), characterized by non-specific nanopolymer–ligand interactions, with low binding affinity, high density of binding sites, and no selectivity. In conclusion, the results are particularly relevant in the synthesis of high-affinity, high-selectivity nanoMIPs as they demonstrate that a significant gain in affinity and selectivity could be achieved with pre-polymerization mixtures containing quantities of cross-linker up to 10–20 mol%, well higher than those normally used in this technique. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Design, Characterization and Application)

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14 pages, 6976 KiB

Open AccessArticle

Synthesis and Properties of Cefixime Core–Shell Magnetic Nano-Molecularly Imprinted Materials

by Li Zhang, Hongbo Mo, Chuan Wang, Xiaofeng Li, Shuai Jiang, Weigang Fan and Yagang Zhang

Polymers 2023, 15(22), 4464; https://doi.org/10.3390/polym15224464 - 20 Nov 2023

Viewed by 907

Abstract

Novel core–shell magnetic molecularly imprinted polymers (MMIPs) were synthesized using the sol–gel method for the adsorption of cefixime (CFX). Fe₃O₄@SiO₂ is the core, and molecularly imprinted polymers (MIPs) are the shell, which can selectively interact with CFX. The preparation conditions, adsorption kinetics, adsorption isotherms, selective adsorption ability, and reutilization performance of the MMIPs were investigated. The adsorption capacity of MMIPs for CFX was 111.38 mg/g, which was about 3.5 times that of MNIPs. The adsorption equilibrium time was 180 min. The dynamic adsorption experiments showed that the adsorption process of MMIPs to CFX conformed to the pseudo-second-order model. Through static adsorption study, the Scatchard analysis showed that MMIPs had two types of binding sites—the high-affinity binding sites and the low-affinity binding sites—while the Langmuir model fit the adsorption isotherms well (R² = 0.9962). Cefepime and ceftiofur were selected as the structural analogs of CFX for selective adsorption studies; the adsorption of CFX by MMIPs was higher than that of other structural analogs; and the imprinting factors of CFX, cefepime, and ceftiofur were 3.5, 1.7, and 1.4, respectively. Furthermore, the MMIPs also showed excellent reusable performance. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Design, Characterization and Application)

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12 pages, 3648 KiB

Open AccessArticle

Application of Chitosan-Based Molecularly Imprinted Polymer in Development of Electrochemical Sensor for p-Aminophenol Determination

by Ani Mulyasuryani, Yuniar Ponco Prananto, Qonitah Fardiyah, Hanandayu Widwiastuti and Darjito Darjito

Polymers 2023, 15(8), 1818; https://doi.org/10.3390/polym15081818 - 07 Apr 2023

Cited by 7 | Viewed by 1858

Abstract

Molecularly Imprinted Polymers (MIPs) have specific recognition capabilities and have been widely used for electrochemical sensors with high selectivity. In this study, an electrochemical sensor was developed for the determination of p-aminophenol (p-AP) by modifying the screen-printed carbon electrode (SPCE) with chitosan-based MIP. The MIP was made from p-AP as a template, chitosan (CH) as a base polymer, and glutaraldehyde and sodium tripolyphosphate as the crosslinkers. MIP characterization was conducted based on membrane surface morphology, FT-IR spectrum, and electrochemical properties of the modified SPCE. The results showed that the MIP was able to selectively accumulate analytes on the electrode surface, in which MIP with glutaraldehyde as a crosslinker was able to increase the signal. Under optimum conditions, the anodic peak current from the sensor increased linearly in the range of 0.5–35 µM p-AP concentration, with sensitivity of (3.6 ± 0.1) µA/µM, detection limit (S/N = 3) of (2.1 ± 0.1) µM, and quantification limit of (7.5 ± 0.1) µM. In addition, the developed sensor exhibited high selectivity with an accuracy of (94.11 ± 0.01)%. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Design, Characterization and Application)

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16 pages, 10171 KiB

Open AccessArticle

Towards Electrochemical Sensor Based on Molecularly Imprinted Polypyrrole for the Detection of Bacteria—Listeria monocytogenes

by Viktorija Liustrovaite, Maksym Pogorielov, Raimonda Boguzaite, Vilma Ratautaite, Almira Ramanaviciene, Greta Pilvenyte, Viktoriia Holubnycha, Viktoriia Korniienko, Kateryna Diedkova, Roman Viter and Arunas Ramanavicius

Polymers 2023, 15(7), 1597; https://doi.org/10.3390/polym15071597 - 23 Mar 2023

Cited by 12 | Viewed by 1891

Abstract

Detecting bacteria—Listeria monocytogenes—is an essential healthcare and food industry issue. The objective of the current study was to apply platinum (Pt) and screen-printed carbon (SPCE) electrodes modified by molecularly imprinted polymer (MIP) in the design of an electrochemical sensor for the detection of Listeria monocytogenes. A sequence of potential pulses was used to perform the electrochemical deposition of the non-imprinted polypyrrole (NIP-Ppy) layer and Listeria monocytogenes-imprinted polypyrrole (MIP-Ppy) layer over SPCE and Pt electrodes. The bacteria were removed by incubating Ppy-modified electrodes in different extraction solutions (sulphuric acid, acetic acid, L-lysine, and trypsin) to determine the most efficient solution for extraction and to obtain a more sensitive and repeatable design of the sensor. The performance of MIP-Ppy- and NIP-Ppy-modified electrodes was evaluated by pulsed amperometric detection (PAD). According to the results of this research, it can be assumed that the most effective MIP-Ppy/SPCE sensor can be designed by removing bacteria with the proteolytic enzyme trypsin. The LOD and LOQ of the MIP-Ppy/SPCE were 70 CFU/mL and 210 CFU/mL, respectively, with a linear range from 300 to 6700 CFU/mL. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Design, Characterization and Application)

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11 pages, 3912 KiB

Open AccessCommunication

Synthesis of Fluorescent, Small, Stable and Non-Toxic Epitope-Imprinted Polymer Nanoparticles in Water

by Perla Benghouzi, Lila Louadj, Aurélia Pagani, Maylis Garnier, Jérôme Fresnais, Carlo Gonzato, Michèle Sabbah and Nébéwia Griffete

Polymers 2023, 15(5), 1112; https://doi.org/10.3390/polym15051112 - 23 Feb 2023

Viewed by 1549

Abstract

Molecularly imprinted polymers (MIPs) are really interesting for nanomedicine. To be suitable for such application, they need to be small, stable in aqueous media and sometimes fluorescent for bioimaging. We report herein, the facile synthesis of fluorescent, small (below 200 nm), water-soluble and water-stable MIP capable of specific and selective recognition of their target epitope (small part of a protein). To synthesize these materials, we used dithiocarbamate-based photoiniferter polymerization in water. The use of a rhodamine-based monomer makes the resulting polymers fluorescent. Isothermal titration calorimetry (ITC) is used to determine the affinity as well as the selectivity of the MIP for its imprinted epitope, according to the significant differences observed when comparing the binding enthalpy of the original epitope with that of other peptides. The toxicity of the nanoparticles is also tested in two breast cancer cell lines to show the possible use of these particle for future in vivo applications. The materials demonstrated a high specificity and selectivity for the imprinted epitope, with a K_d value comparable with the affinity values of antibodies. The synthesized MIP are not toxic, which makes them suitable for nanomedicine. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Design, Characterization and Application)

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14 pages, 3452 KiB

Open AccessArticle

Fluorescent Molecularly Imprinted Polymers Loaded with Avenanthramides for Inhibition of Advanced Glycation End Products

by Pei Zhu, Ying Zhang, Dianwei Zhang, Huilin Liu and Baoguo Sun

Polymers 2023, 15(3), 538; https://doi.org/10.3390/polym15030538 - 20 Jan 2023

Cited by 1 | Viewed by 1359

Abstract

Encapsulating bioactive avenanthramides (AVAs) in carriers to respond to the environmental changes of food thermal processing allows the controlled release of AVAs for the effective inhibition of biohazards. In this study, fluorescent molecular imprinted polymers (FMIPs) loaded with AVAs were prepared by reverse microemulsion. The fluorescent signal was generated by carbon dots (CDs), which were derived from oat bran to determine the load of AVAs. The FMIPs were uniformly spherical in appearance and demonstrated favorable properties, such as thermal stability, protection of AVAs against photodegradation, high encapsulation efficiency, and effective scavenging of free radicals. After consideration of the different kinetics models, the release of AVAs from the FMIPs matched the Weibull model and followed a Fickian diffusion mechanism. The FMIPs exhibited good inhibition of pyrraline in a simulated casein-ribose system and in milk samples, indicating the release of AVAs could inhibit the generation of pyrraline. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Design, Characterization and Application)

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10 pages, 3058 KiB

Open AccessArticle

Effect of Surfactants on the Binding Properties of a Molecularly Imprinted Polymer

by Valentina Testa, Laura Anfossi, Simone Cavalera, Matteo Chiarello, Fabio Di Nardo, Thea Serra and Claudio Baggiani

Polymers 2022, 14(23), 5210; https://doi.org/10.3390/polym14235210 - 30 Nov 2022

Cited by 1 | Viewed by 1051

Abstract

In molecularly imprinted polymers, non-specific interactions are generally based on weak forces between the polymer surface and the sample matrix. Thus, additives able to interfere with such interactions should be able to significantly reduce any non-specific binding effect. Surfactants represent an interesting class of substances as they are cheap and easily available. Here, we present a study of the effect of three surfactants (the anionic sodium dodecylsulphate, SDS, the cationic cetyltrimethylammonium bromide (CTAB) and the non-ionic polyoxyethylene-(20)-sorbitan monolaurate Tween 20) on the binding affinity of a 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)-imprinted polymer for the template and its analogue 2,4-dichlorophenoxyacetic acid (2,4-D). The experimental results indicate that increasing amounts of surfactant decrease the binding affinity for the ligands strongly for the ionic ones, and more weakly for the non-ionic one. This effect is general, as it occurs for both 2,4,5-T and 2,4-D and for both the imprinted and the not-imprinted polymers. It also proves that the magnitude of this effect mainly depends on the presence or absence of an ionic charge, and that the hydrophobic “tail” of surfactants plays only a minor role. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Design, Characterization and Application)

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Review

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20 pages, 4507 KiB

Open AccessReview

Recent Advances in Molecularly Imprinted Polymers and Their Disease-Related Applications

by Celia Cabaleiro-Lago, Sylwia Hasterok, Anette Gjörloff Wingren and Helena Tassidis

Polymers 2023, 15(21), 4199; https://doi.org/10.3390/polym15214199 - 24 Oct 2023

Cited by 1 | Viewed by 1915

Abstract

Molecularly imprinted polymers (MIPs) and the imprinting technique provide polymeric material with recognition elements similar to natural antibodies. The template of choice (i.e., the antigen) can be almost any type of smaller or larger molecule, protein, or even tissue. There are various formats of MIPs developed for different medical purposes, such as targeting, imaging, assay diagnostics, and biomarker detection. Biologically applied MIPs are widely used and currently developed for medical applications, and targeting the antigen with MIPs can also help in personalized medicine. The synthetic recognition sites of the MIPs can be tailor-made to function as analytics, diagnostics, and drug delivery systems. This review will cover the promising clinical applications of different MIP systems recently developed for disease diagnosis and treatment. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Design, Characterization and Application)

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26 pages, 4259 KiB

Open AccessReview

Application of Molecularly Imprinted Electrochemical Biomimetic Sensors for Detecting Small Molecule Food Contaminants

by Yunling Shao, Jiaqi Duan, Miao Wang, Jing Cao, Yongxin She, Zhen Cao, Guangyue Li, Fen Jin, Jing Wang and A. M. Abd El-Aty

Polymers 2023, 15(1), 187; https://doi.org/10.3390/polym15010187 - 30 Dec 2022

Cited by 6 | Viewed by 3697

Abstract

Environmental chemical contaminants in food seriously impact human health and food safety. Successful detection methods can effectively monitor the potential risk of emerging chemical contaminants. Among them, molecularly imprinted polymers (MIPs) based on electrochemical biomimetic sensors overcome many drawbacks of conventional detection methods and offer opportunities to detect contaminants with simple equipment in an efficient, sensitive, and low-cost manner. We searched eligible papers through the Web of Science (2000–2022) and PubMed databases. Then, we introduced the sensing mechanism of MIPs, outlined the sample preparation methods, and summarized the MIP characterization and performance. The classification of electrochemistry, as well as its advantages and disadvantages, are also discussed. Furthermore, the representative application of MIP-based electrochemical biomimetic sensors for detecting small molecular chemical contaminants, such as antibiotics, pesticides, toxins, food additives, illegal additions, organic pollutants, and heavy metal ions in food, is demonstrated. Finally, the conclusions and future perspectives are summarized and discussed. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Design, Characterization and Application)

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