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Molecularly Imprinted Polymers: Design, Characterization and Application

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 25376

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Guest Editor
Center for Physical Sciences and Technology (FTMC), Vilnius, Lithuania
Interests: molecularly imprinted polymers; conducting polymers; electrochemical sensors; electrochemical deposition
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Guest Editor
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
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

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

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Keywords

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

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Related Special Issue

Published Papers (11 papers)

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13 pages, 2019 KiB  
Article
Molecularly Imprinted Polymer-Based Electrochemical Sensor for the Detection of Azoxystrobin in Aqueous Media
by Vu Bao Chau Nguyen, Jekaterina Reut, Jörg Rappich, Karsten Hinrichs and Vitali Syritski
Polymers 2024, 16(10), 1394; https://doi.org/10.3390/polym16101394 - 14 May 2024
Viewed by 1271
Abstract
This work presents an electrochemical sensor detecting a fungicide-azoxystrobin (AZO) in aqueous environments. This AZO sensor utilizes a thin-film metal electrode (TFME) combined with an AZO-selective molecularly imprinted polymer (AZO–MIP). The AZO–MIP was directly generated on TFME through electrochemical polymerization from the solution [...] Read more.
This work presents an electrochemical sensor detecting a fungicide-azoxystrobin (AZO) in aqueous environments. This AZO sensor utilizes a thin-film metal electrode (TFME) combined with an AZO-selective molecularly imprinted polymer (AZO–MIP). The AZO–MIP was directly generated on TFME through electrochemical polymerization from the solution containing two functional monomers: aniline (Ani) and m-phenylenediamine (mPD), and the template: AZO, which was afterwards removed to form AZO-selective cavities in the polymer matrix. The AZO–MIP preparation was characterized by electrochemical and ellipsometry measurements. Optimization of the synthesis parameters, including the charge density applied during electrodeposition, the monomer-to-template ratio, was performed to enhance the sensor’s performance. The results demonstrated that the AZO sensor achieved a low limit of detection (LOD) of 3.6 nM and a limit of quantification (LOQ) of 11.8 nM in tap water, indicating its sensitivity in a complex aqueous environment. The sensor also exhibited satisfactory selectivity for AZO in both ultrapure and tap-water samples and achieved a good recovery (94–119%) for the target analyte. This study highlights the potential of MIP-based electrochemical sensors for the rapid and accurate detection of fungicide contaminants in water, contributing to the advancement of analytical tools for water-quality monitoring and risk assessment. Full article
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<p>Structural formula of Azoxystrobin (AZO) and electropolymerizable monomers examined as potential functional monomers for AZO–MIP synthesis.</p>
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<p>(<b>a</b>) Referenced IRSE spectra of poly(Ani), poly(mPD), and poly(Ani-co-mPD) films on ITO; and (<b>b</b>) referenced IRSE spectra of poly(Ani-co-mPD)/AZO films on ITO before washing (solid red line) and after washing (solid blue line). Vertical dashed lines show varied responses post-washing process, including disappearance or attenuation.</p>
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<p>Optimization of AZO–MIP preparation. Responses of the sensors equipped with various AZO–MIPs after incubation in 10 µM AZO in ultrapure water. AZO–MIPs were prepared using different: (<b>a</b>) charge densities; (<b>b</b>) Ani:mPD ratios; and (<b>c</b>) AZO concentrations at constant Ani:mPD ratio of 10:5.</p>
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<p>(<b>a</b>) Responses of AZO sensor upon incubation in 10 µM AZO solution in ultrapure water of different pH values; and (<b>b</b>) effects of incubation times on the DPV responses of AZO sensor after rebinding in 50 nM AZO solution in ultrapure water.</p>
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<p>Performance of the AZO sensor at low analyte concentrations (6–50 nM) in: (<b>a</b>) ultrapure water; and (<b>b</b>) tap water. The solid line is a linear regression fit. The error bars represent standard deviation of three measurements carried out by three independent AZO sensors.</p>
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<p>Responses of the AZO sensor after incubating in a 50 nM concentration of each different fungicide (AZO, PRC, and KSX) in ultrapure and tap water.</p>
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19 pages, 3983 KiB  
Article
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 1066
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 [...] Read more.
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
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<p>Scheme of the possible interaction mechanism between GA and overoxidate polypyrrole.</p>
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<p>Nyquist plot and Randles equivalent circuit of the bare electrode, eMIP-modified electrode after template removal, eMIP-modified electrode before the template removal, and eNIP-modified electrode. Measurements in 0.1 M KCl/0.05 M K<sub>3</sub>Fe(CN)<sub>6</sub> electrochemical probe solution.</p>
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<p>The electrochemical oxidation reaction of gallic acid. (Reproduced with permission from [<a href="#B60-polymers-16-01076" class="html-bibr">60</a>], open access Creative Common CC license 4.0, MDPI).</p>
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<p>CV registered with the bare electrode in 2.5 mM GA solutions at different pH values. (blue line) LiClO<sub>4</sub> 0.1 M acidified at pH of 2.14; (red line) LiClO<sub>4</sub> 0.1 M acidified at pH of 3.08; (green line) LiClO<sub>4</sub> 0.1 M acidified at pH of 4.03; (violet line) acetate buffer 0.1 M at pH of 4.50; (yellow line) acetate buffer at pH of 5.50; (black line) dihydrogen phosphate 0.1 M at pH of 5.98.</p>
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<p>CV registered in 2.5 mM GA solutions at different scan rates (from 0.01 to 2 V/s). (<b>a</b>) Bare electrode in LiClO<sub>4</sub> 0.1 M at pH of 3; (<b>b</b>) eMIP-modified electrode in LiClO<sub>4</sub> 0.1 M at pH of 3; (<b>c</b>) bare electrode in LiClO<sub>4</sub> 0.1 M at pH of 3 + ethanol 20%; (<b>d</b>) eMIP-modified electrode in LiClO<sub>4</sub> 0.1 M at pH of 3 + ethanol 20%.</p>
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<p>Comparison of three calibration curves in terms of DPV measurements in different ionic media.</p>
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<p>Histograms reporting peak potential (V) and peak current (μa) for 0.2 mM GA solution in LiClO<sub>4</sub> 0.1 M at pH of 3 containing different percentages of ethanol from 0 to 40%. DPV measurements: potential scan from −1 V to +1 V, potential step of 0.015 V, pulse time of 0.02 s, and scan speed of 0.05 v/s.</p>
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<p>DPV in LiClO<sub>4</sub> 0.1 M at pH of 3 with increasing concentrations of GA. Potential scan from −1 V to 1 V, potential step of 0.015 V, pulse width of 0.2 V, pulse duration of 0.02 s, and scan speed of 0.05 v/s.</p>
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<p>Calibration curves for bare electrodes and eMIP- and eNIP-modified electrodes. The error bars correspond to the standard deviation of the measurements performed with three electrodes of each type.</p>
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<p>DPV voltammograms recorded in LiClO<sub>4</sub> 0.1 M at pH of 3 and ethanol 10%, with a fixed GA concentration (red line) and increasing quantities of interferent. DPV measurements: potential scan from −1 V to +1 V, potential step of 0.015 V, pulse width of 0.2 V, pulse duration of 0.02 s, and scan speed of 0.05 v/s. (<b>a</b>) Interferent: catechin; (<b>b</b>) Interferent: ascorbic acid; (<b>c</b>) Interferent: 2-furalhdeyde.</p>
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<p>Example of standard addition method applied to a red wine sample. (<b>a</b>) DPV voltammograms; and (<b>b</b>) standard addition graph of 0.15 mL of red wine diluted with 10 mL of hydroalcoholic solution with 13% ethanol. <span class="html-italic">C</span><sub>x</sub> = 2.23 (7) mg L<sup>−1</sup> GA in the diluted sample corresponding to 150 (5) mg L<sup>−1</sup> GA in the red wine.</p>
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11 pages, 1864 KiB  
Article
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
Cited by 1 | Viewed by 989
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 [...] Read more.
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
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Graphical abstract

Graphical abstract
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<p>Binding isotherm curves for rabbit immunoglobulin G (rIgG). (<b>a</b>) NanoMIPs containing from 0% to 2% BIS (yellow: P0; red: P02; green: P05; blue: P1; violet: P2); (<b>b</b>) nanoMIPs containing from 4% to 50% BIS (yellow: P4; red: P8; green: P18; blue: P32; violet: P50). Error bars: ±1 s.d.</p>
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<p>Binding isotherm curves for bovine immunoglobulin G (bIgG). (<b>a</b>) NanoMIPs containing from 0% to 2% BIS (yellow: P0; red: P02; green: P05; blue: P1; violet: P2); (<b>b</b>) nanoMIPs containing from 4% to 50% BIS (yellow: P4; red: P8; green: P18; blue: P32; violet: P50). Error bars: ±1 s.d.</p>
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<p>Apparent equilibrium binding constants (K<sub>eq</sub>) measured for rIgG (red circles) and bIgG (blue circles). Error bars: ±1 s.d.</p>
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<p>Binding site density (B<sub>max</sub>) measured for rIgG (red circles) and bIgG (blue circles). Error bars: ±1 s.d.</p>
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<p>Green circles: binding selectivity (α) measured as the ratio between binding capacities (β) of nanoMIPs for bIgG and rIgG. Error bars: ±1 s.d. The pale red area indicates no (α ≥ 1) or marginal (0.8 ≤ α &lt; 1) binding selectivity.</p>
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14 pages, 6976 KiB  
Article
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
Cited by 3 | Viewed by 1428
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 [...] Read more.
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
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<p>Schematic of the synthesis of CFX–MMIPs.</p>
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<p>Effect of the crosslinker on the binding property of MMIPs: (<b>a</b>) The adsorption capacity of MMIPs and MNIPs at different polymerization times (<b>b</b>).</p>
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<p>FTIR spectra of Fe<sub>3</sub>O<sub>4</sub> (a), Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub> (b), MMIPs (c), and MNIPs (d).</p>
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<p>XRD pattern of Fe<sub>3</sub>O<sub>4</sub> (a), Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub> (b), and MMIPs (c).</p>
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<p>Magnetic hysteresis loop of Fe<sub>3</sub>O<sub>4</sub> (a), Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub> (b), MMIPs (c), and the inserted figure depicts MMIPs dispersed in solution (left) and collected by an external magnet (right).</p>
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<p>TEM of Fe<sub>3</sub>O<sub>4</sub> (<b>a</b>), Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub> (<b>b</b>), and MMIPs (<b>c</b>).</p>
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<p>SEM of MMIPs (<b>a</b>,<b>b</b>) and MNIPs (<b>c</b>,<b>d</b>).</p>
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<p>Kinetic adsorption curve of MMIPs and MNIIPs (<b>a</b>): Fitting using a pseudo−first−order (<b>b</b>) and pseudo−second−order (<b>c</b>) kinetic model for the binding CFX.</p>
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<p>Adsorption isotherm of MMIPs and MNIPs (<b>a</b>); Scatchard plot analysis of CFX binding onto MMIPs (<b>b</b>) and MNIPs (<b>c</b>); Langmuir and Freundlich adsorption isotherms of CFX onto MMIPs and MNIPs (<b>d</b>).</p>
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<p>Structures of cefixime (<b>a</b>), cefepime (<b>b</b>), and ceftiofur (<b>c</b>).</p>
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<p>Adsorption capacities of CFX and its structural analogs.</p>
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<p>Regeneration properties of MMIPs.</p>
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12 pages, 3648 KiB  
Article
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 - 7 Apr 2023
Cited by 9 | Viewed by 2754
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) [...] Read more.
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
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<p>Voltammogram of <span class="html-italic">p</span>-AP 50 µM in buffer solution pH 6.2. Data were obtained from sensors for various <span class="html-italic">p</span>-AP concentrations in the MIP. SWV parameters at potential step 10 mV; frequency 10 Hz; and scan rate 50 mV/s.</p>
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<p>Oxidation of <span class="html-italic">p</span>-AP to quinonimine and quinone [<a href="#B42-polymers-15-01818" class="html-bibr">42</a>].</p>
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<p>Voltammograms of cyclic voltammetry for <span class="html-italic">p</span>-AP solution in pH 6.2 buffer on SPCE-unmodified, SPCE-M-4G, and SPCE-M-4S.</p>
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<p>FTIR spectra for chitosan, MIP-glutaraldehyde (M-4G) and MIP-STPP (M-4S).</p>
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<p>SEM image of the M-4G (<b>a</b>) and M-4S (<b>b</b>) surfaces.</p>
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<p>Illustration of the formation of chitosan-based MIPs by glutaraldehyde and STPP as crosslinkers [<a href="#B44-polymers-15-01818" class="html-bibr">44</a>].</p>
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<p>SWV voltammogram of <span class="html-italic">p</span>-AP 50 µM solution at various pHs on SPCE-M-4G.</p>
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<p>Structure of <span class="html-italic">p</span>-AP at pH &lt; pK<sub>a1</sub> (<b>A</b>); pK<sub>a1</sub> &lt; pH &lt; pK<sub>a2</sub> (<b>B</b>); pH &gt; pK<sub>a2</sub> (<b>C</b>) and mole fractions of A, B, and C (<b>D</b>).</p>
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<p>Linear regression of the relationship between <span class="html-italic">p</span>-AP concentration and anodic peak current. which is obtained from unmodified SPCE, SPCE-M-4G, and SPCE-M-4S.</p>
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<p>Voltammogram sample F and sample F + 7 µM standard of <span class="html-italic">p</span>-AP.</p>
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16 pages, 10171 KiB  
Article
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 22 | Viewed by 2627
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 [...] Read more.
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
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<p>Electrochemical deposition of NIP-Ppy layers: (<b>A</b>) on Pt electrodes (second electrochemical system); (<b>B</b>) on SPCE electrodes (first electrochemical system), showing the profile of the current registered during the formation of the NIP-Ppy layer from polymerisation solution without any bacteria. Insets—extended profile of the current registered during the indicated potential pulse.</p>
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<p>Current profiles registered during the deposition of Ppy underlayers (<b>A</b>) on Pt electrodes (second electrochemical system), and (<b>B</b>) on SPCE electrodes (first electrochemical system). Current profiles registered during electrochemical deposition of the polypyrrole layers with entrapped <span class="html-italic">Listeria monocytogenes</span> bacteria (<b>C</b>) on Pt electrodes (2nd electrochemical system), and (<b>D</b>) on SPCE electrodes (1st electrochemical system).</p>
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<p>SEM images of NIP-Ppy/SPCE (<b>A</b>,<b>C</b>,<b>E</b>,<b>G</b>) and MIP-Ppy/SPCE (<b>B</b>,<b>D</b>,<b>F</b>,<b>H</b>) electrodes after incubation in different template extraction solutions: (<b>A</b>,<b>B</b>) 10% acetic acid, (<b>C</b>,<b>D</b>) 0.05 M sulphuric acid, (<b>E</b>,<b>F</b>) 10 U/mL trypsin, (<b>G</b>,<b>H</b>) 0.1% L-lysine at 37 °C for 30 min.</p>
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<p>Current density vs. time determined by NIP-Ppy/SPCE (<b>a</b>–<b>d</b>), MIP-Ppy/SPCE (<b>e</b>–<b>h</b>) electrodes (<b>A</b>) and NIP-Ppy/Pt (<b>a</b>–<b>d</b>), MIP-Ppy/Pt (<b>e</b>–<b>h</b>) (<b>B</b>), with a concentration range of 3.4 × 10<sup>6</sup>, 1.0 × 10<sup>7</sup>, 2.3 × 10<sup>7</sup>, 4.0 × 10<sup>7</sup>, 6.7 × 10<sup>7</sup>, 1.0 × 10<sup>8</sup> CFU/mL <span class="html-italic">Listeria monocytogenes</span> bacteria, prepared using different extraction solutions:10% acetic acid (<b>a</b>,<b>e</b>), 0.05 M sulphuric acid (<b>b</b>,<b>f</b>), 10 U/mL trypsin (<b>c</b>,<b>g</b>), and 1% L-lysine (<b>d</b>,<b>h</b>) to remove <span class="html-italic">Listeria monocytogenes</span> bacteria from imprinted cavities.</p>
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<p>The current density of NIP-Ppy/SPCE (solid black lines) and MIP-Ppy/SPCE (dashed red lines) electrodes registered using pulsed amperometric detection after incubation in solutions containing different <span class="html-italic">Listeria monocytogenes</span> bacteria concentrations; <span class="html-italic">Listeria monocytogenes</span> from MIP-Ppy was extracted using different extraction solutions: (<b>A</b>) 10% acetic acid, (<b>B</b>) 0.05 M of sulphuric acid, (<b>C</b>) 10 U/mL of trypsin, (<b>D</b>) 0.1% L-lysine.</p>
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<p>The current density of NIP-Ppy/Pt (solid black lines) and MIP-Ppy/Pt (dashed red lines) electrodes registered using pulsed amperometric detection after incubation in solutions containing different <span class="html-italic">Listeria monocytogenes</span> bacteria concentrations; <span class="html-italic">Listeria monocytogenes</span> from MIP-Ppy was extracted using different extraction solutions: (<b>A</b>) 10% acetic acid, (<b>B</b>) 0.05 M of sulphuric acid, (<b>C</b>) 10 U/mL of trypsin, (<b>D</b>) 0.1% L-lysine.</p>
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<p>Calibration curve Δ<span class="html-italic">I</span> registered by MIP-Ppy/SPCE (black line) and NIP-Ppy/SPCE (red line) vs. <span class="html-italic">Listeria monocytogenes</span> concentration. Error bars are calculated as a percentage standard error.</p>
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<p>Schematic representation of electrode modification.</p>
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11 pages, 3912 KiB  
Communication
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 2062
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 [...] Read more.
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 Kd value comparable with the affinity values of antibodies. The synthesized MIP are not toxic, which makes them suitable for nanomedicine. Full article
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Figure 1
<p>(<b>a</b>) Fourier transform infrared spectroscopy (FT-IR) spectra; (<b>b</b>) dynamic light scattering (DLS); (<b>c</b>) fluorescence spectra.</p>
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<p>(<b>a</b>) Transmission electron microscopy images of MIP at 20,000× magnification. The spherical MIP particles have a size distribution ranging from 20 nm to 300 nm; (<b>b</b>) size distribution of MIP as acquired from TEM; (<b>c</b>) representative fluorescence microscopy images with (right) and without (left) the fluorescent filter.</p>
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<p>Calorimetric data for the binding kinetics between MIP and epitope X (black), MIP and epitope Y (red), covered MIP and epitope X (blue), MIP and water (green) and MIP before epitope extraction and epitope X. (<b>a</b>) Raw data from exothermic binding after continuous titration of MIP in the epitope solution. (<b>b</b>) Results calculated from the raw data as a function of the molar ratio of MIP to epitopes (the first value was excluded from the analysis).</p>
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<p>Calorimetric data for binding kinetics between MIP/epitope X and NIP/epitope X.</p>
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<p>Cell viability in the two breast cancer cell lines MCF7 and SUM-159 after 24 h, 48 h and 72 h in the presence of increasing concentrations of MIP (NT = non treated).</p>
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<p>The MIP was prepared by co-polymerization (1) of monomers and a cross-linker in the presence of the target epitope, which acts as a molecular template. Upon extraction (2), the so-formed material retains molecular cavities, complementary in size, shape and functionality to the template and ready to re-bind it through weak interactions.</p>
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<p>Schematic representation of the different nanoITC experiments with the MIP. The imprinted polymer is loaded into the syringe placed in a very precise injection device. The injection device was inserted into the sample cell containing a solution of epitopes.</p>
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<p>Molecularly imprinted polymer and epitope reaction scheme with <span class="html-italic">n</span> = 1 stoichiometry.</p>
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14 pages, 3452 KiB  
Article
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 1725
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 [...] Read more.
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
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<p>(<b>A</b>) Optimization of synthetic FMIPs. (<b>B</b>) Energy spectrum spectra of FMIPs. (<b>C</b>) SEM image of FMIPs with a scale bar of 50 nm. (<b>D</b>) TEM image of FMIPs with a scale bar of 100 nm. (<b>E</b>) EDS spectrum of FMIPs.</p>
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<p>(<b>A</b>) FT−IR spectrum of FMIPs, FMIPs without AVAs 2f, CDs, and AVAs 2f. (<b>B</b>) XPS spectrum of FMIPs. High-resolution XPS peaks of FMIPs: (<b>C</b>) C<sub>1s</sub>, (<b>D</b>) O<sub>1s</sub>, and (<b>E</b>) N<sub>1s</sub>.</p>
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<p>(<b>A</b>) TGA and (<b>B</b>) DTG curves of FMIPs, FMIPs without AVAs 2f, and CDs, (<b>C</b>) DPPH-scavenging activity of FMIPs, (<b>D</b>) Degradation rates of AVAs 2f and FMIPs under ultraviolet irradiation.</p>
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<p>(<b>A</b>) In vitro release profile of AVAs 2f from FMIPs, (<b>B</b>) Weibull kinetic release model, (<b>C</b>) Firet kinetic release model, (<b>D</b>) Higuchi kinetic release model, (<b>E</b>) Zero kinetic release model, and (<b>F</b>) Hixcon−Crowell kinetic release model of FMIPs at 37, 60, and 80 °C.</p>
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<p>HPLC of PRL (<b>A</b>) without FMIPs, (<b>B</b>) with FMIPs at 60 °C, and (<b>C</b>) with FMIPs at 80 °C in simulated system.</p>
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<p>Schematic diagram of the preparation of FMIPs and its application in the inhibition of AGEs.</p>
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10 pages, 3058 KiB  
Article
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 2 | Viewed by 1458
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 [...] Read more.
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
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<p>Binding affinity of 2,4,5-T for the MIP in presence of increasing amounts of Tween 20. For each group of bars from left to right: water molar fraction from 0 (pure acetonitrile) to 0.24, 0.42, 0.66 and 0.81.</p>
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<p>Binding affinity of 2,4,5-T for the MIP in presence of increasing amounts of SDS. For each group of bars from left to right: water molar fraction from 0 (pure acetonitrile) to 0.24, 0.42, 0.66 and 0.81.</p>
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<p>Binding affinity of 2,4,5-T for the MIP in presence of increasing amounts of CTAB. For each group of bars from left to right: water molar fraction from 0 (pure acetonitrile) to 0.24, 0.42, 0.66 and 0.81.</p>
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<p>(<b>a</b>) Binding affinity of 2,4,5-T for the NIP in presence of increasing amounts of Tween 20; (<b>b</b>) Imprinting factor. For each group of bars from left to right: water molar fraction from 0 (pure acetonitrile) to 0.24, 0.42, 0.66 and 0.81.</p>
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<p>(<b>a</b>) Binding affinity of 2,4,5-T for the NIP in presence of increasing amounts of SDS; (<b>b</b>) Imprinting factor. For each group of bars from left to right: water molar fraction from 0 (pure acetonitrile) to 0.24, 0.42, 0.66 and 0.81.</p>
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<p>(<b>a</b>) Binding affinity of 2,4,5-T for the NIP in presence of increasing amounts of CTAB; (<b>b</b>) Imprinting factor. For each group of bars from left to right: water molar fraction from 0 (pure acetonitrile) to 0.24, 0.42, 0.66 and 0.81.</p>
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<p>(<b>a</b>) Binding affinity of 2,4-D for the MIP in presence of increasing amounts of Tween 20; (<b>b</b>) Binding selectivity. For each group of bars from left to right: water molar fraction from 0 (pure acetonitrile) to 0.24, 0.42, 0.66 and 0.81.</p>
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<p>(<b>a</b>) Binding affinity of 2,4-D for the MIP in presence of increasing amounts of SDS; (<b>b</b>) Binding selectivity. For each group of bars from left to right: water molar fraction from 0 (pure acetonitrile) to 0.24, 0.42, 0.66 and 0.81.</p>
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<p>(<b>a</b>) Binding affinity of 2,4-D for the MIP in presence of increasing amounts of CTAB; (<b>b</b>) Binding selectivity. For each group of bars from left to right: water molar fraction from 0 (pure acetonitrile) to 0.24, 0.42, 0.66 and 0.81.</p>
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<p>Binding affinity of 2,4,5-T for the MIP in presence of additives mimic of the polar part of the surfactants. For each group of bars from left to right: water molar fraction from 0 (pure acetonitrile) to 0.24, 0.42, 0.66 and 0.81.</p>
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<p>Possible dynamic interactions between surfactants, phenoxyacids and phenoxyacid-imprinted polymer. Blue color: hydrophobic surface/functionality. Red color: charged or hydrophilic surface/functionality. Left column (case E &amp; F): interactions onto not-imprinted surfaces; central column (case A &amp; B): interactions in solution; right column (case C &amp; D): interaction in the binding site (see text for further explanation).</p>
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Review

Jump to: Research

20 pages, 4507 KiB  
Review
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 4 | Viewed by 3794
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 [...] Read more.
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
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<p>The MIP imprinting technique includes several components and steps that should be carefully selected for medical applications. The biomarkers representing the template of interest depend on the disease, as well as on the chosen application. The MIP systems developed and described in this review include the diagnosis or treatment of the following diseases: cancer (particularly focusing on glycosylation, drug delivery, and biosensors), neurodegenerative disorders, cardiovascular diseases, renal diseases, and COVID-19. The most common applications of MIP systems within the medical domain are optical and electrical sensors, imaging, flow cytometry, and ELISA. In the case of sensors, four different formats for MIP sensors are presented: polymeric film on electrode, polymeric film with nanomaterials on electrode, MIP deposited on electrode, and polymeric film with nanomaterials on electrode combined with MIPs.</p>
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<p>(<b>A</b>) The layers of the skin comprise the <span class="html-italic">stratum corneum</span>, with cornified flat keratinocytes (<b>upper</b>); the epidermis, with different stages of keratinocytes, melanocytes, and immune cells (<b>middle</b>); and the dermis, with mainly fibroblasts (<b>lower</b>). (<b>B</b>) The expression of monosaccharides and glycosaminoglycans is illustrated on the cell membranes of keratinocytes (<b>upper</b>) and melanoma cells (<b>lower</b>). Since the binding of SA-MIPs to keratinocytes was absent in the unpublished study, the cell membrane of this cell type is proposed to express more glycosaminoglycans than monosaccharides. On the other hand, melanoma cells are proposed to express high amounts of monosaccharides since these cells showed good SA-MIP binding.</p>
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26 pages, 4259 KiB  
Review
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 13 | Viewed by 4561
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 [...] Read more.
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
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<p>Preparation of MIPs. Adapted with permission from Ref. [<a href="#B24-polymers-15-00187" class="html-bibr">24</a>]. Copyright 2019, Elsevier.</p>
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<p>The principle of MIP-based electrochemical sensors. Adapted with permission from Ref. [<a href="#B58-polymers-15-00187" class="html-bibr">58</a>]. Copyright 2020, Elsevier.</p>
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<p>Schematic illustration of nonelectroactive molecular detection. (1) Elution; (2) IAA-S incubation; (3) IAA and labeled IAA-S competition; (4) AgNP labeling; and (5) catalytic copper deposition. Adapted with permission from Ref. [<a href="#B64-polymers-15-00187" class="html-bibr">64</a>]. Copyright 2014, Elsevier.</p>
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<p>Schematic illustration of the MIP-based ISE sensor for neutral bisphenol detection using MIP for recognition on the ISE surface and charged ions as potential signals. Adapted with permission from Ref. [<a href="#B66-polymers-15-00187" class="html-bibr">66</a>]. Copyright 2022, American Chemical Society.</p>
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<p>Schematic illustration of the magnetic imprinted electrochemical sensor. Adapted with permission from Ref [<a href="#B75-polymers-15-00187" class="html-bibr">75</a>]. Copyright 2015, Elsevier.</p>
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<p>Schematic illustration of the experimental procedure of MIP-based SPE sensor fabrication. Adapted with permission from Ref. [<a href="#B94-polymers-15-00187" class="html-bibr">94</a>]. Copyright 2020, Elsevier.</p>
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<p>Schematic preparation of the MIP-based electrochemical sensing platform. Adapted with permission from Ref. [<a href="#B21-polymers-15-00187" class="html-bibr">21</a>]. Copyright 2021, Elsevier.</p>
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<p>A schematic fabrication process of the MIP−based sensor for TBHQ detection. Adapted with permission from Ref. [<a href="#B109-polymers-15-00187" class="html-bibr">109</a>]. Copyright 2029, Elsevier.</p>
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<p>The different steps for the preparation of the sensor. Fe<sub>2</sub>O<sub>3</sub> was used as the carrier to deposit Ru(bpy)<sub>3</sub><sup>2+</sup>, and Fe<sub>2</sub>O<sub>3</sub> @Ru(bpy)<sub>3</sub><sup>2+</sup> was used as a signal recognition layer. The ECL signal increased when the polymer was eluted from the MIPs (a), and the signal decreased (b) when the CLB rebinding to MIPs. Adapted with permission from Ref. [<a href="#B119-polymers-15-00187" class="html-bibr">119</a>]. Copyright 2022, Elsevier.</p>
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<p>Schematic illustration of the electrochemical sensor for selective detection of 2,4-DCP. Adapted with permission from Ref. [<a href="#B122-polymers-15-00187" class="html-bibr">122</a>]. Copyright 2019, Elsevier.</p>
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<p>A schematic fabrication process of Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>@IIP. Adapted with permission from Ref. [<a href="#B125-polymers-15-00187" class="html-bibr">125</a>]. Copyright 2020, Elsevier.</p>
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