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Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds

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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Applications".

Deadline for manuscript submissions: closed (5 February 2025) | Viewed by 22554

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Dr. Ana-Mihaela Gavrila

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Polymers Department-The National Research & Development Institute for Chemistry and Petrochemistry-ICECHIM, 060021 Bucharest, Romania
Interests: polymers; molecularly imprinted polymers; polymeric micro/nanoparticles and films; (bio)sensors for drugs; explosives; pollutants; biological and chemical agents; nanomaterials
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Prof. Dr. Mariana Ionita

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Faculty of Medical Engineering, Advanced Polymer Materials Group, eBio-Hub Research Centre, National University of Science and Technology Politehnica Bucharest, 011061 Bucharest, Romania
Interests: materials science; bioengineering; nanotechnology; tissue regeneration
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Dr. Gabriela Toader

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Military Technical Academy “Ferdinand I”, 39-49 George Cosbuc Boulevard, 050141 Bucharest, Romania
Interests: polymers; nanomaterials; CBRN defence; toxics; decontamination; hazardous materials; thin films; hydrogels; environmental safety; polyurea; ballistic protection; explosives; energetic materials; nanocomposites; electrochemistry
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Special Issue Information

Dear Colleagues,

It is our great pleasure to invite you to submit a manuscript for the upcoming Special Issue “Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds” (IF: 4.967, ISSN 2073-4360) in Polymers. The present Special Issue will focus on innovations in the synthesis methods, characterization and applications of molecularly imprinted polymers and alternative smart polymeric platforms designed for sensing purposes (identification, detection) or decontamination (removal and/or neutralization) of hazardous compounds (e.g., drugs, explosives and pollutants and biological or chemical agents).

Versatile, advanced polymeric materials that possess unique functions in response to external factors have become widespread. Smart polymers, or “stimuli-responsive” polymers, can react to a wide range of stimuli (changes in pH, ion content, temperature, solvent, radiation and biological or chemical agents), and their response can include a variety of changes in structural, chemical, mechanical, optical or electrical properties.

In recent years, major advances have been made in the development of MIPs, which have become the most available and well-known artificial recognition sites, with similarities to antibodies. Due to their unique properties (highly selective recognition properties, reusability, long-term stability and low production cost), various types of MIPs (particles, films) can be used for a wide range of applications, including as sensing/diagnostic devices for different hazardous chemicals, biochemicals and pharmaceuticals and in applications for environmental safety or decontamination purposes.

Hazards associated with highly dangerous pollutants/contaminants necessitate specialized handling techniques and risk-control strategies to be operated within an acceptable level of risk. The following specific actions are essential when encountering hazardous materials threats: detection, identification, neutralization, removal and disposal of the contaminants. In this context, due to their capacity to be especially designed for specific types of contaminants, smart polymers offer a plethora of alternatives and incredibly powerful solutions for addressing challenges associated with hazardous compounds.

Original research articles, short communications, review, mini-reviews and perspective articles are all welcome. The keywords cover a nonexhaustive list of topics of interest.

Dr. Ana-Mihaela Gavrila
Dr. Mariana Ionita
Dr. Gabriela Toader
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

polymers
molecularly imprinted polymers
smart materials
polymeric platforms
decontamination
hazardous compounds
(bio)sensors for drugs/explosives/dyes/pollutants/biological and chemical agents
detection
hydrogels

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Published Papers (10 papers)

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Editorial

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6 pages, 205 KiB

Open AccessEditorial

Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds

by Ana-Mihaela Gavrilă, Mariana Ioniță and Gabriela Toader

Polymers 2025, 17(8), 1092; https://doi.org/10.3390/polym17081092 - 18 Apr 2025

Viewed by 214

Abstract

Addressing hazards from dangerous pollutants requires specialized techniques and risk-control strategies, including detection, neutralization and disposal of contaminants. Smart polymers, designed for specific contaminants, provide powerful solutions for hazardous compound challenges. Their remarkable performance capabilities and potential applications present exciting opportunities for further exploration and development in this field. This editorial aims to provide a comprehensive overview of smart materials with unique features and emerging polymeric technologies that are being developed for isolation, screening, removal, and decontamination of hazardous compounds (e.g., heavy metals, pharmaceutically active contaminants, hormones, endocrine-disrupting chemicals, pathogens, and energetic materials). It highlights recent advancements in synthesis methods, characterization, and the applications of molecularly imprinted polymers (MIPs), along with alternative smart polymeric platforms including hydrogels, ion-imprinted composites, screen-printed electrodes, nanoparticles, and nanofibers. MIPs offer highly selective recognition properties, reusability, long-term stability, and low production costs. Various MIP types, including particles and films, are used in applications like sensing/diagnostic devices for hazardous chemicals, biochemicals, pharmaceuticals, and environmental safety. Full article

(This article belongs to the Special Issue Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds)

Research

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22 pages, 6160 KiB

Open AccessArticle

Preparation and Performance Research of Pb(II)-Imprinted Acrylonitrile-Co-Acrylic Acid Composite Material with Modified Sand Particles as Carrier

by Yixin Sui, Shuaibing Gao, Jiaxiang Qi, Shawket Abliz and Linlin Chai

Polymers 2025, 17(2), 229; https://doi.org/10.3390/polym17020229 - 17 Jan 2025

Cited by 1 | Viewed by 727

Abstract

Lead (Pb) is classified as a prevalent metallic pollutant, significantly impacting the ecological environment, especially human health. Consequently, it is crucial to develop adsorbent materials that are environmentally friendly, cost-effective, and which possess high selectivity. This study aims to fabricate a Pb(II)-imprinted acrylonitrile-co-acrylic acid composite material by using modified sand particles as the carrier, and then to investigate its properties. Through pretreatment of sand particles, acrylonitrile and acrylic acid were polymerized on the surface of modified sand particles, and Pb(II) served as a template ion for imprinting. A variety of characterization methods were used to verify the composite material and conduct an analysis of its morphology, chemical composition, and pore characteristics. The adsorption efficiency of this composite material for Pb(II) is comprehensively explored, with the process involving adsorption kinetics, adsorption isotherms, selective adsorption, and reuse experiments. Through static adsorption experiments, multiple elements influencing the adsorption ability of the composite material towards Pb(II) are investigated. It was demonstrated by the results that the composite material prepared possesses a rich pore structure and excellent Pb(II) recognition ability. The investigation on adsorption kinetics is in line with the quasi-first-order and quasi-second-order kinetic models, while the adsorption isotherm, obeys the Langmuir model. The ideal adsorption conditions were pH = 7, with the adsorption reaching equilibrium within 105 min. Even when multiple interfering ions were present, it still had high selectivity for Pb(II). The composite material showed an adsorption saturation capability reaching 41.83 mg·g⁻¹, considerably surpassing the non-imprinted counterpart. After being reused eight times, the composite material can still maintain an adsorption efficiency for Pb(II) that is above 79% and demonstrates high potential in the practical application environment. Full article

(This article belongs to the Special Issue Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds)

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20 pages, 11792 KiB

Open AccessArticle

Synthesis and Study of Sorption Properties of Zinc-Imprinted Polymer

by Alma Khassenovna Zhakina, Yevgeniy Petrovich Vassilets, Oxana Vasilievna Arnt and Almat Maulenuly Zhakin

Polymers 2024, 16(24), 3545; https://doi.org/10.3390/polym16243545 - 19 Dec 2024

Cited by 1 | Viewed by 628

Abstract

Zinc-imprinted polymer (ZnIP) and non-imprinted polymer (NIP) were synthesized by radical polymerization, and their properties were studied. The novelty of the work lies in the use of humic acids isolated from coals of the Shubarkol deposit (Karaganda, Kazakhstan) as a basis for the imprinted polymer matrix, with methacrylic acid and ethylene glycol dimethacrylate as a functional monomer and a cross-linking agent, respectively. The composition and structure of ZnIP and NIP were characterized using various physicochemical methods. The specific surface area of ZnIP determined by the BET method was 40.60 ± 0.4 m²/g, which is almost twice as high as the similar indicator for NIP (21.50 ± 0.3 m²/g). In sorption tests of solutions with bimetallic ions, ZnIP demonstrates higher adsorption: 96.15% for Zn²⁺ and 74.88% for Pb²⁺, while NIP adsorbs only 81.33% and 60.11%, respectively. Sorption on both polymers is described by a pseudo-first-order equation (r > 0.99). The distribution coefficients for ZnIP are higher than for NIP. ZnIP has a relative selectivity that exceeds NIP by 2.90 times. The research results indicate the promise of using ZnIP for the selective removal of zinc ions from solutions of multicomponent systems, including wastewater, making it a valuable material for solving environmental and technological problems. Full article

(This article belongs to the Special Issue Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds)

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28 pages, 8060 KiB

Open AccessArticle

Electrospinning and Rheological Characterization of Polyethylene Terephthalate and Polyvinyl Alcohol with Different Degrees of Hydrolysis Incorporating Molecularly Imprinted Polymers

by Sisonke Sigonya, Teboho Clement Mokhena, Paul Mayer, Talent Raymond Makhanya and Thabang Hendrica Mokhothu

Polymers 2024, 16(23), 3297; https://doi.org/10.3390/polym16233297 - 26 Nov 2024

Cited by 3 | Viewed by 745

Abstract

This study investigates the electrospinning and rheological properties of polyethylene terephthalate (PET) and polyvinyl alcohol (PVA) with varying degrees of hydrolysis (DH) for molecularly imprinted polymer (MIP) incorporation. The morphology and properties of the electrospun nanofibers were evaluated, revealing that PVA nanofibers exhibited smoother and more uniform structures compared to PET fibers. The rheological behavior of the polymer solutions was also characterized, showing that PVA 99 DH solution exhibited shear-thinning behavior due to the unique structural properties of the polymer chains. The introduction of MIP and NIP additives had no significant impact on the rheological properties, except for PVA 99 MIP and NIP solutions, which showed deviations from Newtonian behavior. The electrospun MIP nanofibers showed a conductivity of 1054 µS/cm for PVA (87–90% DH) and a viscosity of 165.5 mPa·s, leading to optimal fiber formation, while displaying a good adsorption capacity of 0.36 mg for PVA-MIP to effectively target pharmaceuticals such as emtricitabine and tenofovir disoproxil, showing their potential for advanced water treatment applications. The results suggest that the electrospinning process and rheological properties of the polymer solutions are influenced by the molecular structure and interactions within the polymer matrix, which can be exploited to tailor the properties of MIPs for specific applications. Full article

(This article belongs to the Special Issue Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds)

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19 pages, 3986 KiB

Open AccessArticle

Molecularly Imprinted Polypyrrole-Modified Screen-Printed Electrode for Dopamine Determination

by Daniele Merli, Alessandra Cutaia, Ines Hallulli, Alessandra Bonanni and Giancarla Alberti

Polymers 2024, 16(17), 2528; https://doi.org/10.3390/polym16172528 - 6 Sep 2024

Cited by 4 | Viewed by 1837

Abstract

This paper introduces a quantitative method for dopamine determination. The method is based on a molecularly imprinted polypyrrole (e-MIP)-modified screen-printed electrode, with differential pulse voltammetry (DPV) as the chosen measurement technique. The dopamine molecules are efficiently entrapped in the polymeric film, creating recognition cavities. A comparison with bare and non-imprinted polypyrrole-modified electrodes clearly demonstrates the superior sensitivity, selectivity, and reproducibility of the e-MIP-based one; indeed, a sensitivity of 0.078 µA µM⁻¹, a detection limit (LOD) of 0.8 µM, a linear range between 0.8 and 45 µM and a dynamic range of up to 350 µM are achieved. The method was successfully tested on fortified synthetic and human urine samples to underline its applicability as a screening method for biomedical tests. Full article

(This article belongs to the Special Issue Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds)

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25 pages, 5076 KiB

Open AccessArticle

Nanocomposite Hydrogel Films Based on Sequential Interpenetrating Polymeric Networks as Drug Delivery Platforms

by Gabriela Toader, Alice Ionela Podaru, Aurel Diacon, Edina Rusen, Alexandra Mocanu, Oana Brincoveanu, Mioara Alexandru, Florina Lucica Zorila, Mihaela Bacalum, Florin Albota, Ana Mihaela Gavrila, Bogdan Trica, Traian Rotariu, Mariana Ionita and Marcel Istrate

Polymers 2023, 15(15), 3176; https://doi.org/10.3390/polym15153176 - 26 Jul 2023

Cited by 8 | Viewed by 2127

Abstract

In this study, novel materials have been obtained via a dual covalent and ionic crosslinking strategies, leading to the formation of a fully interpenetrated polymeric network with remarkable mechanical performances as drug delivery platforms for dermal patches. The polymeric network was obtained by the free-radical photopolymerization of N-vinylpyrrolidone using tri(ethylene glycol) divinyl ether as crosslinker in the presence of sodium alginate (1%, weight%). The ionic crosslinking was achieved by the addition of Zn²⁺, ions which were coordinated by the alginate chains. Bentonite nanoclay was incorporated in hydrogel formulations to capitalize on its mechanical reinforcement and adsorptive capacity. TiO₂ and ZnO nanoparticles were also included in two of the samples to evaluate their influence on the morphology, mechanical properties and/or the antimicrobial activity of the hydrogels. The double-crosslinked nanocomposite hydrogels presented a good tensile resistance (1.5 MPa at 70% strain) and compression resistance (12.5 MPa at a strain of 70%). Nafcillin was loaded into nanocomposite hydrogel films with a loading efficiency of up to 30%. The drug release characteristics were evaluated, and the profile was fitted by mathematical models that describe the physical processes taking place during the drug transfer from the polymer to a PBS (phosphate-buffered saline) solution. Depending on the design of the polymeric network and the nanofillers included, it was demonstrated that the nafcillin loaded into the nanocomposite hydrogel films ensured a high to moderate activity against S. aureus and S. pyogenes and no activity against E. coli. Furthermore, it was demonstrated that the presence of zinc ions in these polymeric matrices can be correlated with the inactivation of E. coli. Full article

(This article belongs to the Special Issue Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds)

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15 pages, 3609 KiB

Open AccessArticle

“Green” PBX Formulations Based on High Explosives (RDX and HMX) and Water-Soluble pH-Sensitive Polymeric Binders

by Traian Rotariu, Andreea Elena Moldovan, Gabriela Toader, Aurel Diacon, Edina Rusen, Raluca Elena Ginghina, Ovidiu Iorga, Horia Răzvan Botiș and Thomas Klapötke

Polymers 2023, 15(7), 1790; https://doi.org/10.3390/polym15071790 - 4 Apr 2023

Cited by 4 | Viewed by 4929

Abstract

The increasingly harsher and more complex international and European environmental legislation drives the current development of “greener” energetics materials and munitions. The aerospace and defense industries rely on extensive research in the formulation and scale-up production of polymer-bonded explosives (PBX). In this context, this paper aims to present a versatile method for obtaining “green” PBX formulations based on two high explosives (hexogen (RDX) and octogen (HMX)) and acrylic acid—ethyl acrylate copolymeric binders. This study developed an innovative “eco-friendly” technology for coating the RDX and HMX crystals, allowing straightforward and safer manufacture of PBX, avoiding the use of traditional organic solvents. At the same time, these polymeric binders are soluble in water at a slightly alkaline pH and insoluble at acidic or neutral pH, thus ensuring a safer manipulation of the energetic materials during their entire life cycle and a facile recovery of the explosive in its original shape and morphology in demilitarization. The PBX formulations were characterized via specific analytical tools to evaluate the influence of their composition on the safety and performance characteristics: scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), alkaline pH solubility tests, differential thermal analysis (DTA), impact sensitivity test (BAM Fall Hammer Test), friction sensitivity test (BAM Friction Test), electrostatic sensitivity test (ESD), vacuum stability test, small scale shock reactivity test (SSRT), detonation velocity test. The “green” PBX formulations obtained through a simple and innovative coating method, based on the polymeric binders’ adjustable water solubility, demonstrated remarkable energetic performances and a facile recovery of the explosive crystals by the dissolution of the polymeric binder at pH 11 and 30 °C. Full article

(This article belongs to the Special Issue Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds)

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18 pages, 6726 KiB

Open AccessArticle

Preparation of Immobilised 17β-Estradiol-Imprinted Nanoparticles onto Bacterial Cellulose Nanofibres to Use for the Removal of 17β-Estradiol from Wastewater

by İlker Koç, Koray Şarkaya, Deniz Türkmen, Süleyman Aşır and Adil Denizli

Polymers 2023, 15(5), 1201; https://doi.org/10.3390/polym15051201 - 27 Feb 2023

Cited by 2 | Viewed by 1899

Abstract

Estradiol, a phenolic steroid oestrogen, is one of the endocrine-disrupting chemicals (EDCs) found in natural and tap waters. The detection and removal of EDCs is attracting attention daily as they negatively affect animals’ and humans’ endocrine functions and physiological conditions. Therefore, developing a fast and practical method for the selective removal of EDCs from waters is essential. In this study, we prepared 17β-estradiol (E2)-imprinted HEMA-based nanoparticles onto bacterial cellulose nanofibres (E2-NP/BC-NFs) to use for the removal of E2 from wastewater. FT-IR and NMR confirmed the structure of the functional monomer. The composite system was characterised by BET, SEM, µCT, contact angle, and swelling tests. Additionally, the non-imprinted bacterial cellulose nanofibres (NIP/BC-NFs) were prepared to compare the results of E2-NP/BC-NFs. Adsorption of E2 from aqueous solutions was performed in batch mode and investigated via several parameters for optimisation conditions. The effect of pH studies was examined in the 4.0–8.0 range using acetate and phosphate buffers and a concentration of E2 of 0.5 mg/mL. The maximum E2 adsorption amount was 254 µg/g phosphate buffer at 45 °C. The experimental data show that the Langmuir is a relevant isotherm model for E2 adsorption. Additionally, the relevant kinetic model was the pseudo-second-order kinetic model. It was observed that the adsorption process reached equilibrium in less than 20 min. The E2 adsorption decreased with the increase in salt at varying salt concentrations. The selectivity studies were performed using cholesterol and stigmasterol as competing steroids. The results show that E2 is 46.0 times more selective than cholesterol and 21.0 times more selective than stigmasterol. According to the results, the relative selectivity coefficients for E2/cholesterol and E2/stigmasterol were 8.38 and 86.6 times greater for E2-NP/BC-NFs than for E2-NP/BC-NFs, respectively. The synthesised composite systems were repeated ten times to assess the reusability of E2-NP/BC-NFs. Full article

(This article belongs to the Special Issue Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds)

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Review

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29 pages, 5319 KiB

Open AccessReview

Cellulose-Based Hydrogels for Wastewater Treatment: A Focus on Metal Ions Removal

by Francesca Persano, Cosimino Malitesta and Elisabetta Mazzotta

Polymers 2024, 16(9), 1292; https://doi.org/10.3390/polym16091292 - 5 May 2024

Cited by 17 | Viewed by 4252

Abstract

The rapid worldwide industrial growth in recent years has made water contamination by heavy metals a problem that requires an immediate solution. Several strategies have been proposed for the decontamination of wastewater in terms of heavy metal ions. Among these, methods utilizing adsorbent materials are preferred due to their cost-effectiveness, simplicity, effectiveness, and scalability for treating large volumes of contaminated water. In this context, heavy metal removal by hydrogels based on naturally occurring polymers is an attractive approach for industrial wastewater remediation as they offer significant advantages, such as an optimal safety profile, good biodegradability, and simple and low-cost procedures for their preparation. Hydrogels have the ability to absorb significant volumes of water, allowing for the effective removal of the dissolved pollutants. Furthermore, they can undergo surface chemical modifications which can further improve their ability to retain different environmental pollutants. This review aims to summarize recent advances in the application of hydrogels in the treatment of heavy metal-contaminated wastewater, particularly focusing on hydrogels based on cellulose and cellulose derivatives. The reported studies highlight how the adsorption properties of these materials can be widely modified, with a wide range of adsorption capacity for different heavy metal ions varying between 2.3 and 2240 mg/g. The possibility of developing new hydrogels with improved sorption performances is also discussed in the review, with the aim of improving their effective application in real scenarios, indicating future directions in the field. Full article

(This article belongs to the Special Issue Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds)

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15 pages, 1351 KiB

Open AccessReview

Advances in Molecular Imprinting Technology for the Extraction and Detection of Quercetin in Plants

by Kexi Ye, Shufang Xu, Qingqing Zhou, Sitao Wang, Zhigang Xu and Zhimin Liu

Polymers 2023, 15(9), 2107; https://doi.org/10.3390/polym15092107 - 28 Apr 2023

Cited by 13 | Viewed by 3101

Abstract

Quercetin is a kind of flavonoid compound, which has antioxidative, anti-aging and anti-cancer effects, so it is of great importance to study the efficient extraction and highly sensitive detection of quercetin. Molecular imprinting technology has remarkable selectivity and resistance to complex matrix interference, which is often used for extracting quercetin. The methods of molecular imprinted solid phase extraction, molecularly imprinted microsphere extraction, molecularly imprinted electrochemical sensor recognition and molecularly imprinted composite material extraction of quercetin from plant samples were discussed in detail. This review provides valuable information on efficient and sensitive methods for separating and purifying quercetin in plants. It also provides a technical reference for further investigation of the separation and analysis of active ingredients in natural products. Full article

(This article belongs to the Special Issue Recent Advances in Molecularly Imprinted Polymers and Emerging Polymeric Technologies for Hazardous Compounds)

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