Advances in Molecularly Imprinted Polymer Nanomaterials

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Synthesis, Interfaces and Nanostructures".

Deadline for manuscript submissions: closed (20 December 2022) | Viewed by 35461

Special Issue Editors


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Guest Editor
Department of Chemistry, College of Science and Engineering, University of Leicester, Leicester, UK
Interests: development of molecularly imprinted polymer (MIP) nanoparticles (“plastic antibodies”) and their application for life sciences, particularly in imaging, diagnostics, targeted drug delivery and surface proteomics; a design of the bespoke adsorbents for bio-refinery, environmental and clinical applications; a development of the polymers for the control of bacterial quorum sensing and catalytic nanomaterials for prevention of biofilms

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Guest Editor
Department of Biotechnology, University of Verona, 37134 Verona, Italy
Interests: development of protein and peptide recognition; biomimetic nanomaterials; strategy of molecular imprinting of polymers and their integration in analytical methods, assays and bio/sensors; activities at cellular and biomolecular level; molecularly imprinted nanoparticles for protein refolding and as tools for biomolecular interactions
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Special Issue Information

Dear Colleagues,

Molecularly imprinted polymers (MIPs) are synthetic receptors prepared via template-assisted synthesis. Driven by thermodynamics, the template interacts with the monomers forming a pre-polymerization complex, stabilized by molecular interactions that are later “frozen” by polymerization. As a result, molecular impressions of the template are stamped into the formed polymeric material. creating specific binding sites. MIPs have affinity and selectivity similar to those of natural receptors, are robust and tolerant to different pH and temperature conditions and can be manufactured using quick and inexpensive procedures. They can also be easily functionalized with fluorescent, magnetic or drug delivery moieties.

The present Special Issue reviews recent developments of MIPs in the form of nanoparticles and nanolayers, and their applications in the domain of life sciences and medicine. It contains work prepared by leading practitioners in the field. Key papers will discuss the development of solid phase synthesis of MIP nanoparticles, epitope mapping, imprinting of challenging targets, and other innovations in the field of molecular imprinting.

We believe this Issue will be of interest to broad range of readers working in nanotechnology and life sciences.

Prof. Dr. Elena Piletska
Dr. Alessandra Maria Bossi
Guest Editors

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Keywords

  • molecularly imprinted polymers (MIPs)
  • synthetic receptors
  • MIP nanoparticles
  • MIP nanolayers
  • life science
  • medicine
  • nanotechnology

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Published Papers (9 papers)

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Research

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15 pages, 3995 KiB  
Communication
Synthesis of fluorescent Molecularly Imprinted Polymer Nanoparticles Sensing Small Neurotransmitters with High Selectivity Using Immobilized Templates with Regulated Surface Density
by Yasuo Yoshimi, Yuto Katsumata, Naoya Osawa, Neo Ogishita and Ryota Kadoya
Nanomaterials 2023, 13(1), 212; https://doi.org/10.3390/nano13010212 - 3 Jan 2023
Cited by 1 | Viewed by 9637
Abstract
To develop nanosensors to probe neurotransmitters, we synthesized fluorescent-functionalized molecularly imprinted polymeric nanoparticles (fMIP-NPs) using monoamine neurotransmitters (serotonin and dopamine) immobilized on glass beads as templates. The size and fluorescence intensity of the fMIP-NPs synthesized with blended silane couplers increased with the presence [...] Read more.
To develop nanosensors to probe neurotransmitters, we synthesized fluorescent-functionalized molecularly imprinted polymeric nanoparticles (fMIP-NPs) using monoamine neurotransmitters (serotonin and dopamine) immobilized on glass beads as templates. The size and fluorescence intensity of the fMIP-NPs synthesized with blended silane couplers increased with the presence of the target but were insensitive to the target analogs (L-tryptophan and L-dopa, respectively). However, when the template is anchored by a pure silane agent, both the fluorescence intensity and particle size of the fMIP-NPs were sensitive to the structural analog of the template. Another fMIP-NP was synthesized in the presence of poly([2-(methacryloyloxy)ethyl] trimethylammonium chloride (METMAC)-co-methacrylamide) grafted onto glass beads as a dummy template for acetylcholine. Acetylcholine increased the diameter and fluorescence intensity of the fMIP-NP, but choline had no effect. When the homopolymer of METMAC was used as a template, the fluorescence intensity and size of the resulting nanoparticles were not responsive to either acetylcholine or choline. The principle of increased fluorescence intensity due to specific interaction with the target substance is probably due to the increased distance between the fluorescent functional groups and decreased self-quenching due to the swelling caused by the specific interaction with the template. The results also indicate that MIP nanoparticles prepared by solid-phase synthesis can be used for targeting small molecules, such as the neurotransmitters addressed in this study, by adjusting the surface density of the template. Full article
(This article belongs to the Special Issue Advances in Molecularly Imprinted Polymer Nanomaterials)
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10 pages, 3371 KiB  
Article
A Plasmonic Biosensor Based on Light-Diffusing Fibers Functionalized with Molecularly Imprinted Nanoparticles for Ultralow Sensing of Proteins
by Francesco Arcadio, Mimimorena Seggio, Domenico Del Prete, Gionatan Buonanno, João Mendes, Luís C. C. Coelho, Pedro A. S. Jorge, Luigi Zeni, Alessandra Maria Bossi and Nunzio Cennamo
Nanomaterials 2022, 12(9), 1400; https://doi.org/10.3390/nano12091400 - 19 Apr 2022
Cited by 14 | Viewed by 2812
Abstract
Plasmonic bio/chemical sensing based on optical fibers combined with molecularly imprinted nanoparticles (nanoMIPs), which are polymeric receptors prepared by a template-assisted synthesis, has been demonstrated as a powerful method to attain ultra-low detection limits, particularly when exploiting soft nanoMIPs, which are known to [...] Read more.
Plasmonic bio/chemical sensing based on optical fibers combined with molecularly imprinted nanoparticles (nanoMIPs), which are polymeric receptors prepared by a template-assisted synthesis, has been demonstrated as a powerful method to attain ultra-low detection limits, particularly when exploiting soft nanoMIPs, which are known to deform upon analyte binding. This work presents the development of a surface plasmon resonance (SPR) sensor in silica light-diffusing fibers (LDFs) functionalized with a specific nanoMIP receptor, entailed for the recognition of the protein human serum transferrin (HTR). Despite their great versatility, to date only SPR-LFDs functionalized with antibodies have been reported. Here, the innovative combination of an SPR-LFD platform and nanoMIPs led to the development of a sensor with an ultra-low limit of detection (LOD), equal to about 4 fM, and selective for its target analyte HTR. It is worth noting that the SPR-LDF-nanoMIP sensor was mounted within a specially designed 3D-printed holder yielding a measurement cell suitable for a rapid and reliable setup, and easy for the scaling up of the measurements. Moreover, the fabrication process to realize the SPR platform is minimal, requiring only a metal deposition step. Full article
(This article belongs to the Special Issue Advances in Molecularly Imprinted Polymer Nanomaterials)
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18 pages, 4666 KiB  
Article
Room-Temperature, Ionic-Liquid-Enhanced, Beta-Cyclodextrin-Based, Molecularly Imprinted Polymers for the Selective Extraction of Abamectin
by Saqib Farooq, Bochang Chen, Shakeel Ahmad, Ihsan Muhammad, Quaid Hussain and Haiyan Wu
Nanomaterials 2022, 12(6), 1017; https://doi.org/10.3390/nano12061017 - 20 Mar 2022
Cited by 8 | Viewed by 2959
Abstract
To ensure environmental protection and food quality and safety, the trace level detection of pesticide residues with molecularly imprinted polymers using a more economic, reliable, and greener approach is always demanded. Herein, novel, enhanced, imprinted polymers based on beta-cyclodextrin, using room-temperature, ionic liquid [...] Read more.
To ensure environmental protection and food quality and safety, the trace level detection of pesticide residues with molecularly imprinted polymers using a more economic, reliable, and greener approach is always demanded. Herein, novel, enhanced, imprinted polymers based on beta-cyclodextrin, using room-temperature, ionic liquid as a solvent for abamectin were developed with a simple polymerization process. The successful synthesis of the polymers was verified, with morphological and structural characterization performed via scanning electron microscope analysis, nitrogen adsorption experiments, and thermogravimetric analysis. The imprinted polymers showed good adsorption ability, which was confirmed with a pseudo-second-order kinetic model and a Langmuir isotherm model, as they exhibit a theoretical adsorption of 15.08 mg g−1 for abamectin. The polymers showed high selectivity for abamectin and significant reusability without significant performance loss. The MIPs were used to analyze abamectin in spiked apple, banana, orange, and grape samples, and as a result, a good recovery of 81.67−101.47%, with 1.26−4.36% relative standard deviation, and limits of detection and quantitation of 0.02 µg g−1 and 0.05 µg g−1, respectively, was achieved within a linear range of 0.03−1.50 µg g−1. Thus, room-temperature, ionic-liquid-enhanced, beta-cyclodextrin-based, molecularly imprinted polymers for the selective detection of abamectin proved to be a convenient and practical platform. Full article
(This article belongs to the Special Issue Advances in Molecularly Imprinted Polymer Nanomaterials)
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19 pages, 2591 KiB  
Article
A Comparison of EIS and QCM NanoMIP-Based Sensors for Morphine
by Roberta D’Aurelio, Ibtisam E. Tothill, Maria Salbini, Francesca Calò, Elisabetta Mazzotta, Cosimino Malitesta and Iva Chianella
Nanomaterials 2021, 11(12), 3360; https://doi.org/10.3390/nano11123360 - 11 Dec 2021
Cited by 11 | Viewed by 3584
Abstract
In this work we have compared two different sensing platforms for the detection of morphine as an example of a low molecular weight target analyte. For this, molecularly imprinted polymer nanoparticles (NanoMIP), synthesized with an affinity towards morphine, were attached to an electrochemical [...] Read more.
In this work we have compared two different sensing platforms for the detection of morphine as an example of a low molecular weight target analyte. For this, molecularly imprinted polymer nanoparticles (NanoMIP), synthesized with an affinity towards morphine, were attached to an electrochemical impedance spectroscopy (EIS) and a quartz crystal microbalance (QCM) sensor. Assay design, sensors fabrication, analyte sensitivity and specificity were performed using similar methods. The results showed that the EIS sensor achieved a limit of detection (LOD) of 0.11 ng·mL−1, which is three orders of magnitude lower than the 0.19 µg·mL−1 achieved using the QCM sensor. Both the EIS and the QCM sensors were found to be able to specifically detect morphine in a direct assay format. However, the QCM method required conjugation of gold nanoparticles (AuNPs) to the small analyte (morphine) to amplify the signal and achieve a LOD in the µg·mL−1 range. Conversely, the EIS sensor method was labor-intensive and required extensive data handling and processing, resulting in longer analysis times (~30–40 min). In addition, whereas the QCM enables visualization of the binding events between the target molecule and the sensor in real-time, the EIS method does not allow such a feature and measurements are taken post-binding. The work also highlighted the advantages of using QCM as an automated, rapid and multiplex sensor compared to the much simpler EIS platform used in this work, though, the QCM method will require sample preparation, especially when a sensitive (ng·mL−1) detection of a small analyte is needed. Full article
(This article belongs to the Special Issue Advances in Molecularly Imprinted Polymer Nanomaterials)
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17 pages, 3758 KiB  
Article
Development of Silica Nanoparticle Supported Imprinted Polymers for Selective Lysozyme Recognition
by Anika Kotyrba, Mehmet Dinc and Boris Mizaikoff
Nanomaterials 2021, 11(12), 3287; https://doi.org/10.3390/nano11123287 - 3 Dec 2021
Cited by 4 | Viewed by 2227
Abstract
Protein imprinted MIPs show notable potential for applications in many analytical areas such as clinical analysis, medical diagnostics and environmental monitoring, but also in drug delivery scenarios. In this study, we present various modifications of two different synthesis routes to create imprinted core-shell [...] Read more.
Protein imprinted MIPs show notable potential for applications in many analytical areas such as clinical analysis, medical diagnostics and environmental monitoring, but also in drug delivery scenarios. In this study, we present various modifications of two different synthesis routes to create imprinted core-shell particles serving as a synthetic recognition material for the protein hen egg white (HEW) lysozyme. HEW lysozyme is used as food additive E 1105 for preservation due to its antibacterial effects. For facilitating quality and regulatory control analysis in food matrices, it is necessary to apply suitable isolation methods as potentially provided by molecularly imprinted materials. The highest binding capacity achieved herein was 58.82 mg/g with imprinting factors ranging up to 2.74, rendering these materials exceptionally suitable for selectively isolating HEW lysozyme. Full article
(This article belongs to the Special Issue Advances in Molecularly Imprinted Polymer Nanomaterials)
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14 pages, 3207 KiB  
Article
Development and Characterization of Magnetic SARS-CoV-2 Peptide-Imprinted Polymers
by Beatriz Fresco-Cala, Soumya Rajpal, Tamara Rudolf, Benedikt Keitel, Rüdiger Groß, Jan Münch, Alex D. Batista and Boris Mizaikoff
Nanomaterials 2021, 11(11), 2985; https://doi.org/10.3390/nano11112985 - 6 Nov 2021
Cited by 14 | Viewed by 2778
Abstract
The development of new methods for the rapid, sensitive, and selective detection of SARS-CoV-2 is a key factor in overcoming the global pandemic that we have been facing for over a year. In this work, we focused on the preparation of magnetic molecularly [...] Read more.
The development of new methods for the rapid, sensitive, and selective detection of SARS-CoV-2 is a key factor in overcoming the global pandemic that we have been facing for over a year. In this work, we focused on the preparation of magnetic molecularly imprinted polymers (MMIPs) based on the self-polymerization of dopamine at the surface of magnetic nanoparticles (MNPs). Instead of using the whole SARS-CoV-2 virion as a template, a peptide of the viral spike protein, which is present at the viral surface, was innovatively used for the imprinting step. Thus, problems associated with the infectious nature of the virus along with its potential instability when used as a template and under the polymerization conditions were avoided. Dopamine was selected as a functional monomer following a rational computational screening approach that revealed not only a high binding energy of the dopamine–peptide complex but also multi-point interactions across the entire peptide template surface as opposed to other monomers with similar binding affinity. Moreover, variables affecting the imprinting efficiency including polymerization time and amount of peptide and dopamine were experimentally evaluated. Finally, the selectivity of the prepared MMIPs vs. other peptide sequences (i.e., from Zika virus) was evaluated, demonstrating that the developed MMIPs were only specific for the target SARS-CoV-2 peptide. Full article
(This article belongs to the Special Issue Advances in Molecularly Imprinted Polymer Nanomaterials)
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13 pages, 3510 KiB  
Article
Improved Solvothermal Synthesis of γ-Fe2O3 Magnetic Nanoparticles for SiO2 Coating
by Rashmi Mahajan, Subramanian Suriyanarayanan and Ian A. Nicholls
Nanomaterials 2021, 11(8), 1889; https://doi.org/10.3390/nano11081889 - 23 Jul 2021
Cited by 27 | Viewed by 4082
Abstract
Monodisperse magnetic γ-Fe2O3 nanoparticles (MNPs) were prepared by a simple, improved, one-pot solvothermal synthesis using SDS and PEG 6000 as double capping reagents. This double protecting layer afforded better MNP uniformity (Z average 257 ± 11.12 nm, PDI = 0.18) [...] Read more.
Monodisperse magnetic γ-Fe2O3 nanoparticles (MNPs) were prepared by a simple, improved, one-pot solvothermal synthesis using SDS and PEG 6000 as double capping reagents. This double protecting layer afforded better MNP uniformity (Z average 257 ± 11.12 nm, PDI = 0.18) and colloidal stability. Materials were characterized by DLS, SEM, TEM, XPS, and XRD. The use of these MNPs in the synthesis of core–shell structures with uniform and tunable silica coatings was demonstrated, as silica coated MNPs are important for use in a range of applications, including magnetic separation and catalysis and as platforms for templated nanogel synthesis. Full article
(This article belongs to the Special Issue Advances in Molecularly Imprinted Polymer Nanomaterials)
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Review

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25 pages, 2132 KiB  
Review
A Fusion of Molecular Imprinting Technology and Siloxane Chemistry: A Way to Advanced Hybrid Nanomaterials
by Marcin Woźnica, Monika Sobiech and Piotr Luliński
Nanomaterials 2023, 13(2), 248; https://doi.org/10.3390/nano13020248 - 6 Jan 2023
Cited by 16 | Viewed by 2635
Abstract
Molecular imprinting technology is a well-known strategy to synthesize materials with a predetermined specificity. For fifty years, the “classical” approach assumed the creation of “memory sites” in the organic polymer matrix by a template molecule that interacts with the functional monomer prior to [...] Read more.
Molecular imprinting technology is a well-known strategy to synthesize materials with a predetermined specificity. For fifty years, the “classical” approach assumed the creation of “memory sites” in the organic polymer matrix by a template molecule that interacts with the functional monomer prior to the polymerization and template removal. However, the phenomenon of a material’s “memory” provided by the “footprint” of the chemical entity was first observed on silica-based materials nearly a century ago. Through the years, molecular imprinting technology has attracted the attention of many scientists. Different forms of molecularly imprinted materials, even on the nanoscale, were elaborated, predominantly using organic polymers to induce the “memory”. This field has expanded quickly in recent years, providing versatile tools for the separation or detection of numerous chemical compounds or even macromolecules. In this review, we would like to emphasize the role of the molecular imprinting process in the formation of highly specific siloxane-based nanomaterials. The distinct chemistry of siloxanes provides an opportunity for the facile functionalization of the surfaces of nanomaterials, enabling us to introduce additional properties and providing a way for vast applications such as detectors or separators. It also allows for catalyzing chemical reactions providing microreactors to facilitate organic synthesis. Finally, it determines the properties of siloxanes such as biocompatibility, which opens the way to applications in drug delivery and nanomedicine. Thus, a brief outlook on the chemistry of siloxanes prior to the discussion of the current state of the art of siloxane-based imprinted nanomaterials will be provided. Those aspects will be presented in the context of practical applications in various areas of chemistry and medicine. Finally, a brief outlook of future perspectives for the field will be pointed out. Full article
(This article belongs to the Special Issue Advances in Molecularly Imprinted Polymer Nanomaterials)
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25 pages, 6956 KiB  
Review
Hybrid Molecularly Imprinted Polymers: The Future of Nanomedicine?
by Maylis Garnier, Michèle Sabbah, Christine Ménager and Nébéwia Griffete
Nanomaterials 2021, 11(11), 3091; https://doi.org/10.3390/nano11113091 - 16 Nov 2021
Cited by 14 | Viewed by 3400
Abstract
Molecularly imprinted polymers (MIPs) have been widely used in nanomedicine in the last few years. However, their potential is limited by their intrinsic properties resulting, for instance, in lack of control in drug release processes or complex detection for in vivo imaging. Recent [...] Read more.
Molecularly imprinted polymers (MIPs) have been widely used in nanomedicine in the last few years. However, their potential is limited by their intrinsic properties resulting, for instance, in lack of control in drug release processes or complex detection for in vivo imaging. Recent attempts in creating hybrid nanomaterials combining MIPs with inorganic nanomaterials succeeded in providing a wide range of new interesting properties suitable for nanomedicine. Through this review, we aim to illustrate how hybrid molecularly imprinted polymers may improve patient care with enhanced imaging, treatments, and a combination of both. Full article
(This article belongs to the Special Issue Advances in Molecularly Imprinted Polymer Nanomaterials)
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