Advances in the Manufacture of Sensors Based on Molecularly Imprinted Polymers

A special issue of Chemosensors (ISSN 2227-9040). This special issue belongs to the section "Materials for Chemical Sensing".

Deadline for manuscript submissions: closed (31 March 2023) | Viewed by 27456

Special Issue Editors


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Guest Editor
MIP Diagnostics, The Exchange Building, Colworth Park, Bedfordshire MK44 1LQ, UK
Interests: molecularly imprinted polymers (MIPs); MIP-based sensors; nanoMIPs for diagnostic applications

E-Mail Website
Guest Editor
School of Engineering, Newcastle University, Newcastle upon Tyne, Tyne and Wear NE1 7RU, UK
Interests: molecularly imprinted polymers (MIPs); sensors; electrochemistry; polymer synthesis; sustainable healthcare; thermal analysis
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Special Issue Information

Dear colleagues,

Molecularly imprinted polymers (MIPs) have undoubtedly shown a great deal of versatility as they have been successfully applied to a variety of fields such as medicine and diagnostics, food and environmental monitoring, as well as several niche areas. There is still a crucial demand for robust and reliable sensing devices, in particular for in-field testing. The combination of MIPs and electrochemical detection methods represents a valuable approach to the development of cost-effective, robust, and sensitive detection platforms. Whilst electrochemical detection probably represents the most widespread approach, other detection techniques are emerging.

This Special Issue will provide a summary of the latest research activities in the field of MIP-based sensors, ranging from optical to electrochemical and thermal detection. Both review articles and original research papers are welcome, including but not limited to the following areas:

  • Novel concepts and emerging applications of MIP-based sensors;
  • Multiplexed platforms;
  • New imprinting techniques or MIP integration methodologies into sensors;
  • Niche applications and hybrid sensors exploiting dual detection principles simultaneously;
  • Critical reviews on the current state of the art, perspectives on market adoption.

Dr. Francesco Canfarotta
Dr. Marloes Peeters
Guest Editors

If you want to learn more information or need any advice, you can contact the Special Issue Editor Tammy Zhang via <[email protected]> directly.

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Keywords

  • Molecular imprinting
  • Biosensors
  • Electrochemical
  • Optical
  • Thermal
  • Nanoparticles and films

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Published Papers (8 papers)

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Research

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10 pages, 2280 KiB  
Communication
An Upgraded Protocol for the Silanisation of the Solid Phase for the Synthesis of Molecularly Imprinted Polymers
by Fabiana Grillo, Francesco Canfarotta, Thomas Sean Bedwell, Magaly Arnold, William Le Saint, Rajdeep Sahota, Krunal Ladwa, Joshua Crane, Tobias Heavens, Elena Piletska and Sergey Piletsky
Chemosensors 2023, 11(8), 437; https://doi.org/10.3390/chemosensors11080437 - 5 Aug 2023
Viewed by 1493
Abstract
The introduction of solid-phase imprinting has had a significant impact in the molecular imprinting field, mainly due to its advantage of orienting the template immobilisation, affinity separation of nanoMIPs and faster production time. To date, more than 600 documents on Google Scholar involve [...] Read more.
The introduction of solid-phase imprinting has had a significant impact in the molecular imprinting field, mainly due to its advantage of orienting the template immobilisation, affinity separation of nanoMIPs and faster production time. To date, more than 600 documents on Google Scholar involve solid-phase synthesis, mostly relying on silanes mediating template immobilisation on the solid phase. Organosilanes are the most explored functionalisation compounds due to their straightforward use and ability to promote the binding of organic molecules to inorganic substrates. However, they also suffer from well-known issues, such as lack of control in the layer’s deposition and poor stability in water. Since the first introduction of solid-phase imprinting, few efforts have been made to overcome these limitations. The work presented in this research focuses on optimising the silane stability on glass beads (GBs) and iron oxide nanoparticles (IO-NPs), to subsequently function as solid phases for imprinting. The performance of three different aminosilanes were investigated; N-(6-aminohexyl) aminomethyltriethoxy silane (AHAMTES), 3-Aminopropyltriethoxysilane (APTES), and N-(2-aminoethyl)-3-aminopropyltriethoxysilane (AEAPTES), as well as studying the effect of dipodal silane bis(triethoxysilyl)ethane (BTSE). A stable solid phase was consequently achieved with 3% v/v AEAPTES and 2.4% BTSE, providing an upgraded protocol from Canfarotta et al. for the silanisation of the solid phase for molecular imprinting purposes. Full article
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18 pages, 3872 KiB  
Article
Synthesis of Molecularly Imprinted Polymer Nanoparticles for SARS-CoV-2 Virus Detection Using Surface Plasmon Resonance
by Aabha Bajaj, Jakob Trimpert, Ibrahim Abdulhalim and Zeynep Altintas
Chemosensors 2022, 10(11), 459; https://doi.org/10.3390/chemosensors10110459 - 5 Nov 2022
Cited by 19 | Viewed by 4871
Abstract
COVID-19 caused by a SARS-CoV-2 infection was first reported from Wuhan, China, and later recognized as a pandemic on March 11, 2020, by the World Health Organization (WHO). Gold standard nucleic acid and molecular-based testing have largely satisfied the requirements of early diagnosis [...] Read more.
COVID-19 caused by a SARS-CoV-2 infection was first reported from Wuhan, China, and later recognized as a pandemic on March 11, 2020, by the World Health Organization (WHO). Gold standard nucleic acid and molecular-based testing have largely satisfied the requirements of early diagnosis and management of this infectious disease; however, these techniques are expensive and not readily available for point-of-care (POC) applications. The COVID-19 pandemic of the 21st century has emphasized that medicine is in dire need of advanced, rapid, and cheap diagnostic tools. Herein, we report on molecularly imprinted polymer nanoparticles (MIP-NPs/nanoMIPs) as plastic antibodies for the specific detection of SARS-CoV-2 by employing a surface plasmon resonance (SPR) sensor. High-affinity MIP-NPs directed against SARS-CoV-2 were manufactured using a solid-phase imprinting method. The MIP-NPs were then characterized using dynamic light scattering (DLS) and atomic force microscopy (AFM) prior to their incorporation into a label-free portable SPR device. Detection of SARS-CoV-2 was studied within a range of 104–106 PFU mL−1. The MIP-NPs demonstrated good binding affinity (KD = 0.12 pM) and selectivity toward SARS-CoV-2. The AFM, cyclic voltammetry, and square-wave voltammetry studies revealed the successful stepwise preparation of the sensor. A cross-reactivity test confirmed the specificity of the sensor. For the first time, this study demonstrates the potential of molecular imprinting technology in conjunction with miniaturized SPR devices for the detection of SARS-CoV-2 particles with high-affinity and specificity. Such sensors could help monitor and manage the risks related to virus contamination and infections also beyond the current pandemic. Full article
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12 pages, 570 KiB  
Article
A Molecularly Imprinted Polymer-Disposable Pipette Tip Extraction-Capillary Electrophoresis (MISPE-DPX-CE) Method for the Preconcentration and Determination of Scopolamine in Synthetic Urine Samples
by Weida Rodrigues Silva, Michelle M. A. C. Ribeiro, Eduardo Mathias Richter, Alex D. Batista and João Flávio da Silveira Petruci
Chemosensors 2022, 10(10), 387; https://doi.org/10.3390/chemosensors10100387 - 23 Sep 2022
Cited by 6 | Viewed by 1772
Abstract
Alcoholic beverages contaminated with scopolamine (SCP) are often employed for criminal purposes due to their sedative effect. The determination of the residual levels of SCP in body fluids (e.g., urine) can help to track possible victims of induced ingestions. Biological sample analysis usually [...] Read more.
Alcoholic beverages contaminated with scopolamine (SCP) are often employed for criminal purposes due to their sedative effect. The determination of the residual levels of SCP in body fluids (e.g., urine) can help to track possible victims of induced ingestions. Biological sample analysis usually requires a preconcentration step to enhance their detectability and to provide sample clean-up. Molecularly imprinted polymers (MIPs) in lieu of conventional solid sorbents represent an enhancement of selectivity, due to their specific recognition sites. Additionally, the adaptation of the solid-phase extraction (SPE) cartridge into a disposable pipette tip extraction (DPX) contributes to the miniaturization of the sample preparation step. Herein, an analytical method for the determination of SCP in synthetic urine samples via the integration of molecularly imprinted solid-phase extraction (MISPE) with DPX as a preconcentration step prior to capillary electrophoresis analysis (also known as MISPE-DPX-CE) is presented. The extraction and elution steps were optimized using a factorial design. Using the optimized conditions, a preconcentration factor of 20 was obtained, leading to a working range of 0.5–6 µM with LOD of 0.04 µM and repeatability of 6.4% (n = 7) and adequate recovery values (84 and 101%) The proposed MISPE-DPX-CE approach was successfully applied to selective extraction, preconcentration, and determination of SCP in synthetic urine samples. Full article
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18 pages, 2625 KiB  
Article
Imidazole-Based Monomer as Functional Unit for the Specific Detection of Paraxanthine in Aqueous Environments
by Rozalia-Maria Anastasiadi, Federico Traldi and Marina Resmini
Chemosensors 2022, 10(8), 301; https://doi.org/10.3390/chemosensors10080301 - 31 Jul 2022
Cited by 1 | Viewed by 2025
Abstract
In the context of personalized medicine, the paraxanthine-to-caffeine ratio is an accepted standard for the optimization of the dose-response effect of many pharmaceuticals in individual patients. There is a strong drive towards the development of cheaper and portable devices for the detection of [...] Read more.
In the context of personalized medicine, the paraxanthine-to-caffeine ratio is an accepted standard for the optimization of the dose-response effect of many pharmaceuticals in individual patients. There is a strong drive towards the development of cheaper and portable devices for the detection of biomarkers, including paraxanthine and caffeine, which requires materials with high binding efficiency and specificity. We designed a recognition unit specific for paraxanthine which can discriminate molecules with small structural differences and can be used to increase the sensitivity of sensors. A number of functional units were screened by nuclear magnetic resonance for their ability to form specific binding interactions with paraxanthine in water and negligible interactions with its structural analogue caffeine. Imidazole was identified as the unit showing the most promising results and its two polymerizable derivatives were evaluated by isothermal titration calorimetry to identify the best monomer. The data suggested that 4-vinylimidazole was the most promising unit forming specific and strong binding interaction with paraxanthine. The calorimetry experiments allowed also the determination of the thermodynamic parameters of all interactions and the association constant values. Optimization of polymerization protocols in water, achieving high monomer conversions and chemical yields, demonstrate the suitability of the selected functional monomer for polymer preparations, targeting the detection of paraxanthine in aqueous environments. Full article
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20 pages, 1690 KiB  
Article
Red-Emitting Polymerizable Guanidinium Dyes as Fluorescent Probes in Molecularly Imprinted Polymers for Glyphosate Detection
by Martha Kimani, Víctor Pérez-Padilla, Virginia Valderrey, Kornelia Gawlitza and Knut Rurack
Chemosensors 2022, 10(3), 99; https://doi.org/10.3390/chemosensors10030099 - 3 Mar 2022
Cited by 8 | Viewed by 4017
Abstract
The development of methodologies to sense glyphosate has gained momentum due to its toxicological and ecotoxicological effects. In this work, a red-emitting and polymerizable guanidinium benzoxadiazole probe was developed for the fluorescence detection of glyphosate. The interaction of the fluorescent probe and the [...] Read more.
The development of methodologies to sense glyphosate has gained momentum due to its toxicological and ecotoxicological effects. In this work, a red-emitting and polymerizable guanidinium benzoxadiazole probe was developed for the fluorescence detection of glyphosate. The interaction of the fluorescent probe and the tetrabutylammonium salt of glyphosate was studied via UV/vis absorption and fluorescence spectroscopy in chloroform and acetonitrile. The selective recognition of glyphosate was achieved by preparing molecularly imprinted polymers, able to discriminate against other common herbicides such as 2,4-dichlorophenoxyacetic acid (2,4-D) and 3,6-dichloro-2-methoxybenzoic acid (dicamba), as thin layers on submicron silica particles. The limits of detection of 4.8 µM and 0.6 µM were obtained for the sensing of glyphosate in chloroform and acetonitrile, respectively. The reported system shows promise for future application in the sensing of glyphosate through further optimization of the dye and the implementation of a biphasic assay with water/organic solvent mixtures for sensing in aqueous environmental samples. Full article
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Review

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24 pages, 4034 KiB  
Review
Recent Advances in Molecularly Imprinted Polymers for Glucose Monitoring: From Fundamental Research to Commercial Application
by Manlio Caldara, Julia Kulpa, Joseph W. Lowdon, Thomas J. Cleij, Hanne Diliën, Kasper Eersels and Bart van Grinsven
Chemosensors 2023, 11(1), 32; https://doi.org/10.3390/chemosensors11010032 - 1 Jan 2023
Cited by 14 | Viewed by 5079
Abstract
Molecularly imprinted polymers (MIPs) have gained growing interest among researchers worldwide, due to their key features that make these materials interesting candidates for implementation as receptors into sensor applications. In fact, MIP-based glucose sensors could overcome the stability issues associated with the enzymes [...] Read more.
Molecularly imprinted polymers (MIPs) have gained growing interest among researchers worldwide, due to their key features that make these materials interesting candidates for implementation as receptors into sensor applications. In fact, MIP-based glucose sensors could overcome the stability issues associated with the enzymes present in commercial glucose devices. Various reports describe the successful development of glucose MIPs and their coupling to a wide variety of transducers for creating sensors that are able to detect glucose in various matrices. In this review, we have summarized and critically evaluated the different production methods of glucose MIPs and the different transducer technologies used in MIP-based glucose sensors, and analyzed these from a commercial point of view. In this way, this review sets out to highlight the most promising approaches in MIP-based sensing in terms of both manufacturing methods and readout technologies employed. In doing so, we aim at delineating potential future approaches and identifying potential obstacles that the MIP-sensing field may encounter in an attempt to penetrate the commercial, analytical market. Full article
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24 pages, 18053 KiB  
Review
A Critical Review on the Use of Molecular Imprinting for Trace Heavy Metal and Micropollutant Detection
by Patrick Marcel Seumo Tchekwagep, Robert D. Crapnell, Craig E. Banks, Kai Betlem, Uwe Rinner, Francesco Canfarotta, Joseph W. Lowdon, Kasper Eersels, Bart van Grinsven, Marloes Peeters and Jake McClements
Chemosensors 2022, 10(8), 296; https://doi.org/10.3390/chemosensors10080296 - 27 Jul 2022
Cited by 16 | Viewed by 3970
Abstract
Molecular recognition has been described as the “ultimate” form of sensing and plays a fundamental role in biological processes. There is a move towards biomimetic recognition elements to overcome inherent problems of natural receptors such as limited stability, high-cost, and variation in response. [...] Read more.
Molecular recognition has been described as the “ultimate” form of sensing and plays a fundamental role in biological processes. There is a move towards biomimetic recognition elements to overcome inherent problems of natural receptors such as limited stability, high-cost, and variation in response. In recent years, several alternatives have emerged which have found their first commercial applications. In this review, we focus on molecularly imprinted polymers (MIPs) since they present an attractive alternative due to recent breakthroughs in polymer science and nanotechnology. For example, innovative solid-phase synthesis methods can produce MIPs with sometimes greater affinities than natural receptors. Although industry and environmental agencies require sensors for continuous monitoring, the regulatory barrier for employing MIP-based sensors is still low for environmental applications. Despite this, there are currently no sensors in this area, which is likely due to low profitability and the need for new legislation to promote the development of MIP-based sensors for pollutant and heavy metal monitoring. The increased demand for point-of-use devices and home testing kits is driving an exponential growth in biosensor production, leading to an expected market value of over GPB 25 billion by 2023. A key requirement of point-of-use devices is portability, since the test must be conducted at “the time and place” to pinpoint sources of contamination in food and/or water samples. Therefore, this review will focus on MIP-based sensors for monitoring pollutants and heavy metals by critically evaluating relevant literature sources from 1993 to 2022. Full article
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25 pages, 7509 KiB  
Review
Recent Trends in the Development of Carbon-Based Electrodes Modified with Molecularly Imprinted Polymers for Antibiotic Electroanalysis
by Daniel Preda, Iulia Gabriela David, Dana-Elena Popa, Mihaela Buleandra and Gabriel Lucian Radu
Chemosensors 2022, 10(7), 243; https://doi.org/10.3390/chemosensors10070243 - 25 Jun 2022
Cited by 9 | Viewed by 2761
Abstract
Antibiotics are antibacterial agents applied in human and veterinary medicine. They are also employed to stimulate the growth of food-producing animals. Despite their benefits, the uncontrolled use of antibiotics results in serious problems, and therefore their concentration levels in different foods as well [...] Read more.
Antibiotics are antibacterial agents applied in human and veterinary medicine. They are also employed to stimulate the growth of food-producing animals. Despite their benefits, the uncontrolled use of antibiotics results in serious problems, and therefore their concentration levels in different foods as well as in environmental samples were regulated. As a consequence, there is an increasing demand for the development of sensitive and selective analytical tools for antibiotic reliable and rapid detection. These requirements are accomplished by the combination of simple, cost-effective and affordable electroanalytical methods with molecularly imprinted polymers (MIPs) with high recognition specificity, based on their “lock and key” working principle, used to modify the electrode surface, which is the “heart” of any electrochemical device. This review presents a comprehensive overview of MIP-modified carbon-based electrodes developed in recent years for antibiotic detection. The MIP preparation and electrode modification procedures, along with the performance characteristics of sensors and analytical methods, as well as the applications for the antibiotics’ quantification from different matrices (pharmaceutical, biological, food and environmental samples), are discussed. The information provided by this review can inspire researchers to go deeper into the field of MIP-modified sensors and to develop efficient means for reliable antibiotic determination. Full article
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