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Synthesis and Applications of Molecularly Imprinted Polymers

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (30 September 2018) | Viewed by 43252

Special Issue Editors

Department of Chemistry, College of Science and Engineering, University of Leicester, Leicester, UK
Interests: molecular imprinting; polymer synthesis; molecular recognition; organic synthesis; sensors
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Molecular imprinting is the process by which specific binding sites can be created within a polymeric material by performing the polymerization in the presence of an ionic, molecular, or macromolecular template. Success depends on selection of appropriate monomers that interact with the template to create the complementary binding site and upon the nature of the polymer synthesis. Removal of the template allows the molecularly imprinted polymer (MIP) to rebind the intended target species. MIPs prepared in this way may be used in separations, sensors, assays, catalysis, bio-imaging, drug delivery and a host of other applications exploiting specific molecular recognition.

The present Special Issue, “Synthesis and Applications of Molecularly Imprinted Polymers” aims to assemble a diverse collection of articles describing aspects of MIP synthesis and application. In particular, we welcome contributions concerning the synthesis of MIPs for specific applications, the synthesis of new monomers, novel template approaches and methods of MIP design and synthesis. Both research articles and reviews will be considered.

Dr. Michael J. Whitcombe
Prof. Dr. Ian A. Nicholls
Guest Editors

Manuscript Submission Information

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Keywords

  • Molecularly Imprinted Polymers (MIPs)
  • Molecular Recognition
  • Separations
  • Sensors
  • Assays
  • Nanomedicine
  • Catalysis
  • Bio-imaging
  • Drug delivery

Published Papers (9 papers)

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Research

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19 pages, 2575 KiB  
Article
Effect of Formulation on the Binding Efficiency and Selectivity of Precipitation Molecularly Imprinted Polymers
by K. Fremielle Lim and Clovia I. Holdsworth
Molecules 2018, 23(11), 2996; https://doi.org/10.3390/molecules23112996 - 16 Nov 2018
Cited by 26 | Viewed by 3275
Abstract
This study investigated the effect of feed formulation: the template:functional monomer (T:fM) and functional monomer:crosslinker (fM:X) ratios as well as the initiator concentration, on the binding performance and selectivity of caffeine (CAF) and theophylline (THP) imprinted polymers obtained by precipitation polymerisation in acetonitrile [...] Read more.
This study investigated the effect of feed formulation: the template:functional monomer (T:fM) and functional monomer:crosslinker (fM:X) ratios as well as the initiator concentration, on the binding performance and selectivity of caffeine (CAF) and theophylline (THP) imprinted polymers obtained by precipitation polymerisation in acetonitrile at 60 °C using methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) as functional monomer and crosslinker, respectively. Template incorporation, monitored by quantitative 1H-NMR spectroscopy, ranged from 8 to 77% and was found to be more favourable at both high and low T:fM ratios, low fM:X ratio and high initiator concentration. The resulting T:fM ratio in most MIPs were found to be lower than their feed ratios. Incorporation of THP into the polymers was observed to be consistently higher than CAF and, for most MIPs, the observed binding capacities represent less than 10% of the incorporated template. Improved imprinting factors were obtained from molecularly imprinted polymers (MIPs) with high crosslinker content, i.e., fM:X ratio of 1:10, and high initiator concentration, i.e., initiator:total monomer (I:tM) ratio of 1:5, while T:fM ratio (1:2 to 1:8) was found not to influence binding capacities and imprinting factors (IF). The NIPs showed no preference for either CAF or THP in competitive selectivity studies while MIPs were observed to bind preferentially to their template with THP displaying higher selectivity (72–94%) than CAF (63–84%). Template selectivity was observed to increase with increasing initiator concentration, with MIPs from I:tM ratio of 1:5 shown to be the most selective towards CAF (84%) and THP (93%). The fM:X ratio only showed minimal effect on MIP selectivity. Overall, for the MIP systems under study, template incorporation, binding capacity, imprinting factor and selectivity are enhanced at a faster rate of polymerisation using an I:tM ratio of 1:5. Polymer particles obtained were between 66 to 140 nm, with MIPs generally smaller than their NIP counterparts, and have been observed to decrease with increasing T:fM and fM:X ratios and increase with increasing initiator concentration. Full article
(This article belongs to the Special Issue Synthesis and Applications of Molecularly Imprinted Polymers)
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14 pages, 3920 KiB  
Article
Preparation and Evaluation of Oseltamivir Molecularly Imprinted Polymer Silica Gel as Liquid Chromatography Stationary Phase
by Ya-Jun Yang, Xi-Wang Liu, Xiao-Jun Kong, Zhe Qin, Zeng-Hua Jiao, Shi-Hong Li and Jian-Yong Li
Molecules 2018, 23(8), 1881; https://doi.org/10.3390/molecules23081881 - 27 Jul 2018
Cited by 12 | Viewed by 3869
Abstract
To improve the chromatographic performance of an oseltamivir (OS) molecularly imprinted polymer (MIP), silica gel coated with an MIP layer for OS (OSMIP@silica gel) was prepared by the surface molecular imprinting technology on the supporter of porous silica gel microspheres. A nonimprinted polymer [...] Read more.
To improve the chromatographic performance of an oseltamivir (OS) molecularly imprinted polymer (MIP), silica gel coated with an MIP layer for OS (OSMIP@silica gel) was prepared by the surface molecular imprinting technology on the supporter of porous silica gel microspheres. A nonimprinted polymer with the silica gel (NIP@silica gel) was also prepared for comparison. The obtained particles were characterized through FT–IR, scanning electron microscopy, specific surface area analysis, and porosity measurements. The results indicated that the polymer was successfully synthesized and revealed the structural differences between imprinted and nonimprinted polymers. The results of static adsorption experiments showed that adsorption quantity of the OSMIP@silica gel for OS was higher than that for NIP@silica gel, and the OSMIP@silica gel had two kinds of affinity sites for OS but the NIP@silica gel had one. The chromatographic performance of the OSMIP@silica gel column had significant improvement. The imprinting factor of the OSMIP@silica gel column for OS was 1.64. Furthermore, the OSMIP@silica gel column showed good affinity and selectivity for template OS and another neuraminidase inhibitor, peramivir, but not for quinocetone. These results indicated that the prepared OSMIP could be used to simulate the activity center of neuraminidase, and the OSMIP@silica gel column could be also employed in future studies to search for more active neuraminidase inhibitor analogues from traditional Chinese herbs. Full article
(This article belongs to the Special Issue Synthesis and Applications of Molecularly Imprinted Polymers)
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11 pages, 1973 KiB  
Article
Magnetic Porous Molecularly Imprinted Polymers Based on Surface Precipitation Polymerization and Mesoporous SiO2 Layer as Sacrificial Support for Efficient and Selective Extraction and Determination of Chlorogenic Acid in Duzhong Brick Tea
by Mijun Peng, Huan Li, Ruiqing Long, Shuyun Shi, Hanjun Zhou and Shuping Yang
Molecules 2018, 23(7), 1554; https://doi.org/10.3390/molecules23071554 - 27 Jun 2018
Cited by 16 | Viewed by 3603
Abstract
Magnetic porous molecularly imprinted polymers (MPMIPs) for rapid and efficient selective recognition of chlorogenic acid (CGA) were effectively prepared based on surface precipitation polymerization using CGA as template, 4-vinylpyridine (4-VP) as functional monomer, and mesoporous SiO2 (mSiO2) layer as sacrificial [...] Read more.
Magnetic porous molecularly imprinted polymers (MPMIPs) for rapid and efficient selective recognition of chlorogenic acid (CGA) were effectively prepared based on surface precipitation polymerization using CGA as template, 4-vinylpyridine (4-VP) as functional monomer, and mesoporous SiO2 (mSiO2) layer as sacrificial support. A computational simulation by evaluation of electronic binding energy is used to optimize the stoichiometric ratio between CGA and 4-VP (1:5), which reduced the duration of laboratory trials. The porous MIP shell and the rid of solid MIPs by magnet gave MPMIPs high binding capacity (42.22 mg/g) and fast kinetic binding (35 min). Adsorption behavior between CGA and MPMIPs followed Langmuir equation and pseudo-first-order reaction kinetics. Furthermore, the obtained MPMIPs as solid phase adsorbents coupled with high performance liquid chromatography (HPLC) were employed for selective extraction and determination of CGA (2.93 ± 0.11 mg/g) in Duzhong brick tea. The recoveries from 91.8% to 104.2%, and the limit of detection (LOD) at 0.8 μg/mL were obtained. The linear range (2.0–150.0 μg/mL) was wide with R2 > 0.999. Overall, this study provided an efficient approach for fabrication of well-constructed MPMIPs for fast and selective recognition and determination of CGA from complex samples. Full article
(This article belongs to the Special Issue Synthesis and Applications of Molecularly Imprinted Polymers)
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14 pages, 2396 KiB  
Article
Rapid Colorimetric Detection of Cartap Residues by AgNP Sensor with Magnetic Molecularly Imprinted Microspheres as Recognition Elements
by Mao Wu, Huiyun Deng, Yajun Fan, Yunchu Hu, Yaping Guo and Lianwu Xie
Molecules 2018, 23(6), 1443; https://doi.org/10.3390/molecules23061443 - 14 Jun 2018
Cited by 17 | Viewed by 4674
Abstract
The overuse of cartap in tea tree leads to hazardous residues threatening human health. A colorimetric determination was established to detect cartap residues in tea beverages by silver nanoparticles (AgNP) sensor with magnetic molecularly imprinted polymeric microspheres (Fe3O4@mSiO2 [...] Read more.
The overuse of cartap in tea tree leads to hazardous residues threatening human health. A colorimetric determination was established to detect cartap residues in tea beverages by silver nanoparticles (AgNP) sensor with magnetic molecularly imprinted polymeric microspheres (Fe3O4@mSiO2@MIPs) as recognition elements. Using Fe3O4 as supporting core, mesoporous SiO2 as intermediate shell, methylacrylic acid as functional monomer, and cartap as template, Fe3O4@mSiO2@MIPs were prepared to selectively and magnetically separate cartap from tea solution before colorimetric determination by AgNP sensors. The core-shell Fe3O4@mSiO2@MIPs were also characterized by FT-IR, TEM, VSM, and experimental adsorption. The Fe3O4@mSiO2@MIPs could be rapidly separated by an external magnet in 10 s with good reusability (maintained 95.2% through 10 cycles). The adsorption process of cartap on Fe3O4@mSiO2@MIPs conformed to Langmuir adsorption isotherm with maximum adsorption capacity at 0.257 mmol/g and short equilibrium time of 30 min at 298 K. The AgNP colorimetric method semi-quantified cartap ≥5 mg/L by naked eye and quantified cartap 0.1–5 mg/L with LOD 0.01 mg/L by UV-vis spectroscopy. The AgNP colorimetric detection after pretreatment with Fe3O4@mSiO2@MIPs could be successfully utilized to recognize and detect cartap residues in tea beverages. Full article
(This article belongs to the Special Issue Synthesis and Applications of Molecularly Imprinted Polymers)
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11 pages, 2492 KiB  
Article
The Selectivity of Polymers Imprinted with Amines
by Zsanett Dorkó, Anett Nagy-Szakolczai, Blanka Tóth and George Horvai
Molecules 2018, 23(6), 1298; https://doi.org/10.3390/molecules23061298 - 29 May 2018
Cited by 9 | Viewed by 3904
Abstract
One of the main reasons for making molecularly imprinted polymers (MIPs) has been that MIPs interact selectively with a specific target compound. This claim is investigated here with the example of a widely used type of noncovalent MIP, the MIP for the beta [...] Read more.
One of the main reasons for making molecularly imprinted polymers (MIPs) has been that MIPs interact selectively with a specific target compound. This claim is investigated here with the example of a widely used type of noncovalent MIP, the MIP for the beta blocker propranolol. Adsorption isotherms of this MIP and of a nonimprinted control polymer (NIP), respectively, have been measured with a series of compounds in the porogen solvent acetonitrile. The results, visualized as “selectivity ladders”, show that the MIP binds propranolol and many other amines better than the NIP does, but the selectivity of the MIP is actually inferior to that of the NIP. The selectivity of either polymer for propranolol is modest against many amines, but is remarkable with respect to other compounds. The contribution of imprinting towards selectivity can be better appreciated when three MIPs, made with different amine templates, are compared among themselves. Each MIP is seen to bind its own template slightly better than the other two MIPs do. In media different from the porogen, the selectivity patterns may change substantially. Propranolol seems to have properties that make it stand high on the selectivity scale in different solvents, albeit for different reasons. Full article
(This article belongs to the Special Issue Synthesis and Applications of Molecularly Imprinted Polymers)
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13 pages, 3360 KiB  
Article
Determination of Ten Macrolide Drugs in Environmental Water Using Molecularly Imprinted Solid-Phase Extraction Coupled with Liquid Chromatography-Tandem Mass Spectrometry
by Xuqin Song, Tong Zhou, Jiufeng Li, Meiyu Zhang, Jingmeng Xie and Limin He
Molecules 2018, 23(5), 1172; https://doi.org/10.3390/molecules23051172 - 14 May 2018
Cited by 16 | Viewed by 3931
Abstract
With the extensive application of antibiotics in livestock, their contamination of the aquatic environment has received more attention. Molecularly imprinted polymer (MIP), as an eco-friendly and durable solid-phase extraction material, has shown great potential for the separation and enrichment of antibiotics in water. [...] Read more.
With the extensive application of antibiotics in livestock, their contamination of the aquatic environment has received more attention. Molecularly imprinted polymer (MIP), as an eco-friendly and durable solid-phase extraction material, has shown great potential for the separation and enrichment of antibiotics in water. This study aims at developing a practical and economical method based on molecularly imprinted solid phase extraction (MISPE) combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) for simultaneously detecting ten macrolide drugs in different sources of water samples. The MIP was synthesized by bulk polymerization using tylosin as the template and methacrylic acid as the functional monomer. The MIP exhibited a favorable load-bearing capacity for water (>90 mL), which is more than triple that of non-molecularly imprinted polymers (NIP). The mean recoveries of macrolides at four spiked concentration levels (limit of quantification, 40, 100, and 400 ng/L) were 62.6–100.9%, with intra-day and inter-day relative standard deviations below 12.6%. The limit of detection and limit of quantification were 1.0–15.0 ng/L and 3.0–40.0 ng/L, respectively. Finally, the proposed method was successfully applied to the analysis of real water samples. Full article
(This article belongs to the Special Issue Synthesis and Applications of Molecularly Imprinted Polymers)
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536 KiB  
Communication
Molecularly Imprinted Microrods via Mesophase Polymerization
by Ortensia Ilaria Parisi, Luca Scrivano, Sebastiano Candamano, Mariarosa Ruffo, Anna Francesca Vattimo, Maria Vittoria Spanedda and Francesco Puoci
Molecules 2018, 23(1), 63; https://doi.org/10.3390/molecules23010063 - 28 Dec 2017
Cited by 12 | Viewed by 3899
Abstract
The aim of the present research work was the synthesis of molecularly imprinted polymers (MIPs) with a rod-like geometry via “mesophase polymerization”. The ternary lyotropic system consisting of sodium dodecyl sulfate (SDS), water, and decanol was chosen to prepare a hexagonal mesophase to [...] Read more.
The aim of the present research work was the synthesis of molecularly imprinted polymers (MIPs) with a rod-like geometry via “mesophase polymerization”. The ternary lyotropic system consisting of sodium dodecyl sulfate (SDS), water, and decanol was chosen to prepare a hexagonal mesophase to direct the morphology of the synthesized imprinted polymers using theophylline, methacrylic acid, and ethylene glycol dimethacrylate as a drug model template, a functional monomer, and a crosslinker, respectively. The obtained molecularly imprinted microrods (MIMs) were assessed by performing binding experiments and in vitro release studies, and the obtained results highlighted good selective recognition abilities and sustained release properties. In conclusion, the adopted synthetic strategy involving a lyotropic mesophase system allows for the preparation of effective MIPs characterized by a rod-like morphology. Full article
(This article belongs to the Special Issue Synthesis and Applications of Molecularly Imprinted Polymers)
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11078 KiB  
Article
Fast Extraction and Detection of 4-Methylimidazole in Soy Sauce Using Magnetic Molecularly Imprinted Polymer by HPLC
by Zufei Feng, Yan Lu, Yingjuan Zhao and Helin Ye
Molecules 2017, 22(11), 1885; https://doi.org/10.3390/molecules22111885 - 02 Nov 2017
Cited by 7 | Viewed by 3941
Abstract
On the basis of magnetic molecularly imprinted polymer (MMIP) solid-phase extraction coupled with high performance liquid chromatography, we established a new method for the determination of the 4-methylimidazole (4-MEI) in soy sauce. Scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), X-ray diffraction (XRD) [...] Read more.
On the basis of magnetic molecularly imprinted polymer (MMIP) solid-phase extraction coupled with high performance liquid chromatography, we established a new method for the determination of the 4-methylimidazole (4-MEI) in soy sauce. Scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), X-ray diffraction (XRD) and vibrating sample magnetometer (VSM) were used to characterize the synthesized MMIPs. To evaluate the polymers, batch rebinding experiments were carried out. The binding strength and capacity were determined from the derived Freundlich isotherm (FI) equation. The selective recognition capability of MMIPs was investigated with a reference compound and a structurally similar compound. As a selective pre-concentration sorbents for 4-methylimidazole in soy sauce, the MMIPs showed a satisfied recoveries rate of spiked samples, ranged from 97% to 105%. As a result, the prepared MMIPs could be applied to selectively pre-concentrate and determine 4-methylimidazole in soy sauce samples. Full article
(This article belongs to the Special Issue Synthesis and Applications of Molecularly Imprinted Polymers)
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Review

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33 pages, 672 KiB  
Review
Molecularly Imprinted Polymers as Extracting Media for the Chromatographic Determination of Antibiotics in Milk
by Dimitrios Bitas and Victoria Samanidou
Molecules 2018, 23(2), 316; https://doi.org/10.3390/molecules23020316 - 02 Feb 2018
Cited by 50 | Viewed by 10762
Abstract
Milk-producing animals are typically kept stationary in overcrowded large-scale farms and in most cases under unsanitary conditions, which promotes the development of infections. In order to maintain sufficient health status among the herd or promote growth and increase production, farmers administer preventative antibiotic [...] Read more.
Milk-producing animals are typically kept stationary in overcrowded large-scale farms and in most cases under unsanitary conditions, which promotes the development of infections. In order to maintain sufficient health status among the herd or promote growth and increase production, farmers administer preventative antibiotic doses to the animals through their feed. However, many antibiotics used in cattle farms are intended for the treatment of bacterial infections in humans. This results in the development of antibiotic-resistant bacteria which pose a great risk for public health. Additionally, antibiotic residues are found in milk and dairy products, with potential toxic effects for the consumers. Hence the need of antibiotic residues monitoring in milk arises. Analytical methods were developed for the determination of antibiotics in milk, with key priority given to the analyte extraction and preconcentration step. Extraction can benefit from the production of molecularly imprinted polymers (MIPs) that can be applied as sorbents for the extraction of specific antibiotics. This review focuses on the principals of molecular imprinting technology and synthesis methods of MIPs, as well as the application of MIPs and MIPs composites for the chromatographic determination of various antibiotic categories in milk found in the recent literature. Full article
(This article belongs to the Special Issue Synthesis and Applications of Molecularly Imprinted Polymers)
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