Polymers

Research

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12 pages, 1572 KiB

Open AccessArticle

Synthesis of Molecularly Imprinted Polymers for the Selective Extraction of Polymyxins from Environmental Water Samples

by Xuqin Song, Esther Turiel, Limin He and Antonio Martín-Esteban

Polymers 2020, 12(1), 131; https://doi.org/10.3390/polym12010131 - 6 Jan 2020

Cited by 13 | Viewed by 2809

Abstract

The emergence of colistin resistance gen has aroused public concern. It is significant to assess the concentrations of polymyxins residues in aquatic environment since resistant bacteria carrying colistin resistance gen are frequently isolated from wastewater; surface water and ground water. However; no literature [...] Read more.

The emergence of colistin resistance gen has aroused public concern. It is significant to assess the concentrations of polymyxins residues in aquatic environment since resistant bacteria carrying colistin resistance gen are frequently isolated from wastewater; surface water and ground water. However; no literature on the determination of polymyxins in water is available; probably due to the absence of an efficient extraction method. Accordingly; molecularly imprinted polymers were synthesized by precipitation polymerization with colistin as the template. The polymers were successfully used as sorbents for the determination of polymyxins from water based on molecularly imprinted solid-phase extraction and high-performance liquid chromatography–ultraviolet detection. The molecularly imprinted cartridge showed excellent affinity and cross-reactivity to analytes in aqueous media. Recoveries obtained from water samples were between 65.9% and 90.1%, with relative standard deviations lower than 10.2%. Limits of detection were between 1.0 and 2.0 μg L⁻¹ concentration levels. Compared with C₁₈ cartridge; the molecularly imprinted cartridge could remove more interference from co-extracted matrices. This method is practical for the routine monitoring of polymyxin residues in environmental water; which will benefit studies on drug-resistance and occurrence of polymyxins in the environment. Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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14 pages, 2661 KiB

Open AccessArticle

Development of Water-Compatible Molecularly Imprinted Polymers Based on Functionalized β-Cyclodextrin for Controlled Release of Atropine

by Yahui He, Shaomei Zeng, A. M. Abd El-Aty, Ahmet Hacımüftüoğlu, Woldemariam Kalekristos Yohannes, Majid Khan and Yongxin She

Polymers 2020, 12(1), 130; https://doi.org/10.3390/polym12010130 - 6 Jan 2020

Cited by 21 | Viewed by 3930

Abstract

Herein, a novel method for molecularly imprinted polymers (MIPs) using methacrylic acid functionalized beta-cyclodextrin (MAA-β-CD) monomer is presented, which was designed as a potential water-compatible composite for the controlled release of atropine (ATP). The molecularly imprinted microspheres with pH-sensitive characteristics were fabricated using [...] Read more.

Herein, a novel method for molecularly imprinted polymers (MIPs) using methacrylic acid functionalized beta-cyclodextrin (MAA-β-CD) monomer is presented, which was designed as a potential water-compatible composite for the controlled release of atropine (ATP). The molecularly imprinted microspheres with pH-sensitive characteristics were fabricated using thermally-initiated precipitation polymerization, employing ATP as a template molecule. The effects of different compounds and concentrations of cross-linking agents were systematically investigated. Uniform microspheres were obtained when the ratio between ATP, MAA-β-CD, and trimethylolpropane trimethacrylate (TRIM) was 1:4:20 (mol/mol/mol) in polymerization system. The ATP loading equilibrium data was best suited to the Freundlich and Langmuir isotherm models. The in vitro drug release study was assessed under simulated oral administration conditions (pH 1.5 and 7.4). The potential usefulness of MIPs as drug delivery devices are much better than non-molecularly imprinted polymers (NIPs). The study shows that the prepared polymers are a pH stimuli-responsive system, which controlled the release of ATP, indicating the potential applications in the field of drug delivery. Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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19 pages, 2487 KiB

Open AccessArticle

Vinyl Phosphate-Functionalized, Magnetic, Molecularly-Imprinted Polymeric Microspheres’ Enrichment and Carbon Dots’ Fluorescence-Detection of Organophosphorus Pesticide Residues

by Mao Wu, Yajun Fan, Jiawei Li, Danqing Lu, Yaping Guo, Lianwu Xie and Yiqiang Wu

Polymers 2019, 11(11), 1770; https://doi.org/10.3390/polym11111770 - 27 Oct 2019

Cited by 29 | Viewed by 4160

Abstract

The rapid detection of organophosphorus pesticide residues in food is crucial to food safety. One type of novel, magnetic, molecularly-imprinted polymeric microsphere (MMIP) was prepared with vinyl phosphate and 1-octadecene as a collection of dual functional monomers, which were screened by Gaussian09W molecular [...] Read more.

The rapid detection of organophosphorus pesticide residues in food is crucial to food safety. One type of novel, magnetic, molecularly-imprinted polymeric microsphere (MMIP) was prepared with vinyl phosphate and 1-octadecene as a collection of dual functional monomers, which were screened by Gaussian09W molecular simulation. MMIPs were used to enrich organic phosphorus, which then detected by fluorescence quenching in vinyl phosphate-modified carbon dots (CDs@VPA) originated from anhydrous citric acid. MMIPs and CDs@VPA were characterized by TEM, particle size analysis, FT-IR, VSM, XPS, adsorption experiments, and fluorescence spectrophotometry in turn. Through the fitting data from experiment and Gaussian quantum chemical calculations, the molecular recognition properties and the mechanism of fluorescence detection between organophosphorus pesticides and CDs@VPA were also investigated. The results indicated that the MMIPs could specifically recognize and enrich triazophos with the saturated adsorption capacity 0.226 mmol g⁻¹, the imprinting factor 4.59, and the limit of recognition as low as 0.0006 mmol L⁻¹. Under optimal conditions, the CDs@VPA sensor has shown an extensive fluorescence property with a LOD of 0.0015 mmol L⁻¹ and the linear range from 0.0035 mmol L⁻¹ to 0.20 mmol L⁻¹ (R² = 0.9988) at 390 nm. The mechanism of fluorescence detection of organic phosphorus with CDs@VPA sensor might be attributable to hydrogen bonds formed between heteroatom O, N, S, or P, and the O−H group, which led to fluorescent quenching. Meanwhile, HN−C=O and Si−O groups in CDs@VPA system might contribute to cause excellent blue photoluminescence. The fluorescence sensor was thorough successfully employed to the detection of triazophos in cucumber samples, illustrating its tremendous value towards food sample analysis in complex matrix. Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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13 pages, 2450 KiB

Open AccessArticle

Molecularly Imprinted Nanoparticles Assay (MINA) in Pseudo ELISA: An Alternative to Detect and Quantify Octopamine in Water and Human Urine Samples

by Ewa Moczko, Richard Díaz, Bernabé Rivas, Camilo García, Eduardo Pereira, Sergey Piletsky and César Cáceres

Polymers 2019, 11(9), 1497; https://doi.org/10.3390/polym11091497 - 13 Sep 2019

Cited by 17 | Viewed by 3278

Abstract

In 2004, octopamine was added to the list of drugs banned by the world anti-doping agency (WADA) and prohibited in any sport competition. This work aims to develop a new analytical method to detect octopamine in water and human urine samples. We proposed [...] Read more.

In 2004, octopamine was added to the list of drugs banned by the world anti-doping agency (WADA) and prohibited in any sport competition. This work aims to develop a new analytical method to detect octopamine in water and human urine samples. We proposed a pseudo-enzyme-linked immunosorbent assay (pseudo-ELISA) by replacing traditional monoclonal antibodies with molecularly imprinted polymer nanoparticles (nanoMIPs). NanoMIPs were synthesised by a solid-phase approach using a persulfate initiated polymerisation in water. Their performance was analysed in pseudo competitive ELISA based on the competition between free octopamine and octopamine-HRP conjugated. The final assay was able to detect octopamine in water within the range 1 nmol·L⁻¹–0.1 mol·L⁻¹ with a detection limit of 0.047 ± 0.00231 µg·mL⁻¹ and in human urine samples within the range 1 nmol·L⁻¹–0.0001 mol·L⁻¹ with a detection limit of 0.059 ± 0.00281 µg·mL⁻¹. In all experiments, nanoMIPs presented high affinity to the target molecules and almost no cross-reactivity with analogues of octopamine such as pseudophedrine or l-Tyrosine. Only slight interference was observed from the human urine matrix. The high affinity and specificity of nanoMIPs and no need to maintain a cold chain logistics makes the nanoMIPs a competitive alternative to antibodies. Furthermore, this work is the first attempt to use nanoMIPs in pseudo-ELISA assays to detect octopamine. Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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15 pages, 1611 KiB

Open AccessArticle

Preparation and Application of Molecularly Imprinted Monolithic Extraction Column for the Selective Microextraction of Multiple Macrolide Antibiotics from Animal Muscles

by Xuqin Song, Tong Zhou, Jiahui Zhang, Yijuan Su, Hao Zhou and Limin He

Polymers 2019, 11(7), 1109; https://doi.org/10.3390/polym11071109 - 1 Jul 2019

Cited by 18 | Viewed by 3293

Abstract

This study aimed to prepare a molecularly imprinted monolithic extraction column (MIMC) inside a micropipette tip by situ polymerization with roxithromycin as the dummy template. The polymers possessed excellent adsorption capacity and class-specificity to multiple macrolide drugs. MIMC was directly connected to a [...] Read more.

This study aimed to prepare a molecularly imprinted monolithic extraction column (MIMC) inside a micropipette tip by situ polymerization with roxithromycin as the dummy template. The polymers possessed excellent adsorption capacity and class-specificity to multiple macrolide drugs. MIMC was directly connected to a syringe for template removal and for the optimization of extraction conditions without any other post-treatment of polymers. A liquid chromatography-tandem mass spectrometric method was developed for the selective microextraction and determination of macrolide antibiotics in animal muscles based on MIMC. High recoveries of 76.1–92.8% for six macrolides were obtained with relative standard deviations less than 10.4%. MIMC exhibited better retention ability and durability when compared with the traditional C18 and HLB cartridges. The proposed method shows a great potential for the analysis of macrolide drugs at the trace level in animal foodstuffs. Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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12 pages, 3491 KiB

Open AccessEditor’s ChoiceArticle

Fabrication of Water-Compatible Molecularly Imprinted Resin in a Hydrophilic Deep Eutectic Solvent for the Determination and Purification of Quinolones in Wastewaters

by Weiyang Tang and Kyung Ho Row

Polymers 2019, 11(5), 871; https://doi.org/10.3390/polym11050871 - 13 May 2019

Cited by 38 | Viewed by 4255

Abstract

A novel water-compatible molecularly imprinted resin was prepared in a green solvent deep eutectic solvent (DES). Resorcinol and melamine, as functional monomers with an abundant hydrophilic group, such as –OH, –NH₂ and –NH–, were introduced into the molecularly imprinted resin (MIR). Three [...] Read more.

A novel water-compatible molecularly imprinted resin was prepared in a green solvent deep eutectic solvent (DES). Resorcinol and melamine, as functional monomers with an abundant hydrophilic group, such as –OH, –NH₂ and –NH–, were introduced into the molecularly imprinted resin (MIR). Three DESs (choline chloride-ethylene glycol, tetramethylammonium bromide-ethylene glycol and tetramethylammonium chloride-ethylene glycol) were used to synthesize the molecularly imprinted resin and the resulting deep eutectic solvent-based molecularly imprinted resins were characterized by particle size analysis, elemental analysis, scanning electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. The resulting deep eutectic solvent-based molecularly imprinted resins were then applied to the adsorption of quinolones (ofloxacin) in water. The adsorption process of deep eutectic solvent-based molecularly imprinted resin followed the static adsorption model, Langmuir isotherm (R² ≥ 0.9618) and kinetic model pseudo-second-order (R² > 0.9814). The highest theory adsorption ability of the three kinds of deep eutectic solvent-based molecularly imprinted resins was more than 23.79 mg/g. The choline chloride-ethylene glycol-based MIR was applied to solid-phase extraction for the determination and purification of quinolones (e.g., ciprofloxacin and ofloxacin). The detection limit of deep eutectic solvent-based molecularly imprinted resin-solid-phase extraction method was less than 0.018 mg/L. The recoveries of the deep eutectic solvent-based molecularly imprinted resin-solid-phase extraction method at three spiked levels were 88.7–94.5%, with a relative standard deviation of ≤4.8%. The novel deep eutectic solvent-based molecularly imprinted resin-solid-phase extraction method is a simple, selective and accurate pre-treatment method and can be used to determine the quinolones in environmental water. Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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11 pages, 2742 KiB

Open AccessArticle

Luminescent Molecularly Imprinted Polymers Based on Covalent Organic Frameworks and Quantum Dots with Strong Optical Response to Quinoxaline-2-Carboxylicacid

by Ying Zhang, Dianwei Zhang and Huilin Liu

Polymers 2019, 11(4), 708; https://doi.org/10.3390/polym11040708 - 17 Apr 2019

Cited by 21 | Viewed by 4403

Abstract

Three-dimensional molecularly imprinted polymers (MIPs) based on quantum dots-grafted covalent organic frameworks (QDs-grafted COFs) are reported in this study. The compound 1,3,5-triformylphloroglucinol-P-phenylenediamine was used as COF material to react with the amino-modified CdSe/ZnS QDs by Schiff-base reactions. The amino-derived QDs reacted with quinoxaline-2-carboxylicacid [...] Read more.

Three-dimensional molecularly imprinted polymers (MIPs) based on quantum dots-grafted covalent organic frameworks (QDs-grafted COFs) are reported in this study. The compound 1,3,5-triformylphloroglucinol-P-phenylenediamine was used as COF material to react with the amino-modified CdSe/ZnS QDs by Schiff-base reactions. The amino-derived QDs reacted with quinoxaline-2-carboxylicacid (QCA) via a non-covalent interaction. The system combines the advantages of MIPs, COFs, and QDs for highly sensitive and selective QCA detection. The MIPs based on QDs-grafted COFs showed good chemical selectivity and thermal stability, as well as consistency in QCA optosensing. Under optimal conditions, the detection limit for QCA in meat and feed samples was 0.85 μmol L⁻¹, over a linear concentration range of 1–50 μmol L⁻¹. The current findings suggest a potential application of MIPs based on QDs-grafted COFs for the detection of trace levels of hazardous chemicals for food safety and environmental control. Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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13 pages, 4173 KiB

Open AccessArticle

Fabrication of Core-Shell Magnetic Molecularly Imprinted Nanospheres towards Hypericin via Click Polymerization

by Xinxin Wang, Yuxin Pei, Yong Hou and Zhichao Pei

Polymers 2019, 11(2), 313; https://doi.org/10.3390/polym11020313 - 13 Feb 2019

Cited by 16 | Viewed by 4037

Abstract

The core-shell structure molecularly imprinted magnetic nanospheres towards hypericin (Fe₃O₄@MIPs) were prepared by mercapto-alkyne click polymerization. The shape and size of nanospheres were characterized by dynamic light scattering (DLS) and transmission electron microscope (TEM). The nanospheres were analyzed by [...] Read more.

The core-shell structure molecularly imprinted magnetic nanospheres towards hypericin (Fe₃O₄@MIPs) were prepared by mercapto-alkyne click polymerization. The shape and size of nanospheres were characterized by dynamic light scattering (DLS) and transmission electron microscope (TEM). The nanospheres were analyzed by FTIR spectroscopy to verify the thiol-yne click reaction in the presence or absence of hypericin. The Brunauer–Emmet–Teller (BET) method was used for measuring the average pore size, pore volume and surface area. The Fe₃O₄@MIPs synthesized displayed a good adsorption capacity (Q = 6.80 µmol·g⁻¹). In addition, so-prepared Fe₃O₄@MIPs showed fast mass transfer rates and good reusability. The method established for fabrication of Fe₃O₄@MIPs showed excellent reproducibility and has broad potential for the fabrication of other core-shell molecularly imprinted polymers (MIPs). Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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Review

Jump to: Research, Other

33 pages, 2556 KiB

Open AccessReview

Perspectives of Molecularly Imprinted Polymer-Based Drug Delivery Systems in Cancer Therapy

by Andreea Elena Bodoki, Bogdan-Cezar Iacob and Ede Bodoki

Polymers 2019, 11(12), 2085; https://doi.org/10.3390/polym11122085 - 13 Dec 2019

Cited by 46 | Viewed by 6219

Abstract

Despite the considerable effort made in the past decades, multiple aspects of cancer management remain a challenge for the scientific community. The severe toxicity and poor bioavailability of conventional chemotherapeutics, and the multidrug resistance have turned the attention of researchers towards the quest [...] Read more.

Despite the considerable effort made in the past decades, multiple aspects of cancer management remain a challenge for the scientific community. The severe toxicity and poor bioavailability of conventional chemotherapeutics, and the multidrug resistance have turned the attention of researchers towards the quest of drug carriers engineered to offer an efficient, localized, temporized, and doze-controlled delivery of antitumor agents of proven clinical value. Molecular imprinting of chemotherapeutics is very appealing in the design of drug delivery systems since the specific and selective binding sites created within the polymeric matrix turn these complex structures into value-added carriers with tunable features, notably high loading capacity, and a good control of payload release. Our work aims to summarize the present state-of-the art of molecularly imprinted polymer-based drug delivery systems developed for anticancer therapy, with emphasis on the particularities of the chemotherapeutics’ release and with a critical assessment of the current challenges and future perspectives of these unique drug carriers. Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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44 pages, 4935 KiB

Open AccessEditor’s ChoiceReview

Molecularly Imprinted Polymer-Based Hybrid Materials for the Development of Optical Sensors

by Alberto Rico-Yuste and Sergio Carrasco

Polymers 2019, 11(7), 1173; https://doi.org/10.3390/polym11071173 - 11 Jul 2019

Cited by 71 | Viewed by 10423

Abstract

We report on the development of new optical sensors using molecularly imprinted polymers (MIPs) combined with different materials and explore the novel strategies followed in order to overcome some of the limitations found during the last decade in terms of performance. This review [...] Read more.

We report on the development of new optical sensors using molecularly imprinted polymers (MIPs) combined with different materials and explore the novel strategies followed in order to overcome some of the limitations found during the last decade in terms of performance. This review pretends to offer a general overview, mainly focused on the last 3 years, on how the new fabrication procedures enable the synthesis of hybrid materials enhancing not only the recognition ability of the polymer but the optical signal. Introduction describes MIPs as biomimetic recognition elements, their properties and applications, emphasizing on each step of the fabrication/recognition procedure. The state of the art is presented and the change in the publication trend between electrochemical and optical sensor devices is thoroughly discussed according to the new fabrication and micro/nano-structuring techniques paving the way for a new generation of MIP-based optical sensors. We want to offer the reader a different perspective based on the materials science in contrast to other overviews. Different substrates for anchoring MIPs are considered and distributed in different sections according to the dimensionality and the nature of the composite, highlighting the synergetic effect obtained as a result of merging both materials to achieve the final goal. Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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18 pages, 1914 KiB

Open AccessReview

Molecularly Imprinted Polymer Materials as Selective Recognition Sorbents for Explosives: A Review

by Mashaalah Zarejousheghani, Wilhelm Lorenz, Paula Vanninen, Taher Alizadeh, Malcolm Cämmerer and Helko Borsdorf

Polymers 2019, 11(5), 888; https://doi.org/10.3390/polym11050888 - 15 May 2019

Cited by 23 | Viewed by 5729

Abstract

Explosives are of significant interest to homeland security departments and forensic investigations. Fast, sensitive and selective detection of these chemicals is of great concern for security purposes as well as for triage and decontamination in contaminated areas. To this end, selective sorbents with [...] Read more.

Explosives are of significant interest to homeland security departments and forensic investigations. Fast, sensitive and selective detection of these chemicals is of great concern for security purposes as well as for triage and decontamination in contaminated areas. To this end, selective sorbents with fast binding kinetics and high binding capacity, either in combination with a sensor transducer or a sampling/sample-preparation method, are required. Molecularly imprinted polymers (MIPs) show promise as cost-effective and rugged artificial selective sorbents, which have a wide variety of applications. This manuscript reviews the innovative strategies developed in 57 manuscripts (published from 2006 to 2019) to use MIP materials for explosives. To the best of our knowledge, there are currently no commercially available MIP-modified sensors or sample preparation methods for explosives in the market. We believe that this review provides information to give insight into the future prospects and potential commercialization of such materials. We warn the readers of the hazards of working with explosives. Full article

(This article belongs to the Special Issue Molecular Imprinted Polymers: Challenges and Applications)

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