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A scheme for molecularly imprinted polymer preparation, wherein A -formation of a pre-polymerization complex; B -addition of a cross linking monomer and initiator; C -polymerization reaction; D – removal of the template.
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Technology of molecularly imprinted polymers (MIP) has become very popular in recent decades. MIPs are primarily used in medical diagnostics, chromatographic separation and solid phase extraction (SPE); also as sensors and catalysts. In recent years there have been reported benefits of combining molecular imprinted polymers with additional features...
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... the influence of physical factors, such as temperature or electromagnetic radiation, is able to initiate the polymerization reaction. Then the template is subjected to leaching by being removed from the "steric cavity", which both in chemical and spatial terms corresponds to the substance isolated [9]. The scheme of MIP preparation is given in Fig. ...
Citations
... For the effective use of humic acids, it is necessary to consider the peculiarities of their chemical structure and composition, which determine the properties of these highmolecular natural compounds. Humic acids obtained from various humus-containing raw materials are becoming increasingly used in sorption processes as natural sorbents for wastewater treatment from various organic and inorganic ecotoxicants [19,20]. The modification of humic acids is one of the recognized methods used for increasing their reactivity. ...
A magnetic polymer material based on natural polymers—humic acids and magnetite, pre-configured for the sorption of a metal ion—was obtained. The magnetic polymer material was obtained via the interaction of a natural polymer, magnetite nanoparticles and sorbed metal ions that were used as a template. Moreover, the formation of a pre-polymerization complex was followed by copolycondensation with an amine in the presence of a crosslinking agent and further removal of metal ions from the crosslinked copolymer. The physicochemical properties of the resulting materials were determined using various physical methods. The composition of the resulting magnetic polymer materials was characterized by elemental analysis using an Elementar Unicube elemental analyzer. It was found that the carbon content increases by 8.28% and nitrogen by 0.42% for the polymer material Fe3O4:HA:T:AA; for the polymer material Fe3O4:HA:AA, the carbon content increases by 14.61% and nitrogen by 3.01%. Based on the IR spectra data, it is clear that magnetic polymer materials have much in common before hydrolysis (Fe3O4:HA:T:AA) and after hydrolysis (Fe3O4:HA:AA). The structure of the resulting polymer materials was studied using electron microscopy. Micrographs show the presence of pores in magnetic polymer materials after acid hydrolysis, indicating the formation of imprints. The results of the study of the sorption properties of magnetic polymer materials showed that after acid hydrolysis, the sorption capacity of a customized magnetic polymer material increases two times and it can act as a magnetic sorption material.
... Magnetic nanoparticles (MNP) are becoming more popular in extracting different analytes from various samples [26][27][28][29][30][31][32]. The surfaces of MNPs are usually modified and functionalized with different molecules. ...
... However, the polymer coatings of MNPs ensure a large surface area, stability, and biocompatibility. MNPs are also coated with silver or gold [26,32]. MNPs are applied in nucleic acid extraction, enrichment, and nucleic acid detection [32]. ...
Oligonucleotides have many important applications, including as primers in polymerase chain reactions and probes for DNA sequencing. They are proposed as a diagnostic and prognostic tool for various diseases and therapeutics in antisense therapy. Accordingly, it is necessary to develop liquid chromatography and solid phase extraction methods to separate oligonucleotides and isolate them from biological samples. Many reviews have been written about the determination of these compounds using the separation technique or sample preparation for their isolation. However, presumably, there are no articles that critically review the adsorbents used in liquid chromatography or solid phase extraction. The present publication reviews the literature from the last twenty years related to supports (silica, polymers, magnetic nanoparticles) and their modifications. The discussed issues concern reversed phase (alkyl, aromatic, cholesterol, mixed ligands), ion-exchange (strong and weak ones), polar (silica, polyhydroxy, amide, zwitterionic), and oligonucleotide-based adsorbents.
... Furthermore, energy dispersive X-ray (EDX) and X-ray photoelectron play key roles in information on the element component of magnetic materials, allowing us to confirm magnetic material modifications [173]. The vibrating sample magnetometer (VSM) is used to determine the magnetic characteristics, whereas thermogravimetric analysis (TGA) is used to evaluate the thermal properties of the MMIP [208]. ...
... This phase takes the most time and is the cause of the bulk of mistakes in the analysis. As this happens, it will significantly increase the uncertainty of the results of a particular analytical method [208]. The excellent performance of MMIP as an adsorbent in the analytical field has recently sparked much interest. ...
... The presence of a vast number of substances in body fluids (blood, plasma, and urine) and tissues, for example, makes getting the appropriate extracts during the separation phase problematic. Compounds are present in extremely minute concentrations in this sort of sample, necessitating the development of more effective separation and purification techniques [208]. Despite the success of MIP material in the direction of small molecules, biomacromolecules such as proteins, peptides, cells, and viruses remain challenging because of their large size, chemical and structural complexity, delayed mass transfer, and environmental instability [234]. ...
The molecularly imprinted polymers (MIPs) technology, which has been around since the 1970s, has grown in popularity in recent decades. MIPs have shown to be a useful approach for determining target molecules in complicated matrices containing other structurally similar and related chemicals. Despite MIPs have intrinsic polymer features such as stability, robustness, and low-cost production, traditional MIPs have a number of drawbacks. Surface molecular imprinting appears to be an alternative approach that can address some of the drawbacks of traditional MIP by anchoring shells to the surface of matrix carriers such as nanoparticles. The incorporation of nanoparticles into the polymeric structure of MIPs can improve their properties or provide novel capabilities. Magnetic nanoparticles have been widely explored for their separation and extraction capability. Magnetic components in MIP can help develop a regulated rebinding process, allowing magnetic separation to substitute centrifugation and filtration stages in a simple and cost-effective strategy. Polymers are created directly on the surface of a magnetic substrate to create a unique material termed magnetic molecularly imprinted polymer (MMIP). These materials have been widely used to extract molecules from complex matrices in a variety of applications, especially in environmental, food, and biological studies. This paper seeks to summarize and discuss the nanoparticle synthesis and magnetic nanoparticle combination in the MIP preparation. The novel applications of MMIP in environmental, food, and biological analysis are also discussed in this paper.
... Polymers 2022,14, 3008 ...
During the last few years, separation techniques using molecular imprinting polymers (MIPs) have been developed, making certain improvements using magnetic properties. Compared to MIP, Magnetic molecularly imprinted polymers (MMIPs) have high selectivity in sample pre-treatment and allow for fast and easy isolation of the target analyte. Its magnetic properties and good extraction performance depend on the MMIP synthesis step, which consists of 4 steps, namely magnetite manufacture, magnetic coating using modified components, polymerization and template desorption. This review discusses the factors that will affect the performance of MMIP as a selective sorbent at each stage. MMIP, using Fe3O4 as a magnetite core, showed strong superparamagnetism; it was prepared using the co-precipitation method using FeCl3·6H2O and FeCl2·H2O to obtain high magnetic properties, using NH4OH solution added for higher crystallinity. In magnetite synthesis, the use of a higher temperature and reaction time will result in a larger nanoparticle size and high magnetization saturation, while a higher pH value will result in a smaller particle size. In the modification step, the use of high amounts of oleic acid results in smaller nanoparticles; furthermore, determining the correct molar ratio between FeCl3 and the shielding agent will also result in smaller particles. The next factor is that the proper ratio of functional monomer, cross-linker and solvent will improve printing efficiency. Thus, it will produce MMIP with high selectivity in sample pre-treatment.
... MIP selectivity adsorbs the analyte and separates it from the solution. The analyte is then desorbed from the MIP and eluted in the solution to be analyzed [52] . Figure 7 shows an extraction technique by using a MIP as a stationary phase. ...
Molecular imprinted polymers (MIPs) are artificial receptors for a target molecule. These synthetic receptors mimic natural antibodies and enzymes in their function, mode of action, and recognition capability. Herein, the concept and basics of MIPs were discussed with a particular focus on the imprinting process and their synthetic procedures. A lot of ingredients are included in the preparation of MIPs. The analyte or template is the target molecule for creating an imprint in the matrix bearing the configuration of its shape and functional groups. A functional monomer is used to physically interact with the template molecule and chemically with the cross-linker. An initiator is added to promote the polymerization reaction and the network structure formation which provide the mechanical stability of the imprinted sites. Non-covalent and covalent imprinting approaches are the two main types of MIPs depending on the interaction between the template molecule and the functional monomer. MIPs are included in applications such as chromatography, sensors, membranes, drug delivery, etc. There is a particular interest in designing smart MIPs. The intelligence of these polymers stems from their response to an external stimulus such as temperature, pH, biomolecule, and magnetic field which induced more advanced applications for the MIPs.
... First, the preparation of MMIPs can be carried out by forming magnetite using a coprecipitation technique between iron (II) chloride (FeCl 2 ⋅H 2 O) or iron (II) sulfate (FeSO 4 ⋅7H 2 O) and iron (III) cloride (FeCl 3 ⋅6H 2 O) under basic conditions at 80-100 • C (Kwaśniewska et al., 2015). After the magnetite is formed, the surface modification of the magnetite can be carried out by silanization or by adding a surfactant, such as ethylene glycol or oleic acid to increase the amphoteric properties of the magnetite surface and enhance its interaction with polar solutions. ...
In this study, novel magnetic molecularly imprinted polymers (MMIPs) were successfully synthesized for selective separation of di(2-ethylhexyl)phthalate (DEHP) in an PVC sample solution. Polymerization was carried out using Fe3O4 modified by oleic acid, ethylene glycol dimethacrylate (EGDMA), methacrylic acid (MAA), and benzoyl peroxide (BPO) in the presence of DEHP as template molecule to produce MMIPs named Fe3O4@MIPs. Magnetic non-molecularly imprinted polymers (MNIPs) were also prepared for comparison purposes. The structure and physical properties of MMIPs and MNIPs were characterized using FT-IR, SEM, TEM, VSM and zeta potential analysis. The FT-IR spectra showed that MMIPs were successfully synthesized, indicated by the presence of a Fe-O peak at 586 cm⁻¹, a benzene derivative peak at 709, 1072, and 1155 cm⁻¹, a carbonyl peak of MAA at 1728 cm⁻¹ and a C-H peak of oleic acid at 2954 cm⁻¹. SEM and TEM measurements showed that MMIPs were porous polymers with a smaller particle size than MNIPs. VSM measurement showed that MMIPs were superparamagnetic with a saturation magnetism value of 39.92 emu/g. MMIPs have a better adsorption capacity than MNIPs with an imprinting factor (IF) value of 3.37 and a maximum adsorption capacity value of 17.21 mg/g. The sorption studies showed that the adsorption process followed the Langmuir isotherm model and fitted well to a pseudo-second-order kinetic model with ΔHo of -82.17 kJ mol⁻¹. Moreover, MMIPs were more selective to DEHP than dibutyl phthalate (DBP), with a selectivity coefficient value of 4.57. The desorption test showed that MMIPs showed good regeneration with a desorption percentage of 98.42 % and decreasing in adsorption capacity of 11.2% after three times regenerations. DEHP removal from PVC samples using MMIP showed that polymer could reduce the matrixes effect with a recovery percentage of around 91.03-99.68%.
... In recent years, in the world of nanoparticles, molecularly imprinted polymers (MIP) have been synthesized as new innovative sorbents. The development of sorbents and the imprinted particle allows proposing innovative solutions in separation and purification [1][2][3][4]. MIPs are characterized as artificial bio-receptors or as antibody-antigen systems due to the mechanism based on the selective binding of specific molecules in a special cavity, which is similar to the lock-key model [5]. Although a number of methods to synthesize such analytical tools have been proposed so far, the general scheme of operation is similar. ...
... LOD-limit of detection, 2 LOQ-limit of quantification,3 MeP-methylparaben,4 EtP-ethylparaben,5 PpP-propylparaben,6 BuP-butylparaben; 7 BnP-benzylparaben. ...
Magnetic molecularly imprinted polymers (MMIPs) are an invaluable asset in the development of many methods in analytical chemistry, particularly sample preparation. Novel adsorbents based on MMIPs are characterized by high selectivity towards a specific analyte due to the presence of a specific cavity on their polymer surface, enabling the lock–key model interactions to occur. In addition, the magnetic core provides superparamagnetic properties that allow rapid separation of the sorbent from the sample solution. Such a combination of imprinted polymers with a magnetic core has an innovative influence on the development of separation techniques. Hence, the present study describes the synthesis of MMIPs with 17β-estradiol used as a template molecule in the production of imprinted polymers. The as-prepared sorbent was used for a sorption/desorption study of five parabens from breast milk samples. The obtained results were characterized by sorption efficiency exceeding 92%, which shows the high affinity of the analytes to the functional groups on the sorbent. The final determination of the selected analytes was done with high-performance liquid chromatography using a fluorometric detector. The determined linearity ranges for selected parabens were characterized by high determination coefficients (r2 from 0.9992 to 0.9999), and the calculated limit of detection (LOD) and limit of quantification (LOQ) for the identified compounds were low (LOD from 1.1–2.7 ng mL−1; LOQ from 3.6–8.1 ng mL−1), which makes their quantitative analysis in real samples feasible.
... The development of science and the constant insufficiency of the obtained answers lead to challenges undertaken by researchers in order to isolate and determine biologically active compounds (potential markers or precursors of cancer) on increasingly lower levels of concentration. Their isolation from matrices of complex composition (proteins, fats and other co-existing compounds) and those characterized by high heterogeneousness (biological samples: tissues, blood plasma, urine) requires application of selective and specific methods of sample preparation by extraction and chromatographic techniques [1][2][3][4]. Application such materials packing for solid phase extraction or/and preparation as well as flash chromatography possess number of advantage. However, the stage of purifying of the obtained extracts from these complex matrices and enrichment of the analyte have the greatest influence on obtaining reliable and conclusive final results. ...
... If the dimensions of the ferromagnetic material is reduced below the critical value, the creation of such magnetic domain is disadvantageous. However, reduction of their size leads to formation of superparamagnetic particles (ranging in size from 1 to 30 nm) ( Fig. 14.2) [2][3][4][5]. ...
... They are synthetic materials that have artificially generated three-dimensional molecular cavities capable of selectively binding structurally related compounds. They are also characterized by high thermal, mechanical and physicochemical stability, low cost, and high sensitivity; they are also reusable, which is a considerable advantage and makes them a highly attractive alternative to conventional sorbents [38][39][40]. ...
Steroid hormones as endocrine disrupting compounds can interfere with the functioning of hormonal systems of organisms and thus affect the health and reproduction of humans and wildlife. Unfortunately, these types of harmful endocrine disrupting compounds have been found in a variety of environmental samples at very low concentrations. Therefore, a simple, fast and efficient method for enrichment of water samples is needed. A molecularly imprinted solid‐phase extraction combined with high performance liquid chromatography coupled with diode array detection was developed for the determination of six steroid hormones, such as estrone, 17ß‐estradiol, estriol, 17‐α‐ethinylestradiol, progesterone and testosterone in water samples. The recoveries obtained in the proposed method were in the range of 78.7‐101.3%. Matrix effect below 20% suggests that the quantitative and qualitative results of the analysis were not significantly affected by the matrix. The results show that molecularly imprinted polymers based on spherical silica gel had the potential to be a highly innovative and selective sorbent. The proposed method was proved to be applicable for molecularly imprinted solid‐phase extraction in selective and reliable extraction and enrichment of steroid hormones in environmental water samples. This article is protected by copyright. All rights reserved
... A similar approach for the production of spherical particles with a diameter of several nanometers to 10 lm is a dispersion polymerization. [31,59] In this case, the polymerization process starts in a homogeneous medium containing all imprinting components (monomers, solvents, and aninitiator) and surfactants. As the polymerization proceeds, the growing matrix becomes insoluble. ...
The use of excessive antibiotics in medical treatment and animal breeding has led to their prevalence in the environment and foods. Thereby, rapid, cheap, and sustainable techniques are required to detect and control the potential risk related to antibiotics. Actually, immunoassays have wide applications for this purpose, and improved assay formats with enzymatic, fluorescent, nanodispersed, and other tracers have enhanced the efficiency of the technique. However, there are several shortcomings of immunoassay due to the protein nature of antibodies. Thereby, molecular imprinting technology has evolved as growing artificial analytical receptor for molecular recognition with binding properties similar to natural antibodies. Molecularly imprinted polymers (MIPs) are defined as “plastibodies” or substitutes for antibodies in immunoassays. This review gives a general overview of the application of molecular imprinting to analytical systems, its state of art, and perspective. The application of MIP-based assays in the detection of antibiotics in food and environmental samples is explored herein.
