Application of molecularly imprinted polymers as the sorbent for extraction of chemical contaminants from milk.

Milk is one of the most consumed and balanced foods with a high nutritional value which could be contaminated with different chemicals such as antibiotics, melamine, and hormones. Because of the low concentration of these compounds and the complexity of milk samples, there is a need to use sample pre-treatment methods for purification and preconcentration of these compounds before instrumental techniques. Molecular imprinting polymers (MIPs) are synthetic materials with specific recognition sites complementary to the target molecule. MIPs have selectivity for a specific analyte or group of analytes, which could be used to extract and determine contaminants and remove the interfering compounds from complex samples. Compared to other techniques, sample preparation, high selectivity, excellent stability, and low cost are other advantages of using MIPs. The present article gives an overview of the synthesis of MIPs and their application for extracting antibiotics, hormones, and melamine in milk samples.

Molecularly imprinted polymer sheathed mesoporous silica tube as SPME fiber coating for determination of tobacco-specific nitrosamines in water.

Tobacco-specific nitrosamines (TSNAs) are probably carcinogenic disinfection byproducts eliciting health risk concerns. The determination and surveillance of TSNAs in water is still cumbersome due to the lack of advanced sample preparation methods. Herein, we prepared a solid phase microextraction (SPME) fiber coated with the molecularly imprinted polymer (MIP) sheathed mesoporous silica tube (MST) composite material, and developed a highly efficient, selective, and sensitive method for the determination of five TSNAs in water. Benefiting from the TSNAs-specific recognition of MIP and the increased specific surface area derived from MST, the MIP@MST fiber exhibited excellent extraction performance for TSNAs, which was much superior to the commercially available SPME fibers. By coupling to high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), the outstanding analytical merits such as low method detection limits (ranging 0.1-6.7 ng L-1) and good reproducibility (intra-fiber and inter-fiber relative standard deviations ranging 4.1 %-11.6 % and 3.5 %-12.2 %, respectively) were achieved with the consumption of 8 mL water sample and 100 µL methanol solvent in 50 min. The feasibility of the SPME-HPLC-MS/MS method was demonstrated in tap water and chloraminated source water, with relative recoveries for the five TSNAs ranging from 85.2 % to 108.5 %. In result, none of the TSNAs were found in the tap water samples, while 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-Butanol (NNAL) were detected in the chloraminated source water samples. The rapid and convenient SPME-HPLC-MS/MS method developed in this study offers a powerful tool for monitoring TSNAs in water.

Molecularly imprinted polymer-coated paper for the selective extraction of organophosphorus pesticides from fruits, vegetables, and cereal grains.

Biodegradable molecularly imprinted polymer-coated paper (MIP@paper) was effectively produced by polymerization using azinphos-methyl as a template molecule, terephthalic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, and aqueous ethanol as a green porogenic solvent. The material was subsequently composited onto cellulose paper, which served as the natural substrate, by dip coating with the aid of chitosan and citric acid natural adhesive. The properties, such as static and dynamic adsorption, selectivity, and reusability, were assessed. At rapid adsorption equilibrium (10 min), the MIP@paper had a high adsorption capacity in the range of 2.5-3.7 mg g-1 and good recognition with imprinting factors up to 2.1. In addition, the proposed MIP@paper was utilized efficiently as a sorbent for dispersive solid phase extraction (d-SPE) of eight organophosphorus pesticides (OPPs) prior to high-performance liquid chromatography (HPLC) analysis. The d-SPE-HPLC method displayed low detection limits of 1.2-4.5 µg kg-1 and significant enrichment factors (up to 320-fold). The proposed method was effectively applied for the determination of OPP residues in agricultural products, including fruits, vegetables, and cereal grains, with satisfactory spiked recoveries (80.1-119.1 %). Thus, the MIP@paper material provided a selective and environmentally favorable method for extracting and determining organophosphorus pesticides.

Development of a Solid-Phase Dispersive Extraction Method for Molecularly Imprinted Polymers and LC-MS/MS for Analysis of Clenbuterol Residues in Swine Livers and Kidneys.

BACKGROUND: Clenbuterol (CLB) is approved as a veterinary drug because of its tracheal smooth muscle and uterine relaxant effects. However, if improperly administered for the purpose of fattening livestock, CLB can remain in the organs, which may pose a health hazard to humans. OBJECTIVE: We aimed to examine the combination of molecularly imprinted polymer (MIP) and solid-phase dispersive extraction (SPDE) as a pretreatment method for swine liver and kidney, which contain more coexisting impurities than muscle tissue, and attempted to construct an analytical method using liquid chromatography-tandem mass spectrometry (LC-MS/MS). METHODS: Swine livers and kidneys were homogenized and extracted using liquid-liquid partitioning with an ethyl acetate-n-hexane (1 + 1) mixture, followed by SPDE using an MIP gel, and measured using LC-MS/MS. For LC-MS/MS, either an absolute calibration method or isotope dilution mass spectrometry (IDMS) was used. For method validation, a recovery test (additive concentrations: 0.05 and 0.5 ng/g) was conducted, and the data were analyzed using one-way analysis of variance (ANOVA). RESULTS: The recoveries (trueness), repeatability, and intermediate precision obtained using absolute calibration were similar to those obtained using IDMS. CONCLUSION: Using MIP-SPDE as a pretreatment method for CLB in swine liver and kidney samples yielded comparable results for absolute calibration and IDMS in LC-MS/MS analysis. HIGHLIGHTS: MIP-SPDE can be used as a pretreatment method to analyze CLB in swine organs with high accuracy.

Development of Magnetic Molecularly Imprinted Polymer Coupled Nanospray Ion Source for Analysis of Cephalosporin Antibiotics in Food Samples.

A magnetic molecularly imprinted polymer (MMIP) coupled nanospray ion source was developed for analysis of cephalosporin antibiotics in food samples. MIP coated Fe3O4 nanospheres were prepared for magnetic solid-phase extraction (MSPE) of the antibiotics in the extract of samples and then integrated into the nanospray capillary for further desorption and mass spectrometry analysis. The developed device combines the advantages of high extraction efficiency of MSPE, unique selectivity of MIPs, and fast analysis speed of ambient ionization mass spectrometry (AIMS). Five cephalosporin antibiotics in milk, egg, and beef samples were analyzed using the developed methods. High sensitivities with limits of detection (LODs) from 0.3 to 0.5 µg kg-1 were achieved for cephalosporin antibiotics in milk, egg, and beef samples, respectively. Good linearity, determination coefficient values (R2 > 0.992), and precision (RSD < 15%) with recoveries ranging from 72.6% to 115.5% were obtained using the spiked milk, egg, and beef sample matrices.

Study on Molecularly Imprinted Polymers Obtained Sonochemically for the Determination of Aflatoxins in Food.

Aflatoxins (AFs) are fungi secondary metabolites produced by the Aspergillus family. These compounds can enter the food chain through food contamination, representing a risk to human health. Commercial immunoaffinity columns are widely used for the extraction and cleanup of AFs from food samples; however, their high cost and large solvent consumption create a need for alternative strategies. In this work, an alternative strategy for producing molecularly imprinted polymers (MIPs) was proposed to extract aflatoxins AFB1, AFB2, AFG1, and AFG2 from complex food samples, using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The MIPs were synthesized via a low-cost and rapid (5 min) sonochemical free-radical polymerization, using 1-hydroxy-2-naphthoic acid as a dummy template. MIPs-based solid phase extraction performance was tested on 17 dietary supplements (vegetables, fruits, and cereals), obtaining appreciable recovery rates (65-90%) and good reproducibility (RSD ≤ 6%, n = 3); the selectivity towards other mycotoxins was proved and the data obtained compared with commercial immunoaffinity columns. The proposed strategy can be considered an alternative affordable approach to the classical immunoaffinity columns, since it is more selective and better performing.

Determination of 35 sulfonamides in pork by magnetic molecularly imprinted polymer-based dispersive solid-phase extraction and ultra-performance liquid chromatography photodiode array method.

BACKGROUND: Sulfonamide residues in foods of animal origin are potential risks to consumer health, so it is very important to inspect them. Among the previously reported instrumental methods, the best method can only be used to determine at most 22 sulfonamides. Thus, an instrumental method capable of determining more sulfonamide species is desirable. RESULTS: In this study, sulfadoxine was used as a template to synthesize a type of magnetic molecularly imprinted polymer that could recognize 35 sulfonamides. After characterization, this composite was used to develop a dispersive solid-phase extraction method for extraction and purification of the 35 sulfonamides in pork, followed by determination using an ultra-performance liquid chromatography photodiode array method. This composite exhibited high adsorption capacity (11.01-19.21 µg mg-1 ) and high recovery (>89.01%), and could be reused at least ten times. Due to the enrichment effect during sample preparation (enrichment factor 22-66), the limits of detection for determination of the 35 drugs in pork were in the range of 0.08-0.53 ng g-1 . The detection results for some real pork samples were consistent with a liquid chromatographic-tandem mass spectrometric method. After comparison, the present method showed generally better performances than the previously reported sample preparation methods and instrumental methods for detection of sulfonamides. CONCLUSION: The method developed in the present study could be used as a practical tool for routine detection of sulfonamide residues in pork samples. © 2022 Society of Chemical Industry.

A comparative study of photoresponsive molecularly imprinted polymers with different shell thicknesses: Effects on 6-O-α-maltosyl-ß-cyclodextrin separation.

Photoresponsive surface molecularly imprinted polymers (PSMIPs) with controlled nanoshell thicknesses were synthesized using different amounts of precursor materials to determine the effects of polymer shell layer thickness on the separation and purification of 6-O-alpha-maltosyl-beta-cyclodextrin (Mal-ß-CD). The physicochemical properties and adsorption and desorption capacities of PSMIPs with different shell thicknesses were studied. Interestingly, the uniform thickness of the imprinted polymer shell layer could be adjusted from 10 to 60 nm by varying the amount of polymerization precursors, and the average mesopore diameter of PSMIPs was not significantly affected by shell thickness. However, the removal efficiency and selective capacity of PSMIPs on Mal-ß-CD were strongly correlated to their shell thickness. The adsorption behavior of PSMIPs on Mal-ß-CD fitted well with the Langmuir adsorption model and pseudo-second-order kinetic model. Based on the obtained results, PSMIPs with a 30-nm imprinted layer were found to be an excellent adsorbent for Mal-ß-CD separation, with an adsorption capacity of 18.12 mg/g. They can therefore be used for industrial chromatographic separations of Mal-ß-CD in the future. PRACTICAL APPLICATION: This article clearly demonstrated that the shell thickness of core-shell molecularly imprinted materials affected the degree and rate of cyclodextrin separation. Determining the optimal thickness is of great significance for the material in the separation and purification of cyclodextrin.

Selective recognition of tumor cells by molecularly imprinted polymers.

Molecularly imprinted polymers, developed 50 years ago, have garnered enormous attention as receptor-like materials. Lately, molecularly imprinted polymers have been employed as a specific target tool in favor of cancer diagnosis and therapy by the selective recognition of tumor cells. Although the molecular imprinting technology has been well-innovated recently, the cell still remains the most challenging target for imprinting. In this review, we summarize the advances in the synthesis of molecularly imprinted polymers suitable for the selective recognition of tumor cells. Through a sustained effort, three strategies have been developed including peptide-imprinting, polysaccharide-imprinting, and whole-cell imprinting, which have resulted in inspiring applications in effective cancer diagnosis and therapy. The major challenges and perspectives on the further directions related to the synthesis of molecularly imprinted polymers were also outlined.

Functional Molecular Interfaces for Impedance-Based Diagnostics.

In seeking to develop and optimize reagentless electroanalytical assays, a consideration of the transducing interface features lies key to any subsequent sensitivity and selectivity. This review briefly summarizes some of the most commonly used receptive interfaces that have been employed within the development of impedimetric molecular sensors. We discuss the use of high surface area carbon, nanoparticles, and a range of bioreceptors that can subsequently be integrated. The review spans the most commonly utilized biorecognition elements, such as antibodies, antibody fragments, aptamers, and nucleic acids, and touches on some novel emerging alternatives such as nanofragments, molecularly imprinted polymers, and bacteriophages. Reference is made to the immobilization chemistries available along with a consideration of both optimal packing density and recognition probe orientation. We also discuss assay-relevant mechanistic details and applications in real sample analysis.

Recent Advances in the Extraction of Polycyclic Aromatic Hydrocarbons from Environmental Samples.

Polycyclic aromatic hydrocarbons (PAHs) comprise a group of chemical compounds consisting of two or more fused benzene rings. PAHs exhibit hydrophobicity and low water solubility, while some of their members are toxic substances resistant to degradation. Due to their low levels in environmental matrices, a preconcentration step is usually required for their determination. Nowadays, there is a wide variety of sample preparation techniques, including micro-extraction techniques (e.g., solid-phase microextraction and liquid phase microextraction) and miniaturized extraction techniques (e.g., dispersive solid-phase extraction, magnetic solid-phase extraction, stir bar sorptive extraction, fabric phase sorptive extraction etc.). Compared to the conventional sample preparation techniques, these novel techniques show some benefits, including reduced organic solvent consumption, while they are time and cost efficient. A plethora of adsorbents, such as metal-organic frameworks, carbon-based materials and molecularly imprinted polymers, have been successfully coupled with a wide variety of extraction techniques. This review focuses on the recent advances in the extraction techniques of PAHs from environmental matrices, utilizing novel sample preparation approaches and adsorbents.