Computer-aided design of magnetic dummy molecularly imprinted polymers for solid-phase extraction of ten phthalates from food prior to their determination by GC-MS/MS

Abstract

Magnetic dummy molecularly imprinted polymers (MDMIPs) were prepared by combining the surface imprinting technique with computer simulation for selective recognition of phthalate esters (PAEs). A computational study based on the density functional theory was performed to evaluate the template-monomer geometry and interaction energy in the prepolymerization mixture. The MDMIPs were characterized by transmission electron microscopy, scanning electron microscopy, vibrating sample magnetometry, X-ray diffraction, and Fourier transform infrared spectroscopy. They exhibited (a) high saturation magnetization of 53.14 emu g (leading to fast separation), and (b) large adsorption capacity, fast binding kinetics, and high selectivity for PAEs. Subsequently, a molecularly imprinted solid-phase extraction procedure followed by GC-MS was established for selective extraction and determination of 10 PAEs in food samples. Under the optimal experimental conditions, the response (peak area) was linear in the 0.5-100 ng mL concentration range. The limits of detection ranged from 0.15 to 1.64 ng g. The method was applied to the determination of PAEs in spiked real samples. The recoveries for 10 PAEs from various foods were in the range of 73.7%-98.1%, with relative standard deviations of 1.7%-10.2%. Graphical abstract Magnetic dummy molecularly imprinted polymers (MDMIPs) were prepared and successfully were applied as a special sorbent for the selective recognition and fast enrichment of 10 PAEs from different complex matrix.

Sample Preparation Using Molecularly Imprinted Polymers

“…To limit the number of MIPs to be prepared and characterized, a computational approach was as an help to select the monomer or template/monomer ratio. [67][68][69] A MIP is usually synthesized for a specific analytical use that implies the choice of a given template molecule, whose the structure and the functionalities define the subsequent properties of the binding sites. In most of the cases, the molecule selected as template is the molecule that has to be extracted next by the MIP thus ensuring an optimal recognition during the extraction process.…”

“…Another application field is the monitoring of toxins or natural hormones in waters, 94 food 117,168,182 and biological fluids. 181 At last, recent works reported the use of dSPE-MIP for the extraction of pesticides from waters, 160,167 soil, 167 and food extracts, 144,162,185 and of industrial pollutants from waters, 31,33,37,47,158,166,179,183,186 food, 34,68,96,98,180,183 or samples collected in an industrial bioreactor. 53 Another objective of sample purification using MIP is the removal of a class of compounds that interfere with the analysis of the target analytes.…”

“…94 In most of the cases, 5-100 mg of particles are dispersed in the samples. The ratio between the amount of MIP particles and the volume of the sample, that has only been optimized in some cases, 68,180 can be lower than 1, 32,33,44,94,143,158,169,179 between 1 and 10, 45,50,58,59,61,64,65,89,98,106,107,111,114,117,147,154,155,[163][164][165]170,177,178,185 or up to 50 34,66,69,144,149,168,174,181,188 and even 250 mg/mL. 43 Environmental waters were filtered 172 or directly put in contact with the MIP particles for the extraction of target analytes.…”

Improved chiral electrochemical recognition of tryptophan enantiomers based on three‐dimensional molecularly imprinted overoxidized polypyrrole/MnO2/carbon felt composites

“…Molecular imprinting technology, a synthesized artificial receptor with specific recognition sites for the target template molecules, has attracted enormous interest due to its wide application in affinity separation, chemical and biological sensing, solid‐phase extraction, drug delivery, cell and tissue imaging, and catalysis .…”

“…Chiral discrimination has been a long-standing problem because most biomolecules in living system is chiral and the role of isomers is different in nature. 1 Molecular imprinting technology, a synthesized artificial receptor with specific recognition sites for the target template molecules, has attracted enormous interest due to its wide application in affinity separation, 2 chemical and biological sensing, 3,4 solid-phase extraction, 5 drug delivery, 6 cell and tissue imaging, 7 and catalysis. 8 Among them, chiral separation and analysis using molecularly imprinted polymers (MIPs) has been growing steadily.…”