Molecularly imprinted macroporous polymer monolithic layers for L‐phenylalanine recognition in complex biological fluids

Abstract

In present work, the development of macroporous monolithic layers bearing the artificial recognition sites toward L‐phenylalanine has been carried out. The set of macroporous poly(2‐aminoethyl methacrylate‐co‐2‐hydroxyethyl methacrylate‐co‐ethylene glycol dimethacrylate) materials with average pore size ranged in 340–1200 nm was synthesized. The applicability of Hildebrand's and Hansen's theories for the prediction of polymer compatibility with porogenic solvents was evaluated. The dependences of average pore size on theoretically calculated parameters were plotted. The linear trend detected for Hansen's theory has indicated the high suitability of this approach to select appropriate porogens. The synthesized monolithic MIP layers were tested toward the ability to rebind phenylalanine‐derivative in microarray format. The influence of such factors as average pore size of the material, the concentration of template molecule in polymerization mixture, interaction time of analyte with its imprinted sites on binding efficiency were studied. The developed materials demonstrated good analyte rebinding from buffer solution with recognition factors 2.5–3.4 depending on the MIP sample. The comparable rebinding efficiency was also detected when the analysis was carried using complex biological media. The selectivity of phenylalanine binding from the equimolar mixture of structural analogues was 81.9% for free amino acid and 91.2% for labeled one.

Macroporous Polymer Monoliths in Thin Layer Format

“…However, after that time no difference in binding efficiency was observed for monolith with different pore size. Similar effect was observed also for molecular recognition of phenylalanine derivatives by molecularly imprinted monolithic layers based on poly(AEMA-co-HEMA-co-EDMA) [73].…”

“…The functionality of monolithic layers can be achieved either by direct copolymerization of functional and cross-linking monomers or by post-modification of GMA-containing polymers. For instance, besides poly(GMA-co-EDMA), a number of macroporous monolithic layers with different properties have been synthesized in situ using such functional monomers as butyl methacrylate (BMA) [41], 2-hydroxyethyl methacrylate (HEMA) [70], 2-cyanoethyl methacrylate (CEMA) [71,72], 2-aminoethyl methacrylate (AEMA) [52,73], N-hydroxyphtalimide ester of acrylic acid (HPIEAA) [49], chloromethylstyrene (CMST) [57]. Besides EDMA, depending on a goal, more hydrophilic glycerol dimethacrylate (GDMA) [61] or di(ethylene glycol) dimethacrylate (DEGDMA) [53], or more hydrophobic divinylbenzene (DVB) [50,57] crosslinking agents were utilized.…”

“…Recently, Antipchik et al reported the preparation of macroporous molecularly imprinted monoliths for detection of low-molecular compounds in microarray format [73]. A set of macroporous poly(AEMA-co-HEMA-co-EDMA) layers containing the imprint sites of BOC-L-phenylalanine was prepared using non-covalent imprinting technique.…”

Advances in Molecularly Imprinted Polymers Based Affinity Sensors (Review)

“…Recently, to predict and/or optimize the efficiency of newly designed MIPs various computational methods based on DFT [ 157 , 158 ] and molecular dynamics [ 159 ] are applied. Hildebrand’s [ 152 , 153 ] and Hansen’s [ 160 ] theories for the prediction of polymer compatibility with porogenic solvents are used to predict the efficiency of MIP performance in different solvents, as it was well demonstrated in the case of L-phenylalanine imprinted within macroporous poly(2-aminoethyl methacrylate-co-2-hydroxyethyl methacrylate-co-ethylene glycol dimethacrylate) [ 161 ].…”

Flow-Through Macroporous Polymer Monoliths Containing Artificial Catalytic Centers Mimicking Chymotrypsin Active Site

“…Nowadays, macroporous monoliths are widely used as stationary phases for many dynamic processes such as high-performance liquid chromatography [22,23], electrochromatography [24], gas chromatography [25], solid-phase extraction [26], and flow-through catalysis with immobilized enzymes [27]. Moreover, a number of works on the preparation and investigation of molecularly imprinted polymer monoliths for chromatography [28], solid-phase extraction [29], and microarray [30] can be found in the currently. The main advantage of macroporous monoliths over the bead-based stationary phases is their resistance to the high flow rates among with the very low backpressure.…”