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Polymers 2018, 10(2), 192; https://doi.org/10.3390/polym10020192

Affinity Capillary Electrochromatography of Molecularly Imprinted Thin Layers Grafted onto Silica Capillaries Using a Surface-Bound Azo-Initiator and Living Polymerization

1
Laboratory of Bioanalytical Chemistry, Department of Chemistry, Via Giuria 7, University of Torino, 10125, Torino, Italy
2
Bioorganic & Biophysical Chemistry Laboratory, Centre for Biomaterials Chemistry, Department of Chemistry & Biomedical Sciences, Linnaeus University, SE-39182 Kalmar, Sweden
*
Author to whom correspondence should be addressed.
Received: 31 December 2017 / Revised: 12 February 2018 / Accepted: 13 February 2018 / Published: 15 February 2018
(This article belongs to the Special Issue Molecularly Imprinted Polymers)
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Abstract

Molecularly imprinted thin layers were prepared in silica capillaries by using two different surface polymerization strategies, the first using 4,4′-azobis(4-cyanovaleric acid) as a surface-coupled radical initiator, and the second, S-carboxypropyl-S’-benzyltrithiocarbonate as a reversible addition-fragmentation chain transfer (RAFT) agent in combination with 2,2′-azobisisobutyronitrile as a free radical initiator. The ability to generate imprinted thin layers was tested on two different polymerization systems: (i) a 4-vinylpyridine/ethylene dimethacrylate (4VP-EDMA) in methanol-water solution with 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) as a template; and (ii) methacrylic acid/ethylene dimethacrylate (MAA-EDMA) in a chloroform solution with warfarin as the template molecule. The binding properties of the imprinted capillaries were studied and compared with those of the corresponding non-imprinted polymer coated capillaries by injecting the template molecule and by measuring its migration times relative to a neutral and non-retained marker. The role of running buffer hydrophobicity on recognition was investigated by studying the influence of varying buffer acetonitrile concentration. The 2,4,5-T-imprinted capillary showed molecular recognition based on a reversed phase mechanism, with a decrease of the template recognition in the presence of higher acetonitrile content; whereas warfarin-imprinted capillaries showed a bell-shaped trend upon varying the acetonitrile percentage, illustrating different mechanisms underlying imprinted polymer-ligand recognition. Importantly, the results demonstrated the validity of affinity capillary electrochromatography (CEC) to screen the binding properties of imprinted layers. View Full-Text
Keywords: molecularly imprinted polymers; capillary electrophoresis; controlled/living radical polymerization; 2,4,5-trichlorophenoxyacedic acid; warfarin molecularly imprinted polymers; capillary electrophoresis; controlled/living radical polymerization; 2,4,5-trichlorophenoxyacedic acid; warfarin
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
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Giovannoli, C.; Passini, C.; Nardo, F.D.; Anfossi, L.; Baggiani, C.; Nicholls, I.A. Affinity Capillary Electrochromatography of Molecularly Imprinted Thin Layers Grafted onto Silica Capillaries Using a Surface-Bound Azo-Initiator and Living Polymerization. Polymers 2018, 10, 192.

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