Thermo-responsive molecularly imprinted monolith in extraction
Molecularly imprinted polymers (MIPs)
are widely employed sorbents due to their improved selectivity. They are
synthesized in the presence of the analyte, which is called template, and
therefore the polymeric network is constructed around the target leaving
selective chemical cavities when it is washed away. After the bulk synthesis,
the polymer is crashed and sieved to obtain a solid with a particle size as
homogeneous as possible. In a recent article published in Analytical and
Bioanalytical Chemistry, researchers from the Tianjin Medical University at
China have proposed a smart MIP monolith for the extraction of ketoprofen from
milk samples.
In an old post entitled “Smart molecularly imprinted hydrogels for protein recognition”, we discussed the
advantages of these materials that combine the selectivity enhancement of MIPs
with the advantages of smart polymers. In short, a smart polymer is a porous
polymeric network that may respond to external stimulus (mainly pH, ionic
strength or temperature) with a change in its structure or dimension. This
change can be used to control the uptake and release of the analytes with a
negligible effect on the polymeric network that memorizes the imprinting state.
In the new article, the authors synthesized
a monolith avoiding the crashing and sieving process and therefore improving
the reproducibility of the material. A monolith is a one-block polymer
comprising large pores (macropores) that favor the sample flow through the
polymer and small pores (mesopores) that increase the superficial area of the
network. The main challenge that the authors found in their development was the
selection of the porogenic solvent. In fact, the low solubility of the
thermo-responsive monomer in conventional solvents made necessary the use of
dimethylsulfoxide (DMSO) as solvent although it provides the polymeric network
with a low porosity. This shortcoming was avoided using an ionic liquid as
modifier in the synthesis. The IL increases the porosity and permeability of
the resulting polymer.
The smart-MIP showed selective molecular
recognition towards the target analyte when it was compared with the
non-imprinted polymer (NIP), synthesized in the absence of template. This
selectivity was thermo-dependent; at temperatures lower than 35 ºC the MIP
performance was superior to that showed by the NIP while at higher temperatures
both polymers presented a more uniform behavior.
We recommend this article to our
readers. The article describes the synthesis of the polymer, the optimization
of that process, the characterization of the material and its final application
for the extraction of ketoprofen from milk samples.
References
(1) Thermoresponsive ketoprofen-imprinted monolith prepared in ionic
liquid. Link to the article
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