Application of thymine-based nucleobase-modified acrylamide as a functional co-monomer in electropolymerised...

Molecularly imprinted polymers (MIPs) are fast becoming alternatives to biological recognition materials, offering robustness and the ability to work in extreme environments. Here, a modified thymine-based nucleobase, with acrylamide at the 5-postion (AA-dT) was used as a co-monomer in the synthesis of a thin-film electropolymerised MIP system for the molecular recognition of the protein haemoglobin. The AA-dT co-monomer incorporated into a N-hydroxymethylacrylamide (NHMAm) MIP offered a two-fold superior binding affinity of the NHMAm only MIP, with K_D values of 0.72 μM and 1.67 μM, respectively. A unique AA-dT:NHMAm MIP bilayer was created in an attempt to increase the amount AA-dT incorporated into the film, and this obtained a respectable K_D value of 7.03 μM. All MIPs produced excellent selectivity for the target protein and when applied to a sensor platform (Surface Plasma Resonance), the limit of detection for the MIPs is in the nM range (3.87, 3.47, and 3.87 nM, for the NHMAm MIP, AA-dT:NHMAm MIP, and AA-dT:NHMAm MIP bilayer, respectively). The introduction of the modified thymine-based nucleobase offers a promising strategy for improving the properties of a MIP, allowing these MIPs to potentially be a highly robust and selective material for molecular recognition.