Experimental and theoretical investigation of the complexation of methacrylic acid and diisopropyl urea

• Higher-order complexes of a potential genotoxin with methacrylic acid were investigated with NMR, IR and DFT methods.
• Computer script is provided to facilitate the treatment of higher-order complex and self-association data.
• Quantum chemical calculations reaffirmed the experimentally obtained binding strength (ΔG) values.
• The mechanism of complexation was evaluated both in silico and experimentally.

The present paper explores the complexation ability of methacrylic acid which is one of the most abundant functional monomer for the preparation of molecularly imprinted polymers. Host-guest interactions and the mechanism of complex formation between methacrylic acid and potentially genotoxic 1,3-diisopropylurea were investigated in the pre-polymerization solution featuring both experimental (NMR, IR) and in silico density functional theory (DFT) tools. The continuous variation method revealed the presence of higher-order complexes and the appearance of self-association which were both taken into account during the determination of the association constants. The quantum chemical calculations – performed at B3LYP 6-311 ++G(d,p) level with basis set superposition error (BSSE) corrections – are in agreement with the experimental observations, reaffirming the association constants and justifying the validity of computational investigation of such systems. Furthermore, natural bond orbital analysis was carried out to appraise the binding properties of the complexes.

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