Assessment of Cross-reactivity in a Tailor-Made Molecularly Imprinted Polymer for Phenolic Compounds Using Four Adsorption Isotherm Models

Abstract Cross-reactivity is an important feature of molecularly imprinted polymers (MIPs), and is central to successful use of a pseudo-template in molecular imprinting. The adsorption and cross-reactivity of a molecularly imprinted polymer (MIP) designed for recognition of phenols from water was assessed using four different isotherm models (Langmuir (LI), Freundlich (FI), Langmuir–Freundlich (L-FI), and Brunauer, Emmett, and Teller (BET)). The L-FI model succeeded in explaining the cross-reactivity behavior through the total number of binding sites, the affinity constants and heterogeneity indices of the small phenols (phenol (ph), 2-methylphenol (2-MP), 3-methylphenol (3-MP), 2-chlorophenol (2-CP), 2,4-dimethylphenol (DMP), 2,4-dichlorophenol (DCP), 4-chloro-3-methylphenol (CMP)) with evidence that the phenols compete for binding sites based on their hydrophobicity as well as π-π, π-σ and dipole-dipole intermolecular forces. The recognition of the large phenols (2,4,6-trichlorophenol (TCP), pentachlorophenol (PCP), 4-teroctylphenol (4-OP), 4-nonylphenol (4-NP), which have much higher binding affinities than the smaller phenolic compounds, was explained with the BET isotherm model that predicts that multiple layers adsorb to the adsorbed monolayer. The adsorption behavior with MIPs is also shown to be superior to corresponding non-imprinted polymers and applicability of MIPs for trace analysis is highlighted.