Computational Approach to the Rational Design of Molecularly Imprinted Polymers for Voltammetric Sensing of Homovanillic Acid

Abstract

A methodology based on density functional theory calculations for the design of molecularly imprinted polymers (MIPs) is described. The method allows the rational choice of the most suitable monomer and polymerization solvent among a set of chemicals traditionally used in MIP formulations for the molecular imprinting of a given template. It is based on the comparison of the stabilization energies of the prepolymerization adducts between the template and different functional monomers. The effect of the polymerization solvent is included using the polarizable continuum model. A voltammetric sensor for homovanillic acid was constructed using different MIPs as recognition element, confirming that the solvent (toluene) and functional monomer (methacrylic acid) selected according to the theoretical predictions lead to the most efficient molecular recognition sensing phase. With the voltammetric sensor prepared using the MIP designed according to the theoretical predictions, a linear response for concentrations of homovanillic acid between 5 x 10(-8) and 1 x 10(-5) M can be obtained. The limit of detection is 7 x 10(-9) M. The selectivity obtained for homovanillic acid over other structurally related compounds buttresses the validity of this strategy of design.

Molecularly Imprinted Electrochemical Sensors

“…From this, VMA and HVA can be differentiated from closely structural-related compounds, having no such groups [28 -29]. A methodology based on density functional theory calculations for the design of the MIPs has been used for detecting VMA [137].…”

Electrochemical Sensors

“…88 Density functional theory calculations were used to pre-screen for the most suitable monomer and polymerization solvent for the imprinting of a given target template. The predictions included possible interferences and were validated by experiment using an electrochemical sensor for homovanillic acid as a model system.…”

Design of a New Molecularly Imprinted Polymer Selective for Hydrochlorothiazide Based on Theoretical Predictions Using Gibbs Free Energy

“…12, 2016 solvent among a set of reagents traditionally used in the formulation of a non-covalent MIP. [12][13][14][15][16][17] Until recently, molecular modeling has been used predominantly to study the interaction of the template with the FM and its influence on molecular recognition by the MIP. Only few papers reported in the literature have considered the effect of the solvent.…”