title: 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.
authors.affiliation: Departamento de Química Física y Analítica, Universidad de Oviedo, c/Julián Clavería 8, 33006 Oviedo, Spain.
authors.forename: Yolanda
authors.initials: Y
authors.lastname: Diñeiro
authors.forename: M Isabel
authors.initials: MI
authors.lastname: Menéndez
authors.forename: M Carmen
authors.initials: MC
authors.lastname: Blanco-López
authors.forename: M Jesús
authors.initials: MJ
authors.lastname: Lobo-Castañón
authors.forename: Arturo J
authors.initials: AJ
authors.lastname: Miranda-Ordieres
authors.forename: Paulino
authors.initials: P
authors.lastname: Tuñón-Blanco
mesh_terms: D003198:Computer Simulation; D004563:Electrochemistry / Q000379:methods; D006719:Homovanillic Acid / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D011108:Polymers / Q000737:chemistry*; D012680:Sensitivity and Specificity
chemical_list: D011108:Polymers; D006719:Homovanillic Acid