title: Design and development of molecularly imprinted polymers for the selective extraction of deltamethrin in olive oil: An integrated computational-assisted approach.
abstract: This work firstly addresses the design and development of molecularly imprinted systems selective for deltamethrin aiming to provide a suitable sorbent for solid phase (SPE) extraction that will be further used for the implementation of an analytical methodology for the trace analysis of the target pesticide in spiked olive oil samples. To achieve this goal, a preliminary evaluation of the molecular recognition and selectivity of the molecularly imprinted polymers has been performed. In order to investigate the complexity of the mechanistic basis for template selective recognition in these polymeric matrices, the use of a quantum chemical approach has been attempted providing new insights about the mechanisms underlying template recognition, and in particular the crucial role of the crosslinker agent and the solvent used. Thus, DFT calculations corroborate the results obtained by experimental molecular recognition assays enabling one to select the most suitable imprinting system for MISPE extraction technique which encompasses acrylamide as functional monomer and ethylene glycol dimethacrylate as crosslinker. Furthermore, an analytical methodology comprising a sample preparation step based on solid phase extraction has been implemented using this "tailor made" imprinting system as sorbent, for the selective isolation/pre-concentration of deltamethrin from olive oil samples. Molecularly imprinted solid phase extraction (MISPE) methodology was successfully applied for the clean-up of spiked olive oil samples, with recovery rates up to 94%.
authors.affiliation: ICAAM - Instituto de Ciências Agrárias e Ambientais Mediterrânicas, IIFA, Universidade de Évora, Núcleo da Mitra, Ap. 94, 7002-554 Évora, Portugal.
authors.forename: Nuno
authors.initials: N
authors.lastname: Martins
authors.affiliation: Centro de Química de Évora, IIFA, Universidade de Évora, Colégio L.A. Verney, 7000 Évora, Portugal.
authors.forename: Elisabete P
authors.initials: EP
authors.lastname: Carreiro
authors.affiliation: Centro de Química de Évora, IIFA, Universidade de Évora, Colégio L.A. Verney, 7000 Évora, Portugal.
authors.forename: Abel
authors.initials: A
authors.lastname: Locati
authors.affiliation: Centro de Química de Évora, IIFA, Universidade de Évora, Colégio L.A. Verney, 7000 Évora, Portugal; Departamento de Química, Escola de Ciências e Tecnologia, Universidade de Évora, Colégio L.A. Verney, 7000 Évora, Portugal.
authors.forename: João P Prates
authors.initials: JP
authors.lastname: Ramalho
authors.affiliation: Departamento de Fitotecnia, Escola de Ciências e Tecnologia, ICAAM, Universidade de Évora, Núcleo da Mitra, Ap. 94, 7002-554 Évora, Portugal.
authors.forename: Maria João
authors.initials: MJ
authors.lastname: Cabrita
authors.affiliation: Centro de Química de Évora, IIFA, Universidade de Évora, Colégio L.A. Verney, 7000 Évora, Portugal; Departamento de Química, Escola de Ciências e Tecnologia, Universidade de Évora, Colégio L.A. Verney, 7000 Évora, Portugal.
authors.forename: Anthony J
authors.initials: AJ
authors.lastname: Burke
authors.affiliation: ICAAM - Instituto de Ciências Agrárias e Ambientais Mediterrânicas, IIFA, Universidade de Évora, Núcleo da Mitra, Ap. 94, 7002-554 Évora, Portugal. Electronic address: raquelg@uevora.pt.
authors.forename: Raquel
authors.initials: R
authors.lastname: Garcia
mesh_terms: D000178:Acrylamides / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D003198:Computer Simulation; D008958:Models, Molecular; D054802:Molecular Imprinting; D009570:Nitriles / Q000032:analysis* / Q000737:chemistry; D000069463:Olive Oil; D010575:Pesticides / Q000032:analysis* / Q000737:chemistry; D010938:Plant Oils / Q000737:chemistry*; D011109:Polymethacrylic Acids / Q000737:chemistry*; D011722:Pyrethrins / Q000032:analysis* / Q000737:chemistry; D052616:Solid Phase Extraction; D012997:Solvents
chemical_list: D000178:Acrylamides; D009570:Nitriles; D000069463:Olive Oil; D010575:Pesticides; D010938:Plant Oils; D011109:Polymethacrylic Acids; D011722:Pyrethrins; D012997:Solvents; C049146:lymphostim; C017180:decamethrin
keywords: DFT calculations; Deltamethrin; Molecular recognition; Molecularly imprinted polymer; Olive oil; Solid phase extraction