Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Caffeic acid (CA) is one of the phenolic compounds widely found in wines and it is associated to the quality of this beverage and also to various beneficial effects on health. Thus, a novel electrochemical sensor based on molecularly imprinted siloxanes (MIS) film was developed for the highly selective determination of CA. The MIS film was prepared by sol-gel process, using the acid catalyzed hydrolysis and condensation of tetraethoxysilane (TEOS), phenyltriethoxysilane (PTEOS) and 3-aminopropyltrimethoxysilane (3-APTMS) in presence of CA as template molecule. The MIS film was immobilized onto Au electrode surface pre-modified with 3-mercaptopropyltrimethoxysilane (3-MPTS) and then characterized by Differential Pulse Voltammetry (DPV), Field Emission Scanning Electron Micrographs (FESEM) and Cross Polarization-Magic Angle Spinning Nuclear Magnetic Resonance of Si-29 (Si-29 CP-MAS NMR). Under the optimized conditions, the sensor showed a linear current response to the target CA concentration in the range from 0.500 to 60.0 mu mol/L, with a detection limit of 0.15 mu mol/L. The film exhibited high selectivity toward the template CA, as well as good stability and repeatability for CA determinations as well as for sensor preparation. Furthermore, the proposed sensor was applied to determine CA in wines samples and the results were in agreement with those obtained by a chromatographic method. The acceptable values of recovery implied its feasibility for practical application. (C) 2013 Elsevier B.V. All rights reserved.193238246Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Instituto Nacional de Ciencia e Tecnologia em Bioanalitica (INCTBio)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)