Electrochemical sensing of ecstasy with electropolymerized molecularly imprinted poly(o-phenylenediamine) polymer on the surface of disposable screen-printed carbon electrodes

Author(s):Show less -

Couto, Rosa A. S. ^[1] ; Costa, Sefora S. ^[1] ; Mounssef Jr, Bassim ; Pacheco, Joao G. ^[2] ; Fernandes, Eduarda ^[1] ; Carvalho, Felix ^[3] ; Rodrigues, Cecilia M. P. ^[4] ; Delerue-Matos, Cristina ^[2] ; Braga, Ataualpa A. C. ^[5] ; Goncalves, Luis Moreira ^[5] ; Quinaz, M. Beatriz ^[1]

Affiliation

^[1] Univ Porto, Dept Chem Sci, Fac Pharm, Lab Appl Chem, REQUIMTE, LAQV, Porto - Portugal

^[2] Politecn Porto, ISEP, REQUIMTE, LAQV, Porto - Portugal

^[3] Univ Porto, Dept Biol Sci, Fac Pharm, Lab Toxicol, REQUIMTE, UCIBIO, Porto - Portugal

^[4] Univ Lisbon, Fac Pharm, Res Inst Med iMed ULisboa, Lisbon - Portugal

^[5] Mounssef Jr, Jr., Bassim, Univ Sao Paulo, Dept Quim Fundamental, Inst Quim, Sao Paulo, SP - Brazil

• Document type: Journal article
• Source: SENSORS AND ACTUATORS B-CHEMICAL; v. 290, p. 378-386, JUL 1 2019.
• Web of Science Citations: 2

Abstract

This study demonstrates the ability of an electrochemical sensor based on molecularly imprinted polymers (MIPs) to selectively quantify 3,4-methylenedioxymethamphetamine (MDMA), also known as ecstasy, in bio-logical samples. The device was constructed using ortho-phenylenediamine (o-PD) as the MIP's building monomer at the surface of a screen-printed carbon electrode (SPCE). The step-by-step construction of the SPCE-MIP sensor was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Density functional theory (DFT) calculations and modelling were performed not only to understand template-monomer interaction but also to comprehend which possible polymer structure - linear or ramified poly(o-PD) - indeed interacts with the analyte. The prepared sensor worked by directly measuring the MDMA oxidation signal through square-wave voltammetry (SWV) after an incubation period of 10 min. Several parameters were optimized, such as the monomer/template ratio, the number of electropolymerization scanning cycles, and the incubation period, to obtain the best sensing efficiency. Optimized sensors exhibited suitable selectivity, repeatability (2.6%), reproducibility (7.7%) and up to one month of stable response. A linear range up to 0.2 mmol L-1 was found with an r(2) of 0.9990 and a limit of detection (LOD) and quantification (LOQ) of 0.79 and 2.6 mu mol L-1 (0.15 and 0.51 mu g mL(-1)), respectively. The proposed sensor was successfully applied to human blood serum and urine samples, showing its potential for application in medicine and in forensic sciences. (AU)

• FAPESP's process: 18/14425-7 - A new synergetic path for gas-diffusion microextraction (GDME) making use of molecular imprinted polymers (MIPs)
• Grantee: Luís Francisco Moreira Gonçalves
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 14/25770-6 - New frontiers in cross-coupling reactions promoted by palladium: combining enantioselective catalysis, C-H activations, new materials and in flux reactions aiming at high efficiency and sustainability in synthetic processes
• Grantee: Carlos Roque Duarte Correia
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 15/01491-3 - Theoretical study of cross-coupling reactions: homogeneous and heterogeneous catalysis
• Grantee: Ataualpa Albert Carmo Braga
• Support Opportunities: Regular Research Grants