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Master's Dissertation
DOI
https://doi.org/10.11606/D.75.2021.tde-17022022-121903
Document
Author
Full name
Rafael de Jesus Deflon
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2021
Supervisor
Committee
Machado, Sergio Antonio Spinola (President)
Alves, Wendel Andrade
Sgobbi, Lívia Flório
Title in Portuguese
Desenvolvimento de sensores eletroquímicos de grafite de lápis modificado com complexos do tipo [M(salen)] (M= Cu, Mn e Ni)/óxido de grafeno para a quantificação de acetaminofeno
Keywords in Portuguese
acetaminofeno
complexos metálicos
óxido de grafeno
sensores eletroquímicos
sensores químicos
Abstract in Portuguese
Complexos do tipo salen e materiais baseados em grafeno são amplamente estudados em diversas áreas, incluindo sensores eletroquímicos. Neste trabalho, estudou-se materiais preparados pela aplicação de complexos do tipo [M(salen)] em óxido de grafeno (GO, do inglês graphene oxide) na confecção de sensores eletroquímicos de baixo custo para detecção de acetaminofeno (fármaco com potencial hepatotóxico). Para tanto, o GO e os complexos [M(salen)] (M= Cu, Mn e Ni) foram sintetizados, caracterizados por espectroscopia de absorbância na região do ultravioleta-visível, espectroscopia no infravermelho com transformada de Fourrier e difração de raios-X, e então depositados sobre as superfícies de grafite de lápis, os quais também foram devidamente caracterizados. O comportamento eletroquímico dos eletrodos preparados foi caracterizado por métodos eletroquímicos e por espectroscopia de espalhamento Raman in situ, técnica na qual constatou-se a preservação da integridade química da superfície do material depositado, mesmo em exposição a meio ácido e a aplicação de potencial elétrico de interesse (0,62 V). A faixa de concentração de trabalho estudada foi de 0,66 a 7,89 µmol L -1, de paracetamol em sistema aquoso contendo HCl 0,01 mol L-1. Os sensores desenvolvidos a partir de eletrodos de grafite modificado (EGMs) por GO, [Cu(salen)]/GO, [MnCl(salen)]/GO e [Ni(salen)]/GO apresentaram limites de detecção iguais a 0,672, 0,470, 0,440 e 0,506 µmol L-1, respectivamente. Os valores obtidos são condizentes com a literatura, para sensores similares. A repetibilidade dos EGMs foi de 2,767% (GO), 1,185% ([Cu(salen)]/GO), 0,888% ([MnCl(salen)]/GO) e 1,678% ([Ni(salen)]/GO) e reprodutibilidade igual a 31,931% (GO), 8,204% ([Cu(salen)]/GO), 12,586% ([MnCl(salen)]/GO) e 7,712 (Ni(salen)]/GO). Os valores de recuperação em duas concentrações distintas A (2 µmol L-1) e B (6 µmol L-1) dos sensores desenvolvidos em amostra de urina sintética variaram entre 129,12 e 168,09% e em amostra de água de abastecimento entre 58,77 e 91,64%.
Title in English
Development of electrochemical pencil graphite sensors modified with complexes of the type [M(salen)] (M= Cu, Mn and Ni)/graphene oxide for the quantification of acetaminophen
Keywords in English
chemical sensors
electrochemical sensors, acetaminophen
graphene oxide
metal complexes
Abstract in English
Salen-type complexes and graphene-based materials are extensively studied in several areas, including electrochemical sensors. In this work, materials prepared by applying complexes of the type [M(salen)] to graphene oxide (GO) in the manufacture of low-cost electrochemical sensors for the detection of acetaminophen (a drug with hepatotoxic potential) were studied. For this purpose, GO and the complexes [M(salen)] (M= Cu, Mn and Ni) were synthesized, characterized by Ultraviolet-visible (UV-Vis) absorption spectroscopy, Fourier-transform infrared spectroscopy and X-ray diffraction, then deposited on the pencil lead surfaces, which were also duly characterized. The electrochemical behavior of the prepared electrodes was characterized by electrochemical methods and in situ Raman scattering spectroscopy, a technique in which the preservation of the chemical integrity of the surface of the deposited material was observed, even in exposure to acidic solution and the application of electrical potential of interest (0.62V). The working concentration range studied was from 0.66 to 7.89 µmol L-1 of paracetamol in an aqueous system containing 0.01 mol L-1 HCl. Sensors developed from graphite electrodes modified (EGMs) by GO, [Cu(salen)]/GO, [MnCl(salen)]/GO and [Ni(salen)]/GO had detection limits equal to 0.672, 0.470, 0.440 and 0.506 µmol L-1, respectively. The values obtained are consistent with the literature for similar sensors. The repeatability of the EGMs was 2.767% (GO), 1.185 ([Cu(salen)]/GO), 0.888% ([MnCl(salen)]/GO) and 1.678 ([Ni(salen)]/GO) and reproducibility equal to 31.931% (GO), 8.204% ([Cu(salen)]/GO), 12.586% ([MnCl(salen)]/GO) and 7.712% (Ni(salen)]/GO). The recovery values at two different concentrations A (2 µmol L-1) and B (6 µmol L-1) of the sensors developed in a synthetic urine sample varied between 129.12 and 168.09% and in a sample of water supply between 58.77 and 91.64%.
 
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Publishing Date
2022-02-18
 
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