Electroanalytical profiling of cocaine samples by means of an electropolymerized molecularly imprinted polymer using benzocaine as the template molecule

Renata A. Grothe; Alnilan Lobato; Bassim Mounssef; Nikola Tasić; Ataualpa A.C. Braga; Adriano O. Maldaner; Leigh Aldous; Thiago R.L.C. Paixão; Luís Moreira Gonçalves

doi:10.1039/d0an02274h

Electroanalytical profiling of cocaine samples by means of an electropolymerized molecularly imprinted polymer using benzocaine as the template molecule

Renata A. Grothe, Alnilan Lobato, Bassim Mounssef, Nikola Tasić, Ataualpa A.C. Braga, Adriano O. Maldaner, Leigh Aldous, Thiago R.L.C. Paixão^*, Luís Moreira Gonçalves

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

The analysis of 'cutting' or additive agents in cocaine, like benzocaine (BZC), allows police analysts to identify each component of the sample, thus obtaining information like the drugs' provenience. This kind of drug profiling is of great value in tackling drug trafficking. Electropolymerized molecularly imprinted polymers (e-MIPs) on portable screen-printed carbon electrodes (SPCEs) were developed in this study for BZC determination. The MIPs' electropolymerization was performed on a carbon surface using the anaesthetic BZC as the template molecule and 3-Amino-4-hydroxybenzoic acid (3,4-AHBA) as the functional monomer. The build-up of this biomimetic sensor was carefully characterized by cyclic voltammetry (CV) and optimized. Cyclic voltammetric investigation demonstrated that BZC oxidation had a complex and pH-dependent mechanism, but at pH 7.4 a single, well-defined oxidation feature was observed. The BZC-MIP interactions were studied by computer-Aided theoretical modeling by means of density functional theory (DFT) calculations. The electroanalytical methodology was effectively applied to artificial urine samples; BZC molecular recognition was achieved with a low limit of detection (LOD) of 2.9 nmol L-1 employing square-wave voltammetry (SWV). The e-MIPs were then used to 'fingerprint' genuine cocaine samples, assisted by principal component analysis (PCA), at the central forensic laboratory of the Brazilian Federal Police (BFP) with a portable potentiostat. This electroanalysis provided proof-of-concept that the drugs could be voltammetrically 'fingerprinted' using e-MIPs supported by chemometric analysis.

Original language	English
Pages (from-to)	1747-1759
Number of pages	13
Journal	Analyst
Volume	146
Issue number	5
DOIs	https://doi.org/10.1039/d0an02274h
Publication status	Published - 7 Mar 2021

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@article{8a93605a115442d8a51d494a2a2773c4,

title = "Electroanalytical profiling of cocaine samples by means of an electropolymerized molecularly imprinted polymer using benzocaine as the template molecule",

abstract = "The analysis of 'cutting' or additive agents in cocaine, like benzocaine (BZC), allows police analysts to identify each component of the sample, thus obtaining information like the drugs' provenience. This kind of drug profiling is of great value in tackling drug trafficking. Electropolymerized molecularly imprinted polymers (e-MIPs) on portable screen-printed carbon electrodes (SPCEs) were developed in this study for BZC determination. The MIPs' electropolymerization was performed on a carbon surface using the anaesthetic BZC as the template molecule and 3-Amino-4-hydroxybenzoic acid (3,4-AHBA) as the functional monomer. The build-up of this biomimetic sensor was carefully characterized by cyclic voltammetry (CV) and optimized. Cyclic voltammetric investigation demonstrated that BZC oxidation had a complex and pH-dependent mechanism, but at pH 7.4 a single, well-defined oxidation feature was observed. The BZC-MIP interactions were studied by computer-Aided theoretical modeling by means of density functional theory (DFT) calculations. The electroanalytical methodology was effectively applied to artificial urine samples; BZC molecular recognition was achieved with a low limit of detection (LOD) of 2.9 nmol L-1 employing square-wave voltammetry (SWV). The e-MIPs were then used to 'fingerprint' genuine cocaine samples, assisted by principal component analysis (PCA), at the central forensic laboratory of the Brazilian Federal Police (BFP) with a portable potentiostat. This electroanalysis provided proof-of-concept that the drugs could be voltammetrically 'fingerprinted' using e-MIPs supported by chemometric analysis.",

author = "Grothe, {Renata A.} and Alnilan Lobato and Bassim Mounssef and Nikola Tasi{\'c} and Braga, {Ataualpa A.C.} and Maldaner, {Adriano O.} and Leigh Aldous and Paix{\~a}o, {Thiago R.L.C.} and Gon{\c c}alves, {Lu{\'i}s Moreira}",

note = "Funding Information: This work was supported by Funda{\c c}{\~a}o de Amparo {\`a} Pesquisa do Estado de S{\~a}o Paulo (FAPESP – 2019/05569-8, 2018/14425-7, 2019/11214-8, 2018/ 08782-1, 2018/13922-7, 2014/25770-6, and 2015/01491-3), Conselho Nacional de Desenvolvimento Cient{\'i}fico e Tecnol{\'o}gico (CNPq – 117865/2019-2, 465768/2014-8, and 309715/2017-2), and Coordena{\c c}{\~a}o de Aperfei{\c c}oamento de Pessoal de N{\'i}vel Superior (CAPES – 001, 3359/2014 Pr{\'o}-Forenses Edital 25/2014). Authors would like to thank Professor Maria del Pilar Taboada Sotomayor (UNESP, Araraquara – SP, Brazil) for the kind gift of 3,4-AHBA for the initial experiments. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

year = "2021",

month = mar,

day = "7",

doi = "10.1039/d0an02274h",

language = "English",

volume = "146",

pages = "1747--1759",

journal = "Analyst",

issn = "0003-2654",

publisher = "Royal Society of Chemistry",

number = "5",

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TY - JOUR

T1 - Electroanalytical profiling of cocaine samples by means of an electropolymerized molecularly imprinted polymer using benzocaine as the template molecule

AU - Grothe, Renata A.

AU - Lobato, Alnilan

AU - Mounssef, Bassim

AU - Tasić, Nikola

AU - Braga, Ataualpa A.C.

AU - Maldaner, Adriano O.

AU - Aldous, Leigh

AU - Paixão, Thiago R.L.C.

AU - Gonçalves, Luís Moreira

N1 - Funding Information: This work was supported by Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP – 2019/05569-8, 2018/14425-7, 2019/11214-8, 2018/ 08782-1, 2018/13922-7, 2014/25770-6, and 2015/01491-3), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq – 117865/2019-2, 465768/2014-8, and 309715/2017-2), and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES – 001, 3359/2014 Pró-Forenses Edital 25/2014). Authors would like to thank Professor Maria del Pilar Taboada Sotomayor (UNESP, Araraquara – SP, Brazil) for the kind gift of 3,4-AHBA for the initial experiments. Publisher Copyright: © The Royal Society of Chemistry. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/3/7

Y1 - 2021/3/7

N2 - The analysis of 'cutting' or additive agents in cocaine, like benzocaine (BZC), allows police analysts to identify each component of the sample, thus obtaining information like the drugs' provenience. This kind of drug profiling is of great value in tackling drug trafficking. Electropolymerized molecularly imprinted polymers (e-MIPs) on portable screen-printed carbon electrodes (SPCEs) were developed in this study for BZC determination. The MIPs' electropolymerization was performed on a carbon surface using the anaesthetic BZC as the template molecule and 3-Amino-4-hydroxybenzoic acid (3,4-AHBA) as the functional monomer. The build-up of this biomimetic sensor was carefully characterized by cyclic voltammetry (CV) and optimized. Cyclic voltammetric investigation demonstrated that BZC oxidation had a complex and pH-dependent mechanism, but at pH 7.4 a single, well-defined oxidation feature was observed. The BZC-MIP interactions were studied by computer-Aided theoretical modeling by means of density functional theory (DFT) calculations. The electroanalytical methodology was effectively applied to artificial urine samples; BZC molecular recognition was achieved with a low limit of detection (LOD) of 2.9 nmol L-1 employing square-wave voltammetry (SWV). The e-MIPs were then used to 'fingerprint' genuine cocaine samples, assisted by principal component analysis (PCA), at the central forensic laboratory of the Brazilian Federal Police (BFP) with a portable potentiostat. This electroanalysis provided proof-of-concept that the drugs could be voltammetrically 'fingerprinted' using e-MIPs supported by chemometric analysis.

AB - The analysis of 'cutting' or additive agents in cocaine, like benzocaine (BZC), allows police analysts to identify each component of the sample, thus obtaining information like the drugs' provenience. This kind of drug profiling is of great value in tackling drug trafficking. Electropolymerized molecularly imprinted polymers (e-MIPs) on portable screen-printed carbon electrodes (SPCEs) were developed in this study for BZC determination. The MIPs' electropolymerization was performed on a carbon surface using the anaesthetic BZC as the template molecule and 3-Amino-4-hydroxybenzoic acid (3,4-AHBA) as the functional monomer. The build-up of this biomimetic sensor was carefully characterized by cyclic voltammetry (CV) and optimized. Cyclic voltammetric investigation demonstrated that BZC oxidation had a complex and pH-dependent mechanism, but at pH 7.4 a single, well-defined oxidation feature was observed. The BZC-MIP interactions were studied by computer-Aided theoretical modeling by means of density functional theory (DFT) calculations. The electroanalytical methodology was effectively applied to artificial urine samples; BZC molecular recognition was achieved with a low limit of detection (LOD) of 2.9 nmol L-1 employing square-wave voltammetry (SWV). The e-MIPs were then used to 'fingerprint' genuine cocaine samples, assisted by principal component analysis (PCA), at the central forensic laboratory of the Brazilian Federal Police (BFP) with a portable potentiostat. This electroanalysis provided proof-of-concept that the drugs could be voltammetrically 'fingerprinted' using e-MIPs supported by chemometric analysis.

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U2 - 10.1039/d0an02274h

DO - 10.1039/d0an02274h

M3 - Article

AN - SCOPUS:85100314075

SN - 0003-2654

VL - 146

SP - 1747

EP - 1759

JO - Analyst

JF - Analyst

IS - 5

ER -

Electroanalytical profiling of cocaine samples by means of an electropolymerized molecularly imprinted polymer using benzocaine as the template molecule

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