Ultrasensitive and Highly Selective o-Phenylenediamine Molecularly Imprinted Polymer for the Detection of 2,4-Dichlorophenoxyacetic Acid

Angelo Tricase; Verdiana Marchianò; Eleonora Macchia; Nicoletta Ditaranto; Luisa Torsi; Paolo Bollella

doi:10.1016/j.electacta.2024.144430

Ultrasensitive and Highly Selective o-Phenylenediamine Molecularly Imprinted Polymer for the Detection of 2,4-Dichlorophenoxyacetic Acid

Angelo Tricase, Verdiana Marchianò, Eleonora Macchia, Nicoletta Ditaranto, Luisa Torsi, Paolo Bollella^*

^*Corresponding author for this work

Physics

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Abstract

Herein, we report an ultrasensitive and highly selective analytical methods to detect 2,4-dichlorophenoxyacetic acid (2,4-D) using an o-phenylenediamine based molecularly imprinted polymer (o-PD-MIP) sensor. Electrochemical Quartz Crystal Microbalance (EQCM) is used to investigate both the kinetics and the mass of the electropolymerized o-phenylenediamine. Additionally, successful removal of the template from the imprinted cavities is confirmed by comparing the XP spectra of imprinted and o-PD-MIPs after various template removal procedures. The most effective method involves a 70:30 mixture of MeOH:H₂O for 15 min under stirring. The o-PD-MIP sensor exhibits high sensitivity with a LoD of (3 ± 1) × 10⁻¹² M, which is below the EU regulation limits for drinking water by six orders of magnitude, a linear range between 10 and 100pM, and an excellent selectivity. These results proved the effectiveness of template removal procedure by using a 70:30 MeOH:H₂O mixture and are a proof-of-concept for ultrasensitive and selective 2,4-D detection in real samples.

Original language	English
Article number	144430
Journal	Electrochimica Acta
Volume	494
DOIs	https://doi.org/10.1016/j.electacta.2024.144430
Publication status	Published - 1 Aug 2024
MoE publication type	A1 Journal article-refereed

Funding

The following funding agencies are acknowledged: Centro di Innovazione in Single-Molecule Digital Assay – “Digital Assay” from Regione Puglia DGR N. 218 of 21/02/2022; 1LIVEXYLELLA - ID01 - Trasmissione D. M. n. 664519 del 28/12/2022; NoOne-A binary sensor with single-molecule digit to discriminate biofluids enclosing zero or at least one biomarker, ERC Stg2021, GA:101040383; CSGI is acknowledged for partial financial support.

Keywords

2,4-dichlorofenoxyacetic acid
Modified electrodes
Molecularly imprinted polymers (MIPs)
o-phenylenediamine
Template removal

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10.1016/j.electacta.2024.144430Licence: CC BY

1-s2.0-S0013468624006716-mainFinal published version, 2.22 MBLicence: CC BY

https://urn.fi/URN:NBN:fi-fe20241210100670

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title = "Ultrasensitive and Highly Selective o-Phenylenediamine Molecularly Imprinted Polymer for the Detection of 2,4-Dichlorophenoxyacetic Acid",

abstract = "Herein, we report an ultrasensitive and highly selective analytical methods to detect 2,4-dichlorophenoxyacetic acid (2,4-D) using an o-phenylenediamine based molecularly imprinted polymer (o-PD-MIP) sensor. Electrochemical Quartz Crystal Microbalance (EQCM) is used to investigate both the kinetics and the mass of the electropolymerized o-phenylenediamine. Additionally, successful removal of the template from the imprinted cavities is confirmed by comparing the XP spectra of imprinted and o-PD-MIPs after various template removal procedures. The most effective method involves a 70:30 mixture of MeOH:H2O for 15 min under stirring. The o-PD-MIP sensor exhibits high sensitivity with a LoD of (3 ± 1) × 10−12 M, which is below the EU regulation limits for drinking water by six orders of magnitude, a linear range between 10 and 100pM, and an excellent selectivity. These results proved the effectiveness of template removal procedure by using a 70:30 MeOH:H2O mixture and are a proof-of-concept for ultrasensitive and selective 2,4-D detection in real samples.",

keywords = "2,4-dichlorofenoxyacetic acid, Modified electrodes, Molecularly imprinted polymers (MIPs), o-phenylenediamine, Template removal",

author = "Angelo Tricase and Verdiana Marchian{\`o} and Eleonora Macchia and Nicoletta Ditaranto and Luisa Torsi and Paolo Bollella",

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T1 - Ultrasensitive and Highly Selective o-Phenylenediamine Molecularly Imprinted Polymer for the Detection of 2,4-Dichlorophenoxyacetic Acid

AU - Tricase, Angelo

AU - Marchianò, Verdiana

AU - Macchia, Eleonora

AU - Ditaranto, Nicoletta

AU - Torsi, Luisa

AU - Bollella, Paolo

PY - 2024/8/1

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N2 - Herein, we report an ultrasensitive and highly selective analytical methods to detect 2,4-dichlorophenoxyacetic acid (2,4-D) using an o-phenylenediamine based molecularly imprinted polymer (o-PD-MIP) sensor. Electrochemical Quartz Crystal Microbalance (EQCM) is used to investigate both the kinetics and the mass of the electropolymerized o-phenylenediamine. Additionally, successful removal of the template from the imprinted cavities is confirmed by comparing the XP spectra of imprinted and o-PD-MIPs after various template removal procedures. The most effective method involves a 70:30 mixture of MeOH:H2O for 15 min under stirring. The o-PD-MIP sensor exhibits high sensitivity with a LoD of (3 ± 1) × 10−12 M, which is below the EU regulation limits for drinking water by six orders of magnitude, a linear range between 10 and 100pM, and an excellent selectivity. These results proved the effectiveness of template removal procedure by using a 70:30 MeOH:H2O mixture and are a proof-of-concept for ultrasensitive and selective 2,4-D detection in real samples.

AB - Herein, we report an ultrasensitive and highly selective analytical methods to detect 2,4-dichlorophenoxyacetic acid (2,4-D) using an o-phenylenediamine based molecularly imprinted polymer (o-PD-MIP) sensor. Electrochemical Quartz Crystal Microbalance (EQCM) is used to investigate both the kinetics and the mass of the electropolymerized o-phenylenediamine. Additionally, successful removal of the template from the imprinted cavities is confirmed by comparing the XP spectra of imprinted and o-PD-MIPs after various template removal procedures. The most effective method involves a 70:30 mixture of MeOH:H2O for 15 min under stirring. The o-PD-MIP sensor exhibits high sensitivity with a LoD of (3 ± 1) × 10−12 M, which is below the EU regulation limits for drinking water by six orders of magnitude, a linear range between 10 and 100pM, and an excellent selectivity. These results proved the effectiveness of template removal procedure by using a 70:30 MeOH:H2O mixture and are a proof-of-concept for ultrasensitive and selective 2,4-D detection in real samples.

KW - 2,4-dichlorofenoxyacetic acid

KW - Modified electrodes

KW - Molecularly imprinted polymers (MIPs)

KW - o-phenylenediamine

KW - Template removal

UR - https://www.scopus.com/pages/publications/85193439365

U2 - 10.1016/j.electacta.2024.144430

DO - 10.1016/j.electacta.2024.144430

M3 - Article

AN - SCOPUS:85193439365

SN - 0013-4686

VL - 494

JO - Electrochimica Acta

JF - Electrochimica Acta

M1 - 144430

ER -

Ultrasensitive and Highly Selective o-Phenylenediamine Molecularly Imprinted Polymer for the Detection of 2,4-Dichlorophenoxyacetic Acid

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