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. 2022 Apr 25;7(17):15082-15089.
doi: 10.1021/acsomega.2c00926. eCollection 2022 May 3.

Synthesis of Novel One-Walled meso-Phenylboronic Acid-Functionalized Calix[4]pyrrole: A Highly Sensitive Electrochemical Sensor for Dopamine

Ishfaq Ahmad Rather  1 , Feroz Ahmad Sofi  2 , Mohsin Ahmad Bhat  2 , Rashid Ali  1
Affiliations

Synthesis of Novel One-Walled meso-Phenylboronic Acid-Functionalized Calix[4]pyrrole: A Highly Sensitive Electrochemical Sensor for Dopamine

Ishfaq Ahmad Rather et al. ACS Omega. .

Abstract

Facile access to new one-walled meso-substituted phenylboronic acid-functionalized calix[4]pyrrole (C4P) has been revealed for the first time, starting from cost-effective and easily accessible materials. The structures of both the intermediate dipyrromethane (DPM) and the targeted functionalized C4P have been confirmed by means of 1H-NMR, 13C-NMR, IR, and HRMS spectral data. The voltammetric investigations of the functionalized C4P films cast over a glassy carbon electrode (C4P-GCE) clearly establish the redox stability and redox accessibility of the boronic acid functional moiety present in the C4P framework. We demonstrate that the presence of the unique boronic acid functionality in the C4P endows it with an excellent potential for the highly sensitive electrochemical sensing of the neurotransmitter dopamine (DA). A linear correlation between the strength of the Faradaic signals corresponding to the electro-oxidation of DA over C4P-GCE and the concentration of DA was observed in a concentration range as wide as 0.165-2.302 μM. The C4P-GCE has revealed exceptional stability and reproducibility in the electrochemical sensing of DA, with a nanomolar level limit of detection as low as 15 nM.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Retrosynthetic Pathway for the Preparation of a One-Walled C4P System (1)
Scheme 2
Scheme 2. Synthesis of Phenylboronic Acid-Based DPM (2) and One-Walled C4P (1)
Figure 1
Figure 1
(A) CV curves of bare GCE (trace black) and the C4P-based electrochemical sensor (1) (trace red). (B) CV curves of bare GCE (trace pink), modified GCE with C4P (1) (trace red) in the absence of dopamine and catechol, and modified GCE with C4P (1) in the presence of either dopamine (trace black) or catechol (trace blue).
Figure 2
Figure 2
(A) DPV curves of modified GCE/C4P (1) at different concentrations of dopamine. (B) Linear calibration plot depicting linear concentration ranges of dopamine between 0.165 and 2.302 μM. (C) DPV curves of modified GCE/C4P (1) at different concentrations of catechol. (D) Linear calibration plot depicting linear concentration ranges of catechol between 0.5 and 4 μM.
Scheme 3
Scheme 3. Plausible Mechanism for the Electrochemical Sensing of Dopamine (6) by a One-Walled Phenylboronic Acid-Functionalized C4P-Based Electrochemical Sensor (1)
Figure 3
Figure 3
(A) DPV curves of C4P (1) modified GCE in the presence of 0.8 μM DA from day 1 to day 5. (B) Corresponding peak currents in the presence of DA on C4P (1) modified GCE plotted against the day number.
Figure 4
Figure 4
1H-NMR spectral changes of C4P (1) observed upon the addition of proper equivalents of DA. Asterisks (*) represents peaks of ethyl acetate, water, and DMSO.
See this image and copyright information in PMC

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