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Article

Characterization of Inherently Chiral Electrosynthesized Oligomeric Films by Voltammetry and Scanning Electrochemical Microscopy (SECM)

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Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, Via Torino 155, 30172 Mestre-Venezia, Italy
2
Dipartimento di Scienze Agroalimentari, Ambientali e Animali, Università di Udine, Via Cotonificio 108, 33100 Udine, Italy
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Dipartimento di Chimica, Università degli Studi di Milano, 20133 Milano, Italy
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Dipartimento di Scienza ed Alta Tecnologia, Università degli Studi dell’Insubria, 22100 Como, Italy
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Centro Nazionale per il Controllo e la Valutazione dei Farmaci, Istituto Superiore di Sanità, 00161 Roma, Italy
*
Author to whom correspondence should be addressed.
Academic Editor: Koichi Jeremiah Aoki
Molecules 2020, 25(22), 5368; https://doi.org/10.3390/molecules25225368
Received: 23 October 2020 / Revised: 9 November 2020 / Accepted: 14 November 2020 / Published: 17 November 2020
(This article belongs to the Special Issue Advanced Organic Molecular Electroactive Materials)
A voltammetric and scanning electrochemical microscopy (SECM) investigation was performed on an inherently chiral oligomer-coated gold electrode to establish its general properties (i.e., conductivity and topography), as well as its ability to discriminate chiral electroactive probe molecules. The electroactive monomer (S)-2,2′-bis(2,2′-bithiophene-5-yl)-3,3′-bibenzothiophene ((S)-BT2T4) was employed as reagent to electrodeposit, by cyclic voltammetry, the inherently chiral oligomer film of (S)-BT2T4 (oligo-(S)-BT2T4) onto the Au electrode surface (resulting in oligo-(S)-BT2T4-Au). SECM measurements, performed in either feedback or competition mode, using the redox mediators [Fe(CN)6]4− and [Fe(CN)6]3− in aqueous solutions, and ferrocene (Fc), (S)-FcEA, (R)-FcEA and rac-FcEA (FcEA is N,N-dimethyl-1-ferrocenylethylamine) in CH3CN solutions, indicated that the oligomer film, as produced, was uncharged. The use of [Fe(CN)6]3− allowed establishing that the oligomer film behaved as a porous insulating membrane, presenting a rather rough surface. This was inferred from both the approach curves and linear and bidimensional SECM scans, which displayed negative feedback effects. The oligomer film acquired semiconducting or fully conducting properties when the Au electrode was biased at potential more positive than 0.6 V vs. Ag|AgCl|KCl. Under the latter conditions, the approach curves displayed positive feedback effects. SECM measurements, performed in competition mode, allowed verifying the discriminating ability of the oligo-(S)-BT2T4 film towards the (S)-FcEA and (R)-FcEA redox mediators, which confirmed the results obtained by cyclic voltammetry. SECM linear scans indicated that the enantiomeric discriminating ability of the oligo-(S)-BT2T4 was even across its entire surface. View Full-Text
Keywords: Inherently chiral oligomer films; chiral electroactive probes; scanning electrochemical microscopy; enantiodiscrimination in electrochemistry and electroanalysis Inherently chiral oligomer films; chiral electroactive probes; scanning electrochemical microscopy; enantiodiscrimination in electrochemistry and electroanalysis
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MDPI and ACS Style

Donnici, M.; Toniolo, R.; Arnaboldi, S.; Mussini, P.R.; Benincori, T.; Cirilli, R.; Daniele, S. Characterization of Inherently Chiral Electrosynthesized Oligomeric Films by Voltammetry and Scanning Electrochemical Microscopy (SECM). Molecules 2020, 25, 5368. https://doi.org/10.3390/molecules25225368

AMA Style

Donnici M, Toniolo R, Arnaboldi S, Mussini PR, Benincori T, Cirilli R, Daniele S. Characterization of Inherently Chiral Electrosynthesized Oligomeric Films by Voltammetry and Scanning Electrochemical Microscopy (SECM). Molecules. 2020; 25(22):5368. https://doi.org/10.3390/molecules25225368

Chicago/Turabian Style

Donnici, Margherita, Rosanna Toniolo, Serena Arnaboldi, Patrizia R. Mussini, Tiziana Benincori, Roberto Cirilli, and Salvatore Daniele. 2020. "Characterization of Inherently Chiral Electrosynthesized Oligomeric Films by Voltammetry and Scanning Electrochemical Microscopy (SECM)" Molecules 25, no. 22: 5368. https://doi.org/10.3390/molecules25225368

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