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Effect of Copper on the Oxidation Mechanisms of Tertiary and Secondary Amines of Methyl-naphthyl- cyclen-Modified Gold Electrodes

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Abstract

Tetraazamacrocycle such as 1,4,7,10-tetraazacyclododecane “cyclen” are known for efficient complexation of metallic ions and were used as an ionic recognition agents in chemical sensors in aqueous medium.The aim of this paper is to examine in more detail the oxidation mechanism of amines in cyclen before copper complexation and after copper complexation. Gold electrodes modified with mono-N-MNCyclen(mono methyl-naphtyl-cyclen) and tetra-N-MNCyclen thin films were obtained by deposition of mono-N-MNCyclen and the tetra-N-MNCyclensynthesized respectively by bisaminal route in three steps (protection, N-mono-alkylation and deprotection) and direct route. The comparative study of the electrochemical oxidation of amines in both cyclens allowed the identification of the tertiary and of the secondary amines. From the potential-pH relation and the variation of the intensities of the oxidation peaks, the redox mechanisms of both types of amines was proposed. The electrochemical redox behaviour of the amines in the copper-mono-N-MNCyclen complex was studied. From the potential-pH relation and the variation of the intensities of the oxidation peaks, the redox mechanisms of amines and the structure of the copper-mono-N-MNCyclen complex were proposed. The intensities of the oxidation peaks of the amines vary linearly with the copper concentration, in the range 10−12 M to 10–6 M, leading to a detection limit of of 1 pM of Cu2+.

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The authors thank CNRS and DGRST for their financial support through PICS 2017-2020 # 226221.

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Authors and Affiliations

  1. Laboratory of Interfaces and Advanced Materials, Faculty of Sciences de Monastir, University of Monastir, 5000, Monastir, Tunisia

    Hassen Touzi, Ayoub Haj Said & Hafedh Ben Ouada

  2. LAGEP, University of Lyon, 43 bd 11 Novembre, 69622, Villeurbanne, France

    Yves Chevalier

  3. Institute of Analytical Sciences, UMR CNRS 5280, University of Lyon, 5 Rue de la Doua, 69100, Villeurbanne, France

    Nicole Jaffrezic-Renault

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Touzi, H., Haj Said, A., Chevalier, Y. et al. Effect of Copper on the Oxidation Mechanisms of Tertiary and Secondary Amines of Methyl-naphthyl- cyclen-Modified Gold Electrodes. J Inorg Organomet Polym 31, 3011–3026 (2021). https://doi.org/10.1007/s10904-020-01864-4

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