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Electrografting of mono-n-boc-ethylenediamine from an acetonitrile/aqueous NaHCO3 mixture

Electrografting of mono-n-boc-ethylenediamine from an acetonitrile/aqueous NaHCO3 mixture
Electrografting of mono-n-boc-ethylenediamine from an acetonitrile/aqueous NaHCO3 mixture
The electrografting of primary amines to carbon electrodes is now widely used as a method of electrode modification. Using a mixture of acetonitrile and 0.1 M aqueous NaHCO3 in the ratio 4:1 is shown to significantly improve the efficiency of coupling of mono-N-Boc-ethylenediamine (EDA-Boc) to the surface of glassy carbon over that obtained in acetonitrile alone. In the presence of added NaHCO3 the initial current in cyclic voltammetry is higher, the layer of attached amine forms more rapidly, and the electrode passivates more rapidly. The resulting film of EDA-Boc is shown to be more blocking towards [Fe(CN)6]3- electrochemistry and, following removal of the Boc protecting group and coupling of the free amine to anthraquinone-2-carboxylic acid, a higher surface coverage of the anthraquinone is obtained. Modelling of the voltammetry for the electrograftng reaction using a simple kinetic scheme gives good agreement between the simulated voltammograms and experiment. Comparison of the fitting parameters from the model for the reaction in acetonitrile and in acetonitrile/NaHCO3 shows that the competition between reaction of the amine radicals with the carbon surface and reaction in homogeneous solution is shifted more in favour of the surface reaction in acetonitrile/NaHCO3.
electrografting, mono-N-Boc-ethylenediamine, amine oxidation, glassy carbon, surface modification
1006-3471
130-140
Hamzah, Hisham
548f2828-18c9-4034-afa7-518dc11d4219
Denuault, Guy
5c76e69f-e04e-4be5-83c5-e729887ffd4e
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075
Pinczewska, Aleksandra
dc358574-75de-4ac4-9f30-2b7f3ea151cc
Kilburn, Jeremy
8e1fd31d-b633-4c11-abae-40e23aad1fc6
Hamzah, Hisham
548f2828-18c9-4034-afa7-518dc11d4219
Denuault, Guy
5c76e69f-e04e-4be5-83c5-e729887ffd4e
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075
Pinczewska, Aleksandra
dc358574-75de-4ac4-9f30-2b7f3ea151cc
Kilburn, Jeremy
8e1fd31d-b633-4c11-abae-40e23aad1fc6

Hamzah, Hisham, Denuault, Guy, Bartlett, Philip N., Pinczewska, Aleksandra and Kilburn, Jeremy (2017) Electrografting of mono-n-boc-ethylenediamine from an acetonitrile/aqueous NaHCO3 mixture. Journal of Electrochemistry, 23 (2), 130-140.

Record type: Article

Abstract

The electrografting of primary amines to carbon electrodes is now widely used as a method of electrode modification. Using a mixture of acetonitrile and 0.1 M aqueous NaHCO3 in the ratio 4:1 is shown to significantly improve the efficiency of coupling of mono-N-Boc-ethylenediamine (EDA-Boc) to the surface of glassy carbon over that obtained in acetonitrile alone. In the presence of added NaHCO3 the initial current in cyclic voltammetry is higher, the layer of attached amine forms more rapidly, and the electrode passivates more rapidly. The resulting film of EDA-Boc is shown to be more blocking towards [Fe(CN)6]3- electrochemistry and, following removal of the Boc protecting group and coupling of the free amine to anthraquinone-2-carboxylic acid, a higher surface coverage of the anthraquinone is obtained. Modelling of the voltammetry for the electrograftng reaction using a simple kinetic scheme gives good agreement between the simulated voltammograms and experiment. Comparison of the fitting parameters from the model for the reaction in acetonitrile and in acetonitrile/NaHCO3 shows that the competition between reaction of the amine radicals with the carbon surface and reaction in homogeneous solution is shifted more in favour of the surface reaction in acetonitrile/NaHCO3.

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Submitted date: 1 December 2016
e-pub ahead of print date: 29 January 2017
Published date: April 2017
Keywords: electrografting, mono-N-Boc-ethylenediamine, amine oxidation, glassy carbon, surface modification
Organisations: Chemistry, Electrochemistry

Identifiers

Local EPrints ID: 411112
URI: http://eprints.soton.ac.uk/id/eprint/411112
ISSN: 1006-3471
PURE UUID: a8e4d7a4-f674-4e24-9878-5b2cc7a2d24c
ORCID for Guy Denuault: ORCID iD orcid.org/0000-0002-8630-9492
ORCID for Philip N. Bartlett: ORCID iD orcid.org/0000-0002-7300-6900

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Date deposited: 14 Jun 2017 16:31
Last modified: 30 Mar 2021 01:35

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Contributors

Author: Hisham Hamzah
Author: Guy Denuault ORCID iD
Author: Aleksandra Pinczewska
Author: Jeremy Kilburn

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