Abstract
The electrografting of primary amines to carbon electrodes is now widely employed for electrode modification. Using a mixture of acetonitrile and 0.1 mol•L-1 aqueous sodium hydrogen carborate (NaHCO3) in the ratio of 4:1, the efficiency for coupling of mono-N-Boc-ethylenediamine (EDA-Boc) on the surface of glassy carbon was significantly improved as compared with that obtained using acetonitrile alone. In the presence of NaHCO3 the initial current determined in the cyclic voltammogram became higher, and the layer of attached amine was formed more rapidly, accordingly, the electrode was passivated more rapidly. The resulting film of EDA-Boc was shown to be more severely blocking toward the electrochemical reaction of [Fe(CN)6]3-. 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 was obtained. Modelling for the electrograftng reaction using a simple kinetic scheme, it was demonstrated that the simulated voltammograms agreed well with the experimentally measured voltammograms . Comparison between the model fitting parameters obtained from the acetonitrile alone and the acetonitrile/NaHCO3 mixture showed that the competition between reaction of the amine radicals with the carbon surface and reaction in the homogeneous solution became more favourable for the surface reaction in the acetonitrile/NaHCO3 mixture.
Graphical Abstract
Publication Date
2017-04-28
Online Available Date
2017-01-29
Revised Date
2017-01-21
Received Date
2016-12-01
Recommended Citation
Hamzah Hisham, Denuault Guy, Bartlett Philip, Pinczewska Aleksandra, Kilburn Jeremy.
Electrografting of Mono-N-Boc-Ethylenediamine from an Acetonitrile/Aqueous NaHCO3 Mixture[J]. Journal of Electrochemistry,
2017
,
23(2): 161241.
DOI: 10.13208/j.electrochem.161241
Available at:
https://jelectrochem.xmu.edu.cn/journal/vol23/iss2/15
References
[1] Adenier A, Chehimi M M, Gallardo I, et al. Electrochemical oxidation of aliphatic amines and their attachment to carbon and metal surfaces[J]. Langmuir, 2004, 20(19): 8243-8253.
[2] Barbier B, Pinson J, Desarmot G, et al. Electrochemical bonding of amines to carbon fiber surfaces toward improved carbon-epoxy composites[J]. Journal of the Electrochemical Society, 1990, 137(6): 1757-1764.
[3] Downard A J. Electrochemically assisted covalent modification of carbon electrodes[J]. Electroanalysis, 2000, 12(14): 1085-1096.
[4] Bélanger D, Pinson J. Electrografting: a powerful method for surface modification[J]. Chemical Society Reviews, 2011, 40(7): 3995-4048.
[5] Deinhammer R S, Ho M, Anderegg J W, et al. Electrochemical oxidation of amine-containing compounds: a route to the surface modification of glassy carbon electrodes[J]. Langmuir, 1994, 10(4): 1306-1313.
[6] Liu J, Dong S. Grafting of diaminoalkane on glassy carbon surface and its functionalization[J]. Electrochemistry Communications, 2000, 2(10): 707-712.
[7] Holm A H, Vase K H, Winther-Jensen B, et al. Evaluation of various strategies to formation of pH responsive hydroquinone-terminated films on carbon electrodes[J]. Electrochimica Acta, 2007, 53(4): 1680-1688.
[8] Buriez O, Labbé E, Pigeon P, et al. Electrochemical attachment of a conjugated aminoferrocifen complex onto carbon and metal surfaces[J]. Journal of Electroanalytical Chemistry, 2008, 619620(0): 169-175.
[9] Buriez O, Podvorica F I, Galtayries A, et al. Surface grafting of a Ï-conjugated amino-ferrocifen drug[J]. Journal of Electroanalytical Chemistry, 2013, 699(0): 21-27.
[10] Tanaka M, Sawaguchi T, Sato Y, et al. Surface modification of GC and HOPG with diazonium, amine, azide, and olefin derivatives[J]. Langmuir, 2011, 27(1): 170-178.
[11] Geneste F, Moinet C. Electrochemically linking TEMPO to carbon via amine bridges[J]. New Journal of Chemistry, 2005, 29(2): 269-771.
[12] Nasraoui R, Bergamini J-F, Ababou-Girard S, et al. Sequential anodic oxidations of aliphatic amines in aqueous medium on pyrolyzed photoresist film surfaces for the covalent immobilization of cyclam derivatives[J]. Journal of Solid State Electrochemistry, 2011, 15(1): 139-146.
[13] Chrétien J-M, Ghanem M A, Bartlett P N, et al. Covalent tethering of organic functionality to the surface of glassy carbon electrodes by using electrochemical and solid-phase synthesis methodologies[J]. Chemistry a European Journal, 2008, 14(8): 25482556.
[14] Chrétien J-M, Ghanem M A, Bartlett P N, et al. Covalent modification of glassy carbon surfaces by using electrochemical and solid-phase synthetic methodologies: application to bi- and trifunctionalisation with different redox centres[J]. Chemistry a European Journal, 2009, 15(44): 11928-11936.
[15] Ghanem M A, Chrétien J-M, Kilburn J D, et al. Electrochemical and solid-phase synthetic modification of glassy carbon electrodes with dihydroxybenzene compounds and the electrocatalytic oxidation of NADH[J]. Bioelectrochemistry. 2009, 76(1-2): 115-125.
[16] Ghanem M A, Chrétien J-M, Pinczewska A, et al. Covalent modification of glassy carbon surface with organic redox probes through diamine linkers using electrochemical and solid-phase synthesis methodologies[J]. Journal of Materials Chemistry, 2008, 18(41): 4917-4927.
[17] Sosna M, Chretien J-M, Kilburn J D, et al. Monolayer anthracene and anthraquinone modified electrodes as platforms for Trametes hirsuta laccase immobilisation[J]. Physical Chemistry Chemical Physics. 2010, 12(34): 10018-10026.
[18] Pinczewska A, Sosna M, Bloodworth S, et al. High-throughput synthesis and electrochemical screening of a library of modified electrodes for NADH oxidation[J]. Journal of the American Chemical Society, 2012, 134(43): 18022-18033.
[19] Groppi J, Bartlett P N, Kilburn J D. Toward the control of the creation of mixed monolayers on glassy carbon surfaces by amine oxidation[J]. Chemistry a European Journal, 2016, 22(3): 1030-1036.
[20] Baranton S, Bélanger D. Electrochemical derivatization of carbon surface by reduction of in situ generated diazonium cations[J]. Journal of Physical Chemistry B, 2005, 109(51): 24401-24410.
[21] Saby C, Ortiz B, Champagne G Y, et al. Electrochemical modification of glassy carbon electrode using aromatic diazonium salts .1. Blocking effect of 4-nitrophenyl and 4-carboxyphenyl groups[J]. Langmuir, 1997, 13(25): 6805-6813.
[22] Ghanem M A, Kocak I, Al-Mayouf A, et al. Covalent modification of carbon nanotubes with anthraquinone by electrochemical grafting and solid phase synthesis[J]. Electrochimica Acta. 2012, 68: 74-80.
[23] Bhugun I, Savéant J M. Derivatization of surfaces and self-inhibition in irreversible electrochemical reactions - cyclic voltammetry and preparative-scale electrolysis[J]. Journal of the Electrochemical Society, 1995, 395: 127-131.
[24] Allongue P, Delamar M, Desbat B, et al. Covalent modification of carbon surfaces by aryl radicals generated from the electrochemical reduction of diazonium salts[J]. Journal of the American Chemical Society, 1997, 119(1): 201-207.
