title: Characterization by electrochemical and X-ray photoelectron spectroscopic measurements and quantum chemical calculations of N-containing functional groups introduced onto glassy carbon electrode surfaces by electrooxidation of a carbamate salt in aqueous solutions.
abstract: The present paper deals with characterization of an aminated glassy carbon electrode (GCE) surface obtained by electrooxidation of ammonium carbamate in its aqueous solution (amination reaction) using electrochemical and XPS methods. From the XPS analysis, it was found that not only the primary amine group (i.e., aniline-like aromatic amine moiety) but also other N-containing functional groups (i.e., the secondary amine-like moieties containing pyrrole-type nitrogen and quaternary amine-like moieties containing graphitic quaternary nitrogen) are introduced onto the GCE surface during the amination reaction. Moreover, the presence of the primary and secondary amine groups was ascertained based on the difference in the reactivity of a Michael reaction-type addition reaction of amine groups introduced onto the GCE surface with quinone compounds having a carbonyl group and a C═C double bond (i.e., in this case, 1,2-benzoquinone which is in situ prepared by the electrooxidation of catechol) and on the electrochemical redox response of the introduced benzoquinones. This electrochemical treatment of aminated GCE with catechol led to catechol-grafted aminated GCE which indicated two surface redox couples (i.e., the Ia/Ic and IIa/IIc couples with formal potentials of E(0)'(Ia/Ic) = ca. 0.17 V and E(0)'(IIa/IIc) = ca. 0.03 V vs Ag|AgCl|KCl(sat.) in phosphate buffer solution (pH 7)). From the electrochemical behavior of catechols grafted onto the maleimide-treated aminated GCE and on the methylamine-treated GCE, it was found that the catechol associated with the primary amine groups gave the IIa/IIc redox peaks, while the catechol bound to the secondary amine groups gave the Ia/Ic redox peaks. Further electrochemical measurements and quantum chemical calculations concluded that the IIa/IIc redox peaks are ascribed to the surface-redox reaction of the 1,2-dihydroxybenzene/1,2-benzoquinone couple, while those of the 1,2-dihydroxybenzene/1,2-benzoquinone and the N-(4'-hydroxyphenyl)-p-aminophenol/indophenol couples can be associated with the Ia/Ic redox peaks.
authors.affiliation: Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology , 4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan.
authors.forename: Aiko
authors.initials: A
authors.lastname: Kanazawa
authors.forename: Takuro
authors.initials: T
authors.lastname: Daisaku
authors.forename: Takeyoshi
authors.initials: T
authors.lastname: Okajima
authors.forename: Shunichi
authors.initials: S
authors.lastname: Uchiyama
authors.forename: Susumu
authors.initials: S
authors.lastname: Kawauchi
authors.forename: Takeo
authors.initials: T
authors.lastname: Ohsaka