Approaches for multicopper oxidases in the design of electrochemical sensors for analytical applications

Matos, Iorquirene O.; Ferreira, Tiago Luiz; Paixão, Thiago R.L.C.; Lima, Alex Silva; Bertotti, Mauro; Alves, Wendel A.

doi:10.1016/j.electacta.2010.04.049

Cited by 16 publications

(20 citation statements)

References 55 publications

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“…25 Notably, the term A in the mass transport component (0.62nFAD 2/3 v −1/6 c s ϖ 1/2 ) −1 in the Koutecky− Levich equation refers to the geometric area, whereas the term A′ in the kinetic component (nFA′k′ ME c s ) −1 refers to the electroactive area, which itself depends on the film thickness. In this paper, we assume that A is equal to A′ for further calculations.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Self-Assembly of Peptide Nanostructures onto an Electrode Surface for Nonenzymatic Oxygen Sensing

et al. 2014

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We report here the fabrication of a biomimetic sensor for direct oxygen reduction; the sensor consists of multicopper oxidases derived from cyclic-tetrameric copper(II) species containing the ligand (4-imidazolyl)ethylene-2-amino-1-ethylpyridine (apyhist) that are self-assembled with L-diphenylalanine micro/nanostructures (FF-MNTs). The [Cu 4 (apyhist) 4 ] 4+ /FF-MNT complex was immobilized onto the surface of a glassy carbon (GC) electrode by poly ion complex formation with a Nafion film. This hybrid membrane allows regular proton transport to a Cu-based molecular oxygen reduction reaction catalyst, and the imidazole group in the imine ligand (apyhist) acts as a local buffer in the vicinity of the O 2 reducing center, thus aiding the catalyst in retaining its selectivity for 4e − / 4H + oxygen reduction reaction. This nanocomposite provided improved sensing characteristics in the electrode interface with respect to the electroactive surface area, the diffusion coefficient, and the electron transfer kinetics. In addition, the hybrid film [Cu 4 (apyhist) 4 ] 4+ /FF-MNT-coated GC electrode was successfully used as an enzymeless electrochemical sensor for the detection of dissolved oxygen in aqueous media at two concentration intervals, viz., 0.2−3.0 mg L −1 and greater than 3.0 mg L −1 , with sensitivities of 25.0 and 80.2 μA L mg −1 cm −2 , respectively, and a detection limit of 0.1 mg L −1 . Evaluated in terms of relative standard deviation, the repeatability of the proposed sensor was less than 9.0% for ten measurements of a solution of 6.5 mg L −1 oxygen. Experimental efforts were conducted to use this proposed platform for O 2 determination with real samples. Results from theoretical investigations using density functional theory support the hypothesis that the [Cu 4 (apyhist) 4 ] 4+ complex can act as the sole source of protons and electrons in the O 2 reduction reaction.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Self-Assembly of Peptide Nanostructures onto an Electrode Surface for Nonenzymatic Oxygen Sensing

et al. 2014

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“…While there were several isolated reports of synthesis and evaluation of a variety of Cu complexes with N-linked aromatic ligands (e.g. based on poly-L-histidine [10], pyrrole [11], and imidazole groups [12], among others [13]), the works of Gewirth et al with ligands of the tris (2-pyridylmethyl) amine type (TPA and related) and with substituted triazoles [6,[13][14][15] are more promising for the orr. This group has reported the most efficient Cu electrocatalyst to date in an alkaline medium, which is a Cu complex with 3,5-diamino-1,2,4-triazole (Cu2(Hdatzr)2 2+ ) [15].…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Reduction of Oxygen Using a Metal–Organic Complex of Cu2+

Ormachea¹,

Fernández²,

Mancini³

et al. 2019

22nd International Electronic Conference on Synthetic Organic Chemistry

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A biphenyl-based copper complex was evaluated as electrocatalyst for the oxygen reduction reaction (orr), for a possible application as cathode material in fuel cells. To carry out this evaluation, the complex was supported on Vulcan carbon and deposited as a film on a glassy carbon rotating disk electrode by drop-casting a 1-μL drop of a suspension of carbon in a solution of the complex in dimethyl sulfoxide containing Nafion as ionic conductive binder, and drying under vacuum. The cyclic voltammogram in 0.1 M NaOH solution showed voltammetric peaks between 0.8 and 1.0 V vs. reference hydrogen electrode, which suggest the existence of electron transfer processes from/toward the ligand. The orr was tested in oxygen-saturated (1 atm) solution by linear sweep voltammetry, which showed significant orr current at relatively low overpotential (around −0.4 V), demonstrating the ability of the complex to electrocatalyze the orr efficiently.

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“…Esse complexo possui a vantagem de apresentar um sistema redox bem definido, estável em meio fisiológico, com boa reprodutibilidade e sensibilidade. 31 Em solução aquosa, este complexo forma duas espécies mono-e tetranucleares de cobre(II) que estão em equilíbrio em solução aquosa, onde os centros de cobre estão ligados por meio de um ligando ponte imidazolato (Esquema 1). [32][33][34][35][36][37] Estudos eletroanalíticos de detecção amperométrica frente ao peróxido de hidrogênio indicaram que as espécies tetranucleares são melhores eletrocatalisadores do que os compostos de cobre(II) mononucleares.…”

Section: Introductionunclassified

Atividade eletrocatalítica de sistemas biomiméticos da enzima catalase

2011

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Recebido em 2/12/10; aceito em 4/5/11; publicado na web em 8/7/11 ELECTROCATALYTIC ACTIVITY OF CATALASE BIOMIMETIC SYSTEMS. In this work, we describe the immobilization of the dinuclear compound [Cu 2 (apyhist) 2 Cl 2 ](ClO 4 ) 2 (1) and its derived cations complexes, obtained in water solution or by deprotonation of the imidazolate moiety in the ligand leading to a cyclic tetranuclear species, in the Nafion ® membrane on glass carbon electrode surface. After that, we studied the influence of the equilibrium in the electrocatalytic activity towards the reduction of H 2 O 2 in the development of an amperometric sensor for the analytical determination of hydrogen peroxide. This strategy proved successful, and the electrochemical behaviour of the all complexes formed within the Nafion ® coatings was characterized. We also provide evidence that its related cyclic tetranuclear imidazolate-bridged complex acts as a catalysts for the intramolecular, two-electron reduction of H 2 O 2 .

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Approaches for multicopper oxidases in the design of electrochemical sensors for analytical applications

Cited by 16 publications

References 55 publications

Self-Assembly of Peptide Nanostructures onto an Electrode Surface for Nonenzymatic Oxygen Sensing

Self-Assembly of Peptide Nanostructures onto an Electrode Surface for Nonenzymatic Oxygen Sensing

Electrochemical Reduction of Oxygen Using a Metal–Organic Complex of Cu2+

Atividade eletrocatalítica de sistemas biomiméticos da enzima catalase

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