Electrocatalytic sensor devices: (I) cyclopentadienylnickel(II) thiolato Schiff base monolayer self-assembled on gold

Aoife Morrin; Richard M. Moutloali; Anthony J. Killard; Malcolm R. Smyth; James Darkwa; Emmanuel I. Iwuoha

doi:10.1016/j.talanta.2003.11.046

Electrocatalytic sensor devices: (I) cyclopentadienylnickel(II) thiolato Schiff base monolayer self-assembled on gold

Aoife Morrin, Richard M. Moutloali, Anthony J. Killard, Malcolm R. Smyth, James Darkwa, Emmanuel I. Iwuoha

Research output: Contribution to journal › Article › peer-review

29 Citations (Scopus)

Abstract

The fabrication of a self-assembled monolayer (SAM) of a cyclopentadienylnickel(II) thiolato Schiff base compound, [Ni(SC ₆H₄NC(H)C₆H₄OCH₂CH ₂SMe)(η⁵-C₅H₅)]₂ on a gold electrode is described. Effective electronic communication between the Ni(II) centres and the gold surface was established by electrochemically cycling the Schiff base-doped Au electrode in 0.1 M NaOH from -200 mV to +600 mV. The SAM-modified electrode exhibited quasi-reversible electrochemistry. The integrity of this electrocatalytic SAM, with respect to its ability to block and electro-catalyse certain Faradaic processes, was interrogated using cyclic voltammetric experiments. The formal potential, E°′, varied with pH to give a slope of about -30 mV pH^-1. The surface concentration, G, of the nickel redox centres was found to be 1.548×10^-11 mol cm^-2. By electrostatically doping the SAM using an applied potential of +700 mV versus Ag/AgCl, in the presence of horseradish peroxidase (HRP), it was fine-tuned for amperometric determination of H₂O₂. The electrocatalytic-type biosensor displayed typical Michaelis-Menten kinetics and the limit of detection was found to be 6.25 mM.

Original language	English
Pages (from-to)	30-38
Number of pages	9
Journal	Talanta
Volume	64
Issue number	1
DOIs	https://doi.org/10.1016/j.talanta.2003.11.046
Publication status	Published - 8 Sept 2004
Externally published	Yes

Keywords

Biosensor
Cyclopentadienylnickel(II) thiolato Schiff base
Electrostatic doping
Horseradish peroxidase
Self-assembled monolayer

ASJC Scopus subject areas

Analytical Chemistry

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10.1016/j.talanta.2003.11.046

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title = "Electrocatalytic sensor devices: (I) cyclopentadienylnickel(II) thiolato Schiff base monolayer self-assembled on gold",

abstract = "The fabrication of a self-assembled monolayer (SAM) of a cyclopentadienylnickel(II) thiolato Schiff base compound, [Ni(SC 6H4NC(H)C6H4OCH2CH 2SMe)(η5-C5H5)]2 on a gold electrode is described. Effective electronic communication between the Ni(II) centres and the gold surface was established by electrochemically cycling the Schiff base-doped Au electrode in 0.1 M NaOH from -200 mV to +600 mV. The SAM-modified electrode exhibited quasi-reversible electrochemistry. The integrity of this electrocatalytic SAM, with respect to its ability to block and electro-catalyse certain Faradaic processes, was interrogated using cyclic voltammetric experiments. The formal potential, E°′, varied with pH to give a slope of about -30 mV pH-1. The surface concentration, G, of the nickel redox centres was found to be 1.548×10-11 mol cm-2. By electrostatically doping the SAM using an applied potential of +700 mV versus Ag/AgCl, in the presence of horseradish peroxidase (HRP), it was fine-tuned for amperometric determination of H2O2. The electrocatalytic-type biosensor displayed typical Michaelis-Menten kinetics and the limit of detection was found to be 6.25 mM.",

keywords = "Biosensor, Cyclopentadienylnickel(II) thiolato Schiff base, Electrostatic doping, Horseradish peroxidase, Self-assembled monolayer",

author = "Aoife Morrin and Moutloali, {Richard M.} and Killard, {Anthony J.} and Smyth, {Malcolm R.} and James Darkwa and Iwuoha, {Emmanuel I.}",

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T2 - (I) cyclopentadienylnickel(II) thiolato Schiff base monolayer self-assembled on gold

AU - Morrin, Aoife

AU - Moutloali, Richard M.

AU - Killard, Anthony J.

AU - Smyth, Malcolm R.

AU - Darkwa, James

AU - Iwuoha, Emmanuel I.

PY - 2004/9/8

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N2 - The fabrication of a self-assembled monolayer (SAM) of a cyclopentadienylnickel(II) thiolato Schiff base compound, [Ni(SC 6H4NC(H)C6H4OCH2CH 2SMe)(η5-C5H5)]2 on a gold electrode is described. Effective electronic communication between the Ni(II) centres and the gold surface was established by electrochemically cycling the Schiff base-doped Au electrode in 0.1 M NaOH from -200 mV to +600 mV. The SAM-modified electrode exhibited quasi-reversible electrochemistry. The integrity of this electrocatalytic SAM, with respect to its ability to block and electro-catalyse certain Faradaic processes, was interrogated using cyclic voltammetric experiments. The formal potential, E°′, varied with pH to give a slope of about -30 mV pH-1. The surface concentration, G, of the nickel redox centres was found to be 1.548×10-11 mol cm-2. By electrostatically doping the SAM using an applied potential of +700 mV versus Ag/AgCl, in the presence of horseradish peroxidase (HRP), it was fine-tuned for amperometric determination of H2O2. The electrocatalytic-type biosensor displayed typical Michaelis-Menten kinetics and the limit of detection was found to be 6.25 mM.

AB - The fabrication of a self-assembled monolayer (SAM) of a cyclopentadienylnickel(II) thiolato Schiff base compound, [Ni(SC 6H4NC(H)C6H4OCH2CH 2SMe)(η5-C5H5)]2 on a gold electrode is described. Effective electronic communication between the Ni(II) centres and the gold surface was established by electrochemically cycling the Schiff base-doped Au electrode in 0.1 M NaOH from -200 mV to +600 mV. The SAM-modified electrode exhibited quasi-reversible electrochemistry. The integrity of this electrocatalytic SAM, with respect to its ability to block and electro-catalyse certain Faradaic processes, was interrogated using cyclic voltammetric experiments. The formal potential, E°′, varied with pH to give a slope of about -30 mV pH-1. The surface concentration, G, of the nickel redox centres was found to be 1.548×10-11 mol cm-2. By electrostatically doping the SAM using an applied potential of +700 mV versus Ag/AgCl, in the presence of horseradish peroxidase (HRP), it was fine-tuned for amperometric determination of H2O2. The electrocatalytic-type biosensor displayed typical Michaelis-Menten kinetics and the limit of detection was found to be 6.25 mM.

KW - Biosensor

KW - Cyclopentadienylnickel(II) thiolato Schiff base

KW - Electrostatic doping

KW - Horseradish peroxidase

KW - Self-assembled monolayer

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Electrocatalytic sensor devices: (I) cyclopentadienylnickel(II) thiolato Schiff base monolayer self-assembled on gold

Abstract

Keywords

ASJC Scopus subject areas

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