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Synthesis, properties and biosensor application of cycloruthenated 2-phenylimidazoles

Soukharev, V; Ryabov, A and Csöregi, Elisabeth LU (2003) In Journal of Organometallic Chemistry 668(1-2). p.75-81
Abstract
The cycloruthenation of 2-phenylimidazole (phim) by [Ru(6-C6H6)(-Cl)Cl]2 in acetonitrile in the presence of NaOH has been carried out. The unstable intermediate [Ru(phim)(MeCN)4]PF6 formed has been converted into the complexes [Ru(phim)(4,4′-Me2bpy)(MeCN)2]PF6 (2) and [Ru(phim)(LL)2]PF6 (3, LL=phen (a), bpy, 4,4′-Me2bpy), which were characterized by the mass-spectrometry, 1H-NMR spectroscopy, UV–vis spectrophotometry, and cyclic voltammetry. The RuII/III redox potentials of complexes 3 equal 130–250 mV (vs. Ag–AgCl) at pH 7 (0.01 M phosphate). Such potential range is favorable for fast exchange of electrons with the active sites of redox enzymes. In fact, the second-order rate constant for the oxidation of reduced glucose oxidase (GO) from... (More)
The cycloruthenation of 2-phenylimidazole (phim) by [Ru(6-C6H6)(-Cl)Cl]2 in acetonitrile in the presence of NaOH has been carried out. The unstable intermediate [Ru(phim)(MeCN)4]PF6 formed has been converted into the complexes [Ru(phim)(4,4′-Me2bpy)(MeCN)2]PF6 (2) and [Ru(phim)(LL)2]PF6 (3, LL=phen (a), bpy, 4,4′-Me2bpy), which were characterized by the mass-spectrometry, 1H-NMR spectroscopy, UV–vis spectrophotometry, and cyclic voltammetry. The RuII/III redox potentials of complexes 3 equal 130–250 mV (vs. Ag–AgCl) at pH 7 (0.01 M phosphate). Such potential range is favorable for fast exchange of electrons with the active sites of redox enzymes. In fact, the second-order rate constant for the oxidation of reduced glucose oxidase (GO) from Aspergillus niger by the electrochemically generated RuIII derivative of complex 3a equals (8.1×106 M−1 s−1). The second-order rate constant for the oxidation of 3a by the Compound II of horseradish peroxidase is 9.3×107 M−1 s−1. Complexes 3 were used as mediators for the fabrication of enzyme electrodes by simple co-adsorbing with GO or horseradish peroxidase on graphite electrodes. These electrodes were tested in flow-injection systems and showed linear responses in the range of -glucose and H2O2 concentrations 0.1–30 mM and 1–200 M, respectively. The new mediators reported herein seem promising for the construction of amperometric biosensors based on GO, horseradish peroxidase, and similar enzymes. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Ruthenium complexes, Cyclometalation, Electron transfer, Mediators, Glucose oxidase, Horseradish peroxidase, Kinetics, Electrochemistry
in
Journal of Organometallic Chemistry
volume
668
issue
1-2
pages
75 - 81
publisher
Elsevier
external identifiers
  • wos:000181644800012
  • scopus:0037450825
ISSN
0022-328X
DOI
10.1016/S0022-328X(02)02143-5
language
English
LU publication?
yes
id
ff16a51b-5faa-42e8-8674-f34a98e205df (old id 129280)
date added to LUP
2007-07-03 08:58:08
date last changed
2018-01-07 09:26:08
@article{ff16a51b-5faa-42e8-8674-f34a98e205df,
  abstract     = {The cycloruthenation of 2-phenylimidazole (phim) by [Ru(6-C6H6)(-Cl)Cl]2 in acetonitrile in the presence of NaOH has been carried out. The unstable intermediate [Ru(phim)(MeCN)4]PF6 formed has been converted into the complexes [Ru(phim)(4,4′-Me2bpy)(MeCN)2]PF6 (2) and [Ru(phim)(LL)2]PF6 (3, LL=phen (a), bpy, 4,4′-Me2bpy), which were characterized by the mass-spectrometry, 1H-NMR spectroscopy, UV–vis spectrophotometry, and cyclic voltammetry. The RuII/III redox potentials of complexes 3 equal 130–250 mV (vs. Ag–AgCl) at pH 7 (0.01 M phosphate). Such potential range is favorable for fast exchange of electrons with the active sites of redox enzymes. In fact, the second-order rate constant for the oxidation of reduced glucose oxidase (GO) from Aspergillus niger by the electrochemically generated RuIII derivative of complex 3a equals (8.1×106 M−1 s−1). The second-order rate constant for the oxidation of 3a by the Compound II of horseradish peroxidase is 9.3×107 M−1 s−1. Complexes 3 were used as mediators for the fabrication of enzyme electrodes by simple co-adsorbing with GO or horseradish peroxidase on graphite electrodes. These electrodes were tested in flow-injection systems and showed linear responses in the range of -glucose and H2O2 concentrations 0.1–30 mM and 1–200 M, respectively. The new mediators reported herein seem promising for the construction of amperometric biosensors based on GO, horseradish peroxidase, and similar enzymes.},
  author       = {Soukharev, V and Ryabov, A and Csöregi, Elisabeth},
  issn         = {0022-328X},
  keyword      = {Ruthenium complexes,Cyclometalation,Electron transfer,Mediators,Glucose oxidase,Horseradish peroxidase,Kinetics,Electrochemistry},
  language     = {eng},
  number       = {1-2},
  pages        = {75--81},
  publisher    = {Elsevier},
  series       = {Journal of Organometallic Chemistry},
  title        = {Synthesis, properties and biosensor application of cycloruthenated 2-phenylimidazoles},
  url          = {http://dx.doi.org/10.1016/S0022-328X(02)02143-5},
  volume       = {668},
  year         = {2003},
}