High-frequency electrochemiluminescent investigation of the reaction pathway between tris(2,2′-bipyridyl)ruthenium(II) and tripropylamine using carbon fiber microelectrodes

Erin M. Gross, Paolo Pastore, R. Mark Wightman

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Abstract

The electrochemiluminescent (ECL) reaction mechanism between tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) and tripropylamine (TPrA) in aqueous solution at pH 7.4 was examined using fast potential pulses at carbon fiber microelectrodes. High-stability ECL emission was found with 0.5 ms pulses and a 25% duty cycle. In addition, stability was increased with negative rest potentials. Direct evidence for the strongly reducing free radical intermediate was obtained when the light was quenched upon addition of nitrobenzene derivatives. The formation of this free radical becomes rate-limiting at high concentrations of Ru(bpy)32+ and TPrA, as its production can be limited when there is an insufficient supply of one or both of its precursors (TPrA and TPrA.+) relative to Ru(bpy)32+. When TPrA is in sufficient excess of Ru(bpy)32+, the ECL efficiency (photons emitted/Ru(bpy)33+ generated) was determined to be very high (∼90%) by comparison to a Ru(bpy)33+/ Ru(bpy)3+ standard in acetonitrile. Rapid potential pulses also generated ECL from Ru(bpy)32+ when other tertiary amines, trimethylamine, diisopropylethylamine, and histamine, were used as co-reactants. The secondary amine epinephrine also produced light, but not norepinephrine, a primary amine.

Original languageEnglish
Pages (from-to)8732-8738
Number of pages7
JournalJournal of Physical Chemistry B
Volume105
Issue number37
DOIs
StatePublished - Sep 20 2001
Externally publishedYes

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2,2'-Dipyridyl
Ruthenium
Microelectrodes
carbon fibers
ruthenium
Carbon fibers
Amines
amines
Free radicals
free radicals
norepinephrine
pulses
Norepinephrine
epinephrine
histamines
Nitrobenzene
nitrobenzenes
Free Radicals
Acetonitrile
acetonitrile

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

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title = "High-frequency electrochemiluminescent investigation of the reaction pathway between tris(2,2′-bipyridyl)ruthenium(II) and tripropylamine using carbon fiber microelectrodes",
abstract = "The electrochemiluminescent (ECL) reaction mechanism between tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) and tripropylamine (TPrA) in aqueous solution at pH 7.4 was examined using fast potential pulses at carbon fiber microelectrodes. High-stability ECL emission was found with 0.5 ms pulses and a 25{\%} duty cycle. In addition, stability was increased with negative rest potentials. Direct evidence for the strongly reducing free radical intermediate was obtained when the light was quenched upon addition of nitrobenzene derivatives. The formation of this free radical becomes rate-limiting at high concentrations of Ru(bpy)32+ and TPrA, as its production can be limited when there is an insufficient supply of one or both of its precursors (TPrA and TPrA.+) relative to Ru(bpy)32+. When TPrA is in sufficient excess of Ru(bpy)32+, the ECL efficiency (photons emitted/Ru(bpy)33+ generated) was determined to be very high (∼90{\%}) by comparison to a Ru(bpy)33+/ Ru(bpy)3+ standard in acetonitrile. Rapid potential pulses also generated ECL from Ru(bpy)32+ when other tertiary amines, trimethylamine, diisopropylethylamine, and histamine, were used as co-reactants. The secondary amine epinephrine also produced light, but not norepinephrine, a primary amine.",
author = "Gross, {Erin M.} and Paolo Pastore and Wightman, {R. Mark}",
year = "2001",
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T1 - High-frequency electrochemiluminescent investigation of the reaction pathway between tris(2,2′-bipyridyl)ruthenium(II) and tripropylamine using carbon fiber microelectrodes

AU - Gross, Erin M.

AU - Pastore, Paolo

AU - Wightman, R. Mark

PY - 2001/9/20

Y1 - 2001/9/20

N2 - The electrochemiluminescent (ECL) reaction mechanism between tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) and tripropylamine (TPrA) in aqueous solution at pH 7.4 was examined using fast potential pulses at carbon fiber microelectrodes. High-stability ECL emission was found with 0.5 ms pulses and a 25% duty cycle. In addition, stability was increased with negative rest potentials. Direct evidence for the strongly reducing free radical intermediate was obtained when the light was quenched upon addition of nitrobenzene derivatives. The formation of this free radical becomes rate-limiting at high concentrations of Ru(bpy)32+ and TPrA, as its production can be limited when there is an insufficient supply of one or both of its precursors (TPrA and TPrA.+) relative to Ru(bpy)32+. When TPrA is in sufficient excess of Ru(bpy)32+, the ECL efficiency (photons emitted/Ru(bpy)33+ generated) was determined to be very high (∼90%) by comparison to a Ru(bpy)33+/ Ru(bpy)3+ standard in acetonitrile. Rapid potential pulses also generated ECL from Ru(bpy)32+ when other tertiary amines, trimethylamine, diisopropylethylamine, and histamine, were used as co-reactants. The secondary amine epinephrine also produced light, but not norepinephrine, a primary amine.

AB - The electrochemiluminescent (ECL) reaction mechanism between tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) and tripropylamine (TPrA) in aqueous solution at pH 7.4 was examined using fast potential pulses at carbon fiber microelectrodes. High-stability ECL emission was found with 0.5 ms pulses and a 25% duty cycle. In addition, stability was increased with negative rest potentials. Direct evidence for the strongly reducing free radical intermediate was obtained when the light was quenched upon addition of nitrobenzene derivatives. The formation of this free radical becomes rate-limiting at high concentrations of Ru(bpy)32+ and TPrA, as its production can be limited when there is an insufficient supply of one or both of its precursors (TPrA and TPrA.+) relative to Ru(bpy)32+. When TPrA is in sufficient excess of Ru(bpy)32+, the ECL efficiency (photons emitted/Ru(bpy)33+ generated) was determined to be very high (∼90%) by comparison to a Ru(bpy)33+/ Ru(bpy)3+ standard in acetonitrile. Rapid potential pulses also generated ECL from Ru(bpy)32+ when other tertiary amines, trimethylamine, diisopropylethylamine, and histamine, were used as co-reactants. The secondary amine epinephrine also produced light, but not norepinephrine, a primary amine.

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