Considering the Chemical Energy Requirements of the Tri-n-propylamine Co-Reactant Pathways for the Judicious Design of New Electrogenerated Chemiluminescence Detection Systems

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Kerr, E., Doeven, E. H., Wilson, D. J., Hogan, C. F., & Francis, P. S. (2016). Considering the chemical energy requirements of the tri-n-propylamine co-reactant pathways for the judicious design of new electrogenerated chemiluminescence systems. Analyst, 141(1), 62-69. doi: 10.1039/C5AN01462J

ISSN: 0003-2654


030701 Quantum Chemistry

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The introduction of a ‘co-reactant’ was a critical step in the evolution of electrogenerated chemiluminescence (ECL) from a laboratory curiosity to a widely utilised detection system. In conjunction with a suitable electrochemiluminophore, the co-reactant enables generation of both the oxidised and reduced precursors to the emitting species at a single electrode potential, under the aqueous conditions required for most analytical applications. The most commonly used co-reactant is tri-n-propylamine (TPrA), which was developed for the classic tris(2,2’-bipyridine)ruthenium(II) ECL reagent. New electrochemiluminophores such as cyclometalated iridium(III) complexes are also evaluated with this co-reactant. However, attaining the excited states in these systems can require much greater energy than that of tris(2,2’-bipyridine)ruthenium(II), which has implications for the co-reactant reaction pathways. In this tutorial review, we describe a simple graphical approach to characterise the energetically feasible ECL pathways with TPrA, as a useful tool for the development of new ECL detection systems.


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David Wilson is affiliated with Avondale College as a Conjoint Senior Lecturer.