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Towards Determining Kinetics of Annihilation Electrogenerated Chemiluminescence by Concentration-Dependent Luminescent Intensity

  • Klaus MathwigEmail author
  • Neso Sojic
Original Paper
  • 31 Downloads

Abstract

In ion-annihilation electrochemiluminescence (ECL), luminophore ions are generated by oxidation as well as reduction at electrodes surfaces, and subsequently recombine into an electronically excited state, which emits light. The intensity of the emitted light is often limited by the kinetic rate of recombination of the luminophore ion species. Recombination or annihilation rates are high ranging up to approximately 1010 M−1 s−1 and can be difficult to determine using scanning electrochemical microscopy or high-frequency oscillations of an electrode potential. Here, we propose determining annihilation kinetics by measuring the relative change of the emitted light intensity as a function of luminophore concentration. Using finite element simulations of annihilation ECL in a geometry of two closely spaced electrodes biased at constant potentials, we show that, with increasing concentrations, luminescence intensity crosses over from a quadratic dependence on concentration to a linear regime—depending on the rate of annihilation. Our numerical results are applicable to scanning electrochemical microscopy as well as nanofluidic electrochemical devices to determine fast ion-annihilation kinetics.

Keywords

Electrogenerated chemiluminescence Annihilation Mechanisms Ion-annihilation kinetics Redox cycling Nanogap transducer 

Supplementary material

41664_2019_94_MOESM1_ESM.pdf (256 kb)
Supplementary material 1 (PDF 255 kb)

References

  1. 1.
    Richter MM. Electrochemiluminescence (ECL). Chem Rev. 2004;104:3003–36.  https://doi.org/10.1021/cr020373d.CrossRefGoogle Scholar
  2. 2.
    Kirschbaum SEK, Baeumner AJ. A review of electrochemiluminescence (ECL) in and for microfluidic analytical devices. Anal Bioanal Chem. 2015;407:3911–26.  https://doi.org/10.1007/s00216-015-8557-x.CrossRefGoogle Scholar
  3. 3.
    Liu Z, Qi W, Xu G. Recent advances in electrochemiluminescence. Chem Soc Rev. 2015;44:3117–42.  https://doi.org/10.1039/C5CS00086F.CrossRefGoogle Scholar
  4. 4.
    Guo W, Liu Y, Cao Z, Su B. Imaging analysis based on electrogenerated chemiluminescence. J Anal Test. 2017;1:14.  https://doi.org/10.1007/s41664-017-0013-9.CrossRefGoogle Scholar
  5. 5.
    Voci S, Goudeau B, Valenti G, Lesch A, Jović M, Rapino S, Paolucci F, Arbault S, Sojic N. Surface-confined electrochemiluminescence microscopy of cell membranes. J Am Chem Soc. 2018;140:14753–60.  https://doi.org/10.1021/jacs.8b08080.CrossRefGoogle Scholar
  6. 6.
    Méance S, Gamby J, Faure M, Kou Q, Haghiri-Gosnet AM. Electrochemiluminescence on-a-chip: towards a hand-held electrically powered optofluidic source. Talanta. 2014;129:150–4.  https://doi.org/10.1016/j.talanta.2014.05.026.CrossRefGoogle Scholar
  7. 7.
    Kapturkiewicz A. Electrochemical generation of excited intramolecular charge-transfer states. ChemElectroChem. 2017;4:1604–38.  https://doi.org/10.1002/celc.201600865.CrossRefGoogle Scholar
  8. 8.
    Collinson MM, Wightman RM, Pastore P. Evaluation of ion-annihilation reaction kinetics using high-frequency generation of electrochemiluminescence. J. Phys. 1994;98:11942–7.Google Scholar
  9. 9.
    Maloy JT, Prater KB, Bard AJ. Electrogenerated chemiluminescence. V. Rotating-ring-disk electrode. Digital simulation and experimental evaluation. J Am Chem Soc. 1971;93:5959–68.  https://doi.org/10.1021/ja00752a003.CrossRefGoogle Scholar
  10. 10.
    Amatore C, Pebay C, Servant L, Sojic N, Szunerits S, Thouin L. Mapping electrochemiluminescence as generated at double-band microelectrodes by confocal microscopy under steady state. ChemPhysChem. 2006;7:1322–7.  https://doi.org/10.1002/cphc.200500626.CrossRefGoogle Scholar
  11. 11.
    Polcari D, Dauphin-Ducharme P, Mauzeroll J. Scanning electrochemical microscopy: a comprehensive review of experimental parameters from 1989 to 2015. Chem Rev. 2016;116:13234–78.  https://doi.org/10.1021/acs.chemrev.6b00067.CrossRefGoogle Scholar
  12. 12.
    Izquierdo J, Knittel P, Kranz C. Scanning electrochemical microscopy: an analytical perspective. Anal Bioanal Chem. 2018;410:307–24.  https://doi.org/10.1007/s00216-017-0742-7.CrossRefGoogle Scholar
  13. 13.
    Kai T, Zhou M, Johnson S, Ahn HS, Bard AJ. Direct observation of C2O4·– and CO2·– by oxidation of oxalate within nanogap of scanning electrochemical microscope. J Am Chem Soc. 2018.  https://doi.org/10.1021/jacs.8b08900.Google Scholar
  14. 14.
    White HS, McKelvey K. Redox cycling in nanogap electrochemical cells. Curr Opin Electrochem. 2018;7:48–53.  https://doi.org/10.1016/j.coelec.2017.10.021.CrossRefGoogle Scholar
  15. 15.
    Marken F, Mathwig K. Nano- and micro-gap electrochemical transducers: novel benchtop fabrication techniques and electrical migration effects. Curr Opin Electrochem. 2018;7:15–21.  https://doi.org/10.1016/j.coelec.2017.10.004.CrossRefGoogle Scholar
  16. 16.
    Al-Kutubi H, Voci S, Rassaei L, Sojic N, Mathwig K. Enhanced annihilation electrochemiluminescence by nanofluidic confinement. Chem Sci. 2018;9:8946–50.  https://doi.org/10.1039/C8SC03209B.CrossRefGoogle Scholar
  17. 17.
    Rodríguez-López J, Shen M, Nepomnyashchii AB, Bard AJ. Scanning electrochemical microscopy study of ion annihilation electrogenerated chemiluminescence of rubrene and [Ru(bpy)3]2+. J Am Chem Soc. 2012;134:9240–50.  https://doi.org/10.1021/ja301016n.CrossRefGoogle Scholar
  18. 18.
    Amatore C, Bonhomme F, Bruneel JL, Servant L, Thouin L. Mapping dynamic concentration profiles with micrometric resolution near an active microscopic surface by confocal resonance Raman microscopy. Application to diffusion near ultramicroelectrodes: first direct evidence for a conproportionation reaction. J Electroanal Chem. 2000;484:1–17.  https://doi.org/10.1016/s0022-0728(00)00057-7.CrossRefGoogle Scholar
  19. 19.
    Wang Q, Rodríguez-López J, Bard AJ. Evaluation of the chemical reactions from two electrogenerated species in picoliter volumes by scanning electrochemical microscopy. ChemPhysChem. 2010;11:2969–78.  https://doi.org/10.1002/cphc.201000183.CrossRefGoogle Scholar
  20. 20.
    Valenti G, Scarabino S, Goudeau B, Lesch A, Jović M, Villani E, Sentic M, Rapino S, Arbault S, Paolucci F, Sojic N. Single cell electrochemiluminescence imaging: from the proof-of-concept to disposable device-based analysis. J Am Chem Soc. 2017;139:16830–7.  https://doi.org/10.1021/jacs.7b09260.CrossRefGoogle Scholar
  21. 21.
    Caspar JV, Meyer TJ. Photochemistry of Ru(bpy)32+. Solvent effects. J Am Chem Soc. 1983;10:5583–90.  https://doi.org/10.1021/ja00355a009.CrossRefGoogle Scholar
  22. 22.
    Mampallil D, Mathwig K, Kang S, Lemay SG. Redox couples with unequal diffusion coefficients: effect on redox cycling. Anal Chem. 2013;85:6053–8.  https://doi.org/10.1021/ac400910n.CrossRefGoogle Scholar
  23. 23.
    Singh PS, Lemay SG. Stochastic processes in electrochemistry. Anal Chem. 2016;88:5017–27.  https://doi.org/10.1021/acs.analchem.6b00683.CrossRefGoogle Scholar
  24. 24.
    Krause KJ, Mathwig K, Wolfrum B, Lemay SG. Brownian motion in electrochemical nanodevices. Eur Phys J Spec Top. 2014;223:3165–78.  https://doi.org/10.1140/epjst/e2014-02325-5.CrossRefGoogle Scholar

Copyright information

© The Nonferrous Metals Society of China 2019

Authors and Affiliations

  1. 1.Groningen Research Institute of Pharmacy, Pharmaceutical AnalysisUniversity of GroningenGroningenThe Netherlands
  2. 2.Bordeaux INP, Univ. Bordeaux, CNRS, UMR 5255, Site ENSCBPPessacFrance
  3. 3.Department of ChemistrySouth Ural State UniversityChelyabinskRussian Federation

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