Electrogenerated chemiluminescence (ECL) is not only an aesthetic phenomenon, but also of fundamental interest in analytical chemistry Several experiments are presented to introduce students to the capacity of ECL on the basis of tris(2, 2’-bipyridyl)ruthenium (II) (Ru(bpy)32+) with different coreactants.. First, we summarize some spectroscopic and electrochemical features of Ru(bpy)32+ that are important concerning ECL. Easily implemented experimental set-ups are presented, which show the correlation between ECL-intensity and cyclic voltammetry (CV) for different Ru(bpy)32+ / coreactant systems. The time-dependence of the ECL-decay is measured on a millisecond time-scale with a conventional data acquisition system. Finally, we present an ECL detector that can be used in HPLC as an alternative to adsorption and fluorescence detection.
| [1] | J. W. Birks, Chemiluminescence and Photochemical Reaction in Chromatography, VCH, New York (1989). |
| [2] | Miao, W., Choi, J.P., Bard, A. J., Electrogenerated Chemiluminescence 69: The Tris(2,2'-bipyridine)ruthenium(II), (Ru(bpy)32+)/Tri-n-propylamine (TPrA) System Revisited - A New Route Involving TPrA•+ Cation Radicals, J. Am. Chem. Soc., 124(48), 14478-14485 (2002).View Article PubMed |
| [3] | A. Kapturkiewicz, Electrogenerated chemiluminescence from the tris(2,2'-bipyridine)ruthenium(II) complex, Chem. Phys. Lett. 236, 389-394 (1995).View Article |
| [4] | D. M. Hercules, F. E. Lytle, Chemiluminescence from reduction reactions, J. Am. Chem. Soc., 88, 4795-4796 (1966).View Article |
| [5] | M. M. Richter, Electrochemiluminescence (ECL), Chem. Rev. 104, 3003-3036 (2004).View Article PubMed |
| [6] | S. Parveen, M. S. Aslam, L. Hu, G. Xu, Electrogenerated Chemiluminescence. Protocols and Applications, Springer, Heidelberg (2013).View Article |
| [7] | A. J. Bard (Ed.), Electrogenerated Chemiluminescence, Marcel Dekker, New York (2004).View Article |
| [8] | R. M. Wightman, S. P. Forry, R. Maus, D. Badocco, P. Pastore, Rate-determining step in the electrogenerated chemiluminescence from tertiary amines with tris(2,2'-bipyridine)ruthenium(II), J. Phys. Chem. B, 108, 19119-19125 (2004).View Article |
| [9] | W. Jackson, D. R. Bobbitt, Chemiluminescence detection of amino acids using in situ generation Ru(bpy)33+, Anal. Chim. Acta, 285, 309-320 (1994).View Article |
| [10] | S.N. Brune, D. R. Bobbitt, Role of electron-donating/withdrawing character, pH, and stoichiometry on the chemiluminescent reaction of tris(2,2'-bipyridine)ruthenium(II) with amino acids, Anal. Chem. 64, 166-170 (1992).View Article |
| [11] | D. R. Skotty, W-Y. Lee, T. A. Nieman, Determination of dansyl amino acids and oxalate by HPLC with electrogenerated Chemiluminescence detection using tris(2,2’-bipyridyl)ruthenium (II) in the mobile phase, Anal. Chem. 68(9), 1530-1535 (1996).View Article PubMed |
| [12] | W-Y. Lee, T. A. Nieman, Determination of dansyl amino acids using tris(2,2’-bipyridyl)ruthenium (II) chemiluminescence for post column reaction detection in high-performance liquid chromatography, J. Chromatogr. A, 659, 111-118 (1994).View Article |
| [13] | J. S. Riden, G. J. Klopf, T. A. Nieman, Determination of glyphosate and related compounds using HPLC with tris(2,2'-bipyridine) ruthenium(II) electrogenerated chemilumines-cence detection, Anal. Chim. Acta, 341, 195-204 (1997).View Article |
| [14] | J. L. Adock, N. W. Barnett, R. D. Gerardi, C. E. Lenehan, S. W. Lewis, Determination of glyphosate mono-isopropylamine salt in process samples using flow injection analysis with tris(2,2'-bipyridine)ruthenium(II) chemiluminescence detection, Talanta, 64, 534-537 (2004).View Article PubMed |
| [15] | Y. Zu, A. J. Bard, Electrogenerated chemiluminescence. 66. The role of direct coreactant oxidation in the Ruthenium tris[2,2’)bipyridyl/tripropylamine system and the effect of halide ions on the emission intensity, Anal. Chem. 72, 3223-3232 (2000).View Article PubMed |
| [16] | K. Kalyanasundaram, Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium (II) and its analogues, Coord. Chem. Rev. 46, 159-244 (1982).View Article |
| [17] | C-T. Lin, N. Sutin, Quenching of the luminescence of the tris(2,2'-bipyridine) complexes of ruthenium(II) and osmium(II). Kinetic considerations and photogalvanic effects, J. Phys. Chem. 80(2) 97-105 (1976).View Article |
| [18] | R. D. Gerardi, N. W. Barnett, P. Jones, Two chemical approaches for the production of stable solutions of tris(2,2'-bipyridine)ruthenium(III) for analytical chemiluminescence, Anal. Chim. Acta, 388, 1-10 (1999).View Article |
| [19] | J. Jin, F. Takahashi, T. Kaneko, T. Nakamura, Characterization of electrochemiluminescence of tris(2,2'-bipyridine)ruthenium(II) with glyphosate as coreactant in aqueous solution, Electrochim. Acta, 55, 5532-5537 (2010).View Article |
| [20] | H-Y. Chuang, T-P. Hong, C-W. Whang, A simple and rapid screening method for glyphosate in water using flow-injection with electrochemiluminescence detection, Anal. Methods, 5, 6186-6191 (2013).View Article |
| [21] | H-Y Chiu, Z-Y. Lin, H-L. Tu, C-W. Whang, Analysis of glyphosate and aminomethyphosphonic acid by capillary electrophoresis with electroluminescence detection, J. Chromatogr. A 1177, 195-198 (2008).View Article PubMed |
| [22] | Y. Hu, A. Maclennan, T. K. Sham, Electronic structure and optical luminescence studies of Ru based OLED compounds, J. Luminesc. 166, 143-147 (2015).View Article |
| [23] | H. Sevian, S. Müller, H. Rudmann, M. F. Rubner, Using organic light-emitting electrochemical thin-film device to teach material science, J. Chem. Educ. 81, 1620-1623 (2004).View Article |
| [24] | N. Aristov, A. Habekost, Cyclic Voltammetry - A Versatile Electrochemical Method Investigating Electron Transfer Processes, World Journal of Chemical Education. 3(5), 115-119 (2015). |
| [25] | Börjesson, E. and Torstensson, L, New methods for determination of glyphosate and (aminomethyl)phosphonic acid in water and soil, J. Chromatogr., 886, 207-216 (2000).View Article |
