Evaluation of use of tris(2,2'-bipyridyl)ruthenium(III) as a chemiluminescent reagent for quantitation in flowing streams

Three approaches are comparatively evaluated for the use of tris(2,2'-bipyridil)ruthenium(II), Ru(bpy) 3 3+ , as a chemiluminescent reagent in flow streams: (1) external generation of the reactive Ru(bpy) 3 3+ oxidation state followed by contact with the analyte, (2) in situ generation of the Ru(bpy) 3 3+ species from a solution mixture of the analyte and the Ru(bpy) 3 2+ species as it passes through the reaction/observation cell, and (3) in situ generation of the Ru(bpy) 3 3+ species from the Ru(bpy) 3 2+ species immobilized within the observation cell. Oxalate and proline were used as representative analytes for comparison of these three modes with respect to the influence of experimental variables (reagent concentration, flow rate, pH) and resulting analytical performance (detection limit, working range, measurement precision). Additionally, a comparison was made of the relative ECL intensities obtained for a variety of analytes including oxidate, amino acids, aliphatic amines, peptides, and NADH. We find that each approach has its unique set of strengths and weaknesses. The external generation mode yields the most intense emission, especially for simple aliphatic amines, but working curves have poor linearity, and emission intensities have a large dependence on solution flow rate. The in situ immobilized approach results in lower intensities but yields the widest linear dynamic ranges, is most conservative of reagent, and has a particular sensitivity advantage for proline and NADH determinations. The in situ solution mode is superior for the detection of amino acids such as hyptophan, 5-hydroxyhyptophan, and histidine and has time, convenience, and reliability advantages

[1]  D. R. Bobbitt,et al.  Chemiluminescent detection of amino acids using in situ generated Ru(bpy)3+3 , 1994 .

[2]  T. Nieman,et al.  Determination of dansyl amino acids using tris(2,2′-bipyridyl)ruthenium(II) chemiluminescence for post-column reaction detection in high-performance liquid chromatography , 1994 .

[3]  T. Nieman,et al.  Glucose quantitation using an immobilized glucose dehydrogenase enzyme reactor and a tris(2,2′-bipyridyl) ruthenium(II) chemiluminescent sensor , 1993 .

[4]  N. Danielson,et al.  Chemiluminescence reaction of thiazide compounds with tris(2,2′-bipyridine)ruthenium(III) , 1993 .

[5]  K. Uchikura,et al.  Electrochemiluminescence Detection of Primary Amines Using Tris(bipyridine)ruthenium(III) after Derivatization with Divinylsulfone , 1993 .

[6]  T. Nieman,et al.  Chemiluminescence detection using regenerable tris(2,2'-bipyridyl)ruthenium(II) immobilized in Nafion. , 1992, Analytical chemistry.

[7]  Donald R. Bobbitt,et al.  Role of electron-donating/withdrawing character, pH, and stoichiometry on the chemiluminescent reaction of tris(2,2'-bipyridyl)ruthenium(III) with amino acids , 1992 .

[8]  K. Uchikura,et al.  Chemiluminescence of Tryptophan with Electrogenerated Tris(2,2′-bipyridine)ruthenium(III) , 1991 .

[9]  D. R. Bobbitt,et al.  Effect of pH on the reaction of tris(2,2'-bipyridyl)ruthenium(III) with amino-acids: Implications for their detection. , 1991, Talanta.

[10]  N. Danielson,et al.  High-Performance Liquid Chromatography of Clindamycin Antibiotics using Tris(Bipyridine)- ruthenium(III) Chemiluminescence Detection , 1990 .

[11]  A. Tudos,et al.  The transport of catechols through perfluorinated cation-exchange films on electrodes , 1990 .

[12]  N. Danielson,et al.  Chemiluminescence Detection of Amino Acids, Peptides, and Proteins Using Tris-2,2′-Bipyridine Ruthenium (III) , 1990 .

[13]  N. Danielson,et al.  Determination of erythromycin in tablets and capsules using flow injection analysis with chemiluminescence detection. , 1989, Journal of pharmaceutical and biomedical analysis.

[14]  N. Danielson,et al.  Generation of chemiluminescence upon reaction of aliphatic amines with tris(2,2'-bipyridine)ruthenium(III) , 1987 .

[15]  D. Ege,et al.  Electrogenerated chemiluminescent determination of Ru(bpy)3(2+) at low levels. , 1984, Analytical chemistry.

[16]  A. Bard,et al.  Electrogenerated chemiluminescent determination of oxalate. , 1983, Analytical chemistry.

[17]  I. Rubinstein,et al.  Electrogenerated chemiluminescence. 37. Aqueous ecl systems based on tris(2,2'-bipyridine)ruthenium(2+) and oxalate or organic acids , 1981 .

[18]  Allen J. Bard,et al.  Electrogenerated chemiluminescence. IX. Electrochemistry and emission from systems containing tris(2,2'-bipyridine)ruthenium(II) dichloride , 1972 .