Supplementary Material (ESI) for Annual Reports C This journal is (c) The Royal Society of Chemistry 2007

Table S4. High Performance Liquid Chromatography – ECL systems. Analyte Luminophore Limit of Comments Reference(s) /Coreactanta Detection 2+ Amitryptyline Ru(bpy)3 1 nM 266 2+ Ascorbic Acid Ru(bpy)3 0.1 µM 492 2+ Atenolol Ru(bpy)3 0.5 µM 267 2+ Benzylamine Ru(bpy)3 0.56 µM 493 2+ Citric Acid Ru(bpy)3 0.14 µM 494 2+ Clomipramine Ru(bpy)3 5.3 nM 266 2+ Cobalt emetine Ru(bpy)3 1 nM 495 dithiocarbamate metal complex 2+ Copper emetine Ru(bpy)3 1 nM 495 dithiocarbamate metal complex 2+ Dehydroascorbic Ru(bpy)3 0.1 µM 492 Acid 2+ Ru(bpy)3 1.1 nM 266 2+ Diethanolamine Ru(bpy)3 1.25 µM Derivatization by 496 epichlorohydrin to tertiary amines 2+ 2,5-dimethyl-2,4- Ru(bpy)3 0.03 µM 497 hexadiene 2+ Disopyramide Ru(bpy)3 0.44 µM 498 2+ Domoic Acid Ru(bpy)3 1.3 nM 499 2+ Doxepin Ru(bpy)3 1.6 nM 266 2+ Ethanol Ru(bpy)3 2 nM Derivatization with 500 3- (diethylamino)propi onic acid 2+ Gallic Acid Ru(bpy)3 /TP 9 nM Quenching of Ru 73 2+ rA Ru(bpy)3 /TPrA ECL 2+ D-gluconic Acid Ru(bpy)3 0.025 M 494 2+ Glycine Ru(bpy)3 2 µM Amino acids 501 electrochemically oxidized to oxalate. 2+ Glycine Ru(bpy)3 0.338 µM Derivatized with 502 divinylsulfone 2+ Heteropolyacids Ru(bpy)3 ---- 503 2+ Histidine Ru(bpy)3 0.8 µM Derivatized with 502 divinylsulfone 2+ -5 Hydroxyproline Ru(bpy)3 3 x 10 M Rat urine. 504 2+ Hydroxyproline Ru(bpy)3 ---- Serum of bedridden 505 elderly 2+ 2,4-hexadiene Ru(bpy)3 0.05 µM 497 2+ Ibuprofen Ru(bpy)3 0.9 nM Derivatization with 506 2-(2-aminomethyl)- Supplementary Material (ESI) for Annual Reports C This journal is (c) The Royal Society of Chemistry 2007

1-methylpyrrolidine and N-(3-amino- propyl)pyrrolidine. 2+ Ru(bpy)3 2.8 nM 266 2+ Malic Acid Ru(bpy)3 0.16 µM 494 2+ Maprotiline Ru(bpy)3 0.75 nM 266 2+ Matrine Ru(bpy)3 0.24 nM 507 2+ Metoprolol Ru(bpy)3 8 nM 267 2+ Monoethanolamine Ru(bpy)3 1.5 µM Derivatization by 496 epichlorohydrin to tertiary amines 2+ -11 Myristic Acid Ru(bpy)3 5 x 10 M Derivatization with 508 3-isobutyl-9,10- dimethoxy- 1,3,4,6,7,11b- hexahydro-2H- pyrido[2,1- a]isoquinoline-2- ylamine. 2+ Myristic Acid Ru(bpy)3 1.4 nM Derivatization with 504 2-(2-aminomethyl)- 1-methylpyrrolidine and N-(3-amino- propyl)pyrrolidine. 2+ Ru(bpy)3 3.2 nM 509 2+ Ru(bpy)3 0.6 nM 266 2+ Ofloxacin Ru(bpy)3 ~28 µM 510 2+ Oxalate Ru(bpy)3 ---- 511 2+ Ru(bpy)3 1.6 nM 512 2+ Ru(bpy)3 0.55 µM 493 2+ Phenylalanine Ru(bpy)3 10 nM Derivatized with 502 divinylsulfone 2+ -8 Phenylalanine Ru(bpy)3 5 x 10 M Amino acids 501 electrochemically oxidized to oxalate. 2+ -8 Ru(bpy)3 6.5 x 10 M 513 2+ -11 Phenylbutylic Acid Ru(bpy)3 6 x 10 M Derivatization with 508 3-isobutyl-9,10- dimethoxy- 1,3,4,6,7,11b- hexahydro-2H- pyrido[2,1- a]isoquinoline-2- ylamine. 2+ Proline Ru(bpy)3 ---- 511 2+ Proline Ru(bpy)3 ---- Serum of bedridden 514 Elderly 2+ 2-propanone Ru(bpy)3 1.5 nM Derivatized with 515 Supplementary Material (ESI) for Annual Reports C This journal is (c) The Royal Society of Chemistry 2007

methylmalonic acid. 2+ Sophoranol Ru(bpy)3 0.27 nM 507 2+ Sophocarpine Ru(bpy)3 0.4 nM 507 2+ Sophoridine Ru(bpy)3 0.12 nM 507 2+ Sparteine Ru(bpy)3 0.125 nM 516 2+ Tartaric Acid Ru(bpy)3 0.41 µM 494 2+ -8 Threonine Ru(bpy)3 5 x 10 M Amino acids 501 electrochemically oxidized to oxalate. 2+ Tributylamine Ru(bpy)3 0.465 nM 517 2+ Triethanolamine Ru(bpy)3 2 µM Derivatization by 496 epichlorohydrin to tertiary amines 2+ Triethylamine Ru(bpy)3 5.4 nM 517 2+ TPrA Ru(bpy)3 0.61 nM 517 2+ Tryptophan Ru(bpy)3 0.98 µM 493 2+ Trimipramine Ru(bpy)3 2.7 nM 266 2+ Tetramethylthiuram Ru(bpy)3 0.3 µM 518 disulfide 2+ Valine Ru(bpy)3 7 nM Derivatized with 502 divinylsulfone 2+ -8 Yohimbine Ru(bpy)3 8.5 x 10 M 519 aIf no coreactant is listed, then the analyte acted as the ECL coreactant.