Quenched peroxyoxalate chemiluminescence detection in aqueous liquid chromatographic separations |
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Authors: | P van Zoonen H Bock C Gooijer NH Velthorst RW Frei |
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Institution: | Department of General and Analytical Chemistry, Free University, De Boelelaan 1083, 1081 HV Amsterdam The Netherlands |
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Abstract: | Several analytes, such as bromide, iodide, sulphite, nitrite, substituted anilines and organosulphur compounds cause quenching of peroxyoxalate chemiluminescence. This phenomenon, quenched peroxyoxalate chemiluminescence, can be used as a method of detection for liquid chromatography. The potential of quenched chemiluminescence is discussed, with special attention give to its compatibility with aqueous separation systems. An immobilized fluorophore, 3-aminofluoranthene on controlled pore glass, is packed in the detector cell. Liquid-state studies show that the influence of both the nature and concentration of the fluorophore is small, which indicates a more complicated mechanism of the chemiluminescence reaction than previously assumed. It is shown that bis(2-nitrophenyl)oxalat is a more suitable oxalate for quenched chemiluminescence detection than bis(2,4,6-trichlorophenyl) oxalate. This is demostrated for ion-chromatography of bromide and iodide and the aqueous reversed-phase separation of organosulphur compounds. Detection limits in the low nanogram and sub-nanogram region are reported for the above compounds. When an electronic inverter was used, calibration curves were linear over a concentration range of 2–3 decades. The method is quite selective and can be applied to relatively complex matrices without sample pretreatment. |
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