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5,10,15,20-Tetrakis(4-sulfonatophenyl)-21H,23H-porphine manganese(III) chloride is a metal–porphyrin. During luminol chemiluminescence reactions, it can act as a highly sensitive catalyst. On-line chemiluminescence detection with capillary electrophoresis of the product was investigated and the detection limit was determined to be 361 amol and 8.1 × 10^–9?mol L^–1.