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In this work, a novel fluorescence method for the detection of phosphate anions (PO43-) was developed based on porphyrin metalation. Through catalysis by G-quadruplex (G4), Cu2+ could insert into the porphyrins to quench their fluorescence. G4 simultaneously improved the fluorescence of the porphyrins but not that of Cu2+-porphyrin. In the absence of PO43-, the porphyrins were metallized by Cu2+, and no fluorescence was observed. In the presence of PO43-, PO43- could coordinate with Cu2+ to prevent porphyrin metalation. Free porphyrin