Abstract

Serotonin (5-HT) is an important neurotransmitter and also a biomarker closely related to a variety of neurodegenerative diseases. In this work, a dual-emissive europium-copper cluster, as an artificial ultra-small-sized luminescent enzyme (clusterzyme), was specially designed and synthesized for the catalysis and sensing of 5-HT. This clusterzyme is catalysis and luminescence-sensing all-in-one, not only highly tyrosinase-active but also ultra-sensitive for 5-HT, and can sense 5-HT as low as 0.5 nM through the enhanced luminescence of Eu3+. The enzymatic detection for 5-HT is outstandingly specific even if in the presence of similar neurotransmitters such as dopamine (DA), epinephrine (EP) and nomethylephrine (NE). The prepared clusterzyme was found to be able to catalyze the oxidation of 5-HT like tyrosinase to generate a neurotoxic product of tryptamine-4, 5-dione. Mechanism of catalysis and sensing of the clusterzyme for 5-HT have been proposed and demonstrated. Such a luminescent clusterzyme can be used to replace the combination of natural enzymes and chromogenic agents currently widely used in enzyme-based assays, also offering a promising prospect for measuring neurotransmitters in situ and visually due to the unique advantage of its ultra-small-size allowing passage through the blood-brain barrier.

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