Lanthanide coordination polymers as luminescent laccase mimics for ratiometric sensing of dopamine

Abstract

Some metal ions, with inner enzyme-like catalytic activity, could be doped into lanthanide coordination polymers (Ln CPs) through coordination, which has been proved as a facile strategy to prepare the luminescent nanozymes. In this study, Cu-doped Ln CPs with laccase-mimic activity and double luminescence were rationally designed and synthesized by self-assembly of guanine monophosphate (GMP), 2-aminoterephthalic acid (ATA), Cu²⁺ and Tb³⁺ in buffer solution at room temperature. The obtained probes Tb/Cu-GMP/ATA CPs not only emitted green fluorescence of Tb³⁺ and blue fluorescence of ATA simultaneously under irradiation at the same wavelength, but also processed enhanced laccase-like activity for catalyzing the oxidation of phenolic substrates. Upon dopamine (DA), the probes catalyzed the oxidation of DA to polydopamine (PDA), which effectively quenched the fluorescence of Tb³⁺ due to the internal filtration effect. Based on this, a ratiometric fluorescent sensor for DA was constructed accordingly, and the corresponding fluorescence intensity ratio of Tb³⁺ to ATA (F₅₄₇/F₄₂₇) was linearly correlated with the DA concentration in the range of 1 to 400 μM, with a detection limit of 0.44 μM. Besides, this sensor could be used to detect DA in human serum samples with good recovery, which results were highly consistent with that of HPLC method. The constituent and luminescence tunability, as well as the extraordinarily facile synthesis, made Ln CPs a potential platform for designing and preparing the integrated multifunctional probe for special target in sensing applications.