Responsive methylene blue release from lanthanide coordination polymer for label-free, immobilization-free and sensitive electrochemical alkaline phosphatase activity assay

Abstract

Alkaline phosphatase (ALP) is an important enzyme related to many clinical diseases and also widely used as a labeling enzyme for immunoassay. Herein, a new electrochemical sensing strategy for ALP activity was proposed, which was based on the ALP-triggered methylene blue (MB) release from a lanthanide coordination polymer and successive penetration through a self-assembled dodecanethiol monolayer for electrochemical response. The supramolecular lanthanide coordination polymer was constructed by using guanine monophosphate (GMP) and Tb³⁺ as the ligand and the metal ion, respectively, and the encapsulated MB as the signal molecule. ALP catalyzed the cleavage of the phosphate group from the GMP ligand and disrupted the coordination polymer network to release abundant MB molecules for electrochemical responses related to ALP activity. The obtained lanthanide coordination polymers were well characterized by various techniques. The fabricated electrochemical sensor for ALP activity assay shows distinct advantages such as being one-step, label-free, immobilization-free and highly sensitive. The detection limit toward ALP activity was down to 0.5 U L⁻¹. With the aid of a MB enrichment process on the modified electrode before measurement, the detection limit could be further improved to 0.1 U L⁻¹. Moreover, the assay method could be applied for ALP detection in complex matrixes such as human serum and also for efficient inhibitor evaluation. Thus, the current study provides a new pathway to the fabrication of a coordination polymer-based electrochemical sensing platform for applications in disease diagnosis and drug discovery.