The ratiometric detection of the biomarker Ap5A for dry eye disease and physiological temperature using a rare trinuclear lanthanide metal–organic framework

Abstract

Urgent demand for the prevention and diagnosis of physiological diseases is driving the development of biomarkers and physiological temperature fluorometric sensors. In this paper, a rare trinuclear lanthanide metal–organic framework (MOF), [(CH₃)₂NH₂][Eu₃(μ₃-OH)(2,6-NDC)₃(HCOO)₃]·(solv)_x (Eu(2,6-NDC), where 2,6-H₂NDC = 2,6-naphthalenedicarboxylic acid) was synthesized using reticular chemistry via reducing the symmetry of the organic ligand from axisymmetric 1,4-naphthalenedicarboxylic acid (1,4-H₂NDC) to non-axisymmetric 2,6-H₂NDC. Eu(2,6-NDC) shows exceptional chemical and thermal stability in acid–base solutions, PBS solution, and boiling water, and even under an air atmosphere up to 300 °C. As-synthesized Eu(2,6-NDC) exhibits ratiometric detection abilities for P¹,P⁵-di(adenosine-5′) pentaphosphate (Ap5A), for use as a biomarker of dry eye disease, with a limit of detection (LOD) of 0.031 μM, as well as excellent anti-interference properties. As far as is known, it is the first Ap5A sensor based on MOFs. In addition, the results show that the ratiometric parameters of co-doped Eu_0.001Gd_0.999(2,6-NDC) deliver a good linear luminescence response to physiological temperatures (20–60 °C) with high sensitivity.