The concentration of vanillymandelic acid (VMA) in urine
is closely
related with pheochromocytoma diagnosis. Thus, it is essential to
develop more accurate and convenient fluorescence sensing strategies
toward VMA. Until now, the design of double ratiometric detection
methods for VMA was still in the unexplored stage. In this work, novel
Ln3+-based metal–organic frameworks (QBA-Eu and
QBA-Gd0.875Eu0.125) possessing dual emission
peaks was fabricated successfully, which served as isomers of YNU-1
and exhibited more excellent water stability in fluorescence and structure
than the ones of YNU-1. The formation of the complex between QBA ligands
and VMA molecules via hydrogen bonds within QBA-Eu frameworks produced
a new emission band centered at 450 nm and resulted in the decline
of monomer emission intensity for QBA at 390 nm. Owing to the reduced
energy gap [ΔE (S1 – T1)], the antenna effect was hampered and luminescence of Eu3+ ions also decreased. The developed double ratiometric (I
615nm/I
475nm, I
390nm/I
475nm) fluorescence
sensors based on QBA-Eu and QBA-Gd0.875Eu0.125 possessed the advantages of fast response (4 min), low detection
limits (0.58 and 0.51; 0.22 and 0.31 μM), and wide linear ranges
(2–100 and 2–80 μM), which met the requirements
of pheochromocytoma diagnosis. We also applied them to determine VMA
in an artificial urine sample and diluted human urine sample and obtained
satisfactory results. They will become prospective fluorescence sensing
platforms for VMA.