Ratiometric Fluorescence Detection of Mg²⁺ Based on Regulating Crown-Ether Modified Annihilators for Triplet–Triplet Annihilation Upconversion

Abstract

Detection of magnesium ion has been of great significance considering its critical physiological activities. Herein, we report ratiometric fluorescence detection of Mg2+ with high sensitivity and selectivity based on triplet–triplet annihilation (TTA) upconversion for the first time. Crown-ether functionalized anthracene derivatives were synthesized, which bifunctionally acted as not only annihilators to construct TTA upconversion systems but also the recognition probes for Mg2+ based on the photoinduced electron transfer (PET) mechanism. Their photophysical properties with the absence and presence of Mg2+ were comprehensively studied. It was found that solvents strongly influenced the photophysical properties and Mg2+-responsiveness. TTA upconversion systems with PtOEP as the sensitizer were further established and investigated. It turned out PtOEP/9-AEC in DCM exhibited an excellent linear relationship (R 2 = 0.9979) between the intensity ratio (the integrated upconverted luminescence intensity (I UC) over the integrated downshifted phosphorescence intensity (I PL), I UC/I PL) and the concentration of Mg2+ under the excitation of 532 nm with a limit of detection value of 2.52 μM and a high selectivity to Mg2+. This work opened a new perspective of designs and applications of TTA-upconversion-based ratiometric fluorescence for ion detection.

Synthesis and Study of Crown Ether-Appended Tetraplatinum(II) Macrocylic Chemosensors for Cation Detection

“…The relationship of I / I 0 and [Mg 2+ ] presented better linearity ( R 2 = 0.9941) in CH 3 CN before reaching its saturation state. The detection concentration of Mg 2+ under excitation of 371 nm reached 10 –5 M, comparable to that of a 4′-(9-anthraceneacetamido)­benzo-15-crown-5 ether/PtOEP system reported in the literature …”

“…Upon a comparison of the structures of rectangles Pt1 and Pt2, it was found that the presence of benzyl −CH 2 − subunits of Pt2 made the size and binding property of the polyether ring obviously vary from that of Pt1. The 40 In conclusion, a class of novel molecular rectangles functionalized with crown ethers have been readily assembled using a phenanthro crown ether, biphenyl polyether-bridged bicarboxylate ligands, and a Pt-based binuclear molecular clap. We demonstrated that this new macrocyclic class of cation receptors can selectively bind and detect Na + and Mg 2+ cations via an emission spectral technique.…”

Density functional theory study of crown ether–magnesium complexes: from a solvated ion to an ion trap

“…Tian et al 28 proved that benzo[ b ]quinolizinium-benzo-15-crown-15 is selective with respect to NH 4 + , Li + , Na + , K + , and Ba 2+ . Ye and co-workers 29 investigated benzo-15-crown-5-anthracene-derivatives and showed its high sensitivity and selectivity with respect to NH 4 + , Li + , Na + , K + , Zn 2+ , Pb 2+ , Mn 2+ , Cd 2+ , and Ca 2+ . Marraccini et al 30 analyzed diaza-18-crown-6-hydroquinoline derivatives, whereas Zahedi and Ghasemi 31 studied 18-crown-6 for extracting magnesium from seawater, but were not satisfied with its selectivity.…”

NaBH4-Mediated Co-Reduction Synthesis of Glutathione Stabilized Gold/Silver Nanoclusters for Detection of Magnesium Ions

“…Mg 2+ is the most abundant intracellular divalent cation and plays a significant physiological role in numerous cellular processes [16]. Moreover, excessive Mg 2+ ingestion may lead to pathological lesions in the cardiovascular, nervous, urinary, and hematopoietic systems [17,18]. However, most methods for detecting Mg 2+ still need expensive instrumentations, such as atomic absorption spectroscopy (AAS) and inductively coupled plasma-mass spectrometry (ICP-MS), and complex organic fluorescent probes [18][19][20].…”