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. 2024 Sep 9;13(17):2855.
doi: 10.3390/foods13172855.

Enhanced Sensitivity and Accuracy of Tb3+-Functionalized Zirconium-Based Bimetallic MOF for Visual Detection of Malachite Green in Fish

Affiliations

Enhanced Sensitivity and Accuracy of Tb3+-Functionalized Zirconium-Based Bimetallic MOF for Visual Detection of Malachite Green in Fish

Yue Zhou et al. Foods. .

Abstract

The ratiometric fluorescent probe UiO-OH@Tb, a zirconium-based MOF functionalized with Tb3+, was synthesized using a hydrothermal method. This probe employs the fluorescence resonance energy transfer (FRET) mechanism between Tb3+ and malachite green (MG) for the double-inverse signal ratiometric fluorescence detection of MG. The probe's color shifts from lime green to blue with an increasing concentration of MG. In contrast, the monometallic MOFs' (UiO-OH) probe shows only blue fluorescence quenching due to the inner filter effect (IFE) after interacting with MG. Additionally, the composite fluorescent probe (UiO-OH@Tb) exhibits superior sensitivity, with a detection limit (LOD) of 0.19 μM, which is significantly lower than that of the monometallic MOFs (25 μM). Moreover, the content of MG can be detected on-site (LOD = 0.94 μM) using the RGB function of smartphones. Hence, the UiO-OH@Tb probe is proven to be an ideal material for MG detection, demonstrating significant practical value in real-world applications.

Keywords: FRET; UiO-OH@Tb; ratiometric fluorescence; smartphone.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Scheme 1
Scheme 1
Schematic illustration for fluorometric detection of MG (malachite green) by UiO-OH@Tb.
Figure 1
Figure 1
(A) SEM image of UiO-OH@Tb nanosheets. (B) SEM image of UiO-OH nanosheets. (C) EDS of UiO-OH@Tb. (D) PXRD of UiO-OH, UiO-OH@Tb, and UiO-OH@Tb + MG. (E) FTIR spectrum of UiO-OH@Tb, UiO-OH, and BDC-OH. (F) The comparison of XPS spectra of UiO-OH (blue) and UiO-OH@Tb (green).
Figure 2
Figure 2
(A) Emission spectra of UiO-OH (blue) and UiO-OH@Tb (green); inset is the fluorescence image of UiO-OH and UiO-OH@Tb under 254 nm UV light. (B) Mechanism of energy transfer between BDC-OH and Tb3+.
Figure 3
Figure 3
(A) The 3D fluorescence spectra of UiO-OH@Tb in response to MG (0–200 μM). (B) The linear relationship between F450/F548 and the concentration of MG (0–200 μM) (Inset: fluorescence images of UiO-OH@Tb at 0–200 μM MG under 254 nm UV lamp). (C) CIE chromaticity diagram of UiO-OH@Tb treated with different concentrations of MG (0–200 μM) under 254 nm UV irradiation. (D) Relative PI (photoluminescence) (F450/F548) variation in UiO-OH@Tb with time after the addition of 100 μM MG; inset is a photograph of the UiO-OH@Tb suspension under 254 nm UV (ultraviolet–visible) light irradiation before and after the addition of MG. (E) Comparison of the response of different types of interfering antibiotics (100 μM) to probes (1 mg/mL). (F) Effect of interfering substances on the MG assay.
Figure 4
Figure 4
XRD patterns of UiO-OH@Tb (A) and UiO-OH (A’) before and after immersion in 100 μM MG (malachite green). Excitation and emission spectra of UiO-OH@Tb (B) and UiO-OH (B’) with UV absorption spectra of MG. Fluorescence lifetime of UiO-OH@Tb (C), UiO-OH (C’) before and after the presence of MG.
Figure 5
Figure 5
(A) XPS spectra of Tb 3d region before and after MG addition to UiO-OH@Tb. (B) FTIR spectra of UiO-OH@Tb before and after the addition of MG. (C) Schematic diagram of fluorescence change mechanism.
Figure 6
Figure 6
Smartphone-assisted sensing platform based on UiO-OH@Tb probe for MG on-site detection.

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