A ratiometric sensor for selective detection of Hg²⁺ ions by combining second-order scattering and fluorescence signals of MIL-68(In)-NH₂

Ratio fluorescence has attracted much attention because of its self-calibration properties. However, it is difficult to obtain suitable fluorescent materials with well-resolved signals simultaneously under one excitation. In this work, we report a different strategy, using MIL-68(In)-NH₂ as both the fluorescence element and the scattered light unit, and coupling the fluorescence and the scattered light to construct the fluorescence and scattered light ratio system. Based on the optical properties and the second-order scattering (SOS) of the material nanoparticles, the synthesized MIL-68(In)-NH₂ can be used to realize the ratio detection of Hg²⁺. Because the scattering intensity of small particle MIL-68(In)-NH₂ is weak, SOS is not obvious. When Hg²⁺ is introduced the coordination reaction between the amino nitrogen atoms of MIL-68(In)-NH₂ and Hg²⁺ make the particles larger, resulting in the decrease of fluorescence and the enhancement of SOS. As a result, a novel Hg²⁺ ratiometric detection method is developed by using the dual signal responses of the fluorescence and scattering. Under the optimal conditions (pH = 6, reaction time 5 min, room temperature, and the maximum excitation wavelength 365 nm), the linear range of the method is 0-100 μM, and the detection limit is 5.8 nM (Ksv = 9.89 × 10⁹ M^-1). In addition, the probe is successfully used to evaluate Hg²⁺ in actual water samples. Compared with the traditional method of recording only the fluorescence signal, the proposed fluorescence-scattering method provides a new strategy for the design of ratiometric sensors.