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CN-122016965-A - Fluorescence visualization-photoelectrochemistry dual-mode PFOS sensor based on molecular nanocages, preparation method and application

CN122016965ACN 122016965 ACN122016965 ACN 122016965ACN-122016965-A

Abstract

The invention discloses a fluorescence visualization-photoelectrochemistry dual-mode PFOS sensor based on a molecular nano cage, and a preparation method and application thereof, and belongs to the technical field of environmental pollutant detection. Comprises a substrate, a titanium dioxide TiO 2 layer, a lead coordination beta-cyclodextrin molecule nano cage MNCs layer which are sequentially arranged from bottom to top, the titanium dioxide TiO 2 layer and the lead coordination beta-cyclodextrin molecule nano cage MNCs layer form a TiO 2 /MNCs heterostructure. The electron transfer of the TiO 2 /MNCs interface is hindered through the combination of PFOS and the host-guest of MNCs, so that the dependence of photocurrent concentration is reduced, and the PFOS limits the intramolecular movement of the MNCs, inhibits non-radiative decay and enhances fluorescence emission. The sensor provided by the invention has ultrahigh sensitivity, wide linear range, excellent selectivity and visual fluorescence response capability, and can be applied to dual-mode detection of PFOS in complex water.

Inventors

  • Yan Guangkui
  • PAN TIANLONG
  • ZHANG HANHUA
  • HU XINYUE

Assignees

  • 温州医科大学附属第二医院（温州医科大学附属育英儿童医院）
  • 温州医科大学附属第一医院
  • 上海交通大学医学院附属新华医院

Dates

Publication Date
20260512
Application Date
20260129

Claims (10)

  1. 1. The fluorescent visualization-photoelectrochemical dual-mode PFOS sensor based on the molecular nanocages is characterized by comprising a substrate, a titanium dioxide TiO 2 layer and a lead coordination beta-cyclodextrin molecular nanocages MNCs layer which are sequentially arranged from bottom to top, wherein the titanium dioxide TiO 2 layer and the lead coordination beta-cyclodextrin molecular nanocages MNCs layer form a TiO 2 /MNCs heterostructure.
  2. 2. The molecular nanocage-based fluorescence visualization-photoelectrochemical dual-mode PFOS sensor of claim 1, wherein said substrate is an ITO conductive glass substrate.
  3. 3. A method of manufacturing a molecular nanocage-based fluorescence visualization-photoelectrochemical dual-mode PFOS sensor as recited in claim 1, comprising the steps of: step 1, adding beta-cyclodextrin and PbCl 2 into deionized water, adding a cyclohexanol and triethylamine mixed reaction solvent, placing the mixture into a reaction kettle for reaction, cooling, filtering and washing to obtain lead coordination beta-cyclodextrin molecular nanocage MNCs solution; step 2, dropwise adding TiO 2 nano particle suspension on the ITO glass substrate, drying and annealing to obtain an ITO/TiO 2 photoelectrode; And 3, dripping lead coordination beta-cyclodextrin molecule nano cage MNCs solution on the surface of an ITO/TiO 2 photoelectrode, and forming the sensor with the TiO 2 /MNCs heterostructure through hydrogen bond interaction among materials.
  4. 4. The molecular nanocage-based fluorescence visualization-photoelectrochemical dual-mode PFOS sensor of claim 3, wherein in step 1, the molar ratio of beta-cyclodextrin to PbCl 2 is 1:7-9, and in step 1, the volume ratio of cyclohexanol to triethylamine is 1:0.9-1.1.
  5. 5. The molecular nanocage-based fluorescence visualization-photoelectrochemical dual-mode PFOS sensor of claim 4, wherein ethanol and water are used for washing in step 1.
  6. 6. The molecular nanocage-based fluorescence visualization-photoelectrochemical dual-mode PFOS sensor according to claim 5, wherein the reaction temperature in the reaction kettle in step 1 is 100-120 ℃ and the reaction time is 36-60 hours.
  7. 7. The molecular nanocage-based fluorescence visualization-photoelectrochemical dual-mode PFOS sensor of claim 6, wherein the concentration of the TiO 2 nanoparticle suspension in step 2 is 9-11 mg/mL.
  8. 8. The molecular nanocage-based fluorescence visualization-photoelectrochemical dual-mode PFOS sensor of claim 7, wherein the concentration of the lead coordination beta-cyclodextrin molecular nanocage MNCs solution in step 3 is 1.8-2.2 mg/mL.
  9. 9. Use of a molecular nanocage-based fluorescence visualization-photoelectrochemical dual-mode PFOS sensor according to claim 1 in PFOS detection.
  10. 10. The use according to claim 9, characterized in that it comprises: In the PEC mode, the electron transfer of the TiO 2 interface is hindered through the main and guest actions of PFOS and MNCs, so that photocurrent is gradually weakened along with the increase of PFOS concentration; In the fluorescent mode, PFOS limits the intramolecular motion of MNCs, suppressing non-radiative decay channels, resulting in an increase in fluorescence intensity.

Description

Fluorescence visualization-photoelectrochemistry dual-mode PFOS sensor based on molecular nanocages, preparation method and application Technical Field The invention relates to the technical field of environmental pollutant detection, in particular to a dual-mode PFOS sensor based on the synergistic effect of Molecular Nano Cages (MNCs) and TiO 2 photoelectrodes and a preparation method thereof. Background Persistent Organic Pollutants (POPs) are known for their environmental persistence, bioaccumulation, and long-range atmospheric transport capabilities, which together pose a global threat to the ecosystem and human health. Such materials, including pesticides, industrial compounds and unintentionally produced by-products, have a very high resistance to degradation and may still produce toxic effects even at very low concentrations. Among them, perfluorooctane sulfonate (PFOS) is a typical representative of perfluoro and polyfluoroalkyl substances (PFAS), and is receiving increasing regulatory attention due to its wide detection in water systems and its strong correlation with health hazards such as bone health, immunotoxicity, endocrine disruption, and the like. Despite the increasing rigorous regulatory measures, perfluorooctane sulfonate (PFOS) is still widely found in a wide variety of industrial and consumer products. Traditional detection technologies such as liquid chromatography-tandem mass spectrometry (LC-MS/MS) have excellent sensitivity, but rely on expensive instruments and complex pretreatment processes, so that on-site real-time monitoring is difficult to realize in a resource-limited environment. While portable immunoassays are simple to operate, they often cross-react with PFAS substances of similar structure, such as perfluorooctanoic acid (PFOA), resulting in false positive signals in complex sample matrices. More notably, the current majority of sensing platforms cannot meet the nanogram/upgrade detection standard required by new regulations, and particularly in the presence of high-ionic-strength samples and other interference factors, the detection performance of the sensor is often difficult to reach the standard. In recent years, the emerging photoelectrochemical analysis technology has attracted great attention as it can be combined with other analysis methods to construct a sensing platform with dual mode signal output. The technology adopts an optical excitation-electric detection mode, and has the advantages of low background noise, high sensitivity, obvious separation of input and output signals and the like. Meanwhile, the fluorescence detection technique is also a fluorescence signal generated by irradiating a fluorescent substance with specific excitation light. Thus, it is possible to combine fluorescence detection techniques with Photoelectrochemical (PEC) analysis techniques to achieve high accuracy dual mode analysis. However, how to integrate these two approaches remains a challenge. Disclosure of Invention Aiming at the problems of poor selectivity, low sensitivity and easiness in being interfered by complex matrixes in PFOS detection, the invention provides a fluorescence visualization-photoelectrochemical dual-mode PFOS sensor based on a molecular nano cage, which can realize quick qualitative and accurate quantitative detection. The technical scheme adopted by the invention is as follows: A fluorescence visualization-photoelectrochemistry dual-mode PFOS sensor based on a molecular nanocage comprises a substrate, a titanium dioxide TiO 2 layer and a lead coordination beta-cyclodextrin molecular nanocage MNCs layer which are sequentially arranged from bottom to top, wherein the titanium dioxide TiO 2 layer and the lead coordination beta-cyclodextrin molecular nanocage MNCs layer form a TiO 2/MNCs heterostructure. Preferably, the substrate is an ITO conductive glass substrate. The invention further aims to provide a preparation method of the fluorescent visualization-photoelectrochemical dual-mode PFOS sensor based on the molecular nanocages, which comprises the following steps of: step 1, adding beta-cyclodextrin and PbCl 2 into deionized water, adding a cyclohexanol and triethylamine mixed reaction solvent, placing the mixture into a reaction kettle for reaction, cooling, filtering and washing to obtain lead coordination beta-cyclodextrin molecular nanocage MNCs solution; step 2, dropwise adding TiO 2 nano particle suspension on the ITO glass substrate, drying and annealing to obtain an ITO/TiO 2 photoelectrode; And 3, dripping the lead coordination beta-cyclodextrin molecule nanocage MNCs solution on the surface of an ITO/TiO 2 photoelectrode, and drying to form the sensor with the TiO 2/MNCs heterostructure. Preferably, in the step 1, the mol ratio of the beta-cyclodextrin to the PbCl 2 is 1:7-9, and in the step 1, the volume ratio of the cyclohexanol to the triethylamine is 1:0.9-1.1. Preferably, ethanol and water are used for washing in the step 1. Preferably, th