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CN-121991685-A - Electrochemical luminescence perovskite quantum dot probe with stable aqueous phase, and preparation method and application thereof

CN121991685ACN 121991685 ACN121991685 ACN 121991685ACN-121991685-A

Abstract

The invention discloses an electrochemiluminescence perovskite quantum dot probe with stable water phase, and a preparation method and application thereof. Aiming at the technical bottleneck that the existing perovskite quantum dot is unstable in a water phase and is difficult to be directly used for liquid phase detection, the invention provides the Perovskite Quantum Dot (PQDs) probe which is prepared by adopting a water phase co-deposition method and is protected by double ligands of oleylamine/trifluoropropionic acid (OAm/TFPro). The TFPro ligand forms a hydrogen bond interface with water molecules through fluorine-containing groups, and a protective layer is constructed on the PQDs surface, so that the TFPro ligand can be stably dispersed in a water phase for a long time and can maintain high-efficiency electrochemical luminescence (ECL) activity. The ECL sensing platform constructed based on the probe realizes high-sensitivity and high-selectivity detection of tea polyphenol in tea, and has the advantages of wide linear range, low detection limit, strong anti-interference capability and the like. The invention has simple process and low cost, and provides a novel and efficient detection tool for the field of food quality safety.

Inventors

  • WANG ZHONGXIA
  • SUN XINRU
  • LIU KAIQI
  • WANG WEI

Assignees

  • 盐城工学院

Dates

Publication Date
20260508
Application Date
20251223

Claims (10)

  1. 1. The preparation method of the aqueous phase stable electrochemiluminescence perovskite quantum dot probe is characterized by comprising the following steps of: step 1) PbBr 2 , csBr and 2-methylimidazole are dissolved in N, N-dimethylacetamide and stirred for reaction at 60 ℃, and then oleylamine and trifluoropropionic acid are simultaneously added into a reaction system for continuous reaction at 60 ℃; And 2) injecting the reaction liquid obtained in the step 1) into ethyl acetate, standing and crystallizing at 60 ℃, centrifugally collecting precipitate, and ultrasonically dispersing in an aqueous phase to obtain the OAm/TFPro dual-ligand protected PQDs probe with stable aqueous phase.
  2. 2. The method for preparing the aqueous phase stable electrochemiluminescence perovskite quantum dot probe according to claim 1, wherein in the step 1), the dosage of PbBr 2 is 146.8: 146.8 mg, the dosage of CsBr is 85.1: 85.1 mg, the dosage of 2-methylimidazole is 8.2: 8.2 mg, the dosage of N, N-dimethylacetamide is 10: 10 mL, the dosage of oleylamine is 500 mu L, and the dosage of trifluoropropionic acid is 300 mu L.
  3. 3. A PQDs probe produced by the method of claim 1 or claim 2, wherein PQDs comprises a complex crystal form of CsPbBr 3 and CsPb 2 Br 5 , the surfaces of which are co-modified with OAm and TFPro, which can be stably dispersed in an aqueous phase for a long period of time and maintain high ECL luminescence efficiency.
  4. 4. The PQDs probe of claim 3, wherein said TFPro forms a hydrogen bond interface with water molecules through fluorine atoms, preventing water molecules from penetrating into the PQDs core, thereby maintaining structural and luminescent stability of PQDs in the aqueous phase.
  5. 5. Use of PQDs probe according to claim 3 or 4 in the manufacture of a sensor or detection kit for detecting tea polyphenols.
  6. 6. An ECL sensing platform for detecting tea polyphenols, comprising: The PQDs probe dispersion liquid according to claim 3 or 4 is coated on the surface of working electrode to prepare modified electrode, then the modified electrode, reference electrode and counter electrode are formed into a three-electrode system, and placed in PBS buffer solution containing K 2 S 2 O 8 and the object to be tested to make ECL signal acquisition.
  7. 7. The ECL sensing platform of claim 6, wherein the ECL signal acquisition has a potential scan range of 0V to-2.2V, a scan rate of 100 mV/s, and a photomultiplier voltage of 600V.
  8. 8. A method for detecting tea polyphenols in tea leaves, characterized in that the method uses PQDs probe as claimed in claim 3 or 4 to quantitatively detect tea polyphenols by the quenching degree of electrochemiluminescence signals.
  9. 9. The method according to claim 8, wherein the linear range of detection of tea polyphenols is 0.0001 μg/mL to 500 μg/mL.
  10. 10. The method of claim 8, wherein the method has high selectivity for tea polyphenols, and common interferents include histidine, theophylline, theanine, cysteine, glucose, fructose, sucrose 、Hg 2+ 、Ag + 、Fe 2+ 、Al 3+ 、Ca 2 + 、K + 、Mg 2+ 、Cu 2+ 、Zn 2+ 、NO 3 - 、Cl - 、SO 4 2- .

Description

Electrochemical luminescence perovskite quantum dot probe with stable aqueous phase, and preparation method and application thereof Technical Field The invention belongs to the technical field of nano materials and analysis and detection, and particularly relates to an electrochemiluminescence perovskite quantum dot probe with stable water phase, and a preparation method and application thereof. Background Tea polyphenol (TPPs) in the tea is a core active ingredient for determining the quality and health efficacy of the tea, and has obvious physiological functions of resisting oxidation, resisting inflammation, resisting cancer, preventing cardiovascular and cerebrovascular diseases and the like. However, the intake of tea polyphenols needs to be controlled within a reasonable range, and excessive intake may cause adverse reactions. Therefore, the rapid, sensitive and accurate tea polyphenol detection method is established, and has important significance for tea quality control, functional food development and food safety supervision. At present, the detection method of tea polyphenol mainly comprises a high performance liquid chromatography method, a spectrophotometry method, an electrochemical method and the like. These methods either rely on expensive large instruments, are complicated and time-consuming to operate, or suffer from insufficient sensitivity and selectivity. In recent years, nanomaterial-based sensing technologies have received widespread attention due to their high sensitivity and potential portability. Among them, perovskite quantum dots (Perovskite Quantum Dots, PQDs) are regarded as ideal materials for next-generation high-performance luminescent probes with excellent optical performance, high fluorescence quantum yield and tunable emission wavelength, and show great potential in the fields of photoelectricity and sensing. However, the PQDs is applied to an aqueous phase system, particularly to the direct detection of complex samples such as foods, organisms and the like, and faces a fundamental technical bottleneck that PQDs (especially organic-inorganic hybrid perovskite) prepared by the traditional method is extremely unstable in polar solvents such as water, alcohol and the like, and the crystal structure of the PQDs can be rapidly degraded, so that luminescence quenching is caused, and the practical application of the PQDs in liquid phase analysis detection is severely limited. Although studies have been attempted to improve the stability of PQDs by surface ligand engineering or coating strategies, there are often problems such as complicated preparation process, loss of luminous efficiency, or difficulty in functionalization. In addition, the existing novel sensing materials for detecting tea polyphenols (such as the metal nanoclusters based on protein templates disclosed in chinese patent application CN115673311a, and the organic small molecular probes based on borate reaction disclosed in chinese patent application CN114085241A, CN116559157 a) have various characteristics, but the sensitivity, stability or anti-interference capability still have room for improvement, and none of the existing novel sensing materials relates to a technical path for constructing an ECL sensing platform by using high-performance PQDs. Therefore, developing a PQDs probe which can exist in a water phase stably and simultaneously maintain the high-efficiency ECL luminous performance, and establishing a novel method for detecting the tea polyphenol with high sensitivity and high selectivity based on the PQDs probe becomes a technical problem to be solved in the field. Disclosure of Invention Aiming at the defects of the prior art, the invention provides the aqueous phase stable electrochemiluminescence perovskite quantum dot probe, and the preparation method and the application thereof, and the aqueous phase stable perovskite quantum dot electrochemiluminescence probe based on double ligand protection is initiated, so that the high-sensitivity and high-selectivity detection of tea polyphenol in tea is realized. The invention is realized by the following technical scheme: the preparation method of the aqueous phase stable electrochemiluminescence perovskite quantum dot probe comprises the following steps: step 1) PbBr 2, csBr and 2-methylimidazole are dissolved in N, N-dimethylacetamide and stirred for reaction at 60 ℃, and then oleylamine and trifluoropropionic acid are simultaneously added into a reaction system for continuous reaction at 60 ℃; And 2) injecting the reaction liquid obtained in the step 1) into ethyl acetate, standing and crystallizing at 60 ℃, centrifugally collecting precipitate, and ultrasonically dispersing in an aqueous phase to obtain the OAm/TFPro dual-ligand protected PQDs probe with stable aqueous phase. Preferably, in the step 1), the dosage of PbBr 2 is 146.8 mg, the dosage of CsBr is 85.1 mg, the dosage of 2-methylimidazole is 8.2 mg, the dosage of N, N-dimethylacetamide is 1