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CN-119775585-B - Europium-functionalized metal-organic framework-based dual-emission fluorescent probe and preparation method and application thereof

CN119775585BCN 119775585 BCN119775585 BCN 119775585BCN-119775585-B

Abstract

The invention discloses a europium-functionalized metal-organic framework-based dual-emission fluorescent probe, and a preparation method and application thereof, and relates to the field of organic metal frameworks and fluorescence detection, wherein the preparation method comprises the steps of mixing ZrCl 4 , pyromellitic acid, 6-hydroxy-2-naphthoic acid and water, and adding acetic acid to obtain a mixture; the invention has the advantages that the luminescent ligand 6-hydroxy-2-naphthoic acid is adopted to modify the UiO-66 MOF, the Eu 3+ is adopted to carry out post-modification, the Eu 3+ -MOF with blue and red two-band dual emission is reasonably designed and synthesized, and the Crystal Violet (CV) and Quinine (QN) are selectively and rapidly responded through different response modes, so that the detection limit is low and is superior to most reported sensors.

Inventors

  • YUAN HOUQUN
  • YUAN YUAN
  • BAO GUANGMING

Assignees

  • 湖北工业大学

Dates

Publication Date
20260512
Application Date
20250109

Claims (8)

  1. 1. The preparation method of the europium-functionalized metal-organic framework-based dual-emission fluorescent probe is characterized by comprising the following steps of: Mixing ZrCl 4 , pyromellitic acid, 6-hydroxy-2-naphthoic acid and water, and adding acetic acid to obtain a mixture; heating and refluxing the mixture, centrifuging to obtain a residue, and washing and drying the residue to obtain UCHNA; Dispersing UCHNA in Eu (NO 3 ) 3 ·6H 2 O aqueous solution, heating for reaction, collecting white precipitate, washing and drying to obtain a europium-functionalized metal-organic framework-based dual-emission fluorescent probe; the molar ratio of ZrCl 4 to pyromellitic acid to 6-hydroxy-2-naphthoic acid is 1.5-2:2.5-3.5:0.2-0.5; The mass ratio of UCHNA to Eu (NO 3 ) 3 ·6H 2 O) is 0.4-0.6:0.8-1.2.
  2. 2. The method according to claim 1, wherein the ratio of the amount of ZrCl 4 to the amount of water and acetic acid is 1.5mol~2mol:15 mL~25mL:4 mL~6 mL.
  3. 3. The preparation method of claim 1, wherein the temperature of the heating reflux is 80-120 ℃, and the time of the heating reflux is 20-28 h.
  4. 4. The preparation method according to claim 1, wherein the temperature of the heating reaction is 70 ℃ to 90 ℃, and the time of the heating reaction is 20 h to 28 h.
  5. 5. Europium-functionalized metal-organic framework-based dual-emission fluorescent probe, which is characterized by being obtained by the preparation method according to any one of claims 1-4.
  6. 6. Use of a europium-functionalized metal-organic framework-based dual-emission fluorescent probe according to claim 5 for simultaneous detection of crystal violet and quinine in water or an aquatic product.
  7. 7. A fluorescence sensor, characterized by comprising the europium-based functionalized metal-organic framework dual-emission fluorescent probe according to claim 5.
  8. 8. A method for simultaneously detecting crystal violet and quinine in water or an aquatic product, wherein the detection is performed by using the europium-functionalized metal-organic framework-based dual-emission fluorescent probe according to claim 5, and the method comprises the following steps: Adding meat of aquatic products into a mixture of acetonitrile and PBS buffer solution, carrying out ultrasonic treatment, centrifuging, collecting supernatant, and filtering the supernatant with a filter membrane to obtain a pretreated sample, or centrifuging and filtering the collected aquaculture water sample to obtain pretreated water; Adding the europium-based functionalized metal-organic framework dual-emission fluorescent probe into water to prepare EuUCHNA water suspension; adding the pretreated sample or the pretreated water to the EuUCHNA aqueous suspension, and measuring fluorescence spectrum.

Description

Europium-functionalized metal-organic framework-based dual-emission fluorescent probe and preparation method and application thereof Technical Field The invention relates to the field of organic metal frames and fluorescence detection, in particular to a europium-functionalized metal-organic frame-based dual-emission fluorescent probe, and a preparation method and application thereof. Background As large-scale, intensive aquaculture continues to expand, the frequent outbreaks of fungal, bacterial and parasitic infections underscores the necessity for effective disease management. In this regard, crystal Violet (CV) and Quinine (QN) are widely used to protect the health of fish and shrimp, particularly to treat and prevent these infections, providing the necessary solutions in environments where outbreaks of disease may cause significant economic losses. CV is a synthetic triphenylmethane dye which has been widely used for the prevention and treatment of aquarium farming diseases due to its effective anthelmintic, bactericidal and bactericidal actions. However, CV is highly toxic and may cause mutagenesis and carcinogenesis, and thus, many countries have banned its use in aquaculture. QN is a cinchona alkaloid, known as an important antimalarial drug, commonly used to prevent and treat malaria in fish, or as a preservative in aquatic products to extend their shelf life. Unfortunately, QN has high neurotoxicity and cardiovascular toxicity. Excessive use of QN can lead to cancer cartilage disease, blurred vision, and even damage to the nervous system and cardiovascular system. Therefore, monitoring CV and QN values in fish and aquaculture water is of paramount importance. In the past, several analytical techniques have been used to determine CV and QN, including high performance liquid chromatography, ultraviolet-visible spectrophotometry, flow injection chemiluminescence, surface enhanced Raman scattering, and electrochemical analysis. Nevertheless, these techniques have problems, such as the need for expensive instrumentation or specialized technicians, or lack of sensitivity, or the involvement of complex pretreatment procedures. Meanwhile, due to the complex content in the real sample, the requirement for realizing multi-target detection in one system is large, but the method is also a great challenge. To date, there has been no report of simultaneous detection of CV and QN. Therefore, there is a need to develop a simple, sensitive, rapid, low cost method for simultaneously detecting CV and QN in aquatic products. The fluorescence analysis method has the advantages of simplicity, intuitiveness, rapidness and the like, and is a good choice. In addition, multiple emission materials can not only reduce environmental interference by self-referencing, but also achieve multi-target detection by different response modes, and thus are receiving widespread attention. Lanthanide metal organic frameworks (Ln-MOFs), combining the modifiable nature and porosity of MOFs with the unique fluorescent properties of Ln 3+, multiple emissive fluorescence sensors can be easily designed and built with luminescent ligands, ln 3+, and target substances. Many multi-emitted Ln-MOFs have been synthesized and developed as fluorescent sensors for biomarkers, explosives, food products, or pollutants in the environment. However, there are certain limitations to multi-target detection with a single fluorescence sensor. Disclosure of Invention The invention aims to at least solve one of the technical problems in the prior art and provides a europium-functionalized metal-organic framework-based dual-emission fluorescent probe, and a preparation method and application thereof. The invention adopts luminescent ligand 6-hydroxy-2-naphthoic acid to pre-modify UiO-66 MOF, and uses Eu 3+ to post-modify (as shown in figure 16 a), and reasonably designs and synthesizes Eu 3+ -MOF (EuUCHNA) with blue and red wave bands and double emission. The fluorescence spectrum showed that EuUCHNA exhibits different response modes for CV and QN (as shown in fig. 16 b). QN effectively quenches the two emission bands of EuUCHNA, while QN significantly enhances the blue emission band of EuUCHNA, slightly reduces the red emission band of EuUCHNA. By combining the visible fluorescent color change with a smart phone, instrumentalless monitoring of CV and QN can be achieved in the actual sample. Furthermore, the different response modes enable simultaneous quantification of CV and QN. This work will promote the development of fluorescence sensors for multi-target detection. The technical scheme of the invention is as follows: the first aspect of the invention provides a preparation method of a europium-functionalized metal-organic framework-based dual-emission fluorescent probe, which comprises the following steps: Mixing ZrCl 4, pyromellitic acid, 6-hydroxy-2-naphthoic acid and water, adding acetic acid to obtain a mixture, heating and refluxing the mixture, centrifu