Search

CN-116067951-B - FA/Au@COF (Fe) composite system and preparation method and application thereof

CN116067951BCN 116067951 BCN116067951 BCN 116067951BCN-116067951-B

Abstract

The invention discloses an FA/Au@COF (Fe) composite system, a preparation method and application thereof, wherein the composite system comprises folic acid and Au@COF (Fe), and the Au@COF (Fe) consists of COF (Fe) and Au NP. The preparation method of the FA/Au@COF (Fe) composite system comprises the steps of adding an Au solution and sodium borohydride into a solution of an iron porphyrin COF for reaction to obtain the Au@COF (Fe), dispersing the Au@COF (Fe) by using an alcohol solvent, and adding the dispersed Au@COF (Fe) into a solution containing folic acid for reaction to obtain the FA/Au@COF (Fe). The preparation method provided by the invention is simple, low in cost and excellent in effect, and the Au@COF (Fe) composite system has the activity of hydrogen peroxidase, can realize rapid chromogenic detection on H 2 O 2 , can carry out chromogenic detection on tumor cells, has excellent detection performance, and can be produced and utilized on a large scale.

Inventors

  • Wei Meijie
  • WEI ZEQI

Assignees

  • 盐城工学院
  • 盐城工学院技术转移中心有限公司

Dates

Publication Date
20260505
Application Date
20221216

Claims (8)

  1. 1. An FA/Au@COF (Fe) composite system, which is characterized by comprising folic acid and Au@COF (Fe), wherein the Au@COF (Fe) consists of COF (Fe) and Au NP; Firstly adding ferriporphyrin and tetrathiafulvalene monomer, then adding acetic acid, 1,4 dioxane and 1,3,5 mesitylene, carrying out ultrasonic treatment, cooling, degassing, washing and collecting to obtain a COF (Fe) crude product, alternately washing with tetrahydrofuran and acetone, and drying the product to obtain a pure COF (Fe) material; (2) Adding HAuCl 4 into a mixed solution of THF and water, stirring, adding a NaBH 4 solution, centrifugally washing, and freeze-drying to obtain an Au NP product; (3) Adding the Au NP prepared in the step (2) into the mixed solution of DMF and water of the COF (Fe) material prepared in the step (1), stirring overnight, centrifugally washing, drying in vacuum to obtain an Au@COF (Fe) material, and dispersing in an alcohol solvent to obtain an Au@COF (Fe) solution; (4) And (3) adding the Au@COF (Fe) solution prepared in the step (3) into a folic acid-containing solution, centrifugally washing, and filtering and drying to obtain the FA/Au@COF (Fe).
  2. 2. The FA/au@cof (Fe) composite system according to claim 1, wherein in step (1), the molar ratio of ferriporphyrin to tetrathiafulvalene monomer is 1:0.5-2, the volume ratio of acetic acid, 1,4 dioxane and 1,3,5 mesitylene is 1:1-10:1-10, and the ultrasonic treatment time is 5-90min.
  3. 3. The FA/au@cof (Fe) composite system according to claim 1, wherein the volume ratio of HAuCl 4 to NaBH 4 in step (2) is 1:1-10 and the volume ratio of thf to water is 1-10:1.
  4. 4. The FA/au@cof (Fe) composite system according to claim 1, wherein the COF (Fe) material in step (3) has a final concentration of COF (Fe) of 1-5mg/mL in a mixed solution of DMF and water.
  5. 5. The FA/au@cof (Fe) composite system according to claim 1, wherein the alcohol solvent in step (3) is any one of methanol, ethanol, or isopropanol, and the solution solvent of folic acid in step (4) is acetic acid.
  6. 6. Use of the FA/au@cof (Fe) composite system according to claim 1 in the field of rapid detection of H 2 O 2 .
  7. 7. The method according to claim 6, wherein the application process is to add TMB solution and H 2 O 2 solution into Au@COF (Fe) solution, and the H 2 O 2 can be detected by visible light irradiation.
  8. 8. The use according to claim 7, wherein the irradiation time of visible light is 1-5min.

Description

FA/Au@COF (Fe) composite system and preparation method and application thereof Technical Field The invention belongs to the technical field of analysis and detection, and particularly relates to an FA/Au@COF (Fe) composite system, and a preparation method and application thereof. Background Detection of cancer biomarkers plays an important role in early diagnosis and clinical research of cancer. The existing detection methods comprise an isotope internal standard method, a fluorescence time attenuation spectrometry and the like, but have the defects of high cost, complex test, time consumption and the like. As an analysis method, the chromogenic immunoassay method has the advantages of visual phenomenon, simplicity, rapidness, high sensitivity, low cost and the like, is greatly concerned in the field of analysis and detection, and develops an enzyme-linked immunosorbent assay (ELISA), a chemiluminescent immunoassay, an immune chip method and the like. The ELISA has many advantages, such as simple analysis process, short time consumption, high detection efficiency, sample consumption saving, cost reduction and the like. However, in the chromogenic immunoassay using HRP as oxidase, a secondary antibody labeled with HRP is required to complete the oxidation of TMB, and HRP is unstable and easily denatured to lose its peroxidase activity. Therefore, the design and synthesis of high-efficiency HRP chemical mimics simulate the action of catalase, so that the chemical chromogenic immunoassay of tumor cells is realized, and the method is likely to become a more stable and simple immunoassay method and is widely applied to clinic. The ferriporphyrin system (ferrous heme protein such as catalase, horseradish peroxidase, cytochromes and the like) is widely used in nature as an excellent hydrogen peroxide biosensor, and a Covalent Organic Framework (COFs) material constructed by ferriporphyrin is a high-efficiency oxidant, so that the ferriporphyrin COFs material with high catalytic oxidation activity can be designed and synthesized through effective regulation and control of monomers. In addition, the iron porphyrin COFs material has obvious absorption peaks in a visible light region, and can realize the effective separation of photo-generated electrons and holes under the irradiation of visible light, so that the catalytic efficiency is improved. This makes them useful as superior materials in redox sensors, whereas chromogenic detection of H 2O2 concentration and tumor cells using COFs materials as mimic enzymes in chromogenic immunoassay has not been reported so far. Therefore, how to design and synthesize a material for rapid chromogenic detection of H 2O2 and tumor cells with high sensitivity, high stability and simple operation method is a problem to be solved by those skilled in the art. Disclosure of Invention Aiming at the problems existing in the prior art, the invention provides a nano composite system FA/Au@COF (Fe) with catalase-like activity. The invention provides a preparation method of a FA/Au@COF (Fe) composite system with hydrogen peroxidase-like activity, and the prepared composite system can be used for color development detection of H 2O2, so that color development detection of tumor cells is realized. The invention also provides application of the prepared FA/Au@COF (Fe) composite system in the field of biomedical detection. The invention provides an FA/Au@COF (Fe) composite system, which comprises folic acid and Au@COF (Fe), wherein the Au@COF (Fe) consists of COF (Fe) and Au NP. The invention discloses a preparation method of an FA/Au@COF (Fe) composite system, which specifically comprises the following steps: (1) Adding ferriporphyrin and tetrathiafulvalene monomers, adding acetic acid, 1,4 dioxane and 1,3,5 mesitylene, performing ultrasonic treatment, cooling, degassing through a freezing-vacuum-thawing cycle program, heating a sample to a high temperature, maintaining for a plurality of days, washing and collecting to obtain a COF (Fe) crude product, alternately washing with tetrahydrofuran and acetone, and drying the product to obtain a pure COF (Fe) material; (2) Adding HAuCl 4 into a mixed solution of THF and water, stirring, adding a NaBH 4 solution, centrifugally washing, and freeze-drying to obtain an Au NP product; (3) Adding the Au NP prepared in the step (2) into the mixed solution of DMF and water of the COF (Fe) material prepared in the step (1), stirring overnight, centrifugally washing, drying in vacuum to obtain an Au@COF (Fe) material, and dispersing in an alcohol solvent to obtain an Au@COF (Fe) solution; (4) And (3) adding the Au@COF (Fe) solution prepared in the step (3) into a folic acid-containing solution, centrifugally washing, filtering and drying to obtain FA/Au@COF (Fe) powder. Further, in the step (1), the mole ratio of ferriporphyrin to tetrathiafulvalene monomer is 1:1 acetic acid, the volume ratio of 1,4 dioxane to 1,3,5 mesitylene is 1:1-10:1-10, and the ultras