Synthesis method of nano-enzyme containing ferrocene dicarboxylic acid ligand structural unit and having peroxidase-like activity

Abstract

The invention discloses a method for synthesizing a nano enzyme with peroxidase-like activity by taking ferrocene dicarboxylic acid as a ligand structure unit. The metal organic framework material is a porous coordination high-molecular polymer crystal formed by coordination of metal ions and organic ligands. The metal organic framework material is rich in active sites, large in specific surface area, adjustable in structure, large in porosity and remarkable in catalytic performance. On the other hand, ferrocenedicarboxylic acid is used as a ligand structure unit to synthesize the metal organic framework material, and the ferrocene structure unit has a promotion effect on the catalytic activity of the synthesized metal organic framework material as a nano enzyme with peroxidase-like activity. The invention discloses a plurality of metal organic framework materials synthesized by taking ferrocene dicarboxylic acid as a ligand structure unit, and the metal organic framework materials all have peroxidase-like activity. The method has the advantages of simple operation, simple procedure and the like.

Description

Technical Field

[0001] The present invention relates to the fields of metal-organic framework materials and the synthesis of nanozymes with peroxidase-like activity, and particularly to a method for synthesizing nanozymes with peroxidase-like activity containing a structural unit of ferrocenedicarboxylic acid ligand. Background Art

[0002] Metal-organic framework materials are porous coordination polymer crystals formed by the coordination of metal ions and organic ligands. Metal-organic framework materials have rich active sites, a large specific surface area, adjustable structures, and large porosities, and have remarkable catalytic properties. On the other hand, ferrocene and its derivatives are often used as electron transfer mediators. For metal-organic framework materials synthesized with ferrocenedicarboxylic acid (1,1’-ferrocenedicarboxylic acid, FcDC) as a ligand structural unit, the ferrocene structural unit may promote the catalytic activity of the synthesized metal-organic framework materials as nanozymes with peroxidase-like activity. The present invention discloses several metal-organic framework materials synthesized with ferrocenedicarboxylic acid as a ligand structural unit, all of which are nanozymes with peroxidase-like activity. This method has the advantages of simple operation and simple procedure. Summary of the Invention

[0003] In the present invention, several metal ions are used as metal ion coordination centers respectively, and ferrocenedicarboxylic acid is used as a ligand structural unit. The synthesized metal-organic framework materials with ferrocenedicarboxylic acid as a ligand structural unit are all nanozymes with peroxidase-like activity. This method has the advantages of simple operation and simple procedure;

[0004] Furthermore, the method for synthesizing metal-organic framework materials with ferrocenedicarboxylic acid as a ligand structural unit is a method for synthesizing nanozymes with peroxidase-like activity;

[0005] Furthermore, in the synthesis of the metal-organic framework materials, cerium ions, cobalt ions, copper ions, and manganese ions are used as metal ion coordination centers respectively, and ferrocenedicarboxylic acid is used as a ligand structural unit to synthesize metal-organic framework materials with ferrocenedicarboxylic acid as a ligand structural unit;

[0006] Furthermore, in the synthesis of the metal-organic framework materials, ferrocenedicarboxylic acid is used as a ligand structural unit to synthesize metal-organic framework materials with ferrocenedicarboxylic acid as a ligand structural unit, which have peroxidase-like activity. The metal ion coordination centers required for synthesis include but are not limited to cerium ions, cobalt ions, copper ions, and manganese ions. Description of the Drawings

[0007] Figure 1. Verification and comparison of the peroxidase-like activity of Ce-FcDC. Hydrogen peroxide, catalyzed by Ce-FcDC, oxidizes 3,3',5,5'-tetramethylbenzidine (TMB). Oxidized TMB has a characteristic absorption peak at 652 nm, thus verifying the peroxidase-like activity of Ce-FcDC. Working buffer: pH 4.5, 0.2 M HAc-NaAc. [Ce-FcDC]: 30 μg / mL. [TMB]: 0.1 mM; [H2O2]: 0.1 mM. Incubation temperature: 37 o C. Time: 10 min.

[0008] Figure 2. Verification and comparison of the peroxidase-like activity of Co-FcDC. Hydrogen peroxide, catalyzed by Co-FcDC, oxidizes 3,3',5,5'-tetramethylbenzidine (TMB). Oxidized TMB has a characteristic absorption peak at 652 nm, thus verifying the peroxidase-like activity of Co-FcDC. Working buffer: pH 4.0, 0.2 M HAc-NaAc. [Co-FcDC]: 30 μg / mL. [TMB]: 0.1 mM; [H2O2]: 0.1 mM. Incubation temperature: 25 o C. Time: 10 min.

[0009] Figure 3. Verification and comparison of the peroxidase-like activity of Cu-FcDC. Hydrogen peroxide, catalyzed by Cu-FcDC, oxidizes 3,3',5,5'-tetramethylbenzidine (TMB). Oxidized TMB has a characteristic absorption peak at 652 nm, thus verifying the peroxidase-like activity of Cu-FcDC. Working buffer: pH 4.0, 0.2 M HAc-NaAc. [Cu-FcDC]: 30 μg / mL. [TMB]: 0.1 mM; [H2O2]: 0.1 mM. Incubation temperature: 25 o C. Time: 10 min.

[0010] Figure 4. Verification and comparison of the peroxidase-like activity of Mn-FcDC. Hydrogen peroxide, catalyzed by Mn-FcDC, oxidizes 3,3',5,5'-tetramethylbenzidine (TMB). Oxidized TMB has a characteristic absorption peak at 652 nm, thus verifying the peroxidase-like activity of Mn-FcDC. Working buffer: pH 4.0, 0.2 M HAc-NaAc. [Mn-FcDC]: 30 μg / mL. [TMB]: 0.1 mM; [H2O2]: 0.1 mM. Incubation temperature: 25 o C. Time: 10 min. Detailed implementation mode

[0011] The following combines the attached drawings to detail the synthesis method examples of the present invention.

[0012] Synthesis example:

[0013] (1) Ultrasonically treat 4 mmol of cerium(III) chloride and 2 mmol of 1,1’-ferrocenedicarboxylic acid (FcDC) separately in 40 mL of N,N-dimethylformamide (DMF), and then stir for 15 minutes. Then, heat the solution at 120 °C for 12 hours. Collect the obtained precipitate, wash it 3 times with DMF and H2O respectively, and finally dry it at 60 °C for 12 hours to obtain Ce-FcDC.

[0014] (2) Ultrasonically dissolve 1.8 mmol of cobalt(II) chloride in 18 mL of DMF to form a uniform solution A. Subsequently, ultrasonically dissolve 1.8 mmol of FcDC in 18 mL of DMF to form a uniform solution B. Then, under continuous stirring, add solution A dropwise to solution B. After continuing magnetic stirring for 1 h, transfer the mixed solution to a 100 mL polytetrafluoroethylene-lined autoclave and react at 180 °C for 10 h. After it naturally cools to room temperature, collect the generated precipitate by centrifugation and wash it several times with DMF and absolute ethanol. Finally, dry it overnight under vacuum at 60 °C, and name the obtained final product Co-FcDC.

[0015] (3) Ultrasonically dissolve 1.8 mmol of copper(II) chloride in 18 mL of DMF to form a uniform solution A. Subsequently, ultrasonically dissolve 1.8 mmol of FcDC in 18 mL of DMF to form a uniform solution B. Then, under continuous stirring, add solution A dropwise to solution B. After continuing magnetic stirring for 1 h, transfer the mixed solution to a 100 mL polytetrafluoroethylene-lined autoclave and react at 180 °C for 10 h. After it naturally cools to room temperature, collect the generated precipitate by centrifugation and wash it several times with DMF and absolute ethanol. Finally, dry it overnight under vacuum at 60 °C, and name the obtained final product Cu-FcDC.

[0016] (4) 1.8 mmol of manganese(II) chloride was ultrasonically dissolved in DMF to form a homogeneous solution A. Subsequently, 1.8 mmol of FcDC was ultrasonically dissolved in 18 mL of DMF to form a homogeneous solution B. Then, under continuous stirring, solution A was added dropwise to solution B. After continuing magnetic stirring for 1 h, the mixed solution was transferred to a 100 mL Teflon-lined autoclave and reacted at 180 °C for 10 h. After it was naturally cooled to room temperature, the resulting precipitate was collected by centrifugation and washed several times with DMF and absolute ethanol. Finally, it was dried overnight under vacuum at 60 °C, and the final product obtained was named Mn-FcDC.

Claims

1. A method for synthesizing a nanozyme having peroxidase-like activity using ferrocenedicarboxylic acid as a ligand structural unit, characterized in that: Several metal ions are used as metal ion coordination centers and ferrocene dicarboxylic acid is used as a ligand structural unit. The synthesized metal organic framework materials with ferrocene dicarboxylic acid as a ligand structural unit are all nanozymes with peroxidase-like activity. This method has the advantages of easy operation and simple procedures.

2. The method according to claim 1, characterized in that The method for synthesizing a metal organic framework material using ferrocene dicarboxylic acid as a ligand structural unit is a method for synthesizing a nanozyme with peroxidase-like activity.

3. The method according to claim 1, characterized in that In the synthesis of the metal organic framework material, cerium ion, cobalt ion, copper ion and manganese ion are used as metal ion coordination centers respectively, and ferrocene dicarboxylic acid is used as a ligand structural unit to synthesize the metal organic framework material using ferrocene dicarboxylic acid as a ligand structural unit.

4. The method according to claim 1, characterized in that The synthesis of the metal organic framework material uses ferrocene dicarboxylic acid as a ligand structural unit. The metal organic framework material using ferrocene dicarboxylic acid as a ligand structural unit has peroxidase-like activity, and the metal ion coordination center required for the synthesis includes but is not limited to cerium ions, cobalt ions, copper ions and manganese ions.

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