Composite nano-material with photoresponse nano-enzyme activity and preparation method of composite nano-material
By constructing hollow Fe2O3 nanoparticles and growing Cu-TCPP nanosheets on their surface to form Fe2O3@Cu-TCPP composite materials, the problem of low enzyme catalytic efficiency of ferroferric oxide nanoparticles was solved, and stable and efficient photoresponsive catalysis and light-driven therapy were achieved.
Patent Information
- Application Number
- CN202510877522.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-27
- Publication Date
- 2025-10-28
AI Technical Summary
The enzyme catalytic efficiency of existing ferroferric oxide nanoparticles is limited, especially the OXD-like enzyme activity has poor selectivity, is easily agglomerated or oxidized, and has weak light absorption ability, which limits its application in light-driven therapy.
By constructing hollow Fe2O3 nanoparticles and growing Cu-TCPP nanosheets in situ on their surface, a composite nanomaterial Fe2O3@Cu-TCPP is formed, which enhances the active sites and light absorption capacity, thereby achieving photoresponsive catalysis.
The stability and catalytic efficiency of nanozymes are improved, and they can generate ROS under light, achieving controllable photothermal conversion, making them suitable for photothermal and photodynamic therapy.
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Figure CN120837664A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a composite nanomaterial with photoresponsive nanoenzyme activity, and also to a method for preparing the above-mentioned composite nanomaterial. Background Technology
[0002] Nanomaterials with enzyme-like catalytic activity (i.e., nanozymes) have attracted widespread attention in recent years as a novel type of functional material. Existing technologies have successfully developed functional nanomaterials with various enzyme activities, including catalase (CAT), peroxidase (POD), oxidase (OXD), and superoxide dismutase (SOD). These nanozymes not only exhibit catalytic efficiency comparable to natural enzymes but also possess the unique stability advantages of nanomaterials, and have been successfully applied in several high-tech fields such as biomedical detection and environmental pollutant degradation.
[0003] Currently, iron oxide nanoparticles are widely used in fields such as biosensoring and tumor therapy due to their excellent magnetic responsiveness and diverse enzyme activities. However, their enzymatic catalytic efficiency is limited, especially their OXD-like enzyme activity, which exhibits poor selectivity and is prone to aggregation or oxidation in physiological environments, affecting practical application effects. Furthermore, as a semiconductor, iron oxide itself has weak absorption capacity for visible or near-infrared light, making it difficult to efficiently generate ROS or convert light energy into heat energy, thus limiting its role in photodriven therapy. Finally, its band structure is not conducive to the effective separation of photogenerated electron-hole pairs, resulting in low photoinduced reaction efficiency. Therefore, a single iron oxide system is insufficient to meet the needs of efficient and precise photodynamic or photothermal therapy. Summary of the Invention
[0004] Purpose of the invention: The purpose of this invention is to provide a composite nanomaterial Fe2O3@Cu-TCPP that has both stable and good nanozyme activity and photoresponsive properties; another purpose of this invention is to provide a method for preparing the above-mentioned composite nanomaterial Fe2O3@Cu-TCPP.
[0005] Technical solution: The composite nanomaterial Fe2O3@Cu-TCPP of the present invention includes hollow Fe2O3 nanoparticles and Cu-TCPP nanosheets coated on the hollow Fe2O3 nanoparticles. The Cu-TCPP nanosheets are grown in situ on the surface of the hollow Fe2O3 nanoparticles through coordination bonds.
[0006] The hollow Fe2O3 nanoparticles have a particle size of 200–500 nm.
[0007] The preparation method of the above-mentioned composite nanomaterial Fe2O3@Cu-TCPP employs a bottom-up in-situ growth method to prepare the hollow composite nanomaterial Fe2O3@Cu-TCPP, specifically including the following steps:
[0008] (1) Preparation of Prussian blue: K4Fe(CN)6·3H2O and PVP (polyvinylpyrrolidone) were thoroughly mixed in hydrochloric acid solution, and after hydrothermal reaction, the reaction product Fe4[Fe(CN)6]3 was separated.
[0009] (2) The reaction product was dispersed in ethanol, and NaOH solution was added according to the stoichiometric ratio of Fe4[Fe(CN)6]3 to NaOH. After the reaction (etching), Fe(OH)3 nanoparticles with hollow cubes were obtained.
[0010] (3) Calcine Fe(OH)3 nanoparticles to obtain Fe2O3 nanoparticle precursors in the form of hollow cubes;
[0011] (4) Add H4TCPP to an organic solvent and mix well to obtain mixture A. Add copper salt to the solvent to obtain mixture B. Add mixture A and Fe2O3 nanoparticle precursor from step (3) to mixture B and react under heating conditions to obtain composite nanomaterial Fe2O3@Cu-TCPP.
[0012] In step (1), the mass ratio of K4Fe(CN)6·3H2O to PVP is 30:1 to 40:1, preferably 34.5 to 35:1; the concentration of the hydrochloric acid solution is 0.1M; the reaction time of the hydrothermal reaction is 12 to 24 hours, and the reaction temperature is 80℃.
[0013] In step (3), the calcination temperature is 300℃ and the calcination time is 6-8h.
[0014] In step (4), the organic solvent that forms mixture A is a mixture of DMF (N,N-dimethylformamide) and n-hexane, wherein the volume ratio of DMF to n-hexane is 3:1;
[0015] In step (4), the solvent for forming mixture B is ethanol; the copper salt is CuCl2·2H2O; and the mass ratio of the Fe2O3 nanoparticle precursor, CuCl2·2H2O and H4TCPP is 20-40:10-15:2-5.
[0016] In step (4), the reaction is carried out under magnetic stirring for 12 to 24 hours and at a temperature of 80°C.
[0017] This invention achieves synergistic optimization of material morphology and composition by constructing hollow iron oxide nanoparticles and coating their surface with CuTCPP, a metalloporphyrin complex with strong photoresponsiveness. The hollow structure significantly increases the specific surface area and active site exposure, enhancing substrate diffusion and catalytic efficiency, thereby endowing the material with stable and excellent nanozyme activity. Simultaneously, this structure can effectively load and stabilize the outer photosensitive molecules, improving the structural stability of the composite system. CuTCPP, as a functional component with visible light absorption capability, not only endows the material with excellent photoresponsiveness and can be used for photo-driven generation of reactive oxygen species, but also participates in electron transfer through the construction of a heterojunction, enhancing synergistic catalytic activity. Therefore, the composite nanomaterial of this invention achieves stable and efficient nanozyme activity and significant photoresponsive performance.
[0018] Beneficial Effects: Compared with the prior art, the present invention has the following significant advantages: The present invention first prepares hollow Fe2O3 precursor nanoparticles through hydrothermal treatment, etching, and high-temperature calcination, and then grows two-dimensional MOF material Cu-TCPP in situ, so that the two-dimensional MOF material Cu-TCPP coats the Fe2O3 precursor nanoparticles to obtain composite nanomaterial Fe2O3@Cu-TCPP; The present invention, by combining Fe2O3 and Cu-TCPP with a specific morphology, can significantly increase the active sites on the composite material, and effectively enhance the light absorption and electron transport capabilities of the composite material, enabling it to achieve photoresponsive OXD enzyme activity while possessing good OXD enzyme activity; Furthermore, the composite nanomaterial Fe2O3@Cu-TCPP prepared by the present invention can also achieve controllable ROS generation (with light-regulated activity) and controllable photothermal conversion under light irradiation, making it practical in photothermal and photodynamic therapy. Attached Figure Description
[0019] Figure 1 This is a flowchart illustrating the preparation of the composite nanomaterial Fe2O3@Cu-TCPP according to the present invention;
[0020] Figure 2 SEM images of Fe2O3 nanoparticles (a) prepared in Comparative Example 1, Cu-TCPP nanoflowers (b) prepared in Comparative Example 2, and Fe2O3@Cu-TCPP composite nanomaterials (c, d) prepared in Example 1.
[0021] Figure 3 SEM images of the products obtained in Comparative Examples 3 and 4.
[0022] Figure 4 The XRD patterns are of Fe2O3 nanoparticles, Cu-TCPP prepared in Comparative Examples 1 and 2, and the composite nanomaterial Fe2O3@Cu-TCPP prepared in Example 1.
[0023] Figure 5 The image shows the photodynamic response of the composite nanomaterial Fe2O3@Cu-TCPP nanozymes prepared in Comparative Examples 1, 2, 3 and Example 1.
[0024] Figure 6 The image shows the photothermal response of the Fe2O3@Cu-TCPP composite nanomaterial obtained in Example 1, which is a nanozyme. Detailed Implementation
[0025] Example 1
[0026] The preparation method of the composite nanomaterial Fe2O3@Cu-TCPP of the present invention includes the following steps:
[0027] (1) Add 3.8g K4Fe(CN)6·3H2O and 0.11g PVP to 50mL of 0.1M hydrochloric acid aqueous solution and mix thoroughly by magnetic stirring to obtain a mixed solution;
[0028] (2) The mixed solution was transferred into a polytetrafluoroethylene high-pressure reactor and subjected to a hydrothermal reaction at 80°C for 24 hours. After the reaction was completed, the solution was cooled and the reaction products were separated by centrifugation, washing with deionized water and ethanol.
[0029] (3) The reaction product was ultrasonically dispersed in 20 mL of ethanol, and 3.4 mL of 0.2 M NaOH solution was added. The mixture was shaken vigorously until the solution changed from blue (Fe4[Fe(CN)6]3) to yellow (Fe(OH)3). Fe(OH)3 nanoparticles with a hollow cubic structure were obtained by etching.
[0030] (4) The etched Fe(OH)3 nanoparticles were separated by centrifugation, washed, dried, and then placed in a muffle furnace and calcined at 300℃ for 6 h to obtain a Fe2O3 nanoparticle precursor with a hollow cubic structure. Its scanning electron microscope (SEM) results are shown below. Figure 2 As shown in (a), the Fe2O3 nanoparticles have a hollow cubic structure and a particle size of ~350 nm; their X-ray diffraction pattern is as follows. Figure 3 As shown;
[0031] (5) Add 2 mg H4TCPP to 1 mL of DMF / n-hexane solvent with a volume ratio of 3:1 and mix well to obtain mixture A; dissolve 10 mg CuCl2·2H2O in 1 mL of ethanol to obtain mixture B. Add mixture A and 20 mg Fe2O3 nanoparticle precursor prepared in step (4) to mixture B, mix thoroughly by magnetic stirring, react in an oil bath at 80℃ for 12 h, centrifuge, wash, and dry to obtain composite nanomaterial Fe2O3@Cu-TCPP. Its scanning electron microscope (SEM) image is shown below. Figure 2 As shown in (c, d), Fe2O3@Cu-TCPP consists of Fe2O3 nanoparticles coated with a two-dimensional nanosheet, and its X-ray diffraction pattern is shown in the figure. Figure 4 As shown, this demonstrates the successful preparation of the composite material obtained by the in-situ growth method.
[0032] Comparative Example 1
[0033] Comparative Example 1 shows the hollow cubic Fe2O3 nanoparticles prepared in Example 1, and their SEM image is shown below. Figure 1 As shown in (a).
[0034] Comparative Example 2
[0035] Preparation of Cu-TCPP nanozymes: 2 mg H4TCPP was added to 1 mL of DMF / n-hexane solvent with a volume ratio of 3:1 and mixed thoroughly to obtain mixture A; 10 mg CuCl2·2H2O was dissolved in 1 mL of ethanol to obtain mixture B. Mixture A was added to mixture B, and the mixture was thoroughly mixed by magnetic stirring. After reacting in an oil bath at 80℃ for 12 h, the mixture was centrifuged, washed, and dried to obtain Cu-TCPP nanoflowers. The SEM image is shown below. Figure 1 As shown in (b).
[0036] Comparative Example 3
[0037] A method for preparing composite nanomaterials includes the following steps:
[0038] (1) Add 3.8g K4Fe(CN)6·3H2O and 0.11g PVP to 50mL of 0.1M hydrochloric acid aqueous solution and mix thoroughly by magnetic stirring to obtain a mixed solution;
[0039] (2) The mixed solution was transferred into a polytetrafluoroethylene high-pressure reactor and subjected to a hydrothermal reaction at 80°C for 24 hours. After the reaction was completed, the solution was cooled and the reaction products were separated by centrifugation, washing with deionized water and ethanol.
[0040] (3) The reaction product was ultrasonically dispersed in 20 mL of ethanol, and 3.4 mL of 0.2 M NaOH solution was added. The mixture was shaken vigorously until the solution changed from blue (Fe4[Fe(CN)6]3) to yellow (Fe(OH)3). Fe(OH)3 nanoparticles with a hollow cubic structure were obtained by etching.
[0041] (4) The etching product Fe(OH)3 nanoparticles were separated by centrifugation, washed and dried and then placed in a muffle furnace and calcined at 300℃ for 6h to obtain Fe2O3 nanoparticle precursor with a hollow cubic structure. The Fe2O3 nanoparticles have a hollow cubic structure and a particle size of ~350nm.
[0042] (5) Add 2 mg H4TCPP to 1 mL of DMF / n-hexane solvent with a volume ratio of 3:1 and mix well to obtain mixture A; dissolve 10 mg CuCl2·2H2O in 1 mL of ethanol to obtain mixture B; add mixture A and 5 mg Fe2O3 nanoparticle precursor prepared in step (4) to mixture B, mix thoroughly by magnetic stirring, react in an oil bath at 80℃ for 12 h, centrifuge, wash and dry to obtain composite nanomaterial Fe2O3@excess Cu-TCPP.
[0043] Comparative Example 3, due to the excess of copper, resulted in a flower-like composite nanomaterial, the SEM morphology of which is shown below. Figure 3 As shown in (b).
[0044] Comparative Example 4
[0045] Compared to Example 1, Comparative Example 4 changed the amount of alkali solution to cause the structure of Fe(OH)3 nanoparticles to collapse. After high-temperature calcination, Fe2O3 with a collapsed structure was obtained, specifically as follows:
[0046] (1) Add 3.8g K4Fe(CN)6·3H2O and 0.11g PVP to 50mL of 0.1M hydrochloric acid aqueous solution and mix thoroughly by magnetic stirring to obtain a mixed solution;
[0047] (2) The mixed solution was transferred into a polytetrafluoroethylene high-pressure reactor and subjected to a hydrothermal reaction at 80°C for 24 hours. After the reaction was completed, the solution was cooled and the reaction products were separated by centrifugation, washing with deionized water and ethanol.
[0048] (3) The reaction product was ultrasonically dispersed in 20 mL of ethanol, and 5 mL of 0.2 M NaOH solution was added. The mixture was shaken vigorously until the solution changed from blue (Fe4[Fe(CN)6]3) to yellow (Fe(OH)3). Fe(OH)3 nanoparticles were obtained by etching. The above material was washed and dried, and then placed in a muffle furnace and calcined at 300 °C for 6 h to obtain Fe2O3 nanoparticles with cubic collapse. The SEM image is shown below. Figure 3 As shown in (a), adding excessive alkali solution will cause the hollow structure to collapse, making it impossible to successfully prepare hollow cubic iron oxide nanoparticles, and thus impossible to further prepare Fe2O3@Cu-TCPP composite materials.
[0049] Photodynamic response of composite nanomaterials
[0050] The enzyme-like activities of the composite nanomaterial Fe2O3@Cu-TCPP and Cu-TCPP nanozymes prepared in Example 1, under both illumination and without light, were compared using a TMB colorimetric reaction. 10 μL of the prepared sample (1 μmol / mL) was placed in an acetate-sodium acetate buffer solution (pH = 3.5), and the activity was tested under light using TMB as a substrate. The enzyme-like activities at different time points were quantified using a UV spectrophotometer.
[0051] like Figure 5 As shown, Fe2O3@Cu-TCPP cannot oxidize the substrate under light-free conditions, while Fe2O3, Cu-TCPP, Fe2O3@excess Cu-TCPP, and Fe2O3@Cu-TCPP prepared in Example 1 can all generate ROS under light irradiation, and the nanozyme rapidly oxidizes TMB. Compared with Fe2O3 and Cu-TCPP, the composite nanomaterial Fe2O3@Cu-TCPP prepared in Example 1 has significantly improved enzyme activity; in addition, since the addition of excess Cu reduces the effective electron transport area, the activity of Fe2O3@excess Cu-TCPP is significantly lower than that of Fe2O3@Cu-TCPP.
[0052] Photothermal response of composite nanomaterials
[0053] like Figure 6 As shown, the photothermal conversion heating effect of the composite nanomaterial Fe2O3@Cu-TCPP in Example 1 under light-free and light-free cycling was measured using an optical fiber thermometer, and its cycling stability was verified. This demonstrates that the composite nanoenzyme has good stability and is promising for application in disease treatment.
Claims
1. A composite nanomaterial with photoresponsive nanoenzyme activity, characterized in that: The composite nanomaterial includes hollow Fe2O3 nanoparticles and Cu-TCPP nanosheets coated on the hollow Fe2O3 nanoparticles. The Cu-TCPP nanosheets are grown in situ on the surface of the hollow Fe2O3 nanoparticles through coordination bonds.
2. The composite nanomaterial according to claim 1, characterized in that: The hollow Fe2O3 nanoparticles have a particle size of 200–500 nm.
3. The method for preparing the composite nanomaterial according to claim 1, characterized in that, Includes the following steps: (1) Preparation of Prussian blue: K4Fe(CN)6·3H2O and PVP were thoroughly mixed in hydrochloric acid solution, and after hydrothermal reaction, the reaction product Fe4[Fe(CN)6]3 was separated. (2) The reaction product was dispersed in ethanol, and NaOH solution was added according to the stoichiometric ratio of Fe4[Fe(CN)6]3 to NaOH. After the reaction, Fe(OH)3 nanoparticles with hollow cubes were obtained. (3) Calcine Fe(OH)3 nanoparticles to obtain Fe2O3 nanoparticle precursors in the form of hollow cubes; (4) Add H4TCPP to an organic solvent and mix well to obtain mixture A. Add copper salt to the solvent to obtain mixture B. Add mixture A and Fe2O3 nanoparticle precursor from step (3) to mixture B and react under heating conditions to obtain composite nanomaterial Fe2O3@Cu-TCPP.
4. The preparation method according to claim 3, characterized in that: In step (1), the mass ratio of K4Fe(CN)6·3H2O to PVP is 30:1 to 40:
1.
5. The preparation method according to claim 3, characterized in that: In step (1), the hydrothermal reaction takes 12 to 24 hours and the reaction temperature is 80 to 100°C.
6. The preparation method according to claim 3, characterized in that: In step (3), the calcination temperature is 300-350℃ and the calcination time is 6-8h.
7. The preparation method according to claim 3, characterized in that: In step (4), the organic solvent that forms mixture A is a mixture of DMF and n-hexane, wherein the volume ratio of DMF to n-hexane is 3:1 to 1.
5.
8. The preparation method according to claim 3, characterized in that: In step (4), the solvent for forming mixture B is ethanol; the copper salt is CuCl2·2H2O.
9. The preparation method according to claim 8, characterized in that: The mass ratio of Fe2O3 nanoparticle precursor, CuCl2·2H2O and H4TCPP is 20–40:10–15:2–5.
10. The preparation method according to claim 3, characterized in that: In step (4), the reaction is carried out under magnetic stirring for 12 to 24 hours and at a temperature of 80 to 100°C.