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CN-117138041-B - Preparation method and application of polypyrrole-Prussian blue hybrid photothermal nano-enzyme

CN117138041BCN 117138041 BCN117138041 BCN 117138041BCN-117138041-B

Abstract

The invention relates to a preparation method of polypyrrole-Prussian blue hybridization photo-thermal nano enzyme, which comprises the steps of adding polyvinylpyrrolidone into deionized water, stirring until the polyvinylpyrrolidone is completely dissolved, adding pyrrole and potassium ferrocyanide into the obtained polyvinylpyrrolidone solution, stirring uniformly, adding ferric trichloride hexahydrate, fully stirring for reaction to obtain a reaction solution, centrifuging to remove precipitate, dialyzing the supernatant, and performing vacuum freeze drying to obtain the polypyrrole-Prussian blue hybridization photo-thermal nano enzyme. Compared with the existing method, the method has lower requirements on equipment, mild reaction conditions, environment friendliness and suitability for large-scale production, the prepared photo-thermal nano enzyme has good photo-thermal ablation effect under the irradiation of near infrared light, can remarkably inhibit the growth of tumor cells, has good oxygen production performance, can decompose hydrogen peroxide to generate oxygen, further improves the tumor hypoxia microenvironment, enhances the in-situ thermal ablation treatment effect of the tumor, and provides a potential technical means for relieving the tumor hypoxia microenvironment and strengthening in-situ thermal ablation.

Inventors

  • XU XIAO
  • YU HUIJUN
  • DU FENGYI
  • ZOU SHENGQIANG
  • WANG JINLAN

Assignees

  • 镇江市第三人民医院

Dates

Publication Date
20260508
Application Date
20230818

Claims (7)

  1. 1. The preparation method of the polypyrrole-Prussian blue hybrid photothermal nano enzyme is characterized by comprising the following steps of: (1) Adding polyvinylpyrrolidone into deionized water, and stirring until the polyvinylpyrrolidone is completely dissolved to obtain polyvinylpyrrolidone solution; (2) Adding pyrrole and potassium ferrocyanide into polyvinylpyrrolidone solution, stirring uniformly, adding ferric trichloride hexahydrate, and stirring fully for reaction to obtain a reaction solution; (3) Centrifuging the reaction solution, removing the precipitate to obtain a supernatant, dialyzing the supernatant, and performing vacuum freeze drying to obtain polypyrrole-Prussian blue hybridized photothermal nano enzyme; In the step (2), the molar ratio of the pyrrole to the potassium ferrocyanide is (1-15): 1-15.
  2. 2. The preparation method of polypyrrole-Prussian blue hybridization photothermal nano enzyme according to claim 1, wherein in the step (1), the concentration of the polyvinylpyrrolidone solution is 5-20 mg/mL.
  3. 3. The preparation method of polypyrrole-Prussian blue hybridization photothermal nano enzyme according to claim 1, wherein in the step (2), the dosage of ferric trichloride hexahydrate accounts for 25-40% of the total mass of pyrrole and potassium ferrocyanide.
  4. 4. The method for preparing polypyrrole-Prussian blue hybridization photothermal nano enzyme according to claim 1, wherein in the step (3), the centrifugation condition is 3000rpm, and the centrifugation is carried out for 15min.
  5. 5. The method for preparing polypyrrole-Prussian blue hybridization photothermal nano enzyme according to claim 1, wherein in the step (3), a dialysis bag of 100000MWCO is adopted for dialysis, and the dialysis time is 72 hours.
  6. 6. The method for preparing polypyrrole-Prussian blue hybridized photothermal nano enzyme according to any one of claims 1 to 5, wherein in the step (3), the freeze-drying temperature is-80 ℃ and the time is 48h.
  7. 7. The use of polypyrrole-Prussian blue hybridized photothermal nano enzyme prepared by the method of any one of claims 1-6 in preparation of photothermal therapeutic drugs for tumors.

Description

Preparation method and application of polypyrrole-Prussian blue hybrid photothermal nano-enzyme Technical Field The invention belongs to the technical field of medical materials, and particularly relates to a preparation method and application of polypyrrole-Prussian blue hybridization photo-thermal nano-enzyme. Background Photothermal ablation is an emerging tumor in-situ treatment method, and the principle is that near infrared light is used for irradiating a photosensitizer enriched in a tumor area, so that local high Wen Shashang tumor cells are generated. Polypyrrole photo-thermal nano enzyme has been attracting attention in the field of tumor photo-thermal treatment due to its good biocompatibility, excellent photo-stability and good photo-thermal conversion effect. It can generate enough heat under near infrared light irradiation to kill tumor cells and induce anti-tumor immunity, and has therapeutic effect. However, due to the hypoxic microenvironment in the tumor, the photothermal nano-enzyme cannot effectively play a role of photothermal ablation to kill tumor cells, so that the treatment effect is remarkably reduced, and meanwhile, the intensity of photothermal ablation cannot be accurately controlled, so that the photothermal nano-enzyme is challenging in clinical transformation. Therefore, development of the photothermal nanomaterial capable of improving the tumor hypoxia microenvironment and further enhancing the photothermal ablation technology of the tumor is particularly necessary for improving the treatment effect. Prussian blue light thermal nano-enzyme has good biocompatibility and unique performance, and draws attention of extensive biomedical researchers. Studies have proved that Prussian Lan Guangre nano-enzyme can be used as a therapeutic drug based on the inherent biological activity and imaging capability, can remove redundant Reactive Oxygen Species (ROS) in vivo to treat ROS related diseases, and can decompose hydrogen peroxide into oxygen through the catalytic activities of enzymes such as Peroxidase (POD), catalase (CAT) and superoxide dismutase (SOD) to improve the hypoxia state of tumor microenvironment. If photo-thermal ablation and enzyme are combined, the tumor hypoxia microenvironment can be improved, so that the photo-thermal curative effect of the tumor can be enhanced. However, there is currently a lack of technology combining photothermal ablation with enzymes, and thus there is a need for techniques that seek to provide efficient, adjustable, enhanced means of photothermal ablation of tumors in clinical solid tumors. Disclosure of Invention The invention aims to overcome the defects of the prior art and provide a preparation method of polypyrrole-Prussian blue hybridization photo-thermal nano enzyme, and the prepared photo-thermal nano enzyme has double functions of photo-thermal and enzyme catalytic activity, can decompose hydrogen peroxide to generate oxygen to improve the tumor hypoxia microenvironment and can enhance the photo-thermal curative effect of tumors when being applied to photo-thermal treatment of tumors. In order to achieve the technical purpose, the invention adopts the following technical scheme: The preparation method of the polypyrrole-Prussian blue hybrid photothermal nano enzyme comprises the following steps: (1) Adding polyvinylpyrrolidone into deionized water, and stirring until the polyvinylpyrrolidone is completely dissolved to obtain polyvinylpyrrolidone solution; (2) Adding Pyrrole (PY) and potassium ferrocyanide (K 4Fe(CN)6) into polyvinylpyrrolidone solution, stirring uniformly, adding ferric trichloride hexahydrate (Fecl 3·6H2 O), and fully stirring for reaction to obtain a reaction solution; (3) Centrifuging the reaction solution, removing the precipitate to obtain a supernatant, dialyzing the supernatant, and performing vacuum freeze-drying to obtain the polypyrrole-Prussian blue hybridization photothermal nano enzyme (PPY@PB NEs). In the step (2), the molar ratio of the pyrrole to the potassium ferrocyanide is (1-15): 1-15. Further, in the step (1), the concentration of the polyvinylpyrrolidone solution is 5 to 20mg/mL, more preferably 10mg/mL. Further, in the step (2), the usage amount of the ferric trichloride hexahydrate accounts for 25-40% of the total mass of the pyrrole and the potassium ferrocyanide. Further, in the step (3), the centrifugation condition is 3000rpm, and the centrifugation is performed for 15min. Further, in the step (3), the dialysis is performed by using a 100000MWCO dialysis bag, and the dialysis time is 72 hours. Further, in the step (3), the temperature of the freeze drying is-80 ℃ and the time is 48 hours. The polypyrrole-Prussian blue hybridized photothermal nano enzyme prepared by the method is applied to preparation of photothermal therapeutic drugs for tumors. Compared with the prior art, the invention has the beneficial effects that: The invention provides a preparation method of polypyrrole-Prussian