Manganese-containing Prussian blue-cerium oxide composite nanomaterial as well as preparation method and application thereof
The manganese-containing Prussian blue-alumina composite nanomaterial prepared through chemical synthesis combines imaging and antioxidant functions, solving the problem of insufficient ability of a single material in imaging and antioxidant, and achieving versatility and good biocompatibility.
Patent Information
- Application Number
- CN202411914931.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-24
- Publication Date
- 2025-05-16
AI Technical Summary
The existing single Prussian blue, alumina or manganese oxide materials have problems such as poor imaging capabilities and limited antioxidant capabilities in magnetic resonance imaging and antioxidant.
Manganese-containing Prussian blue-alumina composite nanomaterials were prepared by chemical synthesis method, which combined the imaging function of Prussian blue with the antioxidant function of alumina.
It realizes antioxidant and MRI imaging functions inside and outside the organism, has significant versatility and good biocompatibility, and is suitable for early detection and treatment under various pathological conditions such as cancer and cardiovascular diseases.
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Figure CN120004288A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of nano materials, and specifically relates to a manganese-containing Prussian blue-cerium oxide composite nano material and a preparation method and application thereof. Background Art
[0002] Prussian blue (PBNP) is an inorganic nanomaterial that has been approved by the US FDA as an antidote for radioactive substances. It has good biocompatibility and has shown broad application prospects in magnetic resonance imaging and radiotherapy in recent years. PBNPs have a typical mixed valence state (Fe 2+ and Fe 3+ ) coordination compound, the face-centered cubic lattice structure of PBNPs is composed of Fe 2+ and Fe 3+ The valence electrons can pass through the cyano group on Fe 2+ and Fe 3+ This makes PBNPs have good electrochemical properties and can effectively carry out anti-reduction reactions. In addition, PBNPs can shorten the longitudinal relaxation time of water protons and can be used for magnetic resonance imaging. These excellent properties of PBNPs make them widely used in biosensing, bioimaging, antibacterial and anti-tumor fields. However, since the longitudinal relaxation value (r1) of PBNPs is small, metal ions can be added to increase its r1 value.
[0003] Considering the biological toxicity, studies have shown that MnO2 nanoparticles can be decomposed into water-soluble Mn 2+ , so that it can be quickly excreted from the body to avoid long-term accumulation and unnecessary toxicity in the body. Therefore, MnO2-encapsulated Prussian blue not only has good biocompatibility, but also can produce Mn 2+ Improve T1-weighted imaging capabilities. Cerium oxide is a known strong antioxidant that can effectively scavenge reactive oxygen species (ROS) and has potential applications in cancer treatment and neuroprotection. However, due to the single Prussian blue, manganese dioxide or cerium oxide, there are often certain limitations, such as weak imaging capabilities and limited antioxidant capacity. Therefore, combining Prussian blue, manganese dioxide and cerium oxide materials to achieve better performance through synergy is a topic of great research value. Summary of the invention
[0004] The technical problem to be solved by the present invention is to provide a manganese-containing Prussian blue-cerium oxide composite nanomaterial with both antioxidant and imaging enhancement functions. The material is prepared by a simple chemical synthesis method, can achieve antioxidant and MRI imaging functions in vivo and in vitro, and can be used for early detection and treatment of various pathological conditions such as cancer and cardiovascular disease.
[0005] The technical solution adopted by the present invention is as follows:
[0006] A method for preparing a manganese-containing Prussian blue-cerium oxide composite nanomaterial comprises the following steps:
[0007] Polyvinyl pyrrolidone and potassium ferrocyanide were used to prepare polyvinyl pyrrolidone-modified Prussian blue.
[0008] Manganese-containing Prussian blue was prepared by using Prussian blue modified with polyvinyl pyrrolidone and potassium permanganate solution;
[0009] Manganese-containing Prussian blue-cerium oxide composite nanoparticles are prepared by using manganese-containing Prussian blue, cerium nitrate and hexamethylenetetramine.
[0010] Furthermore, the preparation of polyvinyl pyrrolidone-modified Prussian blue using polyvinyl pyrrolidone and potassium ferrocyanide comprises:
[0011] Weigh polyvinyl pyrrolidone and potassium ferrocyanide in a mass ratio of 30:1, disperse them in deionized water by ultrasonication, and stir for 30-60 minutes to fully dissolve the polyvinyl pyrrolidone and potassium ferrocyanide to obtain a solution of polyvinyl pyrrolidone and potassium ferrocyanide;
[0012] Slowly adding anhydrous ethanol to a solution of polyvinyl pyrrolidone and potassium ferrocyanide under the combined action of ultrasound and stirring to make the ethanol concentration 30-50%, continuing stirring until the reaction system becomes a uniform, clear light yellow solution, and then adjusting the pH value of the solution to 2-3 to obtain a reaction solution;
[0013] The obtained reaction solution is heated to 80-100° C., reacted for 3-6 hours, the reaction product is taken out, cooled to room temperature, centrifuged, and washed with anhydrous ethanol and deionized water respectively to obtain polyvinyl pyrrolidone-modified Prussian blue.
[0014] Furthermore, the centrifugal treatment is performed at a speed of 15000 rpm for 20 minutes; and the washing with anhydrous ethanol and deionized water is performed twice with each of anhydrous ethanol and deionized water.
[0015] Furthermore, the preparation of manganese-containing Prussian blue using polyvinyl pyrrolidone-modified Prussian blue and potassium permanganate solution comprises:
[0016] Take an appropriate amount of polyvinyl pyrrolidone-modified Prussian blue and dissolve it in water, perform ultrasonic treatment to disperse it evenly, then stir it, and slowly add potassium permanganate solution dropwise, the mass ratio of potassium permanganate to Prussian blue is 1:2 to 1:1;
[0017] The product is centrifuged and washed with deionized water to remove unreacted ions and by-products, and then dried to obtain manganese-containing Prussian blue.
[0018] Furthermore, the ultrasonic treatment time is 15-30 minutes; the centrifugal treatment time is 15-20 minutes.
[0019] Furthermore, the method of preparing manganese-containing Prussian blue-cerium oxide composite nanoparticles by using manganese-containing Prussian blue, cerium nitrate and hexamethylenetetramine comprises:
[0020] Take an appropriate amount of Prussian blue containing manganese, dissolve it evenly in a mixed solution of ethanol and water, and treat it with ultrasound for a certain period of time;
[0021] Add cerium nitrate and hexamethylenetetramine in sequence, heat the mixed solution to 70-90°C, reflux for 2-4 hours under magnetic stirring, and then cool the solution to room temperature;
[0022] The blue product was collected by centrifugation, washed with deionized water and dried to obtain manganese-containing Prussian blue-cerium oxide composite nanoparticles.
[0023] Furthermore, the volume ratio of the ethanol to water is 1:1 to 2:1, and the mass ratio of the cerium nitrate to hexamethylenetetramine is 10:11 to 15:11.
[0024] The invention also provides a manganese-containing Prussian blue-cerium oxide composite nano material prepared according to the method.
[0025] The present invention also provides application of the manganese-containing Prussian blue-cerium oxide composite nanomaterial in magnetic resonance imaging.
[0026] The present invention also provides application of the manganese-containing Prussian blue-cerium oxide composite nanomaterial in antioxidant therapeutic drugs.
[0027] The beneficial effects of the present invention are as follows:
[0028] 1) Multifunctionality: The manganese-containing Prussian blue-cerium oxide composite nanomaterial of the present invention combines the imaging function of manganese-containing Prussian blue with the antioxidant function of cerium oxide, and has significant multifunctionality.
[0029] 2) Biocompatibility: The manganese-containing Prussian blue and cerium oxide in the manganese-containing Prussian blue-cerium oxide composite nanomaterial of the present invention are both inorganic materials with good biocompatibility and exhibit low toxicity in vivo.
[0030] 3) Simple preparation: The preparation process of the manganese-containing Prussian blue-cerium oxide composite nanomaterial of the present invention is simple, easy to scale up, and suitable for large-scale production.
[0031] In summary, the present invention provides a multifunctional manganese-containing Prussian blue-cerium oxide composite nanomaterial, which can be widely used in the biomedical field, especially in antioxidant therapy and MRI imaging, through optimized preparation methods and surface modification. The versatility and good biocompatibility of this material make it have broad prospects in future clinical applications. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] Figure 1 : Flow chart of the preparation of manganese-containing Prussian blue-cerium oxide composite nanoparticles.
[0033] Figure 2 : Particle size distribution and scanning and transmission electron micrographs of manganese-containing Prussian blue-cerium oxide composite materials. A is a scanning electron micrograph of Prussian blue, B is a scanning electron micrograph of manganese-containing Prussian blue, C is a scanning electron micrograph of a manganese-containing Prussian blue-cerium oxide composite, D is a transmission electron micrograph of manganese-containing Prussian blue, E is a transmission electron micrograph of a manganese-containing Prussian blue-cerium oxide composite, and F is a particle size distribution of manganese-containing Prussian blue-cerium oxide.
[0034] Figure 3 : Schematic diagram of the antioxidant mechanism of composite nanomaterials and detection of the oxidase-like enzyme efficiency. A is the schematic diagram of the antioxidant mechanism of composite nanomaterials, B is the consumption of H2O2 by the nanocomposite, and C is the quenching effect of ·OH by the nanocomposite.
[0035] Figure 4 :Toxicity of composite nanomaterials, in vitro MRI imaging performance detection. A is the H9c2 cell activity detection, B is the linear relationship between the reciprocal of T1 relaxation time and Fe concentration, C is the linear relationship between the reciprocal of T1 relaxation time and Fe+Mn concentration, and D is the T1 weighted image of PB@CeONP and PB-Mn@CeONP.
[0036] Figure 5 :In vitro and in vivo antioxidant efficacy detection of composite nanomaterials. A is the immunofluorescence analysis of the reactive oxygen levels in the heart slices of each group of mice, B is the ROS level detection, DOX represents the group treated with doxorubicin, control represents the control group, i.e., the untreated group, ROS depletion represents the reactive oxygen elimination effect, and the statistical graph in the lower right corner of B is the fluorescence intensity graph. DETAILED DESCRIPTION
[0037] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below through specific embodiments and drawings.
[0038] 1. Preparation method of manganese-containing Prussian blue-cerium oxide composite nanomaterial
[0039] The material adopts a hydrothermal method to synthesize manganese-containing Prussian blue and cerium oxide composite nanoparticles, and the specific steps are as follows:
[0040] Step 1: Weigh polyvinylpyrrolidone K30 (PVP) and potassium ferrocyanide in a mass ratio of 30:1, disperse them in deionized water by ultrasonication, and stir for 30-60 minutes to allow the PVP and potassium ferrocyanide to be fully dissolved, thereby obtaining a solution of PVP and potassium ferrocyanide.
[0041] Step 2: Slowly add anhydrous ethanol to the solution of PVP and potassium ferrocyanide obtained in step 1 under the combined action of ultrasound and stirring to make the ethanol concentration 30-50%. Continue stirring until the reaction system becomes a uniform, clear light yellow solution, and then adjust the pH value of the solution to 2-3 to obtain a reaction solution.
[0042] Step 3: Heat the reaction solution obtained in step 2 to 80-100°C, react for 3-6 hours, then take out the reaction product, cool it to room temperature, centrifuge it for a certain time (e.g., 20-25 minutes), and wash it with anhydrous ethanol and deionized water respectively to obtain PVP-modified Prussian blue.
[0043] Step 4: Take an appropriate amount of PVP-modified Prussian blue obtained in step 3 and dissolve it in water. Ultrasonicate it for 15-30 minutes to disperse it evenly, then stir it, and slowly add freshly prepared KMnO4 solution (1 mg / mL) dropwise, that is, the mass ratio of KMnO4:PBNPs is 1:2 to 1:1, and stir it for a certain time (for example, 25-30 minutes).
[0044] Step 5: The solution obtained in step 4 is centrifuged for 15-20 minutes, repeatedly washed with deionized water to remove unreacted ions and by-products, and dried to obtain manganese-containing Prussian blue.
[0045] Step 6: Take an appropriate amount of the product of step 5, dissolve it evenly in a mixed solution of ethanol and water in a volume ratio of 1:1 to 2:1, and perform ultrasonic treatment for a certain period of time.
[0046] Step 7: Add cerium nitrate and hexamethylenetetramine (HMT) in a mass ratio of 10:11 to 15:11 to the solution obtained in step 6, heat the mixed solution to 70-90° C., reflux for 2-4 hours under magnetic stirring, and then cool the solution to room temperature. The hexamethylenetetramine is used as a precipitant and complexing agent in the reaction system.
[0047] Step 8: Centrifuge the solution obtained in step 7, collect the blue product, wash it once with deionized water, and then dry it for a certain period of time (eg, 10-12 hours) to finally obtain manganese-containing Prussian blue-cerium oxide composite nanoparticles.
[0048] 2. Particle size control of composite nanomaterials
[0049] Particle size has a significant impact on the performance of nanomaterials. In order to control the particle size of the material, the inventor adjusted the reaction conditions, such as reaction time, temperature, pH value, etc. through a large number of experiments, and finally obtained the conditions for controlling the particle size of the manganese-containing Prussian blue-cerium oxide composite material within the range of 80-150 nanometers, ensuring its good biodistribution in the body.
[0050] 3. Magnetic resonance imaging (MRI) contrast agents
[0051] Prussian blue has excellent T1-weighted imaging effect, Mn 2+ The imaging effect can be enhanced. The material can be used to enhance the contrast of MRI images and can be used as a new type of MRI negative contrast agent for early diagnosis of cardiovascular diseases, tumors, etc.
[0052] 4. Antioxidant Therapy
[0053] Cerium oxide, with its unique properties in redox reactions, can dynamically regulate the level of reactive oxygen species in the body and prevent cell damage caused by oxidative stress. This composite nanomaterial can remove reactive oxygen species in the body and reduce oxidative stress in tumor microenvironments or cardiovascular diseases, thereby playing an antioxidant therapeutic role.
[0054] Specific examples of the present invention are provided below.
[0055] Example 1: Preparation of manganese-containing Prussian blue-cerium oxide composite nanomaterials.
[0056] Raw material preparation: polyvinylpyrrolidone K30 (PVP); potassium ferrocyanide; deionized water; anhydrous ethanol; 37% hydrochloric acid; potassium permanganate; Ce(NO3)3·6H2O; hexamethylenetetramine (HMT)
[0057] Preparation process: The preparation method is as follows Figure 1 As shown, this embodiment specifically includes the following steps:
[0058] Step 1: Weigh 15 g of polyvinylpyrrolidone K30 (PVP) and 0.55 g of potassium ferrocyanide, disperse them in 110 ml of deionized water by ultrasonication, and stir for 30 minutes to allow the PVP and potassium ferrocyanide to be fully dissolved, thereby obtaining a solution of PVP and potassium ferrocyanide.
[0059] Step 2: Slowly and accurately add 90 mL of anhydrous ethanol to the solution of PVP and potassium ferrocyanide obtained in step 1 under the combined action of ultrasound and stirring. Continue stirring until the reaction system becomes a uniform, clear light yellow solution, and then adjust the pH value to 2 with hydrochloric acid to obtain a reaction solution.
[0060] Step 3: Place the reaction solution obtained in step 2 in a water bath at 80°C for 3 hours, then take it out and cool it to room temperature. Centrifuge it at a speed of 15,000 rpm for 20 minutes, and wash it twice with ethanol and deionized water to obtain PVP-modified Prussian blue.
[0061] Step 4: Take 10 mg of PVP-modified Prussian blue obtained in step 3 and dissolve it in water. Ultrasonicate for 30 minutes to disperse it evenly, then stir at 400 rpm, and slowly add 10 mL of freshly prepared KMnO4 solution (1 mg / mL), that is, the mass ratio of KMnO4:PBNPs is 1:1, and stir for 25 minutes.
[0062] Step 5: The solution obtained in step 4 was centrifuged at a speed of 15000 rpm for 20 minutes, repeatedly washed with deionized water to remove unreacted ions and by-products, and dried at 37° C. to obtain manganese-containing Prussian blue.
[0063] Step 6: Take 50 mg of the product from step 5, dissolve it evenly in 20 mL of ethanol and 20 mL of water, and treat it with ultrasound for 10 minutes.
[0064] Step 7: 17 mg of Ce(NO3)3·6H2O and 15 mg of hexamethylenetetramine (HMT) were added to the solution obtained in step 6, and the mixed solution was heated to 70°C, refluxed under magnetic stirring for 2 hours, and then the solution was cooled to room temperature.
[0065] Step 8: The solution obtained in step 7 is centrifuged to collect the blue product, which is washed once with deionized water and then dried at 60° C. overnight to finally obtain manganese-containing Prussian blue-cerium oxide composite nanoparticles.
[0066] Particle size control: During the preparation process, the particle size of the nanoparticles can be controlled within the range of 80-150 nanometers by adjusting the reaction time, pH value and temperature conditions of the solution. The particle size distribution of the nanoparticles was determined using a dynamic light scattering instrument (DLS), and their morphology and size were observed using scanning and transmission electron microscopy (SEM). Figure 2 ).
[0067] Example 2: In vitro oxidase-like property verification experiment and MRI imaging experiment of the composite material.
[0068] H2O2 and ·HO are pathological free radicals. These two are used to verify the antioxidant capacity of the material. The antioxidant mechanism diagram is shown in Figure 3 As shown in A. Figure 3 As shown in Figures B and C, the ability of the nanocomplex to quench ·OH was studied by EPR using DMPO (Adamas-beta) as a spin probe.-3 M) was added with TPA-Na (10×10 -3 M). The mixture was shaken at 45°C in the dark for 10 minutes, and then a sample was extracted and measured using a fluorescence spectrometer.
[0069] MRI imaging experiment: A 3T MRI scanner was used to obtain T1W grayscale images of PB@CeONP and PB-Mn@CeONP, and the signal intensity of the region of interest in the grayscale image was quantitatively measured to obtain the longitudinal relaxation rate of the material ( Figure 4 (B, C, D).
[0070] Example 3: Protective effect of composite materials on oxidative stress-induced cell damage (adriamycin-induced cardiomyocytes)
[0071] Cell experimental materials: H9c2 cardiomyocyte cell line, DMEM culture medium (containing 1.5 g NaHCO3), fetal bovine serum (FBS), doxorubicin (DOX), manganese-containing Prussian blue-cerium oxide composite nanomaterials (20 μg / mL).
[0072] Cell culture: H9c2 cardiomyocytes were seeded in 96-well plates and 6-well plates, respectively, and cultured in DMEM medium (containing 1.5 g NaHCO 3 ) containing 10% FBS, and cultured in a 37° C., 5% CO 2 incubator for 24 hours.
[0073] Establishment of oxidative stress injury model: Oxidative stress injury was induced by adding 1 μM DOX to treat cells for 24 hours.
[0074] Cell viability determination: 3.125, 6.25, 12.5, 25, 50, and 100 μg / mL of manganese-containing Prussian blue-cerium oxide composite nanomaterials and simple manganese-containing Prussian blue were added to the cells in the composite nanomaterial treatment group and incubated for 24 hours. The cell viability was evaluated by the MTT method. Figure 4 The results in Figure A showed that the cell survival rate of the group treated with the manganese-containing Prussian blue-cerium oxide composite material was significantly higher than that of the group treated with the manganese-containing Prussian blue alone, indicating that the material has a strong antioxidant effect on cell damage induced by oxidative stress.
[0075] ROS level detection: 20 μg / mL manganese-containing Prussian blue-cerium oxide composite nanomaterials were added to the cells in the composite nanomaterial treatment group and incubated for 24 hours. No nanomaterials were added to the control group. The DCFH-DA fluorescent probe was used to detect the level of reactive oxygen species (ROS) in the cells. Figure 5 The results in Figure B showed that the intracellular ROS level in the composite material treatment group was significantly reduced, further verifying its antioxidant capacity.
[0076] Example 4: Antioxidant effect of the composite material in a mouse myocardial injury model.
[0077] Experimental animals: Healthy 6-8 week old male C57BL / 6 mice (20-25 g) were selected and randomly divided into three groups: control group, model group and material group, with 3 mice in each group.
[0078] Establishment of myocardial injury model: The myocardial injury model of mice was established by injecting 0.5 mg / ml doxorubicin (DOX). Doxorubicin was intraperitoneally injected at a dose of 7.5 mg / kg, administered every other day, twice, with a total dose of 15 mg / kg. Myocardial injury was gradually induced, and the injury model was obtained after one week. The control group was injected with an equal amount of normal saline.
[0079] Injection of manganese-containing Prussian blue-cerium oxide composite nanomaterials: After the last doxorubicin injection, the mice in the material group were injected with manganese-containing Prussian blue-cerium oxide composite nanomaterials (concentration of 1 mg / mL, dose of 1 mL / kg) through the tail vein, and the mice in the control group were injected with normal saline.
[0080] Immunofluorescence section analysis: Figure 5 A was used to analyze and quantify the level of reactive oxygen species in the heart slices of each group of mice. DHE (1:500) was used for staining and incubated in a 37°C incubator in the dark for 3 hours.
[0081] The specific embodiments of the present invention disclosed above are intended to help understand the content of the present invention and implement it accordingly. It can be understood by those skilled in the art that various replacements, changes and modifications are possible without departing from the spirit and scope of the present invention. The present invention should not be limited to the contents disclosed in the embodiments of this specification, and the scope of protection of the present invention shall be subject to the scope defined in the claims.
Claims
1. A method for preparing a manganese-containing Prussian blue-cerium oxide composite nanomaterial, characterized in that: The following steps are involved: Polyvinyl pyrrolidone and potassium ferrocyanide were used to prepare polyvinyl pyrrolidone-modified Prussian blue. Manganese-containing Prussian blue was prepared by using Prussian blue modified with polyvinyl pyrrolidone and potassium permanganate solution; Manganese-containing Prussian blue-cerium oxide composite nanoparticles are prepared by using manganese-containing Prussian blue, cerium nitrate and hexamethylenetetramine.
2. The method according to claim 1, characterized in that The method of preparing polyvinyl pyrrolidone-modified Prussian blue by using polyvinyl pyrrolidone and potassium ferrocyanide comprises: Weigh polyvinyl pyrrolidone and potassium ferrocyanide in a mass ratio of 30:1, disperse them in deionized water by ultrasonication, and stir for 30-60 minutes to fully dissolve the polyvinyl pyrrolidone and potassium ferrocyanide to obtain a solution of polyvinyl pyrrolidone and potassium ferrocyanide; Slowly adding anhydrous ethanol to a solution of polyvinyl pyrrolidone and potassium ferrocyanide under the combined action of ultrasound and stirring to make the ethanol concentration 30-50%, continuing stirring until the reaction system becomes a uniform, clear light yellow solution, and then adjusting the pH value of the solution to 2-3 to obtain a reaction solution; The obtained reaction solution is heated to 80-100° C., reacted for 3-6 hours, the reaction product is taken out, cooled to room temperature, centrifuged, and washed with anhydrous ethanol and deionized water respectively to obtain polyvinyl pyrrolidone-modified Prussian blue.
3. The method according to claim 2, characterized in that The centrifugal treatment is performed at a speed of 15000 rpm for 20 minutes; the washing with anhydrous ethanol and deionized water is performed twice each.
4. The method according to claim 2, characterized in that: The method of preparing manganese-containing Prussian blue by using polyvinyl pyrrolidone-modified Prussian blue and potassium permanganate solution comprises: Take an appropriate amount of polyvinyl pyrrolidone-modified Prussian blue and dissolve it in water, perform ultrasonic treatment to disperse it evenly, then stir it, and slowly add potassium permanganate solution dropwise, the mass ratio of potassium permanganate to Prussian blue is 1:2 to 1:1; The product is centrifuged and washed with deionized water to remove unreacted ions and by-products, and then dried to obtain manganese-containing Prussian blue.
5. The method according to claim 4, characterized in that The duration of the ultrasonic treatment is 15-30 minutes; the duration of the centrifugal treatment is 15-20 minutes.
6. The method according to claim 4, characterized in that The method of preparing manganese-containing Prussian blue-cerium oxide composite nanoparticles by using manganese-containing Prussian blue, cerium nitrate and hexamethylenetetramine comprises: Take an appropriate amount of Prussian blue containing manganese, dissolve it evenly in a mixed solution of ethanol and water, and treat it with ultrasound for a certain period of time; Add cerium nitrate and hexamethylenetetramine in sequence, heat the mixed solution to 70-90°C, reflux for 2-4 hours under magnetic stirring, and then cool the solution to room temperature; The blue product was collected by centrifugation, washed with deionized water and dried to obtain manganese-containing Prussian blue-cerium oxide composite nanoparticles.
7. The method according to claim 6, characterized in that The volume ratio of the ethanol to water is 1:1 to 2:1, and the mass ratio of the cerium nitrate to hexamethylenetetramine is 10:11 to 15:
11.
8. A manganese-containing Prussian blue-cerium oxide composite nanomaterial prepared according to the method of any one of claims 1 to 7.
9. Use of the manganese-containing Prussian blue-cerium oxide composite nanomaterial according to claim 8 in magnetic resonance imaging.
10. Use of the manganese-containing Prussian blue-cerium oxide composite nanomaterial according to claim 8 in antioxidant therapeutic drugs.