Preparation method of nanometer prussian blue material with honeycomb channel structure

Abstract

The application relates to a preparation method of a nano Prussian blue material with a honeycomb channel structure, which is carried out in the following steps: S1, preparing a single-layer structure of a nano Prussian blue cube; S2, coating a copolymer on the single-layer structure obtained in step S1 to form a polymer film on the single-layer structure; wherein the copolymer is a polyetherimide, a polymethyl methacrylate and a polyethylene glycol copolymer; S3, etching the single-layer structure coated with the copolymer film in step S2 by using a strong acid; S4, cleaning, centrifuging and drying, so as to complete the preparation of the nano Prussian blue material with the honeycomb channel structure. The nano Prussian blue material can be filled with the channels of the honeycomb structure, and has high drug loading capacity; the prepared nano Prussian blue material has good light-heat conversion capacity, and has great application prospects in drug carriers, photothermal therapy, photoacoustic imaging and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of functional nanomaterials, and particularly to a preparation method of a nanometer Prussian blue material with a honeycomb channel structure. BACKGROUND

[0002] Prussian blue, as a drug for treating oral acute and chronic thallium poisoning, has good biological safety. Meanwhile, Prussian blue can be effectively photo-thermal converted under 808 nm near-infrared light irradiation, and can be used as a photo-thermal treatment drug. In recent years, there are many reports on Prussian blue. However, in the application of drug carriers, Prussian blue often needs to be surface-modified, such as being covered with a mesoporous silica layer, to improve the drug loading capacity. However, this method has many preparation steps and high cost. SUMMARY

[0003] To solve the above technical problems, the present application provides a preparation method of a nanometer Prussian blue material with a honeycomb channel structure, which can make the nanometer Prussian blue material cover the channels of the honeycomb structure and has high drug loading capacity. The prepared nanometer Prussian blue material has good photo-thermal conversion capacity and has great application prospects in drug carriers, photo-thermal treatment, photo-acoustic imaging and the like.

[0004] The technical scheme adopted by the present application to solve the technical problems is as follows: a preparation method of a nanometer Prussian blue material with a honeycomb channel structure, which is performed according to the following steps:

[0005] S1, making a single-layer structure of nanometer Prussian blue cubes;

[0006] S2, coating a copolymer on the single-layer structure obtained in step S1 to form a polymer film on the single-layer structure; wherein the copolymer is a copolymer of polyetherimide, polymethyl methacrylate and polyethylene glycol;

[0007] S3, etching the single-layer structure coated with the copolymer film in step S2 by using a strong acid;

[0008] S4, cleaning, centrifuging and drying to complete the preparation of the nanometer Prussian blue material with a honeycomb channel structure.

[0009] Further, the weight average molecular weight of the copolymer is 300000-500000; in the copolymer, the mass percentage of polyetherimide is 12-25%, the mass percentage of polymethyl methacrylate is 45-55%, and the mass percentage of polyethylene glycol is 20-40%.

[0010] Further, the mass ratio of the nanometer Prussian blue cube to the copolymer is 1:(120-480).

[0011] Further, in step S1, the method for preparing the single-layer structure of the nanometer Prussian blue cubic is as follows: preparing a nanometer Prussian blue cubic mixed solution and a carrier; then, dropping the nanometer Prussian blue cubic mixed solution on the carrier to form a single-layer structure, and vacuum drying.

[0012] Further, the preparation method of the nanometer Prussian blue cubic mixed solution is as follows: ultrasonic dispersion of the nanometer Prussian blue cubic in a water and ethanol mixed solution; wherein, the volume ratio of water to ethanol in the water and ethanol mixed solution is 1:10-10:1.

[0013] Further, the carrier is a silicon wafer, and the silicon wafer is treated by a piranha solution.

[0014] Further, in step S3, the etching temperature is 80-140℃; the etching pressure is 1-3MPa; and the etching time is 8-14h.

[0015] Further, the strong acid is HCl, and the molar concentration is 0.1-2mol / L.

[0016] Further, in step S4, the cleaning is performed by deionized water; the centrifugal speed is 10000-14000rpm, and the centrifugal time is 10-20min; and the drying is vacuum drying.

[0017] The advantages of the present application are as follows: the preparation method of the nanometer Prussian blue material with a honeycomb-like pore structure can make the nanometer Prussian blue material cover the pores of the honeycomb-like structure, and has a high drug loading capacity; the prepared nanometer Prussian blue material has good light-heat conversion capacity, and has a great application prospect in drug carriers, photothermal therapy, photoacoustic imaging, etc. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 TEM image of the nanometer Prussian blue material prepared by the preparation method of Example 1;

[0019] Figure 2 TEM image of the nanometer Prussian blue material prepared by the preparation method of Example 2. DETAILED DESCRIPTION

[0020] In order to deepen the understanding of the present application, the present application will be further described in detail below in combination with the drawings and examples, which are only used to explain the present application and do not limit the protection scope of the present application.

[0021] The present detailed embodiment provides a preparation method of a nanometer Prussian blue material with a honeycomb-like pore structure, which is performed according to the following steps:

[0022] S1, preparing a single-layer structure of the nanometer Prussian blue cubic;

[0023] S2, coating the single-layer structure obtained in step S1 with a copolymer to form a polymer film on the single-layer structure; wherein the copolymer is a polyetherimide, a polymethyl methacrylate and a polyethylene glycol copolymer;

[0024] S3, etching the single-layer structure coated with the copolymer in step S2 using a strong acid;

[0025] S4, cleaning, centrifuging and drying to complete the preparation of the nano Prussian blue material with a honeycomb channel structure.

[0026] In the preparation method of the nano Prussian blue material with a honeycomb channel structure in the specific embodiment, the weight average molecular weight of the copolymer is 300000-500000; in the copolymer, the mass percentage of polyetherimide is 12-25%, the mass percentage of polymethyl methacrylate is 45-55%, and the mass percentage of polyethylene glycol is 20-40%.

[0027] In the preparation method of the nano Prussian blue material with a honeycomb channel structure in the specific embodiment, the mass ratio of the nano Prussian blue cube to the copolymer is 1:(120-480).

[0028] In the preparation method of the nano Prussian blue material with a honeycomb channel structure in the specific embodiment, in step S1, the method for preparing the single-layer structure of the nano Prussian blue cube is as follows: preparing a nano Prussian blue cube mixed solution and preparing a carrier; then, dropping the nano Prussian blue cube mixed solution on the carrier to form a single-layer structure, and vacuum drying.

[0029] In the preparation method of the nano Prussian blue material with a honeycomb channel structure in the specific embodiment, the preparation method of the nano Prussian blue cube mixed solution is as follows: ultrasonically dispersing the nano Prussian blue cube in a water and ethanol mixed solution; wherein the volume ratio of water to ethanol in the water and ethanol mixed solution is 1:10-10:1.

[0030] In the preparation method of the nano Prussian blue material with a honeycomb channel structure in the specific embodiment, the carrier is a silicon wafer, and the silicon wafer is treated with a piranha solution.

[0031] In the preparation method of the nano Prussian blue material with a honeycomb channel structure in the specific embodiment, in step S3, the etching temperature is 80-140℃; the etching pressure is 1-3MPa; and the etching time is 8-14h.

[0032] In the preparation method of the nanometer Prussian blue material with the honeycomb channel structure of the specific embodiment, the strong acid is HCl, and the molar concentration is 0.1-2 mol / L.

[0033] In the preparation method of the nanometer Prussian blue material with the honeycomb channel structure of the specific embodiment, in step S4, the washing is performed by using deionized water; the centrifugal speed is 10000-14000 rpm, and the centrifugal duration is 10-20 min; and the drying is vacuum drying.

[0034] Example 1

[0035] A preparation method of a nanometer Prussian blue material with a honeycomb channel structure is performed according to the following steps:

[0036] 1. 10 mg of nanometer Prussian blue cubes (PB) is ultrasonically dispersed in a mixed solution of water and ethanol with a volume of 10 mL, wherein the volume ratio (v / v) of water and ethanol is 1:1. The above solution is dropped on a silicon wafer treated by a piranha solution to form a monolayer structure, and is dried in vacuum.

[0037] 2. 2.5 g of a copolymer with a weight average molecular weight of 380000 is coated on the surface of the nanometer Prussian blue monolayer structure by a spin coating method to form a polymer film, wherein the mass percentage of polyetherimide (PEI) in the copolymer is 18%, the mass percentage of polymethyl methacrylate (PMMA) is 50%, and the mass percentage of polyethylene glycol (PEG) is 32%.

[0038] 3. Under the conditions of a temperature of 100 ℃ and a pressure of 3 MPa, 0.5 mol / L of HCl is etched for 10 h to obtain a silicon wafer containing a nanometer Prussian blue material. The nanometer Prussian blue on the silicon wafer is ultrasonically dispersed in deionized water, centrifuged at a speed of 12000 rpm, washed with deionized water for three times, and vacuum dried to obtain a nanometer Prussian blue material with a honeycomb channel structure.

[0039] The nanometer Prussian blue material obtained in Example 1 is subjected to TEM detection, and the obtained electron microscope image is as shown in Figure 1 From Figure 1 , it can be clearly observed that the nanometer Prussian blue cubes are covered with honeycomb channels, and the average particle size of the nanometer Prussian blue material with the honeycomb channel structure is 100 nm.

[0040] The nanometer Prussian blue material obtained in Example 1 is subjected to BET nitrogen adsorption detection, and the obtained specific surface area is 304.3 m 2 ·g -1 .

[0041] The nanometer Prussian blue material obtained in Example One is subjected to ultraviolet-visible spectrophotometry to measure the drug loading amount, and the drug loading amount is 331.25 μg / mg (DOX / material).

[0042] The nanometer Prussian blue material obtained in Example One is configured into a water dispersion solution with a concentration of 500 μg / mL, and is irradiated by using a fiber-coupled laser (808 nm light wavelength). The light irradiation power is adjusted to be 2 W / cm 2 The temperature rising data is recorded by using a thermal imager. After 2.5 min of light irradiation, the material solution can be heated from room temperature (20.0℃) to 62.4℃.

[0043] Example Two

[0044] A preparation method of a nanometer Prussian blue material with a honeycomb pore structure is performed according to the following steps:

[0045] 1. 200 mg of nanometer Prussian blue cubes (PB) is ultrasonically dispersed in a mixed solution of water and ethanol with a volume of 200 mL, wherein the volume ratio (v / v) of water and ethanol is 5:1. The above solution is dropped on a silicon wafer treated by a piranha solution to form a monolayer structure, and is dried in a vacuum.

[0046] 2. 80 g of a copolymer with a weight average molecular weight of 450000 is coated on the surface of the nanometer Prussian blue monolayer structure by a spin coating method to form a polymer film, wherein the mass fraction of polyetherimide (PEI) in the copolymer is 25%, the mass fraction of polymethyl methacrylate (PMMA) is 45%, and the mass fraction of polyethylene glycol (PEG) is 30%.

[0047] 3. Under the conditions of a temperature of 120℃ and a pressure of 2 MPa, the silicon wafer containing the nanometer Prussian blue material is etched by using 1 mol / L of HCl for 12 h. The nanometer Prussian blue on the silicon wafer is ultrasonically dispersed in deionized water, and is centrifuged at a speed of 12000 rpm. The centrifugation is washed three times with deionized water, and is vacuum dried to obtain the nanometer Prussian blue material with a honeycomb pore structure.

[0048] The nanometer Prussian blue material obtained in Example Two is subjected to TEM detection, and the obtained electron microscope image is shown in Figure 2 From the Figure 2 , it can be clearly observed that the nanometer Prussian blue cubes are covered with honeycomb pores, and the average particle size of the nanometer Prussian blue material with a honeycomb pore structure is 100 nm.

[0049] The BET nitrogen adsorption method was used to detect the nano Prussian blue material obtained in Example 2, and the specific surface area obtained was 424.9m 2 ·g -1 .

[0050] The nano Prussian blue material obtained in Example 2 was measured by ultraviolet-visible spectrophotometry to measure the drug loading amount, and the drug loading amount was 472.58 μg / mg (DOX / material).

[0051] The nano Prussian blue material obtained in Example 2 was configured into an aqueous dispersion with a concentration of 500 μg / mL, and was irradiated using a fiber-coupled laser (808 nm light wavelength), and the light irradiation power was adjusted to 2 W / cm 2 The thermal imaging instrument was used to record the temperature rise data, and after 2.5 min of light irradiation, the material solution could be heated from room temperature (20.0℃) to 57.6℃.

[0052] In the preparation method of the nano Prussian blue material with a honeycomb pore structure in the above examples, the copolymer (PEI-b-PMMA-b-PEG) is used as a template; in the copolymer, the PEI part is resistant to acid and high temperature, the PMMA part is easily hydrolyzed under strong acid conditions, and the PEG part can improve the water solubility of the copolymer; when the copolymer forms a polymer film on the surface of the single-layer nano Prussian blue, under the conditions of high temperature and high pressure and strong acid etching, the PMMA and PEG parts in the polymer film will be acidized, and then the strong acid will further etch the Prussian blue along the pores in which the polymer film is acidized, and the area of the Prussian blue covered by the stable PEI will not be etched by the strong acid; finally, the honeycomb pore structure is formed on the Prussian blue.

[0053] The nano Prussian blue material with a honeycomb pore structure prepared by the preparation method has a large specific surface area, and also has high drug loading capacity and good light-heat conversion capacity, and has great application prospects in drug carriers, photothermal therapy, photoacoustic imaging and the like.

[0054] The above examples should not limit the present application in any way, and any technical solutions obtained by equivalent substitution or equivalent conversion fall within the protection scope of the present application.

Claims

1. A method for preparing a nanoscale Prussian blue material having a honeycomb-like channel structure, characterized by: The preparation method is performed according to the following steps: S1, a single-layer structure of nanometer Prussian blue cube is prepared; wherein, the method for preparing the single-layer structure of nanometer Prussian blue cube is as follows: a mixed solution of nanometer Prussian blue cube is prepared, and a carrier is prepared; then, the mixed solution of nanometer Prussian blue cube is dropped on the carrier to form a single-layer structure, and vacuum drying is performed; S2, a copolymer is coated on the single-layer structure obtained in step S1 to form a polymer film on the single-layer structure; wherein, the copolymer is a polyetherimide, a polymethyl methacrylate and a polyethylene glycol copolymer; wherein, in the copolymer, the mass percentage of polyetherimide is 12-25%, the mass percentage of polymethyl methacrylate is 45-55%, and the mass percentage of polyethylene glycol is 20-40%; S3, a strong acid is used to etch the single-layer structure coated with the copolymer film in step S2; S4, cleaning, centrifugation and drying are performed, and the preparation of the nanometer Prussian blue material with a honeycomb-like pore structure is completed.

2. The method of claim 1, wherein the method is characterized by: The weight average molecular weight of the copolymer is 300000-500000.

3. The method according to claim 1 or 2, wherein the method comprises the steps of: (a) mixing a Prussian blue precursor with a reducing agent; (b) adding a base to the mixture; (c) adding a solvent to the mixture; and (d) adding a template to the mixture. The mass ratio of the nanometer Prussian blue cube to the copolymer is 1: (120-480).

4. The method of claim 1, wherein the method is characterized by: The preparation method of the mixed solution of nanometer Prussian blue cube is as follows: the nanometer Prussian blue cube is ultrasonically dispersed in a mixed solution of water and ethanol; wherein, in the mixed solution of water and ethanol, the volume ratio of water to ethanol is 1:10-10:

1.

5. The method of claim 1, wherein the method is characterized by: The carrier is a silicon wafer treated by a piranha solution.

6. The method of claim 1, wherein the method is characterized by: In step S3, the etching temperature is 80-140℃, the etching pressure is 1-3MPa, and the etching time is 8-14h.

7. The method according to claim 1 or 6, wherein the method comprises the steps of: (a) mixing a Prussian blue precursor with a reducing agent; (b) adding a base to the mixture; (c) adding a solvent to the mixture; and (d) adding a template to the mixture. The strong acid is HCl with a molar concentration of 0.1-2mol / L.

8. The method of claim 1, wherein the method is characterized by: In step S4, deionized water is used for cleaning, the centrifugation speed is 10000-14000rpm, the centrifugation time is 10-20min, and vacuum drying is performed.

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