Bimetal-based nano composite material as well as preparation method and application thereof

Abstract

The preparation method comprises the steps that ferric nitrate and bismuth nitrate are dispersed in deionized water and stirred to be dissolved, the pH of the solution is adjusted to be alkaline, ultrasonic dispersion is conducted to be uniform, then the solution is poured into a polytetrafluoroethylene kettle to be subjected to a hydrothermal reaction, a bimetallic-based nano material FBO is obtained, the bimetallic-based nano material FBO is dispersed in a Tris buffer solution, and the bimetallic-based nano material FBO is obtained; and adding dopamine hydrochloride, stirring under a dark condition, centrifuging, washing and drying to obtain a black nano composite material FBO (at) PDA, thereby obtaining the black nano composite material FBO (at) PDA. The bimetal-based nano composite material has the anti-inflammatory, osteogenesis-promoting and vascularization-promoting performance, the preparation method is simple, safe, environmentally friendly, low in cost and easy to operate, can be used as a bone repair material in the field of regeneration and repair of jawbone necrosis, and has wide application prospects.

Description

Technical Field

[0001] This invention belongs to the field of multifunctional nanomaterials technology, specifically relating to a bimetallic nanocomposite material, its preparation method, and its application. Background Technology

[0002] The number of newly diagnosed cases of head and neck malignant tumors has been increasing year by year in recent years. Currently, chemotherapy and radiotherapy are commonly used adjuvant treatments for head and neck malignant tumors. While effectively controlling the tumor, they inevitably cause varying degrees of damage to non-target tissues. Jawbone tissue damage, osteomyelitis, and even osteonecrosis are among the most common serious complications. However, due to the low cell activity, low blood vessel density, and low oxygen content of the jawbone microenvironment after radiotherapy and chemotherapy, this special microenvironment means that jawbone defect repair cannot be completely resolved by traditional therapies.

[0003] Biomaterials, due to their excellent biological, mechanical, and physicochemical properties such as magnetic resonance / fluorescence, have been widely used in fields such as bone tissue engineering, drug and gene delivery, magnetic resonance imaging, magnetothermal therapy, biosensors, and tissue repair. Common bone regeneration and repair materials mainly include bioceramics, bioglasses, porous scaffolds, and bone cement. Although these materials have osteoconductive / inductive properties, their composition design and functional regulation have not yet achieved specific adaptation to the unique pathological microenvironment of osteonecrosis of the jaw. Summary of the Invention

[0004] Therefore, the main objective of this invention is to provide a method for preparing bimetallic nanocomposite materials, which is a mild synthesis method.

[0005] Another object of the present invention is to provide a bimetallic nanocomposite material, which is prepared by the method of preparing the bimetallic nanocomposite material and has anti-inflammatory, osteopromoting and angiogenic properties.

[0006] Another object of the present invention is to provide the application of the bimetallic nanocomposite material in the preparation of osteonecrosis repair materials, which is specifically adapted to osteonecrosis of the jaw after adjuvant therapy for head and neck malignant tumors.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a method for preparing a bimetallic-based nanocomposite material, comprising the following steps:

[0009] (1) Disperse ferric nitrate and bismuth nitrate in deionized water, stir until dissolved, adjust the pH of the solution to alkaline, and obtain a brownish-red precipitate;

[0010] (2) The brown-red precipitate mixture solution described in step (1) is ultrasonically dispersed in a water bath and then poured into a polytetrafluoroethylene kettle for hydrothermal reaction to obtain bimetallic nanomaterial FBO;

[0011] (3) Disperse the bimetallic nanomaterial FBO described in step (2) into Tris buffer, add dopamine hydrochloride, stir under light-protected conditions, centrifuge, wash and dry to obtain black nanocomposite material FBO@PDA, which is the result.

[0012] Preferably, in step (1), the molar ratio of ferric nitrate to bismuth nitrate is 0.1 to 10:1.

[0013] Preferably, in step (1), the pH of the solution is adjusted to 9-10.

[0014] Preferably, in step (2), the hydrothermal reaction temperature is 150-250℃ and the hydrothermal reaction time is 6-72h. The morphology and particle size of the bimetallic nanomaterial FBO can be controlled according to the temperature and time of the hydrothermal reaction.

[0015] Preferably, in step (3), the stirring time under the dark condition is 6 to 48 hours.

[0016] Preferably, in step (3), the nanocomposite material FBO@PDA has the bimetallic nanomaterial FBO as the core and the organic PDA as the shell, and the thickness of the PDA shell increases with the increase of stirring time.

[0017] In a second aspect, the present invention also provides a bimetallic nanocomposite material, which is a nanocomposite material FBO@PDA, prepared by the method for preparing the bimetallic nanocomposite material.

[0018] Preferably, the bimetallic nanocomposite material is a core-shell structured nanoparticle with a particle size of 20-500 nm, which has the bimetallic nanomaterial FBO as the core and the organic PDA as the shell.

[0019] The bimetallic nanocomposite material of the present invention has good anti-inflammatory properties, can induce macrophage M1 to M2 polarization, enhances the ability of BMSCs to osteogenic differentiation in vitro, has the ability to promote angiogenesis, and can enhance the in vitro proliferation and migration properties of HUVECs.

[0020] A third aspect of the present invention also provides the application of the bimetallic nanocomposite material in the preparation of materials for repairing osteonecrosis of the jaw.

[0021] Compared with the prior art, the present invention proposes a bimetallic nanocomposite material, its preparation method and application. The beneficial effects are at least as follows: the raw materials required by the present invention are readily available and inexpensive, the synthesis method is mild and environmentally friendly, and the obtained nanocomposite material FBO@PDA has anti-inflammatory, osteogenic and angiogenic properties, and can be used as a bone repair material in the field of regenerative repair of osteonecrosis of the jaw. Attached Figure Description

[0022] Figure 1 The image shows the XRD pattern of the bimetallic nanomaterial FBO prepared in Example 1.

[0023] Figure 2 This is a TEM image of the bimetallic matrix composite material FBO@PDA prepared in Example 1.

[0024] Figure 3 The results show the anti-inflammatory properties of the bimetallic nanocomposite material FBO@PDA prepared in Example 1.

[0025] Figure 4 The results show the in vitro osteogenic differentiation capacity characterization of the bimetallic nanocomposite FBO@PDA prepared in Example 1.

[0026] Figure 5 The results show the angiogenesis-promoting properties of the bimetallic nanocomposite FBO@PDA prepared in Example 1. Detailed Implementation

[0027] To more fully understand and demonstrate the technical solutions, objectives, and advantages of the present invention, the technical effects produced by the present invention will be further described in detail and completely below with reference to the accompanying drawings and specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. It should be noted that other embodiments obtained by those skilled in the art without departing from the concept of the present invention are all within the protection scope of the present invention.

[0028] Example 1

[0029] This embodiment prepares a bimetallic matrix composite material FBO@PDA, and the steps are as follows:

[0030] (1) Disperse 2.5 mmol of ferric nitrate and an equimolar amount of bismuth nitrate in deionized water, stir until dissolved, adjust the pH of the solution to 9-10, and obtain a brownish-red precipitate;

[0031] (2) The brown-red precipitate mixture in step (1) was ultrasonically dispersed in a water bath and then poured into a polytetrafluoroethylene kettle. A hydrothermal reaction was carried out at 200°C to obtain the bimetallic nanomaterial FBO.

[0032] (3) Disperse the bimetallic nanomaterial FBO from step (2) into Tris buffer, add dopamine hydrochloride, stir for 6 hours in the dark, centrifuge, wash and dry to obtain the black nanocomposite material FBO@PDA.

[0033] The XRD pattern of the bimetallic nanomaterial FBO prepared in Example 1 is shown below. Figure 1 As shown, the product is a hexagonal iron-bismuth oxide, corresponding to the standard card (JCPDS20-0169).

[0034] TEM image of the bimetallic nanocomposite FBO@PDA prepared in Example 1 is shown below. Figure 2 As shown, the FBO with higher contrast is surrounded by the PDA with lower contrast.

[0035] Example 2

[0036] This embodiment prepares a bimetallic matrix composite material FBO@PDA, and the steps are as follows:

[0037] (1) Disperse 2.5 mmol ferric nitrate and 1.25 mmol bismuth nitrate in deionized water, stir until dissolved, adjust the pH of the solution to 9-10, and obtain a brownish-red precipitate;

[0038] (2) The brown-red precipitate mixture in step (1) was ultrasonically dispersed in a water bath and then poured into a polytetrafluoroethylene kettle. A hydrothermal reaction was carried out at 200°C to obtain the bimetallic nanomaterial FBO.

[0039] (3) Disperse the bimetallic nanomaterial FBO from step (2) into Tris buffer, add dopamine hydrochloride, stir for 6 hours in the dark, centrifuge, wash and dry to obtain the black nanocomposite material FBO@PDA.

[0040] Example 3

[0041] This embodiment prepares a bimetallic matrix composite material FBO@PDA, and the steps are as follows:

[0042] (1) Disperse 2.5 mmol of ferric nitrate and an equimolar amount of bismuth nitrate in deionized water, stir until dissolved, adjust the pH of the solution to 9-10, and obtain a brownish-red precipitate;

[0043] (2) The brown-red precipitate mixture in step (1) was ultrasonically dispersed in a water bath and then poured into a polytetrafluoroethylene kettle. A hydrothermal reaction was carried out at 200°C to obtain the bimetallic nanomaterial FBO.

[0044] (3) Disperse the bimetallic nanomaterial FBO from step (2) into Tris buffer, add dopamine hydrochloride, stir for 24 hours in the dark, centrifuge, wash and dry to obtain the black nanocomposite material FBO@PDA.

[0045] Example 4

[0046] The anti-inflammatory properties of the bimetallic nanocomposite material FBO@PDA obtained in Example 1 were determined.

[0047] Mouse macrophages RAW264.7 were co-cultured with lipopolysaccharide (LPS), bisphosphonate drug ZA, and bimetallic nanocomposite material FBO@PDA, respectively. Morphological changes in macrophages were observed, and the expression levels of M1 markers (iNOS and CD86) and M2 markers (CD163 and CD206) in the cells were detected.

[0048] like Figure 3 As shown, mouse macrophages RAW 264.7 exhibited distinct cellular tentacles under the induction of LPS and ZA, compared to the CTL blank. With the addition of the bimetallic nanocomposite FBO@PDA, RAW 264.7 polarized from M1 to M2 type, and the expression level of M1 type markers was significantly inhibited, while the expression level of M2 type markers was significantly increased.

[0049] Example 5

[0050] The in vitro osteogenic properties of the bimetallic nanocomposite material FBO@PDA obtained in Example 1 were determined.

[0051] Bone marrow mesenchymal stem cells (BMSCs) were cultured using the bisphosphonate drug ZA and the composite material FBO@PDA, respectively, and their osteogenic differentiation capacity was assessed by ALP and RAS staining.

[0052] The results are as follows Figure 4 As shown, compared with the blank control CTL group, ZA significantly inhibited the early and late osteogenic differentiation capacity of BMSCs, while FBO@PDA significantly enhanced the early and late osteogenic differentiation capacity of BMSCs.

[0053] Example 6

[0054] The angiogenesis-promoting properties of the bimetallic nanocomposite material FBO@PDA obtained in Example 1 were determined.

[0055] Human umbilical vein endothelial cells (HUVECs) were cultured using the bisphosphonate drug ZA and the composite material FBO@PDA, respectively. The effects of ZA on the in vitro proliferation and migration of HUVECs were evaluated by cell scratch assay and Transwell assay.

[0056] The results are as follows Figure 5 As shown, FBO@PDA can significantly enhance the cell migration ability of HUVECs and increase the number of migrating cells.

[0057] In summary, the bimetallic nanocomposite material FBO@PDA of the present invention has anti-inflammatory, osteogenic, and angiogenic properties, and can be used as a bone repair material in the field of regenerative repair of osteonecrosis of the jaw.

[0058] The above are merely preferred embodiments of the present invention and are not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a bimetallic-based nanocomposite material, characterized in that, Includes the following steps: (1) Disperse ferric nitrate and bismuth nitrate in deionized water, stir until dissolved, adjust the pH of the solution to alkaline, and obtain a brownish-red precipitate; (2) The brown-red precipitate mixture solution described in step (1) is ultrasonically dispersed in a water bath and then poured into a polytetrafluoroethylene kettle for hydrothermal reaction to obtain bimetallic nanomaterial FBO; (3) Disperse the bimetallic nanomaterial FBO described in step (2) into Tris buffer, add dopamine hydrochloride, stir under light-protected conditions, centrifuge, wash and dry to obtain black nanocomposite material FBO@PDA, which is the result.

2. The method for preparing the bimetallic-based nanocomposite material according to claim 1, characterized in that, In step (1), the molar ratio of ferric nitrate and bismuth nitrate is 0.1 to 10:

1.

3. The method for preparing the bimetallic-based nanocomposite material according to claim 2, characterized in that, In step (1), the molar ratio of ferric nitrate and bismuth nitrate is 1:

1.

4. The method for preparing the bimetallic-based nanocomposite material according to claim 1, characterized in that, In step (1), the pH of the solution is adjusted to 9-10.

5. The method for preparing the bimetallic-based nanocomposite material according to claim 1, characterized in that, In step (2), the hydrothermal reaction temperature is 150-250℃ and the hydrothermal reaction time is 6-72h.

6. The method for preparing the bimetallic-based nanocomposite material according to claim 1, characterized in that, In step (3), the stirring time under the dark condition is 6 to 48 hours.

7. The method for preparing the bimetallic-based nanocomposite material according to claim 6, characterized in that, In step (3), the nanocomposite material FBO@PDA has the bimetallic nanomaterial FBO as the core and the organic PDA as the shell, and the thickness of the PDA shell increases with the increase of stirring time.

8. A bimetallic-based nanocomposite material, characterized in that, It is a nanocomposite material FBO@PDA, prepared by the preparation method of the bimetallic nanocomposite material according to any one of claims 1 to 7.

9. The bimetallic nanocomposite material according to claim 8, characterized in that, The bimetallic nanocomposite material consists of core-shell structured nanoparticles with a particle size of 20–500 nm, with the bimetallic nanomaterial FBO as the core and the organic PDA as the shell.

10. The application of the bimetallic nanocomposite material according to claim 8 or 9 in the preparation of osteonecrosis repair materials.

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