A hollow nanocomposite material and its preparation method and application

Abstract

The present application is applicable to the field of material technology, and provides a hollow nanocomposite material and its preparation method and application. The structural formula of the hollow nanocomposite material is Au NBPs@CuS, wherein CuS is an outer semiconductor and Au NBPs is an inner core. The present application is a nanostructure with a gold nanobipyramid as the inner core and a hollow p-type semiconductor as the outer layer, which realizes the first combination of p-type semiconductor and gold nanobipyramid. The tip effect of Au NBPs is better than that of previous Au NPs, and its ultraviolet absorption reaches a maximum at 808nm, and its phototherapy performance is greatly improved. By compounding Au NBPs with CuS, not only its photothermal performance is greatly improved, the photothermal conversion efficiency reaches 43.88%, and it can generate active oxygen under light. 1 O2 and ·OH, their excellent photothermal effect and photodynamic properties provide theoretical support for their application in inhibiting amyloid protein aggregation.

Description

Technical Field

[0001] The present application belongs to the field of material technology, and in particular relates to a hollow nanocomposite material and a preparation method and application thereof. Background Art

[0002] Alzheimer's disease (AD) is a senile neurodegenerative disorder characterized by memory impairment, executive dysfunction, and behavioral changes, posing a serious threat to human health. While the pathogenic mechanism of AD remains unclear, mainstream theory suggests that the key steps in the pathogenesis of AD are the aggregation of amyloid protein monomers (Aβm) into oligomers and the formation of fibrils. Soluble oligomers (Aβo) and insoluble fibrils (Aβf) are believed to be key drivers of neuronal toxicity.

[0003] In recent years, nanomaterials have played a wide range of roles in inhibiting Aβ protein aggregation due to their photothermal and photodynamic properties. Among them, copper sulfide (CuS) nanomaterials, as p-type semiconductors with narrow band gaps, trigger dd-band transitions of Cu(II) ions under near-infrared laser irradiation, resulting in photothermal properties. Gold nanobipyramids (Au NBPs), as emerging and excellent plasmonic light-absorbing nanomaterials, have the potential to improve light utilization efficiency and generate hot electrons. Compared with other materials, Au NBPs have sharp double ends, which exhibit stronger light absorption and enhance the "light enrichment" effect. However, single nanomaterials often fail to produce satisfactory clinical therapeutic results due to their relatively low photoconversion efficiency, which greatly limits their biomedical applications. Therefore, the development of composite nanomaterials with strong photothermal properties will provide new ideas for the clearance of Aβ. Summary of the Invention

[0004] The purpose of the embodiments of the present application is to provide a hollow nanocomposite material, aiming to solve the problems of low light conversion efficiency, poor clinical treatment results, and limited application in biomedicine of existing single nanomaterials.

[0005] The embodiment of the present application is achieved by providing a hollow nanocomposite material, wherein the hollow nanocomposite material is a nanostructure with a gold nanobipyramid as the core and a hollow p-type semiconductor as the outer layer;

[0006] The structural formula of the hollow nanocomposite material is Au NBPs@CuS, wherein CuS is an outer semiconductor and AuNBPs is a core.

[0007] Preferably, the particle size of the hollow nanocomposite material is 125-135 nm.

[0008] The present application also provides a method for preparing the hollow nanocomposite material, comprising:

[0009] Prepare gold nanobipyramids; the particle size of the gold nanobipyramids is 95 to 105 nm;

[0010] The gold nanobipyramids were dropped into a sodium polystyrene sulfonate solution and stirred to obtain a mixture of Au NBPs@PSS;

[0011] The NBPs@PSS mixture was dropped into a polyvinyl pyrrolidone solution and stirred to obtain a mixture of AuNBPs@PSS@PVP;

[0012] 5-10 mL of the mixture Au NBPs@PSS@PVP was added to an aqueous solution containing 1-2 mL of copper nitrate and 9-18 mL of polyvinyl pyrrolidone, followed by rapid addition of 12.8-25.6 μL of hydrazine monohydrate solution for reaction, and then addition of 0.415-0.83 mL of sodium sulfide solution for uniform stirring to obtain a hollow nanocomposite material.

[0013] The hollow nanocomposite material Au NBPs@CuS provided in the embodiment of the present application is a nanostructure with a core of gold nanobipyramid Au NBPs and a hollow p-type semiconductor CuS as the outer layer. By combining Au NBPs with CuS, not only is its photothermal performance greatly improved, the photothermal conversion efficiency reaches 43.88%, and it can also generate active oxygen under light. 1 O2 and ·OH, excellent photothermal effect and photodynamic performance provide theoretical support for its application in inhibiting amyloid protein aggregation. The hollow nanocomposite Au NBPs@CuS can inhibit the formation of fibers under non-light conditions. ThT fluorescence experiments confirmed that Au NBPs@CuS can effectively inhibit Aβ at very low concentrations. 42 The Au NBPs@CuS nanocomposite undergoes a transformation from a random coil structure to a β-pleated structure; atomic force microscopy experiments confirm that it can effectively reduce the fiber content. Furthermore, under exogenous NIR stimulation, the hollow Au NBPs@CuS nanocomposite exhibits strong photothermal efficiency, converting light energy into heat energy in a short period of time, rapidly heating to 60°C and breaking up the already formed fibers.

[0014] The hollow nanocomposite material preparation method provided in the embodiment of the present application is to prepare a hollow Au NBPs@CuS composite material by adopting the principles and technology of surface modification and the Kirkendall effect, realizing the first combination of p-type semiconductor CuS and gold nanobipyramids. The tip effect of Au NBPs is superior to that of previously synthesized Au NPs, and its ultraviolet absorption reaches its maximum at 808nm, greatly improving the phototherapy performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 Schematic diagram of the synthesis of the hollow nanocomposite Au NBPs@CuS provided in the examples of this application;

[0016] Figure 2 TEM (A, B) and EDS (CF) images of the hollow nanocomposite material Au NBPs@CuS provided in Example 1 of the present application;

[0017] Figure 3 The cooling time constant graph (A) of the hollow nanocomposite material Au NBPs@CuS provided in Example 1 of the present application and the ESR graph of the active oxygen species of Au NBPs@CuS under light irradiation (B);

[0018] Figure 4 The different concentrations of Au NBPs@CuS provided in the examples of this application inhibit Aβ 42 The aggregation kinetics curve of

[0019] Figure 5 The hollow nanocomposite Au NBPs@CuS provided in the examples of this application depolymerizes Aβ 42 AFM image of the fiber. DETAILED DESCRIPTION

[0020] In order to make the purpose, technical solutions and advantages of this application more clearly understood, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0021] The embodiment of the present application provides a hollow nanocomposite material, wherein the hollow nanocomposite material is a nanostructure with a gold nanobipyramid as the core and a hollow p-type semiconductor as the outer layer;

[0022] The structural formula of the hollow nanocomposite material is Au NBPs@CuS, wherein CuS is an outer semiconductor and AuNBPs is a core.

[0023] The particle size of the hollow nanocomposite material is 125-135 nm. Under 808 nm infrared laser irradiation, its concentration is between 10 μg / mL and 60 μg / mL, which has good photothermodynamic properties. In addition, when its concentration is between 50 μg / mL and 100 μg / mL, it can absorb 808 nm near-infrared light and quickly heat up in a short time. In addition, the hollow nanocomposite material can generate active oxygen ions induced by near-infrared light. 1 O2 and ·OH.

[0024] like Figure 1The synthetic route shown in the figure, the present embodiment provides a method for preparing the above-mentioned hollow nanocomposite material, comprising:

[0025] Preparation of gold nanobipyramids;

[0026] The gold nanobipyramids were dropped into a sodium polystyrene sulfonate solution and stirred to obtain a mixture of Au NBPs@PSS;

[0027] The NBPs@PSS mixture was dropped into a polyvinyl pyrrolidone solution and stirred to obtain a mixture of AuNBPs@PSS@PVP;

[0028] 5-10 mL of the mixture Au NBPs@PSS@PVP was added to an aqueous solution containing 1-2 mL of copper nitrate and 9-18 mL of polyvinyl pyrrolidone, followed by rapid addition of 12.8-25.6 μL of hydrazine monohydrate solution for reaction, and then addition of 0.415-0.83 mL of sodium sulfide solution for uniform stirring to obtain a hollow nanocomposite material.

[0029] The particle size of the gold nanobipyramid is 95-105 nm, and its ultraviolet absorption is around 780-790 nm.

[0030] In one embodiment of the present application, the method for preparing the gold nanobipyramids (Au NBPs) comprises:

[0031] 2.8 mL of deionized water, 4 mL of 0.1 M hexadecyltrimethylammonium chloride (CTAC), 200 μL of 10 mM HAuCl4, and 400 μL of 0.1 M citric acid were vigorously stirred at room temperature, and then 100 μL of 0.05 M glacial NaBH4 was added. The mixture was stirred at 80 °C for 1.5 hours to obtain a seed solution.

[0032] 50-80 μL of seed solution was added to a mixed solution containing 32 μL of 0.1 M ascorbic acid (AA), 4 mL of 0.1 M hexadecyltrimethylammonium bromide, 200 μL of 0.01 M HAuCl4, 40 μL of 0.01 M AgNO3 and 80 μL of 2 M HCl, and maintained at 30 ° C for 3 hours to obtain gold nanobipyramids.

[0033] Alternatively, the synthesis method for gold nanobipyramids can be as follows: CTAC (0.1M, 4mL), HAuCl4 (10mM, 200μL), and citric acid (0.1M, 400μL) are sequentially added to 2.8mL of stirring deionized water; freshly prepared ice-cold NaBH4 (0.05M, 100μL) is then added to the solution; the solution is then placed in an oil bath at 80°C and 380rpm for 90 minutes, until the color changes to red; the resulting seed solution is stored at 4°C for subsequent use. CTAB (0.1M, 4mL), HAuCl4 (0.01M, 200μL), AgNO3 (0.01M, 40μL), and HCl (2M, 80μL) are sequentially added to a 10mL glass vial, followed by AA (0.1M, 32μL). After the solution becomes colorless, 50-80μL of the seed solution is added. The mixture was kept at 30°C for 3 hours, washed by centrifugation, dispersed in water, and stored at 4°C.

[0034] The ultraviolet absorption wavelength of the gold seed solution is 520 nm. When the added volume of the seed solution is 80 μL, the particle size of the obtained Au NBPs is 100 nm.

[0035] It is worth noting that the present invention first synthesizes Au NBPs with a longitudinal plasma peak near 780nm, and then modifies its surface from CTAB stabilization to PSS and PVP coating, thereby changing its positive charge to negative charge, thereby enabling Cu 2+ The Au NBPs@CuS nanocomposite synthesized in this application exhibits strong photothermal performance, with a power of 1.2-1.5 W / cm2. 2 The nanocomposite material is irradiated with near-infrared light having a wavelength of 808 nm, causing the temperature to rise to 60-70° C. in 5±1 min, with high photothermal conversion efficiency.

[0036] In one embodiment of the present application, the step of dropping the gold nanobipyramids into a sodium polystyrene sulfonate solution and stirring uniformly to obtain a mixture of Au NBPs@PSS includes:

[0037] Gold nanobipyramids were dropped into a sodium polystyrene sulfonate solution containing 6 mM NaCl and stirred overnight to obtain a mixture AuNBPs@PSS.

[0038] In one embodiment of the present application, the concentration of the sodium polystyrene sulfonate solution is 2 g / L, and the volume ratio of the sodium polystyrene sulfonate solution to the added gold nanobipyramids is 1:1.

[0039] In one embodiment of the present application, the step of dripping the Au NBPs@PSS mixture into a polyvinylpyrrolidone solution and stirring uniformly to obtain the Au NBPs@PSS@PVP mixture includes:

[0040] The mixture Au NBPs@PSS solution was dropped into an equal volume of 20 g / L polyvinyl pyrrolidone solution and stirred for 3 h to obtain the mixture Au NBPs@PSS@PVP.

[0041] Alternatively, the hollow nanocomposite material may be prepared by dropping the gold nanobipyramid solution obtained above into 5 mL of PSS solution (2 g / L, 6 mM NaCl) and stirring overnight to obtain an Au NBPs@PSS solution; then, dropping the Au NBPs@PSS solution into a PVP solution (20 g / L, 5 mL) and stirring for three hours to obtain an Au NBPs@PSS@PVP solution; adding a copper nitrate solution (1-2 mL, 0.1 M) to a 9-18 mL aqueous solution containing 0.2-0.4 g of PVP; stirring for 15 minutes, adding 5-10 mL of the Au NBPs@PSS@PVP mixture, followed by the rapid addition of 12.8-25.6 μL of a 17.5 wt% hydrazine monohydrate solution, reacting for 10 minutes, adding 0.415 mL of a 0.2 M sodium sulfide solution, and continuously stirring for 2 hours to obtain a hollow AuNBPs@CuS composite material.

[0042] In one embodiment of the present application, the concentration of the Au NBPs@PSS@PVP mixture is 4.5 mM, the mixture is centrifuged at 1200 rpm for 6 minutes, and washed three times with anhydrous ethanol and deionized water.

[0043] In one embodiment of the present application, the rotation speed during the stirring process is 650-800 rpm, preferably 700 rpm.

[0044] The embodiments of the present application also provide a use of the above-mentioned hollow nanocomposite material in inhibiting the aggregation of β-amyloid protein fibers and / or breaking up β-amyloid protein fiber aggregates.

[0045] Among them, when the hollow Au NBPs@CuS nanocomposite was used to inhibit the aggregation of amyloid protein, different materials were combined with Aβ 42 The specific co-incubation steps can be as follows: CuS, Au NBPs (2.72 μg / mL), Au NBPs+CuS (2.72 μg / mL+10.72 μg / mL) or Au NBPs@CuS (containing 2.72 μg / mL Au NBPs and 10.72 μg / mL CuS) are respectively added to Aβ 42(25 μM) was mixed in a stock solution of PBS buffer (pH = 7.4). When the hollow nanocomposite Au NBPs@CuS was used to inhibit the disaggregation of amyloid, the power was 1.2-1.5 W / cm 2 The hollow nanocomposite material and the prefabricated fibers were irradiated with near-infrared light of 808 nm in wavelength, and the temperature was raised to 60°C in 5±1 min to break up the formed fibers. The results showed that the hollow nanocomposite material Au NBPs@CuS formed by combining Au NBPs with CuS had a strong effect on Aβ 42 The inhibition or depolymerization effect of the fibers is superior to that of Au NBPs, CuS single materials and simple physical composites of Au NBPs+CuS.

[0046] The following are examples of certain embodiments of the present application, which are not intended to limit the scope of the present application.

[0047] In addition, it should be noted that the numerical values ​​given in the following examples are as accurate as possible, but those skilled in the art understand that due to unavoidable measurement errors and experimental operation problems, each number should be understood as an approximate number rather than an absolutely accurate value.

[0048] Example 1

[0049] (1) Preparation of Au NBPs: 2.8 mL of deionized water, 4 mL of 0.1 M CTAC, 200 μL of 10 mM HAuCl4, and 400 μL of 0.1 M citric acid were added sequentially to a 10 mL glass bottle. After vigorous stirring at room temperature for 2 minutes, 100 μL of freshly prepared ice-cold 0.05 M NaBH4 was quickly added to the solution at once; the mixture turned from light yellow to brown. The solution was then placed in an 80 °C oil bath with stirring at 380 rpm for 1.5 hours, causing the color to gradually change from brown to red. The prepared seed solution was stored at 4 °C for subsequent use. To synthesize Au NBPs, 200 μL of 0.01 M HAuCl4, 40 μL of 0.01 M AgNO3, and 80 μL of 2 M HCl were added dropwise sequentially to a solution containing 0.1 M CTAB (4 mL). With continued stirring, 32 μL of 0.1 M ascorbic acid was added, and the solution was observed to fade to colorless within 30 seconds. Then, 80 μL of the prepared gold seed solution was added to the growth solution. Finally, the mixture was allowed to stand at 30°C for 3 hours. After centrifugation at 7000 rpm for 10 minutes and washing once with deionized water, the Au NBPs were redispersed in 4.504 mL of deionized water and stored at 4°C for later use.

[0050] (2) Synthesis of hollow nanocomposite Au NBPs@CuS: A 6 mM NaCl solution in PSS (2 g / L, 5 mL) was added to a glass bottle, and then 5 mL of Au NBPs was added dropwise. The mixture was stirred overnight, centrifuged at 7000 rpm for 10 minutes, and then redispersed in 5 mL of deionized water. The Au NBPs@PSS solution was then added dropwise to 5 mL of 20 g / L PVP solution. Stirring was continued for 3 hours. The resulting Au NBPs@PSS@PVP solution was centrifuged and dispersed in deionized water. 1 mL of 0.1 M Cu(NO3)2·3H2O solution was added to 9 mL of an aqueous solution containing 0.2 g of polyvinylpyrrolidone (PVP, MW=58000) and stirred for 15 minutes. Next, 5 mL of the prepared Au NBPs@PSS@PVP (4.5 mM) mixture was added, followed by the rapid addition of 13.8 μL of a 17.5 wt% hydrazine monohydrate solution. The solution turned yellow-brown. After 10 minutes of reaction, 0.415 mL of a 0.2 M sodium sulfide nonahydrate solution was added to the mixture. After stirring for two hours, the hollow Au NBPs@CuS nanocomposite was obtained. The product was collected by centrifugation and washed with ethanol and deionized water for further characterization.

[0051] Example 2

[0052] (1) Preparation of Au NBPs: 2.8 mL of deionized water, 4 mL of 0.1 M CTAC, 200 μL of 10 mM HAuCl4, and 400 μL of 0.1 M citric acid were added sequentially to a 10 mL glass bottle. After vigorous stirring at room temperature for 2 minutes, 100 μL of freshly prepared ice-cold 0.05 M NaBH4 was quickly added to the solution at one time. The mixture turned from light yellow to brown. The solution was then placed in an 80 °C oil bath with stirring at 380 rpm for 1.5 hours, causing the color to gradually change from brown to red. The prepared seed solution was stored at 4 °C for subsequent use. To synthesize Au NBPs, 200 μL of 0.01 M HAuCl4, 40 μL of 0.01 M AgNO3, and 80 μL of 2 M HCl were added dropwise sequentially to a solution containing CTAB (0.1 M, 4 mL). With continued stirring, 32 μL of 0.1 M ascorbic acid was added, and the solution was observed to fade to colorless within 30 seconds. Then, 80 μL of the prepared gold seed solution was added to the growth solution. Finally, the mixture was allowed to stand at 30°C for 3 hours. After centrifugation at 7000 rpm for 10 minutes and washing once with deionized water, the Au NBPs were redispersed in 4.504 mL of deionized water and stored at 4°C for later use.

[0053] (2) Synthesis of hollow nanocomposite Au NBPs@CuS: A 6 mM NaCl solution in PSS (2 g / L, 5 mL) was added to a glass bottle, and then 5 mL of Au NBPs was added dropwise. The mixture was stirred overnight, centrifuged at 7000 rpm for 10 minutes, and then redispersed in 5 mL of deionized water. The Au NBPs@PSS solution was then added dropwise to 5 mL of 20 g / L PVP solution. Stirring was continued for 3 hours. The resulting Au NBPs@PSS@PVP solution was centrifuged and dispersed in deionized water. 2 mL of 0.1 M Cu(NO3)2·3H2O solution was added to 18 mL of an aqueous solution containing 0.4 g of polyvinylpyrrolidone (PVP, MW=58000) and stirred for 15 minutes. Next, 10 mL of the prepared Au NBPs@PSS@PVP (4.5 mM) mixture was added, followed by the rapid addition of 27.6 μL of a 17.5 wt% hydrazine monohydrate solution. The solution turned yellow-brown. After 10 minutes of reaction, 0.83 mL of a 0.2 M sodium sulfide nonahydrate solution was added to the mixture. After stirring for two hours, the hollow Au NBPs@CuS nanocomposite was obtained. The product was collected by centrifugation and washed with ethanol and deionized water for further characterization.

[0054] The characterization results of Examples 1-2 are consistent. The characterization results of Example 1 are described below. The morphology of the hollow nanocomposite material Au NBPs@CuS prepared in Example 1 was characterized by field emission transmission electron microscopy. The results are shown in FIG. Figure 2 Specifically, the morphology and size distribution of the hollow nanocomposite Au NBPs@CuS were characterized by field emission transmission electron microscopy (JEM-200F, JEOL, Japan) using ultrathin carbon films. Figure 2 The results show that when 5 mL of the above-prepared Au NBPs@PSS@PVP was added as the core for synthesis, the particle size was uniform and had an obvious hollow core-shell structure. Cu and S elements were distributed in the core-shell, and Au elements were distributed in the core. They were evenly dispersed with an average particle size of 125 nm, confirming the successful synthesis of the hollow nanocomposite material AuNBPs@CuS under this condition.

[0055] Furthermore, the photothermal and photodynamic properties of the hollow nanocomposite material Au NBPs@CuS prepared in Example 1 were characterized as follows:

[0056] (1) Photothermal performance test

[0057] The wavelength is 808nm and the power is 1.5W / cm 2The Au NBPs@CuS solution was irradiated with a laser. The temperature was recorded every 30 seconds for a total of 5 minutes. After that, the solution was heated and allowed to cool naturally to room temperature. The cooling temperature curve was recorded over time. The photothermal conversion efficiency (η) was calculated as follows:

[0058]

[0059] Among them, h, S, T max 、T sur and Q s are the heat transfer coefficient, the container surface area, the equilibrium temperature, the ambient temperature, and the heat associated with the light absorption rate of the tube and water, respectively. I and A are the laser power and absorbance of the solution at 808 nm, respectively. D Indicates the weight of water, c D The specific heat capacity of water (4.2 J g -1 ℃ -1 ), τ represents the time constant of Au NBPs@CuS during the cooling period. t(s) is the irradiation time, and τ can be calculated based on the linear regression curve.

[0060] like Figure 3 As shown in Figure 2, the Au NBPs and CuS composite material has a significant improvement in photothermal performance, with a photothermal conversion efficiency of 43.88% and R 2 is 0.99.

[0061] (2) Detection of reactive oxygen species

[0062] 2,2,6,6-Tetramethylpiperidine and 5-tert-butyloxycarbonyl-5-methyl-1-pyrroline N-oxide were used as 1 O2 and ·OH scavengers were used to identify active oxygen species. At 808 nm, the power was 1.5 W / cm 2 The cells were irradiated with laser for 10 minutes to determine the ROS production under light.

[0063] Furthermore, the effects of the hollow nanocomplex prepared in Example 1 on the aggregation morphology of Aβ42 and the disaggregation of Aβ42 fibers were studied as follows:

[0064] (1) Effect of hollow nanocomposite Au NBPs@CuS on Aβ 42 Effect of aggregation morphology

[0065] CuS (10.72 μg / mL), Au NBPs (2.72 μg / mL), Au NBPs+CuS (2.72 μg / mL+10.72 μg / mL), or Au NBPs@CuS (containing 2.72 μg / mL Au NBPs and 10.72 μg / mL CuS) were respectively 42 (25 μM) was mixed in a stock solution of PBS buffer (pH = 7.4). At the same time, in order to monitor the appearance and growth of fibers, Aβ 42 A 15 μL aliquot of the sample was added to 235 μL of ThT (24 μM). The fluorescence intensity of the solution was then measured using a fluorescence spectrophotometer (excitation wavelength 440 nm, emission wavelength 485 nm), and the results were indicative of Aβ. 42 The amount of fibrils, the results Figure 4 shown.

[0066] The synthesis method of CuS is as follows: copper nitrate (1 mL, 0.1 M) solution is added to 9 mL of an aqueous solution containing 0.2 g of PVP, stirred for 15 minutes, and then 5 μL of a 35 wt% hydrazine monohydrate solution is quickly added. After reacting for 10 minutes, 0.3 mL of a 0.2 M sodium sulfide solution is added and stirred continuously for 2 hours to obtain a hollow CuS material.

[0067] (2) Effect of hollow nanocomposite Au NBPs@CuS on Aβ 42 Effect of pre-fiber depolymerization

[0068] After 24 h of culture, Aβ 42 After incubating the fibers with the various materials and irradiating them with light for 10 minutes, 10 μL of the sample was dripped onto a mica sheet. After 30 minutes of immersion, the sheet was slowly rinsed with deionized water to remove any salt ions. The rinsed mica sheet was dried with nitrogen and scanned using tapping mode.

[0069] like Figure 4 As shown, Au NBPs@CuS and Aβ 42 The co-incubation kinetic curve shows that the fiber content is extremely low. The results show that Au NBPs@CuS has a strong affinity for Aβ 42 The inhibitory effect of incubation on fibroblasts was the strongest. Figure 5 The AFM images shown show that Aβ alone 42 After 24 h, dense fibrous aggregates were formed. 42 After irradiation, the fibers disappeared and the depolymerization effect was the strongest compared with other materials. The depolymerization effect of Au NBPs@CuS was better than that of CuS, Au NBPs, and a simple physical mixture of CuS+Au NBPs.

[0070] The above-described embodiments merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person of ordinary skill in the art may make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

[0071] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A hollow nanocomposite material, characterized in that: The hollow nanocomposite material is a nanostructure with a gold nanobipyramid as the core and a hollow p-type semiconductor as the outer layer; The structural formula of the hollow nanocomposite material is Au NBPs@CuS, wherein CuS is the outer semiconductor and Au NBPs is the inner core; The method for preparing the hollow nanocomposite material comprises: Prepare gold nanobipyramids; the particle size of the gold nanobipyramids is 95 to 105 nm; The gold nanobipyramids were dropped into a sodium polystyrene sulfonate solution containing 6 mM NaCl and stirred overnight to obtain a mixture of AuNBPs@PSS; The Au NBPs@PSS mixture solution was added dropwise to an equal volume of 20 g / L polyvinyl pyrrolidone solution and stirred for 3 hours to obtain a Au NBPs@PSS@PVP mixture; the concentration of the Au NBPs@PSS@PVP mixture was 4.5 mM; 5-10 mL of the Au NBPs@PSS@PVP mixture is added to an aqueous solution containing 1-2 mL of copper nitrate and 9-18 mL of polyvinylpyrrolidone, followed by rapid addition of 12.8-25.6 μL of hydrazine monohydrate solution for reaction, followed by addition of 0.415-0.83 mL of sodium sulfide solution for uniform stirring to obtain a hollow nanocomposite material; The concentration of the sodium polystyrene sulfonate solution is 2 g / L, and the volume ratio of the added gold nanobipyramids is 1:1; the concentration of the copper nitrate is 0.1 M; and the concentration of the sodium sulfide is 0.2 M.

2. The hollow nanocomposite material according to claim 1, characterized in that The particle size of the hollow nanocomposite material is 125-135 nm; the particle size of the gold nanobipyramid is 95-105 nm.

3. A method for preparing the hollow nanocomposite material according to claim 1 or 2, characterized in that: include: Prepare gold nanobipyramids; the particle size of the gold nanobipyramids is 95 to 105 nm; The gold nanobipyramids were dropped into a sodium polystyrene sulfonate solution containing 6 mM NaCl and stirred overnight to obtain a mixture of AuNBPs@PSS; The Au NBPs@PSS mixture solution was added dropwise to an equal volume of 20 g / L polyvinyl pyrrolidone solution and stirred for 3 hours to obtain a Au NBPs@PSS@PVP mixture; the concentration of the Au NBPs@PSS@PVP mixture was 4.5 mM; 5-10 mL of the Au NBPs@PSS@PVP mixture is added to an aqueous solution containing 1-2 mL of copper nitrate and 9-18 mL of polyvinylpyrrolidone, followed by rapid addition of 12.8-25.6 μL of hydrazine monohydrate solution for reaction, followed by addition of 0.415-0.83 mL of sodium sulfide solution for uniform stirring to obtain a hollow nanocomposite material; The concentration of the sodium polystyrene sulfonate solution is 2 g / L, and the volume ratio of the added gold nanobipyramids is 1:1; the concentration of the copper nitrate is 0.1 M; and the concentration of the sodium sulfide is 0.2 M.

4. The method for preparing the hollow nanocomposite material according to claim 3, characterized in that: The method for preparing the gold nanobipyramids comprises: 2.8 mL of deionized water, 4 mL of 0.1 M hexadecyltrimethylammonium chloride, 200 μL of 10 mM HAuCl4, and 400 μL of 0.1 M citric acid were vigorously stirred at room temperature, and 100 μL of 0.05 M glacial NaBH4 was added. The mixture was stirred at 80 °C for 1.5 hours to obtain a seed solution. 50-80 μL of seed solution was added to a mixed solution containing 32 μL of 0.1 M ascorbic acid, 4 mL of 0.1 M hexadecyltrimethylammonium bromide, 200 μL of 0.01 M HAuCl4, 40 μL of 0.01 M AgNO3 and 80 μL of 2 M HCl, and maintained at 30°C for 3 hours to obtain gold nanobipyramids.

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