Hydrotalcite nanocomposite, preparation method and application thereof

Abstract

The application discloses a hydrotalcite nanocomposite, a preparation method and application thereof. The composite material comprises hydrotalcite nanosheets and metal nanoclusters uniformly distributed on the hydrotalcite nanosheets; the metal nanoclusters are selected from any two of palladium nanoclusters, rhodium nanoclusters and ruthenium nanoclusters; the metal cations in the hydrotalcite nanosheets are divalent metal ions and trivalent metal ions; the divalent metal ions are selected from one or more of Cu 2+ , Mg 2+ and Ni 2+ ; the trivalent metal ions are selected from Al 3+ and / or Fe 3+ . The hydrotalcite nanocomposite has good catalase-like and glucose oxidase-like activities, can effectively relieve hypoxic microenvironment and consume glucose in tumor cells, further induce bisulfide death, and due to the two-dimensional confinement effect of the hydrotalcite nanosheets, can effectively increase the singlet oxygen production efficiency of noble metals, and realize tumor treatment of drugs.

Description

Technical Field

[0001] This invention relates to the field of cancer drug preparation technology. More specifically, it relates to a hydrotalcite nanocomposite material, its preparation method, and its applications. Background Technology

[0002] Cancer is one of the leading causes of death in humans. Traditional cancer treatments such as surgical resection, radiotherapy, and chemotherapy have limited efficacy and are often highly toxic with severe side effects. Therefore, continuously exploring innovative treatment methods in the field of oncology is particularly important. Furthermore, although traditional treatments can induce cell death through conventional pathways such as apoptosis, many malignant tumors have shown resistance to these treatments. This has prompted researchers to explore therapeutic strategies that induce alternative cell death, such as ferroptosis, copper apoptosis, alkalosis, and pyroptosis. Among these, disulfide death is a novel form of cell death independent of existing programmed cell death mechanisms such as ferroptosis and copper apoptosis. It is a form of cell death caused by disulfide stress resulting from excessive cystine accumulation under glucose starvation, leading to actin collapse. Specifically, in cancer cells with glucose deficiency and high expression of the membrane transport protein SLC7A11, disulfide molecules such as cystine accumulate in large quantities within the cell, leading to abnormal disulfide bonds between actin cytoskeletal proteins, ultimately resulting in actin network collapse and cell death. Therefore, developing biodegradable nanoreagents that can effectively consume and inhibit glucose transport to further induce disulfide death may provide new targets for cancer treatment (J. Hematol. Oncol. 2024, 17, 22).

[0003] Glucose oxidase is a redox enzyme that catalyzes the aerobic oxidation of glucose to hydrogen peroxide and gluconic acid, effectively regulating glucose levels and has been widely used in biosensors and cancer therapy. However, natural glucose oxidase has inherent drawbacks such as poor stability and complex purification processes, which undoubtedly limit its biomedical applications. Noble metal nanozymes are enzyme mimics based on noble metal nanomaterials, possessing various enzyme activities, such as peroxidase, catalase, and superoxide dismutase. Currently, several noble metal nanozymes have been found to have glucose oxidase-like activities, such as single metal or alloy nanoparticles or metal single atoms made of gold, platinum, palladium, rhodium, and iridium (ACS Energy Lett. 2023, 8, 1697-1704). Their catalytic efficiency and selectivity are related to factors such as the size, morphology, composition, and surface modification of the nanoparticles. Furthermore, their catalytic glucose oxidation process is similar to that of natural glucose oxidase, consisting of two steps: the first step is the dehydrogenation of glucose to glucuronide and a reducing cofactor (such as NADH); the second step is the transfer of an electron from the cofactor to oxygen to generate hydrogen peroxide. Both of these reactions require the consumption of an electron. Different noble metal nanozymes may exhibit different catalytic abilities and mechanisms for these two steps of the reaction. Gold nanoparticles can catalyze both steps simultaneously, while other noble metal nanoparticles such as platinum, palladium, rhodium, and iridium show lower catalytic efficiency and selectivity for the second step (Nature Communications 2021, 12, 3375). Hydrotalcite (LDH), as a unique two-dimensional layered material, has been widely used as a catalyst support. Due to its special layered structure and tunable geometric and electronic properties, there is a strong metal-support interaction between the LDH support and the supported metal, which can give the supported catalytic material better catalytic activity and selectivity (Transactions of Tianjin University 2022, 28, 89-111). Furthermore, the positive charge of the LDH layers allows the material to effectively interact with the negatively charged cell membrane, thereby effectively transferring it within the cell; simultaneously, by rationally adjusting the cations in the layers, it can interact with non-cellular components in the tumor microenvironment, inducing apoptosis in cancer cells. Moreover, most of the components of LDH are silicate clay-like minerals that can degrade in acidic environments, ensuring high biocompatibility. These excellent properties of hydrotalcite provide new ideas for improving the glucose oxidase-like activity and biocompatibility of noble metal nanozymes. (Theranostics 2020, 10(22):10057-10074).

[0004] Therefore, it is necessary to provide a simple method for preparing platinum-based bimetallic nanoclusters / hydrotalcite nanocomposites, so that the material can be applied to disulfide death in cancer. Summary of the Invention

[0005] Based on this, the purpose of this invention is to provide a hydrotalcite nanocomposite material, its preparation method, and its application. Drugs prepared using this hydrotalcite nanocomposite material exhibit excellent catalase-like and glucose oxidase-like activities, effectively alleviating the hypoxic microenvironment and consuming glucose in tumor cells, further inducing disulfide death. Simultaneously, due to the two-dimensional confinement effect of the hydrotalcite nanosheets, the singlet oxygen generation efficiency of noble metals can be effectively increased, thereby achieving highly efficient tumor treatment with this drug.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A hydrotalcite nanocomposite material, the composite material comprising hydrotalcite nanosheets and metal nanoclusters uniformly distributed on the hydrotalcite nanosheets;

[0008] The metal nanoclusters are selected from any two of palladium nanoclusters, rhodium nanoclusters, and ruthenium nanoclusters;

[0009] The metal cations in the hydrotalcite nanosheets are divalent and trivalent metal ions;

[0010] The divalent metal ions are selected from Cu. 2+ Mg 2+ and Ni 2+ One or more of them;

[0011] The trivalent metal ions are selected from Al. 3+ and / or Fe 3+ .

[0012] Furthermore, in the metal nanoclusters, the mass ratio of the two different nanoclusters is 1:2-2:1, preferably 1:1.

[0013] Compared to single nanoclusters formed by palladium, rhodium, and ruthenium nanoclusters, the technical solution of this invention selects bimetallic nanoclusters. Due to the efficient charge transfer capability between the bimetals and the possible synergistic effect between different elements, the composite material has more efficient enzyme activity.

[0014] Furthermore, the loading amount of the metal nanoclusters on the hydrotalcite nanosheets is 5-25 wt%.

[0015] It should be noted that the loading amount in this invention refers to the mass ratio of metal nanoclusters to hydrotalcite nanosheets.

[0016] Furthermore, in the hydrotalcite nanosheets, the molar ratio of divalent metal ions to total metal cations is 1 / 3-1 / 4.

[0017] Furthermore, in the hydrotalcite nanosheets, the anion is NO. 3- .

[0018] Furthermore, the hydrotalcite nanosheets have a length and width of 50-100 nm and a thickness of 1-2 nm. In the aforementioned scheme, the length and width of the hydrotalcite nanosheets can be the same or different.

[0019] Furthermore, the composite material has a length and width of 50-150 nm and a thickness of 2-5 nm. In the aforementioned scheme, the length and width of the composite material can be the same or different.

[0020] In the aforementioned hydrotalcite nanocomposite material, the loading of metal nanoclusters has no significant effect on the morphology and size of the hydrotalcite nanosheets, only slightly increasing the thickness.

[0021] In another aspect, the present invention provides a method for preparing the hydrotalcite nanocomposite material as described above, comprising the following steps:

[0022] Aqueous solutions of metal nitrate and sodium hydroxide were simultaneously added dropwise to an aqueous solution of sodium carbonate, maintaining the pH at 9-10. The mixture was stirred at 70-90°C, preferably 80°C, for 0.5-2 hours. After stirring, the mixture was centrifuged, washed, and dried to obtain hydrotalcite nanosheets.

[0023] The hydrotalcite nanosheets are mixed with any two of sodium tetrachloropalladium, sodium hexachlororhodium, and ruthenium trichloride hydrate, and stirred until homogeneous. Then, an aqueous solution of sodium borohydride containing potassium hydroxide is added dropwise. After stirring for 3-12 hours, the mixture is centrifuged, washed, and dried to obtain the hydrotalcite nanocomposite material.

[0024] Furthermore, the metal nitrates include nitrates of divalent metals and nitrates of trivalent metals;

[0025] The divalent metal nitrate is selected from one or more of copper nitrate hexahydrate, magnesium nitrate trihydrate, and nickel nitrate hexahydrate;

[0026] The trivalent metal nitrate is selected from aluminum nitrate nonahydrate and / or ferric nitrate nonahydrate.

[0027] Furthermore, if present, the molar mass ratio of copper nitrate hexahydrate, magnesium nitrate trihydrate, nickel nitrate hexahydrate, aluminum nitrate nonahydrate, and ferric nitrate nonahydrate is 0.1:2:1-1:2:1.

[0028] The phrase "if present" refers to the presence of at least two of the following: copper nitrate hexahydrate, magnesium nitrate trihydrate, nickel nitrate hexahydrate, aluminum nitrate nonahydrate, and ferric nitrate nonahydrate, in a molar ratio between 0.1:2:1 and 1:2:1. For example, if the metal nitrate contains copper nitrate hexahydrate, magnesium nitrate trihydrate, and ferric nitrate nonahydrate, then the molar ratio of the three is 0.1:2:1.

[0029] Furthermore, the mass ratio of the total amount of metal ions in the hydrotalcite nanosheets to any two of the sodium tetrachloropalladium, sodium hexachlororhodium, and ruthenium trichloride hydrate is 5-25%.

[0030] Furthermore, in the sodium borohydride aqueous solution containing potassium hydroxide, the concentration of potassium hydroxide is 1.5-2.5M, preferably 2M; the ratio of the number of moles of sodium borohydride to the total number of moles of metal ions in the metal nitrate is 40:1. Excess sodium borohydride ensures that the metal ions are effectively reduced.

[0031] In another aspect, the present invention provides the use of the hydrotalcite nanocomposite material as described above in the preparation of drugs for treating tumors.

[0032] Unless otherwise specified, all raw materials used in this invention are commercially available or can be obtained through conventional means in the art.

[0033] The beneficial effects of this invention are as follows:

[0034] The hydrotalcite nanocomposite material provided in this invention has excellent glucose oxidase activity that can induce efficient disulfide death, good biosafety, and good therapeutic effect when used in the preparation of drugs for cancer treatment.

[0035] The preparation method of the hydrotalcite nanocomposite material provided in this invention is simple and the conditions are controllable. It uses ultrathin hydrotalcite nanosheets as therapeutic drugs and carriers. The composite material can be obtained by mechanically stirring the ruthenium / rhodium / palladium source solution with the hydrotalcite nanosheet colloidal solution and then further impregnating and reducing it with sodium borohydride and centrifuging. In addition, the preparation method has low energy consumption, low equipment requirements and is environmentally friendly. Attached Figure Description

[0036] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0037] Figure 1 The image shown is a transmission electron microscope (TEM) image of the ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material synthesized in Example 1.

[0038] Figure 2 The X-ray diffraction pattern of the ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material synthesized in Example 1 is shown.

[0039] Figure 3 The absorption spectrum of reactive oxygen species detected by TMB as a probe is shown for the ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material synthesized in Example 1.

[0040] Figure 4 The diagram shows a comparison of the reactive oxygen species generation of the following nanocomposites: RuRh-CuMgAl (RuRh-CuMgAl), RhPd-CuMgAl (RhPd-CuMgAl), RuRh-NiFe (RuRh-NiFe), RhPd-NiFe (RhPd-NiFe), and single-metal nanoclusters / copper-magnesium-aluminum hydrotalcite nanomaterials (Rh-CuMgAl) synthesized in Example 1, Example 2, Example 9, Example 10, and Example 10, Rh-CuMgAl (RuRh-NiFe), and single-metal nanoclusters / copper-magnesium-aluminum hydrotalcite nanomaterials.

[0041] Figure 5 The absorption spectrum of reactive oxygen species detected by TMB as a probe is shown for the rhodium-palladium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material synthesized in Example 2.

[0042] Figure 6 The absorption spectra of the ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite materials synthesized in Example 1, the rhodium-palladium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite materials synthesized in Example 2, the ruthenium-rhodium bimetallic nanoclusters / nickel-iron hydrotalcite nanocomposite materials synthesized in Example 9, and the rhodium-palladium bimetallic nanoclusters / nickel-iron hydrotalcite nanocomposite materials synthesized in Example 10, using fluorescent red as a probe (Example 1, Glu+RuRh-CuMgAl; Example 2, Glu+RhPd-CuMgAl; Example 9, Glu+RuRh-NiFe; Example 10, Glu+RhPd-NiFe) to evaluate the activity of GOD-like enzymes by H2O2 generation. Detailed Implementation

[0043] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further explains the invention. Similar components in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.

[0044] Example 1

[0045] The preparation steps of a ruthenium-rhodium bimetallic nanocluster / copper-magnesium-aluminum hydrotalcite nanocomposite material are as follows:

[0046] 1) Dissolve 19.849g magnesium nitrate hexahydrate, 0.934g copper nitrate trihydrate, and 14.517g aluminum nitrate nonahydrate in 80mL of water and mix well to obtain solution A; dissolve 8.204g sodium carbonate in 50mL of water and mix well to obtain solution B; dissolve 9.6g sodium hydroxide in 160mL of water and mix well to obtain solution C; under stirring in an 80℃ water bath, slowly add solution A to solution B, then add solution C dropwise, adjust the pH to 9, and react mechanically at room temperature for 30min. Centrifuge at 8000-10000rpm / s for 5min. Wash the resulting precipitate twice each with deionized water and anhydrous ethanol, and centrifuge to separate it; dry it overnight in a 60℃ drying oven, grind and sieve it, and the resulting blue powder is copper magnesium aluminum hydrotalcite with a molar ratio of 0.1:2:1.

[0047] 2) Take 0.1 g of the copper-magnesium-aluminum hydrotalcite obtained in step 1) and dissolve it in 50 mL of deionized water. Stir mechanically for about 30 min. Dissolve 0.0052 g of ruthenium trichloride hydrate and 0.0092 g of sodium hexachlororhodium phosphate in 20 mL of deionized water. Then add it to the well-dispersed hydrotalcite nanosheet colloid and continue stirring for 1 h. Next, dissolve 0.074 g of sodium borohydride in 5 mL of deionized water and add two drops of KOH (2M). Then add it dropwise to the above mixed solution of precious metal and hydrotalcite. Impregnate and reduce for 5 h under stirring. After the reaction is completed, centrifuge and wash (twice with deionized water and twice with ethanol) using a centrifuge with a speed of 8000-10000 rpm. After separation, freeze-dry the precipitate for 24 h, and then grind and sieve to obtain ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material, wherein the total loading of precious metals ruthenium-rhodium on the hydrotalcite nanosheets is 5 wt%.

[0048] In this embodiment, the transmission electron microscope (TEM) image of the prepared ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material is shown below. Figure 1 As shown. Figure 1 The composite material exhibits uniform dimensions, ranging from 50 to 150 nm in length and width. The XRD pattern of the ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite is shown below. Figure 2 This indicates the successful synthesis of a ruthenium-rhodium bimetallic nanocluster / copper-magnesium-aluminum hydrotalcite nanocomposite material. TMB and fluorescent red were used as probes to test its reactive oxygen species (ROS) generation and glucose consumption capabilities. Figure 3 , 4 As shown, the composite material exhibits a significantly higher generation of reactive oxygen species, nearly five times higher than the monometallic rhodium nanoclusters / copper-magnesium-aluminum hydrotalcite material. This is likely due to the efficient charge transfer capabilities between multiple metals and potential synergistic effects between different elements. Furthermore, as... Figure 6As shown, the presence of ultrathin hydrotalcite nanosheets can effectively consume glucose and generate hydrogen peroxide, thereby further generating reactive oxygen species to kill cancer cells.

[0049] Example 2

[0050] The preparation steps of a rhodium-palladium bimetallic nanocluster / copper-magnesium-aluminum hydrotalcite nanocomposite material are as follows:

[0051] 1) Dissolve 19.849g magnesium nitrate hexahydrate, 0.934g copper nitrate trihydrate, and 14.517g aluminum nitrate nonahydrate in 80mL of water and mix well to obtain solution A; dissolve 8.204g sodium carbonate in 50mL of water and mix well to obtain solution B; dissolve 9.6g sodium hydroxide in 160mL of water and mix well to obtain solution C; under stirring in an 80℃ water bath, slowly add solution A to solution B, then add solution C dropwise, adjust the pH to 9, and react mechanically at room temperature for 30min. Centrifuge at 8000-10000rpm / s for 5min. Wash the resulting precipitate twice each with deionized water and anhydrous ethanol, and centrifuge to separate it; dry it overnight in a 60℃ drying oven, grind and sieve it, and the resulting blue powder is copper magnesium aluminum hydrotalcite with a molar ratio of 0.1:2:1.

[0052] 2) Take 0.1 g of the copper-magnesium-aluminum hydrotalcite obtained in step 1) and dissolve it in 50 mL of deionized water. Stir mechanically for about 30 min. Dissolve 0.0092 g of sodium hexachlororhodiumate and 0.0068 g of sodium tetrachloropalladiumate in 20 mL of deionized water. Then add it to the well-dispersed hydrotalcite nanosheet colloid and continue stirring for 1 h. Next, dissolve 0.071 g of sodium borohydride in 5 mL of deionized water and add two drops of KOH (2M). Then add it dropwise to the above mixed solution of noble metal and hydrotalcite. Impregnate and reduce for 5 h under stirring. After the reaction is completed, centrifuge and wash (twice with deionized water and twice with ethanol) using a centrifuge with a speed of 8000-10000 rpm / s. After separation, freeze-dry the precipitate for 24 h, and then grind and sieve to obtain the rhodium-palladium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material, wherein the total loading of noble metals rhodium and palladium on the hydrotalcite nanosheets is 5 wt%.

[0053] The obtained rhodium-palladium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material has nanosheets with lengths and widths of 50-150 nm. When dispersed in water, such as... Figure 5 and Figure 6 As shown, the composite material exhibits general reactive oxygen species generation performance and high glucose consumption capacity.

[0054] Example 3 repeats Example 1, except that in step 2), "0.0052 g of ruthenium trichloride hydrate and 0.0092 g of sodium hexachlororhodiumate" are replaced with "0.0103 g of ruthenium trichloride hydrate and 0.0187 g of sodium hexachlororhodiumate", and "0.074 g of sodium borohydride" is replaced with "0.148 g of sodium borohydride"; all other conditions remain unchanged, and a ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum layered double hydroxide nanocomposite material with a loading of 10% is prepared. The resulting composite material has a length and width of 50-150 nm. When dispersed in water, the composite material exhibits good reactive oxygen species generation and glucose consumption capabilities.

[0055] Example 4

[0056] Example 2 was repeated, except that in step 2), "0.0092 g of sodium hexachlororhodiumate and 0.0068 g of sodium tetrachloropalladiumate" were replaced with "0.0187 g of sodium hexachlororhodiumate and 0.0138 g of sodium tetrachloropalladiumate", and "0.071 g of sodium borohydride" was replaced with "0.145 g of sodium borohydride"; all other conditions remained unchanged, and a rhodium-palladium bimetallic nanoclusters / copper-magnesium-aluminum layered double hydroxide nanocomposite material with a loading of 10 wt% was prepared. The resulting composite material had a length and width of 50-150 nm. When dispersed in water, the composite material exhibited good reactive oxygen species generation and glucose consumption capabilities.

[0057] Example 5

[0058] Example 1 was repeated, except that in step 2), "0.0052 g of ruthenium trichloride hydrate and 0.0092 g of sodium hexachlororhodiumate" were replaced with "0.0205 g of ruthenium trichloride hydrate and 0.0374 g of sodium hexachlororhodiumate", and "0.074 g of sodium borohydride" were replaced with "0.297 g of sodium borohydride"; all other conditions remained unchanged, and a ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum layered double hydroxide nanocomposite material with a loading of 20 wt% was prepared. The resulting composite material had a length and width of 50–150 nm. When dispersed in water, the composite material exhibited good reactive oxygen species generation and glucose consumption capabilities.

[0059] Example 6

[0060] Example 2 was repeated, except that in step 2), "0.0092 g of sodium hexachlororhodiumate and 0.0068 g of sodium tetrachloropalladiumate" were replaced with "0.0374 g of sodium hexachlororhodiumate and 0.0276 g of sodium tetrachloropalladiumate", and "0.071 g of sodium borohydride" was replaced with "0.289 g of sodium borohydride"; all other conditions remained unchanged, and a rhodium-palladium bimetallic nanoclusters / copper-magnesium-aluminum layered double hydroxide nanocomposite material with a loading of 20 wt% was prepared. The resulting composite material had a length and width of 50-150 nm. When dispersed in water, the composite material exhibited good reactive oxygen species generation and glucose consumption capabilities.

[0061] Example 7

[0062] Example 1 was repeated, except that "impregnation reduction for 5 hours" in step 2) was replaced with "impregnation reduction for 12 hours"; all other conditions remained unchanged, to prepare a ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material. The resulting composite material had a length and width of 50-150 nm. When dispersed in water, the composite material exhibited good reactive oxygen species generation and glucose consumption capabilities.

[0063] Example 8

[0064] Example 2 was repeated, except that "impregnation reduction for 5 hours" was replaced with "impregnation reduction for 12 hours"; all other conditions remained the same, to prepare a rhodium-palladium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material. The resulting composite material had a length and width of 50-150 nm. When dispersed in water, the composite material exhibited good reactive oxygen species generation and glucose consumption capabilities.

[0065] Example 9

[0066] Example 1 was repeated, except that "magnesium nitrate hexahydrate and copper nitrate trihydrate" in step 1) were replaced with "nickel nitrate," and "aluminum nitrate nonahydrate" was replaced with "ferric nitrate." All other conditions remained unchanged, and a ruthenium-rhodium bimetallic nanocluster / nickel-iron hydrotalcite nanocomposite material was prepared. The resulting composite material had a length and width of 50-150 nm. When dispersed in water, the composite material exhibited good reactive oxygen species generation and glucose consumption capabilities.

[0067] Example 10

[0068] Example 2 was repeated, except that "magnesium nitrate hexahydrate and copper nitrate trihydrate" in step 1) were replaced with "nickel nitrate," and "aluminum nitrate nonahydrate" was replaced with "ferric nitrate." All other conditions remained unchanged, and a rhodium-palladium bimetallic nanoclusters / nickel-iron hydrotalcite nanocomposite material was prepared. The resulting composite material had a length and width of 50-150 nm. When dispersed in water, the composite material exhibited good reactive oxygen species generation and glucose consumption capabilities.

[0069] Comparative Example 1

[0070] The preparation method is basically the same as in Example 1, except that the "ruthenium-rhodium bimetallic nanoclusters / copper-magnesium-aluminum hydrotalcite nanocomposite material" in 2) is replaced with "copper-magnesium-aluminum hydrotalcite". The other conditions remain unchanged. The efficiency of reactive oxygen generation is low, there is no glucose consumption capacity, and the therapeutic effect is average.

[0071] Comparative Example 2

[0072] The preparation method is basically the same as in Example 11, except that the "ruthenium-rhodium bimetallic nanoclusters / nickel-iron hydrotalcite nanocomposite material" in 2) is replaced with "nickel-iron hydrotalcite". The other conditions remain unchanged. The efficiency of reactive oxygen generation is low, there is no glucose consumption capacity, and the therapeutic effect is average.

[0073] Comparative Example 3

[0074] The preparation method is basically the same as in Example 1, except that “pH is controlled at 9” in 1) is replaced with “pH is controlled at 7”, and the other conditions remain unchanged. Copper magnesium aluminum hydrotalcite nanosheets cannot be obtained.

[0075] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A hydrotalcite nanocomposite material, characterized in that, The composite material contains hydrotalcite nanosheets and metal nanoclusters uniformly distributed on the hydrotalcite nanosheets; The metal nanoclusters are selected from any two of palladium nanoclusters, rhodium nanoclusters, and ruthenium nanoclusters; The metal cations in the hydrotalcite nanosheets are divalent and trivalent metal ions; The divalent metal ions are selected from Cu. 2+ Mg 2+ and Ni 2+ One or more of them; The trivalent metal ions are selected from Al. 3+ and / or Fe 3+ .

2. The hydrotalcite nanocomposite material according to claim 1, characterized in that, In the metal nanoclusters, the mass ratio of the two different nanoclusters is 1:2-2:1, preferably 1:

1.

3. The hydrotalcite nanocomposite material according to claim 1, characterized in that, The loading of the metal nanoclusters on the hydrotalcite nanosheets is 5-25 wt%.

4. The hydrotalcite nanocomposite material according to claim 1, characterized in that, In the hydrotalcite nanosheets, the molar ratio of divalent metal ions to total metal cations is 1 / 3 to 1 / 4.

5. The hydrotalcite nanocomposite material according to claim 1, characterized in that, The composite material has a length and width of 50-150 nm and a thickness of 2-5 nm.

6. The method for preparing the hydrotalcite nanocomposite material according to any one of claims 1-5, characterized in that, Includes the following steps: Aqueous solutions of metal nitrate and sodium hydroxide were simultaneously added dropwise to an aqueous solution of sodium carbonate to maintain the pH at 9-10. The mixture was stirred at 70-90℃ for 0.5-2 hours, then centrifuged, washed, and dried to obtain hydrotalcite nanosheets. The hydrotalcite nanosheets are mixed with any two of sodium tetrachloropalladium, sodium hexachlororhodium, and ruthenium trichloride hydrate, and stirred until homogeneous. Then, an aqueous solution of sodium borohydride containing potassium hydroxide is added dropwise. After stirring for 3-12 hours, the mixture is centrifuged, washed, and dried to obtain the hydrotalcite nanocomposite material.

7. The preparation method according to claim 6, characterized in that, The metal nitrates include nitrates of divalent metals and nitrates of trivalent metals; The divalent metal nitrate is selected from one or more of copper nitrate hexahydrate, magnesium nitrate trihydrate, and nickel nitrate hexahydrate; The trivalent metal nitrate is selected from aluminum nitrate nonahydrate and / or ferric nitrate nonahydrate; Preferably, if present, the molar mass ratio of copper nitrate hexahydrate, magnesium nitrate trihydrate, nickel nitrate hexahydrate, aluminum nitrate nonahydrate, and ferric nitrate nonahydrate is 0.1:2:1 to 1:2:

1.

8. The preparation method according to claim 6, characterized in that, The mass ratio of the total amount of metal ions in the hydrotalcite nanosheets to any two of the following: sodium tetrachloropalladium, sodium hexachlororhodium, and ruthenium trichloride hydrate is 5-25%.

9. The preparation method according to claim 6, characterized in that, In the sodium borohydride aqueous solution containing potassium hydroxide, the concentration of potassium hydroxide is 1.5-2.5M, preferably 2M; the ratio of the number of moles of sodium borohydride to the total number of moles of metal ions in the metal nitrate is 40:

1.

10. The use of the hydrotalcite nanocomposite material as described in any one of claims 1-5 in the preparation of a drug for treating tumors.

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