Pt nanoparticle composite material as well as preparation method and application thereof

CuPt Alloy@LDH nanocomposites loaded with Pt nanoparticles in CuCoFe-LDH nanosheets solved the problem of limited performance of nanoenzyme catalyzed ROS production in the prior art, achieved the effect of efficient killing of tumor cells, and significantly improved cancer The treatment effect is simple and environmentally friendly.

CN119097640APending Publication Date: 2024-12-10TECHNICAL INST OF PHYSICS & CHEMISTRY - CHINESE ACAD OF SCI

Patent Information

Application Number
CN202310670068.X
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2023-06-07
Publication Date
2024-12-10

AI Technical Summary

Technical Problem

Existing cancer treatment methods have serious side effects and risks, and nanoenzymes have performance limitations when catalyzing ROS production, making it difficult to effectively increase the ROS content in tumor sites.

Method used

CuCoFe-LDH nanosheets are used as a carrier to load Pt nanoparticles to form CuPt Alloy@LDH nanocomposites. By regulating the size and electron transport structure of the nanomaterial, the catalytic performance of nanoenzymes is improved, the ROS generation capacity is enhanced, and the ultrasonic wave is used. Activate composite materials under excitation to enhance the production of ROS in tumors.

Benefits of technology

It achieves efficient ROS production, kills tumor cells, reduces GSH in tumors, and downregulates the accumulation of HIF-1α and LPO, which significantly improves the tumor treatment effect. At the same time, the preparation method is simple, energy consumption is low, and environmentally friendly.

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Abstract

The invention discloses a Pt nanoparticle composite material as well as a preparation method and application thereof. The structure of the composite material comprises a CuCoFe-LDH (Layered Double Hydroxides) nanosheet and Pt nano particles loaded on the surface of a CuCoFe-LDH nanosheet layer plate. The CuCoFe-LDH in the composite material is used as a carrier, Cu < + >, Co < 2 + > and Fe < 2 + > of the CuCoFe-LDH have a chemical dynamic effect, Fe < 3 + > and Cu < 2 + > can consume GSH in a tumor, and quenching of over-expressed glutathione in the tumor on ROS is reduced. The composite material has excellent ROS generation and down-regulated LPO accumulation of HIF-1alpha, so that ferroptosis and killing of tumor cells are realized, and meanwhile, the composite material can be activated by ultrasonic waves to further realize ROS amplification in tumors, so that an excellent tumor treatment effect is realized.
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Description

Technical Field

[0001] The present invention relates to the technical field of cancer treatment drug preparation, and more specifically, to a Pt nanoparticle composite material and a preparation method and application thereof. Background Art

[0002] Health is the foundation of people's lives, and cancer has become one of the main factors threatening people's health. So far, various treatment strategies, such as surgery, chemotherapy, and radiotherapy, have been applied in clinical treatment. However, the above traditional methods have serious side effects and certain risks to the human body. Reactive oxygen species (ROS), such as hydrogen peroxide (H2O2), superoxide anion (·O 2- ) and hydroxyl radicals (·OH), which play an important role in regulating various physiological functions of organisms. At appropriate concentrations, ROS mediate signal transduction and cell growth. However, excessive ROS can cause irreversible oxidative damage to cells by oxidizing proteins and destroying DNA structure. Therefore, increasing the content of ROS in tumor sites has become an effective strategy for cancer treatment. In recent years, nanozymes have been widely used in ROS-mediated nanozyme-catalyzed therapy because they can mimic natural oxidases (OXD) or peroxidases (POD) and specifically produce a variety of ROS in response to the tumor microenvironment (TME).

[0003] Nanozymes are alternative materials to natural enzymes, and their catalytic activity is comparable to that of natural enzymes, which can greatly promote the catalytic efficiency of biological substrates. In addition, nanozymes can usually catalyze specific biochemical reactions of natural enzyme substrates under physiological conditions (such as catalyzing the decomposition of H2O2, catalyzing the oxidation of GSH to GSSH, etc.), and follow a catalytic mechanism similar to that of natural enzymes. Therefore, nanozymes with multiple enzyme activities can solve the problems of high GSH content and limited H2O2 content while having high catalytic efficiency. In addition, the activity of nanozymes can be adjusted by regulating the size, morphology and electron transport structure of nanomaterials. Compared with natural enzymes, nanozymes are more stable and cost-effective, and they also show unique properties generated by nanoscale size. Although nanozymes have such excellent performance, they are still limited by catalytic performance, so exploring high-performance nanozymes is an important aspect of improving therapeutic effects. Summary of the invention

[0004] Based on the above facts, the purpose of the present invention is to provide a Pt nanoparticle composite material and a preparation method and application thereof.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] In one aspect, the present invention provides a Pt nanoparticle composite material, wherein the structure of the composite material comprises: CuCoFe-LDH nanosheets, and Pt nanoparticles loaded on the surface of the CuCoFe-LDH nanosheet layer.

[0007] In this technical solution, the CuCoFe-LDH nanosheet (i.e., copper-cobalt-iron hydrotalcite nanosheet, CuPt Alloy@LDH) layer is composed of three metals: copper, cobalt, and iron. The surface of the layer has abundant hydroxyl groups and positive charges, and the interlayer has negative charges. Studies have found that the metal composition of the hydrotalcite nanosheet directly affects the performance of the prepared composite material. Only when the hydrotalcite nanosheet is the copper-cobalt-iron hydrotalcite nanosheet mentioned in this technical solution, the composite material has excellent performance in generating ROS.

[0008] Further, the size of the CuCoFe-LDH nanosheet is 100-150 nm. Exemplarily, the size of the CuCoFe-LDH nanosheet includes but is not limited to 50-120 nm, 80-120 nm, 100 nm, etc.

[0009] Furthermore, in the structure of the composite material, Pt nanoparticles are combined with Cu in CuCoFe-LDH nanosheets to exist in the form of an alloy. Under this condition, Cu will further provide electrons to Pt, improve the activity of the nanozyme, and further improve the catalytic performance of the nanozyme under the action of US, so that the composite material has good performance in generating hydroxyl radicals and generating ROS.

[0010] Furthermore, in the structure of the composite material, the actual loading amount of Pt is 1-3wt%, preferably 2.2wt%, as determined by ICP.

[0011] Further, the size of the CuCoFe-LDH nanosheet loaded with Pt nanoparticles is 50-200 nm. Exemplarily, the size of the CuCoFe-LDH nanosheet loaded with Pt nanoparticles includes but is not limited to 50-180 nm, 90-180 nm, 150 nm, 100-200 nm, etc.

[0012] In another aspect, the present invention provides a method for preparing the above-mentioned Pt nanoparticle composite material, comprising the following steps:

[0013] The aqueous solution of CuCoFe-LDH nanosheets is uniformly mixed with hexahydrate chloroplatinic acid and a reducing agent, and the mixture is purified and dried to obtain the Pt nanoparticle composite material.

[0014] Furthermore, in the above preparation method, the reducing agent is selected from NaBH4. 4+ Reduced to Pt nanoparticles and loaded on hydrotalcite.

[0015] Furthermore, the preparation of the CuCoFe-LDH nanosheets comprises the following steps:

[0016] Copper nitrate trihydrate, cobalt nitrate hexahydrate, iron nitrate nonahydrate and an aqueous solution of an alkaline substance are simultaneously added to an aqueous solution containing a template agent, and the CuCoFe-LDH nanosheet is obtained after reaction.

[0017] Furthermore, in the aqueous solution of the alkaline substance, the alkaline substance is selected from sodium hydroxide and / or sodium carbonate.

[0018] If the reaction temperature is too high or too low, the lamella structure cannot be formed. Furthermore, the reaction temperature is 30-100°C, the reaction time is 10-20 minutes, and the reaction is carried out under stirring conditions. Stirring facilitates crystallization and is conducive to the formation of LDH lamellae.

[0019] Furthermore, the molar ratio of the copper nitrate trihydrate, the cobalt nitrate hexahydrate and the ferric nitrate nonahydrate is 2:3:2.

[0020] Furthermore, the template is selected from formamide and / or polyethylene glycol, which can limit the size of the material.

[0021] Furthermore, the volume ratio of the template to water is 0.8-0.9.

[0022] In another aspect, the present invention provides a nanozyme, which is prepared from the Pt nanoparticle composite material as described above.

[0023] In yet another aspect, the present invention provides use of the Pt nanoparticle composite material as described above in the preparation of anti-cancer and / or anti-tumor drugs or devices.

[0024] Furthermore, the application includes: using the Pt nanoparticle composite material under ultrasonic excitation conditions.

[0025] Unless otherwise specified, various raw materials used in the present invention can be purchased commercially or obtained by conventional means in the art.

[0026] The beneficial effects of the present invention are as follows:

[0027] Platinum nanoparticles, as precious metal nanomaterials, have been widely demonstrated to have chemotherapeutic efficacy and oxygen supplementation nanomaterials with catalase (CAT) nanozyme activity. However, we found that the peroxidase-like (POD-like) activity of platinum nanoparticles, i.e., catalyzing endogenous hydrogen peroxide (H2O2) to generate highly toxic hydroxyl radicals (·OH), has rarely been studied due to particle aggregation and lack of suitable carriers. Here, the present invention provides a nanocomposite material based on CuCoFe-LDH, in which CuCoFe-LDH is not only used as a carrier, but also as a carrier. + 、Co + and Fe 2+ Has chemical power effect, Fe 3+ and Cu 2+ It can consume GSH in the tumor and reduce the quenching of ROS by overexpressed glutathione in the tumor. Therefore, the composite material has excellent ROS production and down-regulation of LPO accumulation of HIF-1α, thereby achieving ferroptosis and killing tumor cells. At the same time, the composite material can also be activated by ultrasound to further achieve ROS amplification in the tumor, thereby achieving excellent tumor treatment effect.

[0028] In the preparation method of the composite material provided by the present invention, a one-step method is adopted to prepare a Pt nanoparticle composite material (CuPt Alloy@LDH nanocomposite material). The method has simple process, low energy consumption, low equipment requirements, and is environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The specific implementation modes of the present invention will be further described in detail below in conjunction with the accompanying drawings.

[0030] Figure 1 Shown is a transmission electron microscopy image of the CuPt Alloy@LDH synthesized in Example 1.

[0031] Figure 2 The XRD pattern of CuPt Alloy@LDH synthesized in Example 1 is shown.

[0032] Figure 3 The TMB test of the CuPt Alloy@LDH nanocomposite synthesized in Example 1 is shown.

[0033] Figure 4 The electron spin resonance image of the CuPt Alloy@LDH nanocomposite synthesized in Example 1 generating hydroxyl radicals is shown. DETAILED DESCRIPTION

[0034] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0035] Example 1

[0036] A preparation method of a CuPt Alloy@LDH nanocomposite material comprises the following steps:

[0037] 1) CuCoFe-LDHs were prepared by a simple constant pH coprecipitation method. In short, 483.2 mg Cu(NO3)2.3H2O, 873.3 mg Co(NO3)2.6H2O and 808 mg Fe(NO3)3.9H2O were dissolved in 70 mL of deionized water as solution A. 560 mg NaOH and 4243.9 mg Na2CO3 were dissolved in 70 mL of deionized water as solution B. Liquids A and B were dispersed in ultrasound. Then, the four-necked flask was fixed on an iron stand and placed in a constant temperature (80°C) water bath. A mechanical stirrer was installed on the iron stand, 20 mL of deionized water was added to the four-necked flask, stirred, and liquids A and B were double-dropped. In other words, solution A and solution B were dropped into the four-necked flask at the same time, and the pH of the suspension in the four-necked flask was continuously tested while dropping the solution, and the pH value of the suspension was always kept at 9-10. After the titration is completed, the bottle mouth is closed and the reaction is stirred in a water bath at 80°C for 10 minutes. After the reaction is completed, the CuCoFe-LDHs precursor is washed by centrifugation in a low-speed centrifuge, washed with deionized water, and washed with anhydrous ethanol. The pH of CuCoFe-LDHs is close to neutral. Then the CuCoFe-LDHs precursor is dried in a freeze-drying process for 12 hours.

[0038] 2) Put CuCoFe-LDHs into a 100 ml four-necked flask, add 30 ml of deionized water, and stir mechanically for about 30 minutes to evenly disperse it in the deionized water. Then add an appropriate amount of 0.017 mol / L hexahydrate chloroplatinic acid solution, about 2.4 ml, and stir for about 1 hour to evenly mix the hexahydrate chloroplatinic acid solution and HELOs. Then weigh 40 times the molar amount of sodium borohydride, about 0.146 g (nNaBH4 = 40nPt 4+), excess sodium borohydride ensures that more Pt is reduced. Dissolve it in about 5 ml of deionized water, add two drops of KOH (2M) to make the sodium borohydride solution alkaline. Then add the sodium borohydride solution drop by drop into the mixed solution of hexahydrate chloroplatinic acid and CuCoFe-LDHs. Under stirring, immersion reduction is carried out for 5 hours. After the reaction is completed, the prepared CuPt Alloy@LDH is centrifuged and washed in a high-speed centrifuge. Deionized water and ethanol are used in the washing process, and it is placed in a freeze drying box and dried overnight.

[0039] 3) In this example, the transmission electron microscopy image of the CuPt Alloy@LDH nanocomposite material prepared is as follows: Figure 1 and Figure 2 shown. Figure 1 The CuCoFe-LDH is uniform in size, about 150 nm. Figure 2 The CuPt Alloy@LDH nanocomposite material size is about 150nm, and the XRD pattern of CuPt Alloy@LDH is as follows: Figure 2 As shown, there are characteristic peaks of hydrotalcite (003), (006), (009), etc., and also characteristic peaks of CuPt Alloy@LDH (111), (220), etc. The generation of ROS by CuPt Alloy@LDH was studied by using 3,3,5,5-tetramethylbenzidine (TMB) probe. The UV absorption peak increased at 652nm, proving that it has good ROS generation performance ( Figure 3 ). Figure 4 As shown, a 5 mM DMPO solution was prepared, and 30 uL 1 mg / mL CuPt Alloy@LDH nanocomposite and 20 uL 0.001 mg / mL H2O2 were added. The composite material showed a strong ability to generate hydroxyl radicals through electron paramagnetic resonance testing.

[0040] Example 2

[0041] A preparation method of CuPt Alloy@LDH nanocomposite material is as follows:

[0042] Take 483.2mg Cu(NO3)2.3H2O, 873.3mg Co(NO3)2.6H2O and 808mg Fe(NO3)3.9H2O and dissolve them in 100mL water, mix them evenly to form liquid A; dissolve 0.034g sodium nitrate in 40ml water containing 25% polyethylene glycol, mix them evenly to form liquid B; dissolve 1g sodium hydroxide and 0.1g sodium carbonate in 100ml water, mix them evenly to form liquid C; under stirring in a water bath at 80℃, slowly add liquid A and liquid C into liquid B at the same time, adjust the pH to 9.5, react for 1h, centrifuge, wash and freeze-dry.

[0043] 2) 0.16 g of the hydrotalcite nanosheets obtained in step 1) was placed in a 100 ml four-necked flask, 30 ml of deionized water was added, and mechanical stirring was performed for about 30 minutes to uniformly disperse the nanosheets in the deionized water. Then, about 2.4 ml of a hexahydrate chloroplatinic acid solution with an appropriate loading amount was added, and stirring was performed for about 1 hour to uniformly mix the hexahydrate chloroplatinic acid solution and the HELOs. Then, about 0.146 g of a 40-fold molar amount of sodium borohydride (nNaBH4 = 40 nPt 4+ ), excess sodium borohydride ensures that more Pt is reduced. Dissolve it in about 5 ml of deionized water, add two drops of KOH (2M) to make the sodium borohydride solution alkaline. Then add the sodium borohydride solution drop by drop into the mixed solution of hexahydrate chloroplatinic acid and CuCoFe-LDHs. Under stirring, immersion reduction is carried out for 5 hours. After the reaction is completed, the prepared CuPt Alloy@LDH is centrifuged and washed in a high-speed centrifuge. Deionized water and ethanol are used in the washing process, and it is placed in a freeze drying box and dried overnight. Through the electron paramagnetic resonance method described in Example 1, the composite material exhibits a strong ability to generate hydroxyl radicals.

[0044] Example 3

[0045] A preparation method of CuPt Alloy@LDH nanocomposite material is as follows:

[0046] 1) Dissolve 483.2 mg Cu(NO3)2.3H2O, 873.3 mg Co(NO3)2.6H2O and 808 mg Fe(NO3)3.9H2O in 100 mL water and mix well to form liquid A; dissolve 0.034 g sodium nitrate in 40 mL water containing 25% formamide and mix well to form liquid B; dissolve 1 g sodium hydroxide and 0.1 g sodium carbonate in 100 mL water and mix well to form liquid C; slowly add liquid A and liquid C to liquid B at the same time while stirring in a water bath at 80°C, adjust the pH to 9.5, react for 1 h, centrifuge, wash and freeze-dry.

[0047] 2) 0.16 g of the hydrotalcite nanosheets obtained in step 1) was placed in a 100 ml four-necked flask, 30 ml of deionized water was added, and mechanical stirring was performed for about 30 minutes to uniformly disperse the nanosheets in the deionized water. Then, about 2.4 ml of a hexahydrate chloroplatinic acid solution with an appropriate loading amount was added, and stirring was performed for about 1 hour to uniformly mix the hexahydrate chloroplatinic acid solution and the HELOs. Then, about 0.146 g of a 40-fold molar amount of sodium borohydride (nNaBH4 = 40 nPt 4+ ), excess sodium borohydride ensures more Pt 4+is reduced. Dissolve it in about 5 ml of deionized KOH (2M) to make the sodium borohydride solution alkaline. Then add the sodium borohydride solution drop by drop into the mixture of the above-mentioned chloroplatinic acid hexahydrate and CuCoFe-LDHs. Under stirring, immersion reduction is carried out for 5 hours. After the reaction is completed, the prepared CuPt Alloy@LDH is centrifuged and washed in a high-speed centrifuge. Deionized water and ethanol are used in the washing process, and it is placed in a freeze drying box and dried overnight. Through the electron paramagnetic resonance method as described in Example 1, the composite material exhibits a strong ability to generate hydroxyl radicals.

[0048] Example 4

[0049] A preparation method of CuPt Alloy@LDH nanocomposite material is as follows:

[0050] 1) Dissolve 483.2 mg Cu(NO3)2.3H2O, 873.3 mg Co(NO3)2.6H2O and 808 mg Fe(NO3)3.9H2O in 100 mL water and mix well to form liquid A; dissolve 0.034 g sodium nitrate in 40 mL water containing 25% formamide and mix well to form liquid B; dissolve 1 g sodium hydroxide and 0.1 g sodium carbonate in 100 mL water and mix well to form liquid C; slowly add liquid A and liquid C to liquid B at the same time while stirring in a 30°C water bath, adjust the pH to 9.5, react for 3 h, centrifuge, wash and freeze-dry.

[0051] 2) The steps are the same as in Example 1.

[0052] The obtained platinum nanoparticle / copper-cobalt-iron hydrotalcite nanosheet composite material, CuCoFe-LDH, is about 150 nm in size. It is weighed and prepared into a 1 mg / mL dispersion. The composite material is tested by electron paramagnetic resonance. 30 ul of the dispersion is added to the DMPO capture agent to detect the generation of ROS. By the electron paramagnetic resonance method described in Example 1, the composite material shows a strong ability to generate hydroxyl radicals.

[0053] Example 5

[0054] A preparation method of CuPt Alloy@LDH nanocomposite material is as follows:

[0055] 1) Prepare salt solution: put 483.2mg Cu(NO3)2.3H2O, 873.3mg Co(NO3)2.6H2O and 808mg Fe(NO3)3.9H2O into the first beaker, bring to a boil, measure 60mL and pour into the beaker, dissolve and disperse by ultrasonication;

[0056] 2) Prepare alkaline solution: Put 560 mg NaOH and 4243.9 mg Na2CO3 into a second beaker, bring to a boil, take out 30 mL, pour it into the beaker together with 30 mL ethanol, and dissolve and disperse by ultrasonication.

[0057] 3) Pour the salt solution and 20 mL of formamide into a three-necked flask, use a syringe to draw the alkaline solution into the syringe, turn on the automatic sampler, let the syringe be filled with the alkaline solution, then stop, control the constant temperature water bath at 80°C, turn on the stirring paddle, and then drop the alkaline solution into the three-necked flask at a certain speed. After all the additions are completed, add 1 mol·L -1 NaOH was added to adjust the pH value of the mixed solution to about 8-9, and the reaction was continued with stirring for 10-20 min. After the stirring was completed, the reactants in the round-bottom flask were transferred to a freeze drying oven and taken out after 12 hours.

[0058] 4) Loading process As shown in Example 1, it was weighed into a 1 mg / mL dispersion. The composite material was tested by electron paramagnetic resonance. 30 ul of the dispersion was added to the DMPO capture agent to detect the generation of ROS. The electron paramagnetic resonance composite material showed a strong ability to generate hydroxyl radicals.

[0059] Example 6

[0060] Example 5 was repeated, except that the step 3) "pour the salt solution and 20 mL of formamide into a three-necked flask" was replaced with "pour the salt solution and 20 mL of polyethylene glycol into a three-necked flask". The other conditions remained unchanged, and the CuPt Alloy@LDH nanocomposite material was prepared. The size of the obtained composite material was about 120 nm, which was weighed into a 1 mg / mL dispersion. The composite material was tested by electron paramagnetic resonance, and 20 ul of the dispersion was added to the DMPO capture agent to detect the ROS generation effect. The results showed that the material exhibited good ROS generation performance.

[0061] Example 7

[0062] Example 1 was repeated, except that the step 2) "adding an appropriate amount of 0.017 mol / L of chloroplatinic acid hexahydrate solution, about 2.4 ml" was replaced with "adding an appropriate amount of 0.017 mol / L of chloroplatinic acid hexahydrate solution, about 1.2 ml". The other conditions remained unchanged, and a platinum / copper-cobalt-iron hydrotalcite nanosheet composite material was prepared. The obtained composite material had a size of about 120 nm, which was weighed into a 1 mg / mL dispersion. The composite material was tested by electron paramagnetic resonance, and 20 ul of the dispersion DMPO capture agent was used to detect the ROS effect. The results showed that the material exhibited good ROS generation performance.

[0063] Example 8

[0064] Example 1 was repeated, except that the step 2) "adding an appropriate amount of 0.017 mol / L of chloroplatinic acid hexahydrate solution, about 2.4 ml" was replaced with "adding an appropriate amount of 0.017 mol / L of chloroplatinic acid hexahydrate solution, about 3.6 ml". The other conditions remained unchanged, and a platinum / copper-cobalt-iron hydrotalcite nanosheet composite material was prepared. The obtained composite material had a size of about 120 nm, which was weighed to form a 1 mg / mL dispersion. The composite material was tested by electron paramagnetic resonance, and 20 ul of the dispersion DMPO capture agent was used to detect the ROS effect. The results showed that the material exhibited good ROS generation performance.

[0065] Example 9

[0066] Example 1 was repeated, except that the step 2) "adding an appropriate amount of 0.017 mol / L of chloroplatinic acid hexahydrate solution, about 2.4 ml" was replaced with "adding an appropriate amount of 0.017 mol / L of chloroplatinic acid hexahydrate solution, about 4.8 ml". The other conditions remained unchanged, and a platinum / copper-cobalt-iron hydrotalcite nanosheet composite material was prepared. The obtained composite material had a size of about 120 nm, which was weighed into a 1 mg / mL dispersion. The composite material was tested by electron paramagnetic resonance, and 20 ul of the dispersion DMPO capture agent was used to detect the ROS effect. The results showed that the material exhibited good ROS generation performance.

[0067] Example 10

[0068] Example 1 was repeated, except that the step 2) "adding an appropriate amount of 0.017 mol / L of chloroplatinic acid hexahydrate solution, about 2.4 ml" was replaced with "adding an appropriate amount of 0.017 mol / L of chloroplatinic acid hexahydrate solution, about 6 ml". The other conditions remained unchanged, and a platinum / copper-cobalt-iron hydrotalcite nanosheet composite material was prepared. The obtained composite material had a size of about 120 nm, which was weighed into a 1 mg / mL dispersion. The composite material was tested by electron paramagnetic resonance, and 20 ul of the dispersion DMPO capture agent was used to detect the ROS effect. The results showed that the material exhibited good performance in generating ROS.

[0069] Comparative Example 1

[0070] The preparation method is basically the same as that in Example 1, except that the "20 ml formamide aqueous solution" in 1) is replaced with "aqueous solution" and the other conditions remain unchanged. CuCoFe-LDH nanosheets of about 100 nm cannot be obtained.

[0071] Comparative Example 2

[0072] The preparation method is basically the same as that in Example 1, except that the "PH controlled at 9" in 1) is replaced by "PH controlled at 7", and the other conditions remain unchanged, and no CuCoFe-LDH nanosheets are obtained.

[0073] Comparative Example 3

[0074] The preparation method is basically the same as that in Example 1, except that "stirring at 80°C for 10 min" in 1) is replaced by "stirring at 80°C for 30 min", and the other conditions remain unchanged. The size of the obtained CuPt Alloy@LDH nanocomposite material is larger, and the ESR test shows that its performance in generating free radicals is not as good as that of the small size.

[0075] Comparative Example 4

[0076] The preparation method is basically the same as that in Example 1, except that the "iron nitrate hexahydrate" in 1) is replaced with "aluminum nitrate hexahydrate", and the other conditions remain unchanged to obtain CuCoAl nanosheets. However, the ESR test found that its performance in generating ROS was not as good as that of CuCoFe-LDH.

[0077] Comparative Example 5

[0078] The preparation method is basically the same as that in Example 1, except that step 2) is omitted, that is, Pt is not loaded and other conditions remain unchanged, to obtain CuCoFe-LDH nanosheets. However, the ESR test shows that its performance in generating hydroxyl radicals is significantly worse than that of CuPt Alloy@LDH in the above example.

[0079] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A Pt nanoparticle composite material, It is characterized in that The composite material comprises: CuCoFe-LDH nanosheets and Pt nanoparticles loaded on the surface of the CuCoFe-LDH nanosheet layer.

2. The Pt nanoparticle composite material according to claim 1, It is characterized in that In the structure of the composite material, Pt nanoparticles are combined with Cu in the CuCoFe-LDH nanosheets to exist in the form of an alloy; Preferably, in the structure of the composite material, the actual loading amount of Pt is 1-3 wt %, more preferably 2.2 wt %, as determined by ICP.

3. The Pt nanoparticle composite material according to claim 1, It is characterized in that The size of the CuCoFe-LDH nanosheets is 100-150 nm; and / or The size of the CuCoFe-LDH nanosheets loaded with Pt nanoparticles is 50-200 nm.

4. A method for preparing a Pt nanoparticle composite material according to any one of claims 1 to 3, It is characterized in that The steps include: The aqueous solution of CuCoFe-LDH nanosheets is uniformly mixed with hexahydrate chloroplatinic acid and a reducing agent, and the mixture is purified and dried to obtain the Pt nanoparticle composite material.

5. The preparation method according to claim 4, It is characterized in that The preparation of the CuCoFe-LDH nanosheets comprises the following steps: Copper nitrate trihydrate, cobalt nitrate hexahydrate, iron nitrate nonahydrate and an aqueous solution of an alkaline substance are simultaneously added to an aqueous solution containing a template agent, and the CuCoFe-LDH nanosheet is obtained after reaction.

6. The preparation method according to claim 5, It is characterized in that In the aqueous solution of the alkaline substance, the alkaline substance is selected from sodium hydroxide and / or sodium carbonate.

7. The preparation method according to claim 5, It is characterized in that The reaction temperature is 30-100° C., the reaction time is 10-20 min, and the reaction is carried out under stirring conditions.

8. A nanozyme, It is characterized in that The method is prepared from the Pt nanoparticle composite material as described in any one of claims 1 to 3.

9. Use of the Pt nanoparticle composite material according to any one of claims 1 to 3 in the preparation of anti-cancer and / or anti-tumor drugs or devices.

10. The use according to claim 9, It is characterized in that The Pt nanoparticle composite material is used under ultrasonic excitation conditions.

Citation Information

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