Preparation method and application of copper-manganese doped hexahydroxy stannide nano-enzyme
By preparing copper-manganese doped hexahydroxytinder nanoenzyme, the problems of large size and uneven morphology of perovskite hydroxide materials were solved, and the nanoscale and uniform morphology of materials were achieved, and its catalytic application potential in the field of biomedical science was demonstrated.
Patent Information
- Application Number
- CN202510262333.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-06
- Publication Date
- 2025-06-06
AI Technical Summary
The existing perovskite hydroxide materials have problems such as large size, uneven morphology and inability to be applied to the biomedical field.
The copper-manganese doped hexahydroxytin compound nanoenzyme was prepared by ultrasonic dispersion and water bath reaction. The copper-manganese doped hexahydroxytin compound nanoenzyme with a size of about 110 nm and a uniform morphology.
The prepared copper-manganese doped hexahydroxytin compound nanoenzyme has good catalytic properties and can catalyze the production of hydroxyl radicals and oxygen. It is suitable for biomedical applications such as anti-tumor or antibacterial.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of inorganic materials, and specifically relates to a preparation method and application of a copper-manganese-doped hexahydroxytin compound nanozyme. Background Art
[0002] Perovskite-based nanomaterials have been applied in many fields such as electrode materials, photoelectrocatalysis and biosensors due to their regular structure, easily controllable metal components and excellent catalytic properties.
[0003] In recent years, perovskite nanomaterials have attracted widespread attention due to their stable properties and low preparation cost. Studies have found that compared with perovskite oxides, the synthesis method of perovskite hydroxides is milder and simpler, and is suitable as a template for multi-metal doping. However, the traditional perovskite hydroxides reported so far usually have the disadvantages of large size (micrometer level), uneven morphology, and difficult surface modification. More importantly, large-sized perovskite hydroxides are not conducive to cell uptake and cannot be used in the biomedical field. By doping various metals, such as Fe, Mn, Cu, Zn and Ni, the obtained perovskite hydroxides can synthesize alloys with two or more components. This is beneficial for regulating the catalytic activity of doped perovskite hydroxides composed of different combinations of different metals. On this basis, it is reasonable and feasible to study the enzyme-like catalytic activity of perovskite hydroxides by regulating the doping of metals in perovskite hydroxides. After reviewing the literature, there has been no report on the use of copper-manganese-doped hexahydroxytin compounds as peroxide-like nanozymes. Therefore, it is urgent to seek copper-manganese-doped hexahydroxytin nanozymes with small size, simple availability, low cost and uniform morphology. Summary of the invention
[0004] The purpose of the present invention is to solve the problems of large size, uneven morphology and inability to be applied in the biomedical field of existing perovskite hydroxide materials, and to provide a preparation method and application of copper-manganese-doped hexahydroxytin nanozyme.
[0005] A method for preparing a copper-manganese-doped hexahydroxytin nanozyme is specifically completed by the following steps:
[0006] 1. Prepare solution A:
[0007] Add copper sulfate pentahydrate, manganese acetate tetrahydrate and sodium citrate into deionized water, and perform ultrasonication until the dispersion is uniform to obtain solution A;
[0008] 2. Prepare solution B:
[0009] Add tin tetrachloride pentahydrate into anhydrous ethanol and disperse uniformly by ultrasonication to obtain solution B;
[0010] 3. Prepare Solution C:
[0011] Add sodium hydroxide to deionized water and fully dissolve it by ultrasonication to obtain solution C;
[0012] 4. Water bath reaction:
[0013] Under magnetic stirring, solution B is added dropwise to solution A, stirring is continued for a period of time, and then solution C is added dropwise in a water bath at a temperature of 50°C to 70°C, heated in a water bath for a period of time, and cooled to room temperature to obtain a reaction product;
[0014] The molar ratio of the copper element in solution A to the tin element in solution B described in step 4 is (0.7-0.9):1.
[0015] A copper-manganese-doped hexahydroxytin nanozyme is used as a peroxide-like nanozyme in the biomedical field.
[0016] Principle of the present invention:
[0017] The copper ions in the copper-manganese doped hexahydroxytin nanozyme prepared by the present invention coexist with valences of +1 and +2, and the Mn ions coexist with valences of +2, +3, and +4. The variable-valence metal can promote electron transfer through the change of its own valence state in the Fenton-like reaction, catalyze hydrogen peroxide to produce hydroxyl radicals and oxygen, and can be used as a peroxide-like nanozyme in biomedical fields such as anti-tumor or antibacterial.
[0018] Advantages of the present invention:
[0019] 1. The synthesis method of the present invention is simple, and the raw materials used are cheap and easily available;
[0020] 2. The size of the copper-manganese-doped hexahydroxytin nanozyme prepared by the present invention is about 110 nm, the sample morphology is a uniform cube, the valence states of copper ions coexist as +1 and +2, and the valence states of manganese ions coexist as +2, +3, and +4, and the powder sample has absorption in the range of 200-900 nm;
[0021] 3. The copper-manganese-doped hexahydroxytin nanozyme prepared by the present invention has Fenton-like catalytic properties, catalyzing hydrogen peroxide to produce hydroxyl radicals and oxygen, and can be used as a peroxide-like nanozyme in biomedical fields such as anti-tumor or antibacterial. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 This is a scanning electron microscope image of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1;
[0023] Figure 2 This is the X-ray diffraction spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1;
[0024] Figure 3 This is the full X-ray photoelectron spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1;
[0025] Figure 4 This is a high-resolution X-ray photoelectron spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1, in which a represents the O element, b represents the Sn element, c represents the Cu element, and d represents the Mn element;
[0026] Figure 5 This is the optical absorption spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1;
[0027] Figure 6 This is a scanning electron microscope image of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2;
[0028] Figure 7 This is the X-ray diffraction spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2;
[0029] Figure 8 This is the full X-ray photoelectron spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2;
[0030] Fig. 9 This is a high-resolution X-ray photoelectron spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2, in which a represents the O element, b represents the Sn element, c represents the Cu element, and d represents the Mn element;
[0031] Fig.10 This is the optical absorption spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2;
[0032] Fig.11 This is a scanning electron microscope image of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 3, in which a indicates that 0.2941 g of sodium citrate was added, and b indicates that 1.1764 g of sodium citrate was added;
[0033] Fig.12 This is a scanning electron microscope image of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 4, in which a indicates that 0.3506 g of tin tetrachloride pentahydrate was added, and b indicates that 1.4024 g of tin tetrachloride pentahydrate was added;
[0034] Fig.13 This is a scanning electron microscope image of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 5, in which a indicates that 0.4 g of sodium hydroxide was added, and b indicates that 1.6 g of sodium hydroxide was added;
[0035] Fig.14This is a scanning electron microscope image of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 6, where a indicates a water bath temperature of 20°C, b indicates a water bath temperature of 40°C, c indicates a water bath temperature of 80°C, and d indicates a water bath temperature of 100°C;
[0036] Fig.15 This is a scanning electron micrograph of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 7, where a represents a reaction time of 0.5 h, and b represents a reaction time of 2 h;
[0037] Fig.16 This is a concentration and catalytic activity curve of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1;
[0038] Fig.17 This is a concentration and catalytic activity curve of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2;
[0039] Fig.18 This is a curve diagram of hydrogen peroxide concentration and catalytic activity of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1;
[0040] Fig.19 This is a curve diagram of hydrogen peroxide concentration and catalytic activity of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2;
[0041] Fig. 20 The temperature and catalytic activity curve of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1;
[0042] Fig.21 This is a temperature and catalytic activity curve of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2;
[0043] Fig. 22 This is a graph showing the reaction time and catalytic activity of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1;
[0044] Fig.23 This is a curve diagram of reaction time and catalytic activity of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2. DETAILED DESCRIPTION
[0045] Specific implementation method 1: The preparation method of the copper-manganese-doped hexahydroxytin nanozyme in this implementation method is specifically completed according to the following steps:
[0046] 1. Prepare solution A:
[0047] Add copper sulfate pentahydrate, manganese acetate tetrahydrate and sodium citrate into deionized water, and perform ultrasonication until the dispersion is uniform to obtain solution A;
[0048] 2. Prepare solution B:
[0049] Add tin tetrachloride pentahydrate into anhydrous ethanol and disperse uniformly by ultrasonication to obtain solution B;
[0050] 3. Prepare Solution C:
[0051] Add sodium hydroxide to deionized water and fully dissolve it by ultrasonication to obtain solution C;
[0052] 4. Water bath reaction:
[0053] Under magnetic stirring, solution B is added dropwise to solution A, stirring is continued for a period of time, and then solution C is added dropwise in a water bath at a temperature of 50°C to 70°C, heated in a water bath for a period of time, and cooled to room temperature to obtain a reaction product;
[0054] The molar ratio of the copper element in solution A to the tin element in solution B described in step 4 is (0.7-0.9):1.
[0055] Specific embodiment 2: This embodiment differs from specific embodiment 1 in that the mass ratio of copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is (0.3 g to 0.4 g): (0.09 g to 0.2 g): (0.5 g to 0.6 g): (60 mL to 80 mL). The other steps are the same as those in specific embodiment 1.
[0056] Specific embodiment 3: This embodiment differs from specific embodiment 1 or 2 in that the mass ratio of copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is 0.3996 g: 0.098 g: 0.5882 g: 70 mL. The other steps are the same as those in specific embodiment 1 or 2.
[0057] Specific embodiment 4: This embodiment differs from specific embodiments 1 to 3 in that the mass ratio of tin tetrachloride pentahydrate to anhydrous ethanol in step 2 is (0.7 g to 0.8 g): 10 mL. The other steps are the same as those of specific embodiments 1 to 3.
[0058] Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 in that the mass ratio of tin tetrachloride pentahydrate to anhydrous ethanol in step 2 is 0.7012 g:10 mL. The other steps are the same as those of specific embodiments 1 to 4.
[0059] Specific embodiment 6: This embodiment differs from specific embodiments 1 to 5 in that the mass ratio of sodium hydroxide to deionized water in step 3 is (0.7 g to 0.9 g): 10 mL. The other steps are the same as those of specific embodiments 1 to 5.
[0060] Specific embodiment 7: This embodiment differs from specific embodiments 1 to 6 in that the mass ratio of sodium hydroxide to deionized water in step 3 is 0.8 g:10 mL. The other steps are the same as those of specific embodiments 1 to 6.
[0061] Specific embodiment 8: This embodiment differs from specific embodiments 1 to 7 in that the stirring time in step 4 is 30 min to 60 min, and the water bath heating reaction time in step 4 is 0.5 h to 2 h. The other steps are the same as those in specific embodiments 1 to 7.
[0062] Specific embodiment 9: This embodiment differs from specific embodiments 1 to 8 in that: the volume ratio of solution A to solution C in step 4 is (60 mL to 80 mL): (5 mL to 15 mL); the molar ratio of the copper element in solution A to the tin element in solution B in step 4 is 0.8:1. The other steps are the same as those in specific embodiments 1 to 8.
[0063] Specific embodiment ten: This embodiment is a copper-manganese-doped hexahydroxytin nanozyme used as a peroxide-like nanozyme in the biomedical field.
[0064] The following examples are used to verify the beneficial effects of the present invention:
[0065] Example 1: A method for preparing a copper-manganese-doped hexahydroxytin nanozyme is specifically completed by the following steps:
[0066] 1. Prepare solution A:
[0067] Add copper sulfate pentahydrate, manganese acetate tetrahydrate and sodium citrate into deionized water, and perform ultrasonication until the dispersion is uniform to obtain solution A;
[0068] The volume ratio of the copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is 0.3996 g: 0.098 g: 0.5882 g: 70 mL;
[0069] 2. Prepare solution B:
[0070] Add tin tetrachloride pentahydrate into anhydrous ethanol and disperse uniformly by ultrasonication to obtain solution B;
[0071] The mass ratio of tin tetrachloride pentahydrate described in step 2 to anhydrous ethanol is 0.7012 g:10 mL;
[0072] 3. Prepare Solution C:
[0073] Add sodium hydroxide to deionized water and fully dissolve it by ultrasonication to obtain solution C;
[0074] The mass ratio of sodium hydroxide to deionized water in step 3 is 0.8 g:10 mL;
[0075] 4. Water bath reaction:
[0076] Under magnetic stirring, solution B was added dropwise to solution A, and stirring was continued for 30 min. Then, solution C was added dropwise in a water bath at 60°C, and the mixture was heated in a water bath for 60 min. The mixture was cooled to room temperature to obtain a reaction product.
[0077] The volume ratio of solution A to solution C described in step 4 is 70mL:10mL;
[0078] The molar ratio of the copper element in solution A to the tin element in solution B described in step 4 is 0.8:1.
[0079] The copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1 was observed using a Hitachi SU-70 thermal field emission scanning electron microscope. Figure 1 Scanning electron microscope images at different magnifications show that the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1 has a uniform cubic shape and a size of about 110 nm.
[0080] The crystallinity and phase of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1 were tested using an X-ray diffractometer (Empyrean) from Panalytical Analytical Instruments of the Netherlands. The test results are as follows: Figure 2 As shown, Figure 2 It is an X-ray diffraction spectrum. The top of the figure shows the X-ray diffraction spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1, the middle is the hexahydroxytin copper standard card (JCPDS NO.70-0117), and the bottom is the hexahydroxytin manganese standard card (JCPDS NO.20-0727), indicating that the material obtained in Example 1 has a typical perovskite hydroxide structure.
[0081] The copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1 was analyzed for valence state using an X-ray photoelectron spectrometer (PHI 5600) from Physical Electronics, Inc., USA; Figure 3 and Figure 4 As shown, Figure 3 This is the full X-ray photoelectron spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1. Figure 3 It can be seen that the elements Cu, Mn, Sn and O coexist; Figure 4 This is a high-resolution X-ray photoelectron spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1, in which a represents the O element, b represents the Sn element, c represents the Cu element, and d represents the Mn element; Figure 4 It can be seen that Cu ions coexist in +1 and +2 valence states, and Mn ions coexist in +2, +3, and +4 valence states.
[0082] The ultraviolet absorption performance of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1 in the range of 200-900 nm was tested using a Puxi TU-1901 double-beam ultraviolet-visible spectrophotometer. Figure 5 As shown, Figure 5 is the optical absorption spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1; Figure 5 It can be seen that the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1 has full spectrum absorption in the ultraviolet, visible and near-infrared regions.
[0083] Example 2: A method for preparing a copper-manganese-doped hexahydroxytin nanozyme is specifically completed by the following steps:
[0084] 1. Prepare solution A:
[0085] Add copper sulfate pentahydrate, manganese acetate tetrahydrate and sodium citrate into deionized water, and perform ultrasonication until the dispersion is uniform to obtain solution A;
[0086] The volume ratio of the copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is 0.2497 g: 0.2451 g: 0.5882 g: 70 mL;
[0087] 2. Prepare solution B:
[0088] Add tin tetrachloride pentahydrate into anhydrous ethanol and disperse uniformly by ultrasonication to obtain solution B;
[0089] The mass ratio of tin tetrachloride pentahydrate described in step 2 to anhydrous ethanol is 0.7012 g:10 mL;
[0090] 3. Prepare Solution C:
[0091] Add sodium hydroxide to deionized water and fully dissolve it by ultrasonication to obtain solution C;
[0092] The mass ratio of sodium hydroxide to deionized water in step 3 is 0.8 g:10 mL;
[0093] 4. Water bath reaction:
[0094] Under magnetic stirring, solution B was added dropwise to solution A, and stirring was continued for 30 min. Then, solution C was added dropwise in a water bath at 60°C, and the mixture was heated in a water bath for 60 min. The mixture was cooled to room temperature to obtain a reaction product.
[0095] The volume ratio of solution A to solution C described in step 4 is 70mL:10mL;
[0096] The molar ratio of the copper element in solution A to the tin element in solution B described in step 4 is 0.5:1.
[0097] according to Figure 6 From the scanning electron microscope image, it can be seen that the cubic structure of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2 is unclear and the size is about 30 to 90 nm. Figure 7 This is the X-ray diffraction spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2, indicating that the material obtained in Example 2 has a typical perovskite hydroxide structure. Figure 8 This is the full X-ray photoelectron spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2. Figure 8 It can be seen that the elements Cu, Mn, Sn and O coexist;
[0098] Fig. 9 This is a high-resolution X-ray photoelectron spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2, in which a represents the O element, b represents the Sn element, c represents the Cu element, and d represents the Mn element;
[0099] pass Fig. 9 It can be seen that Cu ions coexist in +1 and +2 valence states, and Mn ions coexist in +2, +3, and +4 valence states.
[0100] Fig.10 is the optical absorption spectrum of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 2; Fig.10 It can be seen that the nanozyme has full spectrum absorption in the range of 200-900nm, but the absorption is weaker than that of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 1.
[0101] Example 3: A method for preparing a copper-manganese-doped hexahydroxytin nanozyme is specifically completed by the following steps:
[0102] 1. Prepare solution A:
[0103] Add copper sulfate pentahydrate, manganese acetate tetrahydrate and sodium citrate into deionized water, and perform ultrasonication until the dispersion is uniform to obtain solution A;
[0104] The volume ratio of the copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is 0.3996 g: 0.098 g: 0.2941 g: 70 mL or 0.3996 g: 0.098 g: 1.1764 g: 70 mL;
[0105] 2. Prepare solution B:
[0106] Add tin tetrachloride pentahydrate into anhydrous ethanol and disperse uniformly by ultrasonication to obtain solution B;
[0107] The mass ratio of tin tetrachloride pentahydrate described in step 2 to anhydrous ethanol is 0.7012 g:10 mL;
[0108] 3. Prepare Solution C:
[0109] Add sodium hydroxide to deionized water and fully dissolve it by ultrasonication to obtain solution C;
[0110] The mass ratio of sodium hydroxide to deionized water in step 3 is 0.8 g:10 mL;
[0111] 4. Water bath reaction:
[0112] Under magnetic stirring, solution B was added dropwise to solution A, and stirring was continued for 30 min. Then, solution C was added dropwise in a water bath at 60°C, and the mixture was heated in a water bath for 60 min. The mixture was cooled to room temperature to obtain a reaction product.
[0113] The volume ratio of solution A to solution C described in step 4 is 70mL:10mL;
[0114] The molar ratio of the copper element in solution A to the tin element in solution B described in step 4 is 0.8:1.
[0115] according to Fig.12 From the scanning electron microscope image, it can be seen that when the mass ratio of copper sulfate pentahydrate, manganese acetate tetrahydrate, sodium citrate to deionized water is 0.3996g:0.098g:0.2941g:70mL ( Fig.11 a), the cubic structure of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 3 is unclear, and the size is about 170-240 nm; when the mass ratio of copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to the volume ratio of deionized water is 0.3996 g: 0.098 g: 1.1764 g: 70 mL ( Fig.11 b), almost no cubic structure is observed.
[0116] Example 4: A method for preparing a copper-manganese-doped hexahydroxytin nanozyme is specifically completed by the following steps:
[0117] 1. Prepare solution A:
[0118] Add copper sulfate pentahydrate, manganese acetate tetrahydrate and sodium citrate into deionized water, and perform ultrasonication until the dispersion is uniform to obtain solution A;
[0119] The volume ratio of the copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is 0.3996 g: 0.098 g: 0.5882 g: 70 mL;
[0120] 2. Prepare solution B:
[0121] Add tin tetrachloride pentahydrate into anhydrous ethanol and disperse uniformly by ultrasonication to obtain solution B;
[0122] The mass ratio of tin tetrachloride pentahydrate described in step 2 to anhydrous ethanol is 0.3506 g:10 mL or 1.4024 g:10 mL;
[0123] 3. Prepare Solution C:
[0124] Add sodium hydroxide to deionized water and fully dissolve it by ultrasonication to obtain solution C;
[0125] The mass ratio of sodium hydroxide to deionized water in step 3 is 0.8 g:10 mL;
[0126] 4. Water bath reaction:
[0127] Under magnetic stirring, solution B was added dropwise to solution A, and stirring was continued for 30 min. Then, solution C was added dropwise in a water bath at 60°C, and the mixture was heated in a water bath for 60 min. The mixture was cooled to room temperature to obtain a reaction product.
[0128] The volume ratio of solution A to solution C described in step 4 is 70mL:10mL;
[0129] The molar ratio of the copper element in solution A to the tin element in solution B described in step 4 is 0.8:0.5 or 0.8:2.
[0130] according to Fig.12 From the scanning electron microscope image, it can be seen that when the mass ratio of tin tetrachloride pentahydrate to ethanol is 0.3506g:10mL ( Fig.12 a) or 1.4024g:10mL( Fig.12 b), the copper-manganese-doped hexahydroxytin nanozymes obtained in Example 4 all had irregular morphologies.
[0131] Example 5: A method for preparing a copper-manganese-doped hexahydroxytin nanozyme is specifically completed by the following steps:
[0132] 1. Prepare solution A:
[0133] Add copper sulfate pentahydrate, manganese acetate tetrahydrate and sodium citrate into deionized water, and perform ultrasonication until the dispersion is uniform to obtain solution A;
[0134] The volume ratio of the copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is 0.3996 g: 0.098 g: 0.5882 g: 70 mL;
[0135] 2. Prepare solution B:
[0136] Add tin tetrachloride pentahydrate into anhydrous ethanol and disperse uniformly by ultrasonication to obtain solution B;
[0137] The mass ratio of tin tetrachloride pentahydrate described in step 2 to anhydrous ethanol is 0.7012 g:10 mL;
[0138] 3. Prepare Solution C:
[0139] Add sodium hydroxide to deionized water and fully dissolve it by ultrasonication to obtain solution C;
[0140] The volume ratio of the mass of sodium hydroxide to deionized water in step 3 is 0.4 g:10 mL or 1.6 g:10 mL;
[0141] 4. Water bath reaction:
[0142] Under magnetic stirring, solution B was added dropwise to solution A, and stirring was continued for 30 min. Then, solution C was added dropwise in a water bath at 60°C, and the mixture was heated in a water bath for 60 min. The mixture was cooled to room temperature to obtain a reaction product.
[0143] The volume ratio of solution A to solution C described in step 4 is 70mL:10mL;
[0144] The molar ratio of the copper element in solution A to the tin element in solution B described in step 4 is 0.8:1.
[0145] according to Fig.13 From the scanning electron microscope image, it can be seen that when the mass ratio of sodium hydroxide to deionized water is 0.4g:10mL ( Fig.13 a) or 1.6g:10mL( Fig.13 b), the copper-manganese-doped hexahydroxytin nanozymes obtained in Example 5 all had irregular morphologies.
[0146] Example 6: A method for preparing a copper-manganese-doped hexahydroxytin nanozyme is specifically completed by the following steps:
[0147] 1. Prepare solution A:
[0148] Add copper sulfate pentahydrate, manganese acetate tetrahydrate and sodium citrate into deionized water, and perform ultrasonication until the dispersion is uniform to obtain solution A;
[0149] The volume ratio of the copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is 0.3996 g: 0.098 g: 0.5882 g: 70 mL;
[0150] 2. Prepare solution B:
[0151] Add tin tetrachloride pentahydrate into anhydrous ethanol and disperse uniformly by ultrasonication to obtain solution B;
[0152] The mass ratio of tin tetrachloride pentahydrate described in step 2 to anhydrous ethanol is 0.7012 g:10 mL;
[0153] 3. Prepare Solution C:
[0154] Add sodium hydroxide to deionized water and fully dissolve it by ultrasonication to obtain solution C;
[0155] The mass ratio of sodium hydroxide to deionized water in step 3 is 0.8 g:10 mL;
[0156] 4. Water bath reaction:
[0157] Under magnetic stirring, solution B was added dropwise to solution A, and stirring was continued for 30 min. Then, solution C was added dropwise in a water bath at 20°C, 40°C, 80°C or 100°C, and the mixture was heated in a water bath for 60 min. The mixture was cooled to room temperature to obtain a reaction product.
[0158] The volume ratio of solution A to solution C described in step 4 is 70mL:10mL;
[0159] The molar ratio of the copper element in solution A to the tin element in solution B described in step 4 is 0.8:1.
[0160] according to Fig.14 Scanning electron microscope images show that when the water bath temperature is 20 or 40°C ( Fig.14 a, b), the Cu-Mn-doped hexahydroxytin nanozyme obtained in Example 6 has almost no observed cubic structure; when the water bath temperature is 80 or 100 °C ( Fig.14 c, d), the sizes of the obtained nanocubes are 210-300 nm and 300-400 nm, respectively.
[0161] Example 7: A method for preparing a copper-manganese-doped hexahydroxytin nanozyme is specifically completed by the following steps:
[0162] 1. Prepare solution A:
[0163] Add copper sulfate pentahydrate, manganese acetate tetrahydrate and sodium citrate into deionized water, and perform ultrasonication until the dispersion is uniform to obtain solution A;
[0164] The volume ratio of the copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is 0.3996 g: 0.098 g: 0.5882 g: 70 mL;
[0165] 2. Prepare solution B:
[0166] Add tin tetrachloride pentahydrate into anhydrous ethanol and disperse uniformly by ultrasonication to obtain solution B;
[0167] The mass ratio of tin tetrachloride pentahydrate described in step 2 to anhydrous ethanol is 0.7012 g:10 mL;
[0168] 3. Prepare Solution C:
[0169] Add sodium hydroxide to deionized water and fully dissolve it by ultrasonication to obtain solution C;
[0170] The mass ratio of sodium hydroxide to deionized water in step 3 is 0.8 g:10 mL;
[0171] 4. Water bath reaction:
[0172] Under magnetic stirring, solution B was added dropwise to solution A, stirring was continued for 30 min, and then solution C was added dropwise in a water bath at 20°C, 40°C, 80°C or 100°C, and the reaction was heated in a water bath for 0.5 h or 2 h, and cooled to room temperature to obtain a reaction product;
[0173] The volume ratio of solution A to solution C described in step 4 is 70mL:10mL;
[0174] The molar ratio of the copper element in solution A to the tin element in solution B described in step 4 is 0.8:1.
[0175] according to Fig.15 From the scanning electron microscope image, it can be seen that the cubic structure of the copper-manganese-doped hexahydroxytin nanozyme obtained in Example 7 is not clear. When the reaction time is 0.5h ( Fig.15 a), the size of the obtained nanomaterials is about 50-85nm; when the reaction is 2h ( Fig.15 b), the size of the obtained nanocubes is about 70-130 nm.
[0176] Example 8: Detection of the peroxidase catalytic activity of copper-manganese-doped hexahydroxytin nanozymes of different concentrations. The specific detection method is as follows: the copper-manganese-doped hexahydroxytin nanozymes are prepared by Example 1 and Example 2 respectively;
[0177] First, the copper-manganese-doped hexahydroxytin nanozyme was dissolved in a buffer solution of pH = 5.5 to prepare gradient solutions with concentrations of 0.5 mg / mL, 0.375 mg / mL, 0.25 mg / mL, 0.125 mg / mL and 0.0625 mg / mL. Subsequently, 100 μL of 6 mg / mL 3,3',5,5'-tetramethylbenzidine solution, 400 μL of different concentrations of copper-manganese-doped hexahydroxytin nanozyme gradient solutions and 1 mL of pH = 5.5 buffer solution were added to a 5 mL centrifuge tube. Finally, 2 to 3 drops of 1 mol / L hydrogen peroxide solution were added to the centrifuge tube. The catalytic reaction temperature was set to 25 ° C and the catalytic reaction time was set to 1 min. After the reaction, the mixed solution was quickly transferred to a cuvette, and the ultraviolet absorption at 652 nm was detected (the scanning time was 900 s, and a recording point was recorded every 20 s), and a curve of the relationship between the concentration of the copper-manganese-doped hexahydroxytin nanozyme and the catalytic activity was plotted. As can be seen from the figure, the catalytic activity of the copper-manganese-doped hexahydroxytin nanozyme prepared in Example 1 ( Fig.16 ) is better than Example 2 ( Fig.17 ), and with the increase of the concentration of copper-manganese-doped hexahydroxytin nanozymes, their catalytic activity tends to gradually increase.
[0178] Example 9: Detection of the peroxidase catalytic activity of copper-manganese-doped hexahydroxytin nanozymes at different hydrogen peroxide concentrations. The specific detection method is as follows: the copper-manganese-doped hexahydroxytin nanozymes are prepared by Example 1 and Example 2, respectively;
[0179] First, the copper-manganese-doped hexahydroxytin nanozyme was dissolved in a buffer solution of pH = 5.5 to prepare a solution with a concentration of 0.25 mg / mL. Subsequently, 100 μL of 6 mg / mL 3,3',5,5'-tetramethylbenzidine solution, 400 μL of copper-manganese-doped hexahydroxytin nanozyme solution and 1 mL of pH = 5.5 buffer solution were added to a 5 mL centrifuge tube in sequence. Finally, 2 to 3 drops of 1000 mmol / L, 500 mmol / L, 250 mmol / L, 125 mmol / L and 62.5 mmol / L hydrogen peroxide solutions were added to the centrifuge tube. The catalytic reaction temperature was set to 25 °C and the catalytic reaction time was set to 1 min. After the reaction was completed, the mixed solution was quickly transferred to a cuvette, the ultraviolet absorption at 652 nm was detected (the scanning time was 900 s, and a recording point was recorded every 20 s), and the relationship curve between hydrogen peroxide concentration and catalytic activity was plotted. As can be seen from the figure, the catalytic activity of the copper-manganese-doped hexahydroxytin nanozyme prepared in Example 1 ( Fig.18 ) is better than Example 2 ( Fig.19 ), and with the increase of hydrogen peroxide concentration, its catalytic activity tends to gradually increase.
[0180] Example 10: Detection of the peroxidase catalytic activity of copper-manganese-doped hexahydroxytin nanozymes at different catalytic reaction temperatures. The specific detection method is as follows: the copper-manganese-doped hexahydroxytin nanozymes are prepared by Example 1 and Example 2 respectively;
[0181] First, the copper-manganese-doped hexahydroxytin nanozyme was dissolved in a buffer solution of pH = 5.5 to prepare a solution with a concentration of 0.25 mg / mL. Subsequently, 100 μL of 6 mg / mL 3,3',5,5'-tetramethylbenzidine solution, 400 μL of copper-manganese-doped hexahydroxytin nanozyme solution and 1 mL of pH = 5.5 buffer solution were added to a 5 mL centrifuge tube in sequence. Finally, 2 to 3 drops of 1000 mM hydrogen peroxide solution were added to the centrifuge tube. The catalytic reaction temperatures were set to 25°C, 30°C, 35°C, 40°C, 45°C and 50°C, respectively, and the catalytic reaction time was set to 5 min. After the reaction was completed, the mixed solution was quickly transferred to a cuvette, and an ultraviolet absorption spectrum was scanned at 500-800 nm, and the catalytic absorption spectrum curves at different buffer solution pH were plotted. As can be seen from the figure, the catalytic activity of the copper-manganese-doped hexahydroxytin nanozyme prepared in Example 1 ( Fig. 20 ) is better than Example 2 ( Fig.21 ), and within a certain temperature range, with the increase of catalytic reaction temperature, its catalytic activity tends to gradually increase, and when the temperature is 50℃, its catalytic performance is the best.
[0182] Example 11: Detection of the peroxidase catalytic activity of copper-manganese-doped hexahydroxytin nanozymes at different catalytic reaction times. The specific detection method is as follows: the copper-manganese-doped hexahydroxytin nanozymes are prepared by Example 1 and Example 2 respectively;
[0183] First, the copper-manganese-doped hexahydroxytin nanozyme was dissolved in a buffer solution of pH = 5.5 to prepare a solution with a concentration of 0.25 mg / mL. Subsequently, 100 μL of 6 mg / mL 3,3',5,5'-tetramethylbenzidine solution, 400 μL of copper-manganese-doped hexahydroxytin nanozyme solution of different concentrations and 1 mL of pH = 5.5 buffer solution were added to a 5 mL centrifuge tube in sequence. Finally, 2 to 3 drops of 1000 mM hydrogen peroxide solution were added to the centrifuge tube. The catalytic reaction temperature was set to 25 ° C, and the catalytic reaction time was set to 2 min, 4 min, and 6 min, respectively. After the reaction was completed, the mixed solution was quickly transferred to a cuvette, and the ultraviolet absorption spectrum was scanned at 500-800 nm, and the catalytic absorption spectrum curves at different catalytic reaction times were plotted. As can be seen from the figure, the catalytic activity of the copper-manganese-doped hexahydroxytin nanozyme prepared in Example 1 ( Fig. 22 ) is better than Example 2 ( Fig.23 ), and with the increase of catalytic reaction time, its catalytic activity tends to gradually increase.
Claims
1. A method for preparing a copper-manganese-doped hexahydroxytin nanozyme, characterized in that The preparation method is specifically completed according to the following steps:
1. Prepare solution A: Add copper sulfate pentahydrate, manganese acetate tetrahydrate and sodium citrate into deionized water, and perform ultrasonication until the dispersion is uniform to obtain solution A; 2. Prepare solution B: Add tin tetrachloride pentahydrate into anhydrous ethanol and disperse uniformly by ultrasonication to obtain solution B; 3. Prepare Solution C: Add sodium hydroxide to deionized water and fully dissolve it by ultrasonication to obtain solution C; 4. Water bath reaction: Under magnetic stirring, solution B is added dropwise to solution A, stirring is continued for a period of time, and then solution C is added dropwise in a water bath at a temperature of 50°C to 70°C, heated in a water bath for a period of time, and cooled to room temperature to obtain a reaction product; The molar ratio of the copper element in solution A to the tin element in solution B described in step 4 is (0.7-0.9):
1.
2. The method for preparing a copper-manganese-doped hexahydroxytin nanozyme according to claim 1, characterized in that The volume ratio of the mass of copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is (0.3g-0.4g):(0.09g-0.2g):(0.5g-0.6g):(60mL-80mL).
3. The method for preparing a copper-manganese-doped hexahydroxytin nanozyme according to claim 2, characterized in that The volume ratio of the copper sulfate pentahydrate, manganese acetate tetrahydrate, and sodium citrate to deionized water in step 1 is 0.3996 g: 0.098 g: 0.5882 g: 70 mL.
4. The method for preparing a copper-manganese-doped hexahydroxytin nanozyme according to claim 1, characterized in that The mass ratio of tin tetrachloride pentahydrate described in step 2 to anhydrous ethanol is (0.7 g to 0.8 g): 10 mL.
5. The method for preparing a copper-manganese-doped hexahydroxytin nanozyme according to claim 4, characterized in that The mass ratio of tin tetrachloride pentahydrate described in step 2 to anhydrous ethanol is 0.7012 g:10 mL.
6. The method for preparing a copper-manganese-doped hexahydroxytin nanozyme according to claim 1, characterized in that The mass ratio of the sodium hydroxide to the volume of deionized water in step 3 is (0.7g-0.9g):10mL.
7. The method for preparing a copper-manganese-doped hexahydroxytin nanozyme according to claim 6, characterized in that The volume ratio of the mass of sodium hydroxide to deionized water in step 3 is 0.8g:10mL.
8. The method for preparing a copper-manganese-doped hexahydroxytin nanozyme according to claim 1, characterized in that The stirring time in step 4 is 30 min to 60 min; the water bath heating reaction time in step 4 is 0.5 h to 2 h.
9. The method for preparing a copper-manganese-doped hexahydroxytin nanozyme according to claim 1, characterized in that The volume ratio of solution A to solution C in step 4 is (60 mL to 80 mL):(5 mL to 15 mL); the molar ratio of the copper element in solution A to the tin element in solution B in step 4 is 0.8:
1.
10. Use of a copper-manganese-doped hexahydroxytin nanozyme prepared by the preparation method according to claim 1, characterized in that A copper-manganese-doped hexahydroxytin nanozyme is used as a peroxide-like nanozyme in the biomedical field.