Mesoporous high polymer material based on soft template method, preparation method and application
Mesoporous polymer materials were prepared by controlling the ratio and reaction conditions of dopamine and nonionic triblock copolymer using a soft template method. This solved the problem of low specific surface area in traditional polydopamine materials, achieving efficient drug loading and rapid photothermal conversion, which is suitable for cancer treatment and drug delivery.
Patent Information
- Application Number
- CN202511208522.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-27
- Publication Date
- 2025-12-16
AI Technical Summary
Traditional polydopamine materials are dense, solid spherical, resulting in low specific surface area, poor drug loading rate and release controllability, making it difficult to meet the needs of practical applications.
Mesoporous polymer materials were prepared by using a soft template method and adjusting the ratio of dopamine to nonionic triblock copolymer surfactant and reaction conditions to form a regular pore structure, thereby improving the specific surface area and photothermal properties.
The prepared mesoporous polymer material has a high specific surface area, good photothermal conversion efficiency, and can be rapidly heated to improve drug loading capacity, making it suitable for cancer treatment and drug delivery.
Smart Images
Figure CN121136070A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of functional photothermal materials technology, specifically relating to a mesoporous polymer material based on the soft template method, its preparation method, and its application. Background Technology
[0002] Organic polymer materials can enhance structural flexibility and functional diversity by adjusting molecular composition and designing novel functional groups, making them indispensable materials in many industries such as medicine, transportation, and electronics. Among them, polydopamine, as an emerging organic polymer material, has attracted considerable attention. This material is formed by the oxidative self-polymerization of dopamine under alkaline conditions, possessing a structure similar to mussel adhesive proteins, containing multiple phenolic hydroxyl and amino groups. Polydopamine exhibits strong self-assembly ability and adhesion, good biocompatibility and antioxidant properties, and can be used as a coating or carrier in various fields such as energy storage, environmental protection, tissue engineering, and biosensing. Furthermore, its absorption spectrum covers almost the entire ultraviolet-visible and near-infrared light regions, enabling it to effectively convert light of different wavelengths into heat energy, greatly expanding the material's application range.
[0003] However, traditional polydopamines are dense, solid spheres with low specific surface area, resulting in limited surface functionality and poor drug loading and release controllability. Therefore, the rational design of the microstructure of polydopamines and further optimization for practical applications remain important research directions. Summary of the Invention
[0004] One of the objectives of this invention is to provide a method for preparing mesoporous polymer materials based on a soft template method. By controlling the introduction time of the soft template and the ratio of raw materials, the surface functionality and photothermal properties of the mesoporous polymer materials are improved. This method has great potential for development in cancer treatment and drug delivery, and provides corresponding theoretical basis and technical support.
[0005] To achieve the above objectives, the present invention adopts the following technical solution:
[0006] A method for preparing mesoporous polymer materials based on a soft template method includes the following steps:
[0007] a. Dissolve 0.01~20 g of dopamine and 0.01~10 g of nonionic triblock copolymer surfactant in a solution composed of water and anhydrous ethanol, wherein the volume ratio of water to anhydrous ethanol is 1:1. After complete dissolution, solution A is obtained.
[0008] b. Add 0.1~10 mL of mesitylene solution dropwise to solution A, and stir for a period of time to obtain solution B;
[0009] c. Add 0.1~10 mL of ammonia water to solution B, adjust the pH to 7~10 and stir for a period of time to obtain solution C;
[0010] d. After centrifuging solution C at a certain speed, the precipitate is collected. After washing, removing impurities, centrifuging, and drying, the product is collected to obtain the mesoporous polymer material, which is polydopamine.
[0011] In the above-mentioned method for preparing mesoporous polymer materials based on the soft template method, in step a, the nonionic triblock copolymer surfactant is a polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer. The nonionic triblock copolymer surfactant is used to guide the polymerization of dopamine inside or on the surface of its micelles to obtain a mesoporous polymer material with excellent dispersion performance.
[0012] In the above-mentioned method for preparing mesoporous polymer materials based on the soft template method, in step b, solution B is obtained after stirring for 0.5~24 h.
[0013] In the above-mentioned method for preparing mesoporous polymer materials based on the soft template method, in step c, solution C is obtained after stirring for 0.5~24 h.
[0014] In the above-mentioned method for preparing mesoporous polymer materials based on the soft template method, in step d, solution C is centrifuged at 10,000 rpm, the collected precipitate is redispersed with anhydrous ethanol, and the mixture is stirred for 2-3 hours during the impurity removal process.
[0015] Another object of the present invention is to provide a mesoporous polymer material based on a soft template method, which is prepared by the above-described preparation method. The mesoporous polymer material exhibits regular spherical pores and has a specific surface area of 21.175 m². 2 / g, with an average pore size of 19.526 nm.
[0016] Another object of the present invention is to provide an application of the above-mentioned mesoporous polymer material based on the soft template method, which is used in the fields of cancer treatment and drug delivery. The mesoporous polymer material has near-infrared photothermal conversion capability, which absorbs 700-1000 nm near-infrared light and converts the light energy into heat energy to kill tumors at high temperature.
[0017] In the above-mentioned application of mesoporous polymer materials based on the soft template method, the power density of the near-infrared light is 0.2~20 W / cm². 2 .
[0018] Compared with the prior art, the present invention brings the following beneficial technical effects:
[0019] This invention proposes a mesoporous polymer material based on a soft template method, its preparation method, and its application. In terms of the preparation method, this invention uses a one-pot method to prepare mesoporous polymer materials from raw materials such as dopamine and nonionic triblock copolymer surfactants. This method is simple to operate; by controlling the reaction, the time and raw material consumption are reduced, the experimental efficiency is improved, and it has great economic benefits and development prospects.
[0020] The mesoporous polymer material provided by this invention has a high specific surface area, good photothermal conversion efficiency, and can absorb near-infrared light of different wavelengths, achieving rapid heating from 10 to 40 °C in a short time, effectively improving the drug loading capacity. Attached Figure Description
[0021] The present invention will be further described below with reference to the accompanying drawings:
[0022] Figure 1 The images are scanning electron microscope images of Example 1, where (a) and (b) are mPDA-24 with target values of 500 nm and 200 nm, respectively; (c) and (d) are mPDA-16 with target values of 500 nm and 200 nm, respectively; and (e) and (f) are mPDA-4 with target values of 500 nm and 200 nm, respectively.
[0023] Figure 2 The particle size distribution is shown in Example 1, where (a) indicates that the particle size of mPDA-24 is approximately 301.3 nm, (b) indicates that the particle size of mPDA-16 is approximately 294.8 nm, and (c) indicates that the particle size of mPDA-4 is approximately 297.9 nm.
[0024] Figure 3 The curves showing the change of hydrated particle size distribution over time in Example 1 are shown; (a), (b), and (c) show the changes in hydrated particle size distribution of mPDA-24, mPDA-16, and mPDA-4 on days 1, 2, 3, 4, 8, and 16, respectively.
[0025] Figure 4 The image shows a scanning electron microscope image of Comparative Example 1; (a) and (b) are the mPDA values at 500 nm and 200 nm, respectively. 0.15 -1, (c) and (d) represent the mPDA at target values of 500 nm and 200 nm, respectively. 0.15 -2, (e) and (f) represent the mPDA at target values of 500 nm and 200 nm, respectively. 0.15 -3;
[0026] Figure 5 The particle size distribution is shown in Comparative Example 1; (a) indicates mPDA 0.15 The particle size of -1 is approximately 306.8 nm, and (b) indicates that mPDA0.15 The particle size of -2 is approximately 308.9 nm, and (c) indicates that mPDA 0.15 The particle size of -3 is approximately 299.3 nm;
[0027] Figure 6 Here are scanning electron microscope images of Example 2; (a) and (b) are mPDA images at different magnifications, respectively. 0.6 ;
[0028] Figure 7 The particle size distribution and hydrated particle size distribution diagram for Example 2 are shown; (a) indicates mPDA 0.6 (a) shows a particle size of approximately 266.0 nm, and (b) shows a hydrated particle size of approximately 311.4 nm.
[0029] Figure 8 The following are the nitrogen adsorption isotherms and corresponding pore size distribution diagrams for Example 2; (a) is the nitrogen adsorption isotherm, and (b) is the corresponding pore size distribution diagram.
[0030] Figure 9 The UV-Vis absorption spectrum of Example 2 is shown as a function of concentration.
[0031] Figure 10 The photothermal temperature change curve of the aqueous solution in Example 2 (continuous irradiation with 808 nm near-infrared light for 6 min); (a) near-infrared light irradiation at the same power density; (b) near-infrared light irradiation at different power densities;
[0032] Figure 11 The photothermal temperature change curve of the aqueous solution in Example 2 (using a power density of 2 W·cm⁻¹) -2 (The laser was continuously irradiated with 808 nm near-infrared light for 6 min, and then the laser was turned off) and τ was calculated using the cooling curve. s The value of . Detailed Implementation
[0033] This invention proposes a mesoporous polymer material based on the soft template method, its preparation method, and its application. To make the advantages and technical solutions of this invention clearer and more explicit, the invention will be further described below with reference to specific embodiments.
[0034] All the raw materials mentioned in this invention can be purchased through commercial channels.
[0035] In this invention, dopamine is the reactive monomer, a nonionic triblock copolymer surfactant is the soft template, and mesitylene is the pore-expanding agent.
[0036] Example 1:
[0037] This invention discloses a method for preparing mesoporous polymer materials based on a soft template method, specifically comprising the following steps:
[0038] Step 1: Dissolve 0.15 g of dopamine and 0.3 g of Pluronic F127 in a solution composed of water and anhydrous ethanol in sequence, wherein the volume ratio of water to anhydrous ethanol is 1:1. Sonicate until the solid is completely dissolved. After complete dissolution, solution A is obtained.
[0039] Step 2: Add 0.15 mL of mesitylene solution dropwise to solution A and stir for X h (X = 24, 16, 4) to obtain solution B;
[0040] Step 3: Add 0.3 mL of ammonia water to solution B, adjust the pH to 7-10, and stir for 4 hours to obtain solution C;
[0041] Step 4: After centrifuging solution C at a certain speed, collect the precipitate. After washing, removing impurities, centrifuging, and drying, collect the product to obtain the mesoporous polymer material, denoted as mPDA-X (X=24, 16, 4).
[0042] like Figure 1 In the middle (a) and (b), mPDA-24 is shown at target values of 500 nm and 200 nm, respectively. Figure 1 In the middle (c) and (d), mPDA-16 is shown at target values of 500 nm and 200 nm, respectively. Figure 1 In the middle (e) and (f), mPDA-4 is shown at target values of 500 nm and 200 nm, respectively; this shows that shortening the introduction time of the soft template Pluronic F127 can reduce the formation of oligomers while ensuring the mesoporous microsphere structure, thus rapidly improving experimental efficiency.
[0043] Figure 2 Image (a) shows that the particle size of mPDA-24 is approximately 301.3 nm. Figure 2 Figure (b) shows that the particle size of mPDA-16 is approximately 294.8 nm. Figure 2 (c) shows that the particle size of mPDA-4 is approximately 297.9 nm; as the introduction time of the soft template Pluronic F127 decreases, the particle size of the material becomes more uniform.
[0044] Figure 3 (a), (b), and (c) show the changes in the hydrated particle size distribution of mPDA-24, mPDA-16, and mPDA-4 on days 1, 2, 3, 4, 8, and 16, respectively. This indicates that as the introduction time of the soft template Pluronic F127 decreases, the hydrated particle size of the material becomes more uniform and stable.
[0045] Comparative Example 1:
[0046] A method for preparing mesoporous polymer materials based on a soft template method is disclosed. The preparation method is basically the same as in Example 1, except that X is fixed at 4, and the resulting solid is redispersed in anhydrous ethanol. The mixture is rapidly stirred at high temperature for 3 h to remove impurities, and the product is collected again by high-speed centrifugation and vacuum drying. The specific amounts of dopamine, Pluronic F127, mesitylene, and ammonia are shown in Table 1.
[0047] Table 1
[0048] Group Dopamine / g Pluronic F127 / g Mesitylene / mL Ammonia / mL Material name （a） 0.15 0.1 0.2 0.3 mPDA 0.15 -1]]> （b） 0.15 0.1 0.15 0.3 mPDA 0.15 -2]]> （c） 0.15 0.2 0.15 0.3 mPDA 0.15 -3]]>
[0049] Figure 4 In the middle (a) and (b), the mPDA values are at target values of 500 nm and 200 nm, respectively. 0.15 -1, Figure 4 (c) and (d) show the mPDA at target values of 500 nm and 200 nm, respectively. 0.15 -2, Figure 4 In the middle (e) and (f), the mPDA values are at target values of 500 nm and 200 nm, respectively. 0.15 -3 indicates that by only increasing the amount of mesitylene, the material gradually changes from a mesoporous microsphere structure to a bowl-shaped structure, while by only increasing the amount of Pluronic F127, the material structure changes very little. In addition, high-temperature ethanol washing and vacuum drying can effectively remove impurities from the material surface and reduce the adhesion between microspheres.
[0050] Figure 5 (a) indicates mPDA 0.15 The particle size of -1 is approximately 306.8 nm. Figure 5 (b) indicates mPDA 0.15 The particle size of -2 is approximately 308.9 nm. Figure 5 (c) indicates mPDA 0.15 The particle size of -3 is approximately 299.3 nm; variations in the feed amounts of mesitylene and Pluronic F127 have little effect on the particle size of this material.
[0051] Example 2:
[0052] A method for preparing mesoporous polymer materials based on soft template method
[0053] The preparation method is basically the same as that of Comparative Example 1. The difference is that the formulation of group b is selected, and the amount of dopamine, Pluronic F127, mesitylene and ammonia water is increased by 4 times simultaneously, denoted as mPDA. 0.6 .
[0054] Figure 6 In the middle (a) and (b), mPDA is shown at different magnifications.0.6 This indicates that by simultaneously increasing the amount of all raw materials, the mesoporous morphology becomes more obvious, exhibiting regular round pores with a more uniform distribution.
[0055] Figure 7 (a) indicates mPDA 0.6 The particle size is approximately 266.0 nm. Figure 7 (b) shows that its hydrated particle size is about 311.4 nm and its dispersibility is good.
[0056] Figure 8 This embodiment shows the nitrogen adsorption isotherm and corresponding pore size distribution diagram, where (a) is the nitrogen adsorption isotherm and (b) is the corresponding pore size distribution diagram, indicating the mPDA. 0.6 Its specific surface area is 21.175 m². 2 / g, with an average pore size of 19.526nm, further demonstrates that its mesoporous structure can improve drug loading capacity.
[0057] Figure 9 Indicates mPDA 0.6 It has a wide absorption band in the near-infrared to visible light region, and its absorbance increases significantly with decreasing concentration.
[0058] Figure 10 In (a), it is shown that at the same power density of 2 W·cm -2 Under 808 nm near-infrared light irradiation, mPDA 0.6 The higher the concentration, the faster the aqueous solution heats up, reaching a maximum of 73.3 ℃; Figure 10 Figure (b) shows that under irradiation with 808 nm near-infrared light at different power densities, the same concentration of 400 μg / mL of mPDA... 0.6 The temperature rise of the aqueous solution increases with increasing power density.
[0059] Figure 11 This indicates that when mPDA 0.6 At a concentration of 400 μg / mL, the photothermal conversion efficiency was 32.02%.
[0060] Any parts not mentioned in this invention can be achieved by referring to existing technologies.
[0061] Those skilled in the art should recognize that the above embodiments are only used to illustrate this application and are not intended to limit this application. Any appropriate changes and variations made to the above embodiments within the essential spirit and scope of this application fall within the scope of protection claimed in this application.
Claims
1. A method for preparing mesoporous polymer materials based on a soft template method, characterized in that, Includes the following steps: a. Dissolve 0.01~20 g of dopamine and 0.01~10 g of nonionic triblock copolymer surfactant in a solution composed of water and anhydrous ethanol, wherein the volume ratio of water to anhydrous ethanol is 1:
1. After complete dissolution, solution A is obtained. b. Add 0.1~10 mL of mesitylene solution dropwise to solution A, and stir for a period of time to obtain solution B; c. Add 0.1~10 mL of ammonia water to solution B, adjust the pH to 7~10 and stir for a period of time to obtain solution C; d. After centrifuging solution C at a certain speed, the precipitate is collected. After washing, removing impurities, centrifuging, and drying, the product is collected to obtain the mesoporous polymer material, which is polydopamine.
2. The method for preparing mesoporous polymer materials based on the soft template method according to claim 1, characterized in that: In step a, the nonionic triblock copolymer surfactant is a polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer. The nonionic triblock copolymer surfactant is used to guide the polymerization of dopamine inside or on the surface of its micelles to obtain a mesoporous polymer material with excellent dispersion performance.
3. The method for preparing mesoporous polymer materials based on the soft template method according to claim 1, characterized in that: In step b, solution B is obtained after stirring for 0.5 to 24 hours.
4. The method for preparing mesoporous polymer materials based on the soft template method according to claim 1, characterized in that: In step c, solution C is obtained after stirring for 0.5 to 24 hours.
5. The method for preparing mesoporous polymer materials based on the soft template method according to claim 1, characterized in that: In step d, solution C is centrifuged at 10,000 rpm, and the collected precipitate is redispersed with anhydrous ethanol, with stirring for 2-3 hours during the impurity removal process.
6. A mesoporous polymer material based on the soft template method, characterized in that: It is prepared by the preparation method described in any one of claims 1 to 5, and the mesoporous polymer material has regular circular pores and a specific surface area of 21.175 m². 2 / g, with an average pore size of 19.526 nm.
7. The application of a mesoporous polymer material based on the soft template method according to claim 6, characterized in that: The application is in the fields of cancer treatment and drug delivery. The mesoporous polymer material has near-infrared photothermal conversion capability. It absorbs 700-1000 nm near-infrared light and converts the light energy into heat energy to kill tumors at high temperature.
8. The application of a mesoporous polymer material based on the soft template method according to claim 7, characterized in that: The power density of the near-infrared light is 0.2~20 W / cm². 2 .