Preparation method and application of tannic acid-cobalt sulfide nano aggregate
By dissolving cobalt salts and sulfides in ethylene glycol and controlling nano size and surface modification in combination with tannin acid, tanninic acid-cobalt sulfide nano-agglomerates that exhibit good photothermal effects in the NIR-II region were prepared, and the current solution was solved There are limitations and stability problems of photothermal materials for deep tissue treatment, which has achieved efficient application of tumor photothermal therapy.
Patent Information
- Application Number
- CN202411438119.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-15
- Publication Date
- 2025-01-10
AI Technical Summary
The existing photothermal nanomaterials mainly respond to the near-infrared zone one, making it difficult to effectively treat deep tissues, and their photostability and in vivo safety need further evaluation. How to easily prepare stable and efficient photothermal materials for the second zone of near-infrared zone is important. question.
By dissolving cobalt salts, thioacetamide/sodium thiosulfate and tannin acid in ethylene glycol, the reaction conditions are regulated to form tanninic acid-cobalt sulfide nano-agglomerates, and using tanninic acid to regulate nano size and surface modification, prepare Nanomaterials with good absorption characteristics.
The prepared tanninic acid-cobalt sulfide nano-agglomerates show good photothermal conversion efficiency in the NIR-II region, have broad application prospects for tumor photothermal therapy, and are simple to operate and rich raw materials, which is suitable for industrial promotion.
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Figure CN119280400A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the field of nano biomedical materials, and in particular to a preparation method and application of tannic acid-cobalt sulfide nano aggregates with near-infrared second-zone photothermal effect. Background Art
[0002] Photothermal therapy (PTT) is a cutting-edge technology in the field of nanomedicine. It destroys cancer cells by generating local high temperatures through precise laser irradiation. Compared with traditional treatment technologies, PTT has unique advantages in tumor diagnosis and treatment due to its high efficiency and minimal invasiveness to normal tissues. At present, the research on PTT is mainly focused on the near-infrared region I (NIR-I, 700-1000 nm), and the near-infrared region II (NIR-II, 1000-1700 nm) has received increasing attention due to its advantages in reducing photodamage to healthy tissues, increasing penetration depth, and reducing energy loss. However, the photostability and long-term safety of existing photothermal nanoformulations need to be further evaluated. In addition, most of the photothermal nanomaterials currently developed have a response band limited to the NIR-I region, which weakens their effective diagnosis and treatment of deep tissues. How to prepare stable and efficient NIR-II region photothermal materials by simple means has become an important issue to be solved in this field.
[0003] Metal sulfides are binary compounds formed by sulfur and metals, and can also be generated by the interaction of hydrogen sulfide and metal oxides or hydroxides. As a semiconductor material, metal sulfides have special properties, such as good structural and thermal stability, narrow optical band gap, quantum size effect, and adjustable morphology and size. Metal sulfides, such as copper-based, molybdenum-based, and iron-based sulfides, have been widely used in biomedicine, photocatalysis, energy and other fields. It is well known that the performance of nanomaterials is determined by the composition and structure of the materials. Different nanostructures determine the unique properties of nanomaterials. By regulating the synthesis conditions, nanomaterials with different structures can be regulated. For example, by regulating the synthesis conditions, zero-dimensional, one-dimensional, and two-dimensional nanosulfides, as well as three-dimensional metal sulfide nanomaterials with cubic structures can be prepared.
[0004] Tannic acid (TA) is a water-soluble polyphenol compound that is widely found in plants, fruit peels and beverages. TA molecules contain a large number of active phenolic groups and have excellent biocompatibility, adhesion and cohesion properties. As a biomimetic adhesion material, it has good application prospects in surface coatings, composite nanoparticle preparation, drug delivery and other fields. At the same time, TA has weak reducing ability under acidic conditions. Depending on the pH value, TA's stabilizing effect on nanoparticles and its own reducing properties are different. The particle size of metal nanoparticles can be regulated based on this property. Based on this, TA shows broad application prospects in the construction of nanodiagnostic and therapeutic materials with specific functions. Summary of the invention
[0005] The invention provides a preparation method of tannic acid-cobalt sulfide nano-aggregates and application thereof. The preparation method is simple and convenient to operate and is conducive to the industrialization and promotion of tannic acid-cobalt sulfide nano-aggregates.
[0006] To achieve the above object, the technical solution of the present invention is: A method for preparing tannic acid-cobalt sulfide nanoaggregates comprises the following steps: S1. Dissolve the cobalt salt in ethylene glycol and stir thoroughly to dissolve to obtain solution A; S2. Dissolving thioacetamide / sodium thiosulfate in ethylene glycol to obtain solution B; S3. Dissolving tannic acid in ethylene glycol to obtain solution C; S4. Solution B was slowly added dropwise to solution A, and after stirring and mixing, solution C was added to the mixed solution, and the clear solution was purple; S5. The resulting mixed solution was transferred into a reactor and heated to obtain a mixed solution containing tannic acid - cobalt sulfide nanoaggregates; S6. The mixed solution containing tannic acid-cobalt sulfide nanoaggregates is centrifuged to obtain a solid D; S7. The solid D was washed by centrifugation several times with ethanol and water; S8. Drying the solid D to obtain tannic acid-cobalt sulfide nano-aggregates.
[0007] In step S1, the cobalt salt is cobalt chloride, and the concentration of cobalt ions in solution A is 0.1 mol / L.
[0008] In step S2, thioacetamide or sodium thiosulfate is used as the sulfur source, and the concentration of thioacetamide or sodium thiosulfate in solution B is 0.5 mol / L.
[0009] In step S3, the mass concentration of tannic acid in solution C is 5 g / L.
[0010] In step S4, solution A, solution B and solution C are mixed at a volume ratio of 1:1:1.
[0011] In step S5, the heating temperature is 120-180°C, and the reaction time is 180 min.
[0012] Experiments show that the tannic acid-cobalt sulfide nanoaggregates prepared by the method of the present invention have good absorption characteristics in all bands, good absorption in the NIR-II region, and good photothermal conversion efficiency.
[0013] Another object of the present invention is to use the tannic acid-cobalt sulfide nanoaggregates prepared by the method described above to prepare anti-tumor diagnostic and therapeutic agents for near-infrared second-zone photothermal therapy.
[0014] The beneficial effects of the present invention are: (1) The present invention uses tannic acid as a regulator to adjust the nanometer size of the prepared cobalt sulfide and effectively form nano-aggregates; (2) The present invention uses tannic acid as a surface modifier to increase the water dispersibility and biocompatibility of cobalt sulfide; (3) The present invention prepares tannic acid-cobalt sulfide nanoaggregates, which has abundant raw material sources, simple and convenient operation, and simple preparation conditions; (4) The tannic acid-cobalt sulfide nanoaggregates prepared by the present invention have good NIR-II photothermal effect, can realize tumor photothermal therapy, and have broad application prospects in the field of cancer treatment. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Figure 1 It is a transmission electron microscope image of tannic acid-cobalt sulfide nanoaggregates of the embodiment; Figure 2 The UV-Vis-NIR spectra of the aqueous solution of tannic acid-cobalt sulfide nanoaggregates of the embodiment (a) and the temperature variation of the aqueous solution and pure water under 1064 nm laser irradiation with irradiation time (b). DETAILED DESCRIPTION
[0016] The present invention is further described below with reference to the embodiments and drawings, but is not intended to limit the present invention. Example 1
[0017] A method for preparing tannic acid-cobalt sulfide nanoaggregates comprises the following steps: S1. Add 10 mL of ethylene glycol to 1.0 mmol of cobalt chloride and stir thoroughly to dissolve completely to obtain solution A; S2. Add 10 mL of ethylene glycol to 5.0 mmol of thioacetamide and stir thoroughly to dissolve completely to obtain solution B; S3. Weigh 50 mg of tannic acid, add 10 mL of ethylene glycol, stir thoroughly to dissolve completely, and obtain solution C; S4. Solution B was slowly added dropwise to solution A, and after stirring and mixing, solution C was added to the mixed solution, and the clear solution was purple; S5. The obtained mixed solution was transferred into a reactor, heated to 150°C, and reacted for 180 min to obtain a mixed solution containing tannic acid-cobalt sulfide nanoaggregates; S6. The mixed solution containing tannic acid-cobalt sulfide nanoaggregates is centrifuged to obtain a solid D; S7. The solid D was washed by centrifugation several times with ethanol and water; S8. After washing, the solid D is dried to obtain tannic acid-cobalt sulfide nano-aggregates. Example 2
[0018] A method for preparing tannic acid-cobalt sulfide nanoaggregates is different from the preparation method in Example 1 in that sodium thiosulfate is used to replace thioacetamide in S2, and the other steps are the same as those in Example 1.
[0019] The experimental results show that the products prepared in Examples 1 and 2 can be well dispersed in aqueous solution and can exist stably.
[0020] The morphology of the tannic acid-cobalt sulfide nanoaggregates prepared in Example 1 or 2 was observed by transmission electron microscopy. The transmission electron microscopy results of the aggregates in Example 1 are shown in FIG. Figure 1 .
[0021] Depend on Figure 1 a It can be seen that tannic acid-cobalt sulfide nanoaggregates have good dispersibility and the average particle size is about 100 nanometers. Figure 1 b It can be seen that due to the surface modification and regulation of TA, cobalt sulfide nanoparticles can effectively aggregate to form tannic acid-cobalt sulfide nanoaggregates.
[0022] The tannic acid-cobalt sulfide nanoaggregates prepared in Example 1 or 2 were prepared into water-dispersed solutions with concentrations of 100 mg / mL and 200 mg / mL, and UV-visible-near infrared spectroscopy tests and photothermal heating experiments were performed.
[0023] Example 1 Aggregate results are shown in Figure 2 ,Depend on Figure 2a It can be seen that tannic acid-cobalt sulfide nanoaggregates have good absorption characteristics in the entire band. Under 1064 nm laser irradiation, the temperature of the tannic acid-cobalt sulfide nanoaggregate aqueous dispersion solution increased significantly with the increase of illumination time. Within 10 minutes, the temperature of the tannic acid-cobalt sulfide nanoaggregate aqueous dispersion solution with a concentration of 200 mg / mL increased by 28.8 ℃, while pure water hardly increased under the same illumination conditions ( Figure 2 b).
[0024] The examples confirm that the tannic acid-cobalt sulfide nanoaggregates prepared by the present invention have good photothermal heating effect and have potential application prospects in tumor photothermal therapy.
Claims
1. A method for preparing tannic acid-cobalt sulfide nanoaggregates, characterized in that: The following steps are involved: S1. Dissolve the cobalt salt in ethylene glycol and stir thoroughly to dissolve to obtain solution A; S2. Dissolve thioacetamide or sodium thiosulfate in ethylene glycol to obtain solution B; S3. Dissolving tannic acid in ethylene glycol to obtain solution C; S4. Solution B was slowly added dropwise to solution A, stirred and mixed, and then solution C was added to the mixed solution, and the clear solution was purple; S5. The resulting mixed solution was transferred into a reactor and heated to obtain a mixed solution containing tannic acid - cobalt sulfide nanoaggregates; S6. The mixed solution containing tannic acid-cobalt sulfide nanoaggregates is centrifuged to obtain a solid D; S7. The solid D was washed by centrifugation several times with ethanol and water; S8. Drying the solid D to obtain tannic acid-cobalt sulfide nano-aggregates.
2. The method for preparing tannic acid-cobalt sulfide nano-aggregates according to claim 1, characterized in that: In step S1, the cobalt salt is cobalt chloride, and the concentration of cobalt ions in solution A is 0.1 mol / L.
3. The method for preparing tannic acid-cobalt sulfide nano-aggregates according to claim 1, characterized in that: In step S2, thioacetamide or sodium thiosulfate is used as the sulfur source, and the concentration of thioacetamide or sodium thiosulfate in solution B is 0.5 mol / L.
4. The method for preparing tannic acid-cobalt sulfide nano-aggregates according to claim 1, characterized in that: In step S3, the mass concentration of tannic acid in solution C is 5 g / L.
5. The method for preparing tannic acid-cobalt sulfide nano-aggregates according to claim 1, characterized in that: In step S4, solution A, solution B and solution C are mixed at a volume ratio of 1:1:
1.
6. The method for preparing tannic acid-cobalt sulfide nano-aggregates according to claim 1, characterized in that: In step S5, the heating temperature is 120-180°C, and the reaction time is 180 min.
7. The tannic acid-cobalt sulfide nano-aggregate obtained by the preparation method according to any one of claims 1 to 6, characterized in that: The tannic acid-cobalt sulfide nano-aggregate has a photothermal effect in the second near-infrared region.
8. Use of the tannic acid-cobalt sulfide nanoaggregates described in claim 7 in the preparation of anti-tumor diagnostic and therapeutic agents for near-infrared second-zone photothermal therapy.