Preparation method and application of polyethersulfone coated Cu / CuFe2O4 microspheres

Abstract

The invention relates to the field of biological functional materials, and discloses a preparation method and application of polyether sulfone coated Cu / CuFe2O4 microspheres. The preparation method comprises the following steps: firstly, synthesizing Cu / CuFe2O4 nanoparticles through a solvothermal method; and then preparing a polyether sulfone (PES) solution by taking N, N-dimethylacetamide (DMAC) as a solvent, changing the mass ratio of the nanoparticles to the PES, and preparing the PES-coated Cu / CuFe2O4 microspheres in an electric injection manner. The microspheres have good hydrophilicity, show excellent uric acid adsorption performance in the blood perfusion process, effectively solve the problem that current conventional blood perfusion agents cannot specifically remove blood toxins, and have good application prospects in the field of blood adsorption.

Description

Technical Field

[0001] The present invention relates to biofunctional materials, and specifically to a method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres. The microspheres exhibit excellent uric acid adsorption performance during blood perfusion, effectively solving the problem that current conventional blood perfusion agents cannot specifically remove blood toxins, and have good application prospects in the field of blood adsorption. Background Art

[0002] The inflammatory response is a key defense mechanism against pathological stimuli, but its overactivation can lead to the abnormal release of proinflammatory cytokines (TNF-α, IL-6, and IL-1β), which can in turn induce systemic inflammatory response syndrome (SIRS) or multiple organ dysfunction. Traditional methods for clearing inflammatory factors include anti-inflammatory drugs (such as glucocorticoids) and biologics (such as monoclonal antibodies), but these methods are associated with high costs, significant side effects, and short half-lives.

[0003] Nanomaterials, with their unique physicochemical properties, such as high specific surface area, tunable surface properties, and excellent adsorption performance, demonstrate enormous potential for application in blood purification. Taking high specific surface area as an example, nanozymes typically range in size from 1 to 100 nanometers. Their tiny particle size gives them a very large specific surface area, with the active surface area per gram of nanozyme reaching tens or even hundreds of square meters. This enables them to provide a vast array of adsorption sites, like countless "nanoscale hooks" that can quickly capture metabolic waste products such as creatinine and urea in the blood. By rationally designing nanomaterials with multifunctional synergistic effects, not only can efficient adsorption of toxic substances be achieved, but therapeutic functions can also be integrated, providing innovative solutions for blood purification.

[0004] In 2023, Weng et al. developed a new composite hemoperfusion material, which was prepared by combining two-dimensional boron carbon nitride (BCN) nanosheets with a sulfonated polyethersulfone (SPES) matrix. The high specific surface area and photothermal properties of BCN nanosheets combined with the mechanical strength and biocompatibility of SPES microspheres significantly improved the adsorbent's adsorption capacity for uremic toxins (such as bilirubin and creatinine). In addition, the photothermal effect of BCN enables the adsorbent to be efficiently regenerated under near-infrared light irradiation, avoiding the complexity of traditional chemical regeneration methods. In 2024, Du et al. successfully designed a new antibacterial bilirubin adsorbent (PSVT) by means of a suspension polymerization reaction between double-bond functionalized TiO2 nanoparticles and styrene. The adsorbent PSVT exhibits excellent bilirubin adsorption capacity and outstanding antibacterial properties. It can not only ensure the efficient removal of bilirubin during hemoperfusion in patients with liver failure, but also effectively prevent bacterial infections, providing a reliable solution for related medical scenarios.

[0005] Based on this research, the present invention employed an electrospray method to prepare PES-coated Cu / CuFe2O4 microspheres with varying mass ratios by adjusting the incorporation ratio of CuFe2O4 nanoparticles. The microspheres' specific adsorption of uric acid was systematically investigated, providing a theoretical basis for the application of nanozymes in the field of blood adsorption. Summary of the Invention

[0006] To address the above-mentioned problems, the present invention provides a method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres. The microspheres have good hydrophilicity and exhibit excellent uric acid adsorption performance during blood perfusion. This effectively solves the problem that current conventional blood perfusion agents cannot specifically remove blood toxins, and has good application prospects in the field of blood adsorption.

[0007] The present invention is achieved through the following technical methods:

[0008] A method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres comprises the following steps: (1) Preparation of Cu / CuFe2O4 nanoparticles A solvothermal method was used, using the triblock copolymer surfactant F127 as a soft template. Ferric chloride, copper chloride, and sodium acetate were added, and ethylene glycol was used as the reaction solvent. The solution was stirred until transparent. The reaction solution was then transferred to an autoclave and heated in an oven. After the system cooled naturally to room temperature, the product was collected with a magnet, washed, and dried to obtain Cu / CuFe2O4 nanoparticles. (2) Preparation of polyethersulfone-coated Cu / CuFe2O4 microspheres A polyethersulfone (PES) solution was prepared using N,N-dimethylacetamide (DMAC) as a solvent, to which the Cu / CuFe2O4 nanoparticles obtained in step (1) were added, and the mass ratio of the nanoparticles to the PES was adjusted. The mixed solution was stirred uniformly using a vortex agitator and then transferred to a specific syringe. The reactants were collected by electrospray using a mixed solution of anhydrous ethanol and deionized water as a coagulation bath, ultimately obtaining polyethersulfone-coated Cu / CuFe2O4 microspheres of varying mass ratios.

[0009] Preferably, the heating reaction conditions in step (1) are 200° C. and the time is 24 h.

[0010] Preferably, the centrifugation conditions in step (1) are a centrifugal speed of 8000-10000 rpm and a centrifugal time of 3-5 min.

[0011] Preferably, the washing conditions in step (1) are washing with anhydrous ethanol and deionized water three times respectively.

[0012] Preferably, the drying conditions in step (1) are a temperature of 60° C. and a time of 24 h.

[0013] Preferably, the mass fraction of the PES solution in step (2) is 20%.

[0014] Preferably, the mass ratio in step (2) is 2:1, 3:1, 4:1, or 5:1, and more preferably, the mass ratio is 5:1.

[0015] Preferably, the syringe in step (2) is a special syringe with a 90° stainless steel needle tube with an inner diameter of 0.6 mm.

[0016] Preferably, the electrospray condition in step (2) is a voltage of 7.2 kV.

[0017] Preferably, the coagulation bath in step (2) is a mixed solution of anhydrous ethanol and deionized water in a volume ratio of 2:1.

[0018] Compared with the existing technology, the advantages of the present invention are:

[0019] (1) The polyethersulfone-coated Cu / CuFe2O4 microspheres prepared by the present invention have a simple preparation method and controllable size and morphology.

[0020] (2) The polyethersulfone-coated Cu / CuFe2O4 microspheres prepared in the present invention have excellent uric acid adsorption performance, which effectively solves the problem that current conventional blood perfusion agents cannot specifically remove blood toxins, and has good application prospects in the field of blood adsorption. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 2 are the XRD patterns of Cu / CuFe2O4 microspheres coated with polyethersulfone at different mass ratios in Example 1.

[0022] Figure 2 This is the SEM of the cross section of the polyethersulfone-coated Cu / CuFe2O4 microspheres with a mass ratio of 5:1 in Example 1.

[0023] Figure 3 The water contact angles of the polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 1.

[0024] Figure 4 The removal rate of uric acid by polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 2.

[0025] Figure 5 These are the adsorption isotherms of uric acid adsorbed by polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 3.

[0026] Figure 6The kinetic curves of uric acid adsorption by polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 4 are shown. Specific implementation methods

[0027] The present invention will be described in further detail below with reference to the embodiments and the accompanying drawings, but the embodiments of the present invention are not limited thereto.

[0028] Example 1, a method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres, the specific operations are as follows: (1) Preparation of Cu / CuFe2O4 nanoparticles The triblock copolymer surfactant F127 (1.0 g) was used as a soft template and dissolved in ethylene glycol (40 mL). 1.081 g of FeCl₃·6H₂O, 0.341 g of CuCl₂·2H₂O, and 1.64 g of sodium acetate were added and stirred thoroughly until the solution became transparent. The reaction solution was then transferred to an autoclave and reacted at 200°C for 24 hours. After the system cooled naturally to room temperature, the product was collected with a magnet and washed three times with deionized water and then ethanol. The resulting product was dried at 60°C for 24 hours to obtain Cu / CuFe₂O₄ nanoparticles. (2) Preparation of polyethersulfone-coated Cu / CuFe2O4 microspheres A 20% PES solution was prepared using N,N-dimethylacetamide (DMAC) as the solvent. 1 mL of PES solution was added to 400 mg of Cu / CuFe2O4 nanoparticles. Subsequently, the nanoparticle mass was varied, adjusting the nanoparticle to PES ratio to 2:1, 3:1, 4:1, and 5:1. The mixed solution was stirred evenly using a vortex mixer and then transferred to a 5 mL syringe with a 0.6 mm inner diameter, 90° stainless steel needle. Electrospray was performed at 7.2 kV, using a 2:1 volume ratio of anhydrous ethanol to deionized water as the coagulation bath, and the microspheres were collected. Ultimately, microspheres with four different nanoparticle to PES ratios of 2:1, 3:1, 4:1, and 5:1 were successfully prepared.

[0029] Figure 1Figure 2 is the XRD pattern of the Cu / CuFe2O4 microspheres coated with polyethersulfone at different mass ratios in Example 1. As shown in the figure, the XRD diffraction pattern of the microspheres after the Cu / CuFe2O4 was coated with the macromolecular PES showed that the diffraction peaks with 2θ values ​​of 30.2°, 35.5°, 37.2°, 43.2°, 53.6°, 57.1°, and 62.8° correspond to the (220), (311), (222), (400), (422), (511), and (440) planes of the CuFe2O4 PDF card (JCPDS No. 77-0010). The 2θ values ​​of 43.3°, 50.4°, and 75.9° correspond to the (111), (200), and (220) planes of the standard CuPDF card (JCPDS No. 04-0836), indicating the presence of Cu / CuFe2O4 nanoparticles in the PES-coated Cu / CuFe2O4. It is noteworthy that the microspheres with a mass ratio of 5:1 exhibit a new diffraction peak at 27.7°, which may be due to chemical changes after PES encapsulation of the nanospheres.

[0030] Figure 2 This is a SEM image of a cross-section of the polyethersulfone-coated Cu / CuFe2O4 microspheres with a mass ratio of 5:1 in Example 1. As shown in the figure, abundant macropores and mesopores, as well as Cu / CuFe2O4 nanoparticles enriched on the PES, can be observed in the cross-sectional image of the microspheres. These features give the microspheres excellent blood toxin adsorption properties.

[0031] Figure 3 The water contact angles of the polyethersulfone-coated Cu / CuFe2O4 microspheres at different mass ratios in Example 1 are shown in the figure. The contact angle measurements of different materials are used to assess the hydrophilicity or hydrophobicity of the material surface. Pure PES exhibits a large contact angle, approaching 90°, indicating a very hydrophobic surface. The contact angle of the microspheres with a mass ratio of 2:1 is slightly smaller than that of pure PES, but still large, indicating a certain degree of hydrophobicity. As the ratio of nanoparticles to PES increases, the corresponding water contact angle gradually decreases. When the ratio of nanoparticles to PES is 5:1, the water contact angle is the smallest. This result indicates that as the proportion of nanoparticles increases, the hydrophilicity of the microspheres also increases accordingly, which also increases the potential for the subsequent use of microspheres for blood adsorption.

[0032] Example 2 Test of the removal rate of uric acid by microspheres According to the Lambert-Beer law, the uric acid test kit has an absorption peak at 690 nm. Uric acid was dissolved in phosphate buffer to an initial concentration of 50 mg mL. -1 The nanoparticles were then added to 10 mL of uric acid toxin solution and adsorbed in a constant temperature shaker at 37°C for 2 h. Finally, the absorbance was measured and the removal rate was calculated.

[0033] Figure 4 This is a test of the uric acid removal rate of polyethersulfone-coated Cu / CuFe2O4 microspheres at different mass ratios in Example 2. As can be seen from the figure, the adsorption effect of pure PES on uric acid is low and negligible. As the ratio of nanoparticles to PES increases, the adsorption effect of the microspheres on uric acid gradually increases. When the microsphere mass is 25 mg, the microspheres with a mass ratio of 5:1 achieve a uric acid removal rate of 100%. When the microsphere mass is 50 mg, the uric acid removal rate of the microspheres with the ratios of 3:1, 4:1, and 5:1 reaches 100%. When the microsphere mass is 100 mg, the uric acid removal rate of the microspheres with the four ratios reaches 100%, indicating that the microspheres have a good removal effect on uric acid and can be used for adsorption of uric acid in the blood.

[0034] Example 3 Determination of the adsorption isotherm of uric acid by microspheres Adsorption isotherm experiments were conducted using different concentrations of uric acid toxin, i.e. the initial concentration of the toxin increased from low to high (6.25, 12.5, 25, 31.25, 50, 62.5 mg·L -1 ) setting, and tested its absorbance after adsorption in a constant temperature shaker at 37 ° C for 2 h, and then drew the adsorption isotherm diagram.

[0035] Figure 5 The adsorption isotherms of uric acid adsorbed by polyethersulfone coated Cu / CuFe2O4 microspheres with different mass ratios in Example 3 are shown in the figure. -1 When the adsorption of uric acid by the microspheres reaches the saturation state, the adsorption saturation state of the microspheres with four mass ratios is approximately 12 mg·g -1 , 25mg·g -1 , 38mg·g -1 , 58mg·g -1 .

[0036] Example 4 Kinetic curve of uric acid adsorption by microspheres At different adsorption time points (20, 40, 60, 80, 100, 120 min), the absorbance of the uric acid concentration was tested in a constant temperature shaker at 37°C, and the adsorption kinetic curve was drawn.

[0037] Figure 6 The kinetic curves of uric acid adsorption by polyethersulfone coated Cu / CuFe2O4 microspheres with different mass ratios in Example 4 are shown. The adsorption rates of uric acid by the four microspheres with different mass ratios are 10 mg·g -1 , 20mg·g -1 , 40mg·g -1 , 60mg·g -1 .

Claims

1. A method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres, characterized in that The following steps are involved: (1) A solvothermal method was used, using triblock copolymer surfactant F127 as a soft template. Ferric chloride, copper chloride, and sodium acetate were added, and ethylene glycol was used as the reaction solvent. The solution was stirred until transparent. The reaction solution was then transferred to an autoclave and heated in an oven for reaction. After the system cooled naturally to room temperature, the product was collected with a magnet, washed, and dried to obtain Cu / CuFe2O4 nanoparticles. (2) A polyethersulfone (PES) solution was prepared using N,N-dimethylacetamide (DMAC) as a solvent, to which the Cu / CuFe2O4 nanoparticles obtained in step (1) were added, and the mass ratio of the nanoparticles to the PES was adjusted. The mixed solution was stirred uniformly using a vortex agitator and then transferred to a specific syringe. The reactants were collected by electrospraying using a mixed solution of anhydrous ethanol and deionized water as a coagulation bath, and finally polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios were obtained.

2. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres according to claim 1, characterized in that The solvent thermal reaction conditions in step (1) are a temperature of 200° C. and a time of 24 h.

3. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres according to claim 1, characterized in that The washing conditions in step (1) are as follows: a centrifugal speed of 8000-10000 rpm and a centrifugal time of 3-5 min.

4. A method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres according to claim 1, characterized in that The washing conditions in step (1) are washing with anhydrous ethanol and deionized water three times respectively.

5. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres according to claim 1, characterized in that The drying conditions in step (1) are a temperature of 60° C. and a time of 24 h.

6. A method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres according to claim 1, characterized in that The mass fraction of the prepared PES solution in step (2) is 20%.

7. A method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres according to claim 1, characterized in that The mass ratios described in step (2) are 2:1, 3:1, 4:1 and 5:

1.

8. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres according to claim 1, characterized in that The syringe described in step (2) is a special syringe with an inner diameter of 0.6 mm and a 90° stainless steel needle tube.

9. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres according to claim 1, characterized in that The electrospray condition in step (2) is a voltage of 7.2 kV.

10. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres according to claim 1, characterized in that The coagulation bath in step (2) is a mixed solution of anhydrous ethanol and deionized water in a volume ratio of 2:1.

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