A method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres and its application

Abstract

This invention relates to the field of biofunctional materials, and discloses a method for preparing and applying polyethersulfone-coated Cu / CuFe2O4 microspheres. The preparation method first synthesizes Cu / CuFe2O4 nanoparticles via a solvothermal method; then, a polyethersulfone (PES) solution is prepared using N,N-dimethylacetamide (DMAC) as a solvent, and the mass ratio of the nanoparticles to PES is varied to prepare PES-coated Cu / CuFe2O4 microspheres via electrospraying. These microspheres exhibit good hydrophilicity and demonstrate excellent uric acid adsorption performance during hemoperfusion, effectively solving the problem that current conventional hemoperfusion agents cannot specifically remove blood toxins, and show promising application prospects in the field of blood adsorption.

Description

Technical Field

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

[0002] Inflammation is a key defense mechanism against pathological stimuli, but its overactivation can lead to the abnormal release of pro-inflammatory factors (TNF-α, IL-6, IL-1β), thereby inducing systemic inflammatory response syndrome or multiple organ dysfunction. Traditional methods for clearing inflammatory factors include anti-inflammatory drugs (such as glucocorticoids) and biological agents (such as monoclonal antibodies), but these methods have problems such as high cost, significant side effects, and short half-life.

[0003] Nanomaterials, with their unique physicochemical properties such as high specific surface area, tunable surface properties, and excellent adsorption performance, have shown great application potential in the field of 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 an extremely large specific surface area; the active surface area per gram of nanozyme can reach tens or even hundreds of square meters. This provides a massive number of adsorption sites, acting like countless "nanoscale hooks," which can rapidly capture metabolic waste products in the blood, such as creatinine and urea. By rationally designing nanomaterials with multifunctional synergistic effects, not only can highly 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 novel composite hemoperfusion material, prepared by combining two-dimensional boron carbonitride (BCN) nanosheets with a sulfonated polyether sulfone (SPES) matrix. The high specific surface area and photothermal properties of the BCN nanosheets, combined with the mechanical strength and biocompatibility of the SPES microspheres, significantly enhanced the adsorption capacity of the adsorbent for uremic toxins (such as bilirubin and creatinine). Furthermore, the photothermal effect of BCN enabled efficient regeneration of the adsorbent under near-infrared light irradiation, avoiding the complexity of traditional chemical regeneration methods. In 2024, Du et al. successfully designed a novel antibacterial bilirubin adsorbent (PSVT) using a suspension polymerization reaction between double-bonded TiO2 nanoparticles and styrene. This PSVT adsorbent exhibited excellent bilirubin adsorption capacity and outstanding antibacterial properties, ensuring efficient bilirubin removal during hemoperfusion in patients with liver failure and effectively preventing bacterial infection, providing a reliable solution for related medical scenarios.

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

[0006] To address the aforementioned issues, this invention provides a method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres. These microspheres exhibit excellent hydrophilicity and demonstrate outstanding uric acid adsorption performance during hemoperfusion, effectively solving the problem that conventional hemoperfusion agents cannot specifically remove blood toxins. This method shows promising application prospects in the field of blood adsorption.

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

[0008] A method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres includes the following steps:

[0009] (1) Preparation of Cu / CuFe2O4 nanoparticles

[0010] A solvothermal method was employed, using triblock copolymer surfactant F127 as a soft template. Ferric chloride, copper chloride, and sodium acetate were added, with ethylene glycol as the reaction solvent. The mixture was stirred until the solution became transparent, and then transferred to a high-pressure reactor, which was placed in an oven for heating. After the system naturally cooled to room temperature, the product was collected using a magnet, washed, and dried to finally obtain Cu / CuFe2O4 nanoparticles.

[0011] (2) Preparation of polyethersulfone-coated Cu / CuFe2O4 microspheres

[0012] A polyethersulfone (PES) solution was prepared using N,N-dimethylacetamide (DMAC) as the solvent. Cu / CuFe2O4 nanoparticles obtained in step (1) were added to the solution, and the mass ratio of nanoparticles to PES was adjusted. The mixture was stirred thoroughly using a vortex stirrer and then transferred to a specific syringe. The reactants were collected by electro-jet injection using a mixture of anhydrous ethanol and deionized water as a coagulation bath, ultimately yielding polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios.

[0013] Preferably, the heating reaction conditions in step (1) are 200°C and the time is 24h.

[0014] Preferably, the centrifugation conditions in step (1) are a centrifugation speed of 8000-10000 rpm and a centrifugation time of 3-5 min.

[0015] Preferably, the washing conditions in step (1) are three washes with anhydrous ethanol and deionized water respectively.

[0016] Preferably, the drying conditions in step (1) are a temperature of 60°C and a time of 24 hours.

[0017] Preferably, the mass fraction of the PES solution in step (2) is 20%.

[0018] 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.

[0019] Preferably, the syringe in step (2) is a specific syringe with a 0.6 mm inner diameter, 90° stainless steel needle tube.

[0020] Preferably, the electro-injection condition in step (2) is a voltage of 7.2 kV.

[0021] Preferably, the coagulation bath in step (2) is a mixed solution of anhydrous ethanol and deionized water in a volume ratio of 2:1.

[0022] Compared with existing technologies, the advantages of this invention are:

[0023] (1) The polyethersulfone-coated Cu / CuFe2O4 microspheres prepared by the present invention are simple to prepare and have controllable size and morphology.

[0024] (2) The polyethersulfone-coated Cu / CuFe2O4 microspheres prepared by this invention have excellent uric acid adsorption performance, which effectively solves the problem that conventional blood perfusion agents cannot specifically remove blood toxins and has good application prospects in the field of blood adsorption. Attached Figure Description

[0025] Figure 1 The images show the XRD patterns of Cu / CuFe2O4 microspheres coated with polyethersulfone at different mass ratios in Example 1.

[0026] Figure 2 The image shows a cross-section of the polyethersulfone-coated Cu / CuFe2O4 microspheres with a mass ratio of 5:1 in Example 1.

[0027] Figure 3 The water contact angles are those of polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 1.

[0028] Figure 4 The removal rate of uric acid by polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 2 is shown.

[0029] Figure 5The adsorption isotherms are shown for the adsorption of uric acid by polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 3.

[0030] Figure 6 The images show the kinetic curves of uric acid adsorption by polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 4. Specific implementation methods

[0031] The present invention will now be described in further detail with reference to the embodiments and accompanying drawings, but the implementation of the present invention is not limited thereto.

[0032] Example 1: Preparation method of polyethersulfone-coated Cu / CuFe2O4 microspheres, the specific operation is as follows:

[0033] (1) Preparation of Cu / CuFe2O4 nanoparticles

[0034] Using a triblock copolymer surfactant F127 (1.0 g) as a soft template, it was dissolved in ethylene glycol (40 mL), and 1.081 g FeCl3·6H2O, 0.341 g CuCl2·2H2O, and 1.64 g sodium acetate were added. The mixture was stirred thoroughly until the solution became transparent. The reaction solution was then transferred to a high-pressure reactor and reacted at 200 °C for 24 hours. After the system cooled naturally to room temperature, the product was collected using a magnet and washed three times each with deionized water and ethanol. The resulting product was dried at 60 °C for 24 hours to obtain Cu / CuFe2O4 nanoparticles.

[0035] (2) Preparation of polyethersulfone-coated Cu / CuFe2O4 microspheres

[0036] A 20% PES solution was prepared using N,N-dimethylacetamide (DMAC) as the solvent. 400 mg of Cu / CuFe₂O₄ nanoparticles were added to 1 mL of PES solution. Subsequently, the mass ratio of nanoparticles to PES was adjusted to 2:1, 3:1, 4:1, and 5:1. After homogenizing the mixture using a vortex stirrer, the solution was transferred to a 5 mL syringe equipped with a 0.6 mm inner diameter, 90° stainless steel needle. Electrospraying was performed at 7.2 kV, using a 2:1 volume ratio of anhydrous ethanol to deionized water as the coagulation bath to collect the microspheres. Finally, four different nanoparticle-to-PES mass ratios of 2:1, 3:1, 4:1, and 5:1 were successfully prepared.

[0037] Figure 1The figures show the XRD patterns of Cu / CuFe2O4 microspheres coated with polyethersulfone at different mass ratios in Example 1. As shown in the figure, the XRD diffraction patterns of the microspheres after coating Cu / CuFe2O4 with macromolecular PES show 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 on 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. Notably, a new diffraction peak at 2θ value of 27.7° appears for the microspheres with a mass ratio of 5:1, which may be due to a chemical change occurring after the PES coating of the nanospheres.

[0038] Figure 2 This is a SEM image of the cross-section of the polyethersulfone-coated Cu / CuFe2O4 microspheres in Example 1 with a mass ratio of 5:1. As shown in the figure, abundant coarse and mesopores, as well as Cu / CuFe2O4 nanoparticles enriched on PES, can be observed in the cross-sectional image of the microspheres. These features endow the microspheres with good blood toxin adsorption properties.

[0039] Figure 3 The figures show the water contact angles of polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 1. The figure illustrates the contact angle measurements of different materials, used to evaluate the hydrophilicity or hydrophobicity of the material surface. Pure PES showed a large contact angle, close to 90°, indicating its highly hydrophobic surface. The contact angle of the microspheres with a mass ratio of 2:1 was slightly smaller than that of pure PES, but still relatively large, showing some hydrophobicity. As the ratio of nanoparticles to PES increased, the corresponding water contact angle gradually decreased. The water contact angle was smallest when the nanoparticle:PES ratio was 5:1. This result indicates that the hydrophilicity of the microspheres increases with the increase of the nanoparticle ratio, which also improves the possibility of subsequent application of the microspheres for blood adsorption.

[0040] Example 2: Test of the removal rate of toxic uric acid by microspheres

[0041] According to Beer-Lambert law, the absorption peak of uric acid was detected at 690 nm using a uric acid assay kit. Uric acid was dissolved in phosphate buffer to achieve an initial concentration of 50 mg / mL. -1 The nanoparticles were then added to 10 mL of a solution of uric acid toxin and adsorbed in a constant temperature shaker at 37 °C for 2 h. Finally, the absorbance was measured and the removal rate was calculated.

[0042] Figure 4 This is a test of the uric acid removal rate of polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 2. The figure shows that 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 mass of the microspheres is 25 mg, the removal rate of uric acid by microspheres with a mass ratio of 5:1 reaches 100%. When the mass of the microspheres is 50 mg, the removal rate of uric acid by microspheres with ratios of 3:1, 4:1, and 5:1 reaches 100%. When the mass of the microspheres is 100 mg, the removal rate of uric acid by microspheres with all four ratios reaches 100%. This indicates that the microspheres have a good removal effect on uric acid and can be used for the adsorption of uric acid in blood.

[0043] Example 3: Determination of the adsorption isotherm of toxic uric acid by microspheres

[0044] Adsorption isotherm experiments were conducted using different concentrations of uric acid toxin, i.e., the initial concentration of toxin increased from low to high (6.25, 12.5, 25, 31.25, 50, 62.5 mg·L⁻¹). -1 The absorbance was measured after adsorption in a constant temperature shaker at 37℃ for 2 hours, and then an adsorption isotherm was plotted.

[0045] Figure 5 This is an adsorption isotherm measurement of uric acid on polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 3. As shown in the figure, the adsorption isotherms were measured at a uric acid concentration of 60 mg·L⁻¹. -1 At that time, the microspheres reached adsorption saturation for uric acid. The adsorption saturation point for the four mass ratios of microspheres was approximately 12 mg·g⁻¹. -1 25mg·g -1 38mg·g -1 58mg·g -1 .

[0046] Example 4: Kinetic curve of uric acid adsorption by microspheres

[0047] The absorbance of uric acid was measured at different adsorption time points (20, 40, 60, 80, 100, 120 min) in a constant temperature shaker at 37℃, and adsorption kinetic curves were plotted.

[0048] Figure 6 These are the kinetic curves of uric acid adsorption by polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios in Example 4. The adsorption rates of uric acid by the four different mass ratios of microspheres were 10 mg·g⁻¹. -1 20mg·g -1 40mg·g -1、60mg·g -1 。

Claims

1. A method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres, characterized in that... Includes the following steps: (1) Using a solvothermal method, triblock copolymer surfactant F127 was used as a soft template. Ferric chloride, copper chloride and sodium acetate were added, and ethylene glycol was used as the reaction solvent. The mixture was stirred until the solution became transparent. Then the reaction solution was transferred to a high-pressure reactor and placed in an oven for heating. After the system cooled naturally to room temperature, the product was collected with a magnet, washed and dried to finally obtain Cu / CuFe2O4 nanoparticles. (2) A polyethersulfone (PES) solution was prepared using N,N-dimethylacetamide (DMAC) as a solvent. Cu / CuFe2O4 nanoparticles obtained in step (1) were added to the solution. The mass ratio of nanoparticles to PES was adjusted. The solution was stirred evenly using a vortex stirrer and then transferred to a syringe. The reactants were collected by electro-jet injection using a mixture of anhydrous ethanol and deionized water as a coagulation bath. Finally, polyethersulfone-coated Cu / CuFe2O4 microspheres with different mass ratios were obtained.

2. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres as described in claim 1, characterized in that... The heating reaction conditions described 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 as described in claim 1, characterized in that... The washing conditions described in step (1) are a centrifugation speed of 8000-10000 rpm and a centrifugation time of 3-5 min.

4. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres as described in claim 1, characterized in that... The washing conditions described in step (1) are three washes each with anhydrous ethanol and deionized water.

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

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

7. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres as described in claim 1, characterized in that... The mass ratio mentioned in step (2) is 2:1, 3:1, 4:1 or 5:

1.

8. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres as described in claim 1, characterized in that... The electro-injection condition described in step (2) is a voltage of 7.2 kV.

9. The method for preparing polyethersulfone-coated Cu / CuFe2O4 microspheres as described in 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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