Polyellagic acid nanofiber as well as preparation and application thereof

Abstract

The invention discloses a polyellagic acid nanofiber as well as preparation and application thereof. The invention relates to a preparation method of polyellagic acid nanofibers, which comprises the following step: by taking ellagic acid as a raw material, an alkaline aqueous solution as a solvent and sodium periodate as an oxidizing agent, reacting to prepare the polyellagic acid nanofibers. The method is simple and easy to implement, and the prepared polyellagic acid is in a nanofiber shape, good in water solubility, large in specific surface area and higher in free radical scavenging capacity.

Description

Technical Field

[0001] The invention relates to a polyellagic acid material, in particular to a polyellagic acid nanofiber and the preparation and application thereof. Background Art

[0002] Bio-based polyphenols are widely found in fruits, vegetables, flowers and other natural plants. They have antioxidant capacity and can treat cardiovascular diseases, acute organ damage, inflammation, etc. by inhibiting oxidative stress. However, defects such as low water solubility and poor stability limit the application of polyphenol compounds. Making bio-based polyphenols into nanomaterials can effectively improve their stability. However, most of the direct polymerization methods reported so far can only obtain three-dimensional spherical polyphenol nanomaterials. Nanomaterials with spherical morphology have the problem of small specific surface area, and a large number of active groups are wrapped inside the material and cannot play a role. Low-dimensional or porous polyphenol materials have a larger specific surface area, but their preparation methods mostly rely on additional components such as templates or metal ions, and the preparation process and reaction system are relatively complicated.

[0003] Ellagic acid (EA) is a natural polyphenol component widely found in various soft fruits, nuts and other plant tissues. The chemical structure of ellagic acid carries four phenolic hydroxyl groups, and it has excellent free radical scavenging properties and metal ion chelating ability. It has great potential in the prevention and treatment of diseases related to oxidative stress, ferroptosis, and copper death mechanisms.

[0004] However, like other bio-based polyphenols, the extremely poor water solubility of ellagic acid hinders its application in the field of biomedicine. At present, Chinese invention patent CN113372540B has reported a method for preparing polyellagic acid nanoparticles, which uses ellagic acid as a monomer and hydrogen peroxide as an oxidant to prepare polyellagic acid nanoparticles, but only spherical particles with a particle size greater than or equal to 400nm can be obtained, and the same problems as the aforementioned small specific surface area exist.

[0005] In order to improve the water solubility of ellagic acid while obtaining a larger specific surface area and more efficient free radical scavenging performance, it is urgent to develop a simple and effective method for preparing low-dimensional polyellagic acid nanomaterials. Summary of the invention

[0006] In order to solve the above technical problems, the present invention provides a polyellagic acid nanofiber and its preparation and application. The method of the present invention is simple and easy to implement. The prepared polyellagic acid is in the form of nanofibers, has good water solubility, large specific surface area, and stronger free radical scavenging ability.

[0007] The technical solution of the present invention:

[0008] The invention discloses a method for preparing polyellagic acid nanofibers. The method uses ellagic acid as a raw material, an alkaline aqueous solution as a solvent and sodium periodate as an oxidant to prepare the polyellagic acid nanofibers through reaction.

[0009] Preferably, the method for preparing the aforementioned polyellagic acid nanofibers comprises the following steps:

[0010] S1. dissolving ellagic acid in an alkaline aqueous solution to obtain an ellagic acid solution;

[0011] S2. sodium periodate was added to the ellagic acid solution to react, and the reaction product was dialyzed to obtain a polyellagic acid nanofiber dispersion;

[0012] S3. The polyellagic acid nanofiber dispersion is concentrated and then dried to obtain the polyellagic acid nanofiber.

[0013] Preferably, in the aforementioned method for preparing polyellagic acid nanofibers, the alkaline aqueous solution is an aqueous solution of one or any combination of sodium hydroxide, potassium hydroxide, sodium bicarbonate or triethylamine.

[0014] Preferably, in the aforementioned method for preparing polyellagic acid nanofibers, the pH value of the alkaline aqueous solution is 7.5-10.

[0015] Preferably, in the aforementioned method for preparing polyellagic acid nanofibers, the concentration of ellagic acid in the ellagic acid solution is 0.1-5 mg / ml.

[0016] Preferably, in the aforementioned method for preparing polyellagic acid nanofibers, in S2, the mixing molar ratio of sodium periodate to ellagic acid is 0.01-2:1.

[0017] Preferably, in the aforementioned method for preparing polyellagic acid nanofibers, in S2, the reaction temperature is 10-40° C., and the reaction time is 5-48 h.

[0018] Preferably, in the aforementioned method for preparing polyellagic acid nanofibers, in S3, the drying is freeze-drying.

[0019] A polyellagic acid nanofiber is prepared according to the above method.

[0020] An application of the aforementioned polyellagic acid nanofiber in the preparation of biomedicine.

[0021] In the scheme of the present invention, the selection of sodium periodate oxidant and the mixing molar ratio of sodium periodate and ellagic acid are key. When traditional hydrogen peroxide is used as the oxidant, or when a mixing molar ratio of sodium periodate and ellagic acid other than the mixing molar ratio of the present invention is used, nanofibrous polyellagic acid cannot be prepared.

[0022] Beneficial effects of the present invention:

[0023] 1. The polyellagic acid nanofiber of the present invention is prepared by using ellagic acid monomer as raw material and sodium periodate as oxidant at room temperature and pressure. The method is simple, the conditions are mild, and it is suitable for industrial promotion.

[0024] 2. The polyellagic acid nanofibers prepared by the method of the present invention have a unique fibrous morphology, a large specific surface area, carry a large number of active phenolic hydroxyl groups, are stably dispersed in water, can efficiently scavenge free radicals, are safe and non-toxic, can be used as a good oxidative stress protection material, and have good application prospects in the field of biomedicine. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The UV comparison of the polyellagic acid nanomaterial (PEA) and ellagic acid (EA) obtained in Example 1;

[0026] Figure 2 This is an infrared comparison of the polyellagic acid nanomaterial obtained in Example 1 and ellagic acid;

[0027] Figure 3 This is a transmission electron microscope photograph of the polyellagic acid nanomaterial obtained in Example 1;

[0028] Figure 4 This is a transmission electron microscope photograph of the polyellagic acid nanomaterial obtained in Example 2;

[0029] Figure 5 The biocompatibility test results of the polyellagic acid nanomaterial obtained in Example 1;

[0030] Figure 6 The protective effect of the polyellagic acid nanomaterial obtained in Example 1 on cells treated with hydrogen peroxide;

[0031] Figure 1 and Figure 2 It was proved that polyellagic acid nanofibers had been successfully prepared.

[0032] Figure 3 and Figure 4 It shows that the morphology of polyellagic acid nanomaterials can be controlled by changing the amount of oxidant used. With the increase of oxidant content, polyellagic acid nanofibers increase and nanoparticles begin to appear. When the mixing molar ratio of oxidant to ellagic acid is greater than 2:1, there is basically only nanoparticle polyellagic acid in the system, and almost no fibrous polyellagic acid.

[0033] Figure 5 and Figure 6 It shows that polyellagic acid nanofibers can be used as biological oxidative stress protection materials. DETAILED DESCRIPTION

[0034] The present invention will be further described below in conjunction with the embodiments, but they are not intended to limit the present invention.

[0035] Embodiments of the present invention

[0036] Embodiment 1:

[0037] A preparation method of polyellagic acid nanofibers is as follows:

[0038] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt NaOH aqueous solution to adjust the pH to 8, and sonicate until the ellagic acid is completely dissolved;

[0039] (2) adding sodium periodate as an oxidant at a molar ratio of 0.01:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0040] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0041] Embodiment 2:

[0042] A preparation method of polyellagic acid nanofibers is as follows:

[0043] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt NaOH aqueous solution to adjust the pH to 8, and sonicate until the ellagic acid is completely dissolved;

[0044] (2) adding sodium periodate as an oxidant at a molar ratio of 0.5:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0045] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0046] Embodiment 3:

[0047] A preparation method of polyellagic acid nanofibers is as follows:

[0048] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt KOH aqueous solution to adjust the pH to 8, and sonicate until the ellagic acid is completely dissolved;

[0049] (2) adding sodium periodate as an oxidant at a molar ratio of 0.01:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0050] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0051] Embodiment 4:

[0052] A preparation method of polyellagic acid nanofibers is as follows:

[0053] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt sodium bicarbonate aqueous solution to adjust the pH to 8, and sonicate until the ellagic acid is completely dissolved;

[0054] (2) adding sodium periodate as an oxidant at a molar ratio of 0.01:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0055] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0056] Embodiment 5:

[0057] A preparation method of polyellagic acid nanofibers is as follows:

[0058] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt triethylamine aqueous solution to adjust the pH to 8, and sonicate until the ellagic acid is completely dissolved;

[0059] (2) adding sodium periodate as an oxidant at a molar ratio of 0.01:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0060] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0061] Embodiment 6:

[0062] A preparation method of polyellagic acid nanofibers is as follows:

[0063] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt NaOH aqueous solution to adjust the pH to 7.5, and sonicate until the ellagic acid is completely dissolved;

[0064] (2) adding sodium periodate as an oxidant at a molar ratio of 0.01:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0065] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0066] Embodiment 7:

[0067] A preparation method of polyellagic acid nanofibers is as follows:

[0068] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt NaOH aqueous solution to adjust the pH to 10, and sonicate until the ellagic acid is completely dissolved;

[0069] (2) adding sodium periodate as an oxidant at a molar ratio of 0.01:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0070] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0071] Embodiment 8:

[0072] A preparation method of polyellagic acid nanofibers is as follows:

[0073] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 1500 mL ultrapure water, add 50% wt NaOH aqueous solution to adjust the pH to 8, and perform ultrasonication until the ellagic acid is completely dissolved;

[0074] (2) adding sodium periodate as an oxidant at a molar ratio of 0.01:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0075] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0076] Embodiment 9:

[0077] A preparation method of polyellagic acid nanofibers is as follows:

[0078] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 30 mL ultrapure water, add 50% wt NaOH aqueous solution to adjust the pH to 8, and sonicate until the ellagic acid is completely dissolved;

[0079] (2) adding sodium periodate as an oxidant at a molar ratio of 0.01:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0080] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0081] Embodiment 10:

[0082] A preparation method of polyellagic acid nanofibers is as follows:

[0083] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt NaOH aqueous solution to adjust the pH to 8, and sonicate until the ellagic acid is completely dissolved;

[0084] (2) adding sodium periodate as an oxidant in a molar ratio of 1:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0085] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0086] Embodiment 11:

[0087] A preparation method of polyellagic acid nanofibers is as follows:

[0088] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt NaOH aqueous solution to adjust the pH to 8, and sonicate until the ellagic acid is completely dissolved;

[0089] (2) adding sodium periodate as an oxidant in a molar ratio of 2:1 to ellagic acid, stirring and reacting at 25° C. for 20 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0090] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0091] Embodiment 12:

[0092] A preparation method of polyellagic acid nanofibers is as follows:

[0093] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt NaOH aqueous solution to adjust the pH to 8, and sonicate until the ellagic acid is completely dissolved;

[0094] (2) adding sodium periodate as an oxidant at a molar ratio of 0.01:1 to ellagic acid, stirring and reacting at 10° C. for 48 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0095] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0096] Embodiment 13:

[0097] A preparation method of polyellagic acid nanofibers is as follows:

[0098] (1) Weigh ellagic acid (0.15 g, 0.0005 mol) monomer and disperse it in 150 mL ultrapure water, add 50% wt NaOH aqueous solution to adjust the pH to 8, and sonicate until the ellagic acid is completely dissolved;

[0099] (2) adding sodium periodate as an oxidant at a molar ratio of 0.01:1 to ellagic acid, stirring and reacting at 40°C for 5 hours, and dialyzing in deionized water (molecular weight cut-off greater than or equal to 3500D) to obtain a polyellagic acid nanofiber dispersion;

[0100] (3) The polyellagic acid nanofiber dispersion was concentrated by ultrafiltration centrifugation (molecular weight cut-off greater than or equal to 3500D), and then freeze-dried to obtain the polyellagic acid nanofiber.

[0101] Embodiment 14:

[0102] The specific application method of polyellagic acid nanofibers in the biomedical field is consistent with the existing application method of polyellagic acid nanoparticles, and there are no special requirements.

[0103] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and inventive concepts of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing polyellagic acid nanofibers, characterized in that: The method uses ellagic acid as a raw material, an alkaline aqueous solution as a solvent and sodium periodate as an oxidant to prepare polyellagic acid nanofibers through reaction.

2. The method for preparing polyellagic acid nanofibers according to claim 1, characterized in that: The steps include: S1. dissolving ellagic acid in an alkaline aqueous solution to obtain an ellagic acid solution; S2. sodium periodate was added to the ellagic acid solution to react, and the reaction product was dialyzed to obtain a polyellagic acid nanofiber dispersion; S3. The polyellagic acid nanofiber dispersion is concentrated and then dried to obtain the polyellagic acid nanofiber.

3. The method for preparing polyellagic acid nanofibers according to claim 2, characterized in that: The alkaline aqueous solution is an aqueous solution of one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate or triethylamine.

4. The method for preparing polyellagic acid nanofibers according to claim 2, characterized in that: The pH value of the alkaline aqueous solution is 7.5-10.

5. The method for preparing polyellagic acid nanofibers according to claim 2, characterized in that: The concentration of ellagic acid in the ellagic acid solution is 0.1-5 mg / ml.

6. The method for preparing polyellagic acid nanofibers according to claim 2, characterized in that: In S2, the mixing molar ratio of sodium periodate to ellagic acid is 0.01-2:

1.

7. The method for preparing polyellagic acid nanofibers according to claim 2, characterized in that: In S2, the reaction temperature is 10-40°C and the reaction time is 5-48h.

8. The method for preparing polyellagic acid nanofibers according to claim 2, characterized in that: In S3, the drying is freeze-drying.

9. A polyellagic acid nanofiber, characterized in that: Prepared according to the method according to any one of claims 1 to 8.

10. Use of the polyellagic acid nanofiber according to claim 9 in the preparation of biomedicine.

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