Electrospun films based on selenium-containing block polymers, methods of making and applications thereof
By using the electrospinning technology of selenium-containing block polymers, spun membranes with both excellent mechanical properties and good hydrophilicity are prepared, which solves the problems of unstable bioactivity and unbalanced mechanical properties in existing technologies, and achieves continuous improvement in physiological activity and biocompatibility, making them suitable for covered stents and artificial blood vessels.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SUZHOU UNIV
- Filing Date
- 2026-02-27
- Publication Date
- 2026-06-05
AI Technical Summary
Existing electrospun nanofiber membranes have problems such as unstable bioactivity, uneven mechanical properties, and poor hydrophilicity in the biomedical field, making it difficult to meet the comprehensive performance requirements of high-end implantable medical devices such as covered stents and artificial blood vessels.
A spinning solution was prepared using a selenium-containing block polymer with a rigid main chain and hydrophilic blocks. The spinning membrane was then prepared by electrospinning technology. The spinning membrane combines the excellent mechanical properties of polyesteramide with the good hydrophilicity of the hydrophilic diselenide polymer. The diselenide structure can catalyze the continuous generation of nitric oxide (NO) and has a stable and reliable structure.
The spun membrane achieved elastic mechanical compatibility, good hydrophilicity, and sustained physiological activity, improving biocompatibility, reducing postoperative risks, and meeting the comprehensive material performance requirements of high-end implantable medical devices.
Smart Images
Figure CN122147620A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrospun membrane technology, specifically to an electrospun membrane based on a selenium-containing block polymer, its preparation method, and its application. Background Technology
[0002] Electrospinning, as a mature additive manufacturing technology, has been widely used to prepare biomedical nanofiber membranes. By selecting synthetic polymers such as polyvinylidene fluoride (PVDF) and polycaprolactone (PCL) or natural polymers such as gelatin and pullulan, or by using methods such as GelMA / PCL blending, membrane materials with nanoscale fiber structures and high porosity can be obtained. Among them, some are endowed with antioxidant and other bioactivities by doping selenium nanoparticles (Se NPs), showing application potential in tissue engineering scaffolds, wound dressings and other fields.
[0003] However, existing technologies still have significant limitations: pure synthetic polymer-based fiber membranes generally lack bioactivity, while natural polymers or blends suffer from insufficient mechanical properties and structural stability. Furthermore, selenium is often introduced in the form of nanoparticle doping, which easily leads to agglomeration, resulting in unstable bioactivity and weak bonding with the polymer matrix. Selenium-containing polymer spun membranes are mostly of a single structure with poor hydrophilicity, making it difficult to adapt to the human physiological environment, and their mechanical properties are uneven (either insufficient tensile strength or poor flexibility).
[0004] In summary, existing electrospun nanofiber membranes cannot simultaneously achieve synergistic optimization of elastic mechanical adaptability, good hydrophilicity, and sustained physiological activity (such as catalytic release of nitric oxide (NO)), and therefore cannot meet the stringent requirements for comprehensive material performance in high-end implantable medical devices such as covered stents and artificial blood vessels. Summary of the Invention
[0005] This invention addresses the shortcomings of existing technologies by providing an electrospun membrane based on a selenium-containing block polymer, its preparation method, and its application. The spinning solution is prepared using a selenium-containing block polymer with a "rigid main chain-hydrophilic block" composite structure, and the spun membrane is prepared by electrospinning. The spun membrane combines the excellent mechanical properties of polyesteramide with the good hydrophilicity of hydrophilic diselenide polymers, solving the problems of poor hydrophilicity and insufficient mechanical properties of single selenium-containing polymers. Furthermore, the diselenide structure can catalyze the continuous generation of NO, ensuring structural stability and reliability, and guaranteeing long-term functionality.
[0006] To address the aforementioned technical problems, the first aspect of this invention provides a method for preparing an electrospun film based on a selenium-containing block polymer, comprising the following steps:
[0007] A selenium-containing block polymer is dissolved in an organic solvent to obtain a spinning solution, and the spinning solution is electrospun through an electrospinning device to prepare the electrospun membrane.
[0008] The selenium-containing block polymer comprises a diselenyl ether polymer chain A and a polyesteramide chain B, and has the following structure:
[0009] , where R is selected from (CH2CH2O). y Alkyl groups with 2-20 carbon atoms or carbon ring-containing groups with 6-20 carbon atoms, where y is an integer between 2 and 10; R 1 Selected from (CH2CH2O) x Alternatively, it may be an alkyl group with 2-20 carbon atoms, where x is an integer between 2-10; p is an integer between 1-5; and m and n are independently selected from positive integers. Preferably, the mass fraction of the hydrophilic diselenyl ether polymer block chain A is 5-20% based on the total mass of the selenium-containing block polymer.
[0010] This invention uses a selenium-containing block polymer to prepare a spinning solution, wherein the selenium-containing block polymer comprises a polyesteramide backbone B and a hydrophilic diselenyl ether polymer block chain A, combining the excellent mechanical properties of polyesteramide with the good hydrophilicity of the hydrophilic diselenyl ether polymer, thus solving the problem of poor hydrophilicity and insufficient mechanical properties of single selenium-containing polymers.
[0011] The selenium-containing block polymer structure of this invention is stable and reliable. The diselenyl ether structure therein can catalyze the continuous production of NO from RSNO in the human body, exhibiting sustained physiological activity and ensuring long-lasting function; it also improves biocompatibility and reduces postoperative risks.
[0012] Furthermore, the concentration of the spinning solution is 0.8-1.2 mol / L.
[0013] Furthermore, the feed rate of the spinning solution is 1.5-2.5 mL / h.
[0014] Furthermore, the electrospinning voltage is 12-18KV, and the spinning solution forms a Taylor cone and is stretched into fibers.
[0015] Furthermore, the receiving distance of the electrospinning is 12-18cm, and the receiving roller speed is 500-700rpm.
[0016] Furthermore, the electrospinning temperature is 20-30℃ and the relative humidity is 30-50%.
[0017] Furthermore, the electrospinning process also includes: peeling the spinning film off the receiving roller and vacuum drying.
[0018] Furthermore, the vacuum drying conditions are: temperature 40-70℃, vacuum degree -0.08 ~ -0.1MPa, and time 8-16h.
[0019] The second aspect of the present invention provides an electrospun membrane based on a selenium-containing block polymer prepared by the preparation method described in the first aspect.
[0020] The third aspect of this invention provides the application of the electrospun membrane based on selenium-containing block polymers described in the second aspect in the fabrication of covered stents and artificial blood vessels.
[0021] The beneficial effects of this invention are:
[0022] This invention uses a selenium-containing block polymer with a "rigid main chain-hydrophilic block" composite structure to prepare a spinning solution, and then uses electrospinning to prepare a spinning film. The selenium-containing block polymer contains a diselenide polymer block chain A and a polyesteramide chain B, which combines the excellent mechanical properties of polyesteramide with the good hydrophilicity of hydrophilic diselenide polymer, thus solving the problem of poor hydrophilicity and insufficient mechanical properties of single selenium-containing polymers.
[0023] The selenium-containing block polymer structure of this invention is stable and reliable. The diselenyl ether structure therein can catalyze the continuous production of NO from RSNO in the human body, exhibiting sustained physiological activity and ensuring long-lasting function; it also improves biocompatibility and reduces postoperative risks. Attached Figure Description
[0024] To more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0025] Figure 1 This is the NMR spectrum of the selenium-containing block polymer obtained in Example 1 of the present invention;
[0026] Figure 2 These are SEM images of the electrospun films obtained in Examples 1-5 and Comparative Example 1 of the present invention;
[0027] Figure 3 These are mechanical property diagrams of the electrospun films obtained in Examples 1-5 and Comparative Example 1 of the present invention before and after drying;
[0028] Figure 4 This is a diagram showing the cyclic tensile properties of the electrospun film obtained in Example 4 of the present invention;
[0029] Figure 5 These are cytotoxicity test diagrams of the electrospun membranes obtained in Examples 1-5 and Comparative Example 1 of the present invention;
[0030] Figure 6 These are NO release rate test graphs of the electrospun films obtained in Examples 1-5 and Comparative Example 1 of the present invention;
[0031] Figure 7 These are blood compatibility test diagrams of the electrospun membranes obtained in Examples 1-5 and Comparative Example 1 of the present invention. Detailed Implementation
[0032] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0033] This embodiment relates to a method for preparing an electrospun membrane based on a selenium-containing block polymer, comprising the following steps: dissolving the selenium-containing block polymer in an organic solvent to obtain a spinning solution, and electrospinning the spinning solution using an electrospinning device to prepare the electrospun membrane; the selenium-containing block polymer comprises a hydrophilic diselenyl ether polymer block chain A and a polyesteramide backbone B, having the following structure:
[0034] , where R is selected from (CH2CH2O). y Alkyl groups with 2-20 carbon atoms or carbon ring-containing groups with 6-20 carbon atoms, where y is an integer between 2 and 10; R 1 Selected from (CH2CH2O) x Alternatively, it may be an alkyl group with 2-20 carbon atoms, where x is an integer between 2-10; p is an integer between 1-5; and m and n are independently selected from positive integers. Preferably, the mass fraction of the hydrophilic diselenyl ether polymer block chain A is 5-20% based on the total mass of the selenium-containing block polymer.
[0035] This embodiment uses a selenium-containing block polymer to prepare a spinning solution. The selenium-containing block polymer comprises a diselenyl ether polymer block chain A and a polyesteramide chain B, combining the excellent mechanical properties of polyesteramide with the good hydrophilicity of hydrophilic diselenyl ether polymers. This solves the problems of poor hydrophilicity and insufficient mechanical properties of single selenium-containing polymers. The selenium-containing block polymer has a stable and reliable structure, and the diselenyl ether structure can catalyze the continuous production of NO from RSNO in the human body, exhibiting continuous physiological activity and ensuring long-term function. Biocompatibility is improved, reducing postoperative risks.
[0036] In a preferred embodiment, the concentration of the spinning solution is 0.8-1.2 mol / L; the feed rate of the spinning solution is 1.5-2.5 mL / h.
[0037] In a preferred embodiment, the electrospinning voltage is 12-18KV, the spinning solution forms a Taylor cone and is stretched into fibers; the receiving distance of the electrospinning is 12-18cm, and the receiving roller speed is 500-700rpm; the electrospinning temperature is 20-30℃, and the relative humidity is 30-50%; the electrospinning process further includes: peeling the spinning film off the receiving roller and vacuum drying; the vacuum drying conditions are: temperature 40-70℃, vacuum degree -0.08 ~ -0.1MPa, and time 8-16h.
[0038] Another embodiment provides an electrospun membrane based on a selenium-containing block polymer prepared by the preparation method described in the above embodiments.
[0039] Another embodiment provides the application of the electrospun membrane based on selenium-containing block polymer described in the above embodiments in the fabrication of covered stents and artificial blood vessels.
[0040] Example 1
[0041] This embodiment relates to a method for preparing an electrospun film based on a selenium-containing block polymer, comprising the following steps:
[0042] (1) Preparation of alkynyl-terminated polyesteramide: In a glove box, 3.7 mol of 4,4'-diaminodicyclohexylmethane and 7.77 mol of selenolactone were added to a 50 ml flask and mixed evenly by magnetic stirring (300 rpm). The ring-opening reaction was carried out in 2.44 ml of hexafluoroisopropanol solution for 12 h under nitrogen atmosphere and room temperature to generate bis-terminated selenool. Then, 4.44 mol of butanediol dipropynate and 2 ml of hexafluoroisopropanol solution were added to the reaction system and the reaction was continued by stirring to complete the selenool alkynyl click polymerization to obtain alkynyl-terminated polyesteramide.
[0043] (2) Preparation of hydrophilic diselenide polymer: First, in a glove box, add 2 mol of amino-polyethylene glycol-amino and 4.4 mol of selenolactone to a 50 mL single-necked flask. Under a nitrogen atmosphere, stir magnetically (300 rpm) to mix evenly and carry out the ring-opening reaction at room temperature for 12 h. Then, introduce oxygen and continue stirring to carry out the oxidative coupling polymerization reaction for 12 h. After the reaction is completed, purify by low-temperature precipitation of diethyl ether: slowly drop the reaction solution into 10 times the volume of diethyl ether, place it in a -8℃ environment to stand and precipitate, filter and collect the precipitate, and place the precipitate in a vacuum drying oven (40℃) to dry for 12 h to obtain the hydrophilic diselenide polymer.
[0044] (3) Preparation of selenium-containing block polymer: Weigh 0.058 mol (5% by mass, based on the total mass of the final block polymer) of the hydrophilic diselenide polymer prepared in step (2), add 0.058 mol of dithreothiol, dissolve in 1 mL of hexafluoroisopropanol, and perform a reduction reaction at room temperature with magnetic stirring (300 rpm) for 3 h to obtain a hydrophilic polymer containing selenol groups; add it to a 1 mol / L polyesteramide-hexafluoroisopropanol solution, stir to complete the block reaction, and obtain the selenium-containing block polymer. The NMR spectrum is shown in [reference needed]. Figure 1 .
[0045] (4) Electrospinning film formation: Prepare a spinning solution with a concentration of 0.9 mol / L by preparing the selenium-containing block polymer-hexafluoroisopropanol solution in step (3); add the spinning solution into the syringe of the electrospinning equipment and set the spinning parameters: receiving roller speed 600 rpm, receiving distance 15 cm, spinning solution feed rate 2 mL / h, voltage 15 KV, and electrospinning for 2 h at room temperature (25℃) and relative humidity 30%.
[0046] (5) After spinning, the film material is peeled off from the receiving roller and placed in a vacuum drying oven (40℃, -0.1MPa) for 12h to obtain a selenium-containing block polymer electrospun film.
[0047] Example 2
[0048] The difference between this embodiment and Example 1 is that the amount of hydrophilic diselenyl ether polymer and dithreothiol added in step (3) is 0.121 mol, and the mass fraction of hydrophilic diselenyl ether polymer is 10% based on the total mass of the final block polymer. Other steps and parameters remain unchanged.
[0049] Example 3
[0050] The difference between this embodiment and Example 1 is that the amount of hydrophilic diselenyl ether polymer and dithreothiol added in step (3) is 0.221 mol, and the mass fraction of hydrophilic diselenyl ether polymer is 15% based on the total mass of the final block polymer. Other steps and parameters remain unchanged.
[0051] Example 4
[0052] The difference between this embodiment and Example 1 is that the amount of hydrophilic diselenyl ether polymer and dithreothiol added in step (3) is 0.313 mol, and the mass fraction of hydrophilic diselenyl ether polymer is 20% based on the total mass of the final block polymer. Other steps and parameters remain unchanged.
[0053] Example 5
[0054] The difference between this embodiment and Example 1 is that the amount of hydrophilic diselenyl ether polymer and dithreothiol added in step (3) is 0.417 mol, and the mass fraction of hydrophilic diselenyl ether polymer is 25% based on the total mass of the final block polymer. Other steps and parameters remain unchanged.
[0055] Example 6
[0056] The difference between this embodiment and embodiment 1 is that the concentration of the spinning solution in step (4) is 1.1 mol / L, while the other steps and parameters remain unchanged.
[0057] Comparative Example 1
[0058] The difference between this comparative example and Example 1 is that the alkynyl-terminated polyesteramide prepared in step (1) is directly mixed with hexafluoroisopropanol to prepare the spinning solution, while other steps and parameters remain unchanged.
[0059] Figure 2 SEM images of the electrospun films prepared in Examples 1-5 and Comparative Example 1 are shown; it can be seen that the diameter distribution is the most uniform, there are no obvious beading defects, and the spinning process window is optimal.
[0060] Figure 3 The mechanical properties of the electrospun membranes prepared in Examples 1-5 and Comparative Example 1 before and after drying are shown in the test results. It can be seen that the introduction of hydrophilic diselenyl ether improves hydrophilicity while maintaining high elasticity. The mechanical window is completely covered and is superior to that of natural veins. The wet state decrease (modulus -56% and strength -15%) did not show any additional degradation. The wet state performance is still significantly better than that of the human saphenous vein target. Therefore, the fiber membrane is mechanically fully qualified.
[0061] Figure 4 This is a cyclic tensile performance diagram of the electrospun film material with a mass fraction of 20% obtained in Example 4 of the present invention. It can be seen that this material is a soft material with low modulus and high ductility.
[0062] Figure 5 These are cytotoxicity test diagrams of the electrospun membranes obtained in Examples 1-5 and Comparative Example 1 of the present invention. It can be seen that the composite material exhibits excellent biocompatibility at an addition amount of ≤20%, but the addition amount needs to be controlled to not exceed 20%, otherwise significant cytotoxicity will occur at a concentration of 25%. Figure 6 The figures show the NO release rate test results of the electrospun membranes obtained in Examples 1-5 and Comparative Example 1 of this invention. As can be seen, the release lasts for more than 14 days (2 weeks), which proves that the material has good structural durability and is suitable for medium- and long-term implantation applications. Figure 7These are blood compatibility test diagrams of the electrospun membranes obtained in Examples 1-5 and Comparative Example 1 of the present invention. According to the negative / positive control groups, the hemolysis rate of the materials is less than 5%, indicating good blood compatibility. In summary, the present invention uses a selenium-containing block polymer with a "rigid main chain-hydrophilic block" composite structure to prepare the spinning solution, and then electrospinns to prepare the spun membrane. This selenium-containing block polymer contains a diselenyl ether polymer block chain A and a polyesteramide chain B, combining the excellent mechanical properties of polyesteramide with the good hydrophilicity of the hydrophilic diselenyl ether polymer, thus solving the problems of poor hydrophilicity and insufficient mechanical properties of single selenium-containing polymers. The selenium-containing block polymer structure is stable and reliable, and the diselenyl ether structure can catalyze the continuous production of NO from RSNO in the human body, exhibiting sustained physiological activity and ensuring long-lasting function. Improved biocompatibility reduces postoperative risks.
[0063] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.
Claims
1. A method for preparing an electrospun film based on a selenium-containing block polymer, characterized in that, Includes the following steps: A selenium-containing block polymer is dissolved in an organic solvent to obtain a spinning solution, and the spinning solution is electrospun through an electrospinning device to prepare the electrospun membrane. The selenium-containing block polymer comprises a diselenyl ether polymer block chain A and a polyesteramide chain B, and has the following structure: , where R is selected from (CH2CH2O). y Alkyl groups with 2-20 carbon atoms or carbon ring-containing groups with 6-20 carbon atoms, where y is an integer between 2 and 10; R 1 Selected from (CH2CH2O) x Or an alkyl group with 2-20 carbon atoms, where x is an integer between 2-10; p is an integer between 1-5; and m and n are independently selected from positive integers.
2. The method for preparing an electrospun membrane based on a selenium-containing block polymer as described in claim 1, characterized in that, The concentration of the spinning solution is 0.8-1.2 mol / L.
3. The method for preparing an electrospun membrane based on a selenium-containing block polymer as described in claim 1, characterized in that, The feed rate of the spinning solution is 1.5-2.5 mL / h.
4. The method for preparing an electrospun film based on a selenium-containing block polymer as described in claim 1, characterized in that, The electrospinning voltage is 12-18KV, and the spinning solution forms a Taylor cone and is stretched into fibers.
5. The method for preparing an electrospun film based on a selenium-containing block polymer as described in claim 1, characterized in that, The receiving distance for electrospinning is 12-18cm, and the receiving roller speed is 500-700rpm.
6. The method for preparing an electrospun film based on a selenium-containing block polymer as described in claim 1, characterized in that, The electrospinning temperature is 20-30℃ and the relative humidity is 30-50%.
7. The method for preparing an electrospun film based on a selenium-containing block polymer as described in claim 1, characterized in that, The electrospinning process also includes: peeling the spinning film off the receiving roller and vacuum drying.
8. The method for preparing an electrospun film based on a selenium-containing block polymer as described in claim 7, characterized in that, The vacuum drying conditions are: temperature 40-70℃, vacuum degree -0.08 ~ -0.1MPa, and time 8-16h.
9. An electrospun membrane based on a selenium-containing block polymer prepared by the preparation method according to any one of claims 1-8.
10. The application of the electrospun membrane based on selenium-containing block polymer as described in claim 9 in the fabrication of covered stents and artificial blood vessels.