A spinning solution of ion-responsive polymer film wrapped active ingredient and its preparation method and application

Abstract

The application discloses a kind of ion response type high polymer film wrapped active ingredient spinning solution and its preparation method and application, the spinning solution includes the following components: polymer matrix, antioxidant and solvent;The polymer matrix includes sodium alginate and polyvinyl alcohol;The mass ratio of sodium alginate and polyvinyl alcohol is 1: (2.5-5). Sodium alginate in spinning solution has good ion response and biocompatibility, under the action of Ca 2+ , Al 3+ And other metal ions can be quickly crosslinked to form gel film, realize the wrapping of active ingredient;Polyvinyl alcohol has excellent spinning performance and mechanical properties, and can improve the stability of spinning solution and the mechanical strength of fiber by compounding with sodium alginate, avoid the problems such as broken wire and needle blockage in spinning process, suitable for electrospinning process application.

Description

Technical Field

[0001] This invention belongs to the field of functional textile materials technology, specifically relating to a spinning solution containing an ion-responsive polymer membrane encapsulating active ingredients, its preparation method, and its application. Background Technology

[0002] With the increasing demand for healthy and environmentally friendly textile products, combining natural plant active ingredients with textile materials to prepare functional textiles has become a research hotspot. Currently, the application of grape seed active ingredients in the textile field is mostly done through direct soaking or coating, which has problems such as low active ingredient loading, easy shedding, and uncontrollable release, making it difficult to achieve long-lasting functionality.

[0003] Polymer membrane encapsulation technology can effectively protect active ingredients, reduce their oxidative deactivation, and achieve controlled release. Ion-responsive encapsulation systems can respond to external ion stimulation, such as sodium ions in human sweat. + Ca 2+ Triggering the release of active ingredients aligns with the usage scenarios of wearable textile products; however, enzyme-responsive encapsulation systems require specific enzyme environments for triggering, have demanding operating conditions, are prone to enzyme inactivation, and lack sufficiently specific enzymes in everyday wearable scenarios, making practical applications difficult. Furthermore, existing spinning solution preparations often rely on complex equipment, resulting in high costs and unsuitability for small-batch production and widespread adoption. Summary of the Invention

[0004] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the present invention proposes a spinning solution in which sodium alginate exhibits good ionic responsiveness and biocompatibility, and in Ca... 2+ Al 3+ Under the action of metal ions, it can quickly crosslink to form a gel film, thereby encapsulating the active ingredients; polyvinyl alcohol has excellent spinning and mechanical properties, and when combined with sodium alginate, it can improve the stability of the spinning solution and the mechanical strength of the fiber, avoiding problems such as fiber breakage and needle blockage during the spinning process, making it suitable for electrospinning applications.

[0005] The present invention also proposes a method for preparing the above-mentioned spinning solution.

[0006] The present invention also proposes a method for preparing an ion-responsive functional fiber membrane.

[0007] The present invention also proposes an ion-responsive functional fiber membrane prepared by the above preparation method.

[0008] The present invention also proposes the application of the above-mentioned spinning solution or ion-responsive functional fiber membrane.

[0009] According to a first aspect of the present invention, a spinning solution is provided, the spinning solution comprising the following components: a polymer matrix, an antioxidant, and a solvent; the polymer matrix comprising sodium alginate and polyvinyl alcohol; the mass ratio of sodium alginate to polyvinyl alcohol being 1:(2.5-5).

[0010] In some embodiments of the present invention, the mass ratio of sodium alginate to polyvinyl alcohol is 1:(3-4).

[0011] In some embodiments of the present invention, the antioxidant includes polyphenols.

[0012] In some embodiments of the present invention, the polyphenolic substances include one or more combinations of proanthocyanidins, catechins, gallic acid and quercetin.

[0013] In some embodiments of the present invention, the polyphenols are extracted from grape seeds.

[0014] In some embodiments of the present invention, the method for obtaining the polyphenolic substance includes the following steps: Grape seed powder is mixed with extraction solvent and subjected to ultrasonic extraction. The liquid phase is collected by filtration, concentrated and dried to obtain the final product.

[0015] In some embodiments of the present invention, the extraction solvent includes an aqueous ethanol solution.

[0016] In some embodiments of the present invention, the extraction solvent comprises a 60%-70% aqueous ethanol solution.

[0017] In some embodiments of the present invention, the conditions for ultrasonic extraction include: ultrasonic extraction at 35℃-45℃ and 100-150 W for 30-40 min.

[0018] The active ingredients in grape seeds include proanthocyanidins or polyphenols from grape seed extract, which are derived from grape processing byproducts. These byproducts are obtained through crushing, ultrasonic extraction, filtration, concentration, and drying, with proanthocyanidin purity ≥80%. Using grape seed byproducts achieves high-value utilization of agricultural waste and reduces raw material costs.

[0019] In some embodiments of the present invention, the spinning solution comprises the following components by mass percentage: 5%-15% polymer matrix and 1%-6% antioxidant, with the balance being solvent.

[0020] In some embodiments of the present invention, the spinning solution comprises the following components by mass percentage: 8%-12% polymer matrix and 2%-5% antioxidant, with the balance being solvent.

[0021] In some embodiments of the present invention, the solvent includes an aqueous solution of ethanol.

[0022] Ethanol aqueous solution can be used as a solvent to improve the solubility of grape seed active ingredients and polymer matrix, avoid precipitation and agglomeration, and at the same time reduce the surface tension of spinning solution and improve spinning stability.

[0023] In some embodiments of the present invention, the aqueous ethanol solution is obtained by mixing deionized water and anhydrous ethanol at a volume ratio of (3-6):1.

[0024] In some embodiments of the present invention, the ethanol aqueous solution is obtained by mixing deionized water and anhydrous ethanol at a volume ratio of (4-5):1.

[0025] In some embodiments of the present invention, the degree of polymerization of the polyvinyl alcohol is 1700-2000.

[0026] In some embodiments of the present invention, the degree of alcoholysis of the polyvinyl alcohol is 88%-99%.

[0027] In some embodiments of the present invention, the sodium alginate has a viscosity of 100-300 mPa in a 1% aqueous solution at 25°C. s.

[0028] The above-mentioned parameter ranges for polyvinyl alcohol and sodium alginate ensure that the spinning solution has suitable viscosity and fluidity to meet the requirements of electrospinning process, while guaranteeing the mechanical properties and ionic response properties of the fiber.

[0029] According to a second aspect of the present invention, a method for preparing the spinning solution described in the first aspect of the present invention is provided, the method comprising the following steps: S1: Mix sodium alginate, polyvinyl alcohol and solvent, heat until completely dissolved, to obtain a polymer matrix solution; S2: Add an antioxidant to the polymer matrix solution obtained in step S1, stir and then ultrasonically disperse to obtain a spinning solution.

[0030] In some embodiments of the present invention, the heating conditions in step S1 include heating at 60°C-80°C.

[0031] In some embodiments of the present invention, the heating to complete dissolution in step S1 is carried out by heating and stirring, and the stirring conditions include stirring at 200-300 r / min for 2-4 h.

[0032] In some embodiments of the present invention, the stirring conditions in step S2 include stirring at room temperature for 1-3 hours.

[0033] In some embodiments of the present invention, the conditions for ultrasonic dispersion in step S2 include: ultrasonic dispersion for 15-40 min at 100-200 W and 30-50 kHz.

[0034] In some embodiments of the present invention, step S2 further includes vacuum degassing after ultrasonic dispersion.

[0035] In some embodiments of the present invention, the antioxidant in step S2 includes polyphenols.

[0036] In some embodiments of the present invention, the polyphenolic substances include one or more combinations of proanthocyanidins, catechins, gallic acid and quercetin.

[0037] In some embodiments of the present invention, the polyphenols are extracted from grape seeds.

[0038] In some embodiments of the present invention, the method for obtaining the polyphenolic substance includes the following steps: Grape seed powder is mixed with extraction solvent and subjected to ultrasonic extraction. The liquid phase is collected by filtration, concentrated and dried to obtain the final product.

[0039] In some embodiments of the present invention, the extraction solvent includes an aqueous ethanol solution.

[0040] In some embodiments of the present invention, the extraction solvent comprises a 60%-70% aqueous ethanol solution.

[0041] In some embodiments of the present invention, the conditions for ultrasonic extraction include: ultrasonic extraction at 35℃-45℃ and 100-150 W for 30-40 min.

[0042] According to a third aspect of the present invention, a method for preparing an ion-responsive functional fiber membrane is provided, the method comprising the following steps: A1: Electrospinning is performed using the spinning solution described in the first aspect of the present invention to obtain a nanofiber membrane; A2: The nanofiber membrane obtained in step A1 is placed in an ion crosslinking agent solution for crosslinking to obtain an ion-responsive functional fiber membrane.

[0043] In some embodiments of the present invention, the voltage for electrospinning in step A1 is 15-25 kV.

[0044] In some embodiments of the present invention, the receiving distance of the electrospinning in step A1 is 10-15 cm.

[0045] In some embodiments of the present invention, the ionic crosslinking agent solution in step A2 contains calcium salt and / or aluminum salt.

[0046] In some embodiments of the present invention, the calcium salt includes calcium chloride.

[0047] In some embodiments of the present invention, the aluminum salt includes aluminum chloride.

[0048] The ionic crosslinking agent is calcium chloride or aluminum chloride, which can undergo an ionic crosslinking reaction with sodium alginate to form a stable core-shell structure encapsulation system, achieving stable loading of the effective components of grape seeds. Under the stimulation of human sweat ions, it can slowly swell and release active ingredients.

[0049] In some embodiments of the present invention, the concentration of calcium salt and / or aluminum salt in the ionic crosslinking agent solution is 0.1-0.2 mol / L.

[0050] In some embodiments of the present invention, the crosslinking time in step A2 is 8-15 min.

[0051] This invention optimizes the ratio of sodium alginate to polyvinyl alcohol, the total concentration of the polymer matrix, the amount of grape seed active ingredients added, and the amount of ionic crosslinking agent added through single-factor optimization screening. The single-factor optimization experiments on the viscosity, spinnability, encapsulation rate of active ingredients, and ionic response sustained-release performance of the spinning solution show that: when the mass ratio of sodium alginate to polyvinyl alcohol is 1:3, the viscosity of the spinning solution is moderate and the fiber continuity is the best; when the total mass fraction of the polymer matrix is ​​8 wt%~12 wt%, the fluidity and formability of the spinning solution are balanced, and the resulting fibers are uniformly formed without bead defects; when the amount of antioxidant added is 2%~3%, the encapsulation rate and functional release are optimally balanced; when the amount of ionic crosslinking agent added is 1%, the degree of crosslinking is appropriate, which can form a stable core-shell structure without affecting the fluidity of the spinning solution.

[0052] According to a fourth aspect of the present invention, an ion-responsive functional fiber membrane prepared by the preparation method described in the third aspect of the present invention is provided.

[0053] According to a fifth aspect of the present invention, the application of the spinning solution described in the first aspect of the present invention or the ion-responsive functional fiber membrane described in the fourth aspect of the present invention in the preparation of at least one of (1)-(5) is proposed: (1) Clothing fabrics; (2) Skin care mask sheet; (3) Antibacterial bedding; (4) Sports protective gear; (5) Medical dressings.

[0054] The present invention has at least the following beneficial effects: 1) The spinning solution provided by this invention is more targeted and innovative in terms of raw material utilization. It abandons the traditional single extraction and utilization mode of effective components of grape seeds, combines agricultural waste resources, solves the problem of grape seed resource waste, and is different from existing general-purpose functional spinning solutions, making it more competitive in the market.

[0055] 2) The ion-responsive functional fiber membrane provided by this invention has an ion-responsive system that is more suitable for wearable scenarios. It uses a polymer membrane composed of sodium alginate and PVA, and constructs a stable three-dimensional network structure through electrospinning followed by ion cross-linking. It does not require complex external stimuli and relies solely on the Na+ in human sweat. + Ca 2+ Plasma can trigger the gradient release of active ingredients, solving the technical pain points of uncontrollable release and easy dissolution and shedding of active ingredients in existing functional textile materials. It enables long-term and stable performance of functions such as anti-oxidation and antibacterial properties, making it more suitable for daily wear, sports skin care and long-term care scenarios.

[0056] 3) The method for preparing ion-responsive functional fiber membranes provided by this invention is simpler and lower in cost. It does not require complex experimental equipment or harsh operating conditions. Steps such as water bath heating, stirring, and ultrasonic dispersion can all be completed in the laboratory. The raw materials are readily available and inexpensive. At the same time, the experiment is highly reproducible and small-batch preparation is easy. Compared with the existing spinning solution preparation technology that relies on professional equipment, it is more feasible to implement.

[0057] 4) The technical threshold is moderate. Compared with enzyme-responsive encapsulation technology, the ion-responsive system of this invention is simple to operate and has strong stability. There is no need to worry about experimental failure caused by enzyme inactivation. At the same time, it can be industrialized and promoted through simple optimization, and the technology transformation difficulty is low. Attached Figure Description

[0058] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein: Figure 1 This is a flowchart of the preparation process in Example 4 of the present invention; Figure 2 This is a graph showing the test results of the antioxidant performance of the ion-responsive grape seed functional fiber membrane in the experimental examples of this invention; Figure 3 This is a graph showing the release detection results of grape seed active ingredients under simulated sweat ion environment in the experimental examples of this invention; Figure 4 This is a graph showing the retention rate of grape seed active ingredients in the experimental examples of this invention. Detailed Implementation

[0059] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0060] Example 1 This embodiment provides a spinning solution, the preparation method of which is as follows: (1) Sodium alginate (SA, viscosity 100 mPa) was placed in a water bath at 60℃. SA and PVA (degree of polymerization 1700, degree of hydrolysis 88%) were added to a mixed solvent (deionized water and anhydrous ethanol mixed at a volume ratio of 4:1), stirred at 200 r / min for 4 h until dissolved, and cooled to obtain a polymer matrix solution; the concentration of SA in this polymer matrix was 2 wt%, and the concentration of PVA was 6 wt%. (2) Add proanthocyanidins (purity ≥85%) to the polymer matrix solution to a concentration of 2 wt%, stir at room temperature for 2 h, ultrasonically disperse at 100 W and 40 kHz for 30 min, and vacuum degas for 20 min to obtain spinning solution.

[0061] The above-mentioned proanthocyanidins were extracted from grape seeds. The proanthocyanidins were prepared by the following method: grape seeds were crushed and sieved, and 60% ethanol-water mixed solvent (solid-liquid ratio 1:20) was added. The mixture was ultrasonically extracted at 40℃ and 120 W for 30 min, filtered, concentrated by rotary evaporation and vacuum dried to obtain grape seed-derived proanthocyanidin powder.

[0062] Example 2 This embodiment provides a spinning solution, the preparation method of which is as follows: (1) Under a water bath at 70℃, SA (viscosity 200 mPa) SA and PVA (degree of polymerization 1800, degree of alcoholysis 95%) were added to a mixed solvent (deionized water and anhydrous ethanol mixed at a volume ratio of 5:1), stirred at 250 r / min for 3 h until dissolved, and cooled to obtain a polymer matrix solution; the concentration of SA in this polymer matrix was 3 wt%, and the concentration of PVA was 9 wt%. (2) Add grape seed polyphenols (purity ≥82%) to the polymer matrix solution to a concentration of 3 wt%, stir at room temperature for 1.5 h, ultrasonically disperse at 150 W and 40 kHz for 20 min, and vacuum degas for 15 min to obtain the spinning solution.

[0063] The above-mentioned grape seed polyphenols were prepared by the following method: grape seeds were crushed and sieved, and 65% ethanol-water solution was added at a material-liquid ratio of 1:20. The mixture was ultrasonically extracted at 40℃ and 120 W for 30 min. After centrifugation, the mixture was concentrated under reduced pressure and vacuum dried to obtain grape seed polyphenol powder with a purity ≥82%.

[0064] The aforementioned grape seed polyphenols are a naturally occurring mixture of polyphenols found in grape seeds. The main active ingredient is proanthocyanidins, and it also contains phenolic substances such as catechins, epicatechins, and gallic acid. Proanthocyanidins are an important component of polyphenols, and the two are inclusive of each other. Example 1 used a 60% ethanol aqueous solution for extraction, resulting in a higher proportion of high-polymerization proanthocyanidins; therefore, it is labeled as proanthocyanidins. Example 2 used a 65% ethanol aqueous solution for extraction, which involved the dissolution of oligomeric polyphenols, resulting in a richer composition; therefore, both are collectively referred to as polyphenols. Both are mixed systems, differing only in purity and component ratios.

[0065] Example 3 This embodiment provides a spinning solution, the preparation method of which is as follows: (1) Under an 80℃ water bath, SA (viscosity 300 mPa) SA and PVA (degree of polymerization 2000, degree of alcoholysis 99%) were added to a mixed solvent (deionized water and anhydrous ethanol mixed at a volume ratio of 4:1), stirred at 300 r / min for 2 h until dissolved, and cooled to obtain a polymer matrix solution; the concentration of SA in this polymer matrix was 4 wt%, and the concentration of PVA was 8 wt%. (2) Add proanthocyanidins (purity ≥88%) to the polymer matrix solution to a concentration of 5 wt%, stir at room temperature for 1 h, disperse ultrasonically at 200 W and 40 kHz for 15 min, and degas under vacuum for 10 min to obtain the spinning solution. The above proanthocyanidins were prepared by the following method: grape seeds were crushed and sieved, and 70% ethanol-water solution was added at a material-liquid ratio of 1:20. The mixture was ultrasonically extracted at 40℃ and 150 W for 35 min, filtered, purified, concentrated, and freeze-dried to obtain high-purity proanthocyanidin powder.

[0066] Example 4 This embodiment provides an ion-responsive grape seed functional fiber membrane, which is prepared using the spinning solution provided in Example 1. The specific preparation method is as follows: Electrospinning was performed using the spinning solution provided in Example 1 at a voltage of 15 kV, a receiving distance of 15 cm, and a feed rate of 0.5 mL / h to obtain a continuous nanofiber membrane without bead-like defects. The nanofiber membrane was then immersed in a 0.1 mol / L calcium chloride solution for 10 min for post-crosslinking, rinsed with deionized water, and dried to obtain an ion-responsive grape seed functional fiber membrane.

[0067] The schematic diagram of the process for preparing the ion-responsive grape seed functional fiber membrane in this embodiment is shown below. Figure 1 As shown.

[0068] Example 5 This embodiment provides an ion-responsive grape seed functional fiber membrane, which is prepared using the spinning solution provided in Example 2. The specific preparation method is as follows: Electrospinning was performed using the spinning solution provided in Example 2 at a voltage of 20 kV, a receiving distance of 12 cm, and a feed rate of 1.0 mL / h to obtain a continuous nanofiber membrane without bead-like defects. The nanofiber membrane was then immersed in a 0.15 mol / L aluminum chloride solution for 8 min for post-crosslinking, rinsed with deionized water, and dried to obtain an ion-responsive grape seed functional fiber membrane, which can be used to prepare functional pillowcases.

[0069] Example 6 This embodiment provides an ion-responsive grape seed functional fiber membrane, which is prepared using the spinning solution provided in Example 3. The specific preparation method is as follows: Electrospinning was performed using the spinning solution provided in Example 3 at a voltage of 25 kV, a receiving distance of 10 cm, and a feed rate of 1.5 mL / h to obtain a continuous nanofiber membrane without bead-like defects. The nanofiber membrane was then immersed in a 0.2 mol / L calcium chloride solution for 15 min for post-crosslinking, rinsed with deionized water, and dried to obtain an ion-responsive grape seed functional fiber membrane, which can be used to prepare functional facial mask fabric.

[0070] Test case This experiment screened and optimized the ratio of polymer matrix in the spinning solution system, the extraction process of effective components from grape seeds, and the addition method of ionic crosslinking agent. The specific experimental methods and results are as follows: 1. Optimization of polymer matrix ratio: To investigate the effect of polymer matrix ratio on fiber forming performance, the process was based on Example 1, with the total polymer mass fraction fixed at 8 wt%. Only the mass ratio of sodium alginate to polyvinyl alcohol was adjusted to 1:2, 1:3, and 1:4, respectively. All other raw material compositions, grape seed polyphenol addition, extraction process, electrospinning parameters, and post-crosslinking conditions remained identical to Example 1. The fiber forming effects under different ratios are shown in Table 1. The comprehensive performance of the spinning solutions obtained with three different polymer matrix ratios was tested.

[0071] The viscosity of the spinning solution was determined using a rotational viscometer under constant temperature conditions of 25℃, according to GB / T 10247-2008 "Methods for Viscosity Measurement". A No. 3 rotor was selected and the dynamic viscosity of the spinning solution was measured at 30 r / min. During measurement, the instrument torque reading was ensured to be within 20%~80% of the effective range. Each sample was measured in triplicate, and the arithmetic mean was taken as the test result to determine the dynamic viscosity of the spinning solution.

[0072] Spinability is comprehensively evaluated through the electrospinning process. Under the set spinning parameters (voltage 15-25kV, receiving distance 10-15cm), the continuity of fiber jetting and the occurrence of phenomena such as fiber breakage, droplets, and needle blockage are observed and divided into three levels: "excellent", "good", and "average".

[0073] The results are shown in Table 1.

[0074] Table 1. Spinning solution properties corresponding to different polymer matrix ratios

[0075] As shown in Table 1, the spinning solution provided by this invention uses a specific polymer matrix compound system. By controlling the mass ratio of SA to PVA, the optimal balance between ionic responsiveness and spinning performance is achieved. This ensures the swelling and slow-release effect of sodium alginate under the stimulation of human sweat ions, while also taking advantage of the excellent mechanical properties of PVA to avoid problems such as fiber breakage and needle blockage during electrospinning. At the same time, it reduces the difficulty of preparing the spinning solution and is suitable for small-batch operation in the laboratory.

[0076] Furthermore, although the spinnability of the spinning solution at an SA:PVA mass ratio of 1:2 was rated as "average" in previous optimization experiments, this ratio exhibited the highest ion-responsive swelling rate. This invention selected this ratio to demonstrate the potential of the formulation in specific applications, such as medical dressings or high-efficiency skincare masks requiring rapid and significant swelling response to release active ingredients. By appropriately adjusting the electrospinning process parameters (e.g., increasing voltage, shortening the receiving distance), the drawback of average spinnability can be overcome, thereby obtaining functional fiber membranes with excellent ion-responsive properties. Therefore, the formulation provided in Example 3 represents a successful practice of a highly ion-responsive formulation after balancing the feasibility of the spinning process with the functionality of the material.

[0077] 2. Optimization of the extraction process for effective components from grape seeds: This experiment used ultrasonic-assisted extraction, setting different ultrasonic power and ultrasonic time during grape seed extraction to explore the optimal process parameters.

[0078] Ultrasonic-assisted extraction utilizes the cavitation effect, mechanical vibration, and thermal effect of ultrasound to significantly shorten extraction time and improve extraction efficiency. The specific extraction steps are as follows: 1) Raw material pretreatment: Hot reflux extraction was adopted: dried grape seed raw material was crushed and sieved to obtain grape seed powder. 60% ethanol aqueous solution was added at a material-to-liquid ratio of 1:20. The mixture was placed in a round-bottom flask and connected to a reflux condenser. It was extracted under constant temperature reflux at 80℃ for 2 h. After extraction, the solid residue was removed by hot filtration. The filtrate was collected and concentrated under reduced pressure at 45℃ and 0.08 MPa until there was no ethanol odor. The filtrate was then freeze-dried to obtain grape seed polyphenol powder, which mainly contains active ingredients such as proanthocyanidins, catechins, and gallic acid.

[0079] 2) Drying: Place the grape seeds in a drying oven and dry them at 40-50℃ until constant weight to remove moisture and prevent mold or hydrolysis during subsequent extraction.

[0080] 3) Grinding: Grind the dried grape seeds using a high-speed universal grinder to make them uniform in size.

[0081] 4) Sieving: Pass the crushed grape seed powder through a 40-60 mesh sieve and collect the sieve-undersized material to ensure the uniformity of the raw materials and increase the contact area between the solvent and the raw materials.

[0082] 5) Weighing and adding solvent: Accurately weigh a certain amount of grape seed powder and place it in the special extraction cup of the ultrasonic extractor. Add the extraction solvent (60% ethanol aqueous solution) at a material-to-liquid ratio of 1:20.

[0083] 6) Ultrasonic extraction: Place the extraction cup in the ultrasonic extractor and set the extraction parameters: set the ultrasonic power to 100W, 150W and 200W respectively, the extraction temperature to 50℃ (40-60℃ is acceptable), which can be controlled by a circulating water bath, and set the extraction time to 15 min, 20 min and 30 min respectively. After the extraction is completed, immediately remove the extraction cup and cool it to room temperature.

[0084] 7) Centrifugation: Subsequently, filter using a Buchner funnel or centrifuge at low speed (4000 r / min) for 15-20 minutes to separate the residue and extract. Collect the supernatant.

[0085] The optimal extraction process for proanthocyanidins, the effective components of grape seeds, was explored, and the results are shown in Tables 2 and 3.

[0086] Table 2. Effects of different ultrasonic powers on the extraction of effective components (proanthocyanidins) from grape seeds.

[0087] Extraction rate calculation: Extraction rate (%) = (Total mass of extract × Extract purity) / Total mass of raw materials × 100%.

[0088] Purity calculation: Purity (%) = (mass of active ingredients in the extract) / total mass of the extract × 100%.

[0089] Table 3. Effects of different ultrasound times on the extraction of active ingredients from grape seeds.

[0090] As shown in Tables 2 and 3, sonication at 150 W for 20 min is the most suitable condition for extracting the active ingredients from grape seeds, which can achieve high purity of the extract while ensuring the extraction rate.

[0091] 3. Optimization of the method for adding ionic crosslinking agents: The traditional crosslinking method was set as a control: the control group added the ionic crosslinking agent directly to the spinning solution before spinning; the experimental group used the process of spinning first and then soaking for crosslinking as described in Example 1 of this invention. The formulations and spinning parameters of the two groups were completely identical. The methods of spinning and then soaking for crosslinking were compared, and the performance of the fiber membranes prepared by the two methods was compared. The results are shown in Table 4.

[0092] The testing methods for each indicator are as follows: Spinning solution condition: Evaluated by visual inspection and viscosity measurement. Observe the appearance, flowability, and presence of particles or gel formation of the spinning solution at room temperature. Assess its spinnability by measuring the viscosity of the spinning solution at a specific shear rate using a rotational viscometer.

[0093] Fiber morphology: Observation was performed using scanning electron microscopy (SEM). After sputter-coating the fiber membrane samples with gold, their surface morphology, fiber diameter distribution, and the presence of defects such as nodules and breaks were observed under a scanning electron microscope. Fiber diameters were measured and statistically analyzed using image analysis software.

[0094] Encapsulation efficiency of active ingredient: determined by high-performance liquid chromatography (HPLC). A certain mass of fiber membrane is dissolved in a specific solvent, which disrupts the fiber structure and releases the active ingredient. The concentration of the active ingredient in the solution is determined by HPLC, the actual encapsulation amount is calculated, and compared with the theoretical dosage to obtain the encapsulation efficiency.

[0095] The cumulative release rate of simulated sweat over 72 hours was determined through an in vitro release experiment. Fiber membrane samples were placed in dialysis bags and immersed in phosphate-buffered saline (PBS) simulating a sweat environment. The release experiment was conducted in a shaker at 37°C. Samples were taken at set time points, and the concentration of the active ingredient in the release medium was determined by HPLC to calculate the cumulative release rate.

[0096] 30-day active ingredient retention rate: determined through long-term stability testing. Fiber membrane samples were stored under specified conditions (e.g., 25°C, 60% relative humidity) for 30 days. After 30 days, the remaining active ingredient content in the samples was determined using the same HPLC method as for "active ingredient encapsulation rate," and the retention rate was calculated.

[0097] Table 4 Optimization of the addition method of ionic crosslinking agent

[0098] As shown in Table 4, this invention abandons the traditional method of directly adding ionic crosslinking agents to the spinning solution. Instead, it adopts a post-treatment process of soaking and crosslinking after electrospinning. The crosslinking process is carried out after the fiber is formed. By controlling the concentration of the crosslinking solution, the soaking time, and the stirring rate, calcium ions are uniformly diffused inside the nanofibers and coordinate crosslink with sodium alginate. This can fundamentally avoid problems such as clumping, gelation, and needle blockage caused by excessive local crosslinking in the spinning solution stage. It significantly improves the uniformity and stability of the core-shell structure encapsulation system, further improves the encapsulation rate of grape seed active ingredients, and achieves a more stable and longer-lasting ion-responsive sustained-release effect.

[0099] 4. Antioxidant performance test of ion-responsive grape seed functional fiber membrane: The DPPH and ABTS methods were used, with the ion-responsive grape seed functional fiber membrane prepared in Example 4 of this invention as the test sample, cut into standard samples of 2 cm × 2 cm. Test working solutions of different concentrations were prepared, and reactions were carried out at 37°C. The free radical scavenging rate at each concentration was measured. Each group was subjected to three parallel experiments, and the average value was taken. The results are shown below. Figure 2 As shown.

[0100] Depend on Figure 2 It was found that the DPPH and ABTS radical scavenging rates both increased significantly with increasing working solution concentration, exhibiting a clear concentration dependence: at a sample concentration of 240 mg / mL, the DPPH radical scavenging rate reached over 93%, and the ABTS radical scavenging rate reached over 70%; even at low concentrations (60 mg / mL), the DPPH scavenging rate remained around 40%, and the ABTS scavenging rate remained around 20%. These results indicate that the ion-responsive grape seed functional fiber membrane provided by this invention possesses excellent and stable antioxidant properties and can effectively scavenge free radicals.

[0101] 5. Simulating the release of grape seed active ingredients under sweat ionization conditions: Using the ion-responsive fiber membrane prepared in Example 4 as the experimental material, with Na-containing... + Ca 2+Using simulated sweat as the release medium, samples were taken at a constant temperature of 37℃ at 1 h, 2 h, 4 h, 8 h, 12 h, 24 h, and 48 h to detect the release of grape seed active ingredients from the ion-responsive grape seed functional fiber membrane. The results are as follows: Figure 3 As shown.

[0102] Depend on Figure 3 It is known that the active ingredients in grape seeds are released slowly in response to ions, with a cumulative release rate of 60%-70% in 24 hours and tending to stabilize after 48 hours, indicating a controllable and long-lasting release.

[0103] 6. Retention rate test of active ingredients in grape seeds: The residual amount of proanthocyanidins, the active ingredient of grape seeds, in the fiber membrane was determined by the Folin-phenol method after being placed at room temperature and normal pressure. The retention rate was calculated with the initial loading amount as 100%. The 30-day retention rate of the encapsulation group of the present invention (the ion-responsive fiber membrane prepared in Example 4) was >60%, indicating that the core-shell encapsulation system of the present invention significantly inhibits oxidative inactivation and greatly improves the stability of the active ingredient.

[0104] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments, and various changes can be made within the scope of knowledge possessed by those skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof can be combined with each other unless otherwise specified.

Claims

1. A spinning solution, characterized in that, The spinning solution comprises the following components: a polymer matrix, an antioxidant, and a solvent; the polymer matrix comprises sodium alginate and polyvinyl alcohol; the mass ratio of sodium alginate to polyvinyl alcohol is 1:(2.5-5).

2. The spinning solution according to claim 1, characterized in that, The antioxidants include polyphenols; Preferably, the polyphenolic substances include one or more combinations of proanthocyanidins, catechins, gallic acid, and quercetin; Preferably, the polyphenols are extracted from grape seeds.

3. The spinning solution according to claim 1, characterized in that, The spinning solution comprises the following components by mass percentage: 5%-15% polymer matrix and 1%-6% antioxidant, with the balance being solvent.

4. The spinning solution according to claim 1, characterized in that, The solvent includes an aqueous solution of ethanol.

5. The method for preparing the spinning solution according to any one of claims 1-4, characterized in that, The preparation method includes the following steps: S1: Mix sodium alginate, polyvinyl alcohol and solvent, heat until completely dissolved, to obtain a polymer matrix solution; S2: Add an antioxidant to the polymer matrix solution obtained in step S1, stir and then ultrasonically disperse to obtain a spinning solution.

6. The preparation method according to claim 5, characterized in that, The conditions for ultrasonic dispersion in step S2 include ultrasonic dispersion for 15-40 min at 100-200 W and 30-50 kHz.

7. A method for preparing an ion-responsive functional fiber membrane, characterized in that, The preparation method includes the following steps: A1: Electrospinning is performed using the spinning solution according to any one of claims 1-4 to obtain a nanofiber membrane; A2: The nanofiber membrane obtained in step A1 is placed in an ion crosslinking agent solution for crosslinking to obtain an ion-responsive functional fiber membrane.

8. The preparation method according to claim 7, characterized in that, The voltage for electrospinning in step A1 is 15-25 kV; Preferably, the receiving distance for electrospinning in step A1 is 10-15 cm; Preferably, the liquid supply rate for electrospinning in step A1 is 0.5-1.5 mL / h; Preferably, the ionic crosslinking agent solution in step A2 contains calcium salt and / or aluminum salt.

9. The ion-responsive functional fiber membrane prepared by the preparation method of claim 7 or 8.

10. The application of the spinning solution of any one of claims 1-4 or the ion-responsive functional fiber membrane of claim 9 in the preparation of at least one of (1)-(5): (1) Clothing fabrics; (2) Skin care mask sheet; (3) Antibacterial bedding; (4) Sports protective gear; (5) Medical dressings.

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