A nanofiber membrane and raw material, preparation method and application thereof

Abstract

The application discloses a nanofiber membrane and raw materials, a preparation method and application thereof. The preparation method of ascorbic palmitate coated cyclodextrin comprises the following steps: (1) under the condition of stirring, ascorbic palmitate ethanol solution is added dropwise into a cyclodextrin aqueous solution, and then ultrasonic treatment is conducted to obtain material A; (2) the material A is mixed with a water-soluble polymer, and stirring is conducted in the dark, and then the solvent is removed, and the preparation is completed. The application uses cyclodextrin, and ascorbic palmitate is coated by using a specific process, so that the dispersion capacity of ascorbic palmitate in water is improved, and the prepared product has ideal coating capacity and release capacity, and the bioavailability of ascorbic palmitate is improved. The ascorbic palmitate coated cyclodextrin is combined with moisturizing agents, film-forming materials and other substances, and a nanofiber membrane prepared by electrospinning has good instant solubility, ideal antioxidant, moisturizing, skin tightening and anti-wrinkle effects, and high use safety.

Description

Technical Field

[0001] This application belongs to the field of nanofiber technology, and in particular relates to a nanofiber membrane, its raw materials, preparation method and application. Background Technology

[0002] Ascorbic acid is commonly used as an additive in food and cosmetics, possessing antioxidant properties and providing reducing power for a series of biochemical reactions. For example, in vivo, ascorbic acid participates in the biosynthesis of carnitine, histamine, and adrenal steroid hormones; it also provides electrons to enzymes, promoting the hydroxylation of hydroxyproline and lysine, essential substances for collagen and connective tissue synthesis; in body fluids, ascorbic acid acts as a protective antioxidant, scavenging free radicals in plasma and protecting cells from reactive oxygen species damage. Ascorbate palmitate retains the physiological activity of ascorbic acid and is used together with it as an antioxidant in food and cosmetics, offering advantages such as nutritional value and safety. Ascorbyl palmitate possesses all the physiological activities of vitamin C, exhibiting anti-inflammatory properties, reducing melanin production, promoting immunoglobulin synthesis, preventing pigmentation caused by trauma, sunburn, acne, etc., whitening the skin, maintaining skin elasticity, reducing wrinkles, and improving rough, pale, and sagging skin. It also delays natural and photoaging of the skin, acting as a highly effective antioxidant and oxygen free radical scavenger with a neutral pH. However, ascorbyl palmitate is insoluble in water and is currently typically used in oil-phase systems; otherwise, its bioavailability is low, greatly limiting its application.

[0003] Traditional face masks consist of a mask sheet and an essence. To prevent bacterial contamination, preservatives are often added. However, preservatives can easily cause allergies in sensitive skin, leading to problems such as redness and itching.

[0004] Therefore, there is an urgent need in this field to develop a cosmetic that can efficiently utilize the beauty benefits of ascorbyl palmitate and has high safety in use, improve the bioavailability of ascorbyl palmitate, broaden its application in the cosmetic field, and produce a face mask with ideal beauty effects and high safety in use. Summary of the Invention

[0005] The technical problem this application aims to solve is to overcome the shortcomings of existing technologies, such as the poor water solubility of ascorbate palmitate, limiting its use to oil-phase cosmetics and the poor safety profile of most face masks containing preservatives. This application provides a nanofiber membrane, its raw materials, preparation method, and applications. This application uses amphiphilic cyclodextrin and employs a specific process to encapsulate ascorbate palmitate, improving its dispersibility in water. The resulting product exhibits ideal encapsulation and release capabilities for ascorbate palmitate, thus enhancing its bioavailability. The cyclodextrin encapsulating ascorbate palmitate is then combined with humectants and film-forming materials to prepare a nanofiber membrane via electrospinning. The nanofiber membrane obtained in this application has good solubility and, when used in the cosmetic field, possesses ideal antioxidant, moisturizing, skin-firming, and anti-wrinkle effects, with high safety profile.

[0006] This application adopts the following technical solution to solve the above-mentioned technical problems:

[0007] This application provides a method for preparing cyclodextrin coated with ascorbate palmitate, specifically including the following steps:

[0008] (1) Under stirring conditions, ascorbate palmitate ethanol solution was added dropwise to cyclodextrin aqueous solution, and then ultrasonicated to obtain material A;

[0009] (2) The material A is mixed with the water-soluble polymer, stirred in the dark, and the solvent is removed.

[0010] In step (1), the concentration of ascorbate palmitate in the ascorbate palmitate ethanol solution can be 0.002 to 0.01 g / mL, preferably 0.005 to 0.00625 g / mL.

[0011] In step (1), the concentration of cyclodextrin in the cyclodextrin aqueous solution can be 0.007 to 0.021 g / mL, preferably 0.01 to 0.012 g / mL.

[0012] In step (1), the power of the ultrasound can be 150-300W, preferably 200-300W.

[0013] In step (1), the ultrasound time can be 10 to 20 minutes.

[0014] In step (2), the water-soluble polymer may include at least one of polyacrylate water-soluble polymers, pyrrolidone water-soluble polymers, and cellulose water-soluble polymers.

[0015] The water-soluble polyacrylate polymer may include sodium polyacrylate.

[0016] The water-soluble pyrrolidone polymer may include polypropylene pyrrolidone.

[0017] The cellulose-based water-soluble polymer may include at least one of sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose.

[0018] In step (2), the water-soluble polymer accounts for 0.1% to 0.5% of the mass of material A, preferably 0.1% to 0.4%, and more preferably 0.1% to 0.3%.

[0019] In step (2), the stirring time in the dark can be 48 to 72 hours.

[0020] In step (2), the temperature of the light-protected stirring can be 20-25°C.

[0021] In step (2), the method for removing the solvent may include vacuum evaporation and / or freeze drying.

[0022] When using the aforementioned reduced-pressure evaporation method, it can be carried out in a rotary evaporator as is customary in the art.

[0023] The temperature of the vacuum evaporation can be 30–45°C.

[0024] The time for vacuum evaporation can be 20 to 30 minutes.

[0025] This application also provides a cyclodextrin coated with ascorbate palmitate, which is prepared by the method described above for preparing cyclodextrin coated with ascorbate palmitate.

[0026] This application provides a raw material composition for an electrospinning solution, comprising the following components in parts by weight: 1 part of cyclodextrin coated with ascorbate palmitate as described above, 0.03 to 0.85 parts of humectant, and 3.33 to 12.5 parts of film-forming material.

[0027] In some embodiments, the humectant may include humectants commonly used in the cosmetics industry, generally including polysaccharide humectants and / or lipid humectants.

[0028] The polysaccharide moisturizer may include at least one of sodium hyaluronate, tremella polysaccharide, oat-β-glucan, chitosan, pullulan, and Ganoderma lucidum polysaccharide.

[0029] The lipid moisturizer may include squalane.

[0030] When the humectant includes sodium hyaluronate, the number-average molecular weight of the sodium hyaluronate can be 100–650 kDa. When the number-average molecular weight of the sodium hyaluronate is greater than 650 kDa, it will lead to excessively high solution viscosity, clogging of the needle, reduced spinning efficiency, and uneven nanofiber membranes produced using this electrospinning solution, resulting in problems such as beading.

[0031] In some embodiments, the film-forming material may include film-forming materials commonly used in the mask industry, generally including at least one of polyvinyl alcohol, pullulan, carboxymethyl agarose, pectin, gelatin, gum arabic, and sodium alginate.

[0032] In some embodiments, the humectant is preferably present in a weight fraction of 0.6 to 0.7 parts, for example, 0.67 parts.

[0033] In some embodiments, the film-forming material is preferably 5 to 7 parts by weight, for example, 6 parts.

[0034] This application also provides an electrospinning solution comprising 1 part of the raw material composition of the electrospinning solution as described above and 12 to 15 parts of water.

[0035] In some embodiments, the water in the electrospinning solution is preferably 12 to 13 parts by weight.

[0036] This application also provides a method for preparing the electrospinning solution as described above, comprising the following steps: mixing the components in the electrospinning solution evenly.

[0037] The mixing time can be the conventional time for this type of operation in the art, generally 12 to 24 hours.

[0038] The mixing temperature can be a temperature commonly used in this type of operation in the art, typically 20–25°C.

[0039] This application also provides a nanofiber membrane, which specifically includes the following steps: the electrospinning solution as described above is obtained by electrospinning.

[0040] In some embodiments, the electrospinning can be carried out on a substrate conventionally used in the field of electrospinning, and the substrate may include at least one of aluminum foil, Tencel film, silk film, pure cotton film, and nonwoven fabric.

[0041] In some embodiments, the voltage of the electrospinning may be 15–24V, preferably 16–20V.

[0042] In some embodiments, the feed rate of the electrospinning process can be 0.2 to 0.5 mL / h, preferably 0.3 to 0.4 mL / h.

[0043] In some embodiments, the receiving distance during the electrospinning process can be 15–20 cm, preferably 17–18 cm. According to conventional art, the receiving distance generally refers to the distance between the tip exit end and the substrate.

[0044] This application also provides the use of the nanofiber membrane described above as a raw material in the preparation of face masks and / or eye masks.

[0045] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of this application.

[0046] All reagents and raw materials used in this application are commercially available.

[0047] The positive and progressive effects of this application are as follows: This application uses amphiphilic cyclodextrin and employs a specific process to coat ascorbate palmitate, thereby improving the dispersibility of ascorbate palmitate in water. Moreover, the resulting product has ideal coating and release capabilities for ascorbate palmitate, thus improving the bioavailability of ascorbate palmitate.

[0048] Cyclodextrin coated with ascorbate palmitate is then combined with humectants and film-forming materials to prepare nanofiber membranes via electrospinning. The nanofiber membranes prepared in this application exhibit good solubility and, when used in the cosmetics field, possess ideal antioxidant, moisturizing, skin-firming, and anti-wrinkle effects, with high safety profile. Furthermore, the preparation method of the nanofiber membranes is simple and easy to implement, requiring only basic equipment, making it suitable for industrial production. This provides a new avenue for the future utilization of ascorbate palmitate and the development of novel facial masks. In addition, due to the porous and thin characteristics of the nanofiber membranes, they offer excellent breathability and adherence when used in facial masks or eye masks. Attached Figure Description

[0049] This application can be better understood by referring to the description given below in conjunction with the accompanying drawings. These drawings, together with the detailed description below, are included in and form part of this specification, and are used to further illustrate preferred embodiments of the application and explain the principles and advantages of the application. Wherein:

[0050] Figure 1 This is a scanning electron microscope image of the nanofiber membrane prepared in Example 4;

[0051] Figure 2 This is a comparison diagram of the water solubility of the nanofiber membrane and ascorbate palmitate powder prepared in Example 4;

[0052] Figure 3 Comparison of infrared spectra of cyclodextrin, ascorbate palmitate, and cyclodextrin coated with ascorbate palmitate in Example 1;

[0053] Figure 4 Comparison of thermogravimetric analysis of ascorbate palmitate and cyclodextrin coated with ascorbate palmitate in Example 1;

[0054] Figure 5 The diagram shows the comparison of ROS content in human skin fibroblasts after treatment of damaged human skin fibroblasts in Example 4, Comparative Example 1, Blank Control Group and Model Group.

[0055] Figure 6 This is a comparison chart of the MDA content in human skin fibroblasts after treatment of damaged human skin fibroblasts in Example 4, Comparative Example 1, Blank Control Group and Model Group.

[0056] Figure 7 This is a comparison chart of COL-I content in human skin fibroblasts after treatment of damaged human skin fibroblasts in Example 4, Comparative Example 1, Blank Control Group and Model Group;

[0057] Figure 8 This is a comparison of catalase activity in human skin fibroblasts after treatment of damaged human skin fibroblasts in Example 4, Comparative Example 1, Blank Control Group and Model Group.

[0058] Figure 9 This is a comparison chart showing the scavenging effects of Example 4 and Comparative Example 1 on DPPH free radicals. Detailed Implementation

[0059] The present application is further illustrated below by way of embodiments, but these embodiments are not intended to limit the scope of the present application. Experimental methods not specifically described in the following embodiments are performed according to conventional methods and conditions, or as selected in accordance with the product instructions.

[0060] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0061] Example 1: Preparation of cyclodextrin coated with ascorbate palmitate

[0062] (1) Dissolve 0.5g of ascorbate palmitate in 80mL of ethanol and stir until homogeneous to obtain an ascorbate palmitate ethanol solution; dissolve 2.2g of cyclodextrin in 180mL of deionized water and stir until homogeneous to obtain a cyclodextrin aqueous solution; under stirring conditions, slowly add the ascorbate palmitate ethanol solution to the cyclodextrin aqueous solution and sonicate for 20min under ultrasonic power of 200W to obtain material A;

[0063] (2) Add sodium polyacrylate to material A obtained in step (1), the sodium polyacrylate accounts for 0.2% of the mass of material A, and stir at 25°C in the dark for 72 hours; put the stirred solution into a rotary evaporator to evaporate under reduced pressure to remove the solvent, the heating temperature of the rotary evaporator is 35°C, and the time of reduced pressure evaporation is 20 minutes; freeze-dry the concentrated solution in a freeze dryer until all the liquid evaporates to obtain cyclodextrin coated with ascorbate palmitate.

[0064] Example 2: Preparation of cyclodextrin coated with ascorbate palmitate

[0065] Compared with Example 1, the only difference is that the sodium polyacrylate added in step (2) is replaced by equal amounts of polypropylene pyrrolidone, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose or hydroxyethyl cellulose. Other conditions and parameters are the same as in Example 1. The cyclodextrins coated with ascorbate palmitate are numbered 2-1, 2-2, 2-3 and 2-4 respectively.

[0066] Example 3: Preparation of cyclodextrin coated with ascorbate palmitate

[0067] Compared with Example 1, the only difference is the amount of sodium polyacrylate added in step (2). The mass percentage of sodium polyacrylate in material A was replaced with 0.1%, 0.3%, 0.4% and 0.5%, respectively, and other conditions and parameters were the same as in Example 1. The cyclodextrins coated with ascorbate palmitate were numbered 3-1, 3-2, 3-3 and 3-4, respectively.

[0068] Example 4: Preparation of Nanofiber Membranes

[0069] (1) Dissolve 0.5g of ascorbate palmitate in 80mL of ethanol and stir until homogeneous to obtain an ascorbate palmitate ethanol solution; dissolve 2.2g of cyclodextrin in 180mL of deionized water and stir until homogeneous to obtain a cyclodextrin aqueous solution; under stirring conditions, slowly add the ascorbate palmitate ethanol solution to the cyclodextrin aqueous solution and sonicate for 20min under ultrasonic power of 200W to obtain material A;

[0070] (2) Add sodium polyacrylate to material A obtained in step (1), the sodium polyacrylate accounts for 0.2% of the mass percentage of material A, and stir at 25°C in the dark for 72 hours; put the stirred solution into a rotary evaporator to evaporate under reduced pressure to remove the solvent, the heating temperature of the rotary evaporator is 35°C, and the time of reduced pressure evaporation is 20 minutes; freeze-dry the concentrated solution in a freeze dryer until all the liquid evaporates to obtain cyclodextrin coated with ascorbate palmitate;

[0071] (3) Mix 1g of cyclodextrin coated with ascorbate palmitate obtained in step (2), 0.67g of sodium hyaluronate and 6g of polyvinyl alcohol, dissolve in 100mL of deionized water, stir at 25℃ for 24h to obtain electrospinning solution, and prepare nanofiber membrane on nonwoven fabric by electrospinning; wherein, the voltage during electrospinning is 16V, the feeding speed is 0.3mL / h and the receiving distance is 17cm.

[0072] Comparative Example 1

[0073] (1) Dissolve 0.5g of ascorbate palmitate in 80mL of ethanol and stir until homogeneous to obtain an ethanol solution of ascorbate palmitate; dissolve 2.2g of cyclodextrin in 180mL of deionized water and stir until homogeneous to obtain an aqueous solution of cyclodextrin; under stirring conditions, slowly add the ethanol solution of ascorbate palmitate to the aqueous solution of cyclodextrin and stir at 25℃ in the dark for 72h; place the stirred solution in a rotary evaporator to evaporate under reduced pressure to remove the solvent. The heating temperature of the rotary evaporator is 35℃ and the time for reduced pressure evaporation is 20min; freeze-dry the concentrated solution in a freeze dryer until all the liquid evaporates to obtain cyclodextrin coated with ascorbate palmitate.

[0074] (2) Mix 1g of cyclodextrin coated with ascorbate palmitate obtained in step (1), 0.67g of sodium hyaluronate and 6g of polyvinyl alcohol, dissolve in 100mL of deionized water, stir at 25℃ for 24h to obtain electrospinning solution, and prepare nanofiber membrane on nonwoven fabric by electrospinning; wherein, the voltage during electrospinning is 16V, the feeding speed is 0.3mL / h and the receiving distance is 17cm.

[0075] Comparative Example 2

[0076] (1) Dissolve 0.5g of ascorbate palmitate in 80mL of ethanol and stir until homogeneous to obtain an ascorbate palmitate ethanol solution; dissolve 2.2g of cyclodextrin in 180mL of deionized water and stir until homogeneous to obtain a cyclodextrin aqueous solution; under stirring conditions, slowly add the ascorbate palmitate ethanol solution to the cyclodextrin aqueous solution and sonicate for 20min under ultrasonic power of 200W to obtain material A;

[0077] (2) Transfer the material A obtained in step (1) to a rotary evaporator to remove the solvent by vacuum evaporation. The heating temperature of the rotary evaporator is 35°C and the vacuum evaporation time is 20 min. The concentrated solution is freeze-dried in a freeze dryer until all the liquid evaporates to obtain cyclodextrin coated with ascorbate palmitate.

[0078] Comparative Example 3

[0079] (1) Dissolve 0.5g of ascorbate palmitate in 80mL of ethanol and stir until homogeneous to obtain an ascorbate palmitate ethanol solution; dissolve 2.2g of cyclodextrin in 180mL of deionized water and stir until homogeneous to obtain a cyclodextrin aqueous solution; under stirring conditions, slowly add the ascorbate palmitate ethanol solution to the cyclodextrin aqueous solution and sonicate for 20min under ultrasonic power of 200W to obtain material A;

[0080] (2) The material A obtained in step (1) was stirred in the dark at 25°C for 72 hours. After stirring, it was transferred to a rotary evaporator to remove the solvent by vacuum evaporation. The heating temperature of the rotary evaporator was 35°C and the vacuum evaporation time was 20 minutes. The concentrated solution was freeze-dried in a freeze dryer until all the liquid evaporated to obtain cyclodextrin coated with ascorbate palmitate.

[0081] Example 1

[0082] The encapsulation rate of ascorbate palmitate in the cyclodextrins coated with ascorbate palmitate prepared in Examples 1, 2-1 to 2-4, 3-1 to 3-4, and Comparative Examples 1 to 3 was tested.

[0083] Take a certain amount (W) of the ascorbate palmitate-coated cyclodextrin prepared in the above examples or comparative examples, dissolve it in water, and measure its ultraviolet absorbance at 247 nm. Calculate the mass of ascorbate palmitate in the solution according to the standard curve. That is, the mass of ascorbate palmitate in the ascorbate palmitate-coated cyclodextrin with a mass of W is labeled as H.

[0084] The encapsulation efficiency of ascorbate palmitate was calculated using the following formula, and the results are shown in Table 1:

[0085] R = H / E × 100%;

[0086] Where H is the mass of ascorbate palmitate in the cyclodextrin coated with ascorbate palmitate; E is the amount of ascorbate palmitate fed when W weight of cyclodextrin coated with ascorbate palmitate is obtained.

[0087] Table 1

[0088] serial number Ascorbate palmitate encapsulation rate Example 1 39.6％ Example 2-1 28.07％ Example 2-2 35.15％ Example 2-3 31.24％ Examples 2-4 25.92％ Example 3-1 35.54％ Example 3-2 42.5％ Example 3-3 43.2％ Examples 3-4 45.1％ Comparative Example 1 17.11％ Comparative Example 2 16.62％ Comparative Example 3 20.8％

[0089] The results showed that, compared with Example 1, in Comparative Examples 1-3, the encapsulation rate of ascorbate palmitate was significantly reduced by using light-protected stirring alone, using ultrasound alone, or not adding water-soluble polymers during the preparation process. This reduced the utilization rate of ascorbate palmitate and increased the preparation cost.

[0090] According to the results of Examples 1, 2-1 to 2-4, when the water-soluble polymers are sodium polyacrylate, sodium carboxymethyl cellulose and hydroxypropyl methylcellulose, the cyclodextrin coated with ascorbate palmitate has a higher encapsulation rate of ascorbate palmitate.

[0091] According to the results of Examples 1, 3-1 to 3-4, when the amount of water-soluble polymer sodium polyacrylate added is 0.1% to 0.5%, the encapsulation rate is between 35.54% and 45.1%, and the encapsulation rate increases with the increase of the amount of water-soluble polymer sodium polyacrylate added.

[0092] Example 2

[0093] The ascorbate palmitate release rate of the cyclodextrins coated with ascorbate palmitate prepared in Examples 1, 3-1 to 3-4 above was tested, and the results are shown in Table 2.

[0094] The test method includes the following steps: 2g of the sample to be tested is placed in a 1000kDa dialysis membrane bag, dissolved in 5mL of PBS, and then the bag is immersed in 30mL of PBS (10mM, 7.4) and sealed with sealing film. The solution is stirred at 150rpm in a shaker. The released sample (3mL) is removed at predetermined time intervals, and the concentration of ascorbate palmitate is measured at 247nm using a UV spectrophotometer. The release rate is calculated according to the following formula. After measurement, the sample is returned to the beaker, and dialysis continues. The results are shown in Table 2.

[0095] Ascorbate palmitate release rate = ascorbate palmitate concentration in solution (mg / mL) × 30mL / ascorbate palmitate mass in nanofiber membrane (mg) × 100%.

[0096] Table 2

[0097]

[0098] The results showed that when the amount of sodium polyacrylate added was in the range of 0.1% to 0.4% of the mass of material A, the release rate could reach more than 80%; when the amount of sodium polyacrylate added was greater than 0.5% of the mass of material A, it had a significant impact on the release rate, and the release rate decreased significantly.

[0099] Example 3

[0100] The microstructure of the nanofiber membrane prepared in Example 4 was observed using a JSM-7800F scanning electron microscope at a test voltage of 5 kV. Figure 1 .

[0101] As can be seen from the figure, the nanofiber membrane prepared in Example 4 has an average diameter of 0.33 μm and no beaded structure is formed, indicating that the cyclodextrin, sodium hyaluronate, and polyvinyl alcohol coated with ascorbate palmitate can be uniformly mixed. In addition, during the preparation process of the nanofiber membrane in Example 4, the liquid spraying during spinning is smooth and it is not easy to clog the needle. When it is cut into face masks and eye masks, it has good conformability.

[0102] Example 4

[0103] Take 1cm 2 The nanofiber membrane and ascorbate palmitate powder prepared in Example 4 were dissolved in 1 mL of water, and the results are shown in [Figure 4]. Figure 2 . Figure 2 In the figures, group a corresponds to the nanofiber membrane prepared in Example 4, and group b corresponds to the ascorbate palmitate powder.

[0104] from Figure 2 As can be seen, the nanofiber membrane prepared in Example 4 has excellent solubility, while the ascorbate palmitate powder is almost insoluble. Therefore, the method of this application can significantly improve the dispersibility of ascorbate palmitate in water.

[0105] Example 5

[0106] Infrared spectroscopy measurements were performed on cyclodextrin (CD), ascorbate palmitate (AP), and the ascorbate palmitate-coated cyclodextrin prepared in Example 1, respectively. The results are as follows: Figure 3 As shown.

[0107] The results showed that the cyclodextrin sample at 1600 cm⁻¹ -1 The surface is smooth with no obvious characteristic peaks, while the ascorbate palmitate sample shows a peak at 1600 cm⁻¹. -1 The cyclodextrin coated with ascorbate palmitate prepared in Example 1 contains a C=O characteristic peak at 1600 cm⁻¹. -1 The presence of characteristic peaks similar to those of ascorbate palmitate nearby confirms that ascorbate palmitate was successfully encapsulated within the cyclodextrin.

[0108] Example 6

[0109] Thermogravimetric analysis was performed on two samples: ascorbate palmitate and the ascorbate-coated cyclodextrin prepared in Example 1. The results are shown in the figure. Figure 4 .

[0110] like Figure 4As shown, the pure ascorbate palmitate sample reached its thermal decomposition temperature at 208.06℃, while the thermal decomposition temperature of the cyclodextrin coated with ascorbate palmitate prepared in Example 1 can reach as high as 290.01℃, which proves that the thermal stability of the system is improved after the cyclodextrin is coated with ascorbate palmitate.

[0111] Example 7

[0112] In this experiment, nanofiber membranes prepared in Example 4 and Comparative Example 1 were used to prepare nanofiber membrane solutions with a concentration of 1 mg / mL in DMEM medium, which were then used as test solutions. Damaged human skin fibroblasts were treated with the above-prepared test solutions, and the expression levels of reactive oxygen species (ROS), collagen (COL-I), malondialdehyde (MDA), and catalase (CAT) in human skin fibroblasts were tested to evaluate the ability of the above-prepared nanofiber membranes to resist oxidative stress damage.

[0113] Experimental group testing method: HSF cells were counted, and the cell concentration was adjusted to achieve a cell density of 1.5 x 10⁻⁶ cells in a 6-well culture plate. 6 Cells / well. Incubate overnight at 37℃ and 5% CO2. After discarding the culture medium, treat HSF cells with 100 μmol / L H2O2 for 2 h, remove, place on ice, wash cells to remove H2O2, and add 2 mL of the test solution to each well for 24 h. After culture, discard the culture medium, wash cells with PBS, add 0.25% trypsin, digest HSF cells from the six-well plate, centrifuge to collect the cell pellet, and follow the ROS detection kit instructions. Detect fluorescence at an excitation wavelength of 488 nm and an emission wavelength of 525 nm. Analyze the effect of the nanofiber membranes prepared in Example 4 and Comparative Example 1 on the reactive oxygen species (ROS) content in HSF. Results are shown in [Figure 1]. Figure 5 And Table 3.

[0114] HSF cells were counted, and the cell concentration was adjusted to a density of 1.5 x 10⁻⁶ cells in a 6-well culture plate. 6 Cells / well. Incubate overnight at 37℃ and 5% CO2. After discarding the culture medium, treat HSF cells with 100 μmol / L H2O2 for 2 h. Remove cells, place on ice, wash cells to remove H2O2, and add 2 mL of the test solution to each well for 24 h. After culture, discard the culture medium, wash with PBS, and add 100 μL of lysis buffer to each well to lyse the cells, obtaining cell lysates. Centrifuge at 12000g for 5 min at 4℃, discard the precipitate, and obtain the supernatant of the cell lysates. Detect the MDA and Col-I content in the supernatant of the cell lysates according to the kit. Analyze the effects of the nanofiber membranes prepared in Example 4 and Comparative Example 1 on the MDA and Col-I content in damaged HSF cells. The results are shown in the table below. Figure 6 and Figure 7And Table 3. The CAT activity in the supernatant of cell lysates was detected according to the kit. The effects of the nanofiber membranes prepared in Example 4 and Comparative Example 1 on CAT activity in damaged HSF cells were analyzed. The results are shown in Table 3. Figure 8 And Table 3.

[0115] Blank control group test method: Compared with the experimental group, the blank control group was not treated with H2O2, and no test solution was added. Other treatment conditions were the same as those of the experimental group.

[0116] Model group testing method: Compared with the experimental group, HSF cells were treated with 100 μmol / L H2O2 for 2 h without any test solution, and other treatment conditions were the same as those in the experimental group.

[0117] Table 3

[0118]

[0119] The free radical aging theory posits that the intensification of the contradiction between excessive ROS production in mitochondria and weakened ROS defense capabilities ultimately leads to aging. Therefore, the antioxidant effect of a product can be assessed by detecting its impact on the ROS content in HSF (Highly Saturated Cells). A decrease in ROS content in cells demonstrates the product's antioxidant efficacy. Figure 5 As shown in Table 3, after treating damaged human skin fibroblasts with the nanofiber membrane prepared in Example 4, the intracellular ROS content was significantly reduced, even falling below that of the blank control group. While the intracellular ROS content was reduced somewhat after treating human skin fibroblasts with the nanofiber membrane prepared in Comparative Example 1, the reduction was limited, and the ROS content remained higher than that of the blank control group.

[0120] Excess free radicals in the body attack unsaturated fatty acids, causing oxidation and increasing the level of lipid peroxidation product MDA. Therefore, the level of MDA directly reflects the level of oxygen free radicals in the body, as well as the intensity and rate of peroxidation, and is an important indicator of the degree of tissue and cell damage caused by peroxidation. Figure 6 As shown, the MDA content in damaged HSF cells decreased significantly under the action of the nanofiber membrane prepared in Example 4. However, under the action of the nanofiber membrane prepared in Comparative Example 1, the MDA content in damaged HSF cells was close to that in the model group, indicating that it had almost no antioxidant capacity. Figure 6 The symbol "**" indicates that the difference compared with the model group is highly significant, and **p<0.01.

[0121] The higher the collagen content in human skin fibroblasts, the better the skin elasticity. For example... Figure 7As shown in Table 3, after treating damaged human skin fibroblasts with the nanofiber membrane prepared in Example 4, the COL-I content in the human skin fibroblasts was significantly higher than that in the model group. After treating damaged human skin fibroblasts with the nanofiber membrane prepared in Comparative Example 1, the intracellular COL-I content also increased slightly, but the increase was significantly lower than that in Example 4. Therefore, the nanofiber membrane prepared in Example 4 has a more ideal anti-aging effect on the skin. Figure 7 The asterisk (*) indicates that the difference compared with the model group is statistically significant (p < 0.05).

[0122] Catalase is a naturally occurring superoxide free radical scavenger in the body, capable of breaking down free radicals into water and oxygen. Higher catalase levels in human skin fibroblasts indicate stronger antioxidant capacity. Figure 8 As shown, the nanofiber membrane prepared in Example 4 significantly increased the intracellular catalase activity of damaged human skin fibroblasts after treatment, exceeding that of the blank control group. In contrast, the nanofiber membrane prepared in Comparative Example 1 had a limited effect on increasing intracellular catalase activity.

[0123] The results above indicate that the nanofiber membrane prepared in Example 4 can better protect human skin fibroblasts from oxidative stress damage.

[0124] Example 8

[0125] The determination of DPPH free radical scavenging activity: DPPH (1,1-disphenyl-2-picry1-hydrazy1), chemically named 1,1-diphenyl-2-trinitrophenylhydrazine, with the molecular formula (C6H5)2N-NC6H5(NO2)3, has an unpaired valence electron on one atom of the nitrogen bridge. The orbital motion of this electron is almost canceled out by the molecular structure. The capture of DPPH free radicals is commonly used as an indicator of antioxidant capacity. A higher DPPH free radical scavenging rate indicates a more ideal antioxidant effect.

[0126] Test method:

[0127] To prepare a 0.12 mg / mL DPPH ethanol solution: Weigh 12 mg of 1,1-diphenyl-2-trinitrophenylhydrazine into a 100 mL volumetric flask and dilute to 100 mL with anhydrous ethanol.

[0128] The nanofiber membranes prepared in Example 4 and Comparative Example 1 were dissolved in deionized water to prepare test solutions of different concentrations. The mass-to-volume ratios of the nanofiber membranes in the test solutions were 0.04 mg / mL, 0.2 mg / mL, 1 mg / mL, and 5 mg / mL, respectively. In a 96-well plate, 100 μL of DPPH radical solution and 100 μL of test solution were added to each well as the sample group; 100 μL of DPPH radical solution and 100 μL of deionized water were added to each well as the blank group; 100 μL of deionized water and 100 μL of test solution were added to each well as the sample baseline group; and 200 μL of deionized water was added to each well as the solvent baseline group. After reacting at room temperature for 30 min, the absorbance at 517 nm was measured using a microplate reader. The DPPH radical scavenging rate was calculated using the following formula:

[0129] DPPH free radical scavenging rate (%) = [1-(A 样品组 -A 样品底值 ) / (A 空白组 -A 溶剂底值 )]×100%.

[0130] The DPPH free radical scavenging rate of the nanofiber membranes prepared in Example 4 and Comparative Example 1 was tested, and the results are shown in Table 4 and 1. Figure 9 The results showed that the nanofiber membrane prepared in Example 4 had a better antioxidant effect than the nanofiber membrane prepared in Comparative Example 1. The nanofiber membrane prepared in Example 4 not only improved the dispersion ability of ascorbate palmitate in water, but also had a more ideal release effect.

[0131] Table 4

[0132]

[0133] Example 9

[0134] In the experimental group, the nanofiber membrane prepared in Example 4 was cut into 4cm × 4cm pieces. A small amount of deionized water was sprayed onto the inner forearm of the subject to moisten it. The nanofiber membrane was then applied to the inner forearm for 15 minutes and removed. The moisture content of the applied sample was measured at 1h, 2h, and 4h using a CK820 skin moisture content meter, and the rate of change in moisture content was calculated. The results are shown in Table 5. Moisture content change rate = (A1 - A0) / A1 × 100%; where A0 is the initial moisture content value without any sample applied; and A1 is the moisture content value after a period of application.

[0135] The control group was sprayed with a small amount of deionized water and did not have a membrane applied. The testing method was the same as that for the experimental group, and the rate of change in moisture content was tested at different time periods.

[0136] Temperature: 20±1℃, Humidity: 50±5%, N=30.

[0137] Table 5

[0138] time Experimental group (Example 4) control group 1h 41.73％ 31.41％ 2h 15.09％ 1.78％ 4h 12.92％ 0.24％

[0139] The results showed that, compared with the control group, the application of the nanofiber membrane prepared in Example 4 significantly increased the skin's moisture content.

[0140] Example 10

[0141] Human patch testing is primarily used to detect the irritation of the final cosmetic product or raw material. This invention conducts a human patch test on the nanofiber membrane obtained in Example 4 to assess its potential skin irritation. According to the Cosmetic Safety Technical Specifications (2015 edition), 30 volunteers aged 18-60 years who met the testing requirements were selected as subjects. A 50mm... 2 The sample was placed in a plaque applicator, and 0.02 mL of deionized water was added to the sample to form the test group plaque applicator. The control plaque applicator was left empty to serve as the blank control group. The test group plaque applicators and the blank control group plaque applicators were fixedly applied to the flexor side of the subject's forearm using non-irritating adhesive tape. The tape was gently pressed with the palm of the hand to ensure even application to the skin, and the application was left on for 24 hours (during which time the volunteers could not remove the plaque applicators or allow the test site to come into contact with water). The plaque applicators were then removed, and the skin reaction was observed 30 minutes after the removal of the plaque applicators.

[0142] Among them, *"-" = negative reaction;

[0143] Grade 1 adverse reaction: "±" = Suspicious reaction: only slight erythema;

[0144] Secondary adverse reactions: "+" = weak positive reaction (erythema reaction): erythema, infiltration, edema, and papules may be present;

[0145] Grade III adverse reaction: "++" = strong positive reaction (herpes reaction): erythema, infiltration, edema, papules, vesicles, the reaction may extend beyond the test area;

[0146] Grade IV adverse reaction: "+++" = extremely strong positive reaction (confluent herpes simplex reaction): obvious erythema, severe infiltration, edema, confluent herpes simplex, reaction beyond the test area.

[0147] As shown in Table 6, the nanofiber membrane prepared in Example 4 did not cause any adverse reactions after being applied for 30 minutes, 24 hours and 48 hours, indicating that the nanofiber membrane prepared in Example 4 has good safety for human skin.

[0148] Table 6

[0149]

[0150] Example 11

[0151] Skin elasticity and firmness testing are important indicators for evaluating the firming effect of cosmetics and are the main methods for evaluating the anti-aging effect of cosmetics. This invention conducts skin elasticity and firmness testing on the nanofiber membrane prepared in Example 4 to evaluate its anti-aging effect.

[0152] According to the "Test Method for the Effect of Cosmetics on Skin Elasticity" (T / ZHCA005-2019), 30 volunteers aged 25-60 years who had not undergone facial cosmetic surgery or other cosmetic procedures that might affect skin elasticity within the past 3 months were selected. After cleansing their faces, the volunteers applied the nanofiber membrane prepared in Example 4 to their cheeks for 20 minutes daily. After application, parameters R0 and R1 were measured using a cutometer. R0 represents the total deformation of the skin during the first absorption phase of the elasticity test, measured in mm, characterizing skin firmness; the smaller the R0, the firmer the skin. R1 represents the ratio of the total extension during the first absorption phase to the reduction during release. The closer R1 is to 100%, the better the skin elasticity. No sample was applied to the blank control group.

[0153] The results are shown in Table 7. After four weeks of continuous use of the nanofiber membrane prepared in Example 4, the skin firmness parameter R0 decreased significantly, while the blank control area showed no significant change. This indicates that the skin firmness was improved after using the nanofiber membrane prepared in Example 4. The skin elasticity parameter R1 increased significantly compared to the initial value, while the blank control area showed no change, indicating that skin elasticity was improved after using the nanofiber membrane prepared in Example 4. Therefore, the nanofiber membrane prepared in this application has ideal anti-aging effects.

[0154] Table 7

[0155]

[0156] Example 12

[0157] According to the "Clinical Evaluation Method for the Efficacy of Cosmetics in Improving Crow's Feet" (T / SHRH 018-2019), 30 volunteers aged 18-60 years with fine lines or wrinkles at the corners of their eyes were selected. These participants had not participated in other clinical studies within the past three months. Rapid optical imaging technology was used to image and analyze the corners of the eyes before and after product use. The sample was applied to the corners of the eyes for 20 minutes daily. The roughness parameter Rz of the wrinkles at the corners of the eyes was measured using the FOITS rapid optical imaging system before and after 4 weeks of application. The results are shown in Table 8. The experimental group applied the nanofiber membrane prepared in Example 4, while the blank control group did not apply any sample.

[0158] The results showed that, compared with the control group, the roughness parameter Rz of the crow's feet wrinkles was significantly improved after 4 weeks of use of the nanofiber membrane prepared in Example 4, indicating that the crow's feet wrinkles were improved, that is, the nanofiber membrane prepared in Example 4 has ideal anti-wrinkle properties.

[0159] Table 8

[0160]

[0161] Finally, it should be noted that the terms “comprising,” “including,” or any other variations thereof in this application are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0162] Although this application has been disclosed above through the description of specific embodiments, it should be understood that those skilled in the art can devise various modifications, improvements, or equivalents to this application within the spirit and scope of the appended solutions. Such modifications, improvements, or equivalents should also be considered to be included within the scope of protection claimed in this application.

Claims

1. A method for preparing a cyclodextrin coated with ascorbyl palmitate for use in cosmetics, characterized in that, Includes the following steps: (1) Under stirring conditions, ascorbate palmitate ethanol solution is added dropwise to cyclodextrin aqueous solution, and then ultrasonicated to obtain material A, wherein the concentration of ascorbate palmitate in the ascorbate palmitate ethanol solution is 0.002~0.01g / mL, and the concentration of cyclodextrin in the cyclodextrin aqueous solution is 0.007~0.021g / mL; (2) The material A is mixed with the water-soluble polymer, stirred in the dark, and the solvent is removed; wherein the water-soluble polymer is sodium polyacrylate; the water-soluble polymer accounts for 0.1% to 0.4% of the mass of the material A.

2. The method for preparing cyclodextrin coated with ascorbate palmitate as described in claim 1, characterized in that, The preparation method satisfies at least one of the following conditions: In step (1), the power of the ultrasound is 150~300W; In step (1), the ultrasound duration is 10-20 minutes; In step (2), the water-soluble polymer accounts for 0.1% to 0.3% of the mass of material A; In step (2), the stirring time in the dark is 48~72h; In step (2), the temperature for stirring in the dark is 20~25℃; In step (2), the solvent removal method includes vacuum evaporation and / or freeze drying.

3. The method for preparing cyclodextrin coated with ascorbate palmitate as described in claim 2, characterized in that, The preparation method satisfies at least one of the following conditions: In step (1), the concentration of ascorbate palmitate in the ascorbate palmitate ethanol solution is 0.005~0.00625g / mL; In step (1), the concentration of cyclodextrin in the cyclodextrin aqueous solution is 0.01~0.012 g / mL; In step (1), the power of the ultrasound is 200~300W.

4. A cyclodextrin coated with ascorbate palmitate, characterized in that, It is prepared by the method for preparing ascorbate palmitate-coated cyclodextrin as described in any one of claims 1-3.

5. A raw material composition for an electrospinning solution, characterized in that, The raw material composition of the electrospinning solution comprises the following components in parts by weight: One part of the cyclodextrin coated with ascorbate palmitate as described in claim 4, 0.03 to 0.85 parts of humectant and 3.33 to 12.5 parts of film-forming material.

6. The raw material composition of the electrospinning solution as described in claim 5, characterized in that, The raw material composition satisfies at least one of the following conditions: The moisturizer includes polysaccharide moisturizers and / or lipid moisturizers; The film-forming material includes at least one of polyvinyl alcohol, pullulan, carboxymethyl agarose, pectin, gelatin, gum arabic, and sodium alginate; The humectant is present in an amount of 0.6 to 0.7 parts by weight; The film-forming material is in the form of 5 to 7 parts by weight.

7. The raw material composition of the electrospinning solution as described in claim 6, characterized in that, The raw material composition satisfies at least one of the following conditions: The polysaccharide moisturizer includes at least one of sodium hyaluronate, tremella polysaccharide, oat-β-glucan, chitosan, pullulan, and Ganoderma lucidum polysaccharide; the lipid moisturizer includes squalane.

8. The raw material composition of the electrospinning solution as described in claim 7, characterized in that, The raw material composition satisfies the following condition: the number average molecular weight of the sodium hyaluronate is 100~650kDa.

9. An electrospinning solution, characterized in that, It comprises 1 part of the raw material composition of the electrospinning solution as described in any one of claims 5-8 and 12-15 parts of water.

10. A method for preparing the electrospinning solution as described in claim 9, characterized in that, The process includes the following steps: mixing all components in the electrospinning solution until homogeneous.

11. A nanofiber membrane, characterized in that, The process includes the following steps: the electrospinning solution as described in claim 9 is obtained by electrospinning.

12. The nanofiber membrane as described in claim 11, characterized in that, The nanofiber membrane satisfies at least one of the following conditions: The electrospinning is carried out on a substrate, which includes at least one of aluminum foil, Tencel film, silk film, pure cotton film, and non-woven fabric. The voltage for electrospinning is 15~24V; The feeding speed of the electrospinning is 0.2~0.5mL / h; The receiving distance in the electrospinning process is 15~20cm.

13. The nanofiber membrane as described in claim 12, characterized in that, The nanofiber membrane satisfies at least one of the following conditions: The voltage for electrospinning is 16~20V; The feed rate of the electrospinning is 0.3~0.4 mL / h; The receiving distance in the electrospinning process is 17~18cm.

14. The use of a nanofiber membrane as described in any one of claims 11-13 as a raw material in the preparation of face masks and / or eye masks.

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