Biomass nanofiber membrane, and preparation method therefor and use thereof

Abstract

The present invention provides a biomass nanofiber membrane, and a preparation method therefor and a use thereof. The biomass nanofiber membrane is formed by interweaving fibers. The diameter of the fibers ranges from 100 nm to 280 nm. The fibers are derived from fiber raw materials, including a modified polysaccharide, gelatin, and a collagen peptide; and in parts by mass, the content of the modified polysaccharide is 8-24 parts, the content of the gelatin is 4-12 parts, and the content of the collagen peptide is 2-10 parts. The biomass nanofiber membrane of the present invention is derived from biomass materials, and has the advantages of good biocompatibility and being environmentally friendly and low-carbon. The biomass nanofiber membrane of the present invention has the advantages of a small fiber diameter, high strength, high toughness, etc., effectively increasing the loading capacity of active components; and in addition, the increase in the strength and toughness can improve the use experience of consumers.

Description

Biomass nanofiber membranes, their preparation methods and applications Technical Field

[0001] This invention relates to a biomass nanofiber membrane, its preparation method and applications, belonging to the field of biomass materials. Background Technology

[0002] The application of nanofiber membranes carrying active ingredients in the mask industry has become a hot research topic. This is because most sheet masks suffer from drawbacks such as easy loss of essence, insufficient absorption of nutrients, and poor skin adhesion. Furthermore, to prevent oxidation, deterioration, and microbial growth, various stabilizers and preservatives are added, which can easily cause allergic and inflammatory reactions in consumers with sensitive skin.

[0003] In recent years, researchers have developed a new type of dry face mask that combines solid essence active ingredients with high efficiency and safety features such as zero preservatives and zero thickeners. This meets consumers' growing safety needs and concepts and represents a trend in the development of materials for the beauty and medical industries.

[0004] Electrospinning is a technology for manufacturing continuous nanofibers. Nanofiber membranes prepared using this technology have advantages such as large specific surface area, high porosity, high loading of active materials, and environmental friendliness. Solution electrospinning technology includes needleless electrospinning and needled electrospinning. Needled electrospinning has relatively lower production efficiency and lower fiber distribution uniformity than needleless electrospinning, but it has the advantage of lower equipment investment costs. Needleless electrospinning has the advantages of high efficiency and good fiber uniformity, and can be used for mass production of nanofibers, but it has high requirements for the spinning solution and high equipment investment costs.

[0005] In recent years, electrospinning technology has gradually gained attention in fields such as biomedicine, environmental filtration, energy, and textiles. Electrospinning technology can overcome the shortcomings of liquid masks by electrospinning and solidifying the skin's moisturizing factors and natural active ingredients onto the mask base fabric. This avoids the need for preservatives and prevents the growth of external bacteria, making it a promising technology for mask applications.

[0006] Reference 1 discloses a dry, quick-dissolving facial mask prepared by electrospinning technology using budding short stalk enzyme polysaccharide and polyethylene glycol as the main raw materials, and a preparation method thereof. The facial mask includes a non-woven fabric substrate layer and a nanofiber layer, wherein the nanofiber layer is formed on the non-woven fabric substrate layer by electrospinning. The nanofiber layer includes: 10-50 parts by weight of budding short stalk enzyme polysaccharide and 4-20 parts by weight of polyethylene glycol, wherein the average molecular weight of polyethylene glycol is between 50 kDa and 600 kDa.

[0007] Reference 2 discloses a solid dry nano-instantaneous facial mask with hyaluronic acid and gelatin as the framework and its preparation method. The method includes dissolving hyaluronic acid and gelatin in a mixed solvent of water and ethanol, heating and stirring until completely dissolved, and then stopping stirring to obtain a spinning solution. An active substance is added to the spinning solution and stirred until homogeneous to obtain a mixed spinning solution. The mixed spinning solution is then electrospun, collected using a collecting device, and cut to obtain the solid dry nano-instantaneous facial mask.

[0008] However, the electrospun masks currently being developed have the following problems. On the one hand, using petroleum-based polymer materials as the main fiber-forming materials results in solid masks with a certain strength and toughness, but these masks are highly dependent on petroleum resources and pose a risk of irritating the skin. On the other hand, using only biomass materials such as gelatin and / or polysaccharides as fiber-forming materials results in solid masks with low strength and poor toughness, leading to a poor customer experience.

[0009] References:

[0010] Reference 1: Patent Application 202210699427.X

[0011] Reference 2: Patent Application 202310763006.3 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] In view of the technical problems existing in the prior art, the present invention first provides a biomass nanofiber membrane. The biomass nanofiber membrane is derived from biomass materials, has good biocompatibility, and possesses the advantages of being low-carbon and environmentally friendly. At the same time, the biomass nanofiber membrane of the present invention has advantages such as small fiber diameter, high strength, and good toughness.

[0014] Furthermore, the biomass nanofiber membrane of the present invention also has excellent antioxidant properties.

[0015] Furthermore, the present invention also provides a method for preparing a biomass nanofiber membrane, which is simple and easy to implement, uses readily available raw materials, and is suitable for mass production.

[0016] Solution for solving the problem

[0017] This invention provides a biomass nanofiber membrane, wherein the biomass nanofiber membrane is composed of interwoven fibers, and the diameter of the fibers is 100 nm to 280 nm; wherein,

[0018] The fiber is derived from fiber raw materials, which include modified polysaccharides, gelatin, and collagen peptides; and...

[0019] The modified polysaccharide contains 8 to 24 parts by weight, the gelatin contains 4 to 12 parts by weight, and the collagen peptide contains 2 to 10 parts by weight.

[0020] According to the biomass nanofiber membrane of the present invention, the modified polysaccharide comprises a polysaccharide modified with nanocellulose;

[0021] Preferably, the nanocellulose-modified polysaccharide is obtained by mixing and modifying nanocellulose and polysaccharide; wherein the mass ratio of nanocellulose to polysaccharide is 0.003–0.01:1; and / or,

[0022] The modification treatment temperature is 40℃~60℃, and the modification treatment time is 0.5h~2h.

[0023] According to the biomass nanofiber membrane of the present invention, the nanocellulose-modified polysaccharide includes carboxylated nanocellulose-modified pullulan polysaccharide;

[0024] Preferably, the carboxyl content in the carboxylated nanocellulose is 0.5 mmol / g to 1.0 mmol / g, and / or the median particle size of the carboxylated nanocellulose is 20 μm to 40 μm;

[0025] More preferably, the pullulan polysaccharide has a weight-average molecular weight of 10 wDa to 30 wDa.

[0026] According to the biomass nanofiber membrane of the present invention, the collagen peptides are derived from pyrolysis products of yak hide;

[0027] Preferably, the collagen peptides are obtained by extracting the pyrolysis products of yak hide using a protease.

[0028] According to the biomass nanofiber membrane of the present invention, the collagen peptides are prepared by the following method:

[0029] Pyrolysis step: The pretreated yak hide is subjected to pyrolysis treatment to obtain the yak hide pyrolysis product; preferably, the temperature of the pyrolysis treatment is 80℃~100℃ and the time of the pyrolysis treatment is 4h~6h.

[0030] Enzymatic hydrolysis step: The pyrolysis product of yak hide is enzymatically hydrolyzed using a protease to obtain the hydrolysate; preferably, the protease includes an alkaline protease and / or a neutral protease, more preferably, the mass ratio of the alkaline protease to the neutral protease is 2:1 to 5:1; even more preferably, the amount of protease used is 6000 U / g to 8000 U / g; and / or,

[0031] The enzymatic hydrolysis treatment is performed at a temperature of 35℃ to 45℃, at a pH value of 8.0 to 8.5, and for a time of 2 hours to 10 hours.

[0032] Optionally, the mass concentration of the yak hide pyrolysis product is adjusted to 5-10%, and then enzymatic hydrolysis is performed.

[0033] According to the biomass nanofiber membrane of the present invention, after the enzymatic hydrolysis step, the method further includes a step of obtaining collagen peptides with a weight-average molecular weight of 0.3kDa to 2.0kDa, preferably 0.3kDa to 1.0kDa, through separation treatment.

[0034] Preferably, the collagen peptides are obtained by separation using a 2.0 kDa filter membrane, more preferably a 1.0 kDa filter membrane, followed by concentration using a 0.3 kDa filter membrane.

[0035] According to the biomass nanofiber membrane of the present invention, the gelatin has a single gelling strength of 100g Bloom to 200g Bloom; and / or,

[0036] The fiber raw material also includes functional additives, wherein the content of the functional additives is 1 to 5 parts; preferably, the functional additives include one or more of the following: biomass glycerin, aloe vera gel, rice hydrolyzed peptides, sodium hyaluronate, hydrolyzed sodium hyaluronate, menthol, and calendula extract.

[0037] More preferably, the weight-average molecular weight of the sodium hyaluronate is between 20 wDa and 130 wDa, and the weight-average molecular weight of the hydrolyzed sodium hyaluronate is between 1000 Da and 5000 Da.

[0038] The present invention also provides a method for preparing a biomass nanofiber membrane according to the present invention, which includes the following steps:

[0039] The fiber raw material is dissolved in a solvent to obtain a spinning solution;

[0040] A film-like product was prepared using a spinning process;

[0041] Preferably, the solvent content is 60 to 80 parts by weight;

[0042] More preferably, the spinning process may include electrospinning and / or centrifugal spinning, with electrospinning being the preferred method.

[0043] According to the preparation method of the present invention, the process parameters of the electrospinning include: controlling the ambient temperature during the electrospinning process to be 30℃~40℃ and the relative humidity to be 30%~45%; adjusting the flow rate to be 0.2mL / h~0.6mL / h and the voltage to be 15kV~26kV; and adjusting the receiving distance of the receiving device to be 15cm~25cm.

[0044] The present invention also provides the use of the biomass nanofiber membrane according to the present invention for preparing facial mask patches.

[0045] The effects of the invention

[0046] The biomass nanofiber membrane of this invention is derived from biomass materials and has the advantages of good biocompatibility and being green and low-carbon. The biomass nanofiber membrane prepared by this invention using modified polysaccharides and gelatin as the main fibrous materials has the advantages of small fiber diameter, high strength, and good toughness, which can effectively improve the loading of functional ingredients. At the same time, the improvement in strength and toughness can enhance the user experience.

[0047] Furthermore, the biomass nanofiber membrane of the present invention also has excellent antioxidant properties.

[0048] Furthermore, the preparation method of the biomass nanofiber membrane of the present invention is simple and easy to implement, and the raw materials are readily available. It can be spun using either needle-type electrospinning equipment or needleless electrospinning equipment with strict requirements on process parameters, which greatly improves the fiber uniformity, yield and efficiency of the biomass nanofiber membrane. Attached Figure Description

[0049] Figure 1 shows a scanning electron microscope image (left) and a diameter distribution diagram (right) of the biomass nanofiber membrane of Example 1 of the present invention;

[0050] Figure 2 shows a scanning electron microscope image (left) and a diameter distribution diagram (right) of the biomass nanofiber membrane of Example 2 of the present invention;

[0051] Figure 3 shows a scanning electron microscope image (left) and a diameter distribution diagram (right) of the biomass nanofiber membrane of Example 3 of the present invention;

[0052] Figure 4 shows a scanning electron microscope image (left) and a diameter distribution diagram (right) of the biomass nanofiber membrane of Example 4 of the present invention;

[0053] Figure 5 shows a scanning electron microscope image (left) and a diameter distribution diagram (right) of the biomass nanofiber membrane of Example 5 of the present invention;

[0054] Figure 6 shows a scanning electron microscope image (left) and a diameter distribution diagram (right) of the biomass nanofiber membrane of Comparative Example 1 of the present invention;

[0055] Figure 7 shows a scanning electron microscope image (left) and a diameter distribution diagram (right) of the biomass nanofiber membrane of Comparative Example 2 of the present invention;

[0056] Figure 8 shows a comparison of the antioxidant test results of the biomass nanofiber membranes of Examples 1-4 and Comparative Example 2.

[0057] Figure 9 shows a comparison of the dissolution of the biomass nanofiber membrane in Example 2 and the dissolution of the fiber raw material in Example 2; where: (a) is the biomass nanofiber membrane, and (b) is the fiber raw material. Detailed Implementation

[0058] Various exemplary embodiments, features, and aspects of the present invention will be described in detail below. The term "exemplary" as used herein means "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as superior to or better than other embodiments.

[0059] Furthermore, to better illustrate the present invention, numerous specific details are set forth in the following detailed embodiments. Those skilled in the art should understand that the present invention can be practiced without certain specific details. In other instances, methods, means, apparatus, and steps well known to those skilled in the art have not been described in detail in order to highlight the spirit of the present invention.

[0060] Unless otherwise stated, all units used in this specification are international standard units, and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors that are unavoidable in industrial production.

[0061] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0062] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "implementation," etc., refer to specific elements (e.g., features, structures, properties, and / or characteristics) related to that embodiment, which are included in at least one of the embodiments described herein and may or may not be present in other embodiments. Furthermore, it should be understood that these elements may be combined in any suitable manner in various embodiments.

[0063] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0064] <First Aspect>

[0065] A first aspect of the present invention provides a biomass nanofiber membrane, wherein the biomass nanofiber membrane is formed by interwoven fibers, the diameter of which is 100 nm to 280 nm; wherein,

[0066] The fiber is derived from fiber raw materials, which include modified polysaccharides, gelatin, and collagen peptides; and...

[0067] The modified polysaccharide contains 8 to 24 parts by weight, the gelatin contains 4 to 12 parts by weight, and the collagen peptide contains 2 to 10 parts by weight.

[0068] The biomass nanofiber membrane of this invention is derived from biomass materials and has the advantages of good biocompatibility and being green and low-carbon. The biomass nanofiber membrane of this invention has advantages such as small fiber diameter, high strength, and good toughness, which can effectively increase the loading of functional ingredients. At the same time, the improved strength and toughness enhance the user experience.

[0069] Modified polysaccharides

[0070] The inventors of this invention have discovered that by using modified polysaccharides and gelatin as the main fiber-forming materials, fibers with small diameter, high strength, and good toughness can be obtained.

[0071] In some specific embodiments, the modified polysaccharide includes a polysaccharide modified with nanocellulose. The inventors of this invention have discovered that using a polysaccharide modified with nanocellulose allows for molecular entanglement between the nanocellulose and the polysaccharide, thereby enhancing the strength and toughness of the polysaccharide-spun fibers. Furthermore, it can further synergize with gelatin, resulting in fibers with smaller and more uniform diameters, and superior strength and toughness. Moreover, it can effectively increase the loading of functional ingredients such as collagen peptides and sodium hyaluronate, while the improved strength and toughness enhance the user experience.

[0072] Preferably, the nanocellulose-modified polysaccharide is obtained by mixing nanocellulose and polysaccharide and then modifying the mixture; wherein the mass ratio of nanocellulose to polysaccharide (dry basis) is 0.003 to 0.01:1, for example: 0.004:1, 0.005:1, 0.006:1, 0.007:1, 0.008:1, 0.009:1, etc.

[0073] Furthermore, in order to better carry out the modification treatment, the polysaccharide can be dissolved in water to form a polysaccharide solution; preferably, the mass fraction of the polysaccharide in the polysaccharide solution is 20% to 40%, for example: 22%, 25%, 28%, 30%, 32%, 35%, 38%, etc.

[0074] In some specific implementations, the temperature of the modification treatment is 40℃~60℃, for example: 42℃, 45℃, 48℃, 50℃, 52℃, 55℃, 58℃, etc.; the time of the modification treatment is 0.5h~2h, for example: 0.8h, 1h, 1.2h, 1.5h, 1.8h, etc.

[0075] Specifically, in this invention, the nanocellulose-modified polysaccharide includes pullulan modified with carboxylated nanocellulose. The inventors of this invention have discovered that carboxylated nanocellulose can further form molecular entanglements with the polysaccharide, thereby improving the strength and toughness of the polysaccharide-spun fibers. Furthermore, by using pullulan modified with carboxylated nanocellulose, spinning can be performed on both needle-based electrospinning equipment and needleless electrospinning equipment with strict process parameter requirements, greatly improving the uniformity, yield, and efficiency of spinning.

[0076] Preferably, in this invention, the carboxylated cellulose nanoparticles contain 0.5 mmol / g to 1.0 mmol / g of carboxyl groups, for example, 0.6 mmol / g, 0.7 mmol / g, 0.8 mmol / g, 0.9 mmol / g, etc. The median particle size of the carboxylated cellulose nanoparticles is 20 μm to 40 μm, for example, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, etc.

[0077] More preferably, the pullulan polysaccharide has a weight-average molecular weight of 10wDa to 30wDa, for example: 12wDa, 15wDa, 18wDa, 20wDa, 22wDa, 25wDa, 28wDa, etc.

[0078] Specifically, the preparation method of carboxyl-modified pullulan polysaccharide using nanocellulose is as follows:

[0079] Pullulan was selected, and an aqueous solution with a mass concentration of 20%–40% was prepared. Carboxymethyl cellulose nanoparticles were added, wherein the mass ratio of carboxymethyl cellulose nanoparticles to pullulan (dry basis) was 0.003–0.01:1. Then, the mixture was modified in a reactor at 40℃–60℃ for 0.5h–2h to obtain the modified polysaccharide.

[0080] In this invention, the content of the modified polysaccharide is 8 to 24 parts by weight, for example: 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, etc. When the content of the modified polysaccharide is 8 to 24 parts, on the one hand, a moisturizing layer can be formed on the skin surface, and on the other hand, the polysaccharide can improve the toughness and strength of the biomass nanofiber membrane, ultimately achieving a uniform fiber formation effect.

[0081] Collagen peptides

[0082] This invention uses collagen peptides to endow biomass nanofiber membranes with specific effects, making them suitable for use as facial mask sheets, which have moisturizing, hydrating, and collagen-replenishing effects on the skin.

[0083] Specifically, in this invention, the collagen peptides are derived from the pyrolysis products of yak hide. The inventors of this invention have discovered that by using yak hide as a raw material for collagen peptides, the antioxidant properties of biomass nanofiber membranes can be further endowed. Preferably, the collagen peptides are obtained by extracting the pyrolysis products of yak hide using a protease, followed by further separation and purification.

[0084] In some specific embodiments, the collagen peptides are prepared by the following methods:

[0085] Pyrolysis step: The pretreated yak hide is subjected to pyrolysis treatment to obtain the pyrolysis product of the yak hide;

[0086] Enzymatic hydrolysis step: The pyrolysis product of the yak hide is enzymatically hydrolyzed using protease to obtain the enzymatic hydrolysate.

[0087] The present invention does not impose any particular limitation on the pretreatment process, and any pretreatment method commonly used in the art can be used. Specifically, the pretreatment may include steps such as washing, hair removal, ash soaking, deashing, and cutting, which will not be elaborated on here.

[0088] This invention promotes the hydrolysis of collagen through pyrolysis and further separates and purifies it to form small molecule collagen peptides. The reduced molecular weight can improve its antioxidant properties and skin absorption rate.

[0089] In some specific implementations, the pyrolysis temperature is 80℃~100℃, for example: 82℃, 85℃, 88℃, 90℃, 92℃, 95℃, 98℃, etc., and the pyrolysis time is 4h~6h, for example: 4.2h, 4.5h, 4.8h, 5h, 5.2h, 5.5h, 5.8h, etc. When the pyrolysis temperature is 80℃~100℃ and the pyrolysis time is 4h~6h, it is more conducive to obtaining the desired small molecule collagen peptides.

[0090] In this invention, before enzymatic hydrolysis, it is preferable to adjust the mass concentration of the yak hide pyrolysis product to 5% to 10%, for example, 6%, 7%, 8%, 9%, etc., which is more conducive to the enzymatic hydrolysis process.

[0091] Specifically, the protease includes alkaline protease and / or neutral protease. The inventors of this invention have discovered that collagen peptides can be obtained by using alkaline protease and / or neutral protease. Specifically, the protease includes alkaline protease and neutral protease, with a mass ratio of alkaline protease to neutral protease of 2–5:1, for example: 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, 4.8:1, etc. When alkaline protease and neutral protease are used simultaneously, smaller molecule collagen peptides with superior effects can be obtained.

[0092] Furthermore, in this invention, the amount of protease used is 6000 U / g to 8000 U / g, for example: 6200 U / g, 6500 U / g, 6800 U / g, 7000 U / g, 7200 U / g, 7500 U / g, 7800 U / g, etc. When the amount of protease used is 6000 U / g to 8000 U / g, the enzymatic hydrolysis treatment can be carried out more effectively.

[0093] Furthermore, to prevent the inactivation of the protease, the temperature of the enzymatic hydrolysis treatment is 35℃~45℃, for example: 36℃, 37℃, 40℃, 41℃, 42℃, 43℃, 44℃, etc., the pH value of the enzymatic hydrolysis treatment is 8.0~8.5, for example: 8.1, 8.2, 8.3, 8.4, etc., and the time of the enzymatic hydrolysis treatment is 2h~10h, for example: 3h, 5h, 7h, 9h, etc.

[0094] In some specific implementations, after the enzymatic hydrolysis step, the method further includes a step of obtaining small molecule collagen peptides with a weight-average molecular weight of 0.3 kDa to 2.0 kDa, preferably 0.3 kDa to 1.0 kDa, through separation processing;

[0095] Preferably, the small molecule collagen peptides are obtained by separation treatment using a 2.0 kDa filter membrane, more preferably a 1.0 kDa filter membrane, followed by concentration treatment using a 0.3 kDa filter membrane.

[0096] In this invention, the effects of small molecule collagen peptides are mainly reflected in the following aspects: First, small molecule collagen peptides have excellent antioxidant properties, which can scavenge free radicals, reduce the damage of free radicals to skin cells, and delay aging; Second, small molecule collagen peptides can promote skin hydration, improve skin elasticity and firmness, thereby reducing the appearance of fine lines and wrinkles; Third, small molecule collagen peptides have good permeability, which can penetrate deep into the skin layer, promote cell regeneration and repair, and enhance the overall health and radiance of the skin.

[0097] Furthermore, this invention utilizes yak skin collagen peptides. The inventors have discovered that the antioxidant properties of small-molecule yak skin collagen peptides are superior to those of ordinary cattle skin. This may be because yaks, living in complex environments such as high altitudes for extended periods, have evolved more effective mechanisms for their collagen to resist oxidative stress.

[0098] In this invention, the content of the collagen peptides, by weight, is 2 to 10 parts, for example: 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, etc. In this invention, since small molecule collagen peptides themselves do not possess fibroblastic properties and are hard and brittle after drying, their content directly affects the strength and toughness of the biomass nanofiber membrane. When the content of the collagen peptides is 2 to 10 parts, a product with superior strength, toughness, and efficacy can be obtained.

[0099] gelatin

[0100] Gelatin is a natural biopolymer obtained by hydrolyzing animal skin or bones. It can form a fibrous structure, providing good support and matrix for fibers. In cosmetics, it can also moisturize, firm the skin, and increase skin elasticity. It also has excellent biocompatibility and biodegradability.

[0101] In some specific implementations, the gelatin has a single gel strength value of 100g Bloom to 200g Bloom, for example: 110g Bloom, 130g Bloom, 150g Bloom, 170g Bloom, 190g Bloom, etc.

[0102] When the gelatin single gel strength value is between 100g Bloom and 200g Bloom, it can provide appropriate viscosity and flowability, thereby promoting the uniform formation of fibers during electrospinning, helping to improve the strength and stability of fibers, and ensuring the quality of the final product.

[0103] In this invention, the content of gelatin, by weight, is 4 to 12 parts, for example: 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, etc. When the content of gelatin is 4 to 12 parts, the combination of gelatin and polysaccharide can give the biomass nanofiber membrane suitable strength, while also endowing the biomass nanofiber membrane with skin care effects.

[0104] Functional additives

[0105] In this invention, the fiber raw material also includes functional additives. By using functional additives, various functions can be imparted to the biomass nanofiber membrane, such as moisturizing, anti-wrinkle, soothing, etc.

[0106] In some specific implementation schemes, the content of the functional additive, by weight, is 1 to 5 parts, for example: 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, etc. When the content of the functional additive is 1 to 5 parts, it can effectively enhance the functionality of the product, such as improving moisturizing and antioxidant effects, while ensuring the safety and stability of the product and improving the user experience.

[0107] Preferably, the efficacy additive of the present invention is a biomass-derived efficacy additive. Specifically, the efficacy additive includes one or more of the following: biomass glycerin, aloe vera gel, rice hydrolyzed peptides, sodium hyaluronate, hydrolyzed sodium hyaluronate, menthol, and calendula extract;

[0108] More preferably, the weight-average molecular weight of the sodium hyaluronate is between 20 wDa and 130 wDa, for example: 25 wDa, 30 wDa, 50 wDa, 60 wDa, 80 wDa, 100 wDa, 120 wDa, etc.; the weight-average molecular weight of the hydrolyzed sodium hyaluronate is between 1000 Da and 5000 Da, for example: 1500 Da, 2000 Da, 2500 Da, 3000 Da, 3500 Da, 4000 Da, 4500 Da, etc.

[0109] <Second aspect>

[0110] A second aspect of the present invention provides a method for preparing a biomass nanofiber membrane according to the first aspect of the present invention, comprising the following steps:

[0111] The fiber raw material is dissolved in a solvent to obtain a spinning solution;

[0112] A film-like product was prepared by using a spinning process to prepare the spinning solution.

[0113] In this invention, the spinning process may include electrospinning and / or centrifugal spinning, preferably electrospinning.

[0114] Furthermore, the principle of electrospinning is that a high voltage is applied to the polymer liquid during the electrospinning process, introducing charge into the liquid. When the charge in the liquid accumulates to a certain amount, the liquid forms a Taylor cone at the nozzle. Under the action of the applied electric field, it overcomes surface tension to form a liquid jet. Then, under the combined action of electrostatic repulsion, Coulomb force, and surface tension, the polymer jet moves along an irregular spiral trajectory. The jet is stretched and pulled in a very short time, and as the solvent evaporates or heat dissipates, the polymer jet solidifies to form micro / nanofibers. During the electrospinning process, many parameters affect the final electrospun fibers. By controlling the process parameters, micro / nanofibers of different sizes, morphologies, and structures can be prepared.

[0115] In the electrospinning process of this invention, the process parameters affect the biomass nanofiber membrane obtained by electrospinning. By controlling the process parameters, biomass nanofiber membranes of different sizes, morphologies, and structures can be prepared. This invention does not have special requirements for the electrospinning method; any electrospinning method commonly used in the field can be used.

[0116] Specifically, in this invention, the process parameters for electrospinning include: controlling the ambient temperature during electrospinning to be 30℃~40℃, for example: 32℃, 35℃, 38℃, etc.; the relative humidity to be 30%~45%, for example: 32%, 35%, 38%, 40%, 42%, etc.; adjusting the flow rate to 0.2mL / h~0.6mL / h, for example: 0.3mL / h, 0.4mL / h, 0.5mL / h, etc.; the voltage to be 15kV~26kV, for example: 18kV, 20kV, 22kV, 24kV, etc.; and adjusting the receiving distance of the receiving device to 15cm~25cm, for example: 17cm, 19cm, 21cm, 23cm, etc. The receiving device can be a roller with an attached film-like product.

[0117] In this invention, the electrospinning process may include the following steps: preparing fiber raw materials in advance, dissolving the fiber raw materials in a suitable solvent to prepare a spinning solution of a certain concentration; and then using an electrospinning process to prepare a film-like product from the spinning solution.

[0118] The fiber raw material may be the same as that described in the first aspect. The mass fraction of the fiber raw material is the same as that described in the first aspect. Preferably, the solvent content is 60-80 parts by mass.

[0119] The film-like products prepared by electrospinning have fibers with suitable diameters, are flexible, have good tensile strength in both dry and wet states, are not easily broken during the spinning process, and have good filamentation effect.

[0120] The spinning solution of the present invention can be used in both needle-type electrospinning equipment and needleless electrospinning equipment with strict requirements on process parameters, which greatly improves the uniformity, output and efficiency of spinning.

[0121] Finally, the prepared membrane product is cut, tested and qualified, packaged and sterilized by irradiation to obtain a biomass nanofiber membrane with high antioxidant activity.

[0122] <Third aspect>

[0123] A third aspect of the present invention provides the use of the biomass nanofiber membrane according to the present invention for preparing facial mask patches.

[0124] Example

[0125] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0126] Example 1

[0127] (1) Preparation of modified polysaccharide CPUL-I:

[0128] Carboxylated nanocellulose with a carboxyl content of 0.5 mmol / g and a median particle size of 40 μm was added to a 30% aqueous solution of pullulan (molecular weight 10 wDa). The mass ratio of carboxylated nanocellulose to pullulan (dry weight) was 0.003:1. The mixture was modified in a reactor at 60℃ for 1 h, then cooled and discharged for later use.

[0129] (2) Preparation of yak skin collagen peptide CPP-I:

[0130] The preparation steps for the yak collagen peptide with high antioxidant activity are as follows:

[0131] ① After deashing, softening, washing, and cutting, yak hide is pyrolyzed at around 92℃ for 5 hours. The pyrolysis liquid is then filtered and centrifuged to obtain the pyrolysis product.

[0132] ② Prepare a pyrolysis product solution with purified water, wherein the mass concentration of the pyrolysis product is 5%. Use protease to hydrolyze the pyrolysis product, wherein the protease includes alkaline protease and neutral protease, and the mass ratio of alkaline protease to neutral protease is 2:1. The total amount of protease used is 6000 U / g. Enzymatic hydrolysis is carried out at 35℃ and pH 8.0 for 8 hours to obtain the enzymatic hydrolysis product.

[0133] ③ After filtering the enzymatic hydrolysis product, the filtrate was separated using a 2.0 kDa filter membrane and concentrated using a 0.3 kDa filter membrane to obtain small molecule collagen peptides with a weight average molecular weight of 0.3 kDa to 2.0 kDa. The filtrate was then freeze-dried or spray-dried to obtain yak skin collagen peptide CPP-I for later use.

[0134] (3) Preparation of spinning solution:

[0135] The following ingredients were prepared: 60 parts purified water, 4 parts gelatin (180g Bloom single gel strength), 8 parts modified polysaccharide CPUL-I, 2 parts yak hide collagen peptide CPP-I, and 3 parts functional additives. The functional additives consisted of biomass glycerol and sodium hyaluronate (weight average molecular weight 80 wDa), with a mass ratio of biomass glycerol to sodium hyaluronate of 1:6. The gelatin and modified polysaccharide CPUL-I were dissolved in deionized water and stirred evenly in a 40°C water bath. The yak hide collagen peptide CPP-I was added to the above solution and stirred evenly. The functional additives were added to the above solution and stirred evenly to obtain the spinning solution for later use.

[0136] (4) Preparation of nanofiber membranes:

[0137] The electrospinning solution was placed in a syringe with a metal needle and then placed in an electrospinning apparatus, with silicone release paper covering the receiving roller. The electrospinning parameters were a flow rate of 0.4 mL / h, a voltage of 16 kV, and a distance of 16 cm between the needle tip and the receiving device. Electrospinning was carried out at an ambient temperature of 35°C and a relative humidity of 35%. The nanofibers were collected on the release paper, yielding a biomass nanofiber membrane. The average diameter of the nanofibers in the membrane was approximately 195 ± 24 nm, and the surface was smooth and uniform.

[0138] Example 2

[0139] (1) Preparation of modified polysaccharide CPUL-II:

[0140] Carboxylated nanocellulose with a carboxyl content of 0.7 mmol / g and a median particle size of 35 μm was added to a 30% aqueous solution of pullulan (weight average molecular weight 20 wDa). The mass ratio of carboxylated nanocellulose to pullulan (dry weight) was 0.003:1. The mixture was modified in a reactor at 60℃ for 1 h, then cooled and discharged for later use.

[0141] (2) Preparation of yak skin collagen peptide CPP-II:

[0142] The preparation steps for the yak collagen peptide with high antioxidant activity are as follows:

[0143] ① After deashing, softening, washing, and cutting, yak hide is pyrolyzed at around 92℃ for 4 hours. The pyrolysis liquid is then filtered and centrifuged to obtain the pyrolysis product.

[0144] ② Prepare a pyrolysis product solution with purified water, wherein the mass concentration of the pyrolysis product is 6%. Use protease to hydrolyze the pyrolysis product, wherein the protease includes alkaline protease and neutral protease, and the mass ratio of alkaline protease to neutral protease is 3:1. The total amount of protease used is 7000 U / g. Enzymatic hydrolysis is carried out at 35℃ and pH 8.0 for 6 hours to obtain the enzymatic hydrolysis product.

[0145] ③ After filtration of the enzymatic hydrolysis product, the filtrate was separated using a 1.0 kDa filter membrane and concentrated using a 0.3 kDa filter membrane to obtain small molecule collagen peptides with a weight average molecular weight of 0.3 kDa to 1.0 kDa. The filtrate was then freeze-dried or spray-dried to obtain yak skin collagen peptide CPP-II for later use.

[0146] (3) Preparation of spinning solution:

[0147] The following ingredients were prepared: 80 parts purified water, 12 parts gelatin (140g Bloom single gel strength), 24 parts modified polysaccharide CPUL-I, 10 parts yak hide collagen peptide CPP-II, and 3 parts functional additives, including sodium hyaluronate (weight average molecular weight 20wDa) and hydrolyzed sodium hyaluronate (weight average molecular weight 5000Da) in a mass ratio of 1:10. The gelatin and modified polysaccharide CPUL-II were dissolved in deionized water and stirred evenly in a 40°C water bath. The yak hide collagen peptide CPP-II was added to the above solution and stirred evenly. The sodium hyaluronate and hydrolyzed sodium hyaluronate were added to the above solution and stirred evenly to obtain the spinning solution for later use.

[0148] (4) Preparation of nanofiber membranes:

[0149] The electrospinning solution was placed in a syringe with a metal needle and then placed in an electrospinning apparatus, with silicone release paper covering the receiving roller. The electrospinning parameters were a flow rate of 0.5 mL / h, a voltage of 26 kV, and a distance of 18 cm between the needle tip and the receiving device. Electrospinning was carried out at an ambient temperature of 40°C and a relative humidity of 35%. The nanofibers were collected on the release paper, yielding a biomass nanofiber membrane. The average diameter of the nanofibers in the membrane was approximately 177 ± 25 nm, and the surface was smooth and uniform.

[0150] Example 3

[0151] (1) Preparation of modified polysaccharide CPUL-III:

[0152] Carboxylated nanocellulose with a carboxyl content of 0.9 mmol / g and a median particle size of 30 μm was added to a 30% aqueous solution of pullulan (weight average molecular weight 30 wDa). The mass ratio of carboxylated nanocellulose to pullulan (dry weight) was 0.004:1. The mixture was modified in a reactor at 55℃ for 0.8 h, cooled, and discharged for later use.

[0153] (2) Preparation of yak skin collagen peptide CPP-III:

[0154] The preparation steps for the yak collagen peptide with high antioxidant activity are as follows:

[0155] ① After deliming, softening, washing, and cutting, yak hide is pyrolyzed at around 92℃ for 6 hours. The pyrolysis liquid is then filtered and centrifuged to obtain the pyrolysis product.

[0156] ② Prepare a pyrolysis product solution with purified water, wherein the mass concentration of the pyrolysis product is 10%. Use protease to hydrolyze the pyrolysis product, wherein the protease includes alkaline protease and neutral protease, and the mass ratio of alkaline protease to neutral protease is 5:1. The total amount of protease used is 8000 U / g. Enzymatic hydrolysis is carried out at 35℃ and pH 8.0 for 4 hours to obtain the enzymatic hydrolysis product.

[0157] ③ After filtration of the enzymatic hydrolysis product, the filtrate was separated using a 1.0 kDa filter membrane and concentrated using a 0.3 kDa filter membrane to obtain small molecule collagen peptides with a weight average molecular weight of 0.3 kDa to 1.0 kDa. The filtrate was then freeze-dried or spray-dried to obtain yak skin collagen peptide CPP-III for later use.

[0158] (3) Preparation of spinning solution:

[0159] The following ingredients were used: 70 parts purified water, 8 parts gelatin (160g Bloom single gel strength), 16 parts modified polysaccharide CPUL-III, 10 parts yak hide collagen peptide CPP-III, and 4 parts functional additive, including sodium hyaluronate (weight average molecular weight 130 wDa). The gelatin and modified polysaccharide CPUL-III were dissolved in deionized water and stirred evenly in a 40°C water bath. The yak hide collagen peptide CPP-III was added to the above solution and stirred evenly. The sodium hyaluronate was added to the above solution and stirred evenly to obtain the spinning solution for later use.

[0160] (4) Preparation of nanofiber membranes:

[0161] The electrospinning solution was placed in a syringe with a metal needle and then placed in an electrospinning apparatus, with silicone release paper covering the receiving roller. The electrospinning parameters were a flow rate of 0.4 mL / h, a voltage of 18 kV, and a distance of 20 cm between the needle tip and the receiving device. Electrospinning was carried out at an ambient temperature of 35°C and a relative humidity of 40%. The nanofibers were collected on the release paper, yielding a biomass nanofiber membrane. The average diameter of the nanofibers in the membrane was approximately 174 ± 19 nm, and the surface was smooth and uniform.

[0162] Example 4

[0163] (1) Preparation of modified polysaccharide CPUL-I:

[0164] Carboxylated nanocellulose with a carboxyl content of 0.5 mmol / g and a median particle size of 40 μm was added to a 30% pullulan (weight average molecular weight 10 wDa) aqueous solution. The mass ratio of carboxylated nanocellulose to pullulan (dry basis) was 0.009:1. The mixture was modified in a reactor at 60℃ for 1 h, cooled, and discharged for later use.

[0165] (2) Preparation of yak skin collagen peptide CPP-I:

[0166] The preparation steps for the yak collagen peptide with high antioxidant activity are as follows:

[0167] ① After deashing, softening, washing, and cutting, yak hide is pyrolyzed at around 92℃ for 5 hours. The pyrolysis liquid is then filtered and centrifuged to obtain the pyrolysis product.

[0168] ② Prepare a pyrolysis product solution with purified water, wherein the mass concentration of the pyrolysis product is 5%. Use protease to hydrolyze the pyrolysis product, wherein the protease includes alkaline protease and neutral protease, and the mass ratio of alkaline protease to neutral protease is 2:1. The total amount of protease used is 6000 U / g. Enzymatic hydrolysis is carried out at 35℃ and pH 8.0 for 8 hours to obtain the enzymatic hydrolysis product.

[0169] ③ After filtration of the enzymatic hydrolysis product, the filtrate was separated using a 2.0 kDa filter membrane and concentrated using a 0.3 kDa filter membrane to obtain small molecule collagen peptides with a weight average molecular weight of 0.3 kDa to 2.0 kDa. The filtrate was then freeze-dried or spray-dried to obtain yak skin collagen peptide CPP-I for later use.

[0170] (3) Preparation of spinning solution:

[0171] The following ingredients were prepared: 80 parts purified water, 6 parts gelatin (190g Bloom single gel strength), 18 parts modified polysaccharide CPUL-I, 8 parts yak collagen peptide CPP-I, and 3 parts functional additive, including hydrolyzed sodium hyaluronate (weight average molecular weight 2000 Da). The gelatin and modified polysaccharide CPUL-I were dissolved in deionized water and stirred evenly in a 40°C water bath. The yak collagen peptide CPP-I was added to the above solution and stirred evenly. The hydrolyzed sodium hyaluronate was added to the above solution and stirred evenly. The spinning solution was then prepared for use.

[0172] (4) Preparation of nanofiber membranes:

[0173] The electrospinning solution was placed in a syringe with a metal needle and then placed in an electrospinning apparatus, with silicone release paper covering the receiving roller. The electrospinning parameters were a flow rate of 0.3 mL / h, a voltage of 20 kV, and a distance of 25 cm between the needle tip and the receiving device. Electrospinning was carried out at an ambient temperature of 40°C and a relative humidity of 40%. The nanofibers were collected on the release paper, yielding a biomass nanofiber membrane. The average diameter of the nanofibers in the membrane was approximately 198 ± 30 nm, and the surface was smooth and uniform.

[0174] Example 5

[0175] (1) Preparation of modified polysaccharide CPUL-III:

[0176] Carboxylated nanocellulose with a carboxyl content of 0.9 mmol / g and a median particle size of 30 μm was added to a 30% pullulan aqueous solution (weight average molecular weight 30 wDa). The mass ratio of carboxylated nanocellulose to pullulan was 0.01:1. The mixture was modified in a reactor at 55℃ for 0.8 h, cooled, and discharged for later use.

[0177] (2) Preparation of yak skin collagen peptide CPP-II:

[0178] The preparation steps for the yak collagen peptide with high antioxidant activity are as follows:

[0179] ① After deashing, softening, washing, and cutting, yak hide is pyrolyzed at around 92℃ for 5.5 hours. The pyrolysis liquid is then filtered and centrifuged to obtain the pyrolysis product.

[0180] ② Prepare a pyrolysis product solution with purified water, wherein the mass concentration of the pyrolysis product is 6%. Use protease to hydrolyze the pyrolysis product, wherein the protease includes alkaline protease and neutral protease, and the mass ratio of alkaline protease to neutral protease is 3:1. The total amount of protease used is 7000 U / g. Enzymatic hydrolysis is carried out at 35℃ and pH 8.0 for 6 hours to obtain the enzymatic hydrolysis product.

[0181] ③ After filtration of the enzymatic hydrolysis product, the filtrate was separated using a 1.0 kDa filter membrane and concentrated using a 0.3 kDa filter membrane to obtain small molecule collagen peptides with a weight average molecular weight of 0.3 kDa to 1.0 kDa. The filtrate was then freeze-dried or spray-dried to obtain yak skin collagen peptide CPP-II for later use.

[0182] (3) Preparation of spinning solution:

[0183] The following ingredients were prepared: 70 parts purified water, 10 parts gelatin (170g Bloom single gel strength), 20 parts modified polysaccharide CPUL-III, 10 parts yak hide collagen peptide CPP-II, and 1 part functional additive, wherein the functional additive consisted of sodium hyaluronate and hydrolyzed sodium hyaluronate in a mass ratio of 1:8. The gelatin and modified polysaccharide CPUL-III were dissolved in deionized water and stirred evenly in a 40°C water bath. The yak hide collagen peptide CPP-II was added to the above solution and stirred evenly. The sodium hyaluronate and hydrolyzed sodium hyaluronate were added to the above solution and stirred evenly to obtain the spinning solution for later use.

[0184] (4) Preparation of nanofiber membranes:

[0185] The electrospinning solution was poured into the liquid tank of the needleless electrospinning apparatus, and the collecting screen was covered with silicone paper. The electrospinning parameters were a flow rate of 130 mL / h, a voltage of 30 kV, and a receiving distance of 19 cm between the nozzle and the receiving device. Electrospinning was carried out at an ambient temperature of 35°C and a relative humidity of 40%. The nanofibers were collected on release paper to obtain a biomass nanofiber membrane. The average diameter of the fibers in the nanofiber membrane was approximately 200 ± 25 nm, and the surface was smooth and uniform.

[0186] Comparative Example 1

[0187] (1) Preparation of spinning solution:

[0188] The following ingredients were prepared: 80 parts purified water, 12 parts gelatin (140g Bloom single gel strength), 24 parts unmodified 30% pullulan aqueous solution (PUL), 10 parts yak collagen peptide CPP-II, and 3 parts functional additives, including sodium hyaluronate (weight average molecular weight 20wDa) and hydrolyzed sodium hyaluronate (weight average molecular weight 5000Da) in a mass ratio of 1:10. The gelatin and 30% pullulan aqueous solution (PUL) were dissolved in deionized water and stirred evenly in a 40°C water bath. The yak collagen peptide CPP-II was added to the above solution and stirred evenly. The sodium hyaluronate and hydrolyzed sodium hyaluronate were then added to the above solution and stirred evenly to obtain the spinning solution for later use.

[0189] (2) Preparation of nanofiber membranes:

[0190] The electrospinning solution was placed in a syringe with a metal needle and then placed in an electrospinning apparatus, with silicone release paper covering the receiving roller. The electrospinning parameters were a flow rate of 0.5 mL / h, a voltage of 26 kV, and a distance of 18 cm between the needle tip and the receiving device. Electrospinning was carried out at an ambient temperature of 40°C and a relative humidity of 35%. The nanofibers were collected on the release paper, yielding a biomass nanofiber membrane. The average diameter of the nanofibers in the membrane was approximately 290 ± 30 nm, and the surface was smooth and uniform.

[0191] Comparative Example 2

[0192] (1) Preparation of spinning solution:

[0193] The following ingredients were prepared: 80 parts purified water, 12 parts gelatin (140g Bloom single gel strength), 24 parts unmodified 30% pullulan aqueous solution (PUL), 10 parts bovine hide collagen peptide (prepared using the same method as in Example 1, except that bovine hide collagen was replaced with bovine hide collagen), and 1 part functional additive, which consisted of sodium hyaluronate (weight average molecular weight 20 wDa) and hydrolyzed sodium hyaluronate (weight average molecular weight 5000 Da) in a mass ratio of 1:10. The gelatin and 30% pullulan aqueous solution (PUL) were dissolved in deionized water and stirred evenly in a 40°C water bath. The bovine hide collagen peptide was added to the above solution and stirred evenly. The sodium hyaluronate and hydrolyzed sodium hyaluronate were added to the above solution and stirred evenly. The spinning solution was then prepared for use.

[0194] (2) Preparation of nanofiber membranes:

[0195] The electrospinning solution was placed in a syringe with a metal needle and then placed in an electrospinning apparatus, with silicone release paper covering the receiving roller. The electrospinning parameters were a flow rate of 0.5 mL / h, a voltage of 26 kV, and a distance of 18 cm between the needle tip and the receiving device. Electrospinning was carried out at an ambient temperature of 40°C and a relative humidity of 35%. The nanofibers were collected on the release paper, yielding a biomass nanofiber membrane. The average diameter of the nanofibers in the membrane was approximately 293 ± 96 nm, and the surface was smooth but exhibited poor uniformity.

[0196] Performance testing

[0197] 1. Scanning electron microscopy observation and fiber diameter distribution

[0198] The morphology of the biomass nanofiber membranes of Examples 1-5 and Comparative Examples 1-2 was observed using scanning electron microscopy, and the results are shown in Figures 1-7.

[0199] The morphology and diameter of the nanofibers were observed using scanning electron microscopy. One hundred nanofibers were randomly selected, and their diameter distribution was statistically analyzed using measurement software.

[0200] As shown in Figures 1-5, the novel all-biomass nanofiber mask containing natural yak protein antioxidant peptides exhibits a good microstructure, without beading or spindle structures. The nanofiber surface is smooth and the diameter distribution is uniform, ranging from 100 to 280 nm. Nanofiber masks made with modified polysaccharides as fibroblasting materials demonstrate better toughness and strength.

[0201] As can be seen from Figures 6 and 7, the nanofibers in Comparative Example 1 have a smooth surface and a uniform diameter distribution, but the diameter is too large, ranging from 260 to 320 nm, which is not conducive to the compounding of functional components.

[0202] 2. Antioxidant test

[0203] Determination of DPPH scavenging capacity: Biomass nanofiber membranes from Examples 1-4 and Comparative Example 2 were accurately weighed and placed in water to prepare a 50 mg / ml sample stock solution. A 0.2 mmol / h DPPH solution was prepared using 95% ethanol. 2 ml of this solution was mixed with 2 ml of the sample stock solution, shaken well, and stored at room temperature in the dark for 30 min before being used as the experimental group. The absorbance of the experimental group was measured at 517 nm. 2 ml of distilled water was used instead of the sample stock solution and mixed with the above DPPH solution for the same treatment, serving as the control group. The absorbance of the control group was measured, and the DPPH free radical scavenging rate was calculated using the following formula (1). The results are shown in Figure 8.

[0204] Where A0 represents the absorbance of the control group;

[0205] A represents the absorbance value of the experimental group.

[0206] ·O 2-Determination of free radical scavenging ability: Accurately weigh the biomass nanofiber membranes from Examples 1-4 and Comparative Example 2, and place them separately in water to prepare a 50 mg / ml sample stock solution. Prepare a 50 mmol / L Tris-HCl buffer solution (pH 8.2), add 4.5 mL to 0.2 mL of the sample stock solution, mix well, and incubate at 25°C for approximately 15 min; this is reagent A. Prepare a 3 mmol / L pyrogallol solution (solvent: 10 mmol / L HCl), take 0.3 mL, and incubate at 25°C for approximately 15 min; this is reagent B. Quickly mix reagent A and reagent B, and shake well; this is the experimental group. Measure the slope of the absorbance change at 320 nm for the experimental group every 30 seconds. Use distilled water instead of the sample stock solution mixed with reagent B as the control group; measure the slope of the absorbance change at 320 nm for the control group. 2- The free radical scavenging rate was calculated using the following formula (2), and the result is shown in Figure 8:

[0207] Wherein, Kc represents the slope of the change in absorbance at 320 nm for the control group;

[0208] Ks represents the slope of the change in absorbance at 320 nm for the experimental group.

[0209] • Determination of OH radical scavenging ability: Accurately weigh the biomass nanofiber membranes from Examples 1-4 and Comparative Example 1, and place them in water to prepare a 50 mg / ml sample stock solution. Prepare 0.75 mmol / L o-phenanthroline solution, 0.2 mol / L pH 7.4 phosphate buffer solution, 0.75 mmol / L FeSO4·7H2O solution, and 0.01% (v / v) H2O2 solution. Mix 1 mL of o-phenanthroline solution with 1 mL of sample stock solution, add 2 mL of phosphate buffer solution, then add 1 mL of FeSO4·7H2O solution and mix well. Finally, place the mixture with 1 mL of H2O2 solution in a 37℃ water bath for 60 min. This mixture is used as the experimental group. Replace the H2O2 solution with 1 mL of distilled water, and perform the same treatment as the experimental group. This mixture is used as the blank control group. Replace the sample stock solution with 1 mL of distilled water, and perform the same treatment as the experimental group. This mixture is used as the negative control group. The absorbance values ​​of the experimental group, blank control group and negative control group were measured at a wavelength of 536 nm. The elimination rate of ·OH free radicals was then calculated according to the following formula (3). The results are shown in Figure 8.

[0210] In the formula, A C : Absorbance value of the blank control group;

[0211] A S : Absorbance values ​​of the experimental group;

[0212] A'0: Absorbance value of the negative control group;

[0213] As can be seen from Figure 8, the biomass nanofiber membranes of Examples 1-4 of the present invention exhibit excellent antioxidant properties. Furthermore, the free radical scavenging rates of Examples 1-4 are all higher than those of Comparative Example 2.

[0214] 3. Mechanical performance testing

[0215] The prepared fiber membrane was cut into 60mm×10mm samples and its mechanical properties were tested using an electronic universal tensile testing instrument. The results are shown in Table 1.

[0216] Table 1

[0217] As can be seen from Table 1, the biomass nanofiber membranes of Examples 1-5 of this application have an elastic modulus of 60 MPa or more and a tensile strength of 4 MPa or more, which are superior to those of Comparative Example 1 in terms of both elastic modulus and tensile strength.

[0218] 4. Solubility test

[0219] The biomass nanofiber membrane and the fiber raw material powder were placed in petri dishes containing water, and the entire dissolution process was recorded with a camera. The results are shown in Figure 9.

[0220] As shown in Figure 9, when the biomass nanofiber membrane slowly comes into contact with the water surface, the water-contaminated portion immediately dissolves and disappears, completely and rapidly dissolving within 7 seconds. However, the raw materials mixed in the specified proportions are difficult to dissolve. This result indicates that the biomass nanofiber membrane has excellent water solubility. This is because the fibrous material has good hydrophilicity, and the biomass nanofiber membrane has a high specific surface area and nanoscale porosity, which allows water to quickly penetrate into the material and dissolve rapidly without stirring.

[0221] It should be noted that although the technical solution of the present invention has been described with specific examples, those skilled in the art will understand that the present invention should not be limited thereto.

[0222] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A biomass nanofiber membrane, characterized by, The biomass nanofiber membrane is composed of interwoven fibers, the diameter of which is 100 nm to 280 nm; wherein, The fiber is derived from fiber raw materials, which include modified polysaccharides, gelatin, and collagen peptides; and... The modified polysaccharide contains 8 to 24 parts by weight, the gelatin contains 4 to 12 parts by weight, and the collagen peptide contains 2 to 10 parts by weight.

2. The biomass nanofiber membrane according to claim 1, wherein, The modified polysaccharide includes a polysaccharide modified with nanocellulose; Preferably, the nanocellulose-modified polysaccharide is obtained by mixing and modifying nanocellulose and polysaccharide; wherein the mass ratio of nanocellulose to polysaccharide is 0.003–0.01:1; and / or, The modification treatment temperature is 40℃~60℃, and the modification treatment time is 0.5h~2h.

3. The biomass nanofiber membrane according to claim 2, wherein, The nanocellulose-modified polysaccharide includes pullulan polysaccharide modified with carboxylated nanocellulose; Preferably, the carboxyl content in the carboxylated nanocellulose is 0.5 mmol / g to 1.0 mmol / g, and / or the median particle size of the carboxylated nanocellulose is 20 μm to 40 μm; More preferably, the pullulan polysaccharide has a weight-average molecular weight of 10 wDa to 30 wDa.

4. The biomass nanofiber membrane according to any one of claims 1-3, wherein, The collagen peptides are derived from the pyrolysis products of yak hide; Preferably, the collagen peptides are obtained by extracting the pyrolysis products of yak hide using a protease.

5. The biomass nanofiber membrane according to claim 4, wherein, The collagen peptides were prepared by the following method: Pyrolysis step: The pretreated yak hide is subjected to pyrolysis treatment to obtain the yak hide pyrolysis product; preferably, the temperature of the pyrolysis treatment is 80℃~100℃ and the time of the pyrolysis treatment is 4h~6h. Enzymatic hydrolysis step: The pyrolysis product of yak hide is enzymatically hydrolyzed using a protease to obtain the hydrolysate; preferably, the protease includes an alkaline protease and / or a neutral protease, more preferably, the mass ratio of the alkaline protease to the neutral protease is 2:1 to 5:1; even more preferably, the amount of protease used is 6000 U / g to 8000 U / g; and / or, The enzymatic hydrolysis treatment is performed at a temperature of 35℃ to 45℃, at a pH value of 8.0 to 8.5, and for a time of 2 hours to 10 hours. Optionally, the mass concentration of the yak hide pyrolysis product is adjusted to 5-10%, and then enzymatic hydrolysis is performed.

6. The biomass nanofiber membrane according to claim 5, wherein, Following the enzymatic hydrolysis step, the method further includes a step of obtaining collagen peptides with a weight-average molecular weight of 0.3 kDa to 2.0 kDa, preferably 0.3 kDa to 1.0 kDa, through separation processing. Preferably, the collagen peptides are obtained by separation using a 2.0 kDa filter membrane, more preferably a 1.0 kDa filter membrane, followed by concentration using a 0.3 kDa filter membrane.

7. The biomass nanofiber membrane according to any one of claims 1-6, wherein, The gelatin has a single gelling strength of 100g Bloom to 200g Bloom; and / or, The fiber raw material also includes functional additives, wherein the content of the functional additives is 1 to 5 parts; preferably, the functional additives include one or more of the following: biomass glycerin, aloe vera gel, rice hydrolyzed peptides, sodium hyaluronate, hydrolyzed sodium hyaluronate, menthol, and calendula extract. More preferably, the weight-average molecular weight of the sodium hyaluronate is between 20 wDa and 130 wDa, and the weight-average molecular weight of the hydrolyzed sodium hyaluronate is between 1000 Da and 5000 Da.

8. A method for producing the biomass nanofiber membrane according to any one of claims 1 to 7, characterized by, Includes the following steps: The fiber raw material is dissolved in a solvent to obtain a spinning solution; A film-like product was prepared using a spinning process; Preferably, the solvent content is 60 to 80 parts by weight; More preferably, the spinning process may include electrospinning and / or centrifugal spinning, with electrospinning being the preferred method.

9. The production method according to claim 8, characterized by, The electrospinning process parameters include: controlling the ambient temperature during the electrospinning process to be 30℃~40℃ and the relative humidity to be 30%~45%; adjusting the flow rate to be 0.2mL / h~0.6mL / h and the voltage to be 15kV~26kV; and adjusting the receiving distance of the receiving device to be 15cm~25cm.

10. The use of a biomass nanofiber membrane according to any one of claims 1-7 in the preparation of a facial mask patch.

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