MCM-41 composite cinnamyl aldehyde-carvacrol essential oil nano edible film and preparation method thereof

Abstract

The invention provides an MCM-41 composite cinnamyl aldehyde-carvacrol essential oil nano edible film and a preparation method thereof. The preparation method comprises the following steps: preparing modified MCM-41, constructing MCM-41 composite cinnamyl aldehyde-carvacrol essential oil nano particles, and preparing a multifunctional composite edible film formula. According to the invention, cinnamyl aldehyde-carvacrol essential oil is wrapped with lecithin and selenoprotein, and MCM-41 is subjected to carboxyl modification. The modified MCM-41 can improve the compatibility with hydrophilic phospholipid and protein, and increase the loading capacity for essential oil nanoparticles. The loaded MCM-41 is compounded with gelatin, dextran and D-selenomethionine to form a film, and the D-selenomethionine has oxidation resistance, so that the edible film is endowed with excellent antibacterial and oxidation resistance, and the problems of single performance, poor stability of active ingredients and the like of a traditional edible film are solved.

Description

Technical Field

[0001] The invention belongs to the field of food science and technology, and particularly relates to an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film and a preparation method thereof. Background Art

[0002] In recent years, with growing environmental awareness, research on food wrap has shifted from wraps made from compounds like polypropylene and polyethylene to edible films made from polysaccharides, proteins, and oils. Polysaccharides have become the primary material for edible film research due to their favorable chemical properties and readily available properties. However, most current polysaccharide-based edible films are primarily based on chitosan, β-cyclodextrin, and modified starch, or blends of these materials. Edible films made from various matrices still have shortcomings during production: (1) There are many types of sugars, and there is currently no optimization of the film-making process and performance characterization of different types of glucans as film-forming matrices. (2) Edible films based on polysaccharides, proteins, oils, etc. have poor antibacterial and antioxidant effects, and poor moisture and oil resistance. (3) Due to cost issues, edible films cannot replace traditional plastic materials as a widespread food packaging material in the short term. Gelatin film, due to its excellent film-forming properties, biodegradability, and biocompatibility, has become a research hotspot. However, gelatin film has inherent flaws. Its molecular structure contains a large number of hydrophilic groups, resulting in poor water resistance. It easily absorbs water and swells in high humidity environments, causing a sharp decline in mechanical properties, limiting its application in food packaging in humid environments. Furthermore, gelatin film alone lacks antimicrobial activity and cannot effectively inhibit the growth and reproduction of microorganisms on food surfaces, making it difficult to extend food shelf life and ensure food safety. Essential oils such as carvacrol and cinnamaldehyde possess broad-spectrum antimicrobial activity, significantly inhibiting foodborne pathogens such as Escherichia coli, Staphylococcus aureus, and Listeria monocytogenes. They exert their antimicrobial efficacy by disrupting bacterial cell membranes and interfering with cellular metabolism. However, essential oils are volatile and unstable. Under the influence of environmental factors (such as light, temperature, and humidity), the active ingredients are easily lost, making it difficult to maintain their antimicrobial effects. Therefore, improving the stability and controlled-release properties of essential oils has become a key challenge in their application in food packaging. Domestic and foreign research has shown that the addition of nanoparticles effectively improves the mechanical properties, biodegradability, and antibacterial properties of the film. At the same time, the application of nanotechnology in edible films has great potential. At present, the nanomaterials used in edible film modification research also have the advantages of environmental friendliness, biodegradability, renewability, biocompatibility, and safety. The chemical properties, size, and shape of nanomaterials are the main factors in improving the overall mechanical properties of composite edible films. The chemical composition of the nanofiller affects its interaction with the substrate polymer, which helps to transfer stress at the interface of the edible film, while the interaction between the nanofillers will lead to the agglomeration of nanomaterials at high volume fractions. Therefore, in the preparation process of nanocomposite edible films, the nanocomponents must be evenly dispersed in the matrix, and the stress transfer of the composite material must be improved by breaking up the nanomaterial agglomerates and ensuring good compatibility with other substrate polymers. MCM-41 mesoporous molecular sieve was first synthesized by Mobil Corporation in the United States in 1992. It has a unique hexagonal mesoporous structure with a pore size between 2-10 nm, uniformly distributed, and a specific surface area of ​​up to 1000 m 2 / g or more, providing ample space for the loading of active substances. Numerous studies on the modification and loading of MCM-41 have shown that its ordered pore structure facilitates the uniform dispersion and slow release of active ingredients, making it an ideal nanocarrier. Summary of the Invention

[0003] Technical problem to be solved: In order to solve the environmental protection and food safety and health problems of traditional synthetic plastic packaging materials and improve the shortcomings of edible films made from different nanoparticles that still exist in the production process, the present invention modifies MCM-41, constructs essential oil nanoparticles, and adjusts the formula of the multifunctional composite edible film to increase the loading of cinnamaldehyde-carvacrol essential oil, thereby improving the stability, mechanical properties and antibacterial properties of the nano edible film. The added selenoprotein and D-selenomethionine have enzyme and oxidation responsiveness, further improving the antioxidant performance.

[0004] Technical solution: A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film, comprising the following steps: Step 1. Preparation of a composite membrane-forming solution: Mix equal amounts of a dextran acetate aqueous solution and a gelatin aqueous solution, add D-selenomethionine, stir at room temperature, add glycerol, mix thoroughly, then add Tween-80, and finally add MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles, and mix thoroughly to obtain a composite membrane-forming solution; Step 2. Preparation of edible film: ultrasonically defoam the multifunctional composite edible film liquid, pour it into a mold and dry it to obtain the MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film. Furthermore, the glucan in the glucan acetic acid aqueous solution in step 1 is any one of konjac glucomannan, highland barley β-glucan, oat β-glucan and yeast β-glucan. Furthermore, in step 1, the concentration of the dextran acetic acid aqueous solution is 1-3wt.%, the concentration of the gelatin aqueous solution is 1-3wt.%, the D-selenomethionine in the multifunctional composite membrane-forming liquid is food grade, with a content of 0.05-0.2wt.%, the contents of glycerol and Tween-80 are both 0.05-0.2wt.%, and the MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles are 0.1-0.25wt.%, and the stirring conditions at room temperature are 300-400rpm for 2-3h. Furthermore, the ultrasonic defoaming time in step 2 is 20-40 minutes, and the drying temperature is 40-50° C. for 8-10 hours. Furthermore, the preparation method of the MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles in step 1 is as follows: S1. Amino-modified MCM-41: MCM-41 was dried and mixed with 3-aminopropyltriethoxysilane in ethanol with continuous stirring. The mixture was then washed with ethanol and water and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate, succinic anhydride was added, and the mixture was evaporated under vacuum to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed as the oil phase, selenoprotein and lecithin were mixed as the aqueous phase, and the oil and aqueous phases were homogenized by microfluidization to obtain a primary emulsion; S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed by ultrasonication, shaken and then dried. Furthermore, in step S1, the drying temperature is 110-120° C., the drying time is 1-3 h, the ratio of MCM-41 to 3-aminopropyltriethoxysilane is 1:(3-5), and the continuous stirring condition is 45-55° C., 4-6 h. Furthermore, the dispersion conditions in step S2 are stirring at 50-60° C. for 18-24 h, the concentration of succinic anhydride is 6-7 mmol, and the vacuum evaporation drying temperature is 25-30° C. for 5-6 h. Furthermore, in step S3, the ratio of cinnamaldehyde to carvacrol is 1:1, the ratio of selenoprotein to lecithin is 1:2, the concentration of the aqueous solution is 2-4 wt.%, the ratio of the oil phase to the aqueous phase is 1:(9-14), and the pressure of the microjet homogenization is 20-30 MPa and the cycle is 2 to 5 times. Furthermore, in step S4, the ratio of MCM-41-COOH to primary emulsion is 1:(40-60), the ultrasonic time is 15-35 min, and the shaking condition is 30° C. for 15-35 h. The MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film prepared by the above preparation method. The MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film prepared by the above preparation method is used in food packaging and preservation. Beneficial effects: 1. The present invention mixes essential oils with phospholipids and proteins to form an emulsion system, preventing the polymerization of cinnamaldehyde. Meanwhile, carboxyl-modified MCM-41 improves its hydrophilicity. The carboxyl groups can bind to the hydrophilic head of the phospholipid through hydrogen bonds, allowing for better binding with the phospholipid. The small-particle emulsion has a larger specific surface area, increasing the contact opportunity with the pores of MCM-41 and promoting physical adsorption or chemical bonding, thereby increasing the loading of MCM-41 on cinnamaldehyde-carvacrol essential oil, achieving slow release of the active ingredient, and prolonging the antibacterial effect. 2. The present invention uses selenoprotein and lecithin to emulsify cinnamaldehyde-carvacrol essential oil. Selenoprotein has antioxidant properties, which can protect cinnamaldehyde and carvacrol from oxidative degradation and maintain their stability. The selenium-containing groups may form hydrogen bonds or electrostatic interactions with the surface-modified carboxyl groups of MCM-41, enhancing the load binding force. At the same time, the selenoprotein is decomposed by proteases secreted by bacteria. Once the selenoprotein structure is destroyed by bacteria, the cinnamaldehyde-carvacrol essential oil is rapidly released to exert its antibacterial effect. 3. The present invention adopts gelatin, dextran and D-selenomethionine to form a composite film. D-selenomethionine can exhibit significant oxidative response characteristics by directly removing ROS, enhancing the activity of antioxidant enzymes and dynamic redox cycling. When in a ROS-enriched environment, selenium atoms may be oxidized to selenium oxides, resulting in changes in molecular conformation or chemical bond breakage, thereby triggering the degradation of the composite edible film and the release of cinnamaldehyde-carvacrol essential oil. 4. The film is formed by combining gelatin, dextran, and D-selenomethionine. Gelatin provides a rigid skeleton, enhancing the tensile strength of the film through hydrogen bonding and electrostatic interactions. Dextran increases flexibility and tear resistance, reduces film brittleness, and improves ductility. The antioxidant capacity of selenium combined with the natural moisturizing properties of gelatin protects the loaded essential oil from oxidative degradation, giving the edible film excellent antibacterial and antioxidant properties. This addresses the problems of traditional edible films with single performance and poor stability of active ingredients. 5. The edible plastic wrap of the present invention is used as a product packaging material. Its main component is natural polymer, which can be rapidly degraded in the natural environment, reducing environmental pollution. Its ingredients are natural and edible, avoiding the health risks caused by the migration of plasticizers in traditional plastics, avoiding the risk of packaging waste contacting food, and also avoiding the risk of children accidentally ingesting it. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 Figure 3: The effects of different essential oil nanoparticle preparation methods on the cinnamic aldehyde-carvacrol embedding efficiency. Figure A shows the effect of ultrasonic time on the cinnamic aldehyde-carvacrol embedding efficiency. Figure B shows the effect of the ratio of oil phase to water phase on the cinnamic aldehyde-carvacrol embedding efficiency. Figure C shows the effect of the ratio of MCM-41-COOH and primary emulsion on the cinnamic aldehyde-carvacrol embedding efficiency. Figure D shows the effect of oscillation time on the cinnamic aldehyde-carvacrol embedding efficiency. Figure 2 This is a graph showing the cinnamaldehyde-carvacrol embedding efficiency of Example 15 and Comparative Examples 1-3; Figure 3 This is a graph showing the release rate of the composite essential oil of Example 15 and Comparative Examples 1-3; Figure 4 Figure 3 shows the influence of different preparation methods of glucan edible films on the mechanical properties of edible films. Figure A shows the influence of glucan concentration on the tensile strength TS of four edible films. Figure B shows the influence of glucan concentration on the elongation E of four edible films. Figure C shows the influence of gelatin concentration on the tensile strength TS of four edible films. Figure D shows the influence of gelatin concentration on the elongation E of four edible films. Figure E shows the influence of glycerol concentration on the tensile strength TS of four edible films. Figure F shows the influence of glycerol concentration on the elongation E of four edible films. Figure G shows the influence of Tween-80 concentration on the tensile strength TS of four edible films. Figure H shows the influence of Tween-80 concentration on the elongation E of four edible films. DETAILED DESCRIPTION The present invention will be further described below with reference to the accompanying drawings and embodiments. The following embodiments are intended to explain the present invention, but the present invention is not limited to the following embodiments: Example 1 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:9 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:9 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:40, sonicated for 15 min, shaken at 30°C for 15 h, and then dried. Example 2 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:9 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:9 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:40, sonicated for 20 min, shaken at 30°C for 15 h, and then dried. Example 3 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:9 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:9 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:40, sonicated for 25 min, shaken at 30°C for 15 h, and then dried. Example 4 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:9 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:9 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:40, sonicated for 30 min, shaken at 30 °C for 15 h, and then dried. Example 5 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:9 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:9 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:40, sonicated for 35 min, shaken at 30°C for 15 h, and then dried. Example 6 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:9 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:10 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the cycle was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:40, sonicated for 30 min, shaken at 30 °C for 15 h, and then dried. Example 7 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:9 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:11 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was cycled three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:40, sonicated for 30 min, shaken at 30 °C for 15 h, and then dried. Example 8 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:2 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:10 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed at a ratio of 1:50, sonicated for 30 min, shaken at 30 °C for 15 h, and then dried. Example 9 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:2 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:10 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed at a ratio of 1:60, sonicated for 30 min, shaken at 30 °C for 15 h, and then dried. Example 10 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:2 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:10 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed at a ratio of 1:50, sonicated for 30 min, shaken at 30 °C for 20 h, and then dried. Example 11 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:2 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:10 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:50, sonicated for 30 min, shaken at 30 °C for 25 h, and then dried. Example 12 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:2 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:10 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:50, sonicated for 30 min, shaken at 30 °C for 30 h, and then dried. Example 13 The preparation method of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles comprises the following steps: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:2 to prepare a 3 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:10 and homogenized by microfluidization to obtain a primary emulsion. The microfluidization pressure was 25 MPa and the mixture was repeated three times. S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:50, sonicated for 30 min, shaken at 30°C for 35 h, and then dried. Comparative Example 1 The difference between this comparative example and Example 2 is that MCM-41 is not modified, as follows: S1. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, selenoprotein and lecithin were mixed in a ratio of 1:2 to prepare a 3 wt.% aqueous solution, and the oil and aqueous phases were mixed in a ratio of 1:10 and homogenized by microfluidization at a pressure of 25 MPa for three cycles to obtain a primary emulsion. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed at a ratio of 1:50, sonicated for 30 min, shaken at 30 °C for 30 h, and then dried. Comparative Example 2 The difference between this comparative example and Example 2 is that no emulsion is prepared with cinnamaldehyde and carvacrol essential oils, specifically as follows: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of mixed oil phase: Mix cinnamaldehyde and carvacrol essential oil in a ratio of 1:1; S4. Preparation of essential oil nanoparticles: MCM-41-COOH and mixed oil phase were mixed in a ratio of 1:5, sonicated for 30 min, shaken at 30°C for 30 h, and then dried. Comparative Example 3 The difference between this comparative example and Example 2 is that no selenoprotein is added, specifically as follows: S1. Amino-modified MCM-41: MCM-41 was dried at 120°C for 2 h, mixed with 3-aminopropyltriethoxysilane in ethanol at a ratio of 1:4, and stirred continuously at 50°C for 5 h. The mixture was then washed twice with ethanol and water, and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate at 60°C and stirred for 24 h. 6 mmol of succinic anhydride was added and the mixture was evaporated and dried under vacuum at 25°C for 6 h to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed in a ratio of 1:1 as the oil phase, lecithin was prepared into a 2 wt.% aqueous solution, the oil phase and the aqueous phase were mixed in a ratio of 1:10 and homogenized by microfluidization to obtain a primary emulsion, the microfluidization pressure was 25 MPa and the cycle was repeated 3 times; S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed in a ratio of 1:50, sonicated for 30 min, shaken at 30 °C for 30 h, and then dried. Indicator testing (1) Determination of embedding efficiency Measure 0.1, 0.2, 0.3, 0.4, and 0.5 mL of a 2.5 mg / mL cinnamaldehyde-carvacrol essential oil ethanol solution and dilute to a 50 mL volumetric flask with anhydrous ethanol to prepare ethanol solutions of the compound essential oil at concentrations of 5, 10, 15, 20, and 25 mg / L. The absorbance was measured at the wavelength of maximum absorption, and a linear regression curve was performed to generate a standard curve for the compound essential oil, with concentration (C) as the abscissa and absorbance (A) as the ordinate. Weigh 0.2g of microcapsules, add 22.5mL of anhydrous ethanol, stir magnetically for 30min, ultrasonicate at 80℃ for 2h, filter, dilute the filtrate to 25mL, measure the absorbance at 218nm, and substitute the standard curve to obtain the total oil content. Surface oil determination method: Weigh 0.2g of microcapsules, add 22.5mL of anhydrous ethanol, shake for 20s and filter, dilute the filtrate to 25mL, measure the absorbance at 298nm, and substitute the standard curve to obtain the surface oil content. Calculate the embedding rate by the formula: Embedding rate (%) = (1-surface oil / total oil) × 100% Figure 1 The results of the effects of ultrasonic time, the ratio of oil phase to water phase, the ratio of MCM-41-COOH to primary emulsion and shaking time on the embedding efficiency (respectively as Figure 1 -A, 1-B, 1-C and 1-D), within the set ultrasonic time range, the embedding rate first decreases and then increases with the ultrasonic time (Examples 1-5) and then tends to be flat. When the ultrasonic time is 30min (Example 4), the embedding rate reaches a maximum value of 89.61%. At this time, the embedding rate will not increase if the ultrasonic time is extended. On the contrary, it may cause the volatilization of the plant essential oil, destroy the hydrophobic force, and the embedding rate will decrease instead. Therefore, the optimal ultrasonic time is set to 30min. With the increase of the ratio of oil phase to water phase (Examples 4, 6-7), the embedding rate of the particles continues to increase, but the rate of increase decreases slightly and gradually tends to be flat. When the ratio is 1:10 (Example 6), the embedding rate is 90.65%, and then tends to be flat. This may be that when the oil phase and the water phase reach a certain ratio, the composite essential oil is close to saturation in the system, and the continued addition of the water phase will have less and less effect on the embedding rate. The effect of the ratio of MCM-41-COOH and primary emulsion on the embedding rate is shown in Figure 2. Figure 1 As shown in Figures 1-C, the embedding efficiency first increases and then decreases with the addition of primary emulsion (Examples 6, 8-9). When the ratio is 1:50 (Example 8), the embedding efficiency reaches its maximum. As the shaking time increases (Examples 8, 10-13), the embedding efficiency first increases and then tends to level off. After 30 hours, the embedding efficiency does not increase with time, and the optimal shaking time is 30 hours (Example 12). The encapsulation efficiency was determined by selecting the best embodiment 12 and comparative examples 1-4. The results are as follows: Figure 2 The encapsulation efficiency of Example 12 is significantly higher than that of the comparative example, which indicates that the modified MCM-41 improves its hydrophilicity and ability to bind to phospholipids. The network structure is more stable after the combination of lecithin and protein. As an amphiphilic substance, it has a significant effect in encapsulating essential oils. (2) Analysis of the release of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles at room temperature 0.010 g of sample was injected into a screw-capped tube containing 5 mL of a 50% aqueous alcohol solution. The tube was then incubated at 25°C (room temperature) and the amount of cinnamaldehyde-carvacrol essential oil present in the supernatant was measured periodically (5, 10, 15, 20, 25 and 30 days). The release rate was calculated using the following formula. Where E (%) is the release efficiency; Pr is the g of essential oil released; and Pt is the total amount of essential oil encapsulated. Figure 3 The percentage of cinnamaldehyde-carvacrol essential oil released at 25°C is illustrated. For all samples, the release is positively correlated with time. Nevertheless, throughout the storage period, the release rate of Example 12 is significantly lower than that of the cinnamaldehyde-carvacrol essential oil in the comparative example (p<0.05). Specifically, the release rate of Example 12 is only 50.56% at 30d, which is much lower than that of Comparative Example 1 with the addition of unmodified MCM-41 and Comparative Example 2 without the addition of lecithin protein. These findings indicate that the MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles prepared in the present invention greatly reduce the volatilization loss of the essential oil and show an efficient sustained-release effect. The encapsulation of the present invention can prolong the release of cinnamaldehyde-carvacrol essential oil, providing broad prospects for its application in prefabricated preservation. (3) Antioxidant activity determination The free radical scavenging ability of the samples was tested using DPPH kit and ABTS kit. As shown in Table 1, the antioxidant activity of Example 12 was significantly better than that of the comparative example. In comparative example 3, no selenoprotein with antioxidant activity was added, which reduced the free radical scavenging rate. In comparative example 2, MCM-41-COOH directly encapsulated the essential oil, lacking the protection of lecithin and protein. The stability and antioxidant activity of the MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were affected. Table 1 Example 14 A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film comprises the following steps: Step 1. Preparation of a composite membrane-forming solution: 2 wt.% konjac glucomannan acetic acid aqueous solution and 2 wt.% gelatin aqueous solution were mixed in equal amounts, 0.1 wt.% D-selenomethionine was added, and the mixture was stirred at 400 rpm at room temperature for 2 hours. 0.15 wt.% glycerol was added and mixed uniformly, followed by 0.15 wt.% Tween-80. Finally, 0.15 wt.% MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were added and mixed uniformly to obtain a composite membrane-forming solution. Step 2. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain konjac glucomannangelatin edible film (KGMF). Example 15 A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film comprises the following steps: Step 1. Preparation of a composite film-forming solution: 2 wt.% highland barley β-glucan acetic acid aqueous solution and 2 wt.% gelatin aqueous solution were mixed in equal amounts, 0.1 wt.% D-selenomethionine was added, and the mixture was stirred at 400 rpm for 2 hours at room temperature. 0.10 wt.% glycerol was added and mixed uniformly, followed by 0.10 wt.% Tween-80. Finally, 0.15 wt.% MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were added and mixed uniformly to obtain a composite film-forming solution. Step 2. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain barley β-glucan-MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film (Barley β-glucan Gelatin edible film, BGF). Example 16 A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film comprises the following steps: Step 1. Preparation of a composite film-forming solution: 2 wt.% oat beta-glucan acetic acid aqueous solution and 2.5 wt.% gelatin aqueous solution were mixed in equal amounts, 0.1 wt.% D-selenomethionine was added, and the mixture was stirred at 400 rpm at room temperature for 2 hours. 0.15 wt.% glycerol was added and mixed uniformly, followed by 0.10 wt.% Tween-80. Finally, 0.15 wt.% MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were added and mixed uniformly to obtain a composite film-forming solution. Step 2. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain oat β-glucan-MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film (Oatsβ-Dextrangelatin edible film, ODF). Example 17 A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film comprises the following steps: Step 1. Preparation of a composite membrane-forming solution: 2 wt.% yeast β-glucan acetic acid aqueous solution and 2 wt.% gelatin aqueous solution were mixed in equal amounts, 0.1 wt.% D-selenomethionine was added, and the mixture was stirred at 400 rpm for 2 h at room temperature. 0.15 wt.% glycerol was added and mixed uniformly, followed by 0.10 wt.% Tween-80. Finally, 0.15 wt.% MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were added and mixed uniformly to obtain a composite membrane-forming solution. Step 2. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain yeast β-glucan-MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film (Yeast β-Dextrangelatin edible film, YDF). Example 18 A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film comprises the following steps: Step 1. Preparation of a composite membrane-forming solution: 2 wt.% highland barley β-glucan acetic acid aqueous solution and 2 wt.% gelatin aqueous solution were mixed in equal amounts, 0.1 wt.% D-selenomethionine was added, and the mixture was stirred at 400 rpm at room temperature for 2 hours. 0.10 wt.% glycerol was added and mixed uniformly, followed by 0.10 wt.% Tween-80. Finally, 0.10 wt.% MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were added and mixed uniformly to obtain a composite membrane-forming solution. Step 2. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain the MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film. Example 19 A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film comprises the following steps: Step 1. Preparation of a composite film-forming solution: 2 wt.% highland barley β-glucan acetic acid aqueous solution and 2 wt.% gelatin aqueous solution were mixed in equal amounts, 0.1 wt.% D-selenomethionine was added, and the mixture was stirred at 400 rpm for 2 hours at room temperature. 0.10 wt.% glycerol was added and mixed uniformly, followed by 0.10 wt.% Tween-80. Finally, 0.20 wt.% MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were added and mixed uniformly to obtain a composite film-forming solution. Step 2. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain the MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film. Example 20 A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film comprises the following steps: Step 1. Preparation of a composite film-forming solution: 2 wt.% highland barley β-glucan acetic acid aqueous solution and 2 wt.% gelatin aqueous solution were mixed in equal amounts, 0.1 wt.% D-selenomethionine was added, and the mixture was stirred at 400 rpm at room temperature for 2 hours. 0.10 wt.% glycerol was added and mixed uniformly, followed by 0.10 wt.% Tween-80. Finally, 0.25 wt.% MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were added and mixed uniformly to obtain a composite film-forming solution. Step 2. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain the MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film. Comparative Example 4 The difference between this comparative example and Example 15 is that MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles are not added, specifically as follows: Step 1. Mix cinnamaldehyde and carvacrol essential oil in a ratio of 1:1 to form an oil phase; Step 2. 2 wt.% highland barley beta-glucan acetic acid aqueous solution and 2 wt.% gelatin aqueous solution were mixed in equal amounts, 0.1 wt.% D-selenomethionine was added, 0.10 wt.% oil phase was added, and the mixture was stirred at 400 rpm for 2 h at room temperature. 0.10 wt.% glycerol was added and mixed uniformly, followed by 0.10 wt.% Tween-80, and the mixture was mixed uniformly to obtain a composite membrane-forming solution; Step 3. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain a common edible film. Comparative Example 5 The difference between this comparative example and Example 15 is that no glycerol is added, specifically as follows: A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film comprises the following steps: Step 1. Preparation of a composite film-forming solution: 2 wt.% highland barley β-glucan acetic acid aqueous solution and 2 wt.% gelatin aqueous solution were mixed in equal amounts, 0.1 wt.% D-selenomethionine was added, and the mixture was stirred at 400 rpm at room temperature for 2 hours. 0.10 wt.% Tween-80 was added, and finally 0.15 wt.% MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were added and mixed uniformly to obtain a composite film-forming solution; Step 2. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain the MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film. Comparative Example 6 The difference between this comparative example and Example 15 is that Tween-80 is not added, as follows: A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film comprises the following steps: Step 1. Preparation of a composite film-forming solution: 2 wt.% highland barley β-glucan acetic acid aqueous solution and 2 wt.% gelatin aqueous solution were mixed in equal amounts, 0.1 wt.% D-selenomethionine was added, and the mixture was stirred at 400 rpm for 2 hours at room temperature. 0.10 wt.% glycerol was added and mixed uniformly, followed by 0.10 wt.% Tween-80. Finally, 0.15 wt.% MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were added and mixed uniformly to obtain a composite film-forming solution. Step 2. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain the MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film. Comparative Example 7 The difference between this comparative example and Example 15 is that D-selenomethionine is not added, specifically as follows: Step 1. Preparation of a composite membrane-forming solution: 2 wt.% highland barley β-glucan acetic acid aqueous solution and 2 wt.% gelatin aqueous solution were mixed in equal amounts, stirred at 400 rpm at room temperature for 2 hours, 0.10 wt.% glycerol was added, mixed evenly, and then 0.10 wt.% Tween-80 was added. Finally, 0.15 wt.% MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles were added and mixed evenly to obtain a composite membrane-forming solution; Step 2. Preparation of edible film: The multifunctional composite edible film liquid was ultrasonically defoamed for 30 minutes, poured into a mold and dried at 40°C for 10 hours to obtain the MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film. Performance measurement: 1. Determination of membrane mechanical properties (1) Film thickness measurement The film thickness was measured using a micrometer. Five points were randomly selected on the sample, and their thickness was measured to obtain the average value. (2) Determination of tensile strength and elongation After measuring the thickness of the composite edible film, cut the film into strips measuring 20 mm x 40 mm. Clamp the film at both ends using the texture analyzer's clamps. Set the initial clamp spacing to 20 mm, the stretching speed to 50 mm / min, and the stretching distance to 20 mm. Repeat this three times. Record the tensile strength (TS) and elongation (E) at film breakage. The calculation formula is: Where: TS, MPa; F—maximum tensile force when the film breaks, N; L—average thickness of the composite edible film, mm; W—width of the composite edible film, mm Where: E, %; L—length of the membrane when it breaks, mm; L0—length of the membrane during testing, mm. As can be seen from Table 2, there is no significant difference in the thickness of the example films, but the film thickness of Example 15 using the same glucan-highland barley β-glucan is higher than that of the comparative example, especially the comparative example 4 has the lowest thickness, which indicates that MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles have a more significant effect on the film thickness. like Figure 4 As shown in the results, the effects of the glucan concentration, gelatin concentration, and Tween-80 concentration on E and TS of the four composite edible films all showed a trend of first increasing and then decreasing, and there were significant differences (p < 0.05). With the increase of glycerol concentration, TS showed a trend of first increasing and then decreasing, while E showed a trend of first increasing and then tending to be stable. Among them, when the Tween-80 concentration was 0.01-0.015 mg / ml, the glycerol concentration was 0.01-0.015 mg / ml, and the Tween-80 concentration was 0.01, the mechanical properties TS and E were higher. As shown in Table 2, the addition of different types of glucan (Examples 14-17) had a significant effect on the TS and E of the composite edible films (P < 0.05). Compared with the comparative example, it can be clearly seen that the TS and E values ​​of the edible film of the embodiment are significantly improved. This may be because the addition of essential oil in the form of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles enhances the interaction of the matrix within the film, and the intervention of glycerol, Tween-80 and D-selenomethionine makes the edible film more stable, thereby improving the mechanical properties of the composite edible film. Table 2 2. Barrier performance analysis (1) Water vapor transmission rate measurement The composite edible film was fixed in a triangle filled with anhydrous CaCl2 and placed in a desiccator maintained at a relative humidity of 75%. The mass was recorded after 7 days. The water vapor transmission rate (WVP) of the edible film was calculated as follows: Where: WVP—water vapor transmission rate, g·mm·m -2 d -1 kPa -1 ; Δm—change in the mass of the composite edible film, g; d—thickness of the composite edible film, mm; S—area of ​​the composite edible film, m 2 Δt—time change, d; ΔP—vapor pressure difference between the inside and outside of the composite edible film, kPa. Repeat three times and take the average value. (2) Determination of oxygen barrier properties Using the sodium thiosulfate titration method, weigh equal amounts of vegetable oil into a conical flask, seal the flask with the sample composite edible film, and place it in a 50°C constant temperature and humidity chamber for 5 days. The peroxide value (PV) reflects the oxygen barrier properties of the edible film. Repeat three times and take the average value. The calculation formula is: In the formula: PV—peroxide value (g / 100g); V—volume of Na2S2O3 standard solution consumed during titration (mL); V0—volume of Na2S2O3 standard solution consumed by the blank control group (mL); C—concentration of Na2S2O3 standard solution (mol / L); 0.1269—grams of iodine corresponding to 1mL Na2S2O3; M—mass of oil to be titrated (g). (3) Oil barrier performance measurement Add an equal amount of vegetable oil to a test tube, seal it with a composite edible film, and place the test tube upside down on filter paper. After standing at 25°C for 1 day, measure the mass of the filter paper. Repeat this three times and take the average value. The oil permeability coefficient (PO) of the edible film is calculated as follows: Where: PO—oil permeability coefficient, g·mm·m -2 ·d -1 ; Δm—mass difference of filter paper before and after test, g; d—thickness of edible film, mm; S—area of ​​oil-permeable part of filter paper, m 2 ; t=1d. The results, as shown in Table 3, show that different types of glucans (Examples 14-17) and their addition significantly affected the water vapor transmission rate, oxygen barrier properties, and oil barrier properties of the edible films. Example 15, which added the same type of glucan—highland barley β-glucan—had a significantly lower water vapor transmission rate than Comparative Examples 4-7, while Example 15 had higher oxygen barrier properties and oil barrier properties than Comparative Examples 4-7. This suggests that the Examples formed a denser film structure. The addition of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles caused a downward trend in PO, WVP, and PV. The composite edible film of Comparative Example 4 showed the highest WVP, PO, and PV values, indicating the worst barrier performance. The PO and PV values ​​of Comparative Example 7 were higher, which was related to the lack of D-selenomethionine. The addition of D-selenomethionine not only strengthened the dense network structure but also improved the barrier to oxygen. The addition of different concentrations of powdered MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles in Examples 15 and 18-20 affected the oil permeability, water vapor permeability, and oxygen permeability of the composite edible film. The results showed that a small amount of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles can enhance the intermolecular forces within the composite edible film, resulting in a more regular arrangement of macromolecules, increased spacing, and improved stability. As the concentration of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles continued to increase, the barrier performance of the composite edible film decreased. Table 3 The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Any person skilled in the art can, without departing from the spirit and technical solution of the present invention, use the methods and technical contents disclosed above to make many possible changes and modifications to the technical solution of the present invention, or modify it into an equivalent embodiment with equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention shall still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing an MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film, characterized in that: The following steps are involved: Step 1. Preparation of a composite membrane-forming solution: Mix equal amounts of a dextran acetate aqueous solution and a gelatin aqueous solution, add D-selenomethionine, stir at room temperature, add glycerol, mix thoroughly, then add Tween-80, and finally add MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles, and mix thoroughly to obtain a composite membrane-forming solution; Step 2. Preparation of edible film: ultrasonically defoam the multifunctional composite edible film liquid, pour it into a mold and dry it to obtain the MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film.

2. The method for preparing a MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film according to claim 1, characterized in that: The glucan in the glucan acetic acid aqueous solution in step 1 is any one of konjac glucomannan, highland barley β-glucan, oat β-glucan and yeast β-glucan; the concentration of the glucan acetic acid aqueous solution is 1-3wt.%, and the concentration of the gelatin aqueous solution is 1-3wt.%; the D-selenomethionine in the multifunctional composite film-forming liquid is food grade, with a content of 0.05-0.2wt.%, the content of glycerol and Tween-80 are both 0.05-0.2wt.%, and the content of MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles is 0.1-0.25wt.%, and the stirring condition at room temperature is 300-400rpm for 2-3h.

3. The method for preparing a MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film according to claim 1, characterized in that: The ultrasonic defoaming time in step 2 is 20-40 minutes, and the drying temperature is 40-50° C. and the drying time is 8-10 hours.

4. The method for preparing a MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film according to claim 1, characterized in that: The preparation method of the MCM-41 composite cinnamaldehyde-carvacrol essential oil nanoparticles in step 1 is as follows: S1. Amino-modified MCM-41: MCM-41 was dried and mixed with 3-aminopropyltriethoxysilane in ethanol with continuous stirring. The mixture was then washed with ethanol and water and dried to obtain amino-modified MCM-41. S2. Preparation of carboxyl-modified MCM-41: Amino-modified MCM-41 was dispersed in isopropyl acetate, succinic anhydride was added, and the mixture was evaporated under vacuum to obtain MCM-41-COOH. S3. Preparation of primary emulsion: Cinnamaldehyde and carvacrol essential oil were mixed as the oil phase, selenoprotein and lecithin were mixed as the aqueous phase, and the oil and aqueous phases were homogenized by microfluidization to obtain a primary emulsion; S4. Preparation of essential oil nanoparticles: MCM-41-COOH and colostrum were mixed by ultrasonication, shaken and then dried.

5. The method for preparing a MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film according to claim 4, characterized in that: In step S1, the drying temperature is 110-120° C., the drying time is 1-3 h, the ratio of MCM-41 to 3-aminopropyltriethoxysilane is 1:(3-5), and the continuous stirring condition is 45-55° C., and the drying time is 4-6 h.

6. The method for preparing a MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film according to claim 4, characterized in that: The dispersion conditions in step S2 are as follows: stirring at 50-60° C. for 18-24 hours, the concentration of succinic anhydride is 6-7 mmol, and the vacuum evaporation drying temperature is 25-30° C. for 5-6 hours.

7. The method for preparing a MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film according to claim 4, characterized in that: In step S3, the ratio of cinnamaldehyde to carvacrol is 1:1, the ratio of selenoprotein to lecithin is 1:2, the concentration of the aqueous phase solution is 2-4 wt.%, the ratio of the oil phase to the aqueous phase is 1:(9-14), and the pressure of the microjet homogenization is 20-30 MPa and the cycle is repeated 2 to 5 times.

8. The method for preparing a MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film according to claim 4, characterized in that: In step S4, the ratio of MCM-41-COOH to primary emulsion is 1:(40-60), the ultrasonic time is 15-35 minutes, and the shaking condition is 30° C. for 15-35 hours.

9. The MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film prepared according to the preparation method according to any one of claims 1 to 8.

10. Use of the MCM-41 composite cinnamaldehyde-carvacrol essential oil nano edible film prepared according to the preparation method according to any one of claims 1 to 8 in food packaging and preservation.

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