Porous milk powder particles for tabletting based on self-assembly and hydrogen bond crosslinking

Abstract

The invention relates to the technical field of food milk powder, and discloses a self-assembly and hydrogen bond crosslinking-based porous milk powder particle for tabletting, which is prepared by the following steps: uniformly mixing milk and whey protein powder to obtain mixed milk a; adding vitamin C into deionized water, stirring until the vitamin C is completely dissolved to obtain a solution, adding the solution into mixed milk, and adjusting the pH value to obtain mixed milk b; and mixing the mixed milk b, a composite additive and phospholipid, homogenizing and emulsifying, preheating, concentrating, collecting a concentrated solution, carrying out spray drying on the concentrated solution, collecting particles, and lightly vibrating the particles to obtain the porous milk powder particles. A hydrogen bond cross-linked network structure formed by the composite additive contains a large number of polar functional groups and can form hydrogen bonds with a large number of polar groups on protein molecular chains in mixed milk, so that a three-dimensional network structure is constructed in the porous milk powder particles, and the compressibility of the porous milk powder particles is further enhanced.

Description

Technical Field

[0001] This invention relates to the field of food and milk powder technology, specifically to a porous milk powder particle for tableting based on self-assembly and hydrogen bond cross-linking. Background Technology

[0002] As an important nutritional product and food base, milk powder is increasingly used in various forms. Among them, milk powder is compressed into milk tablets, which are convenient to carry, accurately measured, and easy to consume. However, due to its poor plasticity, flowability, and compressibility, milk powder is difficult to directly compress into shape and usually requires the addition of a large amount of excipients, which brings unpleasant flavors and affects the pure taste of milk tablets. In order to improve the plasticity, flowability, and compressibility of milk powder, the physical properties of milk powder particles are controlled by spray drying process.

[0003] By employing a physical pretreatment process, a porous milk powder granule suitable for food tableting was developed. By improving the relationship between the microstructure and macrotextural properties of the milk powder granules, a balance was struck between the sufficient bonding strength required for tableting and the appropriate porosity required to maintain a crisp texture. This porous milk powder granule, utilizing the inherent binding and structural characteristics of milk powder, can be combined with various natural ingredients in tableting production, reducing the use of processing aids and additives, maintaining the crisp texture and good oral solubility of the product, and achieving green and clean food processing.

[0004] However, porous milk powder particles have low strength, are easily broken during compression, and have poor formability. Therefore, there is an urgent need in this field to develop a new type of milk powder particle that can have excellent internal compressibility, allowing it to be directly compressed into tablets with very little added material, while ensuring that the compressed milk tablets have sufficient hardness and rapid disintegration, and at the same time retaining the natural nutrition and flavor of the milk powder to the maximum extent. Summary of the Invention

[0005] This invention provides a porous milk powder particle for tableting based on self-assembly and hydrogen bonding cross-linking, which solves the problems of low strength, easy breakage during compression, and poor formability of porous milk powder particles.

[0006] The technical solution of the present invention: A method for preparing porous milk powder particles for tableting based on self-assembly and hydrogen bonding cross-linking includes the following preparation steps: S1. Mix milk and whey protein powder evenly to obtain mixed milk a; S2. Add vitamin C to deionized water and stir at 23-27℃ until completely dissolved to obtain a solution. Add the solution to the mixed milk and adjust the pH to obtain mixed milk b. S3. Mix milk b, compound additives and phospholipids, homogenize and emulsify them, preheat them, concentrate and collect the concentrate, spray dry the concentrate to collect the particles, and then vibrate the particles slightly to obtain porous milk powder particles. The composite additive is obtained by grafting succinic anhydride onto microcrystalline cellulose, and then reacting it with lipid nanoparticles and citric acid. The lipid nanoparticles are obtained by mixing and reacting magnesium stearate, dietary fiber, fucoidan and zein.

[0007] The raw materials and modification processes involved in the composite additive all comply with food safety production standards and are safe and reliable at the specified dosage.

[0008] Furthermore, in step S1, the mass ratio of milk to whey protein powder is 100:(6.8-11.3).

[0009] Furthermore, in step S1, the ratio of whey protein to casein in the mixed milk is 60:40-80:20.

[0010] Furthermore, in step S2, the pH is adjusted to 5.5-6.

[0011] Furthermore, in step S2, the mass ratio of vitamin C to deionized water is (0.1-0.2):1; Further, in step S3, the mass ratio of mixed milk b, compound additives and phospholipids is 100:(0.05-0.1):(0.1-0.2).

[0012] Furthermore, in step S3, homogenization and emulsification are carried out in a homogenizer with a homogenization pressure of 15-22 MPa, a homogenization temperature of 30-55℃, and a homogenization time of 20-30 min.

[0013] Furthermore, in step S3, the preheating temperature is 40-45℃.

[0014] Furthermore, in step S3, the concentration is carried out in a low-temperature vacuum concentrator at a concentration temperature of 45-60°C and a concentration vacuum degree of -0.065 MPa.

[0015] Furthermore, in step S3, the concentration of the concentrate is 45-55%.

[0016] Furthermore, in step S3, during the concentration process, the hydrogen bonds of protein molecules are repeatedly unbound, cross-linked, and self-assembled to form a porous structure.

[0017] Furthermore, in step S3, the spray drying inlet air temperature is 180-200℃, and the spray drying exhaust air temperature is 90-95℃.

[0018] Furthermore, in step S3, the frequency of the light vibration is 40-45Hz, the duration of the light vibration is 2-3min, and the amplitude of the light vibration is 3-5mm.

[0019] Furthermore, the composite additive is prepared by the following steps: A1. Add zein, magnesium stearate and dietary fiber to an ethanol aqueous solution and stir until completely dissolved to obtain solution a. Add fucoidan to deionized water, stir evenly, adjust pH to obtain solution b. Mix solution a and solution b, stir evenly, remove ethanol by rotary evaporation, add deionized water to make up to volume, collect the supernatant by centrifugation, freeze-dry the supernatant to obtain lipid nanoparticles. A2. Succinic anhydride and microcrystalline cellulose were added to an ethanol aqueous solution and stirred evenly. After adjusting the pH with sodium bicarbonate aqueous solution, the mixture was stirred at 35-40℃ to form a solid. The solid was collected by filtration, washed, and dried overnight to obtain modified microcrystalline cellulose. A3. Modified microcrystalline cellulose and citric acid were added to an ethanol aqueous solution and stirred until homogeneous. Lipid nanoparticles were then added, and the mixture was stirred further. The ethanol was then removed by rotary evaporation to obtain a composite additive.

[0020] Furthermore, during the A1 reaction described above, zein exhibits amphiphilicity, allowing magnesium stearate and dietary fiber to disperse within it. After adjusting the pH with apple cider vinegar, fucoidan interacts with the polar functional groups carried by zein through hydrogen bonds and electrostatic interactions. During the removal of the solvent ethanol, the hydrophobicity of zein plays a dominant role, causing it to aggregate and form nuclei due to hydrophobic aggregation. Simultaneously, the hydrophilic segments of fucoidan form a hydration layer on the particle surface, preventing further particle growth or aggregation, ultimately forming nano-sized lipid nanoparticles, in which magnesium stearate and dietary fiber fill the lipid nanoparticles.

[0021] Furthermore, in the A2 reaction process described above, sodium bicarbonate aqueous solution acts as a catalyst, enabling the hydroxyl groups contained in microcrystalline cellulose to undergo esterification with succinic anhydride, thereby grafting succinic anhydride onto the microcrystalline cellulose molecular chain and introducing more oxygen-containing carboxyl groups onto the microcrystalline cellulose to obtain modified microcrystalline cellulose.

[0022] Furthermore, during the A3 reaction process described above, the carboxyl functional groups contained in the modified microcrystalline cellulose can chemically bond with the hydroxyl and carboxyl groups contained in citric acid to form a hydrogen-bonded cross-linked network. In addition, the surface of the lipid nanoparticles has a hydration layer formed by hydrophilic segments of fucoidan, which contains a large number of polar functional groups that can combine with the modified microcrystalline cellulose and citric acid to form a hydrogen-bonded cross-linked network structure on the surface of the lipid nanoparticles, thus obtaining a composite additive.

[0023] Further, in step A1, the mass ratio of zein, magnesium stearate, dietary fiber and ethanol aqueous solution is (1.2-1.5):(1-1.2):(1.1-1.3):(20-22).

[0024] Furthermore, the dietary fiber is composed of resistant dextrin, polydextrose, and inulin in a mass ratio of 1:(0.5-1):(1-1.2).

[0025] Further, in step A1, the mass ratio of fucoidan to deionized water is (1.2-1.5):(20-22).

[0026] Furthermore, in step A1, the mass ratio of solution a to solution b is 1:(4-5).

[0027] Furthermore, in step A2, the mass ratio of succinic anhydride, microcrystalline cellulose, and ethanol aqueous solution is (1.3-1.5):(3-3.5):(70-80).

[0028] Further, in step A3, the mass ratio of modified microcrystalline cellulose, citric acid, aqueous ethanol solution and lipid nanoparticles is (1-1.3):(0.6-0.8):(20-25):(1.8-2).

[0029] The present invention has the following beneficial effects: (1) In the technical solution of the present invention, dietary fiber includes resistant dextrin, polydextrose, and inulin, which, together with magnesium stearate, are added to porous milk powder particles. This can adjust the softness and hardness of the porous milk powder particles, so that the food tablets prepared from the porous milk powder particles have an appropriate hardness. In addition, dietary fiber and magnesium stearate can improve the flowability and dispersibility of porous milk powder particles. Furthermore, resistant dextrin has the effect of reducing blood sugar response and improving intestinal health. As a prebiotic component, it enables the biological functions of beneficial bacteria in the human body, such as lactic acid bacteria and bifidobacteria, to be more fully utilized.

[0030] (2) In the technical solution of the present invention, magnesium stearate and dietary fiber are filled into lipid nanoparticles formed by fucoidan and zein. On the one hand, magnesium stearate and dietary fiber are present in the lipid nanoparticles, which improves the stability of magnesium stearate and dietary fiber in porous milk powder particles. Moreover, the lipid nanoparticles have good fluidity, which can improve the fluidity of porous milk powder particles. On the other hand, the formed lipid nanoparticles can serve as a supporting skeleton for porous milk powder particles, which can absorb and reduce the stress generated during the tableting process, improve the hardness of porous milk powder particles, and make porous milk powder particles have good compressive strength. This avoids the problems of poor compressibility of porous milk powder particles, resulting in insufficient hardness, easy cracking, poor stability, and poor disintegration in the mouth of food tablets.

[0031] (3) In the technical solution of the present invention, microcrystalline cellulose has hydrophilicity and capillary structure. When the tablet comes into contact with water, the water quickly penetrates into the tablet through capillary action, causing the porous milk powder particles to expand and break the tablet, thus having good disintegration properties. Microcrystalline cellulose can also enhance the compressibility of porous milk powder particles. Using succinic anhydride graft modification of microcrystalline cellulose imparts a large number of oxygen-containing functional groups to microcrystalline cellulose, which is beneficial to coating the surface of lipid nanoparticles with a microcrystalline cellulose-based hydrogen bond crosslinking network and improving the dispersibility of lipid nanoparticles in porous milk powder particles.

[0032] (4) In the technical solution of the present invention, modified microcrystalline cellulose is mixed and reacted with lipid nanoparticles and citric acid. On the one hand, a hydrogen bond cross-linking network structure is formed on the surface of lipid nanoparticles, which can also absorb and reduce the stress generated during the tableting process, improve the hardness of porous milk powder particles, and make porous milk powder particles have good compressive strength. On the other hand, the formed hydrogen bond cross-linking network structure contains a large number of polar functional groups, which can form hydrogen bonds with a large number of polar groups on the protein molecular chains in the mixed milk, thereby constructing a three-dimensional network structure in the porous milk powder particles, further enhancing the compressibility of the porous milk powder particles, and improving the dispersibility of lipid nanoparticles in the porous milk powder particles. The prepared porous milk powder particles have high hardness and low brittleness, and are not prone to breakage during the tableting process. Detailed Implementation

[0033] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0034] The raw materials used in the embodiments of this invention are shown below, and all reagents used are analytical grade.

[0035] Among them, whey protein powder (product number G885091), phospholipid (product number L6300) made from soybean phospholipids, succinic anhydride (product number S993441) and microcrystalline cellulose (product number M909921) were purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0036] The zein protein was 99% pure and was purchased from Wuhan Huaxiang Kejie Biotechnology Co., Ltd.

[0037] Dietary fiber is composed of resistant dextrin, polydextrose, and inulin in a mass ratio of 1:0.8:1.1.

[0038] Fucoidan, 98% purity, Shandong Jiejing Group Co., Ltd.

[0039] Example 1 A method for preparing porous milk powder particles for tableting based on self-assembly and hydrogen bonding cross-linking includes the following preparation steps: S1. Mix milk and whey protein powder evenly to obtain mixed milk a; the mass ratio of milk to whey protein powder is 100:6.8; the ratio of whey protein to casein in the mixed milk is 60:40. S2. Add vitamin C to deionized water and stir at 23°C until completely dissolved to obtain a solution. Add the solution to mixed milk and adjust the pH to 5.5 to obtain mixed milk b; the mass ratio of vitamin C to deionized water is 0.1:1. S3. Mix milk b, compound additives and soybean lecithin, homogenize and emulsify, preheat to 40°C, concentrate to a concentration of 45%, spray dry the concentrate to collect particles, and then vibrate the particles slightly to obtain porous milk powder particles; the mass ratio of mixed milk b, compound additives and lecithin is 100:0.05:0.1. Homogenization and emulsification were carried out in a homogenizer at a pressure of 15 MPa, a temperature of 30°C, and a time of 20 min. Concentration is carried out in a low-temperature vacuum concentrator at a concentration temperature of 45°C and a concentration vacuum of -0.065 MPa. The spray drying inlet air temperature is 180℃, and the spray drying outlet air temperature is 90℃. The frequency of the light vibration is 40Hz, the duration of the light vibration is 2min, and the amplitude of the light vibration is 3mm.

[0040] The composite additive is prepared by the following steps: A1. Add zein, magnesium stearate, and dietary fiber to a 75% ethanol aqueous solution and stir until completely dissolved to obtain solution a. Add fucoidan to deionized water and stir evenly. Adjust the pH to 3.5 with 0.2 mol / L apple cider vinegar to obtain solution b. Mix solution a and solution b and stir at 1000 rpm for 60 min. Remove ethanol by rotary evaporation. Add deionized water at pH 3.5 to a final volume of 50 mL. Finally, centrifuge at 1500 rpm to remove insoluble substances. Collect the supernatant and freeze-dry the supernatant at -20℃ for 2 h to obtain lipid nanoparticles. The mass ratio of zein, magnesium stearate, dietary fiber, and ethanol aqueous solution was 1.2:1:1.1:20. The mass ratio of fucoidan to deionized water was 1.2:20; The mass ratio of solution a to solution b is 1:4; A2. Succinic anhydride and microcrystalline cellulose were added to a 75% ethanol aqueous solution and stirred until homogeneous. A 2 mol / L sodium bicarbonate aqueous solution was added to adjust the pH to 8.5. The mixture was stirred at 35°C for 2 hours to form a solid. The solid was collected by filtration, washed three times with ethanol and three times with deionized water, and dried overnight in an oven at 55°C to obtain modified microcrystalline cellulose. The mass ratio of succinic anhydride, microcrystalline cellulose, and ethanol aqueous solution is 1.3:3:70; A3. Modified microcrystalline cellulose and citric acid were added to a 75% ethanol aqueous solution and stirred at 45°C for 20 min. 2 g of lipid nanoparticles were added and stirred for another 20 min. The ethanol was removed by rotary evaporation to obtain the composite additive. The mass ratio of modified microcrystalline cellulose, citric acid, aqueous ethanol solution and lipid nanoparticles was 1:0.6:20:1.8.

[0041] Example 2 A method for preparing porous milk powder particles for tableting based on self-assembly and hydrogen bonding cross-linking includes the following preparation steps: S1. Mix milk and whey protein powder evenly to obtain mixed milk a; the mass ratio of milk to whey protein powder is 100:10; the ratio of whey protein to casein in the mixed milk is 60:40. S2. Add vitamin C to deionized water and stir at 25°C until completely dissolved to obtain a solution. Add the solution to mixed milk and adjust the pH to 5.8 to obtain mixed milk b; the mass ratio of vitamin C to deionized water is 0.15:1. S3. Mix milk b, compound additives and soybean lecithin, homogenize and emulsify, preheat to 43°C, concentrate to a concentration of 50%, spray dry the concentrate to collect particles, and then vibrate the particles slightly to obtain porous milk powder particles; the mass ratio of mixed milk b, compound additives and lecithin is 100:0.08:0.15. Homogenization and emulsification were carried out in a homogenizer at a pressure of 20 MPa, a temperature of 45°C, and a time of 25 min. Concentration is carried out in a low-temperature vacuum concentrator at a temperature of 55°C and a vacuum degree of -0.065 MPa. The spray drying inlet air temperature is 190℃, and the spray drying exhaust air temperature is 93℃. The frequency of the light vibration is 43Hz, the duration of the light vibration is 2.5min, and the amplitude of the light vibration is 3.5mm.

[0042] The composite additive is prepared by the following steps: A1. Add zein, magnesium stearate, and dietary fiber to a 75% ethanol aqueous solution and stir until completely dissolved to obtain solution a. Add fucoidan to deionized water and stir evenly. Adjust the pH to 3.5 with 0.2 mol / L apple cider vinegar to obtain solution b. Mix solution a and solution b and stir at 1000 rpm for 60 min. Remove ethanol by rotary evaporation. Add deionized water at pH 3.5 to a final volume of 50 mL. Finally, centrifuge at 1500 rpm to remove insoluble substances. Collect the supernatant and freeze-dry the supernatant at -20℃ for 2 h to obtain lipid nanoparticles. The mass ratio of zein, magnesium stearate, dietary fiber, and ethanol aqueous solution was 1.3:1.1:1.2:21. The mass ratio of fucoidan to deionized water was 1.3:21; The mass ratio of solution a to solution b is 1:4.5; A2. Succinic anhydride and microcrystalline cellulose were added to a 75% ethanol aqueous solution and stirred until homogeneous. A 2 mol / L sodium bicarbonate aqueous solution was added to adjust the pH to 8.5. The mixture was stirred at 35-40℃ for 2 hours to form a solid. The solid was collected by filtration, washed three times with ethanol and three times with deionized water, and dried overnight in an oven at 55℃ to obtain modified microcrystalline cellulose. The mass ratio of succinic anhydride, microcrystalline cellulose, and ethanol aqueous solution is 1.4:3.3:75; A3. Modified microcrystalline cellulose and citric acid were added to a 75% ethanol aqueous solution and stirred at 45°C for 20 min. Lipid nanoparticles were added and stirred for another 20 min. The ethanol was removed by rotary evaporation to obtain the composite additive. The mass ratio of modified microcrystalline cellulose, citric acid, aqueous ethanol solution and lipid nanoparticles was 1.2:0.7:23:1.9.

[0043] Example 3 A method for preparing porous milk powder particles for tableting based on self-assembly and hydrogen bonding cross-linking includes the following preparation steps: S1. Mix milk and whey protein powder evenly to obtain mixed milk a; the mass ratio of milk to whey protein powder is 100:11.3; the ratio of whey protein to casein in the mixed milk is 80:20; S2. Add vitamin C to deionized water and stir at 27°C until completely dissolved to obtain a solution. Add the solution to mixed milk and adjust the pH to 6 to obtain mixed milk b; the mass ratio of vitamin C to deionized water is 0.2:1. S3. Mix milk b, compound additives and soybean lecithin, homogenize and emulsify, preheat to 45°C, concentrate to a concentration of 55%, spray dry the concentrate to collect particles, and then gently vibrate the particles to obtain porous milk powder particles; the mass ratio of mixed milk b, compound additives and lecithin is 100:0.1:0.2. Homogenization and emulsification were carried out in a homogenizer at a pressure of 22 MPa, a temperature of 55°C, and a time of 30 min. Concentration is carried out in a low-temperature vacuum concentrator at a temperature of 60°C and a vacuum degree of -0.065 MPa. The spray drying inlet air temperature is 200℃, and the spray drying exhaust air temperature is 95℃. The frequency of the light vibration is 45Hz, the duration of the light vibration is 3min, and the amplitude of the light vibration is 5mm.

[0044] The composite additive is prepared by the following steps: A1. Add zein, magnesium stearate, and dietary fiber to a 75% ethanol aqueous solution and stir until completely dissolved to obtain solution a. Add fucoidan to deionized water and stir evenly. Adjust the pH to 3.5 with 0.2 mol / L apple cider vinegar to obtain solution b. Mix solution a and solution b and stir at 1000 rpm for 60 min. Remove ethanol by rotary evaporation. Add deionized water at pH 3.5 to a final volume of 50 mL. Finally, centrifuge at 1500 rpm to remove insoluble substances. Collect the supernatant and freeze-dry the supernatant at -20℃ for 2 h to obtain lipid nanoparticles. The mass ratio of zein, magnesium stearate, dietary fiber, and ethanol aqueous solution was 1.5:1.2:1.3:22. The mass ratio of fucoidan to deionized water was 1.5:22; The mass ratio of solution a to solution b is 1:5; A2. Succinic anhydride and microcrystalline cellulose were added to a 75% ethanol aqueous solution and stirred until homogeneous. A 2 mol / L sodium bicarbonate aqueous solution was added to adjust the pH to 8.5. The mixture was stirred at 40°C for 2 hours to form a solid. The solid was collected by filtration, washed three times with ethanol and three times with deionized water, and dried overnight in an oven at 55°C to obtain modified microcrystalline cellulose. The mass ratio of succinic anhydride, microcrystalline cellulose, and ethanol aqueous solution is 1.5:3.5:80; A3. Modified microcrystalline cellulose and citric acid were added to a 75% ethanol aqueous solution and stirred at 45°C for 20 min. Lipid nanoparticles were added and stirred for another 20 min. The ethanol was removed by rotary evaporation to obtain the composite additive. The mass ratio of modified microcrystalline cellulose, citric acid, aqueous ethanol solution and lipid nanoparticles was 1.3:0.8:25:2.

[0045] Comparative Example 1 The only difference between this comparative example and Example 3 is the preparation of the composite additive, as detailed below: The composite additive is prepared by the following steps: A1. Add zein and dietary fiber to a 75% ethanol aqueous solution and stir until completely dissolved to obtain solution a. Add fucoidan to deionized water and stir evenly. Adjust the pH to 3.5 with 0.2 mol / L apple cider vinegar to obtain solution b. Mix solution a and solution b and stir at 1000 rpm for 60 min. Remove ethanol by rotary evaporation. Add deionized water at pH 3.5 to a final volume of 50 mL. Finally, centrifuge at 1500 rpm to remove insoluble substances. Collect the supernatant and freeze-dry the supernatant at -20℃ for 2 h to obtain lipid nanoparticles. The mass ratio of zein, dietary fiber, and ethanol aqueous solution was 1.5:2.5:22. The mass ratio of fucoidan to deionized water was 1.5:22; The mass ratio of solution a to solution b is 1:5; A2. Succinic anhydride and microcrystalline cellulose were added to a 75% ethanol aqueous solution and stirred until homogeneous. A 2 mol / L sodium bicarbonate aqueous solution was added to adjust the pH to 8.5. The mixture was stirred at 40°C for 2 hours to form a solid. The solid was collected by filtration, washed three times with ethanol and three times with deionized water, and dried overnight in an oven at 55°C to obtain modified microcrystalline cellulose. The mass ratio of succinic anhydride, microcrystalline cellulose, and ethanol aqueous solution is 1.5:3.5:80; A3. Modified microcrystalline cellulose and citric acid were added to a 75% ethanol aqueous solution and stirred at 45°C for 20 min. Lipid nanoparticles were added and stirred for another 20 min. The ethanol was removed by rotary evaporation to obtain the composite additive. The mass ratio of modified microcrystalline cellulose, citric acid, aqueous ethanol solution and lipid nanoparticles was 1.3:0.8:25:2.

[0046] Comparative Example 2 The only difference between this comparative example and Example 3 is the preparation of the composite additive, as detailed below: The composite additive is prepared by the following steps: A1. Add zein and magnesium stearate to a 75% ethanol aqueous solution and stir until completely dissolved to obtain solution a. Add fucoidan to deionized water and stir evenly. Adjust the pH to 3.5 with 0.2 mol / L apple cider vinegar to obtain solution b. Mix solution a and solution b and stir at 1000 rpm for 60 min. Remove ethanol by rotary evaporation. Add deionized water with pH 3.5 to a final volume of 50 mL. Finally, centrifuge at 1500 rpm to remove insoluble substances and collect the supernatant. Freeze-dry the supernatant at -20℃ for 2 h to obtain lipid nanoparticles. The mass ratio of zein, magnesium stearate, and aqueous ethanol solution was 1.5:2.5:22. The mass ratio of fucoidan to deionized water was 1.5:22; The mass ratio of solution a to solution b is 1:5; A2. Succinic anhydride and microcrystalline cellulose were added to a 75% ethanol aqueous solution and stirred until homogeneous. A 2 mol / L sodium bicarbonate aqueous solution was added to adjust the pH to 8.5. The mixture was stirred at 40°C for 2 hours to form a solid. The solid was collected by filtration, washed three times with ethanol and three times with deionized water, and dried overnight in an oven at 55°C to obtain modified microcrystalline cellulose. The mass ratio of succinic anhydride, microcrystalline cellulose, and ethanol aqueous solution is 1.5:3.5:80; A3. Modified microcrystalline cellulose and citric acid were added to a 75% ethanol aqueous solution and stirred at 45°C for 20 min. Lipid nanoparticles were added and stirred for another 20 min. The ethanol was removed by rotary evaporation to obtain the composite additive. The mass ratio of modified microcrystalline cellulose, citric acid, aqueous ethanol solution and lipid nanoparticles was 1.3:0.8:25:2.

[0047] Comparative Example 3 The only difference between this comparative example and Example 3 is the preparation of the composite additive, as detailed below: The composite additive is prepared by the following steps: A1. Mix magnesium stearate and dietary fiber to obtain a complex; The mass ratio of magnesium stearate, dietary fiber, and ethanol aqueous solution is 1.2:1.3; A2. Succinic anhydride and microcrystalline cellulose were added to a 75% ethanol aqueous solution and stirred until homogeneous. A 2 mol / L sodium bicarbonate aqueous solution was added to adjust the pH to 8.5. The mixture was stirred at 40°C for 2 hours to form a solid. The solid was collected by filtration, washed three times with ethanol and three times with deionized water, and dried overnight in an oven at 55°C to obtain modified microcrystalline cellulose. The mass ratio of succinic anhydride, microcrystalline cellulose, and ethanol aqueous solution is 1.5:3.5:80; A3. Modified microcrystalline cellulose and citric acid were added to a 75% (w / w) aqueous ethanol solution and stirred at 45°C for 20 min. The composite was then added and stirred for another 20 min. The ethanol was removed by rotary evaporation to obtain the composite additive. The mass ratio of modified microcrystalline cellulose, citric acid, aqueous ethanol solution and the complex is 1.3:0.8:25:2.

[0048] Comparative Example 4 The only difference between this comparative example and Example 3 is the preparation of the composite additive, as detailed below: The composite additive is prepared by the following steps: A1. Add zein, magnesium stearate, and dietary fiber to a 75% ethanol aqueous solution and stir until completely dissolved to obtain solution a. Add fucoidan to deionized water and stir evenly. Adjust the pH to 3.5 with 0.2 mol / L apple cider vinegar to obtain solution b. Mix solution a and solution b and stir at 1000 rpm for 60 min. Remove ethanol by rotary evaporation. Add deionized water at pH 3.5 to a final volume of 50 mL. Finally, centrifuge at 1500 rpm to remove insoluble substances. Collect the supernatant and freeze-dry the supernatant at -20℃ for 2 h to obtain lipid nanoparticles. The mass ratio of zein, magnesium stearate, dietary fiber, and ethanol aqueous solution was 1.5:1.2:1.3:22. The mass ratio of fucoidan to deionized water was 1.5:22; The mass ratio of solution a to solution b is 1:5; A2. Microcrystalline cellulose and citric acid were added to a 75% ethanol aqueous solution and stirred at 45°C for 20 min. Lipid nanoparticles were added and stirred for another 20 min. The ethanol was removed by rotary evaporation to obtain the composite additive. The mass ratio of microcrystalline cellulose, citric acid, aqueous ethanol solution and lipid nanoparticles was 1.3:0.8:25:2.

[0049] Comparative Example 5 The only difference between this comparative example and Example 3 is the preparation of the composite additive, as detailed below: The composite additive is prepared by the following steps: A1. Add zein, magnesium stearate, and dietary fiber to a 75% ethanol aqueous solution and stir until completely dissolved to obtain solution a. Add fucoidan to deionized water and stir evenly. Adjust the pH to 3.5 with 0.2 mol / L apple cider vinegar to obtain solution b. Mix solution a and solution b and stir at 1000 rpm for 60 min. Remove ethanol by rotary evaporation. Add deionized water at pH 3.5 to a final volume of 50 mL. Finally, centrifuge at 1500 rpm to remove insoluble substances. Collect the supernatant and freeze-dry the supernatant at -20℃ for 2 h to obtain lipid nanoparticles. The mass ratio of zein, magnesium stearate, dietary fiber, and ethanol aqueous solution was 1.5:1.2:1.3:22. The mass ratio of fucoidan to deionized water was 1.5:22; The mass ratio of solution a to solution b is 1:5; A2. Succinic anhydride and microcrystalline cellulose were added to a 75% ethanol aqueous solution and stirred until homogeneous. A 2 mol / L sodium bicarbonate aqueous solution was added to adjust the pH to 8.5. The mixture was stirred at 40°C for 2 hours to form a solid. The solid was collected by filtration, washed three times with ethanol and three times with deionized water, and dried overnight in an oven at 55°C to obtain modified microcrystalline cellulose. The mass ratio of succinic anhydride, microcrystalline cellulose, and ethanol aqueous solution is 1.5:3.5:80; A3. Modified microcrystalline cellulose was added to a 75% ethanol aqueous solution and stirred at 45°C for 20 min. Lipid nanoparticles were added and stirred for another 20 min. The ethanol was removed by rotary evaporation to obtain the composite additive. The mass ratio of modified microcrystalline cellulose, aqueous ethanol solution, and lipid nanoparticles was 2.1:25:2.

[0050] The performance of the porous milk powder particles prepared in Examples 1-3 and Comparative Examples 1-5 was then tested.

[0051] Hardness test: The hardness test was performed using a hardness tester. The porous milk powder particles prepared above were placed in the hardness tester and pressure was applied. The pressure value (N) at which the porous milk powder particles broke was recorded.

[0052] Friability test method: The friability tester is used. The porous milk powder particles prepared above, with an initial weight of M0, are placed in the drum of the friability tester and rotated 100 times at 25 r / min. The particles are taken out, the fine powder is sieved out, the porous milk powder particles with the fine powder removed are collected, and the weight is recorded as M1. Friability = M0 - M1 / M0 × 100%.

[0053] Taste performance test: The porous milk powder granules were compressed into food tablets; ten members of the evaluation panel tasted the tablets and the taste of the majority was taken as the final result. The taste of the food tablets prepared from the porous milk powder granules was recorded as better, better, and worse.

[0054] The test results are shown in Table 1 below.

[0055] Table 1. Performance testing of porous milk powder particles in Examples 1-3 and Comparative Examples 1-5 As can be seen from the data in Table 1, the porous milk powder particles prepared in Examples 1-3 have high hardness and low brittleness, and are not prone to breakage during the tableting process.

[0056] Comparative Example 1, in which magnesium stearate was replaced by dietary fiber, and Comparative Example 2, in which dietary fiber was replaced by magnesium stearate, were added to porous milk powder granules. The compressive strength of the granules decreased, demonstrating that dietary fiber, including resistant dextrin, polydextrose, and inulin, in combination with magnesium stearate, can adjust the hardness of porous milk powder granules when added to them. This allows the food tablets made from porous milk powder granules to have an appropriate hardness. Furthermore, dietary fiber and magnesium stearate can improve the flowability and dispersibility of porous milk powder granules.

[0057] Comparative Example 3 showed that when lipid nanoparticles were replaced with a composite additive prepared from a complex of magnesium stearate and dietary fiber and added to porous milk powder particles, their compressive strength decreased. This demonstrates that the formed lipid nanoparticles can serve as a supporting framework for porous milk powder particles, absorbing and reducing the stress generated during tableting, improving the hardness of porous milk powder particles, and giving them better compressive strength. This avoids the problems of poor compressibility of porous milk powder particles, which can lead to insufficient hardness, easy cracking, poor stability, and poor disintegration in food tablets.

[0058] Comparative Example 4 showed that when the modified microcrystalline cellulose was replaced with a composite additive prepared from microcrystalline cellulose and added to porous milk powder particles, its compressive strength decreased, demonstrating that microcrystalline cellulose has hydrophilicity and capillary structure. When the tablets come into contact with water, the water rapidly penetrates into the tablet interior through capillary action, causing the porous milk powder particles to expand under pressure and break the tablet, exhibiting good disintegration properties. Furthermore, microcrystalline cellulose can also enhance the compressibility of porous milk powder particles. Using succinic anhydride grafting to modify microcrystalline cellulose imparts a large number of oxygen-containing functional groups to the microcrystalline cellulose-based hydrogen bond crosslinking network on the surface of lipid nanoparticles, improving the dispersibility of lipid nanoparticles in porous milk powder particles and enhancing the compressibility of porous milk powder particles.

[0059] Comparative Example 5 showed that when citric acid was replaced by a composite additive prepared from modified microcrystalline cellulose and added to porous milk powder granules, the compressive strength and taste decreased. This demonstrates that the carboxyl functional groups in the modified microcrystalline cellulose can chemically bond with the hydroxyl and carboxyl groups in citric acid, forming a hydrogen-bonded cross-linked network that coats the surface of lipid nanoparticles. This increases the hardness of the porous milk powder granules, resulting in better compressive strength and improved dispersibility of the lipid nanoparticles within the porous milk powder granules. The prepared porous milk powder granules exhibit high hardness and low brittleness, making them less prone to breakage during tableting.

[0060] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0061] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing a tabletting granulate based on self-assembly and hydrogen bond cross-linked porous milk powder particles, characterized in that, Preparation method of the porous milk powder granules comprising the following steps: S1. Mixing the milk and whey protein powder uniformly to obtain mixed milk a; S2. Adding vitamin C into deionized water, stirring until completely dissolved at 23-27 DEG C, obtaining a solution, adding the solution into the mixed milk to adjust pH, obtaining mixed milk b; S3. Mixing the mixed milk b, the composite additive and phospholipid, homogenizing and emulsifying, preheating, concentrating and collecting the concentrated solution, spray drying the concentrated solution to collect granules, and then performing light vibration on the granules to obtain porous milk powder granules; The composite additive is obtained by grafting modification of succinic anhydride on microcrystalline cellulose, and then mixing and reacting with lipid nanoparticles and citric acid; The lipid nanoparticles are obtained by mixing and reacting magnesium stearate, dietary fiber, fucoidan and zein.

2. The method for preparing porous milk powder particles based on self-assembly and hydrogen bond cross-linking for tabletting according to claim 1, characterized in that, The composite additive is specifically prepared by the following steps: A1. Adding zein, magnesium stearate and dietary fiber into an aqueous ethanol solution, stirring until completely dissolved to obtain solution a, adding fucoidan into deionized water, stirring uniformly, adjusting pH to obtain solution b, mixing solution a and solution b, stirring uniformly, removing ethanol by rotary evaporation, adding deionized water to constant volume, collecting supernatant by centrifugation, freeze-drying the supernatant to obtain lipid nanoparticles; A2. Adding succinic anhydride and microcrystalline cellulose into an aqueous ethanol solution, stirring uniformly, adding sodium bicarbonate aqueous solution to adjust pH, stirring at 35-40 DEG C to form a solid, collecting the solid by filtration, washing and drying the solid overnight to obtain modified microcrystalline cellulose; A3. Adding modified microcrystalline cellulose and citric acid into an aqueous ethanol solution, stirring uniformly, adding lipid nanoparticles, continuing to stir, and then removing ethanol by rotary evaporation to obtain a composite additive.

3. A method for preparing porous milk powder particles based on self-assembly and hydrogen bond cross-linking for tabletting according to claim 2, characterized in that, In step A1, the mass ratio of zein, magnesium stearate, dietary fiber and aqueous ethanol solution is (1.2-1.5):(1-1.2):(1.1-1.3):(20-22); In step A1, the mass ratio of fucoidan and deionized water is (1.2-1.5):(20-22); In step A1, the mass ratio of solution a and solution b is 1:(4-5).

4. The method for preparing porous milk powder particles based on self-assembly and hydrogen bond cross-linking for tabletting according to claim 2, characterized in that, In step A2, the mass ratio of succinic anhydride, microcrystalline cellulose, aqueous ethanol solution is (1.3-1.5):(3-3.5):(70-80).

5. The method of claim 2, wherein the method is characterized by, In step A3, the mass ratio of modified microcrystalline cellulose, citric acid, aqueous ethanol solution and lipid nanoparticles is (1-1.3):(0.6-0.8):(20-25):(1.8-2).

6. The method of claim 1, wherein the method is characterized by, In step S1, the ratio of whey protein and casein in the mixed milk is 60:40-80:20; In step S1, the mass ratio of milk and whey protein powder is 100:(6.8-11.3).

7. The method of claim 1, wherein the method is characterized by, In step S2, the pH is adjusted to 5.5-6; In step S2, the mass ratio of vitamin C and deionized water is (0.1-0.2):

1.

8. The method of claim 1, wherein the method is characterized by, In step S3, the mass ratio of mixed milk b, composite additive and phospholipid is 100:(0.05-0.1):(0.1-0.2).

9. The method of claim 1, wherein the method is characterized by, In step S3, the homogenization is performed in a homogenizer, the homogenization pressure is 15-22 MPa, the homogenization temperature is 30-55 ℃, and the homogenization time is 20-30 min.

10. The method of claim 1, wherein the method is characterized by, In step S3, the concentration is performed in a low-temperature vacuum concentrator, the concentration temperature is 45-60 ℃, and the concentration vacuum degree is -0.065 MPa. In step S3, the inlet air temperature of the spray drying is 180-200 ℃, and the exhaust air temperature of the spray drying is 90-95 ℃.

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