Microencapsulated spray-dried 25-hydroxyvitamin d3 and methods of making same
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANDONG HAINENG BIOENG CO LTD
- Filing Date
- 2026-04-21
- Publication Date
- 2026-06-05
Smart Images
Figure CN122139953A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of microencapsulation technology for functional nutritional fortifiers, specifically to a microencapsulation method for spray-dried 25-hydroxyvitamin D3 and its preparation. Background Technology
[0002] 25-Hydroxyvitamin D3, as the main circulating form of vitamin D3 in the body, has higher bioactivity and utilization efficiency, and has been widely used in functional foods, animal nutrition, and pharmaceutical preparations. However, its molecular structure contains multiple unsaturated bonds and active sites, making it extremely sensitive to light, oxygen, and heat processing. During storage and processing, it is prone to oxidation, isomerization, and degradation reactions, leading to a significant decrease in activity. Furthermore, its strong lipid solubility results in poor dispersion stability in aqueous systems, making it susceptible to phase separation and aggregation, further affecting its application efficacy.
[0003] Existing technologies typically employ spray-dried microencapsulation for protection. However, existing encapsulation systems are mostly based on casein, gelatin, maltodextrin, or gum arabic, forming encapsulation wall materials through simple compounding. This type of system has a simple structure and limited interfacial bonding, making it difficult to form a dense and stable multi-level structural barrier. As a result, the encapsulation efficiency is usually low, and there is still activity loss during high-temperature spraying. In addition, existing systems lack effective interfacial regulation mechanisms, resulting in insufficient oil-water interface stability and problems such as emulsion demulsification and encapsulation layer defects, which affect the storage stability and controlled-release performance of the final product.
[0004] Meanwhile, traditional modification methods mostly focus on single crosslinking or single functional introduction, lacking the synergistic construction of multiple mechanisms of action, making it difficult to simultaneously achieve structural enhancement and functional regulation at both the molecular and microstructural scales. Existing systems also rarely introduce small molecule structures with specific self-assembly or interface-enhancing capabilities, making it difficult to form a stable secondary protective layer at the embedding interface. Therefore, developing a system that constructs a dynamic covalent network and supramolecular network coupling structure through multiple synergistic effects and introduces small molecule systems with interface self-assembly capabilities is of great significance for improving the embedding efficiency, thermal stability, antioxidant properties, and controllable release performance of 25-hydroxyvitamin D3. Summary of the Invention
[0005] To overcome the challenges of easy degradation and inactivation of 25-hydroxyvitamin D3 under light, oxygen, and heat processing conditions, as well as the low encapsulation efficiency and insufficient interfacial stability caused by the single structure of existing encapsulation systems, the present invention aims to provide a microencapsulated spray-dried 25-hydroxyvitamin D3 and its preparation method. The present invention employs a dynamically covalent-supramolecularly coupled multi-network synergistic modification of the encapsulation matrix material, jointly constructed by casein and hydroxypropyl-β-cyclodextrin through 1,3,5-tris(bromomethyl)benzene-induced covalent bridging, a three-dimensional aromatic amine crosslinking network constructed from tetrakis(4-aminophenyl)methane, and boron-nitrogen synergistic coordination. Furthermore, isophorone diisocyanate-derived diurea small molecules are introduced to form a hydrogen-bonded self-assembly reinforcement layer at the oil-water interface, thereby achieving multi-structural fixation and interfacial stability regulation of the active ingredient. This results in significantly improved encapsulation efficiency, enhanced thermal stability and antioxidant properties, and controllable release.
[0006] The objective of this invention can be achieved through the following technical solutions: A microencapsulated spray-dried 25-hydroxyvitamin D3 comprises the following raw materials in parts by weight: 0.1-5 parts of 25-hydroxyvitamin D3; 50-120 parts of a synergistically modified embedding matrix material; 0.2-5 parts of isophorone diisocyanate-derived diurea; 20-80 parts of maltodextrin; 5-30 parts of gum arabic; 0.5-5 parts of emulsifier; 0.1-2 parts of antioxidant; 0.5-5 parts of stabilizer; and 100-300 parts of deionized water. The synergistically modified embedding matrix material is a dynamic covalent-supramolecular coupled multi-network structure material formed by covalent bridging of casein and hydroxypropyl-β-cyclodextrin induced by 1,3,5-tris(bromomethyl)benzene, a three-dimensional aromatic amine crosslinking network constructed from tetra(4-aminophenyl)methane, and boron-nitrogen synergistic coordination.
[0007] Optionally, the synergistically modified embedding matrix material comprises the following raw materials in parts by weight: 30-80 parts casein; 5-30 parts hydroxypropyl-β-cyclodextrin; 0.5-5 parts 1,3,5-tris(bromomethyl)benzene; 0.5-6 parts tetra(4-aminophenyl)methane; 0.3-3 parts 4-aminophenylboronic acid; 0.5-5 parts tris(hydroxymethyl)aminomethane; and 0.5-5 parts tetraethoxysilane.
[0008] Optionally, the preparation method of the synergistically modified embedding matrix material includes the following steps: (1) Disperse casein in water, add 1,3,5-tris(bromomethyl)benzene and tetra(4-aminophenyl)methane to react and obtain a primary cross-linked matrix; (2) Hydroxypropyl-β-cyclodextrin and 4-aminophenylboronic acid were added to the primary cross-linked matrix to react and obtain a supramolecular synergistic network intermediate; (3) Tris(hydroxymethyl)aminomethane and tetraethoxysilane were added to the supramolecular synergistic network intermediate to react and obtain the synergistically modified embedded matrix material.
[0009] Optionally, the reaction conditions for step (1) are: in a buffer system with a pH of 7.5 to 8.5, the reaction is carried out at 45 to 60°C with stirring at 300 to 600 rpm for 80 to 120 minutes.
[0010] Optionally, the reaction conditions in step (2) are: at a pH of 8.0 to 9.0, at 35 to 55°C, and with stirring at 300 to 700 rpm for 90 to 180 min.
[0011] Optionally, the reaction conditions in step (3) are: at a pH of 8.5 to 10.0, at a temperature of 50 to 70°C, and with stirring at 400 to 800 rpm for 90 to 180 minutes.
[0012] Optionally, the emulsifier is a mixture of sucrose fatty acid ester and lecithin in a mass ratio of 1:1 to 3; the antioxidant is a mixture of ascorbate palmitate and tocopherol in a mass ratio of 1:1 to 2; and the stabilizer is a mixture of gellan gum and xanthan gum in a mass ratio of 1:1 to 2.
[0013] Optionally, a method for preparing microencapsulated spray-dried 25-hydroxyvitamin D3 includes the following steps: S1, 25-hydroxyvitamin D3 is mixed with isophorone diisocyanate-derived diurea small molecules and dispersed in the oil phase to obtain a functional oil phase; S2, the co-modified embedding matrix material, maltodextrin, gum arabic, emulsifier, antioxidant and stabilizer are added to deionized water for dissolution and dispersion to obtain an aqueous phase system, and the functional oil phase is added to the aqueous phase system for homogenization and emulsification to obtain a stable emulsion; S3, the stabilized emulsion was spray-dried to obtain microencapsulated spray-dried 25-hydroxyvitamin D3.
[0014] Optionally, the reaction conditions for step S1 are: stirring and dispersing at 200-500 rpm for 30-60 min at 20-30°C under light-protected conditions; and the reaction conditions for step S2 are: homogenizing and emulsifying at 8000-15000 rpm for 5-15 min at 25-40°C.
[0015] Optionally, the reaction conditions in step S3 are an inlet air temperature of 140–180°C and an outlet air temperature of 70–90°C.
[0016] The beneficial effects of this invention are: This invention utilizes the covalent bridging effect induced by 1,3,5-tris(bromomethyl)benzene and a three-dimensional aromatic amine crosslinking network constructed from tetrakis(4-aminophenyl)methane to form a dense and stable rigid framework structure at the molecular scale. Simultaneously, it employs the boric acid-diol dynamic coordination between 4-aminophenylboronic acid and hydroxypropyl-β-cyclodextrin to introduce reversible dynamic bonding characteristics, enabling the embedded matrix to possess both structural stability and environmental responsiveness. Furthermore, an inorganic-organic synergistic reinforcing layer is formed at the interface through silane hydrolysis and condensation. Simultaneously, isophorone diisocyanate-derived diurea small molecules form an ordered self-assembled layer at the oil-water interface through multiple hydrogen bonds, significantly improving the interfacial film strength and density. This achieves multiple confinement and synergistic protection of 25-hydroxyvitamin D3, effectively inhibiting its thermal degradation and oxidative deactivation during the high-temperature spray drying process, significantly improving the embedding rate and storage stability, and endowing it with sustained-release behavior, demonstrating a comprehensive performance advantage significantly superior to traditional single wall material systems. Attached Figure Description
[0017] The invention will now be further described with reference to the accompanying drawings.
[0018] Figure 1 Comparison of infrared spectra of casein-based embedding matrix materials and synergistically modified embedding matrix materials; Figure 2 A comparison chart showing the embedding rate test results for samples with different ratios. Detailed Implementation
[0019] The present invention will be further described below with reference to specific embodiments. However, the present invention is not limited to the following embodiments. Equivalent adjustments made without departing from the spirit and essence of the present invention should also be considered to fall within the protection scope of the present invention.
[0020] Example 1: This example aims to verify that the present invention can still achieve basic encapsulation and stabilization effects under conditions of low addition amount and low reaction intensity.
[0021] S1. Add 30 parts of casein to 100 parts of deionized water and disperse at 45℃ and 300 rpm for 60 min at pH 7.5 to obtain a protein dispersion system. Add 0.5 parts of 1,3,5-tris(bromomethyl)benzene and 0.5 parts of tetra(4-aminophenyl)methane and react at 45℃ and 300 rpm for 80 min to obtain a primary cross-linked matrix. Add 5 parts of hydroxypropyl-β-cyclodextrin and 0.3 parts of 4-aminophenylboronic acid and react at 35℃ and 300 rpm for 90 min to obtain a supramolecular synergistic network intermediate. Add 0.5 parts of tris(hydroxymethyl)aminomethane and 0.5 parts of tetraethoxysilane and react at 50℃ and 400 rpm for 90 min to obtain a synergistically modified embedding matrix material. S2, 0.1 parts of 25-hydroxyvitamin D3 and 0.2 parts of isophorone diisocyanate-derived diurea were mixed and stirred at 20°C and 200 rpm for 30 min under light-protected conditions to form a functional oil phase; 20 parts of maltodextrin, 5 parts of gum arabic, 0.5 parts of emulsifier, 0.1 parts of antioxidant, and 0.5 parts of stabilizer were added to 100 parts of deionized water and dissolved and dispersed at 25°C to obtain an aqueous phase system; the functional oil phase was added to the aqueous phase system and homogenized and emulsified at 8000 rpm for 5 min to obtain a stable emulsion; S3, the obtained stable emulsion was spray-dried at an inlet air temperature of 140°C and an outlet air temperature of 70°C to obtain microencapsulated spray-dried 25-hydroxyvitamin D3.
[0022] Example 2: This example aims to provide an implementation method with optimal overall performance, achieving the best balance between encapsulation efficiency, stability, and controlled release performance.
[0023] S1. 55 parts of casein were added to 200 parts of deionized water and dispersed at 52℃ and 450 rpm for 90 min at pH 8.0 to obtain a protein dispersion system. 2.5 parts of 1,3,5-tris(bromomethyl)benzene and 3 parts of tetra(4-aminophenyl)methane were added and reacted at 55℃ and 450 rpm for 100 min to obtain a primary cross-linked matrix. 15 parts of hydroxypropyl-β-cyclodextrin and 1.5 parts of 4-aminophenylboronic acid were added and reacted at 45℃ and 500 rpm for 140 min to obtain a supramolecular synergistic network intermediate. 2.5 parts of tris(hydroxymethyl)aminomethane and 2.5 parts of tetraethoxysilane were added and reacted at 60℃ and 600 rpm for 140 min to obtain a synergistically modified embedding matrix material. Figure 1 Infrared spectroscopy comparison shows that the modified sample exhibits enhanced absorption peaks in the 3300–3400 cm⁻¹ region, indicating a significant enhancement of hydrogen bonding. A slight shift in the amide I band near 1650 cm⁻¹ indicates that the protein structure participates in covalent cross-linking. Simultaneously, the appearance or enhancement of absorption peaks at 1450 cm⁻¹ and 800–860 cm⁻¹ proves the successful introduction of aromatic structures. A new peak near 1320 cm⁻¹ indicates the formation of boric acid-related coordination. Significantly enhanced absorption in the 1000–1100 cm⁻¹ region indicates the formation of a silicon-oxygen network structure. In summary, the modified sample formed a multi-layered synergistic network structure. S2, 2.5 parts of 25-hydroxyvitamin D3 and 2.5 parts of isophorone diisocyanate-derived diurea were mixed and stirred at 25°C and 350 rpm for 45 min under light-protected conditions to form a functional oil phase; 50 parts of maltodextrin, 15 parts of gum arabic, 2.5 parts of emulsifier, 1 part of antioxidant, and 2.5 parts of stabilizer were added to 200 parts of deionized water and dissolved and dispersed at 30°C to obtain an aqueous phase system; the functional oil phase was added to the aqueous phase system and homogenized and emulsified at 12000 rpm for 10 min to obtain a stable emulsion; S3, the obtained stable emulsion was spray-dried at an inlet air temperature of 160°C and an outlet air temperature of 80°C to obtain microencapsulated spray-dried 25-hydroxyvitamin D3.
[0024] Example 3: This example aims to verify the effect of constructing a denser multi-network structure on improving stability under conditions of high component content and high reaction intensity.
[0025] S1. Add 80 parts of casein to 300 parts of deionized water and disperse at 60℃ and 600rpm for 120min at pH 8.5 to obtain a protein dispersion system. Add 5 parts of 1,3,5-tris(bromomethyl)benzene and 6 parts of tetra(4-aminophenyl)methane and react at 60℃ and 600rpm for 120min to obtain a primary cross-linked matrix. Add 30 parts of hydroxypropyl-β-cyclodextrin and 3 parts of 4-aminophenylboronic acid to the matrix and react at 55℃ and 700rpm for 180min to obtain a supramolecular synergistic network intermediate. Add 5 parts of tris(hydroxymethyl)aminomethane and 5 parts of tetraethoxysilane and react at 70℃ and 800rpm for 180min to obtain a synergistically modified embedding matrix material. S2, 35 parts of 25-hydroxyvitamin D and 5 parts of isophorone diisocyanate-derived diurea were mixed and stirred at 30°C and 500 rpm for 60 min under light-protected conditions to form a functional oil phase; 80 parts of maltodextrin, 30 parts of gum arabic, 5 parts of emulsifier, 2 parts of antioxidant and 5 parts of stabilizer were added to 300 parts of deionized water and dissolved and dispersed at 40°C to obtain an aqueous phase system; the functional oil phase was added to the aqueous phase system and homogenized and emulsified at 15000 rpm for 15 min to obtain a stable emulsion; S3, the obtained stable emulsion was spray-dried at an inlet air temperature of 180°C and an outlet air temperature of 90°C to obtain microencapsulated spray-dried 25-hydroxyvitamin D3.
[0026] Comparative Example 1: This comparative example aims to verify the effect of using only covalently bridged cross-linked structures without introducing supramolecular synergistic effects on encapsulation performance.
[0027] S1, 55 parts of casein were added to 200 parts of deionized water and dispersed at 52℃ and 450 rpm for 90 min at pH 8.0 to obtain a protein dispersion system; 2.5 parts of 1,3,5-tris(bromomethyl)benzene and 3 parts of tetra(4-aminophenyl)methane were added and reacted at 55℃ and 450 rpm for 100 min to obtain a primary cross-linked matrix; without adding hydroxypropyl-β-cyclodextrin and 4-aminophenylboronic acid, 2.5 parts of tris(hydroxymethyl)aminomethane and 2.5 parts of tetraethoxysilane were directly added and reacted at 60℃ and 600 rpm for 140 min to obtain a single covalently cross-linked modified embedding matrix material; S2, 2.5 parts of 25-hydroxyvitamin D3 and 2.5 parts of isophorone diisocyanate-derived diurea were mixed and stirred at 25°C and 350 rpm for 45 min under light-protected conditions to form a functional oil phase; 50 parts of maltodextrin, 15 parts of gum arabic, 2.5 parts of emulsifier, 1 part of antioxidant, and 2.5 parts of stabilizer were added to 200 parts of deionized water and dissolved and dispersed at 30°C to obtain an aqueous phase system; the functional oil phase was added to the aqueous phase system and homogenized and emulsified at 12000 rpm for 10 min to obtain a stable emulsion; S3, the obtained stable emulsion was spray-dried at an inlet air temperature of 160°C and an outlet air temperature of 80°C to obtain microencapsulated spray-dried 25-hydroxyvitamin D3.
[0028] Comparative Example 2: This comparative example aims to verify the effect of using only supramolecular coordination and inclusion without constructing a covalent cross-linked network on the embedding performance.
[0029] S1, 55 parts of casein were added to 200 parts of deionized water and dispersed at 52℃ and 450 rpm for 90 min at pH 8.0 to obtain a protein dispersion system; 1,3,5-tris(bromomethyl)benzene and tetra(4-aminophenyl)methane were not added; 15 parts of hydroxypropyl-β-cyclodextrin and 1.5 parts of 4-aminophenylboronic acid were added to the system and reacted at 45℃ and 500 rpm for 140 min to obtain a supramolecular modified system; then 2.5 parts of tris(hydroxymethyl)aminomethane and 2.5 parts of tetraethoxysilane were added and reacted at 60℃ and 600 rpm for 140 min to obtain a single supramolecular modified embedding matrix material; S2, 2.5 parts of 25-hydroxyvitamin D3 and 2.5 parts of isophorone diisocyanate-derived diurea were mixed and stirred at 25°C and 350 rpm for 45 min under light-protected conditions to form a functional oil phase; 50 parts of maltodextrin, 15 parts of gum arabic, 2.5 parts of emulsifier, 1 part of antioxidant, and 2.5 parts of stabilizer were added to 200 parts of deionized water and dissolved and dispersed at 30°C to obtain an aqueous phase system; the functional oil phase was added to the aqueous phase system and homogenized and emulsified at 12000 rpm for 10 min to obtain a stable emulsion; S3, the obtained stable emulsion was spray-dried at an inlet air temperature of 160°C and an outlet air temperature of 80°C to obtain microencapsulated spray-dried 25-hydroxyvitamin D3.
[0030] Comparative Example 3: This comparative example aims to verify the effect of isophorone diisocyanate-derived diurea small molecules on interface structure and stability.
[0031] S1. 55 parts of casein were added to 200 parts of deionized water and dispersed at 52℃ and 450 rpm for 90 min at pH 8.0 to obtain a protein dispersion system. 2.5 parts of 1,3,5-tris(bromomethyl)benzene and 3 parts of tetra(4-aminophenyl)methane were added and reacted at 55℃ and 450 rpm for 100 min to obtain a primary cross-linked matrix. 15 parts of hydroxypropyl-β-cyclodextrin and 1.5 parts of 4-aminophenylboronic acid were added and reacted at 45℃ and 500 rpm for 140 min to obtain a supramolecular synergistic network intermediate. 2.5 parts of tris(hydroxymethyl)aminomethane and 2.5 parts of tetraethoxysilane were added and reacted at 60℃ and 600 rpm for 140 min to obtain a synergistically modified embedding matrix material. S2, without the addition of isophorone diisocyanate-derived diurea small molecules, only 2.5 parts of 25-hydroxyvitamin D3 are dispersed in the oil phase; 50 parts of maltodextrin, 15 parts of gum arabic, 2.5 parts of emulsifier, 1 part of antioxidant, and 2.5 parts of stabilizer are added to 200 parts of deionized water and dissolved and dispersed at 30°C to obtain an aqueous phase system; the oil phase is added to the aqueous phase system and homogenized and emulsified at 12000 rpm for 10 min to obtain a stable emulsion; S3, the obtained stable emulsion was spray-dried at an inlet air temperature of 160°C and an outlet air temperature of 80°C to obtain microencapsulated spray-dried 25-hydroxyvitamin D3.
[0032] Performance testing: 1. Embedding rate test method A certain amount of spray-dried microcapsule powder was taken, and the sample was fully extracted using an organic solvent to completely break the cell walls, thereby releasing the 25-hydroxyvitamin D3 embedded inside the microcapsules. At the same time, the content of unencapsulated free 25-hydroxyvitamin D3 on the surface was determined using a rapid solvent washing method. Subsequently, the extract was centrifuged, and the supernatant was analyzed by high-performance liquid chromatography. The encapsulation effect was calculated based on the difference between the total amount and the amount of free 25-hydroxyvitamin D3 on the surface, in order to evaluate the encapsulation ability of different examples and comparative examples.
[0033] 2. Thermal stability test method Equal amounts of microcapsule samples were placed in a constant temperature forced-air drying oven and subjected to accelerated heat treatment at 80℃. Samples were taken at 0h, 12h, 24h and 48h, respectively. After extraction with organic solvent, the remaining content of 25-hydroxyvitamin D3 was determined by high performance liquid chromatography. The degree of retention was used to evaluate the stability of the samples under high temperature conditions, thereby comparing the thermal protection ability of different systems for active ingredients.
[0034] 3. Antioxidant stability test method Microcapsule samples were placed in an oxygen-containing environment and stored at room temperature in the dark. Air was introduced at a certain flow rate to accelerate the oxidation process. Samples were taken at 0, 7, 14 and 28 days. After extraction with organic solvents, the changes in 25-hydroxyvitamin D3 content were detected by high performance liquid chromatography, and its degradation trend was observed to evaluate the resistance of different samples to the oxidative environment and long-term storage stability.
[0035] 4. In vitro release performance test method A certain amount of microcapsule sample was added to a buffer solution simulating the gastrointestinal environment, and a shaking release experiment was conducted at 37°C. Samples were taken at different time points and centrifuged. The amount of 25-hydroxyvitamin D3 released from the supernatant was measured. At the same time, an equal volume of fresh buffer was added to maintain a constant system volume. By analyzing the release behavior at different time points, the controlled release performance and release uniformity of each example and comparative example were evaluated.
[0036] Table 1. Performance test results of microencapsulated 25-hydroxyvitamin D3
[0037] According to Table 1, Examples 1-3 are significantly better than Comparative Examples 1-3 in terms of encapsulation efficiency, thermal stability, antioxidant stability and in vitro release uniformity. Among them, Example 2 shows the best overall performance, indicating that the multi-network encapsulation system constructed by synergistic modification can significantly improve the overall performance of 25-hydroxyvitamin D3.
[0038] From the perspective of embedding effect Figure 2The encapsulation rate of Example 2 reached 93.8%, which was significantly higher than that of the comparative examples (66.7%–74.8%). This indicates that the dense structure constructed by the covalent cross-linking network and supramolecular synergy can effectively limit the leakage of active ingredients. At the same time, the self-assembled layer formed by the diurea small molecules at the interface further enhances the interfacial encapsulation ability. In contrast, Comparative Examples 1 and 2, due to having only a single modification mechanism, have insufficient structural integrity, resulting in a significant decrease in encapsulation ability.
[0039] From the thermal stability results, Example 2 still maintained a retention rate of 88.7% after 48 hours, which was significantly higher than that of the comparative examples. This indicates that the multi-network synergistic structure can effectively block heat transfer and oxygen diffusion under high temperature conditions, thereby reducing the degradation rate of 25-hydroxyvitamin D3. In contrast, the comparative system had a weaker thermal protection ability due to its loose structure.
[0040] In terms of antioxidant stability, all the systems in the examples showed high long-term stability. Among them, Example 2 still maintained 86.5% content after 28 days, indicating that the boron-nitrogen coordination structure and multiple interfacial barriers have a good barrier effect on oxygen. At the same time, the hydrogen bond network of the bisurea structure further stabilized the interfacial structure, while the stability of Comparative Example 3, which did not introduce organic small molecules, was significantly reduced.
[0041] From the perspective of in vitro release behavior, the release uniformity of Example 2 reached 91.2%, which was significantly better than that of the comparative example. This indicates that the synergistic effect of the dynamic covalent network and supramolecular structure endows the system with good structural response capability, enabling the active ingredient to be released slowly and uniformly, while the single-structure system exhibits uneven release and burst release phenomena.
[0042] In summary, this invention achieves efficient encapsulation and multiple protection of 25-hydroxyvitamin D3 by constructing a dynamic covalent-supramolecular coupled multi-network synergistic modification of the encapsulation matrix material and combining it with an interfacial self-assembled small molecule structure. It significantly outperforms existing technologies in terms of encapsulation rate, stability, and controlled release performance, and has good application prospects.
Claims
1. A microencapsulated spray-dried 25-hydroxyvitamin D3, characterized in that, The raw materials include the following parts by weight: 0.1-5 parts of 25-hydroxyvitamin D3; 50-120 parts of synergistic modified embedding matrix material; 0.2-5 parts of isophorone diisocyanate-derived diurea; 20-80 parts of maltodextrin; 5-30 parts of gum arabic; 0.5-5 parts of emulsifier; 0.1-2 parts of antioxidant; 0.5-5 parts of stabilizer; and 100-300 parts of deionized water. The synergistic modified embedding matrix material is a dynamic covalent-supramolecular coupled multi-network structure material formed by the covalent bridging of casein and hydroxypropyl-β-cyclodextrin induced by 1,3,5-tris(bromomethyl)benzene, the three-dimensional aromatic amine cross-linking network constructed by tetra(4-aminophenyl)methane, and the synergistic coordination of boron and nitrogen.
2. The microencapsulated spray-dried 25-hydroxyvitamin D3 according to claim 1, characterized in that, The synergistically modified embedding matrix material comprises the following raw materials in parts by weight: 30-80 parts casein; 5-30 parts hydroxypropyl-β-cyclodextrin; 0.5-5 parts 1,3,5-tris(bromomethyl)benzene; 0.5-6 parts tetra(4-aminophenyl)methane; 0.3-3 parts 4-aminophenylboronic acid; 0.5-5 parts tris(hydroxymethyl)aminomethane; and 0.5-5 parts tetraethoxysilane.
3. The microencapsulated spray-dried 25-hydroxyvitamin D3 according to claim 1 or 2, characterized in that, The preparation method of the synergistically modified embedded matrix material includes the following steps: (1) Disperse casein in water, add 1,3,5-tris(bromomethyl)benzene and tetra(4-aminophenyl)methane to react and obtain a primary cross-linked matrix; (2) Hydroxypropyl-β-cyclodextrin and 4-aminophenylboronic acid were added to the primary cross-linked matrix to react and obtain a supramolecular synergistic network intermediate; (3) Tris(hydroxymethyl)aminomethane and tetraethoxysilane were added to the supramolecular synergistic network intermediate to react and obtain the synergistically modified embedding matrix material.
4. The microencapsulated spray-dried 25-hydroxyvitamin D3 according to claim 3, characterized in that, The reaction conditions for step (1) are as follows: in a buffer system with a pH of 7.5 to 8.5, the reaction is carried out at 45 to 60°C with stirring at 300 to 600 rpm for 80 to 120 minutes.
5. The microencapsulated spray-dried 25-hydroxyvitamin D3 according to claim 3, characterized in that, The reaction conditions for step (2) are: at a pH of 8.0 to 9.0, at a temperature of 35 to 55°C, and with stirring at 300 to 700 rpm for 90 to 180 minutes.
6. The microencapsulated spray-dried 25-hydroxyvitamin D3 according to claim 3, characterized in that, The reaction conditions for step (3) are: at a pH of 8.5 to 10.0, at a temperature of 50 to 70°C, and with stirring at 400 to 800 rpm for 90 to 180 minutes.
7. The microencapsulated spray-dried 25-hydroxyvitamin D3 according to claim 1, characterized in that, The emulsifier is a mixture of sucrose fatty acid ester and lecithin in a mass ratio of 1:1 to 3; the antioxidant is a mixture of ascorbate palmitate and tocopherol in a mass ratio of 1:1 to 2; and the stabilizer is a mixture of gellan gum and xanthan gum in a mass ratio of 1:1 to 2.
8. A method for preparing microencapsulated spray-dried 25-hydroxyvitamin D3, characterized in that, The preparation method includes the following steps: S1, 25-hydroxyvitamin D3 is mixed with isophorone diisocyanate-derived diurea small molecules and dispersed in the oil phase to obtain a functional oil phase; S2, the co-modified embedding matrix material, maltodextrin, gum arabic, emulsifier, antioxidant and stabilizer are added to deionized water for dissolution and dispersion to obtain an aqueous phase system, and the functional oil phase is added to the aqueous phase system for homogenization and emulsification to obtain a stable emulsion; S3, the stabilized emulsion was spray-dried to obtain microencapsulated spray-dried 25-hydroxyvitamin D3.
9. The method for preparing microencapsulated spray-dried 25-hydroxyvitamin D3 according to claim 8, characterized in that, The reaction conditions for step S1 are: stirring and dispersing at 200-500 rpm for 30-60 min at 20-30°C under light-protected conditions; and homogenizing and emulsifying at 8000-15000 rpm for 5-15 min at 25-40°C.
10. The method for preparing microencapsulated spray-dried 25-hydroxyvitamin D3 according to claim 8, characterized in that, The reaction conditions for step S3 are an inlet air temperature of 140–180°C and an outlet air temperature of 70–90°C.