Sulforaphane hydrogel microspheres and applications thereof

Abstract

The application relates to a sulforaphene hydrogel microsphere and an application thereof. Sulforaphene-konjac gum mixed solution is obtained by dissolving konjac gum into deionized water and adding sulforaphene; epsilon-polylysine solution-calcium chloride mixed solution is obtained by dissolving epsilon-polylysine into deionized water and then dissolving calcium chloride into the epsilon-polylysine solution; the epsilon-polylysine solution-calcium chloride mixed solution is uniformly stirred at room temperature by using a stirrer, the sulforaphene-konjac gum mixed solution is added dropwise into the epsilon-polylysine solution-calcium chloride mixed solution, and sulforaphene hydrogel microspheres are obtained; and sulforaphene hydrogel microspheres are obtained after vacuum freeze-drying. The sulforaphene hydrogel microspheres have the advantages of simple preparation method, mild conditions, good controllability, good sulforaphene stability, high sulforaphene utilization rate, controllable intestinal release, and application in the preparation of sulforaphene gel soft sweets.

Description

Technical Field

[0001] This invention relates to a raphanin hydrogel microsphere and its application. Background Technology

[0002] Radishes are rich in nutrients, including water, polysaccharides, dietary fiber, and glucosinolates, and have the effects of aiding digestion, relieving flatulence, detoxifying, promoting saliva production, and facilitating urination and bowel movements. However, although white radishes have a high yield and are resistant to storage, the main processing methods, such as making them into dried radishes or pickling them, will destroy their bioactive substances, resulting in their underutilization.

[0003] The glucosinolates in radishes are relatively stable in the plant vacuoles. When radishes are chewed or chopped, the glucosinolates come into contact with released myrosinase, producing isothiocyanates, including raphanin. Raphanusin is a plant-based active ingredient with anti-tumor, detoxifying, antibacterial, and antioxidant effects, and it has a blocking effect on various cancers. However, although glucosinolates can be hydrolyzed in the gut microbiota, clinical trials have shown that their conversion efficiency in the human body is very low; therefore, sufficient raphanin cannot be obtained by consuming glucosinolates alone.

[0004] Currently, no functional products containing raphanin have been successfully launched on the market, mainly because raphanin is unstable under ordinary cooking and heating conditions, and extremely unstable in water and alcohol solutions, which limits its application in food processing. Therefore, although radishes are rich in glucosinolates, a precursor to raphanin, their low conversion efficiency in the human body and the inherent stability of raphanin itself pose challenges to the high-value application of radishes.

[0005] CN107162947A discloses "A method for preparing anhydrous raphanin solid dispersion." This method uses a combination of microwave and vacuum drying technology to remove moisture from the raphanin dispersion. The preparation process avoids light and high temperatures, and the obtained product can maintain the stability of raphanin for a long time. The disadvantage is that it cannot come into contact with water. CN107739324A provides "A method for preparing stabilized raphanin liquid formulation," whose excipients are glycerol and polyethylene glycol. It is also a dehydrated raphanin supplement and has the same problem of not being able to come into contact with water. However, many food processing processes require contact with drinking water. For example, the raw materials such as white radish juice in the processing of gummy candies need to contain water, making it unsuitable to add this dehydrated raphanin supplement. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a raphanin hydrogel microsphere and its application. The preparation method of the raphanin hydrogel microsphere is simple, the conditions are mild and the controllability is good. The product has controllable release in the intestine. The raphanin has good stability and high utilization rate. It can be used in the preparation of raphanin gel gummies.

[0007] The technical solution of this invention is:

[0008] A raphanin hydrogel microsphere, characterized in that raphanin is encapsulated within calcium chloride-gellan gum-ε-polylysine hydrogel microspheres.

[0009] A raphanin hydrogel microsphere, wherein the raphanin hydrogel microsphere is prepared as follows:

[0010] (1) Prepare the raphanin-gellan gum mixture

[0011] Gellan gum was dissolved in deionized water to obtain a gellan gum solution with a mass concentration of 0.5-1.5%. Ranaquinone was added to the gellan gum solution to obtain a raphanone-gellan gum mixture with a raphanone concentration of 3 mg / mL.

[0012] (2) Preparation of ε-polylysine solution-calcium chloride mixture

[0013] ε-polylysine was dissolved in deionized water to obtain an ε-polylysine solution with a mass concentration of 0.5-1.5%. Then, calcium chloride was dissolved in the ε-polylysine solution to obtain an ε-polylysine solution-calcium chloride mixture.

[0014] (3) Preparation of raphanin hydrogel microspheres

[0015] At room temperature, the ε-polylysine solution-calcium chloride mixture was gently stirred on a stirrer until homogeneous. An equal volume of raphanin-gellan gum mixture was added dropwise to the ε-polylysine solution-calcium chloride mixture according to a mass ratio of gellan gum to ε-polylysine of 2:1-1:3, to obtain hydrogel-like raphanin microspheres. After vacuum freeze-drying, raphanin hydrogel microspheres were obtained.

[0016] Furthermore, the mass concentration of calcium chloride in the ε-polylysine solution-calcium chloride mixture is 1-1.5%.

[0017] Furthermore, in step (1), the temperature of the deionized water is 60°C.

[0018] The application of the above-mentioned raphanin hydrogel microspheres in the preparation of raphanin gel gummies.

[0019] The application of raphanin hydrogel microspheres in the preparation of raphanin gel gummies, the specific steps are as follows:

[0020] (1) Weigh the raw materials

[0021] The sugar-free radish gel gummy rich in raphanin contains, by weight fraction, 50 parts white radish juice, 0.035-0.0625 parts citric acid, 0.0125-0.05 parts sodium citrate, and 0.0125-0.25 parts raphanin hydrogel microspheres.

[0022] (2) Preparation of white radish juice syrup

[0023] Add maltitol solution and erythritol to white radish juice and dissolve them to obtain white radish juice syrup;

[0024] (3) Preparation of sugar-free radish gel gummies rich in raphanin

[0025] After mixing white radish juice gel and white radish juice syrup, citric acid and sodium citrate are added and mixed evenly. The mass ratio of white radish juice in the white radish juice gel to white radish juice syrup is 1:1. The mixture is heated over low heat with constant stirring until it reaches 110°C. Then, raphanin hydrogel microspheres are added and stirred evenly. After cooling, radish gel soft candy rich in raphanin is obtained.

[0026] Furthermore, in step (1), the mass ratio of the white radish juice to the gelatin is 25:(1.75-3).

[0027] Furthermore, in step (2), the mass ratio of the white radish juice to maltitol solution and erythritol is 25:5-20 and 25:0.5-0.625, respectively.

[0028] The beneficial effects of this invention are:

[0029] (1) ε-polylysine, gellan gum and raphanin are naturally bonded together and gelled at low temperature; raphanin hydrogel microspheres obtained by combining electrostatic self-assembly and low-temperature gelation form stable chemical bonds between the components, which solves the problem of structural instability of raphanin in water and alcohol solutions caused by the unique N=C=S and S=O structures in the raphanin structure, and avoids the water-soluble nature of raphanin.

[0030] (2) The preparation method of the raphanin hydrogel microspheres is simple, the conditions are mild and the controllability is good. The product has controllable release in the intestine, realizing the precise regulation of raphanin nutrition and activity.

[0031] (3) Rhubarb extract was first encapsulated and then added to ragweed gel gummies. The ragweed extract component in the gummies exhibited good heat resistance and stability. In in vitro simulated intestinal fluid digestion experiments, the release rates of ragweed extract in both the ragweed gel and the ragweed gel gummies were much higher than those in simulated gastric fluid. Furthermore, the release rate of ragweed extract in the ragweed gel gummies in simulated gastric fluid was significantly lower than that in the gel. This indicates that, compared to ragweed gel, ragweed gel gummies further improved the stability and utilization rate of ragweed extract, achieving precise delivery of ragweed-like isothiocyanate active ingredients.

[0032] (4) White radish juice is used as raw material. Raphanusole gel is added and processed into functional gel soft candy with radish aroma. It has a unique flavor, good taste and no unpleasant odor. Raphanusole functional component is added to the soft candy, which has a variety of biological functions such as anti-oxidation and anti-cancer.

[0033] (5) The gellan gum in the raphanin hydrogel microspheres helps to improve the gel strength of the gelatin added in the production of raphanin gel gummies. The erythritol added to the raphanin gel gummies has a refreshing sweet taste and is not easily absorbed by the human body. It is stable when heated at high temperature and within a wide pH range. It has a mild cooling sensation when dissolved in the mouth. The added citric acid and sodium citrate can play the role of acidity regulation on the one hand, and buffering on the other hand, which is beneficial to the stability of the system.

[0034] (6) The prepared raphanin gel soft candy has a complete shape, good elasticity and chewiness, and the candy is clear, transparent, non-sticky and uniform. All the ion gel raw materials used are food additives permitted in the GB 2760-2014 National Food Safety Standard and the Food Additives Use Standard. They are edible and suitable for large-scale industrial production. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the process flow for the raphanin gel gummies of the present invention;

[0036] Figure 2 This is a photograph of the raphanin gel gummies of the present invention;

[0037] Figure 3 The XRD pattern of the raphanin-gellan gum / ε-polylysine hydrogel microspheres of the present invention is shown.

[0038] Figure 4 The diagram shows the encapsulation efficiency and drug loading rate of the raphanin hydrogel microspheres of the present invention.

[0039] Figure 5 This is a graph showing the in vitro release rate of the raphanin hydrogel microspheres of the present invention in a simulated gastrointestinal environment;

[0040] Figure 6 This is a graph showing the release rate of raphanin after in vitro digestion of the raphanin gel gummies of the present invention. Detailed Implementation

[0041] Example 1

[0042] like Figure 1 As shown, the manufacturing process of radish extract gel gummies is as follows:

[0043] (1) Preparation of raphanin hydrogel microspheres

[0044] a. Preparation of raphanin-gellan gum mixture

[0045] Gellan gum was dissolved in deionized water at 60°C to obtain a 0.5% gellan gum solution. Rhubarb was added to the gellan gum solution to obtain a 3 mg / mL raphanin-gellan gum mixture.

[0046] b. Preparation of ε-polylysine solution-calcium chloride mixture

[0047] ε-polylysine was dissolved in deionized water to obtain a 1.5% ε-polylysine solution. Then, calcium chloride was dissolved in this solution to obtain a 1% ε-polylysine solution-calcium chloride mixture.

[0048] c. Preparation of raphanin hydrogel microspheres

[0049] At room temperature, the ε-polylysine solution-calcium chloride mixture was gently stirred on a stirrer until homogeneous. The raphanin-gellan gum mixture was then added dropwise to the ε-polylysine solution-calcium chloride mixture at a mass ratio of 1:3 to gellan gum and ε-polylysine, resulting in hydrogel-like raphanin microspheres. After vacuum freeze-drying, raphanin, gellan gum, and ε-polylysine hydrogel microspheres were obtained (abbreviated as: raphanin hydrogel microspheres).

[0050] (2) Preparation of radish juice

[0051] Peel and wash the white radish, crush and stir it, filter it through cheesecloth to remove the white radish residue, and obtain white radish juice;

[0052] (3) Preparation of Radish Gel Soft Candy Rich in Rhubarb Extract

[0053] a. Preparation of white radish juice gel

[0054] Heat 25g of white radish juice to 80℃, remove the foam, cool to 60℃, add 3g of gelatin and dissolve completely to obtain white radish juice gel, keep warm at 60℃ for later use.

[0055] b. Preparation of sugar solution

[0056] Heat 25g of white radish juice to 80℃, remove the foam, cool to 60℃, add 20g of maltitol solution and 0.5g of erythritol, dissolve completely to obtain white radish juice sugar solution, and keep warm at 90±5℃ for later use.

[0057] c. Preparation of sugar-free radish-based soft gels rich in raphanin

[0058] After mixing the white radish juice syrup from step (3)a and the white radish juice sugar syrup from step (3)b, add 0.05g of citric acid and 0.05g of sodium citrate and mix well. Heat over low heat continuously while stirring constantly until it reaches 110℃. Then stop heating and add 0.5g of raphanin hydrogel microspheres and stir well. Finally, pour the prepared liquid into a mold, cool, and shape it to obtain radish gel soft candy rich in raphanin. Figure 2 As shown.

[0059] Example 2

[0060] like Figure 1 As shown, the manufacturing process of radish extract gel gummies is as follows:

[0061] (1) Preparation of raphanin hydrogel microspheres

[0062] a. Preparation of raphanin-gellan gum mixture

[0063] Gellan gum was dissolved in deionized water at 60°C to obtain a 1% gellan gum solution. Rhubarb was added to the gellan gum solution to obtain a 3 mg / mL raphanin-gellan gum mixture.

[0064] b. Preparation of ε-polylysine solution-calcium chloride mixture

[0065] ε-polylysine was dissolved in deionized water to obtain an ε-polylysine solution with a mass concentration of 0.5%. Then, calcium chloride was dissolved in this solution to obtain a ε-polylysine solution-calcium chloride mixture with a calcium chloride mass concentration of 1%.

[0066] c. Preparation of raphanin hydrogel microspheres

[0067] At room temperature, the ε-polylysine solution-calcium chloride mixture was placed on a stirrer and gently stirred until homogeneous. The raphanin-gellan gum mixture was then added dropwise to the ε-polylysine solution-calcium chloride mixture at a mass ratio of 2:1 to gellan gum and ε-polylysine to obtain hydrogel-like raphanin microspheres. After vacuum freeze-drying, raphanin hydrogel microspheres were obtained.

[0068] (2) Preparation of radish juice

[0069] Peel and wash the white radish, crush and stir it, filter it through cheesecloth to remove the white radish residue, and obtain white radish juice;

[0070] (3) Preparation of Radish Gel Soft Candy Rich in Rhubarb Extract

[0071] a. Preparation of white radish juice gel

[0072] Heat 50g of white radish juice to 80℃, remove the foam, cool to 60℃, add 5g of gelatin and dissolve completely to obtain white radish juice gel, keep warm at 60℃ for later use.

[0073] b. Preparation of sugar solution

[0074] Heat 50g of white radish juice to 80℃, remove the foam, cool to 60℃, add 20g of maltitol solution and 1.0g of erythritol, dissolve completely to obtain white radish juice syrup, and keep warm at 90±5℃ for later use.

[0075] c. Preparation of sugar-free radish-based soft gels rich in raphanin

[0076] After mixing the radish juice syrup from step (3)a and the radish juice sugar syrup from step (3)b, add 0.07g of citric acid and 0.05g of sodium citrate and mix well. Heat over low heat with constant stirring until it reaches 110℃. Then stop heating and add 0.5g of raphanin hydrogel microspheres and stir well. Finally, pour the prepared liquid into a mold, cool, and shape it to obtain radish gel soft candy rich in raphanin. Figure 2 As shown.

[0077] Example 3

[0078] like Figure 1 As shown, the manufacturing process of radish extract gel gummies is as follows:

[0079] (1) Preparation of raphanin hydrogel microspheres

[0080] a. Preparation of raphanin-gellan gum mixture

[0081] Gellan gum was dissolved in deionized water at 60°C to obtain a 1.5% (w / w) gellan gum solution. Rhubarb was added to the gellan gum solution to obtain a 3 mg / mL raphanin-gellan gum mixture.

[0082] b. Preparation of ε-polylysine solution-calcium chloride mixture

[0083] ε-polylysine was dissolved in deionized water to obtain a 1% ε-polylysine solution. Then, calcium chloride was dissolved in this solution to obtain a 1% ε-polylysine solution-calcium chloride mixture.

[0084] c. Preparation of raphanin hydrogel microspheres

[0085] At room temperature, the ε-polylysine solution-calcium chloride mixture was placed on a stirrer and gently stirred until homogeneous. The raphanin-gellan gum mixture was then added dropwise to the ε-polylysine solution-calcium chloride mixture at a mass ratio of 3:2 to gellan gum and ε-polylysine, resulting in hydrogel-like raphanin microspheres. After vacuum freeze-drying, raphanin hydrogel microspheres were obtained.

[0086] (2) Preparation of radish juice

[0087] Peel and wash the white radish, crush and stir it, filter it through cheesecloth to remove the white radish residue, and obtain white radish juice;

[0088] (3) Preparation of Radish Gel Soft Candy Rich in Rhubarb Extract

[0089] a. Preparation of white radish juice gel

[0090] Heat 100g of white radish juice to 80℃, remove the foam, cool to 60℃, add 7g of gelatin and dissolve completely to obtain white radish juice gel, keep warm at 60℃ for later use.

[0091] b. Preparation of sugar solution

[0092] Heat 100g of white radish juice to 80℃, remove the foam, cool to 60℃, add 20g of maltitol solution and 2.5g of erythritol, dissolve fully to obtain white radish juice syrup, and keep warm at 90±5℃ for later use.

[0093] c. Preparation of sugar-free radish-based soft gels rich in raphanin

[0094] After mixing the white radish juice syrup from step (3)a and the white radish juice sugar syrup from step (3)b, add 0.25g of citric acid and 0.05g of sodium citrate and mix well. Heat over low heat with constant stirring until it reaches 110℃. Then stop heating and add 0.5g of raphanin hydrogel microspheres and stir well. Finally, pour the prepared liquid into a mold, cool, and shape it to obtain radish gel soft candy rich in raphanin. Figure 2 As shown.

[0095] Comparative Example 1

[0096] (1) Preparation of raphanin hydrogel microspheres

[0097] a. Preparation of gellan gum solution

[0098] Gellan gum was dissolved in deionized water at 60°C to obtain a gellan gum solution with a mass concentration of 0.5%.

[0099] b. Preparation of ε-polylysine solution-calcium chloride mixture

[0100] ε-polylysine was dissolved in deionized water to obtain an ε-polylysine solution with a mass concentration of 1.5%. Then, calcium chloride was dissolved in the ε-polylysine solution to obtain a calcium chloride-ε-polylysine solution mixture with a mass concentration of 1%.

[0101] c. Preparation of hydrogel microspheres

[0102] At room temperature, the ε-polylysine solution-calcium chloride mixture was placed on a stirrer and stirred gently until homogeneous. The raphanin-gellan gum mixture was added dropwise to the ε-polylysine solution-calcium chloride mixture at a mass ratio of 1:3 to gellan gum and ε-polylysine to obtain hydrogel microspheres. After vacuum freeze-drying, the hydrogel microspheres were obtained for later use.

[0103] (2) Preparation of radish juice

[0104] Peel and wash the white radish, crush and stir it, filter it through cheesecloth to remove the white radish residue, and obtain white radish juice;

[0105] (3) Preparation of Radish Gel Soft Candy

[0106] a. Preparation of white radish juice gel

[0107] Heat 25g of white radish juice to 80℃, remove the foam, cool to 60℃, add 3g of gelatin and dissolve completely to obtain white radish juice gel, keep warm at 60℃ for later use.

[0108] b. Preparation of sugar solution

[0109] Heat 25g of white radish juice to 80℃, remove the foam, cool to 60℃, add 20g of maltitol solution and 0.5g of erythritol, dissolve completely, and keep the obtained white radish juice sugar solution at 90±5℃ for later use.

[0110] c. Preparation of sugar-free radish gel gummies

[0111] Add 0.05g of citric acid and 0.05g of sodium citrate to the white radish juice syrup in step (3)a and the white radish juice sugar syrup in step (3)b, mix well, heat over low heat and stir constantly, stop heating when it reaches 110℃, add 0.5g of hydrogel microspheres and stir well, finally pour the prepared liquid into the mold, cool and shape it to get radish gel soft candy rich in raphanin.

[0112] Comparative Example 2

[0113] (1) Preparation of raphanin hydrogel microspheres

[0114] a. Preparation of raphanin-gellan gum mixture

[0115] Gellan gum was dissolved in deionized water at 60°C to obtain a 1% gellan gum solution. Rhubarb was added to the gellan gum solution to obtain a 3 mg / mL raphanin-gellan gum mixture.

[0116] b. Preparation of ε-polylysine solution-calcium chloride mixture

[0117] ε-polylysine was dissolved in deionized water to obtain a 0.5% ε-polylysine solution. Then, calcium chloride was dissolved in the 0.5% ε-polylysine solution to obtain a 1% ε-polylysine solution-calcium chloride mixture.

[0118] c. Preparation of raphanin hydrogel microspheres

[0119] At room temperature, the ε-polylysine solution-calcium chloride mixture was gently stirred on a stirrer until homogeneous. The raphanin-gellan gum mixture was then added dropwise to the ε-polylysine solution-calcium chloride mixture at a mass ratio of 2:1 to gellan gum and ε-polylysine to obtain hydrogel-like raphanin microspheres. After vacuum freeze-drying, raphanin hydrogel microspheres were obtained for later use.

[0120] (2) Preparation of radish juice

[0121] Peel and wash the white radish, crush and stir it, filter it through cheesecloth to remove the white radish residue, and obtain white radish juice;

[0122] (3) Preparation of Radish Gel Soft Candy Rich in Rhubarb Extract

[0123] a. Preparation of white radish juice gel

[0124] Heat 50g of white radish juice to 80℃, remove the foam, cool to 60℃, add 5g of gelatin and dissolve completely to obtain white radish juice gel, keep warm at 60℃ for later use.

[0125] b. Preparation of sugar solution

[0126] Heat 50g of white radish juice to 80℃, remove the foam, cool to 60℃, add 20g of maltitol solution and 3.0g of erythritol, dissolve completely, and keep the obtained white radish juice sugar solution at 90±5℃ for later use.

[0127] c. Preparation of sugar-free radish-based soft gels rich in raphanin

[0128] After mixing the white radish juice syrup from step (3)a and the white radish juice syrup from step (3)b, add 0.07g of citric acid and 0.05g of sodium citrate and mix well. Heat over low heat and stir constantly until it reaches 110°C. Then stop heating and add 0.5g of raphanin hydrogel microspheres and stir well. Finally, pour the prepared liquid into a mold, cool it, and remove it to obtain radish gel soft candy rich in raphanin.

[0129] Comparative Example 3

[0130] (1) Preparation of raphanin hydrogel microspheres

[0131] a. Preparation of raphanin-sodium alginate mixture

[0132] Sodium alginate was dissolved in deionized water at room temperature to obtain a sodium alginate solution with a mass concentration of 1.5%. Rhubarb was added to the sodium alginate solution to obtain a raphanin-sodium alginate mixture with a raphanin concentration of 3 mg / mL.

[0133] b. Preparation of ε-polylysine solution-calcium chloride mixture

[0134] ε-polylysine was dissolved in deionized water to obtain a 1% ε-polylysine solution. Then, calcium chloride was dissolved in this solution to obtain a 1% ε-polylysine solution-calcium chloride mixture.

[0135] c. Preparation of raphanin hydrogel microspheres

[0136] At room temperature, the ε-polylysine solution-calcium chloride mixture was gently stirred on a stirrer until homogeneous. The raphanin-sodium alginate mixture was added dropwise to the ε-polylysine solution-calcium chloride mixture at a mass ratio of sodium alginate to ε-polylysine of 3:2 to obtain hydrogel-like raphanin microspheres. After vacuum freeze-drying, raphanin hydrogel microspheres were obtained for later use.

[0137] (2) Preparation of radish juice

[0138] Peel and wash the white radish, crush and stir it, filter it through cheesecloth to remove the white radish residue, and obtain white radish juice;

[0139] (3) Preparation of Radish Gel Soft Candy Rich in Rhubarb Extract

[0140] a. Preparation of white radish juice gel

[0141] Heat 100g of white radish juice to 80℃, remove the foam, cool to 60℃, add 7g of gelatin and dissolve completely to obtain white radish juice gel, keep warm at 60℃ for later use.

[0142] b. Preparation of sugar solution

[0143] Heat 100g of white radish juice to 80℃, remove the foam, cool to 60℃, add 20g of maltitol solution and 2.5g of erythritol, dissolve completely, and keep the resulting white radish juice syrup at 90±5℃ for later use.

[0144] c. Preparation of sugar-free radish-based soft gels rich in raphanin

[0145] Mix the white radish juice syrup from step (3)a and the white radish juice syrup from step (3)b, then add 0.25g of citric acid and 0.05g of sodium citrate and mix well. Heat over low heat and stir constantly until the mixture reaches 110°C. Add 0.5g of raphanin hydrogel microspheres and stir well. Finally, pour the prepared mixture into a mold, cool it, and remove it to obtain radish gel soft candy rich in raphanin.

[0146] I. Sensory evaluation and full texture testing of Examples 1-3 and Comparative Examples 1-3.

[0147] The sensory evaluation method and standard for sugar-free radish gel gummies rich in raphanin was conducted by an evaluation team of 10 professionals. The evaluation was carried out from six aspects: appearance, softness and hardness, elasticity, taste, chewiness and sweetness. The sensory evaluation standard is shown in Table 1, and the sensory evaluation results and texture data are shown in Tables 2 and 3.

[0148] Table 1. Sensory evaluation criteria of the present invention:

[0149]

[0150] Table 2 Sensory evaluation results of the present invention

[0151] project shape softness and hardness elasticity chewing smell Sweetness Total Score Example 1 7.5 6.8 5.9 8.2 7.5 6.4 42.3 Example 2 7.9 8.1 7.8 7.6 6.6 7.1 45.1 Example 3 7.2 7.6 7.2 6.3 7.5 6.1 41.9 Comparative Example 1 7.1 6.9 6.6 8.1 7.7 6.5 42.9 Comparative Example 2 7.9 7.6 6.9 6.9 5.8 5.1 40.2 Comparative Example 3 6.5 5.4 6.1 4.1 6.2 6.4 37.2

[0152] Table 3. Results of Texture Data in this Invention

[0153] project hardness elasticity Cohesiveness Adhesion Chewability responsive Example 1 449.84 0.88 0.95 426.14 475.67 0.81 Example 2 697.19 1.06 0.95 660.79 700.14 0.89 Example 3 564.70 1.25 0.94 531.84 668.98 0.89 Comparative Example 1 436.37 0.85 0.92 416.18 476.55 0.80 Comparative Example 2 600.94 0.87 0.96 581.46 507.57 0.89 Comparative Example 3 488.60 1.18 0.94 551.32 511.21 0.89

[0154] As shown in Tables 2 and 3, the hardness and elasticity of the gel gummy are related to the amount of gellan gum and erythritol added. The difference between Comparative Example 1 and Example 1 is that the gel microspheres in Comparative Example 1 do not contain raphanin. Tables 2 and 3 show that the addition of raphanin to the gellan gum and ε-polylysine gel microspheres has no effect on the sensory score and texture indices of the resulting gel gummy. The difference between Comparative Example 2 and Example 2 is that the erythritol content used in Comparative Example 2 is increased. Tables 2 and 3 show that the hardness, chewiness, elasticity, sweetness, and taste of the gel gummy in Comparative Example 2 are all reduced, resulting in a lower sensory score. The difference between Comparative Example 3 and Example 3 is that the same amount of sodium alginate was used instead of gellan gum. Compared with gellan gum / ε-polylysine gel microspheres, the ability of sodium alginate / ε-polylysine gel microspheres to encapsulate raphanin was not significantly different (p>0.05). However, sodium alginate / ε-polylysine gel microspheres are highly hydrophilic and quickly turn into a paste-like solution in aqueous solution, causing raphanin to dissolve and degrade upon contact with water. In addition, raphanin-sodium alginate / ε-polylysine gel microspheres form a denser gel structure in simulated gastric juice. Within 2 hours, the release rate of raphanin from the raphanin-sodium alginate / ε-polylysine gel microspheres in gastric juice is lower (15%). Figure 5 Using the same experimental method, after 2 hours, the raphanin-sodium alginate / ε-polylysine gel microspheres were placed in simulated intestinal fluid. The release rates at 4 hours, 6 hours, and 8 hours in the simulated intestinal fluid were 20%, 31%, and 45%, respectively, significantly lower than the release rate of raphanin from gellan gum / ε-polylysine gel microspheres in intestinal fluid. Furthermore, sodium alginate exhibited poor low-temperature gelling properties, failing to enhance the gel strength of the gel in the candy, resulting in a poor final appearance of the gummy candy (see Table 2), decreased softness and chewiness, and a low sensory score.

[0155] Table 4. Mass concentration ratio of each component in the raphanin hydrogel microspheres (equal volume).

[0156]

[0157] XRD patterns of hydrogel microspheres (GG: gellan gum; ε-PL: ε-polylysine; Examples 1-3: mass ratios of gellan gum and ε-polylysine were 1:3, 2:1, and 3:2, respectively; Control 1: Comparative Example 1) are shown below. Figure 3 As shown.

[0158] The infrared spectral results of the hydrogel microspheres (Examples 1-3: the mass ratios of gellan gum and ε-polylysine were 1:3, 2:1, and 3:2, respectively) show that in the FTIR of GG, at 3425 cm⁻¹... -1 2931cm -1 1610cm -11417cm -1 1013 and 1013 are the stretching vibration peaks of the hydroxyl (-OH), CH2, asymmetric and symmetric carboxylates of -C=O, and CO, respectively. In the FTIR curve of ε-PL, 3,500 cm⁻¹... -1 -3,000cm -1 The absorption peaks are due to the stretching vibrations of NH and OH, at 2,931 cm⁻¹. -1 The peak for the stretching vibration of CH is 1,670 cm⁻¹. -1 1,564cm -1 1,256cm -1 These correspond to the stretching vibrations of C=O (amide I band), the bending vibrations of NH (amide II band), and the stretching vibrations of CN (amide III band), respectively. 700cm -1 Corresponding to the bending vibration of NH. After GG crosslinks with ε-PL, the -OH group red-shifts, and hydrogen bonds form between the hydroxyl group of GG and the carboxyl group of ε-PL. These hydrogen bonds lower the position of the stretching vibration peak, and both amide I and amide II bands shift to lower wavenumbers, forming a more intense absorption peak and a more stable structure. The isothiocyanate functional group will be at 2200 cm⁻¹. -1 -2100cm -1 There is a distinct double-shoulder peak between them. This structure appeared in the infrared spectrum of the raphanin-GG / ε-PL gel in Examples 1-3, indicating that raphanin has been embedded in the hydrogel structure.

[0159] from Figure 3 As can be seen, after GG and ε-PL combine through electrostatic interaction, hydrogel microspheres with different proportions all exhibit similar XRD diffraction patterns. The obvious broad peak at 2θ = 21.1° and the small sharp peak at 2θ = 31.9° represent the strong interaction between GG and ε-PL. The isothiocyanate functional group of raphanin shows a diffraction peak at 2θ = 22.76°. After encapsulating raphanin, this diffraction peak was not observed in Examples 1-3, and a new small sharp peak appeared at 2θ = 45.6°, indicating that an interaction has occurred between GG, ε-PL, and SFE.

[0160] HPLC analysis conditions: C18 column (250 mm × 4.6 mm, 5.0 μm), column temperature 40 ℃, wavelength 254 nm, injection 10 μL, mobile phase water:methanol = 7:3 (v / v), flow rate 0.8 mL / min, analysis time 25 min. A standard curve was plotted with raphanin peak area on the x-axis and raphanin content on the y-axis. The equation is: Y = 0.4325X - 2691, and the correlation coefficient R0 is [missing value]. 2 =0.9967.

[0161] Formulas for calculating encapsulation rate and drug loading rate:

[0162]

[0163] Figure 4 The encapsulation efficiency and drug loading rate of raphanin gel are as follows: the encapsulation efficiency is above 60% and the drug loading rate is above 30%.

[0164] II. Determination of raphanin release rate in gel microspheres during simulated in vitro digestion process

[0165] Accurately weigh 1g of raphanin hydrogel microspheres and add 100mL of simulated gastric juice. Shake in a 37℃ constant temperature water bath shaker (100rpm) for 2 hours. At different time points (0, 30, 60, 90, 120min), take 10mL of gastric juice and add the same volume of simulated gastric juice, and continue shaking. After the simulated gastric digestion stage, add simulated small intestinal juice to the reactor and digest under the same conditions for 180min. At different time points (1, 2, 3, 4h), take 10mL of small intestinal juice and add the same volume of simulated small intestinal juice, and continue shaking. After the simulated small intestinal digestion stage, add simulated colonic juice to the reactor and digest under the same conditions for 180min. At different time points (1, 2, 3h), take 10mL of slow-release colonic juice and add the same volume of simulated colonic juice, until digestion is complete. The extracted sustained-release solution was centrifuged at 0℃, 10000 rpm, for 5 min to separate the precipitate from the supernatant. The supernatant was extracted with ethyl acetate solution three times consecutively. The upper ethyl acetate layers were combined and concentrated to dryness using a rotary evaporator. After dissolving in 1 mL of methanol, the solution was filtered through a 0.22 μm filter membrane, and sulforaphane was quantitatively analyzed by HPLC. The release rate of sulforaphane was calculated according to the following formula. Each experiment was repeated three times.

[0166] Release rate of raphanin (%) = w / m × 100

[0167] In the formula: w is the amount of raphanin released from the raphanin hydrogel microspheres, in g; m is the amount of raphanin encapsulated in the hydrogel microspheres, in g.

[0168] III. Determination of raphanin release rate in simulated in vitro digestion process of gel gummies

[0169] 1 g of raphanin hydrogel microspheres were accurately weighed and added to 100 mL of simulated gastric juice. The mixture was shaken in a 37°C water bath shaker (100 rpm) for 2 hours. At 1 hour and 2 hours, 10 mL of gastric juice was collected, and the same volume of simulated gastric juice was added back in. The shaking continued. After the simulated gastric digestion stage, simulated intestinal juice was added to the reactor and digested for 180 minutes under the same conditions. At different time points (1, 2, and 3 hours), 10 mL of sustained-release intestinal juice was collected, and the same volume of simulated intestinal juice was added back in. The shaking continued until digestion was complete. The collected sustained-release solution was centrifuged at 0°C, 10,000 rpm, for 5 minutes to separate the precipitate from the supernatant. The supernatant was extracted with ethyl acetate solution three times. The upper ethyl acetate layer was combined and concentrated to dryness using a rotary evaporator. After dissolving in 1 mL of methanol, the solution was filtered through a 0.22 μm filter membrane, and raphanin was quantitatively analyzed by HPLC. The release rate of raphanin was calculated using the following formula, and each experiment was repeated three times.

[0170] Release rate of raphanin (%) = w / m × 100

[0171] In the formula: w is the amount of raphanin released from the raphanin gummies, in g; m is the amount of raphanin encapsulated in the raphanin gel gummies, in g.

[0172] The encapsulation efficiency and drug loading rate of raphanin hydrogel microspheres are as follows: Figure 5 The release rates are shown in the figures (0-2h in simulated gastric juice, 2-6h in simulated small intestinal juice, and 6-9h in simulated colonic juice); the release rate of raphanin in the raphanin gel gummies after in vitro digestion is shown in the figures. Figure 6 As shown (simulated gastric juice for 2 hours, simulated small intestinal juice for 3 hours);

[0173] This invention chemically binds raphanin into gel microspheres. The gellan gum and ε-polylysine used in the gel are both edible food additives listed in GB2760-2014, effectively solving the problem of structural instability of raphanin upon contact with water. The raphanin gel product gels at low temperatures and is hydrophobic. In subsequent processing of raphanin gel gummies, the addition of raphanin gel microspheres eliminates the need for high-temperature processing steps, thus avoiding high-temperature degradation of raphanin. Figure 5 and Figure 6 It can be seen that ractopamine gel and ractopamine gummies exhibit low ractopamine release rates in simulated gastric juice but high release rates in simulated intestinal juice, achieving precise delivery of ractopamine. Furthermore, ractopamine gel gummies show improved release rates under acidic conditions (…). Figure 6 Its stability is higher than that of raphanin gel microspheres. Figure 5This invention, by adding hydrogel microspheres containing raphanin to gummies, fills a market gap for raphanin products and improves the stability and utilization rate of raphanin. The process utilizes a simple manufacturing process with white radish juice as the main ingredient, supplemented with maltitol solution and sugar-free erythritol, resulting in a novel product suitable for a wide range of consumers. It also imparts a refreshing flavor to the gummies, demonstrating that gelation into gel candies is an effective food processing method for preserving the activity of raphanin.

[0174] Although embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that various changes, modifications, and substitutions can be made to these embodiments without departing from the principles of the invention. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from its scope should be within the protection scope of the present invention.

Claims

1. A method for preparing a water-swellable microsphere of sulforaphane, characterized by: The preparation steps are as follows: (1) Preparation of sulforaphen-konjac gum mixed solution Dissolve konjac gum in deionized water to obtain a konjac gum solution with a mass concentration of 0.5-1.5%, and then add sulforaphen to the konjac gum solution to obtain a sulforaphen-konjac gum mixed solution with a sulforaphen concentration of 3 mg / mL; (2) Preparation of ε-polylysine solution-calcium chloride mixed solution Dissolve ε-polylysine in deionized water to obtain an ε-polylysine solution with a mass concentration of 0.5-1.5%, and then dissolve calcium chloride in the ε-polylysine solution to obtain an ε-polylysine solution-calcium chloride mixed solution; (3) Preparation of sulforaphen hydrogel microspheres Gently stir the ε-polylysine solution-calcium chloride mixed solution at room temperature until it is uniform, and then add an equal volume of the sulforaphen-konjac gum mixed solution to the ε-polylysine solution-calcium chloride mixed solution according to a mass ratio of konjac gum to ε-polylysine of 2:1-1:3 to obtain sulforaphen microspheres in the form of hydrogels, and then vacuum freeze-dry to obtain sulforaphen hydrogel microspheres.

2. The method of claim 1, wherein the sulforgane hydrogel microspheres are prepared by the following steps of: The mass concentration of calcium chloride in the ε-polylysine solution-calcium chloride mixed solution is 1-1.5%.

3. The method of claim 1, wherein the sulforgane hydrogel microspheres are prepared by the steps of: In step (1), the temperature of the deionized water is 60°C.

4. The sulforaphen hydrogel microspheres prepared by the method of claim 1 are used in the preparation of sulforaphen gel gummy candies.

5. A method of preparing the sulforaphane gummy candy according to claim 4, characterized by: The specific steps are as follows: (1) Weigh the raw materials The sulforaphen-rich radish sugar-free gel gummy candy comprises, by weight fraction, 50 parts of white radish juice, 0.035-0.0625 parts of citric acid, 0.0125-0.05 parts of sodium citrate, and 0.0125-0.25 parts of sulforaphen hydrogel microspheres; Preparation of white radish juice gel solution Add gelatin to the white radish juice and dissolve to obtain a white radish juice gel solution; (2) Preparation of white radish juice sugar solution Add maltitol solution and erythritol to the white radish juice and dissolve to obtain a white radish juice sugar solution; (3) Preparation of sulforaphen-rich radish sugar-free gel gummy candy Mix the white radish juice gel solution and the white radish juice sugar solution, add citric acid and sodium citrate, and mix uniformly, the mass ratio of white radish juice in the white radish juice gel solution to white radish juice in the white radish juice sugar solution being 1:1, continuously heat and stir under low heat, stop heating when the temperature reaches 110°C, add sulforaphen hydrogel microspheres, and stir uniformly, and then cool to obtain a sulforaphen-rich radish gel gummy candy. In step (1), the mass ratio of white radish juice to gelatin is 25:(1.75-3).

6. The method of claim 5, wherein the sulforaphane gel chews are prepared by: In step (2), the mass ratios of white radish juice to maltitol solution and erythritol are 25:(5-20) and 25:(0.5-0.625), respectively.

7. The method of claim 5, wherein the method further comprises: ​ ​

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