Natural high-stability anthocyanin toner and preparation method thereof
By combining anthocyanin extract with wolfberry polysaccharides and calcium ions, a stable structure is formed, solving the problem of anthocyanin instability in food processing and achieving efficient and safe coloring effects, suitable for food and health products.
Patent Information
- Application Number
- CN202511494833.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-20
- Publication Date
- 2025-11-21
AI Technical Summary
Anthocyanins are unstable during food processing and storage, and are easily affected by light, temperature and pH. Existing technologies to improve their stability are complex, costly or have limited effectiveness.
A natural, highly stable anthocyanin colorant was prepared by combining anthocyanin extract, wolfberry polysaccharide, and calcium ions to form a stable structure. The preparation process included dissolution, light-protected reaction, alcohol precipitation, dialysis, and freeze-drying.
It significantly improves the thermal stability of anthocyanins, reduces the degradation rate at 80℃, maintains excellent color, and provides a safe, green, and simple coloring solution suitable for food and health products.
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Figure CN120982680A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of functional food preparation, in particular to a natural high-stability anthocyanin color enhancer and a preparation method thereof, which is especially suitable for efficient utilization of natural pigments and development of functional products. BACKGROUND
[0002] In the process of fruit and vegetable processing, fruit and vegetable offal such as black wolfberry, blueberry and purple cabbage are rich in anthocyanins and have high content of bioactive ingredients. Studies have shown that fruit and vegetable offal are rich in natural antioxidants such as polyphenols, flavonoids and anthocyanins. Among them, anthocyanins, as a natural pigment, not only have good antioxidant, anti-inflammatory and anti-tumor biological activities, but also have broad application prospects in food, cosmetics and medicine fields. At present, through modern extraction technologies such as microwave-assisted extraction and enzymatic hydrolysis, high-value compounds in fruit and vegetable offal can be efficiently extracted, thereby realizing the reuse of resources.
[0003] However, anthocyanins face many challenges in practical applications, mainly due to their instability. The stability of anthocyanins is affected by many factors, including light, temperature and pH. When exposed to natural light and artificial light sources, the conjugated double bond system in the molecular structure of anthocyanins easily absorbs light energy, triggering photochemical reactions and causing molecular structure damage, resulting in color fading. In addition, high temperature can accelerate the degradation of anthocyanins. In the food processing process such as baking and sterilization, when the temperature rises, the degradation rate of anthocyanins increases exponentially. In a neutral or alkaline environment, the molecular structure of anthocyanins changes, forming unstable forms such as quinone base and chalcone, accelerating the degradation of pigments and changing their color. Therefore, how to effectively control these factors during processing and storage to improve the stability of anthocyanins is one of the current research focuses.
[0004] Currently, the techniques for improving the stability of anthocyanins mainly include chemical modification (such as acylation, glycosylation), microencapsulation, complexation with biological macromolecules (proteins, polysaccharides), and nanoparticle embedding. For example, by forming complexes with starch, cyclodextrin or polysaccharides, or using nanotechnology to prepare nanoparticles, the anti-degradation ability of anthocyanins can be significantly enhanced. However, the existing technologies still have many shortcomings. Chemical modification can improve stability, but it has the problems of complex process and high cost, making it difficult to achieve industrial production. Microencapsulation and nanotechnology have significant effects, but they face challenges such as complex preparation process, high cost and practical application technical bottlenecks. The auxiliary color effect and metal ion combination method still need to further optimize the process parameters.
[0005] Therefore, developing a new preparation and a preparation method thereof, which has simple process, low cost and can significantly improve the stability of anthocyanin, has important application value. This breakthrough will not only promote the wider application of anthocyanin in food, medicine and cosmetics and other fields, but also provide new development opportunities for the technological innovation of related industries. In view of this, the present application is proposed. SUMMARY
[0006] The present application aims to provide a natural high-stability anthocyanin color enhancer and a preparation method thereof, which takes anthocyanin as the main substance and wolfberry polysaccharide and metal ions as auxiliary substances, so as to solve the problems of insufficient stability, easy degradation and color fading of anthocyanin in the prior art, and provide an anthocyanin composite preparation with simple preparation process and excellent stability.
[0007] In order to solve the above technical problems, the present application adopts the following technical means:
[0008] The present application first discloses a natural high-stability anthocyanin color enhancer, which comprises the following raw materials in the following proportions by weight:
[0009] 5-20 parts of anthocyanin extract, 0.2-0.8 parts of wolfberry polysaccharide and 0.02-0.10 parts of calcium ions.
[0010] Further, the following raw materials are included in the following proportions by weight:
[0011] 10 parts of anthocyanin extract, 0.6 parts of wolfberry polysaccharide and 0.04 parts of calcium ions.
[0012] The present application also discloses a preparation method of the natural high-stability anthocyanin color enhancer according to the above, comprising:
[0013] (1) weigh the anthocyanin extract, wolfberry polysaccharide and calcium ions, and dissolve them in deionized water, and adjust the pH to 4-7 with 0.1 mol / L NaOH solution;
[0014] (2) place the reaction system in a constant-temperature water bath shaker and react in the dark, and after cooling, add 4 times the volume of anhydrous ethanol for alcohol precipitation;
[0015] (3) after low-temperature standing of the alcohol precipitation system, centrifugal treatment is performed, and the precipitate is collected to obtain a crude product, which is placed in a dialysis bag, and dialysis is performed at 4°C for 24 h to remove free ions, and a dialysate is obtained;
[0016] (4) the dialysate is filtered through a 0.22 μm microporous membrane, and freeze-dried to obtain the natural high-stability anthocyanin color enhancer.
[0017] Further, the anthocyanin extract in step (1) is prepared by the following method:
[0018]
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[0020]
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[0022]
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[0024]
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[0028]
[0029]
[0030] Figure 1 A preparation process flow chart for improving the stability of anthocyanin pigments;
[0031] Figure 2 The color stability of solutions of different samples after storage at 80 DEG C for different time, from left to right, 1, 3, 5, 7 h, including three bottles of samples are control sample, sample without metal ions, sample with anthocyanin color enhancer of the application;
[0032] Figure 3 is the effect of anthocyanin residual rate (A) and degradation kinetics (B) of different samples during storage at 80 DEG C. DETAILED DESCRIPTION
[0033] The technical solutions in the embodiments of the application will be apparently and completely described below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work belong to the protection scope of the application.
[0034] The application will be further described below with reference to the embodiments and drawings:
[0035] Embodiment 1
[0036] Preparation method of anthocyanin extract
[0037] (1) Selecting the defective purple cabbage, crushing it with a crusher. Distilled water is added according to the solid-liquid ratio of 1:10 (g / mL), the pH value is 4, water bath is at 40 DEG C, and the extraction is performed for 60 min. Then, centrifugation is performed at 4 000 r / min for 10 min, the supernatant is taken, and 4 DEG C refrigeration is performed for standby.
[0038] (2) Purification of anthocyanin by AB-8 type macroporous resin: the concentration of the sample solution is 200 mg / 100 g, the sample flow rate is 2 mL / min, the elution flow rate is 2 mL / min, the sample volume is 5 BV, and anthocyanin extract is obtained through freeze-drying.
[0039] Embodiment 2
[0040] Preparation method of anthocyanin extract
[0041] (1) Selecting the defective purple cabbage, crushing it with a crusher. Distilled water is added according to the solid-liquid ratio of 1:15 (g / mL), the pH value is 4.5, water bath is at 50 DEG C, and the extraction is performed for 60 min. Then, centrifugation is performed at 4 000 r / min for 10 min, the supernatant is taken, and 4 DEG C refrigeration is performed for standby.
[0042] (2) AB-8 macroporous resin purification of anthocyanins: the sample solution concentration was 200 mg / 100 g, the sample flow rate was 2 mL / min, the elution flow rate was 2 mL / min, the sample volume was 5 BV, and anthocyanin extract was obtained by freeze-drying.
[0043] Example 3
[0044] Preparation method of anthocyanin extract
[0045] (1) Selecting the defective purple cabbage, crushing it with a crusher. Add distilled water according to the ratio of 1:20 (g / mL), the pH value is 5, water bath at 60°C for 60 min, then centrifuge at 4,000 r / min for 10 min, take the supernatant, and store at 4°C for standby.
[0046] (2) AB-8 macroporous resin purification of anthocyanins: the sample solution concentration was 200 mg / 100 g, the sample flow rate was 2 mL / min, the elution flow rate was 2 mL / min, the sample volume was 5 BV, and anthocyanin extract was obtained by freeze-drying.
[0047] Example 4
[0048] A preparation method of a natural high-stability anthocyanin color enhancer, using the anthocyanin extract obtained in Example 1 as raw material:
[0049] (1) Accurately weigh 5 g of anthocyanin (ACN), 0.4 g of wolfberry polysaccharide (LBPs), and 0.02 g of calcium ion, dissolve them in 100 ml of deionized water, and magnetically stir until completely dissolved. Adjust the pH of the reaction system to 4 using 0.1 mol / L NaOH solution.
[0050] (2) Place the reaction system in a 55°C constant temperature water bath shaker and oscillate under dark conditions for 1 h. After the reaction is completed, naturally cool the system to room temperature and slowly add 4 times the volume of anhydrous ethanol for precipitation.
[0051] (3) After the precipitation system is placed at 4°C for 12 h, centrifuge at 4,000 r / min for 10 min at 4°C to collect the precipitate and obtain the crude product. Put the crude product into a dialysis bag and dialyze for 24 h at 4°C to remove unreacted calcium ions.
[0052] (4) After dialysis is completed, filter the dialysate through a 0.22 μm microporous filter, and finally obtain the natural high-stability anthocyanin color enhancer by freeze-drying.
[0053] Example 5
[0054] A preparation method of a natural high-stability anthocyanin color enhancer, using the anthocyanin extract obtained in Example 1 as raw material:
[0055] (1) Accurately take 10 g of anthocyanins (ACN), 0.6 g of wolfberry polysaccharide (LBPs), and 0.04 g of calcium ions, dissolve them in 100 ml of deionized water, and magnetically stir until completely dissolved. Adjust the pH of the reaction system to 5 using 0.1 mol / L NaOH solution.
[0056] (2) Place the reaction system in a 55°C constant temperature water bath shaker and oscillate under dark conditions for 1 h. After the reaction is complete, naturally cool the system to room temperature and slowly add 4 times the volume of anhydrous ethanol for precipitation.
[0057] (3) After the precipitation system is placed at 4°C for 12 h, centrifuge at 4000 r / min for 10 min at 4°C, collect the precipitate to obtain the crude product. Put the crude product into a dialysis bag and dialyze for 24 h at 4°C to remove unreacted calcium ions.
[0058] (4) After dialysis is complete, filter the dialysate through a 0.22 μm microporous filter, and finally obtain the natural high-stability anthocyanin color enhancer through freeze-drying.
[0059] Example 6
[0060] A method for preparing a natural high-stability anthocyanin color enhancer, using the anthocyanin extract obtained in Example 1 as the raw material:
[0061] (1) Accurately take 15 g of anthocyanins (ACN), 0.8 g of wolfberry polysaccharide (LBPs), and 0.06 g of calcium ions, dissolve them in 100 ml of deionized water, and magnetically stir until completely dissolved. Adjust the pH of the reaction system to 6 using 0.1 mol / L NaOH solution.
[0062] (2) Place the reaction system in a 55°C constant temperature water bath shaker and oscillate under dark conditions for 1 h. After the reaction is complete, naturally cool the system to room temperature and slowly add 4 times the volume of anhydrous ethanol for precipitation.
[0063] (3) After the precipitation system is placed at 4°C for 12 h, centrifuge at 4000 r / min for 10 min at 4°C, collect the precipitate to obtain the crude product. Put the crude product into a dialysis bag and dialyze for 24 h at 4°C to remove unreacted calcium ions.
[0064] (4) After dialysis is complete, filter the dialysate through a 0.22 μm microporous filter, and finally obtain the natural high-stability anthocyanin color enhancer through freeze-drying.
[0065] Example 7
[0066] A method for preparing a natural high-stability anthocyanin color enhancer, using the anthocyanin extract obtained in Example 1 as the raw material:
[0067] (1) Accurately weigh 20 g of anthocyanins (ACN), 1.0 g of Lycium barbarum polysaccharide (LBPs), and 0.08 g of calcium ions, dissolve them in 100 ml of deionized water, and magnetically stir until completely dissolved. Adjust the pH of the reaction system to 7 using 0.1 mol / L NaOH solution.
[0068] (2) Place the reaction system in a 55°C constant temperature water bath shaker and shake under dark conditions for 1 h. After the reaction is complete, naturally cool the system to room temperature and slowly add 4 times the volume of anhydrous ethanol for precipitation.
[0069] (3) After the precipitation system is placed at 4°C for 12 h, centrifuge at 4000 r / min for 10 min at 4°C to collect the precipitate and obtain the crude product. Load the crude product into a dialysis bag and dialyze at 4°C for 24 h to remove unreacted calcium ions.
[0070] (4) After dialysis is complete, filter the dialysate through a 0.22 μm microporous filter, and finally obtain the natural high-stability anthocyanin color enhancer by freeze-drying.
[0071] Test Example
[0072] The anthocyanin stability-enhancing preparation was tested for performance, and the experimental results are as follows:
[0073] The anthocyanin stability-enhancing preparation prepared in Example 5 was placed in an 80°C water bath and heated in the dark for 7 h. The anthocyanin content was measured every hour, and the residual rate was calculated. The anthocyanin continuously degraded as the heating time increased, and the longer the heating time, the faster the degradation rate. The residual rates of anthocyanin after heating at 80°C for 7 h were 10.19%, 37.21%, and 39.5%, respectively. The degradation kinetics parameters of anthocyanin at different heating temperatures are shown in Table 1.
[0074] Table 1 Degradation kinetics parameters of anthocyanin at 80°C
[0075]
[0076] According to the results in Table 1, the thermal stability of anthocyanin conforms to first-order kinetics (R 2 >0.96), and the degradation rates K of the three preparations at 80°C were 0.31, 0.10, and 0.09 h -1That is, the degradation rate increases with the increase of time, and the half-life decreases with the increase of heating time. The half-life of the single anthocyanin preparation is only 2.22 h when heated at 80℃ for 7 h, which may be due to the hydrolysis of the sugar group of anthocyanin at high temperature, or the change of the configuration of anthocyanin at high temperature, so long time high temperature treatment is easy to make anthocyanin degradation. The half-life of the complex preparation is 6.73 h and 7.74 h, respectively, which is increased by 4.51 h and 5.52 h compared with the single preparation. Therefore, the complex preparation of wolfberry polysaccharide and metal ions has a certain color protection effect on the stability of anthocyanin.
[0077] The change of the residual rate of the anthocyanin stability enhancing preparation under different heating times with time is shown in Figure 2 The control group: 10 g of extracted anthocyanin is dissolved in 100 ml of deionized water. The group without metal ions: 10 g of extracted anthocyanin and 0.6 g of wolfberry polysaccharide are dissolved in 100 ml of deionized water. The natural high-stability anthocyanin color enhancer: 10 g of extracted anthocyanin, 0.6 g of wolfberry polysaccharide and 0.04 g of calcium ion are dissolved in 100 ml of deionized water. It can be seen from Figure 2 that the color of the three groups changes to different degrees after being stored at 80℃ for different times, and the color gradually becomes lighter with the extension of time, indicating that the stability of the anthocyanin solution is gradually decreasing. The color change of the solution added with the anthocyanin stability preparation is relatively small after being stored at 80℃ for different times, especially at 5 h and 7 h, the color still maintains a high purple concentration, while the color change of the control group and the solution added with only anthocyanin and wolfberry polysaccharide is more obvious, and the color becomes lighter to a greater extent.
[0078] The change of the anthocyanin content with heating time is fitted by first-order kinetics, and the specific results are shown in Figure 3. The control group is the anthocyanin solution (no addition, no treatment sample); the experimental group without metal ions: the solution of anthocyanin + wolfberry polysaccharide (only adding wolfberry polysaccharide, to see the protection of the combination of the two on anthocyanin); the experimental group of anthocyanin color enhancer: the solution of anthocyanin + wolfberry polysaccharide + calcium ion (adding wolfberry polysaccharide and calcium ion, to see the protection of the combination of the three on anthocyanin).
[0079] It is obvious to those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be regarded as exemplary and non-limiting, and the scope of the present application is defined by the appended claims rather than the above description, and therefore all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application. Any reference signs in the claims should not be regarded as limiting the claims involved.
[0080] Furthermore, it should be understood that although the specification is described in terms of embodiments, the specification as a whole, and each embodiment individually, does not contain only one independent technical solution, and the specification is described in this way only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.
Claims
1. A natural, highly stable anthocyanin colorant, comprising the following raw materials in the indicated weight ratios: 5-20 parts anthocyanin extract, 0.2-0.8 parts wolfberry polysaccharide, and 0.02-0.10 parts calcium ions.
2. The natural, highly stable anthocyanin color enhancer according to claim 1, comprising the following raw materials in the indicated weight ratios: 10 parts anthocyanin extract, 0.6 parts wolfberry polysaccharide, and 0.04 parts calcium ions.
3. A method for preparing a natural, highly stable anthocyanin colorant according to claim 1 or 2, comprising: (1) Weigh anthocyanin extract, wolfberry polysaccharide and calcium ions, dissolve them in deionized water and adjust the pH to 4-7; (2) Place the reaction system in a constant temperature water bath shaker to react in the dark, and after cooling, add 4 times the volume of anhydrous ethanol for alcohol precipitation; (3) After the alcohol precipitation system was allowed to stand at low temperature, it was centrifuged, the precipitate was collected and dialyzed for 24 h to remove free ions, and the dialysate was obtained. (4) The dialysate was filtered through a 0.22 μm filter membrane and freeze-dried to obtain a natural, highly stable anthocyanin colorant.
4. The preparation method according to claim 3, wherein: The anthocyanin extract in step (1) is prepared by the following method: ① Select substandard fruits and vegetables rich in anthocyanins, pulp, filter, and centrifuge to obtain clear juice, add purified water to dilute the anthocyanins, and obtain anthocyanin extract for later use; ②The anthocyanin extract was purified and concentrated using AB-8 type macroporous resin, and then freeze-dried to obtain the anthocyanin extract.
5. The preparation method according to claim 4, wherein: The anthocyanin content in the substandard fruits and vegetables mentioned in step ① is ≥90.5 mg / 100 g; The anthocyanin content is diluted to 200 mg / 100 ml.
6. The preparation method according to claim 4, wherein: The purification and concentration conditions described in step ② are as follows: loading flow rate 2 mL / min, loading volume 5 BV, elution with 80% edible alcohol at a flow rate of 2 mL / min and an elution volume of 5 BV.
7. The preparation method according to claim 3, wherein: The step (1) involves adjusting the pH to 5.
8. The preparation method according to claim 3, wherein: The constant temperature water bath in step (2) is 50~60℃, and the reaction time in the dark is 1 h.
9. The preparation method according to claim 3, wherein: The conditions for centrifugation after low-temperature standing in step (3) are: centrifugation after standing at 4℃ for 12 h.
10. A natural, highly stable anthocyanin colorant prepared by the preparation method according to any one of claims 3 to 9.