阅读说明：本技术 一种虾青素酯纳米复合物颗粒的制备方法 (Preparation method of astaxanthin ester nano composite particles ) 是由 周庆新 谷彩霞 徐泽生 韩鑫杰 郭楚璇 王辉 于 2020-12-17 设计创作，主要内容包括：本发明涉及虾青素技术领域,具体涉及一种虾青素酯纳米复合物颗粒的制备方法,包括将蛋白质溶于去离子水或缓冲溶液中水化,得到水相溶液；将虾青素酯溶于油相中制成虾青素酯的油溶液；将虾青素酯油溶液添加到水相溶液中,同时向体系中加入茶多酚,然后采用高压微射流充分均质乳化；将乳化后的体系用碱性物质调节体系pH值到11～13,进行二次均质乳化；将二次乳化后的体系边搅拌边用酸性物质调节体系pH至6.5～7.2；干燥。通过本方法制得的虾青素酯热稳定性和加工储运稳定性明显提高,在水中分散性良好,具备良好的加工应用性能；制备过程不使用醇类溶剂和表面活性剂,避免了醇类溶剂和表面活性剂所造成的残留问题,提高了安全性。(The invention relates to the technical field of astaxanthin, in particular to a preparation method of astaxanthin ester nano composite particles, which comprises the steps of dissolving protein in deionized water or buffer solution for hydration to obtain aqueous phase solution; dissolving astaxanthin ester in the oil phase to prepare an oil solution of astaxanthin ester; adding the astaxanthin ester oil solution into the water phase solution, adding tea polyphenol into the system, and then fully homogenizing and emulsifying by adopting high-pressure micro-jet; adjusting the pH value of the emulsified system to 11-13 by using an alkaline substance, and carrying out secondary homogenizing emulsification; adjusting the pH of the system after the secondary emulsification to 6.5-7.2 by using an acidic substance while stirring; and (5) drying. The astaxanthin ester prepared by the method has obviously improved thermal stability and processing, storage and transportation stability, good dispersibility in water and good processing and application performance; the preparation process does not use alcohol solvent and surfactant, thereby avoiding the residue problem caused by the alcohol solvent and the surfactant and improving the safety.)

1. A preparation method of astaxanthin ester nano-composite particles is characterized by comprising the following steps:

(1) preparation of aqueous phase solution: dissolving protein in deionized water or buffer solution for hydration to obtain water phase solution;

(2) preparation of oil phase solution: dissolving astaxanthin ester in the oil phase to prepare an oil solution of astaxanthin ester;

(3) primary emulsification: adding the astaxanthin ester oil solution prepared in the step (2) into the water phase solution prepared in the step (1), adding tea polyphenol into the system, and then fully homogenizing and emulsifying by adopting high-pressure micro-jet;

(4) primary adjustment of system pH and secondary emulsification: adjusting the pH value of the emulsified system in the step (3) to 11-13 by using an alkaline substance, and then carrying out secondary homogenizing emulsification;

(5) and (3) adjusting the pH value of the system for the second time: adjusting the pH value of the system obtained in the step (4) after secondary emulsification to 6.5-7.2 by using an acidic substance while stirring;

(6) and (5) drying.

2. The method of claim 1, wherein the step (1) is: dissolving protein in deionized water or phosphate buffer solution with the pH of 6.5-7.5 according to the addition amount of 0.5-5 g/100mL in mass-to-volume ratio, and hydrating for 2-12 h at the temperature of 1-20 ℃ to obtain aqueous phase solution;

the protein is one or more of zein, wheat gliadin, kafirin and hordein.

3. The preparation method according to claim 1, wherein the step (1) further comprises adding a stabilizer with a mass-to-volume ratio of 0.1-5 g/100mL into the aqueous phase solution, wherein the stabilizer is one or more of propylene glycol alginate, soy protein, casein, sodium caseinate, whey protein, lysozyme, galactomannan, pectin, carboxymethyl cellulose, chitosan, sodium alginate, acacia and glucan.

4. The method of claim 1, wherein the step (2) is: dissolving astaxanthin ester into an oil phase at the temperature of 10-80 ℃ according to the addition amount of 2-50% by mass fraction to prepare an oil phase solution of the astaxanthin ester;

the oil phase is one or two of linear chain fatty acid ester and fatty glyceride.

5. The method of claim 1, wherein the step (3) is: mixing the astaxanthin ester oil solution prepared in the step (2) according to the mass ratio of 1: 1-20 times of adding the mixture into the aqueous phase solution prepared in the step (1), adding tea polyphenol with the mass volume ratio of 0.0005-1 g/100mL into the system, and then fully homogenizing and emulsifying by adopting high-pressure microjet, wherein the homogenizing pressure is 40-120 MPa, and the treatment times are 1-3 times.

6. The method of claim 1, wherein the step (4) is: adjusting the pH value of the emulsified system in the step (3) to 11-13 by using an alkaline substance, and then carrying out secondary homogeneous emulsification, wherein the emulsification method is at least one of shearing homogeneous emulsification and high-pressure microjet homogeneous emulsification, the rotation speed of the shearing homogeneous emulsification is 3000-30000 rpm, and the time is 1-10 min; the pressure of the high-pressure microjet homogenizing emulsification is 40-120 MPa, and the treatment times are 1-3 times.

7. The method according to claim 6, wherein the alkaline substance is one or more of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, and potassium carbonate.

8. The method according to claim 1, wherein the step (5) is: and (3) adjusting the pH value of the system obtained in the step (4) to 6.5-7.2 by using an acidic substance while stirring under the stirring condition of 200-2000 rpm.

9. The method according to claim 8, wherein the acidic substance is one or more selected from acetic acid, citric acid, hydrochloric acid, malic acid, lactic acid, tartaric acid, phosphoric acid, and gluconolactone.

10. The method according to claim 1, wherein the drying in step (6) is spray drying or freeze drying.

Technical Field

The invention relates to the technical field of astaxanthin, in particular to a preparation method of astaxanthin ester nano composite particles.

Background

Astaxanthin (Astaxanthin) is by far the most potent natural antioxidant found in nature and is known as the super antioxidant. More and more research results show that astaxanthin has various physiological activities, such as aging resistance, tumor resistance, cardiovascular and cerebrovascular disease prevention, liver protection, diabetes resistance, anti-inflammation and motor function improvement, and is the only carotenoid which can penetrate blood-brain and blood-retina barriers and is found at present, and the astaxanthin can have positive effects on central nervous system and brain functions. Therefore, astaxanthin as a dietary functional factor is added to products such as food and cosmetics, and has practical significance for improving health.

In nature, more than 90% of astaxanthin exists as astaxanthin ester. In previous studies, the inventor finds that astaxanthin ester has better stability and bioavailability than free astaxanthin. The studies of SHOWALTER L a, cardountel a J, WADEA N and the like show that as the esterification degree of astaxanthin is increased, the astaxanthin is embodied to have enhanced hydrophobicity and is easier to be absorbed and utilized by animal tissues. In studies with animals such as lobster, it was demonstrated that esterified astaxanthin is more readily absorbed than free astaxanthin and binds to the exoskeleton, thereby effectively coloring the animal. Therefore, astaxanthin ester has wide development space as a novel functional active factor.

However, the astaxanthin ester has a strong hydrophobic structure, is extremely poor in water solubility, and is an oily resin in a condensed state, so that the application of the astaxanthin ester in aqueous medium and solid matrix products is severely limited. In addition, astaxanthin ester is easily oxidized and degraded under natural conditions, so that the active function of the astaxanthin ester is lost, the storage stability is poor, and the application and consumption of the astaxanthin ester are limited due to the property. Therefore, how to improve the solubility of astaxanthin ester in aqueous medium, the applicability in solid matrix and the storage stability becomes a key technical problem in the production and consumption processes of astaxanthin ester.

Disclosure of Invention

Aiming at the problem of poor water solubility and storage stability of astaxanthin ester, the invention provides a preparation method of astaxanthin ester nano composite particles, the heat stability and the processing, storage and transportation stability of the astaxanthin ester prepared by the method are obviously improved, and the dispersibility of the astaxanthin ester in water is good, so that the astaxanthin ester nano composite particles have good processing and application properties; the preparation process does not use alcohol solvent and surfactant, thereby avoiding the residue problem caused by the alcohol solvent and the surfactant and improving the safety.

A method for preparing astaxanthin ester nanocomposite particles, comprising the steps of:

(1) preparation of aqueous phase solution: dissolving protein in deionized water or buffer solution for hydration to obtain water phase solution;

(2) preparation of oil phase solution: dissolving astaxanthin ester in the oil phase to prepare an oil solution of astaxanthin ester;

(3) primary emulsification: adding the astaxanthin ester oil solution prepared in the step (2) into the water phase solution prepared in the step (1), adding tea polyphenol into the system, and then fully homogenizing and emulsifying by adopting high-pressure micro-jet;

(4) primary adjustment of system pH and secondary emulsification: adjusting the pH value of the emulsified system in the step (3) to 11-13 by using an alkaline substance, and then carrying out secondary homogenizing emulsification;

(5) and (3) adjusting the pH value of the system for the second time: adjusting the pH value of the system obtained in the step (4) after secondary emulsification to 6.5-7.2 by using an acidic substance while stirring;

(6) and (5) drying.

Further, the step (1) is as follows: dissolving protein in deionized water or phosphate buffer solution with the pH of 6.5-7.5 according to the addition amount of 0.5-5 g/100mL in mass-to-volume ratio, and hydrating for 2-12 h at the temperature of 1-20 ℃ to obtain aqueous phase solution.

Preferably, the protein is one or more of zein, wheat gliadin, kafirin and hordein.

Preferably, the step (1) further comprises adding a stabilizer with a mass-volume ratio of 0.1-5 g/100mL into the aqueous phase solution, wherein the stabilizer is one or more of propylene glycol alginate, soy protein, casein, sodium caseinate, whey protein, lysozyme, galactomannan, pectin, carboxymethyl cellulose, chitosan, sodium alginate, gum arabic and glucan.

Further, the step (2) is as follows: dissolving astaxanthin ester into an oil phase at the temperature of 10-80 ℃ according to the addition amount of 2-50% by mass fraction to prepare an oil phase solution of the astaxanthin ester.

Preferably, the oil phase is one or two of linear fatty acid ester and fatty acid glyceride.

Further, the step (3) is: mixing the astaxanthin ester oil solution prepared in the step (2) according to the mass ratio of 1: 1-20 times of adding the mixture into the aqueous phase solution prepared in the step (1), adding tea polyphenol with the mass volume ratio of 0.0005-1 g/100mL into the system, and then fully homogenizing and emulsifying by adopting high-pressure microjet, wherein the homogenizing pressure is 40-120 MPa, and the treatment times are 1-3 times.

Further, the step (4) is: adjusting the pH value of the emulsified system in the step (3) to 11-13 by using an alkaline substance, and then carrying out secondary homogeneous emulsification, wherein the emulsification method is at least one of shearing homogeneous emulsification and high-pressure microjet homogeneous emulsification, the rotation speed of the shearing homogeneous emulsification is 3000-30000 rpm, and the time is 1-10 min; the pressure of the high-pressure microjet homogenizing emulsification is 40-120 MPa, and the treatment times are 1-3 times.

Preferably, the alkaline substance is one or more of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate.

Further, the step (5) is: and (3) adjusting the pH value of the system obtained in the step (4) to 6.5-7.2 by using an acidic substance while stirring under the stirring condition of 200-2000 rpm.

Preferably, the acidic substance is one or more of acetic acid, citric acid, hydrochloric acid, malic acid, lactic acid, tartaric acid, phosphoric acid and gluconolactone.

Further, the drying mode of the step (6) is spray drying or freeze drying.

The beneficial effect of the invention is that,

1. the invention constructs an astaxanthin ester nano-composite particle system. The system obviously improves the thermal stability and the processing, storage and transportation stability of the astaxanthin ester; the system has good protection, dispersion and sustained and controlled release effects on astaxanthin ester, so that the water dispersibility and bioavailability of astaxanthin can be effectively improved.

2. The astaxanthin ester nano-composite is prepared by adopting a secondary emulsification and secondary pH response method, and the astaxanthin ester particles with good stability can be prepared without using an alcohol solvent and a surfactant.

3. The embedding rate of the astaxanthin ester in the astaxanthin ester nano composite prepared by the method is more than 95%, the prepared powder is dry and comfortable, the fluidity is good, the particle size distribution after the dispersion in water is near 538nm, and the processing and application performance is good.

4. The preparation method is simple and easy to operate, low in cost and mild in condition, the astaxanthin ester does not undergo chemical change in the process, the structure and the physiological activity of the astaxanthin ester are not changed, and the preparation method is suitable for large-scale industrial popularization; the astaxanthin ester nano-composite particles obtained by the invention can be widely used in the industries of chemical products, daily chemical products, medicines, foods, health products and the like, especially in the field of solid matrix products, and have wide market prospects.

Drawings

In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.

Fig. 1 is a flow chart of a method for preparing astaxanthin ester nanocomposite particles.

Detailed Description

In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

As shown in fig. 1, a method for preparing astaxanthin ester nanocomposite particles comprises the following steps:

(1) preparation of aqueous phase solution: dissolving zein in a phosphate buffer solution with the pH value of 6.5 according to the addition amount of 1g/100mL in mass-volume ratio, and hydrating for 4 hours at the temperature of 5 ℃ to obtain an aqueous phase solution;

(2) preparation of oil phase solution: dissolving astaxanthin ester in linear fatty acid ester at 25 deg.C according to the addition amount of 10g/100mL to obtain astaxanthin ester oil solution;

(3) primary emulsification: mixing the astaxanthin ester oil phase solution prepared in the step (2) according to the mass ratio of 1: 5, adding the mixture into the aqueous phase solution prepared in the step (1), adding tea polyphenol with the mass-volume ratio of 0.0025g/100mL into the system, and then fully homogenizing and emulsifying by adopting high-pressure micro-jet, wherein the emulsifying condition is that the homogenizing pressure is 60MPa, and the treatment times are 2 times;

(4) primary adjustment of system pH and secondary emulsification: regulating the pH value of the emulsified system in the step (3) to 11 by using potassium bicarbonate, and then carrying out secondary homogenizing emulsification by adopting high-pressure microjet under the condition that the homogenizing pressure is 100MPa and the treatment times are 2 times;

(5) and (3) adjusting the pH value of the system for the second time: adjusting the pH value of the system obtained in the step (4) to 6.5 by using hydrochloric acid while stirring under the stirring condition of 500 rpm;

(6) and (5) spray drying to obtain astaxanthin ester nano composite particles.

Example 2

A preparation method of astaxanthin ester nano-composite particles comprises the following steps:

(1) preparation of aqueous phase solution: dissolving a mixture of wheat gliadin and kafirin (the mass ratio of the wheat gliadin to the kafirin is 1: 1) in an adding amount of 4g/100mL according to the mass-volume ratio in a phosphate buffer solution with the pH value of 7.5, and hydrating for 10 hours at 15 ℃ to obtain an aqueous phase solution;

(2) preparation of oil phase solution: dissolving astaxanthin ester in fatty glyceride at 70 deg.C according to the addition amount of 45g/100mL to obtain oil solution of astaxanthin ester;

(3) primary emulsification: mixing the astaxanthin ester oil phase solution prepared in the step (2) according to the mass ratio of 1: 15, adding the mixture into the aqueous phase solution prepared in the step (1), adding tea polyphenol with the mass-volume ratio of 0.75g/100mL into the system, and then fully homogenizing and emulsifying by adopting high-pressure micro-jet under the condition that the homogenizing pressure is 80MPa and the treatment times are 3 times;

(4) primary adjustment of system pH and secondary emulsification: adjusting the pH value of the emulsified system in the step (3) to 13 by using sodium hydroxide, and then carrying out secondary homogeneous emulsification by adopting a shearing method, wherein the emulsifying condition is that the rotating speed is 25000rpm, and the time is 3 min;

(5) and (3) adjusting the pH value of the system for the second time: adjusting the pH value of the system obtained in the step (4) after secondary emulsification to 7.0 by using lactic acid while stirring at 1800 rpm;

(6) and (5) freeze-drying to obtain astaxanthin ester nano composite particles.

Example 3

A preparation method of astaxanthin ester nano-composite particles comprises the following steps:

(1) preparation of aqueous phase solution: dissolving hordein in deionized water with the pH value of 7.0 according to the addition amount of 2.5g/100mL in mass-volume ratio, hydrating for 8 hours at the temperature of 10 ℃ to obtain an aqueous phase solution, and adding a stabilizer with the mass-volume ratio of 2.5g/100mL into the aqueous phase solution, wherein the stabilizer comprises a stabilizer with the mass ratio of 1: 1: 0.5 of soy protein, lysozyme and chitosan;

(2) preparation of oil phase solution: dissolving astaxanthin ester in fatty glyceride at 40 deg.C according to the addition of 30g/100mL to obtain oil solution of astaxanthin ester;

(3) primary emulsification: mixing the astaxanthin ester oil phase solution prepared in the step (2) according to the mass ratio of 1: 10, adding the mixture into the aqueous phase solution prepared in the step (1), adding tea polyphenol with the mass-volume ratio of 0.05g/100mL into the system, and then fully homogenizing and emulsifying by adopting high-pressure micro-jet, wherein the emulsifying condition is that the homogenizing pressure is 80MPa, and the treatment times are 3 times;

(4) primary adjustment of system pH and secondary emulsification: adjusting the pH value of the emulsified system in the step (3) to 12 by using ammonium hydroxide, and then carrying out secondary homogeneous emulsification by adopting a shearing method, wherein the emulsifying condition is that the rotating speed is 5000rpm, and the time is 10 min;

(5) and (3) adjusting the pH value of the system for the second time: adjusting the pH value of the system obtained in the step (4) to 7.0 by using acetic acid while stirring under the stirring condition of 1200 rpm;

(6) and (5) freeze-drying to obtain astaxanthin ester nano composite particles.

Comparative example 1

A preparation method of astaxanthin ester nano-composite particles comprises the following steps:

(1) preparation of aqueous phase solution: dissolving hordein in deionized water with the pH value of 7.0 according to the addition amount of 2.5g/100mL in mass-volume ratio, hydrating for 8 hours at the temperature of 10 ℃ to obtain an aqueous phase solution, and adding a stabilizer with the mass-volume ratio of 2.5g/100mL into the aqueous phase solution, wherein the stabilizer comprises a stabilizer with the mass ratio of 1: 1: 0.5 of soy protein, lysozyme and chitosan;

(2) preparation of oil phase solution: dissolving astaxanthin ester in fatty glyceride at 40 deg.C according to the addition of 30g/100mL to obtain oil solution of astaxanthin ester;

(3) emulsification: mixing the astaxanthin ester oil phase solution prepared in the step (2) according to the mass ratio of 1: 10, adding the mixture into the aqueous phase solution prepared in the step (1), adding tea polyphenol with the mass-volume ratio of 0.05g/100mL into the system, and then fully homogenizing and emulsifying by adopting high-pressure micro-jet, wherein the emulsifying condition is that the homogenizing pressure is 80MPa, and the treatment times are 3 times;

(4) adjusting the pH of the system: adjusting the pH value of the emulsified system obtained in the step (3) to 7.0 while stirring at 1200 rpm;

(6) and (5) freeze-drying to obtain astaxanthin ester nano composite particles.

Test example 1 stability test

The astaxanthin ester nanocomposite particles obtained in example 3 and comparative example 1 were stored in a sealed state under natural conditions for 30 days, and then the embedding rate, the astaxanthin ester retention rate, the particle size distribution, and the change in the state of the product were measured, respectively. The test results are shown in the following tables 1 and 2, respectively.

Table 1 table of stability test data of astaxanthin ester nanocomposite particles prepared in example 3

TABLE 2 stability test data table for astaxanthin ester nanocomposite particles prepared in comparative example 1

The test result shows that the embedding rate of the astaxanthin ester in the astaxanthin ester nano composite particles prepared in example 3 is more than 95%, and the embedding rate, the retention rate, the particle size and the appearance state of the astaxanthin ester are not significantly changed after the astaxanthin ester nano composite particles are stored for 30 days. The embedding rate, retention rate and particle size distribution of the product prepared in the comparative example 1 are all obviously lower than those of the product prepared in the example 3, residual oil stains exist on the surface of the product prepared in the comparative example, the flowability is poor, and the product is caked after being stored for a period of time. The result shows that the nano-composite prepared by the method of secondary emulsification and secondary pH response can effectively improve the embedding rate and stability of the astaxanthin ester, and the product applicability is strong.

In conclusion, the astaxanthin ester nano-composite particles prepared by the method can obviously improve the storage stability of the astaxanthin ester, maintain excellent water dispersion performance, realize the stabilization of the astaxanthin ester, fully meet the requirements of a thermal processing process and ensure the shelf life of products.

Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.