CN111296729A - A kind of water-soluble astaxanthin product and preparation method thereof - Google Patents

Abstract

The invention discloses a water-soluble astaxanthin product and a preparation method thereof. The water-soluble astaxanthin product is composed of astaxanthin, whey protein and ethyl cellulose, the content of astaxanthin is higher than 60%, and the particle size of the product is micron. The preparation method comprises the following steps: mixing astaxanthin alcohol solution, ethyl cellulose alcohol solution and whey solution in batches in a certain proportion, homogeneous emulsification, secondary emulsification, low temperature sedimentation, filtration, low temperature vacuum evaporation, The water-soluble astaxanthin is prepared by treatment such as spray freeze-drying. The technology of the present invention effectively improves the water solubility and stability of astaxanthin, and increases the scope of application of astaxanthin.

Description

A kind of water-soluble astaxanthin product and preparation method thereof

technical field

The invention relates to the technical field of water-soluble marine nutrients, in particular to a water-soluble astaxanthin product and a preparation method thereof.

Background technique

Astaxanthin (3,3′-dihydroxy-4,4′-diketo-β,β′-carotene) is a fat-soluble carotenoid with a molecular formula of C40H52O4 and a relative molecular mass of 596.86, insoluble in water , soluble in most organic solvents such as ethanol, acetone, ether and chloroform. Astaxanthin is mainly found in microalgae, yeast, trout, krill, shrimp and crayfish, and Haematococcus pluvialis is a rich source of natural astaxanthin, the content of astaxanthin is as high as 6% of dry matter, which is Considered a "concentrate" of natural astaxanthin.

Natural astaxanthin is an effective strong antioxidant with strong antioxidant properties and can effectively scavenge free radicals in the body to prevent oxidative damage to tissues, cells and DNA. Therefore, astaxanthin has antioxidant properties, improves immunity, prevents Many physiological functions such as tumor, prevention of cardiovascular disease and maintenance of eyes, etc., make it gradually used in medicine, food, health care products and cosmetics and other industries and have broad application prospects.

Astaxanthin has a highly unsaturated conjugated double chain in its molecular structure, which makes it easy to be degraded and oxidized by light, oxygen, high temperature and ultraviolet radiation, which affects the stability of astaxanthin. The insoluble nature of astaxanthin in water makes its bioavailability low. The water solubility and stability of astaxanthin can be improved by microsphere technology. Drug-loaded microspheres refer to micron-sized spherical entities formed by dissolving or adsorbing active ingredients in a polymer matrix. The microspheres not only protect the active ingredients of the core material from environmental factors such as oxygen, high temperature and pH, but also improve the dispersibility of the active ingredients, mask unpleasant odors and control the release, thereby enhancing the commercial value of astaxanthin products.

At present, scholars at home and abroad mainly study the improvement of the water solubility of astaxanthin by means of structural improvement, emulsification or microencapsulation. Among them, the structural improvement is to improve water solubility by connecting hydrophilic groups on astaxanthin. The Chinese Patent Publication No. CN105646869A discloses water-soluble astaxanthin derivatives and preparation methods thereof. The invention utilizes astaxanthin, Succinic anhydride and polyethylene glycol (PEG) are used to prepare astaxanthin succinic acid diester, a PEG derivative, but this preparation method is carried out in an organic solvent system, and the organic solvent remains, which has potential safety hazards. The Chinese patent of publication number CN101297691A discloses the preparation method of stable water-soluble carotenoid dry powder. In the invention, after astaxanthin is dissolved in acetone, it is mixed with S-40, gum arabic, β-ring 5 times higher than its mass. Various surfactants and stabilizers such as dextrin, xanthan gum and pullulan are mixed and prepared by spray drying. This method mainly disperses astaxanthin in water by adding a stabilizer. Excessive use of additives is not suitable for processed food, and there is a potential safety hazard of organic solvent residues; The spray drying conditions are not conducive to the stabilization of astaxanthin. The public document "Physicochemical properties of whey-protein-stabilized astaxanthin nanodispersion and its transport via a Caco-2monolayer" reported the preparation of astaxanthin nanodispersion by using isolated whey protein as a stabilizer, but the solvent used was acetone/dichloromethane mixed system, there are potential safety hazards, and the product type is not convenient for transportation and storage. The public document "Astaxanthin from Phaffia rhodozyma: Microencapsulation with carboxymethyl cellulose sodium and microcrystalline cellulose and effects of microencapsulated astaxanthin on yogurt properties" reported the use of sodium carboxymethyl cellulose and microcrystalline cellulose as wall materials to improve astaxanthin by microencapsulation technology High water solubility, low content of astaxanthin in the prepared product, uneven particles, and easy stratification when applied to food. The open document "Encapsulation of anastaxanthin-containing lipid extract from shrimp waste by complexcoacervation using a novel gelatinecashew gum complex" reported the use of gelatin and cashew gum complex as a wall material to improve the solubility of astaxanthin by complex coacervation, but this The solubility of the astaxanthin product obtained by the preparation method is only 28.6 percent, and the water-solubility of the astaxanthin is low. The open document "Potato protein-based carriers for enhancing bioavailability of astaxanthin" reported using potato protein as a carrier to improve the solubility of astaxanthin, but this preparation method requires dialysis of the potato protein solution for a week, which is time-consuming and complicated in the production process. . Therefore, it is necessary to study a highly feasible, simple and effective method for improving the water solubility of astaxanthin.

SUMMARY OF THE INVENTION

In view of the problems existing in the prior art, the purpose of the present invention is to provide a water-soluble astaxanthin product and a preparation method thereof.

The technical scheme that the present invention solves the above-mentioned technical problems is as follows:

A water-soluble astaxanthin product and a preparation method thereof, characterized in that: the product is composed of the following raw materials by mass percentage: astaxanthin content of 60% to 80%, whey protein content of 20% to 30%, ethyl cellulose 10% to 20% composition; the preparation method includes the following steps:

1. Mix astaxanthin alcohol solution and ethyl cellulose alcohol solution at a ratio of 1:1 to 2:3. After stirring at 1000 rpm to 1500 rpm for 10 to 20 minutes, inject high-concentration whey solution at a rate of 1 mL/s. 1000rpm～1500rpm rotating speed is homogeneously emulsified for 5～10min to obtain a water-in-oil emulsion; wherein: the astaxanthin alcohol solution is to add astaxanthin into absolute ethanol, stir and dissolve, and prepare a mass-volume ratio of 3%～ 5% astaxanthin alcohol solution; the ethyl cellulose alcohol solution is prepared by adding ethyl cellulose into anhydrous ethanol, and stirring for 4-5 hours to prepare a mass-volume 0.5-1% ethyl cellulose alcohol solution The high whey solution is prepared by dissolving whey protein powder in distilled water, stirring for 0.5 to 1 h, and preparing a whey solution with a mass-to-volume ratio of 2% to 3%; the volume of the high whey solution is 10～10%. 20mL;

2. Inject the low-concentration whey solution into the water-in-oil emulsion prepared in step 1 at a rate of 35-40 mL/s, mix at a rotational speed of 1000-1500 rpm, and emulsify twice for 5-20 minutes to obtain an oil-in-water emulsion; The whey solution is to dissolve the whey protein powder in distilled water, stir for 0.5-1 h, and prepare a whey solution with a mass-volume ratio of 0.1-0.3%; the volume of the low-concentration whey solution is 180-190 mL; oil-in-water The volume ratio of oil-water phase in the emulsion is 1:1.9～1:2.1;

3. Let the oil-in-water emulsion prepared in step 2 stand in the dark at 4°C for 12 to 24 hours to precipitate excess ethyl cellulose and astaxanthin, filter through a 200-mesh gauze, and then remove by low-temperature vacuum evaporation Ethanol, rotary evaporation temperature of 35 ~ 40 ℃, to obtain astaxanthin aqueous solution; spray freeze drying of astaxanthin aqueous solution, the conditions of spray freeze drying are condensation temperature -40 ℃, drying at 30 ℃ for 6 ~ 8 hours, the preparation A water-soluble astaxanthin product was obtained. The content and solubility of astaxanthin in the product are 62.7-75.9% and 42.6-56% respectively.

The whey solution is prepared by adding whey protein to a certain volume of distilled water at a mass volume ratio of 0.5% to 3%, and stirring for 0.5 to 1.0 hours to prepare a whey solution.

The above water-soluble astaxanthin contains 63% astaxanthin, has a solubility of 56%, and the particle size of the water-soluble astaxanthin ranges from 280 nm to 320 nm.

The ethyl cellulose used in the present invention is purchased from Shanghai McLean Biochemical Technology Co., Ltd., and its viscosity is 45-55 mPa.s; the content of astaxanthin used in the present invention is 95%.

Compared with the prior art, the present invention has the following beneficial effects:

1. A kind of water-soluble astaxanthin product provided by the invention and preparation method thereof, adopt twice emulsification method to prepare ethyl cellulose-astaxanthin emulsion, reduce the aggregation of ethyl cellulose in the rich water phase emulsion, thereby Reduce the particle size of the emulsion; use the whey protein solution as an emulsifier to improve the dispersibility and water solubility of astaxanthin; spray freeze drying to maintain the functional activity of astaxanthin under low temperature conditions.

2. The method of the present invention has the advantages of strong feasibility, simple operation process, use of food-grade organic solvents, and no potential safety hazards. The solubility of astaxanthin is 11.81%. Compared with the raw material astaxanthin, the solubility of water-soluble astaxanthin is significantly improved, and the biological activity of astaxanthin is maintained. It can be widely used in food, health products and pharmaceutical industries.

Description of drawings

1 is a particle size distribution diagram of astaxanthin and water-soluble astaxanthin obtained in Example 1 of the present invention.

Figure 2 is a product diagram of the water-soluble astaxanthin obtained in Example 1 of the present invention.

Fig. 3 is a dispersibility diagram of the water-soluble astaxanthin obtained in Example 1 of the present invention in an aqueous solution.

4 is the Zeta equipotentiality of the water-soluble astaxanthin obtained in Example 1 of the present invention after storage for 3 weeks in an aqueous solution of pH ₂ to pH ₈ .

Detailed ways

The present invention will be further illustrated by the following examples and accompanying drawings.

Example 1

A water-soluble astaxanthin product and a preparation method thereof, comprising the steps:

1. Mix the astaxanthin alcohol solution and the ethyl cellulose alcohol solution at 1:1, stir evenly for 20 minutes at 1500 rpm, and inject 10 mL of high-concentration whey solution (2% by mass by volume) at a rate of 1 mL/s, Continue to homogeneously emulsify at 1500 rpm for 10 min to obtain a water-in-oil emulsion; wherein, the astaxanthin alcohol solution is made by adding astaxanthin into absolute ethanol, stirring and dissolving, to prepare a 5% mass/volume astaxanthin alcohol solution; Ethyl cellulose alcohol solution is made by adding ethyl cellulose into absolute ethanol, and stirring for 4 hours to prepare ethyl cellulose alcohol solution with a mass volume of 1%; high-concentration whey solution is to dissolve whey protein powder in distilled water , stir for 0.5h, and prepare a whey solution with a mass-to-volume ratio of 2%; the addition volume of the high-concentration whey solution is 10mL;

2. The low-concentration whey solution was injected into the water-in-oil emulsion prepared in step 1 at a rate of 40 mL/s, mixed at a speed of 1500 rpm, and emulsified for 20 minutes to obtain an oil-in-water emulsion; the low-concentration whey solution was a mixture of whey The protein powder was dissolved in distilled water, stirred for 0.5 h, and prepared into a whey solution with a mass-volume ratio of 0.3%; the volume of the low-concentration whey solution was 190 mL; the oil-water phase volume ratio in the oil-in-water emulsion was 1:2;

3. The oil-in-water emulsion prepared in step 2 was allowed to stand for 12 hours at 4°C in the dark to precipitate excess ethyl cellulose and astaxanthin. After sieving through a 200-mesh gauze, the ethanol was removed by low-temperature vacuum evaporation. The rotary evaporation temperature is 37°C to obtain astaxanthin aqueous solution; the astaxanthin aqueous solution is spray-freeze-dried, and the spray freeze-drying condition is the condensation temperature of -40°C, and dried at 30°C for 7 hours to obtain water-soluble astaxanthin product. The content and solubility of astaxanthin in the product were 75.9% and 56%, respectively.

Example 2

A water-soluble astaxanthin product and a preparation method thereof, comprising the steps:

1. Mix the astaxanthin alcohol solution and the ethyl cellulose alcohol solution at a ratio of 2:1, stir evenly for 20 minutes at 1500 rpm, and inject 20 mL of high-concentration whey solution (3% by mass by volume) at a rate of 1 mL/s, Continue to homogeneously emulsify at 1500 rpm for 10 min to obtain a water-in-oil emulsion; wherein, the astaxanthin alcohol solution is made by adding astaxanthin into absolute ethanol, stirring and dissolving, to prepare a 5% mass/volume astaxanthin alcohol solution; Ethyl cellulose alcohol solution is made by adding ethyl cellulose into absolute ethanol, and stirring for 5 hours to prepare ethyl cellulose alcohol solution with a mass volume of 0.5%; high-concentration whey solution is whey protein powder dissolved in distilled water , stir for 0.5h, and prepare a whey solution with a mass-to-volume ratio of 2.5%; the added volume of the high-concentration whey solution is 15mL;

2. Inject the low-concentration whey solution into the water-in-oil emulsion prepared in step 1 at a rate of 40 mL/s, mix at 1500 rpm, and emulsify twice for 10 minutes to obtain an oil-in-water emulsion; the low-concentration whey solution is a The protein powder was dissolved in distilled water, stirred for 0.5 h, and prepared into a whey solution with a mass-volume ratio of 0.3%; the volume of the low-concentration whey solution was 190 mL; the oil-water phase volume ratio in the oil-in-water emulsion was 1:2.1;

3. The oil-in-water emulsion prepared in step 2 was allowed to stand for 24 hours at 4°C in the dark to precipitate the excess added ethyl cellulose and astaxanthin. After sieving through a 200-mesh gauze, the ethanol was removed by low-temperature vacuum evaporation. The temperature of rotary evaporation is 40°C to obtain an aqueous solution of astaxanthin; the aqueous solution of astaxanthin is subjected to spray freeze-drying, and the conditions of spray freeze-drying are condensation temperature -40°C, and dried at 30°C for 8 hours to obtain water-soluble astaxanthin product. The content and solubility of astaxanthin in the product were 68.7% and 53.8%, respectively.

Example 3

A water-soluble astaxanthin product and a preparation method thereof, comprising the steps:

1. Mix the astaxanthin alcohol solution and the ethyl cellulose alcohol solution at a ratio of 2:3, stir evenly for 10 minutes at 1000 rpm, and then inject 10 mL of high-concentration whey solution (2% by mass by volume) at a rate of 1 mL/s, Continue to homogeneously emulsify at 1000rpm for 5min to obtain a water-in-oil emulsion; wherein, the astaxanthin alcohol solution is obtained by adding astaxanthin into absolute ethanol, and stirring and dissolving to prepare a 3% mass/volume astaxanthin alcohol solution; Ethyl cellulose alcohol solution is made by adding ethyl cellulose into absolute ethanol, and stirring for 4 hours to prepare a 0.5% ethyl cellulose alcohol solution by mass and volume; high-concentration whey solution is a solution of whey protein powder dissolved in distilled water , stir for 1h, and prepare a whey solution with a mass-to-volume ratio of 3%; the added volume of the high-concentration whey solution is 20mL;

2. Inject the low-concentration whey solution into the water-in-oil emulsion prepared in step 1 at a rate of 35 mL/s, mix at a speed of 1000 rpm, and emulsify twice for 5 minutes to obtain an oil-in-water emulsion; the low-concentration whey solution is a mixture of whey The protein powder was dissolved in distilled water, stirred for 1 hour, and prepared into a whey solution with a mass-volume ratio of 0.1%; the volume of the low-concentration whey solution was 180 mL; the oil-water phase volume ratio in the oil-in-water emulsion was 1:1.9;

3. The oil-in-water emulsion prepared in step 2 was allowed to stand for 12 hours at 4°C in the dark to precipitate excess ethyl cellulose and astaxanthin. After sieving through a 200-mesh gauze, the ethanol was removed by low-temperature vacuum evaporation. The temperature of rotary evaporation is 35°C to obtain an aqueous solution of astaxanthin; the aqueous solution of astaxanthin is spray-freeze-dried, and the conditions for spray-freeze-drying are the condensation temperature of -40°C, and the water-soluble astaxanthin is obtained by drying at 30°C for 6 hours. product. The content and solubility of astaxanthin in the product were 62.7% and 42.6%, respectively.

The average particle diameters of the astaxanthin alcohol solution and the water-soluble astaxanthin prepared in Example 1 are 231.7±1.88nm and 307.30±11.36nm respectively, and the specific particle size distribution is shown in FIG. 1 .

The water-soluble astaxanthin product prepared in Example 1 is shown in Figure 2.

The dispersibility of the water-soluble astaxanthin prepared in Example 1 and the raw material astaxanthin powder in the aqueous solution is shown in Figure 3.

Example 1 Preparation of water-soluble astaxanthin The Zeta potential diagram of water-soluble astaxanthin after storage in an aqueous solution in the pH range of 2-8 for 3 weeks is shown in FIG. 4 . According to the absolute value of surface charge ≥30mV, the solution system is stable, and the water-soluble astaxanthin solution has good stability.

Claims (3)

1. a water-soluble astaxanthin product and preparation method thereof, is characterized in that: product is made up of the raw material of following mass percentage content: astaxanthin content 60%～80%, whey protein content 20%～30%, ethyl acetate The composition of cellulose is 10% to 20%; the preparation method includes the following steps: (1) Mix astaxanthin alcohol solution and ethyl cellulose alcohol solution at a ratio of 1:1 to 2:3. After stirring at 1000 rpm to 1500 rpm for 10 to 20 minutes, inject high-concentration whey solution at a rate of 1 mL/s for a continuous period of time. Homogeneous emulsification at 1000rpm～1500rpm rotating speed for 5～10min to obtain a water-in-oil emulsion; wherein: the astaxanthin alcohol solution is made by adding astaxanthin into anhydrous ethanol, stirring and dissolving to prepare a mass-volume ratio of 3%～ 5% astaxanthin alcohol solution; the ethyl cellulose alcohol solution is prepared by adding ethyl cellulose into anhydrous ethanol, and stirring for 4-5 hours to prepare a mass-volume 0.5-1% ethyl cellulose alcohol solution The high-density whey solution is prepared by dissolving whey protein powder in distilled water, stirring for 0.5-1 h, and preparing a whey solution with a mass-volume ratio of 2%-3%; the volume of the high-concentration whey solution is 10 ~20mL; (2) injecting the low-concentration whey solution into the water-in-oil emulsion prepared in step (1) at a rate of 35-40 mL/s, mixing at a rotating speed of 1000-1500 rpm simultaneously, and emulsification for 5-20 min for the second time to obtain an oil-in-water emulsion; The low-concentration whey solution is to dissolve whey protein powder in distilled water, stir for 0.5-1 h, and prepare a whey solution with a mass-volume ratio of 0.1-0.3%; the volume of the low-concentration whey solution is 180-190 mL; The volume ratio of oil-water phase in the oil-in-water emulsion is 1:1.9～1:2.1; (3) The oil-in-water emulsion obtained in step (2) was allowed to stand in the dark at 4°C for 12 to 24 hours to precipitate excess ethyl cellulose and astaxanthin. After sieving through a 200-mesh gauze, The ethanol is removed by vacuum evaporation, and the rotary evaporation temperature is 35～40 ℃ to obtain the astaxanthin aqueous solution; the astaxanthin aqueous solution is spray-freeze-dried, and the condition of the spray freeze-drying is the condensation temperature of -40 ℃, and dried at 30 ℃ for 6～ 8h, a water-soluble astaxanthin product was prepared, and the content and solubility of astaxanthin in the product were 62.7-75.9% and 42.6-56%, respectively. 2. a kind of water-soluble astaxanthin product and preparation method thereof according to claim 1, is characterized in that, described whey solution is added to the distilled water of certain volume by whey protein by the mass volume ratio of 0.5%～3% After stirring for 0.5-1.0 h, the whey solution is prepared. 3. a kind of water-soluble astaxanthin product and preparation method thereof according to claim 1, is characterized in that, described water-soluble astaxanthin contains astaxanthin 63%, solubility 56%, water-soluble astaxanthin The particle size ranges from 280nm to 320nm.

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