Preparation method of squalene and tocopherol composition microcapsule

Abstract

The invention discloses a preparation method of a squalene and tocopherol composition microcapsule, and relates to the technical field of microcapsule preparation, and the preparation method is characterized by comprising the following steps: squalene, tocopherol and an emulsifier form a core material emulsion, Arabic gum, modified corn starch and maltodextrin are compounded to obtain a wall material emulsion, and the wall material emulsion is prepared into the squalene and tocopherol composition microcapsule. Uniformly mixing the core material emulsion and the wall material emulsion, and performing a spray drying process to obtain the squalene and tocopherol composition microcapsule. The obtained microcapsule has good thermal stability and antioxidant activity, and can well protect active components.

Description

Technical Field

[0001] The invention relates to the technical field of microcapsule preparation, in particular to a method for preparing squalene and tocopherol composition microcapsules. Background Art

[0002] Squalene is an oily substance with good biological activity. It is widely used in health care products, cosmetics, food and other industries. Squalene is very similar to red blood cells and has the function of carrying oxygen. After carrying oxygen, it forms an activated oxidized squalene, which is sent to tissue cells throughout the body through the blood circulation system, and then releases oxygen, thereby increasing the body's tissue utilization efficiency of oxygen; Vitamin E (VE) is a general term for tocopherol, tocotrienol and derivatives with physiological activity of tocopherol. It has the functions of scavenging free radicals, anti-cancer, anti-cardiovascular disease, improving immunity and anti-aging. Tocopherol is a natural oil-soluble antioxidant and is widely used in food, medicine and other industries, but its active nature and sensitivity to light and heat limit its application.

[0003] Microcapsule technology refers to the use of natural or synthetic polymer encapsulation materials as wall materials to encapsulate solid, liquid, or even gaseous tiny core materials (core materials) to form a micro-technology with a semi-permeable or sealed capsule membrane. Microcapsule technology has brought breakthrough progress to the food industry. For example, microencapsulation of edible oils and fats can transform liquid oils and fats into solid powders, which improves the convenience of use and storage and transportation, while avoiding oxidation and deterioration, and prolonging the storage period of oils and fats. Microcapsules are now widely used in various fields such as food, medicine, health products, cosmetics, textiles, and pesticides. They have the functions of slow release control, covering up bad odors, and protecting the core materials from deterioration. Summary of the invention

[0004] The object of the present invention is to provide a method for preparing microcapsules of a squalene and tocopherol composition, so as to solve the problems raised in the background technology.

[0005] To achieve the above object, the present invention provides the following technical solution: a method for preparing microcapsules of a squalene and tocopherol composition, comprising the following steps:

[0006] S1, dispersing squalene, tocopherol and an emulsifier in water, and ultrasonically emulsifying to obtain a core material emulsion;

[0007] S2, dissolving gum arabic in water at 40-60° C., then adding modified corn starch and maltodextrin, stirring and mixing evenly to obtain a wall material emulsion;

[0008] S3. Mix the core material emulsion and the wall material emulsion, emulsify the mixture with a high-speed homogenizer at a speed of 10000rpm for 3-5min, add 10% by mass acetic acid solution to adjust the pH of the solution to 3-4, stir at a speed of 500rpm in a 40-50℃ water bath for 1-2h, then adjust the solution temperature to 10-12℃ in an ice water bath, adjust the solution pH to 6.0 with sodium hydroxide solution, add a curing agent, and cure at 10℃ for 6-10h at a stirring speed of 500rpm, filter and remove the supernatant, wash with water to obtain a microcapsule dispersion, and spray dry to obtain squalene and tocopherol composition microcapsules.

[0009] Furthermore, in step S1, the dosage ratio of squalene, tocopherol, emulsifier and water is 1-2 g: 1-2 g: 1-2 g: 30-80 mL.

[0010] Furthermore, the tocopherol is extracted from the deodorized distillate of camellia oil.

[0011] It should be noted that the deodorized distillate of camellia oil contains 750.9 mg / kg of α-tocopherol; the extraction process is: add the deodorized distillate of camellia oil and methanol at a solid-liquid ratio of 1:2, use NKC-9 strong acid cation exchange resin as a catalyst, stir at 65°C for 3 hours, let stand and separate after cooling, and the oil phase obtained by filtering with a separatory funnel is the methylated deodorized distillate; then weigh the methylated deodorized distillate, add anhydrous ethanol at a solid-liquid ratio of 1:4, extract for 40-45 minutes at 60°C and a stirring rate of 126 r / min, seal and let stand to separate, obtain a solvent phase and an oil phase, and vacuum concentrate the solvent phase to obtain.

[0012] Furthermore, the emulsifier in step S1 is polysorbate 80.

[0013] Furthermore, the ultrasonic power is 240W, and the ultrasonic time is 4 minutes.

[0014] Furthermore, in step S2, the dosage ratio of gum arabic, modified corn starch, maltodextrin and water is 1-4 g: 0.1-0.3 g: 0.1-0.2 g: 30-70 mL.

[0015] Furthermore, the preparation method of the modified corn starch in step S2 is:

[0016] The corn starch and enzyme mixture were added to 0.1M sodium acetate buffer, stirred continuously, placed in a 50°C water bath for constant temperature oscillation for 8-9 hours, then added with a 95% ethanol solution by mass, and centrifuged. The precipitate was dried at 40°C for 48 hours, ground with a grinder, and passed through a 325-mesh sieve to obtain modified corn starch.

[0017] Furthermore, the dosage ratio of the corn starch, enzyme mixture, sodium acetate buffer and ethanol solution is 8-12g:1-2g:30-50mL:5-8mL; the enzyme mixture is a mixture of α-amylase and glucoamylase, and the enzyme activity ratio is 1:6; the mass ratio is 3:1.

[0018] Furthermore, in step S3, the usage ratio of the core material emulsion, the wall material emulsion and the curing agent is 30-70 mL: 30-70 mL: 1.0-4.0 g.

[0019] Furthermore, in step S3, the inlet air temperature of the spray drying is 180°C, the outlet air temperature is 105°C, and the spray air flow rate is 1.5 m / s. 3 / h, the feeding rate is 6mL / min; the curing agent is glutamine aminotransferase.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) The development and utilization of tocopherol in the deodorized distillate of camellia oil improves the recovery of beneficial products and turns waste into treasure. It has important social and economic value for improving the comprehensive industrial production of camellia oil and realizing a green economy with efficient utilization. In addition, tocopherol and squalene are co-encapsulated in microcapsules. The two have a high binding affinity and a synergistic effect, which can improve inflammation problems on the skin surface.

[0022] (2) The ternary composite material of gum arabic, maltodextrin and modified corn starch is used as the wall material. The modified corn starch has a complex pore structure and a large enough contact area with the active ingredient, which can promote the hydrogen bond interaction between the active ingredient and the amylose and amylopectin to form new chemical bonds, which is beneficial to maintain the stability of the ingredients. In addition, maltodextrin and gum arabic can act as a coating on the basis of the starch-bioactive ingredient complex, alleviating the limitations of a single material and improving the retention and protection function of the microencapsulated bioactive ingredients. Gum arabic and maltodextrin jointly enhance the stability of the bioactive compounds by acting as pore sealants. The synergistic effect between them can improve the thermal stability and antioxidant properties of the microcapsules while improving the encapsulation efficiency.

[0023] (3) Glutamine aminotransferase, as a new type of curing agent, has the advantages of being non-toxic and having strong cross-linking properties, and can be widely used in the food, medicine and other industries. In addition, the preparation of microcapsules by spray drying is to atomize the uniformly mixed core-wall material emulsion through spraying, so that the solvent that dissolves the wall material is instantly evaporated and removed in the hot air flow to obtain a granular powder microcapsule product. This method is highly efficient and time-saving. The product has good dispersibility and solubility, and the operation is simple and flexible, with low cost, and is suitable for industrial production. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0025] The present invention provides a technical solution:

[0026] The preparation method of modified corn starch is:

[0027] 10.0 g corn starch and 1.0 g enzyme mixture were added to 40 mL of 0.1 M sodium acetate buffer, stirred continuously, placed in a 50° C. water bath for constant temperature oscillation for 8 h, then 6 mL of 95% ethanol solution by mass was added, and centrifuged, the precipitate was dried at 40° C. for 48 h, ground with a grinder, and passed through a 325 mesh sieve to obtain modified corn starch; wherein the enzyme mixture was a mixture of α-amylase and glucoamylase, the enzyme activity ratio was 1:6; the mass ratio was 3:1.

[0028] Embodiment 1:

[0029] A method for preparing squalene and tocopherol composition microcapsules comprises the following steps:

[0030] S1, dispersing 1.0 g of squalene, 1.0 g of tocopherol and 0.5 g of emulsifier in 50.0 mL of water, and emulsifying with ultrasound (ultrasonic power of 240 W, ultrasonic time of 4 min) to obtain a core material emulsion;

[0031] S2, dissolving 2.3 g of gum arabic in 50.0 mL of water at 50° C., then adding 0.2 g of modified corn starch and 0.1 g of maltodextrin, stirring and mixing evenly to obtain a wall material emulsion;

[0032] S3. Mix 50 mL of the core material emulsion and 50 mL of the wall material emulsion, mix the two solutions, emulsify the mixture at a speed of 10000 rpm for 3 min with a high-speed homogenizer, add 10% glacial acetic acid solution to adjust the pH of the solution to 3.6, stir at a speed of 500 rpm in a 45°C water bath for 1 h, then adjust the solution temperature to 10°C in an ice water bath, adjust the solution pH to 6.0 with a sodium hydroxide solution, add 1.0 g of glutamine transaminase, and solidify at 10°C for 6 h at a stirring speed of 500 rpm, filter out the supernatant, wash with water to obtain a microcapsule dispersion, and spray dry (the inlet air temperature of the spray drying is 180°C, the outlet air temperature is 105°C, and the spray air flow rate is 1.5 m 3 / h, the feeding rate is 6mL / min) to obtain a squalene and tocopherol composition microcapsule.

[0033] Embodiment 2:

[0034] A method for preparing squalene and tocopherol composition microcapsules comprises the following steps:

[0035] S1, dispersing 1.5 g of squalene, 1.5 g of tocopherol and 1.0 g of emulsifier in 50.0 mL of water, and emulsifying with ultrasound (ultrasonic power of 240 W, ultrasonic time of 4 min) to obtain a core material emulsion;

[0036] S2, dissolving 3.0 g of gum arabic in 50.0 mL of water at 50° C., then adding 0.4 g of modified corn starch and 0.2 g of maltodextrin, stirring and mixing evenly to obtain a wall material emulsion;

[0037] S3. Mix 50 mL of the core material emulsion and 50 mL of the wall material emulsion, mix the two solutions, emulsify the mixture at a speed of 10000 rpm for 3 min with a high-speed homogenizer, add 10% glacial acetic acid solution to adjust the pH of the solution to 3.6, stir at a speed of 500 rpm in a 40°C water bath for 1 h, then adjust the solution temperature to 10°C in an ice water bath, adjust the solution pH to 6.0 with a sodium hydroxide solution, add 2.0 g of glutamine transaminase, and solidify at 10°C for 6 h at a stirring speed of 500 rpm, filter out the supernatant, wash with water to obtain a microcapsule dispersion, and spray dry (the inlet air temperature of the spray drying is 180°C, the outlet air temperature is 105°C, and the spray air flow rate is 1.5 m 3 / h, the feeding rate is 6mL / min) to obtain a squalene and tocopherol composition microcapsule.

[0038] Embodiment 3:

[0039] A method for preparing squalene and tocopherol composition microcapsules comprises the following steps:

[0040] S1, dispersing 2.0 g of squalene, 2.0 g of tocopherol and 1.0 g of emulsifier in 60.0 mL of water, and emulsifying with ultrasound (ultrasonic power of 240 W, ultrasonic time of 4 min) to obtain a core material emulsion;

[0041] S2, dissolving 3.0 g of gum arabic in 60.0 mL of water at 45° C., then adding 0.2 g of modified corn starch and 0.1 g of maltodextrin, stirring and mixing evenly to obtain a wall material emulsion;

[0042] S3. Mix 60 mL of the core material emulsion and 60 mL of the wall material emulsion, mix the two solutions, emulsify the mixture at a speed of 10000 rpm for 3 min with a high-speed homogenizer, add 10% glacial acetic acid solution to adjust the pH of the solution to 3.6, stir at a speed of 500 rpm in a 50°C water bath for 1 h, then adjust the solution temperature to 10°C in an ice water bath, adjust the solution pH to 6.0 with a sodium hydroxide solution, add 3.0 g of glutamine transaminase, and solidify at 10°C for 6 h at a stirring speed of 500 rpm, filter out the supernatant, wash with water to obtain a microcapsule dispersion, and spray dry (the inlet air temperature of the spray drying is 180°C, the outlet air temperature is 105°C, and the spray air flow rate is 1.5 m 3 / h, the feeding rate is 6mL / min) to obtain a squalene and tocopherol composition microcapsule.

[0043] Embodiment 4:

[0044] A method for preparing squalene and tocopherol composition microcapsules comprises the following steps:

[0045] S1, dispersing 1.0 g of squalene, 1.0 g of tocopherol and 1.0 g of emulsifier in 40.0 mL of water, and emulsifying with ultrasound (ultrasonic power of 240 W, ultrasonic time of 4 min) to obtain a core material emulsion;

[0046] S2, dissolving 4.0 g of gum arabic in 40.0 mL of water at 50° C., then adding 0.2 g of modified corn starch and 0.1 g of maltodextrin, stirring and mixing evenly to obtain a wall material emulsion;

[0047] S3. Mix 40 mL of the core material emulsion and 40 mL of the wall material emulsion, mix the two solutions, emulsify the mixture at a speed of 10000 rpm for 3 min with a high-speed homogenizer, add 10% glacial acetic acid solution to adjust the pH of the solution to 3.6, stir at a speed of 500 rpm in a 50°C water bath for 1 h, then adjust the solution temperature to 10°C in an ice water bath, adjust the solution pH to 6.0 with a sodium hydroxide solution, add 2.0 g of glutamine transaminase, and solidify at 10°C for 6 h at a stirring speed of 500 rpm, filter out the supernatant, wash with water to obtain a microcapsule dispersion, and spray dry (the inlet air temperature of the spray drying is 180°C, the outlet air temperature is 105°C, and the spray air flow rate is 1.5 m 3 / h, the feeding rate is 6mL / min) to obtain a squalene and tocopherol composition microcapsule.

[0048] Comparative Example 1:

[0049] A method for preparing squalene and tocopherol composition microcapsules comprises the following steps:

[0050] S1, dispersing 1.0 g of squalene, 1.0 g of tocopherol and 0.5 g of emulsifier in 50.0 mL of water, and emulsifying with ultrasound (ultrasonic power of 240 W, ultrasonic time of 4 min) to obtain a core material emulsion;

[0051] S2, dissolving 2.3 g of gum arabic in 50.0 mL of water at 50° C., then adding 0.2 g of modified corn starch, stirring and mixing evenly to obtain a wall material emulsion;

[0052] S3. Mix 50 mL of the core material emulsion and 50 mL of the wall material emulsion, mix the two solutions, emulsify the mixture at a speed of 10000 rpm for 3 min with a high-speed homogenizer, add 10% glacial acetic acid solution to adjust the pH of the solution to 3.6, stir at a speed of 500 rpm in a 45°C water bath for 1 h, then adjust the solution temperature to 10°C in an ice water bath, adjust the solution pH to 6.0 with a sodium hydroxide solution, add 1.0 g of glutamine transaminase, and solidify at 10°C for 6 h at a stirring speed of 500 rpm, filter out the supernatant, wash with water to obtain a microcapsule dispersion, and spray dry (the inlet air temperature of the spray drying is 180°C, the outlet air temperature is 105°C, and the spray air flow rate is 1.5 m 3 / h, the feeding rate is 6mL / min) to obtain a squalene and tocopherol composition microcapsule.

[0053] Comparative Example 2:

[0054] A method for preparing squalene and tocopherol composition microcapsules comprises the following steps:

[0055] S1, dispersing 1.0 g of squalene, 1.0 g of tocopherol and 0.5 g of emulsifier in 50.0 mL of water, and emulsifying with ultrasound (ultrasonic power of 240 W, ultrasonic time of 4 min) to obtain a core material emulsion;

[0056] S2, dissolving 2.3 g of gum arabic in 50.0 mL of water at 50° C., then adding 0.1 g of maltodextrin, stirring and mixing evenly to obtain a wall material emulsion;

[0057] S3. Mix 50 mL of the core material emulsion and 50 mL of the wall material emulsion, mix the two solutions, emulsify the mixture at a speed of 10000 rpm for 3 min with a high-speed homogenizer, add 10% glacial acetic acid solution to adjust the pH of the solution to 3.6, stir at a speed of 500 rpm in a 45°C water bath for 1 h, then adjust the solution temperature to 10°C in an ice water bath, adjust the solution pH to 6.0 with a sodium hydroxide solution, add 1.0 g of glutamine transaminase, and solidify at 10°C for 6 h at a stirring speed of 500 rpm, filter out the supernatant, wash with water to obtain a microcapsule dispersion, and spray dry (the inlet air temperature of the spray drying is 180°C, the outlet air temperature is 105°C, and the spray air flow rate is 1.5 m 3 / h, the feeding rate is 6mL / min) to obtain a squalene and tocopherol composition microcapsule.

[0058] Comparative Example 3

[0059] A method for preparing squalene and tocopherol composition microcapsules comprises the following steps:

[0060] S1, dispersing 1.0 g of squalene, 1.0 g of tocopherol and 0.5 g of emulsifier in 50.0 mL of water, and emulsifying with ultrasound (ultrasonic power of 240 W, ultrasonic time of 4 min) to obtain a core material emulsion;

[0061] S2, dissolving 2.3 g of gum arabic in 50.0 mL of water at 50° C., stirring and mixing evenly to obtain a wall material emulsion;

[0062] S3. Mix 50 mL of the core material emulsion and 50 mL of the wall material emulsion, mix the two solutions, emulsify the mixture at a speed of 10000 rpm for 3 min with a high-speed homogenizer, add 10% glacial acetic acid solution to adjust the pH of the solution to 3.6, stir at a speed of 500 rpm in a 45°C water bath for 1 h, then adjust the solution temperature to 10°C in an ice water bath, adjust the solution pH to 6.0 with a sodium hydroxide solution, add 1.0 g of glutamine transaminase, and solidify at 10°C for 6 h at a stirring speed of 500 rpm, filter out the supernatant, wash with water to obtain a microcapsule dispersion, and spray dry (the inlet air temperature of the spray drying is 180°C, the outlet air temperature is 105°C, and the spray air flow rate is 1.5 m 3 / h, the feeding rate is 6mL / min) to obtain a squalene and tocopherol composition microcapsule.

[0063] The encapsulation efficiency, thermal stability and antioxidant activity of the microcapsules in each sample were tested experimentally; the squalene on the surface of the microcapsules was determined as follows: 0.5 g of microcapsules were accurately weighed, filtered with 25 mL of n-hexane, the filtrate was combined, and the amount of surface squalene was calculated by high performance liquid chromatography; the glass transition temperature of the microcapsules was measured by DSC, a total of 6 mg of sample was added to the DSC sample aluminum box, and a blank aluminum box was used as a reference, and the heating rate was changed from 20°C to 200°C at a rate of 10°C / min; the microcapsules were placed in a conical flask with a lid and stored in an oven at 25°C for 30 days, and 1 g of powder sample was taken out of the oven to measure the peroxide value (POV) (GB 5009.227-2016, 2017); the test results are shown in Table 1.

[0064] Table 1: Experimental results of each sample

[0065]

[0066]

[0067] From the analysis of the experimental results, it can be seen that the ternary composite material of gum arabic-maltodextrin-modified corn starch in the embodiment is used as a wall material, and the modified corn starch has a complex pore structure, and the contact area with the active ingredient is large enough, which can promote the hydrogen bond interaction between the active ingredient and the amylose and amylopectin to form a new chemical bond, which is beneficial to maintain the stability of the ingredients. In addition, maltodextrin and gum arabic can act as a coating on the basis of the starch-bioactive ingredient complex, which reduces the limitations of a single material and improves the retention and protection function of the microencapsulated bioactive ingredients. Gum arabic and maltodextrin jointly enhance the stability of the bioactive compounds by acting as pore sealants. The synergistic effect between them can improve the encapsulation rate while also improving the thermal stability and antioxidant properties of the microcapsules; in the comparative example, due to the lack of interaction between gum arabic and maltodextrin or the mutual promotion of maltodextrin and porous corn starch, the protection of the active ingredients by the formed microcapsules is not obvious, and the thermal stability and antioxidant activity of the microcapsules are poor.

[0068] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing microcapsules of a squalene and tocopherol composition, characterized in that: The following steps are involved: S1, dispersing squalene, tocopherol and an emulsifier in water, and ultrasonically emulsifying to obtain a core material emulsion; S2, dissolving gum arabic in water at 40-60° C., then adding modified corn starch and maltodextrin, stirring and mixing evenly to obtain a wall material emulsion; S3. Mix the core material emulsion and the wall material emulsion, emulsify the mixture with a high-speed homogenizer at a speed of 10000rpm for 3-5min, add 10% by mass acetic acid solution to adjust the pH of the solution to 3-4, stir at a speed of 500rpm in a 40-50℃ water bath for 1-2h, then adjust the solution temperature to 10-12℃ in an ice water bath, adjust the solution pH to 6.0 with sodium hydroxide solution, add a curing agent, and cure at 10℃ for 6-10h at a stirring speed of 500rpm, filter and remove the supernatant, wash with water to obtain a microcapsule dispersion, and spray dry to obtain squalene and tocopherol composition microcapsules.

2. The method for preparing a squalene and tocopherol composition microcapsule according to claim 1, characterized in that: In the step S1, the dosage ratio of squalene, tocopherol, emulsifier and water is 1-2g: 1-2g: 1-2g: 30-80mL.

3. The method for preparing a squalene and tocopherol composition microcapsule according to claim 2, characterized in that: The tocopherol is extracted from the deodorized distillate of camellia oil.

4. The method for preparing a squalene and tocopherol composition microcapsule according to claim 1, characterized in that: The emulsifier in step S1 is polysorbate 80.

5. The method for preparing a squalene and tocopherol composition microcapsule according to claim 1, characterized in that: In step S1, the ultrasonic power is 240 W and the ultrasonic time is 4 min.

6. The method for preparing a squalene and tocopherol composition microcapsule according to claim 1, characterized in that: In the step S2, the dosage ratio of gum arabic, modified corn starch, maltodextrin and water is 1-4 g: 0.1-0.3 g: 0.1-0.2 g: 30-70 mL.

7. The method for preparing a squalene and tocopherol composition microcapsule according to claim 1, characterized in that: The preparation method of the modified corn starch in step S2 is: The corn starch and enzyme mixture were added to 0.1M sodium acetate buffer, stirred continuously, placed in a 50°C water bath for constant temperature oscillation for 8-9 hours, then added with a 95% ethanol solution by mass, and centrifuged. The precipitate was dried at 40°C for 48 hours, ground with a grinder, and passed through a 325-mesh sieve to obtain modified corn starch.

8. The method for preparing a squalene and tocopherol composition microcapsule according to claim 7, characterized in that: The dosage ratio of the corn starch, enzyme mixture, sodium acetate buffer and ethanol solution is 8-12g:1-2g:30-50mL:5-8mL; the enzyme mixture is a mixture of α-amylase and glucoamylase, and the enzyme activity ratio is 1:6; the mass ratio is 3:

1.

9. The method for preparing a squalene and tocopherol composition microcapsule according to claim 1, characterized in that: In the step S3, the usage ratio of the core material emulsion, the wall material emulsion and the curing agent is 30-70 mL: 30-70 mL: 1.0-4.0 g.

10. The method for preparing a squalene and tocopherol composition microcapsule according to claim 1, characterized in that: The inlet air temperature of the spray drying in step S3 is 180°C, the outlet air temperature is 105°C, and the spray air flow rate is 1.5m 3 / h, the feeding rate is 6mL / min; the curing agent is glutamine aminotransferase.

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