CN-122005375-A - High-stability antiallergic collagen-chamomile active component hydrogel and large-scale preparation method and application thereof

CN122005375ACN 122005375 ACN122005375 ACN 122005375ACN-122005375-A

Abstract

The invention relates to a highly stable antiallergic collagen-chamomile active component hydrogel, and a large-scale treatment method and application thereof. The preparation method comprises the steps of taking chamomile as a raw material, innovatively combining various chemical extraction and separation and drying extraction technologies, sequentially preparing a chamomile water phase component with higher sugar extraction rate and stronger antioxidant capacity, a chamomile ethanol phase component with higher total flavone content and stronger tyrosinase activity inhibition, and a chamomile volatile component which is comprehensive in composition, complete in main component, definite in marked efficient antiallergic compound (chamomile azulene) and excellent in antiallergic effect, preparing macromolecular collagen by taking sea/freshwater fish scales as raw materials, purifying by anion exchange chromatography/resin, and homogenizing and emulsifying with the chamomile active component (the chamomile water phase component+the chamomile ethanol phase component+the chamomile volatile component) to obtain the collagen-chamomile active component hydrogel which is applicable to cosmetics and is high in stability and antiallergic.

Inventors

CHEN SIJIN
HONG ZHUAN
ZHANG YIPING
CHEN WEIZHU
XIE QUANLING
CHEN HUI
GUO HONGHUI
JIN WENHUI
FANG HUA

Assignees

自然资源部第三海洋研究所
厦门海洋职业技术学院

Dates

Publication Date: 20260512
Application Date: 20241112

Claims (10)

1. A large-scale treatment method of a highly stable antiallergic collagen-chamomile active component hydrogel comprises the following steps: (1) Preparation of chamomile water phase component Drying chamomile raw materials in a hot air drying oven at 60-80 ℃ for 2-5 hours, taking out the chamomile raw materials after drying, putting the chamomile raw materials into a traditional Chinese medicine pulverizer, pulverizing for 5-8 minutes, putting the pulverized chamomile powder into a reaction kettle, adding dilute acid solution with the weight of 5-15 times that of the chamomile powder, stirring and reacting for 2-6 hours, wherein the reaction temperature is 85-100 ℃, the reaction pH is 4.0-5.0, cooling to room temperature after the high-temperature dilute acid hydrolysis reaction is finished, regulating the pH to 6.5-7.5 by using dilute alkali solution, and then carrying out high-speed centrifugation by using a continuous flow centrifuge to obtain first centrifugation residues and first centrifugation supernatant, respectively carrying out desalting concentration on the first centrifugation supernatant by using a nanofiltration membrane with the relative molecular weight of 500-200 Da to obtain chamomile aqueous phase component solution with the mass volume concentration of more than or equal to 10%, and then carrying out rapid drying on the chamomile aqueous phase component solution by using a spray drying technology to obtain chamomile aqueous phase component powder, wherein the mass volume concentration of the dilute acid solution and the dilute alkali solution is 0.01-0.05% to 0.05% respectively; (2) Preparation of chamomile ethanol phase component Drying the first centrifugal residue in a vacuum drying oven at 40-50 ℃ for 2-5 hours, wherein the vacuum degree is-0.06 Mpa to-0.1 Mpa, taking out the dried product after vacuum drying, putting the dried product into a reaction kettle, adding an absolute ethanol solution which is 5-15 times of the weight of the chamomile powder, stirring and reacting for 2-6 hours, wherein the reaction temperature is 70-80 ℃, cooling to room temperature after the absolute ethanol extraction is finished, and obtaining a second centrifugal residue and a second centrifugal supernatant by high-speed centrifugation of a continuous flow centrifuge, wherein the second centrifugal supernatant is subjected to rotary evaporation concentration to obtain chamomile ethanol phase component extractum, the rotary evaporation temperature is 30-40 Mpa, and the rotary evaporation vacuum degree is-0.02 Mpa to-0.06 Mpa; (3) Preparation of volatile components of chamomile Drying the second centrifugal residue in a vacuum drying oven at 30-40 ℃ for 2-5 hours, wherein the vacuum degree is-0.04 Mpa to-0.06 Mpa, taking out the dried second centrifugal residue after vacuum drying, putting the dried second centrifugal residue in a supercritical CO 2 fluid extractor, wherein the extraction temperature is 35-45 ℃, the extraction time is 0.5-1 hour, the extraction pressure is 20-30 Mpa, dissolving the obtained supercritical extract in absolute ethyl alcohol, filtering out insoluble substances by using a filter screen with 1-0.2 mu m, concentrating the filtered clear liquid through rotary evaporation to obtain the chamomile volatile component extract, the rotary evaporation temperature is 30-40 ℃, and the rotary evaporation vacuum degree is-0.02 Mpa to-0.06 Mpa; (4) Degreasing, decalcification and deodorization of fish scale raw materials Adding the fish scale raw materials into a reaction kettle, adding an alkali solution with the weight being 2-10 times of that of the fish scale raw materials, stirring for 0.5-3 hours, removing impurities such as fat and impurity proteins of the fish scales, cleaning with water, adding an acid solution with the weight being 2-10 times of that of the fish scale raw materials, stirring for 0.5-12 hours, cleaning with water, adding an ethanol solution with the weight being 2-10 times of that of the fish scale raw materials, stirring for 1-6 hours, cleaning with water, wherein the mass volume concentration of the alkali solution is 1-4%, the mass volume concentration of the acid solution is 3-8%, the concentration of the ethanol solution is 40% -60%, and the pretreatment temperature is controlled between 15 ℃ and 30 ℃; (5) Macromolecular collagen extraction and filtration Adding 0.5-10 mol/L citric acid as an extracting agent into the defatted and decalcified fish scale raw material, wherein the weight ratio of the raw material to the extracting agent is 1:1-1:10, stirring for 2-6 hours, maintaining the extraction temperature at 5-15 ℃, freezing and centrifuging after the extraction is finished, recycling residues obtained by filtering, repeating the steps of extracting and filtering for 0-5 times, mixing and summarizing the obtained centrifugal supernatant, namely macromolecular collagen crude extract, purifying the macromolecular collagen crude extract by a membrane separation process technology, removing microscopic residues or possible pyrogens which are not seen by naked eyes by using a microfiltration membrane with the aperture of 1-0.2 mu m, removing residual pepsin, small molecular impurities and inorganic salts by using an ultrafiltration membrane with the aperture of 0.1-0.05 mu m or the relative molecular weight of 150KD, and concentrating to obtain macromolecular collagen solution; (6) Anion exchange chromatography/resin purification macromolecular collagen and nanofiltration membrane desalination and concentration Adsorbing the macromolecular collagen solution by using anion exchange chromatography/resin, preparing buffer solution with pH of 2.5-4 and containing 0.5% -1.5% sodium chloride to desorb the macromolecular collagen on the anion exchange chromatography/resin, regulating the pH of the obtained macromolecular collagen solution to 6.5-7.5 by using sodium hydroxide solution, removing small molecular inorganic salt by using nanofiltration membrane with relative molecular weight of 500-200 Da, and concentrating to obtain the macromolecular collagen solution purified by the anion exchange chromatography/resin with mass volume concentration of more than or equal to 5%; (7) Preparation of collagen-chamomile active component hydrogel Dissolving the chamomile aqueous phase component powder prepared in the step (1) in deionized water to prepare a chamomile aqueous phase component solution with the mass volume concentration of 3-15%, dissolving the chamomile ethanol phase component extract prepared in the step (2) in absolute ethanol to prepare a chamomile ethanol phase component solution with the mass volume concentration of 3-15%, dissolving the chamomile volatile component extract prepared in the step (3) in absolute ethanol to prepare a chamomile volatile component solution with the mass volume concentration of 3-15%, adding the chamomile aqueous phase component solution, the chamomile ethanol phase component solution, the chamomile volatile component solution and the macromolecular collagen solution purified by anion exchange chromatography/resin into a reaction kettle according to the volume ratio of (0.5-1.5): (2-4), emulsifying the chamomile volatile component extract prepared in the step (3) by a slurry, stirring and cooling to maintain the temperature of the water gel at the temperature of 5-25 ℃ to obtain the collagen-active component.
2. The method for large-scale treatment of a highly stable antiallergic collagen-chamomile active ingredient hydrogel according to claim 1, wherein the chamomile material in step (1) is German chamomile (Latin name: MATRICARIA CHAMOMILIA) or Roman chamomile (Latin name: anthemis nobilis).
3. The large-scale treatment method of the high-stability antiallergic collagen-chamomile active component hydrogel, which is disclosed in claim 1, is characterized in that centrifuges used in the step (1), the step (2) and the step (5) are large-scale high-speed refrigerated centrifuges of 6000-15000 rpm.
4. The large-scale treatment method of the high-stability antiallergic collagen-chamomile active component hydrogel, which is disclosed in claim 1, is characterized in that the alkali used in the step (1) and the step (4) is sodium bicarbonate, potassium bicarbonate, sodium hydroxide or potassium hydroxide, the acid used in the step (1) and the step (4) is hydrochloric acid or nitric acid, and the ethanol solution used in the step (4) can be a solution prepared from edible alcohol or a solution containing ethanol prepared from white wine, yellow wine or cooking wine.
5. The method for large-scale treatment of the high-stability antiallergic collagen-chamomile active component hydrogel is characterized in that spray-drying air inlet temperature is 120-180 ℃ and air outlet temperature is 70-95 ℃ used in the step (1), the flow rate of a nanofiltration membrane with the relative molecular weight of 500-200 Da used in the step (1) and the step (6) is 5-14 cubic meters/(hour x square meter), the membrane pressure is 0.5-2.5 mpa and the temperature is 20-50 ℃, the flow rate of a microfiltration membrane with the pore diameter of 1-0.2 mu m used in the step (5) is 100-2000 cubic meters/(hour x square meter), the membrane pressure is 0.1-0.6 mpa and the temperature is 0-10 ℃, the flow rate of an ultrafiltration membrane with the pore diameter of 0.1-0.05 mu m or the relative molecular weight of 150 KD-100 KD is 100 cubic meters/(hour x square meter), the membrane pressure is 0.1-0.6 mpa and the temperature is 0-10 ℃.
6. The method for large-scale treatment of the high-stability antiallergic collagen-chamomile active component hydrogel, which is characterized in that the fish scale raw material in the step (4) is marine fish scales or freshwater fish scales.
7. The method for large-scale treatment of the high-stability antiallergic collagen-chamomile active component hydrogel, which is characterized in that anion exchange chromatography/resin used in the step (6) is prepared chromatography or resin with amino groups, primary amine, secondary amine, tertiary amine or quaternary amine groups, and buffer solution with pH of 2.5-4 is disodium hydrogen phosphate-citric acid buffer solution, citric acid-sodium citrate buffer solution, glycine-hydrochloric acid buffer solution, phthalic acid-hydrochloric acid buffer solution, citric acid-sodium hydroxide-hydrochloric acid buffer solution, citric acid-sodium citrate buffer solution and acetic acid-sodium acetate buffer solution.
8. The method for large-scale treatment of a highly stable antiallergic collagen-active component hydrogel according to claim 1, wherein in step (7), a chamomile aqueous phase component solution, a chamomile ethanol phase component solution, a chamomile volatile component solution and an anion exchange chromatography/resin purified macromolecular collagen solution are put into a reaction kettle in a volume ratio of 1:1:1:3.
9. A collagen-chamomile active ingredient hydrogel prepared by the method of any one of claims 1 to 8.
10. Use of the collagen-chamomile active ingredient hydrogel of claim 9 for preparing cosmetics against allergy, oxidation or tyrosinase.

Description

High-stability antiallergic collagen-chamomile active component hydrogel and large-scale preparation method and application thereof Technical Field The invention relates to a high-stability antiallergic collagen-chamomile active component hydrogel, a large-scale treatment method and application thereof, relates to chemical extraction, separation and purification and homogenization and emulsification technologies, and belongs to the field of cosmetics. Background Matricaria chamomilla, matricaria of Compositae, annual herbaceous plants. The Chamomile flower, which is recorded in the Chinese medicinal plant pattern inspection, has the effects of clearing heat and detoxicating, relieving cough and asthma and dispelling wind-damp, and is mainly used for treating cold and fever, sore throat, cough and asthma due to lung heat, swelling and pain due to heat arthralgia and sore. Flos Matricariae Chamomillae essential oil extracted from flos Matricariae Chamomillae is also often used for inhibiting skin inflammation, promoting wound healing, repairing skin laceration, and treating neuralgia. Matricaria chamomilla is an aromatic plant known to people for a long time, and is widely used in europe, the united states, japan, and the like. The chamomile is prepared into a health product, has remarkable effects of moisturizing, moisturizing and astringing pores, and has been used as a medicinal cosmetic ingredient due to various medicinal effects. The chamomile has good effects of relaxing and caring sensitive skin, reducing fine red blood streak, reducing redness, adjusting uneven skin color, and the like, is rich in flavonoid active ingredients, has the effects of resisting oxidation, resisting vascular proliferation, diminishing inflammation, resisting allergy and resisting viruses, and can be applied to anti-sensitive high-end skin care products. The cosmetic cotton wet dressing can be used for mildly supplementing water, relieving skin and having good soothing effect on skin easy to itch. At present, no matter the domestic and foreign patents or the Chinese and English literature, a great deal of reports on extracting single components from chamomile raw materials, such as chamomile polysaccharide (CN 201910716078.6), chamomile total flavonoids (CN 202310641172.6, CN202410642029.3, CN 202211521873.8) or chamomile essential oil (CN 202210720959.7) and the like, are less involved in comprehensive utilization of various active components in the chamomile raw materials. The process technology for comprehensively utilizing various active ingredients in the chamomile raw materials obviously cannot be realized by simply duplicating and superposing the old technologies, but needs an intensive combination type innovation, namely, the difference of respective properties of different components/ingredients is acutely grasped, various extraction, separation, drying and extraction methods are creatively combined in an intensive way, a complete and concise and coherent process flow is formed, and the sequential and efficient extraction of the chamomile water phase component, the chamomile ethanol phase component and the chamomile volatile component is realized. Therefore, the technology of the invention has important scientific value and practical significance. In addition, it is reported in the literature that the soothing effect of chamomile essential oil (volatile component of chamomile) is optimal among the individual active ingredients of chamomile. It can relax anxiety, tension, anger and fear, relax tolerance, feel peaceful, relieve anxiety, calm the mind and help to treat insomnia. In the aspect of skin care, the chamomile essential oil can relieve scalds, blisters, inflamed wounds, ulcers and furuncles, help to improve eczema, facial blisters, herpes, psoriasis, hypersensitive skin and general allergic phenomena, and has excellent effects of improving elasticity and especially on dry and itching-prone allergic skin, and can eliminate edema and strengthen tissues, so that the chamomile essential oil is a very good skin cleaning care product. However, the chamomile essential oil gradually decreases its excellent efficacy with time due to the inclusion of volatile components such as chamomile azulene (azulene), alpha-bisabolol, farnesene, bisabolol, and the like. This clearly requires an efficient and viable technique to ensure the stability of the efficacy of the chamomile essential oil (volatile components of chamomile). This also demonstrates the advancement and breakthrough of the inventive technology from one side. Disclosure of Invention In view of the above, the invention provides a large-scale preparation method of collagen-chamomile active component hydrogel with flexible production process, wide application range, obvious antiallergic effect and good stability, so as to realize high-value development of marine biological resources and comprehensive utilization of land plant resources. In order to solve the technica