CN115554180B - 4-butylresorcinol supermolecule vesicle aggregate, preparation method thereof and cosmetic composition - Google Patents
4-butylresorcinol supermolecule vesicle aggregate, preparation method thereof and cosmetic composition Download PDFInfo
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- CN115554180B CN115554180B CN202211306298.XA CN202211306298A CN115554180B CN 115554180 B CN115554180 B CN 115554180B CN 202211306298 A CN202211306298 A CN 202211306298A CN 115554180 B CN115554180 B CN 115554180B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/347—Phenols
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/14—Liposomes; Vesicles
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/23—Sulfur; Selenium; Tellurium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/345—Alcohols containing more than one hydroxy group
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/60—Sugars; Derivatives thereof
- A61K8/602—Glycosides, e.g. rutin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/68—Sphingolipids, e.g. ceramides, cerebrosides, gangliosides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/736—Chitin; Chitosan; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/738—Cyclodextrins
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/08—Anti-ageing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/74—Biological properties of particular ingredients
- A61K2800/78—Enzyme modulators, e.g. Enzyme agonists
- A61K2800/782—Enzyme inhibitors; Enzyme antagonists
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/82—Preparation or application process involves sonication or ultrasonication
Abstract
The invention provides a 4-butyl resorcinol supermolecule vesicle aggregate, a preparation method thereof and a cosmetic composition, and belongs to the technical field of cosmetics. Dissolving 4-butyl resorcinol into polyalcohol to obtain 4-butyl resorcinol solution, dissolving cyclodextrin into water to obtain cyclodextrin water solution, uniformly mixing the cyclodextrin water solution with the 4-butyl resorcinol solution, adding the relieving active substance and sodium bisulphite, and uniformly mixing to obtain the 4-butyl resorcinol supermolecular vesicle aggregate. The preparation method is environment-friendly and simple, the 4-butyl resorcinol supermolecule vesicle aggregate improves the water solubility, biocompatibility, transdermal absorption performance and stability of 4-butyl resorcinol, is not easy to oxidize and discolor, can better exert the bioactivity of the 4-butyl resorcinol, and relieves the irritation to the skin, so that the 4-butyl resorcinol can be better applied to the field of cosmetics.
Description
Technical Field
The invention relates to the technical field of cosmetics, in particular to a 4-butyl resorcinol supermolecule vesicle aggregate, a preparation method thereof and a cosmetic composition.
Background
4-butylresorcinol is a strong inhibitor of tyrosinase and peroxidase, is an effective skin whitening agent and toner for normal skin, and is effective against chloasma and H 2 O 2 The induced DNA damage has a strong protective effect. It can reduce tyrosinase synthesis by directly inhibiting tyrosinase activity, and has an inhibitory effect on melanin production of B16 melanoma cells without generating any cytotoxicity. And in vitro studies have shown that 4-butylresorcinol inhibits melanin production and tyrosinase-related protein-1 (TRP-1), TRP-1 can catalyze the oxidation of the melanin-producing intermediate 5, 6-dihydroxyindole-2-carbenic acid to reduce melanin production.
However, 4-butylresorcinol is poorly soluble in water, is easily oxidized and discolored, is irritating to the skin, and these factors greatly reduce its bioactivity in cosmetic applications, resulting in a failure to maximize its efficacy. Therefore, how to improve the stability, water solubility, biocompatibility and transdermal absorbability of 4-butylresorcinol, so that the 4-butylresorcinol has wider application range in the field of cosmetics, and plays roles of whitening, removing freckles and resisting oxidation, thus being worthy of research.
Disclosure of Invention
The invention mainly aims to provide a 4-butyl resorcinol supermolecule vesicle aggregate, a preparation method thereof and a cosmetic composition, and aims to solve the technical problems of poor water solubility, biocompatibility, transdermal absorbability and stability, easiness in oxidative discoloration and skin irritation of 4-butyl resorcinol.
In order to achieve the above purpose, the invention provides a 4-butyl resorcinol supermolecule vesicle aggregate, which comprises the following components in parts by weight: 10-30 parts of 4-butylresorcinol, 20-40 parts of polyol, 20-40 parts of cyclodextrin, 0.1-0.4 part of sodium bisulfite and 0.1-3 parts of soothing active.
Optionally, the 4-butylresorcinol supermolecular vesicle aggregate comprises the following components in parts by weight: 12 parts of 4-butylresorcinol, 25 parts of polyol, 25 parts of cyclodextrin, 0.25 part of sodium bisulfite and 1.5 parts of soothing active.
Optionally, the cyclodextrin comprises at least one of α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin, hydroxypropyl- β -cyclodextrin, methyl- β -cyclodextrin, glucose-cyclodextrin, maltodextrin.
Optionally, the soothing active comprises at least one of glucosides, beta-glucan, kava extract, sweet wormwood extract, licorice extract, dendrobium officinale extract, yew leaf extract, centella asiatica extract, sodium carboxymethyl beta-glucan, yeast/rice fermentation product filtrate, aloe vera leaf extract, zingiber zerumbet extract, 4-t-butylcyclohexanol, oat extract, paeonia root extract, tree peony root bark extract, olive leaf extract, chamomile flower extract, scutellaria root extract, golden chamomile extract, carboxymethyl chitosan, ceramide, bisabolol, panthenol.
Optionally, the polyol comprises at least one of propylene glycol, butylene glycol, dipropylene glycol, polyethylene glycol.
In addition, in order to achieve the above object, the present invention also provides a method for preparing 4-butylresorcinol supermolecular vesicle aggregates, comprising the steps of:
s10, dissolving 4-butyl resorcinol into polyalcohol at the temperature of 30-50 ℃ to obtain 4-butyl resorcinol solution;
s20, dissolving cyclodextrin into water to obtain cyclodextrin aqueous solution, uniformly mixing the cyclodextrin aqueous solution with the 4-butylresorcinol solution to obtain clathrate compound solution, dissolving a relieving active substance and sodium bisulphite with water, adding the relieving active substance and sodium bisulphite into the clathrate compound solution, standing and filtering to obtain the 4-butylresorcinol supermolecule vesicle aggregate.
Optionally, in the step S20, the way of uniformly mixing to obtain the clathrate solution includes any one of ultrasound, homogenization, stirring, and micro-jet.
Further alternatively, the way of uniformly mixing to obtain the inclusion compound solution is ultrasonic treatment, the ultrasonic frequency is 19.5kHz-21.5kHz, and the ultrasonic time is 1-2 hours.
The invention also provides a cosmetic composition comprising 4-butylresorcinol supermolecular vesicle aggregates as described above.
Optionally, the mass concentration of the 4-butylresorcinol supermolecular vesicle aggregate in the cosmetic composition is 1% -8%.
The invention has the beneficial effects that:
the invention provides a 4-butyl resorcinol supermolecule vesicle aggregate and a preparation method thereof, which fill the blank of the research on 4-butyl resorcinol in the prior art.
The 4-butyl resorcinol supermolecular vesicle aggregate improves the water solubility, biocompatibility, transdermal absorption performance and stability of 4-butyl resorcinol, is not easy to oxidize and discolor, can better exert the effects of whitening, antioxidation and freckle removal, and relieves the irritation to skin, so that the 4-butyl resorcinol can be better applied to the field of cosmetics, and can exert the effects of whitening, freckle removal and antioxidation.
Drawings
For a clearer description of embodiments of the invention or of solutions in the prior art, the following brief description of the drawings is given for the purpose of illustrating the embodiments or the solutions in the prior art, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained from the structures shown in these drawings without the need for inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a preparation method of 4-butylresorcinol supermolecular vesicle aggregates.
FIG. 2 is a TEM image of 4-butylresorcinol supramolecular vesicle aggregates of example 1.
FIG. 3 is a graph showing the results of the spot feature count, the ultraviolet spot feature count, and the brown spot feature count of the volunteer VISIA test in one of application examples 1.
FIG. 4 is a graph showing the results of red area characteristic counts of the volunteer VISIA test in one of application examples 1.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The description as it relates to "first", "second", etc. in the present invention is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The invention provides a 4-butyl resorcinol supermolecule vesicle aggregate, which comprises the following components in parts by weight: 10-30 parts of 4-butylresorcinol, 20-40 parts of polyol, 20-40 parts of cyclodextrin, 0.1-0.4 part of sodium bisulfite and 0.1-3 parts of soothing active.
In some embodiments, the 4-butylresorcinol supermolecular vesicle aggregates comprise the following components, in parts by weight: 12 parts of 4-butylresorcinol, 25 parts of polyol, 25 parts of cyclodextrin, 0.25 part of sodium bisulfite and 1.5 parts of soothing active.
By the weight proportion of the components, the 4-butyl resorcinol supermolecular vesicle aggregate with high encapsulation efficiency, good stability, water solubility and biocompatibility and no irritation can be obtained, the effects of whitening, freckle removing and oxidation resistance of the 4-butyl resorcinol can be exerted to the greatest extent, and better use experience is brought to users.
The 4-butylresorcinol supermolecular vesicle aggregate of the present invention is a closed aggregate having a hollow sphere or tubular structure. Cyclodextrin can be included with hydrophobic molecules to form supermolecule amphiphilic molecules so as to assemble vesicle aggregates, a cavity of the cyclodextrin has a strong recognition effect on benzene rings in 4-butylresorcinol, the cyclodextrin can be included with the benzene rings of the 4-butylresorcinol to form superamphiphilic molecules, the superamphiphilic molecules are assembled into vesicle aggregates, stability, biocompatibility and transdermal absorption performance of the 4-butylresorcinol are improved, hydrophilic and hydrophobic active ingredients can be carried by the cavity and a fence layer of the vesicle aggregates, and hydrophilicity of the 4-butylresorcinol is improved.
The 4-butyl resorcinol is insoluble in water, and is dissolved by using a polyol, wherein the polyol is preferably at least one of propylene glycol, butanediol, dipropylene glycol and polyethylene glycol. The polyol not only has good dissolving action on 4-butyl resorcinol, but also has the effect of moisturizing the skin, and provides a good environment for assisting in improving the permeability of active substances on the skin.
The invention does not limit the types of cyclodextrin, preferably at least one of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, hydroxypropyl-beta cyclodextrin, methyl-beta cyclodextrin, glucose-cyclodextrin and malt cyclodextrin, wherein the cavity of the cyclodextrin has a strong recognition effect on benzene rings in 4-butyl resorcinol, and can be included with the benzene rings of 4-butyl resorcinol to form super-amphiphilic molecules, so that vesicle aggregates are assembled.
4-butylresorcinol has some irritation to the skin, and particularly high concentrations of 4-butylresorcinol can cause a poor use experience. The supramolecular vesicle aggregate technology of the invention can relieve the irritation of 4-butyl resorcinol, but the irritation is gradually enhanced along with the increase of 4-butyl resorcinol concentration in the process of releasing 4-butyl resorcinol, so the invention relieves the irritation of 4-butyl resorcinol in the slow release process by adding a release active substance. The soothing active comprises at least one of glucosides, beta-glucan, kava extract, sweet wormwood extract, licorice extract, dendrobium officinale extract, yew leaf extract, centella asiatica extract, sodium carboxymethyl beta-glucan, yeast/rice fermentation product filtrate, aloe vera leaf extract, zingiber zerumbet extract, 4-tert-butylcyclohexanol, oat extract, paeonia root extract, tree peony root bark extract, olive leaf extract, chamomile flower extract, scutellaria baicalensis root extract, golden chamomile extract, carboxymethyl chitosan, ceramide, bisabolol and panthenol.
When the 4-butylresorcinol is released from the cyclodextrin cavity under the influence of the soothing active substance, the skin is not stimulated to bring bad use experience, and the sensitive state of the skin can be improved.
In addition, the invention also provides a preparation method of the 4-butylresorcinol supermolecule vesicle aggregate, which comprises the following steps:
s10, dissolving 4-butyl resorcinol into polyalcohol at the temperature of 30-50 ℃ to obtain 4-butyl resorcinol solution;
s20, dissolving cyclodextrin into water to obtain cyclodextrin aqueous solution, uniformly mixing the cyclodextrin aqueous solution with the 4-butylresorcinol solution to obtain clathrate compound solution, dissolving a relieving active substance and sodium bisulphite with water, adding the relieving active substance and sodium bisulphite into the clathrate compound solution, standing and filtering to obtain the 4-butylresorcinol supermolecule vesicle aggregate.
In some embodiments, 4-butylresorcinol is dissolved in the polyol and may be stirred uniformly at 500-1000 rpm.
In some embodiments, the aqueous cyclodextrin solution preferably has a mass concentration of 1% to 5%, it being understood that the mass concentration refers to the mass ratio of cyclodextrin per 100g of water.
The cyclodextrin aqueous solution with the mass concentration is mixed with the 4-butyl resorcinol solution, so that inclusion can be finished on the premise of ensuring that the biological activity of the 4-butyl resorcinol is not destroyed, otherwise, the mass concentration of the cyclodextrin aqueous solution is too high, the collision frequency among molecules is accelerated in the mixing process of the cyclodextrin aqueous solution and the 4-butyl resorcinol, and local temperature rise is easy to occur, so that the biological activity of the 4-butyl resorcinol is reduced.
Preferably, step S20 is accomplished at 30-40℃to avoid damaging the biological activity of 4-butylresorcinol by high temperature.
In some embodiments, after the cyclodextrin aqueous solution and the 4-butylresorcinol solution are mixed, the purpose of obtaining the clathrate solution by uniformly mixing the cyclodextrin aqueous solution and the 4-butylresorcinol solution can be achieved by any one of ultrasonic, homogenizing, stirring and micro-jet.
Specifically, in some embodiments, the purpose of uniform mixing is achieved by means of ultrasound, wherein the frequency of the ultrasound is 19.5kHz-21.5kHz, and the ultrasound time is 1-2 hours.
In some embodiments, after dissolving the soothing active and sodium bisulfite with water, mixing with the clathrate solution at 500-1000rpm, stirring well, standing for 1-2 hours, and then filtering to obtain uniform and stable 4-butylresorcinol supermolecular vesicle aggregates.
The present invention also provides a cosmetic composition comprising 4-butylresorcinol supermolecular vesicle aggregates as described above, preferably at a concentration of 1% to 8% by mass of 4-butylresorcinol supermolecular vesicle aggregates in the cosmetic composition, it being understood that the concentration by mass is the mass fraction of 4-butylresorcinol supermolecular vesicle aggregates per 100g of cosmetic composition.
The cosmetic composition of the invention is not limited in state, can be emulsion, liquid or paste, can exert the biological activity of 4-butylresorcinol, and can exert the whitening, antioxidation and freckle removing effects by adding a small amount.
The technical scheme of the present invention will be further described in detail with reference to the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
Example 1
Referring to fig. 1, fig. 1 is a schematic flow chart of an example 1 of a preparation method of 4-butylresorcinol supermolecular vesicle aggregates of the present invention.
In this embodiment, the preparation method of the 4-butylresorcinol supermolecule vesicle aggregate comprises the following steps:
s10, according to parts by weight, dissolving 12 parts of 4-butyl resorcinol into 25 parts of propylene glycol at 30 ℃, and uniformly stirring at 500rpm to obtain 4-butyl resorcinol solution;
s20, dissolving 25 parts of hydroxypropyl-beta-cyclodextrin into deionized water at the temperature of 30 ℃ to obtain a hydroxypropyl-beta-cyclodextrin aqueous solution with the mass concentration of 4%, mixing the aqueous solution with the 4-butyl resorcinol solution in the step S10, performing ultrasonic treatment at the ultrasonic frequency of 19.5kHz for 2 hours at the temperature of 30 ℃ to obtain an inclusion compound solution, dissolving 0.25 part of sodium bisulphite and 1.5 parts of glyceroglycosides with deionized water, adding the sodium bisulphite and the 1.5 parts of glyceroglycosides into the inclusion compound solution at the rotating speed of 500rpm, stirring uniformly, standing for 1 hour, and filtering to obtain the 4-butyl resorcinol supermolecular vesicle aggregate.
Example 2
Referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment 2 of a preparation method of 4-butylresorcinol supermolecular vesicle aggregates of the present invention.
In this embodiment, the preparation method of the 4-butylresorcinol supermolecule vesicle aggregate comprises the following steps:
s10, dissolving 30 parts of 4-butyl resorcinol into 40 parts of dipropylene glycol at the temperature of 30 ℃, and uniformly stirring at the speed of 1000rpm to obtain 4-butyl resorcinol solution;
s20, dissolving 40 parts of gamma cyclodextrin into deionized water at the temperature of 30 ℃ to obtain a gamma cyclodextrin aqueous solution with the mass concentration of 5%, mixing the gamma cyclodextrin aqueous solution with the 4-butyl resorcinol solution in the step S10, performing ultrasonic treatment at the ultrasonic frequency of 21.5kHz at the temperature of 30 ℃ for 1h to obtain an inclusion compound solution, dissolving 0.3 part of sodium bisulphite and 1.5 parts of carboxymethyl chitosan with deionized water, adding the sodium bisulphite and the carboxymethyl chitosan into the inclusion compound solution at the rotating speed of 1000rpm, stirring uniformly, standing for 1h, and filtering to obtain the 4-butyl resorcinol supermolecular vesicle aggregate.
Example 3
Referring to FIG. 1, FIG. 1 is a schematic flow chart of an example 3 of a preparation method of 4-butylresorcinol supermolecular vesicle aggregates of the present invention.
In this embodiment, the preparation method of the 4-butylresorcinol supermolecule vesicle aggregate comprises the following steps:
s10, dissolving 10 parts of 4-butyl resorcinol into 20 parts of butanediol at 50 ℃, and uniformly stirring at a rotating speed of 800rpm to obtain a 4-butyl resorcinol solution;
s20, dissolving 20 parts of alpha-cyclodextrin into deionized water at the temperature of 30 ℃ to obtain a hydroxypropyl-beta cyclodextrin aqueous solution with the mass concentration of 1%, mixing the hydroxypropyl-beta cyclodextrin aqueous solution with the 4-butyl resorcinol aqueous solution in the step S10, performing ultrasonic treatment at the ultrasonic frequency of 19.5kHz for 1.5 hours at the temperature of 30 ℃ to obtain an inclusion compound solution, dissolving 0.4 part of sodium bisulphite and 1 part of beta-glucan into the inclusion compound solution by using deionized water, adding the sodium bisulphite and the beta-glucan into the inclusion compound solution at the rotating speed of 1000rpm, stirring uniformly, standing for 1 hour, and filtering to obtain the 4-butyl resorcinol supermolecular vesicle aggregate.
Example 4
Referring to FIG. 1, FIG. 1 is a schematic flow chart of the 4 th example of a preparation method of 4-butylresorcinol supermolecular vesicle aggregates of the present invention.
In this embodiment, the preparation method of the 4-butylresorcinol supermolecule vesicle aggregate comprises the following steps:
s10, dissolving 20 parts of 4-butyl resorcinol into 30 parts of polyethylene glycol at 40 ℃, and uniformly stirring at 600rpm to obtain 4-butyl resorcinol solution;
s20, dissolving 28 parts of beta-cyclodextrin into deionized water at 40 ℃ to obtain a beta-cyclodextrin aqueous solution with the mass concentration of 4.5%, mixing the beta-cyclodextrin aqueous solution with the 4-butyl resorcinol solution in the step S10, performing ultrasonic treatment at the ultrasonic frequency of 21.5kHz at 40 ℃ for 2 hours to obtain an inclusion compound solution, dissolving 0.1 part of sodium bisulphite and 0.1 part of carboxymethyl beta-glucan sodium glycoside into the inclusion compound solution by using deionized water, adding the sodium bisulphite and the carboxymethyl beta-glucan sodium glycoside into the inclusion compound solution at the rotating speed of 600rpm, stirring uniformly, standing for 2 hours, and filtering to obtain the 4-butyl resorcinol supermolecular vesicle aggregate.
Example 5
Referring to FIG. 1, FIG. 1 is a schematic flow chart of an example 5 of a preparation method of 4-butylresorcinol supermolecular vesicle aggregates of the present invention.
In this embodiment, the preparation method of the 4-butylresorcinol supermolecule vesicle aggregate comprises the following steps:
s10, dissolving 10 parts of 4-butyl resorcinol into 25 parts of propylene glycol at 35 ℃, and uniformly stirring at a rotating speed of 1000rpm to obtain a 4-butyl resorcinol solution;
s20, dissolving 30 parts of glucose-cyclodextrin into deionized water at 35 ℃ to obtain a glucose-cyclodextrin aqueous solution with the mass concentration of 2%, mixing the glucose-cyclodextrin aqueous solution with the 4-butylresorcinol solution in the step S10, performing ultrasonic treatment at the ultrasonic frequency of 21.5kHz at 35 ℃ for 2 hours to obtain an inclusion compound solution, dissolving 0.2 part of sodium bisulfite and 3 parts of ceramide with deionized water, adding the sodium bisulfite and the 3 parts of ceramide into the inclusion compound solution at the rotating speed of 1000rpm, stirring uniformly, standing for 1 hour, and filtering to obtain the 4-butylresorcinol supermolecular vesicle aggregate.
Comparative example 1
Comparative example 1 was prepared in the same manner as in example 1 except that equal parts by weight of deionized water was used in place of hydroxypropyl-beta-cyclodextrin.
Comparative example 2
Comparative example 2 was prepared in the same manner as in example 1 except that equal parts by weight of deionized water was used in place of sodium bisulfite.
Comparative example 3
Comparative example 3 was the same as the production method of example 1 except that 4-butylresorcinol was added in an amount of 40 parts.
Comparative example 4
Comparative example 4 was the same as example 1 in terms of the feed, but the preparation was different in that step S10 was carried out at 60 ℃.
Comparative example 5
Comparative example 5 the same preparation as in example 1 was fed with the difference that 25 parts of hydroxypropyl-beta-cyclodextrin was dissolved in deionized water in step S20 to obtain an aqueous hydroxypropyl-beta-cyclodextrin solution having a mass concentration of 10%.
Performance testing
1. The 4-butylresorcinol supermolecular vesicle aggregates of example 1 were characterized by projection electron microscopy to give a TEM image, and the results are shown in FIG. 1.
As can be seen from FIG. 1, the 4-butylresorcinol supermolecular vesicle aggregates have a spherical vesicle-like structure, and 4-butylresorcinol is included in cyclodextrin.
2. The encapsulation efficiency (%), tyrosinase inhibition (IC 50 value mg/ml), radical DPPH clearance (IC 50 value mg/ml) and stability of the products of examples 1 to 5 and comparative examples 1 to 5 were measured, respectively. The results are shown in Table 1.
Wherein, in the stability experiment, the 4-butyl resorcinol supermolecular vesicle aggregate presents a light yellow transparent state, and changes color into an unstable state.
Table 1 comparison of the properties of the products obtained in examples 1 to 5 and comparative examples 1 to 5
As can be seen from table 1:
the cyclodextrin of examples 1-5 can be used for clathrating 4-butylresorcinol into a cavity of the cyclodextrin, has very high encapsulation efficiency, can be used for obtaining 4-butylresorcinol supermolecular vesicle aggregate, can be used for effectively inhibiting tyrosinase and scavenging DPPH free radicals, and has the effect of strong whitening and antioxidation of 4-butylresorcinol, in addition, the 4-butylresorcinol supermolecular vesicle aggregate also has very good stability, and can not be discolored after being placed for 90 days under the conditions of cold resistance-15 ℃, low temperature 4 ℃, heat resistance 45 ℃ and light-proof, -15 ℃/45 ℃ cold and hot circulation at room temperature and light resistance respectively.
According to comparative example 1, cyclodextrin is not added to clathrate 4-butylresorcinol, the biological activity of the product is unstable and easy to inactivate, the tyrosinase inhibition effect and DPPH cleaning effect are both poor, and stability tests show that the product is obvious in color change and poor in stability after being placed for 90 days under cold-resistant and 15 ℃ low-temperature 4 ℃, heat-resistant and 45 ℃ light-resistant conditions, and the conditions of cold and heat circulation and light resistance at the temperature of-15 ℃/45 ℃ and light resistance at room temperature.
Comparative example 2, after stability test of the product without sodium bisulphite, the product was left for 90 days under cold-resistant and heat-resistant conditions of-15 ℃ and low-temperature 4 ℃ and-15 ℃/45 ℃ respectively, the color change was obvious, and slight color change appears when the product was left for 90 days under heat-resistant and light-resistant conditions of 45 ℃ and room temperature and light-resistant conditions, and the stability is deteriorated.
The addition amount of 4-butyl resorcinol in comparative example 3 is 40 parts, the addition amount is excessive, part of 4-butyl resorcinol is free outside a cyclodextrin cavity, the encapsulation rate is low, the overall stability of the product is poor, after a stability experiment, the product is respectively placed for 90 days under cold resistance-15 ℃ and low temperature 4 ℃, heat resistance 45 ℃ and heat resistance 45 ℃ in a dark condition, -15 ℃/45 ℃ and in a dark condition at room temperature, and the color change is obvious and the stability is poor.
Comparative example 4 step S10 was performed at 60 c, which reduced the biological activity of 4-butylresorcinol, resulting in a decrease in tyrosinase inhibition rate and DPPH clearance.
Comparative example 5 the cyclodextrin aqueous solution was higher, up to 10%, and when mixed with 4-butylresorcinol solution, the biological activity of 4-butylresorcinol was reduced, possibly due to local warming of the system, and the product performance was slightly inferior.
Application example 1
The 4-butylresorcinol supermolecular vesicle aggregate obtained in example 1 was prepared into an emulsion formulation, in which the mass concentration of 4-butylresorcinol was 4%.
The selection of 12 volunteers with type III or type IV skin ensures that the volunteers are primarily active indoors during the test period, avoiding prolonged exposure to uv light (e.g., performance decisions or travel, etc.).
During the test period, volunteers used the above emulsion twice a day in the morning and evening, respectively, on their whole faces.
The volunteer cheek was selected as the test site and the VISIA test was performed before the test article was used and on days 7 and 14 of the continuous use of the product, respectively, to obtain a spot feature count, an ultraviolet spot feature count, a brown spot feature count, and a red area feature count, and the results are shown in table 2 and fig. 3 to 4.
Fig. 3 to 4 show the results of the vision test of one volunteer, fig. 3 shows the spot feature count, the uv spot feature count, and the brown spot feature count, and fig. 4 shows the feature count of the red area.
TABLE 2 VISIA test results for 12 volunteers
As can be seen from fig. 3, 4 and table 2, the spot feature count, the uv spot feature count, the brown spot feature count and the red spot feature count on day 14 were gradually decreased on day seven before the volunteer's use.
Therefore, the 4-butyl resorcinol supermolecule vesicle aggregate can effectively reduce spots, ultraviolet spots and brown spots of skin, has no irritation, and can even relieve the sensitive state of the skin.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures or equivalent processes disclosed herein or in the alternative, which may be employed directly or indirectly in other related arts.
Claims (6)
1. A4-butylresorcinol supermolecular vesicle aggregate is characterized by comprising the following components in parts by weight
The 4-butylresorcinol supermolecular vesicle aggregates were calculated to include the following components: 10-30 parts of 4-butylresorcinol, 20-40 parts of polyol, 20-40 parts of cyclodextrin, 0.1-0.4 part of sodium bisulfite and 0.1-3 parts of soothing active;
the cyclodextrin is at least one of gamma-cyclodextrin, hydroxypropyl-beta-cyclodextrin, glucose-cyclodextrin and beta-cyclodextrin;
the soothing active comprises at least one of glucosides, beta-glucan, kava extract, sweet wormwood extract, licorice extract, dendrobium officinale extract, yew leaf extract, centella asiatica extract, sodium carboxymethyl beta-glucan, yeast/rice fermentation product filtrate, aloe vera leaf extract, zingiber zerumbet extract, 4-tert-butylcyclohexanol, oat extract, paeonia root extract, tree peony root bark extract, olive leaf extract, chamomile flower extract, scutellaria baicalensis root extract, golden chamomile extract, carboxymethyl chitosan, ceramide, bisabolol and panthenol;
the polyalcohol comprises at least one of propylene glycol, butanediol, dipropylene glycol and polyethylene glycol;
the 4-butylresorcinol supermolecular vesicle aggregate is prepared by the following preparation method:
s10, dissolving 4-butyl resorcinol into polyalcohol at 30-50 ℃ to obtain 4-butyl resorcinol
Resorcinol solutions;
s20, dissolving cyclodextrin into water to obtain cyclodextrin aqueous solution, uniformly mixing the cyclodextrin aqueous solution with the 4-butylresorcinol solution by ultrasonic to obtain clathrate compound solution, dissolving a relieving active substance and sodium bisulphite by water, adding the relieving active substance and sodium bisulphite into the clathrate compound solution, standing and filtering to obtain the 4-butylresorcinol supermolecule vesicle aggregate.
2. 4-butylresorcinol supermolecular vesicle aggregate according to claim 1, characterized in that it comprises the following components in parts by weight: 12 parts of 4-butylresorcinol, 25 parts of polyol, 25 parts of cyclodextrin, 0.25 part of sodium bisulfite and 1.5 parts of soothing active.
3. A method for the preparation of 4-butylresorcinol supermolecular vesicle aggregates according to any one of claims 1 to 2, comprising the steps of:
s10, dissolving 4-butyl resorcinol into polyalcohol at 30-50 ℃ to obtain 4-butyl resorcinol
Resorcinol solutions;
s20, dissolving cyclodextrin into water to obtain cyclodextrin aqueous solution, uniformly mixing the cyclodextrin aqueous solution with the 4-butylresorcinol solution by ultrasonic to obtain clathrate compound solution, dissolving a relieving active substance and sodium bisulphite by water, adding the relieving active substance and sodium bisulphite into the clathrate compound solution, standing and filtering to obtain the 4-butylresorcinol supermolecule vesicle aggregate.
4. The method for preparing 4-butylresorcinol supermolecular vesicle aggregate according to claim 3, wherein the way of uniformly mixing to obtain clathrate solution is ultrasonic treatment, the ultrasonic frequency is 19.5kHz-21.5kHz, and the ultrasonic time is 1-2 h.
5. A cosmetic composition comprising 4-butylresorcinol supermolecular vesicle aggregates according to any one of claims 1 to 2.
6. The cosmetic composition according to claim 5, wherein the mass concentration of the 4-butylresorcinol supermolecular vesicle aggregates in the cosmetic composition is 1% -8%.
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