CN117462450B - Dual-modified 10-hydroxy-2-decenoic acid chitosan microsphere and preparation method and application thereof - Google Patents
Dual-modified 10-hydroxy-2-decenoic acid chitosan microsphere and preparation method and application thereof Download PDFInfo
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- QHBZHVUGQROELI-UHFFFAOYSA-N 10-hydroxydec-2-enoic acid Chemical class OCCCCCCCC=CC(O)=O QHBZHVUGQROELI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 87
- 239000004005 microsphere Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- KUPHXIFBKAORGY-UHFFFAOYSA-N 2-amino-3-iodo-4-methylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(N)=C1I KUPHXIFBKAORGY-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002537 cosmetic Substances 0.000 claims abstract description 28
- 241000191967 Staphylococcus aureus Species 0.000 claims abstract description 21
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 120
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 238000000502 dialysis Methods 0.000 claims description 19
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- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 4
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- QHBZHVUGQROELI-SOFGYWHQSA-N (E)-10-hydroxydec-2-enoic acid Chemical compound OCCCCCCC\C=C\C(O)=O QHBZHVUGQROELI-SOFGYWHQSA-N 0.000 description 2
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
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- CKQVRZJOMJRTOY-UHFFFAOYSA-N octadecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O CKQVRZJOMJRTOY-UHFFFAOYSA-N 0.000 description 2
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- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
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Classifications
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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
- A61K8/30—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
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/005—Antimicrobial preparations
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- A—HUMAN NECESSITIES
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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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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
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- A—HUMAN NECESSITIES
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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
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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
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/592—Mixtures of compounds complementing their respective functions
- A61K2800/5922—At least two compounds being classified in the same subclass of A61K8/18
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- A—HUMAN NECESSITIES
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- 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
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/612—By organic compounds
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- A—HUMAN NECESSITIES
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- 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
- A61K2800/84—Products or compounds obtained by lyophilisation, freeze-drying
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Dermatology (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Emergency Medicine (AREA)
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention belongs to the technical field of cosmetics, and particularly relates to a double-modified 10-hydroxy-2-decenoic acid chitosan microsphere, and a preparation method and application thereof. Specifically, the chitosan microsphere prepared by the invention is prepared by modifying 10-hydroxy-2-decenoic acid and carboxymethyl together, and can remarkably increase the solubility of 10-hydroxy-2-decenoic acid in water. In addition, the invention also unexpectedly discovers that the components of the prepared chitosan microsphere have a certain synergistic effect of inhibiting staphylococcus aureus biomembrane, so that the chitosan microsphere can be used for preparing cosmetics with microecological effect and has good practical application value.
Description
Technical Field
The invention belongs to the technical field of cosmetics, and particularly relates to a double-modified 10-hydroxy-2-decenoic acid chitosan microsphere, and a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Royal jelly is a basic food required by queen bees, and is a product secreted by the swallow glands and the palate glands of worker bees. Royal jelly has been receiving attention because of its pharmacological activities such as immunomodulation, antitumor, antibacterial and vascular activities. Royal jelly is a functional food and has great potential for promoting human health. As a unique component in royal jelly, 10-Hydroxy-2-decenoic acid (10-Hydroxy-2-Decenoic acid, 10-HDA) is an important criterion for evaluating the quality of royal jelly. 10-hydroxy-2-decenoic acid is an important unsaturated fatty acid in Lac Regis Apis, and accounts for about 50% of total fatty acid in Lac Regis Apis. The 10-HDA has the functions of bacteriostasis, antioxidation, anti-tumor, immunity enhancement and the like in many researches at present, and has a plurality of application prospects. The pure product of 10-hydroxy-2-decenoic acid is a powder, and the solubility of the pure product in water and oil is extremely low, so that the application range of the pure product is greatly limited.
Staphylococcus aureus is a common pathogenic bacterium in human skin, and when the flora is unbalanced, skin diseases such as atopic dermatitis and the like can be caused. Studies have shown that Staphylococcus aureus evolves into a variant on the skin of eczema patients, in which a particular gene is mutated, thereby promoting faster growth on the skin. Staphylococcus aureus can form a biofilm itself to provide protection, thus making eradication difficult. At present, related cosmetics of microecology in the market are increased year by year, but the alleged concept of microecology is realized by adding prebiotics, metaplasias and the like, the mechanisms of the products are more general, and few effect targets of the products/raw materials relate to inhibiting staphylococcus aureus biomembrane to realize the improvement of skin microecology. Therefore, the inhibition of staphylococcus aureus biomembrane has certain potential as an action target point of microecological skin care research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a double-modified 10-hydroxy-2-decenoic acid chitosan microsphere, and a preparation method and application thereof. The double-modified 10-hydroxy-2-decenoic acid chitosan microsphere can obviously increase the solubility of 10-hydroxy-2-decenoic acid in water, and meanwhile, each component of the chitosan microsphere has a certain synergistic antibacterial effect. Based on the above results, the present invention has been completed.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
In a first aspect of the present invention, there is provided a method for preparing a double-modified 10-hydroxy-2-decenoic acid chitosan microsphere, the method comprising:
S1, mixing an absolute ethanol solution of 10-hydroxy-2-decenoic acid with an aqueous chitosan solution, and uniformly stirring to form a transparent state to obtain a first solution;
s2, adding the carbodiimide into the first solution, and stirring in a water bath to obtain a second solution;
s3, respectively adding an absolute ethyl alcohol solution of 10-hydroxy-2-decenoic acid and a sodium chloroacetate aqueous solution into the second solution, firstly adding the absolute ethyl alcohol solution of 10-hydroxy-2-decenoic acid, stirring in a water bath, then adding the sodium chloroacetate aqueous solution, continuing stirring in the water bath, and ending the reaction to obtain a third solution;
s4, placing the third solution in a dialysis bag, dialyzing with ultrapure water, and freeze-drying the dialyzed matter to obtain white powder;
S5, washing the white powder with absolute ethyl alcohol, and drying to obtain the white powder.
According to the second aspect of the invention, the double-modified 10-hydroxy-2-decenoic acid chitosan microsphere obtained by the preparation method is provided, and the 10-hydroxy-2-decenoic acid modified chitosan microsphere is identified to be uniform in distribution, good in dispersibility, free of obvious agglomeration phenomenon, round, smooth in surface, uniform in particle size and about 32 mu m in particle size. The prepared chitosan microsphere is prepared by modifying 10-hydroxy-2-decenoic acid and carboxymethyl, and can remarkably increase the solubility of 10-hydroxy-2-decenoic acid in water; and has a certain synergistic effect of inhibiting staphylococcus aureus biomembrane.
Accordingly, in a third aspect of the invention there is provided the use of a doubly modified 10-hydroxy-2-decenoic acid chitosan microsphere as described above in the preparation of a product. Wherein the product can be a cosmetic, in particular a cosmetic of the micro-ecological concept.
In a fourth aspect of the present invention, there is provided a cosmetic comprising at least the above-mentioned doubly modified 10-hydroxy-2-decenoic acid chitosan microsphere.
The beneficial technical effects of one or more of the technical schemes are as follows:
The chitosan microsphere prepared by the technical scheme is prepared by modifying 10-hydroxy-2-decenoic acid and carboxymethyl together, and can remarkably increase the solubility of 10-hydroxy-2-decenoic acid in water. In addition, the invention also unexpectedly discovers that the components of the prepared chitosan microsphere have a certain synergistic effect of inhibiting staphylococcus aureus biomembrane, so that the chitosan microsphere can be used for preparing cosmetics with microecological effect and has good practical application value.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings may be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing inhibition of Staphylococcus aureus biofilm formation by different samples measured using the crystal violet method in Experimental example 2 of the present invention;
FIG. 2 is an infrared spectrum of a different test sample in experimental example 3 of the present invention;
FIG. 3 is an electron micrograph of a sample obtained in example 1 of the present invention at different magnifications.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof. It is to be understood that the scope of the invention is not limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention.
In one exemplary embodiment of the present invention, a method for preparing a dual modified 10-hydroxy-2-decenoic acid chitosan microsphere is provided, the method comprising:
S1, mixing an absolute ethanol solution of 10-hydroxy-2-decenoic acid with an aqueous chitosan solution, and uniformly stirring to form a transparent state to obtain a first solution;
s2, adding the carbodiimide into the first solution, and stirring in a water bath to obtain a second solution;
s3, respectively adding an absolute ethyl alcohol solution of 10-hydroxy-2-decenoic acid and a sodium chloroacetate aqueous solution into the second solution, firstly adding the absolute ethyl alcohol solution of 10-hydroxy-2-decenoic acid, stirring in a water bath, then adding the sodium chloroacetate aqueous solution, continuing stirring in the water bath, and ending the reaction to obtain a third solution;
s4, placing the third solution in a dialysis bag, dialyzing with ultrapure water, and freeze-drying the dialyzed matter to obtain white powder;
S5, washing the white powder with absolute ethyl alcohol, and drying to obtain the white powder.
Wherein, in the step S1,
The mass fraction of the absolute ethanol solution of the 10-hydroxy-2-decenoic acid is 15-22% (preferably 20%), the mass fraction of the chitosan aqueous solution is 1-5% (preferably 2%), and the chitosan aqueous solution further contains 1-10% (preferably 5%) of glacial acetic acid.
The mass ratio of the absolute ethanol solution of the 10-hydroxy-2-decenoic acid to the chitosan aqueous solution is 1:10 to 35, more preferably 1:20.
In the step S2, the specific conditions of water bath stirring are as follows: stirring in water bath at 50-80 deg.c (preferably 65 deg.c) for 30-60min (preferably 45 min);
The mass ratio of the carbodiimide to the absolute ethanol solution of the 10-hydroxy-2-decenoic acid in the step S1 is 2:10-23, preferably 2:15;
In the step S3, the specific conditions of water bath stirring treatment after adding the 10-hydroxy-2-decenoic acid absolute ethanol solution are 60-90 ℃ (preferably 75 ℃) water bath stirring for 10-50min (preferably 25 min); the specific condition of continuing the water bath stirring treatment is that the water bath stirring is carried out for 5 to 15 hours (preferably 8.5 hours) at the temperature of 60 to 90 ℃ (preferably 75 ℃);
wherein, the mass fraction of the absolute ethanol solution of the 10-hydroxy-2-decenoic acid is 15-22% (preferably 20%), and the mass fraction of the sodium chloroacetate aqueous solution is 40-80% (preferably 60%);
The mass ratio of the absolute ethanol solution of the 10-hydroxy-2-decenoic acid to the sodium chloroacetate aqueous solution is 4:0.2 to 3, preferably 4:1, a step of;
the mass ratio of the chitosan aqueous solution in the step S1 to the sodium chloroacetate aqueous solution in the step S3 is 120:0.3 to 2, preferably 120:1;
in the step S4, the water is changed to remove the water-soluble impurities.
In the step S5, the washing times of the absolute ethyl alcohol are 2 to 8 times (preferably 6 times); the drying temperature may be 50 to 70 ℃ (preferably 60 ℃).
In still another embodiment of the present invention, the dual modified 10-hydroxy-2-decenoic acid chitosan microsphere obtained by the preparation method is provided, and the 10-hydroxy-2-decenoic acid modified chitosan microsphere is identified to have uniform distribution, good dispersibility, no obvious agglomeration phenomenon, spherical shape, smoother surface, uniform particle diameter and diameter of about 32 μm. The prepared chitosan microsphere is prepared by modifying 10-hydroxy-2-decenoic acid and carboxymethyl, and can remarkably increase the solubility of 10-hydroxy-2-decenoic acid in water; and has a certain synergistic effect of inhibiting staphylococcus aureus biomembrane.
Accordingly, in a further embodiment of the present invention there is provided the use of the dual modified 10-hydroxy-2-decenoic acid chitosan microsphere described above in the preparation of a product. Wherein the product can be a cosmetic, in particular a cosmetic of the micro-ecological concept.
In still another embodiment of the present invention, there is provided a cosmetic comprising at least the above-mentioned doubly modified 10-hydroxy-2-decenoic acid chitosan microsphere.
The cosmetic may optionally further comprise conventional ingredients of cosmetics, including vehicles (such as diluents, dispersants, carriers, etc.), cosmetic auxiliary materials (such as emulsifiers, thickeners, etc.), etc. any ingredients known in the art, and the type and amount thereof may be selected according to specific needs, and the inventors do not make specific restrictions herein.
Further, in the present invention, the cosmetic should be construed broadly, and includes, but is not limited to, cleansing cream (ointment), face lotion, bath lotion, face cream, astringent, mask, sun cream, and the like.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1: preparation of double-modified 10-hydroxy-2-decenoic acid chitosan microsphere
The preparation method comprises the following steps:
S1: 15g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) and 300g of chitosan water solution (mass fraction 2%, containing 5% glacial acetic acid) are mixed and stirred uniformly to be transparent, so as to obtain solution 1;
S2: adding 2g of carbodiimide into the solution 1, and stirring the solution in a water bath at 65 ℃ for 45min to obtain a solution 2; s3: adding 10g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) into the solution 2, stirring for 25min in a water bath at 75 ℃, then adding 2.5g of sodium chloroacetate aqueous solution (mass fraction 60%), stirring for 8.5h in the water bath at 75 ℃, and ending the reaction to obtain a solution 3;
s4: subpackaging the solution 3 in dialysis bags, dialyzing with ultrapure water for 48 hours, changing water frequently during the dialysis to remove water-soluble impurities, and freeze-drying the dialyzed matter to obtain white powder 1;
S5: washing the white powder 1 with absolute ethyl alcohol for 6 times, and drying at 60 ℃ to obtain the double-modified 10-hydroxy-2-decenoic acid chitosan microsphere.
Example 2: preparation of double-modified 10-hydroxy-2-decenoic acid chitosan microsphere
The preparation method comprises the following steps:
S1: 15g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) and 375g of chitosan water solution (mass fraction 2%, containing 5% glacial acetic acid) are mixed and stirred uniformly to be transparent, so as to obtain a solution 1;
S2: adding 2g of carbodiimide into the solution 1, and stirring the solution in a water bath at 65 ℃ for 45min to obtain a solution 2; s3: adding 10g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) into the solution 2, stirring for 25min in a water bath at 75 ℃, then adding 2.5g of sodium chloroacetate aqueous solution (mass fraction 60%), stirring for 8.5h in a water bath at 75 ℃, and ending the reaction to obtain a solution 3;
S4, subpackaging the solution 3 in dialysis bags, dialyzing with ultrapure water for 48 hours, changing water frequently during the dialysis to remove water-soluble impurities, and freeze-drying the dialyzed matter to obtain white powder 1;
S5, washing the white powder 1 with absolute ethyl alcohol for 6 times, and drying at 60 ℃ to obtain the double-modified 10-hydroxy-2-decenoic acid chitosan microsphere.
Example 3: preparation of double-modified 10-hydroxy-2-decenoic acid chitosan microsphere
The preparation method comprises the following steps:
S1: 15g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) and 225g of chitosan water solution (mass fraction 2%, containing 5% glacial acetic acid) are mixed and stirred uniformly to be transparent, so as to obtain solution 1;
S2: adding 2g of carbodiimide into the solution 1, and stirring the solution in a water bath at 65 ℃ for 45min to obtain a solution 2; s3: adding 10g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) into the solution 2, stirring for 25min in a water bath at 75 ℃, then adding 2.5g of sodium chloroacetate aqueous solution (mass fraction 60%), stirring for 8.5h in a water bath at 75 ℃, and ending the reaction to obtain a solution 3;
s4: subpackaging the solution 3 in dialysis bags, dialyzing with ultrapure water for 48 hours, changing water frequently during the dialysis to remove water-soluble impurities, and freeze-drying the dialyzed matter to obtain white powder 1;
S5: washing the white powder 1 with absolute ethyl alcohol for 6 times, and drying at 60 ℃ to obtain the double-modified 10-hydroxy-2-decenoic acid chitosan microsphere.
Example 4: preparation of double-modified 10-hydroxy-2-decenoic acid chitosan microsphere
The preparation method comprises the following steps:
S1: 10g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) and 300g of chitosan water solution (mass fraction 2%, containing 5% glacial acetic acid) are mixed and stirred uniformly to be transparent, so as to obtain solution 1;
s2: adding 1.33g of carbodiimide into the solution 1, and stirring in a water bath at 50 ℃ for 40min to obtain a solution 2;
S3: adding 10g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) into the solution 2, stirring for 20min in a water bath at 60 ℃, then adding 2.5g of sodium chloroacetate aqueous solution (mass fraction 60%), stirring for 8h in a water bath at 60 ℃, and obtaining a solution 3 after the reaction;
s4: subpackaging the solution 3 in dialysis bags, dialyzing with ultrapure water for 48 hours, changing water frequently during the dialysis to remove water-soluble impurities, and freeze-drying the dialyzed matter to obtain white powder 1;
S5: washing the white powder 1 with absolute ethyl alcohol for 6 times, and drying at 60 ℃ to obtain the double-modified 10-hydroxy-2-decenoic acid chitosan microsphere.
Example 5: preparation of double-modified 10-hydroxy-2-decenoic acid chitosan microsphere
The preparation method comprises the following steps:
s1: mixing 20g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) with 400g of chitosan water solution (mass fraction 2%, containing 5% glacial acetic acid), and stirring uniformly to form a transparent solution 1;
S2: adding 2g of carbodiimide into the solution 1, and stirring the solution in a water bath at 65 ℃ for 45min to obtain a solution 2; s3: 13.22g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) is added into the solution 2, the solution is stirred for 25min in a water bath at 75 ℃, then 3.33g of sodium chloroacetate aqueous solution (mass fraction 60%) is added, the solution is stirred for 8.5h in a water bath at 75 ℃, and the reaction is finished to obtain a solution 3;
S4, subpackaging the solution 3 in dialysis bags, dialyzing with ultrapure water for 48 hours, changing water frequently during the dialysis to remove water-soluble impurities, and freeze-drying the dialyzed matter to obtain white powder 1;
S5, washing the white powder 1 with absolute ethyl alcohol for 6 times, and drying at 60 ℃ to obtain the double-modified 10-hydroxy-2-decenoic acid chitosan microsphere.
Comparative example 1: unmodified 10-hydroxy-2-decenoic acid chitosan microspheres
The preparation method comprises the following steps:
S1: 15g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) and 300g of chitosan water solution (mass fraction 2%, containing 5% glacial acetic acid) are mixed and stirred uniformly to be transparent, so as to obtain solution 1;
s2: subpackaging the solution 1 in dialysis bags, dialyzing with ultrapure water for 48 hours, changing water frequently during the dialysis to remove water-soluble impurities, and freeze-drying the dialyzed matter to obtain white powder 1;
S3: the white powder 1 was washed with absolute ethanol for 6 times and dried at 60 ℃ to obtain an unmodified 10-hydroxy-2-decenoic acid chitosan microsphere.
Comparative example 2: 10-hydroxy-2-decenoic acid chitosan microsphere modified by 10-hydroxy-2-decenoic acid only
The preparation method comprises the following steps:
S1: 15g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 50%) and 300g of chitosan water solution (mass fraction 2%, containing 5% glacial acetic acid) are mixed and stirred uniformly to be transparent, so as to obtain solution 1;
S2: adding 2g of carbodiimide into the solution 1, and stirring the solution in a water bath at 65 ℃ for 45min to obtain a solution 2; s3: 10g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) is added into the solution 2, and the mixture is stirred in a water bath at 75 ℃ for 8.5 hours, and the reaction is finished to obtain a solution 3;
s4: subpackaging the solution 3 in dialysis bags, dialyzing with ultrapure water for 48 hours, changing water frequently during the dialysis to remove water-soluble impurities, and freeze-drying the dialyzed matter to obtain white powder 1;
S5: the white powder 1 is washed by absolute ethyl alcohol for 6 times, and is dried at 60 ℃ to obtain the 10-hydroxy-2-decenoic acid chitosan microsphere modified by 10-hydroxy-2-decenoic acid.
Comparative example 3: carboxymethyl-modified 10-hydroxy-2-decenoic acid chitosan microsphere only
The preparation method comprises the following steps:
S1: 15g of 10-hydroxy-2-decenoic acid absolute ethanol solution (mass fraction 20%) and 300g of chitosan water solution (mass fraction 2%, containing 5% glacial acetic acid) are mixed and stirred uniformly to be transparent, so as to obtain solution 1;
S2: adding 2g of carbodiimide into the solution 1, and stirring the solution in a water bath at 65 ℃ for 45min to obtain a solution 2; s3: adding 2.5g of sodium chloroacetate aqueous solution (mass fraction 60%) into the solution 2, stirring in a water bath at 75 ℃ for 8.5h, and obtaining a solution 3 after the reaction;
s4: subpackaging the solution 3 in dialysis bags, dialyzing with ultrapure water for 48 hours, changing water frequently during the dialysis to remove water-soluble impurities, and freeze-drying the dialyzed matter to obtain white powder 1;
s5: washing the white powder 1 with absolute ethyl alcohol for 6 times, and drying at 60 ℃ to obtain the carboxymethyl modified 10-hydroxy-2-decenoic acid chitosan microsphere.
Application example 1 an emulsion containing double modified 10-hydroxy-2-decenoic acid chitosan microspheres
Phase A: a165 1 g of (emulsifier), 3 g of GTCC, 3 g of white oil, 0.5 g of cetostearyl alcohol and 5g of silicone oil;
And B phase: 4g of glycerin, 4g of butanediol, 0.4g of EMT-10 (thickener), 0.1 g of xanthan gum, 0.4g of Xinxian ketone, 0.4g of hexanediol, 0.2 g of soybean lecithin and 100 g of ionized water TO;
and C phase: 5g of double modified 10-hydroxy-2-decenoic acid chitosan microsphere prepared in example 1.
The preparation steps of the emulsion are as follows:
1) Dispersing EMT-10, xanthan gum and soybean lecithin into glycerol and butanediol, adding fresh ketone, hexanediol and deionized water, heating in water bath at 80deg.C, stirring to dissolve completely to obtain phase B;
2) Heating and melting A165, GTCC, white oil, cetostearyl alcohol and silicone oil in water bath at 83 ℃ to obtain A phase;
3) Heating the phase A and the phase B in a water bath at 83 ℃ when the phases are the same, and slowly adding the phase A into the phase B on the premise of stirring the phase B at 500r/min when the temperatures of the phases are the same;
4) After the phase B and the phase A are mixed, cooling the emulsion at the stirring speed of 430 r/min;
5) Adding the double-modified 10-hydroxy-2-decenoic acid chitosan microspheres into deionized water, and stirring to fully dissolve the microspheres to obtain a C phase;
6) When the temperature of the emulsion is reduced to 40-45 ℃, adding phase C, stirring at 60r/min, and reducing the temperature;
7) When the temperature is reduced to 35 ℃, the product is obtained after stationary cooling.
Application example 2A cream containing double modified 10-hydroxy-2-decenoic acid chitosan microspheres
Phase A: 3g of GTCC, 3g of white oil, 3g of cetostearyl alcohol, 1 g of C14-22 alcohol, 2.0 g of C12-20 alkyl glucose, 1.5 g of glycerol stearic acid vinegar, 1 g of cetostearyl alcohol, 5g of plant squalane and 5g of dioctyl carbonate;
And B phase: glycerol 4g, butanediol 4g, EMT-10 (thickener) 0.4g, AVC (thickener) 0.4g, xanthan gum 0.1g, xinxian ketone 0.4g, hexanediol 0.4g, soybean lecithin 0.2 g, ionized water TO100 g;
and C phase: 5g of double modified 10-hydroxy-2-decenoic acid chitosan microsphere prepared in example 1.
The preparation method of the cream comprises the following steps:
1) Dispersing EMT-10, xanthan gum, AVC and soybean lecithin into glycerol and butanediol, adding fresh ketone, hexanediol and deionized water, heating in water bath at 80deg.C, stirring to dissolve completely to obtain phase B;
2) Heating GTCC, white oil, cetostearyl alcohol, C14-22 alcohol, C12-20 alkyl glucose, glycerol stearic acid vinegar, cetostearyl alcohol, plant squalane and dioctyl carbonate in water bath at 83 ℃ to melt to obtain phase A;
3) Heating the phase A and the phase B in a water bath at 83 ℃ when the phases are the same, and slowly adding the phase A into the phase B on the premise of stirring the phase B at 500r/min when the temperatures of the phases are the same;
4) After the phase B and the phase A are mixed, cooling the cream at the stirring speed of 430 r/min;
5) Adding the double-modified 10-hydroxy-2-decenoic acid chitosan microspheres into deionized water, and stirring to fully dissolve the microspheres to obtain a C phase;
6) When the temperature of the emulsion is reduced to 40-45 ℃, adding phase C, stirring at 60r/min, and reducing the temperature;
7) When the temperature is reduced to 35 ℃, the product is obtained after stationary cooling.
Compared with untreated 10-hydroxy-2-decenoic acid, the double-modified 10-hydroxy-2-decenoic acid chitosan microsphere prepared by the invention can obviously improve the problems of low solubility and easy precipitation of 10-hydroxy-2-decenoic acid in a formula, thereby being easier to apply in the formula.
Experimental example 1 raw Material dissolution and stability investigation experiment
The samples of examples 1 to 6 and comparative examples 1 to 3 were prepared as aqueous solutions having a mass fraction of 10%, respectively, and were subjected to solubility stability examination, which was shown in the following table:
As can be seen from the above table, comparing 1-10 samples, the modified 10-hydroxy-2-decenoic acid and chitosan all have improved water solubility, and their stability is also improved to some extent, and their dissolution stability can be substantially as follows: double modified chitosan microsphere > single modified chitosan microsphere > unmodified chitosan microsphere > solubility of single component, especially the solubility stability of the double modified chitosan microsphere of example 1 is optimal.
Experimental example 2 scavenging action on Staphylococcus aureus mature biofilm
① Strain activation
Staphylococcus aureus ATCC25923 was streaked onto TSA plates, the plates were incubated at 37 ℃ for 24h, individual colonies were isolated into TSB medium, and incubated at 37 ℃ for 12h to give an active bacterial suspension.
② Crystal violet process
Test samples of different concentrations were prepared according to the following table, in particular as follows:
The clearance of the staphylococcus aureus biofilm by the samples of different examples was determined by the crystal violet method. The staphylococcus aureus is diluted to 1.0X10 6 CFU/mL by using a TSB culture medium, the diluted bacterial liquid is added into a 96-well plate, each well is200 mu L, the bacterial liquid is cultured for 24 hours, the bacterial liquid is sucked out, the culture medium is washed for 2 times by using the TSB culture medium, the fresh TSB culture medium is added for 196 mu L and evenly mixed, the culture medium is cultured for 24 hours by using a 37 ℃ incubator, the supernatant in the 96-well plate is taken out, then the 96-well plate with biofilm growth is washed for 3 times by using 200 mu L of PBS buffer solution, and the 96-well plate is placed in a ventilated and dried place for 24 hours. 0.5% crystal violet dye was added to a 96-well plate, stained for 10min, then rinsed with clear water until the water stream had no apparent color, and then left to dry in a through-air-dried place. Finally, 200. Mu.L of 95% ethanol was added to each well, and after complete dissolution, the optical density was measured with an enzyme-labeled instrument at a wavelength of 580 nm.
The smaller the OD at 580nm, the stronger the inhibition of Staphylococcus aureus biofilm formation. As can be seen from fig. 1, the inhibition effect of sample No. 4 (comparative example 1 microsphere powder: unmodified 10-hydroxy-2-decenoic acid chitosan microsphere) on the formation of staphylococcus aureus biofilm is significantly better than that of samples No. 7, 8 and 9, which shows that after 10-hydroxy-2-decenoic acid is prepared into microspheres, the inhibition effect on the formation of staphylococcus aureus biofilm is significantly enhanced, and the 10-hydroxy-2-decenoic acid and chitosan are compounded to have a certain synergistic effect; the inhibition effect of the sample No. 3 (the double-modified chitosan microsphere) on the formation of the staphylococcus aureus biological film is more obviously superior to that of the samples No. 5,6 and 10 (the single-modified chitosan microsphere) and the sample No. 4 (the unmodified chitosan microsphere), which shows that the modification treatment can obviously improve the inhibition effect on the formation of the staphylococcus aureus biological film, and the improvement of the double-modification treatment is more obvious. In summary, the inhibition of Staphylococcus aureus biofilm formation can be in the order from strong to weak: the chitosan microsphere subjected to double modification treatment is more than chitosan microsphere subjected to single modification treatment is more than the chitosan microsphere subjected to non-treatment and pure component composition is more than single component, and a certain synergistic effect exists before each component.
Experimental example 3 Infrared Spectrum test and Transmission Electron microscopy experiment
① Infrared test
The sample of example 1 was selected for infrared testing.
Analysis of FIG. 2, comparing curves (a), (b) and (c), shows that (c) shows a characteristic peak of carboxymethyl chitosan at 2910cm -1～2950cm-1, which indicates that example 1 has been successfully modified by carboxymethyl; a new strong absorption peak appears at 1562cm -1, indicating that the amino group on chitosan forms an amide bond with the carboxyl group on 10-hydroxy-2-decenoic acid, indicating that example 1 has been successfully modified with 10-hydroxy-2-decenoic acid. In connection with the above conclusion, it is illustrated that the sample of example 1 is a 10-hydroxy-2-decenoic acid chitosan microsphere with double modification.
② Electronic photograph
The transmission electron microscope of the sample in example 1 is shown in fig. 3, and it can be seen from the graph that the 10-hydroxy-2-decenoic acid modified chitosan microsphere has uniform distribution, good dispersibility, no obvious agglomeration phenomenon, round sphere shape, smooth surface, uniform particle size and particle size of about 32 μm.
It should be noted that the above examples are only for illustrating the technical solution of the present invention and are not limiting thereof. Although the present invention has been described in detail with reference to the examples given, those skilled in the art can make modifications and equivalents to the technical solutions of the present invention as required, without departing from the spirit and scope of the technical solutions of the present invention.
Claims (11)
1. A method for preparing a double-modified 10-hydroxy-2-decenoic acid chitosan microsphere, which is characterized by comprising the following steps:
S1, mixing an absolute ethanol solution of 10-hydroxy-2-decenoic acid with an aqueous chitosan solution, and uniformly stirring to form a transparent state to obtain a first solution;
s2, adding the carbodiimide into the first solution, and stirring in a water bath to obtain a second solution;
s3, respectively adding an absolute ethyl alcohol solution of 10-hydroxy-2-decenoic acid and a sodium chloroacetate aqueous solution into the second solution, firstly adding the absolute ethyl alcohol solution of 10-hydroxy-2-decenoic acid, stirring in a water bath, then adding the sodium chloroacetate aqueous solution, continuing stirring in the water bath, and ending the reaction to obtain a third solution;
s4, placing the third solution in a dialysis bag, dialyzing with ultrapure water, and freeze-drying the dialyzed matter to obtain white powder;
S5, washing the white powder with absolute ethyl alcohol, and drying to obtain the white powder;
In the step S1 of the above-mentioned process,
15-22% Of absolute ethanol solution of 10-hydroxy-2-decenoic acid, 1-5% of chitosan aqueous solution, and 1-10% of glacial acetic acid;
The mass ratio of the absolute ethanol solution of the 10-hydroxy-2-decenoic acid to the chitosan aqueous solution is 1: 10-35;
The mass ratio of the carbodiimide to the absolute ethanol solution of the 10-hydroxy-2-decenoic acid in the step S1 is 2:10-23;
in the step S3, the mass fraction of the absolute ethanol solution of the 10-hydroxy-2-decenoic acid is 15-22%, and the mass fraction of the sodium chloroacetate aqueous solution is 40-80%;
The mass ratio of the absolute ethanol solution of the 10-hydroxy-2-decenoic acid to the sodium chloroacetate aqueous solution is 4: 0.2-3;
The mass ratio of the chitosan aqueous solution in the step S1 to the sodium chloroacetate aqueous solution in the step S3 is 120: 0.3-2.
2. The preparation method according to claim 1, wherein in the step S2, specific conditions of water bath stirring are: stirring in a water bath at 50-80 ℃ for 30-60min.
3. The preparation method of claim 1, wherein in the step S3, the specific condition of the water bath stirring treatment after adding the 10-hydroxy-2-decenoic acid absolute ethanol solution is that the water bath stirring is performed for 10-50min at 60-90 ℃; the specific condition of continuing the water bath stirring treatment is that the water bath stirring is carried out for 5-15h at the temperature of 60-90 ℃.
4. The preparation method according to claim 1, wherein in the step S5, the washing time with absolute ethanol is 2 to 8 times; the drying temperature is 50-70 ℃.
5. The doubly modified 10-hydroxy-2-decenoic acid chitosan microsphere obtained by the method of any one of claims 1-4.
6. Use of the double modified 10-hydroxy-2-decenoic acid chitosan microsphere of claim 5 in the preparation of cosmetics.
7. The use according to claim 6, wherein the cosmetic is a microecological concept cosmetic; the cosmetic is effective in inhibiting Staphylococcus aureus biofilm.
8. A cosmetic comprising the doubly modified 10-hydroxy-2-decenoic acid chitosan microsphere of claim 5.
9. The cosmetic product of claim 8, wherein the cosmetic product comprises a common component of a cosmetic product;
The cosmetic is selected from cleaning cream, facial cleanser, bath lotion, face cream, astringent or facial mask.
10. The cosmetic product of claim 8, wherein the cosmetic product is a sunscreen.
11. The cosmetic product of claim 8, wherein the cosmetic product is a cleansing cream.
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