CN114983863B - Modified alginate composition for skin repair and application thereof - Google Patents
Modified alginate composition for skin repair and application thereof Download PDFInfo
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- CN114983863B CN114983863B CN202210796407.4A CN202210796407A CN114983863B CN 114983863 B CN114983863 B CN 114983863B CN 202210796407 A CN202210796407 A CN 202210796407A CN 114983863 B CN114983863 B CN 114983863B
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- alginic acid
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- 239000000203 mixture Substances 0.000 title claims abstract description 101
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical class O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 230000008439 repair process Effects 0.000 title claims abstract description 56
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 77
- 229920000615 alginic acid Polymers 0.000 claims abstract description 77
- 239000000783 alginic acid Substances 0.000 claims abstract description 76
- 229960001126 alginic acid Drugs 0.000 claims abstract description 76
- 150000004781 alginic acids Chemical class 0.000 claims abstract description 74
- 229920001661 Chitosan Polymers 0.000 claims abstract description 54
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000770 propane-1,2-diol alginate Substances 0.000 claims abstract description 53
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000007790 solid phase Substances 0.000 claims description 38
- 229910019142 PO4 Inorganic materials 0.000 claims description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 33
- 239000010452 phosphate Substances 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 23
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 21
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 21
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 21
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 21
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 235000019820 disodium diphosphate Nutrition 0.000 claims description 13
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 13
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 235000017550 sodium carbonate Nutrition 0.000 claims description 8
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 8
- 238000000108 ultra-filtration Methods 0.000 claims description 8
- 239000002537 cosmetic Substances 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 241000512259 Ascophyllum nodosum Species 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008591 skin barrier function Effects 0.000 abstract description 9
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 210000004027 cell Anatomy 0.000 abstract description 8
- 229920001282 polysaccharide Polymers 0.000 abstract description 8
- 239000005017 polysaccharide Substances 0.000 abstract description 8
- 210000002421 cell wall Anatomy 0.000 abstract description 7
- 239000003755 preservative agent Substances 0.000 abstract description 7
- 230000002335 preservative effect Effects 0.000 abstract description 7
- 150000004804 polysaccharides Chemical class 0.000 abstract description 5
- -1 alginic acid polysaccharide Chemical class 0.000 abstract description 4
- 230000015271 coagulation Effects 0.000 abstract description 4
- 238000005345 coagulation Methods 0.000 abstract description 4
- 230000007794 irritation Effects 0.000 abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 206010033675 panniculitis Diseases 0.000 abstract description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 3
- 210000004304 subcutaneous tissue Anatomy 0.000 abstract description 3
- 239000013522 chelant Substances 0.000 abstract 1
- 210000003491 skin Anatomy 0.000 description 64
- 238000012360 testing method Methods 0.000 description 24
- 230000037394 skin elasticity Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- 230000003020 moisturizing effect Effects 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 210000000434 stratum corneum Anatomy 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 230000002500 effect on skin Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000036572 transepidermal water loss Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000036074 healthy skin Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 208000017520 skin disease Diseases 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001054 cortical effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000004207 dermis Anatomy 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 210000004927 skin cell Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- A61K8/733—Alginic acid; Salts thereof
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
-
- 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
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Engineering & Computer Science (AREA)
- Dermatology (AREA)
- Molecular Biology (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
A modified alginate composition of the invention useful for skin repair comprising: the phospho-esterified propylene glycol alginate and the micromolecular phospho-esterified chitosan lead the phosphate group and the amino group to the alginic acid polysaccharide molecules by the phospho-esterified propylene glycol alginate, so that the polysaccharide molecules can enter subcutaneous tissues more easily through skin barriers, chelate the combined calcium in the aged cell walls and soften the cell walls. The chitosan has natural antibacterial property, but has low water solubility and can perform coagulation reaction with alginic acid. The modified alginate composition for skin repair has the advantages that all the components act synergistically, obvious repair effect is achieved on skin, cells are enabled to be full of vitality, the skin is smooth and fine, meanwhile, the modified alginate composition has natural antibacterial property, no preservative is needed, no irritation is caused, and the modified alginate composition is convenient to store.
Description
Technical Field
The invention relates to the technical field of cosmetics, in particular to a modified alginate composition for skin repair and application thereof.
Background
Along with the development of economy and society, the life rhythm is also continuously accelerated, various pressures born by people are steadily increased, so that the balance of metabolism of a human body can be destroyed, the nutrition supply required by skin tends to be slow, and pigment parent cells become very active. In addition, the skin can be gradually aged like other organs of a human body, the functions of the skin are weakened and lost, various lesions are generated, and the skin is aged.
Alginic acid is also called alginic acid, alginic acid and alginic acid, is a natural polysaccharide which exists in the cell wall of brown algae and is formed by linear polymerization of monosaccharide aldehyde acid, and has wide sources, and can improve the moisture retention, compactness and ductility of skin, however, due to the excessively high molecular weight of alginic acid, alginic acid cannot penetrate through skin barrier to enter dermis layer, so that deep repair effect on skin is achieved. The low-viscosity small-molecular-weight alginic acid can penetrate through skin barrier and enter deep layers of skin, but can not react with aged cortical cells, and can only play a role in moisturizing.
Chitosan is a product of natural polysaccharide chitin with partial acetyl removed, and has good biocompatibility, no toxic or side effect, antibacterial and antiviral properties, and has wide application prospect in the fields of cosmetics and the like in recent years, but has limited water solubility and can perform coagulation reaction with alginic acid. In CN201810566412X (preparation of a chitosan and propylene glycol alginate blend microcapsule) and application thereof, the description of the chitosan and propylene glycol alginate blend microcapsule is provided, wherein the prepared chitosan and propylene glycol alginate undergo a crosslinking reaction to generate a water-insoluble substance.
In conclusion, alginic acid and chitosan have respective excellent properties, but have single properties, and have certain disadvantages when used for skin repair.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides the modified alginate composition which has obvious repairing effect on skin, enables cells to be full of vigor, is smooth and fine in skin, has natural antibacterial property, does not need to be added with preservative, and is convenient to store and can be used for repairing the skin.
In order to achieve the above purpose, the invention is realized by the following technical scheme: the invention provides a modified alginate composition for skin repair, which comprises the following preparation steps:
(a) Preparing phospho-esterified propylene glycol alginate with specific molecular weight, esterifying alginic acid with specific molecular weight under propylene oxide condition, and performing phospho-esterification treatment on the product to obtain phospho-esterified propylene glycol alginate;
(b) Preparing phosphoesterified chitosan, namely carrying out solid-phase esterification reaction on micromolecular chitosan with the molecular weight of 3000-5000 and mixed phosphate to obtain phosphoesterified chitosan;
(c) And (3) preparing a modified alginate composition for skin repair, namely adding the phosphoesterified propylene glycol alginate prepared in the step (a) and the phosphoesterified chitosan prepared in the step (b) into deionized water, heating and stirring to obtain the modified alginate composition for skin repair.
Preferably, a modified alginate composition of the invention for use in skin repair is prepared by the steps of:
(a) Preparation of phosphoesterified propylene glycol alginate with specific molecular weight, wherein after the alginic acid with specific molecular weight is esterified under the condition of epoxypropane, the product is subjected to phosphoesterification treatment:
(1) Cleaning kelp with clear water, irradiating under ultraviolet lamp for 12-24 hr, adding soda ash 3-5% of kelp by mass, mixing, decocting with microwave, and filtering to obtain filtrate with molecular weight of 3000-5000;
(2) Adding dilute hydrochloric acid into the filtrate under a slow stirring state to adjust the pH to 3-4, so as to obtain flocculent alginic acid;
(3) Dehydrating the flocculent alginic acid prepared in the step (2) in a centrifuge to obtain alginic acid 1 with the moisture content of 50% -60%, soaking the alginic acid 1 in ethanol solution with the concentration of 50% -75% for 5min-10min, centrifuging again to remove the ethanol solution, and putting the obtained alginic acid 2 with the moisture content of 30% -45% into a reaction kettle;
(4) Adding sodium pyrophosphate and sodium polyphosphate mixed powder with the mass fraction of 1-3% of alginic acid 2 into a reaction kettle, injecting propylene oxide into the reaction kettle in a vacuum environment, sealing the reaction kettle, stirring for 2-3 h, and centrifugally dehydrating the obtained product to obtain propylene glycol alginate;
(5) Mixing propylene glycol alginate prepared in the step (4) with mixed phosphate and aminomethylphosphonic acid according to the ratio of 1:0.01-0.03: adding 0.02-0.05 mass percent into a solid phase esterifier, adding Zn (CH 3 COO) 2 accounting for 1-2 percent of the total weight as a catalyst, heating to perform solid phase neutralization for 1-2 hours, and obtaining phosphoesterified propylene glycol alginate;
(b) Preparing phosphoesterified chitosan, namely carrying out solid-phase esterification reaction on micromolecular chitosan with the molecular weight of 3000-5000 and mixed phosphate:
(6) Adding chitosan with molecular weight of 3000-5000 and mixed phosphate into a solid-phase esterifier according to mass ratio of 1:0.05-0.08, heating and solid-phase grinding to obtain powder A;
(7) Cooling the prepared powder A to room temperature, washing in 45% -60% ethanol solution, centrifuging, and drying to obtain phosphoesterified chitosan;
(c) Preparing a modified alginate composition for skin repair, namely adding the phosphoesterified propylene glycol alginate prepared in the step (a) and the phosphoesterified chitosan prepared in the step (b) into deionized water, heating and stirring:
(8) Adding 85-90% of deionized water and 5-8% of glycerol into an emulsifying pot, and stirring and mixing;
(9) Adding 3-5% of phosphoesterified propylene glycol alginate and 1-3% of phosphoesterified chitosan in a mass ratio under a stirring state to obtain a mixture 1;
(10) The prepared mixture 1 is heated and stirred, and cooled after being mixed completely, so as to obtain the modified alginate composition for skin repair.
Preferably, the filtration treatment in step (1) is performed using an ultrafiltration membrane apparatus.
Preferably, in the step (4), the vacuum degree is-0.07 MPa to-0.1 MPa, and alginic acid: the mass ratio of the epoxypropane is 1:1.5-2.5.
Preferably, the solid phase neutralization reaction temperature in the step (5) is 60-80 ℃.
Preferably, in the step (6), the solid-phase grinding reaction temperature is 80-90 ℃ and the reaction time is 2-3 h.
Preferably, the washing times in the step (7) are two times, and the drying process is that the washing is carried out for 1 to 2 hours at the temperature of between 95 and 105 ℃ in a blast drying box.
Preferably, the heating temperature in the step (10) is 70-80 ℃, and the temperature is kept and stirred for 0.5-1 h.
Preferably, the mixed phosphate in the step (5) and the step (6) is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1.
Use of a modified alginate composition of any one of the above for skin repair in the preparation of a cosmetic.
The present invention provides a modified alginate composition useful for skin repair. The beneficial effects are as follows:
(1) The modified alginate composition for skin repair is prepared through esterifying alginic acid with specific molecular weight under propylene oxide condition, phosphating the product to obtain phosphatized propylene glycol alginate, introducing phosphate group and amino group to alginic acid polysaccharide molecule to make polysaccharide molecule enter subcutaneous tissue via skin barrier, chelating calcium in aged cell wall with chelating capacity of phosphate to soften cell wall, repairing aged cell, making cell full of activity and smooth and fine skin.
(2) The modified alginate composition for skin repair has natural antibacterial property, but low water solubility, and can perform coagulation reaction with alginic acid, and the invention uses small molecular weight chitosan with molecular weight of 3000-5000 to perform solid-phase esterification reaction with mixed phosphate to obtain phosphoesterified chitosan, so that the water solubility of chitosan is obviously increased, and chitosan can coexist with alginic acid without coagulation reaction.
The modified alginate composition for skin repair has the advantages that all the components act synergistically, obvious repair effect is achieved on skin, cells are enabled to be full of vigor, the skin is smooth and fine, meanwhile, the modified alginate composition has natural antibacterial property, no preservative is needed, no irritation is caused, and the modified alginate composition is convenient to store.
Detailed Description
The invention will be further described with reference to specific embodiments, and advantages and features of the invention will become apparent from the description. These examples are merely exemplary and do not limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes and substitutions of details and forms of the technical solution of the present invention may be made without departing from the spirit and scope of the present invention, but these changes and substitutions fall within the scope of the present invention.
Example 1
The preparation method of the modified alginate composition for skin repair specifically comprises the following steps:
(a) Preparation of phosphoesterified propylene glycol alginate of specific molecular weight:
(1) Cleaning herba Zosterae Marinae with clear water, irradiating under ultraviolet lamp for 12-24 hr, adding sodium carbonate 3% by mass of herba Zosterae Marinae into herba Zosterae Marinae, mixing, decocting with microwave, and filtering the decoction mixture with ultrafiltration membrane to obtain filtrate with molecular weight of 3000-5000;
(2) Adding dilute hydrochloric acid into the filtrate under a slow stirring state to adjust the pH to 3-4, so as to obtain flocculent alginic acid;
(3) Dehydrating the flocculent alginic acid prepared in the step (2) in a centrifuge to obtain alginic acid 1 with the moisture content of 50%, soaking the alginic acid 1 in ethanol solution with the concentration of 50% for 5min, centrifuging again to remove the ethanol solution, and putting the obtained alginic acid 2 with the moisture content of 30% -45% into a reaction kettle;
(4) Adding sodium pyrophosphate and sodium polyphosphate mixed powder with the mass fraction of 1-3% of alginic acid 2 into a reaction kettle, and injecting propylene oxide and alginic acid into the reaction kettle under the vacuum degree of-0.07 MPa: the mass ratio of the epoxypropane is 1:1.5, the reaction kettle is closed and stirred for 2-3 hours, and the obtained product is centrifugally dehydrated to obtain propylene glycol alginate;
(5) Adding the propylene glycol alginate prepared in the step (4), mixed phosphate and aminomethylphosphonic acid into a solid-phase esterifier according to the mass ratio of 1:0.01:0.02, and adding Zn (CH) accounting for 1% of the total weight 3 COO) 2 As a catalyst, carrying out solid phase neutralization for 1-2 h at the reaction temperature of 60 ℃ to obtain phosphoesterified propylene glycol alginate;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(b) Preparation of phosphoesterified chitosan:
(6) Adding chitosan with molecular weight of 3000-5000 and mixed phosphate into a solid-phase esterifier according to mass ratio of 1:0.05, reacting at 80 ℃, and performing solid-phase grinding reaction for 2h to obtain powder A;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(7) Cooling the prepared powder A to room temperature, washing twice in 45% ethanol solution, centrifugally dehydrating, and drying in a blast drying oven at 95 ℃ for 1h to obtain phosphoesterified chitosan;
(c) Preparation of modified alginate composition for skin repair:
(8) Adding 85% deionized water and 7% glycerol into an emulsifying pot, and stirring and mixing;
(9) Adding 5% of phosphoesterified propylene glycol alginate and 3% of phosphoesterified chitosan in mass ratio under stirring to obtain a mixture 1;
(10) Heating the prepared mixture 1 to 70 ℃, keeping the temperature and stirring for 0.5h, and cooling after the mixture is completely mixed to obtain the modified alginate composition for skin repair.
Example 2
The preparation method of the modified alginate composition for skin repair specifically comprises the following steps:
(a) Preparation of phosphoesterified propylene glycol alginate of specific molecular weight:
(1) Cleaning herba Zosterae Marinae with clear water, irradiating under ultraviolet lamp for 12-24 hr, adding sodium carbonate 3.5% by mass of herba Zosterae Marinae, mixing, decocting with microwave, and filtering the decoction mixture with ultrafiltration membrane to obtain filtrate with molecular weight of 3000-5000;
(2) Adding dilute hydrochloric acid into the filtrate under a slow stirring state to adjust the pH to 3-4, so as to obtain flocculent alginic acid;
(3) Dehydrating the flocculent alginic acid prepared in the step (2) in a centrifuge to obtain alginic acid 1 with the moisture content of 55%, soaking the alginic acid 1 in ethanol solution with the concentration of 55% for 6min, centrifuging again to remove the ethanol solution, and putting the obtained alginic acid 2 with the moisture content of 35% into a reaction kettle;
(4) Adding sodium pyrophosphate and sodium polyphosphate mixed powder with the mass fraction of 1-3% of alginic acid 2 into a reaction kettle, and injecting propylene oxide and alginic acid into the reaction kettle under the vacuum degree of-0.08 MPa: the mass ratio of the epoxypropane is 1:2, the reaction kettle is closed and stirred for 2-3 hours, and the obtained product is centrifugally dehydrated to obtain propylene glycol alginate;
(5) Mixing propylene glycol alginate prepared in the step (4) with mixed phosphate and aminomethylphosphonic acid according to the ratio of 1:0.02:0.03 mass ratio of Zn (CH) accounting for 1.5 percent of the total weight is added into a solid phase esterifier 3 COO) 2 As a catalyst, carrying out solid phase neutralization for 1.5 hours at the reaction temperature of 65 ℃ to obtain phosphoesterified propylene glycol alginate;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(b) Preparation of phosphoesterified chitosan:
(6) Adding chitosan with molecular weight of 3000-5000 and mixed phosphate into a solid-phase esterifier according to mass ratio of 1:0.06, reacting at 85 ℃, and performing solid-phase grinding reaction for 2.5h to obtain powder A;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(7) Cooling the prepared powder A to room temperature, washing twice in 50% ethanol solution, centrifugally dehydrating, and drying in a blast drying oven at 100 ℃ for 1.5 hours to obtain phosphoesterified chitosan;
(c) Preparation of modified alginate composition for skin repair:
(8) Adding 85% deionized water and 6% glycerin into an emulsifying pot, and stirring and mixing;
(9) Adding 5% of phosphoesterified propylene glycol alginate and 3% of phosphoesterified chitosan in mass ratio under stirring to obtain a mixture 1;
(10) The prepared mixture 1 is heated to 75 ℃, stirred for 0.5h under heat preservation, and cooled after being mixed completely, so as to obtain the modified alginate composition for skin repair.
Example 3
The preparation method of the modified alginate composition for skin repair specifically comprises the following steps:
(a) Preparation of phosphoesterified propylene glycol alginate of specific molecular weight:
(1) Cleaning herba Zosterae Marinae with clear water, irradiating under ultraviolet lamp for 12-24 hr, adding sodium carbonate with weight fraction of 4% into herba Zosterae Marinae, mixing, decocting with microwave, and filtering the decoction mixture with ultrafiltration membrane to obtain filtrate with molecular weight of 3000-5000;
(2) Adding dilute hydrochloric acid into the filtrate under a slow stirring state to adjust the pH to 3-4, so as to obtain flocculent alginic acid;
(3) Dehydrating the flocculent alginic acid prepared in the step (2) in a centrifuge to obtain alginic acid 1 with the water content of 60%, soaking the alginic acid 1 in 65% ethanol solution for 7min, centrifuging again to remove the ethanol solution, and putting the obtained alginic acid 2 with the water content of 40% into a reaction kettle;
(4) Adding sodium pyrophosphate and sodium polyphosphate mixed powder with the mass fraction of 1-3% of alginic acid 2 into a reaction kettle, and injecting propylene oxide and alginic acid into the reaction kettle under the vacuum degree of-0.09 MPa: the mass ratio of the epoxypropane is 1:2.5, the reaction kettle is closed and stirred for 2-3 hours, and the obtained product is centrifugally dehydrated to obtain propylene glycol alginate;
(5) Mixing propylene glycol alginate prepared in the step (4) with mixed phosphate and aminomethylphosphonic acid according to the ratio of 1:0.03:0.04 mass ratio of Zn (CH) accounting for 2 percent of the total weight is added into a solid phase esterifier 3 COO) 2 As a catalyst, carrying out solid phase neutralization for 1.5 hours at the reaction temperature of 70 ℃ to obtain phosphoesterified propylene glycol alginate;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(b) Preparation of phosphoesterified chitosan:
(6) Adding chitosan with molecular weight of 3000-5000 and mixed phosphate into a solid-phase esterifier according to mass ratio of 1:0.07, reacting at 90 ℃, and performing solid-phase grinding reaction for 3h to obtain powder A;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(7) Cooling the prepared powder A to room temperature, washing twice in 55% ethanol solution, centrifugally dehydrating, and drying in a blast drying oven at 103 ℃ for 1.5 hours to obtain phosphoesterified chitosan;
(c) Preparation of modified alginate composition for skin repair:
(8) Adding 88% of deionized water and 6% of glycerol into an emulsifying pot, and stirring and mixing;
(9) Adding 4% of phosphoesterified propylene glycol alginate and 2% of phosphoesterified chitosan in mass ratio under stirring to obtain a mixture 1;
(10) The prepared mixture 1 is heated to 80 ℃, stirred for 0.8h under heat preservation, and cooled after being mixed completely, thus obtaining the modified alginate composition for skin repair.
Example 4
The preparation method of the modified alginate composition for skin repair specifically comprises the following steps:
(a) Preparation of phosphoesterified propylene glycol alginate of specific molecular weight:
(1) Cleaning herba Zosterae Marinae with clear water, irradiating under ultraviolet lamp for 12-24 hr, adding sodium carbonate with weight fraction of 4.5% into herba Zosterae Marinae, mixing, decocting with microwave, and filtering the decoction mixture with ultrafiltration membrane to obtain filtrate with molecular weight of 3000-5000;
(2) Adding dilute hydrochloric acid into the filtrate under a slow stirring state to adjust the pH to 3-4, so as to obtain flocculent alginic acid;
(3) Dehydrating the flocculent alginic acid prepared in the step (2) in a centrifuge to obtain alginic acid 1 with the water content of 60%, soaking the alginic acid 1 in 70% ethanol solution for 8min, centrifuging again to remove the ethanol solution, and putting the obtained alginic acid 2 with the water content of 40% into a reaction kettle;
(4) Adding sodium pyrophosphate and sodium polyphosphate mixed powder with the mass fraction of 1-3% of alginic acid 2 into a reaction kettle, and injecting propylene oxide and alginic acid into the reaction kettle under the vacuum degree of-0.09 MPa: the mass ratio of the epoxypropane is 1:2.5, the reaction kettle is closed and stirred for 2-3 hours, and the obtained product is centrifugally dehydrated to obtain propylene glycol alginate;
(5) Mixing propylene glycol alginate prepared in the step (4) with mixed phosphate and aminomethylphosphonic acid according to the ratio of 1:0.02:0.05 mass ratio of Zn (CH) accounting for 2 percent of the total weight is added into a solid phase esterifier 3 COO) 2 As a catalyst, carrying out solid phase neutralization for 1.5 hours at the reaction temperature of 75 ℃ to obtain phosphoesterified propylene glycol alginate;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(b) Preparation of phosphoesterified chitosan:
(6) Adding chitosan with molecular weight of 3000-5000 and mixed phosphate into a solid-phase esterifier according to mass ratio of 1:0.08, reacting at 90 ℃, and performing solid-phase grinding reaction for 3h to obtain powder A;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(7) Cooling the prepared powder A to room temperature, washing twice in 60% ethanol solution, centrifugally dehydrating, and drying in a blast drying oven at 105 ℃ for 1.5 hours to obtain phosphoesterified chitosan;
(c) Preparation of modified alginate composition for skin repair:
(8) Adding 90% deionized water and 5% glycerol into an emulsifying pot, and stirring and mixing;
(9) Adding 4% of phosphoesterified propylene glycol alginate and 1% of phosphoesterified chitosan in mass ratio under stirring to obtain a mixture 1;
(10) The prepared mixture 1 is heated to 75 ℃, stirred for 1h under heat preservation, and cooled after being mixed completely, thus obtaining the modified alginate composition for skin repair.
Example 5
The preparation method of the modified alginate composition for skin repair specifically comprises the following steps:
(a) Preparation of phosphoesterified propylene glycol alginate of specific molecular weight:
(1) Cleaning herba Zosterae Marinae with clear water, irradiating under ultraviolet lamp for 12-24 hr, adding sodium carbonate with weight fraction of 5% into herba Zosterae Marinae, mixing, decocting with microwave, and filtering the decoction mixture with ultrafiltration membrane to obtain filtrate with molecular weight of 3000-5000;
(2) Adding dilute hydrochloric acid into the filtrate under a slow stirring state to adjust the pH to 3-4, so as to obtain flocculent alginic acid;
(3) Dehydrating the flocculent alginic acid prepared in the step (2) in a centrifuge to obtain alginic acid 1 with the water content of 60%, soaking the alginic acid 1 in ethanol solution with the concentration of 75% for 10min, centrifuging again to remove the ethanol solution, and putting the obtained alginic acid 2 with the water content of 45% into a reaction kettle;
(4) Adding sodium pyrophosphate and sodium polyphosphate mixed powder with the mass fraction of 1-3% of alginic acid 2 into a reaction kettle, and injecting propylene oxide and alginic acid into the reaction kettle under the vacuum degree of-0.10 MPa: the mass ratio of the epoxypropane is 1:2.5, the reaction kettle is closed and stirred for 2-3 hours, and the obtained product is centrifugally dehydrated to obtain propylene glycol alginate;
(5) Mixing propylene glycol alginate prepared in the step (4) with mixed phosphate and aminomethylphosphonic acid according to the ratio of 1:0.03:0.05 mass ratio of Zn (CH) accounting for 2 percent of the total weight is added into a solid phase esterifier 3 COO) 2 As a catalyst, carrying out solid phase neutralization for 2 hours at the reaction temperature of 80 ℃ to obtain phosphoesterified propylene glycol alginate;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(b) Preparation of phosphoesterified chitosan:
(6) Adding chitosan with molecular weight of 3000-5000 and mixed phosphate into a solid-phase esterifier according to mass ratio of 1:0.08, reacting at 90 ℃, and performing solid-phase grinding reaction for 2.5h to obtain powder A;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(7) Cooling the prepared powder A to room temperature, washing twice in 60% ethanol solution, centrifugally dehydrating, and drying in a blast drying oven at 105 ℃ for 2 hours to obtain phosphoesterified chitosan;
(c) Preparation of modified alginate composition for skin repair:
(8) Adding 87% deionized water and 5% glycerol into an emulsifying pot, and stirring and mixing;
(9) Adding 5% of phosphoesterified propylene glycol alginate and 3% of phosphoesterified chitosan in mass ratio under stirring to obtain a mixture 1;
(10) The prepared mixture 1 is heated to 80 ℃, stirred for 1h under heat preservation, and cooled after being mixed completely, thus obtaining the modified alginate composition for skin repair.
Comparative example 1
The preparation method of comparative example 1 was the same as the general preparation method of example 1, except that: the molecular weight of chitosan added into the modified alginate composition for skin repair is 3000-5000.
The preparation method of the skin repair composition specifically comprises the following steps:
(a) Preparation of phosphoesterified propylene glycol alginate of specific molecular weight:
(1) Cleaning herba Zosterae Marinae with clear water, irradiating under ultraviolet lamp for 12-24 hr, adding sodium carbonate 3% by mass of herba Zosterae Marinae into herba Zosterae Marinae, mixing, decocting with microwave, and filtering the decoction mixture with ultrafiltration membrane to obtain filtrate with molecular weight of 3000-5000;
(2) Adding dilute hydrochloric acid into the filtrate under a slow stirring state to adjust the pH to 3-4, so as to obtain flocculent alginic acid;
(3) Dehydrating the flocculent alginic acid prepared in the step (2) in a centrifuge to obtain alginic acid 1 with the moisture content of 50%, soaking the alginic acid 1 in ethanol solution with the concentration of 50% for 5min, centrifuging again to remove the ethanol solution, and putting the obtained alginic acid 2 with the moisture content of 30% -45% into a reaction kettle;
(4) Adding sodium pyrophosphate and sodium polyphosphate mixed powder with the mass fraction of 1-3% of alginic acid 2 into a reaction kettle, and injecting propylene oxide and alginic acid into the reaction kettle under the vacuum degree of-0.07 MPa: the mass ratio of the epoxypropane is 1:1.5, the reaction kettle is closed and stirred for 2-3 hours, and the obtained product is centrifugally dehydrated to obtain propylene glycol alginate;
(5) Mixing the propylene glycol alginate prepared in the step (4) with mixed phosphate and aminomethylphosphonic acid according to the following steps1:0.01:0.02 mass ratio was added to a solid phase esterifier, and Zn (CH) was added in an amount of 1% by total weight 3 COO) 2 As a catalyst, carrying out solid phase neutralization for 1-2 h at the reaction temperature of 60 ℃ to obtain phosphoesterified propylene glycol alginate;
the mixed phosphate is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1;
(c) Preparation of modified alginate composition for skin repair:
(6) Adding 85% deionized water and 7% glycerol into an emulsifying pot, and stirring and mixing;
(7) Adding 5% of phosphoesterified propylene glycol alginate by mass and 3% of chitosan with molecular weight of 3000-5000 by mass under stirring to obtain a mixture 1;
(8) Heating the obtained mixture 1 to 70deg.C, maintaining the temperature, stirring for 0.5 hr, mixing completely, and cooling to obtain composition for skin repair.
The performance of the modified alginate composition for skin repair prepared according to the present invention is tested and analyzed as follows.
Test example 1 skin Performance test
Test object: selecting 60 healthy skin disease-free female volunteers 25-50 years old, randomly dividing the healthy skin disease-free female volunteers into 10 groups of 6 persons each, and using the modified alginate composition for skin repair of the embodiment 1-5 of the invention, and using a certain brand of domestic moisturizing water as a positive control group for a random double-blind control test;
the testing method comprises the following steps: the specific method is that the skin of the symmetrical part of the same volunteer is taken for external use, the composition of the embodiment 1-5 and the moisturizing water of the control group are used for 4 weeks in a random double-blind way, and the usage amount is 0.3-0.5mL each time in the morning and evening; skin test is carried out on volunteers before using products, files are established, and the files are recorded as basic values; tracking the test once every 14 days after the start of the experiment;
test equipment: the degree of transepidermal water loss (TEWL) was measured using a tewatter (tm) 210 skin tester from CK corporation, germany, and the hydration degree of the stratum corneum was measured using a MC760 multifunctional skin tester from CK corporation, germany, and the skin elasticity was measured using a skin elasticity tester MPA580 from CK corporation, germany, and the measurement results were averaged.
The test results were as follows:
TABLE 1 results of the test for the degree of transepidermal Water loss of skin and the degree of hydration of the stratum corneum of the skin of examples 1 to 5 and the control group
The TewameterTM210 skin tester, from CK, germany, is one of the usual skin noninvasive test instruments that are commonly used for skin barrier function related detection and assessment, produced based on Fick's diffusion law. Assessing the moisture content lost per unit time of the skin, which is an important parameter of barrier function, the higher the value, the worse the barrier function; conversely, the lower the number, the better the barrier function.
The MC760 skin tester of the German CK company is an instrument for measuring the moisture content of the skin stratum corneum, which is developed based on the principle of capacitance, and is also one of important parameters for evaluating the skin barrier function. The higher the test value, the more water content in the stratum corneum; conversely, a lower value indicates a lower moisture content. The greater the change in skin moisture, the better the improvement in skin barrier function.
The test results in Table 1 show that the reduction in the percutaneous water loss is more pronounced in examples 1-5, the change in the water content of the stratum corneum is greater, the skin barrier moisturizing effect is significantly restored, and the effect is significantly better than that of the control group.
TABLE 2 skin elasticity test results for examples 1-5 and control group
The MPA580 skin elasticity tester of the Germany CK company is based on the suction and stretching principle, a Revisclometer RV600 probe is matched, then the elasticity performance of the skin is determined through MPA software analysis, and the higher the test value is, the stronger the skin elasticity performance is; conversely, a lower value indicates poorer elastic properties.
The test results in Table 2 show that, compared with the control group, the examples 1-5 have more obvious effect of improving the skin elasticity, the variation range of the elasticity is larger, the skin cell repairing and improving functions are obvious, and the effect is obviously better than that of the control group.
Test example 2 use experience assessment
According to the trial conditions of each volunteer on the products corresponding to the examples 1-5 and the control group, the using experience evaluation of the using experience and the irritation index is carried out, the using experience is scored (10 minutes, 10 minutes in full), the result is averaged, and the summarized using experience effect is shown in the table 3:
TABLE 3 evaluation of Using Effect of examples 1-5 and control
The results in Table 3 show that the compositions of examples 1-5, however, are non-irritating to the skin, have a moisturizing and quick-absorbing use feel, significantly improve skin elasticity, increase skin smoothness and brightness, and provide a higher degree of subject satisfaction compared to the control.
Test example 3 preservative test
The experiment refers to a preservative system efficacy evaluation method recommended by American cosmetics, toiletries and essence Association (CTFA), and adopts a classical 28-day preservative single challenge experiment recommended by CTFA;
challenge microorganisms: bacteria and mold;
the testing method comprises the following steps: the compositions of examples 1-5 and comparative example 1 were tested. The experiment followed the CTFA challenge experiment requirement, all samples were inoculated first, 24h sampling, once a week for 4 consecutive times, at the beginning of the study, with a test period of 28 days. At 4 weeks after the initial challenge, the samples were again subjected to challenge testing, following the same sample testing method, with test results shown in table 4.
Table 4 corrosion resistance test results
Note that: in the table, "/indicates too many bacteria and not counted.
The data in Table 4 shows that the modified alginate compositions for skin repair provided in examples 1-5 of the present invention have excellent inhibitory effect on bacteria and mold, whereas the composition of comparative example 1 is free of any antibacterial effect due to the fact that the phosphoesterified chitosan of examples 1-5 is not added, the bacteria grow rapidly.
In summary, according to the modified alginate composition for skin repair, the phosphoesterified propylene glycol alginate introduces phosphate groups and amino groups on the polysaccharide alginate molecules, so that the polysaccharide molecules can enter subcutaneous tissues through skin barriers more easily, and the calcium combined in aged cell walls is chelated to soften the cell walls. The phosphoesterified chitosan obviously increases the water solubility of the chitosan, can coexist with modified alginic acid, has obvious repairing effect on skin by the synergistic effect of the phosphoesterified chitosan and the modified alginic acid, enables cells to be full of vitality, and has the advantages of smoothness and fineness of skin, natural antibacterial property, no need of preservative, no irritation and convenient preservation.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (10)
1. A modified alginate composition useful for skin repair, the preparation steps comprising:
(a) Preparation of phosphoesterified propylene glycol alginate with specific molecular weight, wherein after the alginic acid with specific molecular weight is esterified under the condition of epoxypropane, the product is subjected to phosphoesterification treatment:
(1) Cleaning kelp with clear water, irradiating under ultraviolet lamp for 12-24 hr, adding soda ash 3-5% of kelp by mass, mixing, decocting with microwave, and filtering to obtain filtrate with molecular weight of 3000-5000;
(2) Adding dilute hydrochloric acid into the filtrate under a slow stirring state to adjust the pH to 3-4, so as to obtain flocculent alginic acid;
(3) Dehydrating the flocculent alginic acid prepared in the step (2) in a centrifuge to obtain alginic acid 1 with the moisture content of 50% -60%, soaking the alginic acid 1 in ethanol solution with the concentration of 50% -75% for 5min-10min, centrifuging again to remove the ethanol solution, and putting the obtained alginic acid 2 with the moisture content of 30% -45% into a reaction kettle;
(4) Adding sodium pyrophosphate and sodium polyphosphate mixed powder with the mass fraction of 1-3% of alginic acid 2 into a reaction kettle, injecting propylene oxide into the reaction kettle in a vacuum environment, sealing the reaction kettle, stirring for 2-3 h, and centrifugally dehydrating the obtained product to obtain propylene glycol alginate;
(5) Mixing propylene glycol alginate prepared in the step (4) with mixed phosphate and aminomethylphosphonic acid according to the ratio of 1:0.01-0.03:0.02 to 0.05 mass percent of Zn (CH) accounting for 1 to 2 percent of the total weight is added into a solid phase esterifier 3 COO) 2 As a catalyst, heating to perform solid phase neutralization for 1-2 h to obtain phosphoesterified propylene glycol alginate;
(b) Preparing phosphoesterified chitosan, namely carrying out solid-phase esterification reaction on micromolecular chitosan with the molecular weight of 3000-5000 and mixed phosphate:
(6) Adding chitosan with molecular weight of 3000-5000 and mixed phosphate into a solid-phase esterifier according to mass ratio of 1:0.05-0.08, heating and solid-phase grinding to obtain powder A;
(7) Cooling the prepared powder A to room temperature, washing in 45% -60% ethanol solution, centrifuging, and drying to obtain phosphoesterified chitosan;
(c) Preparation of modified alginate composition for skin repair: adding the phospho-esterified propylene glycol alginate prepared in the step (a) and the phospho-esterified chitosan prepared in the step (b) into deionized water, heating and stirring to obtain the modified alginate composition for skin repair.
2. A modified alginate composition for use in skin repair according to claim 1 wherein step (c) comprises:
(c) Preparing a modified alginate composition for skin repair, namely adding the phosphoesterified propylene glycol alginate prepared in the step (a) and the phosphoesterified chitosan prepared in the step (b) into deionized water, heating and stirring:
(8) Adding 85-90% of deionized water and 5-8% of glycerol into an emulsifying pot, and stirring and mixing;
(9) Adding 3-5% of phosphoesterified propylene glycol alginate and 1-3% of phosphoesterified chitosan in mass ratio under stirring to obtain a mixture 1;
(10) The prepared mixture 1 is heated and stirred, and cooled after being mixed completely, so as to obtain the modified alginate composition for skin repair.
3. A modified alginate composition for use in skin repair according to claim 1 wherein said filtration treatment in step (1) is carried out using ultrafiltration membrane apparatus.
4. The modified alginate composition for skin repair according to claim 1, wherein the vacuum degree in the step (4) is from-0.07 MPa to-0.1 MPa, alginic acid: the mass ratio of the propylene oxide to the mixture is 1:1.5-2.5.
5. A modified alginate composition for use in skin repair according to claim 1 wherein the solid phase neutralisation reaction temperature in step (5) is from 60 ℃ to 80 ℃.
6. A modified alginate composition for use in skin repair according to claim 1 wherein the solid phase milling reaction temperature in step (6) is from 80 ℃ to 90 ℃ and the reaction time is from 2 hours to 3 hours.
7. The modified alginate composition for skin repair according to claim 1, wherein the number of washing in step (7) is two, and the drying process is drying in a forced air drying oven at 95 ℃ to 105 ℃ for 1h to 2h.
8. A modified alginate composition for skin repair according to claim 2 wherein step (10) is heated to a temperature of from 70 ℃ to 80 ℃ and stirred for a period of from 0.5h to 1h.
9. The modified alginate composition for skin repair according to claim 1, wherein the mixed phosphate in step (5) and step (6) is a mixture of sodium pyrophosphate, disodium dihydrogen pyrophosphate and disodium hydrogen phosphate in a mass ratio of 1:0.5:1.
10. Use of a modified alginate composition according to any one of claims 1 to 9 for the preparation of a cosmetic product.
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