CN113244130A - Ultra-strong oxidation-resistant deformable vesicle and preparation method and application thereof - Google Patents

Ultra-strong oxidation-resistant deformable vesicle and preparation method and application thereof Download PDF

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CN113244130A
CN113244130A CN202110482570.9A CN202110482570A CN113244130A CN 113244130 A CN113244130 A CN 113244130A CN 202110482570 A CN202110482570 A CN 202110482570A CN 113244130 A CN113244130 A CN 113244130A
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vesicle
antioxidant
deformation
ethyl bis
imino methyl
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夏强
安冬
欧雪莲
黄一鸣
邓笑颖
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SUZHOU NANOHEALTH BIOTECH CO Ltd
Bloomage Biotech Co Ltd
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SUZHOU NANOHEALTH BIOTECH CO Ltd
Bloomage Biotech Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0291Micelles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60Sugars; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/06Preparations for care of the skin for countering cellulitis
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52Stabilizers
    • A61K2800/522Antioxidants; Radical scavengers

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Abstract

The invention discloses a preparation method of a super-strong antioxidant deformation vesicle, which comprises ethyl bis-imino methyl guaiacol manganese chloride, sucrose laurate, glycerol, PPG-13-decyl tetradecyl alcohol polyether-24 and butanediol in a mass ratio of 3-4: 2-10: 8-15: 10-18: 50-80. The ultra-strong antioxidant deformation vesicle prepared by the invention has the beneficial effects of high active ingredient content, good transdermal absorbability, good stability, low irritation and remarkable antioxidant effect, the preparation method is simple and controllable, the repeatability is good, and the ultra-strong antioxidant deformation vesicle can be directly applied to cosmetics with antioxidant effects of various dosage forms.

Description

Ultra-strong oxidation-resistant deformable vesicle and preparation method and application thereof
Technical Field
The invention relates to the technical field of cosmetics, in particular to a super-strong antioxidant deformation vesicle and a preparation method and application thereof.
Background
With the increase of time, oxidation is the biggest threat of skin aging, factors such as sun, pressure, environmental pollution promote skin cells to accelerate oxidation, and then oxidative stress states such as lipid peroxidation, amino acid and protein denaturation, glycosylation and endogenous DNA damage are generated, skin is damaged, and aging signs are shown, so that the demand of antioxidant products is vigorous, and the market potential is huge.
The ethyl bis-imino methyl guaiacol manganese chloride is a synthetic superoxide dismutase (SOD)/catalase analog, can be used for disproportionating superoxide radicals and eliminating hydrogen peroxide, has strong antioxidant activity, plays a role in catalysis in the process, does not consume the ethyl bis-imino methyl guaiacol manganese chloride, can be repeatedly utilized, and can play a role after being added in a small amount. In vitro research experiments, the manganese ethyl bis (imino methyl guaiacol) chloride shows strong catalase and superoxide dismutase activity, and can protect human fibroblasts from cytotoxicity caused by glucose and glucose oxidase; can prevent A beta-induced microglia cell proliferation in vitro; in SK-N-MC cells, oxidative stress is attenuated by inhibiting MAPK channels, neuronal cells are protected from H2O2 toxicity, expression of pro-apoptotic genes p53 and Bax is reduced, and expression of anti-apoptotic Bcl-2 genes is enhanced. In the aspect of human body efficacy evaluation, the manganese ethyl bis (imino methyl guaiacol) chloride is proved by a large amount of experimental data that the excellent antioxidant effect can be achieved by the lower addition amount of the manganese ethyl bis (imino methyl guaiacol) chloride, and the manganese ethyl bis (imino methyl guaiacol) chloride also has remarkable effects in the aspects of antioxidation, anti-inflammation, reduction of photoaging, protection of skin and DNA thereof from ultraviolet ray damage and the like, and is mild and non-irritant.
However, the manganese ethyl bis imino methyl guaiacol chloride has certain problems in the practical application process, including that the manganese ethyl bis imino methyl guaiacol chloride is not very stable in aqueous solution, is easy to decompose, influences the use effect, cannot be used with an acidic substance at the same time, is easy to oxidize and decompose, and limits the wide application of the manganese ethyl bis imino methyl guaiacol chloride. Therefore, how to solve the problems of application stability, convenience in use and excellent efficacy is a problem to be solved urgently.
Vesicles (vesicles) are a form of ordered assemblies of amphiphilic molecules, which are spherical or ellipsoidal structures of single or multiple cells formed by closed bilayers. On one hand, the vesicle has excellent elasticity/deformability, can deform and penetrate through the stratum corneum of the skin and be scientifically positioned in the deep layer of the epidermis, has higher skin penetrating efficiency than a liposome, can increase the absorption of percutaneous active substances and maximize the efficacy of active ingredients; on the other hand, the vesicle has excellent stability, does not contain phospholipid, avoids the oxidative degradation of the phospholipid and is easy to store; in addition, the vesicles also have good biocompatibility and are highly tolerated in cosmetic systems. Therefore, in order to further strengthen and improve the efficacy of the active ingredients and improve the stability and the use convenience of the product, the product treated by the vesicle carrier technology has wide market prospect and application value.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the ultra-strong oxidation-resistant deformed vesicle and the preparation method and the application thereof, the ethyl bis-imino methyl guaiacol manganese chloride is wrapped in the deformed vesicle, and the obtained ultra-strong oxidation-resistant deformed vesicle has the advantages of good transdermal absorbability, good stability and excellent oxidation resistance.
In order to achieve the purpose, the invention provides the following technical scheme: a super-strong antioxidant deforming vesicle comprises the following components of ethyl bis-imino methyl guaiacol manganese chloride, sucrose laurate and PPG-13-decyl tetradecanol polyether-24.
Preferably, glycerin and butylene glycol are also included.
Preferably, the mass ratio of the manganese ethylbisiminomethylguaiacol chloride to the sucrose laurate to the glycerin to the PPG-13-decyltetradecanol polyether-24 to the butanediol is 3-4: 2-10: 8-15: 10-18: 50-80.
Preferably, the mass ratio of the manganese ethylbisiminomethylguaiacol chloride, the sucrose laurate, the glycerin, the PPG-13-decyltetradecanolpolyether-24 and the butanediol is 2:1-8:9-13:12-15: 56-70.
A preparation method of a super-strong antioxidant deformation vesicle comprises the following steps:
1) weighing ethyl bis-imino methyl guaiacol manganese chloride, sucrose laurate, glycerol, PPG-13-decyltetradecyl alcohol polyether-24 and butanediol according to the mass ratio of 3-4: 2-10: 8-15: 10-18: 50-80;
2) heating the ethyl bis-imino methyl guaiacol manganese chloride, PPG-13-decyl tetradecyl alcohol polyether-24 and butanediol weighed in the step 1) to 55-75 ℃, and mixing and stirring at the rotating speed of 500-1000RPM to obtain a solution A;
3) stirring the sucrose laurate and the glycerol weighed in the step 1) at normal temperature until the sucrose laurate and the glycerol are transparent to obtain a solution B;
4) adding the solution A obtained in the step 2) into the solution B obtained in the step 3), uniformly mixing, and then heating to 55-75 ℃ to obtain a premixed solution;
5) circularly homogenizing the premixed solution obtained in the step 4) for many times through a high-pressure homogenizer, and filtering the homogenized liquid through a filter to prepare the ultra-strong oxidation-resistant deformable vesicle.
Preferably, in the step 2), the heating temperature is 60-65 ℃; in step 4), the heating temperature is 60-65 ℃.
Preferably, in step 5), the premixed solution obtained in step 4) is cyclically homogenized by a high-pressure homogenizer at a temperature of 60-65 ℃ and a pressure of 80-120 MPa.
The application of the ultra-strong antioxidant deformation vesicle in cosmetics is that the ultra-strong antioxidant deformation vesicle is added into the cosmetics as an antioxidant active substance and is used for anti-inflammation, antioxidation and anti-aging.
Application of the ultra-strong antioxidant deformation vesicle in preparation of toning lotion, essence, cream, emulsion, sun-screening agent and facial mask
Preferably, the weight percentage of the ultra-strong antioxidant deformation vesicle in the cosmetic is 0.5% -25%.
In conclusion, the invention has the following beneficial effects:
1. the ethyl bis-imino methyl guaiacol manganese chloride is wrapped in the deformed vesicle, so that the stability and the solubility of the deformed vesicle can be obviously improved, and the ethyl bis-imino methyl guaiacol manganese chloride can better exert the antioxidant effect;
2. the ultrastrong antioxidant deformation vesicle prepared by the invention has good elasticity/deformability, can extrude pores of stratum corneum, can effectively permeate skin, has high bioavailability, and can fully exert antioxidant effect;
3. the ultra-strong antioxidant deformation vesicle prepared by the invention has safe and mild raw material components, and can be directly applied to cosmetics with antioxidant effects in various dosage forms such as water, essence, emulsion, cream, facial mask and the like simply and conveniently.
Drawings
FIG. 1 is a transmission electron microscope image of the ultrastrong antioxidant deformation vesicle prepared by the invention.
Detailed Description
The invention is further described with reference to the accompanying drawings.
The embodiment discloses a super-strong antioxidant deformation vesicle, which comprises the following components, 1) ethyl bis-imino methyl guaiacol manganese chloride; 2) sucrose laurate; 3) PPG-13-decyltetradecanol polyether-24. Further, glycerin and butylene glycol are included.
In the technical scheme, preferably, the mass ratio of the ethyl diiminomethyl guaiacol manganese chloride to the sucrose laurate to the glycerol to the PPG-13-decyltetradecyl alcohol polyether-24 to the butanediol is 34: 2-10: 8-15: 10-18: 50-80. Further, the mass ratio of the ethyl bis imino methyl guaiacol manganese chloride to the sucrose laurate to the glycerin to the PPG-13-decyltetradecanol polyether-24 to the butanediol is 2:1-8:9-13:12-15: 56-70.
A preparation method of a super-strong antioxidant deformation vesicle comprises the following steps:
1) weighing ethyl bis-imino methyl guaiacol manganese chloride, sucrose laurate, glycerol, PPG-13-decyltetradecyl alcohol polyether-24 and butanediol according to the mass ratio of 3-4: 2-10: 8-15: 10-18: 50-80; preferably, the mass ratio of the manganese ethylbisiminomethylguaiacol chloride to the sucrose laurate to the glycerin to the PPG-13-decyltetradecanolpolyether-24 to the butanediol is 2:1 to 8:9 to 13:12 to 15:56 to 70.
2) Heating the ethyl bis-imino methyl guaiacol manganese chloride, PPG-13-decyltetradecanol polyether-24 and butanediol weighed in the step 1) to 55-75 ℃, and mixing and stirring for 20-40 mins under the condition of 500-1000RPM (revolution per minute) for complete dissolution to obtain a solution A; preferably, the heating temperature is 60-65 ℃;
3) stirring the sucrose laurate and the glycerol weighed in the step 1) at normal temperature for 35-55 mins until the mixture is transparent, so as to obtain a solution B;
4) adding the solution A obtained in the step 2) into the solution B obtained in the step 3), uniformly mixing, and then heating to 55-75 ℃ to obtain a premixed solution; preferably, the heating temperature is 60-65 ℃;
5) circularly homogenizing the premixed solution obtained in the step 4) for 3-6 times by a high-pressure homogenizer at 60-65 ℃ under the pressure of 80-120MPa, filtering the homogenized liquid by a stainless steel filter with the aperture of 0.2 mu m to prepare the super-strong oxidation-resistant deformed vesicle, wherein the particle size of the obtained super-strong oxidation-resistant deformed vesicle is uniform, the average particle size of the vesicle is 10-200nm, the transmission electron microscope picture is shown as figure 1, the vesicle is larger than 200nm, the vesicle is unstable, and the vesicle tends to self-fuse to cause product layering; generally vesicles are smaller and better.
When the sucrose laurate and the PPG-13-decyltetradecanol polyether-24 are compounded according to a certain proportion and dissolved in a glycerol-butanediol mixed solvent, a stable nano vesicle structure can be formed after high-pressure homogenization, and the nano vesicle structure has the capacity of solubilizing and wrapping the manganese chloride of the ethyl bis-imino methyl guaiacol. The two emulsifiers form a stable vesicle interface mutually, the sucrose glyceride is inserted into the surface of macromolecules like a wedge, the vesicle structure is stable and the elasticity is good, and the sucrose glyceride can pass through the stratum corneum through intercellular pathways, so that the antioxidant effect is better exerted.
The manganese chloride of ethyl bis-imino methyl guaiacol of the invention, with the serial number of 07715 in catalog of names of used cosmetic raw materials (2015 edition) in China, is a synthetic superoxide dismutase (SOD)/catalase analog with strong antioxidant activity. However, the manganese ethylbisiminomethylguaiacol chloride has the problems of instability of an aqueous solution and poor solubility per se while having a remarkable efficacy, and thus improvement of the stability and the solubility thereof is a problem to be solved in application.
The glycerin has the serial number of 02421 in the directory of names of used cosmetic raw materials (2015 edition) in China and the serial number of 01946 in the directory of names of used cosmetic raw materials (2015 edition) in China, and is common moisture-retaining components of cosmetics and plays a role of a solvent in the invention.
The sucrose laurate of the invention has the serial number of 08562 in catalog (2015 edition) of used cosmetic raw materials in China, the HLB value of 15 and the molecular weight of 524.6, and belongs to a small molecular surfactant. The PPG-13-decyl tetradecanol polyether-24 has the serial number of 00848 in the catalogue of names of used cosmetic raw materials (2015 edition) in China, has the HLB value of 8, has the molecular weight of more than 1 ten thousand, and belongs to a macromolecular surfactant.
The application of the ultra-strong antioxidant deformation vesicle in cosmetics is that the ultra-strong antioxidant deformation vesicle is added into the cosmetics as an antioxidant active substance and is used for anti-inflammation, antioxidation and anti-aging.
The ultrastrong antioxidant deformation vesicle is used for preparing toning lotion, essence, cream, emulsion, sun-screening agent and facial mask. Wherein the weight percentage of the super-strong antioxidant deformation vesicle in the cosmetic is 0.5-25%.
Example 1: the preparation method of the super-strong antioxidant deformation vesicle comprises the following steps:
a: weighing ethyl bis-imino methyl guaiacol manganese chloride, sucrose laurate, glycerol, PPG-13-decyl tetradecanol polyether-24 and butanediol according to the mass ratio of 2:1:9:12: 70;
b: heating the ethyl bis-imino methyl guaiacol manganese chloride, PPG-13-decyl tetradecanol polyether-24 and butanediol weighed in the step A to 60 ℃, and mixing and stirring the materials under the condition of 500RPM (revolution per minute) until the materials are completely dissolved;
c: b, stirring the sucrose laurate and the glycerol weighed in the step A at normal temperature until the sucrose laurate and the glycerol are transparent for later use;
d: b, adding the ethyl bis-imino methyl guaiacol manganese chloride solution obtained in the step B into the mixture obtained in the step C, uniformly mixing, and then heating to 63 ℃ to obtain a premixed solution;
e: and D, circularly homogenizing the premixed solution obtained in the step D for 6 times by a high-pressure homogenizer at 63 ℃ under the pressure of 80MPa, and filtering the homogenized liquid by a stainless steel filter with the aperture of 0.2 mu m to prepare the super-strong oxidation-resistant deformed vesicle, wherein the average particle size of the vesicle is 50 nm.
Example 2: the preparation method of the super-strong antioxidant deformation vesicle comprises the following steps:
a: weighing ethyl bis-imino methyl guaiacol manganese chloride, sucrose laurate, glycerol, PPG-13-decyl tetradecanol polyether-24 and butanediol according to the mass ratio of 2:3:13:15: 56;
b: heating the ethyl bis-imino methyl guaiacol manganese chloride, PPG-13-decyl tetradecanol polyether-24 and butanediol weighed in the step A to 65 ℃, and mixing and stirring the materials under the condition of 1000RPM (revolution per minute) until the materials are completely dissolved;
c: b, stirring the sucrose laurate and the glycerol weighed in the step A at normal temperature until the sucrose laurate and the glycerol are transparent for later use;
d: b, adding the manganese ethyl bis (imino methyl guaiacol) chloride solution obtained in the step B into the mixture obtained in the step C, uniformly mixing, and then heating to 62 ℃ to obtain a premixed solution;
e: and D, circularly homogenizing the premixed solution obtained in the step D for 3 times by a high-pressure homogenizer at 62 ℃ under the pressure of 120MPa, and filtering the homogenized liquid by a stainless steel filter with the aperture of 0.2 mu m to prepare the ultra-strong oxidation-resistant deformed vesicle, wherein the average particle size of the vesicle is 105 nm.
Example 3: the preparation method of the super-strong antioxidant deformation vesicle comprises the following steps:
a: weighing ethyl bis-imino methyl guaiacol manganese chloride, sucrose laurate, glycerol, PPG-13-decyl tetradecanol polyether-24 and butanediol according to the mass ratio of 2:8:9:13: 57;
b: heating the ethyl bis-imino methyl guaiacol manganese chloride, PPG-13-decyl tetradecanol polyether-24 and butanediol weighed in the step A to 65 ℃, and mixing and stirring the materials under the condition of 800RPM (revolution per minute) until the materials are completely dissolved;
c: b, stirring the sucrose laurate and the glycerol weighed in the step A at normal temperature until the sucrose laurate and the glycerol are transparent for later use;
d: b, adding the ethyl bis-imino methyl guaiacol manganese chloride solution obtained in the step B into the mixture obtained in the step C, uniformly mixing, and then heating to 60 ℃ to obtain a premixed solution;
e: and D, circularly homogenizing the premixed solution obtained in the step D for 5 times by a high-pressure homogenizer at the temperature of 60 ℃ and under the pressure of 100Mpa, and filtering the homogenized liquid by a stainless steel filter with the aperture of 0.2 mu m to prepare the super-strong oxidation-resistant deformed vesicle, wherein the average particle size of the vesicle is 200 nm.
Example 4: a preparation method of a super-strong antioxidant deformation vesicle comprises the following steps:
a: weighing ethyl bis-imino methyl guaiacol manganese chloride, sucrose laurate, glycerol, PPG-13-decyl tetradecanol polyether-24 and butanediol according to the mass ratio of 2:7:9:12: 67;
b: heating the ethyl bis-imino methyl guaiacol manganese chloride, PPG-13-decyl tetradecanol polyether-24 and butanediol weighed in the step A to 60 ℃, and mixing and stirring the materials under the condition of 900RPM (revolution per minute) until the materials are completely dissolved;
c: b, stirring the sucrose laurate and the glycerol weighed in the step A at normal temperature until the sucrose laurate and the glycerol are transparent for later use;
d: b, adding the manganese ethyl bis (imino methyl guaiacol) chloride solution obtained in the step B into the mixture obtained in the step C, uniformly mixing, and then heating to 65 ℃ to obtain a premixed solution;
e: and D, circularly homogenizing the premixed solution obtained in the step D for 4 times by a high-pressure homogenizer at 65 ℃ and under the pressure of 110Mpa, and filtering the homogenized liquid by a stainless steel filter with the aperture of 0.2 mu m to prepare the super-strong oxidation-resistant deformed vesicle, wherein the average particle size of the vesicle is 10 nm.
To demonstrate the advantageous effects of the present invention, the following experiment was further performed.
The following is a description of the stability test of the ultra-strong antioxidant deformation vesicle prepared by the invention:
the stability of the ultrastrong antioxidative proteolitic vesicles prepared in example 1 was examined by using the vesicles as test samples. Stability tests included heat resistance, cold resistance, light, centrifugation and retention of the active ingredient manganese ethylbisiminomethylguaiacol chloride. Heat resistance test: putting the sample into an electric heating thermostat at the temperature of (40 +/-1) DEG C to investigate for two months, and observing whether the phenomena of oil production, water production, thinning, color change, odor change and the like exist after the room temperature is recovered so as to judge the heat resistance of the sample; cold resistance test: the sample is put into a refrigerator at minus 18 +/-1) DEG C for two months, and after the room temperature is recovered, whether phenomena of oil production, water production, thinning, color change, taste change and the like exist or not is observed so as to judge the cold resistance of the sample; and (3) illumination test: placing the sample into a colorimetric lamp box UV for two months, and observing whether phenomena such as oil production, water production, thinning, color change, taste change and the like exist under the illumination of D65 so as to judge the ultraviolet illumination resistance of the sample; and (3) centrifugal test: placing the sample in a centrifuge, testing for 10min at the rotating speed of 10000RPM, and observing the separation and layering conditions of the sample after the sample is placed at room temperature for different times; retention test of manganese chloride ethyl bis-iminomethyl guaiacol: and (3) measuring the content of the ethyl bis-imino methyl guaiacol manganese chloride in the ultra-strong antioxidant deformation vesicle by adopting a high performance liquid chromatography for standing at room temperature for different times, wherein the content is 100% by formula weight, and further calculating the retention rate of the ethyl bis-imino methyl guaiacol manganese chloride.
TABLE 1 stability test results for ultrastrong antioxidative deformation vesicles
Time Heat resistance Cold-resistant Illumination of light Centrifugation Retention of active ingredient
1 week Without obvious change Without obvious change Without obvious change Stabilization 98.47%
2 weeks Without obvious change Without obvious change Without obvious change Stabilization 97.52%
4 weeks Without obvious change Without obvious change Without obvious change Stabilization 95.16%
8 weeks Without obvious change Without obvious change Without obvious change Stabilization 91.95%
As can be seen from Table 1, the ultra-strong antioxidant deformation vesicle prepared by the method disclosed by the invention can be kept stable and not delaminated after centrifugal test, is not delaminated, basically does not change color and is not separated out after being stored for two months under the conditions of low temperature, high temperature and illumination, and the retention rate of the manganese chloride of ethyl bis-imino methyl guaiacol in the ultra-strong antioxidant deformation vesicle is still higher than 90% after two months, which indicates that the stability is good.
The following is an experimental description of the present invention for improving permeability of manganese ethylbisiminomethylguaiacol chloride:
transdermal experiments were performed using Franz diffusion cells, and using the episki n full-thickness artificial skin test, skin was opened after comparing the 1, 3-propanediol solution directly coated with the same content of ethyl bis-imino methyl guaiacol manganese chloride, liposomes of ethyl bis-imino methyl guaiacol manganese chloride and vesicles of ethyl bis-imino methyl guaiacol manganese chloride prepared in example 1, wherein the particle sizes of the liposomes and vesicles were similar, and the distribution mass fractions of ethyl bis-imino methyl guaiacol manganese chloride at each skin surface after 12 hours were listed in table 2, as determined using the japan HORIBA + XploRA PLUS confocal raman spectrometer. The data in the table show that, unlike the 1, 3-propylene glycol solution of ethyl bis-imino methyl guaiacol manganese chloride, the liposomes and vesicles containing ethyl bis-imino methyl guaiacol manganese chloride can effectively reach the epidermis and dermis layers through the skin stratum corneum barrier with an ultra-small volume, and compared with the liposomes, the vesicles can promote the absorption of ethyl bis-imino methyl guaiacol manganese chloride by the skin, show higher skin permeability and promote the better anti-oxidation effect.
TABLE 2 distribution of manganese ethylbisiminomethylguaiacol chloride in each layer of the skin
Figure BDA0003048982900000081
The following is an experimental description of the elasticity measurement of the ultra-strong antioxidant deformation vesicle of the invention:
the elasticity of the vesicles determines their ability to penetrate into the deep layers of the skin. If the vesicle is elastic, the vesicle can extrude through the pores of the stratum corneum (20-40nm), and the vesicle returns to the original shape after penetrating through the stratum corneum. The deformability of each vesicle in examples was measured by extrusion, and the average particle diameter of the vesicle before and after extrusion was measured by a Malvern laser particle sizer by passing the vesicle solution through a polycarbonate membrane filter having a pore diameter of 40nm under a constant external pressure (0.5MPa), and the formula DI ═ j × (r) was determined byv/rp)2Calculating a deformation index, wherein rvIs the particle diameter after extrusion, rpThe pore size of the microporous filter membrane, j is the volume of vesicles passing through the filter membrane over a fixed time (20min), and the results are shown in Table 3.
TABLE 3 characterization of deformability of ultrastrong antioxidative deformation vesicles
Test sample Particle size before extrusion (nm) Extruded particle size (nm) Deformation index DI
Example 1 50 49.4 26.7
Example 2 105 104.1 27.1
Example 3 200 198.7 26.4
The data in table 3 show that the particle size of each vesicle is basically unchanged before and after the extrusion test, the deformation index is higher, and the vesicles can better pass through a 40nm filter, so that the ultrastrong antioxidant deformation vesicles prepared by the method have better elasticity, can pass through pores of stratum corneum without breaking, and better exert antioxidant effect.
The following is an experimental description of the evaluation of the ultrastrong antioxidant effect of the deformed vesicle of the invention:
by taking vitamin E which is a common antioxidant representative component with obvious effect in cosmetics as a reference object and adopting the same preparation method, 0.2 mass percent of ethyl bis-imino methyl guaiacol manganese chloride and 0.2 mass percent of vitamin E deformation vesicles are respectively prepared. Manganese ethylbisiminomethylguaiacol chloride and vitamin E were applied before and after UVA irradiation, respectively, and then their effects on lipid peroxidation inhibition after UVA irradiation were measured, and the results are shown in table 4.
TABLE 4 inhibition of lipid peroxidation of active ingredients after UV irradiation
Figure BDA0003048982900000091
As can be seen from the data in Table 4, if the lipid peroxidation inhibition rate of the ethyl bis-imino methyl guaiacol manganese chloride deformation vesicles coated before irradiation is slightly higher than that of the vitamin E deformation vesicles of 0.2%, which indicates that the ethyl bis-imino methyl guaiacol manganese chloride deformation vesicles and the vitamin E deformation vesicles can both have protective effects on oxidative stress; if the cosmetic is applied after irradiation, the inhibition rate of the ethyl bis-imino methyl guaiacol manganese chloride on lipid peroxidation is obviously better than that of vitamin E. This is because manganese ethylbisiminomethylguaiacol chloride is a catalyst, vitamin E is a consumable antioxidant, vitamin E is essentially useless when uv irradiation has occurred, and manganese ethylbisiminomethylguaiacol chloride continues to inhibit lipid peroxidation. Experiments show that the manganese chloride of ethyl bis-imino methyl guaiacol has a catalytic effect in the oxidation resistance process, does not consume the manganese chloride, can be recycled, and has strong oxidation resistance effect.
According to the invention, the ethyl bis-imino methyl guaiacol manganese chloride with low water solubility and stability is wrapped in the deformed vesicle, so that the solubility and stability of the ethyl bis-imino methyl guaiacol manganese chloride can be improved, the elasticity/deformability of the vesicle is good, the vesicle can effectively permeate into the skin, and the antioxidant effect is better exerted.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims (10)

1. A superstrong anti-oxidant deformation vesicle, characterized by: the composition comprises the following components of ethyl bis imino methyl guaiacol manganese chloride, sucrose laurate and PPG-13-decyl tetradecanol polyether-24.
2. The super antioxidant proteotypes of claim 1, wherein: also included are glycerin and butylene glycol.
3. The super antioxidant proteotypes of claim 2, wherein: the mass ratio of the ethyl bis-imino methyl guaiacol manganese chloride to the sucrose laurate to the glycerol to the PPG-13-decyl tetradecanol polyether-24 to the butanediol is 3-4: 2-10: 8-15: 10-18: 50-80.
4. The super antioxidant proteotypes of claim 3, wherein: the mass ratio of the ethyl bis-imino methyl guaiacol manganese chloride to the sucrose laurate to the glycerol to the PPG-13-decyl tetradecanol polyether-24 to the butanediol is 2:1-8:9-13:12-15: 56-70.
5. A preparation method of a super-strong antioxidant deformation vesicle is characterized by comprising the following steps: the method comprises the following steps:
1) weighing ethyl bis-imino methyl guaiacol manganese chloride, sucrose laurate, glycerol, PPG-13-decyltetradecyl alcohol polyether-24 and butanediol according to the mass ratio of 3-4: 2-10: 8-15: 10-18: 50-80;
2) heating the ethyl bis-imino methyl guaiacol manganese chloride, PPG-13-decyl tetradecyl alcohol polyether-24 and butanediol weighed in the step 1) to 55-75 ℃, and mixing and stirring at the rotating speed of 500-1000RPM to obtain a solution A;
3) stirring the sucrose laurate and the glycerol weighed in the step 1) at normal temperature until the sucrose laurate and the glycerol are transparent to obtain a solution B;
4) adding the solution A obtained in the step 2) into the solution B obtained in the step 3), uniformly mixing, and then heating to 55-75 ℃ to obtain a premixed solution;
5) circularly homogenizing the premixed solution obtained in the step 4) for many times through a high-pressure homogenizer, and filtering the homogenized liquid through a filter to prepare the ultra-strong oxidation-resistant deformable vesicle.
6. The super antioxidant proteotypes of claim 5, wherein: in the step 2), the heating temperature is 60-65 ℃; in step 4), the heating temperature is 60-65 ℃.
7. The super antioxidant proteotypes of claim 6, wherein: in the step 5), the premixed solution obtained in the step 4) is circularly homogenized by a high-pressure homogenizer at the temperature of 60-65 ℃ and the pressure of 80-120 Mpa.
8. Use of the ultra-strong antioxidant proteiform vesicles according to any one of claims 1 to 7 in cosmetics as antioxidant active substances added to cosmetics for anti-inflammatory, antioxidant and anti-aging purposes.
9. Use of the ultrastrong antioxidative proteoliposome according to any one of claims 1 to 7 for the preparation of lotions, essences, creams, emulsions, sunscreens and masks.
10. Use according to claim 9, characterized in that: the weight percentage of the ultra-strong antioxidant deformation vesicle in the cosmetics is 0.5% -25%.
CN202110482570.9A 2021-04-30 2021-04-30 Ultra-strong oxidation-resistant deformable vesicle and preparation method and application thereof Pending CN113244130A (en)

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CN113599299A (en) * 2021-08-25 2021-11-05 西藏银美科技股份有限公司 Wrinkle-removing nano cosmetic composite material and preparation thereof
CN115006288A (en) * 2022-06-10 2022-09-06 珀莱雅化妆品股份有限公司 Isoquercitrin vesicle and preparation method thereof
CN115154403A (en) * 2022-08-25 2022-10-11 广州阿基米德生物科技有限公司 Skin repair composition and preparation method and application thereof
CN115518012A (en) * 2022-10-08 2022-12-27 广州阿基米德生物科技有限公司 Composition with effects of inhibiting melanin protein and improving black eye and pouch and application
CN117426999A (en) * 2023-10-23 2024-01-23 王叔和生物医药(武汉)有限公司 Recyclable antioxidant efficient delivery nano-composite and preparation method thereof

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珀莱雅化妆品股份有限公司: "珀莱雅弹润透亮青春精华液,备案编号:浙G妆网备字2021005906", 《国产非特殊用途化妆品备案服务平台》 *
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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN113599299A (en) * 2021-08-25 2021-11-05 西藏银美科技股份有限公司 Wrinkle-removing nano cosmetic composite material and preparation thereof
CN113599299B (en) * 2021-08-25 2024-02-23 西藏银美科技股份有限公司 Wrinkle-removing nano cosmetic composite material and preparation thereof
CN115006288A (en) * 2022-06-10 2022-09-06 珀莱雅化妆品股份有限公司 Isoquercitrin vesicle and preparation method thereof
CN115006288B (en) * 2022-06-10 2023-08-22 珀莱雅化妆品股份有限公司 Isoak element vesicle and preparation method thereof
CN115154403A (en) * 2022-08-25 2022-10-11 广州阿基米德生物科技有限公司 Skin repair composition and preparation method and application thereof
CN115518012A (en) * 2022-10-08 2022-12-27 广州阿基米德生物科技有限公司 Composition with effects of inhibiting melanin protein and improving black eye and pouch and application
CN117426999A (en) * 2023-10-23 2024-01-23 王叔和生物医药(武汉)有限公司 Recyclable antioxidant efficient delivery nano-composite and preparation method thereof
CN117426999B (en) * 2023-10-23 2024-05-28 王叔和生物医药(武汉)有限公司 Recyclable antioxidant efficient delivery nano-composite and preparation method thereof

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