CN112494347B

CN112494347B - Skin care water emulsion and preparation method thereof

Info

Publication number: CN112494347B
Application number: CN202011532685.6A
Authority: CN
Inventors: 张杰良; 郑莉欣
Original assignee: Shantou University
Current assignee: Foshan Siyinuo Biotechnology Co ltd; Hefei Longzhiyun Pharmaceutical Technology Co ltd
Priority date: 2020-12-22
Filing date: 2020-12-22
Publication date: 2023-02-24
Anticipated expiration: 2040-12-22
Also published as: CN112494347A

Abstract

The invention discloses a skin-care water emulsion and a preparation method thereof. The skin care lotion comprises the following raw materials in parts by weight: 10 to 100 portions of propylene glycol, 1 to 50 portions of taro root gracilaria polysaccharide, 0.1 to 30 portions of astaxanthin, 0.1 to 30 portions of glutathione, 0.1 to 30 portions of carnosine, 0.1 to 20 portions of vitamin A, 0.1 to 20 portions of biotin, 0.1 to 20 portions of liquorice extract, 0.1 to 10 portions of water, 0.1 to 5 portions of nicotinamide and 0.1 to 5 portions of polyethylene glycol; the skin care water emulsion is obtained by mixing the raw materials in batches. The skin care water emulsion adopts natural materials as raw materials, greatly improves the use safety, can be suitable for wider crowds, is particularly added with the gracilaria tarda polysaccharide for compounding, and maximally exerts the effect of the polysaccharide, and the prepared skin care water emulsion has various effects of moisturizing, resisting aging, improving skin conditions and the like, and has larger market prospect.

Description

Skin care water emulsion and preparation method thereof

Technical Field

The invention belongs to the field of skin care products, and particularly relates to a skin care water emulsion and a preparation method thereof.

Background

With the development of science and technology and the improvement of living standard of people, people pay more and more attention to the field of beauty and skin care, and the efficacy of skin care products for people is not satisfied with the aim of simply cleaning, and the skin care products are developed towards the aim of effectively moisturizing, resisting oxidation and delaying aging. Based on huge demands, skin care products with various efficacies emerge in the market, but the diversification of the efficacies is mostly realized by accumulating chemical raw materials, and although the skin care products have certain efficacies on the skin, the skin care products have larger potential safety hazards and are not suitable for people with sensitive skin, and meanwhile, the preparation process also can cause pollution to the environment.

The sea occupies more than half of the surface area of the earth, has abundant and diversified resources, marine algae is one of the most abundant resources in the sea, the algae contains various nutrient substances such as polysaccharide, protein, amino acid, fatty acid and the like, and has good edible and medicinal values, and the polysaccharide is a polymer formed by connecting more than 20 monosaccharide molecules by glycosidic bonds, is an important macromolecular substance in higher plants, animals and microbial cells, and has different functions on organisms.

Disclosure of Invention

The invention aims to solve the defects of the prior art and provides a skin-care water emulsion, which specifically adopts the following technical scheme:

the skin care lotion comprises the following raw materials in parts by weight: 10 to 100 portions of propylene glycol, 1 to 50 portions of taro root gracilaria polysaccharide, 0.1 to 30 portions of astaxanthin, 0.1 to 30 portions of glutathione, 0.1 to 30 portions of carnosine, 0.1 to 20 portions of vitamin A, 0.1 to 20 portions of biotin, 0.1 to 20 portions of liquorice extract, 0.1 to 10 portions of water, 0.1 to 5 portions of nicotinamide and 0.1 to 5 portions of polyethylene glycol.

The astaxanthin, the carnosine and the glutathione are used as raw materials of the skin care lotion, so that the effects of resisting oxidation, neutralizing free radicals of cells and maintaining normal metabolism of skin can be achieved, and the carnosine can also be used for effectively preventing skin aging and whitening the skin; the vitamin A is also added as a raw material, so that the skin care product has a good anti-aging effect, and can stimulate the generation of collagen at the bottom layer of the skin and improve fine wrinkles; and the propylene glycol and the polyethylene glycol can be used as the humectant to help the active ingredients in the skin care water emulsion to better permeate into the skin.

Meanwhile, the research of the inventor finds that sugar chains of the gracilaria dasheensis polysaccharide contain a large amount of hydroxyl groups, have high water absorption, can reduce the water evaporation on the surface of the skin, and has good moisturizing effect on the skin; and the gracilaria dasheen polysaccharide also has good antioxidant activity and can effectively remove DPPH, HO and ABTS free radicals. Therefore, the inventor uses the gracilaria taro polysaccharide as one of the raw materials of the skin care water emulsion for the first time, so that the efficacy of the skin care water emulsion is greatly improved, and the high biocompatibility, the use safety and the mild action of the gracilaria taro polysaccharide can also enable the skin care water emulsion to have wider application prospect.

In addition, the efficacy exerted by the polysaccharide is closely related to the dispersibility, aggregative property, molecular mass and conformation of the polysaccharide in liquid, and generally, the dispersibility of the polysaccharide in water is better, the aggregative property is lower, and the polysaccharide is more beneficial to exerting the efficacy; the inventor finds that when the gracilaria taro polysaccharide is added into the skin care milk, compared with the skin care milk, the gracilaria taro polysaccharide has better dispersibility and lower aggregability, so that the gracilaria taro polysaccharide has wider distribution in the skin care milk, the inherent viscosity of the polysaccharide is reduced, the molecular weight of the polysaccharide is reduced, the polysaccharide is more uniformly distributed, and hydroxyl groups of sugar chains in the gracilaria taro polysaccharide are more fully exposed in the skin care milk, so that the moisture retention effect, the antioxidant activity and other effects of the gracilaria taro polysaccharide are effectively exerted.

In some preferred implementation cases, the raw materials of the skin care lotion comprise the following components in parts by weight: 30 to 60 parts of propylene glycol, 5 to 35 parts of gracilaria polysaccharide of taro roots, 1 to 20 parts of astaxanthin, 1 to 20 parts of glutathione, 1 to 22 parts of carnosine, 0.5 to 8 parts of vitamin A, 0.4 to 12 parts of biotin, 2 to 10 parts of liquorice extract, 2 to 8 parts of water, 0.6 to 3 parts of nicotinamide and 1 to 3 parts of polyethylene glycol.

In some preferred implementation cases, the raw materials of the skin care lotion comprise the following components in parts by weight: 35-45 parts of propylene glycol, 8-20 parts of gracilaria polysaccharide of taro roots, 3-10 parts of astaxanthin, 2-12 parts of glutathione, 2-10 parts of carnosine, 1-4 parts of vitamin A, 0.8-8 parts of biotin, 4-8 parts of licorice extract, 4-7 parts of water, 1-2 parts of nicotinamide and 2-3 parts of polyethylene glycol.

In some preferred embodiments, the gracilaria conoides polysaccharide in the skin care milk is prepared by the following steps:

step one, adding gracilaria verrucosa powder into a solvent for extraction, and carrying out solid-liquid separation to obtain a first precipitate, wherein the solvent comprises methanol, dichloromethane and water;

and step two, drying the first precipitate, adding water for extraction, filtering to obtain a filtrate, adding ethanol into the filtrate, standing for more than 8 hours, performing solid-liquid separation to obtain a second precipitate, and drying to obtain the gracilaria dasheensis polysaccharide.

Preferably, in the step one, the ratio of the gracilaria taro powder to the solvent is 1g: (8 to 12) mL, more preferably in a ratio of 1g:10mL; in step two, the ratio of the first precipitate to the water is 1g: (28-35) mL, more preferably in a ratio of 1g:30mL, and the extraction conditions comprise: the temperature is 65-75 ℃, more preferably 70 ℃ and the time is 1.5-2.5 h, more preferably 2h.

Preferably, in the first step, the volume ratio of methanol, dichloromethane and water in the solvent is (3-5): (1-3): (1-2).

Preferably, in the second step, the ethanol is 95% ethanol, and the volume ratio of the filtrate to the ethanol is 1: (2-4); more preferably, the volume ratio is 1.

Preferably, the method further comprises a third step after the second step, and the specific process is as follows: purifying, eluting, dialyzing and drying the gracilaria tarda polysaccharide obtained in the step two to obtain a target product; the target product is the gracilaria tarda polysaccharide with higher purity.

Preferably, in the third step, DEAE ion exchange resin is adopted for purification; eluting with 0.15-0.25M sodium chloride solution; dialyzing by adopting a dialysis bag with the molecular weight of 4000-6000.

The invention also provides a preparation method of the skin care water emulsion, which comprises the following steps:

mixing astaxanthin, glutathione and carnosine to obtain a mixture A; adding vitamin A, biotin, nicotinamide and licorice extract into the mixture A, uniformly stirring, and adding propylene glycol and polyethylene glycol in batches during stirring to obtain a mixture C; dissolving gracilaria verrucosa polysaccharide in water to obtain a liquid B; and finally, uniformly mixing the mixture C and the liquid B to obtain the skin care water emulsion.

The beneficial effects of the invention are as follows: the skin care water emulsion adopts natural materials as raw materials, greatly improves the use safety, can be suitable for wider crowds, is particularly added with the gracilaria tarda polysaccharide for compounding, and maximally exerts the effect of the polysaccharide, and the prepared skin care water emulsion has various effects of moisturizing, resisting aging, improving skin conditions and the like, and has larger market prospect.

Drawings

FIG. 1 is a graph showing the effect of gracilaria verrucosa polysaccharide in scavenging DPPH free radicals;

FIG. 2 is a graph showing the effect of gracilaria verrucosa polysaccharide on scavenging HO free radicals;

FIG. 3 is a graph showing the effect of gracilaria verrucosa polysaccharide in scavenging ABTS free radicals.

Detailed Description

The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, aspects and effects of the present invention. It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict.

Example 1:

the preparation method of the gracilaria taro polysaccharide comprises the following specific steps:

step one, drying and pulverizing gracilaria verrucosa into powder, adding an extracting solution (methanol, dichloromethane and distilled water in a volume ratio of 4;

step two, after freeze-drying the first precipitate, adding distilled water according to the volume ratio of 1g; centrifuging the overnight alcohol precipitated solution to obtain a second precipitate, adding a small amount of distilled water for dissolving, and freeze drying to obtain crude radix Colocasiae Esculentae polysaccharide;

and step three, purifying the crude gracilaria taro polysaccharide by using DEAE ion exchange resin, eluting by using a sodium chloride solution with the concentration of 0.2M, dialyzing by using a dialysis bag with the molecular weight of 5000, and finally freeze-drying to obtain the gracilaria taro polysaccharide.

Example 2:

the gracilaria tenuistipitata polysaccharide prepared in example 1 was characterized:

the gracilaria congoloides polysaccharide is subjected to two-step reduction hydrolysis by adopting a 4-methylmorpholine borane complex and trifluoroacetic acid, and then is subjected to acetylation reaction with ethyl acetate, and then a GC-MS system is adopted to connect with an Rtx-5MS column to determine the content of the dehydrated galactose of the polysaccharide. Measuring the sulfate radical content in the polysaccharide by a barium chloride-gelatin turbidimetry method; the total sugar content of the polysaccharide was determined by phenol-sulfuric acid method.

The results are shown in table 1, the sulfate content of the gracilaria tarda polysaccharide prepared in example 1 is 9.16%, the total sugar content is 18.84%, and the higher the sulfate content of the polysaccharide is, the better the polysaccharide activity is, therefore, the gracilaria tarda polysaccharide has good biological activity.

TABLE 1

Index (I)	Numerical value
		Sulfate radical content (%)	9.16±0.59 ^*
Total sugar content (%)	18.84±0.83 ^*
		3, 6-anhydrogalactose content (%)	17.97±0.46 ^*

Example 3:

(1) Experiments of removing DPPH free radical by gracilaria tarda polysaccharide comprise the following specific processes:

mixing 1mL of 0.004% (w/v) DPPH/dehydrated alcohol solution with 1mL of Gracilaria verrucosa polysaccharide aqueous solution with different concentrations to obtain mixed solution (the concentration of Gracilaria verrucosa polysaccharide in the mixed solution is 0.125, 0.25, 0.5, 1 and 2mg/mL respectively), adding into the mixed solutionThe reaction was left at room temperature in the dark for half an hour, and then the absorbance at 517nm was measured and recorded as A. DPPH radical clearance (%) = (1- (base:Sub>A-base:Sub>A) ₀ )/A ₁ ) X 100%, wherein A ₀ The absorbance (without DPPH) of the corresponding concentration of the aqueous solution of Gracilaria verrucosa polysaccharide at 517nm in dehydrated alcohol is shown as A ₁ As shown in FIG. 1, the result of the absorbance of DPPH in distilled water at 517nm is that vitamin C of 1mg/mL is used as a positive control group (control), and the DPPH free radical scavenging effect is enhanced along with the increase of the concentration of Gracilaria tararistolonifera polysaccharide, which indicates that Gracilaria tararistolonifera polysaccharide has better DPPH free radical scavenging ability, and the DPPH free radical scavenging ability is dose-dependent on the polysaccharide concentration.

(2) The experiment for removing HO free radicals by gracilaria dasheen polysaccharide comprises the following specific processes:

1mL of FeSO ₄ (9 mmol/L) and 1mL of ethanol salicylate (9 mmol/L) are respectively mixed with 1mL of gracilaria verrucosa polysaccharide aqueous solution with different concentrations uniformly, and then 1mL of H is added ₂ O ₂ (9 mmol/L) to obtain mixed solution (the concentration of Gracilaria verrucosa polysaccharide in the mixed solution is 0.125, 0.25, 0.5, 1 and 2mg/mL respectively). The absorbance was measured at 510nm in a water bath at 37 ℃ for 30min and recorded as A. HO scavenging activity (%) = (a) ₁ -A)/A ₁ X 100% where A ₁ The blank absorbance is obtained, the result is shown in fig. 2, 1mg/mL of vitamin C is used as a positive control group (control), and the HO radical scavenging effect is enhanced with the increase of the concentration of the gracilaria tarda polysaccharide, which indicates that the gracilaria tarda polysaccharide has a better HO radical scavenging ability, and the HO radical scavenging ability is dose-dependent with the polysaccharide concentration.

(3) The experiment for eliminating ABTS free radical by gracilaria verrucosa polysaccharide comprises the following specific processes:

5mL ABTS (7 mmol/L) and 88. Mu.L 149mmol/L K ₂ S ₂ O ₈ Mixing to generate ABTS free radicals, taking 1mL of the mixed solution, adding 1mL of gracilaria dasheensis polysaccharide aqueous solution with different concentrations to obtain a solution to be detected (the concentrations of the gracilaria dasheensis polysaccharide in the solution to be detected are respectively 0.125, 0.25, 0.5, 1 and 2 mg/mL), incubating for 16 hours under dark conditions, and measuring the absorbance at 734 nm. ABTS radical scavenging effect (%) = (a) ₀ -A) X 100% where A ₀ The blank (the sample is replaced by the tri-hydrochloric acid buffer solution) is the absorbance at 734nm, A is the absorbance at 734nm after the reaction with a saccharide with a certain concentration in a certain time, the result is shown in fig. 3, the vitamin C with the concentration of 1mg/mL is used as a positive control group (control), the ABTS free radical scavenging effect is enhanced along with the increase of the concentration of the gracilaria tarda polysaccharide, which indicates that the gracilaria tarda polysaccharide has better ABTS free radical capacity, and the ABTS free radical capacity and the polysaccharide concentration are dose-dependent.

Example 4:

the skin care lotion comprises the following raw materials in parts by weight: 40 parts of propylene glycol, 15 parts of gracilaria tarda polysaccharide, 5 parts of astaxanthin, 3 parts of glutathione, 4 parts of carnosine, 2 parts of vitamin A, 2 parts of biotin, 6 parts of licorice extract, 6 parts of water, 2 parts of nicotinamide and 2 parts of polyethylene glycol; wherein, the gracilaria tarda polysaccharide is prepared by the example 1. The preparation process comprises the following steps:

s1, putting astaxanthin, glutathione and carnosine into a stirring container, fully stirring for 10min to obtain a mixture A, and dissolving gracilaria tarda polysaccharide in water to obtain a liquid B;

s2, adding vitamin A, biotin, nicotinamide and licorice extract into the mixture A in a shady and cool aseptic environment, uniformly stirring, and respectively adding propylene glycol and polyethylene glycol which are equally divided into 3 equal parts in the stirring process to obtain a mixture C;

and S3, uniformly mixing the mixture C and the liquid B, filtering to obtain the skin care water emulsion of the embodiment, and storing in a sterile refrigerating chamber.

Example 5:

the skin care lotion comprises the following raw materials in parts by weight: 30 parts of propylene glycol, 25 parts of gracilaria tarda polysaccharide, 12 parts of astaxanthin, 15 parts of glutathione, 0.8 part of carnosine, 6 parts of vitamin A, 10 parts of biotin, 3 parts of liquorice extract, 3 parts of water, 3 parts of nicotinamide and 1 part of polyethylene glycol; wherein, the gracilaria tarda polysaccharide is prepared by the example 1. The preparation process comprises the following steps:

s2, adding the vitamin A, the biotin, the nicotinamide and the licorice extract into the mixture A in a cool sterile environment, uniformly stirring, and respectively adding the propylene glycol and the polyethylene glycol which are evenly divided into 3 equal parts in the stirring process to obtain a mixture C;

Example 6:

the skin care lotion comprises the following raw materials in parts by weight: 70 parts of propylene glycol, 4 parts of taro root gracilaria polysaccharide, 0.8 part of astaxanthin, 0.8 part of glutathione, 25 parts of carnosine, 0.4 part of vitamin A, 0.3 part of biotin, 15 parts of licorice extract, 10 parts of water, 0.9 part of nicotinamide and 5 parts of polyethylene glycol; wherein, the gracilaria verrucosa polysaccharide is prepared by the method of example 1. The preparation process comprises the following steps:

Comparative example 1:

the skin care lotion comprises the following raw materials in parts by weight: 40 parts of propylene glycol, 15 parts of gracilaria verrucosa polysaccharide, 5 parts of astaxanthin, 3 parts of glutathione, 2 parts of vitamin A, 6 parts of water, 2 parts of nicotinamide, 2 parts of polyethylene glycol, 12 parts of green tea extract, 2 parts of vitamin E and 4 parts of shea butter; wherein, the gracilaria tarda polysaccharide is prepared by the example 1. The preparation process comprises the following steps:

s1, putting astaxanthin and glutathione into a stirring container, fully stirring for 10min to obtain a mixture A, and dissolving gracilaria dasheensis polysaccharide in water to obtain a liquid B;

s2, adding vitamin A, biotin, nicotinamide, green tea extract, vitamin E and shea butter into the mixture A in a shady and cool aseptic environment, uniformly stirring, and respectively adding propylene glycol and polyethylene glycol which are evenly divided into 3 equal parts in the stirring process to obtain a mixture C;

and S3, uniformly mixing the mixture C and the liquid B, filtering to obtain the skin care water emulsion of the comparative example, and storing in a sterile refrigerating chamber.

Example 7:

the skin care water emulsions prepared in example 4 and comparative example 1 were filtered with 0.45 μm polyethersulfone filter membrane, and the weight average molecular weight, number average molecular weight, polydispersity coefficient, intrinsic viscosity, hydrodynamic radius and gyration radius of the gracilaria congoloides polysaccharide in the skin care emulsion were measured using high performance gel exclusion chromatography in combination with viscometer, multi-angle laser scattering apparatus and differential refraction detector.

Meanwhile, the gracilaria verrucosa polysaccharide prepared in example 1 was dissolved in the same volume of water as the skin care water emulsion in example 4 as comparative example 2, and the detection was performed by using the same apparatus and procedure.

As shown in table 2, it is understood from table 2 that the polysaccharide has a large weight average molecular weight and a large number average molecular weight in the solvents of comparative example 1 and comparative example 2, but the ratio thereof is small, that is, the polydispersity coefficient is small, the polysaccharide has a small dispersibility in the solvent, and the aggregability is large; the intrinsic viscosity of the polysaccharide in the solvents of comparative examples 1 and 2 was high, and it was also confirmed that the polysaccharide had low dispersibility in the solvent, the molecular weight of the polysaccharide was high, the hydroxyl groups in the polysaccharide chain were not sufficiently exposed to the solvent, and the moisturizing effect and antioxidant activity thereof were weak. In comparative examples 1 and 2, the Mark-Houwink parameter α of the polysaccharide was 0.713 and 0.702, and the p values were 1.547 and 1.571, respectively, indicating that the polysaccharide was in a linear, flexible, random coil conformation, but approached a rigid chain, and the backbone of the polysaccharide was less bent in the solvent. While the weight-average molecular weight and the number-average molecular weight of the gracilaria dasheen polysaccharide in the skin care lotion of the example 4 are both reduced, and the polydispersity coefficient is increased, which shows that the dispersibility of the polysaccharide in the skin care lotion is increased, the aggregability is reduced, and the distribution of the polysaccharide in the water lotion is widened; the polysaccharide has reduced intrinsic viscosity, which indicates that the polysaccharide has reduced molecular weight and is distributed more uniformly in the solution, and the hydroxyl groups of the sugar chains are fully exposed in the solution, thereby enhancing the moisturizing effect and the antioxidant activity of the polysaccharide. Meanwhile, the Mark-Houwink parameter alpha is reduced but still ranges from 0.5 to 0.8, which shows that the polysaccharide presents a random coil in the emulsion, and the p value is increased, but ranges from 1.3 to 1.8, which also proves that the polysaccharide is in a linear, flexible and random coil conformation, and the bending degree of the main chain of the polysaccharide in the solvent is increased.

TABLE 2

The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the above embodiment, and the present invention shall fall within the protection scope of the present invention as long as the technical effects of the present invention are achieved by the same means. The invention is capable of other modifications and variations in its technical solution and/or its implementation, within the scope of protection of the invention.

Claims

1. The skin care lotion is characterized by comprising the following raw materials in parts by weight: 35-45 parts of propylene glycol, 8-20 parts of gracilaria polysaccharide of taro roots, 3-10 parts of astaxanthin, 2-12 parts of glutathione, 2-10 parts of carnosine, 1-4 parts of vitamin A, 0.8-8 parts of biotin, 4-8 parts of licorice extract, 4-7 parts of water, 1-2 parts of nicotinamide and 2-3 parts of polyethylene glycol;

the gracilaria taro polysaccharide is prepared by the following steps:

2. The skin care lotion as claimed in claim 1, wherein in step one, the ratio of the gracilaria dasheensis powder to the solvent is 1g: (8-12) mL; in step two, the ratio of the first precipitate to the water is 1g: (28-35) mL, the extraction conditions include: the temperature is 65-75 ℃, and the time is 1.5-2.5 h.

3. The skin care lotion according to claim 1, wherein in the first step, the volume ratio of methanol to dichloromethane to water in the solvent is (3-5): (1-3): (1-2).

4. The skin care lotion as claimed in claim 1, wherein in step two, the ethanol is 95% ethanol, and the volume ratio of the filtrate to the ethanol is 1: (2-4).

5. The skin care lotion as claimed in claim 1, further comprising a third step after the second step, wherein the specific process comprises: and D, purifying, eluting, dialyzing and drying the gracilaria tarda polysaccharide obtained in the step two to obtain a target product.

6. The skin care lotion according to claim 5, wherein in step three, DEAE ion exchange resin is used for purification; eluting with 0.15-0.25M sodium chloride solution; dialyzing by using a dialysis bag with the molecular weight of 4000-6000.

7. The method for preparing the skin care lotion according to any one of claims 1 to 6, comprising the steps of: