CN116874640B - Long-residence sodium hyaluronate derivative for hair repair and preparation method thereof - Google Patents
Long-residence sodium hyaluronate derivative for hair repair and preparation method thereofInfo
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- CN116874640B CN116874640B CN202310914567.9A CN202310914567A CN116874640B CN 116874640 B CN116874640 B CN 116874640B CN 202310914567 A CN202310914567 A CN 202310914567A CN 116874640 B CN116874640 B CN 116874640B
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- 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
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Abstract
本发明公开了一种长驻留的用于头发修护的透明质酸钠衍生物及其制备方法。本发明利用点击化学反应，合成了一种具有长驻留的透明质酸钠衍生物，用于头发修复具有良好的效果。本发明所合成的透明质酸钠衍生物通过化学键相连提升了透明质酸钠功效分子驻留时间，进而提升了透明质酸钠的护发效果。
The present invention discloses a long-retention sodium hyaluronate derivative for hair repair and its preparation method. This invention utilizes click chemistry to synthesize a long-retention sodium hyaluronate derivative that exhibits excellent hair repair efficacy. The synthesized sodium hyaluronate derivative is chemically bonded to increase the residence time of the sodium hyaluronate's active molecules, thereby enhancing the hair care benefits of sodium hyaluronate.
Description
Technical Field
The invention belongs to the technical field of hair supplies, and particularly relates to a long-residence sodium hyaluronate derivative for hair repair and a preparation method thereof.
Background
Sodium hyaluronate is a macromolecular bioactive substance which is mainly combined with water molecules through hydrogen bonding, so that the sodium hyaluronate has a moisturizing effect and has been widely applied to the field of cosmetics for several years. In recent years, native enterprises also utilize enzyme digestion oligomerization technology to produce sodium hyaluronate with various structures, and the effects of deep moisturizing, repairing and the like of sodium hyaluronate with different molecular weights are developed. In recent years, attention has been paid to the hair care efficacy of sodium hyaluronate, which can affect the mechanical properties of hair by modulating the state of occurrence of water in the hair, and bring about the moisturizing effect of hair strands, giving good combability and glossiness to the hair.
Sodium hyaluronate as a water-soluble polymer presents difficulties in its deposition penetration on hair, which is more serious for large molecular weight sodium hyaluronate. Low affinity to hair and short residence time are major factors limiting the hair care efficacy of sodium hyaluronate molecules. In addition, after sodium hyaluronate permeates into the hair, the sodium hyaluronate is connected with the hair mainly by hydrogen bonds, the acting force is weak, and the sodium hyaluronate is easily influenced by external environment and can cause great loss in the daily cleaning process. Therefore, the development of a functional molecule that is linked by strong forces to achieve enhanced residence time has become a research hotspot.
Meanwhile, with the change of consumption concept, the hair waving frequency of modern consumers is higher and higher, and the original disulfide bonds in the hair can be reduced in the hair waving process to generate free sulfhydryl groups. These free sulfhydryl groups provide a trigger for the development of long-resident sodium hyaluronate molecules.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a long-residence sodium hyaluronate derivative for hair repair and a preparation method thereof. The sodium hyaluronate derivative synthesized by the method has the advantages that the residence time of functional molecules of sodium hyaluronate is prolonged through chemical bond connection, and then the hair care effect of sodium hyaluronate is improved.
The technical scheme of the invention is as follows:
the invention firstly protects a sodium hyaluronate derivative for hair repair, which has the following structural formula:
R 1 includes -CH＝CH2、-C(CH3)＝CH2、-CH＝CH-COOH、-CH＝CH-CH3、-CH＝CH-CH2CH3 or One of them.
Further, the specific structural formula of the sodium hyaluronate derivative is as follows:
any one of the following.
The invention also provides a preparation method of the sodium hyaluronate derivative, which comprises the following steps:
(1) Dissolving sodium hyaluronate in distilled water overnight to obtain sodium hyaluronate solution, adding Tetrahydrofuran (THF), stirring, adding Triethanolamine (TEA) and 4-Dimethylaminopyridine (DMPA), and stirring to obtain reaction solution I;
(2) In a second reaction flask, mixing organic acid with tetrahydrofuran, sequentially adding triethanolamine and 2,4,6 trichlorobenzoyl chloride (TCBC), and stirring for reaction to obtain a reaction solution II;
(3) Adding the reaction solution II into the reaction solution I in the step (1), stirring at room temperature, reacting, adding saturated sodium chloride aqueous solution, precipitating, separating the crude product, washing, standing, precipitating, pouring out the clear solution, and drying the precipitate for 24 hours or more to obtain the sodium hyaluronate derivative.
Further, in the step (1), the molecular weight of the sodium hyaluronate is 42kDa to 1460kDa.
Further, in the step (1), the mass fraction of the sodium hyaluronate solution is 1-10%.
Further, in the step (1), the mass-volume ratio g/mL of the sodium hyaluronate to the tetrahydrofuran is 2-5:50, the mass-volume ratio g/mL of the sodium hyaluronate to the triethanolamine is 5:3.5-4, the mass ratio of the sodium hyaluronate to the 4-dimethylaminopyridine is 5:0.010-0.015, and the stirring temperature is 20-60 ℃.
Further, in the step (2), the organic acid is an organic acid having an α -unsaturated bond.
Further, the organic acid comprises one or more of fumaric acid, maleic acid, acrylic acid, 2-butenoic acid, 2-pentenoic acid and 2-hexenoic acid.
Further, in the step (2), the mass-volume ratio of the organic acid to the tetrahydrofuran is 1-5:50, the molar ratio of the organic acid to the triethanolamine is 0.5-1:1, the molar ratio of the organic acid to the 2,4,6 trichlorobenzoyl chloride is 0.5-1:1, the reaction temperature is room temperature for 0.5h, and the room temperature is 20-30 ℃.
Further, in the step (3), the mass ratio of the organic acid in the reaction liquid II to the sodium hyaluronate in the reaction liquid I is 0.05-0.075:1, the reaction temperature is room temperature, the reaction time is 2-3h, and the volume ratio of the saturated sodium chloride solution to the reaction mixed solution is 4-5:1.
The invention also provides a sodium hyaluronate derivative prepared by the method.
The invention also provides an application of the sodium hyaluronate derivative in hair repair, wherein the sodium hyaluronate derivative realizes residence in hair and improves the mechanical property of the hair through Michael addition reaction and hair free sulfhydryl.
It is also an object of the present invention to protect the sodium hyaluronate derivative obtained from the above reaction by a method of achieving long residence and hair repair by click reaction.
Further, the method comprises the following steps:
(1) Dissolving sodium hyaluronate derivative in deionized water, stirring uniformly, adding triethanolamine, and adjusting pH to 5-7 to obtain sodium hyaluronate derivative repairing agent solution;
(2) Soaking the damaged hair bundle in the sodium hyaluronate derivative restoration agent solution in the step (1), and reacting for 5-30 min at 20-50 ℃.
Further, in the step (1), the sodium hyaluronate derivative restoration agent solution has a sodium hyaluronate derivative content of 0.1% -1%, preferably 0.5%, and the pH is preferably 6.
Further, in the step (2), the reaction temperature is preferably 40 ℃, and the reaction time is preferably 10min-20min.
The beneficial technical effects of the invention are as follows:
the sodium hyaluronate derivative prepared by esterification reaction of sodium hyaluronate and organic acid containing alpha unsaturated bond can be used in the technical field of hair products.
Through click reaction, the carbon-carbon double bond group of the sodium hyaluronate derivative prepared by the invention can generate a covalent bond with free sulfhydryl in hair, so that the sodium hyaluronate derivative is firmly connected to hair keratin, the long residence property on the hair is realized, and the better repairing effect is reflected.
Drawings
FIG. 1 shows the residence effect of the product of example 1 of the present invention on the surface of hair.
FIG. 2 shows the result of 1 H-NMR characterization of the product of example 1 according to the invention.
FIG. 3 shows the result of 1 H-NMR characterization of the product of example 2 according to the invention.
FIG. 4 shows the result of 1 H-NMR characterization of the product of example 3 according to the invention.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples.
The preparation method of the sodium hyaluronate derivative comprises the following steps:
(1) Dissolving sodium hyaluronate in distilled water overnight to obtain sodium hyaluronate solution, adding Tetrahydrofuran (THF), stirring, adding Triethanolamine (TEA) and 4-Dimethylaminopyridine (DMPA), and stirring to obtain reaction solution I;
(2) In a second reaction flask, mixing organic acid with tetrahydrofuran, sequentially adding triethanolamine and 2,4,6 trichlorobenzoyl chloride (TCBC), and stirring for reaction to obtain a reaction solution II;
(3) Adding the reaction solution II into the reaction solution I in the step (1), stirring at room temperature, reacting, adding saturated sodium chloride aqueous solution, precipitating, separating the crude product, washing, standing, precipitating, pouring out the clear solution, and drying the precipitate for 24 hours or more to obtain the sodium hyaluronate derivative.
It should be noted that healthy hair contains substantially no free mercapto groups, and therefore the present invention is not applicable to healthy hair. The hair after the ironing and dyeing treatment contains equivalent free sulfhydryl groups, so the molecule and the using method provided by the invention can be directly applied to the ironing and dyeing of the hair.
In one embodiment of the present invention, in step (1), the sodium hyaluronate is sodium hyaluronate.
In one embodiment of the present invention, in the step (1), the mass fraction of the sodium hyaluronate solution is 1%, 5%, 8% or 10%.
In one embodiment of the invention, in the step (1), the mass-to-volume ratio g/mL of the sodium hyaluronate to the tetrahydrofuran is 3:50, 4:50 or 5:50, the mass-to-volume ratio g/mL of the sodium hyaluronate to the triethanolamine is 5:3.5, 5:3.8 or 5:4, the mass ratio of the sodium hyaluronate to the 4-dimethylaminopyridine is 5:0.010, 5:0.012 or 5:0.015, and the stirring temperature is 20 ℃, 40 ℃, 50 ℃ or 60 ℃.
In the step (2), the organic acid is an organic acid containing an α -unsaturated bond.
In one embodiment of the invention, the organic acid is fumaric acid, maleic acid, acrylic acid, 2-butenoic acid, 2-pentenoic acid or 2-hexenoic acid.
In one embodiment of the invention, in the step (2), the mass-to-volume ratio of the organic acid to the tetrahydrofuran is 1:50, 1.5:50, 3:50, 4:50 or 5:50, the molar ratio of the organic acid to the triethanolamine is 0.5:1, 0.8:1 or 1:1, the molar ratio of the organic acid to the 2,4,6 trichlorobenzoyl chloride is 0.5:1, 0.8:1 or 1:1, the reaction temperature is room temperature for 0.5h, and the room temperature is 20 ℃, 25 ℃ or 30 ℃.
In one embodiment of the present invention, in the step (3), the mass ratio of the organic acid in the reaction solution II to the sodium hyaluronate in the reaction solution I is 0.05:1, 0.06:1 or 0.075:1, the reaction temperature is room temperature, the reaction time is 3 hours, and the volume ratio of the saturated sodium chloride solution to the reaction mixture is 4:1, 4.5:1 or 5:1.
The present invention will be further illustrated by examples and the like.
Example 1
Sodium hyaluronate fumarate is synthesized as follows:
the preparation method comprises the following steps:
(1) Sodium hyaluronate (370 kDa,5 g) was dissolved overnight in 100ml distilled water. To this solution was slowly added 50 ml of Tetrahydrofuran (THF). After the solution was homogeneous, triethanolamine (3.5 ml,25 mmol) and 4-dimethylaminopyridine (DMAP, 0.015g,0.125 mmol) were added and the mixture was stirred until a clear solution was obtained, reaction solution I.
(2) In a reaction flask, fumaric acid was dissolved in tetrahydrofuran (10 ml) at a mass ratio of fumaric acid to sodium hyaluronate=0.05:1. After that, triethanolamine (TEA, 5ml,25 mmol) was added thereto, and then 2,4,6 trichlorobenzoyl chloride (TCBC) in an equimolar amount with fumaric acid was added thereto, and stirred at room temperature for 30 minutes (25 ℃) to obtain a reaction liquid II.
(3) The reaction solution II was added to the reaction solution I. The mixture was allowed to react at room temperature under vigorous stirring for 3 hours to ensure good homogenization of the components to give a reaction mixture, and 100ml of saturated aqueous sodium chloride solution was added to the reaction mixture at a volume ratio of saturated aqueous sodium chloride solution to the reaction mixture of 5:1 to precipitate and separate the crude product. Thereafter, the product was washed with an excess of anhydrous isopropanol (250 ml). The white precipitate was decanted and dried in an oven at 40 ℃ for at least 24 hours to give sodium hyaluronate fumarate. The result of 1 H-NMR characterization of the product is shown in FIG. 2.
Example 2 (molecular development of fumaric acid to 2-pentenoic acid, sodium hyaluronate molecular weight was varied from 370kDa to 1460kDa, molar ratio of organic acid to HA from 1.5:1 to 1.25:1)
The preparation method comprises the following steps:
(1) Sodium hyaluronate (1460 kDa,5g,12.5 mmol) was dissolved overnight in 100ml distilled water. To this solution was slowly added 50 ml of Tetrahydrofuran (THF). After the solution was homogeneous, triethanolamine (3.5 ml,25 mmol) and 4-dimethylaminopyridine (DMPA, 0.015g,0.125 mmol) were added and the mixture stirred until a clear solution was obtained.
(2) In a reaction flask, 2-pentenoic acid was dissolved in tetrahydrofuran (10 ml) in a mass ratio of 2-pentenoic acid to sodium hyaluronate=0.05:1. After that, triethanolamine (TEA, 5ml,25 mmol) was added thereto, followed by addition of 2,4,6 trichlorobenzoyl chloride (TCBC) in an equimolar amount to 2-pentenoic acid, and stirring at room temperature for 30 minutes (25 ℃).
(3) The solution after the reaction was added to the solution obtained in (1). The mixture was allowed to react at room temperature for 3 hours under vigorous stirring to ensure good homogenization of the components, and 100ml of supersaturated aqueous sodium chloride solution was added to precipitate and isolate the crude product at a volume ratio of saturated aqueous sodium chloride to the reaction mixture of 5:1. Thereafter, 0, the product was washed with an excess of anhydrous isopropanol (250 ml). The white precipitate was decanted and dried in an oven at 40 ℃ for at least 24 hours to give sodium hyaluronate 2-pentenoate.
Example 3 (molecular development of fumaric acid to acrylic acid, sodium hyaluronate molecular weight from 370kDa to 42kDa, organic acid to sodium hyaluronate mass ratio=0.05:1 to 0.06:1, step (2) time from 30min to 60 min)
The preparation method comprises the following steps:
(1) Sodium hyaluronate (42 kDa,5 g) was dissolved overnight in 100ml distilled water. To this solution was slowly added 50 ml of Tetrahydrofuran (THF). After the solution was homogeneous, triethanolamine (3.5 ml,25 mmol) and 4-dimethylaminopyridine (DMPA, 0.015g,0.125 mmol) were added and the mixture stirred until a clear solution was obtained.
(2) In a reaction flask, acrylic acid was dissolved in tetrahydrofuran (10 ml) at a mass ratio of acrylic acid to sodium hyaluronate=0.06:1. After that, triethanolamine (TEA, 5ml,25 mmol) was added thereto, followed by addition of 2,4,6 trichlorobenzoyl chloride (TCBC) in an equimolar amount with acrylic acid, and stirring at room temperature for 60 minutes (25 ℃).
(3) The solution after the reaction was added to the solution obtained in (1). The mixture was allowed to react at room temperature for 3 hours under vigorous stirring to ensure good homogenization of the components, and 100ml of supersaturated aqueous sodium chloride solution was added to precipitate and isolate the crude product at a volume ratio of saturated aqueous sodium chloride to the reaction mixture of 5:1. Thereafter, the product was washed with an excess of anhydrous isopropanol (250 ml). The white precipitate was decanted and dried in an oven at 40 ℃ for at least 24 hours to give sodium hyaluronate acrylate.
Application example damaged hair bundle repair
The daily ironing and dyeing operation can lead to the breakage of disulfide bonds of hair to generate free sulfhydryl groups, further damage the hair structure, cause the mechanical property of the hair to be reduced and lead to poor comb property. According to the invention, different experiments are designed to repair damaged hair bundles, wherein the proposed sodium hyaluronate derivative can repair the mechanical property and combing property of the hair.
The damaged hair bundle is self-made in the process of simulating perming, and is obtained by incubating healthy Asian black hair for 3 hours through 6% thioglycollic acid. The sodium hyaluronate derivative repairing agent solution and the repairing method are as in application examples 1-4.
Application example 1:
The damaged hair bundle repairing method specifically comprises the following steps:
(1) Sodium hyaluronate fumarate was prepared as in example 1;
(2) Stirring and dissolving 0.5g of sodium hyaluronate fumarate and 99.5g of deionized water, and adding triethanolamine to adjust the pH to 7.0 to obtain a 0.5wt% repairing agent solution;
(3) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate the self-making process of perming) and soaking in the repairing solution, setting the reaction temperature to 40 ℃, the reaction time to 15 minutes, taking out and airing to obtain the repairing hair bundles.
Application example 2:
The damaged hair bundle repairing method specifically comprises the following steps:
(1) Sodium hyaluronate fumarate was prepared as in example 1;
(2) Stirring and dissolving 0.3g of sodium hyaluronate fumarate and 99.7g of deionized water, and adding citric acid to adjust the pH to be 5.0 to obtain a 0.3%wt repairing agent solution;
(3) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate the self-making process of perming) and soaking in the repairing solution, setting the reaction temperature to 40 ℃, the reaction time to 15 minutes, taking out and airing to obtain the repairing hair bundles.
Application example 3:
The damaged hair bundle repairing method specifically comprises the following steps:
(1) Sodium hyaluronate acrylate was prepared as in example 3;
(2) 2.0g of sodium hyaluronate acrylic ester and 98.0g of deionized water are stirred and dissolved, and triethanolamine is added to adjust the pH to be 6.0, so that 2%wt of repairing agent solution is obtained;
(3) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate the self-making process of perming) and soaking in the repairing solution, setting the reaction temperature to 40 ℃, the reaction time to 5 minutes, taking out and airing to obtain the repairing hair bundles.
Application example 4:
The damaged hair bundle repairing method specifically comprises the following steps:
(1) Sodium hyaluronate fumarate was prepared as in example 1;
(2) Stirring and dissolving 0.5g of sodium hyaluronate fumarate and 99.5g of deionized water, and adding citric acid to adjust the pH to be 5.0 to obtain a repairing agent solution with the concentration of 0.5 wt%;
(3) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate the self-making process of perming) and soaking in the repairing solution, setting the reaction temperature to 25 ℃, the reaction time to 15 minutes, taking out and airing to obtain the repairing hair bundles.
Comparative example 1 was applied:
The damaged hair bundle repairing method specifically comprises the following steps:
(1) Sodium hyaluronate fumarate was prepared as in example 1;
(2) Stirring and dissolving 0.5g of sodium hyaluronate fumarate and 99.5g of deionized water, and adding triethanolamine to adjust the pH to be 3.0 to obtain a repairing agent solution with the concentration of 0.5 wt%;
(3) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate the self-making process of perming) and soaking in the repairing solution, setting the reaction temperature to 40 ℃, the reaction time to 15 minutes, taking out and airing to obtain the repairing hair bundles.
Comparative example 2 was applied:
The damaged hair bundle repairing method specifically comprises the following steps:
(1) Sodium hyaluronate fumarate was prepared as in example 1;
(2) Stirring and dissolving 0.5g of sodium hyaluronate fumarate and 99.5g of deionized water, and adjusting the pH without adding triethanolamine, wherein the pH is about 4.0, so as to obtain a repairing agent solution with the weight of 0.5%;
(3) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate self-made hair waving process), soaking in the repairing solution at 40 ℃ for 15min, taking out and airing to obtain the repairing hair bundles.
Comparative example 3 was applied:
The damaged hair bundle repairing method specifically comprises the following steps:
(1) Sodium hyaluronate fumarate was prepared as in example 1;
(2) Stirring and dissolving 0.5g of sodium hyaluronate fumarate and 99.5g of deionized water, adding triethanolamine to adjust the pH to be 9.0, and obtaining a repairing agent solution with the concentration of 0.5%wt;
(3) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate self-made hair waving process), soaking in the repairing solution at 40 ℃ for 15min, taking out and airing to obtain the repairing hair bundles.
Comparative example 4 was applied:
The damaged hair bundle repairing method specifically comprises the following steps:
(1) Sodium hyaluronate fumarate was prepared as in example 1;
(2) Stirring and dissolving 0.05g of sodium hyaluronate fumarate and 99.95g of deionized water, and adding triethanolamine to adjust the pH to 7.0 to obtain a repairing agent solution with the concentration of 0.05 wt%;
(3) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate self-made hair waving process), soaking in the repairing solution at 40 ℃ for 15min, taking out and airing to obtain the repairing hair bundles.
Comparative example 5 was applied:
The damaged hair bundle repairing method specifically comprises the following steps:
(1) Sodium hyaluronate fumarate was prepared as in example 1;
(2) Stirring and dissolving 0.5g of sodium hyaluronate fumarate and 99.5g of deionized water, and adding triethanolamine to adjust the pH to 7.0 to obtain a 0.5wt% repairing agent solution;
(3) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate self-made hair waving process), soaking in the repairing solution at 40 ℃ for 1min, taking out and airing to obtain the repairing hair bundles.
Comparative example 6 was applied:
The damaged hair bundle repairing method specifically comprises the following steps:
Hair strand repair with fumaric acid:
(1) Stirring and dissolving 0.5g of fumaric acid and 99.5g of deionized water, and adding triethanolamine to adjust the pH to be 7.0, so as to obtain a repairing agent solution with the concentration of 0.5 wt%;
(2) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate self-made hair waving process), soaking in the repairing solution at 40 ℃ for 15min, taking out and airing to obtain the repairing hair bundles.
Comparative example 7 was applied:
The damaged hair bundle repairing method specifically comprises the following steps:
(1) 0.5g of sodium hyaluronate (370 kDa) and 99.5g of deionized water are stirred and dissolved, and triethanolamine is added to adjust the pH to 7.0, so that a repairing agent solution with the concentration of 0.5 weight percent is obtained;
(2) Weighing 0.5g of damaged hair bundles (the damaged hair bundles simulate self-made hair waving process), soaking in the repairing solution at 40 ℃ for 15min, taking out and airing to obtain the repairing hair bundles.
Test example:
(1) Residence performance study:
The penetration residence property of sodium hyaluronate fumarate was determined as follows:
1) The preparation method of the sodium hyaluronate fumarate-FITC fluorescent marker comprises the following steps of:
0.2g of sodium hyaluronate fumarate is taken in a test tube with a plug, 2mL of 0.05mol/L NaOH aqueous solution is added to seal the test tube with the plug, and a vortex mixer is used for vortex for 20min to dissolve the sodium hyaluronate fumarate. 0.04g of Fluorescein Isothiocyanate (FITC) is precisely added into a test tube, the test tube is plugged and sealed, and after being uniformly mixed again by using a vortex mixer, the test tube is placed into a water bath with the temperature of 95 ℃ and is taken out after the temperature is kept constant for 45min, and the test tube is cooled to the room temperature. And adding 18mL of saturated anhydrous ethanol solution of sodium chloride into the obtained mixture, centrifuging, and discarding the supernatant to obtain a precipitate, namely the crude product of FITC fluorescent marked sodium hyaluronate fumarate.
Adding 20mL of sodium chloride saturated absolute ethyl alcohol solution into the crude product, uniformly mixing by vortex, uniformly dispersing the marked sodium hyaluronate fumarate precipitate into the sodium chloride saturated absolute ethyl alcohol solution, centrifuging, discarding the upper alcohol solution, repeatedly washing by alcohol for 6 times, collecting the precipitate, and freeze-drying to obtain the sodium hyaluronate fumarate-FITC fluorescent marker.
2) The permeability test method of the sodium hyaluronate fumarate comprises the following steps:
The damaged hair tresses were taken for the experiment. Accurately weighing 0.05g of sodium hyaluronate fumarate-FITC fluorescent marker in a test tube with a stopper, adding 10mL of deionized water to the test tube, sealing the vortex and dissolving the mixture. Twenty hair strands are randomly selected and immersed in the fluorescent marked sodium hyaluronate fumarate solution, and after being fully immersed for 4 hours, the hair strands are taken out and the surfaces of the hair strands are fully cleaned to remove the sodium hyaluronate fumarate remained on the surfaces. Finally, hairline sections were obtained using frozen sections and observed using a fluorescence microscope.
The above experiment was repeated using underivatized sodium hyaluronate and the resulting hair tress was washed multiple times to examine the residence of sodium hyaluronate or sodium hyaluronate derivatives. The washing method is to simulate the daily cleaning process to wash the hair, the amount of shampoo is 0.2g per gram of hair bundle, the hair is washed by warm water after 5 minutes, the hair is stroked by hands by using a similar force for ten times when the hair is washed by warm water each time, and then the hair is dried under the condition of constant temperature and constant humidity, and the hair is subjected to one-time operation, and the 7 times of shampoo cycle are repeated.
The fluorescence permeability of the hyaluronic acid and the sodium hyaluronate fumarate is shown in fig. 1, and as can be seen from fig. 1, the molecule prepared in example 1 has a good residence effect on the hair surface, and can still reside on the hair surface remarkably after multiple times of washing, while the common sodium hyaluronate basically does not reside on the hair after multiple times of washing.
(2) Tensile property test:
The hair strands treated by the different methods are tested for tensile property, and the specific test method is that an SN-1200W high-definition camera is used for measuring the diameter of the hair, and the specific method is that the diameters of the 3 middle sections are averaged. The single fiber strength test was performed by using a fiber strength tester for 30 hair strands within 10 μm of each of 15 different treated hair strands, and the tensile strength of the hair of the control group and each of the sample groups was calculated and compared by the following formula:
σ=Fb/So
Where σ is the tensile strength, F b is the maximum force that the specimen will bear when broken, and S o is the original cross-sectional area of the specimen. In addition, the average elastic modulus of the starting yarn was also calculated from the elastic modulus region of the tensile curve. The results of the hair tensile strength test are shown in Table 1 below.
TABLE 1 comparison of mechanical Properties of different hair strands
As can be seen from Table 2, the application examples have an obvious effect of improving the mechanical properties of hair, while the application comparative examples 1 to 6 cannot achieve the restoration effect due to unsuitable use conditions. The effect of the application of comparative example 7 is also improved, but the application of examples 1-4 is not obvious, and the derivatized sodium hyaluronate has stronger capability of improving the mechanical property of hair than the underivatized sodium hyaluronate.
(3) Hair tress combing performance test
The specific test steps are as follows:
3 bundles of the same mild damaged human hair are selected, the wig pieces (2%wt of thioglycollic acid is soaked for 30 min), after the wig pieces are dried, carding work of the 3 bundles of the human hair is tested by using a carding instrument, each bundle of the human hair is carded for 10 times, and the value of the carding work is recorded as the initial carding work.
And repairing the hair according to the conditions of the application example and the application comparative example. After the hair is dried, a carding machine is used for testing the carding work of 3 hair bundles, each hair bundle is carded for 10 times, and the carding work value is recorded as the repairing carding work.
After repairing, the hair is cleaned in a simulated daily cleaning process, the hair is washed by warm water after being subjected to sample receiving for 5min according to the dosage of 0.2g of shampoo per gram of hair bundle or the dosage which accords with the sample using method, the hair is stroked by hands with similar force for ten times by each warm water washing, and then the hair is dried under the condition of constant temperature and humidity, so that the hair is repeatedly subjected to 15 times of simulation for a one-month shampoo period. After air drying, a carding machine is used for testing the carding work of 3 hair bundles, each hair bundle is carded for 10 times, and the carding work value is recorded as resident carding work. The results of the hair combing work test are shown in table 2 below.
TABLE 2 comparison of combing work for different hair strands
The results show that the application examples 1-4 have good restoration effect on the combing performance of hair, the combing work is obviously reduced after the application, and the better combing performance can be maintained after the washing for many times. While the combing performance of comparative examples 1-6 was significantly worse, and also lower combing work was demonstrated with comparative example 7, indicating that sodium hyaluronate itself could enhance combing performance of hair, but after multiple washes, combing work was significantly improved, indicating that underivatized sodium hyaluronate did not have long dwell effect, and therefore the enhancing effect of combing performance was lost with the wash.
The above is only a preferred embodiment of the present invention, and the present invention is not limited to the above examples. It is to be understood that other modifications and variations which may be directly derived or contemplated by those skilled in the art without departing from the spirit and concepts of the present invention are deemed to be included within the scope of the present invention.
Claims (7)
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| JP2009530445A (en) * | 2006-03-14 | 2009-08-27 | ノボザイムス バイオポリマー アクティーゼルスカブ | Acrylic hyaluronic acid |
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| CZ2013914A3 (en) * | 2013-11-21 | 2015-02-25 | Contipro Biotech S.R.O. | Nanofibers containing photocurable ester derivative of hyaluronic acid or its salt, photocured nanofibers, method of their synthesis, preparation containing photo-hardened nanofibers and their use |
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