CN109912811B - Preparation method of amphiphilic sericin polymer and application of polymer - Google Patents
Preparation method of amphiphilic sericin polymer and application of polymer Download PDFInfo
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Abstract
The invention discloses a preparation method of an amphiphilic sericin polymer and application of the amphiphilic sericin polymer, wherein histidine and octadecanol are esterified under the catalysis of concentrated sulfuric acid to obtain histidine octadecyl ester, and then the histidine octadecyl ester is condensed with 5-formyl salicylic acid to obtain a compound B, imine is formed by aldehyde amine condensation, and the imine group is connected with a benzene ring, so that the formed imine is of a stable structure, the compound B is stable, sericin contains a large amount of alcoholic hydroxyl groups, the compound B is esterified under the catalysis of concentrated sulfuric acid, the phenolic hydroxyl groups on the compound B are difficult to be directly esterified with carboxylic acid, and the generation of byproducts is reduced, so that the alcoholic hydroxyl groups on the sericin are esterified with carboxyl groups on the compound B to form the amphiphilic sericin polymer with a single structure in a formula C; hydrophobic groups are introduced into sericin, and the prepared amphiphilic sericin polymer can be applied to cosmetics and textiles and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of cosmetics, and particularly relates to a preparation method of an amphiphilic sericin polymer and application of the polymer.
Background
Sericin is a natural water-soluble globular protein, contains multiple polypeptides, consists of 18 amino acids, contains more serine, aspartic acid and glycine, and has 74.61% of polar side chain amino acids. Sericin contains a large amount of hydrophilic groups such as hydroxyl, carboxyl, amino and the like in a molecular structure, so that the sericin has excellent moisture absorption performance, and when the sericin is used in cosmetics, the hydrophilic groups can transfer in-vivo moisture to a skin stratum corneum for combination, so that the skin keeps certain moisture, is soft and smooth and is a natural moisturizing factor; sericin in the existing cosmetics is added as a single raw material, amphiphilic sericin is fresh and available in cosmetics, a preservative added in the cosmetics is not good for a human body, and the single sericin is added into the cosmetics only to play a moisturizing role, so that the antioxidant and anti-aging effects on skin are not obvious.
Disclosure of Invention
The invention aims to provide a preparation method of an amphiphilic sericin polymer and application of the polymer, wherein a hydrophobic group (- (CH)2)CH3、Phenyl) is introduced into sericin, and the prepared amphiphilic sericin polymer can be applied to cosmetics and textiles and has good application prospect.
A preparation method of an amphiphilic sericin polymer specifically comprises the following steps:
the first step is as follows: preparation of sericin powder
Putting the silkworm cocoons into cold water for rinsing to remove dust and impurities, then putting the silkworm cocoons into a sodium hydroxide solution with the temperature of 40-45 ℃ and the mass fraction of 5% for soaking for 40min to fully swell sericin on the silkworm cocoons, then heating and boiling for 40min for degumming, repeatedly washing degummed silkworm cocoon clothes with hot water with the temperature of 60-70 ℃, combining a washing solution and a degumming solution, putting the mixture into a dialysis bag with the intercepted molecular weight of 9000 plus 13000Da, dialyzing in pure water for 2 days to remove ionic salt, and spray-drying to obtain sericin powder;
second step, preparation of hydrophobic Compounds
S1, dissolving 11-12mmol of octadecanol in 50ml of solvent, dropwise adding 5ml of concentrated sulfuric acid, stirring and mixing for 10-15min after dropwise adding, then adding 10mmol of histidine, heating and refluxing for reaction, removing the solvent by rotary evaporation after the reaction is finished, and washing with water and alcohol to obtain a compound A; the reaction formula is as follows:
s2, dissolving the compound A obtained in the step S1 in 100ml of solvent, adding 2g of anhydrous sodium sulfate and 10mml of 5-formyl salicylic acid, heating, refluxing, stirring, reacting for 2-3h, performing rotary evaporation to remove the solvent, and performing column chromatography separation to obtain a hydrophobic compound B; the reaction formula is as follows:
thirdly, preparation of amphiphilic sericin protein polymer
Dissolving the compound B prepared in the step S2 in 200ml of anhydrous DMSO, dropwise adding 5ml of concentrated sulfuric acid, stirring and mixing for 10-15min after dropwise adding, adding 10g of anhydrous sodium sulfate, then adding 10-15g of sericin powder prepared in the first step into the mixed solution, heating to 60-65 ℃, keeping the temperature and stirring for reaction for 6-8h, and after the reaction is finished, purifying to obtain the amphiphilic sericin polymer with the structure of the formula C.
Further, the solvent in step S1 is anhydrous tetrahydrofuran.
Further, in step S1, the heating reflux reaction is specifically heating to 95-105 ℃ for reflux reaction for 4-5 h.
Further, the solvent in step S2 is dried toluene.
Further, in step S2, the eluent used for column chromatography is petroleum ether: dichloromethane: ethyl acetate 6:2: 5.
Further, the purification in the third step specifically comprises: and after the reaction is finished, cooling to 5-8 ℃, adding 300ml of deionized water, precipitating, filtering, washing with 100ml of cold water at 5-10 ℃ for 3 times, washing with 50ml of absolute ethanol at 5-10 ℃ for 3 times, filtering, and finally freeze-drying to obtain the amphiphilic sericin polymer with the structure of the formula C.
An application of an amphiphilic sericin polymer, wherein the amphiphilic sericin polymer is applied to cosmetics.
The invention has the beneficial effects that:
the invention provides a preparation method of an amphiphilic sericin polymer, which comprises the steps of esterifying histidine and octadecanol under the catalysis of concentrated sulfuric acid to obtain histidine octadecyl ester, condensing with 5-formyl salicylic acid to obtain a compound B, condensing aldehyde amine to form imine, wherein the imine group is connected with a benzene ring, so that the formed imine is in a stable structure, the compound B is stable, a large amount of alcoholic hydroxyl groups are contained in sericin, the compound B is esterified under the catalysis of concentrated sulfuric acid, the phenolic hydroxyl groups on the compound B are difficult to be directly esterified with carboxylic acid, and the generation of byproducts is reduced, so the alcoholic hydroxyl groups on the sericin are esterified with carboxyl groups on the compound B, and hydrophobic groups (- (CH)2)CH3、Phenyl) is introduced on the sericin to form an amphiphilic sericin polymer with a single structure as shown in the formula C;
the prepared amphiphilic sericin protein polymer can be applied to cosmetics and textiles; when the amphiphilic sericin protein polymer is applied to cosmetics, the amphiphilic sericin protein polymer has hydrophilicity and lipophilic property, is convenient to be compatible with other formula components in the cosmetics and easier to emulsify into a uniform phase, and contains an antibacterial complexing groupAnd phenolic hydroxyl group, can keep antibacterial and antifungal effects of cosmetic, and does not need to add antiseptic, and in additionand-C ═ N-CH-COO-can absorb and complex heavy metal color cosmetic residues on the skin, phenolic hydroxyl groups can remove free radicals in the skin, and the antioxidant property of sericin is combined, so that the antioxidant and anti-aging effects of the cosmetics are further improved;
the amphiphilic sericin polymer is coated on the surface of the fiber, so that the antibacterial performance of fiber fabrics can be improved, the hydroscopic property and the electrostatic discharge performance of the fabrics can be improved, and the hydrophobic group can improve the stain resistance of textile fibers.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a reaction scheme of Compound A of the present invention;
FIG. 2 is a reaction formula of a hydrophobic compound B;
FIG. 3 is a reaction diagram of an amphiphilic sericin polymer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-3, a preparation method of an amphiphilic sericin polymer and an application of the polymer specifically include the following steps:
the first step is as follows: preparation of sericin powder
Putting the silkworm cocoons into cold water for rinsing to remove dust and impurities, then putting the silkworm cocoons into a sodium hydroxide solution with the temperature of 45 ℃ and the mass fraction of 5% for soaking for 40min to fully swell sericin on the silkworm cocoons, then heating and boiling for 40min, degumming, repeatedly washing the degummed silkworm cocoon clothes with hot water with the temperature of 65 ℃, combining the washing liquid and the degumming liquid, putting the mixture into a dialysis bag with the intercepted molecular weight of 9000 plus 13000Da, dialyzing in pure water for 2 days to remove ionic salt, and performing spray drying to obtain sericin powder;
second step, preparation of hydrophobic Compounds
S1, dissolving 12mmol of octadecanol in 50ml of anhydrous tetrahydrofuran, dropwise adding 5ml of concentrated sulfuric acid, stirring and mixing for 10min after dropwise adding, then adding 10mmol of histidine, heating to 100 ℃, carrying out reflux reaction for 5h, after the reaction is finished, carrying out rotary evaporation to remove the solvent, and washing with water and alcohol to obtain a compound A; the yield is 95.7%; the reaction formula is shown in figure 1;
the mass spectrum result of the obtained compound a is: HRMS m/z (ESI)+)calcd for C24H45N3O2([M]+), 407.58,found 407.3545;
S2, dissolving the compound A obtained in the step S1 in 100ml of dry toluene, adding 2g of anhydrous sodium sulfate and 10mml of 5-formyl salicylic acid, heating, refluxing, stirring, reacting for 3 hours, removing the solvent through rotary evaporation, and performing column chromatography separation to obtain a hydrophobic compound B with the purity of 99.65% and the yield of 92.3%; the eluent used for column chromatography is petroleum ether: dichloromethane: ethyl acetate 6:2: 5; the reaction formula is shown in figure 2;
the mass spectrum of the compound B obtained was: HRMS m/z (ESI)+)calcd for C32H49N3O5([M]+), 555.65,found 555.3714;
Thirdly, preparation of amphiphilic sericin protein polymer
Dissolving the compound B prepared in the step S2 in 200ml of anhydrous DMSO, dropwise adding 5ml of concentrated sulfuric acid, stirring and mixing for 15min after dropwise adding, adding 10g of anhydrous sodium sulfate, then adding 13g of sericin powder prepared in the first step into the mixed solution, heating to 65 ℃, preserving heat, stirring and reacting for 8h, cooling to 5 ℃ after the reaction is finished, adding 300ml of deionized water, separating out a precipitate, filtering, washing with 100ml of cold water at 5-10 ℃ for 3 times, washing with 50ml of absolute ethanol at 5-10 ℃ for 3 times, filtering, and finally freeze-drying at-20 ℃ to obtain the amphiphilic sericin polymer with the structure of the formula C; the reaction formula is shown in figure 3;
the infrared characterization of amphiphilic sericin polymer D is as follows: IR (KBr):(-OH-with a broad peak, which is unreacted-OH on sericin and phenolic hydroxyl group), 3143 (on imidazole-NH-), 3064, 3025 (on imidazole, benzene ring), 1735(-CO-),1675 (-C-N-, on imidazole-C-N-), cm-1。
Measuring the clearance rate of the amphiphilic sericin protein polymer on DPPH free radicals, hydroxyl free radicals and superoxide ion free radicals by an ultraviolet spectrophotometry; the clearance rate to DPPH free radical is 99.1%, the clearance rate to hydroxyl free radical is 98.2%, and the clearance rate to superoxide ion free radical is 98.7%.
Antibacterial property tests show that the antibacterial rates of the amphiphilic sericin polymer on staphylococcus aureus and escherichia coli are 98.8% and 99.4% respectively.
The amphiphilic sericin polymer can be applied to cosmetics and textiles; when the amphiphilic sericin protein polymer is applied to cosmetics, the amphiphilic sericin protein polymer has hydrophilicity and lipophilic property, is convenient to be compatible with other formula components in the cosmetics and easier to emulsify into a uniform phase, and contains an antibacterial complexing groupAnd phenolic hydroxyl, can keep the cosmetics antibacterial and mildewproof, does not need to add any preservative, and in additionand-C ═ N-CH-COO-can absorb and complex heavy metal color cosmetic residues on the skin, phenolic hydroxyl groups can remove free radicals in the skin, and the antioxidant property of sericin is combined, so that the antioxidant and anti-aging effects of the cosmetics are further improved;
the amphiphilic sericin polymer is coated on the surface of the fiber, so that the antibacterial performance of fiber fabrics can be improved, the hydroscopic property and the electrostatic discharge performance of the fabrics can be improved, and the hydrophobic group can improve the stain resistance of textile fibers.
Skin elasticity test
Skin elasticity decreases with skin aging, so skin elasticity is one of important signs for judging skin aging and is an essential item for efficacy test of anti-aging cosmetics.
The formula (parts by weight) of the skin cream is as follows:
the formula I is as follows: 25 parts of glycerol, 12 parts of mineral oil, 15 parts of hyaluronic acid, 8 parts of caprylic triglyceride, 3 parts of amphiphilic sericin, 4 parts of polydimethylsiloxane, 0.2 part of EDTA disodium and 32.8 parts of deionized water;
the comparison formula comprises: replacing the amphiphilic sericin with sericin, and adopting the following formula I;
blank formula: the amphiphilic sericin is not added, and the rest formula is the same as the first formula;
the experimental method comprises the following steps: selecting 30 women with normal healthy skin and no cosmetic allergy history, wherein the women are 20-45 years old, randomly distributing 10 persons to each group, taking 1 treatment course per week and 4 treatment courses in total, cleaning the face before each application, keeping the same time for cleaning the face each time, applying a corresponding product after the skin is dried in the air, and applying the corresponding product for 2 times per day and 1g per time to each group.
Measurement: cheek sections were selected as test areas and tested 10min after use of the product. The skin elasticity tester is used for measuring the skin elasticity curve, and the moisturizing and anti-aging effects of the skin care product can be evaluated according to the stretching amount and resilience data of the skin, and the result is shown in the table I;
TABLE I skin elasticity test results
As can be seen from Table I, the elasticity values of the cheeks gradually increased after the formulation I skin cream was used, and the elasticity values of the skin began to increase significantly after 2 weeks of use. The formula I skin cream can obviously enhance the elasticity of skin, has quick response, and shows that the amphiphilic sericin protein has the functions of enhancing the elasticity of the skin and improving the skin state, and no allergy phenomenon exists in the process of using the formula I skin cream for 10 people.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (6)
1. A preparation method of an amphiphilic sericin polymer is characterized by comprising the following steps: the method specifically comprises the following steps:
the first step is as follows: preparation of sericin powder
Putting the silkworm cocoons into cold water for rinsing to remove dust and impurities, then putting the silkworm cocoons into a sodium hydroxide solution with the temperature of 40-45 ℃ and the mass fraction of 5% for soaking for 40min to fully swell sericin on the silkworm cocoons, then heating and boiling for 40min for degumming, repeatedly washing degummed silkworm cocoon clothes with hot water with the temperature of 60-70 ℃, combining a washing solution and a degumming solution, putting the mixture into a dialysis bag with the intercepted molecular weight of 9000 plus 13000Da, dialyzing in pure water for 2 days to remove ionic salt, and spray-drying to obtain sericin powder;
second step, preparation of hydrophobic Compounds
S1, dissolving 11-12mmol of octadecanol in 50ml of solvent, dropwise adding 5ml of concentrated sulfuric acid, stirring and mixing for 10-15min after dropwise adding, then adding 10mmol of histidine, heating and refluxing for reaction, removing the solvent by rotary evaporation after the reaction is finished, and washing with water and alcohol to obtain a compound A; the reaction formula is as follows:
s2, dissolving the compound A obtained in the step S1 in 100ml of solvent, adding 2g of anhydrous sodium sulfate and 10mml of 5-formyl salicylic acid, heating, refluxing, stirring, reacting for 2-3h, performing rotary evaporation to remove the solvent, and performing column chromatography separation to obtain a hydrophobic compound B; the reaction formula is as follows:
thirdly, preparation of amphiphilic sericin protein polymer
Dissolving the compound B prepared in the step S2 in 200ml of anhydrous DMSO, dropwise adding 5ml of concentrated sulfuric acid, stirring and mixing for 10-15min after dropwise adding, adding 10g of anhydrous sodium sulfate, then adding 10-15g of sericin powder prepared in the first step into the mixed solution, heating to 60-65 ℃, keeping the temperature and stirring for reaction for 6-8h, and after the reaction is finished, purifying to obtain the amphiphilic sericin polymer with the structure of the formula C;
the structural formula of the amphiphilic sericin polymer C is as follows:
2. the method of claim 1, wherein the step of preparing the amphiphilic sericin polymer comprises: the solvent in step S1 is anhydrous tetrahydrofuran.
3. The method of claim 1, wherein the step of preparing the amphiphilic sericin polymer comprises: in step S1, the heating reflux reaction is specifically heating to 95-105 ℃ for reflux reaction for 4-5 h.
4. The method of claim 1, wherein the step of preparing the amphiphilic sericin polymer comprises: the solvent in step S2 is dry toluene.
5. The method of claim 1, wherein the step of preparing the amphiphilic sericin polymer comprises: in step S2, the eluent used for column chromatography is petroleum ether: dichloromethane: ethyl acetate 6:2: 5.
6. The method of claim 1, wherein the step of preparing the amphiphilic sericin polymer comprises: the purification in the third step specifically comprises the following steps: and after the reaction is finished, cooling to 5-8 ℃, adding 300ml of deionized water, precipitating, filtering, washing with 100ml of cold water at 5-10 ℃ for 3 times, washing with 50ml of absolute ethanol at 5-10 ℃ for 3 times, filtering, and finally freeze-drying to obtain the amphiphilic sericin polymer with the structure of the formula C.
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