CN115583985A - Polylysine sunscreen peptide and preparation method thereof - Google Patents
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Abstract
The invention discloses polylysine sunscreen peptide and a preparation method thereof, the polylysine sunscreen peptide is structurally modified by alpha-polylysine or epsilon-polylysine through various micromolecule ultraviolet absorbents under the action of a condensing agent, an additive and the like through a condensation reaction of the polylysine and various micromolecule ultraviolet absorbents to obtain a compound which takes the polylysine as a skeleton structure and contains ultraviolet absorption functional groups on the skeleton structure, and a series of polylysine sunscreen peptides are obtained after the impurity of the compound is removed. The polylysine sunscreen peptide can not be absorbed by skin penetration, has better sunscreen performance than a micromolecule sunscreen agent, overcomes the defect that the micromolecule sunscreen agent commonly used in the current market is easy to absorb through skin to cause potential toxicity, improves the safety of sunscreen products, is an excellent substitute of the existing micromolecule sunscreen agent, and is suitable for the field of sunscreen cosmetics.
Description
Technical Field
The invention belongs to the technical field of sunscreen cosmetics, and particularly relates to polylysine sunscreen peptide and a preparation method thereof.
Background
Prolonged exposure to the sun and ultraviolet radiation can cause a number of adverse effects on the skin, such as sunburn, tanning, aging, and even skin cancer. Sunscreens are often used to help the skin reduce or temporarily prevent the effects of sunlight and ultraviolet radiation. The existing commercial sunscreens mainly comprise two types of physical sunscreens and chemical sunscreens, wherein the physical sunscreens mainly comprise zinc oxide, titanium dioxide and the like, and the chemical sunscreens mainly comprise a plurality of types, such as avobenzone, tianshi M, octocrylene, maifanitum SX, homosalate and the like. These sunscreens have been widely used in ultraviolet protection, having strong and broad absorption/scattering in the short-wavelength ultraviolet (280 to 315 nm) region and long-wavelength ultraviolet (315 to 400 nm) region.
While the problem of broad spectral coverage has been well developed, physical sunscreens have been shown to enhance the production of reactive oxygen species, which can lead to oxidative stress or deoxyribonucleic acid damage to tissues, while chemical sunscreens also suffer from potential toxicity and endocrine disruption due to photodegradation, skin penetration, and the like. New sunscreen products based on bioadhesives or gel systems, plant sunscreens or bioengineered sunscreens also present more or less problems. Therefore, it is necessary to develop a safe and reliable macromolecule sunscreen agent with the advantages of micromolecule sunscreen agents.
Epsilon-polylysine (epsilon-PL) was first discovered by Shima et al, japanese scholars, in culture of Streptomyces albus. The natural preservative is used as a natural preservative due to the characteristics of good water solubility, broad-spectrum antibacterial activity, degradation to lysine which is easy to absorb in vivo and the like, and is approved as a safe food preservative by FDA 10 months in 2003. The epsilon-PL is polymerized by 25-35 lysines, wherein the epsilon-PL with the molecular weight of 3600-4300 has the best bacteriostatic activity, and when the molecular weight is lower than 1300, the epsilon-PL loses the bacteriostatic activity.
Disclosure of Invention
The invention aims to provide polylysine sunscreen peptides and a preparation method thereof, wherein the polylysine sunscreen peptides (including alpha-polylysine and epsilon-polylysine) are obtained by condensation reaction of polylysine and various micromolecule ultraviolet absorbers under the action of a condensing agent, an additive and the like.
The structural formula of the polylysine sunscreen peptide is shown as a formula A or a formula B:
formula A is alpha-polylysine sunscreen peptide; the formula B is epsilon-polylysine sunscreen peptide; in the formula, n represents a natural number of more than 2, R represents a dehydroxylation residue of a micromolecule ultraviolet absorbent containing any one of a cinnamic acid structure, a salicylic acid structure, a benzoic acid structure, a carboxyl structure and a sulfonic acid group structure, and the dehydroxylation residue is specifically as follows: ferulic acid, 4-methoxy cinnamic acid, 3, 4-dimethoxy cinnamic acid, 4-dimethylamino benzoic acid, o-hydroxybenzoic acid, 4-diethylamino keto acid, disalicylic acid, 4-methyl salicylic acid, 2, 6-naphthalene dicarboxylic acid, 1, 8-dihydroxy-3-carboxy anthraquinone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, maifantastic acid SX, disodium phenyl dibenzoimidazole tetrasulfonate, and the like.
The preparation method of the polylysine sunscreen peptide comprises the following steps:
(1) Dissolving a micromolecular ultraviolet absorbent in a solvent A, adding a condensing agent and an additive under the ice bath condition, naturally heating to room temperature, and stirring for activating reaction; wherein the micromolecular ultraviolet absorbent is a micromolecular ultraviolet absorbent containing any one of a cinnamic acid structure, a salicylic acid structure, a benzoic acid structure, a carboxyl structure and a sulfonic group structure;
(2) Adding alpha-polylysine or epsilon-polylysine into a solvent B, adding alkali, and stirring until the alpha-polylysine or the epsilon-polylysine is completely dissolved;
(3) Dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature to perform condensation reaction after dropwise adding;
(4) And (4) removing impurities and purifying the reaction liquid obtained in the step (3), and freeze-drying to obtain the polylysine sunscreen peptide.
In the step (1), the small molecule ultraviolet absorbent is preferably one of ferulic acid, 4-methoxycinnamic acid, 3, 4-dimethoxycinnamic acid, 4-dimethylaminobenzoic acid, o-hydroxybenzoic acid, 4-diethylamino keto acid, disalicylic acid, 4-methyl salicylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-dihydroxy-3-carboxyl anthraquinone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, maifantastic filter SX and phenyl dibenzoimidazole tetrasulfonate disodium.
When the condensation reaction is an anhydrous system, the solvent A and the solvent B are respectively one or more than two mixed solutions of N, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran, and the solvent A and the solvent B can be the same or different; the condensing agent is any one of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, the additive is any one of 1-hydroxybenzotriazole, N-hydroxysuccinimide and 2-oxime ethyl cyanoacetate, and the base is any one of triethylamine and N, N-diisopropylethylamine.
When the condensation reaction is a water system, the solvent A is a mixed solution of one or more than two of N, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran, the solvent B is a mixed solution of at least one of N, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran and deionized water in a volume ratio of 0-1.
In the step (1), the molar ratio of the small-molecule ultraviolet absorber to the condensing agent to the additive is preferably 1 to 3.
In the step (2), the molar ratio of the α -polylysine or the ∈ -polylysine to the base is preferably 1 to 3.
In the step (3), the mol ratio of the alpha-polylysine or the epsilon-polylysine to the micromolecular ultraviolet absorbent is preferably 1 to 0.1, and the condensation reaction time is preferably 17 to 22 hours.
In the step (4), the method for removing impurities and purifying comprises the following steps: transferring the reaction solution into a dialysis bag with the molecular weight cutoff of 1 kD-5 kD, and dialyzing for 2-3 days, wherein the used dialysis solution is one or a mixed solution of ethanol and deionized water.
In the step (4), the method for removing impurities and purifying may further include: adding the reaction solution into one or a mixture of ethanol and deionized water for crystallization, or adding one of isopropanol, ethyl acetate and diethyl ether for crystallization, and centrifuging or filtering.
The invention has the following beneficial effects:
the polylysine sunscreen peptide can not be permeated and absorbed by skin, has better sunscreen performance than a micromolecule sunscreen agent, overcomes the defect that the micromolecule sunscreen agent commonly used in the current market is easy to be absorbed through skin to cause potential toxicity, improves the safety of a sunscreen product, is a good substitute of the existing micromolecule sunscreen agent, and is suitable for the field of sunscreen cosmetics.
Drawings
FIG. 1 is an infrared contrast spectrum of 4-diethylamino keto acid, epsilon-polylysine and epsilon-polylysine-diethylamino keto acid (EPL-TS) sunscreen peptide.
FIG. 2 is nuclear magnetic contrast spectra of 4-diethylamino keto acid, epsilon-polylysine and epsilon-polylysine-diethylamino keto acid (EPL-TS) sunscreen peptides.
FIG. 3 is an IR contrast spectrum of ferulic acid, epsilon-polylysine and epsilon-polylysine-ferulic acid (EPL-AWS) sunscreen peptides.
FIG. 4 is an IR contrast spectrum of 4-methoxycinnamic acid, epsilon-polylysine, and epsilon-polylysine-methoxycinnamic acid (EPL-RGS) sunscreen peptide.
FIG. 5 is an infrared contrast spectrum of 4-dimethylaminobenzoic acid, epsilon-polylysine and epsilon-polylysine-dimethylaminobenzoic acid (EPL-BJS) sunscreen peptides.
FIG. 6 is a graph of UV absorbance vs. EPL-AWS sunscreen peptide from ferulic acid.
FIG. 7 is a graph of UV absorbance comparison of isoamyl p-methoxycinnamate with EPL-RGS sunscreen peptides.
FIG. 8 is a graph of UV absorption comparison of isooctyl p-dimethylaminobenzoate with EPL-BJS sunscreen peptide.
FIG. 9 is a UV absorption contrast spectrum of diethylamino hydroxybenzoyl hexyl benzoate and EPL-TS sunscreen peptide.
Detailed Description
The technical solutions of the present invention are further described in detail by the following examples, which are only for further illustration of the present invention, but do not limit the scope of the present invention.
Example 1
1. Adding 1mmol 4-diethylamino keto acid into 10mL N, N-dimethylformamide, stirring for dissolving, adding 1.5mmol N, N' -diisopropylcarbodiimide and 1.5mmol 2-oxime ethyl cyanoacetate under the ice-bath condition, naturally heating to room temperature, and stirring for activating for 6 hours;
2. adding 0.9mmol of epsilon-polylysine (calculated by monomer, n = 25-35) into 4.5mL of dimethyl sulfoxide, adding 1.8mmol of triethylamine, and stirring until the epsilon-polylysine is completely dissolved;
3. dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature for reacting for 18 hours after dropwise adding;
4. transferring the reaction solution obtained in the step 3 into a dialysis bag with the molecular weight cut-off of 5KD, and mixing the solution with ethanol and deionized water in a volume ratio of 1:1, dialyzing the dialysate for four times for about 2 to 3 days; transferring the dialyzed solution into a penicillin bottle, and freeze-drying to obtain the epsilon-polylysine-diethylaminoketonic acid (EPL-TS) sunscreen peptide with the yield of 85%. The structural characterization results of EPL-TS sunscreen peptide are shown in FIG. 1 and FIG. 2. From the infrared spectrum of FIG. 1, it can be found that epsilon-polylysine is present at 3402cm -1 、3226cm -1 The absorption peak is the stretching vibration of the N-H bond in the alpha amino and the amide, and the EPL-TS only contains the absorption peak positioned at 3287cm -1 Determining that alpha amino group in epsilon-polylysine is completely consumed by determining the absorption peak of N-H bond stretching vibration in single amide, and comparing with epsilon-polylysine, EPL-TS and 4-diethylaminoketonic acid both contain 3060cm -1 And 1337cm -1 The phenolic hydroxyl group stretching vibration absorption peak is positioned, which shows that 4-diethylamino keto acid is successfully connected to epsilon-polylysine, and the EPL-TS structure is correct. As can be seen from the NMR spectrum (solvent is deuterated dimethyl sulfoxide) in FIG. 2, the NMR spectrum of the EPL-TS does not contain hydrogen in the alpha amino group of the epsilon-polylysine and the carboxyl group of the 4-diethylamino keto acid, and hydrogen in other positions in the EPL-TS, the NMR spectrum of the EPL-TS does not contain hydrogen in the alpha amino group of the epsilon-polylysine and the carboxyl group of the 4-diethylamino keto acidHydrogen at other positions in the keto acid corresponds one to one; the results show that 4-diethylaminoketonic acid is successfully connected to epsilon-polylysine, and the EPL-TS structure is correct.
Example 2
In step 1 of this example, N-dimethylformamide in step 1 of example 1 was replaced with an equal volume of dimethyl sulfoxide, N' -diisopropylcarbodiimide in step 1 of example 1 was replaced with an equal mole of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, and the other steps were the same as in example 1 to obtain EPL-TS sunscreen peptide with a yield of 73%.
Example 3
1. Adding 1mmol 4-diethylamino keto acid into 10mL N, N-dimethylformamide, stirring for dissolving, adding 1.5mmol 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide and 1.5mmol 1-hydroxybenzotriazole under the ice-bath condition, naturally heating to room temperature, and stirring for activating for reaction for 6 hours;
2. adding 0.9mmol of epsilon-polylysine (calculated by monomer, n = 25-35) into 4.5mL of deionized water, adding 1.8mmol of sodium hydroxide, and stirring until the epsilon-polylysine is completely dissolved;
3. dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature for reacting for 18 hours;
4. transferring the reaction solution obtained in the step 3 into a dialysis bag with the molecular weight cut-off of 5KD, and mixing the solution with ethanol and deionized water in a volume ratio of 1:1, dialyzing for about 2 to 3 days by using the dialysate; transferring the dialyzed solution into a penicillin bottle, and freeze-drying to obtain the EPL-TS sun-proof peptide with the yield of 65%.
Example 4
EPL-TS sunscreen peptide was obtained in 63% yield by the same procedure as in example 3, except that in step 1 of this example, N-dimethylformamide in step 1 of example 3 was replaced with an equal volume of tetrahydrofuran, in step 2 of this example, sodium hydroxide in step 2 of example 3 was replaced with an equal mole of sodium carbonate, and in step 2 of this example.
Example 5
In step 1 of this example, N' -diisopropylcarbodiimide in step 1 of example 1 was replaced with an equivalent mole of dicyclohexylcarbodiimide, ethyl 2-oxime cyanoacetate in step 1 of example 1 was replaced with an equivalent mole of N-hydroxysuccinimide, and in step 2 of this example, triethylamine in step 2 of example 1 was replaced with an equivalent mole of N, N-diisopropylethylamine, and the other steps were the same as in example 1 to obtain EPL-TS sunscreen peptide with a yield of 83%.
Example 6
In step 2 of this example, the equimolar α -polylysine (n =25 based on the monomer) was used instead of the ∈ -polylysine (based on the monomer) in step 2 of example 1, and the other steps were the same as in example 1 to obtain α -polylysine sunscreen peptide-25 at a yield of 91%.
Example 7
1. Adding 10mmol of 4-diethylamino keto acid into 100mL of N, N-dimethylformamide, stirring and dissolving, adding 15mmol of N, N' -diisopropylcarbodiimide and 15mmol of 2-oxime ethyl cyanoacetate under the ice-bath condition, naturally heating to room temperature, and stirring and activating for 6 hours;
2. adding 9mmol of alpha-polylysine (calculated by the monomer, n = 25) into 45mL of dimethyl sulfoxide, adding 18mmol of triethylamine, and stirring until complete dissolution;
3. dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature for reacting for 18 hours;
4. and (3) adding the reaction liquid in the step (3) into an ethanol water solution with the volume concentration of 30% for crystallization, centrifuging the crystallized product, washing the crystallized product twice by using deionized water, diluting the crystallized product into homogenate by using the deionized water, and freeze-drying the homogenate to obtain the alpha-polylysine sunscreen peptide-25 with the yield of 90%.
Example 8
1. Adding 100mmol 4-diethylamino ketonic acid into 1000mL N, N-dimethylformamide, stirring for dissolving, adding 150mmol N, N' -diisopropylcarbodiimide and 150mmol 2-oxime ethyl cyanoacetate under the ice bath condition, naturally heating to room temperature, and stirring for activating reaction for 6h;
2. adding 90mmol of epsilon-polylysine (calculated by monomer, n = 25-35) into 450mL of dimethyl sulfoxide, adding 180mmol of triethylamine, and stirring until the epsilon-polylysine is completely dissolved;
3. dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature for reacting for 18 hours;
4. and (4) adding the reaction solution obtained in the step (3) into an ethanol aqueous solution with the volume concentration of 30%, centrifuging, washing twice with deionized water, diluting with deionized water to obtain homogenate, and freeze-drying to obtain the EPL-TS sun-screening peptide with the yield of 86%.
In step 1 of the above examples 1 to 6, the 4-diethylaminoketo acid was replaced with equimolar ferulic acid, 4-methoxycinnamic acid, and 4-dimethylaminobenzoic acid, respectively, and the other steps were the same as those of the corresponding examples, to obtain epsilon-polylysine-ferulic acid (EPL-AWS) sunscreen peptide, epsilon-polylysine-methoxycinnamic acid (EPL-RGS) sunscreen peptide, and epsilon-polylysine-dimethylaminobenzoic acid (EPL-BJS) sunscreen peptide, respectively, and the results of structural characterization are shown in fig. 3 to 5.
In order to prove the beneficial effects of the invention, the EPL-AWS sunscreen peptide EPL-RGS sunscreen peptide, EPL-BJS sunscreen peptide and EPL-TS sunscreen peptide prepared by the invention are respectively compared with ferulic acid, isoamyl p-methoxycinnamate, isooctyl p-dimethylaminobenzoate and hexyl diethylaminohydroxybenzoyl benzoate in ultraviolet absorption performance, and the results are shown in FIGS. 6-9 and Table 1.
TABLE 1 molecular weight ranges and UV absorption ranges of four sunscreen peptides
As can be seen from fig. 6 to 9 and table 1, the molecular weight of the micromolecular sunscreen agent is 190 to 400, and the molecular weight of the polylysine sunscreen peptide is greater than 6000, so that skin penetration is avoided, the defect of potential toxicity caused by easy transdermal absorption of the micromolecular sunscreen agent is overcome, and the safety of the sunscreen product is improved; compared with the ultraviolet absorption range, the polylysine sun-screening peptide has wider absorption range than the corresponding micromolecule sun-screening agent, and the highest absorption peaks have red shift, thereby showing that the polylysine sun-screening peptide has more excellent sun-screening performance.
Claims (9)
1. A polylysine sunscreen peptide is characterized in that the structural formula is shown as formula A or formula B:
formula A is alpha-polylysine sunscreen peptide; the formula B is epsilon-polylysine sunscreen peptide; wherein n represents a natural number of 2 or more, and R represents a dehydroxylated residue of a small-molecule ultraviolet absorber having any one of a cinnamic acid structure, a salicylic acid structure, a benzoic acid structure, a carboxyl structure and a sulfonic acid structure.
2. A polylysine sunscreen peptide according to claim 1 wherein R represents a dehydroxylated residue of any one of ferulic acid, 4-methoxycinnamic acid, 3, 4-dimethoxycinnamic acid, 4-dimethylaminobenzoic acid, o-hydroxybenzoic acid, 4-diethylaminoketo acid, disalicylic acid, 4-methylsalicylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-dihydroxy-3-carboxyanthraquinone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, mediterranean filter SX, disodium phenyldibenzoimidazole tetrasulfonate.
3. A method of preparing a polylysine sunscreen peptide according to claim 1, comprising the steps of:
(1) Dissolving a micromolecular ultraviolet absorbent in a solvent A, adding a condensing agent and an additive under the ice bath condition, naturally heating to room temperature, and stirring for activating reaction; wherein the micromolecular ultraviolet absorbent is a micromolecular ultraviolet absorbent containing any one of a cinnamic acid structure, a salicylic acid structure, a benzoic acid structure, a carboxyl structure and a sulfonic group structure;
(2) Adding alpha-polylysine or epsilon-polylysine into a solvent B, adding alkali, and stirring until the alpha-polylysine or the epsilon-polylysine is completely dissolved;
(3) Dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature to perform condensation reaction after dropwise adding;
(4) And (4) removing impurities and purifying the reaction liquid obtained in the step (3), and freeze-drying to obtain the polylysine sunscreen peptide.
4. The method for preparing polylysine sunscreen peptide according to claim 3, wherein in step (1), the small molecule UV absorber is any one of ferulic acid, 4-methoxycinnamic acid, 3, 4-dimethoxycinnamic acid, 4-dimethylaminobenzoic acid, o-hydroxybenzoic acid, 4-diethylamino-keto acid, disalicylic acid, 4-methylsalicylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-dihydroxy-3-carboxyanthraquinone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, maifanitum SX, and disodium phenylbisbenzimidazole tetrasulfonate.
5. The method for preparing polylysine suntan peptide according to claim 3, wherein the solvent A and the solvent B are respectively one or a mixture of two or more of N, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran, the condensing agent is one of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, the additive is one of 1-hydroxybenzotriazole, N-hydroxysuccinimide and 2-oxime ethyl cyanoacetate, and the base is one of triethylamine and N, N-diisopropylethylamine.
6. The method for preparing polylysine sunscreen peptide according to claim 3, wherein the solvent A is a mixture of one or more of N, N-dimethylformamide, dimethylsulfoxide and tetrahydrofuran, the solvent B is a mixture of at least one of N, N-dimethylformamide, dimethylsulfoxide and tetrahydrofuran and deionized water at a volume ratio of 0 to 1.
7. The preparation method of polylysine sunscreen peptide according to any one of claims 3 to 6, wherein in step (1), the mole ratio of the small molecule ultraviolet absorbent to the condensing agent and the additive is 1 to 3; in the step (2), the molar ratio of the alpha-polylysine or the epsilon-polylysine to the alkali is 1-3; in the step (3), the molar ratio of the alpha-polylysine or the epsilon-polylysine to the micromolecule ultraviolet absorbent is 1.1-2, and the condensation reaction time is 17-22 h.
8. The method for preparing polylysine sunscreen peptide according to claim 3, wherein in step (4), the method for removing impurities and purifying comprises: transferring the reaction solution into a dialysis bag with the molecular weight cutoff of 1 kD-5 kD, and dialyzing for 2-3 days, wherein the used dialysis solution is one or a mixed solution of ethanol and deionized water.
9. The method for preparing polylysine sunscreen peptide according to claim 3, wherein in step (4), the method for removing impurities and purifying comprises: adding the reaction solution into one of ethanol and deionized water or the mixture of the two, crystallizing, or adding one of isopropanol, ethyl acetate and diethyl ether, crystallizing, centrifuging or filtering.
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| CN117503986A (en) * | 2024-01-04 | 2024-02-06 | 苏州心锐医疗科技有限公司 | Injectable wet adhesion hydrogel with double-layer network structure and preparation method thereof |
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| CN117503986A (en) * | 2024-01-04 | 2024-02-06 | 苏州心锐医疗科技有限公司 | Injectable wet adhesion hydrogel with double-layer network structure and preparation method thereof |
| CN117503986B (en) * | 2024-01-04 | 2024-03-22 | 苏州心锐医疗科技有限公司 | Injectable wet adhesion hydrogel with double-layer network structure and preparation method thereof |
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