CN110903501B - Preparation method and application of gamma-polyglutamic acid gel nanoparticles - Google Patents
Preparation method and application of gamma-polyglutamic acid gel nanoparticles Download PDFInfo
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Abstract
The invention relates to a preparation method of gamma-polyglutamic acid gel nanoparticles, which comprises the following steps: firstly, adding sodium tripolyphosphate into deionized water to prepare a sodium tripolyphosphate solution, adjusting the pH value to 6.0-6.5 by using an organic acid solution, and filtering for later use; step two, preparing a chitosan solution: adding chitosan into an organic acid solution to prepare a chitosan solution, stirring and swelling for 16-20h, adjusting the pH value of the swelled chitosan solution to 6.0-6.5, and filtering for later use; step three, preparing a gamma-polyglutamic acid-polyvinylpyrrolidone solution: weighing gamma-polyglutamic acid and polyvinylpyrrolidone, putting into deionized water to prepare a gamma-polyglutamic acid-polyvinylpyrrolidone solution, adjusting the pH value to 5.8-6.2, and filtering for later use; fourthly, preparing the gamma-polyglutamic acid nanoparticles: mixing the gamma-polyglutamic acid-polyvinylpyrrolidone solution and the sodium tripolyphosphate solution, and then dropwise adding the mixture into the chitosan solution until obvious blue opalescence appears. And fifthly, freeze-drying the gamma-polyglutamic acid nanoparticles prepared in the fourth step into nanoparticle dry powder.
Description
Technical Field
The invention relates to a preparation method and application of gamma-polyglutamic acid gel nanoparticles, and belongs to the technical field of gel processing.
Background
Gamma-polyglutamic acid (gamma-PGA) is a macromolecular compound prepared by bacillus subtilis through a fermentation technology, and is a polypeptide molecule formed by polymerizing L-glutamic acid and D-glutamic acid monomers through amido bonds. The molecular chain of the material has-COOH groups with strong activity, so that the material can be used for absorbing water, moisture and heavy metals, and the monomer glutamic acid belongs to amino acid, so that the material cannot cause any pollution after being degraded, and is an environment-friendly material. The gamma-polyglutamic acid has strong water retention and slow release because of containing more carboxyl and active groups, and the properties of the gamma-polyglutamic acid in the aspects of water retention and slow release enable the gamma-polyglutamic acid to be widely applied to health care products, medicines and cosmetics.
However, in use, the gamma-polyglutamic acid hydrogel is generally found to become weak after absorbing water, has poor mechanical properties and has great limitation on application. In addition, gamma-polyglutamic acid hydrogel can absorb water thousands times for pure water, but in an ionic solution environment such as saline, the liquid absorption capacity of the hydrogel is greatly reduced. In practical applications, the hydrogel is usually in an environment requiring a certain mechanical strength and an ionic environment having a certain concentration. Therefore, the improvement of the mechanical properties of the hydrogel and the liquid absorption performance of the ionic solution is a problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a preparation method and application of gamma-polyglutamic acid gel nanoparticles.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the gamma-polyglutamic acid gel nanoparticles are prepared by the following steps:
step one, preparing a sodium tripolyphosphate solution: adding sodium tripolyphosphate into deionized water to prepare sodium tripolyphosphate solution, adjusting pH to 6.0-6.5 with organic acid solution, and filtering;
step two, preparing a chitosan solution: adding chitosan into an organic acid solution to prepare a chitosan solution, stirring and swelling for 16-20h, adjusting the pH value of the swelled chitosan solution to 6.0-6.5, and filtering for later use;
step three, preparing a gamma-polyglutamic acid-polyvinylpyrrolidone solution: weighing gamma-polyglutamic acid and polyvinylpyrrolidone, putting into deionized water to prepare a gamma-polyglutamic acid-polyvinylpyrrolidone solution, adjusting the pH value to 5.8-6.2, and filtering for later use;
fourthly, preparing the gamma-polyglutamic acid nanoparticles: mixing the gamma-polyglutamic acid-polyvinylpyrrolidone solution and the sodium tripolyphosphate solution, and then dropwise adding the mixture into the chitosan solution until obvious blue opalescence appears.
And fifthly, freeze-drying the gamma-polyglutamic acid nanoparticles prepared in the fourth step into nanoparticle dry powder.
In practice, the sodium tripolyphosphate is found to promote dissolution and dispersion, improve the uniformity of water absorption expansion of the gamma-polyglutamic acid hydrogel, avoid local performance defects and cause insufficient overall strength, can chelate ions in the gamma-polyglutamic acid solution and reduce the ionic strength, and the salt absorption rate of the gamma-polyglutamic acid nanoparticles is remarkably improved because the ionic strength is inversely proportional to the 5/3 th power of the hydrogel adsorption rate. Secondly, PVP is used as a synthetic water-soluble polymer compound, has the general properties of the water-soluble polymer compound, including film forming property and solubilization, and in practice, the fact that the film forming property of gamma-polyglutamic acid gel can be remarkably improved by adding a certain amount of polyvinylpyrrolidone is found, especially when the gamma-polyglutamic acid gel is used as a drug carrier, the film forming property is important, in addition, the solubility of a drug can be improved, and the drug loading effect and the permeation effect can be improved.
Preferably, the gamma-polyglutamic acid gel nanoparticle is prepared by the following method:
step one, preparing a sodium tripolyphosphate solution: adding sodium tripolyphosphate into deionized water to prepare 1.5-2.5mg/ml sodium tripolyphosphate solution, adjusting pH to 6.0-6.5 with 0.3-0.5% (v/v) organic acid solution, and filtering with microporous membrane;
step two, preparing a chitosan solution: selecting chitosan with molecular weight of 50-90kDa, adding into 0.3-0.5% (v/v) organic acid solution to prepare 2-3mg/ml chitosan solution, stirring and swelling for 16-20h, adjusting pH of the swollen chitosan solution to 6.0-6.5 with 0.08-0.1mol/L alkali solution, and filtering with microporous membrane;
step three, preparing a gamma-polyglutamic acid-polyvinylpyrrolidone solution: weighing 300-400g of gamma-polyglutamic acid and 15-25g of polyvinylpyrrolidone, putting into 1L of deionized water to prepare a gamma-polyglutamic acid-polyvinylpyrrolidone solution, adjusting the pH to 5.8-6.2 by using 0.3-0.5% (v/v) of an organic acid solution, and filtering by using a microporous filter membrane for later use;
fourthly, preparing the gamma-polyglutamic acid nanoparticles: mixing the gamma-polyglutamic acid-polyvinylpyrrolidone solution and the sodium tripolyphosphate solution, and then dropwise adding the mixture into the chitosan solution until obvious blue opalescence appears.
Preferably, the organic acid is any one of acetic acid, formic acid and citric acid.
Preferably, the alkali solution is an aqueous sodium hydroxide solution or aqueous ammonia or aqueous sodium bicarbonate solution.
The application of the gamma-polyglutamic acid gel nanoparticles is used for loading active ingredients of cosmetics and active ingredients of medicines for treating body surface diseases, the loading mode is that the active ingredients are synchronously added in the third step of preparation of the gamma-polyglutamic acid-polyvinylpyrrolidone solution, or the active ingredients are independently prepared and then mixed with the gamma-polyglutamic acid-polyvinylpyrrolidone solution and the sodium tripolyphosphate solution, and the specific loading mode is determined based on the solubility of the active ingredients.
Preferably, the method is used for loading the cosmetic active ingredient, and the loading mode is that the active ingredient is synchronously added in the third step of preparing the gamma-polyglutamic acid-polyvinylpyrrolidone solution to form the gamma-polyglutamic acid-polyvinylpyrrolidone-active ingredient solution.
Has the advantages that:
the gamma-polyglutamic acid gel nanoparticles have good stability, good mechanical strength and liquid absorption performance to ionic solution, and when the gamma-polyglutamic acid gel disclosed by the invention is used as a drug carrier, the film forming property is good, and in addition, the solubility of a drug can be improved, and the drug loading effect and the permeation effect are improved. The method has reasonable process design, easy industrial production and reliable product quality.
Detailed Description
Example 1:
the gamma-polyglutamic acid gel nanoparticles are prepared by the following steps:
step one, preparing a sodium tripolyphosphate solution: adding sodium tripolyphosphate into deionized water to prepare 1.5mg/ml sodium tripolyphosphate solution, adjusting pH to 6.0 with 0.3% (v/v) organic acid solution, and filtering with microporous membrane;
step two, preparing a chitosan solution: selecting chitosan with molecular weight of 50kDa, adding into 0.3% (v/v) organic acid solution to prepare chitosan solution with concentration of 2mg/ml, stirring and swelling for 16h, adjusting pH of the swollen chitosan solution to 6.0 with 0.08mol/L alkali solution, and filtering with microporous membrane for later use;
step three, preparing a gamma-polyglutamic acid-polyvinylpyrrolidone solution: weighing 300g of gamma-polyglutamic acid and 15g of polyvinylpyrrolidone, putting into 1L of deionized water to prepare a gamma-polyglutamic acid-polyvinylpyrrolidone solution, adjusting the pH to 5.8 by using 0.3% (v/v) organic acid solution, and filtering by using a microporous filter membrane for later use;
fourthly, preparing the gamma-polyglutamic acid nanoparticles: mixing the gamma-polyglutamic acid-polyvinylpyrrolidone solution and the sodium tripolyphosphate solution, and then adding the mixture into the chitosan solution until obvious blue opalescence appears
And fifthly, freeze-drying the gamma-polyglutamic acid nanoparticles prepared in the fourth step into nanoparticle dry powder.
In example 1, the organic acid was acetic acid, and the alkali solution was an aqueous sodium hydroxide solution.
The gamma-polyglutamic acid gel nanoparticles of example 1 have a saline absorption rate of 45.8 times measured after swelling equilibrium in physiological saline, and have a compressive strength of 642.8Mpa, a tensile strength of 2.18Mpa, and a tensile elongation at break of 184% based on the gel after swelling by water, which are measured according to the national standard, which are superior to those of the prior art.
Example 2
The gamma-polyglutamic acid gel nanoparticles are prepared by the following steps:
step one, preparing a sodium tripolyphosphate solution: adding sodium tripolyphosphate into deionized water to prepare 2.5mg/ml sodium tripolyphosphate solution, adjusting pH to 6.5 with 0.5% (v/v) organic acid solution, and filtering with microporous membrane;
step two, preparing a chitosan solution: selecting chitosan with the molecular weight of 90kDa, putting the chitosan into 0.5% (v/v) organic acid solution to prepare chitosan solution with the concentration of 3mg/ml, stirring and swelling for 20 hours, adjusting the pH value of the swelled chitosan solution to 6.5 by using 0.1mol/L alkali solution, and filtering by using a microporous filter membrane for later use;
step three, preparing a gamma-polyglutamic acid-polyvinylpyrrolidone solution: weighing 400g of gamma-polyglutamic acid and 25g of polyvinylpyrrolidone, putting into 1L of deionized water to prepare a gamma-polyglutamic acid-polyvinylpyrrolidone solution, adjusting the pH to 6.2 by using 0.5% (v/v) organic acid solution, and filtering by using a microporous filter membrane for later use;
fourthly, preparing the gamma-polyglutamic acid nanoparticles: mixing the gamma-polyglutamic acid-polyvinylpyrrolidone solution and the sodium tripolyphosphate solution, and then dropwise adding the mixture into the chitosan solution until obvious blue opalescence appears.
And fifthly, freeze-drying the gamma-polyglutamic acid nanoparticles prepared in the fourth step into nanoparticle dry powder.
In example 2, the organic acid was citric acid and the alkali solution was ammonia.
The gamma-polyglutamic acid gel nanoparticles of example 2 have a saline absorption rate of 42.8 times measured after swelling equilibrium in normal saline, and have a compressive strength of 632.8Mpa, a tensile strength of 2.08Mpa, and a tensile elongation at break of 174% based on the gel after swelling by water, which are measured by reference to the national standard, which are superior to those of the prior art.
Example 3
The gamma-polyglutamic acid gel nanoparticles are prepared by the following steps:
step one, preparing a sodium tripolyphosphate solution: adding sodium tripolyphosphate into deionized water to prepare 2.0mg/ml sodium tripolyphosphate solution, adjusting pH to 6.2 with 0.4% (v/v) organic acid solution, and filtering with microporous membrane;
step two, preparing a chitosan solution: selecting 60kDa molecular weight chitosan, adding into 0.4% (v/v) organic acid solution to prepare 2.5mg/ml chitosan solution, stirring and swelling for 18h, adjusting pH of the swelled chitosan solution to 6.2 with 0.09mol/L alkali solution, and filtering with microporous membrane for later use;
step three, preparing a gamma-polyglutamic acid-polyvinylpyrrolidone solution: weighing 350g of gamma-polyglutamic acid and 20g of polyvinylpyrrolidone, putting into 1L of deionized water to prepare a gamma-polyglutamic acid-polyvinylpyrrolidone solution, adjusting the pH to 6.0 by using 0.4% (v/v) organic acid solution, and filtering by using a microporous filter membrane for later use;
fourthly, preparing the gamma-polyglutamic acid nanoparticles: mixing the gamma-polyglutamic acid-polyvinylpyrrolidone solution and the sodium tripolyphosphate solution, and then dropwise adding the mixture into the chitosan solution until obvious blue opalescence appears.
Step five, the gamma-polyglutamic acid nanoparticles prepared in the step four are lyophilized into dry nanoparticle powder in example 3, the organic acid is acetic acid, and the aqueous alkali is aqueous sodium hydroxide solution.
The gamma-polyglutamic acid gel nanoparticles of example 3 have a saline absorption rate of 48.2 times measured after swelling equilibrium in physiological saline, and have a compressive strength of 648.8Mpa, a tensile strength of 2.58Mpa, and a tensile elongation at break of 192% based on the gel after swelling with water, which are measured by reference to the national standard, which are superior to those of the prior art.
Example 4
The gamma-polyglutamic acid gel nanoparticles are prepared by the following steps:
step one, preparing a sodium tripolyphosphate solution: adding sodium tripolyphosphate into deionized water to prepare 2.2mg/ml sodium tripolyphosphate solution, adjusting pH to 6.3 with 0.35% (v/v) organic acid solution, and filtering with microporous membrane;
step two, preparing a chitosan solution: selecting chitosan with the molecular weight of 80kDa, putting the chitosan into 0.35% (v/v) organic acid solution to prepare 2.0mg/ml chitosan solution, stirring and swelling for 16 hours, adjusting the pH value of the swelled chitosan solution to 6.2 by using 0.1mol/L alkali solution, and filtering by using a microporous filter membrane for later use;
step three, preparing a gamma-polyglutamic acid-polyvinylpyrrolidone solution: weighing 380g of gamma-polyglutamic acid and 20g of polyvinylpyrrolidone, putting into 1L of deionized water to prepare a gamma-polyglutamic acid-polyvinylpyrrolidone solution, adjusting the pH to 6.1 by using 0.35% (v/v) organic acid solution, and filtering by using a microporous filter membrane for later use;
fourthly, preparing the gamma-polyglutamic acid nanoparticles: mixing the gamma-polyglutamic acid-polyvinylpyrrolidone solution and the sodium tripolyphosphate solution, and then dropwise adding the mixture into the chitosan solution until obvious blue opalescence appears.
In example 4, the organic acid was acetic acid, and the alkali solution was an aqueous sodium hydroxide solution.
And fifthly, freeze-drying the gamma-polyglutamic acid nanoparticles prepared in the fourth step into nanoparticle dry powder.
The gamma-polyglutamic acid gel nanoparticles of example 4 have a saline absorption rate of 46.8 times measured after swelling equilibrium in physiological saline, and have a compressive strength of 632.8Mpa, a tensile strength of 2.25Mpa, and a tensile elongation at break of 179.5% based on the gel after swelling by water, which are measured by reference to the national standard, which are superior to those of the prior art.
Comparative example 1
The gamma-polyglutamic acid gel nanoparticles are prepared by the following steps:
step one, preparing a sodium tripolyphosphate solution: adding sodium tripolyphosphate into deionized water to prepare 2.0mg/ml sodium tripolyphosphate solution, adjusting pH to 6.2 with 0.4% (v/v) organic acid solution, and filtering with microporous membrane;
step two, preparing a chitosan solution: selecting 60kDa molecular weight chitosan, adding into 0.4% (v/v) organic acid solution to prepare 2.5mg/ml chitosan solution, stirring and swelling for 18h, adjusting pH of the swelled chitosan solution to 6.2 with 0.09mol/L alkali solution, and filtering with microporous membrane for later use;
step three, preparing a gamma-polyglutamic acid solution: weighing 350g of gamma-polyglutamic acid, putting into 1L of deionized water to prepare gamma-polyglutamic acid solution, adjusting the pH value to 6.0 by using 0.4% (v/v) organic acid solution, and filtering by using a microporous filter membrane for later use;
fourthly, preparing the gamma-polyglutamic acid nanoparticles: the gamma-polyglutamic acid solution and the sodium tripolyphosphate solution are mixed and then are dripped into the chitosan solution until obvious blue opalescence appears.
Fifthly, freeze-drying the gamma-polyglutamic acid nanoparticles prepared in the fourth step into nanoparticle dry powder, wherein the organic acid is acetic acid, and the aqueous alkali is sodium hydroxide aqueous solution.
Comparative example 2
The gamma-polyglutamic acid gel nanoparticles are prepared by the following steps:
step one, preparing a sodium tripolyphosphate solution: adding sodium tripolyphosphate into deionized water to prepare 2.2mg/ml sodium tripolyphosphate solution, adjusting pH to 6.3 with 0.35% (v/v) organic acid solution, and filtering with microporous membrane;
step two, preparing a chitosan solution: selecting chitosan with the molecular weight of 80kDa, putting the chitosan into 0.35% (v/v) organic acid solution to prepare 2.0mg/ml chitosan solution, stirring and swelling for 16 hours, adjusting the pH value of the swelled chitosan solution to 6.2 by using 0.1mol/L alkali solution, and filtering by using a microporous filter membrane for later use;
step three, preparing a gamma-polyglutamic acid solution: weighing 380g of gamma-polyglutamic acid, putting the gamma-polyglutamic acid into 1L of deionized water to prepare gamma-polyglutamic acid solution, adjusting the pH value to 6.1 by using 0.35% (v/v) organic acid solution, and filtering by using a microporous filter membrane for later use;
fourthly, preparing the gamma-polyglutamic acid nanoparticles: the gamma-polyglutamic acid solution and the sodium tripolyphosphate solution are mixed and then are dripped into the chitosan solution until obvious blue opalescence appears.
The organic acid is acetic acid, and the alkali solution is sodium hydroxide aqueous solution.
And fifthly, freeze-drying the gamma-polyglutamic acid nanoparticles prepared in the fourth step into nanoparticle dry powder.
The film-forming properties and solubilization of the gamma-polyglutamic acid gel nanoparticles of examples 1-4 and the gamma-polyglutamic acid gel nanoparticles of comparative examples 1-2 were verified as follows:
1. film forming property
The gamma-polyglutamic acid gel nanoparticles of examples 1-4 and the gamma-polyglutamic acid gel nanoparticles of comparative examples 1-2 are prepared by respectively adding 50g of water to fully swell, and then spreading a film on a clean glass flat plate with the film thickness of 1 cm. The film forming property of the gamma-polyglutamic acid gel nanoparticles of comparative examples 1-2 is inferior to that of the gamma-polyglutamic acid gel nanoparticles added with PVK, and the problem of poor uniformity exists locally.
2. With respect to solubilization
The applicant takes an okra extract as an example to carry out verification experiments, the okra extract contains viscous polysaccharide colloid which is a covalent complex formed by polysaccharide and protein consisting of galactose, arabinose, rhamnose and the like, and simultaneously contains high-content flavone, so that the okra extract has good moisturizing, thickening, antioxidant and whitening effects, is used as a humectant, a thickener, a whitening agent and an antioxidant of natural plant cosmetics, and the solubilization effect of the gel prepared by the gamma-polyglutamic acid gel nanoparticles of the examples 1-4 on the effective components of the okra extract is obviously stronger than that of the gamma-polyglutamic acid gel nanoparticles of the comparative examples 1-2, so that the feeling of users of the examples 1-4 is obviously improved when the gel is used for moisturizing, thickening and whitening. In the public repair class classroom of the applicant, 100 students performed a usage test, and the feedback information shows that the proportion of examples 1-4 is preferred to be 92%.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (7)
1. A preparation method of gamma-polyglutamic acid gel nanoparticles is characterized by comprising the following steps:
step one, preparing a sodium tripolyphosphate solution: adding sodium tripolyphosphate into deionized water to prepare 1.5-2.5mg/ml sodium tripolyphosphate solution, adjusting pH to 6.0-6.5 with 0.3-0.5% (v/v) organic acid solution, and filtering;
step two, preparing a chitosan solution: selecting chitosan with molecular weight of 50-90kDa, adding into 0.3-0.5% (v/v) organic acid solution to prepare 2-3mg/ml chitosan solution, stirring and swelling for 16-20h, adjusting p of the swelled chitosan solution to 6.0-6.5 with 0.08-0.1mol/L alkali solution, and filtering for later use;
step three, preparing a gamma-polyglutamic acid-polyvinylpyrrolidone solution: weighing 300-400g of gamma-polyglutamic acid and 15-25g of polyvinylpyrrolidone, putting into 1L of deionized water to prepare gamma-polyglutamic acid solution, adjusting the pH value to 5.8-6.2 by using 0.3-0.5% (v/v) of organic acid solution, and filtering for later use;
fourthly, preparing the gamma-polyglutamic acid nanoparticles: mixing the gamma-polyglutamic acid-polyvinylpyrrolidone solution and the sodium tripolyphosphate solution, and then dropwise adding the mixture into the chitosan solution until obvious blue opalescence appears.
And fifthly, freeze-drying the gamma-polyglutamic acid nanoparticles prepared in the fourth step into nanoparticle dry powder.
2. The method for preparing gamma-polyglutamic acid gel nanoparticles as claimed in claim 1, wherein in the fourth step, the gamma-polyglutamic acid-polyvinylpyrrolidone solution is mixed with the sodium tripolyphosphate solution and then added dropwise to the chitosan solution at a rate of 3-4 drops/second until blue opalescence is observed.
3. The method for preparing gamma-polyglutamic acid gel nanoparticles of claim 1, wherein in the fifth step, the temperature of lyophilization is-80 to-60 ℃.
4. The method for preparing gamma-polyglutamic acid gel nanoparticles according to claim 1, wherein the organic acid is any one of acetic acid, formic acid and citric acid.
5. The method for preparing gamma-polyglutamic acid gel nanoparticles as claimed in claim 1, wherein the aqueous alkali is aqueous sodium hydroxide solution or aqueous ammonia or aqueous sodium bicarbonate solution.
6. Use of the gamma-polyglutamic acid gel nanoparticles prepared according to any one of claims 1 to 5 for the loading of cosmetic active ingredients and pharmaceutical active ingredients for the treatment of body surface diseases, in such a manner that the active ingredients are simultaneously added in the third formulation step of the gamma-polyglutamic acid-polyvinylpyrrolidone solution, or the active ingredients are separately formulated and then mixed with the gamma-polyglutamic acid-polyvinylpyrrolidone solution and the sodium tripolyphosphate solution.
7. The use according to claim 6, for the loading of cosmetic active ingredients by simultaneous addition of the active ingredients in the third step of the formulation of a solution of gamma-polyglutamic acid-polyvinylpyrrolidone, to form a solution of gamma-polyglutamic acid-polyvinylpyrrolidone-active ingredient.
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