CN116143954A - Preparation and purification method of hydroxybutyl chitosan-gallic acid - Google Patents
Preparation and purification method of hydroxybutyl chitosan-gallic acid Download PDFInfo
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- CN116143954A CN116143954A CN202310247756.5A CN202310247756A CN116143954A CN 116143954 A CN116143954 A CN 116143954A CN 202310247756 A CN202310247756 A CN 202310247756A CN 116143954 A CN116143954 A CN 116143954A
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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Abstract
The invention discloses a method for purifying hydroxybutyl chitosan-gallic acid, belonging to the technical field of biological medicine. The method specifically comprises the following steps: the graft copolymer is obtained by taking chitosan with wide natural sources as a raw material, respectively realizing the modified grafting of the hydroxybutyl and the gallic acid by a two-step method, and realizing the high-purity hydroxybutyl chitosan-gallic acid copolymer by soaking and washing with ethanol for a plurality of times, so as to solve the problem that the related impurity removal process is not beneficial to scale. The invention adopts low-cost ethanol, has simple impurity removal method, high purity, good controllability and preparation stability, is suitable for industrial production, can prepare high-purity hydroxybutyl chitosan-gallic acid raw materials meeting the requirements of medical products, and is expected to realize various local administration scenes.
Description
Technical Field
The invention relates to a purification method of a hydroxybutyl chitosan grafted copolymer, in particular to a purification method of hydroxybutyl chitosan-gallic acid, belonging to the technical field of biological medicine.
Background
Chitosan is the only natural cationic basic polysaccharide in nature and is used as a wound healing hydrogel and tissue repair material due to its biological activities such as antibacterial, hemostatic and anti-inflammatory activities. HBC-centric functional biomaterials based on hydroxybutyl chitosan (HBC) have been designed and applied in biological applications including wound dressing, drug delivery, tissue repair, etc. However, based on the defects of poor tissue adhesiveness, lack of long-term adhesion with a dynamic wet interface and the like of HBC hydrogel at present, a hydroxybutyl chitosan grafting process is developed, and gallic acid and hydroxybutyl chitosan are combined by utilizing amino groups with stronger reactivity to obtain the temperature-sensitive hydrogel with excellent adhesion performance.
1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC. HCl) and N-hydroxysuccinimide (NHS) are widely used for amidation of proteins, providing an alternative chemical method for modification of chitosan. The gallic acid can be grafted onto chitosan through amide or ester bonds, the method only needs mild reaction conditions, the operation is simple, and EDC, HCl and NHS reagents can be easily removed after the reaction is completed. At present, the impurities after the grafting reaction are mainly removed by a dialysis method, which is unfavorable for mass process and industrial production, so that a purification method which is high in purity and can be produced in mass is necessary to develop a method for eluting raw materials from samples.
Disclosure of Invention
The invention aims to provide a high-efficiency, low-cost and safe preparation and purification method of hydroxybutyl chitosan-gallic acid, which solves the technical requirements of industrialized mass production and reduces the purification cost in the production process.
A preparation and purification method of hydroxybutyl chitosan-gallic acid comprises the following steps:
dispersing chitosan powder in NaOH solution for alkalization, dispersing in mixed solution of isopropanol/water (the volume ratio of isopropanol to water is 1:0.5-1.5), adding 1, 2-epoxybutane, stirring and reacting to obtain hydroxybutyl chitosan, and modifying the hydroxybutyl chitosan by gallic acid in an ethanol/water solution system to obtain a hydroxybutyl chitosan-gallic acid mixture;
pulverizing the hydroxybutyl chitosan-gallic acid mixture, soaking and stirring with ethanol, and repeatedly washing to obtain high-purity hydroxybutyl chitosan-gallic acid copolymer.
The invention provides a purified hydroxybutyl chitosan-gallic acid mixture comprising:
dispersing chitosan powder in NaOH solution for alkalization, dispersing in isopropanol/water mixed solution, adding 1, 2-epoxybutane, and stirring for reaction to obtain hydroxybutyl chitosan mixed solution. In an ethanol/water solution system, the hydroxybutyl chitosan is modified by gallic acid to obtain a hydroxybutyl chitosan-gallic acid mixture. Purification was then carried out by the following purification principle. The method comprises the steps of utilizing citric acid to adjust the pH value of a solution after reaction to 6.85-6.95, immediately adding 2-5 times of hot water with the volume of 42-55 ℃, stirring to uniformly disperse flocculent in the water, standing for precipitation, filtering, putting filter residues into a beaker again, adding hot water, stirring for standing for precipitation, repeating the operation of filtering for 2-3 times or stopping filtering when the filtering is slower, and washing the supernatant by using a centrifugal washing mode to obtain a hydroxybutyl chitosan sample, wherein colloid cannot be separated or the conductivity is less than 80 mu s/cm, and drying.
Dissolving the obtained hydroxybutyl chitosan in acetic acid solution with pH=4.0-6.0, and stirring and mixing uniformly; 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC. HCl) and N-hydroxysuccinimide (NHS) are weighed and dissolved in ethanol/water solution (the ethanol/water solution is composed of ethanol and water in a volume ratio of 4-6:6-4, more preferably 50%, v/v), gallic acid powder is added, and stirring carboxylation is carried out for 20-30min; and then dropwise adding the carboxylated gallic acid solution into an acetic acid solution of hydroxybutyl chitosan to obtain a mixed solution, and stirring and reacting for 24 hours at room temperature. After the reaction is finished, ethanol is evaporated by rotary evaporation, or the mixture is put into an oven to be dried for 1 to 2 hours until the solvent is reduced to 2/3 to 1/2, and the mixture of hydroxybutyl chitosan and gallic acid is obtained by drying. Therefore, the mixture contains a large amount of raw materials, isourea by-products, and the like, in addition to the produced hydroxybutyl chitosan-gallic acid.
Pulverizing solid mixture of hydroxybutyl chitosan and gallic acid, soaking in ethanol under stirring, and repeatedly washing to obtain high purity hydroxybutyl chitosan-gallic acid copolymer. The purification principle of the invention is that according to the principle that hydroxybutyl chitosan-gallic acid is insoluble in ethanol and raw materials gallic acid, EDC, HCl, NHS, isourea byproducts and the like are soluble in ethanol, the mixture obtained after freeze-drying is directly added into a certain volume of ethanol, so that the raw materials and the byproducts are dissolved in the ethanol and removed. Further, the solid and the ethanol solution are separated by conventional separation methods such as filtration, so that the high-purity hydroxybutyl chitosan-gallic acid can be obtained.
The specific technical scheme of the invention is as follows:
and after the hydroxybutyl chitosan-gallic acid reaction is finished, evaporating ethanol by rotary evaporation, or placing the mixture in an oven to be dried for 1-2 hours until the solvent is reduced to 2/3-1/2, and drying to obtain the hydroxybutyl chitosan-gallic acid mixture.
And (3) crushing the freeze-dried solid mixture of the hydroxybutyl chitosan and the gallic acid by a crusher. The crushed sample mixture is placed in a beaker, and absolute ethyl alcohol is added for soaking and stirring for a period of time.
Filtering by suction filtration, washing with ethanol for 3-5 times, placing the residue in a beaker again, adding equal amount of absolute ethanol, and stirring.
The above washing steps were repeated several times until the ultraviolet absorption of the supernatant gallic acid was close to 0 or several subsequent absorption peak changes were not evident.
And drying the sample after alcohol washing to obtain the high-purity hydroxybutyl chitosan-gallic acid copolymer.
Preferably, the hydroxybutyl chitosan-gallic acid reaction is completed and the solution is lyophilized.
Preferably, the alcohol washing proportion is that the mass of the hydroxybutyl chitosan raw material and the volume ratio of ethanol are 1g:100-200mL.
Preferably, the soaking and washing time is 1-2h.
Preferably, the filtration mode after washing is suction filtration.
Preferably, after each suction filtration, the washing is performed 3-5 times with ethanol to ensure that the surface residual quantity is as small as possible.
Preferably, the sample after the alcohol washing is dried in vacuum or in an oven at 35-39 ℃, and more preferably, the sample after the alcohol washing is dried in vacuum or in an oven at 37 ℃.
The invention has the advantages that:
(1) the purification method of the invention utilizes the special property that the hydroxybutyl chitosan-gallic acid is insoluble in ethanol, only ethanol with low price is used in the purification process, thereby reducing the production cost and the potential safety hazard in the production process and being beneficial to large-scale production.
(2) The purification method of the invention has short time, saves a great amount of purification time and greatly improves the separation and purification efficiency.
(3) The high-purity hydroxybutyl chitosan-gallic acid raw material meeting the requirements of medical products can be prepared through multiple purification.
Drawings
FIG. 1 is a graph showing the UV-visible absorption spectra of supernatants corresponding to different times of alcohol washing according to the present invention.
FIG. 2 is a thin layer chromatography of free gallic acid (a), hydroxybutyl chitosan (b) and hydroxybutyl chitosan-gallic acid (c).
FIG. 3 shows high performance liquid chromatograms of EDC & HCl (a), NHS (b) and free gallic acid (c) standards.
FIG. 4 is a high performance liquid chromatogram of hydroxybutyl chitosan-gallic acid of the present invention.
Detailed Description
Example 1
This example provides a hydroxybutyl chitosan-gallic acid mixture preparation comprising:
1.0g of chitosan was dispersed in 10mL of NaOH solution (50%, w/w) at room temperature, alkalized for 24h at room temperature, and the NaOH solution was filtered; dispersing the alkalized chitosan in 20mL of isopropanol/water solution (isopropanol: water=1:1), stirring for 30min, mixing uniformly, adding 20mL of 1, 2-epoxybutane into the flask, and stirring for 24h at 55 ℃; and (3) regulating the pH value of the reacted solution to 6.85-6.95 by using citric acid, immediately adding 2-5 times of 42-55 ℃ hot water, stirring to uniformly disperse flocculent in water, standing for precipitation, putting filter residues into a beaker again, adding hot water, stirring for standing for precipitation, repeating the above operation for 2-3 times or stopping the suction filtration when the suction filtration is slower (the temperature is not lower than 35 ℃), and washing the supernatant by using a centrifugal washing mode to obtain a hydroxybutyl chitosan sample, wherein the colloid cannot be separated or the conductivity is smaller than 80 mu s/cm, and drying.
1.0g of the obtained hydroxybutyl chitosan is dissolved in acetic acid solution with pH=4.0-6.0, and the mixture is stirred and mixed uniformly; weighing 0.49g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC. HCl) and 0.29g of N-hydroxysuccinimide (NHS) dissolved in an ethanol/water solution (50%, v/v), adding 0.36g of gallic acid powder, stirring and carboxylating for 20-30min; and then dropwise adding the carboxylated gallic acid solution into an acetic acid solution of hydroxybutyl chitosan to obtain a mixed solution, and stirring and reacting for 24 hours at room temperature. After the reaction is finished, ethanol is evaporated by rotary evaporation, or the mixture is put into an oven to be dried for 1 to 2 hours until the solvent is reduced to 2/3 to 1/2, and the mixture is frozen and dried to obtain the hydroxybutyl chitosan-gallic acid mixture.
Example 2
This example provides a method for purifying hydroxybutyl chitosan-gallic acid comprising:
1g of solid mixture of hydroxybutyl chitosan and gallic acid prepared from hydroxybutyl chitosan raw material is freeze-dried and crushed by a crusher. The crushed sample mixture is placed in a beaker, and 100mL of absolute ethyl alcohol is added for soaking and stirring for 1h. Filtering, flushing with ethanol for 3-5 times, putting the filter residue into a beaker again, adding 100mL of absolute ethanol, and stirring. The above washing steps were repeated several times until the ultraviolet absorption of the supernatant gallic acid was close to 0 or several subsequent absorption peak changes were not evident. And drying the sample after alcohol washing to obtain the high-purity hydroxybutyl chitosan-gallic acid copolymer.
The hydroxybutyl chitosan-gallic acid obtained in example 2 was taken out to prepare a 10mg/mL aqueous solution, spotted on GF254 type silica gel plate (3 cm. Times.10 cm), developed with chloroform-ethyl acetate-acetic acid solution (50:100:1) as developing agent at room temperature, and the developed silica gel plate was subjected to a 254nm ultraviolet lamp to develop the color to obtain FIG. 2. As can be seen from fig. 2, the free gallic acid migrates a distance on the thin layer chromatography, and a large yellow spot appears; the hydroxybutyl chitosan-gallic acid presents a yellow spot at the initial line and does not migrate, indicating that gallic acid has been successfully grafted onto hydroxybutyl chitosan and that no free gallic acid is contained in the graft.
The hydroxybutyl chitosan-gallic acid obtained in example 2 was prepared as a 1mg/mL aqueous solution, and tested using a high performance liquid chromatograph (test conditions: mobile phase: acetonitrile; detection wavelength: 254nm; peak time: 5.25 min), to obtain the liquid chromatogram of FIG. 3. In FIG. 3, the peak-out times of standard substances EDC, HCl, NHS and gallic acid are 2.241min, 2.855min and 5.266min as references, and the peaks of EDC, HCl and NHS are not detected by the purified hydroxybutyl chitosan-gallic acid, namely, the raw materials EDC, HCl and NHS are completely removed.
Example 3
This example provides a method for purifying hydroxybutyl chitosan-gallic acid comprising:
1g of solid mixture of hydroxybutyl chitosan and gallic acid prepared from hydroxybutyl chitosan raw material is freeze-dried and crushed by a crusher. The crushed sample mixture is placed in a beaker, and 100mL of absolute ethanol is added for soaking and stirring for 2 hours. Filtering, flushing with ethanol for 3-5 times, putting the filter residue into a beaker again, adding 100mL of absolute ethanol, and stirring. The above washing steps were repeated several times until the ultraviolet absorption of the supernatant gallic acid was close to 0 or several subsequent absorption peak changes were not evident. And drying the sample after alcohol washing to obtain the high-purity hydroxybutyl chitosan-gallic acid copolymer.
Example 4
This example provides a method for purifying hydroxybutyl chitosan-gallic acid comprising:
1g of solid mixture of hydroxybutyl chitosan and gallic acid prepared from hydroxybutyl chitosan raw material is freeze-dried and crushed by a crusher. The crushed sample mixture is placed in a beaker, and 200mL of absolute ethanol is added for soaking and stirring for 2h. Filtering, flushing with ethanol for 3-5 times, putting the filter residue into a beaker again, adding 200mL of absolute ethanol, and stirring. The above washing steps were repeated several times until the ultraviolet absorption of the supernatant gallic acid was close to 0 or several subsequent absorption peak changes were not evident. And drying the sample after alcohol washing to obtain the high-purity hydroxybutyl chitosan-gallic acid copolymer.
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure herein. This application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.
It is to be understood that the present application is not limited to the precise arrangements and instrumentalities shown in the drawings, which have been described above, and that various modifications and changes may be effected without departing from the scope thereof. The scope of the application is limited only by the appended claims.
Claims (10)
1. The preparation and purification method of the hydroxybutyl chitosan-gallic acid is characterized by comprising the following steps:
dispersing chitosan powder in NaOH solution for alkalization, dispersing in isopropanol/water mixed solution, adding 1, 2-epoxybutane, stirring and reacting to obtain hydroxybutyl chitosan, and modifying hydroxybutyl chitosan with gallic acid in an ethanol/water solution system to obtain hydroxybutyl chitosan-gallic acid mixture;
pulverizing the hydroxybutyl chitosan-gallic acid mixture, soaking and stirring with ethanol, and repeatedly washing to obtain high-purity hydroxybutyl chitosan-gallic acid copolymer.
2. The preparation and purification method according to claim 1, wherein the chitosan powder is dispersed in NaOH solution for alkalization, and is dispersed in isopropanol/water mixed solution, 1, 2-butylene oxide is added, and hydroxybutyl chitosan is obtained after stirring reaction, specifically comprising:
dispersing chitosan in NaOH aqueous solution, alkalizing for 18-30 h, and filtering the NaOH solution; dispersing the alkalized chitosan in isopropanol/water solution, stirring and mixing uniformly, then adding 1, 2-epoxybutane, and stirring for 18-30 h at 50-60 ℃; and (3) regulating the pH value of the reacted solution to 6.85-6.95 by using citric acid, immediately adding 2-5 times of hot water with the volume of 42-55 ℃, stirring to uniformly disperse flocculent in the water, standing for precipitation, filtering, putting filter residues into a beaker again, adding hot water, stirring for standing for precipitation, repeating the operation, filtering, and washing and drying by using a centrifugal washing mode to obtain the hydroxybutyl chitosan.
3. The method for preparing and purifying a plant according to claim 2, wherein the volume ratio of isopropyl alcohol to water in the isopropyl alcohol/water solution is 1:0.5-1.5.
4. The preparation and purification method according to claim 1, wherein the hydroxybutyl chitosan is modified with gallic acid in an ethanol/water solution system to obtain a hydroxybutyl chitosan-gallic acid mixture, comprising:
dissolving hydroxybutyl chitosan in acetic acid solution with pH=4.0-6.0, and uniformly mixing to obtain acetic acid solution of hydroxybutyl chitosan;
dissolving 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide in an ethanol/water solution, adding gallic acid powder, stirring and carboxylating to obtain carboxylated gallic acid solution;
and then dropwise adding the carboxylated gallic acid solution into an acetic acid solution of the hydroxybutyl chitosan to obtain a mixed solution, stirring and reacting for 18-30 h, evaporating ethanol by rotary evaporation after the reaction is finished, or placing the mixture into an oven until the solvent is reduced to 2/3-1/2, and drying to obtain the hydroxybutyl chitosan-gallic acid mixture.
5. The method according to claim 4, wherein the ethanol/water solution comprises ethanol and water in a volume ratio of 4-6:6-4.
6. The preparation and purification method according to claim 1, wherein the high-purity hydroxybutyl chitosan-gallic acid copolymer is obtained by crushing a hydroxybutyl chitosan-gallic acid mixture, immersing and stirring the mixture in ethanol, and repeatedly washing the mixture, and specifically comprises the following steps:
drying the solid mixture of hydroxybutyl chitosan and gallic acid, shearing, adding absolute ethyl alcohol, soaking and stirring, filtering, washing the mixture with ethanol, putting filter residues into a container again, adding absolute ethyl alcohol, soaking and stirring, repeating the ultraviolet absorption of gallic acid in the supernatant to be close to 0 or less obvious change of absorption peaks after several times, washing the finished sample with ethanol, and drying to obtain the high-purity hydroxybutyl chitosan-gallic acid.
7. The method of claim 6, wherein the solid mixture of hydroxybutyl chitosan and gallic acid is freeze-dried.
8. The method for preparing and purifying according to claim 1, wherein the ratio of the absolute ethanol to the solid mixture of hydroxybutyl chitosan and gallic acid added each time is 100-200 mL/1 g.
9. The preparation and purification method according to claim 1, wherein the mixture is soaked in absolute ethanol and stirred for 1-2 hours.
10. The method for preparing and purifying a sample according to claim 1, wherein the sample after the alcohol washing is dried in vacuum or in an oven at 35 to 39 ℃.
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Cited By (1)
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| CN117567982A (en) * | 2023-11-17 | 2024-02-20 | 杭州东兴电讯材料有限公司 | Environment-friendly high-strength adhesive for aluminum-plastic compounding |
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