CN113209382A - Three-dimensional reticular chitosan slow-release coating and preparation method thereof - Google Patents
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Abstract
The invention discloses chitosan-methacrylic anhydride/calcium carbonate (CSMA/CaCO)3) The preparation method of the hydrogel slow-release coating is characterized in that the surface of the coating is of a porous reticular structure. The preparation method comprises the following steps: 1) preparing a chitosan solution dissolved in dilute acetic acid; 2) adding Methacrylic Anhydride (MA) into the chitosan solution obtained in the step 1), and grafting the methacrylic anhydride on chitosan by a hydrothermal method under a high-temperature condition to prepare chitosan-methacrylic anhydride (CSMA); 3)neutralizing, dialyzing the chitosan-methacrylic anhydride obtained in the step 2); 4) adding a photoinitiator I2959 and a calcium chloride solution into the solution obtained in the step 3), and performing ultraviolet irradiation crosslinking to obtain the slow-release hydrogel. 5) And 4) introducing ammonium carbonate into the hydrogel obtained in the step 4) to prepare the polysaccharide-methacrylic anhydride/calcium carbonate hydrogel slow-release coating. The method has the advantages of simple preparation process, mild and controllable conditions, good repeatability and low production cost, and is suitable for industrial production; the prepared porous network hydrogel slow-release coating has the advantages of good biocompatibility, easy degradation, high loading rate and the like, and has wide application prospects in the fields of medicine and chemical industry.
Description
Technical Field
The invention belongs to the technical field of preparation of biological materials, and particularly relates to a three-dimensional reticular chitosan slow-release coating and a preparation method thereof.
Background
The hydrogel as a coating on the titanium material has the characteristics of good biocompatibility, in-situ injection molding and the like. The soft and moist nature of the hydrogel, also possessing low friction, can be used as artificial cartilage in total joint prostheses, while demonstrating suitability for cell adhesion proliferation and differentiation. The three-dimensional porous structure of the hydrogel can imitate the extracellular matrix structure, and is beneficial to substance transportation and cell growth in organisms when implanted in vivo. On the other hand, the hydrogel coatings improve the biocompatibility of titanium, can carry antibiotic drugs in situ, can be used for drug release, and reduce the immunogenicity and infection effect of the drugs.
Chitosan is the only polycation alkalescent polysaccharide with active amino (-NH 2) in nature obtained by deacetylation of chitin, is used as a broad-spectrum bacteriostatic agent, has good biocompatibility and easy chemical modification, and is widely used for construction of sustained-release coatings on the surfaces of implants. The UV cross-linked chitosan modified by Ultraviolet (UV) irradiation photosensitive groups has the characteristics of excellent space designability, capability of loading drugs/cells in situ, rapid formation of gel and the like, and can be used for preparing uniform slow-release gel coatings in pores of porous materials. Meanwhile, the UV cross-linked chitosan can further synthesize a novel chitosan derivative with stimulus response through molecular design, so that intelligent slow release of the loaded drug is realized. However, the water prepared by the traditional methods of electrochemical deposition, layer-by-layer self-assembly and the likeThe bonding strength between the gel coat and the substrate material is low, and the gel coat cannot be firmly adhered to the surface of the material with a complex shape. Thus, Gong Jian Nu et al (Advanced Materials Interfaces, 2018, 5: 1801018.) proposed a simple method of applying particle-based double-network gel (P-DN) to the surface of three-dimensional solid Materials. Firstly, treating the solid surface to form a bottom layer containing a free radical initiator for bridging the substrate and the P-DN gel; and then coating the pre-gel solution containing the first network gel particles and the second network monomer on the treated surface, and carrying out photoinduced polymerization, thus successfully coating the P-DN gel on the surface of the substrate. The gel particles of the first network can effectively improve the mechanical property of the P-DN gel coating, and the peel strength can reach 1000J/m in a 90-degree peel experiment2. Cuhao et al (Journal of Materials Chemistry B, 2018, 6: 3859-3864.) also utilized calcium-based particles to firmly coat various hydrogels on non-porous titanium surfaces with shear strengths up to 120 kPa. Recently, the patent applicant adopts a biomimetic mineralization method to construct a chitosan/calcium carbonate composite hydrogel coating on the surface of porous titanium, and finds that calcium carbonate particles growing in situ can obviously improve the mechanical strength of the hydrogel, and the mineralized coating can also promote the adhesion and spreading of mesenchymal stem cells. Therefore, by using the calcium-based particles as the adhesive and combining the stimulation responsiveness of the modified chitosan and the intrinsic bone conduction/inductivity of the calcium-based particles, an intelligent responsive slow-release coating which is uniform and firmly combined is probably constructed on the outer surface and the inner pore surface of the 3D printed porous titanium, so that the intelligent slow release of the loaded medicine is realized, and the purpose of high-efficiency osseointegration is achieved.
Disclosure of Invention
The invention aims to provide a method for preparing a three-dimensional reticular chitosan slow-release coating with simple preparation method, good repeatability, low friction force, porous structure, good dispersibility and high drug loading rate, wherein a chitosan solution is prepared, methacrylic anhydride is added into the chitosan solution, the methacrylic anhydride is grafted on chitosan by a hydrothermal method under the high-temperature condition to prepare chitosan-methacrylic anhydride, and the chitosan-methacrylic anhydride is neutralized and dialyzed; adding a photoinitiator I2959 and a calcium chloride solution, and performing ultraviolet irradiation crosslinking to obtain the slow-release hydrogel. And (3) introducing ammonium carbonate into the hydrogel to prepare the polysaccharide-methacrylic anhydride/calcium carbonate hydrogel slow-release coating. The specific technical scheme is as follows:
a three-dimensional reticular chitosan slow release coating has a porous structure on the surface, and the pore size is 0.2-0.4 mm; dense calcium carbonate crystals are distributed in the coating, and the crystal morphology is a calcite structure.
The preparation method of the three-dimensional reticular chitosan slow-release coating comprises the following steps:
dissolving chitosan powder in 1% (v/v) acetic acid solution to obtain 1% (w/v) chitosan solution;
step (2) dripping methacrylic anhydride (the ratio of anhydride to amino is 2: 1) into the prepared chitosan solution at a constant speed; all reaction systems are stirred at a constant speed from beginning to end and are heated in a water bath at 60 ℃ for reaction for 12 hours;
adjusting the pH of the solution reacted in the step (3) to be neutral by using sodium bicarbonate for later use;
step (4), putting the prepared chitosan derivative solution into a dialysis bag and dialyzing the solution for 4 to 5 days in the environment of deionized water to remove unreacted substances;
step (5) adding 0.2 wt% of I2959 photoinitiator and a proper amount of 4M CaCl into CSMA prepolymerization solution2Uniformly mixing the solution by a magnetic stirrer, and then irradiating for 10 min by low-dose ultraviolet;
step (6), putting the hydrogel coating into a special device containing ammonium carbonate for mineralization; after being placed at room temperature for a certain time, CSMA/CaCO can be successfully constructed3And (3) compounding a hydrogel coating.
Further, the chitosan in the step (1) has a deacetylation degree of more than 95% and a viscosity of 100-200 mpa.s.
Further, the concentration of the methacrylic anhydride solution in the step (2) is 94%, and the stirring speed is 60 revolutions per minute.
Further, the concentration of the sodium bicarbonate solution in the step (3) is 1M.
Further, the cut-off molecular weight of the dialysis bag in the step (4) is 12000 daltons.
Further, the purity of the ammonium carbonate in the step (6) is analytically pure, and the ammonium carbonate can be decomposed into CO at normal temperature2And NH3，CO2Will gradually diffuse into the hydrogel to combine with calcium ions to generate CaCO3，NH3Provides necessary alkaline environment for the whole biomimetic mineralization.
The surface of the three-dimensional reticular chitosan slow-release coating is of a porous structure, and the pore size is 0.2 mm; dense calcium carbonate crystals are distributed in the coating, and the crystal morphology is a calcite structure.
The invention has the beneficial effects that:
the invention uses chitosan as the alkalescent polysaccharide of polycation containing active amino (-NH 2), has certain antibacterial property, good biocompatibility and easy chemical modification.
The invention has the advantages of mild and controllable experimental conditions, high reaction rate, short reaction time, simple experimental process and high production efficiency.
Drawings
FIG. 1 is a Field Emission Scanning Electron Microscope (FESEM) image of a product obtained in example 1 of the present invention.
FIG. 2 is a Field Emission Scanning Electron Microscope (FESEM) image of the product obtained in example 2 of the present invention.
FIG. 3 is an Optical Microscope (OM) image of the product obtained in example 3 of the present invention.
FIG. 4 is an Optical Microscope (OM) image of the product obtained in example 4 of the present invention.
FIG. 5 is a graph showing cytotoxicity tests of the products obtained in examples 1, 2, 3 and 4 of the present invention.
Detailed Description
In order to make the present invention more easily understood, and the technical solutions and advantages thereof more clearly understood, the present invention is further described in detail below with reference to the following embodiments and the accompanying drawings. It is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, and that specific experimental procedures not mentioned in the following examples are generally conducted in accordance with routine experimentation.
Example 1
Dissolving 1g of chitosan powder in 100 ml of 1% (v/v) acetic acid solution to obtain 1% (w/v) chitosan solution, dropwise adding methacrylic anhydride (the ratio of anhydride to amino is 2: 1) into the prepared chitosan solution at a constant speed, maintaining the whole reaction system at a constant speed from beginning to end, heating the mixture in a water bath at 60 ℃ for 12 hours, adjusting the pH of the solution after reaction to be neutral by using sodium bicarbonate for later use, filling the prepared chitosan derivative solution into a dialysis bag, dialyzing the solution in a deionized water environment for 4-5 days to remove unreacted substances, adding 0.2 wt% of I2959 photoinitiator and a proper amount of 4M CaCl into CSMA prepolymerization solution, and adding a proper amount of 4M CaCl into the CSMA prepolymerization solution2And uniformly mixing the solution by a magnetic stirrer, and then irradiating for 10 min by low-dose ultraviolet to successfully construct the CSMA hydrogel coating.
Example 2
Dissolving 1g of chitosan powder in 100 ml of 1% (v/v) acetic acid solution to obtain 1% (w/v) chitosan solution, dropwise adding methacrylic anhydride (the ratio of anhydride to amino is 2: 1) into the prepared chitosan solution at a constant speed, maintaining the constant speed stirring of all reaction systems from beginning to end, heating the reaction systems in a water bath at 60 ℃ for 12 hours, adjusting the pH of the solution after reaction to be neutral by using sodium bicarbonate for later use, filling the prepared chitosan derivative solution into a dialysis bag, dialyzing the solution in a deionized water environment for 4-5 days to remove unreacted substances, heating and concentrating the solution to one third of the original volume, adding 0.2 wt% of I2959 photoinitiator into CSMA prepolymer solution, uniformly mixing the solution by using a magnetic stirrer, and then irradiating the CSMA hydrogel coating for 10 minutes by using low-dose ultraviolet light to successfully construct a CSMA hydrogel coating.
Example 3
Dissolving 1g chitosan powder in 100 ml 1% (v/v) acetic acid solution to obtain 1% (w/v) chitosan solution, uniformly dropping methacrylic anhydride (the ratio of anhydride to amino is 2: 1) into the prepared chitosan solution, maintaining the uniform stirring of all reaction systems from beginning to end, heating in 60 ℃ water bath for reaction for 12 h, adjusting the pH of the solution after reaction to be neutral by using sodium bicarbonate, filling the prepared chitosan derivative solution into a dialysis bag, and adding deionized water into the dialysis bagDialyzing for 4-5 days in the environment to remove unreacted substances, and adding 0.2 wt% of I2959 photoinitiator and a proper amount of 4M CaCl into CSMA prepolymerization solution2And uniformly mixing the solution by a magnetic stirrer, then irradiating for 10 min by low-dose ultraviolet, and putting the hydrogel coating into a special device containing ammonium carbonate for mineralization. After being placed at room temperature for a certain time, CSMA/CaCO can be successfully constructed3And (3) compounding a hydrogel coating.
Example 4
1g of chitosan powder was dissolved in 100 ml of 1% (v/v) acetic acid solution, dropping methacrylic anhydride (the ratio of anhydride to amino is 2: 1) into the prepared chitosan solution at a constant speed, keeping the whole reaction system at the constant speed from beginning to end, heating in a water bath at 60 ℃ for reaction for 12 hours, adjusting the pH of the solution after reaction to be neutral by using sodium bicarbonate for later use, filling the prepared chitosan derivative solution into a dialysis bag, dialyzing in a deionized water environment for 4-5 days to remove unreacted substances, heating and concentrating to one third of the original volume, adding 0.2 wt% of I2959 photoinitiator into the CSMA prepolymerization solution, uniformly mixing by a magnetic stirrer, then, the hydrogel coating is placed into a special device containing ammonium carbonate for mineralization after being irradiated for 10 min by low-dose ultraviolet. After being placed at room temperature for a certain time, CSMA/CaCO can be successfully constructed3And (3) compounding a hydrogel coating.
The obtained three-dimensional reticular chitosan slow release coating is subjected to field emission scanning electron microscope analysis, optical microscope analysis and cytotoxicity detection, and the results are respectively shown in figures 1, 2, 3, 4 and 5. The aperture size and the diameter of the obtained three-dimensional reticular chitosan slow-release coating are 0.2-0.4mm, dense calcium carbonate crystals are distributed in the coating, and the crystal morphology is a calcite structure.
Claims (7)
1. A three-dimensional reticular chitosan slow-release coating is characterized in that: the surface of the slow release coating is of a porous structure, and the pore size is 0.2-0.4 mm; dense calcium carbonate crystals are distributed in the coating, and the crystal morphology is a calcite structure.
2. A method for preparing the three-dimensional reticular chitosan slow-release coating as claimed in claim 1, wherein: the method comprises the following steps:
dissolving chitosan powder in 1% (v/v) acetic acid solution to obtain 1% (w/v) chitosan solution;
step (2) dripping methacrylic anhydride (the ratio of anhydride to amino is 2: 1) into the prepared chitosan solution at a constant speed; all reaction systems are stirred at a constant speed from beginning to end and are heated in a water bath at 60 ℃ for reaction for 12 hours;
adjusting the pH of the solution reacted in the step (3) to be neutral by using sodium bicarbonate for later use;
step (4), putting the prepared chitosan derivative solution into a dialysis bag and dialyzing the solution for 4 to 5 days in the environment of deionized water to remove unreacted substances;
step (5) adding 0.2 wt% of I2959 photoinitiator and a proper amount of 4M CaCl into CSMA prepolymerization solution2Uniformly mixing the solution by a magnetic stirrer, and then irradiating for 10 min by low-dose ultraviolet;
step (6), putting the hydrogel coating into a special device containing ammonium carbonate for mineralization; after being placed at room temperature for a certain time, CSMA/CaCO can be successfully constructed3And (3) compounding a hydrogel coating.
3. The preparation method of the three-dimensional reticular chitosan slow-release coating according to claim 2, characterized in that: the deacetylation degree of the chitosan in the step (1) is more than 95%, and the viscosity is 100-200 mpa.s.
4. The preparation method of the three-dimensional reticular chitosan slow-release coating according to claim 2, characterized in that: the concentration of the methacrylic anhydride solution in the step (2) is 94%, and the stirring speed is 60 r/min.
5. The preparation method of the three-dimensional reticular chitosan slow-release coating according to claim 2, characterized in that: and (4) the concentration of the sodium bicarbonate solution in the step (3) is 1M.
6. The preparation method of the three-dimensional reticular chitosan slow-release coating according to claim 2, characterized in that: the cut-off molecular weight of the dialysis bag in the step (4) is 12000 daltons.
7. The preparation method of the three-dimensional reticular chitosan slow-release coating according to claim 2, characterized in that: the purity of the ammonium carbonate in the step (6) is analytically pure, and the ammonium carbonate can be decomposed into CO at normal temperature2And NH3，CO2Will gradually diffuse into the hydrogel to combine with calcium ions to generate CaCO3，NH3Provides necessary alkaline environment for the whole biomimetic mineralization.
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| CN113667037A (en) * | 2021-08-19 | 2021-11-19 | 中国石油大学(华东) | Photosensitive modified chitosan and preparation method and application thereof |
| CN114395385A (en) * | 2022-01-21 | 2022-04-26 | 大庆中联信实石油科技开发有限公司 | Temporary plugging ball made of degradable polymer composite gel |
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