CN112999434B - Preparation method of cartilage scaffold based on PVA hydrogel - Google Patents
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Abstract
The invention provides a preparation method of a cartilage scaffold based on PVA hydrogel, aiming at the problems of poor mechanical property, insufficient stability and the like of the PVA hydrogel in the prior art, the preparation method of the process is optimized, and the preparation method comprises the following steps: s1.1: preparing a PVA solution; s1.2: preparing composite hydroxyapatite gel; s1.3: preparing composite PVA hydrogel; s1.4: preparing the crosslinked composite PVA hydrogel; s1.5: molding; s1.6: and (5) post-treatment. Meanwhile, the mixing and adding sequence of raw materials in the preparation process, the temperature, the reaction time and other specific process parameters are limited, and the preparation method of hydroxyapatite is also limited, so that the stability of the cartilage scaffold is further improved, and finally, the PVA hydrogel-based cartilage scaffold material with better mechanical properties, particularly the Young modulus of the surface and higher bioactivity is prepared.
Description
Technical Field
The invention relates to the technical field of medical materials, in particular to a preparation method of a cartilage scaffold based on PVA hydrogel.
Background
The problem of articular cartilage damage due to aging, strenuous exercise, mechanical beds, and cartilage lesions is frequently encountered. However, the articular cartilage lacks nerves and blood vessels inside and has a small number of chondrocytes, resulting in that the articular cartilage has little ability to repair each self-injury. The regeneration and repair of cartilage damage is a problem to be solved clinically at present. Autologous osteochondral transplantation is currently recognized as the clinical gold standard for the treatment of osteochondral defects. However, this technique has many inherent limitations, including donor site morbidity and the limited number of suitable host tissues, as well as the difficulty of properly matching the morphology of the graft to the defect area, among others. Therefore, the use of cartilage tissue engineering is an important method for cartilage defect repair.
Currently, periosteum, non-degradable or degradable biological materials are mainly used for clinical repair, but these treatment methods have inherent defects. Such as adverse reaction of the degradation product to the organism, rejection reaction of the organism caused by non-degradable materials, poor long-term effect and the like. Most of the current applications are to use a high polymer material scaffold to transfer chondrocytes to repair cartilage defects, but medical high polymer materials are expensive and degradation products thereof are destructive to tissues, so that hydrogel materials are generally adopted for preparing cartilage scaffolds in biological tissue engineering.
Compared with human tissues, the traditional polymer hydrogel material needs to be improved in the aspects of mechanical strength, biocompatibility, swelling resistance and the like. However, the polyvinyl alcohol (PVA) hydrogel has potential application prospects as a medical substitute material due to the advantages of low toxicity, relatively excellent mechanical properties, good biocompatibility and the like. But the mechanical property of the cartilage is still different from that of human cartilage. How to develop a hydrogel cartilage scaffold with good mechanical properties and good stability is still a problem to be solved urgently.
Disclosure of Invention
The invention provides a preparation method of a cartilage scaffold based on PVA hydrogel, which is used for solving the problems of poor mechanical property, insufficient stability and the like of the PVA hydrogel in the prior art, optimizing the process preparation method and preparing the cartilage scaffold material based on the PVA hydrogel, which has better mechanical property, particularly surface Young modulus and higher bioactivity.
The technical scheme adopted by the invention is as follows:
a preparation method of a PVA hydrogel-based cartilage scaffold comprises the following steps:
s1.1: preparing a PVA solution; adding 5-20 parts by weight of PVA into 100 parts by weight of water, heating to 60-90 ℃, stirring for 10-30 minutes, and standing at room temperature for 0.5-2 hours to obtain a PVA solution;
s1.2: preparing composite hydroxyapatite gel; dissolving 20-50 parts by weight of hydroxyapatite and 2-10 parts by weight of inorganic auxiliary active ingredients in 200-400 parts by weight of organic solvent, and stirring for 12-48 hours to obtain the composite hydroxyapatite gel;
s1.3: preparing composite PVA hydrogel; combining the composite hydroxyapatite gel with the PVA solution, heating to 60-90 ℃, stirring for 1-2 hours, and obtaining the composite PVA hydrogel after full reaction;
s1.4: crosslinking; adding a cross-linking agent into the composite PVA hydrogel, stirring for 10-30 minutes, performing injection molding, standing for 1-5 hours, and fully crosslinking to obtain a crosslinked composite PVA hydrogel which is marked as x-composite PVA hydrogel;
s1.5: molding; and freezing and drying the x-composite PVA hydrogel for 12-48 hours, and then demolding to obtain the PVA hydrogel-based cartilage scaffold.
Further optimization, the preparation method of the PVA hydrogel-based cartilage scaffold further comprises an S1.6 post-treatment step:
s1.6: post-treatment; after the demoulding operation, washing, freezing and drying are carried out; repeating the step for 3-5 times to obtain the PVA hydrogel based cartilage scaffold.
The further optimization is carried out, and the method,
in the step S1.2, the preparation method of the hydroxyapatite comprises:
s2.1: preparing a solution; adding 0.5-2 parts by weight of 2-aminoethyl phosphoric acid into 100 parts by weight of water to prepare a 2-aminoethyl phosphoric acid solution; adding 0.3-2 parts by weight of calcium nitrate into 100 parts by weight of water to prepare a calcium nitrate solution; adding 2-5 parts by weight of ammonium phosphate into 100 parts by weight of water to prepare an ammonium phosphate solution;
s2.2: adjusting the pH value; adjusting the pH values of the 2-aminoethyl phosphoric acid solution, the calcium nitrate solution and the ammonium phosphate solution to 9.8-10.2 by using a weak alkaline reagent;
s2.3: mixing; adding the calcium nitrate solution into the 2-aminoethyl phosphoric acid solution, uniformly stirring, and then adding a silicon source to obtain a mixed solution I; dropwise adding the ammonium phosphate solution into the mixed solution I step by step, and stirring uniformly to obtain a mixed solution II;
s2.4: carrying out reaction; heating the mixed solution II to 50-80 ℃, stirring for reaction for 3-5 hours, cooling to room temperature, and then carrying out ultrasonic treatment for 3-5 hours to obtain a mixed solution III;
s2.5: post-treatment; and centrifuging, washing, freezing and drying the mixed solution III to obtain the hydroxyapatite.
And further optimizing, in the step S2.3, the weight fraction of silicon element in the silicon source in the hydroxyapatite is 0.002-0.05%.
In a further optimization, in the step S1.2, the inorganic auxiliary active ingredient is nano silver, and the particle diameter of the nano silver is not greater than 50 nm.
Further optimization, in the step S1.3, the volume ratio of the composite hydroxyapatite gel to the PVA solution is 1: (2-5).
Further preferably, in the step S1.4, the cross-linking agent is any one of carbodiimide, thiosuccinimide, glutaraldehyde, dimethylol urea, and trimethylol melamine.
Further optimization, in the step S1.5, the freezing temperature is-50 to-20 ℃.
The invention has the beneficial effects that:
in the process for preparing the cartilage scaffold based on the PVA hydrogel, the composite hydroxyapatite gel is added on the basis of the PVA as the basic raw material, and after the two are combined, the cartilage scaffold material with better mechanical property, particularly the Young modulus of the surface and higher bioactivity is prepared by further post-treatment processes such as crosslinking and the like.
Further optimization, the invention defines the preparation method of the hydroxyapatite again, and the silicon source is introduced into the hydroxyapatite, so that the adhesion of osteoblasts on the surface of the cartilage scaffold can be effectively promoted. Meanwhile, 2-aminoethyl phosphoric acid is additionally added aiming at the defects of poor dispersibility and insufficient stability of the hydroxyapatite, the hydrophilicity and hydrophobicity of the surface of the hydroxyapatite is changed through grafting, the dispersion of the hydroxyapatite is promoted, and more stable hydroxyapatite gel is prepared, so that the stability of the cartilage scaffold is further improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments will be briefly described below.
FIG. 1 is a schematic flow chart of a preparation process of a PVA hydrogel-based cartilage scaffold provided by an embodiment of the invention;
fig. 2 is a schematic flow chart of a preparation process of hydroxyapatite provided by an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to specific embodiments and accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation process of a PVA hydrogel-based cartilage scaffold is shown in figure 1, and specifically comprises the following steps:
s1.1: preparing a PVA solution; adding 10 parts by weight of PVA into 100 parts by weight of water, heating to 60 ℃, stirring for 20 minutes, and then standing for 1 hour at room temperature to obtain a PVA solution;
s1.2: preparing composite hydroxyapatite gel; dissolving 20 parts by weight of hydroxyapatite and 2 parts by weight of nano-silver in 300 parts by weight of organic solvent, and stirring for 24 hours to obtain the composite hydroxyapatite gel;
s1.3: preparing composite PVA hydrogel; combining the composite hydroxyapatite gel with the PVA solution, heating to 80 ℃, stirring for 1 hour, and obtaining the composite PVA hydrogel after full reaction;
s1.4: crosslinking; adding a cross-linking agent into the composite PVA hydrogel, stirring for 20 minutes, performing injection molding, standing for 3 hours, and fully crosslinking to obtain a crosslinked composite PVA hydrogel which is marked as x-composite PVA hydrogel;
s1.5: molding; the x-composite PVA hydrogel was cooled at-50 ℃ and then demolded after 24 hours of drying to give the PVA hydrogel based cartilage scaffold.
Further optimization, the preparation method of the PVA hydrogel-based cartilage scaffold further comprises an S1.6 post-treatment step:
s1.6: post-treatment; after the demoulding operation, washing, freezing and drying are carried out; repeating the step for 3-5 times to obtain the PVA hydrogel based cartilage scaffold.
The hydroxyapatite used in the step S1.2 of this embodiment can be prepared by the following method, and the schematic process flow diagram is shown in fig. 2:
s2.1: preparing a solution; adding 0.5 part by weight of 2-aminoethyl phosphoric acid into 100 parts by weight of water to prepare a 2-aminoethyl phosphoric acid solution; adding 0.3 part by weight of calcium nitrate into 100 parts by weight of water to prepare a calcium nitrate solution; adding 2 parts by weight of ammonium phosphate into 100 parts by weight of water to prepare ammonium phosphate solution;
s2.2: adjusting the pH value; adjusting the pH of the 2-aminoethyl phosphoric acid solution, the calcium nitrate solution and the ammonium phosphate solution to 10 by using ammonia water;
s2.3: mixing; adding the calcium nitrate solution into the 2-aminoethyl phosphoric acid solution, uniformly stirring, and then adding nano silicon dioxide to obtain a mixed solution I; dropwise adding the ammonium phosphate solution into the mixed solution I step by step, and stirring uniformly to obtain a mixed solution II;
s2.4: carrying out reaction; heating the mixed solution II to 60 ℃, stirring for reaction for 4 hours, cooling to room temperature, and then carrying out ultrasonic treatment for 3 hours to obtain a mixed solution III;
s2.5: post-treatment; and centrifuging, washing, freezing and drying the mixed solution III to obtain the hydroxyapatite.
In this embodiment, the weight fraction of silicon element in the nano-silica in the hydroxyapatite is 0.005%.
The addition of the trace silicon element can reduce the size of the hydroxyapatite, increase the contact energy of the hydroxyapatite, and simultaneously form silicic acid which can optimize the microenvironment of cells and change the structure of transmembrane proteins of the cells, thereby facilitating the combination of the proteins and the cells on the surface of the material and promoting the adhesion of osteoblasts on the surface of the cartilage scaffold.
In addition, the inherent poor dispersibility of hydroxyapatite can be overcome by grafting with 2-aminoethylphosphoric acid. The 2-aminoethyl phosphoric acid is used for modifying the hydroxyapatite, so that the hydrophilicity and hydrophobicity of the surface of the hydroxyapatite can be changed, stable hydroxyapatite gel is prepared, and the problem of particle agglomeration is solved.
In another embodiment, in the step S1.2, the particle diameter of the inorganic auxiliary active ingredient nano silver is preferably 20 to 50 nm.
The nano-scale silver particles, such as the nano-silver particles with the diameter of not more than 50nm used in the invention, have unique small-size effect and surface effect, can easily enter pathogens, can be rapidly combined with sulfydryl in bacteria, and can reduce the activity of bacterial synthetase, thereby achieving the purpose of killing bacteria. The hydroxyapatite is loaded on hydroxyapatite, at the moment, the hydroxyapatite with larger surface energy can be used as an adsorbent to improve the adsorption capacity of the cartilage scaffold to bacteria, and the hydroxyapatite is matched with loaded nano silver particles to achieve a good sterilization effect and simultaneously have the advantages of lasting effect, safety and no secondary pollution.
In this embodiment, in the step S1.3, the volume ratio of the composite hydroxyapatite gel to the PVA solution is 1: 2.
in other embodiments, in the S1.3 step, the volume ratio of the composite hydroxyapatite gel to the PVA solution may be in a range of 1: (2-5) in the range of. This is because cartilage is generally distributed in the joint area of the human body and carries a certain load, and different joint areas have different requirements on the mechanical properties of cartilage. In addition, different patients have different requirements on the mechanical properties of the cartilage scaffold at the same joint part. Therefore, the mechanical properties of the ideal cartilage scaffold must be matched with the individual specificity of a patient, and the adjustment of the mechanical properties of the cartilage scaffold can be realized by adjusting the volume ratio of the composite hydroxyapatite gel and the PVA solution according to clinical needs.
In this embodiment, in the step S1.4, the crosslinking agent is carbodiimide; in other embodiments, any one of thiosuccinimide, glutaraldehyde, dimethylol urea, and trimethylol melamine may be used instead of carbodiimide to achieve the object of the present invention.
Example 2:
a preparation process of a PVA hydrogel-based cartilage scaffold comprises the following steps:
s1.1: preparing a PVA solution; adding 20 parts by weight of PVA into 100 parts by weight of water, heating to 60 ℃, stirring for 30 minutes, and then standing for 2 hours at room temperature to obtain a PVA solution;
s1.2: preparing composite hydroxyapatite gel; dissolving 50 parts by weight of hydroxyapatite and 2 parts by weight of nano-silver in 300 parts by weight of ethanol, and stirring for 24 hours to obtain the composite hydroxyapatite gel;
s1.3: preparing composite PVA hydrogel; combining the composite hydroxyapatite gel with the PVA solution, heating to 80 ℃, stirring for 1 hour, and obtaining the composite PVA hydrogel after full reaction;
s1.4: crosslinking; adding a cross-linking agent into the composite PVA hydrogel, stirring for 20 minutes, performing injection molding, standing for 3 hours, and fully crosslinking to obtain a crosslinked composite PVA hydrogel which is marked as x-composite PVA hydrogel;
s1.5: molding; cooling the x-composite PVA hydrogel at-50 ℃, then drying for 24 hours, and then demolding;
s1.6: post-treatment; after the demoulding operation, washing, freezing and drying are carried out; repeating the step for 3-5 times to obtain the PVA hydrogel based cartilage scaffold.
In the hydroxyapatite used in the step S1.2 in this example, the weight fraction of silicon element in the hydroxyapatite was 0.01%, and the other conditions were the same as in example 1.
In this example, the concentration of hydroxyapatite in the composite hydroxyapatite gel was increased, and the young's modulus of the prepared cartilage scaffold was higher than that of the product obtained in example 1.
Example 3:
in this embodiment, a schematic process flow diagram of the prepared PVA hydrogel-based cartilage scaffold is shown in fig. 1, wherein in the step S1.3, a volume ratio of the composite hydroxyapatite gel to the PVA solution is 1: the other conditions were the same as in example 1.
In this embodiment, the ratio of the composite hydroxyapatite in the cartilage scaffold is reduced by reducing the volume ratio of the composite hydroxyapatite gel to the PVA solution, and the young modulus of the prepared cartilage scaffold is lower than that of the product obtained in embodiment 1.
Comparative example 1:
in this comparative example, the schematic process flow of the PVA hydrogel-based cartilage scaffold was as shown in FIG. 1, wherein hydroxyapatite used in the S1.2 step was not modified with 2-aminoethyl phosphate, and the other conditions were the same as in example 1.
Although hydroxyapatite is added in the preparation process of the product obtained by the comparative example, the utilization rate of the hydroxyapatite is extremely low due to poor dispersibility of the hydroxyapatite, and the Young modulus of the product is not obviously improved.
Other embodiments of the present invention than the preferred embodiments described above, and those skilled in the art can make various changes and modifications according to the present invention without departing from the spirit of the present invention, should fall within the scope of the present invention defined in the claims.
Claims (7)
1. A preparation method of a cartilage scaffold based on PVA hydrogel is characterized by comprising the following steps:
the method comprises the following steps:
s1.1: preparing a PVA solution; adding 5-20 parts by weight of PVA into 100 parts by weight of water, heating to 60-90 ℃, stirring for 10-30 minutes, and standing at room temperature for 0.5-2 hours to obtain a PVA solution;
s1.2: preparing composite hydroxyapatite gel; dissolving 20-50 parts by weight of hydroxyapatite and 2-10 parts by weight of inorganic auxiliary active ingredients in 200-400 parts by weight of organic solvent, and stirring for 12-48 hours to obtain the composite hydroxyapatite gel;
s1.3: preparing composite PVA hydrogel; combining the composite hydroxyapatite gel with the PVA solution, heating to 60-90 ℃, stirring for 1-2 hours, and obtaining the composite PVA hydrogel after full reaction;
s1.4: crosslinking; adding a cross-linking agent into the composite PVA hydrogel, stirring for 10-30 minutes, performing injection molding, standing for 1-5 hours, and fully crosslinking to obtain a crosslinked composite PVA hydrogel which is marked as x-composite PVA hydrogel;
s1.5: molding; freezing and drying the x-composite PVA hydrogel for 12-48 hours, and then demolding to obtain the PVA hydrogel-based cartilage scaffold;
in the step S1.2, the preparation method of the hydroxyapatite comprises:
s2.1: preparing a solution; adding 0.5-2 parts by weight of 2-aminoethyl phosphoric acid into 100 parts by weight of water to prepare a 2-aminoethyl phosphoric acid solution; adding 0.3-2 parts by weight of calcium nitrate into 100 parts by weight of water to prepare a calcium nitrate solution; adding 2-5 parts by weight of ammonium phosphate into 100 parts by weight of water to prepare an ammonium phosphate solution;
s2.2: adjusting the pH value; adjusting the pH values of the 2-aminoethyl phosphoric acid solution, the calcium nitrate solution and the ammonium phosphate solution to 9.8-10.2 by using a weak alkaline reagent;
s2.3: mixing; adding the calcium nitrate solution into the 2-aminoethyl phosphoric acid solution, uniformly stirring, and then adding a silicon source to obtain a mixed solution I; dropwise adding the ammonium phosphate solution into the mixed solution I step by step, and stirring uniformly to obtain a mixed solution II;
s2.4: carrying out reaction; heating the mixed solution II to 50-80 ℃, stirring for reaction for 3-5 hours, cooling to room temperature, and then carrying out ultrasonic treatment for 3-5 hours to obtain a mixed solution III;
s2.5: post-treatment; and centrifuging, washing, freezing and drying the mixed solution III to obtain the hydroxyapatite.
2. The method for preparing a PVA hydrogel based cartilage scaffold according to claim 1, wherein:
the preparation method of the PVA hydrogel-based cartilage scaffold further comprises the following S1.6 post-treatment steps:
s1.6: post-treatment; after the demoulding operation, washing, freezing and drying are carried out; repeating the step for 3-5 times to obtain the PVA hydrogel based cartilage scaffold.
3. The method for preparing a PVA hydrogel based cartilage scaffold according to claim 2, wherein:
in the step S2.3, the weight fraction of silicon element in the silicon source in the hydroxyapatite is 0.002-0.05%.
4. The method for preparing a PVA hydrogel based cartilage scaffold according to claim 2, wherein:
in the step S1.2, the inorganic auxiliary active ingredient is nano silver, and the particle diameter of the nano silver is not more than 50 nm.
5. The method for preparing a PVA hydrogel based cartilage scaffold according to claim 2, wherein:
in the step S1.3, the volume ratio of the composite hydroxyapatite gel to the PVA solution is 1: (2-5).
6. The method for preparing a PVA hydrogel based cartilage scaffold according to claim 2, wherein:
in the step S1.4, the crosslinking agent is any one of carbodiimide, thiosuccinimide, glutaraldehyde, dimethylol urea, and trimethylol melamine.
7. The method for preparing a PVA hydrogel based cartilage scaffold according to claim 2, wherein:
in the step S1.5, the freezing temperature is-50 to-20 ℃.
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