CN102772823A - Preparation method of hyaluronic acid/gelatin/chondroitin sulfate bone repair bionic scaffold - Google Patents
Preparation method of hyaluronic acid/gelatin/chondroitin sulfate bone repair bionic scaffold Download PDFInfo
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Abstract
The invention discloses a preparation method of hyaluronic acid/gelatin/chondroitin sulfate bone repair bionic scaffold. The method comprises the steps of adding activator and furfurylamine into MES buffer solution of hyaluronic acid to obtain modified hyaluronic acid solid; adding EDC/NHS (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide/N-hydroxysuccinimide) into gelatin aqueous solution, and adding furancarboxylic acid to obtain modified gelatin solid; dissolving the above two solids into MES buffer solution to obtain a mixed solution; dissolving MAL-PEG-MAL (maleimide-polyethylene glycol-maleimide) into MES buffer solution, adding into the mixed solution, and reacting in 37 DEG C water bath to form transparent cross-linked hydrogel; soaking the hydrogel in MES buffer solution of sodium chondroitin sulfate, adding EDC/NHS, and reacting under stirring to obtain the cartilage repair bionic scaffold. The bionic scaffold has the advantages of interpenetrating network structure, excellent biocompatibility and bioactivity, better compression strength, anti-washout property and degradability, simple preparation process, and easy operation.
Description
Technical field
The invention belongs to the bioactive materials field, relate to cartilaginous tissue reparation, filling and organizational project repair materials, be specifically related to the method for preparing that a kind of hyaluronic acid/gelatin/chondroitin sulfate bone is repaired biomimetic scaffolds.
Background technology
Articular cartilage is a kind of tissue comparatively special in the human body, and it does not have blood vessel, nerve and lymphocyte, thereby self-reparing capability is very poor.At present clinically traditional treatment mainly contain attrition under little fracture art, subchondral bone Drilling, the cartilage, from body cartilage transplantation and autogenous cell transplantation art etc., but there are many deficiencies in these methods, and can bring the secondary wound to patient.Also do not have at present the alternative damage location that a kind of method can success and reach the purpose of regenerating bone or cartilage.
Cartilage tissue engineered is the hottest a kind of method of studying at present; Be with cell, envirment factor, timbering material triplicity; The best microenvironment of in-vitro simulated cells survival makes cytoactive and the phenotype all can be similar with situation in the body, thereby reaches the purpose of repairing cartilaginous tissue.
In repair of cartilage, the interaction between chondrocyte and the substrate is most important, and good hydrogel timbering material should provide with natural cartilage and organize similar structure and performance.Cartilage cell epimatrix mainly is made up of type and polysaccharide.Collagen is network structure and is distributed in the whole cartilage matrix, and its major function is for chondrocyte provides tension force and holding capacity, for the adhesion of chondrocyte provides the basis, and participates in the adjusting of chondrocyte phenotypic differentiation.
In this type cartilaginous tissue repair materials, the aquagel tissue engineering rack has received concern widely owing to having similar characteristic with cartilage cell epimatrix.The method for preparing at present hydrogel has physical crosslinking method and chemical crosslink technique: the physical crosslinking method is utilized the intermolecular hydrogen bonding effect; Ion electrostatic interaction or close and distant water effect etc.; Because intermolecular force is not strong, cause the hydrogel of physical crosslinking method preparation unstable, hydrolysis or fusion easily; The hydrogel structure stable performance of chemical crosslink technique preparation, mechanical strength is better, but most of chemical reaction need add various deleterious initiators and cross-linking agent.To these shortcomings, the method for effectively nontoxic fast Diels-Alder click chemistry prepared in reaction hydrogel soft bone tissue engineering scaffold had appearred utilizing in recent years.
At present, the material that is used for the repair of cartilage hydrogel comprises natural biologic material, as: collagen, chitosan, hyaluronic acid (be called for short: HA), gelatin (be called for short: G) etc., and synthesized polymer material, like two big types of PLGA, PLA, PCL etc.Synthetic high polymer hydrogel mechanical property is excellent, but limits its application on repair of cartilage owing to lacking cell binding site and biocompatibility; For natural biologic material, general difficultly form aquogel system, and have shortcomings such as the fast and mechanical property of degradation rate can not satisfy the demands.Natural material and synthetic material are carried out the compound biocompatibility that can when improving mechanical property, improve material, differ greatly but compare with natural cartilage cell epimatrix.Also has one type through collagen being modified the method for preparing the hydrogel repair materials with modification; But the tropocollagen molecule amount is big; Be not easy and the mutual bonding of other materials; Except hexafluoroisopropanol is dissolved in any solvent hardly, and the hexafluoroisopropanol strong toxicity is not suitable for being used in field of biomedical materials.Therefore to obtain very difficulty of collagen solution, collagen modified with modification extremely difficult especially, cause it not to be suitable as a kind of hydrogel material.
Summary of the invention
The objective of the invention is to shortcoming to above-mentioned prior art, the method for preparing that provides a kind of hyaluronic acid/gelatin/chondroitin sulfate bone to repair biomimetic scaffolds, and be applied to the cartilage joint reparation.
In order to achieve the above object, the present invention has adopted following technical scheme:
Hyaluronic acid/gelatin/chondroitin sulfate bone is repaired the method for preparing of biomimetic scaffolds, comprises the steps:
(1) in hyaluronic 2-(N-morphine quinoline) ethyl sulfonic acid buffer, stirs 0.5 ~ 1h behind adding 4-(4,6-dimethoxy-triazine-2-yl)-4-methyl morpholine hydrochloride activator; Dropwise add furfuryl amine again; Reaction 24 ~ 48h dialysed 3 ~ 5 days, and lyophilization obtains modification hyaluronic acid solid;
(2) after adding carbodiimide and N-hydroxy-succinamide stir in aqueous gelatin solution, add furancarboxylic acid, reaction 24 ~ 48h dialysed 3 ~ 5 days, and lyophilization obtains the modified gelatin solid;
(3) the modified gelatin solid that obtains in modification hyaluronic acid solid that obtains in the step (1) and the step (2) is dissolved in 2-(N-morphine quinoline) the ethyl sulfonic acid buffer jointly obtains mixed solution;
(4) both-end base maleimide polyvinyl alcohol is dissolved in 2-(N-morphine quinoline) the ethyl sulfonic acid buffer obtains both-end base maleimide poly-vinyl alcohol solution;
(5) in the mixed solution that the both-end base maleimide poly-vinyl alcohol solution adding step (3) that step (4) is obtained obtains, after stirring, in 37 ~ 50 ℃ of water-baths, carry out the click chemistry reaction until forming transparent cross-linked hydrogel state;
(6) hydrogel that step (5) is obtained is immersed in 2-(N-morphine quinoline) the ethyl sulfonic acid buffer of sodium chondroitin sulfate; Add carbodiimide and N-hydroxy-succinamide stirring reaction 24 ~ 48h, obtain hyaluronic acid/gelatin/chondroitin sulfate bone and repair biomimetic scaffolds.
In the step (1), the mass volume ratio of said hyaluronic acid and 2-(N-morphine quinoline) ethyl sulfonic acid buffer is 0.2 ~ 0.8%; The mol ratio of said hyaluronic acid, furfuryl amine and 4-(4,6-dimethoxy-triazine-2-yl)-4-methyl morpholine hydrochloride is 1:2: (2 ~ 6).
In the step (2), the concentration of said aqueous gelatin solution is 0.5 ~ 1.5% w/v; The mass ratio of said carbodiimide and N-hydroxy-succinamide is 3:2, and the gross mass of carbodiimide and N-hydroxy-succinamide is 4/5 of a gelatin quality; The mass ratio of said furancarboxylic acid and gelatin is (1 ~ 3): 4.
In step (1) and the step (2), the molecular cut off of said dialysis is 14000; Said cryodesiccated step is: become the ice shape prior to-20 ~-70 ℃ of freezing 24 ~ 48h, continue lyophilizing 48 ~ 72h then.
In the step (3), the solid concentration of modification hyaluronic acid is 1 ~ 2% w/v in the said mixed solution, and the solid concentration of modified gelatin is 0.5 ~ 1.5% w/v.
The ratio of the quality of said both-end base maleimide polyvinyl alcohol and modification hyaluronic acid solid and the solid quality sum of modified gelatin is 1:4.
In the step (6), the mass volume ratio of said sodium chondroitin sulfate and 2-(N-morphine quinoline) ethyl sulfonic acid buffer is 1 ~ 3%; The mass ratio of said carbodiimide and N-hydroxy-succinamide is 3:2, and the gross mass of carbodiimide and N-hydroxy-succinamide is 4/5 of a sodium chondroitin sulfate quality.
The concentration of said 2-(N-morphine quinoline) ethyl sulfonic acid buffer is 100mmol/L, pH=5.5.
The present invention compared with prior art has the following advantages and beneficial effect:
(1) the present invention adopts Diels-Alder click chemistry prepared in reaction composite aquogel biomimetic scaffolds; Gelation time is short, and the gentle selectivity of reaction condition is high, and no coupling product; Need not to add any cross-linking agent and initiator, guaranteed the avirulence and the cell compatibility of hydrogel biomimetic scaffolds;
(2) the present invention can prepare the regulatable composite aquogel biomimetic scaffolds of different crosslink densities and mechanical property and degradation property through the mol ratio of control reactive group;
(3) the present invention is through the control crosslink density, and the composite aquogel biomimetic scaffolds of preparation can obtain the network structure of different size, thus the aperture network of the most suitable chondrocyte growth of screening;
(4) hyaluronic acid, gelatin and the chondroitin sulfate selected for use of the present invention (is called for short: CS) as the material preparation hydrogel; Simulated the natural cartilage extracellular matrix of collagen protein and polysaccharide from composition, for the growth and the metabolism of chondrocyte provides a more similar microenvironment.
Description of drawings
Fig. 1 is the scanning electron microscope picture that hyaluronic acid/gelatin of the present invention/chondroitin sulfate bone is repaired biomimetic scaffolds.
Fig. 2 is the stress-strain curve diagram that the embodiment of the invention 1 and two kinds of different proportion bones of embodiment 2 preparations are repaired biomimetic scaffolds.
Fig. 3 is the degradation curve figure that the embodiment of the invention 1 and two kinds of different proportion bones of embodiment 2 preparations are repaired biomimetic scaffolds.
The specific embodiment
Below in conjunction with embodiment the present invention is done further explain, but the scope that the present invention requires to protect is not limited thereto.
(1) be that 0.2% hyaluronic 2-(N-morphine quinoline) ethyl sulfonic acid (is called for short: MES) in the buffer (the hyaluronic acid quality is 0.5g) in concentration; Adding 0.654g 4-(4,6-dimethoxy-triazine-2-yl)-4-methyl morpholine hydrochloride (is called for short: DMTMM), stir 0.5h; Dropwise add 220 μ L furfuryl amine again; Reaction 24h dialysed 3 days, and lyophilization obtains modification hyaluronic acid solid;
(2) be to add the 400mg carbodiimide among 0.5% the aqueous gelatin solution 100ml (to be called for short: EDC) (be called for short: after NHS) stirring in concentration with the 267mg N-hydroxy-succinamide; Add the 125mg furancarboxylic acid; Reaction 24h dialysed 3 days, and lyophilization obtains the modified gelatin solid;
(3) the modified gelatin solid 45mg that obtains in modification hyaluronic acid solid 30mg that obtains in the step (1) and the step (2) is dissolved in the MES buffer jointly obtains mixed solution, the two volumetric concentration is respectively 1% and 1.5%;
(4) the both-end base maleimide polyvinyl alcohol with 37.5mg (is called for short: MAL-PEG-MAL) be dissolved in and obtain MAL-PEG-MAL solution in the MES buffer;
(5) in the mixed solution that the MAL-PEG-MAL solution adding step (3) that step (4) is obtained obtains, after stirring, in 37 ℃ of water-baths, carry out the click chemistry reaction until forming transparent cross-linked hydrogel state;
(6) it is that 1% sodium chondroitin sulfate (is called for short: in MES buffer CS) that the hydrogel that step (5) is obtained is immersed in concentration; Adding 500mg EDC and 330mg NHS also puts into shaking table and reacts 24h, obtains hyaluronic acid/gelatin/chondroitin sulfate bone and repairs biomimetic scaffolds.
Fig. 1 is the scanning electron microscope collection of illustrative plates after the hyaluronic acid/gelatin/chondroitin sulfate bone of the embodiment of the invention 1 preparation is repaired the biomimetic scaffolds lyophilizing, can find out that biomimetic scaffolds has the RF that runs through each other, and network size is 150 ~ 250 μ m.
Embodiment 2
(1) in concentration is 0.4% hyaluronic MES buffer (the hyaluronic acid quality is 0.5g), add 1.38g DMTMM, stir 1h, dropwise add 220 μ L furfuryl amine again, reaction 36h dialysed 4 days, and lyophilization obtains modification hyaluronic acid solid;
(2) be to add in 1% the aqueous gelatin solution after 800mg EDC stirs with 533mg NHS in concentration, add the 500mg furancarboxylic acid, react 36h, dialysed 4 days, lyophilization obtains the modified gelatin solid;
(3) the modified gelatin solid 105mg that obtains in modification hyaluronic acid solid 45mg that obtains in the step (1) and the step (2) is dissolved in the MES buffer of 3ml jointly obtains mixed solution, the two volumetric concentration is respectively 1.5% and 3.5%;
(4) MAL-PEG-MAL of 75mg is dissolved in obtains MAL-PEG-MAL solution in the MES buffer;
(5) in the mixed solution that the MAL-PEG-MAL solution adding step (3) that step (4) is obtained obtains, after stirring, in 45 ℃ of water-baths, carry out the click chemistry reaction until forming transparent cross-linked hydrogel state;
(6) hydrogel that step (5) is obtained is immersed in the MES buffer that concentration is 2% CS, adds 1g EDC and 660 mg NHS and also puts into shaking table and react 24h, obtains hyaluronic acid/gelatin/chondroitin sulfate bone reparation biomimetic scaffolds.
Fig. 2 is the stress-strain curve diagram that the embodiment of the invention 1 and two kinds of different proportion bones of embodiment 2 preparations are repaired biomimetic scaffolds; Can find out; The modulus of compressibility maximum of the composite aquogel biomimetic scaffolds of the present invention preparation can reach 1278Pa, apparently higher than the mechanical property of the gelatin and the hyaluronic acid composite aquogel of prepared by other.
Fig. 3 is the degradation curve figure that the embodiment of the invention 1 and two kinds of different proportion bones of embodiment 2 preparations are repaired biomimetic scaffolds, can find out, in the PBS buffer, signs of degradation did not take place in 21 days the hydrogel biomimetic scaffolds of the different proportion of the present invention's preparation; Although in the hyaluronic acid enzymatic solution, the enzymolysis phenomenon can take place in hydrogel, compares degradation rate with traditional hydrogel and obviously descends.The composite aquogel biomimetic scaffolds that the present invention's preparation is described has good anti-degradation property.
Embodiment 3
(1) in concentration is 0.8% hyaluronic MES buffer (the hyaluronic acid quality is 0.5g), add 2.02g DMTMM, stir 1h, dropwise add 220 μ L furfuryl amine again, reaction 48h dialysed 5 days, and lyophilization obtains modification hyaluronic acid solid;
(2) be to add in 1.5% the aqueous gelatin solution after 1.2g EDC stirs with 0.8g NHS in concentration, add the 1.1g furancarboxylic acid, react 48h, dialysed 5 days, lyophilization obtains the modified gelatin solid;
(3) the modified gelatin solid 165mg that obtains in modification hyaluronic acid solid 60mg that obtains in the step (1) and the step (2) is dissolved in jointly obtains mixed solution among the MES, the two volumetric concentration is respectively 2% and 5.5%;
(4) MAL-PEG-MAL of 150mg is dissolved in obtains MAL-PEG-MAL solution in the MES buffer;
(5) in the mixed solution that the MAL-PEG-MAL solution adding step (3) that step (4) is obtained obtains, after stirring, in 50 ℃ of water-baths, carry out the click chemistry reaction until forming transparent cross-linked hydrogel state;
(6) hydrogel that step (5) is obtained is immersed in the MES buffer that concentration is 3% CS, adds 1.5g EDC and 1g NHS and also puts into shaking table and react 24h, obtains hyaluronic acid/gelatin/chondroitin sulfate bone reparation biomimetic scaffolds.
Claims (8)
1. hyaluronic acid/gelatin/chondroitin sulfate bone is repaired the method for preparing of biomimetic scaffolds, it is characterized in that, comprises the steps:
(1) in hyaluronic 2-(N-morphine quinoline) ethyl sulfonic acid buffer, stirs 0.5 ~ 1h behind adding 4-(4,6-dimethoxy-triazine-2-yl)-4-methyl morpholine hydrochloride activator; Dropwise add furfuryl amine again; Reaction 24 ~ 48h dialysed 3 ~ 5 days, and lyophilization obtains modification hyaluronic acid solid;
(2) after adding carbodiimide and N-hydroxy-succinamide stir in aqueous gelatin solution, add furancarboxylic acid, reaction 24 ~ 48h dialysed 3 ~ 5 days, and lyophilization obtains the modified gelatin solid;
(3) the modified gelatin solid that obtains in modification hyaluronic acid solid that obtains in the step (1) and the step (2) is dissolved in 2-(N-morphine quinoline) the ethyl sulfonic acid buffer jointly obtains mixed solution;
(4) both-end base maleimide polyvinyl alcohol is dissolved in 2-(N-morphine quinoline) the ethyl sulfonic acid buffer obtains both-end base maleimide poly-vinyl alcohol solution;
(5) in the mixed solution that the both-end base maleimide poly-vinyl alcohol solution adding step (3) that step (4) is obtained obtains, after stirring, in 37 ~ 50 ℃ of water-baths, carry out the click chemistry reaction until forming transparent cross-linked hydrogel state;
(6) hydrogel that step (5) is obtained is immersed in 2-(N-morphine quinoline) the ethyl sulfonic acid buffer of sodium chondroitin sulfate; After adding carbodiimide and N-hydroxy-succinamide stirring reaction 24 ~ 48h, obtain hyaluronic acid/gelatin/chondroitin sulfate repair of cartilage biomimetic scaffolds.
2. method for preparing according to claim 1 is characterized in that, in the step (1), the mass volume ratio of said hyaluronic acid and 2-(N-morphine quinoline) ethyl sulfonic acid buffer is 0.2 ~ 0.8%; The mol ratio of said hyaluronic acid, furfuryl amine and 4-(4,6-dimethoxy-triazine-2-yl)-4-methyl morpholine hydrochloride is 1:2: (2 ~ 6).
3. method for preparing according to claim 2 is characterized in that, in the step (2), the concentration of said aqueous gelatin solution is 0.5 ~ 1.5% w/v; The mass ratio of said carbodiimide and N-hydroxy-succinamide is 3:2, and the gross mass of carbodiimide and N-hydroxy-succinamide is 4/5 of a gelatin quality; The mass ratio of said furancarboxylic acid and gelatin is (1 ~ 3): 4.
4. method for preparing according to claim 3 is characterized in that, in step (1) and the step (2), the molecular cut off of said dialysis is 14000; Said cryodesiccated step is: become the ice shape prior to-20 ~-70 ℃ of freezing 24 ~ 48h, continue lyophilizing 48 ~ 72h then.
5. method for preparing according to claim 4 is characterized in that, in the step (3), the solid concentration of modification hyaluronic acid is 1 ~ 2% w/v in the said mixed solution, and the solid concentration of modified gelatin is 0.5 ~ 1.5% w/v.
6. method for preparing according to claim 5 is characterized in that, the ratio of the quality of said both-end base maleimide polyvinyl alcohol and modification hyaluronic acid solid and the solid quality sum of modified gelatin is 1:2 ~ 2:1.
7. method for preparing according to claim 6 is characterized in that, in the step (6), the mass volume ratio of said sodium chondroitin sulfate and 2-(N-morphine quinoline) ethyl sulfonic acid buffer is 1 ~ 3%; The mass ratio of said carbodiimide and N-hydroxy-succinamide is 3:2, and the gross mass of carbodiimide and N-hydroxy-succinamide is 4/5 of a sodium chondroitin sulfate quality.
8. method for preparing according to claim 7 is characterized in that, the concentration of said 2-(N-morphine quinoline) ethyl sulfonic acid buffer is 100mmol/L, pH=5.5.
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