CN105086001A - Hyaluronic acid-gelatin/acrylamide double-network aquagel and preparation method thereof - Google Patents
Hyaluronic acid-gelatin/acrylamide double-network aquagel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hyaluronic acid-gelatin/acrylamide double-network aquagel which is formed by interpenetrating a first network aquagel and a second network aquagel, wherein the first network is the aquagel formed by carrying out Michael addition reaction crosslinking on modified hyaluronic acid and gelatin, and the second network is the aquagel formed by carrying out chemical crosslinking on acrylamide. The modifiable site of the hyaluronic acid is modified, and the hyaluronic acid is combined with the gelatin to form the first network aquagel, so that the aquagel has favorable biocompatibility; and the aquagel can have wide applicability in the field of medical materials by utilizing favorable biocompatibility between the hyaluronic acid and gelatin. Meanwhile, the acrylamide is introduced as the second network into the aquagel, so that the aquagel has favorable biocompatibility and favorable mechanical properties. The compression strength of the hyaluronic acid-gelatin/acrylamide double-network aquagel is up to 302.56 KPa. The application range of the aquagel is widened.
Description
Technical field
The invention provides a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel and preparation method thereof, belong to macromolecule hydrogel technical field.
Background technology
Hydrogel (hydrogel) is a kind of is dispersion medium with water, and being cross-linked with each other by effects such as covalent linkage, hydrogen bond or Van der Waals forces forms the hydrogel of three-dimensional polymer mesh structure.Have in the water-soluble polymer of cross-linked network and introduce a part of hydrophobic grouping and hydrophilic residue, hydrophilic residue and water molecules, and hydrophobic residue runs into water expansion formation polymkeric substance. hydrogel has good biocompatibility, compared with hydrophobic polymer, the biomolecule activity be fixed in hydrogel can keep the long period, with the enzyme that is immobilized or cell interaction much weak, therefore hydrogel has many purposes in the field such as biological chemistry, medical science.
Chinese patent (CN104327311A) describes a kind of hyaluronic acid composite crosslinking hydrogel and preparation method thereof.This hydrogel can be used as the feature in chemically modified site and the characteristic of polyanion electrolyte thereof in conjunction with hyaluronic acid active group, utilize 1, the different group that the materials such as 4-butanediol diglycidyl ether, polyoxyethylene glycol, sodium alginate and gelatin have and different space conformations, carry out composite crosslinking modification with hyaluronic acid simultaneously, and by analyzing the ratio of various component, determine the optimum formula of each component of crosslinking reaction, the hyaluronic acid composite aquogel molecular weight of preparation is significantly improved, and particularly significantly increases its dynamic viscosity.This hydrogel molecules amount is large, kinetic viscosity is large, has stronger space obstacle effect, lubrication, and the advantage such as good biocompatibility, good stability, can be used for tissue bulking material, joint cavity internal lubricant and surgical prophylaxis tissue adhesion material.This patent describe good biocompatibility and the stability of its hyaluronic acid gel, but not mentioned mechanical property.
Chinese patent (CN103435951A) describes a kind of Nanometer composite high-molecular dual-network hydrogel and preparation method thereof.Specifically comprise the steps: first first network monomer, linking agent and initiator to be dissolved in containing in nanoparticle aqueous dispersions, pour the mixing solutions obtained in mould heated polymerizable, obtain first network hydrogel.Second network monomer, linking agent and initiator are dissolved in the water, then first network hydrogel is put into this solution, swelling 24 hours, then heated polymerizable, obtain high-strength nano composite high-molecular double-network hydrogel.Gained hydrogel superior performance, is strengthened by nanometer, not only can improve the compressive strength of double-network hydrogel, and can also keep its comparatively high tensile.This hydrogel effectively raises mechanical property, but not mentioned biocompatibility.
Chinese patent (CN103467754A) describes a kind of aquagel and preparation method thereof, comprises step: chitosan is dissolved in diluted acid solvent by S1, preparation chitosan solution; S2 in the presence of an oxidizer, makes described chitosan solution generation redox reaction, obtains prepolymer solution; S3 in acid condition, makes described prepolymer solution generation self-crosslinking reaction, obtains aquagel.The present invention adopts body self-crosslinking method to prepare aquagel, and technique is simple, and the aquagel of acquisition, while possessing satisfactory stability, also maintains good biocompatibility.This hydrogel maintains good biocompatibility, but its mechanical property not mentioned.
Summary of the invention
In order to solve prior art Problems existing, the invention provides a kind of preparation method of hyaluronic acid-gelatin/acrylamide double-network hydrogel.
A kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel of the present invention, it is characterized in that, it is consisted of first network and second network IPN, described first network is the hydrogel that the hyaluronic acid of modification and gelatin are cross-linked to form by Michael reaction, and second network is the hydrogel that acrylamide chemically crosslinked is formed.
Step and the condition of the preparation method of a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel of the present invention are as follows:
(1) preparation of modified hyaluronic acid
A. the hyaluronic acid aqueous solution that massfraction is 1-4% is mixed with, pH to 4 ~ 6 of hyaluronic acid aqueous solution are regulated with hydrochloric acid, then EDC and N-hydroxy-succinamide is added, stirred at ambient temperature 15 ~ 25min, then add ethylcysteine hydrochloride reaction 4 ~ 8 hours, obtain solution; Ethylcysteine hydrochloride: N-hydroxy-succinamide: EDC: hyaluronic mol ratio is 1 ~ 2:0.5 ~ 1:0.25 ~ 1:1;
B. add methacrylic anhydride in solution step a obtained, regulate pH to 7.0 ~ 9.0 by NaOH solution, react 20 ~ 48 hours at 2 ~ 6 DEG C, dialyse 5 ~ 7 days, lyophilize, obtains modified hyaluronic acid solid; The hyaluronic mol ratio of described methacrylic anhydride and step a is 1 ~ 10:1;
(2) preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution, more admixed together with aqueous gelatin solution, light trigger, and under room temperature, lucifuge stirs 20 ~ 30min, with UV-irradiation 20 ~ 40min, forms first network hydrogel; Described light trigger is the one in 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone and α-ketoglutaric acid; The concentration of the modified hyaluronic acid aqueous solution is 1g ~ 4g/100mL; Gelatin concentration is 2g ~ 10g/100mL; The volume ratio of modified hyaluronic acid solution and gelatin solution is 4:1 ~ 16; Described light trigger consumption and the mass ratio of modified hyaluronic acid are 40:1 ~ 6;
(3) preparation of second network hydrogel
Preparation massfraction is the acrylamide solution of 5 ~ 20%, add light trigger and linking agent again, under room temperature, lucifuge stirs 20 ~ 30min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 24 ~ 48 hours, take out swelling after hydrogel, with UV-irradiation 20 ~ 40min, obtain target compound second network hydrogel; The same step of described light trigger (2), linking agent is N, N ' one or more in-methylene-bisacrylamide, ethylene glycol dimethacrylate and Diethylene Glycol methacrylic ester; Light trigger: linking agent: the proportion of acylamide is 1 ~ 6:1 ~ 4:200.
The equation of described a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel and preparation method thereof is as follows:
beneficial effect:a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel of the present invention is cross-linked to form first network water of constitution gel by the hyaluronic acid of modification and gelatin by Michael reaction, and the second network water of constitution gel formed with acrylamide chemically crosslinked is formed.The present invention can carry out modification to it by decorating site by hyaluronic, then be combined with gelatin and form first network hydrogel, make hydrogel have good biocompatibility, utilize hyaluronic acid and the good biocompatibility of gelatin that this hydrogel can be made to have a wide range of applications in medical material field.Simultaneously, introducing acrylamide introduces in hydrogel as second network, make hydrogel while having good biocompatibility, have good mechanical property, the compressive strength of a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel of the present invention is up to 302.56KPa.Widen the Application Areas of hydrogel.
Embodiment
A kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel is consisted of first network and the second net glue IPN, described first network is the hydrogel that the hyaluronic acid of modification and gelatin are cross-linked to form by Michael reaction, and second network is the hydrogel that acrylamide chemically crosslinked is formed.The step of its preparation method and condition are as following examples.
embodiment 1the step of a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel preparation method and condition are as following:
(1) preparation of modified hyaluronic acid
A. taking quality is 4g (0.005moL) hyaluronic acid, be mixed with the hyaluronic acid aqueous solution that massfraction is 4%, the pH to 6 of hyaluronic acid solution is regulated with 1moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, add the EDC (EDC) of 0.005moL and the N-hydroxy-succinamide (NHS) of 0.005moL, stirred at ambient temperature 25min, then the ethylcysteine hydrochloride adding 0.01moL reacts 8 hours, obtains solution;
B. add 0.05mol methacrylic anhydride in the solution obtained in step (a), regulate pH to 9.0 by the NaOH solution of 10moL/L, react 48 hours at 6 DEG C, dialyse 7 days, lyophilize obtains modified hyaluronic acid solid;
(1) preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 4%, get 10ml massfraction be 4% hyaluronic acid aqueous solution and 10mL massfraction be 10% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 6:40, under room temperature, lucifuge stirs 30min, forms first network hydrogel with UV-irradiation 40min;
(2) preparation of second network hydrogel
Preparation massfraction is the acrylamide solution 100mL of 20%, by light trigger, linking agent by being that 6:4:200 joins in acrylamide solution with the proportion of acylamide, under room temperature, lucifuge stirs 30min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel.
The compression performance measuring method of the hyaluronic acid-gelatin/acrylamide double-network hydrogel of preparation: the hydrogel style that preparation upper and lower surface is smooth, CT3 Texture instrument is utilized to carry out compression verification, deformation quantity is 80%, trigger point load is 0.067N, test speed is 0.50mm/s, and retum speed is 0.5mm/s.
In embodiment 1, the compressive strength of the hyaluronic acid-gelatin/acrylamide double-network hydrogel of preparation is 302.56KPa.
embodiment 2the step of a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel preparation method and condition are as following:
(1) hyaluronic modification
A. taking quality is 2g(0.0025moL) hyaluronic acid, its mole number is, be mixed with the hyaluronic acid aqueous solution that massfraction is 2%, the pH to 5.5 of hyaluronic acid solution is regulated with 1moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, add the EDC (EDC) of 0.0025moL and the N-hydroxy-succinamide (NHS) of 0.0025moL, stirred at ambient temperature 20min, then the ethylcysteine hydrochloride adding 0.005moL reacts 6 hours, obtains solution;
B. add 0.015moL methacrylic anhydride in the solution obtained in step (a), regulate pH to 8.0 by the NaOH solution of 10moL/L, react 24 hours at 4 DEG C, dialyse 7 days, lyophilize obtains modified hyaluronic acid solid;
(2) preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 2%, get 10mL massfraction be 2% hyaluronic acid aqueous solution and 10mL massfraction be 5% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 2:40, under room temperature, lucifuge stirs 20min, forms first network hydrogel with UV-irradiation 40min;
(3) preparation of second network hydrogel
Preparation massfraction is the acrylamide solution 100mL of 10%, by light trigger, linking agent by being that 2:2:200 joins in acrylamide solution with the proportion of acylamide, under room temperature, lucifuge stirs 20min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel;
With the measuring method of embodiment 1, in embodiment 2, the compressive strength of the hyaluronic acid-gelatin/acrylamide double-network hydrogel of preparation is 171.42KPa.
embodiment 3the step of a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel preparation method and condition are as following:
(1) hyaluronic modification
A. taking quality is 2g(0.0025moL) hyaluronic acid, be mixed with the hyaluronic acid aqueous solution that massfraction is 2%, the pH to 5.5 of hyaluronic acid solution is regulated with 1moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, 0.0025moL1-(3-dimethylamino-propyl is added)-3-ethyl carbodiimide (EDC) and 0.0025moLN-N-Hydroxysuccinimide (NHS), stirred at ambient temperature 20min, then add 0.005moL ethylcysteine hydrochloride and react 6 hours, obtain solution;
B. add 0.015moL methacrylic anhydride in the solution obtained in step (a), regulate pH to 8.0 by the NaOH solution of 10moL/L, react 24 hours at 4 DEG C, dialyse 7 days, lyophilize obtains modified hyaluronic acid solid;
(2) preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 2%, get 10mL massfraction be 2% hyaluronic acid aqueous solution and 10mL massfraction be 5% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 2:40, under room temperature, lucifuge stirs 20min, forms first network hydrogel with UV-irradiation 40min;
(3) preparation of second network hydrogel
Preparation massfraction is the acrylamide solution 100mL of 15%, by light trigger, linking agent by being that 2:2:200 joins in acrylamide solution with the proportion of acylamide, under room temperature, lucifuge stirs 20min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel.
With the measuring method of embodiment 1, in embodiment 3, the compressive strength of the hyaluronic acid-gelatin/acrylamide double-network hydrogel of preparation is 201.86KPa.
embodiment 4the step of a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel preparation method and condition are as following:
(1) preparation of modified hyaluronic acid
A. taking quality is 2g(0.0025moL) hyaluronic acid, be mixed with the hyaluronic acid aqueous solution that massfraction is 2%, the pH to 5.5 of hyaluronic acid aqueous solution is regulated with 1moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, 0.0025moL1-(3-dimethylamino-propyl is added)-3-ethyl carbodiimide (EDC) and 0.0025moLN-N-Hydroxysuccinimide (NHS), stirred at ambient temperature 20min, then add 0.005moL ethylcysteine hydrochloride and react 6 hours, obtain solution;
B. add 0.015moL methacrylic anhydride in the solution obtained in step (a), regulate pH to 8.0 by the NaOH solution of 10moL/L, react 24 hours at 4 DEG C, dialyse 7 days, lyophilize obtains modified hyaluronic acid solid;
(2) preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 2%, get 10mL massfraction be 2% hyaluronic acid aqueous solution and 10mL massfraction be 5% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 2:40, under room temperature, lucifuge stirs 20min, forms first network hydrogel with UV-irradiation 40min;
(3) preparation of second network hydrogel
Preparation massfraction is the acrylamide solution 100mL of 20%, by light trigger, linking agent by being that 2:2:200 joins in acrylamide solution with the proportion of acylamide, under room temperature, lucifuge stirs 20min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel.
With the measuring method of embodiment 1, in embodiment 4, the compressive strength of the hyaluronic acid-gelatin/acrylamide double-network hydrogel of preparation is 257.32KPa.
embodiment 5the step of a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel preparation method and condition are as following:
(1) preparation of modified hyaluronic acid
A. taking quality is 2g(0.0025moL) hyaluronic acid, be mixed with the hyaluronic acid aqueous solution that massfraction is 2%, the pH to 5.5 of hyaluronic acid aqueous solution is regulated with 1moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, 0.0025moL1-(3-dimethylamino-propyl is added)-3-ethyl carbodiimide (EDC) and 0.0025moLN-N-Hydroxysuccinimide (NHS), stirred at ambient temperature 20min, then add 0.005moL ethylcysteine hydrochloride and react 6 hours, obtain solution;
B. add 0.015moL methacrylic anhydride in the solution obtained in step (a), regulate pH to 8.0 by the NaOH solution of 10moL/L, react 24 hours at 4 DEG C, dialyse 7 days, lyophilize obtains modified hyaluronic acid solid;
(2) preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 2%, get 8mL massfraction be 2% hyaluronic acid aqueous solution and 12mL massfraction be 5% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 2:40, under room temperature, lucifuge stirs 20min, forms first network hydrogel with UV-irradiation 40min;
(3) preparation of second network hydrogel
Preparation massfraction is the acrylamide solution 100mL of 10%, by light trigger, linking agent by being that 2:2:200 joins in acrylamide solution with the proportion of acylamide, under room temperature, lucifuge stirs 20min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel.
With the measuring method of embodiment 1, in embodiment 5, the compressive strength of the hyaluronic acid-gelatin/acrylamide double-network hydrogel of preparation is 185.49KPa.
embodiment 6the step of a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel preparation method and condition are as following:
(1) preparation of modified hyaluronic acid
A. taking quality is 2g(0.0025moL) hyaluronic acid, be mixed with the hyaluronic acid aqueous solution that massfraction is 2%, the pH to 5.5 of hyaluronic acid aqueous solution is regulated with 1moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, 0.0025moL1-(3-dimethylamino-propyl is added)-3-ethyl carbodiimide (EDC) and 0.0025moLN-N-Hydroxysuccinimide (NHS), stirred at ambient temperature 20min, then add 0.005moL ethylcysteine hydrochloride and react 6 hours, obtain solution;
B. add 0.015moL methacrylic anhydride in the solution obtained in step (a), regulate pH to 8.0 by the NaOH solution of 10moL/L, react 24 hours at 4 DEG C, dialyse 7 days, lyophilize obtains modified hyaluronic acid solid;
(2) preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 2%, get 12mL massfraction be 2% hyaluronic acid aqueous solution and 8mL massfraction be 5% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 2:40, under room temperature, lucifuge stirs 20min, forms first network hydrogel with UV-irradiation 40min;
(3) preparation of second network hydrogel
Preparation massfraction is the acrylamide solution 100mL of 10%, by light trigger, linking agent by being that 2:2:200 joins in acrylamide solution with the proportion of acylamide, under room temperature, lucifuge stirs 20min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel.
With the measuring method of embodiment 1, in embodiment 6, the compressive strength of the hyaluronic acid-gelatin/acrylamide double-network hydrogel of preparation is 193.72KPa.
embodiment 7the step of a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel preparation method and condition are as following:
(1) preparation of modified hyaluronic acid
A. taking quality is 2g(0.0025moL) hyaluronic acid, be mixed with the hyaluronic acid aqueous solution that massfraction is 2%, the pH to 5.5 of hyaluronic acid aqueous solution is regulated with 1moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, 0.0025moL1-(3-dimethylamino-propyl is added)-3-ethyl carbodiimide (EDC) and 0.0025moLN-N-Hydroxysuccinimide (NHS), stirred at ambient temperature 20min, then add 0.005moL ethylcysteine hydrochloride and react 6 hours, obtain solution;
B. add 0.015moL methacrylic anhydride in the solution obtained in step (a), regulate pH to 8.0 by the NaOH solution of 10moL/L, react 24 hours at 4 DEG C, dialyse 7 days, lyophilize obtains modified hyaluronic acid solid;
(2) preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 2%, get 16mL massfraction be 2% hyaluronic acid aqueous solution and 4ml massfraction be 5% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 2:40, under room temperature, lucifuge stirs 20min, forms first network hydrogel with UV-irradiation 40min;
(3) preparation of second network hydrogel
Preparation massfraction is the acrylamide solution 100mL of 10%, by light trigger, linking agent by being that 2:2:200 joins in acrylamide solution with the proportion of acylamide, under room temperature, lucifuge stirs 20min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel.
With the measuring method of embodiment 1, in embodiment 7, the compressive strength of the hyaluronic acid-gelatin/acrylamide double-network hydrogel of preparation is 234.65KPa.
embodiment 8the step of a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel preparation method and condition are as following:
(1) preparation of modified hyaluronic acid
A. taking quality is 1g(0.00125moL) hyaluronic acid, be mixed with the hyaluronic acid aqueous solution that massfraction is 1%, the pH to 4 of hyaluronic acid aqueous solution is regulated with 0.5moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, 0.0003moL1-(3-dimethylamino-propyl is added)-3-ethyl carbodiimide (EDC) and 0.0006moLN-N-Hydroxysuccinimide (NHS), stirred at ambient temperature 15min, then add 0.00125moL ethylcysteine hydrochloride and react 6 hours, obtain solution;
B. add 0.00125moL methacrylic anhydride in the solution obtained in step (a), regulate pH to 8.0 by the NaOH solution of 5moL/L, react 24 hours at 4 DEG C, dialyse 5 days, lyophilize obtains modified hyaluronic acid solid;
(2) preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 1%, get 10ml massfraction be 1% hyaluronic acid aqueous solution and 10mL massfraction be 2% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 1:40, under room temperature, lucifuge stirs 20min, forms first network hydrogel with UV-irradiation 20min;
(3) preparation of second network hydrogel
Preparation massfraction is the acrylamide solution 100mL of 5%, by light trigger, linking agent by being that 1:1:200 joins in acrylamide solution with the proportion of acylamide, under room temperature, lucifuge stirs 20min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel.
With the measuring method of embodiment 1, in embodiment 8, the compressive strength of the hyaluronic acid-gelatin/acrylamide double-network hydrogel of preparation is 63.73KPa.
Claims (5)
1. hyaluronic acid-gelatin/acrylamide double-network hydrogel, it is characterized in that, it is consisted of first network and second network IPN, described first network is the hydrogel that the hyaluronic acid of modification and gelatin are cross-linked to form by Michael reaction, and second network is the hydrogel that acrylamide chemically crosslinked is formed.
2.. a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel as claimed in claim 1, it is characterized in that, step and the condition of its preparation method are as follows:
(1) preparation of modified hyaluronic acid
A. the hyaluronic acid aqueous solution that massfraction is 1-4% is mixed with, pH to 4 ~ 6 of hyaluronic acid aqueous solution are regulated with hydrochloric acid, then EDC and N-hydroxy-succinamide is added, stirred at ambient temperature 15 ~ 25min, then add ethylcysteine hydrochloride reaction 4 ~ 8 hours, obtain solution; Ethylcysteine hydrochloride: N-hydroxy-succinamide: EDC: hyaluronic mol ratio is 1 ~ 2:0.5 ~ 1:0.25 ~ 1:1;
B. add methacrylic anhydride in solution step a obtained, regulate pH to 7.0 ~ 9.0 by NaOH solution, react 20 ~ 48 hours at 2 ~ 6 DEG C, dialyse 5 ~ 7 days, lyophilize, obtains modified hyaluronic acid solid; The hyaluronic mol ratio of described methacrylic anhydride and step a is 1 ~ 10:1;
(2) preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution, more admixed together with aqueous gelatin solution, light trigger, and under room temperature, lucifuge stirs 20 ~ 30min, with UV-irradiation 20 ~ 40min, forms first network hydrogel; Described light trigger is the one in 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone and α-ketoglutaric acid; The concentration of the modified hyaluronic acid aqueous solution is 1g ~ 4g/100mL; Gelatin concentration is 2g ~ 10g/100mL; The volume ratio of modified hyaluronic acid solution and gelatin solution is 4:1 ~ 16; Described light trigger consumption and the mass ratio of modified hyaluronic acid are 40:1 ~ 6;
(3) preparation of second network hydrogel
Preparation massfraction is the acrylamide solution of 5 ~ 20%, add light trigger and linking agent again, under room temperature, lucifuge stirs 20 ~ 30min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 24 ~ 48 hours, take out swelling after hydrogel, with UV-irradiation 20 ~ 40min, obtain target compound second network hydrogel; The same step of described light trigger (2), linking agent is N, N ' one or more in-methylene-bisacrylamide, ethylene glycol dimethacrylate and Diethylene Glycol methacrylic ester; Light trigger: linking agent: the proportion of acylamide is 1 ~ 6:1 ~ 4:200.
3. a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel as claimed in claim 2, it is characterized in that, step and the condition of its preparation method are as follows:
(1) preparation of modified hyaluronic acid
A. taking quality is 4g (0.005moL) hyaluronic acid, be mixed with the hyaluronic acid aqueous solution that massfraction is 4%, the pH to 6 of hyaluronic acid solution is regulated with 1moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, add the EDC (EDC) of 0.005moL and the N-hydroxy-succinamide (NHS) of 0.005moL, stirred at ambient temperature 25min, then the ethylcysteine hydrochloride adding 0.01moL reacts 8 hours, obtains solution;
B. add 0.05mol methacrylic anhydride in the solution obtained in step (a), regulate pH to 9.0 by the NaOH solution of 10moL/L, react 48 hours at 6 DEG C, dialyse 7 days, lyophilize obtains modified hyaluronic acid solid;
The preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 4%, get 10ml massfraction be 4% hyaluronic acid aqueous solution and 10mL massfraction be 10% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 6:40, under room temperature, lucifuge stirs 30min, forms first network hydrogel with UV-irradiation 40min;
The preparation of second network hydrogel
Preparation massfraction is the acrylamide solution 100mL of 20%, by light trigger, linking agent by being that 6:4:200 joins in acrylamide solution with the proportion of acylamide, under room temperature, lucifuge stirs 30min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel.
4. a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel as claimed in claim 2, it is characterized in that, step and the condition of its preparation method are as follows:
The preparation of modified hyaluronic acid
A. taking quality is 2g(0.0025moL) hyaluronic acid, be mixed with the hyaluronic acid aqueous solution that massfraction is 2%, the pH to 5.5 of hyaluronic acid aqueous solution is regulated with 1moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, 0.0025moL1-(3-dimethylamino-propyl is added)-3-ethyl carbodiimide (EDC) and 0.0025moLN-N-Hydroxysuccinimide (NHS), stirred at ambient temperature 20min, then add 0.005moL ethylcysteine hydrochloride and react 6 hours, obtain solution;
B. add 0.015moL methacrylic anhydride in the solution obtained in step (a), regulate pH to 8.0 by the NaOH solution of 10moL/L, react 24 hours at 4 DEG C, dialyse 7 days, lyophilize obtains modified hyaluronic acid solid;
The preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 2%, gets 10mL
Massfraction be 2% hyaluronic acid aqueous solution and 10mL massfraction be 5% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 2:40, under room temperature, lucifuge stirs 20min, forms first network hydrogel with UV-irradiation 40min;
The preparation of second network hydrogel
Preparation massfraction be 20% acrylamide solution 100mL, by light trigger, linking agent by with
The proportion of acylamide is that 2:2:200 joins in acrylamide solution, under room temperature, lucifuge stirs 20min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel.
5. a kind of hyaluronic acid-gelatin/acrylamide double-network hydrogel as claimed in claim 2, it is characterized in that, step and the condition of its preparation method are as follows:
The preparation of modified hyaluronic acid
A. taking quality is 2g(0.0025moL) hyaluronic acid, be mixed with the hyaluronic acid aqueous solution that massfraction is 2%, the pH to 5.5 of hyaluronic acid aqueous solution is regulated with 1moL/L hydrochloric acid soln, then in hyaluronic acid aqueous solution, 0.0025moL1-(3-dimethylamino-propyl is added)-3-ethyl carbodiimide (EDC) and 0.0025moLN-N-Hydroxysuccinimide (NHS), stirred at ambient temperature 20min, then add 0.005moL ethylcysteine hydrochloride and react 6 hours, obtain solution;
B. add 0.015moL methacrylic anhydride in the solution obtained in step (a), regulate pH to 8.0 by the NaOH solution of 10moL/L, react 24 hours at 4 DEG C, dialyse 7 days, lyophilize obtains modified hyaluronic acid solid;
The preparation of first network hydrogel
The modified hyaluronic acid obtained in step (1) is mixed with the aqueous solution that massfraction is 2%, get 16mL massfraction be 2% hyaluronic acid aqueous solution and 4ml massfraction be 5% aqueous gelatin solution mixing, and to add with the mass ratio of modified hyaluronic acid be the light trigger of 2:40, under room temperature, lucifuge stirs 20min, forms first network hydrogel with UV-irradiation 40min;
The preparation of second network hydrogel
Preparation massfraction is the acrylamide solution 100mL of 10%, by light trigger, linking agent by being that 2:2:200 joins in acrylamide solution with the proportion of acylamide, under room temperature, lucifuge stirs 20min, the first network hydrogel lucifuge obtained in step (2) to be immersed in this solution 48 hours, take out swelling after hydrogel, use UV-irradiation 40min, obtain target compound second network hydrogel.
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