CN113292743A - Injectable high-pressure-resistant high-strength anti-freezing genipin crosslinked gelatin hydrogel and preparation method thereof - Google Patents
Injectable high-pressure-resistant high-strength anti-freezing genipin crosslinked gelatin hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of hydrogel material preparation, and particularly relates to a preparation method of injectable high-pressure-resistant high-strength anti-freezing genipin cross-linked gelatin hydrogel. Firstly, dissolving gelatin to obtain a gelatin water solution; dissolving genipin in ethanol, dropwise adding gelatin solution while stirring, mixing, standing to obtain genipin gelatin hydrogel, and soaking in glycerol solution to obtain glycerol-genipin gelatin hydrogel. The genipin cross-linked gelatin hydrogel prepared by the invention has high strength, frost resistance, long-term stability, and excellent anti-fatigue and pressure resistance. The hydrogel added with the glycerol can keep the original properties of the hydrogel after long-term storage, can keep high flexibility at low temperature, and has excellent freezing resistance and long-term stability. Meanwhile, the mechanical properties of the genipin gelatin hydrogel can be regulated according to different crosslinking degrees, and the prepared hydrogel has injectability and is expected to be widely applied to the fields of biomedical materials and the like.
Description
Technical Field
The invention belongs to the technical field of hydrogel material preparation, and particularly relates to a preparation method of injectable high-pressure-resistant high-strength anti-freezing genipin cross-linked gelatin hydrogel.
Background
The hydrogel is a three-dimensional polymer network material containing a large amount of water inside, is mainly applied to the fields of food, medicine, materials and the like, and has wide application prospects in the aspects of drug delivery, tissue engineering scaffolds, artificial articular cartilage, flexible devices and the like. Gelatin is a common hydrogel material, is a product obtained by hydrolyzing collagen through acid, alkali or enzyme, the raw material price is low, and the formed gelatin hydrogel has good biocompatibility, biodegradability and environmental friendliness.
At present, the preparation and performance research of high-strength hydrogel is still a hot spot. However, the hydrogel formed by pure gelatin only forms a three-dimensional network structure through physical interactions such as triple helix structures based on hydrogen bonds, hydrophobic interactions, microcrystalline domains and the like, so that the traditional gelatin hydrogel is weak in mechanical properties, is easy to permanently damage, is easily influenced by environments (such as pH, temperature and the like), and is difficult to realize application of multiple functions. The mechanical properties of gelatin-based hydrogel are improved to different degrees by improving the method, but the research on the natural macromolecular gelatin hydrogel with the strength of more than MPa is not enough, so that the method has a large research space. And most of the gelatin composite hydrogel is easy to break and poor in fatigue resistance under large compressive strain. By introducing a cross-linking agent (aldehydes such as glutaraldehyde are common cross-linking agents), chemical cross-linking is formed, cytotoxicity is caused, safety and potential risks exist, and the method is not suitable for the fields of biomedicine and the like.
To solve the above problems, genipin, a natural bio-cross-linking agent, is used in the hydrogel. It is a product of geniposide hydrolyzed by beta-glucosidase, and can be cross-linked with protein, collagen, gelatin, chitosan and the like to prepare a biological material. Genipin has low cytotoxicity, and also has medical values of anti-inflammation, antibiosis, gastritis treatment and the like. The genipin and the gelatin are combined to form the hydrogel, so that the mechanical property of the hydrogel can be greatly improved, and the safety is ensured. The multifunctional glue gel is used for exploring and developing multifunctional glue gels at present, and particularly, the properties of freezing resistance, long-term stability and the like are beneficial to exploring the application in the fields of food, biological medicine and the like, so that the multifunctional glue gel has a wide development prospect.
Based on the requirements, the invention provides an injectable high-pressure-resistant high-strength anti-freezing genipin crosslinked gelatin hydrogel and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a preparation method for preparing injectable high-pressure-resistant high-strength anti-freezing genipin crosslinked gelatin hydrogel. The genipin cross-linked gelatin hydrogel prepared by the invention has high strength, pressure resistance, fatigue resistance, frost resistance and long-term stability. Wherein the water content of 0.5GP25GEL is 73.5 percent, the crosslinking degree is 75.97 percent, the compressive fracture stress is 10.95MPa under the strain of 97 percent, and the fracture strength is high; 0.1GP25GEL and 0.1GP25GEL (1:2) can bear 3000 compression loading-unloading cycles under the compression strain of 85 percent, and have excellent anti-fatigue and pressure-resistant performances.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of injectable high-pressure-resistant high-strength antifreeze genipin cross-linked gelatin hydrogel specifically comprises the following steps:
(1) preparation of genipin solution: dissolving genipin in ethanol solution, and dissolving with oscillator to obtain genipin solution;
(2) preparing a gelatin solution: dissolving gelatin in deionized water, heating, stirring and dissolving to prepare a gelatin solution;
(3) sucking the genipin solution by a needle cylinder, dropwise adding the genipin solution into the gelatin solution (1 drop per second), heating and stirring the mixed solution for 5-20min, ultrasonically removing bubbles, and standing at room temperature for 24h to obtain genipin gelatin hydrogel;
(4) preparing a glycerol solution, and soaking the genipin gelatin hydrogel in the glycerol solution;
(5) and taking out the soaked hydrogel, and washing with deionized water to obtain the glycerol-genipin gelatin hydrogel.
Wherein the genipin solution in the step (1) has a mass fraction of 1wt% -10 wt%.
Wherein the mass fraction of the gelatin solution in the step (2) is 5-25 wt%.
Wherein, the heating temperature in the step (2) is 50 ℃.
Wherein, the heating temperature in the step (3) is 50 ℃.
Wherein, the mass ratio of water to glycerol in the glycerol solution in the step (4) is 1:1, 1:2 or 0: 1.
Preferably, the ratio of water: the mass ratio of the glycerol is 1: 2.
wherein the soaking time in the step (4) is 3 hours.
Wherein, the hydrogel comprises the following components: according to the mass fraction, 0.1-1wt% of genipin, 5-25wt% of gelatin and the balance of water, ethanol and glycerol.
Preferably, the content of genipin is 0.1wt% to 0.5 wt%.
The genipin gelatin organic hydrogel is named as xGPyGEL (a: b), wherein GP represents genipin, GEL represents gelatin, and x and y represent the mass percentages of the genipin and the gelatin in the hydrogel respectively. (a: b) represents water in the glycerol soak: mass ratio of glycerin.
The invention has the beneficial effects that: the method is simple and easy to operate, and the prepared genipin cross-linked gelatin hydrogel has high strength, pressure resistance, fatigue resistance, frost resistance and long-term stability. Wherein the water content of 0.1GP25GEL is 74.9 percent, the compressive stress is 9.83MPa under the strain of 99 percent, and the hydrogel is not cracked and has high elasticity; 0.5GP25GEL has a water content of 73.5 percent and a crosslinking degree of 75.97 percent, has a compressive fracture stress of 10.95MPa under 97 percent strain and has high fracture strength; 0.1GP25GEL and 0.1GP25GEL (1:2) can bear 3000 compression loading-unloading cycles under the compression strain of 85 percent, and have excellent anti-fatigue and pressure-resistant performances. The hydrogel added with the glycerol can keep the original properties of the hydrogel after long-term storage, can keep high flexibility at low temperature, and has excellent freezing resistance and long-term stability. Meanwhile, the mechanical properties of the genipin gelatin hydrogel can be regulated according to different crosslinking degrees, and the prepared hydrogel has injectability and is expected to be widely applied to the fields of biomedical materials and the like.
Drawings
FIG. 1 is a schematic diagram of genipin gelatin hydrogel and glycerol-genipin gelatin hydrogel preparation;
FIG. 2 shows the degree of crosslinking of genipin-crosslinked gelatin hydrogel at different mass ratios;
figure 3 compression performance of genipin gelatin hydrogel;
figure 4 different genipin cross-linked gelatin hydrogel compressive stress strain curves;
FIG. 5 is a graph of material properties of gum-based, soy protein-based, whey protein-based hydrogels;
FIGS. 60.1 GP25GEL (A) and 0.1GP25GEL (1:2) (B) 3000 compression cycle load-unload curves at 85% strain; stress retention and plastic deformation rates at different cycle times for 0.1GP25GEL (C) and 0.1GP25GEL (1:2) (D);
FIG. 7 is a schematic drawing showing (A)0.1GP25GEL (1:2) being stored at-20 ℃ for 72 h stretching and twisting; (B) the hydrogel is stored for 72 h at the temperature of-20 ℃ and a tensile stress-strain curve is obtained;
FIG. 8 is a digital image of hydrogel in its initial state after being stored at 20 ℃ and 50% humidity for 2 weeks; (B) weight change of the gel during storage at 20 ℃ and 50% humidity for 14 days;
figure 9 example genipin gelatin hydrogel injectable in water (a) and on glass plate (B).
Detailed Description
Example 1:
a preparation method of injectable genipin cross-linked gelatin hydrogel with high pressure resistance and high strength and fatigue resistance comprises the following steps:
(1) dissolving 0.01g of genipin in an ethanol solution, and oscillating and dissolving the genipin in an oscillator to prepare a 1wt% genipin solution;
(2) dissolving 2.5g of gelatin in 9ml of deionized water, heating and stirring at 50 ℃, and dissolving to prepare a gelatin solution;
(3) sucking 1wt% genipin solution with 1ml syringe, adding dropwise (1 drop per second) into gelatin solution, heating and stirring at 50 deg.C for 14min, removing bubbles by ultrasonic wave, and standing at room temperature for 24 hr to obtain 0.1GP25GEL (genipin mass fraction of 0.1wt%, gelatin mass fraction of 25 wt%).
(4) Preparing the components according to the mass ratio (water: glycerol) of 1:2 in glycerol. 0.1GP25GEL was soaked in different glycerol solutions for 3 h.
(5) The soaked hydrogel was removed and rinsed 3 times with deionized water to give 0.1GP25GEL (1: 2).
As shown in fig. 2 and 4, the 0.1GP25GEL water content was 73.9% and the degree of crosslinking was 45.33%; under 99% strain, the compressive stress is 9.83MPa, and the hydrogel is not cracked; as shown in fig. 8, the hydrogel was injected from the syringe immediately after gelation of 0.1GP25GEL for 30 minutes, and when injected in water, no sign of diffusion was found in the water, maintaining the intact GEL state. When the hydrogel is injected into the surface of dry glass, any character and symbol can be smoothly written, and the hydrogel also shows good gel forming property.
As shown in FIG. 7, after 0.1GP25GEL (1:2) soaking in glycerol, the hydrogel is not easy to freeze, still remains transparent and has high flexibility at-20 ℃, and can be bent and stretched. The tensile strain at break of 0.1GP25GEL (1:2) is 133.11%, the tensile stress at break is 1.31MPa, and the hydrogel soaked in glycerol can still keep high tensile property at the temperature of minus 20 ℃.
As shown in FIG. 9, after 0.1GP25GEL (1:2) soaking in glycerol, the product retains its original shape and long-term stability after being stored at 20 ℃ and 50% humidity for 14 days. The weight of the hydrogel can reach more than 90 percent of retention rate, and the hydrogel added with the glycerol can keep the original properties after long-term storage.
As in FIG. 6, 0.1GP25GEL and 0.1GP25GEL (1:2) can withstand 3000 compression load-unload cycles with 85% compressive strain: after 100 compression cycles of 0.1GP25GEL, the hydrogel still shows good cyclic compression performance, and is kept at about 90% of the maximum stress, and the plastic deformation rate is kept at 20.52%. After 500 cycles, the stress can still be maintained at 74% of the original stress, and the plastic deformation rate is not obviously increased. After 1000 cycles, the stress remained around 70% of the maximum stress and stabilized around this value within 1000-2000 cycles. After 3000 cycles, the maximum stress at 85% strain drops to about 58% of the initial compressive maximum stress. We found that the stress gradually decreased over the first 500 cycles and then gradually stabilized over the following 1500 cycles, indicating that the hydrogel could withstand a large number of cycles without further fatigue damage. The hydrogel compressive strength gradually decreased with increasing number of compression cycles. This is because the gelatin molecular chains are not pressed and deformed to recover in time under a plurality of pressure cycles, and are plastically deformed, thereby exhibiting low compressive strength. But the gel still has better energy dissipation capability after multi-cycle compression. In addition to the physical interactions provided by groups such as hydrogen bonding of the gelatin chains themselves, it is possible that during long-range crosslinking, genipin multimers produce hydrophobic, electrostatic interactions between hydrogen bonding and gelatin, thereby providing more non-covalent interactions. Therefore, different crosslinking chemical crosslinking structures in the genipin gelatin hydrogel can provide high-energy chemical bonds to maintain the integral network structure of the gel in the cyclic compression process, and meanwhile, the physical interaction in the hydrogel network is dynamic and reversible and can be formed again after being dissociated, so that the genipin gelatin hydrogel can show high-efficiency and stable energy dissipation level and high fatigue resistance in multiple loading-unloading processes. 0.1GP25GEL (1:2) retains better energy dissipation capability than 0.1GP25GEL, is more able to withstand a larger number of cycles without further fatigue damage and therefore has a lower plastic deformation rate. Strong hydrogen bonding clusters are used for energy dissipation, and the broken physical interaction can be rapidly reconstructed in unloading to protect the integrity of the internal network structure of the gel. The 0.1GP25GEL (1:2) hydrogel exhibits better energy dissipation and fatigue resistance than the 0.1GP25 GEL.
Example 2:
a preparation method of genipin cross-linked gelatin hydrogel with high pressure resistance and high strength comprises the following steps: :
(1) dissolving 0.05g of genipin in an ethanol solution, and oscillating and dissolving the genipin in an oscillator to prepare a 5wt% genipin solution;
(2) dissolving 2.5g of gelatin in 9ml of deionized water, heating and stirring at 50 ℃, and dissolving to prepare a gelatin solution;
(3) sucking 5wt% genipin solution with 1ml syringe, adding dropwise (1 drop per second) into gelatin solution, heating and stirring at 50 deg.C for 11min, removing bubbles by ultrasonic wave, and standing at room temperature for 24 hr to obtain 0.5GP25GEL (genipin mass fraction of 0.5wt% and gelatin mass fraction of 25 wt%).
As shown in fig. 2 and 4, the 0.5GP25GEL water content was 73.5% and the degree of crosslinking was 75.97%; the compressive breaking stress is 10.95MPa at 97% strain, and the breaking strength is high. As shown in fig. 5, the compressibility of genipin gelatin hydrogel was generally better than most protein-based hydrogels, including gelatin-based hydrogel, soy protein-based hydrogel, whey protein-based hydrogel, and exhibited high strength. Compared with other high-strength gelatin hydrogels in the prior art, the method used in the application is simple, the water content (> 75%) of the prepared gelatin is higher than that of most documents, and special conditions such as high-concentration salt ions and the like are not required to be introduced, so that the method has great advantages.
Example 3:
a preparation method of low-strength genipin cross-linked gelatin hydrogel comprises the following steps:
(1) dissolving 0.005g of genipin in an ethanol solution, and oscillating and dissolving the genipin in an oscillator to prepare a 0.5wt% genipin solution;
(2) dissolving 0.5g of gelatin in 9ml of deionized water, heating and stirring at 50 ℃, and dissolving to prepare a gelatin solution;
(3) 0.5wt% genipin solution was sucked up with a 1ml syringe, added dropwise (1 drop per second) to the gelatin solution, and the mixed solution was heated and stirred at 50 ℃ for 40 min, defoamed by ultrasound, and allowed to stand at room temperature for 24h to give 0.05GP5GEL (genipin mass fraction 0.05wt%, gelatin mass fraction 5 wt%).
As shown in FIG. 4, 0.05GP5GEL has a compressive breaking stress of 0.21MPa under 75% strain, and both the breaking compressive stress and the strain are weak and are lower than those of the gelatin hydrogel in the most suitable genipin concentration range (in the hydrogel, the genipin solution accounts for 0.1-1wt% and the gelatin solution accounts for 5-25 wt%).
Example 4:
a preparation method of low-strength genipin cross-linked gelatin hydrogel comprises the following steps: :
(1) dissolving 0.2g of genipin in an ethanol solution, and oscillating and dissolving the genipin in an oscillator to prepare a genipin solution with the concentration of 20 wt%;
(2) dissolving 0.5g of gelatin in 9ml of deionized water, heating and stirring at 50 ℃, and dissolving to prepare a gelatin solution;
(3) sucking 20wt% genipin solution with 1ml syringe, adding dropwise (1 drop per second) into gelatin solution, heating and stirring the mixed solution at 50 deg.C for 10 min, removing bubbles by ultrasonic wave, and standing at room temperature for 24h to obtain 2GP5GEL (genipin mass fraction of 2wt% and gelatin mass fraction of 5 wt%).
As shown in fig. 4, 2GP5GEL has a compressive stress at break of 0.33MPa at 67% strain, and both the compressive stress at break and the strain are weak and lower than those of gelatin hydrogel in the most suitable genipin concentration range (in terms of mass fraction, genipin solution is in the range of 0.1-1wt%, and gelatin solution is in the range of 5-25 wt%).
Claims (10)
1. A method for preparing injectable high-pressure-resistant high-strength antifreeze genipin cross-linked gelatin hydrogel is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) preparation of genipin solution: dissolving genipin in ethanol solution, and dissolving with oscillator to obtain genipin solution;
(2) preparing a gelatin solution: dissolving gelatin in deionized water, heating, stirring and dissolving to prepare a gelatin solution;
(3) sucking the genipin solution by using a needle cylinder, dropwise adding the genipin solution into the gelatin solution while heating and stirring the mixed solution, ultrasonically removing bubbles, and standing at room temperature for 24 hours to obtain genipin gelatin hydrogel;
(4) preparing a glycerol solution, and soaking the genipin gelatin hydrogel in the glycerol solution;
(5) and taking out the soaked hydrogel, and washing with deionized water to obtain the glycerol-genipin gelatin hydrogel.
2. The method of claim 1, wherein the injectable high pressure resistant high strength antifreeze genipin crosslinked gelatin hydrogel comprises: the genipin solution in the step (1) has a mass fraction of 1wt% -10 wt%.
3. The method of claim 1, wherein the injectable high pressure resistant high strength antifreeze genipin crosslinked gelatin hydrogel comprises: the mass fraction of the gelatin solution in the step (2) is 5-25 wt%.
4. The method of claim 1, wherein the injectable high pressure resistant high strength antifreeze genipin crosslinked gelatin hydrogel comprises: the heating temperature in the step (2) is 50 ℃.
5. The method of claim 1, wherein the injectable high pressure resistant high strength antifreeze genipin crosslinked gelatin hydrogel comprises: in the step (3), the dropping speed is one drop per second, the heating temperature is 50 ℃, and the time is 5-20 min.
6. The method of claim 1, wherein the injectable high pressure resistant high strength antifreeze genipin crosslinked gelatin hydrogel comprises: and (4) the mass ratio of water to glycerol in the glycerol solution is 1:1, 1:2 or 0: 1.
7. The method of claim 6, wherein the injectable high pressure resistant high strength antifreeze genipin crosslinked gelatin hydrogel comprises: water: the mass ratio of the glycerol is 1: 2.
8. the method of claim 1, wherein the injectable high pressure resistant high strength antifreeze genipin crosslinked gelatin hydrogel comprises: and (4) soaking for 3 hours.
9. The method of claim 1, wherein the injectable high pressure resistant high strength antifreeze genipin crosslinked gelatin hydrogel comprises: the hydrogel composition comprises: according to the mass fraction, 0.1-1wt% of genipin, 5-25wt% of gelatin and the balance of water, ethanol and glycerol.
10. The method of claim 9, wherein the injectable high pressure resistant, high strength antifreeze genipin-crosslinked gelatin hydrogel comprises: the content of genipin is 0.1-0.5 wt%.
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