CN111978568B - Preparation method of catechol modified chitosan-alginate double-network hydrogel - Google Patents
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Abstract
The invention discloses a preparation method of catechol modified chitosan-alginate double-network hydrogel, which comprises the following steps: (1) Reacting chitosan with a modifier to obtain a chitosan derivative, wherein the chitosan derivative is catechol grafted and modified chitosan; (2) Adding an oxidant into the chitosan derivative and the alginate, and carrying out oxidation crosslinking reaction to obtain catechol modified chitosan single-network hydrogel; (3) And adding a metal salt solution into the catechol modified chitosan single-network hydrogel to perform secondary crosslinking and curing, wherein metal cations in the metal salt solution are more than divalent, so as to prepare the catechol modified chitosan-alginate double-network gel. The double-network gel prepared by adopting the specific crosslinking sequence has good mechanical property and fatigue resistance.
Description
Technical Field
The invention relates to the field of high-molecular hydrogel, in particular to a preparation method of catechol modified chitosan-alginate double-network hydrogel.
Background
The hydrogel is a soft material which is rich in a large amount of water molecules and has a three-dimensional reticular cross-linked structure, and is widely applied to tissue engineering, regenerative medicine and drug delivery systems. The traditional hydrogel is generally composed of only one layer of covalent cross-linked network or physical cross-linked network, and the mechanical property of the traditional hydrogel is weaker and is far different from the strength of human tissues, so the application of the traditional hydrogel is greatly limited. The traditional chitosan single-network hydrogel has the defect of insufficient mechanical properties due to the single composition of a cross-linked network, and the application of the chitosan single-network hydrogel in tissue engineering is limited, so that the construction of the high-strength hydrogel is very important.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of catechol modified chitosan-alginate double-network hydrogel, and the catechol modified chitosan-alginate double-network hydrogel has excellent mechanical strength.
The technical scheme adopted by the invention is as follows:
the invention provides a preparation method of catechol modified chitosan-alginate double-network hydrogel, which comprises the following steps:
(1) Reacting chitosan with a modifier to obtain a chitosan derivative, wherein the chitosan derivative is catechol grafted and modified chitosan;
(2) Adding an oxidant into the chitosan derivative and the alginate, and performing oxidation crosslinking reaction to obtain catechol modified chitosan single-network hydrogel;
(3) And carrying out secondary crosslinking and curing on the catechol-modified chitosan single-network hydrogel and a metal salt solution, wherein metal cations in the metal salt solution are more than divalent, so as to prepare the catechol-modified chitosan-alginate double-network gel.
According to some embodiments of the present invention, the catechol-modified chitosan-alginate double-network hydrogel is prepared by using 3, 4-dihydroxybenzaldehyde as a modifying agent.
According to some embodiments of the preparation method of the catechol-modified chitosan-alginate double-network hydrogel, the step (1) is specifically as follows: dissolving chitosan in acetic acid solution, adding 3, 4-dihydroxy benzaldehyde for reaction, adding sodium cyanoborohydride for continuous reaction to obtain chitosan derivative, and adding cold ethanol for precipitation of the chitosan derivative.
Further according to some embodiments of the invention, the concentration of the acetic acid solution is 0.5% -5% w/v.
Further according to some embodiments of the invention, the 3, 4-dihydroxybenzaldehyde: the molar ratio of the sodium cyanoborohydride is 1: (1-10).
According to some embodiments of the present invention, in the preparation method of the catechol-modified chitosan-alginate double-network hydrogel, the chitosan in step (1): the molar ratio of the 3, 4-dihydroxy benzaldehyde is (0.5-5): (1-100).
According to some embodiments of the method for preparing the catechol-modified chitosan-alginate double-network hydrogel, the metal cations are calcium ions or aluminum ions.
According to the preparation method of the catechol-modified chitosan-alginate double-network hydrogel provided by the invention, the reaction temperature in the step (1) is 4-30 ℃, and the reaction time is 2-48 h.
According to some embodiments of the present invention, in the method for preparing the catechol-modified chitosan-alginate double-network hydrogel, the oxidizing agent is sodium periodate.
According to the preparation method of the catechol-modified chitosan-alginate double-network hydrogel provided by the invention, the alginate is sodium alginate, and the viscosity of the sodium alginate is 20-800mpa.s.
According to the preparation method of the catechol-modified chitosan-alginate double-network hydrogel provided by the invention, in the step (1), the viscosity of the chitosan is 100-500mpa.s.
According to some embodiments of the invention, in the step (2), the chitosan derivative and the alginate are respectively dissolved in an acetic acid solution or an aqueous solution, and after mixing, an oxidant is added to perform an oxidation crosslinking reaction to obtain the catechol-modified chitosan single-network hydrogel.
According to some embodiments of the invention, the concentration of the chitosan derivative in step (2) is 3% -10% w/v, the concentration of alginate is 0.5% -5% w/v.
According to some embodiments of the invention, the temperature of the oxidative crosslinking reaction in step (2) is 10 to 30 ℃ and the crosslinking time is 0.5 to 3 hours.
According to the preparation method of the catechol-modified chitosan-alginate double-network hydrogel provided by the embodiments of the invention, the concentration of the metal cations in the metal salt solution is 0.1-5 mol/L.
According to some embodiments of the invention, the metal cation is a calcium ion or an aluminum ion.
According to some embodiments of the invention, the pyrocatechol modified chitosan single-network hydrogel is soaked in the metal salt solution for secondary crosslinking and curing in the step (3), and the soaking time is preferably 2-500 min.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a preparation method of catechol modified chitosan-alginate double-network hydrogel, which has the following advantages:
(1) The used raw materials of chitosan and sodium alginate are natural polysaccharides which are widely existed in nature, and the raw materials have wide sources and low price, are beneficial to subsequent large-scale application and have certain economic and practical values. The chitosan skeleton has positive charge, the sodium alginate skeleton has negative charge, the chitosan skeleton and the sodium alginate skeleton have certain interaction, and the chitosan skeleton and the sodium alginate skeleton can well swell in water as natural polyelectrolyte materials, so that the full interweaving and the action of two crosslinked networks are facilitated, which is a necessary precondition for synthesizing the double-network hydrogel. The catechol group is the main undertaker of the adhesion function of mussel byssus, and the catechol group is modified on the chitosan skeleton, so that the prepared hydrogel has high mechanical strength, certain biological tissue adhesion capacity and wide application range.
(2) The double-network hydrogel synthesized at present has almost no fatigue resistance, and cannot completely recover by itself after one deformation, because the cross-linked network is composed of covalent bonds, and the bonds of the type cannot self-heal once being broken. According to the embodiment of the invention, according to a specific crosslinking sequence, the formed loose chitosan covalent crosslinking network is prepared firstly, so that the interpenetrating function of the physical crosslinking network of sodium alginate-cation is facilitated, and the natural high-strength double-network hydrogel is finally formed.
(3) The traditional chitosan single-network hydrogel or sodium alginate single-network hydrogel has weak mechanical property and is not suitable for being applied to tissue engineering independently, and the chitosan single-network hydrogel or the sodium alginate single-network hydrogel is organically combined to form the high-mechanical-strength double-network hydrogel with obviously improved mechanical property, so that the application range is expanded, and the chitosan single-network hydrogel or the sodium alginate single-network hydrogel has good application prospect in wound healing dressings, artificial skins and biological tissue substitute materials.
Drawings
FIG. 1 is a schematic diagram of the preparation process of catechol-grafted chitosan;
FIG. 2 is a schematic diagram of the preparation process of catechol-modified chitosan-alginate double-network gel;
FIG. 3 is a digital photograph of catechol-modified chitosan-alginate double-network gel prepared in example 1;
FIG. 4 is a graph showing the results of adhesion test of catechol-modified chitosan single-network hydrogel to pigskin in example 1;
FIG. 5 is a digital photograph of the catechol-modified chitosan-alginate double-network gel bearing the weight in example 1;
fig. 6 is a graph showing the comparison of the compression resistance and recovery performance of the catechol-modified chitosan single-network hydrogel, the sodium alginate single-network hydrogel, and the catechol-modified chitosan-alginate double-network gel in effect example 1;
FIG. 7 is a graph showing the comparison of the maximum breaking strengths of the catechol-modified chitosan single-network hydrogel, the sodium alginate single-network hydrogel, and the catechol-modified chitosan-alginate double-network gel in effect example 1;
FIG. 8 is a graph showing the comparison of mechanical properties of hydrogels prepared by different gel formation sequences in Effect example 2.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment provides a catechol-modified chitosan-alginate double-network hydrogel, which is prepared by the following steps:
(1) Referring to fig. 1, chitosan (CS) is used as a raw material, and is reacted with 3, 4-dihydroxybenzaldehyde to obtain catechol-grafted and modified chitosan (i.e., chitosan derivative Cat-CS).
The specific process comprises the following steps: and (3) fully dissolving 1g of Chitosan (CS) in 200mL of 1% acetic acid solution, and fully stirring until the chitosan is fully dissolved to obtain a colorless and clear chitosan solution. 50mL of a DMF solution containing 3g of 3, 4-dihydroxybenzaldehyde was added dropwise to the above chitosan solution, and the mixture was stirred at room temperature for 6 hours. Then 100mL of NaBH 3g dissolved 3 And dropwise adding CN aqueous solution into the solution, stirring at room temperature for 6h, after the reaction is finished, introducing the mixed solution into 2000mL of cold ethanol for precipitation to obtain a plurality of flocculent products, filtering and recovering, repeatedly washing a filter cake with water and ethanol for a plurality of times, and drying in vacuum at room temperature to obtain an off-white solid, namely the catechol-grafted modified chitosan (namely the chitosan derivative Cat-CS).
(2) Referring to FIG. 2, the obtained chitosan derivative (Cat-CS) and sodium Alginate (Alginate) were dissolved in acetic acid solution or aqueous solution, respectively, mixed well, and then sodium periodate (NaIO) was added 4 ) The compound is used as an oxidant to initiate the formation of catechol modified chitosan single-network hydrogel.
The specific process comprises the following steps: 100mg of Cat-CS was dissolved in 1mL of a 3% acetic acid solution, and the solution was sufficiently stirred until completely dissolved, and then 50mg of sodium alginate was added and sufficiently stirred until completely dissolved. Thereafter, 0.1mL of a 1% strength sodium periodate solution was added. Fully stirring at room temperature until the hydrogel is formed to form the catechol modified chitosan single-network hydrogel.
(3) And (3) soaking the crosslinked catechol-modified chitosan single-network hydrogel into an aluminum ion solution, and performing secondary crosslinking and curing to obtain the catechol-modified chitosan-alginate double-network gel with good mechanical strength.
The specific process comprises the following steps: and (3) soaking the catechol-modified chitosan single-network hydrogel into 0.5M aluminum ion solution for secondary crosslinking, and taking out after 10min to obtain the catechol-modified chitosan-alginate double-network gel, as shown in figure 3.
And (3) taking the catechol-modified chitosan single-network hydrogel prepared in the step (2), and measuring the adhesion force of the hydrogel to the pigskin, wherein the result is shown in figure 4, the catechol-modified chitosan single-network hydrogel prepared has a certain biomaterial adhesion capacity, and the adhesion force to the pigskin reaches 0.12MPa.
Referring to fig. 5, the catechol-modified chitosan-alginate double-network gel prepared in step (3) has good mechanical strength, and can support 4500g of heavy objects.
Effect example 1
Comparative example 1: adding 0.5M of aluminum ion solution into the sodium alginate solution, and crosslinking to form the sodium alginate single-network hydrogel.
The catechol-modified chitosan single-network hydrogel, the catechol-modified chitosan-alginate double-network gel in example 1 and the sodium alginate single-network hydrogel in comparative example 1 were subjected to pressure-resistant-recovery performance comparison, and the results are shown in fig. 6, and it can be seen from the figure that after being compressed under the same pressure, the catechol-modified chitosan single-network hydrogel and the sodium alginate single-network hydrogel could not recover to the original shapes when the external force is removed after being squeezed and deformed by the external force.
The maximum breaking strength of the catechol-modified chitosan single-network hydrogel, the catechol-modified chitosan-alginate double-network hydrogel in example 1 and the sodium alginate single-network hydrogel in comparative example 1 were tested, and the results are shown in fig. 7, and the mechanical strength of the three samples also proves that the mechanical properties of the double-network hydrogel are not only the simple superposition of the single-network hydrogels, the maximum breaking strength of the catechol-modified chitosan single-network hydrogel is about 0.1MPa, and the maximum breaking strength of the sodium alginate single-network hydrogel is about 0.4MPa, while the maximum breaking strength of the double-network hydrogel formed by the two samples in sequence in the embodiment of the present invention reaches 4MPa, and the overall mechanical strength is significantly improved.
Effect example 2
Comparative example 2: comparative example 2 provides a hydrogel prepared in the order of first cross-linking sodium alginate and then cross-linking chitosan, the specific preparation process being as follows:
(1) A catechol-graft-modified chitosan derivative (Cat-CS) was prepared in the manner of example 1;
(2) Dissolving 100mg of Cat-CS in 1mL of 3% acetic acid solution, fully stirring until the solution is completely dissolved, then adding 50mg of sodium alginate, fully stirring until the solution is completely dissolved, and adding 0.5M of aluminum ion solution for primary crosslinking;
(3) To the gel formed after the first crosslinking, 0.1mL of a 1% strength sodium periodate solution was added to perform the second crosslinking. And fully stirring at room temperature until the hydrogel is formed.
The mechanical properties of the hydrogels prepared in the two different gelling sequences were tested using the hydrogel of comparative example 2 (labeled as sodium alginate-chitosan sequence) and the catechol-modified chitosan-alginate double-network hydrogel of example 1 (labeled as chitosan-sodium alginate sequence), and the results are shown in fig. 8. The embodiment of the invention adopts the following reasons that the catechol-modified chitosan crosslinking system is formed firstly and then the sodium alginate metal ion crosslinking system is formed: the chitosan cross-linked network is generally relatively loose (30-60 microns), while the sodium alginate cross-linked network is very dense (5-10 microns). A loose crosslinked network facilitates the uniform formation of the next layer of crosslinked network, while a too dense crosslinked network severely limits the diffusion of the polymer or crosslinking agent within the system, making the crosslinking process slow or non-uniform. As shown in fig. 8, the stress-strain curves of the hydrogels prepared by two different crosslinking sequences can directly prove the importance of the gelling sequence, when a chitosan covalent crosslinking network is formed first and then a sodium alginate crosslinking network is formed, the system shows obvious mechanical properties of the double-network hydrogel, and the breaking strength reaches 4MPa; in contrast, in comparative example 2, when the sodium alginate crosslinked network is formed first and then the chitosan crosslinked network is formed, the mechanical strength of the system completely fails to reach the standard of the double-network hydrogel, because the dense crosslinked network of sodium alginate and metal ions can limit the diffusion of the crosslinking agent and the covalent crosslinking reaction caused by the contact of the crosslinking agent and catechol-modified chitosan, the mechanical properties cannot be effectively improved. Experimental results show that the crosslinking sequence adopted by the embodiment of the invention is the key for successfully preparing the high-strength catechol modified chitosan-alginate double-network hydrogel.
Example 2
The embodiment provides a catechol-modified chitosan-alginate double-network hydrogel, which is prepared by the following steps:
(1) 0.5g of Chitosan (CS) is fully dissolved in 100mL of 1% acetic acid solution, and fully stirred until the chitosan is fully dissolved, so that colorless and clear chitosan solution is obtained. 30mL of a DMF solution containing 2g of 3, 4-dihydroxybenzaldehyde was added dropwise to the above chitosan solution, and the mixture was stirred at room temperature for 3 hours. Then 50mL of NaBH dissolved with 3g 3 And dropwise adding CN aqueous solution into the solution, stirring at room temperature for 6h, after the reaction is finished, introducing the mixed solution into 1000mL of cold ethanol for precipitation to obtain a plurality of flocculent products, filtering and recovering, repeatedly washing a filter cake with water and ethanol for a plurality of times, and drying in vacuum at room temperature to obtain an off-white solid, namely the catechol-grafted modified chitosan (namely the chitosan derivative Cat-CS).
(2) 150mg of Cat-CS was dissolved in 1mL of a 3% acetic acid solution, and the solution was stirred well until it was completely dissolved, and then 20mg of sodium alginate was added and stirred well until it was completely dissolved. Thereafter, 0.1mL of a 1% strength sodium periodate solution was added. And fully stirring at room temperature until the hydrogel is formed.
(3) And (3) immersing the hydrogel into 1M calcium ion solution for secondary crosslinking, and taking out after 5min to obtain the catechol modified chitosan-alginate double-network hydrogel.
The double-network hydrogel prepared in the embodiment is tested, has good mechanical strength, and can support 4500g of weight.
Claims (9)
1. The preparation method of the catechol modified chitosan-alginate double-network hydrogel is characterized by comprising the following steps:
(1) Reacting chitosan with a modifier to obtain a chitosan derivative, wherein the chitosan derivative is catechol grafted and modified chitosan;
(2) Adding an oxidant into the chitosan derivative and the alginate, and carrying out oxidation crosslinking reaction to obtain catechol modified chitosan single-network hydrogel;
(3) Performing secondary crosslinking curing on the catechol-modified chitosan single-network hydrogel and a metal salt solution, wherein metal cations in the metal salt solution are more than divalent, so as to prepare catechol-modified chitosan-alginate double-network gel; respectively dissolving chitosan derivatives and alginate in an acetic acid solution or an aqueous solution, mixing, adding an oxidant, and carrying out oxidation crosslinking reaction to obtain catechol modified chitosan single-network hydrogel;
the metal cation is an aluminum ion.
2. The method for preparing the catechol-modified chitosan-alginate double-network hydrogel according to claim 1, wherein the modifier is 3, 4-dihydroxybenzaldehyde.
3. The preparation method of the catechol-modified chitosan-alginate double-network hydrogel according to claim 2, wherein the step (1) is specifically: dissolving chitosan in acetic acid solution, adding 3, 4-dihydroxy benzaldehyde for reaction, adding sodium cyanoborohydride for continuous reaction to obtain chitosan derivative, and adding cold ethanol for precipitation of the chitosan derivative.
4. The method for preparing catechol-modified chitosan-alginate double-network hydrogel according to claim 2, wherein the chitosan in step (1): the molar ratio of the 3, 4-dihydroxy benzaldehyde is (0.5-5): (1-100).
5. The method for preparing the catechol-modified chitosan-alginate double-network hydrogel according to any one of claims 1 to 4, wherein the reaction temperature in the step (1) is 4-30 ℃ and the reaction time is 2-48 h.
6. The method for preparing the catechol-modified chitosan-alginate double-network hydrogel according to any one of claims 1 to 4, wherein the oxidizing agent is sodium periodate.
7. The method for preparing the catechol-modified chitosan-alginate double-network hydrogel according to any one of claims 1 to 4, wherein the alginate is sodium alginate, and the viscosity of the sodium alginate is 20-800mpa.s.
8. The method for preparing catechol-modified chitosan-alginate double-network hydrogel according to any one of claims 1 to 4, wherein the viscosity of the chitosan in the step (1) is 100 to 500mpa.s.
9. The method for preparing the catechol-modified chitosan-alginate double-network hydrogel according to any one of claims 1 to 4, wherein the concentration of the metal cation in the metal salt solution is 0.1 to 5mol/L.
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