CN110982092A - Method for temporarily repairing high molecular material based on kinetic stability of enzymatic reaction regulation and control - Google Patents
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Abstract
The invention relates to a method for temporarily repairing a high molecular material based on the regulation and control of dynamics stability of enzymatic reaction. The temporary repairing method of the invention is that biological enzyme and reversible covalent bond or supermolecule interaction are simultaneously introduced into the high molecular material, when the high molecular material is fractured by external force, the fracture surface of the high molecular material is coated with repairing liquid, and the components in the repairing liquid realize the repairing of the high molecular material in the aspects of structure and performance by triggering biochemical reaction in the high molecular material or changing the physical and chemical environment of the high molecular material. The method for temporarily repairing the high molecular material based on the regulation and control of the kinetics of the enzymatic reaction can repair the high molecular material as required, the dynamic stability of the high molecular material can be ensured before the repair, the repair is carried out after the high molecular material is broken, and the temporary repair of the high molecular material is enough to repair the defects of the material and recover the performance of the material.
Description
Technical Field
The invention relates to a method for temporarily repairing a high polymer material based on the regulation and control of dynamics stability of enzymatic reaction, belonging to the technical field of high polymer materials.
Background
Since the first discovery of the regeneration phenomenon of the deformed polymer by R.P.Wool, research and development of self-repairing materials have been in history for more than 40 years. Various reversible covalent bonds and supramolecular interactions are used to build intrinsic self-healing materials to extend lifetime and improve reliability. Spontaneous intrinsic self-healing occurs in kinetically unstable systems and is widely accepted due to the simple and efficient healing process. It is not an ignorable fact that such instability may lead to undesired merging of materials, which adversely affects the dynamic stability of the material. How to balance the dynamic stability and intrinsic self-repairing ability of the material is a key problem. Scientists have solved this problem in films/coatings by temporarily activating the chemical stability and/or physical flowability of materials at micron-scale thicknesses by external intervention such as heat and light. However, this intervention is less efficient for the internal efficiency of the prosthesis phase material due to the energy attenuation of the light propagation and heat conduction in the material.
Self-repair processes exist in life from molecular level (such as DNA repair) to macroscopic level (such as healing of small skin wounds), and enzymes play an extremely important role in repairing damaged life. Inspired by nature, many systems for promoting self-repair of high molecular materials by utilizing enzymatic reactions have been designed. In 2014, a repairable hydrogel containing bovine serum albumin, glutaraldehyde, glucose oxidase and catalase is prepared by a professor of Liujunqiu, and the damaged hydrogel can accelerate the repair of mechanical properties under the stimulation of glucose. The enzymatic reaction is utilized to promote the repair of the material, the service life of the material can be effectively prolonged, the safety of the material is improved, the waste is reduced, and the method has important scientific significance and practical value. However, a method for endowing a dynamically stable polymer material with intrinsic self-repairing capability is still lacking so far, which severely restricts the practical application of the self-repairing material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for temporarily repairing a high polymer material with stable regulation and control dynamics based on an enzymatic reaction.
Description of terms:
4A-PEG-His: histidine-modified 4-arm polyethylene glycol;
PAM-co-PDAAM: copolymers of Acrylamide (AM) and diacetone acrylamide (DAAM);
ADH: adipic acid dihydrazide;
PAA: polyacrylic acid;
PEO: polyethylene oxide;
room temperature: having a meaning well known in the art, typically 25. + -. 2 ℃.
The technical scheme of the invention is as follows:
a method for regulating and controlling the temporary repair of a kinetically stable high molecular material based on an enzymatic reaction comprises the following steps:
biological enzyme and reversible covalent bond or supermolecule interaction are simultaneously introduced into the high polymer material, when the high polymer material is fractured due to external force, a repairing liquid is coated on the fractured surface of the high polymer material, and the components in the repairing liquid realize the repairing of the high polymer material in the aspects of structure and performance by triggering biochemical reaction in the high polymer material or changing the physical and chemical environment of the high polymer material.
Preferably according to the invention, the biological enzyme is glucose oxidase, urease, esterase, catalase, glutathione reductase, or amylase.
According to the invention, the high molecular materials have high dynamic stability and reversible covalent bond or supermolecular interaction force; more preferably, the polymer material is Co3+-4A-PEG-His、PAM-co-PDAAMAnd ADH, or polyethylene oxide-polyacrylic acid-calcium carbonate (PEO-PAA-CaCO)3)。
According to the invention, the repair liquid preferably contains a reaction substrate corresponding to the biological enzyme; further preferably, the repair liquid contains glucose, urea, ethyl acetate, hydrogen peroxide, glutathione, or cyclodextrin.
The invention proposes that reversible covalent bonds or supermolecule interaction exists in the high polymer material, for example, the high polymer material containing a plurality of functional groups and metal ions form a complex with redox response, the high polymer material is coordinated with low-valence metal ions to form hydrogel with self-repairing capability, and the hydrogel formed after the low-valence metal ions are oxidized into high-valence metal ions has high mechanical strength but does not have self-repairing capability; for example, PAM-co-PDAAM and adipic acid dihydrazide form a hydrazone bond, the hydrazone bond has reversibility at pH 3-5, and is kinetically stable above pH 7; for example, polyethylene oxide and polyacrylamide can form a coating material with pH response through hydrogen bond interaction, hydrogen bonds are weakened at high pH, and hydrogen bonds are reformed at low pH.
According to the invention, the high polymer material is preferably glucose oxidase and Co3+4A-PEG-His, and the repair liquid is ascorbic acid solution containing glucose. When the hydrogel breaks due to external force, ascorbic acid solution containing glucose is coated on the broken surface, and the ascorbic acid can remove Co in the hydrogel3+Rapidly reduced to Co2+The fracture surface becomes sol with fluidity and self-repairability; at the same time, H produced by glucose oxidase slowly decomposing glucose2O2Mixing Co2+Oxidation to Co3+And the time difference between the chemical reaction and the enzymatic reaction is utilized to finish the repair of the hydrogel.
Further preferably, the concentration of the glucose oxidase in the hydrogel is 0.1-0.5 mg/mL, and the concentration of Co in the hydrogel is 0.1-0.5 mg/mL3+The concentration of (A) is 6.7 to 20mM, and the concentration of 4A-PEG-His is 5 to 15 mM.
More preferably, the concentration of the ascorbic acid in the repair liquid is 1-15 mM, and the concentration of the glucose is 25-70 mM.
According to the invention, the high polymer material is hydrogel composed of urease, PAM-co-PDAAM and ADH, and the repair liquid is an acidic buffer solution containing urea. When the hydrogel is fractured due to external force, an acidic buffer solution containing urea is smeared on the fractured surface, the pH of the fractured surface is rapidly reduced by the acidic buffer solution to activate hydrazone bonds, the fracture and re-bonding process of the hydrazone bonds after the hydrazone bonds are activated can guide the repair of the material, and then ammonia generated by the urea is slowly decomposed by urease to raise the pH value and lock the formed hydrazone bonds, so that the repair of the structure and performance of the material is completed.
Further preferably, the concentration of urease in the hydrogel is 2-5 mg/mL, the concentration of PAM-co-PDAAM is 100-300 mg/mL, and the concentration of ADH is 10-40 mg/mL.
Preferably, the pH value of the repair liquid is 3-5, the concentration of urea is 20-150 mg/mL, and the acidic buffer solution is 1M citric acid/sodium citrate buffer solution.
According to the invention, the high polymer material is preferably prepared from glucose oxidase, PEO-PAA-CaCO3The repair liquid is neutral buffer liquid containing glucose. When the coating material is damaged, coating neutral buffer solution containing glucose on the damaged part, wherein the neutral buffer solution can weaken the hydrogen bond acting force between PEO and PAA, so that the fluidity of the polymer is improved, and the contact with the damaged part of the coating material is promoted; then, the glucose acid generated by glucose oxidase decomposing glucose reduces the pH of the system, so that hydrogen bonds on the contacted damaged part are formed again, and the structure and the performance of the material are recovered.
Preferably, the concentration of the glucose oxidase in the coating material is 0.1-0.5 mg/mL, the concentration of PEO is 1-10 mg/mL, the concentration of PAA is 1-10 mg/mL, CaCO3The concentration of (B) is 0.001 to 0.01 mM.
Preferably, the concentration of glucose in the repair liquid is 1-50 mg/mL, and the neutral buffer solution is 0.1M phosphate buffer solution.
The invention has the technical characteristics that:
in the invention, the temporary repair refers to repair of a high polymer material by smearing a repair liquid when the high polymer material is broken or damaged, the high polymer material in the invention has high dynamic stability and no spontaneous combination capability, and compared with a spontaneous intrinsic self-repairing high polymer material, the stability and reliability of the high polymer material in the using process can be ensured, but the high polymer material in the invention has no self-repairing capability, and after the broken or damaged high polymer material is subjected to temporary repair by adopting the method in the invention, the dynamic stability of the broken or damaged high polymer material can be recovered while the structure of the broken or damaged high polymer material is repaired.
Has the advantages that:
1. the high molecular material related in the invention has high dynamic stability, the stability is preferably considered in the design of the material, but the repairability is not, the high molecular material with high dynamic stability has no spontaneous combination and self-repairability, the temporary high molecular material repairing method based on the regulation and control of the dynamic stability of the enzymatic reaction can repair as required, the dynamic stability of the high molecular material can be ensured before the repair, and the repair is carried out after the high molecular material is broken.
2. For the temporary repair of the high polymer material, the defect of the high polymer material can be repaired and the performance of the high polymer material can be recovered, and in contrast, the dynamic stability of the material can be reduced by the self-repair based on the dynamic chemical bond.
3. The temporary repair method for the high polymer material is based on the principle of enzymatic reaction, the enzymatic reaction is a simple, efficient and low-energy-consumption strategy, and the preparation and temporary repair performance of the high polymer material can be adjusted.
Drawings
FIG. 1 shows the results of the stretching treatment of the hydrogel in comparative example 1 after being repaired with different repair liquids; in the figure, the repairing solution of the hydrogel in the group A is an ascorbic acid solution containing glucose, the repairing solution of the hydrogel in the group B is an ascorbic acid solution, the repairing solution of the hydrogel in the group C is an aqueous solution containing ascorbic acid and hydrogen peroxide, and the repairing solution of the hydrogel in the group D is a glucose solution;
FIG. 2 shows the results of the superimposed contact and separation treatments of the hydrogels of comparative example 2 after being repaired with different repair solutions; in the figure, the repair solution for the hydrogel in group a is an acidic buffer solution containing urea, and the repair solution for the hydrogel in group B is an acidic buffer solution containing no urea.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
The materials mentioned in the examples are, unless otherwise specified, all common commercial products.
In the examples, the preparation of PAM-co-PDAAM: 4g of Acrylamide (AM), 1.06g of diacetone acrylamide (DAAM), and 25mL of dimethyl sulfoxide were put into a three-necked flask, stirred, and N was introduced thereinto2And (3) 30 min. In N2With the protection of (3), Azobisisobutyronitrile (AIBN) was added in an amount of 5.1mg, followed by reaction at 70 ℃ for 24 hours. After the reaction is finished, the reactant is dropwise added into a large amount of acetone which is continuously stirred, the precipitate is filtered, the ether is used for washing for a plurality of times, and the copolymer PAM-co-PDAAM is obtained after vacuum drying for 24 hours at room temperature.
The preparation method of the 4A-PEG-His comprises the following steps: in a three-necked flask, 5g of a four-armed polyethylene glycol amino group (4arm-PEG-amine), 2.0g of 2.0g N-Boc-N '-trityl-L-histidine, 0.54g of 1-hydroxybenzotriazole and 15mL of N, N-dimethylformamide were added and dissolved with stirring, and then 0.62mL of LN, N' -diisopropylcarbodiimide and 1.07mL of N, N-diisopropylethylamine were added to conduct a reaction at room temperature for 24 hours. After the reaction, the reaction mass was added to a large amount of ether, the precipitate was filtered 3 times and dried under vacuum at room temperature for 24 h. Adding the obtained product into a mixture of 95mL of trifluoroacetic acid, 2.5mL of triisopropylsilane and 2.5mL of water, stirring at room temperature for reaction for 3h, removing the trifluoroacetic acid by rotary evaporation after the reaction is finished, adding the reactant into a large amount of diethyl ether, precipitating and filtering for 3 times, and performing vacuum drying at room temperature for 24h to obtain the 4A-PEG-His.
Example 1
From Co3+4A-PEG-His and glucose oxidase to form hydrogel, wherein Co in the hydrogel3+The concentration of (A) is 13.3mM, the concentration of 4A-PEG-His is 10mM, and the concentration of glucose oxidase is 0.4 mg/mL; using ascorbic acid solution containing glucose as repairing solution, wherein the ascorbic acid in the repairing solutionThe concentration of ascorbic acid was 4mM and the concentration of glucose was 53.2 mM.
Co in the above hydrogel3+Forming a redox-responsive complex with 4A-PEG-His, 4A-PEG-His and Co3+After coordination, hydrogel with high mechanical strength can be formed, the hydrogel has high kinetic stability but does not have self-repairing capability, and 4A-PEG-His and Co2+When coordinated, hydrogel with self-repairing capability can be formed. When the hydrogel is fractured by external force, the repairing liquid is coated on the fracture surface, and the ascorbic acid is used for dissolving Co in the hydrogel3+Rapidly reduced to Co2+The fracture surface becomes sol with fluidity and self-repairability; at the same time, H produced by glucose oxidase slowly decomposing glucose2O2Mixing Co2+Oxidation to Co3+The time difference between chemical reaction and enzymatic reaction is utilized to complete the repair of the hydrogel, and the repair rate of the hydrogel is more than 90 percent.
Comparative example 1
After the hydrogel in example 1 is cut and fractured, a repair solution is coated on the fractured surface, and then the hydrogel is repaired by the repair solution, and then the repairing solution is stretched, wherein the repair solution used in example 1 is ascorbic acid solution containing glucose, ascorbic acid solution (reducing agent), aqueous solution containing ascorbic acid and hydrogen peroxide (reducing agent and oxidizing agent), and glucose solution (generating oxidizing agent hydrogen peroxide after enzymolysis), the processing process and the processing result are shown in fig. 1, after the stretching treatment, the tensile fracture position of the ascorbic acid solution repair group containing glucose is different from the cutting fracture position, and the tensile fracture positions of other three groups are the same, which indicates that the structure and mechanical properties of the hydrogel can not be completely repaired by only adding ascorbic acid, simultaneously adding ascorbic acid and hydrogen peroxide, or only adding glucose on the fractured surface of the hydrogel, the structure and mechanical properties of the hydrogel can be completely restored only by simultaneously adding ascorbic acid and glucose.
Example 2
The hydrogel consists of urease, PAM-co-PDAAM and ADH, wherein the concentration of the urease in the hydrogel is 3mg/mL, the concentration of the PAM-co-PDAAM is 270mg/mL, and the concentration of the ADH is 28 mg/mL; and taking an acidic buffer solution containing urea as a repair solution, wherein the pH of the repair solution is 4, the concentration of the urea in the repair solution is 80mg/mL, and the acidic buffer solution is a 1M citric acid/sodium citrate buffer solution.
In the hydrogel, PAM-co-PDAAM and adipic Acid Dihydrazide (ADH) form a hydrazone bond, the hydrazone bond has stable kinetics at a pH value of 7 or more, and has reversibility at a pH value of 3-5. When the hydrogel is fractured due to external force, the repairing liquid is smeared on the fractured surface, the pH of the fractured surface is rapidly reduced by the acidic buffer solution to activate hydrazone bonds, the material repairing can be guided by the processes of fracturing and re-bonding of the hydrazone bonds after the hydrazone bonds are activated, then the ammonia generated by the urea is slowly decomposed by the urease to raise the pH value and lock the formed hydrazone bonds, so that the repairing of the material structure and performance is completed, and the repairing rate of the hydrogel is more than 90%.
Comparative example 2
After the hydrogel in example 2 is cut and fractured, repair liquid is coated on the fractured surface, after the repair is finished, two pieces of repaired hydrogel are overlapped and contacted for 3 hours, then the two pieces of hydrogel are separated by tweezers, wherein the used repairing solutions are the acidic buffer solution containing urea and the acidic buffer solution (pH 4) without urea in example 2, the treatment process and the treatment result are shown in FIG. 2, the two hydrogels can be completely separated by the acidic buffer solution treatment group containing urea, and the two hydrogels of the acidic buffer solution treatment group without urea are both fractured, which indicates that the hydrogel repaired by only adding the acidic buffer solution can not restore the dynamic stability of the hydrogel, and the addition of the acidic buffer solution containing urea not only can repair the structure of the hydrogel, but also can restore the dynamic stability of the hydrogel to the initial state.
Example 3
Composed of glucose oxidase, PEO-PAA-CaCO3Forming a coating material, wherein the concentration of glucose oxidase in the coating material is 0.4mg/mL, the concentration of PEO is 4mg/mL, the concentration of PAA is 4mg/mL, CaCO3Is 0.005 mM; using neutral buffer solution containing glucose as repairing solution, wherein the concentration of glucose in the repairing solution is 35mM, and the neutral buffer solution is 0.1M phosphate bufferAnd (4) liquid.
In the coating material, polyethylene oxide and polyacrylamide can form the coating material with pH response through hydrogen bond interaction, hydrogen bonds are weakened at high pH, and hydrogen bonds are reformed at low pH. When the coating material is damaged, the repair liquid is dripped into the damaged part, firstly, the neutral buffer solution can weaken the hydrogen bond acting force between PEO and PAA, and further the fluidity of the polymer is improved and the contact with the damaged part of the coating material is promoted; then, the glucose acid generated by glucose oxidase decomposing glucose reduces the pH of the system, so that the hydrogen bond on the contacted damaged part is formed again, and the structure and the performance of the material are recovered.
Claims (10)
1. A method for temporarily repairing a high molecular material with stable regulation and control dynamics based on an enzymatic reaction is characterized by comprising the following steps:
biological enzyme and reversible covalent bond or supermolecule interaction are simultaneously introduced into the high polymer material, when the high polymer material is fractured due to external force, a repairing liquid is coated on the fractured surface of the high polymer material, and the components in the repairing liquid realize the repairing of the high polymer material in the aspects of structure and performance by triggering biochemical reaction in the high polymer material or changing the physical and chemical environment of the high polymer material.
2. The method of claim 1, wherein the biological enzyme is glucose oxidase, urease, esterase, catalase, glutathione reductase, or amylase.
3. The method of claim 1, wherein the polymer material is Co3+-4A-PEG-His, PAM-co-PDAAM and ADH, or polyethylene oxide-polyacrylic acid-calcium carbonate.
4. The method of claim 1, wherein the repair fluid comprises glucose, urea, ethyl acetate, hydrogen peroxide, glutathione, or cyclodextrin.
5. A method for temporarily repairing a high molecular material based on the regulation and control of kinetic stability of enzymatic reaction is characterized in that the high molecular material is prepared from glucose oxidase and Co3+-4A-PEG-His, the repair solution being a glucose solution containing ascorbic acid; when the hydrogel breaks due to external force, glucose solution containing ascorbic acid is coated on the broken surface, and the ascorbic acid makes Co in the hydrogel3+Rapidly reduced to Co2+The fracture surface becomes sol with fluidity and self-repairability; at the same time, H produced by glucose oxidase slowly decomposing glucose2O2Mixing Co2+Oxidation to Co3+And the time difference between the chemical reaction and the enzymatic reaction is utilized to finish the repair of the hydrogel.
6. The method of claim 5, wherein the concentration of glucose oxidase in the hydrogel is 0.1-0.5 mg/mL, Co3+The concentration of the 4A-PEG-His is 6.7-20 mM, and the concentration of the 4A-PEG-His is 5-15 mM;
preferably, the concentration of the ascorbic acid in the repair liquid is 1-15 mM, and the concentration of the glucose is 25-70 mM.
7. A method for temporarily repairing a high polymer material with stable dynamics based on enzymatic reaction regulation is characterized in that the high polymer material is hydrogel consisting of urease, PAM-co-PDAAM and ADH, and the repairing solution is an acidic buffer solution containing urea; when the hydrogel is fractured due to external force, an acidic urea solution is smeared on the fractured surface, the acidic solution firstly quickly reduces the pH of the fractured surface to activate hydrazone bonds, the fracture and re-bonding processes of the hydrazone bonds after the hydrazone bonds are activated can guide the repair of the material, and then the urease slowly decomposes ammonia generated by the urea to raise the pH value and lock the formed hydrazone bonds, so that the repair of the structure and the performance of the material is completed.
8. The method according to claim 7, wherein the concentration of urease in the hydrogel is 2-5 mg/mL, the concentration of PAM-co-PDAAM is 100-300 mg/mL, and the concentration of ADH is 10-40 mg/mL;
preferably, the pH value of the repair liquid is 3-5, the concentration of urea is 20-150 mg/mL, and the acidic buffer solution is 1M citric acid/sodium citrate buffer solution.
9. A method for temporarily repairing a high molecular material stabilized by regulation and control of kinetics based on enzymatic reaction is characterized in that the high molecular material is prepared from glucose oxidase, PEO-PAA-CaCO3The coating material is composed of a repairing solution and a coating layer, wherein the repairing solution is a neutral buffer solution containing glucose; when the coating material is damaged, coating neutral buffer solution containing glucose on the damaged part, wherein the neutral buffer solution can weaken the hydrogen bond acting force between PEO and PAA, so that the fluidity of the polymer is improved, and the contact with the damaged part of the coating material is promoted; then, the glucose acid generated by glucose oxidase decomposing glucose reduces the pH of the system, so that hydrogen bonds on the contacted damaged part are formed again, and the structure and the performance of the material are recovered.
10. The method of claim 9, wherein the concentration of glucose oxidase in the coating material is 0.1-0.5 mg/mL, the concentration of PEO is 1-10 mg/mL, the concentration of PAA is 1-10 mg/mL, CaCO3The concentration of (A) is 0.001-0.01 mM;
preferably, the concentration of glucose in the repair liquid is 1-50 mg/mL, and the neutral buffer solution is 0.1M phosphate buffer solution.
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