CN111484634A - Self-healing multi-bridged network chitosan-derived hydrogel and preparation method thereof - Google Patents

Self-healing multi-bridged network chitosan-derived hydrogel and preparation method thereof Download PDF

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CN111484634A
CN111484634A CN202010345112.6A CN202010345112A CN111484634A CN 111484634 A CN111484634 A CN 111484634A CN 202010345112 A CN202010345112 A CN 202010345112A CN 111484634 A CN111484634 A CN 111484634A
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chitosan
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cyclodextrin
carboxymethyl chitosan
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王路
王笑
李书彬
刘延浩
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Harbin Institute of Technology
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Abstract

A self-healing multi-bridging network chitosan derivative hydrogel and a preparation method thereof relate to a multi-bridging network hydrogel and a preparation method thereof. The invention aims to solve the problem that the mechanical property and the self-healing property of the existing natural polysaccharide hydrogel cannot be obtained at the same time. According to the invention, chitosan is used as a raw material, carboxyl, cyclodextrin and sulfydryl are introduced into the chitosan through carboxylation, free radical polymerization and amidation, and host-object coordination between the cyclodextrin and ferrocene, disulfide bonds between dimercaptos and hydrogen bonds between hydroxyl oxygen and hydrogen are used to obtain the multi-bridging network hydrogel. The method comprises the following steps: firstly, preparing O-carboxymethyl chitosan; secondly, preparing vinyl-cyclodextrin-itaconate; thirdly, preparing cyclodextrin carboxymethyl chitosan; fourthly, preparing thiolated cyclodextrin carboxymethyl chitosan; fifthly, preparing polyacrylamide ferrocene; sixthly, preparing the hydrogel material. The advantages are that: the elastic modulus of the hydrogel reaches 1500KPa, and the mechanical property is reduced by 80 percent after self-healing. The invention is used as a high-strength self-healing hydrogel material.

Description

Self-healing multi-bridged network chitosan-derived hydrogel and preparation method thereof
Technical Field
The invention relates to a self-healing multi-bridged network chitosan-derived hydrogel and a preparation method thereof.
Background
The intact tissue of the body is one of the indispensable important signs for human health, but because of various damage inducers and complicated and changeable damage forms, the actual damage speed and degree of the tissue generally far exceed the self-healing capacity, so that sufferers may face permanent irreparable damage, and the life quality is finally seriously affected. The natural polysaccharide-based hydrogel has higher similarity with the texture and possible functions of organism biological tissues and is suitable for being used as an ideal tissue engineering substitute material, but the existing synthesized natural polysaccharide-based hydrogel exposes a plurality of series defects for restraining the application of the hydrogel in the relevant fields of organism tissue repair and substitution, such as material basic properties including special strength, toughness and the like, the synergistic effect of composite functional properties is to be improved, the environmental biocompatibility and stress coordination reaction in an organism are to be improved, and the like. In recent years, the main solutions to the above drawbacks are: a diverse and different advantageous crosslinking method is explored to cooperatively construct the multi-network composite hydrogel, but the problems that the hydrogel mark performance cannot be synchronously enhanced, such as the mechanical strength is enhanced and the self-healing performance is reversely weakened, still exist in practice. Therefore, how to fully utilize the modification sites of the finite natural polysaccharide-based structure, combine various characteristic crosslinking acting forces to realize the synergistic effect and explore the hydrogel synthesis preparation method which gives consideration to various mark performance indexes becomes a research hotspot at home and abroad in the field, and the research hotspots comprise the development and research of new natural polysaccharide hydrogel biological materials with synchronously enhanced mechanical properties and self-healing properties.
Disclosure of Invention
The invention aims to solve the problem of insufficient mechanical properties of the existing chitosan-derivatized hydrogel, and provides a self-healing multi-bridging-network chitosan-derivatized hydrogel and a preparation method thereof.
A self-healing multi-bridging network chitosan derivatization hydrogel takes chitosan as a raw material, firstly, O-carboxymethyl chitosan is obtained based on an etherification reaction between chloroacetic acid and chitosan, and the O-carboxymethyl chitosan simultaneously carries active carboxyl, hydroxyl and amino; then, introducing a cyclodextrin functional unit into an O-carboxymethyl chitosan structure by utilizing free radical polymerization reaction to obtain cyclodextrin carboxymethyl chitosan; secondly, introducing sulfydryl into a cyclodextrin carboxymethyl chitosan structure by using an amidation reaction to obtain thiolated cyclodextrin carboxymethyl chitosan, wherein the thiolated cyclodextrin carboxymethyl chitosan simultaneously carries active carboxyl, sulfydryl and cyclodextrin functional units; introducing a ferrocene functional unit into a polyacrylamide structure to obtain polyacrylamide-ferrocene; mixing thiolated cyclodextrin carboxymethyl chitosan and polyacrylamide-ferrocene, and bridging by utilizing the interaction between a cyclodextrin functional unit and a host and an object between the ferrocene, bridging by utilizing a dimercapto disulfide bond on the thiolated cyclodextrin carboxymethyl chitosan and bridging by utilizing a hydrogen bond between hydroxyl oxygen and hydrogen to obtain the multi-bridge networking hydrogel, namely the self-healing multi-bridge networking chitosan-derived hydrogel.
The preparation method of the self-healing multi-bridged network chitosan-derived hydrogel specifically comprises the following steps:
①, dispersing chitosan in isopropanol, stirring and reacting for 30-60 min under the conditions of temperature of 20-26 ℃ and rotating speed of 800-1300 r/min to obtain an isopropanol solution of chitosan, wherein the concentration of chitosan in the isopropanol solution of chitosan is 0.3 mmol/L-1.2 mmol/L, ②, adding a sodium hydroxide aqueous solution into the isopropanol solution of chitosan 4-6 times, stirring and reacting for 30-60 min under the conditions of temperature of 20-26 ℃ and rotating speed of 800-1300 r/min to obtain a reaction solution I, wherein the concentration of sodium hydroxide in the sodium hydroxide aqueous solution is 8 mol/L-12 mol/L, the volume ratio of the sodium hydroxide aqueous solution to the isopropanol solution of chitosan is 1 (3-5), ③, dissolving chloroacetic acid in the isopropanol to obtain an isopropanol solution of chloroacetic acid, adding the isopropanol solution of chloroacetic acid into a blowing reaction tank, washing the isopropanol solution of chloroacetic acid for 1-35 min, washing the isopropanol solution of chloroacetic acid, and drying the product of the obtained by reaction at 354-2 mol/1-1300 r of chloroacetic acid, and drying the obtained product of chloroacetic acid in a blowing reaction tank to obtain a reaction solution of chloroacetic acid, wherein the product is obtained by stirring and the reaction solution of chloroacetic acid, and the reaction product obtained by stirring and the reaction is carried out the reaction at the temperature of 20-26 r/2-1-35 m of isopropanol solution I, and the reaction solution of chloroacetic acid is obtained by stirring and the reaction solution of chloroacetic acid, and the reaction solution of chloroacetic acid is obtained by stirring and the reaction solution of chloroacetic acid is carried out reaction solution of acetic acid, and the reaction product obtained by reaction solution of;
①, dissolving β -cyclodextrin in 25% ethanol solution to obtain β -cyclodextrin ethanol solution, adding itaconic acid, and stirring and reacting for 1-3 hours under the conditions that the temperature is 90-100 ℃ and the rotating speed is 1000-1300 r/min to obtain reaction solution II, wherein the 25% ethanol solution is prepared from deionized water and ethanol according to the volume ratio of 3:1, the concentration of β -cyclodextrin in the β -cyclodextrin ethanol solution is 16 mmol/L-18 mmol/L, the molar ratio of β -cyclodextrin to itaconic acid in β -cyclodextrin ethanol solution is 1:1, ②, carrying out rotary drying on the solvent of the reaction solution II by using a vacuum rotary evaporator to obtain a reaction product, placing the reaction product in a Soxhlet extractor, extracting by using isopropanol for 5-7 hours to obtain a reaction product, wherein the vacuum rotary evaporator is 0.09MPa to 0.1MPa in vacuum degree, the temperature is 50 ℃ and the temperature is 50-70 ℃, and drying the reaction product in a white extraction tank to obtain white itaconate, and drying the product at the temperature of 50-3- β 0 ℃ to obtain white itaconate;
①, dissolving O-carboxymethyl chitosan in a hydrochloric acid solution to obtain a hydrochloric acid solution of carboxymethyl chitosan, adding ammonium nitrate and vinyl-cyclodextrin-itaconate, stirring and reacting for 2-5 h under the conditions that the temperature is 20-25 ℃ and the rotating speed is 800-1300 r/min to obtain a reaction product, wherein the concentration of hydrochloric acid in the hydrochloric acid solution is 0.1 mol/L-0.3 mol/L, the concentration of O-carboxymethyl chitosan in the hydrochloric acid solution of carboxymethyl chitosan is 0.5 mmol/L-3 mmol/L, the molar ratio of O-carboxymethyl chitosan to vinyl-cyclodextrin-itaconate in the hydrochloric acid solution of carboxymethyl chitosan is 1 (200-600), the mass ratio of O-carboxymethyl chitosan in the hydrochloric acid solution of ammonium nitrate to carboxymethyl chitosan is 1 (1-2), ②, transferring the reaction product into a dialysis bag, and dialyzing the molecular weight of the dialysis bag is 4000-3000 h, dialyzing the reaction bag for 48-24 h to obtain a pale yellow cyclodextrin freeze-dialyzed product, and drying the product to obtain a product;
preparing thiolated cyclodextrin carboxymethyl chitosan L, dissolving N-acetyl-L-cysteine in distilled water, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide to obtain an aqueous solution of N-acetyl-L-cysteine, stirring and reacting for 20-40 min under the conditions that the temperature is 20-25 ℃ and the rotating speed is 600-1200 r/min to obtain a reaction solution III, dialyzing the aqueous solution of N-acetyl-L-cysteine with the concentration of 0.5 mol/L-1 mol/L, dialyzing the aqueous solution of N-acetyl-L-cysteine with the concentration of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride in the aqueous solution of N-acetyl-L-cysteine 0-638-0.5 mol/366, dialyzing the aqueous solution of N-acetyl-631-cysteine with the concentration of 0.1 mol/L mol/368 mol/600 mol/2000 mol/600-2000 mol/2000 min to obtain a product III, dialyzing the aqueous solution of N-acetyl-L-cysteine with the concentration of 0.5-5 mol/468, dialyzing the aqueous solution of chitosan with the concentration of carboxymethyl chitosan under the concentration of 20-600-200 mol/600-1200 r/10 h, dialyzing the aqueous solution of chitosan, dialyzing the product with the concentration of carboxymethyl chitosan, dialyzing the aqueous solution of carboxymethyl chitosan, dialyzing the product with the concentration of carboxymethyl chitosan under the concentration of carboxymethyl chitosan, dialyzing unit, the concentration of carboxymethyl chitosan, dialyzing the concentration of carboxymethyl chitosan, the concentration of carboxymethyl chitosan, dialyzing the product III, the concentration of the aqueous solution of carboxymethyl chitosan, the product III, dialyzing the concentration of carboxymethyl chitosan, the concentration of carboxymethyl chitosan, the concentration of carboxymethyl chitosan, the concentration of chitosan, the concentration of the chitosan, the chitosan;
preparing polyacrylamide-ferrocene ①, redistilling dichloromethane with calcium chloride to obtain anhydrous dichloromethane ②, dissolving ferrocenecarboxylic acid in anhydrous dichloromethane to obtain dichloromethane solution of ferrocenecarboxylic acid, adding oxalyl chloride, and performing N-phase reaction at 40-50 deg.C and 1000-1600 r/min2Stirring and reacting for 2-4 h under the atmosphere to obtain a primary reaction solution, wherein the concentration of ferrocenecarboxylic acid in the dichloromethane solution of the ferrocenecarboxylic acid is 60 mmol/L-80 mmol/L, the molar ratio of oxalyl chloride to the ferrocenecarboxylic acid is 1 (2-3), ③, removing dichloromethane from the primary reaction solution by adopting a vacuum rotary evaporator to obtain a primary reaction product, the vacuum rotary evaporator is under the conditions that the vacuum degree is 0.09-0.1 MPa and the temperature is 30-50 ℃, ④, dissolving the primary reaction product in anhydrous dichloromethane containing triethylamine, adding polyacrylamide, and reacting at the temperature of 20-25 ℃, the rotating speed of 600-1200 r/min and N2Stirring and reacting for 10-15 h under the atmosphere to obtain a reaction solution IV, wherein the volume fraction of triethylamine in the anhydrous dichloromethane containing triethylamine is 4-8%, the mass ratio of the volume of the anhydrous dichloromethane containing triethylamine to the primary reaction product is (25-40): 1, the mass ratio of polyacrylamide to the primary reaction product is 1 (5-10), ⑤, washing the reaction solution IV by deionized water for 3-5 times, standing and layering, collecting a dichloromethane layer, evaporating dichloromethane to obtain a reaction product, washing the reaction product by a mixed solution of hexane and ethyl acetate, and rotating at the temperature of 10-25 ℃ and the rotating speed of 3000 r/min-4000 r/minCentrifuging and collecting the precipitate under the condition, and drying the precipitate in a blast drying oven at the temperature of between 30 and 50 ℃ to obtain yellowish-brown powder, namely polyacrylamide-ferrocene; the volume ratio of the hexane to the ethyl acetate in the mixed solution of the hexane and the ethyl acetate is (8-9) to (2-1);
sixthly, preparing the hydrogel material: respectively preparing polyacrylamide-ferrocene and thiolated cyclodextrin carboxymethyl chitosan into aqueous solutions, uniformly mixing and standing to obtain the self-healing multi-bridged network chitosan-derivatized hydrogel.
The invention has the beneficial effects that:
1. the self-healing multi-bridged network chitosan-derived hydrogel prepared by the invention adopts chitosan and polyacrylamide as raw materials, and both the chitosan and the polyacrylamide are nontoxic and have high biocompatibility and safety.
2. The self-healing multi-bridging network chitosan derivatization hydrogel prepared by the invention adopts chitosan to be modified by multi-site functional molecules, and obtains a novel chitosan derivative with active carboxyl, sulfhydryl group and cyclodextrin functional unit.
3. The self-healing multi-bridging network chitosan-derived hydrogel prepared by the invention utilizes the mutual action of the cyclodextrin functional unit and the host and the guest between ferrocene, the bridging of disulfide bonds between dimercaptos and the bridging of hydrogen bonds between hydroxyl oxygen and hydrogen as acting forces, has excellent mechanical properties, and has the elastic modulus of 1500 KPa.
4. The self-healing multi-bridged network chitosan-derivatized hydrogel prepared by the invention has good self-healing characteristics, and is specifically represented as follows: the hydrogel is placed for 6 hours after artificial damage, self-recovery can be realized, and the storage modulus of the hydrogel after self-healing damage repair can be reduced by 83 percent.
5. The self-healing multi-bridged network chitosan-derived hydrogel prepared by the invention is used as a novel high-strength self-healing hydrogel biomaterial.
Drawings
FIG. 1 is a diagram of a three-step one reaction mechanism according to an embodiment;
FIG. 2 is a diagram of a three-step three-reaction mechanism according to an embodiment;
FIG. 3 is a diagram of a three-step four reaction mechanism according to an embodiment;
FIG. 4 is a diagram of a three-step five reaction mechanism according to an embodiment;
FIG. 5 is a diagram of a three-step six reaction mechanism according to an embodiment;
FIG. 6 is a comparison graph of the IR spectra of chitosan and O-carboxymethyl chitosan in example 1, wherein a represents chitosan and b represents O-carboxymethyl chitosan;
FIG. 7 is a comparison of the IR spectra of β -cyclodextrin and vinyl-cyclodextrin-itaconate in example 1, wherein a represents β -cyclodextrin and b represents vinyl-cyclodextrin-itaconate;
FIG. 8 is an infrared spectrum of cyclodextrin carboxymethyl chitosan obtained in step three of example 1;
FIG. 9 is an infrared spectrum of thiolated cyclodextrin carboxymethyl chitosan obtained in step four of example 1;
FIG. 10 is a comparison of IR spectra for polyacrylamide and polyacrylamide-ferrocene of example 1, where a represents polyacrylamide and b represents polyacrylamide-ferrocene;
FIG. 11 is the reaction of O-carboxymethyl chitosan, cyclodextrin carboxymethyl chitosan and thiolated cyclodextrin carboxymethyl chitosan of example 1 with D2A nuclear magnetic resonance hydrogen spectrum comparison diagram with O as a solvent, wherein a represents O-carboxymethyl chitosan, b represents cyclodextrin carboxymethyl chitosan, and c represents thiolated cyclodextrin carboxymethyl chitosan;
FIG. 12 is polyacrylamide-ferrocene as D obtained in step five of example 12A nuclear magnetic resonance hydrogen spectrum with O as a solvent;
FIG. 13 is a graph comparing the X-ray diffraction spectra of chitosan, O-carboxymethyl chitosan, cyclodextrin carboxymethyl chitosan, and thiolated cyclodextrin carboxymethyl chitosan in example 1, wherein a represents chitosan, b represents O-carboxymethyl chitosan, c represents cyclodextrin carboxymethyl chitosan, and d represents thiolated cyclodextrin carboxymethyl chitosan;
FIG. 14 is a differential scanning calorimetry thermogram of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1;
FIG. 15 is a thermogravimetric analysis curve of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1;
FIG. 16 is an electron microscopic scan at 100X magnification of a self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1;
FIG. 17 is an electron microscopic scan at 200X magnification of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1;
FIG. 18 is a scanning electron microscope scan 500 times magnified of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1;
FIG. 19 is a plot of swelling ratio versus time for the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1;
FIG. 20 is the elastic modulus versus time curve of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1 under cyclic compression;
fig. 21 is a graph comparing rheological property tests of example 1 and example 2, wherein ■ represents the storage modulus of the self-healing multi-bridging network chitosan-derivatized hydrogel obtained in step six of example 1, and □ represents the storage modulus of the self-healing multi-bridging network chitosan-derivatized hydrogel obtained in example 2 after self-healing;
FIG. 22 is a graph of the weight change over time in the degradability test for the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1;
FIG. 23 is a graph of the biocompatibility test results of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1;
FIG. 24 is a physical change diagram of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in the sixth step of example 1, which is manually subjected to fracture damage and then left to stand for 6 hours after docking;
fig. 25 is a comparative graph of rheological performance testing, wherein ■ represents the storage modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1, □ represents the storage modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 2, ▲ represents the loss modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1, and △ represents the loss modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step 2.
Detailed Description
The first embodiment is as follows: according to the self-healing multi-bridging network chitosan-derivatized hydrogel, chitosan is used as a raw material, firstly, O-carboxymethyl chitosan is obtained based on an etherification reaction between chloroacetic acid and chitosan, and the O-carboxymethyl chitosan simultaneously carries active carboxyl, hydroxyl and amino; then, introducing a cyclodextrin functional unit into an O-carboxymethyl chitosan structure by utilizing free radical polymerization reaction to obtain cyclodextrin carboxymethyl chitosan; secondly, introducing sulfydryl into a cyclodextrin carboxymethyl chitosan structure by using an amidation reaction to obtain thiolated cyclodextrin carboxymethyl chitosan, wherein the thiolated cyclodextrin carboxymethyl chitosan simultaneously carries active carboxyl, sulfydryl and cyclodextrin functional units; introducing a ferrocene functional unit into a polyacrylamide structure to obtain polyacrylamide-ferrocene; mixing thiolated cyclodextrin carboxymethyl chitosan and polyacrylamide-ferrocene, and bridging by utilizing the interaction between a cyclodextrin functional unit and a host and an object between the ferrocene, bridging by utilizing a dimercapto disulfide bond on the thiolated cyclodextrin carboxymethyl chitosan and bridging by utilizing a hydrogen bond between hydroxyl oxygen and hydrogen to obtain the multi-bridge networking hydrogel, namely the self-healing multi-bridge networking chitosan-derived hydrogel.
The self-healing multi-bridged network chitosan-derivatized hydrogel adopts chitosan and polyacrylamide as raw materials, and both the chitosan and the polyacrylamide are nontoxic, biocompatible and high in safety.
The self-healing multi-bridging network chitosan-derived hydrogel disclosed by the embodiment has good mechanical properties by utilizing the self-oxidation reaction between double sulfydryl groups, and the elastic modulus of the self-healing multi-bridging network chitosan-derived hydrogel reaches 1500 KPa.
The self-healing multi-bridging network chitosan-derivatized hydrogel is formed by host-guest interaction, disulfide bond, hydrogen bond bridging between hydroxyl oxygen and hydrogen, and the hydrogel has self-healing characteristics due to dynamic host-guest interaction force, which is specifically represented as follows: the self-healing multi-bridged network chitosan derivatized hydrogel prepared by the embodiment has good mechanical properties and self-healing characteristics; after the self-healing multi-bridging network chitosan-derivatized hydrogel prepared by the embodiment is cut and placed still for bonding, the reduction of the rheological property of the hydrogel by more than 80% is found, which shows that the self-healing multi-bridging network chitosan-derivatized hydrogel prepared by the embodiment has good self-healing characteristics.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the deacetylation degree of the chitosan is 90%, and the molecular weight of the chitosan is 80000-140000. The rest is the same as the first embodiment.
The third concrete implementation mode: the preparation method of the self-healing multi-bridged network chitosan-derivatized hydrogel comprises the following steps:
①, dispersing chitosan in isopropanol, stirring and reacting for 30-60 min under the conditions of temperature of 20-26 ℃ and rotating speed of 800-1300 r/min to obtain an isopropanol solution of chitosan, wherein the concentration of chitosan in the isopropanol solution of chitosan is 0.3 mmol/L-1.2 mmol/L, ②, adding a sodium hydroxide aqueous solution into the isopropanol solution of chitosan 4-6 times, stirring and reacting for 30-60 min under the conditions of temperature of 20-26 ℃ and rotating speed of 800-1300 r/min to obtain a reaction solution I, wherein the concentration of sodium hydroxide in the sodium hydroxide aqueous solution is 8 mol/L-12 mol/L, the volume ratio of the sodium hydroxide aqueous solution to the isopropanol solution of chitosan is 1 (3-5), ③, dissolving chloroacetic acid in the isopropanol to obtain an isopropanol solution of chloroacetic acid, adding the isopropanol solution of chloroacetic acid into a blowing reaction tank, washing the isopropanol solution of chloroacetic acid for 1-35 min, washing the isopropanol solution of chloroacetic acid, and drying the product of the obtained by reaction at 354-2 mol/1-1300 r of chloroacetic acid, and drying the obtained product of chloroacetic acid in a blowing reaction tank to obtain a reaction solution of chloroacetic acid, wherein the product is obtained by stirring and the reaction solution of chloroacetic acid, and the reaction product obtained by stirring and the reaction is carried out the reaction at the temperature of 20-26 r/2-1-35 m of isopropanol solution I, and the reaction solution of chloroacetic acid is obtained by stirring and the reaction solution of chloroacetic acid, and the reaction solution of chloroacetic acid is obtained by stirring and the reaction solution of chloroacetic acid is carried out reaction solution of acetic acid, and the reaction product obtained by reaction solution of;
①, dissolving β -cyclodextrin in 25% ethanol solution to obtain β -cyclodextrin ethanol solution, adding itaconic acid, and stirring and reacting for 1-3 hours under the conditions that the temperature is 90-100 ℃ and the rotating speed is 1000-1300 r/min to obtain reaction solution II, wherein the 25% ethanol solution is prepared from deionized water and ethanol according to the volume ratio of 3:1, the concentration of β -cyclodextrin in the β -cyclodextrin ethanol solution is 16 mmol/L-18 mmol/L, the molar ratio of β -cyclodextrin to itaconic acid in β -cyclodextrin ethanol solution is 1:1, ②, carrying out rotary drying on the solvent of the reaction solution II by using a vacuum rotary evaporator to obtain a reaction product, placing the reaction product in a Soxhlet extractor, extracting by using isopropanol for 5-7 hours to obtain a reaction product, wherein the vacuum rotary evaporator is 0.09MPa to 0.1MPa in vacuum degree, the temperature is 50 ℃ and the temperature is 50-70 ℃, and drying the reaction product in a white extraction tank to obtain white itaconate, and drying the product at the temperature of 50-3- β 0 ℃ to obtain white itaconate;
①, dissolving O-carboxymethyl chitosan in a hydrochloric acid solution to obtain a hydrochloric acid solution of carboxymethyl chitosan, adding ammonium nitrate and vinyl-cyclodextrin-itaconate, stirring and reacting for 2-5 h under the conditions that the temperature is 20-25 ℃ and the rotating speed is 800-1300 r/min to obtain a reaction product, wherein the concentration of hydrochloric acid in the hydrochloric acid solution is 0.1 mol/L-0.3 mol/L, the concentration of O-carboxymethyl chitosan in the hydrochloric acid solution of carboxymethyl chitosan is 0.5 mmol/L-3 mmol/L, the molar ratio of O-carboxymethyl chitosan to vinyl-cyclodextrin-itaconate in the hydrochloric acid solution of carboxymethyl chitosan is 1 (200-600), the mass ratio of O-carboxymethyl chitosan in the hydrochloric acid solution of ammonium nitrate to carboxymethyl chitosan is 1 (1-2), ②, transferring the reaction product into a dialysis bag, and dialyzing the molecular weight of the dialysis bag is 4000-3000 h, dialyzing the reaction bag for 48-24 h to obtain a pale yellow cyclodextrin freeze-dialyzed product, and drying the product to obtain a product;
preparing thiolated cyclodextrin carboxymethyl chitosan L, dissolving N-acetyl-L-cysteine in distilled water, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide to obtain an aqueous solution of N-acetyl-L-cysteine, stirring and reacting for 20-40 min under the conditions that the temperature is 20-25 ℃ and the rotating speed is 600-1200 r/min to obtain a reaction solution III, dialyzing the aqueous solution of N-acetyl-L-cysteine with the concentration of 0.5 mol/L-1 mol/L, dialyzing the aqueous solution of N-acetyl-L-cysteine with the concentration of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride in the aqueous solution of N-acetyl-L-cysteine 0-638-0.5 mol/366, dialyzing the aqueous solution of N-acetyl-631-cysteine with the concentration of 0.1 mol/L mol/368 mol/600 mol/2000 mol/600-2000 mol/2000 min to obtain a product III, dialyzing the aqueous solution of N-acetyl-L-cysteine with the concentration of 0.5-5 mol/468, dialyzing the aqueous solution of chitosan with the concentration of carboxymethyl chitosan under the concentration of 20-600-200 mol/600-1200 r/10 h, dialyzing the aqueous solution of chitosan, dialyzing the product with the concentration of carboxymethyl chitosan, dialyzing the aqueous solution of carboxymethyl chitosan, dialyzing the product with the concentration of carboxymethyl chitosan under the concentration of carboxymethyl chitosan, dialyzing unit, the concentration of carboxymethyl chitosan, dialyzing the concentration of carboxymethyl chitosan, the concentration of carboxymethyl chitosan, dialyzing the product III, the concentration of the aqueous solution of carboxymethyl chitosan, the product III, dialyzing the concentration of carboxymethyl chitosan, the concentration of carboxymethyl chitosan, the concentration of carboxymethyl chitosan, the concentration of chitosan, the concentration of the chitosan, the chitosan;
preparing polyacrylamide-ferrocene ①, redistilling dichloromethane with calcium chloride to obtain anhydrous dichloromethane ②, dissolving ferrocenecarboxylic acid in anhydrous dichloromethane to obtain dichloromethane solution of ferrocenecarboxylic acid, adding oxalyl chloride, and performing N-phase reaction at 40-50 deg.C and 1000-1600 r/min2Stirring and reacting for 2-4 h under the atmosphere to obtain a primary reaction solution, wherein the concentration of ferrocenecarboxylic acid in the dichloromethane solution of the ferrocenecarboxylic acid is 60 mmol/L-80 mmol/L, the molar ratio of oxalyl chloride to the ferrocenecarboxylic acid is 1 (2-3), ③, removing dichloromethane from the primary reaction solution by adopting a vacuum rotary evaporator to obtain a primary reaction product, the vacuum rotary evaporator is under the conditions that the vacuum degree is 0.09-0.1 MPa and the temperature is 30-50 ℃, ④, dissolving the primary reaction product in anhydrous dichloromethane containing triethylamine, adding polyacrylamide, and reacting at the temperature of 20-25 ℃, the rotating speed of 600-1200 r/min and N2Stirring and reacting for 10-15 h under the atmosphere to obtain a reaction solution IV, wherein the volume fraction of triethylamine in the anhydrous dichloromethane containing triethylamine is 4-8%, the mass ratio of the volume of the anhydrous dichloromethane containing triethylamine to a primary reaction product is (25-40): 1, the mass ratio of polyacrylamide to the primary reaction product is 1 (5-10), ⑤, washing the reaction solution IV by deionized water for 3-5 times, standing and layering, collecting a dichloromethane layer, evaporating dichloromethane to obtain a reaction product, washing the reaction product by a mixed solution of hexane and ethyl acetate, centrifugally collecting precipitates at the temperature of 10-25 ℃ and the rotating speed of 3000 r/min-4000 r/min, drying in a blast drying box at the temperature of 30-50 ℃ to obtain yellowish-brown powder, namely polyacrylamide-ferrocene, and the volume ratio of hexane to ethyl acetate in the mixed solution of hexane and ethyl acetate is (8-9): 2-1);
sixthly, preparing the hydrogel material: respectively preparing polyacrylamide-ferrocene and thiolated cyclodextrin carboxymethyl chitosan into aqueous solutions, uniformly mixing and standing to obtain the self-healing multi-bridged network chitosan-derivatized hydrogel.
The self-healing multi-bridged network chitosan-derived hydrogel prepared by the embodiment adopts chitosan and polyacrylamide as raw materials, and both the chitosan and the polyacrylamide are non-toxic and have high biocompatibility and safety.
The self-healing multi-bridging network chitosan-derived hydrogel prepared by the embodiment has good mechanical properties by using the self-oxidation reaction between double sulfydryl groups, and the elastic modulus of the self-healing multi-bridging network chitosan-derived hydrogel reaches 1500 KPa.
The self-healing multi-bridging network chitosan derivatization hydrogel prepared by the embodiment is formed by host-guest interaction, disulfide bond, hydrogen bond bridging between hydroxyl oxygen and hydrogen, and the hydrogel has self-healing characteristics due to dynamic host-guest interaction force, and the self-healing multi-bridging network chitosan derivatization hydrogel is specifically represented as follows: the self-healing multi-bridged network chitosan derivatized hydrogel prepared by the embodiment has good mechanical properties and self-healing characteristics; after the self-healing multi-bridging network chitosan-derivatized hydrogel prepared by the embodiment is cut and placed still for bonding, the reduction of the rheological property of the hydrogel by more than 80% is found, which shows that the self-healing multi-bridging network chitosan-derivatized hydrogel prepared by the embodiment has good self-healing characteristics.
FIG. 1 is a reaction mechanism diagram of three steps, i.e., a reaction mechanism diagram, in which chloroacetic acid and chitosan hydroxyl are subjected to etherification reaction to introduce carboxymethyl into the chitosan molecular structure, thereby obtaining O-carboxymethyl chitosan.
Fig. 2 is a diagram of a three-step and three-reaction mechanism in a specific embodiment, and a carbon-carbon double bond of vinyl-cyclodextrin-itaconate and a hydroxyl group of carboxymethyl chitosan are subjected to radical polymerization to introduce a cyclodextrin functional unit into a carboxymethyl chitosan structure, so as to obtain the cyclodextrin carboxymethyl chitosan.
FIG. 3 is a diagram of a three-step four-reaction mechanism in a specific embodiment, wherein N-acetyl-L-cysteine carboxyl group and cyclodextrin carboxymethyl chitosan amino group are subjected to amidation reaction, and a sulfhydryl group is introduced into a cyclodextrin carboxymethyl chitosan structure to obtain thiolated cyclodextrin carboxymethyl chitosan.
Fig. 4 is a reaction mechanism diagram of a third step and a fifth step in the specific embodiment, and the acyl chloride and the amino group are subjected to nucleophilic substitution reaction to introduce the ferrocene functional unit into a polyacrylamide structure, so as to obtain polyacrylamide-ferrocene.
Fig. 5 is a diagram of a three-step six-reaction mechanism in a specific embodiment, which is to add polyacrylamide ferrocene into a thiolated cyclodextrin carboxymethyl chitosan aqueous solution to allow the cyclodextrin and ferrocene to generate a host-guest interaction, and obtain the self-healing multi-bridged network chitosan-derivatized hydrogel by using a dimercapto to generate an autoxidation reaction and a hydrogen bond reaction between hydroxyl hydrogen and another hydroxyl oxygen.
Fourth embodiment the present embodiment is different from the third embodiment in that the chitosan in the first step ① has a deacetylation degree of 90% and a molecular weight of 80000 to 140000.
Fifth embodiment is different from the third or fourth embodiment in that the third ① is stirred and reacts for 3 to 5 hours at a temperature of 20 to 25 ℃ and a rotation speed of 800 to 1000r/min to obtain a reaction product, the molar ratio of the O-carboxymethyl chitosan to the vinyl-cyclodextrin-itaconate in the hydrochloric acid solution of the carboxymethyl chitosan is 1 (300 to 500), and the rest is the same as the third or fourth embodiment.
Sixth embodiment the present embodiment is different from the third to fifth embodiments in that the reaction is performed for 2 to 3 hours in step III ① under the conditions of 20 to 25 ℃ and 1000 to 1300r/min of rotation speed.
The seventh embodiment is different from the third to sixth embodiments in that in the fourth ②, the reaction is performed for 5 to 8 hours under the conditions of 30 to 40 ℃ and 600 to 900r/min of rotation speed, the molar ratio of N-acetyl-L-cysteine to cyclodextrin carboxymethyl chitosan in the hydrochloric acid solution of cyclodextrin carboxymethyl chitosan in the reaction solution III is (200 to 400):1, and the rest is the same as the third to sixth embodiments.
The eighth embodiment is different from the third to seventh embodiments in that the stirring reaction is carried out for 5 to 8 hours at the temperature of 25 to 30 ℃ and the rotation speed of 900 to 1300r/min in the fourth ② to obtain a reaction product, the molar ratio of the N-acetyl-L-cysteine in the aqueous solution of the N-acetyl-L-cysteine to the cyclodextrin carboxymethyl chitosan in the hydrochloric acid solution of the cyclodextrin carboxymethyl chitosan is (400 to 600):1, and the rest is the same as the third to seventh embodiments.
Ninth embodiment this embodiment differs from the third to eighth embodiments in that the average molecular weight of the polyacrylamide in step five ④ is 100 ten thousand, and the functional unit of ferrocene in the first order reaction product is introduced into the amino group of polyacrylamide by nucleophilic substitution.
The specific embodiment mode ten is that in the sixth step, polyacrylamide-ferrocene and thiolated cyclodextrin carboxymethyl chitosan are respectively prepared into aqueous solutions, uniformly mixed and placed to obtain the self-healing multi-bridged network chitosan-derived hydrogel, the specific process is ①, polyacrylamide-ferrocene is dissolved in distilled water to obtain a polyacrylamide-ferrocene aqueous solution with the mass fraction of 3% -5%, ②, thiolated cyclodextrin carboxymethyl chitosan is dissolved in distilled water to obtain a thiolated cyclodextrin carboxymethyl chitosan aqueous solution with the mass fraction of 3% -5%, ③, the thiolated cyclodextrin carboxymethyl chitosan aqueous solution and the polyacrylamide-ferrocene aqueous solution are uniformly mixed and placed for 6 h-12 h according to the volume ratio of 1:1 to obtain the self-healing multi-bridged network chitosan-derived hydrogel, and the self-healing multi-bridged network chitosan-derived hydrogel is synthesized by multiple bridging forces of main-object interaction, disulfide bond bridging, hydrogen bonding, hydroxyl oxygen and hydrogen.
The effects of the present invention were verified by the following tests:
example 1: the preparation method of the self-healing multi-bridged network chitosan-derived hydrogel comprises the following steps:
①, dispersing chitosan in isopropanol, stirring and reacting for 45min under the conditions of 25 ℃ and 1000r/min of rotation speed to obtain an isopropanol solution of chitosan, ②, adding a 4m L sodium hydroxide aqueous solution into the isopropanol solution of chitosan 5 times, stirring and reacting for 45min under the conditions of 25 ℃ and 1000r/min of rotation speed to obtain a reaction solution I, dissolving 2g chloroacetic acid in 10m L isopropanol to obtain an isopropanol solution of chloroacetic acid, wherein the concentration of the isopropanol solution of chloroacetic acid is 2 mol/L, adding the isopropanol solution of chloroacetic acid into the reaction solution I5 times, stirring and reacting for 4h under the conditions of 60 ℃ and 1100 min of rotation speed, filtering to obtain a reaction product, washing the isopropanol solution of chloroacetic acid in a reaction tank for 5 times, drying a product in a light yellow chloride-free water, and washing the product in a blowing washing tank to obtain a product, wherein the product is obtained by drying in a blowing washing tank, and the product is dried at a temperature of 1-78 ℃, and the product is obtained by using 3637-78 parts of chloroacetic acid;
①, dissolving β -cyclodextrin in 25% ethanol solution to obtain β -cyclodextrin ethanol solution, adding itaconic acid, and stirring and reacting for 2 hours at the temperature of 100 ℃ and the rotating speed of 1000r/min to obtain reaction solution II, wherein the 25% ethanol solution is prepared from deionized water and ethanol according to the volume ratio of 3:1, the concentration of β -cyclodextrin in the β -cyclodextrin ethanol solution is 17 mmol/L, the molar ratio of β -cyclodextrin to itaconic acid in the β -cyclodextrin ethanol solution is 1:1, ② is obtained by spin-drying the solvent of the reaction solution II by using a vacuum rotary evaporator to obtain a reaction product, and the reaction product is placed in a Soxhlet extractor to be extracted by using isopropanol for 6 hours to obtain an extracted product, wherein the vacuum rotary evaporator is 0.1MPa, the temperature of 60 ℃, ③ is obtained by placing the extracted product in a 50 ℃ blast drying oven for 4 hours to obtain white powder, namely the vinyl-cyclodextrin-itaconate;
①, dissolving O-carboxymethyl chitosan in 0.2 mol/L hydrochloric acid solution to obtain hydrochloric acid solution of carboxymethyl chitosan, adding ammonium nitrate and vinyl-cyclodextrin-itaconate, and stirring and reacting for 3 hours under the conditions that the temperature is 25 ℃ and the rotating speed is 1000r/min to obtain a reaction product, wherein the concentration of the carboxymethyl chitosan in the hydrochloric acid solution of the carboxymethyl chitosan is 1 mmol/L, the molar ratio of the O-carboxymethyl chitosan to the vinyl-cyclodextrin-itaconate in the hydrochloric acid solution of the carboxymethyl chitosan is 1:300, the mass ratio of the O-carboxymethyl chitosan in the hydrochloric acid solution of the ammonium nitrate to the O-carboxymethyl chitosan in the hydrochloric acid solution of the carboxymethyl chitosan is 1:1.5, ②, transferring the reaction product into a dialysis bag, wherein the molecular weight cut-off of the dialysis bag is 3500, deionized water dialyzes for 24 hours to obtain a dialyzed product, and performing vacuum freeze drying on the dialyzed product to obtain faint yellow powder, namely cyclodextrin carboxymethyl chitosan;
l, dissolving N-acetyl-L-cysteine in distilled water, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide to obtain an aqueous solution of N-acetyl-L-cysteine, stirring and reacting for 30min at 25 ℃ and 700r/min to obtain a reaction solution III, dissolving 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride in the aqueous solution of N-acetyl-L-cysteine at 0.6 mol/L, dissolving 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride in the aqueous solution of N-acetyl-L-cysteine at 0.2 mol/L, transferring the concentration of N-hydroxysuccinimide in the aqueous solution of N-acetyl-L-cysteine at 0.2 mol/L, dissolving L6-carboxymethyl chitosan in a hydrochloric acid solution to obtain a solution of carboxymethyl chitosan, transferring the solution of carboxymethyl chitosan to a dialysis bag at a dialysis concentration of 0.2 mol/5966 h, dialyzing the aqueous solution of carboxymethyl chitosan with a sodium chloride solution of carboxymethyl chitosan under a dialysis concentration of 300-4000 mol/3 h, dialyzing the aqueous solution of chitosan with a dialysis product of carboxymethyl chitosan under a dialysis temperature of 25-2, dialyzing reaction product of carboxymethyl chitosan with a dialysis solution of sodium chloride and a dialysis solution of carboxymethyl chitosan under a dialysis concentration of sodium chloride at a dialysis concentration of sodium chloride of 300-2, dialyzing reaction product of carboxymethyl chitosan, wherein the concentration of chitosan is obtained by stirring and a dialysis solution of sodium chloride, and a dialysis product of sodium chloride, and a dialysis solution of chitosan, and the concentration of sodium chloride, and the concentration of chitosan, and the concentration of sodium chloride, and the concentration of chitosan is obtained by dialyzing reaction product of sodium chloride, and dialyzing reaction product of sodium chloride in the concentration of chitosan, and dialyzing reaction product of chitosan, and dialyzing the concentration of chitosan under a dialysis bag under a dialysis product of sodium chloride solution of chitosan under a dialysis bag under a;
preparing polyacrylamide-ferrocene ①, redistilling dichloromethane with calcium chloride to obtain anhydrous dichloromethane ②, dissolving ferrocenecarboxylic acid in anhydrous dichloromethane to obtain dichloromethane solution of ferrocenecarboxylic acid, adding oxalyl chloride, and stirring at 45 deg.C and 1000r/min under N2Stirring and reacting for 3 hours under the atmosphere to obtain a primary reaction solution, wherein the concentration of ferrocenecarboxylic acid in dichloromethane solution of the ferrocenecarboxylic acid is 60 mmol/L-80 mmol/L, the molar ratio of oxalyl chloride to the ferrocenecarboxylic acid is 1:2, ③, removing dichloromethane from the primary reaction solution by using a vacuum rotary evaporator to obtain a primary reaction product, wherein the vacuum rotary evaporator is used for removing dichloromethane under the conditions that the vacuum degree is 0.1MPa and the temperature is 40 ℃, ④, dissolving the primary reaction product in 85m L of anhydrous dichloromethane containing triethylamine, adding polyacrylamide, and rotating at the temperature of 25 ℃, the rotating speed of 800r/min and N2Stirring and reacting for 12 hours under the atmosphere to obtain a reaction solution IV, wherein the volume fraction of triethylamine in the anhydrous dichloromethane containing triethylamine is 5%, the mass ratio of the volume of the anhydrous dichloromethane containing triethylamine to the primary reaction product is 32.5:1, the mass ratio of polyacrylamide to the primary reaction product is 1:7.5, ⑤, washing the reaction solution IV by deionized water for 4 times, standing and layering, collecting a dichloromethane layer, evaporating dichloromethane to obtain a reaction product, washing the reaction product by a mixed solution of hexane and ethyl acetate, centrifuging and collecting precipitates under the conditions of the temperature of 20 ℃ and the rotating speed of 3000r/min, drying in a blast drying box at the temperature of 40 ℃ to obtain yellowish brown powder, namely polyacrylamide-ferrocene, and mixing and dissolving the hexane and ethyl acetate to obtain a reaction solution IVThe volume ratio of hexane to ethyl acetate in the solution is 9: 1;
preparing polyacrylamide-ferrocene and thiolated cyclodextrin carboxymethyl chitosan into aqueous solution, uniformly mixing and standing to obtain the self-healing multi-bridging network chitosan-derivatized hydrogel, wherein ① the polyacrylamide-ferrocene is dissolved in distilled water to obtain 4% by mass of polyacrylamide-ferrocene aqueous solution, ② the thiolated cyclodextrin carboxymethyl chitosan is dissolved in distilled water to obtain 4% by mass of thiolated cyclodextrin carboxymethyl chitosan aqueous solution, ③ the thiolated cyclodextrin carboxymethyl chitosan aqueous solution and the polyacrylamide-ferrocene aqueous solution are uniformly mixed and stand for 6 hours according to the volume ratio of 1:1 to obtain the self-healing multi-bridging network chitosan-derivatized hydrogel.
Example 1 step one the chitosan degree of deacetylation was 90% and the average molecular weight was 10 ten thousand.
Example 1 step five the polyacrylamide has an average molecular weight of 100 ten thousand.
FIG. 6 is a comparison graph of the IR spectra of chitosan and O-carboxymethyl chitosan in example 1, wherein a represents chitosan and b represents O-carboxymethyl chitosan; as can be seen from the figure, the infrared spectrum of the chitosan is 3390cm-1Is a wider spectral band formed by overlapping O-H and N-H stretching vibration absorption peaks of chitosan molecular chains, and 1600cm in an O-carboxymethyl chitosan infrared spectrogram-1Point sum 1420cm-1The asymmetric stretching vibration absorption peak and the symmetric stretching vibration specific peak of carboxyl appear at the position, which proves that the carboxyl is connected to the chitosan structure through etherification reaction, and 1030cm at the same time-1The absorption peak is 897cm and is the characteristic absorption peak of chitosan C6-OH-1Is chitosan C2-NH2And absorption peaks show that the O-carboxymethyl chitosan structure simultaneously carries active carboxyl, hydroxyl and amino.
FIG. 7 is a comparison of the IR spectra of β -cyclodextrin and vinyl-cyclodextrin-itaconate of example 1, wherein a represents β -cyclodextrin and b represents vinyl-cyclodextrin-itaconate, showing that β -cyclodextrin and vinyl-cyclodextrin-itaconate have substantially the same peak patterns, indicating that they have similar chemical structures, but are the same as β -cyclodextrin IR spectrumIn the infrared spectrum of the specific, vinyl-cyclodextrin-itaconate, 1713cm-1A characteristic absorption peak of carbonyl (-C ═ O) at 1580cm-1The carboxyl characteristic stretching vibration absorption peak appears, and the β -cyclodextrin is proved to be connected to the itaconic acid structure through esterification reaction.
FIG. 8 is an infrared spectrum of cyclodextrin carboxymethyl chitosan obtained in step three of example 1; as can be seen, 1030cm-1The absorption peak of carboxymethyl chitosan C6-OH disappears at 1650cm-1The peak of absorption of stretching vibration of carbonyl (C ═ O) appears at 1593cm-1There appears a carboxyl group COO-characteristic vibration absorption peak, 1044cm-1The position of the strain shows β -cyclodextrin framework characteristic stretching vibration absorption peak of 900cm-1At C2-NH2Characteristic absorption peaks, demonstrating that vinyl-CD-itaconate has been attached by free radical polymerization to the hydroxyl group at C6 in the carboxymethyl chitosan structural chain.
FIG. 9 is an infrared spectrum of thiolated cyclodextrin carboxymethyl chitosan obtained in step four of example 1; as can be seen, 900cm-1The cyclodextrin carboxymethyl chitosan C2-NH2Disappearance of characteristic absorption Peak, 1650cm-1The peak of absorption of stretching vibration of carbonyl (C ═ O) in vinyl-CD-itaconate appears, 1590cm-1A characteristic vibration absorption peak of carboxyl group, 1070cm-1Has a characteristic absorption peak of C-O-C, 2390cm-1The peak of sulfydryl telescopic vibration infrared characteristic absorption shows that sulfydryl is connected to the C2 amino position of cyclodextrin carboxymethyl chitosan through amidation reaction.
FIG. 10 is a comparison of IR spectra for polyacrylamide and polyacrylamide-ferrocene of example 1, where a represents polyacrylamide and b represents polyacrylamide-ferrocene; as can be seen from the figure, the polyacrylamide-ferrocene infrared spectrogram is 1590cm-1The characteristic absorption peak at the position of amide (-CO-NH-) disappears, 1380cm-1And 720cm-1The position of the sample shows a stretching vibration absorption peak of imide (-CO-NH-CO-), 1100cm-1And a strong characteristic absorption peak of C-C on the cyclopentadienyl ring appears, so that the ferrocene functional unit is proved to be connected to the polyacrylamide structure through nucleophilic substitution reaction.
FIG. 11 shows the structure of O-carboxymethyl chitosan of example 1,Cyclodextrin carboxymethyl chitosan and thiolated cyclodextrin carboxymethyl chitosan as D2The nuclear magnetic resonance hydrogen spectrum comparison graph shows that in the nuclear magnetic resonance hydrogen spectrum graph of the carboxymethyl chitosan, the vibration signal of C6 carboxymethyl hydrogen atom in the carboxymethyl chitosan structure is shown at 4.4ppm, which indicates that carboxyl is modified to the hydroxyl of C6 in the chitosan structure, the peak of carboxymethyl hydrogen atom appears near 4.37ppm, the peak of β -cyclodextrin intracavity hydrogen atom appears at 4.98ppm and 5.22ppm, which indicate that the cyclodextrin functional unit is modified to the carboxymethyl chitosan structure, and the peak of thiol-bonded carboxymethyl chitosan nuclear magnetic resonance hydrogen atom appears at 4.38ppm, the peak of β -CD intracavity hydrogen atom appears at 4.9-5.3ppm, and the peak of thiol-bonded methylene hydrogen atom appears near 2.79ppm, which indicates that the thiol is bonded to the carboxymethyl chitosan structure through amidation reaction, and the carboxyl is carried by the carboxymethyl chitosan structure and the cyclodextrin structure.
FIG. 12 is polyacrylamide-ferrocene as D obtained in step five of example 12A nuclear magnetic resonance hydrogen spectrum with O as a solvent; as can be seen from the figure, the chemical shifts caused by the ferrocene cyclopentadienyl ring proton signals are at 4.08 and 4.26ppm, and the chemical shifts caused by the ferrocene cyclopentadienyl ring proton signals are at 2.26ppm and 1.32ppm, respectively, of-CH in polyacrylamide2-and-CH-group hydrogen atom peaks, demonstrating that the ferrocene functional unit has been linked to a polyacrylamide structure.
FIG. 13 is a graph comparing the X-ray diffraction spectra of chitosan, O-carboxymethyl chitosan, cyclodextrin carboxymethyl chitosan, and thiolated cyclodextrin carboxymethyl chitosan in example 1, wherein a represents chitosan, b represents O-carboxymethyl chitosan, c represents cyclodextrin carboxymethyl chitosan, and d represents thiolated cyclodextrin carboxymethyl chitosan; as can be seen from the figure, compared with the X-ray diffraction spectrogram of chitosan, the diffraction peak intensities of O-carboxymethyl chitosan, cyclodextrin carboxymethyl chitosan and thiolated cyclodextrin carboxymethyl chitosan are obviously weakened, and the original high crystallinity of chitosan is destroyed, which indicates that the chitosan molecule modification reaction is successfully carried out.
FIG. 14 is a differential scanning calorimetry thermogram of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1; it can be seen from the figure that a first endothermic peak appears near 274.77 ℃, and after a relatively stable plateau, another relatively weak endothermic peak appears at 503.32 ℃, and the two endothermic peaks are respectively endothermic peaks caused by physical acting force of the host and the guest and breakage of chemical acting force of the disulfide bond, which indicates that a plurality of bridging acting forces exist in the self-healing multi-bridging network chitosan-derivatized hydrogel structure in step six of example 1.
FIG. 15 is a thermogravimetric analysis curve of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1; it can be seen from the figure that the first significant mass reduction occurs at room temperature to 180 ℃ with a mass loss of about 7%, this partial weight loss being mainly due to water evaporation; the second obvious quality reduction occurs at 246.33 ℃ until the temperature is about 670.57 ℃ and gradually becomes gentle, the quality loss is about 50 percent, and the decomposition of bridging bonds in the gel structure mainly occurs at the stage corresponding to a differential scanning calorimetry spectrogram; the gel sample was heated to 1000 ℃ and the thermal decomposition was substantially complete.
FIG. 16 is an electron microscopic scan at 100X magnification of a self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1; FIG. 17 is an electron microscopic scan at 200X magnification of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1; FIG. 18 is a scanning electron microscope scan 500 times magnified of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1; from fig. 16 to 18, it can be seen that, through different magnification, the microstructure of the self-healing multi-bridging network chitosan-derivatized hydrogel obtained in the sixth step of example 1 shows a compact reticular pore structure, which is caused by the combined actions of host-guest interaction bridging, disulfide bridge bridging, and hydrogen bond bridging between hydroxyl oxygen and hydrogen.
FIG. 19 is a plot of swelling ratio versus time for the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1; and (3) weighing the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in the sixth step of the example 1, placing the self-healing multi-bridged network chitosan-derivatized hydrogel into deionized water, taking out the self-healing multi-bridged network chitosan-derivatized hydrogel at different time intervals, wiping off surface moisture by using filter paper, and weighing the self-healing multi-bridged network chitosan-derivatized hydrogel until the mass does not change any. As can be seen from the figure, the hydrogel continuously swells within 12h, and the swelling ratio reaches 300%, which shows that the obtained hydrogel has good swelling performance.
FIG. 20 is the elastic modulus versus time curve of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1 under cyclic compression; as can be seen from the figure, the elastic modulus of the hydrogel was maintained substantially constant at about 1500KPa by repeated compression at 37 ℃ and the hydrogel was found to have excellent mechanical properties.
Fig. 21 is a comparison graph of rheological property tests of example 1 and example 2, wherein ■ represents the storage modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1, □ represents the storage modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in example 2 after self-healing, and it can be seen from the graph that the storage modulus of the hydrogel is significantly greater than the loss modulus, which indicates that the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1 is in a good gel state and shows solid-like properties, and the storage modulus of the hydrogel has a certain frequency dependence, namely the storage modulus increases with increasing shear frequency, and is as low as 6.41KPa and as high as 10.1KPa, which indicates that the hydrogel has good rheological property, namely the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1 has good dynamic mechanical property.
FIG. 22 is a graph of the weight change over time in the degradability test for the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1; as can be seen from the figure, the hydrogel is continuously degraded within 40 days, and the degradation rate can reach 30 percent, which shows that the hydrogel has good biodegradability.
FIG. 23 is a graph of the biocompatibility test results of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in step six of example 1; as can be seen from the figure, the cells cultured for different times in the hydrogel environment all had higher survival rates, indicating that the hydrogel had good biocompatibility.
Example 2: testing self-healing characteristics:
placing the self-healing multi-bridging network chitosan-derivatized hydrogel obtained in the sixth step of the embodiment 1 in a plate, artificially breaking and damaging the self-healing multi-bridging network chitosan-derivatized hydrogel obtained in the sixth step of the embodiment 1, abutting, standing for 3 hours to obtain the self-healing multi-bridging network chitosan-derivatized hydrogel after self-healing, and then performing rheological property comparison test on the self-healing multi-bridging network chitosan-derivatized hydrogel obtained in the sixth step of the embodiment 1 and the self-healing multi-bridging network chitosan-derivatized hydrogel after self-healing by using a shear rheometer.
FIG. 24 is a physical change diagram of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in the sixth step of example 1, which is manually subjected to fracture damage and then left to stand for 6 hours after docking; as can be seen from the figure, after the self-healing multi-bridging network chitosan-derivatized hydrogel obtained in the sixth step in example 1 is artificially damaged, the self-healing multi-bridging network chitosan-derivatized hydrogel is butted for 6 hours, cracks of the self-healing multi-bridging network chitosan-derivatized hydrogel almost disappear after self-healing, the self-healing multi-bridging network chitosan-derivatized hydrogel is in a complete gel state, and the self-organization state can still be maintained under the action of gravity, which indicates that the self-healing multi-bridging network chitosan-derivatized hydrogel obtained in the sixth step in example 1 is self-restored after being damaged, and has good self-healing capability.
Fig. 25 is a comparative graph of rheological property tests, wherein ■ represents the storage modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in the sixth step of example 1, □ represents the storage modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in the sixth step of example 2, ▲ represents the loss modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in the sixth step of example 1, and △ represents the loss modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in the example 2, it can be known from the graph that the storage modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in the sixth step of example 1 and the storage modulus of the self-healing multi-bridged network chitosan-derivatized hydrogel obtained in the sixth step of example 2 are far greater than the loss modulus, which shows that the self-healing multi-bridged network chitosan-derivatized hydrogel has a solid-like property before and after self-healing, and under the condition of a shear frequency of 1Hz, the storage modulus of the self-healing multi-healing network chitosan-bridged network derivatized hydrogel obtained in the sixth step of example 1 is 8660Pa, and the storage modulus of the self-healing multi-bridged network derivatized hydrogel obtained after self-healing hydrogel has a reduction property of 7213 Pa.

Claims (8)

1. A self-healing multi-bridging network chitosan derivatization hydrogel is characterized in that the self-healing multi-bridging network chitosan derivatization hydrogel takes chitosan as a raw material, firstly O-carboxymethyl chitosan is obtained based on an etherification reaction between chloroacetic acid and chitosan, and the O-carboxymethyl chitosan simultaneously carries active carboxyl, hydroxyl and amino; then, introducing a cyclodextrin functional unit into an O-carboxymethyl chitosan structure by utilizing free radical polymerization reaction to obtain cyclodextrin carboxymethyl chitosan; secondly, introducing sulfydryl into a cyclodextrin carboxymethyl chitosan structure by using an amidation reaction to obtain thiolated cyclodextrin carboxymethyl chitosan, wherein the thiolated cyclodextrin carboxymethyl chitosan simultaneously carries active carboxyl, sulfydryl and cyclodextrin functional units; introducing a ferrocene functional unit into a polyacrylamide structure to obtain polyacrylamide-ferrocene; mixing thiolated cyclodextrin carboxymethyl chitosan and polyacrylamide-ferrocene, and bridging by utilizing the interaction between a cyclodextrin functional unit and a host and an object between the ferrocene, bridging by utilizing a dimercapto disulfide bond on the thiolated cyclodextrin carboxymethyl chitosan and bridging by utilizing a hydrogen bond between hydroxyl oxygen and hydrogen to obtain the multi-bridge networking hydrogel, namely the self-healing multi-bridge networking chitosan-derived hydrogel.
2. A self-healing multi-bridged network chitosan-derivatized hydrogel according to claim 1, wherein the chitosan has a deacetylation degree of 90% and a molecular weight of 80000 to 140000.
3. The method for preparing a self-healing multi-bridging-network chitosan-derivatized hydrogel according to claim 1, wherein the method for preparing the self-healing multi-bridging-network chitosan-derivatized hydrogel comprises the following steps:
①, dispersing chitosan in isopropanol, stirring and reacting for 30-60 min under the conditions of temperature of 20-26 ℃ and rotating speed of 800-1300 r/min to obtain an isopropanol solution of chitosan, wherein the concentration of chitosan in the isopropanol solution of chitosan is 0.3 mmol/L-1.2 mmol/L, ②, adding a sodium hydroxide aqueous solution into the isopropanol solution of chitosan 4-6 times, stirring and reacting for 30-60 min under the conditions of temperature of 20-26 ℃ and rotating speed of 800-1300 r/min to obtain a reaction solution I, wherein the concentration of sodium hydroxide in the sodium hydroxide aqueous solution is 8 mol/L-12 mol/L, the volume ratio of the sodium hydroxide aqueous solution to the isopropanol solution of chitosan is 1 (3-5), ③, dissolving chloroacetic acid in the isopropanol to obtain an isopropanol solution of chloroacetic acid, adding the isopropanol solution of chloroacetic acid into a blowing reaction tank, washing the isopropanol solution of chloroacetic acid for 1-35 min, washing the isopropanol solution of chloroacetic acid, and drying the product of the obtained by reaction at 354-2 mol/1-1300 r of chloroacetic acid, and drying the obtained product of chloroacetic acid in a blowing reaction tank to obtain a reaction solution of chloroacetic acid, wherein the product is obtained by stirring and the reaction solution of chloroacetic acid, and the reaction product obtained by stirring and the reaction is carried out the reaction at the temperature of 20-26 r/2-1-35 m of isopropanol solution I, and the reaction solution of chloroacetic acid is obtained by stirring and the reaction solution of chloroacetic acid, and the reaction solution of chloroacetic acid is obtained by stirring and the reaction solution of chloroacetic acid is carried out reaction solution of acetic acid, and the reaction product obtained by reaction solution of;
①, dissolving β -cyclodextrin in 25% ethanol solution to obtain β -cyclodextrin ethanol solution, adding itaconic acid, and stirring and reacting for 1-3 hours under the conditions that the temperature is 90-100 ℃ and the rotating speed is 1000-1300 r/min to obtain reaction solution II, wherein the 25% ethanol solution is prepared from deionized water and ethanol according to the volume ratio of 3:1, the concentration of β -cyclodextrin in the β -cyclodextrin ethanol solution is 16 mmol/L-18 mmol/L, the molar ratio of β -cyclodextrin to itaconic acid in β -cyclodextrin ethanol solution is 1:1, ②, carrying out rotary drying on the solvent of the reaction solution II by using a vacuum rotary evaporator to obtain a reaction product, placing the reaction product in a Soxhlet extractor, extracting by using isopropanol for 5-7 hours to obtain a reaction product, wherein the vacuum rotary evaporator is 0.09MPa to 0.1MPa in vacuum degree, the temperature is 50 ℃ and the temperature is 50-70 ℃, and drying the reaction product in a white extraction tank to obtain white itaconate, and drying the product at the temperature of 50-3- β 0 ℃ to obtain white itaconate;
①, dissolving O-carboxymethyl chitosan in a hydrochloric acid solution to obtain a hydrochloric acid solution of carboxymethyl chitosan, adding ammonium nitrate and vinyl-cyclodextrin-itaconate, stirring and reacting for 2-5 h under the conditions that the temperature is 20-25 ℃ and the rotating speed is 800-1300 r/min to obtain a reaction product, wherein the concentration of hydrochloric acid in the hydrochloric acid solution is 0.1 mol/L-0.3 mol/L, the concentration of O-carboxymethyl chitosan in the hydrochloric acid solution of carboxymethyl chitosan is 0.5 mmol/L-3 mmol/L, the molar ratio of O-carboxymethyl chitosan to vinyl-cyclodextrin-itaconate in the hydrochloric acid solution of carboxymethyl chitosan is 1 (200-600), the mass ratio of O-carboxymethyl chitosan in the hydrochloric acid solution of ammonium nitrate to carboxymethyl chitosan is 1 (1-2), ②, transferring the reaction product into a dialysis bag, and dialyzing the molecular weight of the dialysis bag is 4000-3000 h, dialyzing the reaction bag for 48-24 h to obtain a pale yellow cyclodextrin freeze-dialyzed product, and drying the product to obtain a product;
preparing thiolated cyclodextrin carboxymethyl chitosan L, dissolving N-acetyl-L-cysteine in distilled water, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide to obtain an aqueous solution of N-acetyl-L-cysteine, stirring and reacting for 20-40 min under the conditions that the temperature is 20-25 ℃ and the rotating speed is 600-1200 r/min to obtain a reaction solution III, dialyzing the aqueous solution of N-acetyl-L-cysteine with the concentration of 0.5 mol/L-1 mol/L, dialyzing the aqueous solution of N-acetyl-L-cysteine with the concentration of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride in the aqueous solution of N-acetyl-L-cysteine 0-638-0.5 mol/366, dialyzing the aqueous solution of N-acetyl-631-cysteine with the concentration of 0.1 mol/L mol/368 mol/600 mol/2000 mol/600-2000 mol/2000 min to obtain a product III, dialyzing the aqueous solution of N-acetyl-L-cysteine with the concentration of 0.5-5 mol/468, dialyzing the aqueous solution of chitosan with the concentration of carboxymethyl chitosan under the concentration of 20-600-200 mol/600-1200 r/10 h, dialyzing the aqueous solution of chitosan, dialyzing the product with the concentration of carboxymethyl chitosan, dialyzing the aqueous solution of carboxymethyl chitosan, dialyzing the product with the concentration of carboxymethyl chitosan under the concentration of carboxymethyl chitosan, dialyzing unit, the concentration of carboxymethyl chitosan, dialyzing the concentration of carboxymethyl chitosan, the concentration of carboxymethyl chitosan, dialyzing the product III, the concentration of the aqueous solution of carboxymethyl chitosan, the product III, dialyzing the concentration of carboxymethyl chitosan, the concentration of carboxymethyl chitosan, the concentration of carboxymethyl chitosan, the concentration of chitosan, the concentration of the chitosan, the chitosan;
preparing polyacrylamide-ferrocene ①, redistilling dichloromethane with calcium chloride to obtain anhydrous dichloromethane ②, dissolving ferrocenecarboxylic acid in anhydrous dichloromethane to obtain dichloromethane solution of ferrocenecarboxylic acid, adding oxalyl chloride, and performing N-phase reaction at 40-50 deg.C and 1000-1600 r/min2Stirring and reacting for 2-4 h under the atmosphere to obtain a primary reaction solution, wherein the concentration of ferrocenecarboxylic acid in the dichloromethane solution of the ferrocenecarboxylic acid is 60 mmol/L-80 mmol/L, the molar ratio of oxalyl chloride to the ferrocenecarboxylic acid is 1 (2-3), ③, removing dichloromethane from the primary reaction solution by adopting a vacuum rotary evaporator to obtain a primary reaction product, the vacuum rotary evaporator is under the conditions that the vacuum degree is 0.09-0.1 MPa and the temperature is 30-50 ℃, ④, dissolving the primary reaction product in anhydrous dichloromethane containing triethylamine, adding polyacrylamide, and reacting at the temperature of 20-25 ℃, the rotating speed of 600-1200 r/min and N2Stirring and reacting for 10-15 h under the atmosphere to obtain a reaction solution IV, wherein the volume fraction of triethylamine in the anhydrous dichloromethane containing triethylamine is 4-8%, the mass ratio of the volume of the anhydrous dichloromethane containing triethylamine to a primary reaction product is (25-40): 1, the mass ratio of polyacrylamide to the primary reaction product is 1 (5-10), ⑤, washing the reaction solution IV by deionized water for 3-5 times, standing and layering, collecting a dichloromethane layer, evaporating dichloromethane to obtain a reaction product, washing the reaction product by a mixed solution of hexane and ethyl acetate, centrifugally collecting precipitates at the temperature of 10-25 ℃ and the rotating speed of 3000 r/min-4000 r/min, drying in a blast drying box at the temperature of 30-50 ℃ to obtain yellowish-brown powder, namely polyacrylamide-ferrocene, and the volume ratio of hexane to ethyl acetate in the mixed solution of hexane and ethyl acetate is (8-9): 2-1);
sixthly, preparing the hydrogel material: respectively preparing polyacrylamide-ferrocene and thiolated cyclodextrin carboxymethyl chitosan into aqueous solutions, uniformly mixing and standing to obtain the self-healing multi-bridged network chitosan-derivatized hydrogel.
4. The preparation method of the self-healing multi-bridged network chitosan-derivatized hydrogel according to claim 3, wherein in step three ①, the reaction is carried out for 3h to 5h under the conditions of a temperature of 20 ℃ to 25 ℃ and a rotation speed of 800r/min to 1000r/min, so as to obtain a reaction product, wherein the molar ratio of O-carboxymethyl chitosan to vinyl-cyclodextrin-itaconate in the hydrochloric acid solution of carboxymethyl chitosan is 1 (300-500).
5. The preparation method of the self-healing multi-bridged network chitosan-derivatized hydrogel according to claim 3, characterized in that in step four ②, the reaction is carried out for 5 to 8 hours under the conditions of a temperature of 30 to 40 ℃ and a rotation speed of 600 to 900r/min, and a reaction product is obtained, wherein the molar ratio of N-acetyl-L-cysteine to cyclodextrin carboxymethyl chitosan in the hydrochloric acid solution of cyclodextrin carboxymethyl chitosan in the aqueous solution of N-acetyl-L-cysteine is (200 to 400): 1.
6. The preparation method of the self-healing multi-bridged network chitosan-derivatized hydrogel according to claim 3, wherein in step four ②, the reaction is carried out for 5 to 8 hours under the conditions of a temperature of 25 to 30 ℃ and a rotation speed of 900 to 1300r/min, and a reaction product is obtained, wherein the molar ratio of N-acetyl-L-cysteine to cyclodextrin carboxymethyl chitosan in the hydrochloric acid solution of cyclodextrin carboxymethyl chitosan is (400 to 600): 1.
7. The method for preparing a self-healing multi-bridged network chitosan-derivatized hydrogel according to claim 3, wherein the average molecular weight of the polyacrylamide in step five ④ is 100 ten thousand, and the nucleophilic substitution reaction is employed to introduce the ferrocene functional unit in the first-order reaction product to the amino group of the polyacrylamide.
8. The preparation method of the self-healing multi-bridged network chitosan-derivatized hydrogel according to claim 3, which is characterized in that in the sixth step, polyacrylamide-ferrocene and thiolated cyclodextrin carboxymethyl chitosan are respectively prepared into aqueous solutions, uniformly mixed and stood to obtain the self-healing multi-bridged network chitosan-derivatized hydrogel, and the specific processes are ①, dissolving polyacrylamide-ferrocene in distilled water to obtain a polyacrylamide-ferrocene aqueous solution with the mass fraction of 3% -5%, ②, dissolving thiolated cyclodextrin carboxymethyl chitosan in distilled water to obtain a thiolated cyclodextrin carboxymethyl chitosan aqueous solution with the mass fraction of 3% -5%, and ③, the thiolated cyclodextrin carboxymethyl chitosan aqueous solution and the polyacrylamide-ferrocene aqueous solution are uniformly mixed according to the volume ratio of 1:1 and stood for 6 h-12 h to obtain the self-healing multi-bridged network chitosan-derivatized hydrogel.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113321753A (en) * 2021-05-19 2021-08-31 山东滨州智源生物科技有限公司 Preparation method of poly glycosyl amino acid cyclodextrin derivative and hydrogel
CN115337272A (en) * 2022-07-15 2022-11-15 汕头大学 Natural polysaccharide-based chemical-physical double-crosslinking hydrogel particle and preparation and application thereof
CN115746167A (en) * 2022-10-31 2023-03-07 中国科学院大学 Room-temperature phosphorescent material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101693125A (en) * 2009-10-12 2010-04-14 北京科技大学 Process for preparing biocompatible directional carbon nanotube array reinforced composite hydrogel
US20150110772A1 (en) * 2012-02-20 2015-04-23 Cambridge Enterprise Limited Cucurbituril-based hydrogels
US20190143302A1 (en) * 2017-11-13 2019-05-16 Honeywell International Inc. Gels for removing air pollutants
CN110204742A (en) * 2019-07-15 2019-09-06 吉林大学 A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101693125A (en) * 2009-10-12 2010-04-14 北京科技大学 Process for preparing biocompatible directional carbon nanotube array reinforced composite hydrogel
US20150110772A1 (en) * 2012-02-20 2015-04-23 Cambridge Enterprise Limited Cucurbituril-based hydrogels
US20190143302A1 (en) * 2017-11-13 2019-05-16 Honeywell International Inc. Gels for removing air pollutants
CN110204742A (en) * 2019-07-15 2019-09-06 吉林大学 A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
VENKANNA AZMEERA等: "Solution and microwave assisted synthesis of β-Cyclodextrin grafted polyacrylamide: Water treatment and In-vitro drug release study", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 *
王笑: "新型功能修饰壳聚糖衍生化水凝胶合成制备及性能研究", 《万方数据库》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113321753A (en) * 2021-05-19 2021-08-31 山东滨州智源生物科技有限公司 Preparation method of poly glycosyl amino acid cyclodextrin derivative and hydrogel
CN115337272A (en) * 2022-07-15 2022-11-15 汕头大学 Natural polysaccharide-based chemical-physical double-crosslinking hydrogel particle and preparation and application thereof
CN115337272B (en) * 2022-07-15 2023-08-04 汕头大学 Natural polysaccharide-based chemical-physical double-crosslinked hydrogel particles and preparation and application thereof
CN115746167A (en) * 2022-10-31 2023-03-07 中国科学院大学 Room-temperature phosphorescent material and preparation method and application thereof
CN115746167B (en) * 2022-10-31 2023-11-14 中国科学院大学 Room-temperature phosphorescent material, and preparation method and application thereof

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