CN116531554A - Visual double-network hydrogel and preparation method and application thereof - Google Patents

Visual double-network hydrogel and preparation method and application thereof Download PDF

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Publication number
CN116531554A
CN116531554A CN202310563714.2A CN202310563714A CN116531554A CN 116531554 A CN116531554 A CN 116531554A CN 202310563714 A CN202310563714 A CN 202310563714A CN 116531554 A CN116531554 A CN 116531554A
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mixed solution
hydrogel
polyethylene glycol
visualized
network
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吕建华
吴攀
赵岩
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Ji Hua Laboratory
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Ji Hua Laboratory
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061Use of materials characterised by their function or physical properties
    • A61L26/008Hydrogels or hydrocolloids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0009Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
    • A61L26/0023Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061Use of materials characterised by their function or physical properties
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention provides a visual double-network hydrogel and a preparation method and application thereof, and relates to the technical field of biomedical materials. According to the method, modified anionic polyelectrolyte, carboxymethyl chitosan and a cross-linking agent are mixed in deionized water and dissolved, then an initiator is added to obtain a prepolymer solution, wherein the cross-linking agent and the modified anionic polyelectrolyte/carboxymethyl chitosan are subjected to cross-linking reaction to form a reactant with a covalent cross-linking network, amino groups in carboxymethyl chitosan chain segments are protonated after acetic acid fumigation, and then the amino groups are combined with carboxyl groups in the modified anionic polyelectrolyte chain segments by means of electrostatic interaction force to form a polyelectrolyte network, so that the hydrogel with a double-network structure is finally obtained. The mechanical property of the hydrogel prepared by the method is greatly improved, and the hydrogel has high light transmittance, so that the wound healing condition can be observed through the dressing on the premise of not uncovering the dressing when the hydrogel is used as the dressing.

Description

Visual double-network hydrogel and preparation method and application thereof
Technical Field
The invention relates to the technical field of biomedical materials, in particular to a visual double-network hydrogel and a preparation method and application thereof.
Background
In the prior art, there are two main types of wound dressings:
1. traditional dressings, such as dry gauze and oilyarn, etc.; however, such conventional dressings have only a limited protective effect by covering injuries and absorbing wound exudates;
2. novel dressings such as foam dressing, hydrogel dressing, silver ion dressing, and the like; the novel dressing can not only play a role of a traditional dressing, but also prevent bacteria from invading to achieve the effect of reducing wound infection, simultaneously allow gas exchange, can maintain a wet environment, is beneficial to protecting new granulation tissues and achieves the effect of promoting wound healing.
The most representative of hydrogel dressing is polysaccharide-based polyelectrolyte hydrogel, which is a polyelectrolyte network composed of natural polysaccharide (or artificial synthesis), and has good biocompatibility, liquid absorption and environmental sensitivity due to the existence of a large number of active functional groups such as amino, amide, carboxyl, hydroxyl and the like on the sugar chain and electrostatic interaction. The hydrogel is used as an excellent carrier for drug release, has good permeability to low molecular weight drug solutes, and also endows the drug delivery system with functions. Therefore, polysaccharide-based polyelectrolyte hydrogels are widely used in the field of wound repair as wound dressings.
However, since the polysaccharide-based polyelectrolyte hydrogel is formed by electrostatic interaction forces between different functional groups of different components, the components in the hydrogel are unevenly distributed due to the electrostatic interaction, and the mechanical properties and the light transmittance of the hydrogel are poor, so that the hydrogel is easy to break and when the hydrogel is used as a dressing, the wound healing condition is difficult to visually observe through the dressing.
In view of the above problems, no effective technical solution is currently available.
Disclosure of Invention
The invention aims to provide a visual double-network hydrogel, a preparation method and application thereof, which greatly improve the mechanical properties of the traditional hydrogel dressing, and simultaneously have high light transmittance, and when the visual double-network hydrogel is used as a dressing, the healing condition of a wound can be directly observed through the dressing.
In a first aspect, the invention provides a method for preparing a visual double-network hydrogel, comprising the following steps:
s1, mixing and dissolving modified anionic polyelectrolyte, carboxymethyl chitosan and a cross-linking agent in deionized water, and then adding an initiator to obtain a prepolymer solution;
s2, vacuumizing the prepolymer solution to remove residual air in the solution;
s3, sealing the prepolymer solution subjected to the vacuumizing treatment, and placing the prepolymer solution under a preset temperature condition for reacting for a first preset time to obtain a reactant;
s4, placing the reactant in acetic acid atmosphere, fumigating for a second preset time, and obtaining the hydrogel dressing.
According to the preparation method of the visual double-network hydrogel, a covalent cross-linking network is introduced on the basis of a polyelectrolyte network to form a double-network structure, so that the microstructure of the hydrogel is changed, the mechanical property of the dressing is greatly improved, and the dressing has high compressive strength, high elastic modulus and high elongation at break; the change of the microstructure simultaneously ensures that the wound has high light transmittance, and when the wound is used as a dressing, the healing condition of the wound can be observed on the premise of not uncovering the dressing, so that the secondary damage of the wound surface is avoided.
Further, the specific steps in step S1 include:
s11, mixing 0.5-5 parts of the modified anionic polyelectrolyte, 0.5-5 parts of the carboxymethyl chitosan and 100 parts of the deionized water to prepare a first mixed solution;
s12, adding the cross-linking agent into the first mixed solution, and mixing to obtain a second mixed solution;
s13, adding 0.1-0.3 part of the initiator into the second mixed solution, and mixing to obtain the prepolymer solution.
The obtained hydrogel has good mechanical properties (high compressive strength, high elastic modulus, high elongation at break and the like) and light transmittance.
Further, the cross-linking agent is any one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, multi-arm polyethylene glycol acrylate, methacrylic amylopectin, methacrylic cellulose, dialdehyde polyethylene glycol, dimercapto polyethylene glycol, dialdehyde cellulose, dialdehyde-beta-cyclodextrin and dialdehyde dextran.
Further, the specific steps in step S12 include:
S12A, adding 0.1-1 part of polyethylene glycol diacrylate with the relative molecular weight of 200-4000 Da into the first mixed solution, and mixing to obtain the second mixed solution.
Further, the specific steps in step S12 include:
S12B, adding 0.1-1 part of polyethylene glycol dimethacrylate with the relative molecular weight of 550-10000 Da into the first mixed solution, and mixing to obtain the second mixed solution.
Further, the multi-arm polyethylene glycol acrylate comprises a four-arm polyethylene glycol acrylate;
the specific steps in step S12 include:
S12C, adding-0.1-1 part of quadrifilar polyethylene glycol acrylate with the relative molecular weight of 2000-10000 Da into the first mixed solution, and mixing to obtain the second mixed solution.
The comparison experiment results prove that the covalent cross-linked network can reduce the risk of excessive imbibition and swelling of the hydrogel.
Further, the specific steps in step S12 include:
S12D, adding 0.1-1 part of dialdehyde polyethylene glycol with the relative molecular weight of 400-20000 Da into the first mixed solution, and mixing to obtain the second mixed solution.
Further, the specific steps in step S12 include:
S12E, adding 0.1-1 part of dimercapto polyethylene glycol with the relative molecular weight of 400-20000 Da into the first mixed solution, and mixing to obtain the second mixed solution.
In a second aspect, the invention also provides a visualized double-network hydrogel, which is prepared by any one of the preparation methods of the visualized double-network hydrogel.
The visual double-network hydrogel has good mechanical property and high light transmittance, and when the visual double-network hydrogel is used as a dressing, a user can observe the healing condition of a wound on the premise of not uncovering the dressing.
In a third aspect, the invention also provides the application of the visualized double-network hydrogel in dressing.
From the above, the preparation method of the visual double-network hydrogel introduces a covalent cross-linking network on the basis of a polyelectrolyte network, so as to form a double-network structure, change the microstructure of the hydrogel and further greatly improve the mechanical property of the hydrogel; meanwhile, due to the change of the microstructure, the hydrogel has high light transmittance, when the hydrogel is used as a dressing, a user can observe the healing condition of a wound on the premise of not uncovering the dressing, and secondary damage of the wound surface is avoided; in addition, the double-network structure can effectively avoid excessive imbibition and swelling of the hydrogel during use, so that the service life of the dressing is greatly prolonged.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the embodiments of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
Fig. 1 is a flowchart of a method for preparing a visualized dual-network hydrogel according to an embodiment of the present invention.
Fig. 2 is a schematic diagram illustrating microstructure adjustment of a visualized dual-network hydrogel according to an embodiment of the present invention.
FIG. 3 is a scanning pattern of hydrogels prepared according to comparative example 1 and examples 1 to 6 of the present invention.
FIG. 4 is a graph showing the transmittance of the hydrogels prepared according to comparative example 1 and examples 1 to 6 of the present invention.
FIG. 5 is a graph showing the comparison of the water absorption rates of hydrogels prepared in accordance with comparative example 1 and examples 1 to 6 of the present invention.
FIG. 6 is a first comparative graph of mechanical properties of hydrogels prepared according to comparative example 1 and examples 1-6 of the present invention.
FIG. 7 is a second comparative graph showing the mechanical properties of hydrogels prepared according to comparative example 1 and examples 1 to 6 of the present invention.
FIG. 8 is a graph showing the comparison of drug release properties of hydrogel dressings prepared in accordance with comparative example 1 and examples 1 to 6 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures. Meanwhile, in the description of the present invention, the terms "first", "second", and the like are used only to distinguish the description, and are not to be construed as indicating or implying relative importance.
Referring to fig. 1, fig. 1 is a flow chart of a method for preparing a visualized dual-network hydrogel. The preparation method of the visual double-network hydrogel comprises the following steps:
s1, mixing and dissolving modified anionic polyelectrolyte, carboxymethyl chitosan and a cross-linking agent in deionized water, and then adding an initiator to obtain a prepolymer solution;
s2, vacuumizing the prepolymer solution to remove residual air in the solution;
s3, sealing the prepolymer solution subjected to the vacuumizing treatment and placing the prepolymer solution at a preset temperature (for example, but not limited to 60 ℃, and the following examples are exemplified by 60 ℃) for a first preset time to obtain a reactant;
s4, placing the reactant in acetic acid atmosphere, fumigating for a second preset time, and obtaining the hydrogel dressing.
In the prior art, modified anionic polyelectrolyte and carboxymethyl chitosan react under certain conditions to form a polyelectrolyte network, but the polyelectrolyte network is formed by electrostatic interaction forces among different functional groups among different components, and belongs to a disordered and uneven three-dimensional network structure, so that the mechanical property and the light transmittance are poor.
In this embodiment, a cross-linking agent is added to perform a cross-linking reaction with the modified anionic polyelectrolyte (or carboxymethyl chitosan), so that a portion of the polysaccharide chain segments are immobilized, and a hydrogel (i.e., a reactant) with a covalent cross-linking network is obtained, after that, the reactant is placed in an acetic acid atmosphere, so that the amino groups in the carboxymethyl chitosan chain segments are protonated, and then are combined with the carboxyl groups in the modified anionic polyelectrolyte chain segments by means of electrostatic interaction force, so as to form a polyelectrolyte network, thereby obtaining a visualized double-network hydrogel (when the hydrogel is applied as a dressing, the dressing is hereinafter simply referred to as a hydrogel dressing).
According to the embodiment, a covalent cross-linking network is introduced on the basis of an original polyelectrolyte network, and the modified anionic polyelectrolyte chain segments (or carboxymethyl chitosan chain segments) are fixed in advance, so that the polyelectrolyte network formed later is uniformly distributed in gel, and the light transmittance of the hydrogel dressing is increased; meanwhile, the hydrogel has a double-network structure due to the introduction of the covalent cross-linking network, so that the mechanical property of the hydrogel is greatly improved, the risk of excessive imbibition and swelling of the hydrogel is reduced, and the replacement times of hydrogel dressing are further reduced (the conventional hydrogel dressing cannot be normally used due to excessive imbibition and swelling, and only a new hydrogel dressing can be replaced).
Referring to fig. 2, fig. 2 discloses a microstructure of hydrogel obtained by mixing a modified anionic polyelectrolyte with carboxymethyl chitosan in a prior art manner, reacting to obtain a first mixed solution, and then placing the first mixed solution in an acetic acid atmosphere for fumigation; meanwhile, the change process of the microstructure in the preparation process of the visual double-network hydrogel is also disclosed.
The circular marks in fig. 2 are related chemical bonds which generate electrostatic interaction force between different functional groups among different components in the polyelectrolyte network; triangle marks are the relevant chemical bonds of the covalent cross-linking network where the modified anionic polyelectrolyte chain segments (or carboxymethyl chitosan chain segments) are fixed.
Further, the modified anionic polyelectrolyte is any one of modified sodium alginate, modified carrageenan and modified hyaluronate (but not limited to the above, and also comprises other hydrophilic polyanion biological macromolecules). The modified starch is prepared by adding methacrylic anhydride into alginate, sodium hyaluronate, carrageenan, sodium carboxymethyl cellulose, sodium carboxymethyl starch and carboxymethyl pachyman, and is not described in detail in the prior art.
Further, the cross-linking agent is any one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, multi-arm polyethylene glycol acrylate, methacrylic acid amylopectin, methacrylic acid cellulose, dialdehyde polyethylene glycol, dimercapto polyethylene glycol, dialdehyde cellulose, dialdehyde-beta-cyclodextrin and dialdehyde dextran.
Wherein the multi-arm polyethylene glycol acrylate is, for example, four-arm polyethylene glycol acrylate, six-arm polyethylene glycol acrylate and the like; methacrylic acid amylopectin and methacrylic acid cellulose are modified biological macromolecules; dialdehyde cellulose, dialdehyde-beta-cyclodextrin, dialdehyde dextran are dialdehyde polysaccharides.
Further, the initiator is any one of ammonium persulfate, potassium persulfate and sodium persulfate. In actual preparation, the polymerization of reactants can be accelerated by adding TEMED (tetramethyl ethylenediamine) as a catalyst to catalyze an initiator to generate free radicals.
Further, the first preset time is 6 hours, and the second preset time is 12 hours, but not limited thereto.
In certain embodiments, the specific steps in step S1 comprise:
s11, mixing 0.5-5 parts of the modified anionic polyelectrolyte, 0.5-5 parts of the carboxymethyl chitosan and 100 parts of the deionized water to prepare a first mixed solution;
s12, adding the cross-linking agent into the first mixed solution, and mixing to obtain a second mixed solution;
s13, adding 0.1-0.3 part of the initiator into the second mixed solution, and mixing to obtain the prepolymer solution.
In this embodiment, the first mixed solution prepared by mixing the modified anionic polyelectrolyte and the carboxymethyl chitosan does not initiate a reaction to form a polyelectrolyte network when the reaction condition is not satisfied, but the mixing ratio of the modified anionic polyelectrolyte and the carboxymethyl chitosan needs to be prepared in advance to ensure the quality of the polyelectrolyte network formed subsequently.
Adding a proper amount of cross-linking agent and initiator to obtain a prepolymer solution, and then initiating reaction by controlling reaction conditions to obtain the hydrogel dressing;
specifically, after vacuumizing treatment, placing the prepolymer solution at 60 ℃ to initiate a crosslinking reaction to form a reactant; and then placing the reactant in acetic acid atmosphere for fumigation, and initiating polymerization reaction to form the visual double-network hydrogel.
Comparative example 1 (prior art means):
referring to fig. 3, fig. 4, fig. 5, fig. 6 and fig. 7,5 parts of modified anionic polyelectrolyte and 5 parts of carboxymethyl chitosan were mixed with 100 parts of deionized water to prepare a first mixed solution, which was then fumigated in an acetic acid atmosphere, and the resulting hydrogel was poor in mechanical properties, low in light transmittance (light transmittance at 600nm was only 23.74%), and 64.36 times in water absorption (water absorption was related to swelling by imbibition).
The hydrogel prepared in comparative example 1 corresponds to the partial schematic diagram denoted by a in fig. 3, the curve denoted by CM in fig. 4, the column denoted by CM in fig. 5, the curve denoted by CM in fig. 6, the column denoted by CM in fig. 7, and the curve denoted by CM in fig. 8.
It should be noted that the mechanical properties of the hydrogel can be evaluated according to the values shown in fig. 6 (stress-strain data) and fig. 7 (compressive strength data, elastic modulus data and elongation at break data).
Example 1:
referring to fig. 3, fig. 4, fig. 5, fig. 6 and fig. 7,5 parts of modified anionic polyelectrolyte and 5 parts of carboxymethyl chitosan are mixed with 100 parts of deionized water to prepare a first mixed solution, then 1 part of polyethylene glycol diacrylate with a relative molecular weight of 200-4000 Da is added and mixed to obtain a second mixed solution, step S13 is performed, after the reaction condition is controlled according to step S3 to initiate the crosslinking reaction, the second mixed solution is placed in an acetic acid atmosphere according to step S4 to fumigate, and compared with comparative example 1, the mechanical properties of the obtained visualized double-network hydrogel are slightly improved, and the light transmittance is improved (the light transmittance at 600nm reaches 93.39%).
The visualized dual-network hydrogel prepared in example 1 corresponds to the partial schematic diagram denoted by b in fig. 3, the curve denoted by CMP1 in fig. 4, the column denoted by CMP1 in fig. 5, the curve denoted by CMP1 in fig. 6, the column denoted by CMP1 in fig. 7, and the curve denoted by CMP1 in fig. 8.
Example 2:
referring to fig. 3, fig. 4, fig. 5, fig. 6 and fig. 7,5 parts of modified anionic polyelectrolyte and 5 parts of carboxymethyl chitosan are mixed with 100 parts of deionized water to prepare a first mixed solution, then 1 part of polyethylene glycol dimethacrylate with a relative molecular weight of 550-10000 Da is added, the second mixed solution is obtained by mixing, step S13 is executed, after the crosslinking reaction is initiated according to the reaction condition controlled in step S3, the mixture is placed in an acetic acid atmosphere for fumigation according to step 4, and compared with comparative example 1, the mechanical property and the light transmittance of the obtained visual double-network hydrogel are greatly improved.
The visualized dual-network hydrogel prepared in example 2 corresponds to the partial schematic diagram denoted by c in fig. 3, the curve denoted by CMP2 in fig. 4, the column denoted by CMP2 in fig. 5, the curve denoted by CMP2 in fig. 6, the column denoted by CMP2 in fig. 7, and the curve denoted by CMP2 in fig. 8.
Example 3:
referring to fig. 3, fig. 4, fig. 5, fig. 6 and fig. 7,5 parts of the modified anionic polyelectrolyte and 5 parts of carboxymethyl chitosan are mixed with 100 parts of deionized water to prepare a first mixed solution, then 1 part of polyethylene glycol diacrylate having a relative molecular weight of 200-4000 Da is added and mixed to obtain a second mixed solution, and step S13 is performed and only a crosslinking reaction is initiated according to the reaction conditions controlled in step S3, thereby obtaining a reactant (the hydrogel having a covalent crosslinked network obtained by the crosslinking reaction itself is a hydrogel but does not have a double network structure), which has substantially improved chemical properties (compressive strength is improved to 3 times), and light transmittance is improved compared with comparative example 1.
The covalent cross-linked network introduced by the embodiment can improve the mechanical property and the light transmittance of the hydrogel.
The hydrogel prepared in example 3 corresponds to the partial schematic diagram denoted by d in fig. 3, the curve denoted by CMP in fig. 4, the column denoted by CMP in fig. 5, the curve denoted by CMP in fig. 6, the column denoted by CMP in fig. 7, and the curve denoted by CMP in fig. 8.
Example 4:
referring to fig. 3, fig. 4, fig. 5, fig. 6 and fig. 7,5 parts of modified anionic polyelectrolyte and 5 parts of carboxymethyl chitosan are mixed with 100 parts of deionized water to prepare a first mixed solution, then 1 part of quadrifilar polyethylene glycol acrylate with a relative molecular weight of 2000-10000 Da is added, the mixture is mixed to obtain a second mixed solution, step S13 is executed, after the crosslinking reaction is initiated according to the reaction condition controlled in step S3, the mixture is placed in an acetic acid atmosphere for fumigation according to step S4, and compared with comparative example 1, the obtained visualized double-network hydrogel has the advantages of greatly improved mechanical properties (the compressive strength is improved to 8.15 times, the elastic modulus is improved to 19.70 times, the elongation at break is improved to 7.56 times), the light transmittance is improved, and the water absorption rate is 30.11 times (the liquid absorption swelling behavior is effectively controlled).
The present example demonstrates that the introduction of a covalently crosslinked network can reduce the risk of excessive imbibition swelling of the hydrogel.
The visualized dual-network hydrogel prepared in example 4 corresponds to the partial schematic view labeled e in fig. 3, the curve labeled CMP3 in fig. 4, the column labeled CMP3 in fig. 5, the curve labeled CMP3 in fig. 6, the column labeled CMP3 in fig. 7, and the curve labeled CMP3 in fig. 8.
Example 5:
referring to fig. 3, fig. 4, fig. 5, fig. 6 and fig. 7,5 parts of modified anionic polyelectrolyte and 5 parts of carboxymethyl chitosan are mixed with 100 parts of deionized water to prepare a first mixed solution, then 1 part of dialdehyde polyethylene glycol with the relative molecular weight of 400-20000 Da is added, the second mixed solution is obtained by mixing, step S13 is executed, after the crosslinking reaction is initiated according to the reaction condition controlled in step S3, the mixture is placed in an acetic acid atmosphere for fumigation according to step 4, and compared with comparative example 1, the mechanical property and the light transmittance of the obtained visual double-network hydrogel are greatly improved.
The visualized dual-network hydrogel prepared in example 5 corresponds to the partial schematic diagram denoted by f in fig. 3, the curve denoted by CMP4 in fig. 4, the column denoted by CMP4 in fig. 5, the curve denoted by CMP4 in fig. 6, the column denoted by CMP4 in fig. 7, and the curve denoted by CMP4 in fig. 8.
Example 6:
referring to fig. 3, fig. 4, fig. 5, fig. 6 and fig. 7,5 parts of modified anionic polyelectrolyte and 5 parts of carboxymethyl chitosan are mixed with 100 parts of deionized water to prepare a first mixed solution, then 1 part of dimercapto polyethylene glycol with a relative molecular weight of 400-20000 Da is added, the second mixed solution is obtained by mixing, step S13 is performed, after the crosslinking reaction is initiated according to the reaction condition controlled in step S3, the obtained mixture is placed in an acetic acid atmosphere for fumigation according to step S4, and compared with comparative example 1, the mechanical properties of the obtained visualized double-network hydrogel are greatly improved, but compared with example 4, the light transmittance of the visualized double-network hydrogel is slightly reduced (the light transmittance at 600nm reaches 87.15%).
The visualized dual-network hydrogel prepared in example 6 corresponds to the partial schematic diagram denoted by g in fig. 3, the curve denoted by CMP5 in fig. 4, the column denoted by CMP5 in fig. 5, the curve denoted by CMP5 in fig. 6, the column denoted by CMP5 in fig. 7, and the curve denoted by CMP5 in fig. 8.
The invention also provides the visualized double-network hydrogel, which is prepared by the preparation method of the visualized double-network hydrogel in the embodiment.
The visual double-network hydrogel has good mechanical property and high light transmittance, and when the visual double-network hydrogel is used as a dressing, a user can observe the healing condition of a wound on the premise of not uncovering the dressing, so that the defect that when the traditional dressing is used, if the healing condition of the wound needs to be observed, the dressing needs to be uncovered, and the wound surface is secondarily destroyed is overcome.
The invention also provides application of the visualized double-network hydrogel in dressing.
In practical application, a specific drug can be added into the second mixed solution when the step S13 is executed, so that the hydrogel dressing capable of acting on the wound is prepared, the hydrogel dressing can play roles in carrying the drug and releasing slowly, when the hydrogel dressing is attached to the wound, the hydrogel dressing can play a role in isolating and protecting the wound, and the drug is released continuously and acts on the wound, so that wound repair can be promoted. In step S13, the following steps are performed:
s131, adding 0.05 part of berberine hydrochloride into the second mixed solution, and mixing to obtain a third mixed solution;
s132, adding an initiator into the third mixed solution, and mixing to obtain a prepolymer solution.
In order to prove that the hydrogel dressing has medicine carrying and sustained release effects, the berberine hydrochloride is used as a specific medicine to be added into the preparation process of the hydrogel.
Specifically, for example:
referring to fig. 8, 0.05 part of berberine hydrochloride is added in comparative example 1, and the hydrogel dressing has no drug release effect (1 hour of complete drug release); the hydrogel dressing produced corresponds to the column labeled CM in fig. 8.
Referring to fig. 8, 0.05 part of berberine hydrochloride is added in the embodiment 1, and the hydrogel dressing has obvious drug release effect (the drug release amount in 2 hours is less than 80 percent); the hydrogel dressing produced corresponds to the curve labeled CMP1 in fig. 8.
Referring to fig. 8, 0.05 part of berberine hydrochloride is added in the embodiment 2, and the hydrogel dressing has obvious drug release effect (the drug release amount in 2 hours is less than 80 percent); the hydrogel dressing produced corresponds to the curve labeled CMP2 in fig. 8.
Referring to fig. 8, 0.05 part of berberine hydrochloride is added in the embodiment 3, and the hydrogel dressing has obvious drug release effect (the drug release amount in 2 hours is less than 60 percent); the hydrogel dressing produced corresponds to the curve labeled CMP in fig. 8.
Referring to fig. 8, 0.05 part of berberine hydrochloride is added in the embodiment 4, and the hydrogel dressing has obvious drug release effect (the drug release amount in 2 hours is less than 60 percent); the hydrogel dressing produced corresponds to the curve labeled CMP3 in fig. 8.
Referring to fig. 8, 0.05 part of berberine hydrochloride is added in the embodiment 5, and the hydrogel dressing has obvious drug release effect (the drug release amount in 2 hours is less than 40 percent); the hydrogel dressing produced corresponds to the curve labeled CMP4 in fig. 8.
Referring to fig. 8, 0.05 part of berberine hydrochloride is added in the embodiment 6, and the hydrogel dressing has obvious drug release effect (the drug release amount in 2 hours is less than 20 percent); the hydrogel dressing produced corresponds to the curve labeled CMP5 in fig. 8.
In this document, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions.
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the visual double-network hydrogel is characterized by comprising the following steps of:
s1, mixing and dissolving modified anionic polyelectrolyte, carboxymethyl chitosan and a cross-linking agent in deionized water, and then adding an initiator to obtain a prepolymer solution;
s2, vacuumizing the prepolymer solution to remove residual air in the solution;
s3, sealing the prepolymer solution subjected to the vacuumizing treatment, and placing the prepolymer solution under a preset temperature condition for reacting for a first preset time to obtain a reactant;
s4, placing the reactant in acetic acid atmosphere, fumigating for a second preset time, and obtaining the hydrogel dressing.
2. The method for preparing a visualized dual-network hydrogel according to claim 1, wherein the specific steps in step S1 include:
s11, mixing 0.5-5 parts of the modified anionic polyelectrolyte, 0.5-5 parts of the carboxymethyl chitosan and 100 parts of the deionized water to prepare a first mixed solution;
s12, adding the cross-linking agent into the first mixed solution, and mixing to obtain a second mixed solution;
s13, adding 0.1-0.3 part of the initiator into the second mixed solution, and mixing to obtain the prepolymer solution.
3. The method for preparing the visualized dual-network hydrogel according to claim 2, wherein the cross-linking agent is any one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, multi-arm polyethylene glycol acrylate, methacrylated pullulan, methacrylated cellulose, dialdehyde polyethylene glycol, dimercapto polyethylene glycol, dialdehyde cellulose, dialdehyde-beta-cyclodextrin and dialdehyde dextran.
4. The method for preparing a visualized dual-network hydrogel according to claim 3, wherein the specific steps in step S12 include:
S12A, adding 0.1-1 part of polyethylene glycol diacrylate with the relative molecular weight of 200-4000 Da into the first mixed solution, and mixing to obtain the second mixed solution.
5. The method for preparing a visualized dual-network hydrogel according to claim 3, wherein the specific steps in step S12 include:
S12B, adding 0.1-1 part of polyethylene glycol dimethacrylate with the relative molecular weight of 550-10000 Da into the first mixed solution, and mixing to obtain the second mixed solution.
6. The method for preparing a visualized dual-network hydrogel of claim 3, wherein the multi-arm polyethylene glycol acrylate comprises a four-arm polyethylene glycol acrylate;
the specific steps in step S12 include:
S12C, adding 0.1-1 part of four-arm polyethylene glycol acrylate with the relative molecular weight of 2000-10000 Da into the first mixed solution, and mixing to obtain the second mixed solution.
7. The method for preparing a visualized dual-network hydrogel according to claim 3, wherein the specific steps in step S12 include:
S12D, adding 0.1-1 part of dialdehyde polyethylene glycol with the relative molecular weight of 400-20000 Da into the first mixed solution, and mixing to obtain the second mixed solution.
8. The method for preparing a visualized dual-network hydrogel according to claim 3, wherein the specific steps in step S12 include:
S12E, adding 0.1-1 part of dimercapto polyethylene glycol with the relative molecular weight of 400-20000 Da into the first mixed solution, and mixing to obtain the second mixed solution.
9. A visualized dual-network hydrogel prepared by the method of preparing a visualized dual-network hydrogel according to any one of claims 1-8.
10. Use of a visualized dual-network hydrogel as claimed in claim 9 in a dressing.
CN202310563714.2A 2023-05-18 2023-05-18 Visual double-network hydrogel and preparation method and application thereof Pending CN116531554A (en)

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