CN113817114A - Hydrogel, method for producing same, and medical material - Google Patents
Hydrogel, method for producing same, and medical material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention relates to the technical field of hydrogel, in particular to hydrogel, a preparation method thereof and a medical material. The hydrogel is a gel material which is mainly formed by modified polyethylene glycol, micromolecules providing hydrogen bond acting force, a photoinitiator and water through curing and crosslinking reaction. The hydrogel has good transparency, high strength and resistance to biological contamination.
Description
Technical Field
The invention relates to the technical field of hydrogel, in particular to hydrogel, a preparation method thereof and a medical material.
Background
The hydrogel is a three-dimensional network cross-linked structure polymer material with rich water filled inside, and is widely applied to the fields of water pollution treatment, food industry, agriculture, biomedicine and the like. In recent years, researchers have diversely excavated the chemical components and network topology of hydrogels to synthesize various functional hydrogel materials, and these new hydrogel materials have diversified properties: such as stimulus responsiveness to external environments such as temperature, electric field, ph value, etc., smart release characteristics as a drug carrier for drugs, lubrication action, anti-fouling action, strong adhesion, etc. by structural design. Hydrogel materials have great medical potential due to the natural biocompatibility of hydrogels, and typical applications include contact lenses, wound sealing, drug delivery, tissue scaffolds, and the like.
Nonspecific contamination of biomolecules, cells and microorganisms (i.e., biological contamination) presents a significant challenge in the process of drug delivery from a medical device. When implanted in the body, medical implants become covered with a layer of host proteins that cause an irreversible foreign body response that leads to a range of complications including inflammation, infection, tissue fibrosis, and the like, resulting in implant failure. Therefore, the reduction or elimination of "bio-contamination" is critical to the safety and efficacy of medical devices and drugs. A great deal of research has found that some hydrophilic materials can effectively reduce the biological contamination on the surface of the material substrate, because the hydrophilic materials can form a hydrated shell through hydration, prevent biomolecules or cells from contacting the surface, and make the substrate at the bottom layer invisible, thereby obtaining a pollution-free biological material surface. Hydration of the surface of the material plays a significant role. These materials have been shown to form a hydrated shell that prevents biomolecules or cells from contacting the surface, leaving the underlying substrate "stealthy".
However, most hydrophilic materials have insufficient hydration capability to form a contamination-free surface. Polyethylene glycol (PEG), as a hydrophilic synthetic biopolymer material approved by the FDA, is widely used in the development of medical devices and drugs as the "gold standard". However, PEG is susceptible to oxidative damage and can cause adverse immune responses, with serious concerns about its safety in recent years. Furthermore, most hydrophilic materials, including PEG, do not have sufficient hydration capability to completely hide the surface and are difficult to meet the non-fouling requirements of practical applications, especially in complex physiological environments.
The adsorption of protein on the surface of a solid material and the adhesion of cells and other microorganisms can cause serious biological pollution, the hydrogel has the stability of solid and the liquidity of liquid, can effectively inhibit the adhesion of fouling organisms, and has the advantages of low toxicity, good biocompatibility and the like, thereby being a green antifouling material. However, the defects of poor mechanical property, single function and the like of the traditional hydrogel greatly limit the practical application of the hydrogel as a corneal contact lens, a medical implant, a drug sustained-release carrier, a biochip and the like.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The present invention aims to provide a hydrogel, a method for producing the same, and a medical material. The hydrogel provided by the embodiment of the invention has good transparency, high strength and biological pollution resistance.
The invention is realized by the following steps:
in a first aspect, the present invention provides a hydrogel, which is a gel material formed by a curing and crosslinking reaction of modified polyethylene glycol, a small molecule providing a hydrogen bonding force, a photoinitiator and water.
In an alternative embodiment, the modified polyethylene glycol is modified with an acrylate compound or an acrylamide compound;
preferably, the modified polyethylene glycol is selected from any one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylamide, polyethylene glycol dimethylacrylamide, multi-arm polyethylene glycol acrylate, multi-arm polyethylene glycol acrylamide, multi-arm polyethylene glycol methacrylate and multi-arm polyethylene glycol methacrylamide.
In alternative embodiments, the small molecule comprises an acrylamide-based species or a pyrimidine-based species;
preferably, the small molecule comprises any one of acrylamide glycinamide, acrylamide and 2-amino-4-hydroxy-6-methylpyrimidine.
In alternative embodiments, the photoinitiator is a water-soluble photoinitiator;
preferably, the photoinitiator is selected from at least one of lithium phenyl-2, 4, 6-trimethylbenzoylphosphinate and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone.
In an alternative embodiment, the amount of the modified polyethylene glycol is 20-60% of the mass of water;
preferably, the amount of the small molecules is 10-60% of the mass of water;
preferably, the photoinitiator is used in an amount of 0.05 to 2% by mass of water.
In a second aspect, the present invention provides a method for preparing the hydrogel according to the previous embodiment, including: mixing modified polyethylene glycol, micromolecules providing hydrogen bond acting force, photoinitiator and water, and then carrying out curing and crosslinking reaction.
In an alternative embodiment, the method comprises the following steps: and dissolving the modified polyethylene glycol, the small molecules and the photoinitiator in water to form a prepolymer solution, transferring the prepolymer solution to a curing plate, and performing curing crosslinking by using ultraviolet light.
In an alternative embodiment, the intensity of the ultraviolet light is 15-30mW/mm 2; the curing and crosslinking time is 5-30 min.
In an alternative embodiment, the gel material formed after curing and crosslinking has a thickness of 0.5 to 1.5 mm.
In a third aspect, the present invention provides a medical material comprising a hydrogel according to the previous embodiments;
preferably, the medical material comprises any one of a corneal contact lens, a medical implant, a drug sustained-release carrier, a wound dressing, a tissue patch, a tissue engineering scaffold, a biochip, a biological antifouling coating and a tissue anti-adhesion gel.
The invention has the following beneficial effects: according to the embodiment of the invention, the modified polyethylene glycol and the micromolecules capable of providing hydrogen bonds are adopted, and the photoinitiator and water are subjected to a crosslinking reaction, so that the formed hydrogel is not only transparent, but also has high-strength mechanical properties, good tensile rate and excellent biological pollution resistance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a graph showing the results of transparency measurement according to Experimental example 1 of the present invention;
FIG. 2 is a graph showing a comparison of the actual transparency provided by Experimental example 1 of the present invention;
FIG. 3 is a graph showing the results of the test provided in Experimental example 2 of the present invention;
FIG. 4 is a graph showing the results of the test provided in Experimental example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment of the invention provides hydrogel which is a gel material formed by mainly carrying out curing and crosslinking reaction on modified polyethylene glycol, micromolecules for providing hydrogen bond acting force, a photoinitiator and water. The modified polyethylene glycol can provide excellent hydrophilicity for the hydrogel, the micromolecules can provide hydrogen bond acting force, chemical bonds formed between the modified polyethylene glycol and the micromolecules and physical bonds such as the hydrogen bonds can be formed, the mechanical performance of the hydrogel can be enhanced, meanwhile, the modified polyethylene glycol and the micromolecules are dissolved in water under the action of a photoinitiator, and the hydrogel obtained through a curing crosslinking technology has an excellent biological pollution resistance effect.
Further, the modified polyethylene glycol is modified by an acrylate compound or an acrylamide compound; for example, the modified polyethylene glycol is selected from any one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylamide, polyethylene glycol dimethacrylamide, multi-arm polyethylene glycol acrylate, multi-arm polyethylene glycol acrylamide, multi-arm polyethylene glycol methacrylate, and multi-arm polyethylene glycol methacrylamide. The modified polyethylene glycol can be used for improving the biological pollution resistance and the mechanical strength of the hydrogel.
Further, the small molecule comprises acrylamide substances or pyrimidine substances; for example, the small molecule includes any one of acrylamide glycinamide, acrylamide and 2-amino-4-hydroxy-6-methylpyrimidine. The use of the small molecules can enhance the mechanical strength of the hydrogel through the leave-on effect, improve the defects of fragility and fragility of the traditional hydrogel, and regulate the strength of the gel to be matched with biological tissues (kidney, liver, cartilage, blood vessel, muscle and the like) through regulating the content of the small molecules.
Meanwhile, the modified polyethylene glycol and the small molecules capable of providing hydrogen bonding can form a hydrated shell through hydration, so that proteins, glycoproteins or cells are effectively prevented from contacting the surface of the material, and the substrate at the bottom layer is hidden, thereby having the function of resisting biological pollution.
Further, the photoinitiator is a water-soluble photoinitiator; for example, the photoinitiator is selected from at least one of lithium phenyl-2, 4, 6-trimethylbenzoylphosphinate and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone. The water-soluble photoinitiator can solve the problem of reduced hydrogel transparency caused by water insolubility of the initiator.
Further, the using amount of the modified polyethylene glycol is 20-60% of the mass of water; the amount of the small molecules is 10-60% of the mass of water; the dosage of the photoinitiator is 0.05-2% of the mass of water. The adoption of the proportion can be beneficial to the formation of hydrogel and the performance of the hydrogel is improved.
In a second aspect, an embodiment of the present invention provides a method for preparing a hydrogel, including: mixing modified polyethylene glycol, micromolecules providing hydrogen bond acting force, photoinitiator and water, and then carrying out curing and crosslinking reaction.
Specifically, the modified polyethylene glycol, the small molecule and the photoinitiator are dissolved in water to form a prepolymer solution, and then the prepolymer solution is transferred to a curing plate and is cured and crosslinked by ultraviolet light. Wherein the light intensity of the ultraviolet light is 15-30mW/mm 2; the curing and crosslinking time is 5-30 min; the thickness of the gel material formed after curing and crosslinking is 0.5-1.5 mm. The use of the above procedures and conditions facilitates the formation of the hydrogel and the performance of the hydrogel.
In a third aspect, the present invention provides a medical material comprising a hydrogel according to the previous embodiments;
preferably, the medical material comprises any one of a corneal contact lens, a medical implant, a drug sustained-release carrier, a wound dressing, a tissue patch, a tissue engineering scaffold, a biochip, a biological antifouling coating and a tissue anti-adhesion gel.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment of the invention provides a preparation method of hydrogel, which comprises the following steps:
firstly, 0.8g of polyethylene glycol dimethacrylate, 0.4g of acrylamide glycinamide (NAGA) and 0.1g of lithium phenyl-2, 4, 6-trimethylbenzoyl phosphinate are weighed and placed in a 5ml centrifuge tube, 2ml of deionized water is added, the mixture is stirred and dissolved at room temperature to obtain a prepolymer solution, the prepolymer solution is stirred for a period of time to be fully dissolved uniformly, and the prepolymer solution is placed for defoaming; the prepared prepolymer solution was then transferred to a concave glass plate having a height of 1.0mm and then placed in a uv curing oven at a light intensity of 30mW/mm2 for 20 minutes to cure and crosslink to produce a transparent, high-strength and anti-biofouling hydrogel, which was designated PN-1.
Example 2
The embodiment of the invention provides a preparation method of hydrogel, which comprises the following steps:
firstly, 0.8g of 4-arm polyethylene glycol dimethacrylate, 0.6g of acrylamide glycinamide (NAGA) and 0.1g of lithium phenyl-2, 4, 6-trimethylbenzoyl phosphinate are weighed and placed in a 5ml centrifuge tube, 2ml of deionized water is added, stirred and dissolved at room temperature to obtain a prepolymer solution, stirred for a period of time to be fully dissolved uniformly, and kept stand for defoaming; the prepolymer solution thus prepared was subsequently transferred to a concave glass plate having a height of 1.0mm and then placed in a UV curing oven under UV irradiation at a light intensity of 15mW/mm2 for 10 minutes to cure and crosslink to produce a transparent, high-strength and anti-microbial hydrogel, designated 4-arm PN-1.
Comparative example 1: a hydrogel was prepared by referring to the preparation method of example 1, except that acrylamide glycinamide was not used in the present comparative example, and the hydrogel obtained in this comparative example was designated as PEG.
Comparative example 2: a hydrogel was prepared by referring to the preparation method of example 2, except that acrylamide glycinamide was not used in the present comparative example, and the hydrogel obtained in this comparative example was designated as 4-arm PEG.
Comparative example 3: a hydrogel was prepared by referring to the preparation method of example 1 except that the comparative example was changed from polyethylene glycol dimethacrylate to polyethylene glycol dimethylacrylamide, and the hydrogel obtained in this comparative example was designated as PN-2.
Comparative example 4: a hydrogel was prepared by referring to the preparation method of example 2 except that 4-arm polyethylene glycol dimethacrylate was changed to 4-arm polyethylene glycol dimethylacrylamide in this comparative example, and the hydrogel obtained in this comparative example was designated as 4-arm PN-2.
Experimental example 1
The hydrogels of example 1, comparative example 1 and comparative example 3 were tested for transparency and the results are shown in fig. 1 and fig. 2.
As can be seen from FIG. 1, the three hydrogels of PEG, PN-1 and PN-2 have good transmittance, and the transmittance under visible light of 400-800 nm is not less than 92%, wherein the transmittance of the PEG hydrogel is the highest, and after the NAGA molecules are added, the intermolecular aggregation structure in the PEG hydrogel is changed due to intermolecular hydrogen bonding, and the transmittance is slightly reduced. As can be seen from FIG. 2, all three hydrogels had good light transmission properties, and the opposite letters could be clearly seen through the hydrogels.
Experimental example 2
The hydrogels of example 2, comparative example 2 and comparative example 4 were tested for tensile rate and breaking strength, see GB/T1040.
As can be seen from FIG. 3, the 4-arm PEG hydrogel has a breaking strength of about 210KPa and an elongation at break of less than 100%, and when a NAGA molecule providing hydrogen bonding is added, the 4-arm PN-1, 4-arm PN-2 hydrogel has better stretchability and higher breaking strength, wherein the 4-arm PN-2 has the highest breaking tensile strength of 386KPa and the elongation at break of about 1050%, as shown in FIG. 3. Experiments show that the mechanical strength of the gel is enhanced by hydrogen bonding among the molecules in the hydrogel.
Experimental example 3
The hydrogels of example 1 and comparative example 1 were prepared as disc-shaped hydrogel materials of 10mm diameter, and then placed in a 24-well plate together with a glass plate, respectively, then added to 1ml of bovine serum albumin phosphate buffer solution, incubated at 37 ℃ for 4 hours, then washed 3 times with phosphate buffer solution, stained with coomassie brilliant blue for 10 minutes, tested for protein adsorption by an ultraviolet spectrophotometer, and the anti-protein adsorption effect of the hydrogels was evaluated according to the absorbance of the solution.
The detection results are shown in figure 4, and according to figure 4, compared with PEG hydrogel, the protein adsorption content of PN-1 hydrogel is less, which shows that the hydrogel has better anti-bioadhesion property than PEG, and has potential application value for biological anti-fouling coating.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement 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 hydrogel is characterized in that the hydrogel is a gel material which is mainly formed by modified polyethylene glycol, micromolecules providing hydrogen bond acting force, a photoinitiator and water through curing and crosslinking reaction.
2. The hydrogel according to claim 1, wherein the modified polyethylene glycol is a polyethylene glycol modified with an acrylate compound or an acrylamide compound;
preferably, the modified polyethylene glycol is selected from any one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylamide, polyethylene glycol dimethylacrylamide, multi-arm polyethylene glycol acrylate, multi-arm polyethylene glycol acrylamide, multi-arm polyethylene glycol methacrylate and multi-arm polyethylene glycol methacrylamide.
3. The hydrogel of claim 1, wherein the small molecule comprises an acrylamide-based species or a pyrimidine-based species;
preferably, the small molecule comprises any one of acrylamide glycinamide, acrylamide and 2-amino-4-hydroxy-6-methylpyrimidine.
4. The hydrogel of claim 1, wherein the photoinitiator is a water soluble photoinitiator;
preferably, the photoinitiator is selected from at least one of lithium phenyl-2, 4, 6-trimethylbenzoylphosphinate and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone.
5. The hydrogel according to claim 1, wherein the modified polyethylene glycol is used in an amount of 20 to 60% by mass of water;
preferably, the amount of the small molecules is 10-60% of the mass of water;
preferably, the photoinitiator is used in an amount of 0.05 to 2% by mass of water.
6. A method for preparing the hydrogel according to claim 1, comprising: mixing modified polyethylene glycol, micromolecules providing hydrogen bond acting force, photoinitiator and water, and then carrying out curing and crosslinking reaction.
7. The method of claim 6, comprising: and dissolving the modified polyethylene glycol, the small molecules and the photoinitiator in water to form a prepolymer solution, transferring the prepolymer solution to a curing plate, and performing curing crosslinking by using ultraviolet light.
8. The method of claim 7, wherein the intensity of the ultraviolet light is 15-30mW/mm 2; the curing and crosslinking time is 5-30 min.
9. The method according to claim 7, wherein the thickness of the gel material formed after the curing and crosslinking is 0.5 to 1.5 mm.
10. A medical material comprising the hydrogel of claim 1,
preferably, the medical material comprises any one of a corneal contact lens, a medical implant, a drug sustained-release carrier, a wound dressing, a tissue patch, a tissue engineering scaffold, a biochip, a biological antifouling coating and a tissue anti-adhesion gel.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618005A (en) * | 2022-03-31 | 2022-06-14 | 浙江大学 | Photoinitiated self-adhesive hydrogel film type wound dressing, preparation method and application |
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