CN115028872B - Protein adsorption resistant hydrogel material and preparation method and application thereof - Google Patents
Protein adsorption resistant hydrogel material and preparation method and application thereof Download PDFInfo
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- CN115028872B CN115028872B CN202210679062.4A CN202210679062A CN115028872B CN 115028872 B CN115028872 B CN 115028872B CN 202210679062 A CN202210679062 A CN 202210679062A CN 115028872 B CN115028872 B CN 115028872B
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- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 claims description 2
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Images
Classifications
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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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
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/02—Lenses; Lens systems ; Methods of designing lenses
- G02C7/04—Contact lenses for the eyes
- G02C7/049—Contact lenses having special fitting or structural features achieved by special materials or material structures
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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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a protein adsorption resistant hydrogel material, a preparation method and application thereof, wherein methacrylic acid-beta-Hydroxyethyl (HEMA) is used as a main monomer to prepare crosslinked hydrogel, and the physical and chemical properties of the hydrogel are changed by adding a second monomer. After hydroxyl groups on the surface of the hydrogel are activated into amino groups, a chain transfer reagent is coupled, and a polymer brush containing carboxyl groups and zwitter ions is grown on the surface of the hydrogel material in situ through reversible addition-fragmentation chain transfer (RAFT) free radical polymerization, so that the hydrogel material with excellent protein adsorption resistance can be obtained, and the hydrogel material can be used as a contact lens for a long time.
Description
Technical Field
The invention belongs to the field of hydrogel materials, and particularly relates to a protein adsorption resistant hydrogel material, a preparation method thereof and application thereof in preparation of contact lenses.
Background
With the popularization of electronic products, the myopia population is increasing. The contact lens is a lens for correcting vision, which is made according to the cornea shape of human eyes, is physiologically compatible with human eyes, and has the purposes of vision correction, beauty treatment and the like. The advantages of convenience, beautiful appearance, softness, uneasiness and the like are accepted by consumers. The base material mainly comprises a hard airtight material, a hard breathable material, a soft non-hydrophilic material and a hydrogel material. The hydrogel has a three-dimensional network structure and is formed by molecular crosslinking, and the contact lens prepared from the hydrogel has the advantages of good light transmittance, hydrophilicity, biocompatibility and the like, wherein the hydrophilic soft contact lens prepared from hydroxyethyl methacrylate (HEMA) occupies a main position in the market of the contact lens.
Although contact lenses have made great progress in correcting vision and the like, there are still some disadvantages in wearing contact lenses, in which protein adsorption is a major problem facing current contact lenses. In the wearing process, proteins secreted by lacrimal glands are deposited on the surface of the contact lens to cause bacterial infection of eyes, so that the oxygen permeability and the light transmittance of the lens are reduced, and various adverse reactions such as eye edema are caused. Moreover, the method is also applicable to the field of the present invention. When protein remains on the surface of the lens, bacteria and other microorganisms can multiply in large quantity, and keratitis and other diseases can be caused by long-term wearing.
The zwitterionic polymer contains both cationic and anionic groups, so that a hydration layer is easily formed on the surface, nonspecific protein adsorption and bacterial adhesion can be effectively resisted, and the polymer has excellent biocompatibility. At present, amphoteric ions are mainly introduced in the preparation process of the contact lens, for example, the contact lens prepared by water-phase free radical copolymerization of 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone and betaine type amphoteric ion compounds in the invention patent CN201710251511.4 has good protein adsorption resistance, but the water content and mechanical property of the contact lens can be influenced by adopting a copolymerization method. Because the bacterial surface is negative, the protein in human tears is also in most of negative charge, so that the polymer brush containing amphoteric ions and negative charges is constructed on the surface, the protein adsorption resistance can be achieved under the condition that the original basic physical and chemical properties of hydrogel are not affected, the reduction of the incidence rate of ocular inflammation of people wearing contact lenses for a long time is facilitated, and the method has important significance for solving the problem of biological infection caused by wearing contact lenses.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a protein adsorption resistant hydrogel material and a preparation method thereof, aiming at the defects of the prior art.
The invention also aims to apply the protein adsorption resistant hydrogel material to contact lenses, so that the protein adsorption resistant hydrogel material has good protein adsorption performance and can be worn for a long time while maintaining good comprehensive performance of the contact lenses.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a protein adsorption resistant hydrogel material comprises the following steps:
(1) Uniformly mixing methacrylic acid-beta-Hydroxyethyl Ester (HEMA) serving as a monomer m with a monomer n, an initiator and a cross-linking agent, and carrying out curing reaction to obtain a pHEMA matrix product A;
(2) Activating hydroxyl on the surface of the pHEMA substrate product A obtained in the step (1) into amino to obtain a pHEMA-based amination modified product B;
(3) Carrying out surface modification on the pHEMA-based amination modified product B in the step (2) by adopting a RAFT chain transfer agent to obtain a product C;
(4) And (3) carrying out reversible addition-fragmentation chain transfer free radical polymerization on the product C in the step (3), and grafting and growing a polymer brush containing carboxyl and amphoteric ions on the surface of the product C to obtain the polymer brush.
Specifically, in the step (1), the monomer N is selectively added and is selected from any one or more than two of methacrylic acid (MAA), acrylic Acid (AA), acrylamide, N-vinyl pyrrolidone (NVP), 3- (triethoxysilane) propyl methacrylate, 3-methacrylate oxypropyl tri (trimethylsiloxy) silane, N-methylolacrylamide, N-hydroxyethyl acrylamide and 2-hydroxypropyl methacrylate.
The initiator is azo compound initiator, peroxide initiator or ultraviolet initiator. Initiator 1299 is preferred.
The cross-linking agent is selected from any one or more than two of Ethylene Glycol Dimethacrylate (EGDMA), ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, glycerol trimethacrylate, glycerol triacrylate, glycerol dimethacrylate and glycerol diacrylate. Ethylene Glycol Dimethacrylate (EGDMA) is preferred.
The mixing ratio of the monomer m, the monomer n, the initiator and the cross-linking agent is 100:0-30:0.05-5:0.5-10.
Specifically, in step (2), pHEMA base product a is reacted with 3-aminopropyl triethoxysilane to activate the hydroxyl groups of the surface to amino groups.
Preferably, in the step (2), the pHEMA base product A and the pHEMA base product A of 3-aminopropyl triethoxysilane are reacted in ethanol or acetone solution for 6-24 hours in a molar ratio of 1:5-1:30.
Specifically, in the step (3), sodium fatty acid methyl sulfonate, a RAFT chain transfer agent and a catalyst are heated and dissolved in deionized water, pHEMA-based amination modified product B is added after the dissolution is completed, and the reaction is carried out for 5 to 24 hours at the temperature of between room temperature and 50 ℃ to obtain a product C.
Specifically, in the step (3), the RAFT chain transfer agent is selected from any one of benzyl dithiobenzoate, isobutyl dithiobenzoate, trithiocarbonate, 4-cyano dithiobenzoyl valerate or carboxymethyl thiobenzoate.
The catalyst is selected from any one or more than two of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), N-hydroxysuccinimide (NHS) and Dicyclohexylcarbodiimide (DCC). N-hydroxysuccinimide (NHS) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) are preferred.
Wherein, the concentration of the fatty acid methyl ester sodium sulfonate in the solution is 0.05-1M, and the mole ratio of the RAFT chain transfer agent, the catalyst and the pHEMA-based amination modified product B is 2-5:5-50:1.
Specifically, in the step (4), the product C is added into a mixed reagent of a monomer containing carboxyl, a monomer containing amphoteric ions, an initiator and absolute ethyl alcohol, and the mixture is reacted for 6 to 12 hours at the temperature of 60 to 100 ℃ to graft the polymer on the surface of the product C.
Preferably, in the step (4), the monomer containing a carboxyl group is selected from any one of Acrylic Acid (AA), methacrylic acid (MAA), itaconic acid, or trifluoromethyl acrylic acid. Methacrylic acid (MAA) is preferred.
The amphoteric ion-containing monomer is selected from any one of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, carboxylic acid betaine methyl methacrylate (CBMA), 2-Methacryloyloxyethyl Phosphorylcholine (MPC), polycarboxylic acid betaines and methacryloylethyl Sulfobetaine (SBMA). Methacryloyl ethyl Sulfobetaine (SBMA) is preferred.
The initiator is selected from any one of Azodiisobutyronitrile (AIBN), azodiisoheptonitrile (ABVN), benzoyl peroxide, benzoyl tert-butyl peroxide and methyl ethyl ketone peroxide. Azobisisobutyronitrile (AIBN) is preferred.
The monomer containing carboxyl, the monomer containing amphoteric ion, the initiator and the product C are mixed according to the mass ratio of 0.2-1:0.2-1:0.005-0.1:1 respectively.
Furthermore, the protein adsorption resistant hydrogel material prepared by the preparation method is also in the protection scope of the invention.
Furthermore, the use of the above protein adsorption resistant hydrogel material for the preparation of contact lenses is also claimed.
The beneficial effects are that:
(1) The hydrogel material prepared by taking HEMA as a main monomer and adding other components has high water content, hydrophilicity and transmittance, and hydroxyl groups on the surface can be used for subsequent surface modification.
(2) According to the invention, the RAFT chain transfer agent is grafted on the surface of the contact lens, and then the polymer is grafted through the subsequent RAFT polymerization reaction. The RAFT polymerization molecular chain length is controllable, the molecular weight distribution is narrower, the prepared hydrogel has uniform surface performance, and the adjustable chain segment length is beneficial to researching the influence of the length of the surface graft polymer brush on the comprehensive performance of the hydrogel, and guiding the selection of the optimal length of the graft polymer brush.
(3) Because most proteins in bacteria and tears show electronegativity, a comonomer containing carboxyl is introduced to the surface of the contact lens, so that the surface of the contact lens is negatively charged, the wettability of the surface of the contact lens can be improved, and the adhesion of the proteins and bacteria can be reduced through charge repulsive force.
(4) And introducing a zwitterionic monomer on the surface of the contact lens through copolymerization, so that the non-specific protein adsorption and bacterial adhesion are effectively resisted, and the contact lens has excellent biocompatibility.
(5) The method of grafting the polymer chain on the surface of the contact lens has little influence on the water content and mechanical properties of the contact lens matrix material, and is favorable for keeping good comprehensive properties.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is an infrared spectrum characterization of a hydrogel contact lens prepared in example 1 of the present invention.
FIG. 2 is the transmittance of the hydrogel contact lens prepared in example 1 of the present invention.
FIG. 3 is a graph of water contact angles for hydrogel contact lenses of examples 1-3 of the present invention.
FIG. 4 is a graph showing the comparison of the adsorption amount of lysozyme by hydrogel contact lenses of examples 1-3 of the present invention.
FIG. 5 is a graph showing the comparison of adsorption amounts of BSA protein by hydrogel contact lenses of examples 1-3 of the present invention.
FIG. 6 is a fluorescence spectrum of example 5 of the present invention.
Detailed Description
The invention will be better understood from the following examples.
Example 1: preparation of surface sulfobetaine type amphoteric ion modified hydrogel contact lenses.
Step 1:
HEMA (0.85 mL), ethylene Glycol Dimethacrylate (EGDMA) (15 mu L) serving as a crosslinking agent and a photoinitiator 1299 (20 mg) are placed into a contact lens preparation mold, reacted for 30min in an ultraviolet curing reactor, placed into a mixed solution of ethanol and water, and demolded to obtain the pHEMA hydrogel contact lens A.
Step 2:
the contact lens prepared in the step 1 and 3-aminopropyl triethoxysilane (1.11 g,5 mmol) were placed in an ethanol solution, stirred at room temperature for reaction for 8 hours, and after the reaction was completed, the contact lens was washed 2 times with ethanol and water, and immersed in distilled water for 24 hours, to obtain hydrogel contact lens B.
Step 3:
sodium fatty acid Methyl Ester Sulfonate (MES) (195.24 mg, 0.1M) and 10mL of deionized water were added to a dry beaker with a pre-placed stirrer, and after complete dissolution, RAFT chain transfer agent (428 mg,1 mmol), NHS (1.15 g,10 mmol), EDC (960 mg,5 mmol) were added and reacted on a magnetic stirrer for 4h. And after the reaction is finished, placing the contact lens B into the water bath kettle at 40 ℃ for reaction for 6 hours, and after the reaction is finished, cleaning the contact lens B for 2 times by using ethanol and distilled water respectively, and soaking the contact lens B in the distilled water for 24 hours to obtain the hydrogel contact lens C.
Step 4:
SBMA is taken as a zwitterionic monomer, AIBN (10 mg), MAA (800 mg), SBMA (800 mg) and the contact lens C in the step 3 are added into a dry two-mouth flask with a preset stirrer, and oxygen in a reaction tube is removed through three times of vacuumizing and nitrogen circulation. 20mL of absolute ethanol was added. The mixture was placed in an oil bath at 70℃for 8 hours. After completion of the reaction, a P (MAA-SBMA) contact lens is obtained. Infrared signatures of contact lens a, contact lens C, and contact lens D are shown in fig. 1. 1164cm -1 A sulfate radical stretching vibration peak is arranged at the position; at 1484cm -1 The absorption peak of the corresponding SBMA quaternary ammonium group methyl; at 1657cm -1 And 1727cm -1 The corresponding carbonyl absorption peak on SBMA shows that SBMA polymerization is successful according to the result; 2945cm -1 Is saturated hydrocarbon stretching vibration and has strong absorption peak of 3423cm -1 The corresponding stretching vibration of the hydroxyl group indicates that MAA is present in the contact lens. Analysis as above may indicate successful grafting of MAA and SBMA onto contact lenses. FIG. 2 is a graph showing pHEMA versus transmittance of contact lenses prepared after grafting, as can be seen: the transmittance of the grafted contact lens is slightly reduced, but still kept above 90%, so that the application requirement is met.
Example 2: preparation of surface sulfobetaine type amphoteric ion modified hydrogel contact lenses.
Step 1:
HEMA (0.85 mL), N-vinyl pyrrolidone (NVP) (150 mu L), a crosslinking agent Ethylene Glycol Dimethacrylate (EGDMA) (15 mu L) and a photoinitiator 1299 (20 mg) are placed in a contact lens preparation mold, reacted for 30min in an ultraviolet curing reactor, and placed in a mixed solution of ethanol and water for demolding, so that the contact lens is obtained.
Step 2, step 3 and step 4 are the same as those in example 1.
Example 3: preparation of surface carboxylic acid betaine type amphoteric ion modified hydrogel contact lenses.
Step 1, step 2 and step 3 are the same as those in example 1.
Step 4: AIBN (10 mg), acrylic Acid (AA) (800 mg), methyl carboxylate betaine methacrylate (800 mg) and the contact lens in step 3 were added to a dry two-neck flask with a preset stirrer, and oxygen in the reaction tube was removed by three cycles of vacuum pumping and nitrogen gas introduction. 20mL of absolute ethanol was added. The mixture was placed in an oil bath at 70℃for 8 hours. After the reaction is completed, the contact lens with the protein adsorption resistance is obtained.
Example 4: contact lens surface wettability test
The contact angle of the reference pHEMA with the surface of the contact lens after the graft modification was measured using contact angle measurement instrument DSA 25 and used to characterize the surface wettability of the contact lens. After the surface of the contact lens was wiped dry, the sample was spread on a glass plate, 2 μl of deionized water was added dropwise to the surface, 3 sets of contact angle photographs were collected, and the average value was taken. The surface wettability of the resulting contact lens is shown in figure 3. The comparison of pHEMA group (corresponding to the product of step 1 in example 1), and the surface wettability of the contact lenses of examples 1, 2, and 3, can be concluded that the hydrophilicity of the surface modified contact lenses is significantly improved.
Example 5: contact lens anti-lysozyme (lys) adsorption test
The contact lenses prepared in reference pHEMA, example 1, example 2, example 3 were placed in NaCl (0.85%) solution containing lysozyme (1 mg/mL) and cultured with shaking at 100rpm in a constant temperature shaking oven at 37℃for 24 hours. Subsequently, the supernatant was taken, absorbance was measured, and the concentration of the protein adsorbed by the sample and the amount of the protein were calculated from the standard curve.
As can be seen from the results of FIG. 4, the adsorption amounts of lysozyme by the control pHEMA group and the contact lenses of example 1, example 2 and example 3 were 0.4.+ -. 0.01%, 0.28.+ -. 0.006%, 0.29.+ -. 0.006% and 0.28.+ -. 0.006%, respectively. The adsorption capacity of the three groups of surface modified contact lenses to lysozyme is lower than that of a reference, and the result shows that the surface modified contact lenses can effectively reduce the adsorption capacity of lysozyme.
Example 6: contact lens anti-Bovine Serum Albumin (BSA) adsorption test
The contact lenses prepared in reference pHEMA, example 1, example 2, example 3 were immersed in an aqueous solution containing FITC-labeled bovine serum albumin (0.4 mg/mL) for 24 hours. Shake-culturing in a constant temperature shaking oven at 37deg.C at 100rpm for 24 hr. Subsequently, the supernatant was taken, absorbance was measured, and the concentration of the protein adsorbed by the sample and the amount of the protein were calculated from the standard curve.
FIG. 5 shows the fluorescence spectra of pHEMA and example 2, and the adsorption amounts of BSA by the contact lenses of example 1, example 2 and example 3. From fig. 5 and 6, it can be concluded that the surface-modified hydrogel contact lens can better resist BSA adsorption. In connection with the conclusion of example 4, hydrogel contact lenses having zwitterionic polymers grafted on their surfaces can reduce protein adsorption.
The invention provides a protein adsorption resistant hydrogel material, a preparation method and an application thought and a method thereof, and particularly the method and the method for realizing the technical scheme are a plurality of methods, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by one of ordinary skill in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (8)
1. The preparation method of the protein adsorption resistant hydrogel material is characterized by comprising the following steps of:
(1) Uniformly mixing methacrylic acid-beta-hydroxyethyl HEMA serving as a monomer m with a monomer n, an initiator and a cross-linking agent, and carrying out curing reaction to obtain a pHEMA matrix product A;
(2) Activating hydroxyl on the surface of the pHEMA substrate product A obtained in the step (1) into amino to obtain a pHEMA-based amination modified product B;
(3) Carrying out surface modification on the pHEMA-based amination modified product B in the step (2) by adopting a RAFT chain transfer agent to obtain a product C;
(4) Carrying out reversible addition-fragmentation chain transfer free radical polymerization on the product C in the step (3), and growing a polymer brush containing carboxyl and amphoteric ions on the surface of the product C in situ to obtain the polymer brush;
in the step (1), the monomer N is selected from any one or more than two of methacrylic acid, acrylic acid, acrylamide, N-vinyl pyrrolidone, 3- (triethoxysilyl) propyl methacrylate, 3-methacrylate oxypropyl tri (trimethylsiloxy) silane, N-methylolacrylamide, N-hydroxyethyl acrylamide and 2-hydroxypropyl methacrylate;
in the step (2), pHEMA base product A is reacted with 3-aminopropyl triethoxysilane to activate the hydroxyl groups on the surface into amino groups;
in the step (3), sodium fatty acid methyl sulfonate, a RAFT chain transfer agent and a catalyst are heated and dissolved in deionized water, pHEMA-based amination modified product B is added after complete dissolution, and the reaction is carried out for 5 to 24 hours at the temperature of between room temperature and 50 ℃ to obtain a product C;
the mixing ratio of the monomer m to the monomer n to the initiator to the cross-linking agent is 100:0-30:0.05-5:0.5-10.
2. The method for preparing the protein adsorption resistant hydrogel material according to claim 1, wherein in the step (1), the initiator is azo compound initiator, peroxide initiator or ultraviolet light initiator;
the cross-linking agent is selected from any one or more than two of ethylene glycol dimethacrylate, ethylene glycol diacrylate, glycerol triacrylate, glycerol dimethacrylate and glycerol diacrylate.
3. The method for preparing the protein adsorption resistant hydrogel material according to claim 1, wherein in the step (2), the molar ratio of hydroxyl groups of the pHEMA base product A to 3-aminopropyl triethoxysilane is 1:5-1:30, and the reaction is performed in ethanol or acetone solution for 6-24 hours.
4. The method for preparing the protein adsorption resistant hydrogel material according to claim 1, wherein in the step (3), the RAFT chain transfer agent is selected from any one of benzyl dithiobenzoate, isobutyl dithiobenzoate, trithiocarbonate, 4-cyano dithiobenzoyl valerate and carboxymethyl thiobenzoate;
the catalyst is selected from any one or more than two of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and dicyclohexylcarbodiimide;
wherein the concentration of the fatty acid methyl ester sodium sulfonate in the solution is 0.05-1M, and the molar ratio of the RAFT chain transfer agent to the catalyst to the pHEMA-based amination modified product B is 2-5:5-50:1.
5. The method for preparing the protein adsorption resistant hydrogel material according to claim 1, wherein in the step (4), the product C is added into a mixed reagent of a monomer containing carboxyl, a monomer containing amphoteric ions, an initiator and absolute ethyl alcohol, and the mixture is reacted for 6-12 hours at 60-100 ℃, so that the polymer is grafted onto the surface of the product C.
6. The method for producing an anti-protein adsorption hydrogel material according to claim 5, wherein in step (4), the carboxyl group-containing monomer is selected from any one of acrylic acid, methacrylic acid, itaconic acid and trifluoromethylacrylic acid;
the monomer containing the amphoteric ion is selected from any one of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, 2-methacryloyloxyethyl phosphorylcholine, carboxylic acid betaine methyl methacrylate and methacryloylethyl sulfobetaine;
the initiator is selected from any one of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, benzoyl tert-butyl peroxide and methyl ethyl ketone peroxide;
the monomer containing carboxyl, the monomer containing amphoteric ion, the initiator and the product C are mixed according to the mass ratio of 0.2-1:0.2-1:0.005-0.1:1.
7. The protein adsorption resistant hydrogel material prepared by the preparation method of any one of claims 1-6.
8. Use of the protein adsorption resistant hydrogel material of claim 7 for the preparation of contact lens.
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