CN116854971A - Preparation method and application of double-network hydrogel coating - Google Patents
Preparation method and application of double-network hydrogel coating Download PDFInfo
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- CN116854971A CN116854971A CN202310581401.XA CN202310581401A CN116854971A CN 116854971 A CN116854971 A CN 116854971A CN 202310581401 A CN202310581401 A CN 202310581401A CN 116854971 A CN116854971 A CN 116854971A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 49
- 238000000576 coating method Methods 0.000 title claims abstract description 49
- 239000000017 hydrogel Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000000741 silica gel Substances 0.000 claims abstract description 72
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 72
- 239000000758 substrate Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 108010010803 Gelatin Proteins 0.000 claims description 19
- 239000008273 gelatin Substances 0.000 claims description 19
- 229920000159 gelatin Polymers 0.000 claims description 19
- 235000019322 gelatine Nutrition 0.000 claims description 19
- 235000011852 gelatine desserts Nutrition 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 230000009977 dual effect Effects 0.000 claims description 4
- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical group CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 claims description 2
- KHDZXBKJADQNKK-UHFFFAOYSA-N P(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C Chemical compound P(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C KHDZXBKJADQNKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ATXASKQIXAJYLM-UHFFFAOYSA-N 1-hydroxypyrrolidine-2,5-dione;prop-2-enoic acid Chemical group OC(=O)C=C.ON1C(=O)CCC1=O ATXASKQIXAJYLM-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000008961 swelling Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 210000001835 viscera Anatomy 0.000 abstract description 5
- 230000001678 irradiating effect Effects 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 12
- 229920002379 silicone rubber Polymers 0.000 description 11
- 239000004945 silicone rubber Substances 0.000 description 11
- 238000000502 dialysis Methods 0.000 description 8
- 238000000635 electron micrograph Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 210000000056 organ Anatomy 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008363 phosphate buffer Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 210000004185 liver Anatomy 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 206010018910 Haemolysis Diseases 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000003636 conditioned culture medium Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000008588 hemolysis Effects 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YXMISKNUHHOXFT-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) prop-2-enoate Chemical group C=CC(=O)ON1C(=O)CCC1=O YXMISKNUHHOXFT-UHFFFAOYSA-N 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 108010087230 Sincalide Proteins 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 238000010609 cell counting kit-8 assay Methods 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 231100001083 no cytotoxicity Toxicity 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/145—Hydrogels or hydrocolloids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
-
- 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
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- 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
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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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
- C08J2433/00—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
- C08J2433/04—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
- C08J2433/14—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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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Heart & Thoracic Surgery (AREA)
- Animal Behavior & Ethology (AREA)
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- Surgery (AREA)
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- Materials Engineering (AREA)
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Abstract
The invention discloses a preparation method of a double-network hydrogel coating, which relates to the technical field of biomedical materials, and comprises the steps of firstly immersing a silica gel substrate into SBMA prepolymer solution for a certain time after surface modification, and then heating in a water bath at 60-65 ℃ for a certain time; then taking out the silica gel substrate and immersing the silica gel substrate into the DST prepolymerization liquid for a certain time; finally, taking out the soaked silica gel substrate, and irradiating the soaked silica gel substrate for a certain time under ultraviolet light to prepare a double-network hydrogel coating; the double-network hydrogel coating prepared by the invention has a relatively stable swelling rate, and can be used for micro-swelling and filling micro-texture grooves existing in viscera or skin when being applied to the coating on the inner surface of the silica gel sucker, so that the adsorption air tightness is increased, and the adsorption effect of the silica gel sucker on the viscera or skin can be effectively improved.
Description
Technical Field
The invention relates to the technical field of biomedical materials, in particular to a preparation method and application of a double-network hydrogel coating.
Background
Due to the good hydrophilicity, biocompatibility and three-dimensional structure retention of the hydrogel, the hydrogel has unique advantages and huge development space in the biomedical material field. The excellent biocompatibility makes it widely used in tissue engineering fields, such as artificial skin, artificial blood vessel, artificial cornea, contact lens, artificial joint, various artificial organs, medicine slow release carrier, etc.
The applicant discloses in patent number CN 211460332U a double-sided suction cup for liver retraction, which is used for sucking and pulling organs such as liver in laparoscopic epigastric operation so as to avoid the problems of poor exposure of the operation field, narrow operation space and the like caused by blocking the organs. However, since the surface of viscera or skin is not smooth and dense, but has fine texture grooves, the conventional silica gel sucker has a poor negative pressure maintaining time due to slow air leakage at the texture grooves, and the adsorption effect is not ideal.
Disclosure of Invention
The present invention is directed to at least partially overcoming the above and/or other potential problems in the art: provides a preparation method and application of a double-network hydrogel coating. The double-network hydrogel coating has stable swelling rate and stability, and can effectively improve the adsorption effect of the silica gel sucker on organs or skin when being used as a coating on the inner surface of the silica gel sucker.
The technical scheme of the invention is as follows: the preparation method of the double-network hydrogel coating comprises the following steps:
1) Adding SBMA monomer into deionized water, stirring and dissolving, then continuously adding a cross-linking agent, stirring to make the SBMA monomer react and crosslink, and finally adding a thermal initiator, stirring to obtain SBMA prepolymer liquid;
2) Dissolving acrylic acid, gelatin, AAc-NHS ester, gelMa and a photoinitiator LAP in deionized water, and deoxidizing after complete dissolution to obtain DST prepolymer liquid;
3) After the surface of the silica gel substrate is modified, firstly immersing the silica gel substrate in the SBMA prepolymer solution for a certain time, and then heating the silica gel substrate in a water bath at 60-65 ℃ for a certain time; then taking out the silica gel substrate and immersing the silica gel substrate into the DST prepolymerization liquid for a certain time; finally, the soaked silica gel substrate is taken out and irradiated for a certain time under ultraviolet light to prepare the PSBMA-DST double-network hydrogel coating.
The SBMA monomer is [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide.
Preferably, the crosslinking agent is N, N' -methylenebisacrylamide.
Preferably, the thermal initiator is ammonium persulfate.
The photoinitiator LAP is phenyl-2, 4, 6-trimethyl benzoyl lithium phosphite.
The AAc-NHS ester is acrylic acid N-hydroxysuccinimide ester.
The GelMa is methacryloylated gelatin.
Preferably, in the step 2), the mass percentage concentration of each component in the DST prepolymer solution is as follows: 10-50% of acrylic acid; 10-20% of gelatin; 1-5% of AAc-NHS ester; gelMa 0.1-0.3%; 0.2-5% of photoinitiator LAP.
Preferably, in the step 2), the mass percentage concentration of each component in the DST prepolymer solution is as follows: acrylic acid 30%; gelatin 10%; AAc-NHS ester 1%; gelMa 0.1%; 0.2% of photoinitiator LAP.
Preferably, in the step 3), the surface modification method of the silica gel substrate specifically comprises the following steps: firstly, treating the surface of a silica gel substrate by adopting glow discharge plasma, then soaking the silica gel substrate in BPO-acetone solution, and finally washing off residual substances on the surface of the silica gel substrate by using isopropanol; the BPO-acetone solution is an acetone solution with the mass percentage of the dimethylbenzene acyl oxide of 10 percent.
Preferably, the wavelength of the ultraviolet light in step 3) is 365nm.
The invention also provides application of the PSBMA-DST double-network hydrogel coating, which is used as a coating on the inner surface of the silica gel sucker so as to improve the adsorption capacity of the silica gel sucker on the surface of an organ. In particular for use as a coating on a liver traction cup.
The beneficial effects of the invention are as follows: the PSBMA-DST double-network hydrogel coating prepared by the invention has relatively stable swelling rate, and can be used for micro-swelling and filling micro-texture grooves existing in viscera or skin when being applied to the coating on the inner surface of a silica gel sucker, so that the adsorption air tightness is increased, and the adsorption effect of the silica gel sucker on the viscera or skin is effectively improved.
Drawings
FIG. 1 is an electron micrograph of a PSBMA-DST dual network hydrogel coating of example 1.
FIG. 2 is an electron micrograph of the PSBMA hydrogel coating of comparative example 1.
Fig. 3 is an electron micrograph of the DST hydrogel coating of comparative example 2.
FIG. 4 is an electron micrograph of the PSBMA-DST double network hydrogel of example 2.
FIG. 5 is an electron micrograph of the PSBMA hydrogel of comparative example 3.
FIG. 6 is an electron micrograph of the DST hydrogel of comparative example 4.
Fig. 7 is a graph showing the data of the diameter, height and weight of PSBMA-DST prepared in example 2 in deionized water as a function of time.
Fig. 8 is a graph showing the diameter, height and weight of PSBMA prepared in comparative example 3 in deionized water as a function of time.
Fig. 9 is a graph of data for diameter, height and weight as a function of time in deionized water for DST prepared in comparative example 4.
FIG. 10 is a graph showing the blood compatibility of PSBMA-DST prepared in example 2.
FIG. 11 is a graph showing the comparison of the OD values of PSBMA-DST prepared in example 2 with those of the control group.
FIG. 12 is a schematic of the mechanism of PSBMA-DST coating of example 1.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited to the following specific examples.
Example 1
Preparation of methacryloylated gelatin (GelMa)
10g of gelatin was dissolved in 100ml of phosphate buffer, slowly heated to 50℃and allowed to react well at this temperature for 1h. 2ml of methacrylic anhydride solution was slowly dropped into the above solution, and the reaction was continued for 3 hours while maintaining the temperature. 400ml of phosphate buffer was then added and the reaction was stopped. Taking 8000-14000 kDa dialysis bag, adding the solution into the dialysis bag, and then placing into deionized water for dialysis for 24 hours, wherein deionized water is changed every 6 hours in the dialysis process. Dialyzing for 3-5 days, lyophilizing to obtain methacryloylated gelatin (GelMa), and storing in a refrigerator at-20deg.C.
Configuration of SBMA prepolymerization liquid
1mol/L SBMA monomer is added into 20ml deionized water at room temperature, and is put into a rotary stirrer to be stirred and fully dissolved, then 0.04mol/L MBAA cross-linking agent N, N' -methylene bisacrylamide is continuously put into the deionized water to be fully stirred for 30min to fully react and crosslink, and then 0.001mol/L thermal initiator ammonium persulfate is put into the deionized water to be fully stirred for 15min.
Preparation of DST prepolymerization liquid
For the preparation of gelatin-based DST, acrylic acid, gelatin, AAc-NHS ester, gelMa and photoinitiator LAP were dissolved in deionized water at room temperature at the following mass percentage concentrations: acrylic acid 30%; gelatin 10%; AAc-NHS ester 1%; gelMa 0.1%; 0.2% of photoinitiator LAP. After complete dissolution, the gel is put into nitrogen to fully remove oxygen in the gel, and then is put into a refrigerator with the temperature of minus 20 ℃ for cooling for standby.
Preparation of a coating on a silica gel suction cup
In order to tightly adhere the double-network hydrogel coating to the upper surface of the silica gel sucker, firstly, modifying the surface of the silica gel sucker; cleaning a silica gel sucker, soaking in 75% alcohol, placing into an ultrasonic cleaning instrument for cleaning for 30min, placing into a 37 ℃ oven after cleaning until the surface of the material is completely dried, taking out, placing the silica gel sucker into a glow discharge mass spectrometer for 5min, soaking in a BPO-acetone solution for 5min, and cleaning residual substances with isopropanol. The BPO-acetone solution is an acetone solution with the mass percentage of the dimethylbenzene acyl oxide of 10 percent.
And (3) placing the cleaned silica gel sucker into SBMA prepolymerization liquid for 1h, and then placing the silica gel sucker into a water bath kettle at 60 ℃ for water-separating and heating for 1h. Immersing the treated silica gel sucker in DST prepolymerization liquid, placing in a refrigerator at 4 ℃ for 4 hours, taking out the immersed silica gel sucker, and irradiating the soaked silica gel sucker for 20 minutes by ultraviolet light with the wavelength of 365nm, wherein both sides of the soaked silica gel sucker are required to be irradiated for 20 minutes; the obtained PSBMA-DST double-network hydrogel coating electron microscope images are shown in fig. 1 and 12: the silica gel is tightly combined with the double-layer hydrogel. Because the initiator BPO swells in the silicone rubber by dipping, when the silicone rubber is dipped into SBMA prepolymerization liquid, part of monomers can enter the silicone rubber, and after heating to initiate free radical polymerization, a PSBMA hydrogel coating combined with the silicone rubber can be formed on the surface. On the basis, the silicone rubber of the PSBMA coating is immersed into DST prepolymer liquid, so that components of the DST prepolymer liquid fully shuttle in a PSBMA gel network, and then the components are crosslinked and grafted by a photoinitiator to be tightly combined, so that a stable and firm double-layer hydrogel coating is formed on the surface of silica gel.
Comparative example 1
Configuration of SBMA prepolymerization liquid
1mol/L SBMA monomer is added into 20ml deionized water at room temperature, and is put into a rotary stirrer to be stirred and fully dissolved, then 0.04mol/L MBAA cross-linking agent N, N' -methylene bisacrylamide is continuously put into the deionized water to be fully stirred for 30min to fully react and crosslink, and then 0.001mol/L thermal initiator ammonium persulfate is put into the deionized water to be fully stirred for 15min.
Preparation of a coating on a silica gel suction cup
Firstly, modifying the surface of a silica gel sucker; cleaning a silica gel sucker, soaking in 75% alcohol, placing into an ultrasonic cleaning instrument for cleaning for 30min, placing into a 37 ℃ oven after cleaning until the surface of the material is completely dried, taking out, placing the silica gel sucker into a glow discharge mass spectrometer for 5min, soaking in a BPO-acetone solution for 5min, and cleaning residual substances with isopropanol. The BPO-acetone solution is an acetone solution with the mass percentage of the dimethylbenzene acyl oxide of 10 percent.
Placing the cleaned silica gel sucker into SBMA prepolymerization liquid for 1h, and then placing the silica gel sucker into a water bath kettle at 60 ℃ for water-separating and heating for 1h; the electron microscope image of the obtained PSBMA hydrogel coating is shown in figure 2: the silica gel surface is seen to adhere strongly to a thin coating. Because the initiator BPO swells in the silicone rubber by dipping, when the silicone rubber is dipped into SBMA prepolymerization liquid, part of monomers can enter the silicone rubber, and after heating to initiate free radical polymerization, a PSBMA hydrogel coating combined with the silicone rubber can be formed on the surface. But the PSBMA hydrogel coating thus formed was thinner.
Comparative example 2
Preparation of methacryloylated gelatin (GelMa)
10g of gelatin was dissolved in 100ml of phosphate buffer, slowly heated to 50℃and allowed to react well at this temperature for 1h. 2ml of methacrylic anhydride solution was slowly dropped into the above solution, and the reaction was continued for 3 hours while maintaining the temperature. 400ml of phosphate buffer was then added and the reaction was stopped. Taking 8000-14000 kDa dialysis bag, adding the solution into the dialysis bag, and then placing into deionized water for dialysis for 24 hours, wherein deionized water is changed every 6 hours in the dialysis process. Dialyzing for 3-5 days, lyophilizing to obtain methacryloylated gelatin (GelMa), and storing in a refrigerator at-20deg.C.
Preparation of DST prepolymerization liquid
Acrylic acid, gelatin, AAc-NHS ester, gelMa and a photoinitiator LAP are dissolved in deionized water at room temperature, and the mass percentage concentration of each component is as follows: acrylic acid 30%; gelatin 10%; AAc-NHS ester 1%; gelMa 0.1%; 0.2% of photoinitiator LAP. After complete dissolution, the gel is put into nitrogen to fully remove oxygen in the gel, and then is put into a refrigerator with the temperature of minus 20 ℃ for cooling for standby.
Preparation of a coating on a silica gel suction cup
Firstly, modifying the surface of a silica gel sucker; cleaning a silica gel sucker, soaking in 75% alcohol, placing into an ultrasonic cleaning instrument for cleaning for 30min, placing into a 37 ℃ oven after cleaning until the surface of the material is completely dried, taking out, placing the silica gel sucker into a glow discharge mass spectrometer for 5min, soaking in a BPO-acetone solution for 5min, and cleaning residual substances with isopropanol. The BPO-acetone solution is an acetone solution with the mass percentage of the dimethylbenzene acyl oxide of 10 percent.
Placing the cleaned silica gel sucker into DST prepolymerization liquid, soaking for 4 hours in a refrigerator at 4 ℃, taking out the soaked silica gel sucker, and irradiating the silica gel sucker for 20 minutes by ultraviolet light with the wavelength of 365nm, wherein both sides of the silica gel sucker are required to be irradiated for 20 minutes; the electron microscope image of the obtained DST hydrogel coating is shown in figure 3. No obvious coating phenomenon is seen on the surface of the silica gel. This is because macromolecules in the DST prepolymer solution are difficult to enter the surface of the swelled silicone rubber and polymerize with an initiator inside the swelled silicone rubber to form a stable hydrogel coating structure.
Example 2
The substrate silica gel suction cup in example 1 was replaced with a silica gel sheet of 2mm×20mm, and the other conditions were the same as in example 1, to prepare a silica gel sheet coated with a PSBMA-DST double-network hydrogel coating, the sample was designated as PSBMA-DST, and an electron microscope image is shown in FIG. 4.
Comparative example 3
The substrate silica gel suction cup in comparative example 1 was replaced with a silica gel sheet of 2mm×20mm, and the remaining conditions were the same as those in comparative example 1, to prepare a silica gel sheet coated with a PSBMA hydrogel coating, the sample was designated as PSBMA, and an electron microscope image was shown in FIG. 5.
Comparative example 4
The substrate silica gel suction cup in comparative example 2 was replaced with a silica gel sheet of 2mm×20mm, and the remaining conditions were the same as those in comparative example 2, to prepare a silica gel sheet coated with a DST hydrogel coating, the sample was recorded as DST, and an electron microscopic image was shown in fig. 6.
Coating swelling ratio comparative test
The PSBMA-DST, PSBMA, DST prepared in example 2 and comparative examples 3-4 were placed in deionized water, and raw data were recorded by measuring the diameter, height and weight of the PSBMA-DST in 0 hours, 1 hour, 3 hours, 5 hours, 7 hours, 9 hours and 12 hours, respectively, as shown in fig. 7, the PSBMA-DST diameter, height and weight were slowly increased, and the swelling property was good, and the texture was hardly changed after soaking; as shown in fig. 8, PSBMA showed a decrease in diameter, high and weight, possibly due to incomplete cross-linking species being cleared and possibly due to enhanced interactions between the hydrated zwitterionic groups, a decrease in swelling rate, and a softer gel coat texture; as shown in fig. 9, DST hydrogels exhibited too high swellability and after swelling the texture became gradually brittle.
Hemolysis experiment
Hemolysis experiment: as shown in fig. 10, the positive control group (water) was dark in color, while PSBMA-DST was colorless, similar to the negative control group. The dissolution rates of PSBMA-DST are 2.00% respectively, which shows that the PSBMA-DST hydrogel has good blood compatibility.
Biocompatibility of
In vitro biocompatibility experiments were performed using the PSBMA-DST prepared in example 2 for cell culture. PSBMA-DST was incubated in 1 ml Dulbecco's Modified Eagle's Medium (DMEM) at 37℃for 24 hours. Original DMEM was used as a control. NiH3T3 was seeded in 96-well plates (dst conditioned medium n=10; for DMEM n=10). The cells were then treated with dst conditioned medium and at 37 ℃ at 5% CO 2 Incubate in incubator for 24 hours. The complete medium of 110ul CCK-8 reagent was added to each well, the incubator was incubated for 2h, OD was measured at 450nm with an ELISA reader, and PSBMA-DST cell compatibility was studied by direct contact test of PSBMA-DST with NiH3T3 as shown in FIG. 11. After co-incubation for 1, 2 and 3 days, the cell viability of the PSBMA-DST group is not obviously different from that of the control group, which shows that the PSBMA-DST has no cytotoxicity effect.
The above is merely exemplary embodiments of the present invention, and the scope of the present invention is not limited in any way. All technical schemes formed by adopting equivalent exchange or equivalent substitution fall within the protection scope of the invention.
Claims (10)
1. The preparation method of the double-network hydrogel coating is characterized by comprising the following steps of:
1) Adding SBMA monomer into deionized water, stirring and dissolving, then continuously adding a cross-linking agent, stirring to make the SBMA monomer react and crosslink, and finally adding a thermal initiator, stirring to obtain SBMA prepolymer liquid;
2) Dissolving acrylic acid, gelatin, AAc-NHS ester, gelMa and a photoinitiator LAP in deionized water, and deoxidizing after complete dissolution to obtain DST prepolymer liquid;
3) After the surface of the silica gel substrate is modified, firstly immersing the silica gel substrate in the SBMA prepolymer solution for a certain time, and then heating the silica gel substrate in a water bath at 60-65 ℃ for a certain time; then taking out the silica gel substrate and immersing the silica gel substrate into the DST prepolymerization liquid for a certain time; finally, the soaked silica gel base material is taken out and irradiated for a certain time under ultraviolet light to prepare the double-network hydrogel coating.
2. The method of claim 1, wherein the SBMA monomer is [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide.
3. The method for preparing a dual-network hydrogel coating according to claim 1, wherein the cross-linking agent is N, N' -methylenebisacrylamide.
4. The method of claim 1, wherein the thermal initiator is ammonium persulfate.
5. The method of preparing a dual network hydrogel coating according to claim 1, wherein the photoinitiator LAP is phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite.
6. The method of preparing a dual network hydrogel coating according to claim 1, wherein the AAc-NHS ester is N-hydroxysuccinimide acrylate.
7. The method of preparing a dual network hydrogel coating according to claim 1, wherein GelMa is a methacryloylated gelatin.
8. The preparation method of the double-network hydrogel coating according to claim 1, wherein the mass percentage concentration of each component in the DST prepolymer solution is as follows: 10-50% of acrylic acid; 10-20% of gelatin; 1-5% of AAc-NHS ester; gelMa 0.1-0.3%; 0.2-5% of photoinitiator LAP.
9. The method for preparing the double-network hydrogel coating according to claim 8, wherein in the step 2), the mass percentage concentration of each component in the DST prepolymer solution is as follows: acrylic acid 30%; gelatin 10%; AAc-NHS ester 1%; gelMa 0.1%; 0.2% of photoinitiator LAP.
10. The method for preparing a dual-network hydrogel coating according to claim 1, wherein in step 3), the method for modifying the surface of the silica gel substrate specifically comprises: firstly, treating the surface of a silica gel substrate by adopting glow discharge plasma, then soaking the silica gel substrate in BPO-acetone solution, and finally washing off residual substances on the surface of the silica gel substrate by using isopropanol; the BPO-acetone solution is an acetone solution with the mass percentage of the dimethylbenzene acyl oxide of 10 percent.
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