CN117567698B - Photo-curing biocompatible material and drainage tube - Google Patents
Photo-curing biocompatible material and drainage tube Download PDFInfo
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- CN117567698B CN117567698B CN202311355058.3A CN202311355058A CN117567698B CN 117567698 B CN117567698 B CN 117567698B CN 202311355058 A CN202311355058 A CN 202311355058A CN 117567698 B CN117567698 B CN 117567698B
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- drainage tube
- biocompatible material
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- 238000000016 photochemical curing Methods 0.000 title claims abstract description 31
- 239000000560 biocompatible material Substances 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 66
- 108010010803 Gelatin Proteins 0.000 claims abstract description 47
- 229920000159 gelatin Polymers 0.000 claims abstract description 47
- 235000019322 gelatine Nutrition 0.000 claims abstract description 47
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 47
- 239000008273 gelatin Substances 0.000 claims abstract description 46
- 239000002256 antimetabolite Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000000340 anti-metabolite Effects 0.000 claims abstract description 13
- 229940100197 antimetabolite Drugs 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 22
- OHAMXGZMZZWRCA-UHFFFAOYSA-N 5-formyluracil Chemical compound OC1=NC=C(C=O)C(O)=N1 OHAMXGZMZZWRCA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- ZSZRUEAFVQITHH-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-(trimethylazaniumyl)ethyl phosphate Chemical compound CC(=C)C(=O)OCCOP([O-])(=O)OCC[N+](C)(C)C ZSZRUEAFVQITHH-UHFFFAOYSA-N 0.000 claims description 13
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical class O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims description 13
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 11
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 10
- 230000021164 cell adhesion Effects 0.000 claims description 10
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 claims description 8
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- NJNWCIAPVGRBHO-UHFFFAOYSA-N 2-hydroxyethyl-dimethyl-[(oxo-$l^{5}-phosphanylidyne)methyl]azanium Chemical group OCC[N+](C)(C)C#P=O NJNWCIAPVGRBHO-UHFFFAOYSA-N 0.000 claims description 5
- SIDLLBGYFXERTQ-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,3-dithiol Chemical compound C1CC2C(S)C(S)C1C2 SIDLLBGYFXERTQ-UHFFFAOYSA-N 0.000 claims description 5
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- -1 photoinitiator TPO-L Chemical compound 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- KMTUBAIXCBHPIZ-UHFFFAOYSA-N pentane-1,5-dithiol Chemical compound SCCCCCS KMTUBAIXCBHPIZ-UHFFFAOYSA-N 0.000 claims 1
- 208000010412 Glaucoma Diseases 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 14
- 230000035755 proliferation Effects 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 8
- 238000002513 implantation Methods 0.000 abstract description 7
- 210000000254 ciliated cell Anatomy 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 24
- 210000004027 cell Anatomy 0.000 description 13
- 210000002950 fibroblast Anatomy 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000001678 irradiating effect Effects 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 8
- 239000002504 physiological saline solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 4
- 230000036573 scar formation Effects 0.000 description 4
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-UHFFFAOYSA-N 0.000 description 3
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000012091 fetal bovine serum Substances 0.000 description 3
- 230000004410 intraocular pressure Effects 0.000 description 3
- 230000002980 postoperative effect Effects 0.000 description 3
- 230000037390 scarring Effects 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000001028 anti-proliverative effect Effects 0.000 description 2
- 210000001742 aqueous humor Anatomy 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000032823 cell division Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000002502 liposome Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000002483 medication Methods 0.000 description 2
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- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 description 2
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 108010087230 Sincalide Proteins 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010609 cell counting kit-8 assay Methods 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 206010020718 hyperplasia Diseases 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 210000001328 optic nerve Anatomy 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 231100000241 scar Toxicity 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
- 239000000243 solution Substances 0.000 description 1
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- 229960005322 streptomycin Drugs 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000747 viability assay Toxicity 0.000 description 1
- 238000003026 viability measurement method Methods 0.000 description 1
Classifications
-
- 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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/041—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/044—Proteins; Polypeptides; Degradation products thereof
- A61L29/046—Gelatin
-
- 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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention provides a photo-curing biocompatible material and a drainage tube, and relates to the technical field of medical appliances; the photocuring biocompatible material comprises the following components in parts by weight: 0.01-0.08 part of A component; 100 parts of a component B; 0.1-1 part of photoinitiator; wherein the component A is a sulfhydryl-containing compound; the component B comprises a functional material I, a functional material II and modified gelatin; the functional material I contains an antimetabolite structure; the functional material II contains an anti-cell adhesion structure. According to the invention, through the synergistic effect of the sulfhydryl-containing compound, the modified gelatin, the antimetabolite structure and the anti-cell adhesion structure, the drainage tube prepared from the prepared photocuring biocompatible material by the photocuring method has excellent biocompatibility and mechanical property, can meet the physical and chemical property requirements of the glaucoma drainage tube, has the function of resisting the proliferation of ciliated cells, and ensures the drainage and filtration effects of the drainage tube under the condition of long-term implantation.
Description
Technical Field
The invention relates to the technical field of medical instruments, in particular to a photo-curing biocompatible material and a drainage tube.
Background
Glaucoma is the second leading blinding factor worldwide and the first irreversible blinding factor worldwide. For the treatment of glaucoma, the principle of reducing intraocular pressure, preventing or slowing down damage to the optic nerve of a patient as much as possible, and preserving existing vision has been used. Laser trabeculoplasty treatment may be used when traditional medications are poorly effective, or when patients cannot tolerate long-term medications; minimally Invasive Glaucoma Surgery (MIGS) with implanted drainage tubes can be performed when laser trabeculoplasty treatment also fails to bring the eye pressure down to a safe range or fails to maximally withstand drug treatment.
The glaucoma drainage tube is a tubular structure which can be implanted in a minimally invasive manner, has an outer diameter of only 100-900 mu m and an inner diameter of 10-100 mu m, is usually very fine, soft and elastic, and can guide aqueous humor out of the eye so as to reduce intraocular pressure.
In order to obtain a small, soft and elastic drainage tube, the existing drainage tube can be prepared by adopting a compatible material through a photo-curing mode; the existing photo-curing compatible material can meet the performance requirements of good compliance of a drainage tube and eye tissues, is safe to use, has no toxicity and the like, but under the condition that the drainage tube is implanted into a body for a long time, the drainage tube is easy to be blocked by post-operation fibroblast hyperplasia, cells in tissue fluid can be adhered to the drainage tube, and finally, the filtration effect of the drainage tube is poor and fails.
In view of the above, it is an urgent need to provide a photocurable compatible material that can make the prepared drainage tube have both anti-proliferation and good biocompatibility.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to solve the problem that a drainage tube prepared from the photo-curing compatible material in the prior art is easy to block due to proliferation of a fibroblast, the invention provides the photo-curing compatible material, and the photo-curing compatible material enables the drainage tube prepared from the photo-curing compatible material to have excellent anti-proliferation performance of the fibroblast by introducing an anti-metabolism structure and an anti-cell adhesion structure, so that the problem that the drainage tube is easy to block due to proliferation of the fibroblast is solved.
The technical scheme adopted for solving the technical problems is as follows:
The photocuring biocompatible material comprises the following components in parts by weight:
0.01-0.08 part of A component;
100 parts of a component B;
0.1-1 part of photoinitiator;
wherein the A component is a sulfhydryl-containing compound;
the component B comprises a functional material I, a functional material II and modified gelatin;
the functional material I contains an antimetabolite structure;
the functional material II contains an anti-cell adhesion structure.
Optionally, the A component is at least one selected from 3-mercapto-beta, 4-dimethylcyclohexanediethane thiol, bicyclo [2.2.1] heptane-2, 3-dithiol, 1, 5-pentanediol, ethylene glycol bis (3-mercaptopropionate) and trimethylolpropane tris (3-mercaptopropionate).
Optionally, the mass ratio of the functional material I, the functional material II and the modified gelatin in the component B is (0.1-0.5): (1-3): 100.
Optionally, the functional material I contains a carbon-carbon double bond.
Optionally, the functional material I is modified uracil.
Optionally, the modified uracil is prepared as follows: under the protection of inert gas, mixing 5-formyl uracil, allylamine, anhydrous magnesium sulfate and methylene dichloride, stirring at 15-25 ℃, filtering, taking filtrate, distilling under reduced pressure, and drying at normal temperature in vacuum to obtain the modified uracil.
Optionally, the molar ratio of the 5-formyluracil, the allylamine, the anhydrous magnesium sulfate is 1: (0.8-1.2): (0.5-1.5).
Optionally, the molar ratio of the 5-formyluracil, the allylamine, the anhydrous magnesium sulfate is 1:1:1.
Optionally, the anti-cell adhesion structure is a phosphorylcholine structure.
Optionally, the functional material II is 2-methacryloyloxyethyl phosphorylcholine.
Optionally, the modified gelatin is prepared according to the following method: mixing gelatin with water, regulating pH value to be alkaline, then dripping allyl glycidyl ether to react, regulating pH value to be neutral, and sequentially dialyzing, and freeze-drying to obtain the modified gelatin.
Optionally, the mass ratio of the gelatin to the allyl glycidyl ether is 20: (0.8-1.5).
Optionally, the mass ratio of the gelatin to the allyl glycidyl ether is 20:1.
Optionally, the photoinitiator is selected from at least one of photoinitiator 2959, photoinitiator TPO-L, and photoinitiator 184.
Another object of the present invention is to provide a drainage tube prepared from the photo-curable biocompatible material as described above by a photo-curing method.
The beneficial effects of the invention are as follows:
According to the photocuring biocompatible material provided by the invention, through the synergistic effect of the sulfhydryl-containing compound, the modified gelatin, the antimetabolite structure and the anti-cell adhesion structure, the drainage tube prepared by the photocuring biocompatible material through the photocuring method has excellent biocompatibility and mechanical property, can meet the physical and chemical property requirements of the glaucoma drainage tube, has the function of resisting the proliferation of ciliated cells, and ensures the drainage and filtration effects of the drainage tube under the condition of long-term implantation.
Detailed Description
The present invention will now be described in further detail. The embodiments described below are exemplary and intended to illustrate the invention and should not be construed as limiting the invention, as all other embodiments, based on which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of the invention.
In order to solve the problem that a drainage tube is easy to block due to proliferation of a fibroblast in the prior art, the invention provides a photocuring biocompatible material, which comprises the following components in parts by weight:
0.01-0.08 part of A component;
100 parts of a component B;
0.1-1 part of photoinitiator;
wherein the component A is a sulfhydryl-containing compound; the component B comprises a functional material I, a functional material II and modified gelatin; the functional material I contains an antimetabolite structure; the functional material II contains an anti-cell adhesion structure.
Because the component A is a sulfhydryl-containing compound, the modified gelatin of the component B contains a carbon-carbon double bond, the drainage tube can be prepared by a sulfhydryl-alkene material through a photocuring method, and meanwhile, the prepared drainage tube can be endowed with good microbial compatibility and mechanical property due to excellent biocompatibility and mechanical property of the sulfur-containing material and gelatin; in addition, the functional material I in the component B is introduced into an antimetabolite structure, so that the prepared drainage tube can prevent cell division, has excellent antimetabolite effect, and can reduce scar formation at a postoperative operation site; meanwhile, the functional material II in the component B is introduced into an anti-cell adhesion structure, the anti-cell adhesion structure is easy to form hydrophobic hydration combination with water, and the anti-cell adhesion structure shows super-lubrication characteristic similar to ice surface, so that biological components such as protein, liposome and the like are difficult to adhere to the surface of the material, and the anti-cell adhesion structure has excellent anti-cell adhesion property, so that postoperation scar formation can be further reduced, and drainage filtering effect is improved.
According to the photocuring biocompatible material provided by the invention, through the synergistic effect of the sulfhydryl-containing compound, the modified gelatin, the antimetabolite structure and the anti-cell adhesion structure, the drainage tube prepared by the photocuring biocompatible material through the photocuring method has excellent biocompatibility and mechanical property, can meet the physical and chemical property requirements of the glaucoma drainage tube, has the function of resisting the proliferation of ciliated cells, and ensures the drainage and filtration effects of the drainage tube under the condition of long-term implantation.
In order to ensure that the biocompatibility and mechanical property of the drainage tube meet the performance requirements of long-term implantation, the A component is preferably at least one of 3-mercapto-beta, 4-dimethylcyclohexanediethiol, bicyclo [2.2.1] heptane-2, 3-dithiol, 1, 5-pentanediol, ethylene glycol bis (3-mercaptopropionate) and trimethylolpropane tris (3-mercaptopropionate).
In order to consider the physical and chemical properties and the anti-fibroblast proliferation property of the drainage tube, the invention preferably selects the mass ratio of the functional material I, the functional material II and the modified gelatin in the component B to be (0.1-0.5): (1-3): 100.
Furthermore, the functional material I preferably contains carbon-carbon double bonds, so that the functional material I can be reacted with the A component through sulfydryl-alkene to fix the antimetabolite structure in a material system, and the damage to a human body caused by the fact that the antimetabolite structure exists in free small molecules and cannot be accurately controlled in quantity is avoided, and therefore the safety can be ensured while the anti-ciliated cell proliferation performance of the material is improved.
Specifically, the preferred functional material I of the present invention is modified uracil.
Further, the preferred modified uracil of the present invention is prepared as follows: under the protection of inert gas, mixing 5-formyl uracil, allylamine, anhydrous magnesium sulfate and methylene dichloride, stirring at 15-25 ℃, filtering, taking filtrate, distilling under reduced pressure, and drying at normal temperature in vacuum to obtain the modified uracil.
The modified uracil has the same structure as thymine, can prevent cell division, has excellent antimetabolite effect, and can reduce scar formation at the postoperative operation site; meanwhile, the modified uracil is fixed in a material system, so that free small molecules are avoided, and the damage to the body caused by the fact that the amount cannot be accurately controlled is avoided.
Specifically, the preferred molar ratio of 5-formyl uracil, allylamine and anhydrous magnesium sulfate is 1: (0.8-1.2): (0.5-1.5).
Further, the invention preferably has a molar ratio of 5-formyluracil, the allylamine, the anhydrous magnesium sulfate of 1:1:1.
In order to ensure the cell adhesion resistance of the drainage tube during long-term implantation, the cell adhesion resistance structure is preferably a phosphorylcholine structure, the phosphorylcholine structure is easy to form hydrophobic hydration combination with water, the super-lubrication characteristic similar to ice surface is shown, biological components such as protein, liposome and the like are difficult to attach on the surface of the material, so that the material has excellent cell adhesion resistance, postoperative scar is further reduced, and the drainage filtering effect is improved.
Specifically, the preferable functional material II is 2-methacryloyloxyethyl phosphorylcholine, and the phosphorylcholine structure is fixed in a material system through the 2-methacryloyloxyethyl phosphorylcholine, so that the cell adhesion resistance of the drainage tube during long-term implantation is ensured.
The preferred modified gelatin of the present invention is prepared as follows: mixing gelatin with water, regulating pH value to be alkaline, then dripping allyl glycidyl ether to react, regulating pH value to be neutral, and sequentially dialyzing, and freeze-drying to obtain the modified gelatin.
The photocuring biocompatible material provided by the invention mainly comprises modified gelatin and a sulfur-containing structure, and has excellent biocompatibility; the drainage tube prepared by the photo-curing method of the mercapto-alkene material with good compatibility has good biocompatibility and mechanical properties.
Specifically, the mass ratio of gelatin to allyl glycidyl ether is preferably 20: (0.8-1.5), and further preferably the mass ratio of gelatin to allyl glycidyl ether is 20:1.
The photoinitiator is preferably at least one selected from the group consisting of photoinitiator 2959, photoinitiator TPO-L and photoinitiator 184.
Another object of the present invention is to provide a drainage tube prepared from the photo-curable biocompatible material as described above by a photo-curing method.
Specifically, the preparation method of the drainage tube is preferably as follows: mixing the component A, the component B and the photoinitiator according to the formula amount, injecting the mixture into a microfluidic mould, irradiating the mixture by ultraviolet light, and placing the mixture in physiological saline at 37 ℃ for oscillation after curing to obtain the glaucoma drainage tube.
The drainage tube provided by the invention is prepared from a photo-curing biocompatible material with good compatibility by a photo-curing method; the photocuring biocompatible material enables the prepared drainage tube to have excellent biocompatibility and mechanical property through the synergistic effect of the sulfhydryl compound, the modified gelatin containing carbon-carbon double bond, the antimetabolite structure and the anti-cell adhesion structure, can meet the physical and chemical property requirements of the glaucoma drainage tube, has the function of resisting the proliferation of ciliated cells, and ensures the drainage and filtration effects of the drainage tube under the condition of long-term implantation.
In particular, the drainage tube is preferably in a tubular structure, namely the whole glaucoma drainage tube is tubular, and a drainage channel is arranged in the drainage tube so as to drain aqueous humor in the eye of a patient to a subconjunctival space through the drainage channel, thereby reducing the intraocular pressure of the glaucoma patient; the specific appearance structure, the size and the like of the glaucoma drainage tube can be selected according to actual requirements or corresponding prior art; the internal drainage channel can be an equal-diameter drainage channel or a non-equal-diameter drainage channel.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
The preparation methods of the modified uracils in the examples of the present invention and comparative examples are as follows, unless otherwise specified:
Under the protection of nitrogen, adding 5-formyl uracil, allylamine, anhydrous magnesium sulfate and methylene dichloride into a three-neck flask, stirring for 20 hours at 20 ℃, filtering, taking filtrate, distilling under reduced pressure, and drying at normal temperature in vacuum to obtain the modified uracil, namely the functional material I.
The molar ratio of the 5-formyl uracil, the allylamine and the anhydrous magnesium sulfate is 1:1:1, a step of; the addition mass ratio of the 5-formyl uracil to the dichloromethane is 1: (10-15).
The prepared modified uracil has the following infrared data: 1555cm -1: -NH- (amide) present; 1676cm -1: -c=o (ketone group in pyrimidine ring) is present; 1512cm -1: -C-N- (stretching vibration of C-N in pyrimidine ring) is present; 1720cm -1、2870cm-1、2720cm-1: h-c=o (aldehyde group) disappears; 1634cm -1: -c=c-present.
The preparation methods of the modified gelatins in the examples of the present invention and comparative examples were as follows, unless otherwise specified:
5g of gelatin was mixed with 60mL of water, the pH of the solution was adjusted to 10.5 with a 3mol/L aqueous solution of sodium hydroxide, then 0.25g of allyl glycidyl ether was added dropwise thereto for 4 hours, and the pH of the reaction mixture was adjusted to neutral by a 3mol/L aqueous solution of hydrochloric acid, dialyzed for 3 days, and freeze-dried to obtain a modified gelatin.
The infrared data are as follows: 3350-3550cm -1: -OH is present; 1720cm -1: -c=o present; 1636cm -1: -c=c-present.
The mass content of the carbon-carbon double bond in the modified gelatin was 0.028% as determined by iodometric titration.
Example 1
The embodiment provides a drainage tube, and the preparation method of the drainage tube is as follows:
Mixing the component A, the component B and the photoinitiator 2959, injecting into a microfluidic mould, irradiating for 30s by ultraviolet light with the wavelength of 355nm, curing, and then placing into physiological saline with the temperature of 37 ℃ for oscillation for 7d to obtain a glaucoma drainage tube;
The component A is a mixture of 3-mercapto-beta, 4-dimethylcyclohexanediol and ethylene glycol bis (3-mercaptopropionate) according to a molar ratio of 3/2;
The component B is a functional material I, 2-methacryloyloxyethyl phosphorylcholine and modified gelatin according to the mass ratio of 0.3:2: 100.
The mass ratio of the component A, the component B and the photoinitiator 2959 is 0.01:100:0.1.
Example 2
The embodiment provides a drainage tube, and the preparation method of the drainage tube is as follows:
mixing the component A, the component B and the photoinitiator TPO-L, injecting into a microfluidic mould, irradiating for 30s by ultraviolet light with the wavelength of 355nm, curing, and then placing into physiological saline with the temperature of 37 ℃ for oscillation for 7d to obtain a glaucoma drainage tube;
the component A is a mixture of bicyclo [2.2.1] heptane-2, 3-dithiol and ethylene glycol bis (3-mercaptopropionate) according to a molar ratio of 3/7;
The component B is a functional material I, 2-methacryloyloxyethyl phosphorylcholine and modified gelatin according to the mass ratio of 0.1:3: 100.
The mass ratio of the component A, the component B and the photoinitiator TPO-L is 0.04:100:0.5.
Example 3
The embodiment provides a drainage tube, and the preparation method of the drainage tube is as follows:
Mixing the component A, the component B and the photoinitiator 184, injecting into a microfluidic mould, irradiating for 30s by ultraviolet light with the wavelength of 355nm, curing, and then placing into physiological saline with the temperature of 37 ℃ for oscillation for 7d to obtain a glaucoma drainage tube;
The component A is a mixture of 1, 5-glutaryl dithiol and trimethylolpropane tri (3-mercaptopropionate) according to a mole ratio of 7/3;
The component B is a functional material I, 2-methacryloyloxyethyl phosphorylcholine and modified gelatin according to the mass ratio of 0.5:1: 100.
The mass ratio of the component A, the component B and the photoinitiator 184 is 0.08:100:1.
Example 4
The embodiment provides a drainage tube, and the preparation method of the drainage tube is as follows:
mixing the component A, the component B and the photoinitiator TPO-L, injecting into a microfluidic mould, irradiating for 30s by ultraviolet light with the wavelength of 355nm, curing, and then placing into physiological saline with the temperature of 37 ℃ for oscillation for 7d to obtain a glaucoma drainage tube;
the component A is a mixture of ethylene glycol bis (3-mercaptopropionate) and trimethylolpropane tris (3-mercaptopropionate) according to a molar ratio of 3/2;
The component B is a functional material I, 2-methacryloyloxyethyl phosphorylcholine and modified gelatin according to the mass ratio of 0.2:2: 100.
The mass ratio of the component A, the component B and the photoinitiator TPO-L is 0.04:100:0.5.
Example 5
The embodiment provides a drainage tube, and the preparation method of the drainage tube is as follows:
Mixing the component A, the component B and the photoinitiator 184, injecting into a microfluidic mould, irradiating for 30s by ultraviolet light with the wavelength of 355nm, curing, and then placing into physiological saline with the temperature of 37 ℃ for oscillation for 7d to obtain a glaucoma drainage tube;
The component A is a mixture of 3-mercapto-beta, 4-dimethylcyclohexanediol and trimethylolpropane tri (3-mercaptopropionate) according to a mol ratio of 9/1;
The component B is a functional material I, 2-methacryloyloxyethyl phosphorylcholine and modified gelatin according to the mass ratio of 0.4:2: 100.
The mass ratio of the component A, the component B and the photoinitiator 184 is 0.04:100:0.5.
Example 6
The embodiment provides a drainage tube, and the preparation method of the drainage tube is as follows:
Mixing the component A, the component B and the photoinitiator 2959, injecting into a microfluidic mould, irradiating for 30s by ultraviolet light with the wavelength of 355nm, curing, and then placing into physiological saline with the temperature of 37 ℃ for oscillation for 7d to obtain a glaucoma drainage tube;
The component A is a mixture of bicyclo [2.2.1] heptane-2, 3-dithiol, ethylene glycol bis (3-mercaptopropionate) and trimethylolpropane tri (3-mercaptopropionate) according to a molar ratio of 2/7/1;
The component B is a functional material I, 2-methacryloyloxyethyl phosphorylcholine and modified gelatin according to the mass ratio of 0.3:3: 100.
The mass ratio of the component A, the component B and the photoinitiator 2959 is 0.04:100:0.5.
Example 7
The embodiment provides a drainage tube, and the preparation method of the drainage tube is as follows:
Mixing the component A, the component B and the photoinitiator 2959, injecting into a microfluidic mould, irradiating for 30s by ultraviolet light with the wavelength of 355nm, curing, and then placing into physiological saline with the temperature of 37 ℃ for oscillation for 7d to obtain a glaucoma drainage tube;
The component A is ethylene glycol bis (3-mercaptopropionate);
the component B is a functional material I, 2-methacryloyloxyethyl phosphorylcholine and modified gelatin according to the mass ratio of 0.3:1: 100.
The mass ratio of the component A, the component B and the photoinitiator 2959 is 0.04:100:0.5.
The following comparative examples are each compared to example 1:
comparative example 1
This comparative example differs from example 1 in that the mass ratio of the a component, the B component, and the photoinitiator 2959 is 0.15:100:0.1.
Comparative example 2
This comparative example differs from example 1 in that the mass ratio of the a-component, the B-component and the photoinitiator 2959 is 0.01:120:0.1.
Comparative example 3
This comparative example differs from example 1 in that the modified gelatin was replaced with gelatin.
Comparative example 4
This comparative example differs from example 1 in that the B component is a modified gelatin.
Comparative example 5
The comparative example differs from example 1 in that the B component is 2-methacryloyloxyethyl phosphorylcholine and modified gelatin in a mass ratio of 2.3: 100.
Comparative example 6
The comparative example is different from example 1 in that the B component is 5-formyl uracil, 2-methacryloyloxyethyl phosphorylcholine and modified gelatin according to the mass ratio of 0.3:2: 100.
Comparative example 7
The comparative example is different from example 1 in that the component B is a functional material I and modified gelatin according to a mass ratio of 2.3: 100.
The performance of the drainage tubes prepared in each example and comparative example was examined as follows:
(1) Cell inhibition effect test:
The effect of cell inhibition was evaluated by the response of the cells, primary fibroblasts (10 cells/well) were cultured with fire Kong Peiyang base (DMEM) containing 10% by mass of fetal bovine serum. After the fibroblast cell was precipitated, the migration test was inserted into the glaucoma drainage tube so that it was completely immersed in the medium. After 5 days of culture, the status of fibroblasts was examined with live/dead staining and CCK-8, and the 5-day live/dead ratio of fibroblasts (HTFs) was calculated, the higher the activity of the fibroblasts, the more severe the scarring.
(2) Cell adhesion test:
3T3 mouse embryo bromoblasts were maintained in T-75Falcon cell culture using sterile Dulbecco's modified French Kong Peiyang base (DMEM) containing 10% Fetal Bovine Serum (FBS) and 100 units/ml penicillin and 0.1mg/ml streptomycin by mass fraction. 6 samples (36 samples total) of each overlay were placed in 6 well tissue culture plates and irradiated under ultraviolet light for 10-15 minutes. Cells were seeded onto the cover film at a density of approximately 11 000 cells/cm. The cells were then incubated at 37℃for 24h with 5% carbon dioxide, and the medium was then poured off and gently rinsed once with PBS. The adherent cell number is defined as the number of viable cells per 100 x field. The percentage of control was calculated by multiplying the ratio of the percentage of viable cells on the treated substrate to the percentage of viable cells on the untreated substrate by 100. The average control adhesion per sample group was determined and statistical comparisons of the viability assays were made as described above.
(3) Monomer residue test: gas chromatography testing was used. Monomer residue representation method: < 1ppm is noted "OK"; the "NG" is recorded at > 1 ppm.
(4) Mechanical strength test: after the drainage tube is folded in half, whether a crack crease phenomenon exists or not is observed. The method for expressing the mechanical strength comprises the following steps: the non-broken crease marks "o", the non-broken crease marks "very good", and the broken crease marks "∈".
(5) Elastic modulus test: the raw materials in the examples were injected in a 5B dumbbell type mold in proportions for curing, and tested with reference to GB/T1040.3-2006.
The test results are shown in Table 1:
TABLE 1
As can be seen from the data in Table 1, the drainage tubes prepared in the examples of the present invention all have excellent anti-cell proliferation and anti-cell adhesion properties, as well as excellent mechanical properties and extremely low monomer residues.
Compared with the example 1, the comparative examples 1-2 adjust the reaction proportion of mercapto and carbon-carbon double bond, and the mechanical property of the prepared drainage tube is poor because any component is excessive and is not in a reasonable interval.
Comparative example 3 compared with example 1, unmodified gelatin was used as a filler, and thiol and alkene materials had too high a reactive crosslinking density to be molded, and a drainage tube could not be produced.
Compared with the embodiment 1, the comparative example 4 has better mechanical property in the drainage tube prepared by not adding the functional materials I and II into the component B, but the activity/death ratio of HTFs ciliated cells is obviously increased in 5 days, and the risk of scar formation is increased; the cell adhesion is also obviously increased, and the risk of blockage of the drainage tube is greatly increased.
Compared with the embodiment 1, the comparative example 5 has the advantages that only the functional material II is added into the component B, and the prepared drainage tube has excellent cell adhesion resistance and better mechanical property; however, not only the 5-day HTFs have significantly increased fibroblast survival/death ratio, but also cell adhesion was significant, and the risk of scarring increased.
Comparative example 6 compared with example 1, the addition of functional material II and unmodified functional material I (5-formyluracil) to the B component produced drainage tube cells with reduced HTFs ciliated cell activity/death ratio for 5 days, reduced risk of scarring; meanwhile, the anti-adhesion performance is excellent, and the mechanical property is good; however, the monomer residue exceeds the standard due to the presence of the unmodified functional material I.
Compared with the embodiment 1, the comparative example 7 has better mechanical property by only adding the functional material I into the component B; however, 5 days HTFs have increased fibroblast survival/death compared to example 1 and poor cell adhesion resistance, with risk of drain blockage.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (12)
1. The photocuring biocompatible material is characterized by comprising the following components in parts by weight:
0.01-0.08 part of A component;
100 parts of a component B;
0.1-1 part of photoinitiator;
wherein the A component is a sulfhydryl-containing compound;
the component B comprises a functional material I, a functional material II and modified gelatin;
the functional material I contains an antimetabolite structure;
the functional material II contains an anti-cell adhesion structure;
the functional material I contains carbon-carbon double bonds;
The functional material I is modified uracil;
The modified uracil is prepared according to the following method: under the protection of inert gas, mixing 5-formyl uracil, allylamine, anhydrous magnesium sulfate and methylene dichloride, stirring at 15-25 ℃, filtering, taking filtrate, distilling under reduced pressure, and drying at normal temperature in vacuum to obtain the modified uracil.
2. The photocurable biocompatible material of claim 1, wherein the a component is selected from at least one of 3-mercapto- β, 4-dimethylcyclohexanediethiol, bicyclo [2.2.1] heptane-2, 3-dithiol, 1, 5-pentanedithiol, ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate).
3. The photocurable biocompatible material according to claim 1, wherein the mass ratio of the functional material I, the functional material II, and the modified gelatin in the B component is (0.1-0.5): (1-3): 100.
4. The photocurable biocompatible material of claim 1, wherein said 5-formyluracil, said allylamine, said anhydrous magnesium sulfate are present in a molar ratio of 1: (0.8-1.2): (0.5-1.5).
5. The photocurable biocompatible material of claim 1, wherein said 5-formyluracil, said allylamine, said anhydrous magnesium sulfate are present in a molar ratio of 1:1:1.
6. The photocurable biocompatible material of claim 1, wherein said cell adhesion resistant structure is a phosphorylcholine structure.
7. The photocurable biocompatible material according to claim 6, wherein the functional material II is 2-methacryloyloxyethyl phosphorylcholine.
8. The photocurable biocompatible material according to claim 1, wherein the modified gelatin is prepared according to the following method: mixing gelatin with water, regulating pH value to be alkaline, then dripping allyl glycidyl ether to react, regulating pH value to be neutral, and sequentially dialyzing, and freeze-drying to obtain the modified gelatin.
9. The photocurable biocompatible material of claim 8, wherein the mass ratio of said gelatin to said allyl glycidyl ether is 20: (0.8-1.5).
10. The photocurable biocompatible material of claim 8, wherein the mass ratio of said gelatin to said allyl glycidyl ether is 20:1.
11. The photocurable biocompatible material according to any one of claims 1-10, wherein the photoinitiator is selected from at least one of photoinitiator 2959, photoinitiator TPO-L, and photoinitiator 184.
12. A drainage tube prepared from the photocurable biocompatible material according to any one of claims 1-11 by a photocuring process.
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