CN107376020B - Artificial ligament surface modification method - Google Patents
Artificial ligament surface modification method Download PDFInfo
- Publication number
- CN107376020B CN107376020B CN201710565623.7A CN201710565623A CN107376020B CN 107376020 B CN107376020 B CN 107376020B CN 201710565623 A CN201710565623 A CN 201710565623A CN 107376020 B CN107376020 B CN 107376020B
- Authority
- CN
- China
- Prior art keywords
- ligament
- fabric
- washing
- ligament fabric
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic System
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/30—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M14/32—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/15—Proteins or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Abstract
The invention relates to a surface modification method of an artificial ligament. The main treatment steps comprise: 1. deeply cleaning the artificial ligament fabric; 2. a step of peroxidation of the fiber surface; 3. a step of graft polymerization of the fiber surface; 4. a second cleaning process; 5. and (5) a segmented coating process. The method is characterized in that a multi-step ultrasonic/washing liquid synergistic treatment mode is adopted, so that a more excellent surface can be obtained; the ozone/ultraviolet combined oxidation method is beneficial to improving the grafting efficiency and reducing the generation of homopolymer. The grafted hydrophilic polymer layer is in a three-dimensional net-shaped gel-like structure, and provides a better environment for the development of cells. Through cleaning again, ligament fabric surface is cleaner, more is favorable to the adhesion of cell, growth, proliferation. By coating biochemical reagents and mineralized coatings in sections, the ligament joint cavity section can induce the growth of autologous synovial tissues more easily, and the ligament automization is facilitated; the osteogenesis of the bone tunnel segment is enhanced, and the ligament and the bone are better healed.
Description
Technical Field
The invention relates to the field of biological materials, in particular to a surface modification method of an artificial ligament.
Background
Knee cruciate ligament injury is one of the most common injuries of the knee joint, and is usually caused by violent knee joint movement, so that the knee joint is unstable and cartilage is degenerated if the injuries are not treated in time, and the life quality of a patient is influenced. In the current cruciate ligament reconstruction treatment, the use of artificial ligaments is more and more widespread.
Currently, most of the artificial ligaments clinically applied mainly include LARS, Ligustic, Leeds-Keio and Neolignes, which are all made of polyethylene terephthalate (PET). Because the PET molecular structure is symmetrical, the crystallinity is high, and no strong polar group exists in the molecule, the surface affinity is poor, and the PET molecular structure is easy to cause postoperative complications such as infection, chronic synovitis, stiffness and the like after being implanted into a human body. Therefore, the PET material must be surface-modified to improve compatibility with human tissues.
At present, the PET surface modification mostly adopts a method of chemical grafting on the PET surface, and attempted grafting layers mainly comprise sodium styrene sulfonate, (methyl) acrylic acid, acrylamide, heparin, chitosan, hyaluronic acid, gelatin, 2-methacryloyloxyethyl phosphorylcholine and the like. These graft layers can improve the morphology and distribution uniformity of cells on the surface of ligament fibers. However, further observation shows that the anchoring points of the cells on the fiber surface are still few, obvious gaps exist between autologous fiber tissues and artificial ligament fibers, the grown-in fiber tissues cannot feel repeated stimulation of proper stress and basically have no mechanical property, and the main function of the artificial ligament fiber anchoring device is to avoid direct contact between the artificial ligament fibers and between bones and artificial ligaments. In addition, due to the existence of biological factors and mechanical factors, the fusion of the artificial ligament graft and the bone tunnel is poor, and the phenomenon of bone tunnel enlargement is common clinically. The bone tunnel needs to be repaired after being enlarged, the bone defect of the enlarged part makes the attachment and the fixation of the graft more difficult, the operation needs to be carried out in stages, and the operation cost and the pain of the patient are obviously increased.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a surface-modified artificial ligament, wherein a hydrophilic polymer layer in a three-dimensional net-shaped gel-like structure is grafted on the surface of ligament fiber, so that the artificial ligament has better biocompatibility, stronger capability of inducing the regeneration of functional tissues and more stable anchoring. The mineralized coating is coated on the bone tunnel parts at the two ends of the ligament, so that the combination of the graft and the bone interface is better, and the mechanical property is enhanced.
The invention discloses a method for carrying out artificial ligament fiber surface modification, which mainly comprises the following preparation procedures: 1. deeply cleaning the artificial ligament fabric; 2. a step of peroxidation of the fiber surface; 3. a step of graft polymerization of the fiber surface; 4. a second cleaning process; 5. and (5) a segmented coating process.
1. Deep cleaning process
The purpose of cleaning the artificial ligament fabric is to eliminate various impurities carried on the surface thereof. These impurities inhibit smooth progress of the subsequent peroxidation step and graft polymerization step. More importantly, the impurities are important reasons for causing chronic synovitis and preventing adhesion and proliferation of tissue cells on the fiber surface. Therefore, it must be removed.
The deep cleaning process is characterized in that impurities contained in a certain depth on the surface of the fiber are removed by a specific cleaning method without obviously influencing the main performance of the fiber body.
The specific cleaning method is characterized by adopting a multi-step and ultrasonic/washing liquid synergistic treatment mode. Specifically, in the presence of ultrasonic waves, the ligament fabric is sequentially washed by acid washing liquor, deionized water and alkaline washing liquor and finally by the deionized water until the pH value of the washing water is restored to 7.
The certain depth is preferably controlled to be 1 to 1000nm, preferably 5 to 500nm, more preferably 10 to 200nm below the surface layer of the fiber.
2. Peroxidation of fiber surface
In order for the hydrophilic monomer to be successfully grafted onto the fiber surface, the peroxy group must first be prepared on the fiber surface. The surface graft polymerization of the hydrophilic monomer is initiated by the free radical generated by the decomposition of the peroxy group.
The peroxy group can be prepared by one or more methods selected from peroxide method, ozonization method, high energy ray method (gamma ray, ultraviolet ray, electron beam, etc.), and preferably by ozone/ultraviolet combined oxidation method from the viewpoint of easy realization.
The oxidation rate can be further increased by using fiber swelling agents such as toluene, butanone, heptanone, tetrahydrofuran, nitromethane, N-dimethylformamide and the like, with tetrahydrofuran being preferably used.
After ozonization is finished, in order to remove residual ozone, oxygen and other useless groups, the ligament fabric is sequentially passed through a solution of distilled water, absolute ethyl alcohol and tetrahydrofuran, and repeated for no less than 3 times, and finally placed in a vacuum oven, and vacuum-pumping is continuously carried out for 30min at room temperature.
3. Surface graft polymerization step
The peroxidized ligament fiber is placed in a hydrophilic monomer solution, and the reaction conditions are controlled, so that the hydrophilic monomer is subjected to graft polymerization on the surface of the fiber to form a hydrophilic polymer layer coated on the surface of the fiber, the biocompatibility of the fiber is increased, and the adhesion, growth and proliferation of fibroblasts are facilitated.
The hydrophilic polymer layer is characterized in that the hydrophilic polymer layer is a three-dimensional network structure formed by polymerizing hydrophilic monomers and a cross-linking agent, has better water absorption and water retention capacity, and has the characteristic of slight water absorption swelling to provide a uniform gel-like environment for the development of cells.
The hydrophilic monomer comprises carboxylate, phosphate, sulfonate, and sulfate esters. Preferably one or more of (meth) acrylic acid, methyl methacrylate, (meth) acrylamide-N-phenylsulfonate, sodium styrenesulfonate, and ethylene glycol methacrylate phosphate. In view of the excellent biological activity of these hydrophilic monomers, methacrylic acid and sodium p-styrenesulfonate are more preferable.
The crosslinking agent is preferably a polyhydric alcohol such as propylene glycol, butylene glycol, trimethylolpropane, glycerol, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerol; polyunsaturated esters having more than two vinyl groups, such as diethylene glycol diacrylate, polyethylene glycol diacrylate; bisacrylamides, such as N, N-methylenebisacrylamide; polyglycidyl compounds, such as (poly) ethylene glycol diglycidyl ether, (poly) ethylene glycol triglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) glycerol diglycidyl ether, (poly) glycerol triglycidyl ether, and (poly) glycerol polyglycidyl ether. These crosslinking agents may be used alone, or two or more kinds may be used in combination. In view of the excellent reactivity of these crosslinking agents, N-methylenebisacrylamide and (poly) ethylene glycol diglycidyl ether are preferable.
4. Re-cleaning process
The composition range of the radical graft polymer is wide, and unreacted monomers, a small amount of homopolymers, and the like are mixed in a large amount. And (3) basically performing the same action as the procedure 1, and cleaning the grafted ligament fabric again. Preparing for the subsequent coating process and facilitating the adhesion, growth and proliferation of cells.
The re-cleaning process is characterized in that the fabric grafted with the hydrophilic polymer layer is taken out of the reactor and the fabric is cleaned in a multi-step ultrasonic/washing liquor synergistic treatment mode. Specifically, the ligament fabric is placed into washing liquor, washed by ultrasonic oscillation, and finally washed by deionized water until the pH value of the washing water returns to 7. This step may be repeated multiple times.
5. And (5) a segmented coating process.
After the hydrophilic polymer layer is grafted on the surface, the hydrophilicity of the fiber is greatly enhanced, and the ligament fabric is coated in a segmented mode in order to further enhance the biocompatibility of the ligament fabric.
The segmented coating is characterized in that biochemical reagents are injected into the ligament joint cavity segment, and the bone tunnel segment is subjected to bone layer coating.
The biochemical reagent comprises a growth factor, such as a fibroblast growth factor; biologically active proteins such as fibronectin, type I collagen and type III collagen. From the viewpoint of production cost and safety, a mixture of fibronectin and type I or type III collagen is preferable.
The injection mode of the biochemical reagent can be realized by immersing the ligament fabric into a solution containing the biochemical reagent. In order to accelerate the diffusion speed, the diffusion of the biochemical reagent into a swelling network formed by the hydrophilic polymer can be promoted by cooperatively adopting an ultrasonic oscillation mode.
The bone-promoting layer comprises mineralized coating with osteoconduction and osteoinduction, such as hydroxyapatite, bioglass, tricalcium phosphate, silicon dioxide, titanium dioxide, bioceramic and the like. Preferably hydroxyapatite.
The bone layer may be applied by immersing the ligament fabric in a solution containing the mineralising substance. In order to enhance the penetration depth, the stability and the bonding force of the coating, the diffusion of mineral substances into a swelling network formed by the hydrophilic polymer can be promoted by cooperatively adopting an ultrasonic oscillation mode.
Finally, taking out the ligament fabric, placing the ligament fabric in a vacuum oven, and drying until the water content is less than 10%.
Compared with the prior art, the artificial ligament surface modification method has the following main beneficial effects:
1) a multi-step ultrasonic/washing liquid synergistic treatment mode is adopted, so that a cleaner, excellent and more suitable grafted surface can be obtained;
2) the ozone/ultraviolet combined oxidation method has the advantages of rapid oxidation, deep oxidation degree, high peroxy group content and the like, and is beneficial to improving grafting efficiency and reducing the generation of homopolymers.
3) The hydrophilic polymer layer is in a three-dimensional net-shaped gel-like structure, has better water absorption and retention capacity, and provides a better environment for the development of cells.
4) Through cleaning again, ligament fabric surface is cleaner, more is favorable to the adhesion of cell, growth, proliferation.
5) Through segmented coating, the growth of autologous synovial tissue is more easily induced by the ligament joint cavity segment, and the ligament automization is facilitated; the osteogenesis of the bone tunnel segment is enhanced, and the ligament and the bone are better healed.
Detailed Description
The process of the invention is described as follows by taking polyethylene terephthalate (PET) fiber fabric as an example:
soaking the PET artificial ligament fabric into an acid washing solution consisting of hydrochloric acid, tetrahydrofuran and sodium dodecyl benzene sulfonate, starting ultrasonic oscillation (frequency of 40KHz and power of 70W), treating for 10min, and washing with deionized water until the pH value of the washing water is restored to 7. And then soaking the PET artificial ligament fabric into alkaline washing liquor consisting of sodium carbonate, tetrahydrofuran and sodium dodecyl benzene sulfonate, starting ultrasonic oscillation (frequency is 40KHz and power is 70W), treating for 10min, and washing with deionized water until the pH value of the washing water is restored to 7. The cleanness degree of the fiber surface is observed by a scanning electron microscope, and the fiber in the visual field is smooth and has no obvious granular residue. The percentage of weight gain per unit volume of fiber is used as an indication of the depth of treatment and should be < 10%. And (5) performing mechanical property test, and entering the next working procedure when the tensile resistance and the elongation at break change by less than 5%.
Putting the cleaned PET artificial ligament fabric into an ultraviolet ozonization reactor, wherein the flow rate of ozone is 50mg/L, the ultraviolet lamp is 10W, the wavelength is 185nm, the irradiation distance is 20cm, and the treatment time is 30 min. After the oxidation is finished, the ligament fabric is sequentially put through solutions of distilled water, absolute ethyl alcohol and tetrahydrofuran for at least 3 times, and finally the ligament fabric is placed in a vacuum oven and is continuously vacuumized for 30min at room temperature. The peroxide content of the ligament fabric was determined as described in GB/T32102-2015.
The peroxidized ligament fabric is placed in a polymerization reactor, and added with deionized water, refined sodium p-styrenesulfonate and methacrylic acid with the same mass, the total concentration of the monomers is 30 percent, and the dosage of N, N-methylene-bisacrylamide is 0.01 percent. Using argon to remove oxygen to O2When the content is less than 6ppm, the mixture is heated to 70 ℃ and reacted for 2 hours.
Taking out the ligament fabric grafted with the hydrophilic polymer layer from the polymerization reactor, putting the ligament fabric into ethanol washing liquor, washing for 15min by ultrasonic oscillation, and finally washing with deionized water until the pH value of the washing water is restored to 7. This step may be repeated multiple times. The grafting was determined by toluidine blue-absorptiometry.
Immersing the intermediate joint segment of the ligament fabric into a mixture solution containing fibronectin and type I collagen, ultrasonically oscillating for 5min, and taking out. Then, two ends of the ligament fabric are immersed in the solution containing the hydroxyapatite, and the ultrasonic oscillation is carried out for 10 min. And finally, taking out the ligament fabric, placing the ligament fabric in a vacuum oven, and drying until the water content is 8%.
The above examples are merely illustrative of the process of the present invention and should not be so limited.
Claims (1)
1. A surface modification method of an artificial ligament is characterized by comprising the following steps: the processing steps comprise: 1. deeply cleaning the artificial ligament fabric; 2. a step of peroxidation of the fiber surface; 3. a step of graft polymerization of the fiber surface; 4. a second cleaning process; 5. a step of segmented coating; wherein:
soaking the polyethylene glycol terephthalate artificial ligament fabric into an acid washing solution consisting of hydrochloric acid, tetrahydrofuran and sodium dodecyl benzene sulfonate, starting ultrasonic oscillation with the frequency of 40KHz and the power of 70W, treating for 10min, and washing with deionized water until the pH value of the washing water returns to 7; then, soaking the polyethylene terephthalate artificial ligament fabric into alkaline washing liquor consisting of sodium carbonate, tetrahydrofuran and sodium dodecyl benzene sulfonate, starting ultrasonic oscillation with the frequency of 40KHz and the power of 70W, treating for 10min, and washing with deionized water until the pH value of the washing water returns to 7; observing the cleanliness of the fiber surface by using a scanning electron microscope, wherein the fiber in a visual field is smooth and has no obvious granular residue, the percentage of the increased weight of the fiber in unit volume is used as the representation of the treatment depth, the value is less than 10%, and the fiber enters the next procedure when the tensile resistance and the elongation at break change by less than 5% after the mechanical property test is carried out;
putting the cleaned polyethylene terephthalate artificial ligament fabric into an ultraviolet ozonization reactor, wherein the flow of ozone is 50mg/L, the ultraviolet lamp is 10W, the wavelength is 185nm, the irradiation distance is 20cm, and the treatment time is 30 min; after the oxidation is finished, sequentially passing the ligament fabric through solutions of distilled water, absolute ethyl alcohol and tetrahydrofuran, repeating the steps for at least 3 times, and finally placing the ligament fabric in a vacuum oven for continuously vacuumizing for 30min at room temperature; the peroxide content of the ligament fabric was determined as described in GB/T32102-2015.
Placing the peroxidized ligament fabric into a polymerization reactor, adding deionized water, refined sodium p-styrenesulfonate and methacrylic acid with the same mass, wherein the total monomer concentration is 30 percent, and the N, N-methylene-bisacrylamide consumption is 0.01 percent; using argon to remove oxygen to O2When the content is less than 6ppm, heating to 70 ℃, and reacting for 2 hours;
taking out the ligament fabric grafted with the hydrophilic polymer layer from the polymerization reactor, putting the ligament fabric into ethanol washing liquor, washing for 15min by ultrasonic oscillation, finally washing with deionized water until the pH value of the washing water returns to 7, and repeating the step; measuring the grafting rate by toluidine blue-absorption photometry;
immersing the intermediate joint section of the ligament fabric into a mixture solution containing fibronectin and type I collagen, ultrasonically oscillating for 5min, and taking out; then immersing both ends of the ligament fabric into a hydroxyapatite-containing solution, and ultrasonically oscillating for 10 min; and finally, taking out the ligament fabric, placing the ligament fabric in a vacuum oven, and drying until the water content is 8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710565623.7A CN107376020B (en) | 2017-07-13 | 2017-07-13 | Artificial ligament surface modification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710565623.7A CN107376020B (en) | 2017-07-13 | 2017-07-13 | Artificial ligament surface modification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107376020A CN107376020A (en) | 2017-11-24 |
| CN107376020B true CN107376020B (en) | 2020-06-26 |
Family
ID=60339396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710565623.7A Active CN107376020B (en) | 2017-07-13 | 2017-07-13 | Artificial ligament surface modification method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107376020B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754014A (en) * | 2017-11-29 | 2018-03-06 | 上海纳米技术及应用国家工程研究中心有限公司 | The antibacterial on PET surface promotees preparation method of bone composite coating and products thereof and application |
| CN110384824B (en) * | 2019-07-19 | 2021-12-10 | 上海市第六人民医院 | Three-section type functional degradable artificial ligament regeneration scaffold and preparation method thereof |
| CN111728737A (en) * | 2020-07-06 | 2020-10-02 | 花沐医疗科技(上海)有限公司 | Multilayer composite bionic artificial ligament and preparation method thereof |
| CN113663128B (en) * | 2021-09-29 | 2022-05-10 | 东华大学 | High-strength composite coating artificial ligament and preparation method and application thereof |
| CN114949353B (en) * | 2022-01-24 | 2023-05-30 | 东华大学 | Biological function differentiated adaptive musculoskeletal system prosthesis and preparation method thereof |
| CN114904048B (en) * | 2022-06-28 | 2022-11-25 | 清华大学 | Polyether-ether-ketone substrate composite material and preparation method and application thereof |
| CN115382018B (en) * | 2022-09-29 | 2023-06-23 | 吉林大学 | Bionic artificial ligament and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143354A (en) * | 1999-02-08 | 2000-11-07 | Medtronic Inc. | One-step method for attachment of biomolecules to substrate surfaces |
| CN1777450A (en) * | 2003-01-17 | 2006-05-24 | 拉思公司-科学研究与应用试验室 | Biomimetic prosthetic ligament and production method thereof |
| WO2009057502A1 (en) * | 2007-11-01 | 2009-05-07 | Iwatani Corporation | Process for production of calcium phosphate composites |
| CN103289020A (en) * | 2013-06-25 | 2013-09-11 | 周婕 | Modification method of medical polyethylene terephthalate (PET) |
| CN103315827A (en) * | 2013-06-25 | 2013-09-25 | 周婕 | Artificial ligament and preparation method thereof |
| CN104119551A (en) * | 2014-07-29 | 2014-10-29 | 复旦大学附属华山医院 | Preparation method of calcium-strontium/gelatin biomimetic coating modified artificial ligament |
-
2017
- 2017-07-13 CN CN201710565623.7A patent/CN107376020B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143354A (en) * | 1999-02-08 | 2000-11-07 | Medtronic Inc. | One-step method for attachment of biomolecules to substrate surfaces |
| CN1777450A (en) * | 2003-01-17 | 2006-05-24 | 拉思公司-科学研究与应用试验室 | Biomimetic prosthetic ligament and production method thereof |
| WO2009057502A1 (en) * | 2007-11-01 | 2009-05-07 | Iwatani Corporation | Process for production of calcium phosphate composites |
| CN103289020A (en) * | 2013-06-25 | 2013-09-11 | 周婕 | Modification method of medical polyethylene terephthalate (PET) |
| CN103315827A (en) * | 2013-06-25 | 2013-09-25 | 周婕 | Artificial ligament and preparation method thereof |
| CN104119551A (en) * | 2014-07-29 | 2014-10-29 | 复旦大学附属华山医院 | Preparation method of calcium-strontium/gelatin biomimetic coating modified artificial ligament |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107376020A (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107376020B (en) | Artificial ligament surface modification method | |
| RU2339407C2 (en) | Biomimetic prosthesis of ligament and method for its manufacturing | |
| JP2566548B2 (en) | Surface-modified surgical instruments, instruments, implants, contact lenses and the like | |
| US5804263A (en) | Combined plasma and gamma radiation polymerization method for modifying surfaces | |
| CN106730051B (en) | Anticoagulation polymer biological material and preparation method and application thereof | |
| DE60214513T2 (en) | PROCESS FOR SURFACE MODIFICATION | |
| EP0611792B1 (en) | Graft polymerization | |
| US5376400A (en) | Combined plasma and gamma radiation polymerization method for modifying surfaces | |
| US6387379B1 (en) | Biofunctional surface modified ocular implants, surgical instruments, medical devices, prostheses, contact lenses and the like | |
| US5094876A (en) | Surface modified surgical instruments, devices, implants, contact lenses and the like | |
| JPH09506665A (en) | Surface modified medical device | |
| CA2252877A1 (en) | Method and composition for modifying the surface of an object by graft polymerization | |
| CN113164645A (en) | Method for obtaining a decellularized extracellular matrix, use and kit thereof | |
| CN111978490A (en) | Method for preparing elastic wood based on ultraviolet light initiated graft polymerization | |
| WO1996040301A1 (en) | Man-made hair for hair implanting and process for producing the same | |
| Yang et al. | Effect of MMA‐g‐UHMWPE grafted fiber on mechanical properties of acrylic bone cement | |
| Zhang et al. | Surface modification of polymethyl methacrylate intraocular lenses by plasma for improvement of antithrombogenicity and transmittance | |
| Gupta et al. | Radiation grafting of acrylic acid/N‐vinyl pyrrolidone binary mixture onto poly (ethylene terephthalate) fabric and growth of human mesenchymal stem cell | |
| JP5393473B2 (en) | Method for producing calcium phosphate complex | |
| CN102743788B (en) | Method for performing surface treatment on material for boosting cell growth and resisting biological pollution | |
| KR100210473B1 (en) | Man-made hair for hair implanting and process for producing the same | |
| CN117860433A (en) | Intraocular lens conveying device and preparation method thereof | |
| KR20030026076A (en) | Immobilization method of antithrombotic proteins on polyurethane surface using plasma treatment | |
| CN117482303A (en) | Heparin anticoagulation coating and preparation method and application thereof | |
| CN116556055A (en) | Quaternary ammonium salt modification of polyester substrate by solution post-grafting method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |