CN103656749A - Composite degradable antibacterial artificial cerebral dura mater and preparation method thereof - Google Patents
Composite degradable antibacterial artificial cerebral dura mater and preparation method thereof Download PDFInfo
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Abstract
The invention provides a composite degradable antibacterial artificial cerebral dura mater, comprising a vancomycin or ofloxacin hydrochloride injection, chitosan and sodium beta-glycerophosphate. The invention is characterized in that a spongy collagen biomembrane stent is prepared from a decellularized membrane-like derivative material, a chitosan solution with a concentration of 2% (w/v) and a sodium beta-glycerophosphate solution with a concentration of 56% (w/v) are used and mixed, and since a hydrogel formed by a compound of the chitosan solution and the sodium beta-glycerophosphate solution at a temperature of 37 DEG C has the characteristic of temperature sensitivity, the vancomycin or ofloxacin hydrochloride injection is added into the compound to form a solution which is used for soaking of the prepared spongy collagen biomembrane stent to prepare a suture-free cerebral dura mater, and the hydrogel compound uniformly infiltrates into the spongy collagen biomembrane stent after disposition in an incubator with a temperature of 37 DEG C for 10 min so as to form the absorbable artificial cerebral dura mater with antibacterial activity. The invention further provides a preparation method. The preparation method has the characteristics of convenience in preparation, easy film formation, low cost, convenient operation, etc.
Description
Technical field
The invention belongs to technical field of biological materials, belong to the biomaterial that the public can access, specifically, is a kind of compound degradable antibacterial artificial dura mater and preparation method thereof.
Background technology
Chitosan, English chitosan, is the copolymer of p (1-4) one 2 one acetylamino one 2 one deoxidation one D glucosans and 2 one amino one 2 one deoxidation one D glucosans, the biological dimer of this polycation is mainly by obtaining chitin deacetylation.Due to wide material sources, avirulence, there is good histocompatibility, biodegradability and adhesive attraction, this material has obtained further investigation and extensive use in medical science, field of biology.Chenite etc. (are shown in CheniteA, ChaputC, WangD, et al. Novel injectable neutral solutions ofchitosan form biodegradable gels in situ[J]. Biomaterials, 2000, 21 (21): 2155-2161.) in application sodium glycerophosphate and after chitosan, obtained pH value neutrality and can keep for a long time at normal temperatures liquid chitosan/β shape to generate hydrogel, and have not carcinogenic, unlikely deformity, not mutagenic characteristic, through sterilizing, become a kind of medicine of injectable non-vein, being widely used in tissue engineering becomes carrier and the cytoskeleton material of medicine.
Biological substitution material has and uses safe and effective, easy operating, more pliable and tougher, wide material sources, the advantage such as cheap, good biocompatibility as dural substitutes.Normal cattle tendon, Cor Sus domestica bag, bovine pericardium, Cor Caprae seu ovis bag, cattle peritoneum, pig peritoneum, the mesentery of using replaces dura mater.But there is again the adhesion of causing simultaneously, be difficult for preserving, be difficult for sterilization, the shortcomings such as immunoreation likely occur.
Comparatively desirable artificial dura mater should possess following characteristics: 1. without immunological rejection, non-toxic reaction, without carcinogenic, teratogenesis; 2. be ductile, pliability, can prevent and treat infection; 3. through sewing up or pasting, can prevent cerebrospinal leak, effectively protecting cerebral tissue, with cerebral tissue without adhesion, without cicatrix; 4. after generating, newborn class meninges sample tissue can be absorbed completely by body; 5. material source is convenient, easily preserves; 6. price is relatively moderate.
The more artificial dura mater of existing clinical practice is main mainly with import, as sky justice good fortune (DuraMax), hat sky (NormalGEN), auspiciously ly come (DuraGen), that one hundred core is thought (Dura scaffold) is expensive, has the case of more intracranial infection and rejection.The patient of cerebrospinal leak is also more, all can not meet above-mentioned requirements completely.
The present invention is intended to develop the dural substitutes that is more suitable for clinical needs.
Summary of the invention
The object of the invention is prior art to carry out substantial improvements and innovation, a kind of compound degradable antibacterial artificial dura mater is provided, and its preparation method is provided.Its preparation method has easy to make, and easily film forming, with low cost, the features such as convenient operation.Prepared compound degradable antibacterial artificial hard brain is that dura defect position provides and is beneficial to the spongy collagen biomembrane support that fibroblast is grown into and drills tissue regeneration promoting dura mater tissue, with add vancomycin or ofloxacin hydrochloride for temperature sensitive chitosan/sodium β-glycerophosphate complex 37 ℃ of combinations, prepare and there is good histocompatibility and degradability, can effectively reduce the seepage of intracranial infection and cerebrospinal fluid, also reduce the ulotic NEW TYPE OF COMPOSITE artificial dura mater of shape between cerebral tissue and adjacent tissue simultaneously.
The object of the invention is to be realized by following technical scheme: a kind of compound degradable antibacterial artificial dura mater, comprise vancomycin or ofloxacin hydrochloride injection, chitosan and sodium β-glycerophosphate, it is characterized in that: will take off the membranaceous bio-derived material of cell and make spongy collagen biomembrane support, application 2% (w/v) chitosan solution 8ml, 56% (w/v) sodium β-glycerophosphate solution 1ml mixes, according to chitosan and the solution combined thing of sodium β-glycerophosphate, form the characteristic of the temperature sensitivity of hydrogel 37 ℃ time, by 0.1g vancomycin or 0.1g ofloxacin hydrochloride injection lml, the spongy collagen biomembrane support that adds the solution of chitosan and the solution combined thing of sodium β-glycerophosphate to immerse to have made exempt to sew up cerebral dura mater, in 37 ℃ of incubators, place 10min, hydrogel composites evenly immerses spongy collagen biomembrane support and forms the absorbable artificial dura mater with antibacterial activity.
The described membranaceous bio-derived material of de-cell comprises any one in cattle tendon, Cor Sus domestica bag, bovine pericardium, Cor Caprae seu ovis bag, cattle peritoneum, pig peritoneum, Intestinum Bovis seu Bubali, Intestinum Sus domestica and Intestinum caprae seu ovis.
A preparation method for compound degradable antibacterial artificial dura mater, is characterized in that, it comprises the following steps:
1) preparation of spongy collagen biomembrane support; After utilizing collagem membrane lyophilization, be prepared from, there is porosity and looseness shape structure, there is good infiltration and water absorbing capacity, adopt the de-membranaceous bio-derived material of cell to be placed in 75% alcoholic solution and peracetic acid soaking disinfection 2h, with phosphate buffer, repeatedly rinse 3 times; Be placed on sodium hydroxide solution and soak 2h, then rinse and be dipped to PH7.4 with phosphate buffer; Place it in freezing 24 h in-80 ℃ of low temperature liquid nitrogens, be placed in vacuum freeze-drying machine lyophilization 24 h, liquid nitrogen freezing pulverizer is pulverized 40 min, No. 9 screen cloth is got the following collagen particle of particle diameter 80 μ m, by collagen particle and 0.5% trypsin, 0.2% ethylenediaminetetraacetic acid, be that EDTA mixes for 1: 5 by volume, 4 ℃ of refrigerators, 24 h that vibrate, with centrifugal radius 8 cm, the centrifugal 20 min supernatant discarded liquid of 5000 r/min; Phosphate buffer cleans 3 times repeatedly, after the same method is centrifugal, abandon supernatant, centrifugal rear collagen particle is mixed with 1 mol/L glacial acetic acid for 1: 5 by volume, collagen particle mixes in mass ratio with pepsin at 100: 1,4 ℃ of refrigerator continuous oscillation 24h, in removal collagen particle, the unspiralized region of tropocollagen molecule, regulates pH value to 7.4 with 1 mol/L sodium hydroxide, with centrifugal radius 8 cm, centrifugal 20 min of 5000 r/min; Supernatant discarded liquid, tri-distilled water cleans 3 times repeatedly, with centrifugal radius 8 cm, centrifugal 20 min of 5000 r/min; Supernatant discarded liquid, precipitate is placed in special cylindrical die, and specification has 6cm * 6cm; 8cm * 8cm; 10cm * 10cm; 12cm * 120cm, thickness 2-4 millimeter, with the lyophilization of vacuum freeze-drying machine, in-80 ℃ of low temperature liquid nitrogens after freezing 24 h, take out after being placed in freezer dryer molding 24 h, obtain the de-spongy collagen biomembrane of cell, vacuum packaging, ethylene oxide sterilizing, 4 ℃ of Refrigerator stores are standby;
2) preparation of chitosan/sodium β-glycerophosphate complex: get 36% concentrated hydrochloric acid 0.43ml, adding tri-distilled water to total liquid measure is 50ml, get in the 50ml volumetric flask that 0.43ml hydrochloric acid adds tri-distilled water, adding tri-distilled water standardize solution is 50 milliliters, be mixed with the dilute hydrochloric acid of 0.1M, chitosan specification is: viscosity 150mPa.s, molecular weight 8.13 ten thousand dalton, de-second phthalein degree 91%, 2g chitosan is dissolved in the dilute hydrochloric acid of 0.1M, under 23 ℃ of room temperatures, with magnetic stirring apparatus, fully stir 30 minutes, rotating speed 450r/min, mix and make total amount 100ml solution, be prepared into 2% (w/v) chitosan solution, 121 ℃ of autoclave sterilization 30min, 4 ℃ of Refrigerator stores are standby, 56% (w/v) sodium β-glycerophosphate solution preparation 56g sodium β-glycerophosphate, adding tri-distilled water dissolves completely, be settled to 100ml, filtration sterilization, 121 ℃ of autoclave sterilization 30min, 4 ℃ of Refrigerator stores are standby, 2% (w/v) chitosan and 56% (w/v) sodium β-glycerophosphate are with the ratio preparation of 8:1, pH value is 7.25, in 37 ℃ of water-baths, becoming the hydrogel time is 6 minutes,
3) get 2% (w/v) chitosan solution 8ml:56% (w/v) sodium β-glycerophosphate solution 1ml:0.1g vancomycin or 0.1g ofloxacin hydrochloride injection lml, three is after 4 ℃ of even mixing, to take off the spongy collagen biomembrane of cell, immerse above-mentioned mixed solution, in 37 ℃ of incubators, place 10 minutes, mixed solution forms hydrogel and collagen biomembrane combines together.
A kind of compound degradable antibacterial artificial dura mater of the present invention, by adopting hydrogel composites evenly to immerse spongy collagen biofilm formation, because there be existing in art of hydrogel can not need to sew up, there is the good compatibility with tissue, through experimental results show that without cerebrospinal leak, occur; Vancomycin in hydrogel or ofloxacin hydrochloride slowly discharge in hydrogel is degraded gradually, reach the object of control intracranial infection; Collagen sponge membrane degradation speed and human body self the dura mater speed of growth is similar, has good absorbability and histology's compatibility; Material source is extensive, cheap, uses safety, and the life-span is long.
The preparation method science of compound degradable antibacterial artificial dura mater of the present invention, reasonable, preparation flow is easily controlled, and quality of forming film is good, and biological characteristics is good.
The specific embodiment
Below in conjunction with embodiment, the invention will be further described.
A kind of compound degradable antibacterial artificial dura mater, comprise vancomycin or ofloxacin hydrochloride injection, chitosan and sodium β-glycerophosphate, it is characterized in that: will take off the membranaceous bio-derived material of cell and make spongy collagen biomembrane support, application 2% (w/v) chitosan solution 8ml, 56% (w/v) sodium β-glycerophosphate solution 1ml mixes, according to chitosan and the solution combined thing of sodium β-glycerophosphate, form the characteristic of the temperature sensitivity of hydrogel 37 ℃ time, the spongy collagen biomembrane support that 0.1g vancomycin or 0.1g ofloxacin hydrochloride injection lml are added the solution of chitosan and the solution combined thing of sodium β-glycerophosphate to immerse to have made exempt to sew up cerebral dura mater, in 37 ℃ of incubators, place 10min, hydrogel composites evenly immerses spongy collagen biomembrane support and forms the absorbable artificial dura mater with antibacterial activity.
The described membranaceous bio-derived material of de-cell comprises any one in cattle tendon, Cor Sus domestica bag, bovine pericardium, Cor Caprae seu ovis bag, cattle peritoneum, pig peritoneum, Intestinum Bovis seu Bubali, Intestinum Sus domestica and Intestinum caprae seu ovis.
The present invention, by the concrete enforcement of 9 embodiment, adopts respectively cattle tendon, Cor Sus domestica bag, bovine pericardium, Cor Caprae seu ovis bag, cattle peritoneum, pig peritoneum, Intestinum Bovis seu Bubali, Intestinum Sus domestica and Intestinum caprae seu ovis to be prepared compound degradable antibacterial artificial dura mater, all succeeds.
Embodiment 1: existing take as the cattle tendon of one of de-membranaceous bio-derived material of cell as example illustrate its specifically compound degradable antibacterial artificial dura mater be prepared method, for the membranaceous bio-derived material of described other de-cell with embodiment 1: comprise the following steps:
1) preparation of spongy collagen biomembrane support; After utilizing collagem membrane lyophilization, be prepared from, there is porosity and looseness shape structure, there is good infiltration and water absorbing capacity, adopt the cattle tendon of one of de-membranaceous bio-derived material of cell to be placed in 75% alcoholic solution and peracetic acid soaking disinfection 2h, with phosphate buffer, repeatedly rinse 3 times; Be placed on sodium hydroxide solution and soak 2h, then rinse and be dipped to PH7.4 with phosphate buffer; Place it in freezing 24 h in-80 ℃ of low temperature liquid nitrogens, be placed in vacuum freeze-drying machine lyophilization 24 h, liquid nitrogen freezing pulverizer is pulverized 40 min, No. 9 screen cloth is got the following collagen particle of particle diameter 80 μ m, by collagen particle and 0.5% trypsin, 0.2% ethylenediaminetetraacetic acid, be that EDTA mixes for 1: 5 by volume, 4 ℃ of refrigerators, 24 h that vibrate, with centrifugal radius 8 cm, the centrifugal 20 min supernatant discarded liquid of 5000 r/min; Phosphate buffer cleans 3 times repeatedly, after the same method is centrifugal, abandon supernatant, centrifugal rear collagen particle is mixed with 1 mol/L glacial acetic acid for 1: 5 by volume, collagen particle mixes in mass ratio with pepsin at 100: 1,4 ℃ of refrigerators 24h that shakes continuously, removes the unspiralized region of tropocollagen molecule in collagen particle, by 1 mol/L sodium hydroxide adjusting pH value to 7.4, with centrifugal radius 8 cm, centrifugal 20 min of 5000 r/min; Supernatant discarded liquid, tri-distilled water cleans 3 times repeatedly, with centrifugal radius 8 cm, centrifugal 20 min of 5000 r/min; Supernatant discarded liquid, precipitate is placed in special cylindrical die, and specification has 6cm * 6cm; 8cm * 8cm; 10cm * 10cm; 12cm * 120cm, thickness 2-4 millimeter, with the lyophilization of vacuum freeze-drying machine, in-80 ℃ of low temperature liquid nitrogens after freezing 24 h, take out after being placed in freezer dryer molding 24 h, obtain the de-spongy collagen biomembrane of cell, vacuum packaging, ethylene oxide sterilizing, 4 ℃ of Refrigerator stores are standby;
2) preparation of chitosan/sodium β-glycerophosphate complex: get 36% concentrated hydrochloric acid 0.43ml, adding tri-distilled water to total liquid measure is 50ml, get in the 50ml volumetric flask that 0.43ml hydrochloric acid adds tri-distilled water, adding tri-distilled water standardize solution is 50 milliliters, be mixed with the dilute hydrochloric acid of 0.1M, chitosan specification is: viscosity 150mPa.s, molecular weight 8.13 ten thousand dalton, de-second phthalein degree 91%, 2g chitosan is dissolved in the dilute hydrochloric acid of 0.1M, under 23 ℃ of room temperatures, with magnetic stirring apparatus, fully stir 30 minutes, rotating speed 450r/min, mix and make total amount 100ml solution, be prepared into 2% (w/v) chitosan solution, 121 ℃ of autoclave sterilization 30min, 4 ℃ of Refrigerator stores are standby, 56% (w/v) sodium β-glycerophosphate solution preparation 56g sodium β-glycerophosphate, adding tri-distilled water dissolves completely, be settled to 100ml, filtration sterilization, 121 ℃ of autoclave sterilization 30min, 4 ℃ of Refrigerator stores are standby, 2% (w/v) chitosan and 56% (w/v) sodium β-glycerophosphate are with the ratio preparation of 8:1, pH value is 7.25, in 37 ℃ of water-baths, becoming the hydrogel time is 6 minutes,
3) get 2% (w/v) chitosan solution 8ml:56% (w/v) sodium β-glycerophosphate solution 1ml:0.1g vancomycin or 0.1g ofloxacin hydrochloride injection lml, three is after 4 ℃ of even mixing, to take off the spongy collagen biomembrane of cell, immerse above-mentioned mixed solution, in 37 ℃ of incubators, place 10 minutes, mixed solution forms hydrogel and collagen biomembrane combines together.
The compound degradable antibacterial artificial dura mater of making by a kind of compound degradable antibacterial artificial dura mater preparation method of the present invention, through the use of the 1-10 of 30Li colony month, respond well, realize the object of the invention and reached described effect.
Claims (3)
1. a compound degradable antibacterial artificial dura mater, comprise vancomycin or ofloxacin hydrochloride injection, chitosan and sodium β-glycerophosphate, it is characterized in that: will take off the membranaceous bio-derived material of cell and make spongy collagen biomembrane support, application 2% (w/v) chitosan solution 8ml, 56% (w/v) sodium β-glycerophosphate solution 1ml mixes, according to chitosan and the solution combined thing of sodium β-glycerophosphate, form the characteristic of the temperature sensitivity of hydrogel 37 ℃ time, the spongy collagen biomembrane support that 0.1g vancomycin or 0.1g ofloxacin hydrochloride injection lml are added the solution of chitosan and the solution combined thing of sodium β-glycerophosphate to immerse to have made exempt to sew up cerebral dura mater, in 37 ℃ of incubators, place 10min, hydrogel composites evenly immerses spongy collagen biomembrane support and forms the absorbable artificial dura mater with antibacterial activity.
2. a kind of compound degradable antibacterial artificial dura mater according to claim 1, is characterized in that: the de-membranaceous bio-derived material of cell comprises any one in cattle tendon, Cor Sus domestica bag, bovine pericardium, Cor Caprae seu ovis bag, cattle peritoneum, pig peritoneum, Intestinum Bovis seu Bubali, Intestinum Sus domestica and Intestinum caprae seu ovis.
3. the preparation method of a kind of compound degradable antibacterial artificial dura mater according to claim 1, is characterized in that, it comprises the following steps:
1) preparation of spongy collagen biomembrane support; After utilizing collagem membrane lyophilization, be prepared from, there is porosity and looseness shape structure, there is good infiltration and water absorbing capacity, adopt the de-membranaceous bio-derived material of cell to be placed in 75% alcoholic solution and peracetic acid soaking disinfection 2h, with phosphate buffer, repeatedly rinse 3 times; Be placed on sodium hydroxide solution and soak 2h, then rinse and be dipped to PH7.4 with phosphate buffer; Place it in freezing 24 h in-80 ℃ of low temperature liquid nitrogens, be placed in vacuum freeze-drying machine lyophilization 24 h, liquid nitrogen freezing pulverizer is pulverized 40 min, No. 9 screen cloth is got the following collagen particle of particle diameter 80 μ m, by collagen particle and 0.5% trypsin, 0.2% ethylenediaminetetraacetic acid, be that EDTA mixes for 1: 5 by volume, 4 ℃ of refrigerators, 24 h that vibrate, with centrifugal radius 8 cm, the centrifugal 20 min supernatant discarded liquid of 5000 r/min; Phosphate buffer cleans 3 times repeatedly, after the same method is centrifugal, abandon supernatant, centrifugal rear collagen particle is mixed with 1 mol/L glacial acetic acid for 1: 5 by volume, collagen particle mixes in mass ratio with pepsin at 100: 1,4 ℃ of refrigerator continuous oscillation 24h, in removal collagen particle, the unspiralized region of tropocollagen molecule, regulates pH value to 7.4 with 1 mol/L sodium hydroxide, with centrifugal radius 8 cm, centrifugal 20 min of 5000 r/min; Supernatant discarded liquid, tri-distilled water cleans 3 times repeatedly, with centrifugal radius 8 cm, centrifugal 20 min of 5000 r/min; Supernatant discarded liquid, precipitate is placed in special cylindrical die, and specification has 6cm * 6cm; 8cm * 8cm; 10cm * 10cm; 12cm * 120cm, thickness 2-4 millimeter, with the lyophilization of vacuum freeze-drying machine, in-80 ℃ of low temperature liquid nitrogens after freezing 24 h, take out after being placed in freezer dryer molding 24 h, obtain the de-spongy collagen biomembrane of cell, vacuum packaging, ethylene oxide sterilizing, 4 ℃ of Refrigerator stores are standby;
2) preparation of chitosan/sodium β-glycerophosphate complex: get 36% concentrated hydrochloric acid 0.43ml, adding tri-distilled water to total liquid measure is 50ml, get in the 50ml volumetric flask that 0.43ml hydrochloric acid adds tri-distilled water, adding tri-distilled water standardize solution is 50 milliliters, be mixed with the dilute hydrochloric acid of 0.1M, chitosan specification is: viscosity 150mPa.s, molecular weight 8.13 ten thousand dalton, de-second phthalein degree 91%, 2g chitosan is dissolved in the dilute hydrochloric acid of 0.1M, under 23 ℃ of room temperatures, with magnetic stirring apparatus, fully stir 30 minutes, rotating speed 450r/min, mix and make total amount 100ml solution, be prepared into 2% (w/v) chitosan solution, 121 ℃ of autoclave sterilization 30min, 4 ℃ of Refrigerator stores are standby, 56% (w/v) sodium β-glycerophosphate solution preparation 56g sodium β-glycerophosphate, adding tri-distilled water dissolves completely, be settled to 100ml, filtration sterilization, 121 ℃ of autoclave sterilization 30min, 4 ℃ of Refrigerator stores are standby, 2% (w/v) chitosan and 56% (w/v) sodium β-glycerophosphate are with the ratio preparation of 8:1, pH value is 7.25, in 37 ℃ of water-baths, becoming the hydrogel time is 6 minutes,
3) get 2% (w/v) chitosan solution 8ml:56% (w/v) sodium β-glycerophosphate solution 1ml:0.1g vancomycin or 0.1g ofloxacin hydrochloride injection lml, three is after 4 ℃ of even mixing, to take off the spongy collagen biomembrane of cell, immerse above-mentioned mixed solution, in 37 ℃ of incubators, place 10 minutes, mixed solution forms hydrogel and collagen biomembrane combines together.
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| CN104189955A (en) * | 2014-08-08 | 2014-12-10 | 苗九昌 | Degradable endocranium repair stent compounded by human amniotic membrane and bull dorsal aponeurosis and preparation method of repair stent |
| CN105903077A (en) * | 2016-04-14 | 2016-08-31 | 山东景源生物科技有限公司 | Preparation method of biological matrix gel material for promoting regeneration and repair of cartilage, gel performance determination method and application |
| CN106474563A (en) * | 2016-12-02 | 2017-03-08 | 上海其胜生物制剂有限公司 | A kind of method that reversal temperature sensitive technology prepares artificial dura mater |
| CN106725743A (en) * | 2017-01-11 | 2017-05-31 | 首都医科大学附属北京天坛医院 | A kind of huge and very significant meningioma overall cutting method |
| CN109260472A (en) * | 2018-09-28 | 2019-01-25 | 上海理工大学 | Multi-functional temperature sensitive aquagel of one kind and its preparation method and application |
| CN112089890A (en) * | 2020-08-28 | 2020-12-18 | 广东乾晖生物科技有限公司 | Acellular matrix hydrogel and preparation method and application thereof |
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| CN114887119A (en) * | 2022-05-09 | 2022-08-12 | 浙江大学医学院附属第一医院 | High-molecular artificial dura mater with anti-infection capacity and preparation method thereof |
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| CN104189955A (en) * | 2014-08-08 | 2014-12-10 | 苗九昌 | Degradable endocranium repair stent compounded by human amniotic membrane and bull dorsal aponeurosis and preparation method of repair stent |
| CN105903077A (en) * | 2016-04-14 | 2016-08-31 | 山东景源生物科技有限公司 | Preparation method of biological matrix gel material for promoting regeneration and repair of cartilage, gel performance determination method and application |
| CN105903077B (en) * | 2016-04-14 | 2019-05-21 | 山东景源生物科技有限公司 | For promoting the preparation method, gelling performance measuring method and application of the bio-matrix gel rubber material of regenerating bone or cartilage reparation |
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| CN113769168A (en) * | 2021-08-16 | 2021-12-10 | 江苏优创生物医学科技有限公司 | Acellular matrix particle product for soft tissue filling repair and preparation method thereof |
| CN114887119A (en) * | 2022-05-09 | 2022-08-12 | 浙江大学医学院附属第一医院 | High-molecular artificial dura mater with anti-infection capacity and preparation method thereof |
| CN117547653A (en) * | 2023-12-28 | 2024-02-13 | 深圳市迈捷生命科学有限公司 | Hyaluronic acid modified decellularized scaffold and preparation method thereof |
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