CN101417151A - Biology source type calcified-layer containing cartilage tissue engineer bracket - Google Patents
Biology source type calcified-layer containing cartilage tissue engineer bracket Download PDFInfo
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- CN101417151A CN101417151A CNA2008101305694A CN200810130569A CN101417151A CN 101417151 A CN101417151 A CN 101417151A CN A2008101305694 A CNA2008101305694 A CN A2008101305694A CN 200810130569 A CN200810130569 A CN 200810130569A CN 101417151 A CN101417151 A CN 101417151A
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Abstract
The invention discloses an engineering bracket made of biogenic cartilage tissue containing calcified layer bone. The bracket is a multi-layer structure, with one side of a substrate which contains at least one layer of acellular component and mainly takes II-typed collagen as main, the other side of subchondral bone structure containing at least one layer of acellular component and the middle of a calcified layer structure containing one acellular component. The calcified layer acellular structure removes the cell component structure and has the functions of normal calcified layer structure such as connection, stress decentralization, and separation of micro-environment between cartilage and subchondral bone. The engineering bracket is especially suitable for guiding the regeneration of bone and cartilage tissues and is beneficial for restoring the missing or destroyed bone and cartilage in vivo.
Description
Technical field
The present invention relates to medical apparatus and instruments, specifically, the present invention is a kind of biogenic calcified-layer containing cartilage tissue engineer bracket.
Background technology
At present, the diarthrosis end osteochondral defect that wound, infection, tumor and regression etc. cause is the clinical common disease of orthopaedics, often show as intractable pain, joint movement disorder, but severe patient lost-motion function, and the cartilage injury can cause the damage of further cartilage wearing and tearing and articular surface.Along with being on the increase and the aged tendency of population process of high energy, high speed wound, cause and the illness of quickening articular cartilage damage and regression will significantly increase.The articular cartilage damage that becomes increasingly conspicuous has become the multidisciplinary severe challenges that face such as the traumatology department, orthopaedics, old subject and sports medical science.Because articular cartilage does not have blood vessel, nerve and lymphsystem, diameter surpasses the osteochondral defect of 2～4mm and almost can not repair fully.All there is open defect in existing Therapeutic Method, is difficult to make it really to reach the nature reparative regeneration: joint debridement art respite symptom can not stop course of disease development; Arthrodesis, excision-arthroplasty are seriously lost function of joint; There are problems such as bone dissolving at a specified future date and prosthetic loosening in artificial joint replacement; Arthroscope sending down the fishbone cartilage piece transplantation, autotransplantation cause that then there are drawbacks such as rejection and potential communicate illness in damaged and limited, the heteroplastic transplantation of originating for the district.Developing rapidly of tissue engineering technique is for the Regeneration and Repair of ossa articularia cartilage defect provides new solution.
Present tissue engineering method repairing articular cartilage has been obtained certain clinical effectiveness in clinical research or animal experiment study, be organized in the cartilage that replaces infringement on structure or the function but these methods all can not generate persistent hyaline cartilage.Reason can be summed up as substrate degradation, differentiation substantially or integrate losing of not enough or transplanted cells and tissue.There are not blood vessel and nerve in the articular cartilage tissue, the growth response of chondrocyte and the reparation of tissue are mediated by the microenvironment of chondrocyte, the excretory cytokine of synovial tissue and mechanical stress, and the structure that connects cartilage and subchondral bone interface possesses the function of support, isolation, mechanical couplings and buffering stress.Think that at present the reparation at bone cartilage interface is a key factor of keeping the cartilage microenvironment in the osteochondral defect reparation strategy, and a lot of scholar has done certain research to bone cartilage interface and osteochondro tissue.(Indications and implementation of recommendations ofthe working group ＂ Tissue Regeneration and Tissue Substitutes ＂ forautologous chondrocyte transplantation (ACT) .Z Orthop Ihre Grenzgeb.2004Sep-Oct such as Behrens P; 142 (5): 529-39.) utilize biogum close simulation tide line structure, prevent the interference of subchondral bone microenvironment.But the repair of cartilage support that Most scholars is attempted adopting integrated structure bone cartilage compound rest or possessed the calcification layer, Kreklau B (Tissue engineering ofbiphasic joint cartilage transplants.Biomaterials.1999Sep; 20 (18): 1743-9) wait, confirm that integrated being configured with is beneficial to the raising integration ability to promoting integration to carry out the research of (comprising cartilage, subchondral bone and damp line structure) of external two-phase graft.The strategy of integrated structure bone cartilage compound rest comprises: (1) divides layer building: promptly make up cartilage and osseous tissue respectively, sew up with absorbable thread then or mode such as fibrin glue bond is bonded into an integral body with both, In vitro culture a period of time or do not cultivate after the repair deficiency that implants.Schaefer (In vitro generation of osteochondral composites.Biomaterials.2000Dec; 21 (24): 2599-606) grade is inoculated in poly-Acetic acid, hydroxy-, bimol. cyclic ester (PGA) non-woven fiber network with chondrocyte and makes up cartilage, and the mixture (80: 20) that osteoblast is inoculated in polylactide-poly-glycolide copolymer (PLGA) and Polyethylene Glycol (PEG) makes up subchondral bone; Both cultivate the back respectively and with absorbable thread the outer continuation of both suture bodies were cultivated for 4 weeks altogether, morphologic detection shows that both are in conjunction with having formed osteochondro tissue, zoopery shows subchondral bone and host bone integration on every side well, but the cartilage that makes up is not good enough with host's cartilage integration on every side.(Tissue-engineered osteochondral constructs in the shape of an articularcondyle.J Bone Joint Surg Am.2005 May such as Alhadlaq; 87 (5): 936-44.) utilize the poly-ethanol fat (PEGDA) of two acrylic acids to make up cartilage and osseous tissue respectively, adopt the uv photopolymerization method that the timbering material of two kinds of tissues is aggregated into then and be used for experiment in the body after as a whole, detect in 12 weeks of postoperative and find have cartilage sample or osteoid tissue to form, but do not form damp line structure between tissue at respective regions; (2) one makes up: the identical or different integrated bone cartilage compound rest of prepared composition and structure at first, inoculate into the cartilage seed cell in the cartilage zone then, skeletonization zone inoculation or do not inoculate the skeletonization seed cell, the structure osteochondro tissue.(Repair of large articular osteochondral defects using hybrid scaffoldsand bone marrow-derived mesenchymal stem cells in a rabbitmodel.Tissue Eng.2006 Jun such as Shao X; 12 (6): 1539-51.) the interior experiment of the PCL bone stake body that utilizes incorporate PCL cartilage frame compound phosphoric acid DFP to strengthen shows osteochondral defect repair ability preferably.(Formation of biphasic constructs containingcartilage with a calcified zone interface.Tissue Eng.2007Jan such as Allan KS; 13 (1): 167-77.) wait by the deep layer articular chondrocytes, CPP support and β-glycerol effect is configured to contain the double structure of calcification layer and transparent sample cartilage, it possesses better compressive stress and interface shearing power, emphasizes the importance of the existence of calcification layer to the biological engineering cartilage.(Human mesenchymal progenitor cell-based tissue engineering of asingle-unit osteochondral construct.Tissue Eng.2004Jul-Aug such as Tuli R; 10 (7-8): 1169-79.) utilize mesenchymal stem/progenitor cells and biodegradable polylactic acid bracket, form bone cartilage compound rest and simulation formation bone cartilage syndeton by specific culture liquid, its biomechanical parameter prolongs with incubation time and improves.(Athree-dimensional osteochondral composite scaffold for articular cartilagerepair.Biomaterials.2002Dec such as Sherwood; 23 (24): 4739-51.) the integrated bone cartilage compound rest that is made of heterogeneity with TheriFormTM 3 D-printing fabrication techniques, cartilage portion be by D, and L-PLGA/l-PLA constitutes, and porosity 90% is column, in channels interleaved is arranged; Osseous part is made of L-PLGA/TCP, and porosity 55% is cloverleaf (four-leaf clover) shape, changes in gradient at cartilage and bone junctional area material and porosity.Cartilage frame inoculation chondrocyte, osseous part is 6 weeks of inoculating cell In vitro culture not, and the groupization detection shows has cartilaginous part to have cartilage to form, and the osseous part mechanical property is similar to the fresh spongy bone intensity of people.
Adopt tissue engineering technique to reproduce single bone of cell component or extensively success of cartilaginous tissue acquisition in addition, the part achievement has entered clinical practice.Reproducing from making up Preliminary Feasibility Exploration of through engineering approaches osteochondro tissue obtained phasic results to animal experiment study; Reproducing the liver mass defective, can't keeping that chondrocyte growth microenvironment, graft and host integrate not good enough and lack corresponding mechanical function is the main bottleneck that limits its clinical practice.Because the complexity of the structure of bone cartilage and conjunctive tissue thereof, accurately duplicate at present and comprise hyaline cartilage layer, calcification layer and subchondral bone layer and also require further study at the good natural joint bone cartilage of interior and mutual integration.
Summary of the invention
The present invention has overcome above-mentioned shortcoming, has proposed a kind of biogenic calcified-layer containing cartilage tissue engineer bracket.This support can be used for guiding and repairs osteochondral defect.
The technical scheme that proposes in order to solve the problems of the technologies described above really is:
The invention provides a kind of calcification layer osteochondral tissue engineering rack that contains and be used for guiding and repair osteochondral defect, a side is a cartilage layers, contains the II Collagen Type VI substrate of the acellular composition of one deck at least, helps the damage Regeneration and Repair of cartilage side; Opposite side is the subchondral bone structure that the subchondral bone layer contains the acellular composition of one deck at least, helps the subchondral bone reparation; A calcification layer structure that plays the acellular composition of interconnect function is contained in the centre, possesses the function of physiology bone cartilage syndeton.The three-decker of this support, each layer all possess different biotic components and inner space organizational structure, closely connect by middle calcification layer between the two outside layers.
Between described cartilage layers and calcification layer, be provided with cementing line, between calcification layer and subchondral bone layer, be provided with damp line.
In the described substrate, the II Collagen Type VI accounts for 80%～90wt% of substrate gross weight, and Portugal's ammonia polysaccharide mixture accounts for 10%～20wt% of substrate gross weight.
In the described calcification layer, the II Collagen Type VI accounts for 60～70wt% of calcification layer gross weight, and calcium salt accounts for 30～40wt% of calcification layer gross weight.
The present invention is mentioned contains calcification layer osteochondral tissue engineering rack and derives from natural diarthrosis and comprise shoulder, elbow, wrist, hip, knee joint, ankle and interphalangeal joint, and such diarthrosis after the sexual maturity all contains three layers of supporting structure of the present invention.Because its natural origin, this support can absorb alternative in vivo fully, can be because of degraded does not produce cytotoxic substance, and biocompatibility is fabulous.
The ideal source that contains the bone cartilage frame of calcification layer is the condyle of femur of allosome condyle of femur or large mammals such as pig, cattle and horse.All comprising cell in the bone cartilage of allosome or xenogenesis diarthrosis reaches disadvantageous chemistry of seed cell and physiologically substance.Therefore we want to utilize the syndeton between the natural bone cartilage to prepare the just essential removal disadvantageous chemistry of these cell growth of the osteochondral tissue engineering rack that contains the calcification layer and the physiologically substance of biogenic, and will guarantee that the immunogenicity material of allosome or heteroplasm is removed.
Present known cartilaginous tissue extracellular matrix structure is fine and close, porosity is also lower, chondrocyte is difficult to deviate from common method, syndeton between cartilage and the subchondral bone: the cell component between the calcification layer structure is few, but structure is fine and close, and the calcification layer is unfavorable for taking off Cell sap and enters between cartilage and bone.And we are the essential integrity of wanting minimal infringement calcification layer 26S Proteasome Structure and Function when supporting structure is cell free.So providing a kind of, the inventor can remove the cellular material of band cartilage, calcification layer and subchondral bone biogenetic derivation structure and the method for disadvantageous chemistry of other cell growth and biological substance.
The human synovial osteochondro tissue is the very complicated functional organization of The Nomenclature Composition and Structure of Complexes, the bone cartilage linkage interface of external structure need possess following function: (1) bone cartilage linkage interface structure can be securely fixed in cartilage on the subchondral bone, the back cartilage that prevents to implant breaks away from from subchondral bone, thereby helps graft and host's integration of interface; The function that also need possess dispersive stress simultaneously.(2) osteochondro tissue that utilizes the compactness of bone cartilage syndeton to make to implant becomes the cartilage microenvironment as what the host was divided into oxygen and nutritious skeletonization microenvironment, oxygen and malnutrition naturally, prevent to implant cell and move with becoming between the cartilage support, promote the specific region cell to utilize separately microenvironment to specific direction propagation, differentiation at skeletonization.The tissue engineering product that possesses ideal bone cartilage linkage interface certainly will solve and reproduce liver mass defective, graft and host and integrate problems such as not good enough.
Because the calcification layer thickness is less and be difficult to separation, imperfection is gone back in the research that its structure is formed, and external very difficult structure possesses the calcification layer structure of physiological structure function.There was research to adopt traditional methods such as lamination, fusion cast and fiber bonding to make bone cartilage compound rest in the past, complex process, repeated relatively poor, be difficult to realize industrialization production, and the three-dimensional rack regular shape of making, normal is rectangle or cylindrical, is difficult to satisfy the changeable osteochondral defect of shape.3 D-printing technique construction bone and cartilage tissue engineered also in conceptual phase, adopt this technology can realize the integrated manufacturing of bone cartilage compound rest, simultaneously can also make it have the specific anatomical profile and the interior spatial structure of clinical needs, but, can satisfy the timbering material that the mechanics of implant site requires because technology limitation can't construct at present and possess the favorable mechanical characteristic.We find that calcification layer inner cell composition is few, calcification layer below spongy bone porosity height.Thereby the inventor imagines and utilizes the bone cartilage syndeton that makes up the osteochondral tissue engineering rack behind the biological calcification pull-up cell, and utilizes the II Collagen Type VI of cartilage acellular matrix to make up the chondrocyte support that possesses the physiology hole.
According to the ISO10993 series standard, adopt methods such as SEM, XRD, FTIR, Experiments of Machanics, penetration experiment, degradation test, cell toxicity test, genetic toxicity test that the physicochemical properties such as morphosis, mechanical property, biological safety and degraded and absorbed of support are detected.(SEM: support cartilage layers aperture is testing result: 226.8-56.7 μ m; .XRD: the hydroxyapatite in the support calcification layer accounts for organizes 63% ± 4% of dry weight; Hydroxyapatite in the subchondral bone accounts for organizes 81% ± 5% of dry weight; FTIR:19 seed amino acid total content accounts for respectively organizes the percentage ratio of dry weight to be respectively: articular cartilage 63.37% ± 0.58%, calcification layer 1.32% ± 0.87%, subchondral bone 16.29% ± 0.83%; Compressive stress is 35.3-83.7% of a normal control; Shear stress is the 20.3-68.5% of normal control; Calcification layer penetrating power compared with normal control does not have significant difference, and cell toxicity test, genetic toxicity test are all negative) prove that osteochondro tissue engineering rack of the present invention has proximate interior spatial structure of physiology and proportion of composing; Have the favorable tissue compatibility and biological safety, be beneficial to cell adhesion, hypertrophy; Have excellent mechanical intensity, can satisfy the mechanics requirement of implant site; Have the controlled degradation absorbability, can make by artificial regulatory that the cambium speed of growth is complementary in its degraded and absorbed speed and the body.
Adopt this support to cover in conjunction with seed cell technology of preparing, periosteum or perichondrium or covering of biogenetic derivation artificial collagen membrane and piece of tissue In vitro culture technique construction through engineering approaches osteochondro tissue; Large animal (pig) body is implanted into to be repaired experimental result and shows that the through engineering approaches osteochondro tissue that adopts osteochondro tissue engineering rack of the present invention the to make up back that implants is fully integrated with normal surrounding tissue, and degradation time mates substantially with the cambium speed of growth on every side; The repair tissue cartilage portion has biological characteristics, the subchondral bone part of similar natural joint cartilage can within a short period of time and host bone tissue generation synostosis.
Advantage of the present invention is:
(1) the cartilage layers support is a cartilage acellular matrix composition, and main component is two Collagen Type VIs, has the interior spatial structure and the substrate microenvironment composition of suitable chondrocyte proliferation, differentiation;
(2) subchondral bone layer support has the interior spatial structure of suitable osteoblastic proliferation, differentiation, its primary structure is not for containing the spongy bone of cell component, main matter is type i collagen and calcium salt, helps osteoblast adhesion, hypertrophy and differentiation, keeps the mechanical strength of original subchondral bone;
(3) utilize the interfacial structure of natural calcification layer to connect cartilage and cartilage lower floor, the firm earth anchor of cartilage frame is combined on the subchondral bone, prevent layering between tissue.The factor of utilizing calcification layer compact texture stop to implant cell and influencing the bone cartilage-derived growth is moved with becoming between the cartilage support at skeletonization, the cell that is beneficial to the specific region utilizes separately microenvironment to specific direction propagation, differentiation, thereby strengthens the integration of interface between graft and the host.The buffer action that keeps the calcification layer can guarantee the stable of microenvironment under cartilage microenvironment and the cartilage, guarantees cartilage differentiation and regenerated microenvironment.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Description of reference numerals: 1. cartilage shallow-layer, 2. cartilage deep layer, 3. calcification layer, 4. subchondral bone layer, the 5. cementing line between cartilage layers and the calcification layer, the 6. damp line between calcification layer and the subchondral bone layer.
The specific embodiment
Embodiment 1
As shown in Figure 1, support of the present invention, form by cartilage shallow-layer 1, cartilage deep layer 2, calcification layer 3 and subchondral bone layer 4 from top to bottom, cartilage layers 1,2 with calcification layer 3 between, be connected by natural cementing line 5 and damp line 6 between calcification layer 4 and the subchondral bone layer 4, be connected by covalent bond by after mechanical stress and the crosslinking Treatment between cartilage shallow-layer 1 and the cartilage deep layer 2.The composition material of cartilage layers 1 is II Collagen Type VI (medical) or II Collagen Type VI (medical) and GAG (Portugal's ammonia polysaccharide) mixture; II Collagen Type VI weight ratio is 80%～90%, the GAG weight ratio is 10%～20%, II Collagen Type VI/GAG connects with the covalent bond form by crosslinked, can adopt business-like (Switzerland Gai Shi company) cartilage acellular matrix slurry, its main component is: II Collagen Type VI and GAG; The composition material of cartilage layers 2 is through defat and the chondrocyte substrate after taking off the cell processing, and its composition is: II Collagen Type VI and GAG; The composition material of calcification layer 3 is II Collagen Type VI and calcium salt, and II Collagen Type VI weight ratio is 60-70%, and the weight of calcium salt ratio is 30-40%, and upper surface (cementing line 5) is wavy and is complementary with lower surface cartilage layers; Lower surface (damp line 6) be rough and uneven in surface broach shape and subchondral bone upper surface mutually anchor close; The composition material of subchondral bone layer 4 is type i collagen and calcium salt, and the type i collagen weight ratio is 70-80%, and the weight of calcium salt ratio is 20-30%, and the aperture of cartilage layers 1 is less, and generally between 80 μ m-200 μ m, the hole passband is 100%; Generally between 150 μ m-600 μ m, the hole passband is 100% in the aperture of subchondral bone layer 4.The thickness of cartilage layers 1,2 is generally 2.8mm-5.5mm, and the thickness of calcification layer 3 is generally 0.1mm-0.5mm, the dense structure of calcification layer 3, and the thickness of subchondral bone layer 4 is generally 6mm-40mm, and its thickness can reference and the change of receptor fixing means; Its diameter (width) usually and human body cartilage wound site match, when repairing operation, be transplanted in the human body.
The support preparation method:
Contain the preparation of calcification layer support: osteochondro tissue, takes out under aseptic condition and delivers to laboratory by ice PBS in 6h taking-up after death.1. mechanical treatment: intercepting diameter 8-30mm articular cartilage, it is thick to strike off the about 2-3mm of articular surface cartilage, does not destroy calcification layer structure, the reservation hyaline cartilage structure of trying one's best few, opposite side reservation 3-4mm left and right sides spongy bone.2. decontamination and destroy cell: under the aseptic condition, calcification layer piece PBS washing adds protease and suppresses liquid, and is centrifugal.Be soaked in the low Tris-HCl liquid of opening that contains TritonX-100, add protease inhibitor, slight vibration.3. defat: calcification layer structure is by the chloroform/formaldehyde defat of 1:1 equal-volume ratio.4. take off nucleic acid: be soaked in the Tris-HCl liquid that contains deoxyribonuclease and ribonuclease then, do not add protease inhibitor, vibration.5. clean: distilled water flushing 24h.
The cartilage acellular matrix is prepared: the cartilage sheet is 500nm-3mm fritter by organizing pulverizer to pulverize.Under the aseptic condition, the PBS washing adds protease and suppresses liquid, and is centrifugal.Be soaked in the low Tris-HCl liquid 12h of opening that contains TritonX-100, add protease inhibitor, slight vibration.Be soaked in the Tris-HCl liquid that contains deoxyribonuclease and ribonuclease then, vibration; PBS liquid flushing 24h.
Because it is thick to take off before the cell calcification layer support cartilage surface cellular matrix about 2-3mm that pruned.Contain the suitable lyophilizing of support of calcification layer or dry cell free, be positioned in the sizeable mould, it is thick on it cartilage acellular matrix slurry to be soaked in the about 2mm of calcification layer support cartilage surface, because containing calcification layer support does not have moisture, so pass through adsorption, cartilage acellular matrix slurry can be adsorbed on and contain on the calcification layer support, by the lyophilizing down of the certain mechanical pressure (2-50MPa) in mould upper end, at first by the crosslinked 5-72 of severe dehydration hour, cross-linking agent is crosslinked then, all cross-linking agent that can be used for medical product all can be selected for use, such as: glutaraldehyde, carbodiimide salt, nordihydroguaiaretic acid (NDGA), N-hydroxy-succinamide etc.The crosslinked method of severe dehydration also can be considered to use in the physics aspect.
More than biogenic calcified-layer containing cartilage tissue engineer bracket provided by the present invention has been carried out more in detail introducing, used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that all can change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (4)
1. biogenic calcified-layer containing cartilage tissue engineer bracket, it is characterized in that: the one side is a cartilage layers, this cartilage layers comprises the substrate of being made up of II Collagen Type VI and Portugal's ammonia polysaccharide mixture of the acellular composition of one deck at least; Opposite side is for containing the subchondral bone layer of the acellular composition of one deck at least, and the calcification layer of an acellular composition is contained in the centre.
2. biogenic calcified-layer containing cartilage tissue engineer bracket according to claim 1 is characterized in that: be provided with cementing line between described cartilage layers and calcification layer, be provided with damp line between calcification layer and subchondral bone layer.
3. biogenic calcified-layer containing cartilage tissue engineer bracket according to claim 1 is characterized in that: in the described substrate, the II Collagen Type VI accounts for 80%～90wt% of substrate gross weight, and Portugal's ammonia polysaccharide mixture accounts for 10%～20wt% of substrate gross weight.
4. biogenic calcified-layer containing cartilage tissue engineer bracket according to claim 1 is characterized in that: in the described calcification layer, the II Collagen Type VI accounts for 60～70wt% of calcification layer gross weight, and calcium salt accounts for 30～40wt% of calcification layer gross weight.
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| CN102430151A (en) * | 2011-09-05 | 2012-05-02 | 西安交通大学 | Tissue engineering bone cartilage composite bracket and integrated photocuringable forming method thereof |
| CN102526806A (en) * | 2012-01-20 | 2012-07-04 | 陕西博鸿生物科技有限公司 | Tissue engineering cartilage and preparation method thereof |
| CN102860884A (en) * | 2012-09-17 | 2013-01-09 | 清华大学 | Tissue engineered osteochondral composite stent and preparation method thereof |
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| CN102430151B (en) * | 2011-09-05 | 2013-12-04 | 西安交通大学 | Tissue engineering bone cartilage composite bracket and integrated photocuringable forming method thereof |
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| JP2018529499A (en) * | 2015-12-07 | 2018-10-11 | ハンチョウ フアマイ メディカル デバイシズ カンパニー リミテッド | Composite material for bone repair based on decellularized biological tissue matrix material and method for preparing it |
| US10821207B2 (en) | 2015-12-07 | 2020-11-03 | Hangzhou Huamai Medical Devices Co., Ltd. | Composite materials for bone repair based on decellularized biological tissue matrix material and the preparation method thereof |
| CN109730812A (en) * | 2019-01-31 | 2019-05-10 | 重庆凝骄生物科技有限公司 | A kind of focal cartilage defect repair body |
| CN109730812B (en) * | 2019-01-31 | 2022-02-08 | 重庆凝骄生物科技有限公司 | Focal cartilage defect prosthesis |
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| CN115414532B (en) * | 2022-09-13 | 2023-12-19 | 华东交通大学 | Bacterial cellulose-based integrated osteochondral scaffold with interface barrier layer and preparation method thereof |
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Application publication date: 20090429 |