CN101507661B - Nano artificial dura mater with multi functional-layers and preparation method thereof - Google Patents
Nano artificial dura mater with multi functional-layers and preparation method thereof Download PDFInfo
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Abstract
The invention provides a nano artificial dura mater with a plurality of functional layers, which comprises a structure with at least two layers; the layer facing the brain is a hydrophobic anti-adhesion electrospun layer; and the layer back to the brain is a hydrophilic nano cytoskeletal layer. The invention also provides a method for preparing the nano artificial dura mater, which comprises the following steps: preparing an electrospun solution of a hydrophobic polymer; preparing an electrospun solution of a hydrophilic polymer; preparing the prepared electrospun solution of the hydrophobic polymer into the hydrophobic anti-adhesion electrospun layer through static spinning; and preparing the hydrophilic nano cytoskeletal layer on the anti-adhesion electrospun layer from the prepared electrospun solution of the hydrophilic polymer through static spinning, receiving a membrane structure, and obtaining the nano artificial dura mater. The mechanical features of the nano artificial dura mater can meet the requirements on tensile strength and flexibility of adaptation diseases; and the nano artificial dura mater can be freely cut as required, and has wide application prospect.
Description
Technical field
The present invention relates to a kind of nano artificial cerebral dura mater that possesses a plurality of functional layers and preparation method thereof, belong to field of biomedicine technology.
Background technology
Dura defect is common in the neurosurgery clinical position, and open craniocerebral injury (industry, traffic, war etc.), the erosion of tumor, congenital defect of meninges and other brain disorder reason all can cause dura defect.Dura defect needs in time to repair in case cerebrospinal fluid is excessive, prevents the bulging and the atmospheric compressing of brain, otherwise will jeopardize human life.Dura defect can also cause complication such as intracranial infection, brain adhesion, hypohydrops, causes as diseases such as insane pain, headache, disordered brain functioies through regular meeting.
Though present dural succedaneum has a lot, repairing dural material can be divided into: from body fascia, allogeneic material, natural and synthetic material, foreign material 4 classes.Product respectively has its pluses and minuses in the market.The shortcoming of prior art is as follows:
1. at present self fascia is rebuild the standard that cerebral dura mater remains clinical practice, but the incidence rate of early stage cerebrospinal leak of postoperative and hypohydrops is still higher, easily causes complication such as adhesion, may cause for the district not more not or dysfunction.
2. allogeneic and foreign material can't be avoided immunologic rejection fully, and residual antigen can cause inflammatory reaction in various degree, cause fibre modification and brain adhesion.Easily cerebral tissue is produced paralysed trace, stimulate.The allogeneic material source is limited, is difficult to form commercially produce.Simultaneously because allosome or xenogenesis are originated the danger that can't avoid bringing virus disseminating safely.For example derive from the artificial meninges of the material of cattle, after European bovine spongiform encephalopathy generation, have a greatly reduced quality in its source, and safety also receives greatly to suspect.
3. synthetic natural material is natural collagen protein substantially.But dietary protein origin makes it can't avoid immunologic rejection fully.Used collagen protein was absorbed easily when row was repaired, and can't play abundant isolation scalp soft tissue and cerebral tissue effect and was unfavorable for problems such as cranioplasty surgery afterwards being unfavorable for post surgery treatment.
4. absorbable material/what partially absorb material can not absorption portion not be foreign body to receptor forever, may cause chronic inflammatory reaction, art district to infect, delay hemorrhage, in cranium brain sensitizing range, can produce the compressing of maincenter and causes other complication.
5. can not absorb/partially absorb the material long-term existence in body, also can produce connective tissue proliferation parcel in various degree, more seriously swelling is cracked forms fibroid parcel, i.e. what is called " diaphragm is carcinogenic " with implantation back surrounding tissue concrescent.
6. different not absorbable materials also respectively has deficiency: also be unfavorable for CT, nuclear-magnetism and radioscopy and treatment as metal species; Silicone rubber has blood coagulation, it is can swelling cracked to absorb behind the lipoid, problems such as tensile strength difference, and terylene dry goods outside can form thicker paralysed trace, and its below is easily and shortcoming such as brain adhesion; The mechanical performance of carbon fiber own is limited.
7. existing adsorbable artificial meninges product is having certain defective on degradation speed, degradation property, clinical application range is limited.
In a word, at present artificial meninges exists deficiency in clinical practice, be unfavorable for large-scale industrialized production and clinical expansion.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of nano artificial cerebral dura mater that possesses a plurality of functional layers is provided, described nano bionic artificial dura mater can be absorbed fully, and has good pliability, elasticity and biological tissue's compatibility have the brain of preventing adhesion, degraded and absorbed and degradation speed are moderate fully, can promote the dura mater process, not malicious in spite of illness, no immunologic rejection, can cut randomly as required, cost is lower, with short production cycle, preserve, transportation easily, clinical practice is simple to operate, the nano bionic artificial dura mater that has wide range of applications.
Another object of the present invention provides the dural preparation method of above-mentioned nano artificial.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of nano artificial cerebral dura mater that possesses a plurality of functional layers comprises double-layer structure at least, is hydrophobic anti electrospinning layer towards one deck of brain, and one deck of brain is hydrophilic nano cell shelf layer dorsad; Between two-layer transition zone can also be arranged; Connected mode between any two adjacent layers preferably connects by electrospinning.
Described hydrophilic nano cell shelf layer is become by electro-spinning, promptly the electrospinning layer of cerebral surface is the cytoskeleton layer dorsad, be for effective induced dry-cell and fibroblastic moving into, this layer then adopts the hydrophilic material of good biocompatibility, moreover, by the electrostatic spinning parameter adjustment, in the design average pore size reached 20～100 μ M.Help so fibroblasticly moving into, adhere to, propagation and Growth and Differentiation.
Described antiblocking layers is to adopt hydrophobic material, is unfavorable for moving into of cell, thereby reaches the purpose of anti; The electrostatic spinning parameter for preparing this layer material is adjusted, and its hole aperture than little one to two order of magnitude of cell, thereby stops cell to enter below nanometer, prevents that the brain adhesion from producing.Because the human body cell diameter is on average at 10～20 μ M, general fibroblast diameter is between 20～30 μ M.Meninges mainly is scattered in fibrocyte and excretory collagen fiber thereof.Average pore size can effectively prevent the generation of brain adhesion below 3 μ M.The pore size distribution that electrostatic spinning fiber obtains depends on fibre diameter to a great extent, and when the known fiber diameter reduced, the aperture also reduced at the same time.According to the document of having delivered, fibre diameter is when 4～10 μ M, and the aperture is from 20～45 μ M.The average pore size that bibliographical information, static spin the regenerated silk fibrous nonwoven webs can reach 2 μ M.
The present invention provides a kind of above-mentioned dural preparation method of nano artificial that possesses a plurality of functional layers simultaneously, may further comprise the steps:
(1) the electrospinning solution of preparation hydrophobic polymer; The electrospinning solution of preparation hydrophilic polymer;
(2) the electrospinning solution with the hydrophobic polymer that makes becomes hydrophobic anti electrospinning layer by electro-spinning;
(3) the electrospinning solution with the hydrophilic polymer that makes is equipped with hydrophilic cytoskeleton layer by electro-spinning on described anti electrospinning layer, is received as membrane structure and obtains the nano bionic artificial dura mater.
The artificial dura mater that makes stores after cleaning, sterilize, packing.
The electrospinning solution of the hydrophilic polymer of preparation described in the above-mentioned steps (1) also can carry out between step (2) and step (3); Described step (2), (3) can repeated several times, reach suitable thickness.
The technological parameter that the static of described antiblocking layers spins is:
The speed of micro-injection pump is 0.1～5.0 milliliter/hour, and the voltage of high tension generator is 5～40KV, and the receiving range of receiving system is 5.0～30.0 centimetres.The technological parameter that the static of cytoskeleton layer spins is: the speed of micro-injection pump is 0.5～20.0 milliliter/hour, and the voltage of regulating high tension generator is 10～45KV, and the receiving range of regulating receiving system is 5.0～30.0 centimetres.
Described hydrophobic electrospinning solution can be selected hydrophobic L～polylactic acid and 6-caprolactone, both weight ratios are 50: 50 or 30: 70 or 70: 30, as the copolymerized macromolecule material, number-average molecular weight is 150000～500000, is dissolved in hexafluoroisopropanol or dichloromethane; The chloroform/methanol mixed solution of the polycaprolactone of available total solution weight 8～14%; Perhaps other suitable polymers and solvent.
Above-mentioned solution is added in the syringe of electrostatic spinning device, the speed of regulating micro-injection pump is 0.1～10 milliliter/hour, the voltage of regulating high tension generator is 10～45KV, and the receiving range of regulating receiving system is 10～40 centimetres, and fiber is received as membrane structure.
Obtain the fibre diameter average pore size fully at 3 μ M or following by electro-spinning herein, fibre diameter is between 50～1000nM.
The hydrophilic material that described hydrophilic electrospinning solution is selected is made preparation cytoskeleton layer, can select hydrophilic materials such as hydrophilic polyurethane or natural gelatin, cellulose, chitosan, chondroitin sulfate for use; Preferred scheme: hydrophilic polyurethane, with/or natural gelatin, chondroitin sulfate, Polyethylene Glycol, weight ratio 20～80: 80～20, spinning liquid is 3～15% of a total solution weight; Perhaps use hydrophilic polyurethane and natural gelatin, or chondroitin sulfate, weight ratio 20～80: 80～20, spinning liquid is 3～15% of a total solution weight; Also can select other suitable polymers and solvent for use.
The electrostatic spinning parameter of above-mentioned hydrophilic polymer electrospinning solution is: receiving range is from 15～25cm, voltage 15～45KV, and hydrophilic nano cell shelf layer aperture is 20～200 μ M.Nano cell shelf layer fibre diameter is opened electrostatic spinning between 5-200 μ M, continues to spin the cytoskeleton layer on the antiblocking layers that has spun.
The electrospinning solution that described electrospinning solution is one or more polymer mixed, hydrophilic polymer material is selected from chondroitin sulfate, heparin, agar, the peptide polymer of glucosan, alginic acid, modified cellulose, alginic acid, starch, cellulose, gelatin, fibrin, fibroin, elastin mimicry, collagen protein, chitosan, modification of chitosan, hydrophilic polyurethane, Polyethylene Glycol, polymethyl methacrylate, poly butyric valerate, poly butyric alkyl caproate, polyvinyl alcohol or polylactide; Hydrophobic polymer material is selected from hydrophobicity polyurethane, Merlon, polylactic acid, pla-pcl, poly-Acetic acid, hydroxy-, bimol. cyclic ester or polyethylene terephthalate.Because polymer modification research at present is in continuous development, hydrophilic material is modified as hydrophobic or hydrophobic material is modified as hydrophilic all more and more commonly originally, and scope is also more and more wider.
Above-mentioned material is dissolved in certain solvent, forms electrospinning liquid, just can make the nano bionic support by electrostatic spinning technique.
The solvent of described electrospinning solution can be formic acid, acetic acid, ethanol, acetone, dimethyl formamide, dimethyl acetylamide, oxolane, dimethyl sulfoxide, hexafluoroisopropanol, trifluoroethanol, dichloromethane, chloroform, methanol, chloroform, diox, HFC-143a, trifluoroacetic acid, water or their any mixture.Macromolecular material and solvent mentioned above are used for electrostatic spinning, and this class is reported in considerable quantity in the existing document.
The product that makes is through cleaning, sterilizing, and store the packing back.
Compared with prior art, the present invention has following beneficial effect:
(1) the artificial cerebral dura mater mechanical property of the present invention can satisfy indication to tensile strength and flexible requirement, has reliable intensity and good pliability, elasticity; Can support suture needle, waterproof, can bear certain power when surgical repair and after repairing and produce distortion and not damaged, make cerebrospinal fluid be unlikely to seepage, play the effect of protection cerebral tissue, and can cut randomly as required;
(2) the artificial dural medial surface of the present invention one side of brain (promptly towards) is smooth, can anti, can play a part to isolate well scalp soft tissue and cerebral tissue, and lateral surface (promptly the one side of brain) dorsad and side then are loose structure, the permission cell is grown into; Can impel as early as possible and soak into the growth infiltration to collagen inside, impel meninges to repair early from body fibroblast and some undifferentiated cell.Be beneficial to and carry out the skull prosthesis in the future;
(3) material of cerebral dura mater employing of the present invention is proved and can be absorbed fully after cambium generates, and has avoided diaphragm carcinogenic;
(4) the artificial meninges of nano bionic of the present invention itself does not contain the living cells composition, does not use foreign cell and albumen, has exempted many risks of therefore bringing immunologic rejection, virus disseminating, disease propagation; Can stop pathophoresis;
(5) material used in the present invention is at present verifiedly the nontoxic safe biologic material of human body to be had good biological tissue's compatibility, no foreign body rejection, non-toxic reaction, no carcinogenic, teratogenesis.Can not bring many risks of immunologic rejection, virus disseminating, disease propagation, can not bring other toxic action yet;
(6) mechanical brains membrane material of the present invention is originated fully, and cost is lower, has avoided the natural material source not enough, the cost height, and the shortcoming of modification complexity, storage is transported simple;
(7) the preparation method processing step of artificial meninges of the present invention is simplified, and the production time is short, can avoid effectively that product is polluted in the course of processing, and product quality is easy to control, and product standard realizes that easily product can be realized low cost, high efficiency industrialization production.
(8) artificial meninges clinical practice prepared in accordance with the present invention is simple, owing in processing, do not introduce toxicants such as glutaraldehyde, when clinical practice, do not need to carry out again strict immersion and cleaning, therefore avoided yet owing to soaking the not enough situation that makes product rejection of the pre-selected size that causes in advance.
Description of drawings
The mechanical brains membrane structure sketch map that Fig. 1 makes for embodiment 1, wherein 1 is the cytoskeleton layer, 2 is antiblocking layers.
The specific embodiment
Below further specify technical scheme of the present invention by specific embodiment.
(1) preparation antiblocking layers: select hydrophobic L～polylactic acid and 6-caprolactone, both ratios are 50: 50, and as the copolymerized macromolecule material, number-average molecular weight is 260000, is dissolved in hexafluoroisopropanol.
Above-mentioned solution is added in the syringe of electrostatic spinning device, the speed of regulating micro-injection pump is 5 milliliters/hour, and the voltage of regulating high tension generator is 30KV, and the receiving range of regulating receiving system is 20 centimetres, and fiber is received as membrane structure.
Obtain the average 300nm of fibre diameter fully by electro-spinning herein.。
Close electrostatic equipment.
(2) preparation cytoskeleton layer: present embodiment is selected following scheme for use: Polyethylene Glycol and chondroitin sulfate mass ratio are 70: 30, and the spinning liquid mass fraction is 9%.
Open electrostatic spinning, on the antiblocking layers that has spun, continue to spin the cytoskeleton layer.
Receiving range is from 11cm, voltage 20KV, and average fibre diameter is at 10 μ m.The artificial dura mater structure that makes is seen shown in Figure 1, and wherein 1 is the cytoskeleton layer, and 2 is antiblocking layers.
The artificial meninges that makes is taken out from culture dish, with distilled water rinsing 5 times, through lyophilizing final vacuum packing, negative 20 degrees centigrade of cryopreservation after 25kGy cobalt-60 sterilization.
(1) preparation antiblocking layers: select hydrophobic L～polylactic acid and 6-caprolactone, both ratios are 50: 50, and as the copolymerized macromolecule material, number-average molecular weight is 260000, is dissolved in hexafluoroisopropanol.
Above-mentioned solution is added in the syringe of electrostatic spinning device, the speed of regulating micro-injection pump is 5 milliliters/hour, and the voltage of regulating high tension generator is 30KV, and the receiving range of regulating receiving system is 20 centimetres, and fiber is received as membrane structure.
Obtain the average 300nm of fibre diameter fully by electro-spinning herein.。
Close electrostatic equipment.
(2) preparation transition zone: present embodiment is selected following scheme for use: polyurethane and hyaluronic mass ratio are 70: 30, and the spinning liquid mass fraction is 10%.
Open electrostatic spinning, on the antiblocking layers that has spun, continue to spin transition zone.
Receiving range is from 11cm, voltage 20KV, and average fibre diameter is at 5 μ m.
Closing static spins.
(3) preparation cytoskeleton layer: present embodiment is selected following scheme for use: Polyethylene Glycol and chondroitin sulfate mass ratio are 70: 30, and the spinning liquid mass fraction is 9%.
Open electrostatic spinning, on the transition zone that has spun, continue to spin the cytoskeleton layer.
Receiving range is from 11cm, voltage 20KV, and average fibre diameter is at 10 μ m.
Cleaning, preserving type are with embodiment 1.
Embodiment 3
The cerebral dura mater that makes with embodiment 1 carries out the dog zoopery:
Experimental dog body weight 15～20KG, at 1.5～2 years old age, male and female are regardless of, totally 5.With ketamine intramuscular injection general anesthesia, after hair is shaved in anesthesia, animal is placed on the special-purpose operating table ventral decubitus.With 2% iodine tincture and 75% alcohol disinfecting.Vertically cut center, the animal crown.Separate periosteum with detacher, expose Double Tops portion skull plate, open skull with high speed abrasive drilling mill, Double Tops portion forms the bone window.Cut the rectangle cerebral dura mater of bilateral top 3cm * 3cm size with little shears, produce the dura defect at top.Fulgerize on the brain surface that exposes, cause the impaired loci of 6 1mm * 1mm size.To be trimmed to the patching material of respective shapes and size with the embodiment of the invention 1 prepared artificial meninges, antiblocking layers is to the brain surface, and with 4/0 not damaged wire discontinuous sewing, needle gage 4mm repairs damaged in the dog top.With No. 4 silk suture muscle of round needle.Postoperative carries out conventional nursing and observation to animal.It is good that the postoperative animal recovers, and wound healing is good, and no cerebrospinal fluid leaks, and no epilepsy takes place.Postoperative feed water inlet is normal, and the outdoor activities of animal are normal, do not find the dyskinesia, survive to intended duration.
Postoperative 18 months, animal are the center with the operative site, are cutting specimen greater than operative site 1cm scope, make it comprise the cerebral tissue of artificial meninges and peripheral cerebral dura mater and inner face.After cutting out specimen, visible artificial meninges and dural junction are involutory smooth, do not have boundary, healing fully, the silk thread of rarely seen stitching.Do not see obvious hyperemia between the primary cerebral dura mater, rejection such as hemorrhage grade.
Embodiment 4
The cerebral dura mater that makes with embodiment 2 carries out the new zealand rabbit zoopery:
The animal of experiment is implemented the top and opens cranium, and artificial fabrication portion dura defect and brain tissue impairment are implemented the duramater reparation art respectively with artificial meninges then.Postoperative carries out conventional nursing and observation to animal.It is good that the postoperative animal recovers.Postoperative 18 months, animal are the center with the operative site, are cutting specimen greater than operative site 1cm scope, make it comprise the cerebral tissue of artificial meninges and peripheral cerebral dura mater and inner face.After cutting out specimen, as seen the visible epithelial cell of inner surface covers, go up subcutaneous visible proliferation of fibrous tissue, the fibroblast hypertrophy, collagen fiber increase, and cause the cambium hypertrophy of band blood fortune in the material, host's cambium is invaded, material degradation, total amount obviously reduces, inner visible blood capillary.The old and new organizational interface does not have neutrophilic granulocyte, and the reaction of inflammatory cells such as lymphocyte does not have cyst wall at the interface and forms.Arachnoidea and cerebral tissue are normal.
Claims (10)
1. a nano artificial cerebral dura mater that possesses a plurality of functional layers is characterized in that comprising double-layer structure at least, is hydrophobic anti electrospinning layer towards one deck of brain, and one deck of brain is hydrophilic nano cell shelf layer dorsad; Described hydrophilic nano cell shelf layer is obtained fully by electro-spinning.
2. nano artificial cerebral dura mater as claimed in claim 1 is characterized in that also having transition zone between described anti electrospinning layer and the hydrophilic nano cell shelf layer.
3. nano artificial cerebral dura mater as claimed in claim 1 or 2 is characterized in that described hydrophilic nano cell shelf layer aperture is 20～200 μ M, and fibre diameter is between 5～200 μ M.
4. nano artificial cerebral dura mater as claimed in claim 1 or 2 is characterized in that described anti electrospinning layer aperture below 3 μ M, and fibre diameter is between 50～1000nM.
5. dural preparation method of the described nano artificial of claim 1 is characterized in that may further comprise the steps:
(1) the electrospinning solution of preparation hydrophobic polymer; The electrospinning solution of preparation hydrophilic polymer;
(2) the electrospinning solution with the hydrophobic polymer that makes becomes hydrophobic anti electrospinning layer by electro-spinning;
(3) the electrospinning solution with the hydrophilic polymer that makes is equipped with hydrophilic cytoskeleton layer by electro-spinning on described anti electrospinning layer, is received as membrane structure and obtains the nano bionic artificial dura mater.
6. preparation method as claimed in claim 5 is characterized in that the electrospinning solution of the hydrophilic polymer of preparation described in the step (1) carries out between step (2) and step (3).
7. as claim 5 or 6 described preparation methoies, it is characterized in that the technological parameter that the described static of step (2) spins is: the speed of micro-injection pump is 0.1～5.0 milliliter/hour, the voltage of high tension generator is 5～40KV, and the receiving range of receiving system is 5.0～30.0 centimetres.
8. as claim 5 or 6 described preparation methoies, it is characterized in that the technological parameter that the described static of step (3) spins is: the speed of micro-injection pump is 0.5～20.0 milliliter/hour, the voltage of regulating high tension generator is 10～45KV, and the receiving range of regulating receiving system is 5.0～30.0 centimetres.
9. as preparation method as described in claim 5 or 6, it is characterized in that described hydrophilic polymer is selected from any one or a few mixture of the peptide polymer of chondroitin sulfate, heparin, agar, glucosan, alginic acid, modified cellulose, alginic acid, starch, cellulose, gelatin, fibrin, fibroin, elastin mimicry, collagen protein, chitosan, modification of chitosan, hydrophilic polyurethane, Polyethylene Glycol, polymethyl methacrylate, poly butyric valerate, poly butyric alkyl caproate, polyvinyl alcohol or polylactide; Described hydrophobic polymer is selected from any one or a few mixture of hydrophobicity polyurethane, Merlon, polylactic acid, polycaprolactone, poly-Acetic acid, hydroxy-, bimol. cyclic ester or polyethylene terephthalate;
The solvent of described electrospinning solution is any mixture of any one or they of formic acid, acetic acid, ethanol, acetone, dimethyl formamide, dimethyl acetylamide, oxolane, dimethyl sulfoxide, hexafluoroisopropanol, trifluoroethanol, dichloromethane, chloroform, methanol, chloroform, diox, HFC-143a, trifluoroacetic acid, water.
10. as claim 5 or 6 described preparation methoies, it is characterized in that step (2) and step (3) repeated several times.
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100377365A CN101507661B (en) | 2009-03-10 | 2009-03-10 | Nano artificial dura mater with multi functional-layers and preparation method thereof |
| BRPI1006250 BRPI1006250B1 (en) | 2009-03-10 | 2010-02-08 | dura mater and artificial production method |
| JP2011553264A JP5658175B2 (en) | 2009-03-10 | 2010-02-08 | Artificial dura mater and method for producing the same |
| MX2015008386A MX345864B (en) | 2009-03-10 | 2010-02-08 | Artificial dura mater and manufacturing method thereof. |
| MX2011009282A MX2011009282A (en) | 2009-03-10 | 2010-02-08 | Artificial dura mater and manufacturing method thereof. |
| KR1020117023555A KR20110133599A (en) | 2009-03-10 | 2010-02-08 | Artificial dura mater and manufacturing method thereof |
| EP10750329.4A EP2340785B1 (en) | 2009-03-10 | 2010-02-08 | Artificial dura mater and manufacturing method thereof |
| KR1020147018543A KR20140090704A (en) | 2009-03-10 | 2010-02-08 | Artificial dura mater and manufacturing method thereof |
| RU2011140225/15A RU2491961C2 (en) | 2009-03-10 | 2010-02-08 | Artificial dura mater and method of its production |
| PCT/CN2010/070566 WO2010102533A1 (en) | 2009-03-10 | 2010-02-08 | Artificial dura mater and manufacturing method thereof |
| MX2015008387A MX345863B (en) | 2009-03-10 | 2010-02-08 | Artificial dura mater and manufacturing method thereof. |
| US13/255,356 US8795708B2 (en) | 2009-03-10 | 2010-02-08 | Treating defective dura with synthetic artificial dura substitute |
| US14/225,051 US9211180B2 (en) | 2009-03-10 | 2014-03-25 | Method for treating defective dura mater |
| US14/225,136 US9271822B2 (en) | 2009-03-10 | 2014-03-25 | Artificial dura mater and manufacturing method thereof |
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| CN2009100377365A CN101507661B (en) | 2009-03-10 | 2009-03-10 | Nano artificial dura mater with multi functional-layers and preparation method thereof |
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Assignee: Shenzhen Medprin Regenerative Medical Technologies Co., Ltd. Assignor: Medprin Regenerative Medical Technologies Co., Ltd. Contract record no.: 2011440000998 Denomination of invention: Nano artificial dura mater with multi functional-layers and preparation method thereof Granted publication date: 20101110 License type: Common License Open date: 20090819 Record date: 20111010 |
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