CN109833516A - A kind of graphene catheter combination object, conduit preparation method and application - Google Patents
A kind of graphene catheter combination object, conduit preparation method and application Download PDFInfo
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- CN109833516A CN109833516A CN201711208696.7A CN201711208696A CN109833516A CN 109833516 A CN109833516 A CN 109833516A CN 201711208696 A CN201711208696 A CN 201711208696A CN 109833516 A CN109833516 A CN 109833516A
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- graphene
- conduit
- combination object
- bioadhesion
- catheter combination
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Abstract
The present invention relates to a kind of graphene catheter combination object, conduit preparation method and application, the graphene catheter combination object, each components including following mass percentage: biodegradable material 90-99.5%;Graphene 0.5-10%.Graphene conduit of the invention includes conduit and bioadhesion material layer, and the bioadhesion material layer is arranged in pipe inner wall;The conduit is prepared using graphene catheter combination object.Preparation method is that graphene catheter combination object is carried out 3D printing or electrostatic spinning, and conduit is made, and the inside of conduit is sprayed one layer of bioadhesion substance using 3D printing or electrostatic spinning, and carry out crosslinking curing to get the graphene conduit.The conduit can promote the regeneration such as nerve, blood vessel, proliferation, differentiation etc..Experiment in vivo shows that such as sciatic nerve reparation of animal peripheral nerve is better than nerve autograft, has reality and clinical value.
Description
Technical field
The present invention relates to field of biomedicine technology, and in particular to a kind of graphene catheter combination object, conduit preparation method
And application.
Background technique
Various bio-medical conduits include at present degradation and non-degradable conduit, are once used to do if polyethylene pipe
Nerve trachea studies nerve regneration situation, non-degradable due to conduit,, may if conduit is not handled after the completion of nerve regneration
Tissue fibrosis is caused, the toxic side effects such as inflammation are caused, clinical application effect is not very ideal.It is currently advancing to various biologies
Degradation material prepares various bio-medical conduits, such as collagen, polylactic acid, but since these materials are used alone
The disadvantages of there are some problems such as, intensity, the speed of nerve regneration and toxic side effect.To latest developments to these conduits into
One step research, such as in the surface of conduit or the various regeneration for being conducive to various cavities damage in vivo of internal progress, as in conduit
Surface carries out cell modification, carries the various active materials for promoting cavity growth, as the nerve growth factor of nerve trachea, blood are prosperous thin
Born of the same parents etc..
Nerve trachea is although have been achieved with certain progress, such as Chinese invention patent CN100479785C (grant date
2009.4.12 a kind of method for preparing nerve trachea) is disclosed, but there is also a certain distance with autologous nerve reparation.Separately
It is outer to disclose different preparation methods (Chinese invention patent CN101439205A, publication date 2009.5.27 there are also multiple patents;
CN101507842A, publication date 2009.8.19, CN106668938A, publication date 2017.05.17;CN106924820A, it is open
Day 2017.07.07), but these conduits or the problems such as there are intensity, toxic side effect, quality control or costs.In spite of each
The preparation report of kind conduit, but all do not have ideal biomedical conduit.Ideal conduit should be included with enough
Intensity, elasticity, hardness etc.;Degradability and wait until that damaged regeneration is complete in vivo, and it is degradable, it does not need again
It is secondary to carry out operation taking-up;Material has no toxic side effect as far as possible;Suitable degradation cycle;Tissue is able to guide to grow towards suitable direction;Have
Prevent unwanted regeneration etc..
Summary of the invention
For the defects in the prior art, overcome the problems, such as that existing nerve trachea or other conduits exist, it is such as artificial at present
Nerve trachea is unable to reach the effect etc. of nerve autograft, and the present invention provides a kind of graphene catheter combination objects, conduit system
Preparation Method and application.Using can achieve with the artificial nerve catheter of the degradable material preparation of graphene and other bio-compatibles
Regenerated nervous function even better than after nerve autograft, in addition to technological prevention of the invention can achieve, currently without appoint
What artificial nerve catheter can achieve such performance.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides a kind of graphene catheter combination object, each component including following mass percentage:
Biodegradable material 90-99.5%;
Graphene 0.5-10%.
Preferably, the graphene catheter combination object, each component including following mass percentage:
Biodegradable material 95-99%;
Graphene 1-5%.
Preferably, the biodegradable material is selected from polylactic acid (PLA), polyglycolic-polylactic acid (PLGA), gathers oneself
One of lactone (PCL), silk-fibroin, collagen, gelatin, hyaluronic acid, chitosan or a variety of any combination.
Preferably, the graphene is one of single-layer graphene, multi-layer graphene, graphene oxide, two kinds any
Or three kinds of mixture.The conductive energy of graphene is got well and strong л-л key, these are conducive to regeneration.
The present invention also provides a kind of graphene conduit, including conduit and bioadhesion material layer, the biological slime addendums
Matter layer is arranged in pipe inner wall;The conduit is prepared using graphene catheter combination object above-mentioned.
Preferably, the average pore size of the conduit is 0.01cm to 10cm, and the average pore size of bioadhesion material layer is
0.001-5000μm。
Preferably, the average pore size of the conduit is 0.01 to 10 μm, and the average pore size of bioadhesion material layer is 10-
1000μm。
Preferably, the bioadhesion substance is any in dopamine, bioadhesion peptide (RGD), extracellular matrix
One or more mixtures.
Preferably, the conduit with a thickness of 0.002 μm -10000 μm, bioadhesion material layer with a thickness of 0.001 μm -
5000μm。
The present invention also provides a kind of preparation method of graphene conduit, the method specifically includes the following steps:
A, each component in the graphene catheter combination object is mixed into obtain mixture in proportion;
B, mixture made from step A is subjected to 3D printing or electrostatic spinning, conduit is made;
C, the inside of conduit is sprayed into one layer of bioadhesion substance using 3D printing or electrostatic spinning, and be crosslinked solid
Change to get the graphene conduit.
Preferably, in the step A, the preparation of mixture includes mixing system using by biodegradable material and graphene
Standby suspension, or be mixed to prepare using graphene to be added in the biodegradable material of melting.
Preferably, it the method also includes carrying out disinfection and sterilizing graphene conduit made from step C, then packs
Step.
The graphene conduit preparation method is total using 3D printing or the biodegradable material of electrostatic spinning and graphene
Melt or organic solvent, forms the conduit of various biomedical applications, especially nerve trachea;After conduit molding, as needed
In one layer of bioadhesion substance of inner wall printing or spraying of conduit, be conducive to inducing cell in duct differentiation and growth.
The present invention also provides a kind of application of the graphene conduit of preceding method preparation, the application includes for nerve
Regeneration, revascularization, bile duct regeneration, lymphatic vessel regeneration, oesophagus regeneration, tracheae regenerates, enteron aisle regenerates, appointing in ureter regeneration
It anticipates a kind of or its cavity assisted Regeneration.
Preferably, the application is nerve regneration and revascularization.
Compared with prior art, the present invention have it is following the utility model has the advantages that
The present invention provides one kind to have catheter holder required for biology, and has ideal Biomedical function material
Material, prepare simple, at low cost, quality be easy to control, using it is wide the advantages that.Using biodegradable material composition of the invention
The conduit of preparation can promote the regeneration such as nerve, blood vessel, proliferation, differentiation etc..Experiment in vivo shows animal peripheral nerve such as ischium
Neural restoration is better than nerve autograft, has reality and clinical value.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is nerve trachea shape appearance figure prepared by the present invention;Wherein, Fig. 1 a is the external morphology of nerve trachea;Fig. 1 b is
The internal morphology of nerve trachea;
Fig. 2 is regenerating nerve transmission electron microscope testing result figure of the embodiment of the present invention 3 using pure PCL conduit;
Fig. 3 is regenerating nerve transmission electron microscope testing result figure of the embodiment of the present invention 3 using nerve autograft;
Fig. 4 is the regenerating nerve for the nerve trachea that the embodiment of the present invention 3 is prepared using 1% graphene and PCL composition
Transmission electron microscope testing result figure;
Fig. 5 is the cell in vitro biocompatibility result figure of conduit prepared by the present invention.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Following embodiment provides a kind of graphene catheter combination object, each component including following mass percentage:
Biodegradable material 90-99.5%;
Graphene 0.5-10%.
The biodegradable material is selected from polylactic acid (PLA), polyglycolic-polylactic acid (PLGA), polycaprolactone
(PCL), one of silk-fibroin, collagen, gelatin, hyaluronic acid, chitosan or a variety of any combination.
The graphene is one of single-layer graphene, multi-layer graphene, graphene oxide, two or three any
Mixture.The conductive energy of graphene is got well and strong л-л key, these are conducive to regeneration.
Following embodiment additionally provides a kind of graphene conduit, including conduit and bioadhesion material layer, the biological slime
Attached material layer is arranged in pipe inner wall;The conduit is prepared using graphene catheter combination object above-mentioned.
The average pore size of the conduit is 0.01cm to 10cm, and the average pore size of bioadhesion material layer is 0.001-5000
μm。
The bioadhesion substance be selected from dopamine, bioadhesion peptide (RGD), in extracellular matrix any one or it is more
The mixture of kind.
The conduit with a thickness of 0.002 μm -10000 μm, bioadhesion material layer with a thickness of 0.001 μm -5000 μm.
The preparation method of the graphene conduit, the method specifically includes the following steps:
A, each component in the graphene catheter combination object is mixed into obtain mixture in proportion;
B, mixture made from step A is subjected to 3D printing or electrostatic spinning, conduit is made;
C, the inside of conduit is sprayed into one layer of bioadhesion substance using 3D printing or electrostatic spinning, and be crosslinked solid
Change to get the graphene conduit.
In the step A, the preparation of mixture includes being mixed with suspension using by biodegradable material and graphene
Liquid, or be mixed to prepare using graphene to be added in the biodegradable material of melting.
The method also includes carrying out disinfection by graphene conduit made from step C and sterilize, then pack.
The preparation of 1 graphene catheter combination object of embodiment
In terms of total weight 100%, by graphene (at least one in single-layer graphene, multi-layer graphene, graphene oxide
Kind) weight ratio is respectively 0.5%, 1%, 2%, 5% and 10% and biodegradable material (PCL, PLA, PLGA, collagen, gelatin
Or their arbitrary composition) weight ratio is respectively that 99.5%, 99%, 98%, 95% and 90% mix well;The mixing
Method includes: that (temperature is higher than the melting temperature of material, as PLA temperature is Celsius higher than 80 using hot melt biodegradable material
Degree) or with organic solvent (such as methylene chloride, ethyl acetate) or water dissolution biodegradable material (such as biodegradable material
To be dissolved when PCL, PLA or PLGA using organic solvent, biodegradable material is dissolved when being collagen or gelatin with water), then
It is mixed after graphene is added, obtains graphene catheter combination object.
The preparation of 2 graphene conduit of embodiment
The conduit material of above-described embodiment 1 is carried out electrostatic spinning and prepares conduit, using conventional electrostatic spinning technique system
The conduit of standby various needs;Or 3D printing technique is used, print various conduits;Or it is prepared using catheter mold various required
The conduit wanted, such as single-layer graphene or multi-layer graphene PLA conduit, graphene oxide PLA conduit, single-layer graphene or multilayer stone
Black alkene PCL conduit, graphene oxide PCL conduit, single-layer graphene or multi-layer graphene PCLA conduit, graphene oxide PCLA are led
Pipe etc. method can be prepared through this embodiment.If 3D printing and 1% graphene PCL nerve trachea is (such as Fig. 1 institute
Show) there is the pure PCL printing of good nerve regneration performance such as modular ratio to get well (being 48.32 and 31.77MPa respectively) etc..
Periphery nerve regneration in 3 animal body of embodiment
Conduit (we have chosen the nerve trachea of the PCL material 3D printing of 1% graphene) prepared by embodiment 2 is planted
The sciatic nerve (damage for repairing 15MM) for entering rat, as a result as shown in figure 4, simultaneously compared simultaneously using pure PCL conduit and oneself
Somatic nerves skin grafing and mending as a result, as Figure 2-3.The result of comparison diagram 2-4 is it is found that the graphene PCL conduit using 1% is bright
It is aobvious to be better than autologous nerve and pure PCL conduit.
Safety and biocompatibility inside and outside 4 animal body of embodiment
The conduit of above-mentioned preparation is carried out vitro Cytotoxicity Evaluation and vivo biodistribution Compatibility Evaluation, cell in vitro by we
Biocompatibility result such as Fig. 5, our conduit is better than control group in biological safety and biocompatibility as the result is shown.I
In 6 months and December, 24 months in conduit implantation animal body, then conduit is taken out and is dried and is weighed compared with initial conduit
It was found that reducing 10%, 40%, 90% respectively, i.e. conduit is degraded and by body absorption.
Preparation and evaluation of the embodiment 5 containing bioadhesive layer zinc oxide catheter combination object
Prepare conduit according to embodiment 2, in terms of total weight 100%, by graphene (weight ratio difference 0.5%, 1%, 2%,
10%) and biodegradable material (PCL, PLA, PLGA, collagen, gelatin or their arbitrary composition) weight score 5% and
It 99.5%, 99%, 98%, 95% and 90% Wei not mix well;The mixed method includes: using hot melt biodegradable
Material (temperature is higher than the melting temperature of material, as PLA temperature is higher than 80 degrees Celsius) or with organic solvent (such as methylene chloride, second
Acetoacetic ester) or water dissolution biodegradable material (such as biodegradable material be PCL, PLA or PLGA when using organic solvent it is molten
Solution, biodegradable material are dissolved when being collagen or gelatin with water), it is mixed after then graphene is added, obtains zinc oxide
Catheter combination object.Then one layer of 1% bioadhesion substance (dopamine, bioadhesion peptide are sprayed according on the surface of conduit
(RGD), the mixture of any one or more in extracellular matrix).And the test carried out as described in embodiment 3 and 4 is gone forward side by side
Row effect assessment.After the present embodiment sprays one layer of bioadhesion substance in conduit, the knot of periphery nerve regneration in animal body
Safety and biocompatibility are superior to the conduit of the not bioadhesive layer of the preparation of embodiment 2 inside and outside fruit and animal body.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (10)
1. a kind of graphene catheter combination object, which is characterized in that each component including following mass percentage:
Biodegradable material 90-99.5%;
Graphene 0.5-10%.
2. graphene catheter combination object according to claim 1, which is characterized in that including each of following mass percentage
Component:
Biodegradable material 95-99%;
Graphene 1-5%.
3. graphene catheter combination object according to claim 1 or 2, which is characterized in that the biodegradable material choosing
From one of polylactic acid, polyglycolic-polylactic acid, polycaprolactone, silk-fibroin, collagen, gelatin, hyaluronic acid, chitosan
Or a variety of any combination.
4. graphene catheter combination object according to claim 1 or 2, which is characterized in that the graphene is mono-layer graphite
One of alkene, multi-layer graphene, graphene oxide, any two or three of mixture.
5. a kind of graphene conduit, which is characterized in that including conduit and bioadhesion material layer, the bioadhesion material layer is set
It sets in pipe inner wall;The conduit is using the described in any item graphene catheter combination object preparations of claim 1-4.
6. graphene conduit according to claim 5, which is characterized in that the average pore size of the conduit arrives for 0.01cm
10cm, the average pore size of bioadhesion material layer are 0.001-5000 μm.
7. graphene conduit according to claim 5, which is characterized in that the bioadhesion substance is selected from dopamine, life
The mixture of any one or more in object adhesin polypeptide, extracellular matrix.
8. the preparation method of graphene conduit according to claim 5, which is characterized in that the conduit with a thickness of
0.002 μm -10000 μm, bioadhesion material layer with a thickness of 0.001 μm -5000 μm.
9. a kind of preparation method according to the described in any item graphene conduits of claim 5-8, which is characterized in that the method
Specifically includes the following steps:
A, each component in the graphene catheter combination object is mixed into obtain mixture in proportion;
B, mixture made from step A is subjected to 3D printing or electrostatic spinning, conduit is made;
C, the inside of conduit is sprayed into one layer of bioadhesion substance using 3D printing or electrostatic spinning, and carries out crosslinking curing, i.e.,
Obtain the graphene conduit.
10. it is a kind of according to any one of claim 5-8 graphene conduit application, which is characterized in that the application includes
Again for nerve regneration, revascularization, bile duct regeneration, lymphatic vessel regeneration, oesophagus regeneration, tracheae regeneration, enteron aisle regeneration, ureter
Any one in life or its cavity assisted Regeneration.
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CN110975008A (en) * | 2019-12-18 | 2020-04-10 | 武汉理工大学 | Preparation method of nerve repair drug delivery system with electrical stimulation and angiogenesis promotion effects |
CN111028983A (en) * | 2019-12-16 | 2020-04-17 | 天新福(北京)医疗器材股份有限公司 | Conductive composite material and preparation method and application thereof |
CN111359019A (en) * | 2020-03-16 | 2020-07-03 | 四川大学 | Preparation method of graphene and chitosan composite conductive nerve scaffold with longitudinal pore channels |
KR102180865B1 (en) * | 2019-09-30 | 2020-11-19 | 한림대학교 산학협력단 | Photocurable bioink with electroconductivity and a preparation thereof |
CN112494719A (en) * | 2021-02-05 | 2021-03-16 | 重庆石墨烯研究院有限公司 | Magnetic 3D gel catheter for repairing nerve defects and preparation method and application thereof |
CN112999415A (en) * | 2021-03-24 | 2021-06-22 | 兰州大学 | Graphene-based polymer composite nerve conduit and preparation method thereof |
CN113476656A (en) * | 2021-06-30 | 2021-10-08 | 增广生物工程(上海)有限公司 | Preparation method and application of nano material of collagen and graphene oxide |
CN113679893A (en) * | 2021-10-14 | 2021-11-23 | 河南科技学院 | Preparation method of double-effect anticoagulant antibacterial artificial catheter |
CN114306753A (en) * | 2021-12-15 | 2022-04-12 | 海宁市产业技术研究院 | Implantable electric stimulation conductive stent and preparation method thereof |
CN115463251A (en) * | 2022-09-09 | 2022-12-13 | 四川大学 | Optogenetic nerve repair scaffold compounded with up-conversion nanoparticles and preparation method thereof |
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CN110975008B (en) * | 2019-12-18 | 2021-06-08 | 武汉理工大学 | Preparation method of nerve repair drug delivery system with electrical stimulation and angiogenesis promotion effects |
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CN111359019A (en) * | 2020-03-16 | 2020-07-03 | 四川大学 | Preparation method of graphene and chitosan composite conductive nerve scaffold with longitudinal pore channels |
CN112494719A (en) * | 2021-02-05 | 2021-03-16 | 重庆石墨烯研究院有限公司 | Magnetic 3D gel catheter for repairing nerve defects and preparation method and application thereof |
CN112999415A (en) * | 2021-03-24 | 2021-06-22 | 兰州大学 | Graphene-based polymer composite nerve conduit and preparation method thereof |
CN112999415B (en) * | 2021-03-24 | 2022-05-24 | 兰州大学 | Graphene-based polymer composite nerve conduit and preparation method thereof |
CN113476656A (en) * | 2021-06-30 | 2021-10-08 | 增广生物工程(上海)有限公司 | Preparation method and application of nano material of collagen and graphene oxide |
CN113679893A (en) * | 2021-10-14 | 2021-11-23 | 河南科技学院 | Preparation method of double-effect anticoagulant antibacterial artificial catheter |
CN114306753A (en) * | 2021-12-15 | 2022-04-12 | 海宁市产业技术研究院 | Implantable electric stimulation conductive stent and preparation method thereof |
CN115463251A (en) * | 2022-09-09 | 2022-12-13 | 四川大学 | Optogenetic nerve repair scaffold compounded with up-conversion nanoparticles and preparation method thereof |
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