CN111028983A - Conductive composite material and preparation method and application thereof - Google Patents
Conductive composite material and preparation method and application thereof Download PDFInfo
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- CN111028983A CN111028983A CN201911296315.4A CN201911296315A CN111028983A CN 111028983 A CN111028983 A CN 111028983A CN 201911296315 A CN201911296315 A CN 201911296315A CN 111028983 A CN111028983 A CN 111028983A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The invention provides a conductive composite material, which comprises a compound of natural polymer collagen and reduced graphene oxide; the natural polymer collagen is prepared from collagen slurry with the mass volume concentration of 3% -10%, and the mass ratio of the reduced graphene oxide to the natural polymer collagen is 0.5% -20%. The conductive composite material provided by the invention has proper collagen concentration and reduced graphene oxide content, can show good conductive capability and suture capability, overcomes the defects of non-conductivity and weak suture capability of the existing nerve repair material, and is closer to an ideal nerve repair catheter; and the preparation method is simple to operate, stable in process, rich and cheap in raw material source and easy to industrialize.
Description
Technical Field
The invention belongs to the fields of medical biomaterials, medical instruments and nerve repair, and particularly relates to a conductive composite material and a preparation method and application thereof.
Background
The peripheral nerve injury is commonly seen in traffic accidents, production accidents, earthquakes, medical events and the like, and 1000-1500 ten thousand of trauma cases are newly added in the world every year, wherein the peripheral nerve injury accounts for 1.5-4.0%. The number of peripheral nerve defect patients in China is as high as 50 per year. At present, the methods for clinically treating the nerve defects mainly comprise autologous nerve transplantation and severed end suturing, but have certain defects, such as limited donor sources, donor part function loss, immune rejection, short repair distance, secondary nerve necrosis caused by over-tension of the severed ends and the like, and the repair failure can be caused.
The nerve tissue engineering takes nerve tissue cells, cell factors and scaffold materials as research objects, and utilizes cell biology and material science technologies to construct an artificial nerve conduit so as to promote the rapid repair and regeneration of defective nerves. Wherein, the scaffold material is an important component of the neural tissue engineering, and the character characteristics of the scaffold material can influence the repair effect of the neural defect. Early used artificial materials such as arteries, veins, fascia, fallopian tubes, heterologous nerves, acellular muscles and decalcified tubular bones bridge, which have some success but are not ideal.
The ideal nerve conduit can simulate the in vivo growth environment to the maximum extent, provides good space, mechanical property and nutrient substances for nerve regeneration, and at least has excellent mechanical property and stable mechanical property; the tissue compatibility is good, and the organism immune reaction is not generated; the nerve regeneration speed is matched with the catheter degradation speed; electrical conductivity to mimic the conductive function of the myelin sheath of a nerve, thereby stimulating and guiding nerve growth and axon regeneration; has certain tissue permeability, and can absorb necessary substances such as oxygen, nutrition and the like; can prevent invasion of fibrous tissue and maintain secretion of trophic factors; is convenient for processing, molding, aseptic disinfection, long-term storage and transportation. Therefore, how to obtain an ideal nerve conduit becomes an important research topic for current nerve tissue engineering.
The graphene is formed by carbon atoms passing through SP2Hybridization forms a hexagonal honeycomb of two-dimensional nanostructures. The unique structure endows the graphene with unique physical and electrical properties, excellent mechanical properties, electrical conductivity, larger specific surface area, good biocompatibility, certain biodegradability and the like. Widely used in solar cell, superCapacitor, dye cell, sensor, etc. Many researchers now research the application of the compounds in the biomedical field, such as the fields of biological detection, biosensor drug delivery, tumor treatment, nerve repair and the like, which can make drugs, biomolecules, cells and the like adhere and fixed on the surface thereof and can promote the adhesion, differentiation, proliferation and neurite growth of nerve tissue cells. Graphene has become a current research hotspot in multiple fields, and has a great application prospect in the field of tissue engineering.
Currently, the research of graphene in the field of nerve defect repair mainly focuses on the conductivity of graphene, such as simulating the conductivity function of myelin sheaths of nerves, so as to stimulate and guide nerve growth and axon regeneration. However, the conductive composites in the field of nerve repair provided in the prior art have a large difference in conductive properties and have failed to provide composites with significant repair capabilities, particularly long-distance nerve damage repair greater than 15 mm.
CN105194729A provides a conductive polymer nano nerve conduit material prepared from polylactic acid and polypyrrole, but the conductivity of the material is general, and electrical stimulation is required to be applied to implant in vivo to repair nerves. CN107432952A adopts a chemical vapor deposition method to prepare a three-dimensional graphene-collagen composite scaffold, has complex operation and is not suitable for industrial production. CN109833516A and CN109453430A provide a graphene catheter and a collagen-graphene oxide material containing a hydroxyapatite coating, respectively, and both of them contain graphene, but fail to provide a material having both better conductive effect and repair capability.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the conductive composite material which is naturally absorbable, has good biocompatibility, certain three-dimensional pores, plasticity and mechanical strength, and is simple in preparation method and easy to industrialize.
In one aspect, the present invention provides a conductive composite material comprising a composite of natural polymeric collagen and reduced graphene oxide; the natural polymer collagen is prepared from collagen slurry with the mass volume concentration of 3% -10%, and the mass ratio of the reduced graphene oxide to the natural polymer collagen is 0.5% -10%.
Further, the collagen slurry is an acetic acid solution of collagen, and the concentration of the acetic acid is 0.5M; preferably, the collagen is type I collagen.
In one embodiment, the collagen slurry is prepared by mixing collagen with acetic acid; the type I collagen is extracted from bovine achilles tendon.
Further, the reduced graphene oxide is graphene oxide treated by a reducing agent, and the reducing agent is vitamin C, chitosan and glucose, preferably vitamin C; more preferably, the mass ratio of the graphene oxide to the reducing agent is 1: 2-15, and more preferably 1: 10.
Further, the reduction conditions for treating the graphene oxide by using the reducing agent are 48-120h, preferably 72h at 25 +/-2 ℃.
In one embodiment, graphene oxide is prepared by subjecting 300 mesh graphite to a modified Hummers method; the graphene oxide aqueous solution is prepared by ultrasonically dispersing graphene oxide in an aqueous solution, and the concentration of the graphene oxide aqueous solution is 10-25 mg/ml.
Further, the natural polymer collagen is prepared from collagen slurry with the mass volume concentration of 4% -8%, and the mass ratio of the reduced graphene oxide to the natural polymer collagen is 1% -8%; preferably, the natural polymer collagen is prepared from a collagen slurry with a mass volume concentration of 5%, and the mass ratio of the reduced graphene oxide to the natural polymer collagen is 1% -4%.
In another aspect, the present invention also provides a method for preparing the above conductive composite material, comprising the steps of:
(1) respectively preparing collagen slurry with certain mass volume concentration and an aqueous solution of reduced graphene oxide, and uniformly mixing;
(2) and (2) centrifuging the solution obtained in the step (1), injecting into a mold, freezing, drying, crosslinking, packaging and sterilizing.
Further, the mass volume concentration of the aqueous solution of the reduced graphene oxide is 10-25 mg/ml.
Further, the centrifugation conditions are that the temperature is 5-20 ℃, the rotating speed is 3000-; preferably 10 ℃ and 4000rpm for 100 min.
Further, the crosslinking is selected from one of glutaraldehyde steam crosslinking, ultraviolet crosslinking and high-temperature vacuum crosslinking; preferably high-temperature vacuum crosslinking under the conditions of-0.09 MPa of pressure, 105 +/-2 ℃ of temperature and 24 hours of fixing time.
In one embodiment, the above method wherein the freeze-drying is divided into two steps of prefreezing and lyophilizing, the prefreezing step is as follows: after the mould is fixed, the sample is slowly injected along the axial direction, and is frozen and formed. The speed of the uniform speed elevator is 10 r/min, the angle is adjusted for 9, the time interval is 5s, the temperature stops decreasing after being reduced to minus 60 ℃, the elevator is taken out when the temperature is reduced to minus 80 +/-10 ℃, and the temperature is adjusted to minus 20 ℃ in a freezing chamber of a refrigerator for more than 1 hour. The lyophilization procedure was as follows:
in one embodiment, the sterilization method in the above method is ethylene oxide gas sterilization or cobalt 60 irradiation sterilization, preferably ethylene oxide gas sterilization.
In another aspect, the invention also provides a conductive composite material prepared by the method of the invention.
On the other hand, the invention also provides application of the conductive composite material and/or the conductive composite material prepared by the method in preparing a nerve repair catheter with high suture strength. Preferably, the nerve repair conduit has a pore size of 50-220 microns and a wall thickness of 0.4 +/-0.3 mm.
Further, the conductivity of the conductive composite material is measured by an RTS-8 four-probe tester. Experiments show that the conductivity of the material is not lower than 1.5 multiplied by 10-3S/m, preferably not less than 3.9X 10-3S/m, more preferably not less than 4.1X 10-3S/m, more preferably not less than 4.8X 10-3S/m。
Further, the repairing strength of the conductive composite material is measured by an MED-01 medical packaging performance tester, and the set condition is 10 mm/min. Experiments show that the maximum repair strength of the material is not less than 1.7N, preferably not less than 2.1N, more preferably not less than 2.2N, more preferably not less than 2.3N, more preferably not less than 2.5N.
The invention has the beneficial effects that:
1. the conductive composite material is prepared by a freeze drying technology in one step, and the preparation method is simple to operate, stable in process, rich in raw materials and low in cost, and easy to industrialize.
2. The conductive composite material provided by the invention has proper collagen concentration and reduced graphene oxide content, can show better conductive effect and suture capability, overcomes the defects of non-conductivity and weak suture capability of the existing product, and is closer to an ideal nerve repair catheter; experiments show that when the conductive composite material contains 5 percent (mass-volume ratio) of collagen and 4 percent (mass ratio of reduced graphene oxide to collagen), the conductive effect and the suture capability are relatively better.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a conductive composite prepared in example 3;
fig. 2 is a Scanning Electron Microscope (SEM) image of a longitudinal section of the conductive composite of example 3.
Detailed Description
In order to more clearly explain the overall concept of the present application, the following detailed description is given by way of example. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present application. It will be apparent, however, to one skilled in the art, that the present application may be practiced without one or more of these specific details. In other instances, well-known features of the art have not been described in order to avoid obscuring the present application.
Unless otherwise specified, the starting materials in the following examples are all commercially available; experimental equipment for performance testing adopted RTS-8 four-probe tester (conductivity) and MED-01 medical package performance tester (suture strength).
In the following examples, the following steps were used for freeze-drying:
first-step pre-freezing: after the mould is fixed, the sample is slowly injected along the axial direction, and is frozen and formed. The speed of the uniform speed elevator is 10 r/min, the angle is adjusted for 9, the time interval is 5s, the temperature stops decreasing after being reduced to minus 60 ℃, the elevator is taken out when the temperature is reduced to minus 80 +/-10 ℃, and the temperature is adjusted to minus 20 ℃ in a freezing chamber of a refrigerator for more than 1 hour. And a second step of freeze-drying, wherein the freeze-drying process is as follows:
in the following examples, high temperature vacuum crosslinking was used, wherein the crosslinking conditions were: the pressure is-0.09 MPa, the temperature is 105 +/-2 ℃, and the fixing time is 24 h.
Example 1
Example 1 provides an oriented porous conductive composite prepared by the following method:
(1) dispersing graphene oxide in pure water to prepare a 20mg/ml graphene oxide aqueous solution;
(2) dissolving 1g of collagen in 19.5ml of 0.5M acetic acid solution, dissolving 0.1g of vitamin C in 0.5ml of the graphene oxide aqueous solution, uniformly mixing the two solutions, and reducing the two solutions at 25 ℃ for 72 hours;
(3) centrifuging at 4 deg.C and 4000rpm for 100min, and injecting into a mold;
(4) freeze drying;
(5) high-temperature vacuum crosslinking;
(6) cutting, packaging, and sterilizing with ethylene oxide.
Example 2
Embodiment 2 provides a conductive composite prepared by the following method:
(1) dispersing graphene oxide in pure water to form a 20mg/ml graphene oxide aqueous solution;
(2) dissolving 1g of collagen in 19ml of 0.5M acetic acid solution, dissolving 0.2g of vitamin C in 1ml of graphene oxide aqueous solution, uniformly mixing the two solutions, and reducing the two solutions at 25 ℃ for 72 hours;
(3) centrifuging at 4 deg.C and 4000rpm for 100min, and injecting into a mold;
(4) freeze drying;
(5) high-temperature vacuum crosslinking;
(6) cutting, packaging, and sterilizing with ethylene oxide.
Example 3
Example 3 provides a conductive composite prepared by the following method:
(1) dispersing graphene oxide in pure water to form a 20mg/ml graphene oxide aqueous solution;
(2) dissolving 1g of collagen in 20ml of 0.5M acetic acid solution, dissolving 0.4g of vitamin C in 2ml of graphene oxide aqueous solution, uniformly mixing the two solutions, and reducing the two solutions at 25 ℃ for 72 hours;
(3) centrifuging at 4 deg.C and 4000rpm for 100min, and injecting into a mold;
(4) freeze drying;
(5) high-temperature vacuum crosslinking;
(6) cutting, packaging, and sterilizing with ethylene oxide.
Example 4
Example 4 provides a conductive composite prepared by the following method:
(1) dispersing graphene oxide in pure water to form a 20mg/ml graphene oxide aqueous solution;
(2) dissolving 1g of collagen in 16ml of 0.5M acetic acid solution, dissolving 0.8g of vitamin C in 4ml of graphene oxide aqueous solution, uniformly mixing the two solutions, and reducing the two solutions at 25 ℃ for 72 hours;
(3) centrifuging at 4 deg.C and 4000rpm for 100min, and injecting into a mold;
(4) freeze drying;
(5) high-temperature vacuum crosslinking;
(6) cutting, packaging, and sterilizing with ethylene oxide.
Example 5
Example 5 provides a conductive composite prepared by the following method:
(1) dispersing graphene oxide in pure water to form a 20mg/ml graphene oxide aqueous solution;
(2) dissolving 1g of collagen in 12ml of 0.5M acetic acid solution, dissolving 1.6g of vitamin C in 8ml of graphene oxide aqueous solution, uniformly mixing the two solutions, and reducing the two solutions at 25 ℃ for 72 hours;
(3) centrifuging at 4 deg.C and 4000rpm for 100min, and injecting into a mold;
(4) freeze drying;
(5) high-temperature vacuum crosslinking;
(6) cutting, packaging, and sterilizing with ethylene oxide.
Example 6: performance testing
The conductivity of the composite nerve repair conduit obtained in each example in a wet state was measured by a four-probe method, and the results obtained by using a pure collagen conduit without graphene as a comparison are shown in table 1:
TABLE 1 conductivity of the exemplary nerve repair catheters
| Examples of the invention | Collagen concentration | Mass ratio of | Electrical conductivity (10)-3S/m) | p value |
| Pure collagen catheter | 5％ | - | 0.20±0.07 | - |
| Example 1 | 5％ | Reducing graphene oxide: 1% of collagen | 1.52±0.71** | 0.002 |
| Example 2 | 5％ | Reducing graphene oxide: 2% of collagen | 4.14±1.91** | 0.004 |
| Example 3 | 5％ | Reducing graphene oxide: collagen protein 4% | 4.82±1.23** | 0.004 |
| Example 4 | 5％ | Reducing graphene oxide: collagen protein 8% | 3.98±1.72* | 0.017 |
Note: p < 0.05 shows significant differences compared to pure collagen catheters, p < 0.01 shows very significant differences compared to pure collagen catheters
The suture ability of the composite nerve repair catheter obtained in each example was tested by the following method: fixing one end of the catheter, puncturing the other end of the catheter at a position 2mm away from the edge by using a 5-0 nylon monofilament suture, connecting the suture with a tensile machine, stretching at a speed of 10mm/min, and recording the maximum bearing force during instantaneous stretch-breaking, wherein the obtained results are shown in a table 2:
TABLE 2 suture Strength of the example nerve repair catheters
| Examples of the invention | Collagen concentration | Composition of matter | Stitching Strength (N) | p value |
| Pure collagen catheter | 5％ | - | 1.78±0.39 | - |
| Example 1 | 5％ | Reducing graphene oxide: 1% of collagen | 2.37±0.44* | 0.013 |
| Example 2 | 5％ | Reducing graphene oxide: 2% of collagen | 2.25±0.35* | 0.021 |
| Example 3 | 5％ | Reducing graphene oxide: collagen protein 4% | 2.52±0.47** | 0.005 |
| Example 4 | 5％ | Reducing graphene oxide: collagen protein 8% | 2.17±0.37 | 0.059 |
Note: p < 0.05 shows significant differences compared to pure collagen catheters, p < 0.01 shows very significant differences compared to pure collagen catheters
By combining the data in tables 1 and 2, it can be found that compared with a pure collagen catheter, the conductivity and suture strength of the conductive composite material added with the reduced graphene oxide component are both significantly improved, so that the conductive composite material provided by the invention has a significant conductive effect and a better suture repair capability.
The results in the table also show that although the reduced graphene oxide can improve the conductivity and mechanical effect of the collagen repair catheter, when the content of the reduced graphene oxide is too high, the conductivity and mechanical property are not improved more obviously, and conversely, a descending trend even appears. The reason why the theoretical analysis shows the result may be that the content of the reduced graphene oxide is too high, the aggregation and accumulation phenomenon is caused by strong van der waals force, the dispersion in the solution is not uniform, the connection of the conductive network is influenced, the conductivity is influenced, the viscosity of the solution is too high, the stress transmission is not facilitated, the stress concentration is increased, and the mechanical property is also reduced. Meanwhile, the concentration of the collagen is moderate at 5%, if the concentration of the collagen is too low, the material is soft and easy to collapse after being wetted, the collagen is not favorable for playing a good supporting role in the repairing process, and if the concentration of the collagen is too high, the collagen is not completely dissolved, and the material after freeze-drying is brittle.
In addition, the graphene oxide is not high in strength, but certain inter-group static electricity or hydrogen bond action may exist between the residual unreduced carboxyl and hydroxyl and the amino and carboxyl of the collagen after the reduction of the vitamin C, and the graphene oxide can also play a certain role in improving the mechanical property of the collagen.
After comprehensive evaluation, when the conductive composite material provided by the invention contains collagen with a mass volume concentration of 5% (mass-volume ratio) and reduced graphene oxide with a content of 4% (reduced graphene oxide/collagen mass ratio), both the conductivity and the suture performance are more ideal.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (10)
1. The conductive composite material is characterized by comprising a compound of natural polymer collagen and reduced graphene oxide;
the natural polymer collagen is prepared from collagen slurry with the mass volume concentration of 3% -10%, and the mass ratio of the reduced graphene oxide to the natural polymer collagen is 0.5% -20%.
2. The conductive composite as claimed in claim 1, wherein the collagen slurry is an acetic acid solution of collagen, the acetic acid concentration being 0.2-0.8M; preferably, the collagen is type I collagen.
3. The conductive composite of claim 1, wherein the reduced graphene oxide is graphene oxide treated with a reducing agent, wherein the reducing agent is vitamin C, chitosan, glucose, preferably vitamin C; more preferably, the mass ratio of the graphene oxide to the reducing agent is 1: 2-15.
4. The conductive composite material as claimed in any one of claims 1 to 3, wherein the natural polymer collagen is made of collagen slurry with a mass volume concentration of 4% to 8%, and the mass ratio of the reduced graphene oxide to the natural polymer collagen is 1% to 8%; preferably, the natural polymer collagen is prepared from a collagen slurry with a mass volume concentration of 5%, and the mass ratio of the reduced graphene oxide to the natural polymer collagen is 1% -4%.
5. A method of making the conductive composite of any of claims 1-4, comprising:
(1) respectively preparing collagen slurry with certain mass volume concentration and an aqueous solution of reduced graphene oxide, and uniformly mixing;
(2) and (2) centrifuging the mixed solution obtained in the step (1), injecting into a mold, freezing, drying, crosslinking, packaging and sterilizing.
6. The method according to claim 5, wherein the aqueous solution of reduced graphene oxide has a mass volume concentration of 10-25 mg/ml.
7. The method as claimed in claim 5, wherein the centrifugation is performed at 5-20 deg.C and 3000-5000rpm for 40-120 min; preferably 10 ℃ and 4000rpm for 100 min.
8. The method of claim 5, wherein the cross-linking is selected from the group consisting of glutaraldehyde vapor cross-linking, ultraviolet light cross-linking, high temperature vacuum cross-linking; preferably high-temperature vacuum crosslinking under the conditions of-0.09 MPa of pressure, 105 +/-2 ℃ of temperature and 24 hours of fixing time.
9. Use of the conductive composite material according to any one of claims 1 to 4 and/or the conductive composite material obtained by the method according to any one of claims 5 to 8 for the preparation of a nerve repair catheter with high suture strength.
10. The use of claim 9, wherein the nerve repair conduit has a pore size of 50-220 microns and a wall thickness of 0.4 ± 0.3 mm.
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