CN114957588B - Bioabsorbable nerve scaffold and preparation method thereof - Google Patents
Bioabsorbable nerve scaffold and preparation method thereof Download PDFInfo
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- CN114957588B CN114957588B CN202210739148.1A CN202210739148A CN114957588B CN 114957588 B CN114957588 B CN 114957588B CN 202210739148 A CN202210739148 A CN 202210739148A CN 114957588 B CN114957588 B CN 114957588B
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- A61L2430/32—Materials or treatment for tissue regeneration for nerve reconstruction
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Abstract
The invention provides a bioabsorbable nerve scaffold and a preparation method thereof, which takes hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano materials as raw materials, and the raw materials are blended and processed into a hollow tubular structure. The nerve scaffold can be gradually degraded in human tissues, has good mechanical properties and good nerve repair effect. Wherein the hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone, which are obtained by hydroxyl end group encapsulation, and the prepolymer is obtained by reacting hydrophilic block molecule, hydrophobic block molecule and isocyanate. The main structure of the invention is obtained by polymerization reaction of hydrophilic block molecules, hydrophobic block molecules and isocyanate, has good mechanical properties, can be gradually degraded in human tissues, promotes nerve regeneration and plays a role in nerve repair.
Description
Technical Field
The invention relates to the technical field of medical stent materials, in particular to a bioabsorbable nerve stent and a preparation method thereof.
Background
The damage of the nervous system mainly comprises spinal cord injury, brain injury, peripheral nerve injury and the like, once the nervous system is diseased, the recovery degree is limited, the treatment effect is poor, and serious sequelae often still exist after the treatment. Therefore, implantation of a neural scaffold to replace tissue that has been thoroughly damaged, promote regeneration of neural tissue, has become a common clinical treatment for treating damage to the nervous system today.
The development of neural scaffolds goes through the following three main phases:
1. autologous venous vessels, amniotic membranes, etc. are used to bridge the defective nerves, mainly because these biological grafts contain basement membranes similar to those of schwann cells.
2. The non-degradable materials such as polyethylene, polyvinyl chloride and the like are used for providing a microenvironment for nerve regeneration, and after repair is finished, the materials are taken out by secondary operation, so that secondary injury is easily caused.
3. The biological absorbable material is adopted to provide a temporary microenvironment for nerve regeneration, and the biological absorbable material is automatically degraded after nerve repair is completed and finally absorbed by a human body or discharged out of the body.
The use of bioabsorbable neural scaffold materials is the best choice, both in terms of therapeutic effect and patient affliction.
For example, collagen is a commonly used bioabsorbable nerve scaffold material, which has good degradability, biocompatibility, low immunity and modifiable properties, and can promote the regeneration of the axon of the dorsal root ganglion. However, in the collagen production process, it is generally necessary to dissolve the collagen in acetic acid, and if a solid collagen material is to be obtained, it is generally necessary to neutralize acetic acid with an alkaline solution, and the salt produced after neutralization is mixed in the solution, so that it is necessary to further remove the salt by dialysis, and thus the production method of the collagen material currently used is complicated and has a high cost. Compared with collagen, the synthetic high molecular polymer has natural cost advantage.
Patent CN104645409B discloses a polylactic acid nerve scaffold and a preparation method thereof, comprising a scaffold film material and degradable metal wires wrapped by the scaffold film material, wherein the degradable metal wires are distributed along the transverse direction and the longitudinal direction of the scaffold, and the main component of the scaffold film material is polylactic acid. The nerve scaffold of the patent has relatively poor mechanical property and poor nerve repair effect.
Disclosure of Invention
The invention aims to provide a bioabsorbable nerve scaffold and a preparation method thereof, which have good mechanical properties and good nerve repair effect.
In order to achieve the above purpose, the invention is realized by the following scheme:
a preparation method of a bioabsorbable nerve scaffold is characterized in that hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano materials are used as raw materials, and are blended and processed into a hollow tubular structure; wherein the hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone and is obtained by packaging a hydroxyl end group, and the prepolymer is obtained by reacting the hydrophilic block molecule, the hydrophobic block molecule and isocyanate; the magnetic nano material is prepared by the following method:
(A) Firstly, preparing amino magnetic nanospheres by taking ferric chloride, sodium acetate and hexamethylenediamine as raw materials, and then mixing the amino magnetic nanospheres with methyl acrylate and hexamethylenediamine for reaction to obtain amino hyperbranched magnetic nanospheres;
(B) And then reacting the amino hyperbranched magnetic nanospheres, the chitosan-coated carbon nanotubes with polylactic acid to obtain the magnetic nanomaterial.
Preferably, the hollow tubular structure is prepared by any one of melt extrusion, 3D printing or melt spinning.
More preferably, the temperature of the melt extrusion is 120 to 260 ℃, still more preferably 150 to 220 ℃, still more preferably 170 to 200 ℃; the treatment time is 30-40 minutes.
Further preferably, the specific method of 3D printing is: the powder is spread on a workbench of a 3D printer, the set temperature is 100 ℃, the laser power is 60W, the scanning interval is 0.2mm, the powder spreading thickness is 0.12mm, and the scanning speed is 7.3m/s.
Further preferably, the process conditions of melt spinning are: the temperature is 170-180 ℃, the stretching multiple of the spinneret is 2-4 times, and the heat setting temperature is 50-60 ℃.
Preferably, the inner diameter of the hollow tubular structure is 1-5 mm, more preferably 1.5-3 mm; the thickness is 0.2 to 1mm, more preferably 0.3 to 0.6mm.
Preferably, the hydrophobic block molecules are prepared by the following method in parts by weight: mixing 1 part of polylactic acid, polyglycolide or polycaprolactone with 1.2-1.3 parts of glycol, heating to 130-140 ℃ under the condition of 0.5-0.6 MPa, preserving heat and stirring for 2-3 hours, heating to 150-160 ℃, preserving heat and stirring for 5-7 hours, cooling and crushing to obtain the hydrophobic block molecule.
Preferably, the prepolymer is prepared by the following method in parts by weight: firstly, hydrophilic block molecules, hydrophobic block molecules, isocyanate, ethylenediamine and ferric acetylacetonate are mixed according to a mole ratio of 1:0.3 to 0.5: 8-10: 1-2: mixing 0.005-0.008, adding into N, N-dimethylformamide with the weight 5-7 times of the total weight of the mixture, stirring and reacting for 2-3 hours at 65-75 ℃ under the protection of nitrogen, and removing the N, N-dimethylformamide to obtain the prepolymer.
Preferably, the molecular weight of the prepolymer is 100 to 5000g/mol, more preferably 200 to 2000g/mol, still more preferably 300 to 1000g/mol.
Preferably, the prepolymer contains 1 to 20% by weight of isocyanate functional groups, more preferably 3 to 12%.
Preferably, the isocyanate is selected from any one of diphenylmethane diisocyanate, toluene 2, 4-diisocyanate, p-phenylene diisocyanate or hexamethylene diisocyanate.
Preferably, in the step (a), the preparation method of the amino magnetic nanospheres comprises the following steps in parts by weight: firstly, adding 1 part of ferric chloride, 3-4 parts of sodium acetate and 4-5 parts of hexamethylenediamine into 12-15 parts of ethylene glycol, stirring and reacting for 7-9 hours at 160-180 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the finished product.
Preferably, in the step (A), the preparation method of the amino hyperbranched magnetic nanospheres comprises the following steps of: firstly, 1 part of amino magnetic nanospheres, 0.3-0.4 part of absolute ethyl alcohol and 0.15-0.25 part of methyl acrylate are mixed and stirred for 5-7 hours, then 0.15-0.25 part of ethylenediamine is added, stirred and reacted for 4-6 hours at 50-60 ℃, and the amino hyperbranched magnetic nanospheres are obtained after centrifugation, washing and drying.
Preferably, the specific method of the step (B) is as follows in parts by weight: firstly adding 1 part of amino hyperbranched magnetic nanospheres and 0.1-0.2 part of chitosan coated carbon nano tubes into 5-7 parts of chloroform, dispersing uniformly by ultrasonic waves, then adding 2.2-2.5 parts of polylactic acid, stirring and reacting for 25-30 hours, and distilling under reduced pressure to remove chloroform, thus obtaining the magnetic nano material.
Preferably, in the step (B), the chitosan-coated carbon nanotubes are prepared by the following method in parts by weight: adding 0.1 part of chitosan into 100-110 parts of acetic acid solution with the mass concentration of 1%, stirring and dispersing uniformly to obtain chitosan acetic acid solution, adding 0.01-0.02 part of carbon nano tube into the chitosan acetic acid solution, dispersing uniformly by ultrasonic wave, adjusting pH to 7-8, dropwise adding glutaraldehyde water solution with the mass concentration of 1% while stirring, continuing stirring for 70-80 minutes after the dropwise adding, centrifuging, washing and drying to obtain the chitosan.
Further preferably, the stirring rate is 300 to 500 rpm.
The invention also claims a bioabsorbable nerve scaffold obtained by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention takes hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano material as raw materials, and the raw materials are blended and processed into the bioabsorbable nerve scaffold with a hollow tubular structure. The nerve scaffold can be gradually degraded in human tissues, has good mechanical properties and good nerve repair effect;
(2) The hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone, the hydrophilic block molecule is obtained by packaging hydroxyl end groups, and the prepolymer is obtained by reacting hydrophilic block molecules, hydrophobic block molecules and isocyanate. The main structure of the invention is obtained by polymerization reaction of hydrophilic block molecules, hydrophobic block molecules and isocyanate, has good mechanical properties, can be gradually degraded in human tissues, promotes nerve regeneration and plays a role in nerve repair;
(3) The technical key of the invention is that the magnetic nano material is introduced, and the magnetic nano material is prepared by the following method: firstly, preparing amino magnetic nanospheres by taking ferric chloride, sodium acetate and hexamethylenediamine as raw materials, and then mixing the amino magnetic nanospheres with methyl acrylate and hexamethylenediamine for reaction to obtain amino hyperbranched magnetic nanospheres; and then reacting the amino hyperbranched magnetic nanospheres, the chitosan-coated carbon nanotubes with polylactic acid to obtain the amino hyperbranched magnetic nanospheres. The magnetic nano material has magnetism, and can induce and accelerate nerve regeneration and improve nerve repair effect under the influence of a micro magnetic field in a human body. The magnetic nanomaterial has a nanoscale, and the nanomaterial induces and promotes degradation as the degradation of the nerve scaffold proceeds. In addition, the magnetic nano material has good mechanical properties, and is favorable for improving the mechanical properties of the nerve scaffold. In addition, the polylactic acid is introduced into the magnetic nano material, so that the dispersibility and compatibility in a system are effectively improved, and the mechanical property of the product is further improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a bioabsorbable nerve scaffold is characterized in that hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano materials are used as raw materials, and are blended and processed into a hollow tubular structure; wherein the hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone and is obtained by packaging a hydroxyl end group, and the prepolymer is obtained by reacting the hydrophilic block molecule, the hydrophobic block molecule and isocyanate; the magnetic nano material is prepared by the following method:
(A) Firstly, preparing amino magnetic nanospheres by taking ferric chloride, sodium acetate and hexamethylenediamine as raw materials, and then mixing the amino magnetic nanospheres with methyl acrylate and hexamethylenediamine for reaction to obtain amino hyperbranched magnetic nanospheres;
(B) And then reacting the amino hyperbranched magnetic nanospheres, the chitosan-coated carbon nanotubes with polylactic acid to obtain the magnetic nanomaterial.
The processing method is melt extrusion, and the temperature of the melt extrusion is 170 ℃; the treatment time was 40 minutes.
The inner diameter of the hollow tubular structure is 1.5mm; the thickness was 0.6mm.
The preparation method of the hydrophobic block molecule comprises the following steps: mixing 1g of polylactic acid, polyglycolide or polycaprolactone with 1.2g of glycol, heating to 130 ℃ under the condition of 0.6MPa, preserving heat and stirring for 3 hours, then heating to 150 ℃, preserving heat and stirring for 7 hours, cooling and crushing to obtain the hydrophobic block molecule.
The preparation method of the prepolymer comprises the following steps: firstly, hydrophilic block molecules, hydrophobic block molecules, isocyanate, ethylenediamine and ferric acetylacetonate are mixed according to a mole ratio of 1:0.3:10:1: mixing 0.008, adding into N, N-dimethylformamide with the total weight being 5 times of that of the mixture, stirring and reacting for 2 hours at 75 ℃ under the protection of nitrogen, and removing the N, N-dimethylformamide to obtain the prepolymer.
The molecular weight of the prepolymer was 1000g/mol.
The prepolymer contained 3% by weight of isocyanate functional groups.
The isocyanate is diphenylmethane diisocyanate.
In the step (A), the preparation method of the amino magnetic nanospheres comprises the following steps: firstly, adding 1g of ferric chloride, 4g of sodium acetate and 4g of hexamethylenediamine into 15g of ethylene glycol, stirring and reacting for 9 hours at 160 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the finished product.
In the step (A), the preparation method of the amino hyperbranched magnetic nanospheres comprises the following steps: firstly, mixing and stirring 1g of amino magnetic nanospheres, 0.3g of absolute ethyl alcohol and 0.25g of methyl acrylate for 5 hours, then adding 0.25g of ethylenediamine, stirring and reacting at 50 ℃ for 6 hours, centrifuging, washing and drying to obtain the amino hyperbranched magnetic nanospheres.
The specific method of the step (B) is as follows: firstly adding 1g of amino hyperbranched magnetic nanospheres and 0.1g of chitosan coated carbon nano tubes into 7g of chloroform, dispersing uniformly by ultrasonic waves, then adding 2.2g of polylactic acid, stirring and reacting for 30 hours, and distilling under reduced pressure to remove chloroform, thus obtaining the magnetic nano material.
In the step (B), the chitosan-coated carbon nanotubes are prepared by the following method: adding 0.1g of chitosan into 100g of acetic acid solution with the mass concentration of 1%, stirring and dispersing uniformly to obtain chitosan acetic acid solution, adding 0.02g of carbon nano tube into the chitosan acetic acid solution, dispersing uniformly by ultrasonic wave, regulating pH to be 7, dropwise adding glutaraldehyde water solution with the mass concentration of 1% while stirring, continuing stirring for 80 minutes after the dropwise adding, centrifuging, washing and drying to obtain the chitosan. The stirring rate was 300 revolutions per minute.
Example 2
A preparation method of a bioabsorbable nerve scaffold is characterized in that hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano materials are used as raw materials, and are blended and processed into a hollow tubular structure; wherein the hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone and is obtained by packaging a hydroxyl end group, and the prepolymer is obtained by reacting the hydrophilic block molecule, the hydrophobic block molecule and isocyanate; the magnetic nano material is prepared by the following method:
(A) Firstly, preparing amino magnetic nanospheres by taking ferric chloride, sodium acetate and hexamethylenediamine as raw materials, and then mixing the amino magnetic nanospheres with methyl acrylate and hexamethylenediamine for reaction to obtain amino hyperbranched magnetic nanospheres;
(B) And then reacting the amino hyperbranched magnetic nanospheres, the chitosan-coated carbon nanotubes with polylactic acid to obtain the magnetic nanomaterial.
The processing method is 3D printing, and the specific method of the 3D printing is as follows: the powder is spread on a workbench of a 3D printer, the set temperature is 100 ℃, the laser power is 60W, the scanning interval is 0.2mm, the powder spreading thickness is 0.12mm, and the scanning speed is 7.3m/s.
The inner diameter of the hollow tubular structure is 3mm; the thickness was 0.3mm.
The preparation method of the hydrophobic block molecule comprises the following steps: mixing 1g of polylactic acid, polyglycolide or polycaprolactone with 1.3g of glycol, heating to 140 ℃ under the condition of 0.5MPa, preserving heat and stirring for 2 hours, then heating to 160 ℃, preserving heat and stirring for 5 hours, cooling and crushing to obtain the hydrophobic block molecule.
The preparation method of the prepolymer comprises the following steps: firstly, hydrophilic block molecules, hydrophobic block molecules, isocyanate, ethylenediamine and ferric acetylacetonate are mixed according to a mole ratio of 1:0.5:8:2: mixing 0.005, adding into N, N-dimethylformamide 7 times of the total weight of the mixture, stirring at 65 ℃ under the protection of nitrogen for 3 hours, and removing the N, N-dimethylformamide to obtain the prepolymer.
The molecular weight of the prepolymer was 300g/mol.
The prepolymer contained 12% by weight of isocyanate functional groups.
The isocyanate is toluene 2, 4-diisocyanate.
In the step (A), the preparation method of the amino magnetic nanospheres comprises the following steps: firstly, adding 1g of ferric chloride, 3g of sodium acetate and 5g of hexamethylenediamine into 12g of ethylene glycol, stirring and reacting for 7 hours at 180 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the finished product.
In the step (A), the preparation method of the amino hyperbranched magnetic nanospheres comprises the following steps: firstly, mixing and stirring 1g of amino magnetic nanospheres, 0.4g of absolute ethyl alcohol and 0.15g of methyl acrylate for 7 hours, then adding 0.15g of ethylenediamine, stirring at 60 ℃ for reaction for 4 hours, centrifuging, washing and drying to obtain the amino hyperbranched magnetic nanospheres.
The specific method of the step (B) is as follows: firstly adding 1g of amino hyperbranched magnetic nanospheres and 0.2g of chitosan coated carbon nano tubes into 5g of chloroform, dispersing uniformly by ultrasonic waves, then adding 2.5g of polylactic acid, stirring and reacting for 25 hours, and distilling under reduced pressure to remove chloroform, thus obtaining the magnetic nano material.
In the step (B), the chitosan-coated carbon nanotubes are prepared by the following method: adding 0.1g of chitosan into 110g of acetic acid solution with the mass concentration of 1%, stirring and dispersing uniformly to obtain chitosan acetic acid solution, adding 0.01g of carbon nano tube into the chitosan acetic acid solution, dispersing uniformly by ultrasonic wave, regulating pH to 8, dropwise adding glutaraldehyde water solution with the mass concentration of 1% while stirring, continuing stirring for 70 minutes after the dropwise adding, centrifuging, washing and drying to obtain the chitosan. The stirring rate was 500 rpm.
Example 3
A preparation method of a bioabsorbable nerve scaffold is characterized in that hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano materials are used as raw materials, and are blended and processed into a hollow tubular structure; wherein the hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone and is obtained by packaging a hydroxyl end group, and the prepolymer is obtained by reacting the hydrophilic block molecule, the hydrophobic block molecule and isocyanate; the magnetic nano material is prepared by the following method:
(A) Firstly, preparing amino magnetic nanospheres by taking ferric chloride, sodium acetate and hexamethylenediamine as raw materials, and then mixing the amino magnetic nanospheres with methyl acrylate and hexamethylenediamine for reaction to obtain amino hyperbranched magnetic nanospheres;
(B) And then reacting the amino hyperbranched magnetic nanospheres, the chitosan-coated carbon nanotubes with polylactic acid to obtain the magnetic nanomaterial.
The processing method is melt spinning, and the process conditions of the melt spinning are as follows: the temperature is 175 ℃, the spinneret stretching multiple is 3 times, and the heat setting temperature is 55 ℃.
The inner diameter of the hollow tubular structure is 2mm; the thickness was 0.4mm.
The preparation method of the hydrophobic block molecule comprises the following steps: mixing 1g of polylactic acid, polyglycolide or polycaprolactone with 1.25g of glycol, heating to 135 ℃ under the condition of 0.55MPa, preserving heat and stirring for 2.5 hours, then heating to 155 ℃, preserving heat and stirring for 6 hours, cooling and crushing to obtain the hydrophobic block molecule.
The preparation method of the prepolymer comprises the following steps: firstly, hydrophilic block molecules, hydrophobic block molecules, isocyanate, ethylenediamine and ferric acetylacetonate are mixed according to a mole ratio of 1:0.4:9:1.5: mixing 0.006, adding into N, N-dimethylformamide with the total weight being 6 times of that of the mixture, stirring and reacting for 2.5 hours at 70 ℃ under the protection of nitrogen, and removing the N, N-dimethylformamide to obtain the prepolymer.
The molecular weight of the prepolymer was 800g/mol.
The prepolymer contained 9% by weight of isocyanate functional groups.
The isocyanate is terephthalyl isocyanate.
In the step (A), the preparation method of the amino magnetic nanospheres comprises the following steps: firstly, adding 1g of ferric chloride, 3.5g of sodium acetate and 4.5g of hexamethylenediamine into 13g of ethylene glycol, stirring and reacting for 8 hours at 170 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the finished product.
In the step (A), the preparation method of the amino hyperbranched magnetic nanospheres comprises the following steps: firstly, mixing and stirring 1g of amino magnetic nanospheres, 0.35g of absolute ethyl alcohol and 0.2g of methyl acrylate for 6 hours, then adding 0.2g of ethylenediamine, stirring and reacting at 55 ℃ for 5 hours, centrifuging, washing and drying to obtain the amino hyperbranched magnetic nanospheres.
The specific method of the step (B) is as follows: firstly adding 1g of amino hyperbranched magnetic nanospheres and 0.15g of chitosan-coated carbon nano tubes into 6g of chloroform, dispersing uniformly by ultrasonic waves, then adding 2.4g of polylactic acid, stirring and reacting for 28 hours, and distilling under reduced pressure to remove chloroform, thus obtaining the magnetic nano material.
In the step (B), the chitosan-coated carbon nanotubes are prepared by the following method: adding 0.1g of chitosan into 105g of acetic acid solution with the mass concentration of 1%, stirring and dispersing uniformly to obtain chitosan acetic acid solution, adding 0.015g of carbon nano tube into the chitosan acetic acid solution, dispersing uniformly by ultrasonic wave, regulating pH=7.5, dropwise adding glutaraldehyde water solution with the mass concentration of 1% while stirring, continuing stirring for 75 minutes after the dropwise adding, centrifuging, washing and drying to obtain the chitosan. The stirring rate was 400 rpm.
Comparative example 1
A preparation method of a bioabsorbable nerve scaffold is characterized in that hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano materials are used as raw materials, and are blended and processed into a hollow tubular structure; wherein the hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone and is obtained by packaging a hydroxyl end group, and the prepolymer is obtained by reacting the hydrophilic block molecule, the hydrophobic block molecule and isocyanate; the magnetic nano material is prepared by the following method:
(A) Firstly, preparing amino magnetic nanospheres by taking ferric chloride, sodium acetate and hexamethylenediamine as raw materials;
(B) And then reacting the amino magnetic nanospheres, the chitosan coated carbon nanotubes with polylactic acid to obtain the magnetic nanomaterial.
The processing method is melt extrusion, and the temperature of the melt extrusion is 170 ℃; the treatment time was 40 minutes.
The inner diameter of the hollow tubular structure is 1.5mm; the thickness was 0.6mm.
The preparation method of the hydrophobic block molecule comprises the following steps: mixing 1g of polylactic acid, polyglycolide or polycaprolactone with 1.2g of glycol, heating to 130 ℃ under the condition of 0.6MPa, preserving heat and stirring for 3 hours, then heating to 150 ℃, preserving heat and stirring for 7 hours, cooling and crushing to obtain the hydrophobic block molecule.
The preparation method of the prepolymer comprises the following steps: firstly, hydrophilic block molecules, hydrophobic block molecules, isocyanate, ethylenediamine and ferric acetylacetonate are mixed according to a mole ratio of 1:0.3:10:1: mixing 0.008, adding into N, N-dimethylformamide with the total weight being 5 times of that of the mixture, stirring and reacting for 2 hours at 75 ℃ under the protection of nitrogen, and removing the N, N-dimethylformamide to obtain the prepolymer.
The molecular weight of the prepolymer was 1000g/mol.
The prepolymer contained 3% by weight of isocyanate functional groups.
The isocyanate is diphenylmethane diisocyanate.
In the step (A), the preparation method of the amino magnetic nanospheres comprises the following steps: firstly, adding 1g of ferric chloride, 4g of sodium acetate and 4g of hexamethylenediamine into 15g of ethylene glycol, stirring and reacting for 9 hours at 160 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the finished product.
The specific method of the step (B) is as follows: firstly adding 1g of amino magnetic nanospheres and 0.1g of chitosan coated carbon nano tubes into 7g of chloroform, uniformly dispersing by ultrasonic waves, then adding 2.2g of polylactic acid, stirring and reacting for 30 hours, and distilling under reduced pressure to remove chloroform, thus obtaining the magnetic nano material.
In the step (B), the chitosan-coated carbon nanotubes are prepared by the following method: adding 0.1g of chitosan into 100g of acetic acid solution with the mass concentration of 1%, stirring and dispersing uniformly to obtain chitosan acetic acid solution, adding 0.02g of carbon nano tube into the chitosan acetic acid solution, dispersing uniformly by ultrasonic wave, regulating pH to be 7, dropwise adding glutaraldehyde water solution with the mass concentration of 1% while stirring, continuing stirring for 80 minutes after the dropwise adding, centrifuging, washing and drying to obtain the chitosan. The stirring rate was 300 revolutions per minute.
Comparative example 2
A preparation method of a bioabsorbable nerve scaffold is characterized in that hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano materials are used as raw materials, and are blended and processed into a hollow tubular structure; wherein the hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone and is obtained by packaging a hydroxyl end group, and the prepolymer is obtained by reacting the hydrophilic block molecule, the hydrophobic block molecule and isocyanate; the magnetic nano material is prepared by the following method: firstly, ferric chloride, sodium acetate and hexamethylenediamine are used as raw materials to prepare amino magnetic nanospheres, and then the amino magnetic nanospheres are mixed with methyl acrylate and hexamethylenediamine for reaction to obtain the magnetic nanomaterial.
The processing method is melt extrusion, and the temperature of the melt extrusion is 170 ℃; the treatment time was 40 minutes.
The inner diameter of the hollow tubular structure is 1.5mm; the thickness was 0.6mm.
The preparation method of the hydrophobic block molecule comprises the following steps: mixing 1g of polylactic acid, polyglycolide or polycaprolactone with 1.2g of glycol, heating to 130 ℃ under the condition of 0.6MPa, preserving heat and stirring for 3 hours, then heating to 150 ℃, preserving heat and stirring for 7 hours, cooling and crushing to obtain the hydrophobic block molecule.
The preparation method of the prepolymer comprises the following steps: firstly, hydrophilic block molecules, hydrophobic block molecules, isocyanate, ethylenediamine and ferric acetylacetonate are mixed according to a mole ratio of 1:0.3:10:1: mixing 0.008, adding into N, N-dimethylformamide with the total weight being 5 times of that of the mixture, stirring and reacting for 2 hours at 75 ℃ under the protection of nitrogen, and removing the N, N-dimethylformamide to obtain the prepolymer.
The molecular weight of the prepolymer was 1000g/mol.
The prepolymer contained 3% by weight of isocyanate functional groups.
The isocyanate is diphenylmethane diisocyanate.
In the step (A), the preparation method of the amino magnetic nanospheres comprises the following steps: firstly, adding 1g of ferric chloride, 4g of sodium acetate and 4g of hexamethylenediamine into 15g of ethylene glycol, stirring and reacting for 9 hours at 160 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the finished product.
In the step (A), the preparation method of the magnetic nano material comprises the following steps: firstly, mixing and stirring 1g of amino magnetic nanospheres, 0.3g of absolute ethyl alcohol and 0.25g of methyl acrylate for 5 hours, then adding 0.25g of ethylenediamine, stirring and reacting for 6 hours at 50 ℃, centrifuging, washing and drying to obtain the amino magnetic nanospheres.
Comparative example 3
A preparation method of a bioabsorbable nerve scaffold is characterized in that hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano materials are used as raw materials, and are blended and processed into a hollow tubular structure; wherein the hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone and is obtained by packaging a hydroxyl end group, and the prepolymer is obtained by reacting the hydrophilic block molecule, the hydrophobic block molecule and isocyanate; the magnetic nano material is prepared by the following method:
(A) Firstly, preparing amino magnetic nanospheres by taking ferric chloride, sodium acetate and hexamethylenediamine as raw materials, and then mixing the amino magnetic nanospheres with methyl acrylate and hexamethylenediamine for reaction to obtain amino hyperbranched magnetic nanospheres;
(B) And then reacting the amino hyperbranched magnetic nanospheres with polylactic acid to obtain the magnetic nanomaterial.
The processing method is melt extrusion, and the temperature of the melt extrusion is 170 ℃; the treatment time was 40 minutes.
The inner diameter of the hollow tubular structure is 1.5mm; the thickness was 0.6mm.
The preparation method of the hydrophobic block molecule comprises the following steps: mixing 1g of polylactic acid, polyglycolide or polycaprolactone with 1.2g of glycol, heating to 130 ℃ under the condition of 0.6MPa, preserving heat and stirring for 3 hours, then heating to 150 ℃, preserving heat and stirring for 7 hours, cooling and crushing to obtain the hydrophobic block molecule.
The preparation method of the prepolymer comprises the following steps: firstly, hydrophilic block molecules, hydrophobic block molecules, isocyanate, ethylenediamine and ferric acetylacetonate are mixed according to a mole ratio of 1:0.3:10:1: mixing 0.008, adding into N, N-dimethylformamide with the total weight being 5 times of that of the mixture, stirring and reacting for 2 hours at 75 ℃ under the protection of nitrogen, and removing the N, N-dimethylformamide to obtain the prepolymer.
The molecular weight of the prepolymer was 1000g/mol.
The prepolymer contained 3% by weight of isocyanate functional groups.
The isocyanate is diphenylmethane diisocyanate.
In the step (A), the preparation method of the amino magnetic nanospheres comprises the following steps: firstly, adding 1g of ferric chloride, 4g of sodium acetate and 4g of hexamethylenediamine into 15g of ethylene glycol, stirring and reacting for 9 hours at 160 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the finished product.
In the step (A), the preparation method of the amino hyperbranched magnetic nanospheres comprises the following steps: firstly, mixing and stirring 1g of amino magnetic nanospheres, 0.3g of absolute ethyl alcohol and 0.25g of methyl acrylate for 5 hours, then adding 0.25g of ethylenediamine, stirring and reacting at 50 ℃ for 6 hours, centrifuging, washing and drying to obtain the amino hyperbranched magnetic nanospheres.
The specific method of the step (B) is as follows: firstly adding 1g of amino hyperbranched magnetic nanospheres into 7g of chloroform, dispersing uniformly by ultrasonic waves, then adding 2.2g of polylactic acid, stirring and reacting for 30 hours, and distilling under reduced pressure to remove chloroform, thus obtaining the magnetic nanomaterial.
Comparative example 4
A preparation method of a bioabsorbable nerve scaffold is characterized in that hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano materials are used as raw materials, and are blended and processed into a hollow tubular structure; wherein the hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone and is obtained by packaging a hydroxyl end group, and the prepolymer is obtained by reacting the hydrophilic block molecule, the hydrophobic block molecule and isocyanate; the magnetic nano material is prepared by the following method:
(A) Firstly, preparing amino magnetic nanospheres by taking ferric chloride, sodium acetate and hexamethylenediamine as raw materials, and then mixing the amino magnetic nanospheres with methyl acrylate and hexamethylenediamine for reaction to obtain amino hyperbranched magnetic nanospheres;
(B) And then mixing the amino hyperbranched magnetic nanospheres and the chitosan coated carbon nano tubes to obtain the magnetic nano material.
The processing method is melt extrusion, and the temperature of the melt extrusion is 170 ℃; the treatment time was 40 minutes.
The inner diameter of the hollow tubular structure is 1.5mm; the thickness was 0.6mm.
The preparation method of the hydrophobic block molecule comprises the following steps: mixing 1g of polylactic acid, polyglycolide or polycaprolactone with 1.2g of glycol, heating to 130 ℃ under the condition of 0.6MPa, preserving heat and stirring for 3 hours, then heating to 150 ℃, preserving heat and stirring for 7 hours, cooling and crushing to obtain the hydrophobic block molecule.
The preparation method of the prepolymer comprises the following steps: firstly, hydrophilic block molecules, hydrophobic block molecules, isocyanate, ethylenediamine and ferric acetylacetonate are mixed according to a mole ratio of 1:0.3:10:1: mixing 0.008, adding into N, N-dimethylformamide with the total weight being 5 times of that of the mixture, stirring and reacting for 2 hours at 75 ℃ under the protection of nitrogen, and removing the N, N-dimethylformamide to obtain the prepolymer.
The molecular weight of the prepolymer was 1000g/mol.
The prepolymer contained 3% by weight of isocyanate functional groups.
The isocyanate is diphenylmethane diisocyanate.
In the step (A), the preparation method of the amino magnetic nanospheres comprises the following steps: firstly, adding 1g of ferric chloride, 4g of sodium acetate and 4g of hexamethylenediamine into 15g of ethylene glycol, stirring and reacting for 9 hours at 160 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the finished product.
In the step (A), the preparation method of the amino hyperbranched magnetic nanospheres comprises the following steps: firstly, mixing and stirring 1g of amino magnetic nanospheres, 0.3g of absolute ethyl alcohol and 0.25g of methyl acrylate for 5 hours, then adding 0.25g of ethylenediamine, stirring and reacting at 50 ℃ for 6 hours, centrifuging, washing and drying to obtain the amino hyperbranched magnetic nanospheres.
The specific method of the step (B) is as follows: firstly, adding 1g of amino hyperbranched magnetic nanospheres and 0.1g of chitosan-coated carbon nanotubes into 7g of chloroform, dispersing uniformly by ultrasonic waves, and distilling under reduced pressure to remove chloroform to obtain the magnetic nanomaterial.
Comparative example 5
A preparation method of a bioabsorbable nerve scaffold is characterized in that hydrophilic block molecules, hydrophobic block molecules and prepolymers containing isocyanate functional groups are used as raw materials, and the mixture is processed into a hollow tubular structure; the hydrophilic block molecules are polyester polyol or polyether polyol, the hydrophobic block molecules are polylactic acid, polyglycolide or polycaprolactone and are obtained by packaging hydroxyl end groups, and the prepolymer is obtained by reacting hydrophilic block molecules, hydrophobic block molecules and isocyanate.
The processing method is melt extrusion, and the temperature of the melt extrusion is 170 ℃; the treatment time was 40 minutes.
The inner diameter of the hollow tubular structure is 1.5mm; the thickness was 0.6mm.
The preparation method of the hydrophobic block molecule comprises the following steps: mixing 1g of polylactic acid, polyglycolide or polycaprolactone with 1.2g of glycol, heating to 130 ℃ under the condition of 0.6MPa, preserving heat and stirring for 3 hours, then heating to 150 ℃, preserving heat and stirring for 7 hours, cooling and crushing to obtain the hydrophobic block molecule.
The preparation method of the prepolymer comprises the following steps: firstly, hydrophilic block molecules, hydrophobic block molecules, isocyanate, ethylenediamine and ferric acetylacetonate are mixed according to a mole ratio of 1:0.3:10:1: mixing 0.008, adding into N, N-dimethylformamide with the total weight being 5 times of that of the mixture, stirring and reacting for 2 hours at 75 ℃ under the protection of nitrogen, and removing the N, N-dimethylformamide to obtain the prepolymer.
The molecular weight of the prepolymer was 1000g/mol.
The prepolymer contained 3% by weight of isocyanate functional groups.
The isocyanate is diphenylmethane diisocyanate.
Performance tests were performed on the neural scaffolds obtained in examples 1 to 3 and comparative examples 1 to 5.
1. Mechanical properties:
the mechanical property test method comprises the following steps: tensile strength was measured by a universal tester, and elongation at a loading strength of 0.5kg/cm was measured. The test results are shown in Table 2.
TABLE 2 mechanical test results
| Tensile Strength (MPa) | Elongation (%) | |
| Example 1 | 8.45 | 530.1 |
| Example 2 | 8.28 | 519.3 |
| Example 3 | 8.34 | 535.7 |
| Comparative example 1 | 7.52 | 440.3 |
| Comparative example 2 | 7.03 | 319.1 |
| Comparative example 3 | 7.08 | 338.5 |
| Comparative example 4 | 7.15 | 422.4 |
| Comparative example 5 | 6.02 | 220.3 |
As is clear from Table 2, the neural scaffolds obtained in examples 1 to 3 were large in tensile strength, high in elongation, and excellent in mechanical properties.
Comparative example 1 replaces amino hyperbranched magnetic nanospheres with amino hyperbranched magnetic nanospheres, comparative example 2 replaces magnetic nanomaterial with amino hyperbranched magnetic nanospheres, comparative example 3 omits chitosan-coated carbon nanotubes when preparing magnetic nanomaterial, comparative example 4 omits polylactic acid when preparing magnetic nanomaterial, comparative example 5 omits magnetic nanomaterial, the mechanical properties of the obtained neural scaffold are obviously deteriorated, and the surface modification of the magnetic nanomaterial and the compounding with carbon nanotubes and the like are synergistic to play an enhancement effect, so that the mechanical properties of the product are improved.
3. Nerve repair effect
New SD rats (purchased from Nanjing Junko bioengineering Co., ltd.) 10, sciatic nerve isolated, nerve tissue sheared, digested and centrifuged, and Xuewang cells purified and cultured by differential adherence method. And (3) performing double fluorescent staining identification on the third generation of schwann cells by using S-100 and DAPI immune cells, and determining the concentration of seed cells to be 99%. The sterilized neural scaffold was then cut into cylinders of 5mm in length and 2mm in diameter, placed in 96-well plates, and seed cells were plated at 1X 10 5 The density per well is composited with the neural scaffold. After 24 hours, pulsed electromagnetic field (0.1 mM, 50 Hz) was used for 24 hours of intervention treatment to examine cell proliferation rate and adhesion rate. The results are shown in Table 3.
TABLE 3 investigation of nerve repair Effect
| Proliferation Rate (%) | Adhesion Rate (%) | |
| Example 1 | 96.9 | 99.3 |
| Example 2 | 95.8 | 98.5 |
| Example 3 | 97.3 | 99.2 |
| Comparative example 1 | 87.3 | 92.1 |
| Comparative example 2 | 84.9 | 90.1 |
| Comparative example 3 | 89.5 | 93.6 |
| Comparative example 4 | 90.1 | 91.1 |
| Comparative example 5 | 80.7 | 82.5 |
As is clear from Table 3, the nerve scaffolds obtained in examples 1 to 3 significantly promoted nerve regeneration, and had a good nerve repairing effect.
Comparative example 1 replaces the amino hyperbranched magnetic nanospheres with the amino magnetic nanospheres, comparative example 2 replaces the magnetic nanomaterial with the amino hyperbranched magnetic nanospheres, comparative example 3 omits the chitosan-coated carbon nanotubes when preparing the magnetic nanomaterial, comparative example 4 omits the polylactic acid when preparing the magnetic nanomaterial, and comparative example 5 omits the magnetic nanomaterial, and the nerve repair effect of the obtained nerve scaffold is obviously deteriorated, which indicates that the specific composition of the magnetic material synergistically promotes nerve regeneration, thereby improving the nerve repair effect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
1. A preparation method of a bioabsorbable nerve scaffold is characterized in that hydrophilic block molecules, hydrophobic block molecules, isocyanate functional group-containing prepolymer and magnetic nano materials are used as raw materials, and are blended to prepare a hollow tubular structure; wherein the hydrophilic block molecule is polyester polyol or polyether polyol, the hydrophobic block molecule is polylactic acid, polyglycolide or polycaprolactone and is obtained by packaging a hydroxyl end group, and the prepolymer is obtained by reacting the hydrophilic block molecule, the hydrophobic block molecule and isocyanate; the magnetic nano material is prepared by the following method:
(A) The method comprises the steps of preparing amino magnetic nanospheres from ferric chloride, sodium acetate and hexamethylenediamine, and then mixing and reacting the amino magnetic nanospheres with methyl acrylate and hexamethylenediamine to obtain amino hyperbranched magnetic nanospheres;
(B) Reacting the amino hyperbranched magnetic nanospheres prepared in the step (1), the chitosan-coated carbon nanotubes and polylactic acid to obtain the magnetic nanomaterial;
wherein, the preparation method of the hydrophobic block molecule comprises the following steps in parts by weight: mixing 1 part of polylactic acid, polyglycolide or polycaprolactone with 1.2-1.3 parts of glycol, heating to 130-140 ℃ under the condition of 0.5-0.6 MPa, preserving heat and stirring for 2-3 hours, heating to 150-160 ℃, preserving heat and stirring for 5-7 hours, cooling and crushing to obtain the hydrophobic block molecule;
wherein, the prepolymer is prepared by the following steps in parts by weight: firstly, hydrophilic block molecules, hydrophobic block molecules, isocyanate, ethylenediamine and ferric acetylacetonate are mixed according to a mole ratio of 1:0.3 to 0.5: 8-10: 1-2: mixing 0.005-0.008, adding into N, N-dimethylformamide with the weight 5-7 times of the total weight of the mixture, stirring and reacting for 2-3 hours at 65-75 ℃ under the protection of nitrogen, and removing the N, N-dimethylformamide to obtain the prepolymer;
in the step (A), the preparation method of the amino magnetic nanospheres comprises the following steps of: firstly, adding 1 part of ferric chloride, 3-4 parts of sodium acetate and 4-5 parts of hexamethylenediamine into 12-15 parts of ethylene glycol, stirring and reacting for 7-9 hours at 160-180 ℃, naturally cooling to room temperature, centrifuging, washing and drying to obtain the finished product;
wherein, the specific method of the step (B) is as follows in parts by weight: firstly adding 1 part of amino hyperbranched magnetic nanospheres and 0.1-0.2 part of chitosan coated carbon nano tubes into 5-7 parts of chloroform, dispersing uniformly by ultrasonic waves, then adding 2.2-2.5 parts of polylactic acid, stirring and reacting for 25-30 hours, and distilling under reduced pressure to remove chloroform, thus obtaining the magnetic nano material.
2. The method of manufacturing according to claim 1, wherein the method of manufacturing the hollow tubular structure is any one selected from the group consisting of melt extrusion, 3D printing, and melt spinning.
3. The method of claim 1, wherein the hollow tubular structure has an inner diameter of 1 to 5mm.
4. The process according to claim 1, wherein the prepolymer has a molecular weight of 100 to 5000g/mol.
5. The process according to claim 1, wherein the prepolymer contains 1 to 20% by weight of isocyanate functional groups.
6. The method according to claim 1, wherein the isocyanate is selected from any one of diphenylmethane diisocyanate, toluene 2, 4-diisocyanate, p-phenylene diisocyanate and hexamethylene diisocyanate.
7. A bioabsorbable nerve scaffold produced by the method of any one of claims 1-6.
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