CN108340573B - 3D printing material, nerve repair catheter and preparation method thereof - Google Patents
3D printing material, nerve repair catheter and preparation method thereof Download PDFInfo
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Materials For Medical Uses (AREA)
Abstract
本发明涉及生物工程和生物医学领域，具体涉及3D打印材料、神经修复导管及其制备方法。本发明提供了一种新型的3D打印材料，在常规打印生物材料的原料中添加减少紫外光透过的物质，从而得到一种可进行高精度打印的3D打印材料。将该材料通过3D打印设备能够制备出具有高精度的生物材料，如神经修复导管。
The invention relates to the fields of bioengineering and biomedicine, in particular to a 3D printing material, a nerve repair catheter and a preparation method thereof. The present invention provides a new type of 3D printing material. Substances that reduce the transmission of ultraviolet light are added to the raw materials of conventional printing biological materials, thereby obtaining a 3D printing material capable of high-precision printing. Using this material through 3D printing equipment can produce high-precision biomaterials, such as nerve repair catheters.
Description
Technical Field
The invention relates to the fields of bioengineering and biomedicine, in particular to a 3D printing material, a nerve repair catheter and a preparation method thereof.
Background
At present, partial or whole damage of the nervous system is caused by various traumas such as compression, traction, laceration, cutting and the like, so that the nerve causes loss of function and other neurological diseases. For a damaged nerve, the neuronal axons of the nerve can regenerate under appropriate conditions. With the development of neurosurgery, and in particular micro-neurosurgery, repair and regeneration of nerve damage has become possible. The current neural repair techniques studied and clinically applied are mainly: direct suturing, nerve transplantation (autograft or allograft), and repair through nerve repair promoting tubes. Aiming at long-distance nerve defects, the nerve repair catheter has the advantages of wide synthetic material source, good biocompatibility, controllable mechanical properties and the like, and is a hotspot of current research. However, the existing nerve repair catheter has the defects of high preparation cost, complex process, difficult control of microstructure, difficult rapid personalized production and the like, and has a plurality of problems in clinical application. There is an urgent need in the art to develop techniques that enable rapid batch preparation of personalized neural restoration tubes.
The 3D printing technology is an additive manufacturing technology developed in recent years, and is a strategic emerging technology that can prepare various materials or devices by layer-by-layer building based on computer design. The 3D printing technology has unique advantages in personalized preparation and complex structure manufacturing, can be used for preparing biological materials or biological tissues with various shapes, structures, sizes and functions, has important application in the field of biomedicine, and provides a new choice for preparing the nerve repair promoting tube.
The 3D printing technology comprises a fused deposition technology FDM, a three-dimensional printing bonding technology 3DP, a laser selective sintering technology SLS, a light-cured three-dimensional forming technology SLA, a digital light processing technology DLP and the like, and the printing forming modes have the characteristics and different application ranges. The manufacturing technology of the rapid prototyping such as FDM, 3DP, SLS, SLA and the like can only print in a small area from point to line and from line to surface no matter a nozzle is used for extruding, laser sintering or laser curing materials, and finally, the materials are overlapped layer by layer; however, the Digital Micromirror Device (DMD) used in DLP projection is composed of numerous small lens arrays, each small lens array can independently control a small area to print, the whole device can project a light beam with a desired shape, and can complete printing of one layer at a time, the printing time is independent of the area size, and thus the printing speed is much higher than the FDM, SLS, SLA and other technologies. The 3D printing technology based on the DLP principle has wide application prospect in the fields of tissue repair, drug delivery, tissue structure preparation and the like due to unique advantages.
However, it is difficult to continuously and accurately prepare a complicated 3D structure by a DLP3D printing system, and we have prepared a novel 3D printing material, and a DLP3D printed matter with high precision can be prepared by adding a material for reducing ultraviolet light transmission, such as vitamin B12, to a biological 3D printing material. And the novel 3D printing material is printed by DLP3D to construct a high-precision nerve repair catheter.
Disclosure of Invention
Aiming at the problem of poor printing precision of the continuous DLP3D printing technology, the invention provides a novel 3D printing material. According to the 3D printing material, substances capable of reducing ultraviolet light transmission are added into raw materials of conventional printing biological materials. Thereby reducing the printing speed and improving the printing precision of the continuous DLP 3D.
Further, in the 3D printing material, the biomaterial is a stent, a blood vessel, or a nerve repair catheter.
Preferably, in the 3D printing material, the substance capable of reducing transmission of ultraviolet light is vitamin B12 or eosin a.
Preferably, the 3D printing material is prepared by dissolving a photo-polymerization biomaterial, a substance capable of reducing ultraviolet light transmission, and a photoinitiator in water; wherein, the concentration of the photopolymerization biomaterial is 0.1-99%, the concentration of the substance capable of reducing the transmission of ultraviolet light is 0.01-99%, and the concentration of the photoinitiator is 0.01-99%.
Furthermore, in the 3D printing material, the concentration of the photopolymerization biological material is 3-30%, the concentration of the substance capable of reducing ultraviolet light transmission is 0.01-1%, and the concentration of the photoinitiator is 0.01-5%.
Preferably, in the 3D printing material, the photopolymerizable biomaterial is any one of a photocrosslinkable gelatin derivative, a photocrosslinkable alginate derivative, a photocrosslinkable polycaprolactone derivative, or a polyethylene glycol diacrylate.
Further, in the 3D printing material, the photo-crosslinkable gelatin derivative is a gelatin derivative having a carbon-carbon double bond.
Furthermore, in the 3D printing material, the gelatin derivative having a carbon-carbon double bond is a methacrylated gelatin and a derivative thereof.
Further, in the 3D printing material, the photo-crosslinkable alginate derivative is an alginate derivative having a carbon-carbon double bond.
Furthermore, in the 3D printing material, the alginate derivative having a carbon-carbon double bond is sodium methylacrylated alginate.
Further, in the 3D printing material, the photo-crosslinkable polycaprolactone derivative is a polycaprolactone derivative having a carbon-carbon double bond.
Furthermore, in the 3D printing material, the polycaprolactone derivative having a carbon-carbon double bond is polycaprolactone diacrylate.
Preferably, in the 3D printing material, the photoinitiator is any one of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (I2959), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), or lithium 2,4, 6-trimethylbenzoylphenylphosphinate (LAP).
The invention also provides application of the 3D printing material in preparation of a nerve repair catheter, a stent or a blood vessel.
The invention also provides a nerve repair catheter, a stent or a blood vessel which is obtained by printing the 3D printing material.
The invention also provides a printing method of the nerve repair conduit, the bracket or the blood vessel, which comprises the following steps: constructing a digital model corresponding to the nerve repair catheter, the stent or the blood vessel, and importing the digital model into a 3D printer; adding the 3D printing material into a sample pool of a 3D printer, and then printing and forming; and (4) soaking the formed biological material in water, and taking out.
Further, in the printing method, the soaking time is 12 hours or more.
Further, the printing method further includes the following steps: and (3) soaking the soaked and taken out biological material in a solution with a cross-linking agent for secondary cross-linking, and then drying.
Further, in the printing method, the drying manner is natural drying, drying or critical point drying.
Further, in the above printing method, the crosslinking agent is 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (edc. hcl) or genipin.
Further, in the printing method, the concentration of the cross-linking agent solution is 0.01-99%.
The invention has the beneficial effects that: the invention designs a novel DLP3D printing material, and substances capable of reducing ultraviolet light transmission are added into a conventional printing material, so that the printing speed is reduced, and the precision of printing biological materials can be improved. The 3D printing material can be used for preparing high-precision biological materials such as nerve repair catheters and the like, and has the characteristics of personalized production, batch preparation, reduction of material usage and the like; and various performance aspects of the prepared biological material can meet the application requirements. The nerve repair catheter prepared by the method can be degraded along with time, secondary operation is avoided, a good microenvironment is provided for repairing peripheral nerves, and a good treatment method is provided for repairing peripheral nerves.
Drawings
Fig. 1a, b are nerve conduits printed using PEGDA (20%), c, d are nerve conduits printed using GelMA (20%); wherein, 0.1 percent of vitamin B12 is added into the a and the c; b. d vitamin B12 was not added. a-d are all hollow conduits printed with the same printing pattern. As can be seen from fig. 1, the hollow catheter printed with the material without vitamin B12 added has no hollow structure inside, and the hollow structure nerve catheter printed with the material with vitamin B12 added has the same pattern as the original printed pattern. As can be seen from fig. 1, the addition of vitamin B12 can improve the printing accuracy.
Figure 2 schematic diagram of nerve conduit printed with GelMA material for rat sciatic nerve repair.
Detailed Description
Aiming at the defect of low precision of the existing 3D printing, the inventor finds that substances capable of reducing ultraviolet light transmittance can be added into the raw materials of the biological materials such as a conventional printing bracket, a blood vessel or a nerve repair catheter and the like through a large amount of research, and the printed biological materials have the advantage of high precision by using the conventional method for printing.
The invention adds the substances capable of reducing the light transmission of ultraviolet light into the conventional raw materials of the original 3D printing biological material, thereby providing a novel 3D printing material. Then, the high-precision biological material can be obtained through 3D printing. The substance capable of reducing transmission of ultraviolet light is vitamin B12 or eosin a.
Preferably, the 3D printing material is prepared from a photo-polymerization biomaterial, a substance capable of reducing ultraviolet light transmission, and a photoinitiator; the concentration of the photopolymerization biological material in the 3D printing material is 0.1-99%, the concentration of substances capable of reducing ultraviolet light transmission in the 3D printing material is 0.01-99%, and the concentration of the photoinitiator in the 3D printing material is 0.01-99%.
Furthermore, in the 3D printing material, the concentration of the photopolymerization biological material is 3-30%, the concentration of the substance capable of reducing ultraviolet light transmission is 0.01-1%, and the concentration of the photoinitiator is 0.01-5%.
Preferably, in the 3D printing material, the photopolymerizable biomaterial is any one of a photocrosslinkable gelatin derivative, a photocrosslinkable alginate derivative, a photocrosslinkable polycaprolactone derivative, or a polyethylene glycol diacrylate.
Further, in the 3D printing material, the photo-crosslinkable gelatin derivative is a gelatin derivative having a carbon-carbon double bond. Further, the gelatin derivative having a carbon-carbon double bond is a methacrylated gelatin and a derivative thereof. The above-mentioned substances can be prepared by the methods disclosed in the prior art.
Further, in the 3D printing material, the photo-crosslinkable alginate derivative is an alginate derivative having a carbon-carbon double bond. Further, the alginate derivative having a carbon-carbon double bond is methacrylated sodium alginate. The above-mentioned substances can be prepared by the methods disclosed in the prior art.
Further, in the 3D printing material, the photo-crosslinkable polycaprolactone derivative is a polycaprolactone derivative having a carbon-carbon double bond. Furthermore, the polycaprolactone derivative with carbon-carbon double bonds is polycaprolactone diacrylate. The above-mentioned substances can be prepared by the methods disclosed in the prior art.
Preferably, in the 3D printing material, the photoinitiator is any one of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (I2959), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), or lithium 2,4, 6-trimethylbenzoylphenylphosphinate (LAP).
The invention also provides application of the 3D printing material in preparation of a nerve repair catheter, a stent or a blood vessel.
The invention also provides a nerve repair catheter, a stent or a blood vessel which is obtained by printing the 3D printing material.
The invention also provides a printing method of the nerve repair conduit, the bracket or the blood vessel, which comprises the following steps: constructing a digital model corresponding to the nerve repair catheter, the stent or the blood vessel, and importing the digital model into a 3D printer; adding the 3D printing material into a sample pool of a 3D printer, and then printing and forming; and (3) soaking the formed biological material in water for a period of time to remove the photoinitiator, and then taking out the biological material.
Further, the printing method further includes the following steps: and (3) soaking the soaked biological material in a solution added with a cross-linking agent for a period of time to carry out secondary cross-linking so as to improve the stability of the biological material and prolong the degradation time, and then taking out and drying.
Further, in the above printing method, the crosslinking agent is 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (edc. hcl) or genipin.
Further, in the printing method of the nerve repair conduit, the concentration of the cross-linking agent solution is 0.01-99%.
In the products and methods of the invention, a concentration of 1% indicates 1mg of solute in 100uL of solution. For example: the concentration of the photo-polymerization biomaterial is 0.1-99%, which means that the solution of 100uL contains 0.1-99 mg of photo-polymerization biomaterial.
Example 1 preparation and use of the inventive catheter for promoting nerve repair
(1) Constructing a 3D digital model of the nerve repair promoting tube: according to the diameter of a nerve in a body, a nerve repair promoting pipe model with the inner diameters of 1.5mm, 5mm and 8.5mm is constructed through three-dimensional model building software;
(2) configuring a printing material: preparing a printing material, wherein the concentration of methyl propylene gelatin (GelMA) is 20%, the concentration of vitamin B12 is 0.1%, and the concentration of photoinitiator LAP is 1%;
(3) printing: adding the prepared printing material into the sample cell, starting a program, and taking out the nerve repair promoting tube after printing is finished;
(4) cleaning the nerve repair tube: and (3) soaking the printed nerve repair catheter in water to remove the photoinitiator and reduce ultraviolet light transmission materials, taking out and drying to obtain a finished product.
Example 2 preparation and use of the inventive catheter for promoting nerve repair
(1) Constructing a 3D digital model of the nerve repair promoting tube: according to the diameter of a nerve in a body, a nerve repair promoting pipe model with the inner diameters of 1.5mm, 5mm and 8.5mm is constructed through three-dimensional model building software;
(2) configuring a printing material: preparing a printing material, wherein the concentration of polycaprolactone diacrylate (PEGDA) is 20%, the concentration of vitamin B12 is 0.1%, and the concentration of photoinitiator LAP is 1%;
(3) printing: adding the prepared printing material into the sample cell, starting a program, and taking out the nerve repair promoting tube after printing is finished;
(4) cleaning the nerve repair tube: and (3) soaking the printed nerve repair catheter in water to remove the photoinitiator and reduce ultraviolet light transmission materials, taking out and drying to obtain a finished product.
Example 3 preparation and use of the inventive catheter for promoting nerve repair
(1) Constructing a 3D digital model of the nerve repair promoting tube: according to the diameter of a nerve in a body, a nerve repair promoting pipe model with the inner diameters of 1.5mm, 5mm and 8.5mm is constructed through three-dimensional model building software;
(2) configuring a printing material: preparing a printing material, wherein the concentration of methyl allenyl sodium alginate is 5%, the concentration of vitamin B12 is 0.1%, and the concentration of photoinitiator LAP is 1%;
(3) printing: adding the prepared printing material into the sample cell, starting a program, and taking out the nerve repair promoting tube after printing is finished;
(4) cleaning the nerve repair tube: and (3) soaking the printed nerve repair catheter in water to remove the photoinitiator and reduce ultraviolet light transmission materials, taking out and drying to obtain a finished product.
The dimensions of the nerve repair conduit, such as the inner diameter, the length, the wall thickness and the like, printed by the method are very close to the design dimensions of the model, and the effect of high printing precision is achieved.
And (3) internal operation: the resulting nerve repair catheter was printed using example 1 for rat sciatic nerve repair. Rats (SD rat, 200-220g, purchased from Soudou laboratory animals Co., Ltd., SPF grade breeding) were cut off 1cm of sciatic nerve and then the cut ends were sutured on both sides of the nerve repair catheter using the nerve catheter. After 4 months, the sciatic nerve of the SD rats was found to be morphologically connected (see fig. 2a, 2b), fig. 2a shows the repaired nerve with a nerve repair catheter that has not been completely degraded, and fig. 2b shows the nerve after removal of the catheter covering, with a more detailed portion being the regenerated nerve.
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710060008 | 2017-01-24 | ||
| CN2017100600080 | 2017-01-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108340573A CN108340573A (en) | 2018-07-31 |
| CN108340573B true CN108340573B (en) | 2021-02-05 |
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| CN110962340A (en) * | 2019-12-18 | 2020-04-07 | 北京工业大学 | A kind of preparation method of photocuring 3D printing woven mesh sodium alginate hydrogel vascular stent |
| CN111166933B (en) * | 2020-01-10 | 2020-09-04 | 苏州诺普再生医学有限公司 | 3D prints composite support of degradable polymer support and photocrosslinking aquogel |
| CN113713179B (en) * | 2021-09-06 | 2022-08-02 | 山东大学 | High comprehensive performance photocurable bio-3D printing composite hydrogel and its preparation method and application |
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| WO2015111366A1 (en) * | 2014-01-23 | 2015-07-30 | Ricoh Company, Ltd. | Three-dimensional object and method for forming same |
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| WO2016071811A1 (en) * | 2014-11-04 | 2016-05-12 | Dws S.R.L. | Stereolithographic method and composition |
| CN105131201A (en) * | 2015-09-21 | 2015-12-09 | 东莞市盟大塑化科技有限公司 | A kind of UV curing photosensitive material and its application in photocuring 3D printer |
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