CN108744051B - Composite fiber for artificial anterior cruciate ligament and preparation method and application thereof - Google Patents
Composite fiber for artificial anterior cruciate ligament and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of biological materials, and discloses a composite fiber for an artificial anterior cruciate ligament and a preparation method and application thereof. The invention compounds the polyhydroxybutyrate and polyglycolic acid, and the obtained composite fiber combines the advantages of the polyhydroxybutyrate and the polyglycolic acid, has the performances of good biocompatibility and the like of the polyhydroxybutyrate and also has the performances of excellent physical and mechanical properties and cell affinity and the like endowed by the polyglycolic acid. In addition, the composite fiber has superior properties to the single component based on a synergistic enhancement mechanism. When the composite fiber is used for preparing the artificial anterior cruciate ligament, the novel composite ligament has the characteristics of strong wear resistance, good histocompatibility, cell affinity and high mechanical property, and can meet the basic requirements of the artificial anterior cruciate ligament.
Description
Technical Field
The invention belongs to the field of biological materials, and particularly relates to a composite fiber for an artificial anterior cruciate ligament, and a preparation method and application thereof.
Background
Among the knee ligament injuries in everyday life and sports activities, anterior cruciate ligament injury is one of the most common types. In addition, it is difficult to self-heal after injury, and conservative treatment is largely ineffective, with incomplete functional recovery. For this, the treatment is generally an anterior cruciate ligament reconstruction, and three types of implants are generally available for selection: autologous tendons, allogeneic tendons, and artificial ligaments. The application of the autologous tendon is wide, but the possibility of generating complications such as graft supply area defect, postoperative pain and the like exists; for allogeneic tendons, it can avoid sacrificing autologous tendon tissue, but it has problems of limited source, disease transmission, risk of immune rejection, etc. (Cooper J A, Lu H, Ko F K, Laurencin C T. fiber-based tissue engineered scaffold for tolerance replacement, design constraints and in vitro evaluation [ J ]. Biomaterials, 2005, 26 (13): 1523-1532.).
The artificial ligament has no defects, and has the advantages of simplified operation, small wound, certain strength during operation, quicker recovery after operation and the like, so the artificial ligament is favored by people and deeply researched, and has wide and good application prospect. Currently, a variety of artificial ligaments have been used in ligament reconstruction grafts, including the Meadox ligament, the Gore-Tex ligament, the Leeds-Keio ligament, the ABC ligament, the Kennedy LAD ligament, and the Trevira ligament, among others (Bernardino S.ACL prosthesis: any prosthesis for the future? [ J ]. Knee Surg.Sport.Tr.A., 2010, 18 (6): 797-.
Among different artificial ligaments, the LARS ligament has the characteristics of resisting repeated torsion, bending, over-traction and the like, and is a popular and mature artificial anterior cruciate ligament in the world at present. The use of LARS artificial ligaments may show a higher satisfaction in clinical applications, such as improved post-operative joint function, better post-operative efficacy, etc. (Machotka Z, Scarborough I, Duncan W, Kumar S, perrate l.antioxidant concrete repair with LARS: "systematic advanced repair system": a systematic review [ J ]. Sports med.arthrosc.repair. the r.the. technique, 2010, 2: 29.). In order to further improve the comprehensive performance of the LARS ligament, the plummacro (plummacro. development of a novel surface-modified polyethylene terephthalate (PET) artificial ligament [ D ]. shanghai: university of compound denier, 2012.) adopts substances such as hydroxyapatite and bioglass to perform surface modification on the LARS ligament, so as to enhance the clinical curative effect of the LARS ligament. However, the LARS ligament composed of hydrophobic polyethylene terephthalate fiber still has its own inherent defects such as insufficient strength, low abrasion resistance, and poor cell affinity (Bernardino S. ACL prosthesis: any simulation for the future [ J ]. Knee Surg. Sport. Tr. A., 2010, 18 (6): 797-804). Therefore, the preparation and development of an ideal artificial anterior cruciate ligament having excellent physical properties and biocompatibility has been a research focus in this field.
Disclosure of Invention
To overcome the above-mentioned drawbacks and deficiencies of the prior art, it is a primary object of the present invention to provide a composite fiber for an artificial anterior cruciate ligament.
The invention also aims to provide a preparation method of the composite fiber for the artificial anterior cruciate ligament.
It is still another object of the present invention to provide use of the above composite fiber for an artificial anterior cruciate ligament.
The purpose of the invention is realized by the following scheme:
a preparation method of composite fiber for artificial anterior cruciate ligament mainly comprises the following steps:
(1) taking and drying the poly hexyl hydroxybutyrate and the polyglycolic acid respectively for later use;
(2) adding the poly (hexyl hydroxybutyrate) and the polyglycolic acid dried in the step (1) into a solvent, heating and refluxing under the condition of stirring to fully dissolve, filtering to remove insoluble impurities, and defoaming to obtain a mixed solution for later use;
(3) extruding the mixed solution in the step (2) from capillary holes of a spinning nozzle to form solution trickles into a spinning channel by adopting a dry spinning technology, rapidly volatilizing a solvent in the solution trickles under the action of hot air in the spinning channel, and concentrating and solidifying the solution trickles while gradually removing the solvent so as to form the poly (hexylhydroxybutyrate/polyglycolic acid) nascent fiber;
(4) and (4) auxiliary drawing the nascent fiber in the step (3) through a godet and a winding drum, washing and drying to obtain the poly (hexyl hydroxybutyrate)/poly (glycolic acid) composite fiber.
The numerical molecular weight of the polyhydroxybutyrate described in the step (1) is preferably 1.9X 105～2.6×105(ii) a The molecular weight of the polyglycolic acid is preferably 55000-72000.
The drying in the step (1) refers to vacuum drying at 50-70 ℃ for 12-24 h;
the mass ratio of the dried hexyl polyhydroxybutyrate to the polyglycolic acid in the step (2) is 1: 1-6;
the solvent in the step (2) is one of deionized water, absolute ethyl alcohol, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexafluoroisopropanol, trifluoroethanol, dichloromethane, trichloromethane, diethyl ether and petroleum ether.
The heating reflux under the stirring condition in the step (2) is that the mixture is heated to 80-95 ℃ and refluxed for 3-8 hours at the stirring speed of 500-850 r/min;
the filtration in the step (2) is reduced pressure filtration;
and (3) defoaming in the step (2) in a vacuum state at the temperature of 70-85 ℃ for 1-3 hours.
And (3) the total solute concentration of the mixed solution obtained in the step (2) is 2-8 wt.%.
The hot air in the step (3) is a mixed gas of air and water vapor, and the flow rate ratio of the air to the water vapor is 1: 10-20.
And (4) the retention time of the nascent fiber in the step (3) in the shaft is 15-45 s.
And (4) washing by using absolute ethyl alcohol and deionized water in sequence, wherein the washing times are 3-5.
The drying in the step (4) is natural air drying at normal temperature and normal pressure.
A composite fiber for artificial anterior cruciate ligament prepared by the method.
The application of the composite fiber for the artificial anterior cruciate ligament in preparing the artificial anterior cruciate ligament.
The application of the composite fiber for the artificial anterior cruciate ligament in the preparation of the artificial anterior cruciate ligament is realized by the following steps: the method comprises the steps of twisting 1 bundle of composite fibers with a certain amount into 1 strand, twisting 3 strands into a string, doubling the string, twisting into a rope-shaped object with the diameter of 4-6 mm, cutting the rope to the length of 20-30 cm, fastening two ends with steel wires, fixing two ends with silk threads again in a sewing and binding mode, sequentially ultrasonically washing with absolute ethyl alcohol and deionized water with the ultrasonic power of 200-400W, washing for 10-20 min, washing for 2-3 times, and naturally drying at normal temperature and normal pressure to obtain the polyhydroxy butyric acid hexyl ester/polyglycolic acid composite ligament.
The mechanism of the invention is as follows:
the composite fiber obtained by compounding the polyhexamethylene hydroxybutyrate and the polyglycolic acid combines the advantages of the polyhexamethylene hydroxybutyrate and the polyglycolic acid, and has the performances of good biocompatibility and the like of the polyhexamethylene hydroxybutyrate and the excellent physical and mechanical properties and cell affinity and the like of the polyglycolic acid.
In addition, the composite fiber has superior properties to the single component based on a synergistic enhancement mechanism. When the composite fiber is used for preparing the artificial anterior cruciate ligament, the novel composite ligament has the characteristics of strong wear resistance, good histocompatibility, cell affinity and high mechanical property, and can meet the basic requirements of the artificial anterior cruciate ligament.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the poly (hexyl hydroxybutyrate)/polyglycolic acid composite fiber obtained by the invention is used as a novel fiber material, and the preparation method is simple. Based on a synergistic enhancement mechanism, the composite fiber organically combines the advantages of all components, has the advantages of good histocompatibility, excellent mechanical property, strong cell affinity, high wear resistance and the like, basically meets the requirements of artificial anterior cruciate ligaments, and can be applied to related fields.
(2) Through researches such as the preparation method, the performance analysis and the like of the composite fiber, theoretical and experimental basis and reference can be provided for further exploration and application of the artificial anterior cruciate ligament material in the future.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
(1) Polyhexylhydroxybutyrate (available from Plastic plastics Co., Ltd., Dongguan, having a number average molecular weight of 1.9X 10) was weighed out5) And polyglycolic acid (purchased from Bollier biomaterial, Inc. in Shenzhen, with a number average molecular weight of 55000) which is dried under vacuum at 50 ℃ for 12h for later use.
(2) Adding the poly (hexyl hydroxybutyrate) and the polyglycolic acid dried in the step (1) into deionized water according to the mass ratio of 1: 1, heating to 80 ℃ at the stirring speed of 500r/min, refluxing for 3h to fully dissolve, then carrying out vacuum filtration, and defoaming at 70 ℃ for 1h in a vacuum state to obtain a mixed solution with the total solute concentration of 2 wt.% for later use.
(3) And (3) extruding the mixed solution in the step (2) from capillary holes of a spinning nozzle into a spinning channel by adopting a dry spinning technology, rapidly volatilizing the solvent in the solution trickle under the action of hot air (mixed gas of air and steam, wherein the flow speed ratio of the air to the steam is 1: 10) in the spinning channel, and concentrating and solidifying the solution trickle while gradually removing the solvent to form the polyhexamethylene hydroxybutyrate/polyglycolic acid nascent fiber.
(4) And (3) the nascent fiber in the step (3) is subjected to auxiliary traction through a godet and a winding drum, the retention time of the nascent fiber in a channel is 15s, the nascent fiber is sequentially washed for 3 times by absolute ethyl alcohol and deionized water, and the nascent fiber is naturally dried under normal temperature and normal pressure to obtain the poly (hexylhydroxybutyrate)/polyglycolic acid composite fiber.
Example 2
(1) Polyhexylhydroxybutyrate (obtained from Plastic plastics Co., Ltd., Dongguan having a number average molecular weight of 2.0X 10) was weighed5) And polyglycolic acid (obtained from Bolii biological material of Shenzhen city)Limited, number average molecular weight 58000), dried under vacuum at 50 ℃ for 18h, ready for use.
(2) Adding the poly (hexyl hydroxybutyrate) and the polyglycolic acid dried in the step (1) into absolute ethyl alcohol according to the mass ratio of 1: 2, heating to 85 ℃ at the stirring speed of 550r/min, refluxing for 4h to fully dissolve, then carrying out vacuum filtration, and defoaming at 75 ℃ for 1h in a vacuum state to obtain a mixed solution with the total solute concentration of 3 wt.% for later use.
(3) And (3) extruding the mixed solution in the step (2) from capillary holes of a spinning nozzle into a spinning channel by adopting a dry spinning technology, rapidly volatilizing the solvent in the solution trickle under the action of hot air (mixed gas of air and steam, wherein the flow speed ratio of the air to the steam is 1: 10) in the spinning channel, and concentrating and solidifying the solution trickle while gradually removing the solvent to form the polyhexamethylene hydroxybutyrate/polyglycolic acid nascent fiber.
(4) And (3) the nascent fiber in the step (3) is subjected to auxiliary traction through a godet and a winding drum, the nascent fiber stays in a channel for 20s, is washed for 3 times by absolute ethyl alcohol and deionized water in sequence, and is naturally dried under normal temperature and normal pressure to obtain the poly (hexyl hydroxybutyrate)/polyglycolic acid composite fiber.
Example 3
(1) Polyhexylhydroxybutyrate (obtained from Plastic plastics Co., Ltd., Dongguan having a number average molecular weight of 2.1X 10) was weighed5) And polyglycolic acid (purchased from Bollier biomaterial, Ltd., Shenzhen, number average molecular weight of 61000), and vacuum drying at 50 ℃ for 24h for later use.
(2) Adding the poly (hexyl hydroxybutyrate) and the polyglycolic acid dried in the step (1) into dimethylacetamide according to the mass ratio of 1: 3, heating to 85 ℃ at the stirring speed of 600r/min, refluxing for 6h to fully dissolve, then carrying out vacuum filtration, and defoaming at 75 ℃ for 1.5h in a vacuum state to obtain a mixed solution with the total solute concentration of 4 wt.% for later use.
(3) And (3) extruding the mixed solution in the step (2) from capillary holes of a spinning nozzle into a spinning channel by adopting a dry spinning technology, rapidly volatilizing the solvent in the solution trickle under the action of hot air (mixed gas of air and steam, wherein the flow speed ratio of the air to the steam is 1: 15) in the spinning channel, and concentrating and solidifying the solution trickle while gradually removing the solvent to form the polyhexamethylene hydroxybutyrate/polyglycolic acid nascent fiber.
(4) And (3) the nascent fiber in the step (3) is subjected to auxiliary traction through a godet and a winding drum, the retention time of the nascent fiber in a channel is 25s, the nascent fiber is sequentially washed for 4 times by absolute ethyl alcohol and deionized water, and the nascent fiber is naturally dried under normal temperature and normal pressure to obtain the poly (hexylhydroxybutyrate)/polyglycolic acid composite fiber.
Example 4
(1) Polyhexylhydroxybutyrate (obtained from Plastic plastics Co., Ltd., Dongguan having a number average molecular weight of 2.2X 10) was weighed out5) And polyglycolic acid (purchased from Bollier biomaterial, Ltd., Shenzhen, number average molecular weight of 65000), and vacuum-dried at 60 ℃ for 24h for later use.
(2) Adding the poly (hexyl hydroxybutyrate) and the polyglycolic acid dried in the step (1) into dimethyl sulfoxide according to the mass ratio of 1: 4, heating to 90 ℃ at the stirring speed of 650r/min, refluxing for 7h to fully dissolve, then carrying out vacuum filtration, and defoaming at 80 ℃ for 2h in a vacuum state to obtain a mixed solution with the total solute concentration of 5 wt.% for later use.
(3) And (3) extruding the mixed solution in the step (2) from capillary holes of a spinning nozzle into a spinning channel by adopting a dry spinning technology, rapidly volatilizing the solvent in the solution trickle under the action of hot air (mixed gas of air and steam, wherein the flow speed ratio of the air to the steam is 1: 15) in the spinning channel, and concentrating and solidifying the solution trickle while gradually removing the solvent to form the polyhexamethylene hydroxybutyrate/polyglycolic acid nascent fiber.
(4) And (3) the nascent fiber in the step (3) is subjected to auxiliary traction through a godet and a winding drum, the nascent fiber stays in a channel for 30s, is washed for 4 times by absolute ethyl alcohol and deionized water in sequence, and is naturally dried under normal temperature and normal pressure to obtain the poly (hexylhydroxybutyrate)/polyglycolic acid composite fiber.
Example 5
(1) Polyhexylhydroxybutyrate (obtained from Plastic plastics Co., Ltd., Dongguan having a number average molecular weight of 2.4X 10) was weighed out5) And polyglycolic acid (purchased from Bollier biomaterial, Ltd., Shenzhen, number average molecular weight of 69000) which was dried under vacuum at 70 ℃ for 12 hours for use.
(2) Adding the poly (hexyl hydroxybutyrate) and the polyglycolic acid dried in the step (1) into trichloromethane according to the mass ratio of 1: 5, heating to 90 ℃ at the stirring speed of 750r/min, refluxing for 8h to fully dissolve, then carrying out vacuum filtration, and defoaming at 80 ℃ for 2.5h in a vacuum state to obtain a mixed solution with the total solute concentration of 6 wt.% for later use.
(3) And (3) extruding the mixed solution in the step (2) from capillary holes of a spinning nozzle into a spinning channel by adopting a dry spinning technology, rapidly volatilizing the solvent in the solution stream under the action of hot air (mixed gas of air and steam, wherein the flow speed ratio of the air to the steam is 1: 20) in the spinning channel, and concentrating and solidifying the solution stream while gradually removing the solvent to form the polyhexamethylene hydroxybutyrate/polyglycolic acid nascent fiber.
(4) And (3) the nascent fiber in the step (3) is subjected to auxiliary traction through a godet and a winding drum, the retention time of the nascent fiber in a channel is 35s, the nascent fiber is sequentially washed for 5 times by absolute ethyl alcohol and deionized water, and the nascent fiber is naturally dried under normal temperature and normal pressure to obtain the poly (hexylhydroxybutyrate)/polyglycolic acid composite fiber.
Example 6
(1) Polyhexylhydroxybutyrate (obtained from Plastic plastics Co., Ltd., Dongguan having a number average molecular weight of 2.6X 10) was weighed out5) And polyglycolic acid (purchased from Bollier biomaterial, Ltd., Shenzhen, with a number average molecular weight of 72000) which was dried under vacuum at 70 ℃ for 24 hours for use.
(2) Adding the poly (hexyl hydroxybutyrate) and the polyglycolic acid dried in the step (1) into petroleum ether according to the mass ratio of 1: 6, heating to 95 ℃ at the stirring speed of 850r/min, refluxing for 8h to fully dissolve, then carrying out vacuum filtration, and defoaming at 85 ℃ for 3h in a vacuum state to obtain a mixed solution with the total solute concentration of 8 wt.% for later use.
(3) And (3) extruding the mixed solution in the step (2) from capillary holes of a spinning nozzle into a spinning channel by adopting a dry spinning technology, rapidly volatilizing the solvent in the solution stream under the action of hot air (mixed gas of air and steam, wherein the flow speed ratio of the air to the steam is 1: 20) in the spinning channel, and concentrating and solidifying the solution stream while gradually removing the solvent to form the polyhexamethylene hydroxybutyrate/polyglycolic acid nascent fiber.
(4) And (3) the nascent fiber in the step (3) is subjected to auxiliary traction through a godet and a winding drum, the nascent fiber stays in a channel for 45s, is washed for 5 times by absolute ethyl alcohol and deionized water in sequence, and is naturally dried under normal temperature and normal pressure to obtain the poly (hexyl hydroxybutyrate)/polyglycolic acid composite fiber.
Example 7
The method is characterized in that the poly (hexyl hydroxybutyrate)/polyglycolic acid composite fiber prepared in the embodiment 1-6 is applied to the artificial anterior cruciate ligament, and the specific process and steps are as follows:
the method comprises the steps of twisting 1 bundle of 50 composite fibers, twisting 3 bundles of the composite fibers into 1 strand, twisting 3 strands of the composite fibers into a string, doubling the string, twisting the folded string into a rope-shaped object with the diameter of 5mm, cutting the rope to the length of 25cm, fastening two ends by using steel wires, fixing the two ends by using silk threads in a sewing and binding mode again, sequentially performing ultrasonic washing by using absolute ethyl alcohol and deionized water, wherein the ultrasonic power is 300W, the washing time is 15min, the washing times are 3 times, and naturally drying the object under normal temperature and normal pressure to obtain the polyhydroxybutyrate/polyglycolic acid composite ligament.
Meanwhile, setting the comparative examples of the examples 1 to 6, replacing all the hexyl polyhydroxybutyrate in the step (1) of the example 1 with polyglycolic acid, and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparative sample 1A; replacing all polyglycolic acid in the step (1) of example 1 with hexyl polyhydroxybutyrate, and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 1B; the hexyl polyhydroxybutyrate in the step (1) of the example 2 is completely replaced by polyglycolic acid, the rest is unchanged, and the obtained artificial anterior cruciate ligament is marked as a comparison sample 2A; replacing all polyglycolic acid in the step (1) of the example 2 with poly (hexylhydroxybutyrate) and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 2B; the hexyl polyhydroxybutyrate in the step (1) of the example 3 is completely replaced by polyglycolic acid, the rest is unchanged, and the obtained artificial anterior cruciate ligament is marked as a comparison sample 3A; replacing all polyglycolic acid in the step (1) of the example 3 with hexyl polyhydroxybutyrate, and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 3B; the total amount of the hexyl polyhydroxybutyrate obtained in the step (1) of example 4 was replaced with polyglycolic acid, and the remaining amount was unchanged, and the obtained artificial anterior cruciate ligament was designated as a control 4A; replacing all polyglycolic acid in the step (1) of the example 4 with hexyl polyhydroxybutyrate, and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 4B; the total amount of hexyl polyhydroxybutyrate obtained in the step (1) of example 5 was replaced with polyglycolic acid, and the remaining amount was unchanged, and the obtained artificial anterior cruciate ligament was designated as comparative sample 5A; replacing all polyglycolic acid in the step (1) of example 5 with hexyl polyhydroxybutyrate, and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparative sample 5B; the total amount of hexyl polyhydroxybutyrate obtained in the step (1) of example 6 was replaced with polyglycolic acid, and the remaining amount was unchanged, and the obtained artificial anterior cruciate ligament was designated as a control 6A; the polyglycolic acid obtained in step (1) of example 6 was entirely replaced with hexyl polyhydroxybutyrate, and the remainder was unchanged, and the obtained artificial anterior cruciate ligament was designated as comparative example 6B.
And (3) investigating the mechanical property, the wear resistance, the cell affinity and the tissue compatibility of the obtained poly hexyl hydroxybutyrate/polyglycolic acid composite ligament and the artificial anterior ligament product obtained by the corresponding comparative example, wherein the specific test process and the steps are as follows:
(1) mechanical properties
The mechanical property test is carried out by using a universal testing machine (LLOYD LR100K, China). After the both ends were fixed by clamps, the resultant was stretched at a speed of 10 mm/min. The experiment was repeated 5 times, and the results are shown as (mean. + -. standard deviation) in tables 1 to 6.
TABLE 1 test results of mechanical properties of the composite ligament obtained in example 1 and its comparative sample
| Sample (I) | Maximum load (N) | Tensile strength (MPa) | Modulus of elasticity (GPa) |
| Example 1 | 690.33±11.09 | 36.23±2.12 | 0.36±0.04 |
| Comparative sample 1A | 600.01±12.01 | 30.89±1.73 | 0.22±0.03 |
| Comparative sample 1B | 420.51±10.03 | 24.11±1.89 | 0.11±0.03 |
Table 2 results of mechanical property test of composite ligament obtained in example 2 and comparative sample thereof
Table 3 results of mechanical property test of composite ligament obtained in example 3 and comparative sample thereof
| Sample (I) | Maximum load (N) | Tensile strength (MPa) | Modulus of elasticity (GPa) |
| Example 3 | 710.89±12.84 | 39.44±2.45 | 0.38±0.03 |
| Comparative sample 3A | 612.76±11.39 | 33.05±1.79 | 0.26±0.03 |
| Comparative sample 3B | 448.03±15.04 | 29.31±2.05 | 0.16±0.04 |
Table 4 results of mechanical property test of composite ligament obtained in example 4 and comparative sample thereof
| Sample (I) | Maximum load (N) | Tensile strength (MPa) | Modulus of elasticity (GPa) |
| Example 4 | 739.58±16.21 | 44.62±2.17 | 0.44±0.04 |
| Comparative sample 4A | 654.84±15.09 | 35.11±2.13 | 0.32±0.02 |
| Comparative sample 4B | 473.12±13.69 | 29.35±1.97 | 0.19±0.02 |
TABLE 5 results of mechanical Properties test of the composite ligament obtained in example 5 and its control
| Sample (I) | Maximum load (N) | Tensile strength (MPa) | Modulus of elasticity (GPa) |
| Example 5 | 778.41±13.27 | 50.38±2.51 | 0.51±0.05 |
| Comparative sample 5A | 697.31±11.78 | 39.89±1.19 | 0.37±0.03 |
| Comparative sample 5B | 514.34±11.52 | 31.25±2.01 | 0.23±0.03 |
Table 6 results of mechanical property test of composite ligament obtained in example 6 and comparative sample thereof
| Sample (I) | Maximum load (N) | Tensile strength (MPa) | Modulus of elasticity (GPa) |
| Example 6 | 751.32±16.55 | 47.26±2.19 | 0.47±0.02 |
| Comparative sample 6A | 668.91±13.02 | 38.97±2.21 | 0.32±0.04 |
| Comparative sample 6B | 500.16±18.09 | 31.62±2.54 | 0.23±0.02 |
As can be seen from tables 1-6, the obtained polyhexamethylene hydroxybutyrate/polyglycolic acid composite ligament has better mechanical property than a single component, organically combines the mechanical properties of the two components, and has high mechanical strength.
(2) Wear resistance
The abrasion resistance test was carried out on a universal friction tester, model MMW-1A. The sample was held in a holder and fixed below the rotating shaft and slid circumferentially on a GCr15 counter plate centered on the spindle. Wherein the movement radius is 12mm, the sliding speed is 100r/min, the sliding time is 5min, the sliding distance is 150m, the weight of the weight is 10N, and the lever moment is 0.35 MPa.
Before the experiment, the mass of the sample is weighed by an electronic analytical balance; after the experiment, the sample was washed 3 times with deionized water and dried, and then the mass of the sample was weighed with an electronic analytical balance. And calculating the wear rate of the sample by using a weight loss method, and measuring the wear resistance of the sample. The experiment was repeated 3 times, and the results were averaged with the experimental data, as shown in tables 7-12.
Table 7 abrasion resistance test results of the composite ligament obtained in example 1 and its comparative sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 1 | 0.32×10-3 |
| Comparative sample 1A | 0.41×10-3 |
| Comparative sample 1B | 0.66×10-3 |
Table 8 abrasion resistance test results of the composite ligament obtained in example 2 and its comparative sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 2 | 0.28×10-3 |
| Comparative sample 2A | 0.39×10-3 |
| Comparative sample 2B | 0.68×10-3 |
TABLE 9 abrasion resistance test results of the composite ligament obtained in example 3 and its control sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 3 | 0.31×10-3 |
| Comparative sample 3A | 0.44×10-3 |
| Comparative sample 3B | 0.69×10-3 |
TABLE 10 abrasion resistance test results of the composite ligament obtained in example 4 and its control sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 4 | 0.25×10-3 |
| Comparative sample 4A | 0.37×10-3 |
| Comparative sample 4B | 0.64×10-3 |
TABLE 11 abrasion resistance test results of the composite ligament obtained in example 5 and its control sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 5 | 0.21×10-3 |
| Comparative sample 5A | 0.33×10-3 |
| Comparative sample 5B | 0.59×10-3 |
TABLE 12 abrasion resistance test results of the composite ligament obtained in example 6 and its control sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 6 | 0.23×10-3 |
| Comparative sample 6A | 0.34×10-3 |
| Comparative sample 6B | 0.61×10-3 |
As can be seen from tables 7-12, the obtained poly (hexyl hydroxybutyrate)/polyglycolic acid composite ligament organically combines the performances of the two components, has good wear resistance, and can meet the requirement of artificial anterior cruciate ligament.
(3) Affinity of cell
According to ISO 10993-5: 1999 and GB/T16886.5-2003, which uses MTT colorimetry of polyhexamethylene hydroxybutyrate/polyglycolic acid complex ligament leaching liquor to test the cell affinity of complex ligaments. Wherein, the cytotoxicity grading rating standard is shown in Table 13, the smaller the grading numerical value is, the lower the cytotoxicity of the material is, the better the cell affinity of the material is, and the cell affinity results are shown in tables 14-19.
TABLE 13 cytotoxicity grading Scale rating standards
(4) Tissue compatibility
According to ISO 10993-6: 1994 and GB/T16886.6-1997, to test the histocompatibility of complex ligaments using a subcutaneous tissue short-term implantation (9 weeks) method. The results of histocompatibility are shown in tables 14 to 19.
TABLE 14 results of cell affinity and histocompatibility of the complex ligament obtained in example 1 and its control
TABLE 15 results of cell affinity and histocompatibility of the complex ligament obtained in example 2 and its control
TABLE 16 results of cell affinity and histocompatibility of the composite ligament obtained in example 3 and its control
TABLE 17 results of cell affinity and histocompatibility of the composite ligament obtained in example 4 and its control
TABLE 18 results of cell affinity and histocompatibility of the composite ligament obtained in example 5 and its control
TABLE 19 results of cell affinity and histocompatibility of the complex ligaments obtained in example 6 and their control
From tables 14 to 19, it is clear that the obtained polyhydroxybutyrate-polyglycolic acid complex ligament organically combines the biological properties of the two components, and the cytotoxicity is 0 grade, that is, the cytotoxicity is not high and the cell affinity is good. And the tissue compatibility is excellent, and the organic tissue organ is not obviously influenced.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of composite fiber for artificial anterior cruciate ligament is characterized by mainly comprising the following steps:
(1) taking and drying the poly hexyl hydroxybutyrate and the polyglycolic acid respectively for later use;
(2) adding the poly (hexyl hydroxybutyrate) and the polyglycolic acid dried in the step (1) into a solvent, heating and refluxing under the condition of stirring to fully dissolve, filtering to remove insoluble impurities, and defoaming to obtain a mixed solution for later use;
(3) extruding the mixed solution in the step (2) from capillary holes of a spinning nozzle to form solution trickles into a spinning channel by adopting a dry spinning technology, rapidly volatilizing a solvent in the solution trickles under the action of hot air in the spinning channel, and concentrating and solidifying the solution trickles while gradually removing the solvent so as to form the poly (hexylhydroxybutyrate/polyglycolic acid) nascent fiber;
(4) the nascent fiber in the step (3) is drawn out in an auxiliary mode through a godet and a winding drum, and then washing and drying are carried out to obtain the poly (hexyl hydroxybutyrate)/polyglycolic acid composite fiber;
the hot air in the step (3) is a mixed gas of air and water vapor, and the flow rate ratio of the air to the water vapor is 1: 10 to 20.
2. The method for preparing a composite fiber for an artificial anterior cruciate ligament according to claim 1, wherein:
the number average molecular weight of the polyhydroxybutyrate in the step (1) is 1.9X 105~2.6×105(ii) a The number average molecular weight of the polyglycolic acid is 55000-72000;
the drying in the step (1) refers to vacuum drying at 50-70 ℃ for 12-24 h.
3. The method for preparing a composite fiber for an artificial anterior cruciate ligament according to claim 1, wherein:
the mass ratio of the dried hexyl polyhydroxybutyrate to the polyglycolic acid in the step (2) is 1: 1-6;
and (3) the total solute concentration of the mixed solution obtained in the step (2) is 2-8 wt.%.
4. The method for preparing a composite fiber for an artificial anterior cruciate ligament according to claim 1, wherein:
the solvent in the step (2) is one of deionized water, absolute ethyl alcohol, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexafluoroisopropanol, trifluoroethanol, dichloromethane, trichloromethane, diethyl ether and petroleum ether.
5. The method for preparing a composite fiber for an artificial anterior cruciate ligament according to claim 1, wherein:
the heating reflux under the stirring condition in the step (2) is that the mixture is heated to 80-95 ℃ and refluxed for 3-8 hours at the stirring speed of 500-850 r/min;
the filtration in the step (2) is reduced pressure filtration;
and (3) defoaming in the step (2) in a vacuum state at the temperature of 70-85 ℃ for 1-3 hours.
6. The method for preparing a composite fiber for an artificial anterior cruciate ligament according to claim 1, wherein:
the retention time of the nascent fiber in the step (3) in the shaft in the step (4) is 15-45 s;
washing in the step (4) is washing with absolute ethyl alcohol and deionized water in sequence, wherein the washing times are 3-5 times;
the drying in the step (4) is natural air drying at normal temperature and normal pressure.
7. A composite fiber for an artificial anterior cruciate ligament prepared according to any one of claims 1 to 6.
8. Use of a composite fiber for an artificial anterior cruciate ligament according to claim 7 in the preparation of an artificial anterior cruciate ligament.
9. Use of a composite fibre for an artificial anterior cruciate ligament according to claim 8, in the preparation of an artificial anterior cruciate ligament, characterised in that it is mainly achieved by the following steps:
the method comprises the steps of twisting 1 bundle of composite fibers with a certain amount into 1 strand, twisting 3 strands into a string, doubling the string, twisting into a rope-shaped object with the diameter of 4-6 mm, cutting the rope to the length of 20-30 cm, fastening two ends with steel wires, fixing two ends with silk threads again in a sewing and binding mode, sequentially ultrasonically washing with absolute ethyl alcohol and deionized water with the ultrasonic power of 200-400W, washing for 10-20 min, washing for 2-3 times, and naturally drying at normal temperature and normal pressure to obtain the polyhydroxy butyric acid hexyl ester/polyglycolic acid composite ligament.
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| CN103628174A (en) * | 2013-10-30 | 2014-03-12 | 清华大学 | Absorbable suture containing medium-chain PHA (Polyhydroxyalkanoate) |
| CN104043151A (en) * | 2013-03-15 | 2014-09-17 | 深圳兰度生物材料有限公司 | Composite artificial ligament and preparation method thereof |
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| CN104043151A (en) * | 2013-03-15 | 2014-09-17 | 深圳兰度生物材料有限公司 | Composite artificial ligament and preparation method thereof |
| CN103628174A (en) * | 2013-10-30 | 2014-03-12 | 清华大学 | Absorbable suture containing medium-chain PHA (Polyhydroxyalkanoate) |
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