阅读说明：本技术 生物可降解材料及缝合钉 (Biodegradable material and suturing nail ) 是由 张晓芳 宋保组 逄永刚 储成生 谢勇 于 2021-07-31 设计创作，主要内容包括：本发明提供了一种生物可降解材料,包括聚酯类生物降解材料和活性成分,所述活性成分包括表面活性剂和生物活性玻璃中的至少一种；以占所述聚酯类生物降解材料的总质量百分比计,所述活性成分的含量小于40％,所述表面活性剂的含量小于等于15％；所述聚酯类生物降解材料包括共混改性成分,所述共混改性成分包括聚羟基乙酸、乙交酯、己内酯、丙交酯、聚乙二醇中的至少一种,使得生物可降解材料同时具备良好的降解性能、生物活性、生物相容性、机械性能和降解的可控性。本发明还提供了一种缝合钉,所述缝合钉采用所述的生物可降解材料制备而成,使得缝合钉同时具备良好的降解性能和机械性能。(The invention provides a biodegradable material, which comprises a polyester biodegradable material and an active ingredient, wherein the active ingredient comprises at least one of a surfactant and bioactive glass; the content of the active ingredients is less than 40 percent and the content of the surfactant is less than or equal to 15 percent in terms of the total mass percentage of the polyester biodegradable material; the polyester biodegradable material comprises blending modification components, wherein the blending modification components comprise at least one of polyglycolic acid, glycolide, caprolactone, lactide and polyethylene glycol, so that the biodegradable material has good degradation performance, bioactivity, biocompatibility, mechanical property and degradation controllability. The invention also provides a suturing nail which is prepared from the biodegradable material, so that the suturing nail has good degradation performance and mechanical performance.)

1. A biodegradable material, characterized by comprising a polyester-based biodegradable material and an active ingredient, wherein the active ingredient comprises at least one of a surfactant and bioactive glass;

the content of the active ingredient is less than or equal to 40 percent and the content of the surfactant is less than or equal to 15 percent in terms of the total mass percentage of the polyester biodegradable material;

the polyester biodegradable material comprises blending modification components, wherein the blending modification components comprise at least one of polyglycolic acid, glycolide, caprolactone, lactide and polyethylene glycol.

2. The biodegradable material according to claim 1, characterized in that said bioactive glass has an equivalent particle size of less than 45 microns.

3. The biodegradable material according to claim 1, wherein the blending modification component is contained in an amount of 5 to 95% by mass based on the total mass of the polyester-based biodegradable material.

4. The biodegradable material according to claim 3, wherein said polyester-based biodegradable material further comprises any one of polylactic acid, poly (lactide-co-glycolide), polycaprolactone, polydioxanone, and polytrimethylene carbonate.

5. The biodegradable material of claim 1, wherein said bioactive glass comprises any of a silicate glass, a glass ceramic, and a borate-based glass.

6. Biodegradable material according to claim 1, characterized in that said surfactant is a polyoxyethylene polyoxypropylene ether triblock copolymer.

7. Biodegradable material according to claim 6, characterized in that said polyoxyethylene polyoxypropylene ether triblock copolymer is any one of F127, L61, L64, F68, P85, P94, P104, P105, P123, L121 and L122.

8. The biodegradable material according to claim 1, wherein the weight average molecular weight of said polyester-based biodegradable material is 5000-.

9. A staple, characterized in that it is made of a biodegradable material according to any one of claims 1 to 8.

10. The staple of claim 9 including a body, and a driver portion and a cap portion disposed at opposite ends of the body, respectively, the cap portion being disposed perpendicular to the body.

11. The staple of claim 10 wherein the overall axial length of the staple is 2-5mm, the axial length of the body is 1.5-3.5mm, the radial length of the body is 0.3-0.8mm, the maximum length of the radially-acting surface of the cap portion is 1.2-3mm, and the maximum width of the radially-acting surface of the cap portion is 0.4-1 mm.

12. The staple of claim 10 wherein the cap portion is any one of an I-shaped structure, a circular structure, and a cross-shaped structure.

13. The staple of claim 10 wherein the driver is any one of a hook-shaped structure and a tapered structure.

Technical Field

The invention relates to the technical field of biodegradable materials, in particular to a biodegradable material and a suturing nail.

Background

Various biodegradable polymers have been commercialized for manufacturing bioabsorbable sutures, such as polyglycolic acid (PGA), Polydioxanone (PDS), polylactic acid (PLA), polylactic-glycolic acid (PLGA), and the like. However, staples require higher mechanical strength and young's modulus than surgical staples. Although PLA has good mechanical strength, its brittleness limits its use in high tension environments. L-polylactic acid (PLLA) has a glass transition temperature Tg of about 55-60 deg.C, a melting temperature Tm of about 180 deg.C, and a half-life of about 4-6 months in physiological saline at 37 deg.C, but its degradation is highly dependent on its molecular weight, ambient pH. Thus, the polymer is well suited for biomedical applications, but it needs to be modified to use polymers that possess high mechanical strength and fast degradation times. Since the degradation performance and the mechanical performance are two directly proportional correlation properties of the degradable polylactic acid material, the mechanical performance of the material with fast degradation is relatively weak, and the degradation time of the material with strong mechanical performance is increased.

Therefore, there is a need to provide a novel biodegradable material and a suturing nail to solve the above problems in the prior art.

Disclosure of Invention

The invention aims to provide a biodegradable material and a suturing nail, so that the biodegradable material has good mechanical property while having degradation performance, and is favorable for improving the bioactivity, biocompatibility and degradation controllability of the biodegradable material.

In order to achieve the above object, the biodegradable material of the present invention comprises a polyester-based biodegradable material and an active ingredient, wherein the active ingredient comprises at least one of a surfactant and bioactive glass,

the content of the active ingredient is less than or equal to 40 percent and the content of the surfactant is less than or equal to 15 percent in terms of the total mass percentage of the polyester biodegradable material;

the polyester biodegradable material comprises blending modification components, wherein the blending modification components comprise at least one of polyglycolic acid, glycolide, caprolactone, lactide and polyethylene glycol.

The biodegradable material has the beneficial effects that: the biodegradable polyester film comprises a polyester biodegradable material and an active ingredient, wherein the active ingredient comprises at least one of a surfactant and bioactive glass; the polyester biodegradable material comprises a blending modification component, wherein the blending modification component comprises at least one of polyglycolic acid, glycolide, caprolactone, lactide and polyethylene glycol, so that a degradation product of bioactive glass can promote the generation of growth factors, promote the proliferation of cells, enhance the gene expression of osteoblasts and the growth of bone tissues, ensure good biocompatibility and small tissue reaction, improve the mechanical strength and toughness of the biodegradable material, have better biocompatibility and degradability, and increase the mechanical property and degradation controllability of the material through a surfactant, so that the biodegradable material has good mechanical property while having degradation performance; the content of the active ingredients is less than or equal to 40 percent and the content of the surfactant is less than or equal to 15 percent, which are calculated by the total mass percentage of the polyester biodegradable material, so that the biological activity, the biocompatibility, the mechanical property and the degradation controllability of the biodegradable material are favorably improved.

Preferably, the bioactive glass has an equivalent particle size of less than 45 microns. The beneficial effects are that: so that the bioactive glass is easy to be fused in the polyester biodegradable material.

Preferably, the content of the blending modification component is 5-95% by weight of the total mass percentage of the polyester biodegradable material. The beneficial effects are that: is favorable for improving the controllability of the degradability of the biodegradable material.

Further preferably, the polyester biodegradable material further comprises any one of polylactic acid, poly (glycolide-co-lactide), polycaprolactone, polydioxanone, and polytrimethylene carbonate. The beneficial effects are that: the biodegradable material has good degradability and the degradation product has good biocompatibility.

Preferably, the bioactive glass comprises any one of silicate glass, glass ceramic and borate-based glass. The beneficial effects are that: is helpful for promoting the generation of growth factors, promoting the multiplication of cells, enhancing the gene expression of osteoblasts and the growth of bone tissues, and ensuring good biocompatibility and small tissue reaction.

Preferably, the surfactant is a polyoxyethylene polyoxypropylene ether triblock copolymer. The beneficial effects are that: has good compatibility with skin, and can increase skin permeability and promote absorption of topical medicine.

More preferably, the polyoxyethylene polyoxypropylene ether triblock copolymer is any one of F127, L61, L64, F68, P85, P94, P104, P105, P123, L121 and L122. The beneficial effects are that: has good compatibility with skin, and can increase skin permeability and promote absorption of topical medicine.

Preferably, the weight average molecular weight of the polyester biodegradable material is 5000-80000 daltons. The beneficial effects are that: providing the desired mechanical properties and degradation time.

Preferably, the invention also provides a suturing nail which is prepared from the biodegradable material.

The suturing nail has the beneficial effects that: through the suturing nail adopts the biodegradable material prepare and form, make the suturing nail still have sufficient holding power when possessing the degradation performance, and can be light pass tissue such as implanting nasal septum.

Preferably, the suturing nail comprises a nail body, and a nail-in part and a nail cap part which are respectively arranged at two ends of the nail body, wherein the nail cap part is perpendicular to the nail body. The beneficial effects are that: make and pass through tissues such as the department of pegging into can relax and pass and implant tissues such as nasal septum, can fix tissues such as nasal septum steadily through the cap portion, make can implant the nail through nasal septum nail fixing device and sew up the mucosa bilayer that runs through the nasal septum, or further run through the cartilage between the mucosa layer, make the nail can closely stimulate the mucosa layer, prevent the formation of hematoma, the soft tissue of connecting internal tissue and both sides can be sewed up fast in the operation of nasal septum, compare with the stylolite, nasal septum nail fixing device cooperation is sewed up the nail and is sewed up and save time, reduce edema, and it is inseparabler to sew up fixedly relatively the stylolite, make the postoperative wound can heal up naturally, do not need extra splint or filler, improve patient's postoperative comfort level, and reduce postoperative complication, help healing.

Preferably, the total axial length of the suturing nail is 2-5mm, the axial length of the nail body is 1.5-3.5mm, the radial length of the nail body is 0.3-0.8mm, the maximum length of the radial acting surface of the nail cap part is 1.2-3mm, and the maximum width of the radial acting surface of the nail cap part is 0.4-1 mm. The beneficial effects are that: the nail head part can be used for fixing the tissues such as the nasal septum and the like stably, and has better mechanical performance.

Preferably, the spike cap portion has any one of an I-shaped structure, a circular structure and a cross-shaped structure. The beneficial effects are that: so that the said nail cap can fix the nasal septum and other tissues stably.

Preferably, the nail penetration portion has any one of a hook structure and a taper structure. The beneficial effects are that: so that the tissues implanted in the nasal septum and the like can be easily penetrated through the nail penetration part.

Drawings

FIG. 1 is a perspective view of a staple according to a first embodiment of the present invention;

FIG. 2 is a front view of the staple shown in FIG. 1;

FIG. 3 is a right side view of the staple shown in FIG. 1;

FIG. 4 is a schematic structural view of a staple according to a second embodiment of the present invention;

FIG. 5 is a schematic structural view of a staple according to a third embodiment of the present invention;

FIG. 6 is a schematic structural view of a staple according to a fourth embodiment of the present invention;

FIG. 7 is a schematic structural view of a staple according to a fifth embodiment of the present invention;

FIG. 8 is a graph showing the change of tensile modulus of elasticity with time of the staple manufactured according to the formulation of example 1;

FIG. 9 is a graph showing the change of tensile modulus of elasticity with time of the staple manufactured according to the formulation of example 2;

FIG. 10 is a graph showing the change of tensile modulus of elasticity with time of a staple manufactured according to the formulation of example 3;

FIG. 11 is a graph showing the change of tensile modulus of elasticity with time of a staple manufactured according to the formulation of example 4;

FIG. 12 is a graph showing the change of tensile modulus of elasticity with time of staples according to the formulation of example 5;

FIG. 13 is a graph showing the change of tensile modulus with time of the staple manufactured according to the formulation of example 6.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. As used herein, the word "comprising" and similar words are intended to mean that the element or item listed before the word covers the element or item listed after the word and its equivalents, but does not exclude other elements or items.

In order to solve the problems in the prior art, the embodiment of the invention provides a biodegradable material and a suturing nail, so that the biodegradable material has good mechanical properties while having degradation performance, and is favorable for improving the bioactivity, biocompatibility and degradation controllability of the biodegradable material.

In some embodiments of the invention, the biodegradable material comprises a polyester-based biodegradable material and an active ingredient comprising at least one of a surfactant and bioactive glass,

the content of the active ingredient is less than or equal to 40 percent and the content of the surfactant is less than or equal to 15 percent in terms of the total mass percentage of the polyester biodegradable material;

the polyester biodegradable material comprises blending modification components, wherein the blending modification components comprise at least one of polyglycolic acid, glycolide, caprolactone, lactide and polyethylene glycol.

Specifically, by applying the degradation principle of bioactive glass, cations released by the bioactive glass can form a layer of osteocarbonic acid hydroxyapatite on the surface of the biodegradable material during degradation, the surface of the material body is protected in a short period, the mechanical property of the composite material of the bioactive glass and the polyester biodegradable material can be improved in a short period, and more than 50% of initial tensile strength can be maintained in one week, so that the mechanical property of the material which needs to be maintained clinically is met; and the surfactant can enhance the hydrophilicity of the biodegradable material and promote the entry of nutrient substances so as to promote the regeneration of tissues sutured by the biodegradable material.

In some embodiments of the invention, the active ingredient is comprised of at least one of a surfactant and a bioactive glass.

In some embodiments of the present invention, the active ingredient is a surfactant, and the content of the surfactant is less than or equal to 15% by mass of the total mass of the polyester-based biodegradable material.

In other embodiments of the present invention, the active ingredient is bioactive glass, and the content of the bioactive glass is less than or equal to 40% by weight of the total mass of the polyester-based biodegradable material.

In still other embodiments of the present invention, the active ingredient comprises a surfactant and bioactive glass, and the sum of the content of the surfactant and the content of the bioactive glass is less than or equal to 40% and the content of the surfactant is less than or equal to 15% of the total mass percentage of the polyester-based biodegradable material.

In some embodiments of the present invention, the active ingredient is a surfactant, or the active ingredient is composed of a surfactant and bioactive glass, and the content of the surfactant is less than or equal to 5% by mass of the total mass percentage of the polyester-based biodegradable material.

In some embodiments of the present invention, the bioactive glass has an equivalent particle size of less than 45 microns, such that the bioactive glass is easily incorporated into polyester-based biodegradable materials.

In some embodiments of the invention, the content of the blending modification component is 5-95% by total mass of the polyester biodegradable material, which is beneficial to improving the controllability of the degradability of the biodegradable material.

In some embodiments of the present invention, the polyester-based biodegradable material further comprises any one of polylactic acid, poly (glycolide), polycaprolactone, polydioxanone, and polytrimethylene carbonate. Specifically, the polylactic acid comprises any one of L-polylactic acid, racemic polylactic acid, L-polylactic acid and D-polylactic acid.

Polyglycolic acid (PGA), also known as polyglycolic acid, is derived from an alpha hydroxy acid, i.e., glycolic acid. Glycolic acid is produced by normal humans during metabolic processes. Polyglycolic acid is a synthetic polymer material having good biodegradability and biocompatibility, and unlike conventional polymer materials having stable properties, such as plastics, rubbers, etc., polyglycolic acid as a material is gradually degraded after use for a certain time and finally becomes water and carbon dioxide harmless to the human body, animals and plants, and natural environments. The application of polyglycolic acid mainly shows two aspects of biomedicine and ecology. The biomedical application of polyglycolic acid is mainly shown in medical sutures, drug controlled release carriers, fracture fixation materials, tissue engineering scaffolds and suture reinforcement materials.

Polylactic acid, also known as Polylactide (PLA), belongs to the family of polyesters. The polylactic acid is a polymer obtained by polymerizing lactic acid serving as a main raw material, has sufficient and renewable raw material sources, and mainly takes corn, cassava and the like as raw materials. The polylactic acid has good biodegradability, can be completely degraded by microorganisms in the nature under specific conditions after being used, finally generates carbon dioxide and water, does not pollute the environment, is very beneficial to environmental protection, and is a well-known environment-friendly material.

Polycaprolactone (PCL, CAS number: 24980-41-4) is also called poly epsilon-caprolactone, is a high molecular organic polymer formed by ring-opening polymerization of epsilon-caprolactone monomer under the catalysis of metal anion complex catalyst, and different molecular weights can be obtained by controlling the polymerization conditions. The appearance of the product is white solid powder, which is non-toxic, insoluble in water and easily soluble in various polar organic solvents. PCL has good biocompatibility, good organic polymer compatibility and good biodegradability, can be used as a cell growth support material, can be compatible with various conventional plastics, and can be completely degraded in natural environment within 6-12 months.

Specifically, the content of the blending modification component is 5-95% by mass of the total polyester biodegradable material, the balance of the polyester biodegradable material is the content of any one of the polylactic acid, the poly (glycolide-co-lactide), the polycaprolactone, the poly (p-dioxanone) and the polytrimethylene carbonate, namely 5-95% by mass of the total polyester biodegradable material is the blending modification component, and the balance of the polyester biodegradable material is the content of any one of the polylactic acid, the poly (glycolide-co-lactide), the polycaprolactone, the poly (p-dioxanone) and the polytrimethylene carbonate.

In some embodiments of the present invention, the surfactant is a polyoxyethylene polyoxypropylene ether triblock copolymer, which has good compatibility with skin, increases skin permeability, and promotes absorption of external agents.

Specifically, the general formula of the polyoxyethylene polyoxypropylene ether triblock copolymer is HO (C)₂H₄O)a(C₃H₆O)b(C₂H₄O) cH. Wherein a and c are 2-130 and b is 15-67. The polyoxyethylene content is 81.8 +/-1.9%. It is soluble in water or ethanol, soluble in anhydrous ethanol, ethyl acetate, and chloroform, and insoluble in diethyl ether or petroleum ether, and has certain foamability. The pH value of the 2.5% water solution is 5.0-7.5, and the pH value of the injection user is 6.0-7.0. The aqueous solution is stable in the air, and the pH value is reduced when the aqueous solution is exposed to light. The product is stable to acid and alkali aqueous solution and metal ions.

In some embodiments of the present invention, the polyoxyethylene polyoxypropylene ether triblock copolymer is any one of F127, L61, L64, F68, P85, P94, P104, P105, P123, L121, and L122. Theoretically, there are countless compounds having such a basic structure, and the NF standard specifies that the molecular weight thereof varies from 1000 to 7000 or more, and that a suitable amount of polyoxypropylene and a suitable amount of polyoxyethylene are copolymerized into compounds having different hydrophilic-oil balance values.

In some embodiments of the present invention, the bioactive glass includes any one of silicate glass, glass ceramic and borate-based glass, which is helpful for promoting the generation of growth factors, promoting the proliferation of cells, enhancing the gene expression of osteoblasts and the growth of bone tissues, so that the biocompatibility is good and the tissue reaction is small.

In some embodiments of the invention, the silicate glass comprises 45S5 bioactive glass, the glass-ceramic comprises S53P4 bioactive glass, and the borate-based glass comprises 19-93B3 bioactive glass. 45S5 bioactive glass with a composition of 24.5 wt% Na₂O, 24.5 wt% CaO, 6.0 wt% P₂O₅And 45 wt% SiO₂45S means 45 mass% SiO₂And 5 represents a molar ratio of Ca to P of 5: 1.

In some embodiments of the invention, the weight average molecular weight of the polyester-based biodegradable material is 5000-.

In some embodiments of the invention, a suturing nail is further provided, and the suturing nail is prepared from the biodegradable material.

In some embodiments of the invention, the staple comprises a staple body, and a staple inlet part and a staple cap part which are respectively arranged at two ends of the staple body, wherein the staple cap part is arranged perpendicular to the staple body. So that the tissues such as the nasal septum and the like can be easily penetrated and implanted through the nail-in part, and the tissues such as the nasal septum and the like can be stably fixed through the nail cap part.

In some embodiments of the present invention, the staple is of a unitary construction.

In some embodiments of the invention, the total axial length of the suturing nail is 2-5mm, the axial length of the nail body is 1.5-3.5mm, the radial length of the nail body is 0.3-0.8mm, the maximum length of the radial acting surface of the nail cap part is 1.2-3mm, and the maximum width of the radial acting surface of the nail cap part is 0.4-1 mm.

In an embodiment of the present invention, the axial length is a length in a direction in which the body extends, the radial length is a length in a direction perpendicular to the direction in which the body extends, and the radial acting surface of the nut portion is an upper surface of the nut portion in the direction perpendicular to the direction in which the body extends.

In some embodiments of the present invention, the cap portion has any one of an I-shaped structure, a circular structure and a cross-shaped structure, i.e., the upper surface of the cap portion has any one of an I-shaped structure, a circular structure and a cross-shaped structure. The area of the acting surface of the cap part with the circular structure and the area of the acting surface of the cap part with the cross structure are large, so that the fixing area of the cap part and tissues such as the nasal septum is larger, and the fixation is firmer. The I-shaped structure is a cuboid structure or a cylindrical structure.

In some embodiments of the invention, the driving portion has any one of a hook-shaped structure and a tapered structure. The nailing part of the hook-shaped structure is suitable for tissues such as nasal septum with different thicknesses, and the universality is higher; the nailing part of the conical structure is suitable for scenes with small tissue areas such as the residual nasal septum and the like, and can be effectively fixed when the tissue areas such as the nasal septum and the like are small.

In some embodiments of the present invention, the nail-in part of the hook structure is provided with at least 1 hook body, and one end of the hook body is fixedly arranged at the action end of the nail-in part.

FIG. 1 is a perspective view of a staple according to a first embodiment of the present invention; FIG. 2 is a front view of the staple shown in FIG. 1; FIG. 3 is a right side view of the staple shown in FIG. 1.

In some embodiments of the present invention, referring to fig. 1, the first staple 10 includes a first I-shaped staple cap 11, a hook-shaped staple inlet 12 and a first staple body 13, the first I-shaped staple cap 11 and the hook-shaped staple inlet 12 are disposed at two ends of the first staple body 13, and in particular, the first I-shaped staple cap 11 has a rectangular parallelepiped structure.

Specifically, referring to fig. 2 and 3, the total axial length L1 of the first staple 10 is 2 to 5mm, the axial length L2 of the first body 13 is 1.5 to 3.5mm, the radial length W1 of the first body 13 is 0.3 to 0.8mm, the maximum length W2 of the radially acting surface of the first I-shaped staple cap 11 is 1.2 to 3mm, and the maximum width W3 of the radially acting surface of the first I-shaped staple cap 11 is 0.4 to 1 mm.

FIG. 4 is a schematic structural view of a staple according to a second embodiment of the present invention.

In some embodiments of the present invention, referring to fig. 4, the second staple 20 includes a second I-shaped staple cap 21, a first tapered driver 22 and a second staple body 23, the second I-shaped staple cap 21 and the first tapered driver 22 are disposed at two ends of the second staple body 23, and in particular, the second I-shaped staple cap 21 has a cylindrical structure.

FIG. 5 is a schematic structural view of a staple according to a third embodiment of the present invention.

In some embodiments of the present invention, referring to fig. 5, the third staple 30 includes a circular staple cap 31, a second tapered driver 32 and a third staple body 33, and the circular staple cap 31 and the second tapered driver 32 are disposed at two ends of the third staple body 33.

FIG. 6 is a schematic structural view of a staple according to a fourth embodiment of the present invention.

In some embodiments of the present invention, referring to fig. 6, the fourth staple 40 includes a first cross-shaped cap portion 41, a single-hook driving portion 42, and a fourth shank 43, and the first cross-shaped cap portion 41 and the single-hook driving portion 42 are provided at both ends of the fourth shank 43.

FIG. 7 is a schematic structural view of a staple according to a fifth embodiment of the present invention.

In some embodiments of the present invention, referring to fig. 7, the fifth staple 50 includes a second cross-shaped cap portion 51, a four-hook-shaped nail-entering portion 52 and a fifth nail body 53, the second cross-shaped cap portion 51 and the four-hook-shaped nail-entering portion 52 are disposed at both ends of the fifth nail body 53, the four-hook-shaped nail-entering portion 52 includes four hook bodies (not shown), and one end of each of the four hook bodies (not shown) is fixedly disposed at an action end of the four-hook-shaped nail-entering portion 52.

In examples 1 to 6 of the present invention, the polyester-based biodegradable material in the biodegradable material is composed of polyglycolic acid (PGA) and polylactic acid (PLA), and the polyglycolic acid (PGA) is added to the polylactic acid (PLA), so that the liquid absorption of the biodegradable material can be controlled, thereby controlling the degradation time of the staples; the active component comprises at least one of a surfactant and bioactive glass, wherein the surfactant is an F127 surfactant, and the bioactive glass is 45S5 bioactive glass; the active ingredients and the polyester biodegradable material are prepared into the biodegradable material in a melt blending mode, and then the biodegradable material is prepared into the suturing nail by methods such as extrusion, compression or injection molding.

Specifically, the content wt% of each component in the mixture ratio of the embodiments 1 to 6 of the present invention is shown in table 1, in terms of the total mass percentage of the polyester-based biodegradable material.

TABLE 1

In examples 1 to 6 of the present invention, taking example 1 as an example, the weight of the polyester-based biodegradable material in the biodegradable material was 100g, i.e., the total weight of the polyglycolic acid (PGA) and the polylactic acid (PLA) is 100g, wherein the polyglycolic acid (PGA) accounts for 95 wt% of the total mass percent of the polyester biodegradable material, the weight of the polyglycolic acid (PGA) is 95g, the polylactic acid (PLA) accounts for 5 wt% of the total mass percent of the polyester-based biodegradable material, the weight of the polyglycolic acid (PGA) is 5g, the F127 surfactant accounts for 5 wt% of the total mass percent of the polyester biodegradable material, the weight of the F127 surfactant is 5g, the weight of the 45S5 bioactive glass accounts for 5 wt% of the total mass percent of the polyester biodegradable material, and the weight of the 45S5 bioactive glass is 5 g.

In examples 1 to 6 of the present invention, the staples prepared according to the formulation shown in table 1 were prepared in the following manner:

each prepared staple sample was weighed, wherein the total axial length of the staple was 5mm, the maximum length of the radially acting surface of the cap portion was 3mm and was recorded as Wo, and then the samples were soaked in 1mL of tissue culture water (Sigma Aldrich, china) for 1 day, 3 days, 7 days, 14 days and 21 days (n ═ 9) respectively. According to the requirements of GB/T16886-part 12, each sample was stored in a 10mL polypropylene tube, kept at 37 ℃ in a shaking water bath (electric thermostat water bath, Shanghai Bowen), and stirred at 2HZ (longitudinal motion). After each incubation period, the undegraded sections were stapled gently with sterile forceps and the extracted individual extract solutions were filtered using a 0.2micron sterile filter (Thermo Fisher Scientific, china). Then, 0.5ml of each filtrate was diluted with tissue culture water to 5ml of an extract, and stored at 4 ℃ for later evaluation in vitro.

In inventive examples 1-6, the prepared samples were subjected to a mass loss test:

after the end of each incubation period, the cement was blotted dry and the weight of each sample was recorded as Wt (n-3). The staple samples were then collected in 48-well plates, dried at 37 ℃ ambient temperature for 24h, and the mass of the staple samples was measured as Wd, and the mass loss of the staples (m) as a function of incubation time was determined using the following equation:

m(％)＝[(Wo-Wd)/Wo]×100％

wherein: wo is the initial mass of the sample, and Wd is the mass of the degraded sample after being dried at 37 ℃ for 24 h; m is the mass loss of the sample, assuming no mass loss during drying.

Specifically, the mass loss (m) of the staples of examples 1-6 of the present invention was varied with the number of days of culture as shown in Table 2.

Table 2 shows the mass loss measurements for the staple samples of examples 1-6 over the 3, 7, 14 and 21 day incubation periods. As can be seen from Table 2, the staples of examples 1-6 had a substantial loss of between 3.15% and 46.9% during the 1-21 day culture period; after 21 days of culture, the mass loss of example 2 is nearly 50%, while the mass loss of examples 1 and 6 is even more than 30%, and it can be seen that the addition of at least one of the F127 surfactant and the 45S5 bioactive glass to the polyglycolic acid (PGA) and the polylactic acid (PLA) can make the staple sufficiently supported to the surgical site and then degraded after the surgical site is completely healed, and the addition of the F127 surfactant and the 45S5 bioactive glass simultaneously to the polyglycolic acid (PGA) and the polylactic acid (PLA) or the addition of a larger amount of the 45S5 bioactive glass can make the staple complete degradation within 4 to 8 weeks, which is beneficial to the closure of the wound at the surgical site.

TABLE 2

In examples 1 to 6 of the present invention, the prepared samples were subjected to mechanical property test:

in the process of preparing the leaching liquor by the sample, after each culture period is finished, an uncultured suturing nail sample and a wet suturing nail (N is 3) which is just taken out are tested by a universal material testing machine, and a 10N sensor is used in a handle (2710-100 series screw side-moving handle) on a uniaxial stretcher; measuring the length of the staple, recording as L1, and marking the width of a contact surface as W2 and W3; the cross traction speed is 10mm/min, and the Young modulus is calculated from a stress-strain curve generated in the test process.

FIG. 8 is a graph showing the change of tensile modulus of elasticity with time of the staple manufactured according to the formulation of example 1; FIG. 9 is a graph showing the change of tensile modulus of elasticity with time of the staple manufactured according to the formulation of example 2; FIG. 10 is a graph showing the change of tensile modulus of elasticity with time of a staple manufactured according to the formulation of example 3; FIG. 11 is a graph showing the change of tensile modulus of elasticity with time of a staple manufactured according to the formulation of example 4; FIG. 12 is a graph showing the change of tensile modulus of elasticity with time of staples according to the formulation of example 5; FIG. 13 is a graph showing the change of tensile modulus with time of the staple manufactured according to the formulation of example 6.

Referring to FIGS. 8 to 13, the staples manufactured according to examples 1 to 3, 5 and 6 all had Young's moduli of more than 20MPa after 21 days of culture and maintained initial tensile strengths of more than 50% for one week, which was extremely satisfactory for the mechanical properties of clinically required continuous materials.

In examples 1 to 6 of the present invention, cytotoxicity evaluation was performed according to the standard ISO 10993-5, specifically including:

(1) the staple finger prepared in examples 1-6 was dissected from that extract to hatch L929 cells: MTT assay was performed using L929 cells passaged 7 passages. Cell counts and viability were determined using trypan blue staining and cytometry. The positive control of the cells is that the experimental wells of the cells, the culture medium and the 24-well plate are inoculated with 1 multiplied by 10⁴Cell density per ml. The medium served only as a negative control. The plates were then incubated at 37 deg.C (5% CO)₂A/95% air atmosphere) for 24 hours. After 24h, 100. mu.l of sterile tissue culture water was added to the control wells. To the corresponding well, 100. mu.l of the relevant experimental extract (n-3) (extract prepared according to the sample preparation procedure) was added for detection. The plates were then incubated at 37 deg.C (5% CO)₂/95% air atmosphere) in a cell culture chamberIncubate for 24 hours.

(2) Performing MTT test: after 24 hours of incubation, each well was incubated with 10% MTT of the volume of the medium (100. mu.l). The dish was then returned to the incubator for 3 hours. After incubation, MTT plus solution was added to each well in a volume equal to the original medium volume (1 ml). To enhance the dissolution of the crystals, each well was titrated with a pipette and the absorbance of each well was measured spectrophotometrically at a wavelength of 570nm (TriStar LB 941, Berthold Technologies, USA). The metabolic activity of the cell control wells was assumed to be 100% and the percentage of metabolic activity of the cells exposed to the experimental extract was calculated therefrom. Results were analyzed using the T-contrast method with p <0.05 significant difference.

TABLE 3

Table 3 shows the MTT assay cell activity for the staple samples of examples 1-6 at 1 day, 3 days, 7 days, 14 days, and 21 days of culture. As can be seen from Table 3, the suturing nail in the embodiments 1-6 can meet the requirement of GB/T16886 on the cytotoxicity of medical instruments, and the biodegradable material and the suturing nail prepared by the biodegradable material have good biocompatibility and small tissue reaction.

Although the embodiments of the present invention have been described in detail hereinabove, it is apparent to those skilled in the art that various modifications and variations can be made to these embodiments. However, it is to be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention as described herein is capable of other embodiments and of being practiced or of being carried out in various ways.