技术领域technical field
本发明涉及生物材料领域，特别涉及一种人工韧带的表面改性方法。The invention relates to the field of biological materials, in particular to a surface modification method of artificial ligament.
背景技术Background technique
膝关节交叉韧带损伤是最常见的膝关节损伤之一，通常是由于剧烈的膝关节运动造成的，若不及时治疗，将会导致膝关节不稳和软骨退变，影响患者的生活质量。在目前的交叉韧带重建治疗中，人工韧带的使用越来越广泛。Knee cruciate ligament injury is one of the most common knee injuries, usually caused by strenuous knee movement. If not treated in time, it will lead to knee instability and cartilage degeneration, affecting the quality of life of patients. In the current cruciate ligament reconstruction treatment, artificial ligament is more and more widely used.
目前在临床上应用较多的人工韧带主要有LARS、Ligastic、Leeds-Keio和Neoligaments，均以聚对苯二甲酸乙二醇酯(PET)为材料。由于PET分子结构对称、结晶度高，且分子中无强极性基团，故其表面亲和性较差，植入人体后容易引起感染、慢性滑膜炎、僵硬等术后并发症。因此，必须对PET材料进行表面改性，以提高与人体组织的相容性。At present, the most commonly used artificial ligaments are LARS, Ligastic, Leeds-Keio and Neoligaments, all of which are made of polyethylene terephthalate (PET). Because PET has a symmetrical molecular structure, high crystallinity, and no strong polar groups in the molecule, its surface affinity is poor, and it is easy to cause postoperative complications such as infection, chronic synovitis, and stiffness after implantation in the human body. Therefore, surface modification of PET materials is necessary to improve compatibility with human tissues.
目前PET表面改性多采用在PET表面进行化学接枝的方法，尝试的接枝层组成主要有对苯乙烯磺酸钠、(甲基)丙烯酸、丙烯酰胺、肝素、壳聚糖、透明质酸、明胶、2-甲基丙烯酰氧基乙基磷酰胆碱等。这些接枝层可改善细胞在韧带纤维表面的形态及分布均匀性。但进一步的观察表明，细胞在纤维表面的锚定点依然较少，自体纤维组织和人工韧带纤维之间存在明显的空隙，长入的纤维组织无法感受到适当应力的反复刺激，基本不具力学性能，其主要作用是避免人工韧带纤维之间、骨与人工韧带之间的直接接触。此外，由于生物学因素和机械性因素的存在，人工韧带移植物与骨隧道的融合性欠佳，骨隧道扩大现象在临床上较为常见。骨隧道扩大后需再行修复手术，而扩大部位的骨缺损使得移植物的附着及固定更加困难，手术需分期进行，显著增加了手术费用和患者痛苦。At present, the surface modification of PET mostly adopts the method of chemical grafting on the surface of PET. The main components of the grafted layer are sodium p-styrene sulfonate, (meth)acrylic acid, acrylamide, heparin, chitosan, and hyaluronic acid. , gelatin, 2-methacryloyloxyethylphosphorylcholine, etc. These grafted layers can improve the morphology and distribution uniformity of cells on the surface of ligament fibers. However, further observations showed that the anchor points of cells on the fiber surface were still few, and there were obvious gaps between the autologous fibrous tissue and the artificial ligament fibers. Its main function is to avoid direct contact between artificial ligament fibers and between bone and artificial ligament. In addition, due to the existence of biological factors and mechanical factors, the fusion of artificial ligament grafts and bone tunnels is not good, and the phenomenon of bone tunnel enlargement is common in clinical practice. After the bone tunnel is enlarged, a repair operation is required, and the bone defect in the enlarged part makes the attachment and fixation of the graft more difficult.
发明内容SUMMARY OF THE INVENTION
本发明解决的技术问题在于提供一种经表面修饰的人工韧带，该韧带纤维表面接枝有呈三维网状、类凝胶结构的亲水聚合物层，因而具有更好的生物相容性，诱导功能性组织再生的能力更强，锚固也更加稳定。通过对韧带两端的骨隧道部分涂覆矿化涂层，使得移植物与骨界面的结合更优，力学性能得以加强。The technical problem solved by the present invention is to provide a surface-modified artificial ligament. The surface of the ligament fiber is grafted with a hydrophilic polymer layer in a three-dimensional network and a gel-like structure, so that it has better biocompatibility, The ability to induce functional tissue regeneration is stronger and the anchorage is more stable. By coating the bone tunnel parts at both ends of the ligament with mineralized coating, the combination of the graft and the bone interface is better, and the mechanical properties are enhanced.
本发明公开了一种进行人工韧带纤维表面修饰的方法，其制备工序主要包括：1.人工韧带织物的深度清洗工序；2.纤维表面的过氧化工序；3.纤维表面的接枝聚合工序；4.再清洗工序；5.分段涂覆工序。The invention discloses a method for modifying the surface of artificial ligament fibers. The preparation process mainly includes: 1. a deep cleaning process of artificial ligament fabrics; 2. a peroxidation process on the fiber surface; 3. a graft polymerization process on the fiber surface; 4. Re-cleaning process; 5. Segmented coating process.
1.深度清洗工序1. Deep cleaning process
对人工韧带织物进行清洗的目的在于消除其表面上携带的各类杂质。因这些杂质一方面妨害后续过氧化工序、接枝聚合工序的顺利进行。更重要的是，这些杂质是引起慢性滑膜炎，阻碍组织细胞在纤维表面粘附、增殖的重要原因。因此，必须予以除去。The purpose of cleaning artificial ligament fabric is to eliminate various impurities carried on its surface. On the one hand, these impurities hinder the smooth progress of the subsequent peroxidation process and the graft polymerization process. More importantly, these impurities are an important cause of chronic synovitis and hinder the adhesion and proliferation of tissue cells on the fiber surface. Therefore, it must be removed.
所述深度清洗工序的特征在于，通过特定的清洗方法，清除纤维表面一定深度内所含有的杂质，而对纤维本体的主要性能没有明显影响。The feature of the deep cleaning process is that impurities contained in a certain depth of the fiber surface are removed by a specific cleaning method, and the main properties of the fiber body are not significantly affected.
所述特定的清洗方法，其特征在于采用多步骤、超声/洗液协同处理的方式。具体的，在超声波存在下，将韧带织物依次通过酸性洗液、去离子水、碱性洗液，最后用去离子水冲洗，直至洗出水的pH回复至7。The specific cleaning method is characterized in that a multi-step, ultrasonic/washing solution co-processing method is adopted. Specifically, in the presence of ultrasonic waves, the ligament fabric is sequentially passed through an acidic washing solution, deionized water, an alkaline washing solution, and finally washed with deionized water until the pH of the washed water returns to 7.
所述一定深度宜控制在纤维表层以下1-1000nm，优选为5-500nm，更优选为10-200nm。The certain depth should be controlled to be 1-1000 nm below the fiber surface layer, preferably 5-500 nm, more preferably 10-200 nm.
2.纤维表面的过氧化工序2. Peroxidation process of fiber surface
为使亲水性单体顺利接枝到纤维表面，必须首先在纤维表面制得过氧基团。通过过氧基团分解产生的自由基，引发亲水性单体发生表面接枝聚合。In order to successfully graft the hydrophilic monomer onto the fiber surface, the peroxy group must be prepared on the fiber surface first. The free radicals generated by the decomposition of peroxy groups initiate surface graft polymerization of hydrophilic monomers.
所述过氧基团的制备可选择以下方法中的一种或几种配合使用，如过氧化物法、臭氧化法、高能射线法(γ射线、紫外线、电子束等)，从容易实现的角度考虑，优选臭氧/紫外联合氧化法。The preparation of the peroxy group can be selected from one or more of the following methods, such as peroxide method, ozonation method, high-energy ray method (γ ray, ultraviolet light, electron beam, etc.), from easily achievable methods. Considering the point of view, the ozone/ultraviolet combined oxidation method is preferred.
使用纤维溶胀试剂可进一步提高氧化速度，如甲苯、丁酮、庚酮、四氢呋喃、硝基甲烷、N，N-二甲基甲酰胺等，优选使用四氢呋喃。The oxidation rate can be further increased by using a fiber swelling agent, such as toluene, butanone, heptanone, tetrahydrofuran, nitromethane, N,N-dimethylformamide, etc., preferably tetrahydrofuran is used.
臭氧化完成后，为除去残留的臭氧、氧气及其它无用基团，依次将韧带织物通过蒸馏水、无水乙醇、四氢呋喃的溶液，并重复进行不少于3次，最后将其置于真空烘箱中，室温下持续抽真空30min。After the ozonation is completed, in order to remove the residual ozone, oxygen and other useless groups, the ligament fabric is passed through the solution of distilled water, absolute ethanol and tetrahydrofuran in turn, and repeated no less than 3 times, and finally it is placed in a vacuum oven. , and continued to vacuumize for 30 min at room temperature.
3.表面接枝聚合工序3. Surface graft polymerization process
将过氧化的韧带纤维置于亲水性单体溶液中，控制反应条件，则亲水性单体在纤维表面发生接枝聚合，形成包裹于纤维表面的亲水聚合物层，增加了纤维的生物相容性，有利于成纤细胞的粘附、生长、增殖。The peroxidized ligament fibers are placed in a solution of hydrophilic monomers, and the reaction conditions are controlled, and the hydrophilic monomers undergo graft polymerization on the surface of the fibers to form a hydrophilic polymer layer wrapped around the surface of the fibers, increasing the fiber's properties. Biocompatibility is beneficial to the adhesion, growth and proliferation of fibroblasts.
所述亲水聚合物层的特征在于其由亲水性单体、交联剂聚合而成的三维网状结构，具有更优的吸水、保水能力，其轻度的吸水膨胀特性能为细胞的发育提供均一的类凝胶环境。The hydrophilic polymer layer is characterized by a three-dimensional network structure formed by the polymerization of hydrophilic monomers and cross-linking agents, and has better water absorption and water retention capabilities, and its mild water absorption and swelling characteristics can be used by cells. Development provides a homogeneous gel-like environment.
所述亲水性单体包含羧酸盐/酯、磷酸盐/酯、磺酸盐/酯和硫酸盐酯。优选为(甲基)丙烯酸、异丁烯酸甲酯、(甲基)丙烯酰胺-N-苯基磺酸钠、苯乙烯磺酸钠和乙二醇甲基丙烯酸酯磷酸盐类中的一种或多种。鉴于这些亲水性单体优良的生物活性，更优选为甲基丙烯酸和对苯乙烯磺酸钠。The hydrophilic monomers include carboxylate, phosphate, sulfonate and sulfate esters. It is preferably one or more of (meth)acrylic acid, methyl methacrylate, sodium (meth)acrylamide-N-phenylsulfonate, sodium styrenesulfonate and ethylene glycol methacrylate phosphate. kind. In view of the excellent biological activity of these hydrophilic monomers, methacrylic acid and sodium p-styrenesulfonate are more preferred.
所述交联剂优选为多元醇类，如丙二醇、丁二醇、三羟甲基丙烷、甘油、聚氧乙烯二醇、聚氧丙烯二醇和聚甘油；具有两个以上乙烯基的多不饱和酯类，如二乙二醇双丙烯酸酯、聚乙二醇双丙烯酸酯；双丙烯酰胺类，如N，N-亚甲基双丙烯酰胺；多缩水甘油化合物类，如(聚)乙二醇二缩水甘油醚、(聚)乙二醇三缩水甘油醚、(聚)丙二醇多缩水甘油醚、(聚)甘油二缩水甘油醚、(聚)甘油三缩水甘油醚、(聚)甘油多缩水甘油醚。这些交联剂可单独使用，或将两种以上合并使用。鉴于这些交联剂的优良反应性，优选为N，N-亚甲基双丙烯酰胺、(聚)乙二醇二缩水甘油醚。The crosslinking agent is preferably polyols, such as propylene glycol, butylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol and polyglycerol; polyunsaturated with two or more vinyl groups Esters, such as diethylene glycol diacrylate, polyethylene glycol diacrylate; bisacrylamides, such as N,N-methylenebisacrylamide; polyglycidyl compounds, such as (poly)ethylene glycol Diglycidyl ether, (poly)ethylene glycol triglycidyl ether, (poly)propylene glycol polyglycidyl ether, (poly)glycerol diglycidyl ether, (poly)glycerol triglycidyl ether, (poly)glycerol polyglycidyl ether ether. These crosslinking agents may be used alone or in combination of two or more. In view of the excellent reactivity of these crosslinking agents, N,N-methylenebisacrylamide and (poly)ethylene glycol diglycidyl ether are preferred.
4.再清洗工序4. Re-cleaning process
自由基接枝聚合物的组成范围宽泛，多混有未反应的单体、少量均聚物等。与工序1的作用基本相同，对接枝后的韧带织物进行再次清洗。为后续的涂覆工序做准备，并有利于细胞的粘附、生长、增殖。The composition range of the free radical graft polymer is wide, mostly mixed with unreacted monomer and a small amount of homopolymer. The function is basically the same as that of step 1, and the grafted ligament fabric is washed again. Prepare for subsequent coating procedures and facilitate cell adhesion, growth and proliferation.
所述再清洗工序的特征在于，将接枝了亲水聚合物层的织物从反应器中取出，采用多步骤、超声/洗液协同处理的方式，进行织物的清洗。具体的，将韧带织物置入洗液中，超声波震荡洗涤，最后用去离子水冲洗，直至洗出水的pH回复至7。可重复此步骤多次。The re-cleaning process is characterized in that the fabric with the grafted hydrophilic polymer layer is taken out of the reactor, and the fabric is cleaned by means of multi-step, ultrasonic/washing synergistic treatment. Specifically, the ligament fabric was placed in the lotion, washed with ultrasonic vibration, and finally rinsed with deionized water until the pH of the washed water returned to 7. This step can be repeated multiple times.
5.分段涂覆工序。5. Segmented coating process.
表面接枝亲水聚合物层后，纤维的亲水性大大增强，为进一步加强韧带织物的生物相容性，对韧带织物再进行分段涂覆。After the hydrophilic polymer layer is grafted on the surface, the hydrophilicity of the fiber is greatly enhanced. In order to further enhance the biocompatibility of the ligament fabric, the ligament fabric is coated in sections.
所述分段涂覆的特征在于，对韧带关节腔段进行生化试剂注入，对骨隧道段进行促成骨层涂覆。The segmented coating is characterized in that the ligament joint cavity segment is injected with biochemical reagents, and the bone tunnel segment is coated with an osteogenic layer.
所述生化试剂包含生长因子，如成纤细胞生长因子；生物活性蛋白，如纤维连接蛋白、I型胶原蛋白和III型胶原蛋白。从制备成本和安全性考虑，优选纤维连接蛋白和I型或III型胶原的混合物。The biochemical reagents include growth factors, such as fibroblast growth factor; biologically active proteins, such as fibronectin, collagen type I and collagen type III. From the viewpoint of production cost and safety, a mixture of fibronectin and type I or type III collagen is preferred.
所述生化试剂的注入方式可以采用将韧带织物浸入含生化试剂的溶液中来实现。为加快扩散速度，可协同采用超声震荡的方式，促进生化试剂向亲水聚合物所形成的溶胀网络中扩散。The injection method of the biochemical reagent can be realized by immersing the ligament fabric in a solution containing the biochemical reagent. In order to speed up the diffusion speed, ultrasonic vibration can be used synergistically to promote the diffusion of biochemical reagents into the swollen network formed by the hydrophilic polymer.
所述促成骨层包含具有骨传导及骨诱导性的矿化涂层，如羟基磷灰石、生物玻璃、磷酸三钙、二氧化硅、二氧化钛、生物陶瓷等。优选为羟基磷灰石。The osteopromoting layer includes mineralized coatings with osteoconductive and osteoinductive properties, such as hydroxyapatite, bioglass, tricalcium phosphate, silicon dioxide, titanium dioxide, bioceramics, and the like. Hydroxyapatite is preferred.
所述促成骨层的涂覆方式可以采用将韧带织物浸入含矿化物质的溶液中来进行。为增强涂层的渗入深度、稳定性和结合力，可协同采用超声震荡的方式，促进矿物质向亲水聚合物所形成的溶胀网络中扩散。The coating method of the osteopromoting layer can be performed by dipping the ligament fabric into a solution containing mineralized substances. In order to enhance the penetration depth, stability and bonding force of the coating, ultrasonic vibration can be used synergistically to promote the diffusion of minerals into the swollen network formed by the hydrophilic polymer.
最后将韧带织物取出，置于真空烘箱中，干燥至含水率＜10％。Finally, the ligament fabric is taken out, placed in a vacuum oven, and dried to a moisture content of less than 10%.
与现有技术相比，本发明的人工韧带表面修饰方法的有益效果主要有：Compared with the prior art, the beneficial effects of the artificial ligament surface modification method of the present invention mainly include:
1)采用多步骤、超声/洗液协同处理的方式，可以获得更为洁净、优良、更适于接枝的表面；1) By adopting multi-step, ultrasonic/lotion synergistic treatment, a cleaner, better and more suitable surface for grafting can be obtained;
2)采用臭氧/紫外联合氧化法，具有氧化快速、氧化程度深、过氧基团含量高等优点，有助于提高接枝效率，减少均聚物的产生。2) The use of ozone/ultraviolet combined oxidation method has the advantages of rapid oxidation, deep oxidation degree and high content of peroxide groups, which helps to improve the grafting efficiency and reduce the production of homopolymers.
3)亲水聚合物层呈三维网状、类凝胶结构，具有更优的吸水、保水能力，为细胞的发育提供了更好的环境。3) The hydrophilic polymer layer has a three-dimensional network and a gel-like structure, which has better water absorption and water retention capabilities, and provides a better environment for cell development.
4)通过再清洗，韧带织物表面更洁净，更有利于细胞的粘附、生长、增殖。4) Through re-cleaning, the surface of the ligament fabric is cleaner, which is more conducive to the adhesion, growth and proliferation of cells.
5)通过分段涂覆，韧带关节腔段更易诱导自体滑膜组织生长，有利于进行韧带自体化；骨隧道段的成骨性增强，韧带与骨的愈合更佳。5) By segmental coating, the ligament joint cavity segment is more likely to induce the growth of autologous synovial tissue, which is beneficial to the ligament autogenation; the osteogenicity of the bone tunnel segment is enhanced, and the healing of the ligament and the bone is better.
具体实施方式Detailed ways
本发明的工艺过程以聚对苯二甲酸乙二醇酯(PET)纤维织物为例简述如下：The technological process of the present invention is briefly described as follows with polyethylene terephthalate (PET) fiber fabric as an example:
将PET人工韧带织物浸入到由盐酸、四氢呋喃、十二烷基苯磺酸钠组成的酸性洗液中，开启超声震荡(频率40KHz，功率70W)，处理时间10min，用去离子水冲洗，直至洗出水的pH回复至7。再将PET人工韧带织物浸入到由碳酸钠、四氢呋喃、十二烷基苯磺酸钠组成的碱性洗液中，开启超声震荡(频率40KHz，功率70W)，处理时间10min，用去离子水冲洗，直至洗出水的pH回复至7。用扫描电镜观察纤维表面的洁净程度，视野内纤维应光滑、无明显颗粒状残留。用单位体积的纤维所增加重量的百分比作为处理深度的表征，其值应＜10％。进行力学性能测试，抗拉力、断裂伸长率变化＜5％的进入下一工序。The PET artificial ligament fabric was immersed in an acidic lotion composed of hydrochloric acid, tetrahydrofuran, and sodium dodecylbenzenesulfonate, and ultrasonic vibration was turned on (frequency 40KHz, power 70W), and the treatment time was 10min. The pH of the effluent returned to 7. Then the PET artificial ligament fabric was immersed in an alkaline washing solution consisting of sodium carbonate, tetrahydrofuran, and sodium dodecylbenzene sulfonate, and ultrasonic vibration was turned on (frequency 40KHz, power 70W), and the treatment time was 10min. Rinse with deionized water , until the pH of the washing water returned to 7. Observing the cleanliness of the fiber surface with a scanning electron microscope, the fibers should be smooth and without obvious granular residues in the field of view. The percentage of weight gain per unit volume of fiber is used as an indication of the depth of treatment, and its value should be <10%. Carry out the mechanical property test, and those whose tensile strength and elongation at break change less than 5% go to the next process.
将清洗干净的PET人工韧带织物置于紫外臭氧化反应器中，臭氧流量50mg/L，紫外灯10W，波长185nm，辐照距离20cm，处理时间30min。氧化完成后，依次将韧带织物通过蒸馏水、无水乙醇、四氢呋喃的溶液，并重复进行不少于3次，最后将其置于真空烘箱中，室温下持续抽真空30min。用GB/T 32102-2015所述方法测定韧带织物中过氧化物的含量。The cleaned PET artificial ligament fabric was placed in an ultraviolet ozonation reactor, the ozone flow rate was 50 mg/L, the ultraviolet lamp was 10 W, the wavelength was 185 nm, the irradiation distance was 20 cm, and the treatment time was 30 min. After the oxidation is completed, the ligament fabric is passed through a solution of distilled water, anhydrous ethanol, and tetrahydrofuran in sequence, and the process is repeated no less than 3 times. The content of peroxide in the ligament fabric was determined by the method described in GB/T 32102-2015.
过氧化的韧带织物置于聚合反应器中，加入去离子水中、精制过的等质量的对苯乙烯磺酸钠和甲基丙烯酸，单体总浓度30％，N，N-亚甲基双丙烯酰胺用量0.01％。使用氩气除氧，待O2含量＜6ppm时，加热至70℃，反应2小时。The peroxidized ligament fabric was placed in a polymerization reactor, deionized water, purified sodium p-styrenesulfonate and methacrylic acid of equal quality were added, the total monomer concentration was 30%, N,N-methylenebispropylene The amount of amide is 0.01%. Use argon to remove oxygen, and when the O2 content is less than 6 ppm, heat to 70° C. and react for 2 hours.
将接枝了亲水聚合物层的韧带织物从聚合反应器中取出，置入乙醇洗液中，超声波震荡洗涤15min，最后用去离子水冲洗，直至洗出水的pH回复至7。可重复此步骤多次。用甲苯胺蓝-吸光光度法测定接枝率。The ligament fabric grafted with the hydrophilic polymer layer was taken out of the polymerization reactor, placed in an ethanol washing solution, washed with ultrasonic vibration for 15 min, and finally washed with deionized water until the pH of the washing water returned to 7. This step can be repeated multiple times. Grafting ratio was measured by toluidine blue-absorptiometry.
将韧带织物的中间关节段浸入含纤维连接蛋白和I型胶原的混合物溶液中，超声震荡5min，取出。再将韧带织物的两端浸入含羟基磷灰石的溶液中，超声震荡10min。最后将韧带织物取出，置于真空烘箱中，干燥至含水率8％。The middle articular segment of the ligament fabric was immersed in a mixture solution containing fibronectin and type I collagen, ultrasonically oscillated for 5 min, and taken out. Then, both ends of the ligament fabric were immersed in a solution containing hydroxyapatite, and ultrasonically oscillated for 10 min. Finally, the ligament fabric was taken out, placed in a vacuum oven, and dried to a moisture content of 8%.
以上实例仅为进一步说明本发明的方法，不应受此限制。The above examples are only to further illustrate the method of the present invention, and should not be limited thereto.
| Application Number | Priority Date | Filing Date | Title |
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| CN201710565623.7ACN107376020B (en) | 2017-07-13 | 2017-07-13 | A kind of artificial ligament surface modification method |
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| CN201710565623.7ACN107376020B (en) | 2017-07-13 | 2017-07-13 | A kind of artificial ligament surface modification method |
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| CN201710565623.7AActiveCN107376020B (en) | 2017-07-13 | 2017-07-13 | A kind of artificial ligament surface modification method |
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