CN110721348B - 一种天然蚕丝增强羟基磷灰石/壳聚糖复合膜及制备方法 - Google Patents
一种天然蚕丝增强羟基磷灰石/壳聚糖复合膜及制备方法 Download PDFInfo
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Abstract
本发明公开了一种天然蚕丝增强羟基磷灰石/壳聚糖复合膜及制备方法，采用溶液浇铸及纤维原位增强相结合的方法而得到的复合膜。该复合膜是指首先将纳米羟基磷灰石与壳聚糖制备成均匀复合液，然后将一半的纳米羟基磷灰石/壳聚糖复合溶液浇铸成膜，接着将天然蚕丝铺于其上，最后再将剩余的一半纳米羟基磷灰石/壳聚糖复合溶液浇铸于蚕丝上，自然干燥即得复合膜。该新型复合膜所用原料来源丰富，制备方法简单，且复合膜的力学性能、降解性能、骨传导性及抗菌性能可通过复合膜组分含量调控，有望获得性能优异的复合膜用于引导骨组织再生膜。
Description
技术领域
本发明涉及一种天然蚕丝增强羟基磷灰石/壳聚糖复合膜及制备方法，属于生物医用材料领域。
背景技术
壳聚糖的化学名称为(1-4)-2-氨基-2-脱氧- β-D-葡萄糖，它是甲壳素的脱乙酰化产物，是自然界中少见的一种带正电荷的碱性多糖。由于其降解产物为氨基葡萄糖，对人体及组织无毒、无害、无刺激、生物相容性好，对多种组织细胞的黏附和增殖具有促进作用，因而已广泛用于生物医用领域。尤其是壳聚糖基膜，在牙周病的治疗、牙种植区骨量不足、其它骨缺损的修复、骨折的愈合等方面的治疗中，将其置于缺损处作为一种机械屏障膜，它可以选择性地将周围软组织隔开，阻止上皮细胞和成纤维细胞向缺损处生长，同时能在膜下产生特殊的再生空间，从而使骨生成细胞优先生长，产生新骨组织，进而达到促进骨性愈合的目的。这种采用引导骨组织再生膜的治疗手段，目前是牙科、骨科领域的研究热点之一。
但单纯壳聚糖本身力学性能较差，尤其是低分子量的壳聚糖，力学性能较低，且体内降解较快。为进一步提高其性能，添加与自然骨无机成分类似的纳米羟基磷灰石，一方面可提高成骨活性，以提高其引导骨组织再生的能力，另一方面也可发挥其纳米粒子的增强增韧作用，以提高其力学性能。然而，由于纳米粒子的易团聚性，导致其力学性能增强并不明显。虽然添加一些如戊二醛等小分子进行化学交联可适当提高其力学性能及减缓其降解速度，但残存的戊二醛的毒性不利于其生物相容性。随着人们对天然纤维的研究，将天然麻类、竹纤维、蚕丝等是增强聚合物是一种有效途径。
天然蚕丝来源广泛，与其他天然纤维相比，蚕丝纤维是一种天然蛋白纤维，主要由丝素和丝胶两部分组成，里面为两根平行的丝素，外面包裹着丝胶，其他物质为蜡质、色素和无机物等。蚕丝纤维的蛋白质是由一条长链和一条短链构成的亚单位结构，长链主要由甘氨酸、丙氨酸和丝氨酸等组成，短链含有较多疏松残基的氨基酸。由于其具有良好的排列结构，因而蚕丝纤维强具有拉伸度好、细而柔软、富有弹性、光泽好、吸湿性好等优点，且有一定的抗菌性，被誉为“纤维皇后”。 在纤维复合材料领域有着广阔的应用前景。目前对于蚕丝生物复合材料的研究大部分是关于蚕丝蛋白的添加，通常需要将天然蚕丝经过脱胶、溶解、透析、过滤等多种繁琐步骤后，再用于与其他聚合物进行复合而增强，由于蚕丝经过溶解后，纤维的增强效果显著降低。因而有待于探索将天然蚕丝原位增强聚合物的研究，尤其是将天然蚕丝原位增强纳米羟基磷灰石/壳聚糖复合膜的研究更未见报道。
基于上述技术，针对壳聚糖力学性能较低及降解过快的问题，若将天然蚕丝织物直接作为骨架原位增强壳聚糖膜，则有望获得一种天然蚕丝增强的纳米羟基磷灰石/壳聚糖复合膜，即力学性能、降解性能更优越且生物相容性更好，且赋予一定抗菌性的复合膜用做引导骨组织再生膜。
发明内容
针对上述情况，本发明的目的在于提供一种能用做引导骨组织再生膜的性能更优异的新型组合物复合膜及其制备方法。
本发明的复合膜的组合物为天然蚕丝与纳米羟基磷灰石/壳聚糖复合物，采用溶液浇铸及纤维原位增强相结合而得到的复合膜。
本发明中天然蚕丝与纳米羟基磷灰石/壳聚糖复合膜的制备方法，其特征是指先将壳聚糖溶于2 %的冰醋酸保持浓度为2 %（m/v），再将纳米羟基磷灰石粉末（平均粒径为30nm）超声分散后加入壳聚糖溶液中，其中壳聚糖和纳米羟基磷灰石质量比为（6:4~9:1），室温下搅拌4小时，即得纳米羟基磷灰石/壳聚糖复合液，取上述复合液一半在玻璃平板上流延成膜，再将一定厚度的天然蚕丝覆盖在纳米羟基磷灰石/壳聚糖复合膜上，随后再将剩余的一半纳米羟基磷灰石/壳聚糖复合液浇铸于天然蚕丝上，自然风干后即得天然蚕丝为骨架的增强型纳米羟基磷灰石/壳聚糖复合膜。
本发明提供的用于引导骨组织再生膜组合物及其制备方法，具有以下优势：
（1）在膜的选材上，本发明的引导骨组织再生膜选用天然蚕丝、壳聚糖和纳米羟基磷灰石，其中的壳聚糖和天然蚕丝都是天然可降解高分子，具有较好的生物相容性；同时又具有可降解性，完成骨修复后在体内可自行降解；更重要的是天然蚕丝和壳聚糖都具有天然抗菌性，用于引导骨组织再生膜时还可持续缓慢发挥抗菌作用，防止伤口感染；另外纳米羟基磷灰石具有骨传导性，可加速骨生长。综上所述，本发明所选用的各种材料有利于提高复合膜的力学性能、降解性能及骨传导性，同时还可赋予其抗菌性，更适合用做引导骨组织再生膜。
（2）本发明的引导骨组织再生膜的组合物原料易得，复合膜制备方法采用溶液浇铸及纤维原位增强相结合的方法，其中的天然蚕丝直接以织物形式铺膜，与天然蚕丝以繁琐的溶液状态添加相比，本发明的天然蚕丝未经脱胶、溶解、透析、过滤等步骤，制备方法简单，实验条件温和，更重要的是可充分发挥天然纤维对聚合物的增强作用，且可通过复合膜组分含量的改变来调控复合膜的力学性能、降解性能、骨传导性及抗菌性能，以获得满足各种性能要求的膜材料，同时还可添加不同药物或其他生长因子得到性能更好的引导骨组织再生膜。
附图说明
图1为不同蚕丝与壳聚糖、n-HA复合膜的SEM照片。
具体实施方式
实施例1：将1.0 g壳聚糖溶于50 ml 2 %的冰醋酸，得淡黄色透明粘液，将0.2 g纳米羟基磷灰石粉末（平均粒径为25 nm）加去离子水10 ml超声分散20分钟后高速搅拌下逐滴加入上述壳聚糖溶液中，继续室温下搅拌4小时后，静置脱泡，取上述复合液一半在光滑干燥的玻璃平板上流延成膜，再在其上将1.0 g未脱胶蚕丝拉直铺开，再将上述复合液剩余的一半浇铸在蚕丝上，自然干燥后得光滑的致密膜。复合膜拉伸强度为33 MPa，断裂伸长率为20 %；该膜在模拟体液中浸泡24小时，经SEM观察其表面已被类骨磷灰石全部覆盖；浸泡持续至8周，膜拉伸强度为6 MPa，至12周，膜开始失去强度。
实施例2：将1.0 g壳聚糖溶于50 ml 2 %的冰醋酸，得淡黄色透明粘液，将0.1 g纳米羟基磷灰石粉末（平均粒径为25 nm）加去离子水20 ml超声分散25分钟后高速搅拌下逐滴加入上述壳聚糖溶液中，继续室温下搅拌4小时后，静置脱泡，取上述复合液一半在光滑干燥的玻璃平板上流延成膜，再在其上将1.5 g未脱胶蚕丝拉直铺开，再将上述复合液剩余的一半浇铸在蚕丝上，自然干燥后得光滑的致密膜。复合膜拉伸强度为36 MPa，断裂伸长率为27 %；该膜在模拟体液中浸泡24小时，经SEM观察其表面大部分被类骨磷灰石覆盖；浸泡持续至8周，膜拉伸强度为9 MPa，至12周，膜开始失去强度。
实施例3：将1.0 g壳聚糖溶于50 ml 2 %的冰醋酸，得淡黄色透明粘液，将0.2 g纳米羟基磷灰石粉末（平均粒径为25 nm）加去离子水10 ml超声分散25分钟后高速搅拌下逐滴加入上述壳聚糖溶液中，继续室温下搅拌4小时后，静置脱泡，取上述复合液一半在光滑干燥的玻璃平板上流延成膜，再在其上将0.5 g未脱胶蚕丝拉直铺开，再将上述复合液剩余的一半浇铸在蚕丝上，自然干燥后得光滑的致密膜。复合膜拉伸强度为29 MPa，断裂伸长率为24 %；该膜在模拟体液中浸泡24小时，经SEM观察其表面已被类骨磷灰石全部覆盖；浸泡持续至8周，膜拉伸强度为3 MPa，至12周，膜开始失去强度。
对比实施例1：将1.0 g壳聚糖溶于50 ml 2 %的冰醋酸，得淡黄色透明粘液，将0.2g纳米羟基磷灰石粉末（平均粒径为30 nm）加去离子水10 ml超声分散30分钟后高速搅拌下逐滴加入上述壳聚糖溶液中，继续室温下搅拌4小时后，将0.6 g脱胶的蚕丝用六氟异丙醇溶解后缓慢加入上述复合液中，继续室温下搅拌2小时后，静置脱泡在玻璃平板上流延成光滑的致密膜。复合膜拉伸强度为25 MPa，断裂伸长率为18%；该膜在模拟体液中浸泡12小时，经SEM观察其表面已被类骨磷灰石全部覆盖；浸泡持续至8周，膜开始失去强度。
对比实施例2：将1.0 g壳聚糖溶于50 ml 2 %的冰醋酸，得淡黄色透明粘液，将0.2g纳米羟基磷灰石粉末（平均粒径为25 nm）加去离子水10 ml超声分散20分钟后，高速搅拌下逐滴加入上述壳聚糖溶液中，继续室温下搅拌2小时。另取1.0 g天然蚕丝经脱胶、CaCl2-EtOH-H2O体系溶解、透析、离心过滤后，再用六氟异丙醇溶解，缓慢滴加于上述纳米羟基磷灰石/壳聚糖复合液中，继续搅拌2小时，静置脱泡后，在玻璃平板上流延成光滑的致密膜。复合膜拉伸强度为23 MPa，断裂伸长率为16 %；该膜在模拟体液中浸泡24小时，经SEM观察其表面已被类骨磷灰石全部覆盖；浸泡持续至6周，膜开始失去强度。
对比实施例3：将1.2 g壳聚糖溶于60 ml 2 %的冰醋酸，得淡黄色透明粘液，将0.3g纳米羟基磷灰石粉末（平均粒径为30 nm）加去离子水20 ml超声分散30分钟后高速搅拌下逐滴加入上述壳聚糖溶液中，继续室温下搅拌4小时后，静置脱泡后在玻璃平板上流延成光滑的致密膜。复合膜拉伸强度为22 MPa，断裂伸长率为15 %；该膜在模拟体液中浸泡12小时，经SEM观察其表面已被类骨磷灰石全部覆盖；浸泡持续至6周，膜开始失去强度。
Claims (1)
1.一种天然蚕丝增强羟基磷灰石/壳聚糖复合膜，其特征是指先将一半的纳米羟基磷灰石/壳聚糖复合液浇铸成膜，然后将未经脱胶且未溶解的天然蚕丝以织物形式铺于其上，再将剩余的一半纳米羟基磷灰石/壳聚糖复合液浇铸于天然蚕丝上，自然干燥即得复合膜；所述天然蚕丝质量占总复合膜的20~50%，羟基磷灰石占总复合膜的5~30%。
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