Chinese Journal of Tissue Engineering Research ›› 2022, Vol. 26 ›› Issue (21): 3319-3326.doi: 10.12307/2022.638
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Liu Longzhu1, Long Yuanzhu2, Yang Chengxue1, Zhong Xinqi1, Wang Yifang1, Liu Jianguo1
Received:
2021-09-09
Accepted:
2021-10-28
Online:
2022-07-28
Published:
2022-01-27
Contact:
Liu Jianguo, Professor, Doctoral supervisor, School of Stomatology, Zunyi Medical University, Zunyi 563099, Guizhou Province, China
About author:
Liu Longzhu, Master candidate, Physician, School of Stomatology, Zunyi Medical University, Zunyi 563099, Guizhou Province, China
Supported by:
CLC Number:
Liu Longzhu, Long Yuanzhu, Yang Chengxue, Zhong Xinqi, Wang Yifang, Liu Jianguo. Preparation and characterization of the composites of amino-modified artificial jaw nano-hydroxyapatite/polylactic acid[J]. Chinese Journal of Tissue Engineering Research, 2022, 26(21): 3319-3326.
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图3中,相比于Fmoc-DGA,Fmoc-DGA-P引入了磷酸基团,活泼氢#的峰面积大幅度增加。此外,和磷酸基团邻近的a1、b1、c1峰相对于a、b、c峰的位置发生了明显变化,但各个峰的面积没有发生变化,这也说明Fmoc-DGA-P对比于Fmoc-DGA只是羟基变成了磷酸基团。Fmoc-DGA-P除Fmoc基团后得到的DGA-P,在大于7×10-6处没有了典型的二苯并五环的结构峰,说明成功制备出了DGA-P。 由于实验制备的DGA-HA和LA-HA都是固体,因此不能得到相应的核磁氢谱图谱。 接枝侧链GC-LA是甘油碳酸酯和DL-丙交酯反应而成,DL-丙交酯的结构是3,6-二甲基-1,4-二氧杂环己烷-2,5-二酮的对称环状结构,只分别在1.7×10-6和5.1×10-6的位置有2个峰。对于GC-LA曲线,见图3,q、p、o三个峰来源于甘油碳酸酯结构,而2.0×10-6以下的位置的k和m两个峰,与DL-丙交酯区别明显,这属于DL-丙交酯的环状结构开环后得到的与烷基相连的-CH3峰。DL-丙交酯开环后和甘油碳酸酯反应形成了酯基,而相连的n峰就显示在5.2×10-6的位置。DL-丙交酯开环和-OH相连的烷基则在4.4 ×10-6的位置,和q峰形成了重叠峰。GC-LA的化学式显示甘油碳酸酯上基团的氢原子数是确定的,可以计算出GC-LA中源于DL-丙交酯上基团的重复单元数。以p峰为基准峰,设置峰的面积为1,则k+m为11.98,而n为2.96,通过这些数据可以看出图中的GC-LA源于DL-丙交酯的重复单元数约为3。 因此,由图3可知,不仅成功合成每一步的产物,而且计算出了GC-LA侧链的具体重复单元。 除了进行核磁氢谱测试,还对制备侧链改性HA过程中各物质进行了傅里叶红外光谱测试。图4中,Fmoc-DGA的曲线在1 694 cm-1出现C=O基团的伸缩振动峰,1 539 cm-1处出现氨基甲酸酯基团中氨基的振动峰,这2个特征峰说明芴甲氧羰酰氯与二甘醇胺的氨基反应并生成氨基甲酸酯基团。此外,Fmoc-DGA在3 324 cm-1处为-OH基团的峰,3 063 cm-1处则是苯环上的碳氢键伸缩振动形成的峰,2 882,2 940 cm-1处为亚甲基形成的峰。这些特征峰都说明成功制备出Fmoc-DGA。"
相对于Fmoc-DGA,Fmoc-DGA-P在3 422 cm-1处出现了磷酸根上氢的振动峰,在1 052 cm-1处出现P-O键形成的强峰,这都说明Fmoc-DGA-P制备成功。DGA-P相对于Fmoc-DGA-P在傅里叶红外光谱曲线上没有芳环的烷基峰和氨基甲酸酯基团上的C=O特征峰,表示DGA-P上已经没有了Fmoc基团。此外,DGA-P在1 000-1 132 cm-1范围内的磷酸基团仍然存在,说明DGA-P的成功制备。 DGA-HA是以DGA-P作为原料之一制备得到的。图4中代表HA的特征基团,包含3 431 cm-1处-OH的峰和1 034 cm-1处-PO3的峰相对于DGA-P得到了明显增强,而2 928 cm-1处亚甲基的峰说明DGA-P参与反应并得到DGA-HA。 图3和图4说明接枝侧链GC-LA和DGA-HA都已经制备成功。因此可以通过GC-LA的甲基二氧杂戊环酮结构和DGA-HA表面的氨基结构反应,得到GC-LA侧链改性的LA-HA。图4中LA-HA和DGA-HA红外光谱曲线十分类似,但是2 993和2 870 cm-1上甲基伸缩振动峰的强度明显增强,这是源于GC-LA侧链上的甲基基团的作用。而LA-HA在1 747 cm-1有一个很强的峰,这是源于GC-LA上的C=O基团。LA-HA含有源于GC-LA的特征峰,证实了GC-LA对DGA-HA进行接枝改性得到了LA-HA。 图5A中标记为(002)(211)(202)(310)(222)(213)(004)的7个峰都是HA在X射线衍射得出的晶体特征峰,因此LA-HA中属于HA的晶体结构没有改变。图3、4和图5A中的数据都可以说明成功制备出了LA-HA,而LA-HA中有机成分,即接枝侧链和氨基改性剂的含量可以通过图5B中的热失重测试获取。LA-HA在200 ℃之前几乎没有质量损失,而在200-400 ℃温度范围显示出有机物分解,挥发并失去质量;剩余的无机HA成分在600 ℃之内不会分解,从而可以知道失去的质量即为LA-HA中的有机成分,质量占比为LA-HA的3.75%。"
2.2.2 机械性能测试结果 对PLA-HA复合材料作为人工骨的机械性能进行表征,可以发现随着LA-HA含量的增加,材料的拉伸强度先增加再降低,见图8A。其中PLA-10%HA复合材料的拉伸强度最高,达到了75.6 MPa,比纯PLA材料的拉伸强度增加了36.3%;当LA-HA的含量达到30%时,复合材料的拉升强度相对于纯PLA材料不再增加,进一步增加LA-HA的含量,复合物的拉升强度甚至低于纯PLA材料。不同于拉升强度,随着LA-HA的增加,材料的弹性模量大幅增加。PLA-10%HA、PLA-30%HA和PLA-50%HA复合材料的弹性模量分别为1.87,2.33,2.85 GPa,分别比纯PLA材料提升了28.1%,59.3%,94.5%。图8B中PLA-HA复合材料的伸长率的变化趋势和图8A中的拉伸强度变化趋势类似,不同的是,PLA-10%HA的伸长率相对于纯PLA材料无统计学差异。 从图8可以看出,PLA-10%HA复合材料的拉伸强度和弹性模量相对于纯PLA材料有了明显提升,而且伸长率没有降低,提示PLA-10%HA复合材料作为人造颌骨的综合机械性能可能是最佳的。"
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