化工学报 ›› 2020, Vol. 71 ›› Issue (1): 388-396.DOI: 10.11949/0438-1157.20191317
李莹莹1,2(),邓谦谦1,2,刘浩1,2,刘其春1,2,顾正桂2,王昉1()
收稿日期:
2019-11-04
修回日期:
2019-11-18
出版日期:
2020-01-05
发布日期:
2020-01-05
通讯作者:
王昉
作者简介:
李莹莹(1994—),女,硕士研究生,基金资助:
Yingying LI1,2(),Qianqian DENG1,2,Hao LIU1,2,Qichun LIU1,2,Zhenggui GU2,Fang WANG1()
Received:
2019-11-04
Revised:
2019-11-18
Online:
2020-01-05
Published:
2020-01-05
Contact:
Fang WANG
摘要:
基于丝素的高分子复合材料可以广泛地应用于组织工程、生物医药和半导体材料等领域。通过物理-共混技术制备了一种新型生物高分子丝素/聚乳酸复合膜。利用扫描电镜、傅里叶红外光谱、拉曼光谱、X射线衍射和热分析技术对其形貌、结构和相态组分以及热稳定性进行了表征,探究了不同比例复合膜的微结构、相互作用机理和热稳定性。结果表明:随着丝素含量的增加,复合膜中的β-折叠含量增多,α-螺旋和无规卷曲含量减少,玻璃化转变温度提高;由于丝素与聚乳酸间的相互作用,提高了复合膜的热稳定性。
中图分类号:
李莹莹, 邓谦谦, 刘浩, 刘其春, 顾正桂, 王昉. 新型丝素复合膜的微结构表征及热稳定性[J]. 化工学报, 2020, 71(1): 388-396.
Yingying LI, Qianqian DENG, Hao LIU, Qichun LIU, Zhenggui GU, Fang WANG. Microstructure characterization and thermal stability of new silk fibroin composite films[J]. CIESC Journal, 2020, 71(1): 388-396.
图1 不同质量比例制备的MSF/PLA复合膜的电镜图(上层图a~e分别表示丝素蛋白/聚乳酸混合溶液,MSF/PLA-0∶5,MSF/PLA-1∶5,MSF/PLA-5∶5, MSF/PLA-5∶1和MSF/PLA-5∶0;下层图a'~e'分别是对应比例丝素聚乳酸复合膜电镜图)
Fig.1 SEM of MSF/PLA composite film prepared with different mass ratios(The upper layer a—e are silk fibroin/polylactic acid mixed solution, MSF/PLA-0∶5, MSF/PLA-1∶5, MSF/PLA-5∶5, MSF/PLA-5∶1 and MSF/PLA-5∶0, respectively; The lower layer a'—e' are SEM images corresponding to the ratio of the silk fibroin and polylactic acid composite films, respectively)
Sample | β-sheet/% | α-helix & random coils /% | Turns/% | Side chains/% |
---|---|---|---|---|
MSF/PLA-1∶5 | 12.23 | 73.89 | 12.56 | 1.32 |
MSF/PLA-5∶5 | 15.54 | 71.03 | 10.79 | 2.64 |
MSF/PLA-5∶1 | 18.24 | 68.99 | 9.56 | 3.21 |
MSF/PLA-5∶0 | 23.29 | 66.80 | 8.55 | 1.36 |
表1 复合材料中桑蚕丝素蛋白各组分含量
Table 1 Contents of silk fibroin protein in composite materials
Sample | β-sheet/% | α-helix & random coils /% | Turns/% | Side chains/% |
---|---|---|---|---|
MSF/PLA-1∶5 | 12.23 | 73.89 | 12.56 | 1.32 |
MSF/PLA-5∶5 | 15.54 | 71.03 | 10.79 | 2.64 |
MSF/PLA-5∶1 | 18.24 | 68.99 | 9.56 | 3.21 |
MSF/PLA-5∶0 | 23.29 | 66.80 | 8.55 | 1.36 |
Item | MSF/PLA-0∶5 | MSF/PLA-1∶5 | MSF/PLA-5∶5 | MSF/PLA-5∶1 | MSF/PLA-5∶0 |
---|---|---|---|---|---|
Tg/℃ | 55.81 | 58.68 | 65.02 | 74.33 | 154.32 |
Tm /℃ | 150.29 | 150.01 | 147.11 | 144.98 | — |
ΔHm/(J·g-1) | 30.23 | 25.37 | 18.68 | 14.57 | — |
ΔCp/(J·g-1·℃-1) | 0.39 | 0.40 | 0.43 | 0.46 | — |
XC-DSC | 0.33 | 0.27 | 0.19 | 0.11 | — |
XMAP-DSC | 0.63 | 0.66 | 0.70 | 0.75 | — |
XRAP-DSC | 0.04 | 0.07 | 0.11 | 0.14 | — |
XC-XRD | 0.35 | 0.30 | 0.21 | 0.12 | — |
XMAP-XRD | 0.59 | 0.63 | 0.69 | 0.74 | — |
XRAP-XRD | 0.06 | 0.07 | 0.10 | 0.14 | — |
Tonset /℃ | 346.27 | 330.19 | 305.38 | 283.37 | 272.76 |
Tp/℃ | 350.69 | 336.95 | 316.06 | 289.62 | 280.27 |
ΔYw /% | 0.42 | 1.73 | 4.80 | 6.07 | 6.99 |
表2 复合膜的热力学参数、相态的相对含量以及TG数据
Table 2 Thermodynamic parameters, phase component content and TG data of composite film
Item | MSF/PLA-0∶5 | MSF/PLA-1∶5 | MSF/PLA-5∶5 | MSF/PLA-5∶1 | MSF/PLA-5∶0 |
---|---|---|---|---|---|
Tg/℃ | 55.81 | 58.68 | 65.02 | 74.33 | 154.32 |
Tm /℃ | 150.29 | 150.01 | 147.11 | 144.98 | — |
ΔHm/(J·g-1) | 30.23 | 25.37 | 18.68 | 14.57 | — |
ΔCp/(J·g-1·℃-1) | 0.39 | 0.40 | 0.43 | 0.46 | — |
XC-DSC | 0.33 | 0.27 | 0.19 | 0.11 | — |
XMAP-DSC | 0.63 | 0.66 | 0.70 | 0.75 | — |
XRAP-DSC | 0.04 | 0.07 | 0.11 | 0.14 | — |
XC-XRD | 0.35 | 0.30 | 0.21 | 0.12 | — |
XMAP-XRD | 0.59 | 0.63 | 0.69 | 0.74 | — |
XRAP-XRD | 0.06 | 0.07 | 0.10 | 0.14 | — |
Tonset /℃ | 346.27 | 330.19 | 305.38 | 283.37 | 272.76 |
Tp/℃ | 350.69 | 336.95 | 316.06 | 289.62 | 280.27 |
ΔYw /% | 0.42 | 1.73 | 4.80 | 6.07 | 6.99 |
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