Spider silk-inspired peptide multiblock hybrid copolymers for self-healable thin film materials
Spider silk-inspired peptide multiblock hybrid copolymers for self-healable thin film materials
复制标题
DOI：
10.1039/d1ma00823d
复制
发表时间：
2021-10-28
影响因子：
5
通讯作者：
Higashi, Nobuyuki
中科院分区：
文献类型：
--
作者：
Koga, Tomoyuki;Morishita, Tomotaka;Higashi, Nobuyuki
天然生物高分子因其优化合理的分子结构而具有智能功能和优异的物理性能。在纳米尺度上理解和模仿这种结构原理为设计新型功能聚合物材料提供了有希望的机会。在此，我们报告了独特的纳米/微米膜材料制作蜘蛛丝启发肽多嵌段混合共聚物。多嵌段共聚物由自组装寡肽（Ala、Gly、瓦尔和基于Leu的肽）和非结晶柔性聚丙二醇组成。自支撑微膜是通过β-折叠网络形成的聚合物溶液通过流延容易地获得的，并且其结构和机械性能被全面地表征。所得的蜘蛛丝样特异性纳米结构包括平衡的结晶和非结晶区域;此外，它表现出基于多个氢键的肽块之间的可逆相互作用。这使得薄膜具有机械韧性和自修复特性。此外，这样的膜特性，包括愈合效率，可以通过操纵肽嵌段的序列和长度来调节。此外，这些混合多嵌段共聚物用于制备独立的和超柔性的纳米膜，其表现出基于膜厚度的纳米级粗糙度的优异的跟随性，并用作具有离子阻挡功能的纳米涂层。本文提出的仿生方法是开发高性能聚合物膜的一种简便有效的方法，并且在工业、纳米技术和生物医学材料领域等各个领域都很有前途。
Natural biopolymers exhibit smart functions and extraordinary physical properties because of their optimized and rational molecular structures. Understanding and mimicking such architectural principles on a nanoscale offer promising opportunities for designing novel functional polymer materials. Herein, we report unique nano/microfilm materials fabricated using spider silk-inspired peptide multiblock hybrid copolymers. The multiblock copolymers are composed of self-assembling oligopeptides (Ala, Gly, Val, and Leu-based peptides) and non-crystalline flexible polypropylene glycol. Self-supporting microfilms are easily obtained by casting from polymer solutions via beta-sheet network formation, and their structural and mechanical properties are characterized comprehensively. The resulting spider silk-like specific nanostructure comprises balanced crystalline and non-crystalline regions; additionally, it exhibits reversible interactions among peptide blocks based on multiple hydrogen bonds. This enables mechanical toughness and self-healing characteristics in the thin films. Moreover, such film characteristics, including healing efficiency, can be modulated by manipulating the sequence and length of the peptide blocks. Additionally, these hybrid multiblock copolymers are used to prepare free-standing and ultraflexible nanofilms, which demonstrate excellent followability to nanoscale roughness based on film thickness and serve as a nano-coating with ion barrier function. The biomimetic approach presented herein is a facile and effective method for the development of high-performance polymer films and is promising in various fields, such as industrial, nanotechnological, and biomedical material fields.