Abstract：
Morphology-transformational self-assembly of peptides allows for manipulation of the performance of nanostructures and thereby advancing the development of biomaterials. Acceleration of the morphological transformation process under a biological microenvironment is important to efficiently implement the tailored functions in living systems. Herein, we report redox-regulated in situ seed-induced assembly of peptides via design of two co-assembled bola-amphiphiles serving as a redox-resistant seed and a redox-responsive assembly monomer, respectively. Both of the peptides are able to independently assemble into nanoribbons, while the seed monomer exhibits stronger assembling propensity. The redox-responsive monomer undergoes morphological transformation from well-defined nanoribbons to nanoparticles. Kinetics studies validate the role of the assembled inert monomer as the seeds in accelerating the assembly of the redox-responsive monomer. Alternative addition of oxidants and reductants into the co-assembled monomers promotes the redox-regulated assembly of the peptides facilitated by the in situ-formed seeds. The reduction-induced assembly of the peptide could also be accelerated by in situ-formed seeds in cancer cells with a high level of reductants. Our findings demonstrate that through precisely manipulating the assembling propensity of co-assembled monomers, the in situ seed-induced assembly of peptides could be achieved. Combining the rapid assembly kinetics of the seed-induced assembly with the common presence of redox agents in a biological microenvironment, this strategy potentially offers a new method for developing biomedical materials in living systems.
摘要：
肽的形态转化自组装允许操纵纳米结构的性能,从而促进生物材料的发展。在生物微环境下加速形态转变过程对于有效实现生命系统中的定制功能很重要。在这里，我们报告了氧化还原调节的原位种子诱导的肽的组装，通过设计两种共组装的BALA-两亲物作为抗氧化还原种子和氧化还原响应组装单体，分别。这两种肽都能够独立组装成纳米带，而种子单体表现出更强的组装倾向。氧化还原响应性单体经历从明确定义的纳米带到纳米颗粒的形态转变。动力学研究验证了组装的惰性单体作为种子在加速氧化还原响应性单体的组装中的作用。将氧化剂和还原剂交替添加到共组装的单体中促进了由原位形成的种子促进的肽的氧化还原调节的组装。还可以通过在具有高水平还原剂的癌细胞中原位形成的种子来加速肽的还原诱导的组装。我们的发现表明，通过精确操纵共组装单体的组装倾向，可以实现原位种子诱导的肽组装。将种子诱导组装的快速组装动力学与生物微环境中常见的氧化还原剂相结合，这种策略可能为在生命系统中开发生物医学材料提供了一种新方法。
