van Rijt Mark M J, Ciaffoni Adriano, Ianiro Alessandro, Moradi Mohammad-Amin, Boyle Aimee L, Kros Alexander, Friedrich Heiner, Sommerdijk Nico A J M, Patterson Joseph P
Laboratory of Materials and Interface Chemistry , Centre for Multiscale Electron Microscopy , Department of Chemical Engineering and Chemistry , Eindhoven University of Technology , P. O. Box 513 , 5600 MB Eindhoven , The Netherlands . Email:
Institute for Complex Molecular Systems , Eindhoven University of Technology , P. O. Box 513 , 5600 MB Eindhoven , The Netherlands.
Chem Sci. 2019 Aug 7;10(39):9001-9008. doi: 10.1039/c9sc00800d. eCollection 2019 Oct 21.
Natural materials, such as collagen, can assemble with multiple levels of organization in solution. Achieving a similar degree of control over morphology, stability and hierarchical organization with equilibrium synthetic materials remains elusive. For the assembly of peptidic materials the process is controlled by a complex interplay between hydrophobic interactions, electrostatics and secondary structure formation. Consequently, fine tuning the thermodynamics and kinetics of assembly remains extremely challenging. Here, we synthesized a set of block co polypeptides with varying hydrophobicity and ability to form secondary structure. From this set we select a sequence with balanced interactions that results in the formation of high-aspect ratio thermodynamically favored nanotubes, stable between pH 2 and 12 and up to 80 °C. This stability permits their hierarchical assembly into bundled nanotube fibers by directing the pH and inducing complementary zwitterionic charge behavior. This block co-polypeptide design strategy, using defined sequences, provides a straightforward approach to creating complex hierarchical peptide-based assemblies with tunable interactions.
天然材料，如胶原蛋白，在溶液中能够以多种组织层次进行组装。要通过平衡的合成材料实现对形态、稳定性和层次组织的类似程度的控制仍然难以捉摸。对于肽类材料的组装，该过程由疏水相互作用、静电作用和二级结构形成之间的复杂相互作用控制。因此，精确调节组装的热力学和动力学仍然极具挑战性。在这里，我们合成了一组具有不同疏水性和形成二级结构能力的嵌段共多肽。从这一组中，我们选择了一个具有平衡相互作用的序列，该序列导致形成高纵横比的热力学有利的纳米管，在pH 2至12和高达80°C的温度下稳定。这种稳定性允许通过调节pH值并诱导互补的两性离子电荷行为，将它们分层组装成束状纳米管纤维。这种使用确定序列的嵌段共多肽设计策略，提供了一种直接的方法来创建具有可调相互作用的复杂层次肽基组装体。
