Understanding Pathway Complexity of Organic Micro/Nanofiber Growth in Hydrogen-Bonded Coassembly of Aromatic Amino Acids

Rational engineering of one-dimensional (1D) self-assembled aggregates to produce desired materials for versatile functions remains a challenge. In this work, we report the noncovalent modulation of 1D aggregates at the micro/nanoscale using a coassembly protocol. Aromatic amino acids were employed as the model building blocks, and melamine (Mm) behaves as a modulator to form coassembly arrays with aromatic amino acids selectively. The selective self-assembly behavior between aromatic amino acids and Mm allows distinguishing and detecting Mm and aromatic amino acids from their analogues in macroscopic and microscopic scales. Dimensions and sizes of fibrous aggregates prepared from different amino acids show two opposite pathways from pristine assemblies to coassemblies induced by the addition of Mm. This pathway complexity could be controlled by the molecular conformation determined by α-positioned substituents. The developed hypothesis presents an excellent expansibility to other substrates, which may guide us to rationally design and screen 1D materials with different dimensions and sizes including the production of high-quality self-standing hydrogels.