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Nucleation and Growth of Amino Acid and Peptide Supramolecular Polymers through Liquid–Liquid Phase Separation
Author(s) -
Yuan Chengqian,
Levin Aviad,
Chen Wei,
Xing Ruirui,
Zou Qianli,
Herling Therese W.,
Challa Pavan Kumar,
Knowles Tuomas P. J.,
Yan Xuehai
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201911782
Subject(s) - nucleation , supramolecular chemistry , metastability , phase transition , chemical physics , chemistry , phase (matter) , amphiphile , materials science , chemical engineering , polymer , nanotechnology , thermodynamics , molecule , organic chemistry , physics , engineering , copolymer
The transition of peptides and proteins from the solution phase into fibrillar structures is a general phenomenon encountered in functional and aberrant biology and is increasingly exploited in soft materials science. However, the fundamental molecular events underpinning the early stages of their assembly and subsequent growth have remained challenging to elucidate. Here, we show that liquid–liquid phase separation into solute‐rich and solute‐poor phases is a fundamental step leading to the nucleation of supramolecular nanofibrils from molecular building blocks, including peptides and even amphiphilic amino acids. The solute‐rich liquid droplets act as nucleation sites, allowing the formation of thermodynamically favorable nanofibrils following Ostwald's step rule. The transition from solution to liquid droplets is entropy driven while the transition from liquid droplets to nanofibrils is mediated by enthalpic interactions and characterized by structural reorganization. These findings shed light on how the nucleation barrier toward the formation of solid phases can be lowered through a kinetic mechanism which proceeds through a metastable liquid phase.