Tuning Supramolecular Structure and Functions of Peptide bola-Amphiphile by Solvent Evaporation–Dissolution

Abstract

Solvent molecules significantly affect the supramolecular self-assembly, for example, in forming solvent-bridged hydrogen bonding networks. Even small changes in solvent composition can have dramatic impact on supramolecular assembly. Herein, we demonstrate the use of trace solvents (as low as 0.04%) to tune the morphology and consequent functions of supramolecular nanostructures based on an aromatic peptide bola-amphiphile. Specifically, perylene bisimide-(di)glycine-tyrosine (PBI-[GY]) bola-amphiphile was shown to give rise to red-emitting nanofibers when assembled in water, while exposure to trace organic solvents such as tetrahydrofuran (THF) and others via solvent-evaporation followed by aqueous assembly gave rise to white-light-emitting nanospheres. Differential hydrogen bonding between water (donor and acceptor) and THF (acceptor only) impacts supramolecular organization, which was verified using a density functional theory (DFT) simulation. The tunable consequent surface hydrophobicity was utilized in staining the cytoplasm and membrane of cells, respectively. The trace-solvent effect achieved through evaporation-dissolution provides a methodology to mediate the morphologies and consequent functions for supramolecular biomaterials controlled by the self-assembly pathway.

Self-assembly of chiral supra-amphiphiles

“…Amphiphiles are one type of unique chemical compounds in colloidal science, which usually contain two main parts, a hydrophilic head and a lipophilic tail. [1][2][3][4][5][6][7][8][9][10][11] They show excellent self-assembly capability in aqueous solution to give varied structures like vesicles, micelles and tubules, [12][13][14][15][16][17][18] which not only provide satisfactory platforms for the mimicking of lipid bilayers in living organisms, [19][20][21] but also exhibit extraordinary applications in modern industry and humans' daily lives, such as the preparation of crude oil viscosity reducers 22 and the production of soaps and detergents. [23][24][25][26] On the other hand, the fast development of supramolecular chemistry, which is based on a variety of non-covalent interactions, [27][28][29][30][31] brings new opportunities for organic chemistry, materials chemistry and colloidal chemistry.…”

Role of Thermolysin in Catalytic-Controlled Self-Assembly of Fmoc-Dipeptides

“…Our current study provides a thorough understanding of the catalytic mechanism of thermolysin, in particular, a new methodology for bottom-up nanofabrication of future soft-gel materials, and has instructive significance on the regulation of peptide sequences, secondary structure, morphology, and mechanical property of self-assembled hydrogels with precise design and control in molecular level by thermolysin and functional applications of peptide materials. [49][50][51][52][53][54]…”

Self‐assembled chiral nanostructures of amphiphilic peptide: from single molecule to aggregate

“…The single molecular and aggregated level evidences in this work will shed light on the understanding of the hierarchical chiral self-assembly pathway and the underlying mechanism. In other aspect, self-assembled amphiphilic peptide nanostructures have been considered not only as pathological aggregates but also as advanced materials in material sciences [6][7][8]13,14,[23][24][25][26][27]34,[37][38][39][40][41][42][43], such as for biocatalyst [37][38][39][40][41][42][43], stabilizing diverse membrane as a fundamental component [15][16][17][18]. The final function of peptides depends on the self-assembled and properties of hierarchical structures, the mechanisms of peptide aggregation (the driving forces needed to understand) [44][45][46].…”