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The exploration of short peptide-based assembly is vital for understanding protein-misfolding-associated diseases and seeking strategies to attenuate aggregate formation. While, the molecular mechanism of their structural evolution remains poorly studied in view of the dynamic and unpredictable assembly process. Herein, infrared (IR) spectroscopy, which serves as an in situ and real-time analytical technique, was intelligently employed to investigate the mechanism of phase transition and aggregate formation during the dynamic assembly process of diphenylalanine. Combined with other spectroscopy and electron microscopy technologies, three stages of gel formation and the main driving forces in different stages were revealed. A variety of stoichiometric methods such as continuous wavelet transform, principal component analysis, and two-dimensional correlation spectroscopy techniques were conducted to analyze the original time-dependent IR spectra to obtain detailed information on the changes in the amide bands and hydration layer. The microenvironment of hydrogen bonding among amide bands was significantly changed with the addition of pyridine derivatives, resulting in great differences in the properties of co-assembled gels. This work not only provides a universal analytical way to reveal the dynamic assembly process of dipeptide-based supramolecular gel but also expands their applications in supramolecular regulation and high-throughput screens in situ.

The co-assembly of zwitterionic amphiphile and polyoxometalate is a new and promising technique to construct a hierarchical and multifunctional supramolecular hydrogel. To comprehensively investigate the assemble mechanism, zwitterionic amphiphiles with different cations, namely, 3-(1-hexadecyl-3-imidazolio) propanesulfonate (C 16 IPS) and 3-(1-hexadecyl-2-methyl-3-imidazolio) propanesulfonate (C 16 bIPS), were designed to complex with silicotungstic acid (HSiW). Hydrogen bonding between the oxygen atoms of HSiW and the protons on C-2 of the imidazolium rings and the steric effect significantly influence the morphology and rheological property of the hydrogel. Interestingly, cross-linked worm-like micelles in parallel, vertical, and tilted distribution were observed using cryogenic transmission electron microscopy. In addition, these aggregates were further stacked into hexagonal phases on a large scale. Hence, deep insights into the relationship among the structure of zwitterionic amphiphile, self-assembled architecture, and the mechanical property of a polyoxometalate-based hydrogel were disclosed.

Supramolecular thermotropic ionic liquid crystals (ILCs) with hexagonal and lamellar phases were fabricated by the self-assembly of zwitterionic ionic liquids, which were formed by 3-(1-alkyl-3-imidazolio) propanesulfonate with different alkyl chain lengths C n IPS ( n = 12, 14, 16) and 3,4,5-tris(dodecyloxy)benzoic acid (TDBA) based on intermolecular electrostatic interactions. The phase behaviors of ILCs were investigated by differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and polarized optical microscopy (POM). The highly ordered and well-defined microstructure of ILCs can be considered to be proton pathways and to radically improve the ionic conductivity, suggesting the induction of proton conduction through a hopping mechanism.

We herein report a smart amphiphilic supramolecular complex ([MimA-EDA-MimA]@[DBS] 2 ) with stimuli-responsive self-assembly, constructed by 3-(3-formyl-4-hydroxybenzyl)-1-methylimidazolium chloride (MimACl), sodium dodecyl benzene sulfonate (SDBS), and ethylenediamine (EDA). The self-assembly of [MimA-EDA-MimA]@[DBS] 2 shows triple-sensitivities in response to pH, concentration, and salt. At a low pH, only micelles are formed, which can transform into vesicles spontaneously when the pH increases to 11.8. Vesicles can gradually fuse into vesicle clusters and elongated assemblies with increasing concentration of [MimA-EDA-MimA]@[DBS] 2 . Chainlike aggregates, ringlike aggregates, or giant vesicles can be formed by adding inorganic salts (i.e., NaCl and NaNO 3 ), which could be derived from the membrane fusion of vesicles. The noncovalent interactions, including π-π stacking, hydrogen bonding, and electrostatic interactions, were found to be responsible for the topology evolution of assemblies. Thus, it provides an opportunity to construct smart materials through the regulation of the role of noncovalent interactions in self-assembly.

Supramolecular ionogels were prepared by self-assembly of small molecules through host-guest interaction between β-cyclodextrin (β-CD) and a room-temperature ionic liquid (IL) 3-(1-methyl-3-imidazolio)propanesulfonate-lithium bis(trifluoromethanesulfonyl)imide (MIPS-LiTFSI) which contains zwitterion MIPS. 19 F NMR and 2D ROESY 1 H NMR have been used to prove that only TFSI - is involved in the complexation. 1 H NMR, FT-IR, and comparative tests indicated that the electrostatic interaction between imidazole cation and TFSI - anion and intermolecular hydrogen bonding between three compounds also contribute to the formation of supramolecular ionogel. Ionogels with different gel-sol phase transition temperatures can be obtained by adjusting the molar ratio between β-CD and MIPS-LiTFSI. In addition, the supramolecular ionogels composed of "channel type" structural β-CD have been constructed. The ionogel with high conductivity and low activation energy open a door to new fields for special applications.

A novel photoresponsive surface active ionic liquid (SAIL) 1-(4-methyl azobenzene)-3-tetradecylimidazolium bromide ([C14mimAzo]Br) with azobenzene located in the headgroup was designed. Reversible vesicle formation and rupture can be finely controlled by photostimuli without any additives in the aqueous solution of the single-tailed ionic liquid. The photoisomerization of the azobenzene derivative was investigated by (1)H NMR and UV-vis spectroscopy. Density functional theory (DFT) calculations further demonstrate that trans-[C14mimAzo]Br has less negative interaction energy, which is beneficial to aggregate formation in water. The incorporation of trans-azobenzene group increases the hydrophobicity of the headgroup and reduces the electrostatic repulsion by delocalization of charge, which are beneficial to the formation of vesicles. However, the bend of cis-azobenzene makes the cis-isomers have no ability to accumulate tightly, which induces the rupture of vesicles. Our work paves a convenient way to achieve controlled topologies and self-assembly of single SAIL.