Search

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 construction of pseudogemini surfactants based on noncovalent interactions (such as electrostatic interaction and π–π stacking) was a powerful method to assemble well-defined aggregates in aqueous solution. The mixtures of butane-1,4-bis(methylimidazolium bromide) ([mim-C4-mim]Br2) and positional isomers of sodium dodecyl benzene sulfonate (SDBS-0,11 or SDBS-3,8) in a molar ratio of 1:2 were studied to characterize the effect of straight and branched alkyl chains on the aggregation behavior of pseudogemini surfactants. Spontaneous phase transition from micelles to vesicles was formed by these two kinds of complexes. Interestingly, a densely stacked onion-like structure (multilamellar vesicles) with more than one dozen layers was fabricated. The micelle and vesicle phases were characterized in detail by cryogenic transmission electron microscopy, polarized optical microscopy, dynamic light scattering, and rheological measurements. It can be clearly demonstrated that the structure of alkyl chain can significantly influence the surface adsorption, solution self-assembly, and aqueous two-phase system of pseudogemini surfactants. Our work provided a convenient technique to achieve controlled self-assembly by introducing positional isomers of surfactants.

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 (C16IPS) and 3-(1-hexadecyl-2-methyl-3-imidazolio) propanesulfonate (C16bIPS), 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 CnIPS (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.

Polymer electrolytes are considered as the good candidates for the new-generation-safe lithium-ion battery. Herein, a free-standing and flexible polymer electrolyte film based on a lithium-containing zwitterionic poly(ionic liquid) (PIL) was constructed with and without propylene carbonate (PC) by in-situ photopolymerization. In this system, the lithium-containing IL synthesized by equimolecular neutralization of imidazolium-type zwitterion 3-(1-vinyl-3-imidazolio)propanesulfonate (VIPS) and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) can both serve as the polymeric matrix of the polymer electrolytes to maintain sufficient mechanical strength and form Li+-rich channels for lithium-ion transportation. The ion–dipole interaction between the lithium ion and the polar solvent PC can further improve the lithium-ion conduction, resulting in a comparable ionic conductivity of ∼10–3S/cm at 30 °C. Charge–discharge cycling performance of Li/LiFePO4half-cell equipped with the PIL-based polymer electrolyte indicates the possibility of practical application. Simultaneously, the lithium-containing zwitterionic PIL fabricated by this facile method provides a promising model system for understanding the molecular interactions in promoting the lithium-ion conduction.