Spatiotemporal-Dependent Confinement Effect of Bubble Swarms Enables a Fractal Hierarchical Assembly with Promoted Chirality.

The submarine-confined bubble swarm is considered an important constraining environment for the early evolution of living matter due to the abundant gas/water interfaces it provides. Similarly, the spatiotemporal characteristics of the confinement effect in this particular scenario may also impact the origin, transfer, and amplification of chirality in organisms. Here, we explore the confinement effect on the chiral hierarchical assembly of the amphiphiles in the confined bubble array stabilized by the micropillar templates. Compared with the other confinement conditions, the assembly in the bubble scenario yields a fractal morphology and exhibits a unique level of the chiral degree, ordering, and orientation consistency, which can be attributed to the characteristic interfacial effects of the rapidly formed gas/water interfaces. Thus, molecules with a balanced amphiphilicity can be more favorable for the promotion. Not limited to the pure enantiomers, chiral amplification of the enantiomer-mixed assembly is observed only in the bubble scenario. Beyond the interfacial mechanism, the fast formation kinetics of the confined liquid bridges in the bubble scenario endows the assembly with the tunable hierarchical morphology when regulating the amphiphilicity, aggregates, and confined spaces. Furthermore, the chiral-induced spin selectivity (CISS) effect of the fractal hierarchical assembly was systematically investigated, and a strategy based on photoisomerization was developed to efficiently modulate the CISS effect. This work provides insights into the robustness of confined bubble swarms in promoting a chiral hierarchical assembly and the potential applications of the resulting chiral hierarchical patterns in solid-state spintronic and optical devices.

Aggregate-state-dependent photochromism and circularly polarized luminescence of a chiral biquinoline amphiphile.

The photophysical and chiroptical properties of a chiral biquinoline amphiphile were found to be closely related to its aggregate states. Photochromism through photo-induced radical and circularly polarized luminescence were realized in its gel state and thin film state, respectively.

Photoisomerization and thermal reconstruction induced supramolecular chirality inversion in nanofiber determined by minority isomer.

Here, amphiphile GCH based on glutamide-cyanostilbene is designed and synthesized, it is found that it can assembly in acetonitrile, and shows circular dichroism signals. After Z-E isomerizaition by UV irradiation, the CD signal of the assembly can be inverted. Unexpectedly, after another heating and cooling process, the circular dichroism signals can be totally inverted even though the E-isomers are in minority. Finally, the molecular dynamics (MD) simulations deeply elucidate the supramolecuar chirality inversion mechanism. This work brings some new insights into the control of chirality inversion, which may provide a perspective for the smart chiroptical materials construction.

Substituent alkyl-chain-dependent supramolecular chirality, tunable chiroptical property, and dye adsorption in azobenzene-glutamide-amphiphile based hydrogel.

Controlling the supramolecular chirality of a self-assembly system by molecular structure design and external stimuli in aqueous solution is significant but challenging. Here, we design and synthesize several glutamide-azobenzene-based amphiphiles with different length alkyl chains. The amphiphiles can form self-assemblies in aqueous solution and show CD signals. As the number of the alkyl chain of amphiphiles increases, the CD signals of the assemblies can be enhanced. However, the long alkyl chains conversely restrict the isomerization of the azobenzene and the corresponding chiroptical property. Moreover, the alkyl length can determine the nanostructure of the assemblies and exert critical influence on the dye adsorption efficiency. This work exhibits some insights into the tunable chiroptical property of the self-assembly by delicate molecular design and external stimuli, and emphasizes the molecular structure can determine the corresponding application.

Stoichiometric Ratio Controlled Dimension Transition and Supramolecular Chirality Enhancement in a Two-Component Assembly System.

To control the dimension of the supramolecular system was of great significance. We construct a two component self-assembly system, in which the gelator LHC18 and achiral azobenzene carboxylic acid could co-assembly and form gels. By modulating the stoichiometric ratio of the two components, not only the morphology could be transformed from 1D nanaotube to 0D nanospheres but also the supramolecualr chirality could be tuned. This work could provide some insights to the control of dimension and the supramolecular chirality in the two-component systems by simply modulating the stoichiometric ratio.

Solvent-regulated chiral exciton coupling and CPL sign inversion of an amphiphilic glutamide-cyanostilbene.

The chiral exciton couplings within a Y-shaped amphiphilic glutamide-cyanostilbene (GCS) could be significantly biased by solvent polarity and hydration effects, which led to sign inversion of both the circular dichroism and circularly polarized luminescence of the GCS assemblies.

Self-assembled Möbius strips with controlled helicity.

Different from molecular level topology, the development of supramolecular topology has been limited due to a lack of reliable synthetic methods. Here we describe a supramolecular strategy of accessing Möbius strip, a fascinating topological object featured with only a single edge and single side. Through bending and cyclization of twisted nanofibers self-assembled from chiral glutamate amphiphiles, supramolecular nano-toroids with various twist numbers were obtained. Electron microscopic techniques could clearly identify the formation of Möbius strips when twist numbers on the toroidal fibers are odd ones. Spectroscopic and morphological analysis indicates that the helicity of the Möbius strips and nano-toroids stems from the molecular chirality of glutamate molecules. Therefore, M- and P-helical Möbius strips could be formed from L- and D-amphiphiles, respectively. Our experimental results and theoretical simulations may advance the prospect of creating chiral topologically complex structures via supramolecular approach.

Histidine Proton Shuttle-Initiated Switchable Inversion of Circularly Polarized Luminescence.

Switchable inversion of the sign of circularly polarized luminescence (CPL) in chiral supramolecular systems has gained remarkable interest because of its role in understanding the chirality-switching phenomena in biological systems and developing smart chiral luminescent materials. Herein, inspired by the histidine proton shuttle in natural enzymes, we synthesized a histidine π-gel (PyC3H) and realized reversible inversion of supramolecular chirality and CPL by receiving and then transferring a proton. It was found that in the course of histidine protonation by adding an external proton source, the transcription of intrinsic molecular chirality of PyC3H to the supramolecular level biased, achieving dynamic control over the PyC3H gel with left-handed CPL inversed into the right-handed one. The mechanism study revealed that the supramolecular chirality and CPL inversion are mainly affected by the cooperation adjustment of hydrogen bonds and π-π stacking upon histidine protonation and deprotonation, which causes the re-orientations of pyrene chromophores. This work sets up an alternative effective method to fabricate tunable CPL-active materials while using the same chiral small molecules, which provides a new insight into developing bio-inspired switchable supramolecular materials.

Dimension-Tunable Circularly Polarized Luminescent Nanoassemblies with Emerging Selective Chirality and Energy Transfer.

The selective interplay between dimensional morphology transition and signal transfer is an important feature for both nanomaterials and biosystems. While most of those reported examples considered either dimensional transition or signal transfer, the integrated interplay or selectivity for these two aspects in single self-assembled system has been rarely studied. Here, we report that a positively charged chiral π-building block could self-assemble into multidimensional nanostructures, which showed tunable circularly polarized luminescence (CPL). Impressively, when these CPL-active multidimensional structures interacted with two achiral dyes (positively charged ThT and negatively charged CNA), 3D nanocubes and 0D nanospheres showed neither chirality transfer nor energy transfer, while 2D nanoplates could successfully trigger a selective chirality or energy transfer depending on the charge type of acceptor dyes, which then emitted an enhanced CPL signal. This work demonstrated rational design of charged π-building block for the construction of dimension controllable and selective signal transfer self-assembly system, which might deepen the understanding the interplay of dimensional structures and signal transfer functions in natural and nano systems.

Host-guest interaction enabled chiroptical photo-switching and enhanced circularly polarized luminescence.

A cyanostilbene conjugated gelator was incorporated into the cavities of cyclodextrins via the host-guest interaction and the resulting supra-gelator from γ-CyD enabled chiroptical photo-switching, while the other gels showed enhanced circularly polarized luminescences.