Fluorescent chemosensors represent fast response to analytes with pronounced luminescent variations. They are promising as potential candidates in controlling luminescence and chiroptical activities of self-assembled chiral systems, which however have not been accomplished to date. We present a coassembled multiple component system that could respond to SO2 derivatives, giving rise to dynamic aggregation behaviors and switchable luminescence as well as circularly polarized luminescence (CPL). Cholesteryl-naphthalimide and coumarin derivatives coassemble into vesicles and nanohelices under the solvent strategy, behaving as energy transfer donor and accepter respectively. Energy transfer enables CPL transition from green to red depending on the molar fraction. After the addition of SO2 derivatives, hypochromic shifts occur to CPL due to the nucleophilic addition reaction to coumarin domain, hindering energy transfer and allow for the emergence of pristine luminescence. Here, we show a protocol to control over luminescence and chiroptical features of supramolecular chiral self-assemblies using fluorescent chemosensors.
Solvent is regarded as a factor in tuning the supramolecular chirality of self-assemblies. Deep eutectic solvents (DESs) show diverse properties in contrast to other common solvents, which are emerging in fabricating functional aggregates and nanoarchitectures. Nevertheless, the emergence and manipulation of supramolecular chirality in DES still remain mysterious. Exploring supramolecular chirality in DES would produce tunable chiroptical materials considering their feasible preparation process and abundant hydrogen bonding sites. In this work, we explored the occurrence and manipulation of supramolecular chirality in DES. Transfer from inherent chiral DES to solutes in either aggregated or monomeric building units is blocked. However, the chiral assembly of π-conjugated amino acids was realized. Compared to aqueous media, self-assembly in DES hinders the spontaneous structural and chirality evolution that benefit from efficient solvation, where the π-conjugated amino acids were involved as hydrogen bonding donors. DES performs as a dye-friendly matrix to afford chiroptical eutectogels with tunable circularly polarized luminescence, whereby a large dissymmetry g-factor of up to 0.015 was realized. DES behaves as feasible and flexible solvents to fabricate and stabilize functional soft chiral self-assemblies with controllable chiroptical properties.
Though phospholipids possess chiral centers, their chiral aggregation within bilayer cell membranes has seldom been referred and recognized. Insight into the chirality at higher levels in artificial molecular bilayer assemblies such as vesicles or liposomes is important to better understand biomembrane functions. In this work, we illustrate the fabrication of chiral vesicles with photoresponsive supramolecular chirality and structural transformation property. Cholesterol was conjugated to azobenzene via different spacers, of which molecular chirality underwent transfer to supramolecular level upon aggregation in water. The resultant building block self-assembled into unilamellar vesicles that could respond to light irradiation by showing reversible extension/contraction behavior. Such “breathing” behavior was accompanied with supramolecular chirality inversion from M- to P-handedness, confirmed by the solid-state crystal structure and electronic circular dichroism spectra based on density functional theory. The vesicle membrane behaves as a matrix to accommodate guest molecules via aromatic interactions, which significantly elevated the UV light resistance with respect to the structural and supramolecular chirality transformation. This work offers an unprecedented rational control over supramolecular chirality using photoresponsiveness in vesicular membranes.
Photoresponsive hydrogels with on/off luminescence show a promising application potential in writable information recording and display materials. However, it still remains a tremendous challenge to fabricate such hydrogels on account of the intrinsic fluorescence quenching effect and the lack of suitable responsive groups. Herein, we present fluorescent imprintable hydrogels constructed via organic/inorganic supramolecular coassembly. A photoisomeric cyanostilbene conjugated cationic surfactant exhibited an aggregation-induced emission behavior upon clay (laponite) complexation, along with excellent thixotropism brought by laponite. Macrocyclic cucurbituril[7] and β-cyclodextrin rings capable of forming host−guest complexes with the surfactant were utilized to give ternary hybrid hydrogels with luminescence and photoresponsive properties. On the account of trans−cis photoisomerization of the cyanostilbene unit, the fluorescence of the multicomponent hydrogels could undergo rapid quenching within a short irradiation period under UV light and be recovered when subjected to an annealing process. According to these properties, the imprinted fluorescent patterns using the hybrid hydrogels were erasable and rewritable. Thus, this research successfully integrates host−guest complexation and supramolecular coassembly into the fabrication of fluorescent imprintable hydrogels.
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