Kecheng Jie

Nanoparticles with Near-Infrared Emission Enhanced by Pillararene-Based Molecular Recognition in Water

Here we report the unprecedented preparation of nanoparticles with near-infrared (NIR) emission enhanced by host-guest complexation between a water-soluble pillar[5]arene (WP5) and a cyanostilbene derivative (1) in water. Amphiphilic 1 self-assembles in water to form nanoribbons with relatively weak NIR emission at low concentrations. However, after addition of equimolar WP5, these nanoribbons transform into nanoparticles with stronger NIR emission due to the formation of a supramolecular amphiphile and host-guest complexation-enhanced aggregation. These nanoparticles show pH responsiveness, and collapse after treatment with acid. More importantly, these nanoparticles can be used in living cell imaging.

CO₂-Responsive Pillar[5]arene-Based Molecular Recognition in Water: Establishment and Application in Gas-Controlled Self-Assembly and Release.

Here we developed a novel CO2-responsive pillararene-based molecular recognition motif established from a water-soluble pillar[5]arene and an anionic surfactant, sodium dodecyl sulfonate (SDS). The inclusion complex acted as a supramolecular amphiphile and self-assembled into spherical bilayer vesicles as confirmed by DLS, SEM, and TEM experiments. These vesicles were disrupted upon bubbling N2 or adding much more SDS to eliminate the inclusion complex. The assembly and disassembly of vesicles were successfully employed in gas and surfactant triggered releases of calcein, a water-soluble dye.

Supramolecular Construction of Multifluorescent Gels: Interfacial Assembly of Discrete Fluorescent Gels through Multiple Hydrogen Bonding.

Multifluorescent supramolecular gels with complex structures are constructed from discrete fluorescent gels, which serve as the building blocks, through hydrogen bonding interactions at interfaces. The multifluorescent gel can realize rapid healing within only ≈100 s.

Styrene Purification by Guest-Induced Restructuring of Pillar[6]arene

The separation of styrene (St) and ethylbenzene (EB) mixtures is important in the chemical industry. Here, we explore the St and EB adsorption selectivity of two pillar-shaped macrocyclic pillar[n]arenes (EtP5 and EtP6; n = 5 and 6). Both crystalline and amorphous EtP6 can capture St from a St-EB mixture with remarkably high selectivity. We show that EtP6 can be used to separate St from a 50:50 v/v St:EB mixture, yielding in a single adsorption cycle St with a purity of >99%. Single-crystal structures, powder X-ray diffraction patterns, and molecular simulations all suggest that this selectivity is due to a guest-induced structural change in EtP6 rather than a simple cavity/pore size effect. This restructuring means that the material “self-heals” upon each recrystallization, and St separation can be carried out over multiple cycles with no loss of performance.

A CO2-responsive pillar[5]arene: synthesis and self-assembly in water

The aggregate morphology of a CO2-responsive pillar[5]arene was reversibly controlled between toroid-like assemblies and irregular aggregates by bubbling CO2 and N2 repeatedly.

Reversible Iodine Capture by Nonporous Pillar[6]arene Crystals

Here we report that easily obtained per-ethylated pillar[6]arene (EtP6) is a new adsorbent for iodine capture with high chemical and thermal stability. Nonporous EtP6 solids are shown to capture not only volatile iodine in the air but also iodine dissolved in an organic solvent and aqueous solution. Uptake of iodine leads to a structural transformation of EtP6 in the solid state. In the single crystal structure of iodine-doped EtP6 (I2@EtP6), each adsorbed iodine molecule is located between two adjacent EtP6 molecules to form a linear supramolecular polymer. Iodine is released spontaneously from I2@EtP6 solids when they are immersed in cyclohexane. These EtP6 solids can be reused many times without losing iodine capture capacity.

A Water-Soluble Cyclotriveratrylene-Based Supra-amphiphile: Synthesis, pH-Responsive Self-Assembly in Water, and Its Application in Controlled Drug Release

A new water-soluble cyclotriveratrylene (WCTV) was designed and synthesized, and benzyldimethyldodecylammonium chloride (G) was chosen as the guest molecule to construct a supra-amphiphile by the host-guest interaction between WCTV and G in water, which is pH responsive. The supra-amphiphiles self-assembled into vesicles in water. When the pH of the solution was below 7.0, the supra-amphiphile disassociated, and the vesicles collapsed. Then, the pH-responsive self-assembly system was utilized for controlled drug release.

Linear Positional Isomer Sorting in Nonporous Adaptive Crystals of a Pillar[5]arene

Here we show a new adsorptive separation approach using nonporous adaptive crystals of a pillar[5]arene. Desolvated perethylated pillar[5]arene crystals (EtP5α) with a nonporous character selectively adsorb 1-pentene (1-Pe) over its positional isomer 2-pentene (2-Pe), leading to a structural change from EtP5α to 1-Pe loaded structure (1-Pe@EtP5). The purity of 1-Pe reaches 98.7% in just one cycle and EtP5α can be reused without losing separation performance.

Near-Ideal Xylene Selectivity in Adaptive Molecular Pillar[n]arene Crystals

The energy-efficient separation of alkylaromatic compounds is a major industrial sustainability challenge. The use of selectively porous extended frameworks, such as zeolites or metal–organic frameworks, is one solution to this problem. Here, we studied a flexible molecular material, perethylated pillar[n]arene crystals (n = 5, 6), which can be used to separate C8 alkylaromatic compounds. Pillar[6]arene is shown to separate para-xylene from its structural isomers, meta-xylene and ortho-xylene, with 90% specificity in the solid state. Selectivity is an intrinsic property of the pillar[6]arene host, with the flexible pillar[6]arene cavities adapting during adsorption thus enabling preferential adsorption of para-xylene in the solid state. The flexibility of pillar[6]arene as a solid sorbent is rationalized using molecular conformer searches and crystal structure prediction (CSP) combined with comprehensive characterization by X-ray diffraction and 13C solid-state NMR spectroscopy. The CSP study, which takes into account the structural variability of pillar[6]arene, breaks new ground in its own right and showcases the feasibility of applying CSP methods to understand and ultimately to predict the behavior of soft, adaptive molecular crystals.

A redox-responsive supramolecular amphiphile fabricated by selenium-containing pillar[5]arene-based host–guest recognition

A novel molecular recognition motif was built between a selenium-containing pillar[5]arene and a pyridinium bromide salt in water. Furthermore, a supramolecular amphiphile based on this new host–guest recognition motif with redox-responsiveness was fabricated and applied in the controlled release of small molecules.