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Efficient incorporation of supramolecular hosts in polymeric membranes can impart the overall matrix with new properties for a range of cutting-edge applications. Here, we introduce a Supramolecular Interfacial Assembly (SIA) method for the fabrication of polymeric membranes featuring embedded macrocycles. Through harnessing the quasi-liquid nature of the concentrated polymer solution, SIA orchestrates the homogenous spreading of macrocycles in an aqueous layer on its surface, leading to the creation of an interface between "water/water" phases, subsequently forming a cross-linked membrane driven by supramolecular electrostatic interactions. Remarkably, compared to the traditional interfacial polymerization, SIA adheres to a "green" paradigm without the need for organic solvents. The resultant composite membrane exhibits superior performance in organic solvent nanofiltration (OSN), owing to the precise molecular sieving property provided by the macrocycles with well-defined permanent cavities. This fabrication method holds great promise for the innovative design of composite membranes, which can greatly impact the production of smart membrane materials for advanced technology applications in the future., (© 2024 Wiley‐VCH GmbH.)

The endoplasmic reticulum (ER) plays an important role in protein synthesis and its disruption can cause protein unfolding and misfolding. Accumulation of such proteins leads to ER stress, which ultimately promotes many diseases. Routine screening of ER activity in immune cells can flag serious conditions at early stages, but the current clinically used bio-probes have limitations. Herein, an ER-specific fluorophore based on a biocompatible benzothiadiazole-imine cage (BTD-cage) with excellent photophysical properties is developed. The cage outperforms commercially available ER stains in long-term live cell imaging with no fading or photobleaching over time. The cage is responsive to different levels of ER stress where its fluorescence increases accordingly. Incorporating the bio-probe into an immune disorder model, a 6-, 21-, and 48-fold increase in intensity is shown in THP-1, Raw 246.7, and Jurkat cells, respectively (within 15 min). These results strongly support that this system can be used for rapid visual and selective detection of ER stress. It is envisaged that tailoring molecular interactions and molecular recognition using supramolecular improved fluorophores can expand the library of biological probes for enhanced selectivity and targetability toward cellular organelles., (© 2024 The Author(s). Advanced Healthcare Materials published by Wiley‐VCH GmbH.)

The discovery of safe platforms that can circumvent the endocytic pathway is of great significance for biological therapeutics that are usually degraded during endocytosis. Here we show that a self-assembled and dynamic macrocycle can passively diffuse through the cell membrane and deliver a broad range of biologics, including proteins, CRISPR Cas9, and ssDNA, directly to the cytosol while retaining their bioactivity. Cell-penetrating macrocycle CPM can be easily prepared from the room temperature condensation of diketopyrrolopyrrole lactams with diamines. We attribute the high cellular permeability of CPM to its amphiphilic nature and chameleonic properties. It adopts conformations that partially bury polar groups and expose hydrophobic side chains, thus self-assembling into micellar-like structures. Its superior fluorescence makes CPM trackable inside cells where it follows the endomembrane system. CPM outperformed commercial reagents for biologics delivery and showed high RNA knockdown efficiency of CRISPR Cas9. We envisage that this macrocycle will be an ideal starting point to design and synthesize biomimetic macrocyclic tags that can readily facilitate the interaction and uptake of biomolecules and overcome endosomal digestion., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Porous molecular sorbents have excellent selectivity towards hydrocarbon separation with energy saving techniques. However, to realize commercialization, molecular sieving processes should be faster and more efficient compared to extended frameworks. In this work, we show that utilizing fluorine to improve the hydrophobic profile of leaning pillararenes affords a substantial kinetic selective adsorption of benzene over cyclohexane (20 : 1 for benzene). The crystal structure shows a porous macrocycle that acts as a perfect match for benzene in both the intrinsic and extrinsic cavities with strong interactions in the solid state. The fluorinated leaning pillararene surpasses all reported organic molecular sieves and is comparable to the extended metal-organic frameworks that were previously employed for this separation such as UIO-66. Most importantly, this sieving system outperformed the well-known zeolitic imidazolate frameworks under low pressure, which opens the door to new generations of molecular sieves that can compete with extended frameworks for more sustainable hydrocarbon separation., (© 2023 Wiley-VCH GmbH.)

The fabrication of smart materials, which can efficiently mimic biological systems through the introduction of soft components, is of great importance in the emerging fields of sensors and actuators. Herein, a smart composite film that can mechanically respond to vapors trigger then readily restores its original shape upon the removal of the stimuli is reported. This actuating composite film was prepared by mixing the highly elastic poly (vinylidene fluoride) (PVDF) polymer with the flexible and crystalline organic cages (Oba-cage) at variable concentrations. The mechanism of the mechanical response could be accurately recorded due to the ordered cage crystals. This work highlights the importance of designing smart materials at the molecular level to precisely control the response or reaction upon the introduction of different triggers, which can ultimately lead to a monumental leap in the field of soft robotics., (© 2022 Wiley-VCH GmbH.)

Developing the competence of molecular sorbents for energy-saving applications, such as C8 separations, requires efficient, stable, scalable, and easily recyclable materials that can readily transition to commercial implementation. Herein, we report an azobenzene-based cage for the selective separation of p-xylene isomer across a range of C8 isomers in both vapor and liquid states with selectivity that is higher than the reported all-organic sorbents. The crystal structure shows non-porous cages that are separated by p-xylene molecules through selective CH-π interactions between the azo bonds and the methyl hydrogen atoms of the xylene molecules. This cage is stable in solution and can be regenerated directly under vacuum to be used in multiple cycles. We envisage that this work will promote the investigation of the azo bond as well as guest-induced crystal-to-crystal phase transition in non-porous organic solids for energy-intensive separations., (© 2020 Wiley-VCH GmbH.)

Efficient and energy-saving separation of benzene isomers bearing a diverse range of functional groups is a great challenge due to their overlapping physicochemical properties. Here, we report the successfully use of a water-soluble pillar[5]arene (WP5) as a multifunctional material for the separation and detection of meta/ortho-substituted benzene isomers in water. A liquid-liquid extraction strategy was used for the separation of these benzene isomers based on their different affinity for WP5 in water. The selectivities for the meta over the ortho isomer for xylenes, chlorotoluene, and bromotoluene was 88.6 %, 88.3 %, and 95.0 % respectively, in one extraction cycle. Furthermore, a fluorescence indicator system based on WP5 and a fluorescent dye molecule (10-methylacridinium, D) was adopted and exhibited significant fluorescence and optical discrimination upon the addition of meta- compared to ortho-xylene, which implies that a simple "turn-on" detection can be performed prior to engaging in the separation process., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, we report the synthesis of a new class of functional silver nanoclusters (AgNCs) capped with pillar[5]arene (P5)-based host ligands. These NCs are readily prepared through direct synthesis or ligand exchange synthesis and are stable at room temperature for over 4 months. The pillar[5]arene-stabilized NCs (Ag 29 (LA-P5) 12 (TPP) 2 ) endorse reversible host-guest interactions with neutral alkylamines and cationic quaternary ammonium guests. This results in the formation of spherical assemblies with unparalleled changes in their optical properties including an astonishing circa 2000-fold luminescence enhancement. This is the highest luminescence enhancement ratio reported so far for such atomically precise NCs. Our synthetic protocol paves the way for the preparation of a new generation of metal nanoclusters protected by macrocyclic ligands with molecular recognition and selectivity toward specific guests., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Supramolecular self-assembly of histidine-capped-dialkoxy-anthracene (HDA) results in the formation of light-responsive nanostructures. Single-crystal X-ray diffraction analysis of HDA shows two types of hydrogen bonding. The first hydrogen bond is established between the imidazole moieties while the second involves the oxygen atom of one amide group and the hydrogen atom of a second amide group. When protonated in acidic aqueous media, HDA successfully complexes siRNA yielding spherical nanostructures. This biocompatible platform controllably delivers siRNA with high efficacy upon visible-light irradiation leading up to 90 % of gene silencing in live cells., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Colloidosome capsules possess the potential for the encapsulation and release of molecular and macromolecular cargos. However, the stabilization of the colloidosome shell usually requires an additional covalent crosslinking which irreversibly seals the capsules, and greatly limits their applications in large-cargos release. Herein we report nanoscaled colloidosomes designed by the electrostatic assembly of organosilica nanoparticles (NPs) with oppositely charged surfaces (rather than covalent bonds), arising from different contents of a bridged nitrophenylene-alkoxysilane [NB; 3-nitro-N-(3-(triethoxysilyl)propyl)-4-(((3-(triethoxysilyl)propyl)-amino)methyl)benzamid] derivative in the silica. The surface charge of the positively charged NPs was reversed by light irradiation because of a photoreaction in the NB moieties, which impacted the electrostatic interactions between NPs and disassembled the colloidosome nanosystems. This design was successfully applied for the encapsulation and light-triggered release of cargos., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Metal-free fullerene (C(60)) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH(4). Use of NaBH(4) by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C(60) catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C(60) to interact with electron-donor moieties in azo dyes., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)