Supramolecular Modular Assembly of Imaging-Trackable Enzymatic Nanomotors.

Self-propelled micro/nanomotors (MNMs) have shown great application potential in biomedicine, sensing, environmental remediation, etc. In the past decade, various strategies or technologies have been used to prepare and functionalize MNMs. However, the current preparation strategies of the MNMs were mainly following the pre-designed methods based on specific tasks to introduce expected functional parts on the various micro/nanocarriers, which lacks a universal platform and common features, making it difficult to apply to different application scenarios. Here, we have developed a modular assembly strategy based on host-guest chemistry, which enables the on-demand construction of imaging-trackable nanomotors mounted with suitable driving and imaging modules using a universal assembly platform, according to different application scenarios. These assembled nanomotors exhibited enhanced diffusion behavior driven by enzymatic reactions. The loaded imaging functions were used to dynamically trace the swarm motion behavior of assembled nanomotors with corresponding fuel conditions both in vitro and in vivo. The modular assembly strategy endowed with host-guest interaction provides a universal approach to producing multifunctional MNMs in a facile and controllable manner, which paves the way for the future development of MNMs systems with programmable functions.

Recent Advances in Functional Materials for Optical Data Storage.

In the current data age, the fundamental research related to optical applications has been rapidly developed. Countless new-born materials equipped with distinct optical properties have been widely explored, exhibiting tremendous values in practical applications. The optical data storage technique is one of the most significant topics of the optical applications, which is considered as the prominent solution for conquering the challenge of the explosive increase in mass data, to achieve the long-life, low-energy, and super high-capacity data storage. On this basis, our review outlines the representative reports for mainly introducing the functional systems based on the newly established materials applied in the optical storage field. According to the material categories, the representative functional systems are divided into rare-earth doped nanoparticles, graphene, and diarylethene. In terms of the difference of structural features and delicate properties among the three materials, the application in optical storage is comprehensively illustrated in the review. Meanwhile, the potential opportunities and critical challenges of optical storage are also discussed in detail.

Multifunctional metal-organic framework (MOF)-based nanoplatforms for cancer therapy: from single to combination therapy.

Cancer remains a severe threat to human health. To date, although various therapeutic methods, including radiotherapy (RT), chemotherapy, chemodynamic therapy (CDT), phototherapy, starvation therapy, and immunotherapy, have entered a new stage of rapid progress in cancer theranostics, their limited therapeutic effect and significant side effects need to be considered carefully. With the rapid development of nanotechnology, the marriage of nanomaterials and therapeutic methods provides the practical possibility to improve the deficiencies in cancer therapy. Notably, metal-organic frameworks (MOFs) composed of ions/clusters and bridging ligands through coordination bonds have been widely applied in cancer therapy to deal with the drawbacks of different therapeutic methods, such as severe side effects, low stability, and poor efficacy, owing to their controllable morphologies, tailorable diameters, diverse compositions, tunable porosities, high specific surface areas, facile functionalization, and good biocompatibility. This review summarizes the recent advanced developments and achievements of multifunctional MOF-based nanoplatforms for cancer therapy through single therapy methods, including RT, chemotherapy, CDT, phototherapy (photodynamic and photothermal therapy), starvation therapy and immunotherapy, and combination therapy methods. Moreover, the prospects and challenges of MOF-based nanoplatforms used in tumor therapy are also discussed.

Guest-induced amorphous-to-crystalline transformation enables sorting of haloalkane isomers with near-perfect selectivity.

The separation of haloalkane isomers with distillation-free strategies is one of the most challenging research topics in fundamental research and also gave high guiding values to practical industrial applications. Here, this contribution provides a previously unidentified solid supramolecular adsorption material based on a leggero pillararene derivative BrP[5]L, which can separate 1-/2-bromoalkane isomers with near-ideal selectivity. Activated solids of BrP[5]L with interesting amorphous and nonporous features could adsorb 1-bromopropane and 1-bromobutane from the corresponding equal volume mixtures of 1-/2-positional isomers with purities of 98.1 and 99.0%, respectively. Single-crystal structures incorporating theoretical calculation reveal that the high selectivity originates from the higher thermostability of 1-bromoalkane-loaded structures compared to its corresponding isomer-loaded structures, which could be further attributed to the perfect size/shape match between BrP[5]L and 1-bromoalkanes. Moreover, control experiments using its counterpart macrocycle of traditional pillararene demonstrate that BrP[5]L has better adsorptive selectivity, benefiting from the intrinsic free-rotation phenylene subunit on its backbone.

Supramolecular Assemblies with Aggregation-Induced Emission Properties for Sensing and Detection.

The fabrication of new supramolecular materials for real-time detection of analytes including ions, organic pollutants, gases, biomolecules, and drugs is of pivotal importance in industrial manufacture, clinical treatment, and environmental remediation. Incorporating fluorescent molecules with distinct aggregation-induced emission (AIE) effects into supramolecular assemblies has received much attention over the past two decades, owing to the remarkable performance of the AIE-active supramolecular materials in sensing and detection. In this minireview, we summarize the recent progress of superior detection systems on the basis of supramolecular assemblies accompanied with AIE features. We envision that this minireview will be helpful and timely for relevant researchers to stimulate new thinking for constructing new AIE-based supramolecular materials with advanced architectures for effective sensing and detection.

Bottom-Up Solid-State Molecular Assembly via Guest-Induced Intermolecular Interactions.

The manipulation of molecular motions to construct highly ordered supramolecular architectures from chaos in the solid state is considered to be far more complex and challenging in comparison to that in solution. In this work, a bottom-up molecular assembly approach based on a newly designed skeleton-trimmed pillar[5]arene analogue, namely the permethylated leggero pillar[5]arene MeP[5]L, is developed in the solid state. An amorphous powder of MeP[5]L can take up certain guest vapors to form various ordered linker-containing solid-state molecular assemblies, which can be further used to construct a thermodynamically favored linker-free superstructure upon heating. These approaches are driven by vapor-induced solid-state molecular motions followed by a thermally triggered phase-to-phase transformation. The intermolecular interactions play a crucial role in controlling the molecular arrangements in the resulting assemblies. This research will open new insights into exploring controllable molecular motions and assemblies in the solid state, providing new perspectives in supramolecular chemistry and materials.

MOF-based multi-stimuli-responsive supramolecular nanoplatform equipped with macrocycle nanovalves for plant growth regulation.

Controllable and on-demand delivery of agrochemicals such as plant hormones is conducive to improving agrochemicals utilization, tackling water and environmental pollution, reducing soil acidification, and realizing the goals of precision agriculture. Herein, a smart plant hormone delivery system based on metal-organic frameworks (MOFs) and supramolecular nanovalves, namely gibberellin (GA)-loaded CLT6@PCN-Q, is constructed through supramolecular host-guest interaction to regulate the growth of dicotyledonous Chinese cabbage and monocotyledonous wheat. The porous nanoscale MOF (NMOF) with a uniform diameter of 97 nm modified by quaternary ammonium (Q) stalks is served as a cargo reservoir, followed by the decoration of carboxylated leaning tower[6]arene (CLT6) based nanovalves on NMOF surfaces through host-guest interactions to fabricate CLT6@PCN-Q with a diameter of ∼101 nm and a zeta potential value of -13.2 mV. Interestingly, the as-fabricated supramolecular nanoplatform exhibits efficient cargo loading and multi-stimuli-responsive release under various external stimuli including pH, temperature, and competitive agent spermine (SPM), which can realize the on-demand release of cargo. In addition, GA-loaded CLT6@PCN-Q is capable of effectively promoting the seeds germination of wheat and stem growth of dicotyledonous Chinese cabbage and monocotyledonous wheat (1.86 and 1.30 times of control groups, respectively). The smart supramolecular nanoplatform based on MOFs and supramolecular nanovalves paves a way for the controlled delivery of plant hormones and other agrochemicals for promoting plant growth, offering new insights and methods to realize precision agriculture. STATEMENT OF SIGNIFICANCE: To achieve controllable and sustainable release of cargos such as agrochemicals, a smart MOF-based multi-stimuli-responsive supramolecular nanoplatform equipped with supramolecular nanovalves was fabricated via the host-guest interaction between quaternary ammonium stalks-functionalized nanoMOFs and water-soluble leaning tower[6]arene. The as-prepared supramolecular nanoplatform with uniform diameter distribution demonstrated good cargo release in response to various external stimuli. The installation of synthetic macrocycles could effectively reduce cargo loss in the pre-treatment process. This type of supramolecular nanoplatform exhibited good promoting effect on seed germination and plant growth dicotyledonous Chinese cabbage and monocotyledonous wheat. As an eco-friendly, controlled, and efficient cargo delivery system, this supramolecular nanoplatform will be a promising candidate in precision agriculture and controlled drug release to attract the broad readership.

Recyclable Supramolecular Assembly-Induced Emission System for Selective Detection and Efficient Removal of Mercury(II).

An efficient strategy for simultaneously detecting and removing Hg2+ from water is vital to address mercury pollution. Herein a supramolecular assembly G⊂H with photoluminescent properties is facilely constructed through the self-assembly of a functional pillar[5]arene bearing two N,N-dimethyldithiocarbamoyl binding sites (H) and an AIE-active tetraphenylethene derivative (G). Remarkably, the fluorescence of G⊂H can be exclusively quenched by Hg2+ among the 30 cations due to the formation of non-luminous ground state complex and only L-cysteine can restore fluorescence in the common 20 amino acids. Meanwhile, the probe G⊂H has a considerable thermal and pH stability, a good anti-interference property from various cations, and a satisfactory sensitivity. More importantly, G⊂H exhibits a prominent capability of Hg2+ removal with rapid capture rate (within 1 h) and excellent adsorption efficiency (98 %), as well as a highly efficient recyclability without losing any adsorption activity.

Macrocyclic Arenes-Based Conjugated Macrocycle Polymers for Highly Selective CO2 Capture and Iodine Adsorption.

Incorporating synthetic macrocycles with unique structures and distinct conformations into conjugated macrocycle polymers (CMPs) can endow the resulting materials with great potentials in gas uptake and pollutant adsorption. Here, four CMPs (CMP-n, n=1-4) capable of reversibly capturing iodine and efficiently separating carbon dioxide are constructed from per-triflate functionalized leaning tower[6]arene (LT6-OTf) and [2]biphenyl-extended pillar[6]arene (BpP6-OTf) via Pd-catalyzed Sonogashira-Hagihara cross-coupling reaction. Intriguingly, owing to the appropriate cavity size of LT6-OTf and the numerous aromatic rings in the framework, the newly designed CMP-4 possesses an outstanding I2 affinity with a large uptake capacity of 208 wt % in vapor and a great removal efficiency of 94 % in aqueous solutions. To our surprise, with no capacity to accommodate nitrogen, CMP-2 constructed from BpP6-OTf is able to specifically capture carbon dioxide at ambient conditions.

Stabilization of Grignard reagents by a pillar[5]arene host - Schlenk equilibria and Grignard reactions.

Grignard reagents (RMgX) are widely used in organic synthesis. However, these highly reactive compounds are supplied in inflammable solvents, which causes extra complexity in their transportation. Herein we report that Grignard reagents with linear alkyl chains can be entrapped and stabilized by the macrocyclic host pillar[5]arene while preserving their reactivity.

Supramolecular nanomaterials based on hollow mesoporous drug carriers and macrocycle-capped CuS nanogates for synergistic chemo-photothermal therapy.

Multifunctional supramolecular nanoplatforms that integrate the advantages of different therapeutic techniques can trigger multimodal synergistic treatment of tumors, thus representing an emerging powerful tool for cancer therapeutics. Methods: In this work, we design and fabricate a multifunctional supramolecular drug delivery platform, namely Fa-mPEG@CP5-CuS@HMSN-Py nanoparticles (FaPCH NPs), consisting of a pyridinium (Py)-modified hollow mesoporous silica nanoparticles-based drug reservoir (HMSN-Py) with high loading capacity, a layer of NIR-operable carboxylatopillar[5]arene (CP5)-functionalized CuS nanoparticles (CP5-CuS) on the surface of HMSN-Py connected through supramolecular host-guest interactions between CP5 rings and Py stalks, and another layer of folic acid (Fa)-conjugated polyethylene glycol (Fa-PEG) antennas by electrostatic interactions capable of active targeting at tumor lesions, in a controlled, highly integrated fashion for synergistic chemo-photothermal therapy. Results: Fa-mPEG antennas endowed the enhanced active targeting effect toward cancer cells, and CP5-CuS served as not only a quadruple-stimuli responsive nanogate for controllable drug release but also a special agent for NIR-guided photothermal therapy. Meanwhile, anticancer drug doxorubicin (DOX) could be released from the HMSN-Py reservoirs under tumor microenvironments for chemotherapy, thus realizing multimodal synergistic therapeutics. Such a supramolecular drug delivery platform showed effective synergistic chemo-photothermal therapy both in vitro and in vivo. Conclusion: This novel supramolecular nanoplatform possesses great potential in controlled drug delivery and tumor cellular internalization for synergistic chemo-photothermal therapy, providing a promising approach for multimodal synergistic cancer treatment.

N-doped carbon dots covalently functionalized with pillar[5]arenes for Fe3+ sensing.

Fluorescent N-doped carbon dots (CN-dots) covalently functionalized with carboxylatopillar[5]arene (CP[5]), namely CCDs, have been prepared the first time. Compared with CN-dots without pillarene units, the newly constructed fluorescent CCDs could recognize Fe3+ with high selectivity. Therefore, such CCDs can potentially serve as a promising chemical sensor for Fe3+ ions.

Supramolecular Assembly-Induced Emission Enhancement for Efficient Mercury(II) Detection and Removal.

New strategies that can simultaneously detect and remove highly toxic environmental pollutants such as heavy metal ions are still in urgent need. Herein, through supramolecular host-guest interactions, a fluorescent supramolecular polymer has been facilely constructed from a newly designed [2]biphenyl-extended pillar[6]arene equipped with two thymine sites as arms (H) and a tetraphenylethylene (TPE)-bridged bis(quaternary ammonium) guest (G) with aggregation-induced emission (AIE) property. Interestingly, supramolecular assembly-induced emission enhancement (SAIEE) could be switched on upon addition of Hg2+ into the above-mentioned supramolecular polymer system to generate spherical-like supramolecular nanoparticles, due to the restriction of intramolecular rotation (RIR)-related AIE feature of G. Significantly, this supramolecular polymer with integrated modalities has been successfully used for real-time detection and removal of toxic heavy metal Hg2+ ions from water with quick response, high selectivity, and rapid adsorption rates, which could be efficiently regenerated and recycled without any loss via a simple treatment with Na2S. The newly developed supramolecular polymer system combines the inherent rigid and spacious cavity of novel extended-pillarene host with the AIE characteristics of TPE-based guest, suggesting a great potential in the treatment of heavy metal pollution and environmental sustainability.