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.

Incorporating synthetic macrocycles with unique structures and distinct conformations into conjugated macrocycle polymers (CMPs) can endowthe 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,o wing to the appropriate cavity sizeo f LT6-OTf and the numerous aromatic rings in the framework, the newly designed CMP-4 possesses an outstanding I 2 affinity with alarge uptake capacity of 208 wt %i nv apor and ag reat removal efficiency of 94 %i na queous solutions.T oo ur surprise,w ith no capacity to accommodate nitrogen, CMP-2 constructed from BpP6-OTf is able to specifically capture carbon dioxide at ambient conditions.

Severe disease and environmental pollution derived from heavy metal ions has become one of the major problems in global public health. In particular, mercury(II) as one type of highly poisonous pollutant can destroy human metabolism, central nervous system, and immune system, representing a critical threat to living systems. Therefore, exploitation of new strategies for designing and synthesizing eco‐friendly, efficient, and economical materials for selective detection and removal of Hg2+ is of great importance. Among the various measures for sensing, detection, and removal of mercury ions, advanced functional systems including nanomaterials, polymers, aggregation‐induced emission luminogens, and porous materials have attracted considerable attention over the past years due to their capabilities of real‐time detection, rapid removal, great anti‐interference, quick response, high selectivity, and low limit of detection. In this review, some efficient techniques and strategies for the detection and removal of mercury in aqueous solutions using the abovementioned functional materials are overviewed and the ways in which these advanced material systems are used to tackle the problem of mercury pollution are also discussed.

Supramolecular approaches have opened up vast possibilities in the construction of versatile functional materials, especially those with stimuli-responsiveness and integrated functionalities of multi-modal diagnosis and synergistic therapeutics. In this study, a hybrid theranostic nanosystem named TTPY-PyÌCP5@AuNR is constructed via facile host-guest interactions, where TTPY-Py is a photosensitizer with aggregation-induced emission and CP5@AuNR represents the carboxylatopillar[5]arene (CP5)-modified Au nanorods. TTPY-PyÌCP5@AuNR integrates the respective advantages of TTPY-Py and CP5@AuNR such as the high performance of reactive oxygen species (ROS) generation and photothermal conversion, and meanwhile shows fluorescence responses to both temperature and pH stimuli due to the non-covalent interactions. The successful modification of CP5 macrocycles on AuNRs surfaces can eliminate the cytotoxicity of AuNRs and enable them to serve as the nanocarrier of TTPY-Py for further theranostic application. Significantly, both in vitro and in vivo evaluations demonstrate that this supramolecular nanotheranostic system possesses multiple phototheranostic modalities including intensive fluorescence imaging (FLI), photoacoustic imaging (PAI), efficient photodynamic therapy (PDT), and photothermal therapy (PTT), indicating its great potentials for FLI-PAI imaging-guided synergistic PDT-PTT therapy. Besides, TTPY-Py can be released from the nanocarriers upon activating by the acidic environment of lysosomes and then specifically light up mitochondria. This study brings up a new strategy into the design of versatile nanotheranostics for accurate tumor imaging and cancer therapies. File list (2) download file view on ChemRxiv NanSong-AuNR-ChemRxiv-main.pdf (1.97 MiB) download file view on ChemRxiv NanSong-AuNR-ChemRxiv-SI.pdf (4.34 MiB)

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.

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.

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.

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