Metal–organic frameworks (MOFs) are an interesting and useful class of coordination polymers, constructed from metal ion/cluster nodes and functional organic ligands through coordination bonds, and have attracted extensive research interest during the past decades. Due to the unique features of diverse compositions, facile synthesis, easy surface functionalization, high surface areas, adjustable porosity, and tunable biocompatibility, MOFs have been widely used in hydrogen/methane storage, catalysis, biological imaging and sensing, drug delivery, desalination, gas separation, magnetic and electronic devices, nonlinear optics, water vapor capture, etc. Notably, with the rapid development of synthetic methods and surface functionalization strategies, smart MOF‐based nanocomposites with advanced bio‐related properties have been designed and fabricated to meet the growing demands of MOF materials for biomedical applications. This work outlines the synthesis and functionalization and the recent advances of MOFs in biomedical fields, including cargo (drugs, nucleic acids, proteins, and dyes) delivery for cancer therapy, bioimaging, antimicrobial, biosensing, and biocatalysis. The prospects and challenges in the field of MOF‐based biomedical materials are also discussed.

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.

A tetraphenylethene-bridged pillarene tetramer with aggregation-induced emission properties forms an A4/B2-type supramolecular polymer and a gel with a symmetric neutral guest linker, showing a remarkable fluorescence emission enhancement in solution and the solid state and a good responsiveness to temperature and solvent composition.

Sodium-ion batteries are similar in concept and function to lithium-ion batteries, but their development and commercialization lag far behind. One obstacle is the lack of a standard reference electrode. Unlike Li foil reference electrodes, sodium is not easily processable or moldable and it deforms easily. Herein we fabricate a processable and moldable composite Na metal anode made from Na and reduced graphene oxide (r-GO). With only 4.5 % percent r-GO, the composite anodes had improved hardness, strength, and stability to corrosion compared to Na metal, and can be engineered to various shapes and sizes. The plating/stripping cycling of the composite anode was significantly extended in both ether and carbonate electrolytes giving less dendrite formation. We used the composite anode in both Na-O and Na-Na V (PO ) full cells.

An intelligent theranostic nanoplatform based on nanovalve operated metal-organic framework (MOF) core-shell hybrids, incorporating tumorous microenvironment-triggered drug release, magnetic resonance imaging (MRI) guidance, sustained release, and effective chemotherapy in one pot is reported. The core-shell hybrids are constructed by an in situ growth method, in which Fe O particles with superior abilities of MRI and magnetic separation form the core and UiO-66 MOF with high loading capacity compose the shell, and then are surface-installed with pillararene-based pseudorotaxanes as tightness-adjustable nanovalves. This strategy endows the system with the ability of targeted, multistimuli responsive drug release in response to pH changes, temperature variations, and competitive agents. Water-soluble carboxylatopillar[6]arene system achieved sustained drug release over 7 days due to stronger host-guest binding, suggesting that the nanovalve tightness further reinforces the desirable release of anticancer agent over a prolonged time at the lesion site.

health concerns across the world. [1] Particularly significant is the effort directed toward the treatment of cancer, which has remained as one of the leading causes of rapidly growing morbidity and mortality rates for centuries. Among a number of significant advances achieved in this domain, cancer theranostics is one such advancement that allows the ingenious integration of accurate diagnosis with therapeutic intervention in a single formulation within spatial colocalization. This phenomenon has captivated the interest of researchers for the evaluation of the potential in fundamental studies and clinical application, [2] primarily due to the attribution of various intrinsic advantages to theranostics, including maximized therapeutic efficacy, optimized drug safety, and improved pharmacokinetics. [3] Notably, in comparison with the conventional therapeutic methods for cancers such as surgical removal, chemotherapy, and radiotherapy, [4] theranostics involves some burgeoning therapeutic strategies including photothermal therapy (PTT), [5] photodynamic therapy (PDT), [6] and gene therapy. It has become one of the most intensive areas of research during recent years due to high efficiency, minimal side effects, excellent tumor suppression, and non-invasive conversion. One of the major pursuits of biomedical science is to develop advanced strategies for theranostics, which is expected to be an effective approach for achieving the transition from conventional medicine to precision medicine. Supramolecular assembly can serve as a powerful tool in the development of nanotheranostics with accurate imaging of tumors and real-time monitoring of the therapeutic process upon the incorporation of aggregation-induced emission (AIE) ability. AIE luminogens (AIEgens) will not only enable fluorescence imaging but will also aid in improving the efficacy of therapies. Furthermore, the fluorescent signals and therapeutic performance of these nanomaterials can be manipulated precisely owing to the reversible and stimuli-responsive characteristics of the supramolecular systems. Inspired by rapid advances in this field, recent research conducted on nanotheranostics with the AIE effect based on supramolecular assembly is summarized. Here, three representative strategies for supramolecular nanomaterials are presented as follows: a) supramolecular self-assembly of AIEgens, b) the loading of AIEgens within nanocarriers with supramolecular assembly, and c) supramolecular macrocycle-guided assembly via host-guest interactions. Meanwhile, the diverse applications of such nanomaterials in diagnostics and therapeutics have also been discussed in detail. Finally, the challenges of this field are listed in this review.

All reagents were purchased from commercial suppliers (Aldrich or Fisher) and used without further purification. Cyclobis(paraquat-p-phenylene) hexafluorophosphate S1 (CBPQT•4PF 6), and compounds S1 S2 , 2 S3 , 3 S4 , as well as the [2]rotaxane R1•4PF 6 S5 were all prepared according to literature procedures. Thin layer chromatography (TLC) was performed on silica gel 60 F254 (E. Merck). Column chromatography was carried out on silica gel 60F (Merck 9385, 0.040-0.063 mm). UV/Vis spectra were recorded on a Varian 100-Bio UV-Vis spectrophotometer in MeCN at room temperature. Nuclear magnetic resonance (NMR) spectra were recorded on Bruker Avance 600 or Varian P-Inova 500 spectrometers, with working frequencies of 600 and 500 MHz for 1 H, and 150 and 125 MHz for 13 C nuclei, respectively. Chemical shifts are reported in ppm relative to the signals corresponding to the residual non-deuterated solvents (CDCl 3 : δ = 7.26 ppm, CD 3 CN: δ =1.94 ppm). High-resolution mass spectra were measured, either on an Applied Biosystems Voyager DE-PRO MALDI TOF mass spectrometer (HR-TOF), or on a Finnigan LCQ iontrap mass spectrometer (HR-ESI). Cyclic voltammetry (CV) experiments were carried out at room temperature in argon-purged solutions in MeCN with a Gamry Multipurpose instrument (Reference 600) interfaced to a PC. CV Experiments were performed using a glassy carbon working electrode (0.071 cm 2). The electrode surface was polished routinely with 0.05 μm alumina-water slurry on a felt surface immediately before use. The counter electrode was a Pt coil and the reference electrode was silver/silver chloride. The concentration of the sample and supporting electrolyte (tetrabutylammonium hexafluorophosphate or tetrabutylammonium chloride) were 1.0 × 10 −3 mol L −1 and 0.1 mol L −1 , respectively. For the visible light lamp, we employed a standard incandescent bulb (60 W) without taking any extra precautions to select for specific wavelengths. S3 2. Synthetic Procedures S2: Compound S1 (490 mg, 1 mmol), 2-isopropylphenol (150 mg, 1.1 mmol) and K 2 CO 3 (1.38 g, 10 mmol) were added to a round-bottomed flask (250 mL) containing dry DMF (50 mL). The reaction mixture was stirred at 80 °C for 8 h. After cooling to room temperature, the solution was poured into H 2 O (200 mL). The resulting mixture was extracted with EtOAc (3 x 20 mL) and the combined organic phases were washed three times with saturated aqueous NaCl solution (3 x 100 mL). After drying (MgSO 4), the solvent was removed in vacuo and the resulting residue was purified by column chromatography (SiO 2 : Hexanes / EtOAc 50:50) to afford the desired product S2 (354 mg, 78%) as a light-yellow oil. 1