Self-healing ability is crucial to increasing the lifetime and reliability of materials. In this study, spatiotemporal control of the healing of a polysiloxane material is achieved using a cleavable cage compound encapsulating a fluoride ion (F- ), which triggeres the dynamic rearrangement of the siloxane (Si-O-Si) networks. A self-healing siloxane-based elastomer is prepared by cross-linking polydimethylsiloxane (PDMS) with a F- -encapsulating cage-type germoxane (Ge-O-Ge) compound. This material can self-heal repeatedly under humid conditions. The F- released by hydrolytic cleavage of the cage framework contributes to rejoining of the cut pieces by promoting the local rearrangement of the siloxane networks. The use of a molecular cage encapsulating a catalyst for dynamic bond rearrangement provides a new concept for designing self-healing polysiloxane materials based on integrated extrinsic and intrinsic mechanisms.

Polyhedral molecules are appealing for their eye-catching architecture and distinctive chemistry. Perfluorination of such, often greatly strained, compounds is a momentous challenge. It drastically changes the electron distribution, structure and properties. Notably, small high-symmetry perfluoropolyhedranes feature a centrally located, star-shaped low-energy unoccupied molecular orbital that can host an extra electron within the polyhedral frame, thus producing a radical anion, without loss of symmetry. This predicted electron-hosting capacity was definitively established for perfluorocubane, the first perfluorinated Platonic polyhedrane to be isolated pure. Hosting atoms, molecules, or ions in such \"cage\" structures is, however, all but forthright, if not illusionary, offering no easy access to supramolecular constructs. While adamantane and cubane have fostered numerous applications in materials science, medicine, and biology, specific uses for their perfluorinated counterparts remain to be established. Some aspects of highly fluorinated carbon allotropes, such as fullerenes and graphite, are briefly mentioned for context.

Mechanically interlocked structures are fascinating synthetic targets and the topological complexity achieved through catenation offers numerous possibilities for the construction of new molecules with exciting properties. In the structural space of catenated organic cage molecules, only few examples have been realized so far, and control over the catenation process in solution is still barely achieved. Herein, we describe the formation of a quadruply interlocked catenane of giant chiral [8+12] salicylimine cubes. The formation could be controlled by the choice of solvent used in the reaction. The interlocked structure was unambiguously characterized by single crystal X-ray diffraction and weak hydrogen bonding was identified as a central driving force for the catenation. Furthermore, scrambling experiments using partially deuterated cages were performed, revealing that the catenane formation occurs through mechanical interlocking of preformed single cages.

Natural products with diverse structures and significant biological activities are essential sources of drug lead compounds, and play an important role in the research and development of innovative drugs. Cage-like compounds have various structures and are widely distributed in nature, especially caged xanthones isolated from Garcinia genus, paeoniflorin and its derivatives isolated from Paeonia lactiflora Pall, tetrodotoxin (TTX) and its derivatives, and so on. In recent years, the development and utilization of cage-like compounds have been a research hotspot in chemistry, biology and other fields due to their special structures and remarkable biological activities. In this review, we mainly summarized the cage-like compounds with various structures found and isolated from natural drugs since 1956, summarized its broad biological activities, and introduced the progress in the biosynthesis of some compounds, so as to provide a reference for the discovery of more novel compounds, and the development and application of innovative drugs.

The incorporation of reactive functional groups onto the exterior of metal-organic cages (MOCs) opens up new opportunities to link their well-defined scaffolds into functional porous solids. Amine moieties offer access to a rich catalogue of covalent chemistry; however, they also tend to coordinate undesirably and interfere with MOC formation, particular in the case of Cu2 paddlewheel-based MOCs. We demonstrate that tuning the basicity of an aniline-functionalized ligand enables the self-assembly of a soluble, amine-functionalized Cu4L4 lantern cage (1). Importantly, we show control over the coordinative propensity of the exterior amine of the ligand, which enables us to isolate a crystalline, two-dimensional metal-organic framework composed entirely of MOC units (2). Furthermore, we show that the nucleophilicity of the exterior amine of 1 can be accessed in solution to generate a cross-linked cage polymer (3) via imine condensation.

Two analogous M4 L4 -type tetrahedral cages (smaller: MOC-19; larger: MOC-22) were synthesized and investigated for their interactions with the anticancer drug 5-fluoracil (5-FU) by NMR spectroscopy, high-resolution electrospray-ionization mass spectrometry (HR-ESI-MS), and molecular simulation. The cage\'s size and window are of importance for the host-guest binding, and consequently the smaller MOC-19 with a more suitable size of cavity window was found to have much stronger hydrogen-bond interactions with 5-FU. The porous nanoparticles of MOC-19 exhibited outstanding behavior for the controlled release of 5-FU in a simulated human body with liquid phosphate-buffered saline solution.

The spatial and temporal aspects of immune cell signaling are key parameters in defining the magnitude of an immune response. Toll-like receptors (TLRs) on innate immune cells are important in the early detection of pathogens and initiation of an immune response. Controlling the spatial and temporal signaling of TLRs would enable further study of immune synergies and assist in the development of new vaccines. Here, we show a light-based method for the spatial control of TLR4 signaling. A TLR4 agonist, pyrimido[5,4-b]indole, was protected with a cage at a position critical for receptor binding. This afforded a photocontrollable agonist that was inactive while caged, yet effected NF-κB activity in cells following UV photocontrolled deprotection. We demonstrated spatial control of NF-κB activation within a population of cells by treating all cells with the caged TLR4 agonist and constraining light exposure and consequent activation to a region of interest.