Water-soluble Cage Research Articles

Solvato-Controlled Assembly and Structural Transformation of Emissive Poly-NHC-Based Organometallic Cages and Their Applications in Amino Acid Sensing and Fluorescence Imaging.

Stimuli-induced structural transformation of supramolecular cages has drawn increasing attention because of their sensitive feature to external variations as model systems to simulate biological processes. However, combining structural transformation and useful functions has remained a difficult task. This study reports the solvato-controlled self-assembly of two unique topologies with different emission characteristics, a water-soluble Ag8 L4 cage (A) and an Ag4 L2 cage (B), produced from the same sulfonate-pendant tetraphenylethene (TPE) bridged tetrakis-(1,2,4-triazolium) ligand. Both cages show interesting solvent-responsive reversible structural transformation, and the change of fluorescence signals can efficiently track the process. Additionally, water-soluble cage A exhibits unique properties in thermochromism, thiol amino acid sensing, and subcellular imaging in aqueous media.

A fluorescent, chirality-responsive, and water-soluble cage as a multifunctional molecular container for drug delivery.

In recent years, the rational design and construction of drug delivery systems (DDSs) via a supramolecular approach for improving chemical therapeutics have gained significant attention. Here, we report a host-guest DDS formed from a fluorescent, chirality-responsive, and water-soluble tetraphenylethene-based octacationic cage as a fluorescent/chiral probe, solubilizer, and molecular cargo, which can recognize chiral nucleoside drugs, enhance the solubility of insoluble drugs, and protect drugs from the outside environment by forming host-guest complexes in aqueous solution. Given the fluorescence properties and dynamically rotational conformation of tetraphenylethene (TPE) units, this fluorescent and chirality-responsive cage exhibits different responses including turn-on/turn-off fluorescence and negative/positive circular dichroism (CD) when binding with different chiral nucleoside drugs in water, resulting in multiple-responsive photophysical behaviors for these chiral drugs. Furthermore, this water-soluble cationic cage with a hydrophobic cavity can improve the water solubility of insoluble drugs (e.g., CPT) by forming host-guest complexes in water. More importantly, this multifunctional cage exhibits a low toxicity to both human colon and breast cancer cell lines in vitro, and drugs encapsulated by the cage are more effective in killing cancer cells than drugs alone. Finally, the on-off-on fluorescence responses in the formation and dissociation processes of the cage⊃drug complexes have been successfully used to monitor drug release and track drug delivery by fluorescence microscopy in vitro. Therefore, this fluorescent, chirality-responsive, and water-soluble cage as a multifunctional molecular container can be used to construct a smart drug delivery system with several functions of fluorescence and CD detection, water solubilization, real-time monitoring, and chemotherapy.

Anion Binding in Water Drives Structural Adaptation in an Azaphosphatrane-Functionalized FeII4L4 Tetrahedron.

Anion-templated aqueous self-assembly resulted in the formation of an endohedrally functionalized FeII4L4 tetrahedron from azaphosphatrane-based subcomponents. This new water-soluble cage is flexible and able to encapsulate anions with volumes ranging from 35 to 219 Å3 via hydrogen bonding and electrostatic interactions. It structurally adapts in response to the size and shape of the template anions, dynamically adopting a conformation either where all four azaphosphatrane +P-H vectors point inward, or else where one points outward and the other three inward. The two cage isomers can coexist in solution and interconvert. A shape memory phenomenon was observed during guest displacement because guest exchange occurs more rapidly than structural reconfiguration.