2D Materials Kill Bacteria from Within.

Early work demonstrated that some two-dimensional (2D) materials could kill bacteria by using their sharp edges to physically rupture the bacteria envelope, which presents distinct advantages over traditional antibiotics, as bacteria are not able to evolve resistance to the former. This mechano-bactericidal mode of action, however, suffers from low antibacterial efficiency, fundamentally because of random orientation of 2D materials outside the bacteria, where the desirable "edge-to-envelope" contacts occur with low probability. Here, we demonstrate a proof-of-concept approach to significantly enhance the potency of the mechano-bactericidal activity of 2D materials.

Intracellularly Self-Assembled 2D Materials Induce Apoptotic Cell Death by Impeding Cytosolic Transport.

Using a photochemically isomerizable cucurbit[6]uril derivative as a building block, we succeeded in generating a large number of oversized 2D materials within the cytosol of a living cell controlled self-assembly. Fluorescence recovery after a photobleaching assay indicated that the resulting 2D material pieces posed discernible hindrance to not only diffusive spreading but also motor-driven motion of intracellular components in the cytosol, which eventually induced apoptotic cell death. Such behavior was seldom observed in previous 2D material-bearing cells prepared by endocytosis, as the total lateral size constituted by the endocytosed 2D materials per cell failed to exceed a threshold level, leading to a tortuosity of transport path inadequate to impede cytosolic transport in an appreciable manner.

Spiropyran-Appended Cucurbit[6]uril Enabling Direct Generation of 2D Materials inside Living Cells.

The unique structural advantage and physicochemical properties render some 2D materials emerging platforms for intracellular bioimaging, biosensing, or disease theranostics. Despite recent advances in this field, one major challenge lies in bypassing the endocytic uptake barrier to allow internalization of very large 2D materials that have longer retention time in cells, and hence greater potency as intracellular functional platforms than small, endocytosable counterparts. Here, an engineered cucurbit[6]uril carrying at its periphery multiple spiropyran pendants that readily translocates into cytosol, and then polymerizes laterally and non-covalently in a controlled manner, enabling direct generation of 2D materials inside living cells, is reported.

Beyond temperature: controlling collagen fibrillogenesis under physiological conditions via interaction with cucurbit[7]uril.

Under physiological ionic strength and pH, temperature has long been appreciated as the only stimulus that can be applied to induce in vitro self-assembly of tropocollagen. Here, we report a second, mechanistically new control strategy that uses non-covalent and selective binding of cucurbit[7]uril, a macrocyclic cavitand, with midchain aromatic residues on the tropocollagen surface. This strategy directly demonstrates the decisive role hydrophobic interactions play in collagen fibrillogenesis.