Pathway Complexity in Nanotubular Supramolecular Polymerization: Metal-Organic Nanotubes with a Planar-Chiral Monomer.

Here, we report an anomalous pathway complexity in the supramolecular polymerization of a chiral monomer, which displays an unusual chiroptical feature that does not follow any of the known stereochemical rules such as "chiral self-sorting" and "majority rule". We newly developed a planar-chiral ferrocene-cored tetratopic pyridyl monomer , which underwent AgBF-mediated supramolecular polymerization to give nanotubes s composed of metal-organic nanorings s. Although s must be homochiral because of a strong geometrical constraint, s were formed even efficiently from racemic and AgBF.

Intracellular Photoactivation of Caspase-3 by Molecular Glues for Spatiotemporal Apoptosis Induction.

Caspase-3 (Casp-3) is an enzyme that efficiently induces apoptosis, a form of programmed cell death. We report a dendritic molecular glue Glue that enables intracellular delivery of Casp-3 and its photoactivation. Glue carrying multiple guanidinium (Gu) ion pendants via photocleavable linkages can tightly adhere to Casp-3 and deliver it into the cytoplasm mainly by direct penetration through the plasma membrane.

Nitrobenzoxadiazole-Appended Cell Membrane Modifiers for Efficient Optoporation with Noncoherent Light.

NBD-BAM, bearing a nitrobenzoxadiazole (NBD) unit and an oleyl terminus conjugated via a poly(ethylene glycol) (PEG) spacer ( M = 2,000), was designed to fluorescently label cell membranes by docking its hydrophobic oleyl terminus. During laser scanning microscopy in a minimal essential medium (MEM), human hepatocellular carcinoma Hep3B cells labeled with NBD-BAM appeared to undergo optoporation at their plasma membrane. We confirmed this unprecedented possibility by a series of cellular uptake experiments using negatively charged and therefore membrane-impermeable quantum dots (QDs; D = 4.