Thiosquaramide-Based Supramolecular Polymers: Aromaticity Gain in a Switched Mode of Self-Assembly.

Despite a growing understanding of factors that drive monomer self-assembly to form supramolecular polymers, the effects of aromaticity gain have been largely ignored. Herein, we document the aromaticity gain in two different self-assembly modes of squaramide-based bolaamphiphiles. Importantly, O → S substitution in squaramide synthons resulted in supramolecular polymers with increased fiber flexibility and lower degrees of polymerization. Computations and spectroscopic experiments suggest that the oxo- and thiosquaramide bolaamphiphiles self-assemble into "head-to-tail" versus "stacked" arrangements, respectively. Computed energetic and magnetic criteria of aromaticity reveal that both modes of self-assembly increase the aromatic character of the squaramide synthons, giving rise to stronger intermolecular interactions in the resultant supramolecular polymer structures. These examples suggest that both hydrogen-bonding and stacking interactions can result in increased aromaticity upon self-assembly, highlighting its relevance in monomer design.

Stab2-Mediated Clearance of Supramolecular Polymer Nanoparticles in Zebrafish Embryos.

Supramolecular polymers are attractive scaffolds for use as nanocarriers in drug delivery thanks to their modularity and easy fabrication; however, a molecular view into their in vivo behavior is lacking. Herein, we prepare fluorescent squaramide-based supramolecular polymer nanoparticles that range from fibers to spheres while maintaining their surface chemistry and near-neutral surface charge by a co-assembly approach involving a sulfo-cyanine-labeled monomer to track their in vivo biodistribution behavior and clearance in optically transparent zebrafish embryos. Evasion of macrophages, localization of the fibrillar aggregates in the caudal vein, and association with scavenger endothelial cells are observed. The interaction of the fibrillar supramolecular nanoparticles with the caudal vein is abrogated in gene-edited zebrafish lacking Stabilin-2, a receptor analogously found in the mammalian liver, providing a molecular view into their interaction with scavenger endothelial cells. We further show that this interaction can be tuned based on the choice of monomer and its resultant self-assembly.

Photoresponsive Circular Supramolecular Polymers: A Topological Trap and Photoinduced Ring-Opening Elongation.

Topological features of one-dimensional macromolecular chains govern the properties and functionality of natural and synthetic polymers. To address this issue in supramolecular polymers, we synthesized two topologically distinct supramolecular polymers with intrinsic curvature, circular and helically folded nanofibers, from azobenzene-functionalized supramolecular rosettes. When a mixture of circular and helically folded nanofibers was exposed to UV light, selective unfolding of the latter open-ended supramolecular polymers was observed as a result of the curvature-impairing internal force produced by the trans-to-cis photoisomerization of the azobenzene. This distinct sensitivity suggests that the topological features of supramolecular polymers define their mechanical stability. Furthermore, the exposure of circular supramolecular polymers in more polar media to UV irradiation resulted in ring opening followed by chain elongation, thus demonstrating that the circular supramolecular polymer can function as a topological kinetic trap.

Green synthesis of a plant-derived protein protected copper quantum cluster for intrauterine device application.

Fluorescent copper quantum clusters (CuQCs) have received great interest in recent times due to their attractive features, such as water solubility, low cost, wide availability of Cu and good biocompatibility. Recently, considerable efforts have been devoted to the preparation and applications of CuQCs. Herein, we report a simple one-pot green method for the preparation of fluorescent CuQCs using a plant-derived protein, gluten, as a stabilizing agent. Gluten, a naturally abundant, low-cost and sustainable plant-protein derived from wheat, was employed both as a reducing and stabilizing agent to produce blue emitting CuQCs. The CuQCs were characterized by UV-Vis absorption, fluorescence, FT-IR, TEM, and XPS. We further incorporated CuQCs into a polymer to study the release rate of Cu2+ ions from a CuQC-polymer composite, since copper ions are well known for their fungicidal properties and contraceptive action in copper-T (CuT). The CuQCs were incorporated into a model polymer, polyurethane (PU), by melt compounding, and the mixtures were extruded in the form of a wire. It was observed that the CuQCs were uniformly dispersed within the polymer matrix. An in vitro experiment was carried out to quantify the potential release of Cu(ii) ions for contraceptive applications. The developed nanocomposite releases Cu(ii) ions for 90 days, which suggests the potential application of the CuQCs in the medical field like the development of short-term intrauterine devices (IUDs). Compared to conventional IUDs, here the CuQC-PU nanocomposite reduces the burst release of the Cu2+, and the release rates can be tuned by changing the composition of the materials. These results suggest that the CuQC-PU nanocomposites have great potential to replace current commercial intrauterine devices.