Enhanced Mechanical and Helical Properties with Achiral Calix[4]arene in a Co‐Assembled Hydrogel with a Helical Structure

Abstract

A mixture of the building blocks 1A and 2G, featuring d‐alanine moieties and glycine‐functionalized calix[4]arene moieties, respectively, formed a co‐assembled hydrogel. In particular, the remarkable enhancement of helical intensity of co‐assembled gel was controlled by achiral calix[4]arene 2G, which was attributed to the bridging effect between 1A and 2G, similar to a helical structure. Furthermore, the improvement of the mechanical strength (G′ and G′′ values) of the co‐assembled hydrogel prepared with 1.0 equivalent of 2G were around 7000 % and 4400 % stronger, respectively, compared to the gel prepared from the 0.25 equivalents of 2G. The improved mechanical strength was attributed to the formation of a network structure with a H‐bonding interaction between 1A and 2G. The results indicate that the enhanced helical and mechanical strength of the co‐assembled gel could be controlled by achiral component 2G.

Transformable Helical Self-Assembly for Cancerous Golgi Apparatus Disruption

“…To further understand the helix effect on membrane disruption, we compared the rigidity of L-HFs self-assembly of F 4 KY with that of fibrils of F 3 KY and F 5 KY (Figure i,k). Compared to F 3 KY (127.1 MPa) soft fibrils and F 5 KY (225.5 MPa) fibrils, the Young’s modulus of L-HFs of F 4 KY (278.8 MPa) has an abnormal increase (Figure r, Figures S22 and S23), which may be attributed to the helical-enhanced rigidity − and helical winding induced thick helical fibrils (Figure b, Figure S11). The helical-enhanced rigidity led to the enhanced MLV membrane disruption ability of L-HFs compared to fibrils of F 3 KY and F 5 KY (Figure n,p,q).…”

“…We speculate that the biomembrane disruption ability of in situ self-assembled fibrils may be positively related to their rigidity, which drive us to explore rigid fibril assembly. Inspired by the twisted structure of Aβ amyloid fibrils in Alzheimer’s brain tissue and the phenomenon of enhancing the rigidity of fibrils through helical self-assembly in nature, − we decide to use in situ self-assembly of helical fibrils to disrupt the Golgi membrane of cancer cells.…”