Unveiling the Topology-Property Relationship in the Polyethers: A Story of 10 Years and Beyond

Topology has emerged as a key design element in polymer chemistry, governing how molecular connectivity translates into material functions. Over the past decade, our research has focused on establishing the fundamental relationship between polymer topology and physicochemical properties using polyethers as a versatile model system.[1] By developing diverse synthetic routes—ranging from linear and hyperbranched to cyclic architectures—we have systematically uncovered how topology modulates hydrogen-bonding dynamics, molecular mobility, and interactions with water. These insights have led to the creation of topology-tunable polyethers exhibiting unique macroscopic behaviors, such as biomimetic materials,[2,3] hydrogels,[4,5] adhesives,[6] and cryoprotectants.[7,8] This presentation will summarize our ten-year journey in unveiling how molecular topology dictates the emergent functions of polyethers, and discuss future directions toward topology-guided materials design beyond conventional polymer paradigms. In the last part, we briefly discuss our recent effort in the unconventional mechanochemical approach for the synthesis of polymers.[9,10]

[1] “Topology-Controlled Polyethers: A Synthetic Platform for Tunable Properties and Applications” Acc. Mater. Res. 2025, 6, 1204.

[2] "Peptidomimetic Wet-Adhesive PEGtides with Synergistic and Multimodal Hydrogen Bonding" J. Am. Chem. Soc. 2022, 144, 6261

[3] “Synergistic Anion-π Interactions in Peptidomimetic Polyethers” PNAS 2025, 122, e2419404122

[4] “Precisely Programmable Degradation and Drug Release Profiles in Triblock Copolyether Hydrogels with Cleavable Acetal Pendants” J. Am. Chem. Soc. 2024, 146, 13836

[5] “Self-Assembly of Amorphous 2D Polymer Nanodiscs with Tuneable Size, pH-Responsive Degradation and Controlled Drug Release” Angew. Chem. Int. Ed. 2025, 64, e202424269

[6] "Design of Topology-Controlled Polyethers toward Robust Cooperative Hydrogen Bonding" Adv. Funct. Mater. 2023, 33, 2302086

[7] "Janus Regulation of Ice Growth by Hyperbranched Polyglycerols Generating Dynamic Hydrogen Bonding" Nat. Commun. 2022, 13, 6532

[8] “Na+-Complexed Dendritic Polyglycerols for Recovery of Frozen Cells and Their Network in Media” Adv. Mater. 2025, 37, 2416304

[9] "Anionic Ring-Opening Polymerization of Functional Epoxide Monomers in the Solid State" Nat. Commun. 2023, 14, 5855

[10] “Mechanochemical Atom Transfer Radical Polymerization Unlocks Functional Methacrylate Lifecycles of Controlled Synthesis, Force-Activated Degradation, and Depolymerization” Nat. Commun. 2026 in press