Elastic-Modulus-Dependent Macroscopic Supramolecular Assembly of Poly(dimethylsiloxane) for Understanding Fast...

Macroscopic supramolecular assembly (MSA) is a new concept of supramolecular science with an emphasis on noncovalent interactions between macroscopic building blocks with sizes exceeding 10 μm. Owing to a similar noncovalently interactive nature with the phenomena of bioadhesion, self-healing, etc. and flexible features in tailoring and designing modular building blocks, MSA has been developed as a simplified model to interpret interfacial phenomena and a facile method to fabricate supramolecular materials. However, at this early stage, MSA has always been limited to hydrogel materials, which provide flowability for high molecular mobility to the interfacial binding. The extension to a wide range of materials for MSA is desired. Herein, we have developed a strategy of adjusting intrinsic properties (e.g., elastic modulus) of nonhydrogel materials to realize MSA, which could broaden the material choices of MSA. Using the widely used elastomer of poly(dimethylsiloxane) (PDMS) as building blocks, we have demonstrated the elastic-modulus-dependent MSA of PDMS based on the host/guest molecular recognition between supramolecular groups of β-cyclodextrin and adamantane. In the varied elastic modulus range of 0.38 to 3.84 MPa, we obtained the trend of the MSA probability decreasing from 100% at 0.38 MPa to 0% at 3.84 MPa. Meanwhile, in situ measurements of interactive forces between PDMS building blocks have supported the observed assembly phenomena. The underlying reasons are interpreted with the low-modulus flexible surfaces favoring for high molecular mobility to achieve interactions between multiple sites at the interface based on the theory of multivalency. Taken together, we have demonstrated the feasibility of directly adjusting the modulus of bulk materials to realize MSA of nonhydrogel materials, which may provide clues to the fast wet adhesion and new solutions to the additive manufacture of elastomer materials.