Robust Electrostatically Interactive Hydrogel Coatings for Macroscopic Supramolecular Assembly via Rapid Wet Adhesion

A macroscopic supramolecular assembly (MSA) refers to non-covalent interactions between building blocks over a micrometer scale, which provides insights into bio-/wet adhesion, self-healing, and so on and new fabrication strategies to heterogeneous structures and bio-scaffolds. The key to realize the MSA of rigid materials is pre-modifying a compliant coating known as a “flexible spacing coating” beneath the interactive moieties. However, available coatings are limited to polyelectrolyte multilayers with shortcomings of tedious fabrication, weak adhesion to substrates, susceptibility to external reagents, and so on. Here, we develop a facile method to induce a new “flexible spacing coating” of a poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogel with electrostatic interactions to achieve MSA of diverse rigid materials (quartz, metal, rubber, and plastics). Selective self-assembly of positive–negative charged surfaces is observed by the naked eye under 3 min of shaking in water, providing strategies to rapid wet adhesion. The interfacial binding force between positive–negative interacted surfaces is 1018.1 ± 299.2 N/m², which is over two magnitudes larger than that of control groups, that is, positive–positive (24.4 ± 10.0 N/m²) and negative–negative (67.5 ± 16.7 N/m²) interacted surfaces. In situ force measurements and control experiments of identically charged building blocks have strongly supported the improved binding strength and chemical selectivity between interactive building blocks. The coating is advantageous with a simple fabrication, strong adhesion to materials, robust solvent tolerance to assembly solutions, and feasibility of photo-patterning. We envision that the above strategy would broaden the material choices of flexible spacing coatings for efficient MSA and new methods for rapid interfacial adhesion.