Enzymatically Covalent and Noncovalent Weaving toward Highly Efficient Synthesis of 2D Monolayered Molecular Fabrics

Molecular fabrics with fascinating physical characteristics, such as structural flexibility and single-layered thinness, have attracted much attention. Chemists worldwide have been working on building unique molecularly woven structures in two dimensions. However, the synthesis of two-dimensional molecular weaving remains a challenging task, especially in water. Herein, we propose a straightforward and practical method to construct 2D molecular fabrics by enzymatically covalent and noncovalent syntheses in water. In particular, aromatic helical pentamers with two-terminal tyrosine residues (<b>Penta-Tyr</b>) can spontaneously dimerize via π-π interactions into double-helical interlocking structure, and the two-terminal tyrosine moieties of <b>Penta-Tyr</b> can undergo oxidative polymerization catalyzed by horseradish peroxidase (HRP) and hydrogen peroxide (H₂O₂) for effective covalent cross-linking. The 2D monolayered molecular fabrics can be readily prepared by the catalysis of HRP and H₂O₂ under mild conditions, which exhibit concentration-dependent weaving behavior. This work not only demonstrates an enzyme-catalyzed approach for the highly efficient synthesis of 2D monolayered molecular fabrics for the first time but also will promote the controllable preparation and application of water-soluble 2D molecular fabrics.