Peptide-Controlled Assembly of Macroscopic Calcium Oxalate Nanosheets

[Image: see text] The fabrication of two-dimensional (2D) biomineral nanosheets is of high interest owing to their promise for applications in electronics, filtration, catalysis, and chemical sensing. Using a facile approach inspired by biomineralization in nature, we fabricate laterally macroscopic calcium oxalate nanosheets using β-folded peptides. The template peptides are composed of repetitive glutamic acid and leucine amino acids, self-organized at the air–water interface. Surface-specific sum frequency generation spectroscopy and molecular dynamics simulations reveal that the formation of oxalate nanosheets relies on the peptide–Ca(2+) ion interaction at the interface, which not only restructures the peptides but also templates Ca(2+) ions into a calcium oxalate dihydrate lattice. Combined, this enables the formation of a critical structural intermediate in the assembly pathway toward the oxalate sheet formation. These insights into peptide–ion interfacial interaction are important for designing novel inorganic 2D materials.