Assembly and Biomineralization of Polymorphic Gold–Peptide Superstructures Using Tyrosine‐Rich Short Peptides

Abstract Peptides show tremendous promise in synthesizing metal–peptide superstructures with tailored shapes and functions. However, bottom‐up control of the polymorphs of these superstructures using a single short peptide without molecular modification has not been mechanistically clarified. Therefore, an approach to constructing gold–peptide superstructures with unprecedented structural diversity using a tyrosine‐rich short peptide is developed, based on the assembling and mineralizing attributes of tyrosine. One‐step UV irradiation of peptide/gold‐salt systems enables on‐site mineralization of gold ions, permitting controlled solvent‐dependent fabrication of various superstructures. 0D colloids, 2D sheets, 3D superspheres, and 3D hollow capsules are produced via one‐pot reactions in a pH‐10 buffer, at the interface of a toluene–water biphasic system, in water, and in toluene‐in‐water emulsions, respectively, whereas 1D rod/fibril structures are produced using rapidly assembling peptides (A, F, I, L, N, V, Y, and D as X in YY‐X‐YY) in a two‐step process. Several peptide derivatives, which also exhibit assembling and biomineralizing abilities and form various superstructures, validate the functionality of the tyrosine‐rich peptide. This study sheds light on the design and development of diverse gold‐peptide superstructures for applications including catalysis, sensing, imaging, and photothermal therapy.