Crystallization and self-assembly of flowerlike superstructures of calcium carbonate regulated by pepsin Langmuir monolayers

Flowerlike superstructures of calcium carbonate were synthesized at air–water interface in the presence of pepsin Langmuir monolayers as the biomimetic template. The phase structure, morphology, and microstructure of the products obtained at various crystallization stages were characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction and high resolution transmission electron microscopy. The structural and morphological evolution processes of the products from monodispersed nanoparticles to nanoparticle aggregates and flowerlike superstructures were investigated. Results indicate that the flowerlike superstructures of calcium carbonate are assembled from amorphous calcium carbonate nanoparticles. The growth and assembly of calcium carbonate minerals are significantly regulated by the pepsin Langmuir monolayers. Namely, the pepsin Langmuir monolayers stabilize amorphous calcium carbonate nanoparticles and direct their transformation to amorphous aggregates via non-oriented aggregation. The present approach presents a feasible way to manipulate the growth of inorganic crystal, which, hopefully, is to help better reveal the role of proteins in mineralization process and understand the mechanism of biomineralization. -- Highlights: ► Pepsin Langmuir monolayer as biomimetic template. ► Flower-like calcite crystals experience a novel assembly and growth process. ► The morphologic evolution and phase transformation were observed. ► The trace of initial nucleation site of CaCO3 at the interface was observed. ► The template directs the crystallization and growth process.