Petunia-shaped superstructures of CaCO3 aggregates modulated by modified chitosan

This paper presents the crystallization behavior of calcium carbonate at the air/liquid interface of aqueous systems of carboxymethyl chitosan (CMCS) using the Kitano method. Although the synthesized CMCS (Mw approximately 100,000) with 1.57 degree of carboxymethyl substitution shows no surface activity, it controls the crystallization of calcium carbonate to form a petunia-shaped superstructure. The shuttlecock-like head of this superstructure strongly supports Colfen's opinion (Rudloff, J.; Colfen, H. Langmuir 2004, 20, 991-996) for the existence of a gas template of CO2 bubbles temporarily captured by polymer molecules, while formation of the stem of this superstructure is provisionally attributed to the presence of the strong electrostatic interactions between calcium ions and the carboxylate groups. The CaCO3 superstructure and its morphology depend not only on the polymer concentration but also on the combined number of calcium ions per CMCS molecule. These results imply that this simple and versatile method expands the morphological investigation of mineralization processes.