Influence of conducting polymers based on carboxylated polyaniline on in vitro CaCO3 crystallization

Conducting polymers are interesting materials of technological applications, while the use of polymers as additives controlling crystal nucleation and growth is a fast growing research field. In the present article, we make a first step in combining both topics and report the effect of conducting polymer derivatives, which are based on carboxylated polyanilines (c-PANIs), on in vitro CaCO3 crystallization by the Kitano and gas diffusion method. This is the first example of the mineralization control of CaCO3 by a rigid carboxylated polymer. Both the concentration of c-PANI and the presence of carboxylate groups have a strong influence on the CaCO3 crystallization behavior and crystal morphology. X-ray diffraction (XRD) analysis shows crystalline calcite particles confirmed by FTIR spectra. pH and Ca2+ measurements during CaCO3 crystallization utilizing the Kitano and a constant-pH approach show a defined nucleation period of CaCO3 particles. The measurements allow for the calculation of the supersaturation time development, and the kinetic data can be combined with time-dependent light microscopy. The presence of c-PANIs delays the time of nucleation indicative of calcite nucleation inhibition. Microscopy illustrates the morphologies of CaCO3 crystals at all crystallization stages, from homogeneous spherical amorphous CaCO3 (ACC) particles corresponding to the first steps of crystallization to transition stage calcite crystals also involving a dissolution-recrystallization process in a late stage of crystallization. The data show that it is not possible to conclude the crystallization mechanism even for a very simple additive controlled crystallization process without time-resolved microscopic data supplemented by the analysis of the species present in the solution. Finally, fluorescence analysis indicates that conducting polymer derivatives can be incorporated into precipitated calcite particles. This gives rise to CaCO3 particles with novel and interesting optical properties.