Journal Article
Proceedings of the National Academy of Sciences, vol. 111, iss. 4, pp. 1304-1309, 2014
Authors
Laura M. Hamm, Anthony J. Giuffre, Nizhou Han, Jinhui Tao, Debin Wang, James J. De Yoreo, Patricia M. Dove
Abstract
Significance
Organisms use specialized macromolecules to direct the timing and placement of crystals during biomineral formation. This phenomenon has inspired synthetic approaches to templating but remains poorly understood. One view holds that the organic matrix promotes nucleation through stereochemical matching to guide the organization of solute ions, while another equates binding strength to promotion of nucleation. Our study reconciles these views with a mechanistic explanation for template-directed nucleation. Through measurements of calcite nucleation kinetics and substrate–crystal binding we show that nucleation barriers and binding free energies are linearly related for all functional group chemistries and conformations as predicted from classical nucleation theory. This model reconciles long-standing concepts of stereochemical matching with the conventional wisdom that good binders are good nucleators.
