Recent work has highlighted the relevance of so-called prenucleation clusters during the nucleation of biominerals in vitro (1, 2). These stable ion clusters form in solution prior to nucleation, and the initial precipitation of amorphous nanoparticles appears to proceed via aggregation of the prenucleation clusters. In case of calcium carbonate, the processes lead to the development of distinct short-range structural features in amorphous intermediates (3). The distinct amorphous forms can be considered within the physical notion of amorphous polymorphism (polyamorphism), which is also observed in biomineralization, and may form the basis of polymorph selection (4).

The present contribution will summarize the notion of the prenucleation cluster pathway outlined above, paying special attention to most recent developments. Inter alia, this includes the physicochemical characterization of the multiple roles of different organic additives, which are relevant for biomineralization, during the early stages of precipitation.

1. D. Gebauer, A. Völkel, H. Cölfen, Science 322, 1819 (2008).

2. D. Gebauer, H. Cölfen, Nano Today 6, 564 (2011).

3. D. Gebauer, P. N. Gunawidjaja, J. Y. P. Ko, Z. Bacsik, B. Aziz, L. J. Liu, Y. F. Hu, L. Bergström, C.-W. Tai, T.-K. Sham, M. Edén, N. Hedin, Angew. Chem. Int. Ed. 49, 8889 (2010).

4. J. H. E. Cartwright, A. G. Checa, J. D. Gale, D. Gebauer, C. I. Sainz-Díaz, Angew. Chem. Int. Ed. 51, 11960 (2012).

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1. Non-Classical Nucleation of Calcium Sulfate: A Novel View on the Origin of Scale Formation