Nature 381, 56 - 58 (02 May 1996); doi:10.1038/381056a0

Control of crystal phase switching and orientation by soluble mollusc-shell proteins

A. M. Belcher^*†, X. H. Wu^‡, R. J. Christensen^‡, P. K. Hansma^§, G. D. Stucky^*‡ & D. E. Morse^†

Materials Research Laboratory and ^* Department of Chemistry, ^† Marine Biotechnology Center, ^‡ Department of Materials, ^§ Department of Physics, Department of Molecular, Cellular and Developmental Biology, University of California, Santa Barbara, California 93106, USA

IN the initial stages of the biomineralization of abalone shells, a primer layer of oriented calcite crystals grows on a nucleating protein sheet^1,2. The deposition of this primer is followed by an abrupt transition to c-axis-oriented crystals of aragonite, another crystalline form of calcium carbonate. The formation of each of the two crystal types is accompanied by the synthesis of specific polyanionic proteins^1–3, suggesting that cooperative interactions between these proteins and the inorganic ions during crystal nucleation and growth control the phase of the deposited mineral and that differential expression of the proteins allows the organism to induce phase changes. It is known that soluble shell proteins can control crystal morphology^4–10, but it has been suspected that the switch in phase—from calcite to aragonite—might require the deposition of a new nucleating protein sheet. Here we describe in vitro studies of the crystallization of calcium carbonate in the presence of soluble polyanionic proteins extracted from abalone shell. We find that these proteins alone are sufficient to control the crystal phase, allowing us to switch abruptly and sequentially between aragonite and calcite without the need for deposition of an intervening protein sheet. These results show that soluble organic components can exert greater control over hierarchical biomineral growth than hitherto suspected, offering the prospect of similar phase control in materials chemistry.

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