Sequential switch of biomineral crystal morphology using trivalent ions

Many biominerals are laminated such that crystal shape or habit changes from layer to layer thus yielding exquisitely designed composite materials with tightly controlled properties. Although lamination in biominerals is usually performed using peptides and proteins, here we introduce a new strategy by which sequential addition or depletion of inorganic trivalent ions in a supersaturated solution can be used to switch the surface morphology of calcium oxalate monohydrate (COM) back and forth, resulting in either the growth of flat crystalline sheets or of nanostructures oriented perpendicular to the surface. We propose that the occupation of a Ca(2+) site by Eu(3+) ion switches the orientation of the COM unit cell. The need to compensate the third charge forces coordination of Eu(3+) to an additional oxalate ion ((-)OOC-COO(-)) in an orientation that is not compatible with the initial unit cell. This mechanism of switching the orientation of the unit cell is unique, as it does not involve the use of expensive and thermally labile biomolecules. Suggestions of how to extend this strategy to engineer non-biological nanocomposites are given.