Template‐Dependent Morphogenesis of Oriented Calcite Crystals in the Presence of Magnesium Ions

Abstract

This paper presents a study of the morphogenesis of oriented crystals caused by solution growth modifiers. Self-assembled monolayers of HS-(CH 2 ) 15 -CO 2 H, HS-(CH 2 ) 10 -CO 2 H, HS-(CH 2 ) 11 -SO 3 H, HS-(CH 2 ) 11 -OH supported on gold that induce the oriented nucleation of calcite from the (013), (113), (106)+(1.0.12) and (104) planes respectively, were used as templates for calcite crystallization from solutions containing Mg ions (Mg/Ca = 0-4). We show that when crystal growth in the presence of an additive is coupled with the control over the nucleation process, the formation of crystal arrays with extremely uniform size, shape, facets and orientation is achieved. This study for the first time demonstrates that crystal morphogenesis depends on the orientation of the crystals on the surface, such that crystals grown on different substrates exhibit uniform, but template-specific characteristics. The possible mechanisms of this new phenomenon -an additive-induced morphogenesis of differently oriented crystals -are discussed. We believe that this approach can be used as a potent crystallization strategy that would allow the synthesis of homogeneous crystals with finely-tailored morphologies.

Nucleation of metastable aragonite CaCO 3 in seawater

“…Although our study focuses on calcium carbonate nucleation in inorganic abiotic environments, macromolecule proteins and organic matrices can also influence polymorph selection between calcite and aragonite during crystallization (46,47). These macromolecules can influence calcium carbonate interfacial energies during heterogeneous nucleation on substrates (48), modify the local Mg 2+ concentrations around nascent nuclei (49), template polymorph selection epitaxially (50), and influence the selective binding strength of aqueous ions (51). Mg 2+ also incorporates into the transient prenucleation clusters and amorphous calcium carbonate phases (52), which can be stabilized in the presence of macromolecules (53), and whose dissolution may further alter local Mg 2+ concentrations from that of the bulk solution.…”

Molecular Dynamics Simulation to Understand the Ability of Anionic Polymers to Alter the Morphology of Calcite

“…The (104) is the typical face observed in the well-shaped crystals of calcite [29,30]. The (110) is used to represent {hk0} faces [10,12,14].…”

Micro‐ to nanostructure and geochemistry of extant crinoidal echinoderm skeletons

“…Indeed, many surveys indicated a link between Mg-enriched first-formed regions, distribution of organic components and formation of precursory ACC skeleton phase in various invertebrates (e.g. Aizenberg et al, 2002;Han et al, 2005;Weiner et al, 2005;Meibom et al, 2008;Gong et al, 2012). It has been suggested that Asprich proteins that induce and stabilize the ACC phase include a domain that is capable of binding Mg ions (Politi et al, 2007).…”