Lattice Shrinkage by Incorporation of Recombinant Starmaker‐Like Protein within Bioinspired Calcium Carbonate Crystals

Abstract

The biological mediation of mineral formation (biomineralization) is realized through diverse organic macromolecules that guide this process in a spatial and temporal manner. Although the role of these molecules in biomineralization is being gradually revealed, the molecular basis of their regulatory function is still poorly understood. In this study, the incorporation and distribution of the model intrinsically disordered starmaker‐like (Stm‐l) protein, which is active in fish otoliths biomineralization, within calcium carbonate crystals, is revealed. Stm‐l promotes crystal nucleation and anisotropic tailoring of crystal morphology. Intracrystalline incorporation of Stm‐l protein unexpectedly results in shrinkage (and not expansion, as commonly described in biomineral and bioinspired crystals) of the crystal lattice volume, which is described herein, for the first time, for bioinspired mineralization. A ring pattern was observed in crystals grown for 48 h; this was composed of a protein‐enriched region flanked by protein‐depleted regions. It can be explained as a result of the Ostwald‐like ripening process and intrinsic properties of Stm‐l, and bears some analogy to the daily growth layers of the otolith.

Surfactin as a Green Agent Controlling the Growth of Porous Calcite Microstructures

“…Moreover, the edges of the crystals were not so sharp and were significantly deformed ( Figure 3 C–F). The deformation of calcite crystal microstructures after adding compounds of biological origin has been widely described in the literature [ 24 , 25 , 26 , 27 , 28 ]. Biomolecules, especially anionic molecules, can bind calcium ions in solution as well as on the surface of created crystals, changing the direction of growth or blocking the growth of the crystal surface [ 2 ].…”

Multiscale analysis on otolith structural features reveals differences in ontogenesis and sex in Merluccius merluccius in the western Adriatic Sea

“…Indeed, the organic matrix contains various organic compounds (e.g. proteins, amino acids, collagens, proteoglycans) which are known to guide temporally and spatially the biomineralization process controlling and promoting the crystallites nucleation, orientation and growth [40][41][42]. Furthermore, the number of touching branch-like structures (referred to as protuberances) increased with fish TL.…”

“…Otolith crystalline features also changed with fish size. Earlier studies have shown that the time-dependent distribution of a protein involved in the formation of otoliths (Starmaker-like protein) can have a significant effect on the crystallite size of growing crystals [ 42 ]. Therefore, the increment in aragonite crystallite size during otolith growth observed in M. merluccius could depend on variations in organic matrix composition [ 42 ].…”

“…Earlier studies have shown that the time-dependent distribution of a protein involved in the formation of otoliths (Starmaker-like protein) can have a significant effect on the crystallite size of growing crystals [ 42 ]. Therefore, the increment in aragonite crystallite size during otolith growth observed in M. merluccius could depend on variations in organic matrix composition [ 42 ]. Concerning otolith microchemistry, most of the investigated trace elements (element : Ca molar ratio) showed a negative correlation with fish size (Ba, Co, Li, Mg, P, S, Sr, Zn) which could depend on: (i) different water chemistry associated with water depth (Sr and Ba) [ 49 ], probably related to fish migration, and consequently (ii) shift in dietary sources (S) [ 50 ], and (iii) ontogenetic changes of the organic matrix content (P and Zn) [ 51 ].…”

Functional derivatives of human dentin matrix protein 1 modulate morphology of calcium carbonate crystals

“…Interestingly, a lot of proteins involved in the biomineralization of calcium phosphate and calcium carbonate are IDPs . These include, for example, mammalian proteins: osteopontin (OPN), bone sialoprotein (BSP), dentin sialophosphoprotein (DSPP), as well as a zebrafish otolith matrix protein Starmaker (Stm), and its homologs from other fish species . However, more ordered proteins are also involved, for example: otoconin‐90 (OC90), amorphous calcium carbonate‐binding protein (ACCBP), otolin‐1 …”