Inorganic Biominerals in Crustaceans are Structurally Independent of Organic Framework

Abstract:

Biomineralization of calcium carbonate (CaCO₃) as crystalline calcite or amorphous CaCO₃ (ACC) occurs in the exoskeletons of all crustaceans. These cuticles are complex composites of inorganic mineral and organic macromolecules with highly divergent morphologies that are adapted to the extreme variations in environmental pressures within their diverse ecological niches. The remarkable variations and adaptations that form, infer a highly efficient and regulated mechanism for biomineralization that is most likely orchestrated by a myriad of biomacromolecules (Ziegler A 2012).

The roles of these peptides and organic metabolites during CaCO₃ biomineralization are not well understood. In part, this is due to a lack of knowledge of crustacean homeostasis. In a step toward understanding cuticle mineralization in crustaceans, this study asks: Which molecules affect biomineralization? Do the biomineral-active molecules vary greatly between species and body parts? Recent studies of polysaccharide controls on mineralization also raise the question of whether small heterogeneities in chitin, the most abundant biopolymer of the composite, could be primarily responsible for differences in CaCO₃ crystallinity.

This study used a novel spectroscopic approach to characterize the mineral and organic components of exoskeletons from three Malacostraca organisms — American Lobster (Homarus americanus), Dungeness Crab (Metacarcinus magister), and Red Rock Crab (Cancer productus). Using high-energy x-ray diffraction and Raman spectroscopy, the cuticles of three major body parts from these organisms were analyzed for the structure and bulk chemistry of its chitin and CaCO₃ components. The findings indicate that Raman spectroscopy provides adequate resolution to show that crystallinity of chitin and the CaCO₃ mineral component are chemically independent of each other, although their crystallinities co-vary for Brachyura species (Dungeness and Red Rock Crabs). Insights from this study suggest chitin provides the structural framework of the cuticle, without direct chemical control on the biomineralization of CaCO₃. Peptides and small metabolites are likely to be more directly involved in the mechanisms controlling polymerization, crystallization, and composition of both chitin and CaCO₃.