Acidic Monosaccharides become Incorporated into Calcite Single Crystals*.

Carbohydrates, along with proteins and peptides, are known to represent a major class of biomacromolecules involved in calcium carbonate biomineralization. However, in spite of multiple physical and biochemical characterizations, the explicit role of saccharide macromolecules (long chains of carbohydrate molecules) in mineral deposition is not yet understood. In this study, we investigated the influence of two common acidic monosaccharides (MSs), the two simplest forms of acidic carbohydrates, namely glucuronic and galacturonic acids, on the formation of calcite crystals in vitro. We show here that the size, morphology, and microstructure of calcite crystals are altered when they are grown in the presence of these MSs. More importantly, these MSs were found to become incorporated into the calcite crystalline lattice and induce anisotropic lattice distortions, a phenomenon widely studied for other biomolecules related to CaCO3 biomineralization, but never before reported in the case of single MSs. Changes in the calcite lattice induced by MSs incorporation were precisely determined by high-resolution synchrotron powder X-ray diffraction. We believe that the results of this research may deepen our understanding of the interaction of saccharide polymers with an inorganic host and shed light on the implications of carbohydrates for biomineralization processes.

A fungal mycelium templates the growth of aragonite needles.

Fungi live within diverse environments and survive well under extreme conditions that are usually beyond the tolerance of most other organisms. In different environments fungi are known to induce precipitation of a wide range of minerals. Various species of fungi have been shown to facilitate calcium carbonate mineralization. Here, inspired by examples of needle-fiber calcite formed via fungus-induced biomineralization typically observed in soils and sediments, we utilized inactivated fungus to synthetically induce precipitation of CaCO3 needles. To our knowledge, the feasibility of growing aragonitic needles within fungal mycelium in vitro has not been previously demonstrated. The needles we obtained were curved, displayed hexagonal facets, and demonstrated high-aspect ratios close to 60. The size and shape of these synthetic needles matched those of the mycelium of the natural fungus. Utilizing high-resolution characterization techniques, we studied the morphology and the micro- and nanostructures of the aragonitic needles. Our findings showed that even inactivated fungal mycelium, if present in the crystallization environment, can serve as a template for the formation of high-aspect ratio fibers and can stabilize metastable polymorphs.